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WO2020175702A1 - Waterproof moisture-permeable fabric and production method for same - Google Patents

Waterproof moisture-permeable fabric and production method for same Download PDF

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Publication number
WO2020175702A1
WO2020175702A1 PCT/JP2020/008524 JP2020008524W WO2020175702A1 WO 2020175702 A1 WO2020175702 A1 WO 2020175702A1 JP 2020008524 W JP2020008524 W JP 2020008524W WO 2020175702 A1 WO2020175702 A1 WO 2020175702A1
Authority
WO
WIPO (PCT)
Prior art keywords
fabric
waterproof
amino acid
protein
seq
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/008524
Other languages
French (fr)
Japanese (ja)
Inventor
和秀 関山
佑之介 安部
貴之 児島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Spiber Inc
Goldwin Inc
Original Assignee
Spiber Inc
Goldwin Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Spiber Inc, Goldwin Inc filed Critical Spiber Inc
Priority to JP2021502665A priority Critical patent/JPWO2020175702A1/ja
Publication of WO2020175702A1 publication Critical patent/WO2020175702A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P21/00—Preparation of peptides or proteins
    • C12P21/02—Preparation of peptides or proteins having a known sequence of two or more amino acids, e.g. glutathione
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425—Cellulose series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4266—Natural fibres not provided for in group D04H1/425
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

  • the present invention relates to a waterproof and moisture-permeable fabric, and a method for producing the same.
  • a cloth used as a material such as various clothing and tents, and a covering sheet that protects a predetermined article from a liquid such as water prevents the intrusion of a liquid such as water from the outside. It is desired to have a waterproof and moisture-permeable property that allows vapor to pass therethrough.
  • Patent Document 1 discloses that in order to provide a required shape-retaining property by reinforcing a first layer, which is a porous film having waterproofness and moisture permeability, and the first layer.
  • a waterproof material having excellent moisture permeability, characterized in that the second layer, which is a woven or knitted fabric, is laminated with a hydrophilic adhesive which contains a hydrophilic functional group and swells in water but does not dissolve.
  • Patent Document 2 discloses a laminated fabric in which a non-woven web made of fibers having a diameter of less than 1 is laminated on at least one side of a fabric with an adhesive, and the adhesive has a thickness of the non-woven fabric. It is impregnated with 10% or more in the depth direction, and the peel strength between the fabric and the nonwoven web is 120 A laminated fabric characterized by the above is disclosed.
  • Patent Document 1 Japanese Patent Laid-Open No. 1595-15982
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2 0 10 -3 0 2 8 9
  • the laminated fabric disclosed in Patent Document 2 is composed of a nonwoven fabric web having high flexibility, for example, even if the nonwoven fabric web is thickened to enhance the robustness, the entire laminated fabric The decrease in flexibility can be suppressed.
  • the waterproofness and the moisture permeability are both dependent on the fiber density of the nonwoven web, so if the fiber density is increased to increase the moisture permeability, the waterproofness is increased.
  • Even in the case of laminated fabrics it is necessary to reduce the fiber density and the like in order to improve waterproofness, but for that purpose, it is necessary to perform troublesome operations such as making the fibers that provide the nonwoven fabrics thinner. There wasn't.
  • non-woven fabric is made of synthetic fibers, it was not possible to reduce the environmental burden.
  • even such a laminated fabric is desired to further have functionality such as water resistance.
  • a second object of the present invention is to provide a waterproof and moisture-permeable fabric capable of improving robustness and strength without impairing the flexibility of the entire fabric and having sufficient waterproofness. ..
  • Another object of the present invention is to provide a method for producing a waterproof and breathable fabric, which can easily produce such a waterproof and breathable fabric.
  • a third object of the present invention is to improve waterproofness and strength without impairing the flexibility and moisture permeability of the entire fabric, and yet to ensure sufficient waterproofness and moisture permeability. Is to provide the dough. It is another object of the present invention to provide a method for producing a waterproof and breathable fabric, which can easily produce such a waterproof and breathable fabric.
  • a fifth object of the present invention is to improve the robustness and strength of the fabric without impairing the flexibility of the fabric as a whole, and to realize a reduction in environmental load by de-oiling the fabric. Is to provide.
  • Another object of the present invention is to provide a method for producing a waterproof and breathable fabric, which can easily produce such a waterproof and breathable fabric.
  • a sixth object of the present invention is to provide robustness and durability without impairing the flexibility of the entire fabric. ⁇ 2020/175 702 4 ⁇ (: 171? 2020 /008524
  • the present invention (first invention) that achieves the above-mentioned first object relates to the following respective inventions, for example.
  • a waterproof/moisture permeable layer made of a non-woven fabric containing ultrafine fibers with a fiber diameter of 10 or less is bonded to a skin layer made of a weave, and the ultrafine fibers contain at least one of natural fibers and naturally derived fibers.
  • a waterproof/moisture permeable fabric comprising a waterproof/moisture permeable layer made of a non-woven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less and a surface layer made of a knitted fabric.
  • a waterproof/moisture permeable layer forming step of forming a waterproof/moisture permeable layer made of a non-woven fabric containing a protein ultrafine fiber having a fiber diameter of 10 or less on a skin layer made of a knitted woven fabric is provided.
  • a method for producing a waterproof and breathable fabric which comprises forming the nonwoven fabric by accumulating the protein ultrafine fibers on the skin layer by electrospinning using a dope solution.
  • the present invention (second invention) that achieves the above-mentioned second object relates to the following respective inventions, for example.
  • a waterproof/moisture permeable fabric comprising a waterproof and moisture permeable layer made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less and a skin layer made of a knitted woven body containing a first water resistance-imparting substance.
  • the modified fibroin and the first water resistance-imparting substance are covalently bonded
  • the waterproof/moisture permeable fabric according to any one of [2-1] to [2-4], wherein the first water resistance-imparting substance is at least one selected from silicone polymers and fluorine polymers.
  • the waterproof/moisture permeable fabric according to any one of [2_1] to [2_5], in which the nonwoven fabric contains a second water resistance-imparting substance.
  • a method of manufacturing a waterproof and moisture-permeable fabric comprising the step of joining the nonwoven fabric and the knitted fabric.
  • the modified fibroin and the first water resistance-imparting substance are covalently bonded
  • the present invention (third invention) that achieves the third object described above, for example, relates to the following respective inventions. 20/175702 7 ⁇ (: 171? 2020 /008524
  • a waterproof and moisture-permeable layer made of a non-woven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less and a skin layer made of a knitted fabric are joined together,
  • a waterproof and breathable fabric in which the above nonwoven fabric is water-shrinked is water-shrinked.
  • Fiber density increase rate ⁇ (fiber density of non-woven fabric after water shrinkage/fiber density of non-woven fabric before water shrinkage) 1 1 ⁇ X 100 (%) (Formula I)
  • the above protein ultrafine fiber is the waterproof and moisture-permeable fabric according to [3 _ 1] or [3 _ 2], which has a shrinkage ratio when wet defined by the following formula of 2% or more.
  • the above-mentioned protein ultrafine fiber is the waterproof and moisture-permeable fabric according to any one of [3-1] to [3-3], which has a dry shrinkage rate of more than 7% as defined by the following formula.
  • Shrinkage during drying ⁇ 1-(length of dried protein microfibers after contact with water to make them wet/length of protein microfibers before contact with water) ⁇ X 100 (%) (Formula III)
  • the waterproof/breathable fabric according to any one of [3-1] to [3-4], wherein the nonwoven fabric has a fiber density of 0 049/01 2 or more.
  • the above protein ultrafine fibers contain modified fibroin, [3-1] to [3
  • the above-mentioned knitted or woven body is the waterproof/moisture permeable fabric according to any one of [3 _ 1] to [3 _ 7], wherein the surface on the side opposite to the side where the nonwoven fabric is joined is treated to be water repellent.
  • the waterproof/moisture permeable fabric according to any one of [3-1] to [3-8], wherein the knitted fabric contains protein fibers.
  • the water-shrinkable non-woven fabric was contracted by contacting moisture with a non-woven fabric formed by accumulating protein ultrafine fibers with a fiber diameter of 10 or less by electrospinning using a dope containing protein.
  • a method of manufacturing a waterproof and breathable fabric was used.
  • Fiber density increase rate ⁇ (fiber density of non-woven fabric after water shrinkage/fiber density of non-woven fabric before water shrinkage) 1 1 ⁇ X 100 (%) (Formula I)
  • Fiber density of the nonwoven fabric after the water shrinkage is ⁇ . 04 9 / Rei_1 2 or more, [3- 1 2] - The process according to any one of [3 1 6].
  • the modified fibroin is a modified spider silk fibroin production method according to [3-1 8].
  • the present invention (fourth invention) that achieves the above-mentioned fourth object relates to the following respective developments, for example.
  • a waterproof/moisture permeable fabric comprising a waterproof/moisture permeable layer made of a non-woven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less, and a skin layer made of a knitted fabric, which are joined without an intervening layer.
  • the method for producing a waterproof and moisture-permeable fabric comprising the step of obtaining a fabric in which the waterproof and moisture-permeable layer and the skin layer are bonded to each other.
  • a covalent bond is formed by a radical reaction by irradiating plasma to one or both of the joint surface of the waterproof/moisture permeable layer made of non-woven fabric containing protein ultrafine fibers with a fiber diameter of 10 or less, and the joint surface of the skin layer made of the woven fabric.
  • the method for producing a waterproof and moisture-permeable fabric comprising the step of obtaining a fabric in which the waterproof and moisture-permeable layer is joined to the skin layer.
  • a method for producing a waterproof and moisture-permeable fabric comprising the step of obtaining a fabric in which the waterproof and moisture-permeable layer and the skin layer are joined by forming the fabric.
  • the modified fibroin is a modified spider silk fibroin production method according to [4-1 1].
  • modified fibroin is a modified spider silk fibroin.
  • the present invention (fifth invention) that achieves the above fifth object relates to the following respective inventions, for example.
  • a waterproof and breathable fabric which is formed by joining a nonwoven fabric made of biodegradable fibers containing biodegradable ultrafine fibers having a fiber diameter of 10 or less and a knitted woven body made of biodegradable material.
  • the waterproof and breathable fabric according to any one of [5 _ 1] to [5 _ 3], wherein the biodegradable material contains a modified fibroin.
  • the present invention (sixth invention) that achieves the above sixth object relates to the following respective inventions, for example.
  • a waterproof and moisture-permeable layer made of non-woven fabric containing ultrafine fibers with a fiber diameter of 10 or less, and functions ⁇ 2020/175 702 13 ⁇ (: 171-1? 2020/008524
  • a waterproof and breathable fabric that is joined to a skin layer made of a knitted fabric
  • the protein fiber contains a crosslinked protein
  • the above-mentioned crosslinked protein is a polypeptide skeleton, a first residue which is a residue of a first reactive agent having two or more first reactive groups capable of reacting with a protein to form a bond, and A second residue, which is a residue of a second reactive agent having one second reactive group capable of reacting with the first reactive group to form a bond, and each having a plurality of
  • At least one of the first residues crosslinks the polypeptide backbone
  • the waterproof/moisture permeable fabric according to any one of [6-1] to [6-5], wherein the knitted fabric further contains a modified hydroxyl group-containing polymer in which a functional group is bonded to the hydroxyl group-containing polymer. ..
  • the waterproof and breathable fabric according to any one of [6 _ 1] to [6 _ 6], wherein the ultrafine fibers are protein ultrafine fibers.
  • the protein ultrafine fiber contains a protein cross-linked product
  • the above-mentioned crosslinked protein is a polypeptide skeleton, a first residue which is a residue of a first reactive agent having two or more first reactive groups capable of reacting with a protein to form a bond, and A second residue, which is a residue of a second reactive agent having one second reactive group capable of reacting with the first reactive group to form a bond, and each having a plurality of
  • At least one of the first residues crosslinks the polypeptide backbone
  • the waterproof/moisture permeable fabric according to any one of [6-1] to [6-10], wherein the nonwoven fabric further contains a modified hydroxyl group-containing polymer in which a functional group is bonded to the hydroxyl group-containing polymer.
  • the waterproof and moisture-permeable fabric according to the first invention has a waterproof and moisture-permeable layer made of a nonwoven fabric containing protein microfibers having a fiber diameter of 10 or less, and therefore depends on the diameter of the pores and the fiber density. Can achieve sufficient moisture permeability without increasing the flexibility and permeability of the entire fabric. ⁇ 2020/175 702 15 ⁇ (:171? 2020/008524
  • the thickness of the waterproof breathable layer can be easily changed without impairing the wettability.
  • Protein ultrafine fibers constituting the waterproof moisture-permeable layer to have a hygroscopicity to prevent intrusion of liquid such as water is _ who, by releasing vapor (gas) from the fiber itself, can provide excellent moisture permeability ..
  • the waterproof/breathable fabric according to the second invention has a waterproof/breathable layer made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less, so that the waterproof/breathable fabric is not impaired in its flexibility and moisture permeability.
  • the thickness of the wet layer can be increased, and the robustness and strength can be improved.
  • the knitted fabric (skin layer) contains the water resistance-imparting substance, so that the waterproof property is improved.
  • the waterproof/moisture permeable fabric according to the third invention has a waterproof/moisture permeable layer made of a non-woven fabric containing protein fine fibers having a fiber diameter of 10 or less, it depends on the diameter of the pores, the fiber density and the like. It is possible to achieve sufficient moisture vapor permeability without changing the thickness of the waterproof moisture vapor permeable layer without impairing the flexibility and moisture permeability of the entire fabric. Protein ultrafine fibers constituting the waterproof moisture-permeable layer to have a hygroscopicity to prevent intrusion of liquid such as water is _ who, by releasing vapor (gas) from the fiber itself, can provide excellent moisture permeability .
  • the waterproof/moisture permeable fabric according to the third aspect of the present invention is provided with a water-shrinkable nonwoven fabric as the waterproof/moisture permeable layer, the diameter of the through hole is reduced and the waterproof property is improved. Therefore, according to the third aspect of the present invention, it is possible to provide a waterproof and moisture-permeable fabric that can improve the robustness and strength without impairing the flexibility and moisture permeability of the entire fabric and that can easily realize sufficient waterproofness. It is possible to provide. According to the third aspect of the invention, it is also possible to provide a method for producing a waterproof and breathable fabric, which can easily produce such a waterproof and breathable fabric.
  • the fourth invention sufficient moisture permeability can be realized irrespective of the diameter of the pores, the fiber density, etc., and the decrease in moisture permeability due to the joining of the waterproof moisture-permeable layer and the skin layer can be suppressed. It is possible to provide a possible waterproof and breathable fabric.
  • Waterproof and breathable fabric according to the fourth invention ⁇ 2020/175 702 16 ⁇ (: 171-1? 2020/008524
  • a waterproof and moisture-permeable fabric capable of improving robustness and strength without deteriorating the flexibility of the fabric as a whole and realizing reduction of environmental load by de-oiling. It becomes possible to provide. Since the waterproof breathable fabric according to the fifth invention comprises a non-woven fabric made of biodegradable fibers including biodegradable ultrafine fibers having a fiber diameter of 10 or less, the flexibility and moisture permeability of the entire fabric are impaired. Without increasing the thickness of the nonwoven fabric, it is possible to improve the robustness and strength. Further, since the waterproof and moisture-permeable fabric according to the fifth invention is biodegradable, it is possible to reduce the environmental load by removing petroleum.
  • the waterproof and moisture-permeable fabric according to the sixth invention comprises a waterproof and moisture-permeable layer made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less, so that the waterproof and moisture-permeable fabric does not impair the flexibility and moisture permeability of the entire transparent fabric.
  • the thickness of the moisture permeable layer can be increased, and the robustness and strength can be improved.
  • the waterproof and moisture-permeable fabric according to the sixth aspect of the present invention can impart arbitrary functionality (for example, water resistance) to the knitted fabric (skin layer).
  • Fig. 1 is a schematic view of a waterproof and moisture-permeable fabric according to an embodiment.
  • FIG. 2 is a schematic view of the waterproof/moisture permeable fabric according to the embodiment.
  • FIG. 3 is a schematic view of the waterproof/moisture permeable fabric according to the embodiment.
  • FIG. 4 is an explanatory diagram of an electrospinning device according to an embodiment.
  • FIG. 5 is a schematic diagram showing an example of a modified fibroin domain sequence.
  • Fig. 7 is a diagram showing a distribution of /so (%) values of fibroin derived from nature. ⁇ 2020/175 702 17 ⁇ (:171? 2020/008524
  • FIG. 8 is a schematic diagram showing an example of a domain sequence of modified fibroin.
  • FIG. 9 is a schematic diagram showing an example of a domain sequence of modified fibroin.
  • FIG. 10 is a graph showing an example of the results of a moisture absorption and heat generation test.
  • FIG. 11 This is a photograph of the waterproof breathable fabric obtained in Test Example 2.
  • FIG. 12 A cross-sectional photograph of the waterproof and moisture-permeable fabric obtained in Test Example 2.
  • FIG. 13 is an explanatory view schematically showing an example of a spinning apparatus for producing protein fibers (filaments).
  • the waterproof and moisture-permeable fabric means a material that has both waterproofness and moisture permeability, and includes, for example, a fabric that allows vapor to pass through while preventing liquids such as water from entering from the outside. ..
  • FIG. 1 is a schematic view of a waterproof and moisture-permeable fabric according to one embodiment.
  • the waterproof/moisture permeable fabric 10 shown in Fig. 1 is formed by joining the waterproof/moisture permeable layer 2 and the skin layer 1.
  • the skin layer 1 also functions as a shape-retaining layer for holding the shape of the waterproof breathable fabric.
  • FIG. 2 is a schematic view of a waterproof and moisture-permeable fabric according to another embodiment.
  • the waterproof/moisture permeable material 20 shown in FIG. 2 is composed of the waterproof/moisture permeable layer 2 and the skin layer 1 bonded to both surfaces thereof.
  • the skin layer 1 also functions as a shape-retaining layer for maintaining the shape of the waterproof/moisture permeable material.
  • two skin layers 1 may be formed of the same kind of material or different kinds of materials.
  • one of the two skin layers 1 may be a backing layer.
  • the waterproof/moisture permeable fabric 20 includes a waterproof/moisture permeable layer 2 and a waterproof/moisture permeable layer 20. ⁇ 2020/175 702 18 ⁇ (: 171? 2020 /008524
  • the water vapor permeable layer (2) is provided with a skin layer (1) joined to one surface thereof, and a backing layer joined to the surface of the waterproof moisture permeable layer (2) opposite to the surface thereof joined.
  • Fig. 3 is a schematic view of a waterproof and moisture-permeable fabric according to another embodiment.
  • the waterproof/breathable fabric 30 shown in Fig. 3 has the waterproof/moisture permeable layer 2 on one side of which the skin layer 1 is joined, and further on the opposite side of the waterproof/breathable layer 2 to which the skin layer 1 is joined.
  • the backing layer 3 is bonded to the surface of the.
  • the outer skin layer 1 and/or the backing layer 3 also functions as a shape-retaining layer for retaining the shape of the waterproof breathable fabric.
  • the waterproof and moisture-permeable fabric according to the first embodiment includes a waterproof and moisture-permeable layer 2 made of a nonwoven fabric containing ultrafine fibers having a fiber diameter of 10 or less (hereinafter also simply referred to as “nonwoven fabric”), and a skin layer 1 made of a knitted fabric. And are joined.
  • the ultrafine fibers are ultrafine fibers containing at least one of natural fibers and naturally derived fibers.
  • the waterproof/moisture permeable layer 2 may be made of a nonwoven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less.
  • the waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the first embodiment is made of a nonwoven fabric containing ultrafine fibers having a fiber diameter of 10 or less.
  • the fiber diameter of the ultrafine fibers means the diameter of the smallest circle that surrounds the cross section of the short fibers perpendicular to the longitudinal direction.
  • the fiber diameter of ultrafine fibers is 1
  • the fiber diameter of the ultrafine fiber is, for example, 10 doors or more, 2 0 1 ⁇ ⁇ ! or more, that's all, Or more, 5 0 1 ⁇ or more,
  • the ultrafine fiber may be an ultrafine fiber containing at least one of a natural fiber and a naturally derived fiber.
  • the ultrafine fibers include ultrafine fibers containing at least one selected from the group consisting of proteins, cellulose such as cotton and hemp, and regenerated cellulose such as cupra and rayon.
  • the non-woven fabric may contain only ultrafine fibers containing at least one of natural fibers and naturally derived fibers, and may contain other fibers such as protein fibers in addition to the ultrafine fibers. It may be. That is, as the fibers (also referred to as “material yarns”) used for forming the non-woven fabric, a single yarn composed of only ultrafine fibers containing at least one of natural fibers and naturally derived fibers, at least one of natural fibers and naturally derived fibers Composite yarns (for example, blended yarns, blended yarns, covering yarns, etc.) obtained by combining ultrafine fibers containing one or the other with other fibers such as protein fibers are used alone or in combination. May be taken.
  • the single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are fired together.
  • a filament yarn is preferably used as the single yarn and the composite yarn.
  • other fibers include synthetic fibers such as nylon and polyester, regenerated fibers such as cupra and rayon, and natural fibers such as cotton and hemp, in addition to protein fibers.
  • the proportion of ultrafine fibers containing at least one of natural fibers and natural fibers in the nonwoven fabric is, for example, 30% by mass or more based on the total weight of the nonwoven fabric. , 40 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.
  • the non-woven fabric can be manufactured by a known manufacturing method using, for example, a fiber containing at least a portion of ultrafine fibers having a fiber diameter of 10 or less.
  • a web including a single-layer web and a laminated web
  • a dry method is formed by a dry method, a wet method, an air-laid method, or the like from a fiber including at least a part of ultrafine fibers having a fiber diameter of 10 or less.
  • chemical bond method immersion method, spray method, etc.
  • the nonwoven fabric can be obtained by binding the fibers of the web together by the needle punch method or the like.
  • Nonwoven fabrics also include, for example, proteins such as dimethyl sulfoxide (mouth 1 ⁇ /13 ⁇ ), 1 ⁇ 1, 1 ⁇ 1-dimethylformamide (01 ⁇ /1), formic acid, or hexafluoroisopropanol (1 ⁇ 1 I) etc., if necessary, together with an inorganic salt as a dissolution accelerator, and then dissolved to prepare a dope solution, and then using the dope solution to perform an electrospinning method (electrostatic spinning method). It can also be obtained by spinning with.
  • the average fiber diameter (average fiber diameter) of protein ultrafine fibers obtained by the electrospinning method is usually 1 0000 nm or less, preferably 1 0001 ⁇ 111 or less, 00001 ⁇ 111, 1 0011111
  • the fiber diameter of protein ultrafine fiber is
  • the nonwoven fabric is appropriately set such that the numerical values of the fiber density (area weight), the porosity, the bulk density, etc. are within a range in which waterproofness and moisture permeability can be sufficiently ensured.
  • the unit weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of layers.
  • the skin layer 1 of the waterproof/moisture permeable fabric according to the first embodiment is made of a knitted fabric.
  • a knitted fabric is a generic term for knitted fabrics and woven fabrics.
  • a knitted fabric is a knitted fabric having a weft knitting structure such as a flat knitted fabric or a circular knitted fabric (also simply referred to as a “weft knitted fabric”), a knitted fabric having a warp braided fabric such as tricot, Russell (only Also referred to as ".”.
  • the woven fabric may be a woven fabric having any one of a plain weave, a twill weave, and a Tsumago weave.
  • the knitted or woven body may be an unprocessed knitted or woven body itself obtained by knitting or weaving, or may be a knitted or woven body subjected to a process such as water repellent treatment after knitting or weaving.
  • the knitted or woven body can be obtained by knitting or weaving raw material threads. Knitting method and weaving ⁇ 2020/175 702 21 ⁇ (: 171? 2020/008524
  • a publicly known method can be used as the method of formation.
  • the knitting machine to be used for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used.
  • the flat knitting machine there are a forming knitting machine, a non-sewn knitting machine, and the like.
  • the non-sewn knitting machine is more preferable.
  • the loom to be used include a hauling loom, and a non-tapping loom such as a gripper loom, a rapier loom, a water jet loom, and an air jet loom.
  • the raw material yarn of the knitted fabric may be a single yarn, a composite yarn (for example, a mixed yarn, a mixed yarn, a covering yarn, etc.), or may be a combination of these. ..
  • the single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or may be filament yarn in which long fibers are twisted together.
  • the fibers contained in the raw yarn include protein fibers, synthetic fibers such as nylon, polyester and polytetrafluoroethylene, regenerated fibers such as cupra, rayon and lyocell, and natural fibers such as cotton, hemp and silk. ..
  • the surface of the knitted or woven body on the side opposite to the side joined to the nonwoven fabric may be water-repellent. This makes it possible to obtain a waterproof and moisture-permeable fabric that is more waterproof.
  • the water repellent treatment can be carried out by a conventionally known method such as chemical coating such as plasma processing, physical coating such as coating with a water repellent coating agent, or chemical modification of the surface.
  • the waterproof/moisture permeable fabric according to the first embodiment further comprises a backing layer (woven body) further bonded to the surface opposite to the surface of the waterproof/moisture permeable layer (nonwoven fabric) bonded to the skin layer (woven body). It may have been done.
  • Preferred embodiments of the backing layer include the embodiments exemplified for the skin layer.
  • the skin layer and the backing layer may be knitted fabrics made of the same material, or may be knitted fabrics made of different materials.
  • the waterproof/moisture permeable fabric according to the first embodiment can be obtained by joining a waterproof/moisture permeable layer and a skin layer.
  • the method for joining the waterproof moisture-permeable layer and the skin layer can be appropriately selected according to the materials used for the nonwoven fabric and the knitted fabric.
  • a joining method for example, a method of welding a waterproof moisture-permeable layer and a skin layer with heat or a solvent, and a waterproof method. ⁇ 2020/175 702 22 ⁇ (: 171-1? 2020 /008524
  • Examples include a method of joining the wet layer and the epidermal layer.
  • both the non-woven fabric and the woven fabric contain a protein (protein ultrafine fiber or protein fiber), a solvent that dissolves the protein in one or both of the joint surfaces of the waterproof and moisture permeable layer and the epidermis layer (for example, dimethyl sulfoxide).
  • Organic solvent such as 1 ⁇ 1, 1 ⁇ 1-dimethylformamide (0 1 ⁇ /1 ), formic acid, or hexafluoroisopropanol (1 to 1 I), and a solution prepared by adding an inorganic salt as a dissolution accelerator to them.
  • a solution prepared by adding an inorganic salt as a dissolution accelerator to them.
  • water, or an aqueous solution in which an inorganic salt or the like is added to water) and then the waterproof moisture-permeable layer and the skin layer are bonded together, and the solvent is further removed to bond the waterproof moisture-permeable layer and the skin layer. can do.
  • the waterproof and moisture-permeable fabric can be obtained by a manufacturing method including a waterproof and moisture-permeable layer forming step of forming a waterproof and moisture-permeable layer on the skin layer.
  • the waterproof/moisture permeable layer forming step includes forming electro-spinning using a dope solution containing a protein to accumulate protein ultrafine fibers on the epidermis layer to form a nonwoven fabric.
  • the electrospinning method is a method in which a voltage is applied between a supply-side electrode (which can also be used as a spinneret) and a collection-side electrode (for example, a metal nozzle or a metal net) to perform spinning. An electric charge is given to the dope solution extruded from the die and blown to the collection side electrode. At this time, the dope solution is stretched to form fibers.
  • the applied voltage is usually 5 to 100 V, and preferably 10 to 50 V.
  • the distance between the electrodes is It is preferably 2 to 200.
  • FIG. 4 is an explanatory diagram of an electrospinning apparatus 100 according to an embodiment.
  • a voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35.
  • the dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36.
  • protein fine fibers can be ⁇ 2020/175702 23 ⁇ (: 171-1? 2020/008524
  • a nonwoven fabric 39 containing fibers can be obtained.
  • the solvent may be removed from the obtained non-woven fabric. Examples of the method of removing the solvent include drying under reduced pressure and immersing in a desolvent tank.
  • a superficial layer (textile body) is placed on the surface of the metal net 38 so that the ultrafine fibers of the protein are accumulated on the superficial layer.
  • an adhesive layer or the like made of a predetermined adhesive or a solvent capable of dissolving the protein ultrafine fibers is formed on the surface of the skin layer on the protein ultrafine fiber accumulation side by coating or the like.
  • the nonwoven fabric 39 is formed on the skin layer and at the same time integrally bonded to the skin layer, and the desired waterproof and moisture-permeable fabric can be manufactured advantageously and efficiently.
  • the adhesive layer is formed on the surface of the skin layer, an operation of solidifying the adhesive or an operation of removing the solvent may be added.
  • the protein used as the raw material for the protein ultrafine fibers or protein fibers contained in the nonwoven fabric or the knitted fabric is not particularly limited, and any protein can be used.
  • the protein used is preferably a hydrophobic protein.
  • hydrophobic protein means the sum of the hydrophobicity indices (1 to 1 I) of all amino acid residues that compose a protein, and then the sum is expressed as the total number of amino acid residues. Means a protein whose divided value (average! II) is greater than 0.
  • modified fibroin is preferable as the protein, and modified spider silk fibroin is more preferable.
  • the waterproof and moisture-permeable fabric according to the present embodiment has heat-retaining property, moisture-absorbing heat-generating property, and/or flame-retardant property. It is possible to add more sexual character, and it becomes more valuable as a fabric.
  • the modified fibroin according to the present embodiment has the formula 1: [( )"Motif [3 ⁇ 4mi]” or the formula 2: [(8) One (eight) bornrepresented by the motif ⁇ 2020/175 702 24 ⁇ (: 171? 2020 /008524
  • the modified fibroin may further have an amino acid sequence (terminal sequence and ⁇ 3 terminal sequence) added to the 1 ⁇ ] terminal side of the domain sequence and/or both of the 3 terminal side. And (three-terminal sequence is not limited to this, but is typically a region having no repeat of the amino acid motif characteristic of fibroin, and has amino acid residues of about 100 residues. Consists of.
  • modified fibroin means artificially produced fibroin (artificial fibroin).
  • the modified fibroin may be a fibroin whose domain sequence is different from the amino acid sequence of naturally occurring fibroin, or may be the same fibroin as the naturally occurring fibroin.
  • naturally-derived fibroin as used herein is also represented by the formula 1: [(8) n motif- ⁇ mi] or the formula 2: [(8) “motif-[3 ⁇ 4mi] (8)" motif. It is a protein containing a domain sequence.
  • the "modified fibroin” may be one that uses the amino acid sequence of naturally occurring fibroin as it is, or one that has its amino acid sequence modified depending on the amino acid sequence of naturally occurring fibroin (for example, cloning Amino acid sequence modified by modifying the gene sequence of naturally-occurring fibroin) or artificially designed and synthesized independently of naturally-occurring fibroin (eg, designed amino acid It may have a desired amino acid sequence by chemically synthesizing a nucleic acid encoding the sequence).
  • the "domain sequence” means a crystalline region (typically corresponding to the (8)" motif of an amino acid sequence) and an amorphous region (typically, an amino acid, which are unique to fibroin.
  • a crystalline region typically corresponding to the (8)" motif of an amino acid sequence
  • an amorphous region typically, an amino acid, which are unique to fibroin.
  • the ratio of the number of alanine residues to the total number of amino acid residues in the (A) motif may be 40% or more, and is 60% or more, 70% or more, 80% or more, 83% or more, 85% or more.
  • At least 7 motifs may be composed of only alanine residues REP represents an amino acid sequence composed of 2 to 200 amino acid residues REP, amino acid composed of 10 to 200 amino acid residues M may be an integer of 2 to 300, or an integer of 10 to 300.
  • Multiple (A) n motifs may have the same amino acid sequence or different amino acids.
  • a plurality of REPs may be the same amino acid sequence or different amino acid sequences.
  • the modified fibroin according to the present embodiment is obtained by, for example, substituting, deleting, inserting and/or adding one or more amino acid residues with respect to the gene sequence of the cloned naturally-occurring fibroin. It can be obtained by modifying the amino acid sequence corresponding to. Substitution, deletion, insertion and/or addition of amino acid residues can be performed by a method known to those skilled in the art, such as a partial directed mutagenesis method. Specifically, according to the method described in the literature such as Nucleic Acid Res. 1 0, 64 87 (1 982), Me thodsin E nz ymo I ogy, 1 00, 448 (1 983). Can be done.
  • a naturally-derived fibroin is represented by the formula 1: [(A) deliberatelymotif-REP] m or the formula 2: [(A) n motif-REP] m — (A) n motif.
  • a protein containing a domain sequence, and specific examples thereof include fibroin produced by insects or arachnids.
  • fibroin produced by insects include Bombix mori (B om byx mo ri), mulberry (B om byxmandarina), ⁇ (A ntheraeay am am ai), Ne ⁇ (A nteraeapernyi), Silk proteins produced by silkworms such as sam iacynthia, chestnuts (C aligurajaponica), chusser syrup (A ntheraeamylitta), stag beetle (A ntheraeaassama), and vespid (Ve spasimi II imaxanthoptera) This includes hornet silk protein.
  • fibroin produced by insects include, for example, silkworm fibroin L chain (Gen Bank accession number M76430 (salt sequence), and AAA 27840.1 (amino acid sequence)). Can be mentioned.
  • Examples of fibroin produced by arachnids include spider silk proteins produced by arachnids belonging to the order Aranea. More specifically, spiders belonging to the genus Araneus (Araneus spp.), such as Onigumo, Ani spider, Red-bellied spider, Blue-headed spider, and Araneus spider, etc. Spiders that belong to the genus Cronata, such as spiders and spiders belonging to the genus P ronus, spiders that belong to the genus Cyrtarachne, such as genus Cyrtarachne, and spiders that belong to the genus Cyrtarachne.
  • spiders belonging to the genus Araneus such as Onigumo, Ani spider, Red-bellied spider, Blue-headed spider, and Araneus spider, etc.
  • Spiders that belong to the genus Cronata such as spiders and spiders belonging to the genus P ronus
  • Spiders belonging to the genus (genus G asteracantha), Spiders belonging to the genus Grace ( ⁇ rdgarius) such as Mamei Taiseki spider and Mutsugai spider, Genus Argiosus (Argi) belonging to the genus Argio (Argi genus).
  • Spiders belonging to the genus A rachnura such as spiders and white-breasted spiders, spiders belonging to the genus Acusi I as such as spiders such as ant spiders, spiders such as spiders, brown spiders and dwarf spiders (C yt ⁇ ph ⁇ ra) Spiders belonging to the genus) Spiders belonging to the genus Pho tys, spiders belonging to the genus Cyc osa, such as spiders, wolf spiders, marsupial spiders, and black spiders, and genus C horizopes, such as Yamato kana spiders Spider silk proteins produced by spiders belonging to the genus T.
  • spiders belonging to the genus Acusi I such as spiders such as ant spiders, spiders such as spiders, brown spiders and dwarf spiders (C yt ⁇ ph ⁇ ra) Spiders belonging to the genus) Spiders belonging to the genus Pho tys
  • spider silk spiders belonging to the genus Tetragnatha such as the spider spider, the herring spider, the spider duck spider Spiders belonging to the genus L eucauge, spiders belonging to the genus Nephila (genus N ephi ⁇ a) such as Nephila and Nephila spp. Spiders belonging to the genus D yschiriognatha, black spiders, black-backed spiders, black-spotted spiders and spiders belonging to the genus Latrodectus and spiders belonging to the genus E uprosthenops. Spider silk proteins produced by spiders belonging to the family (T etragnathidae).
  • spider silk proteins examples include dragline proteins such as M a S p (M a S p 1 and M a S p 2) and ADF (ADF 3 and ADF 4), and M i S p (M i S p 1). And M i S p 2)
  • spider silk proteins produced by arachnids include, for example, fibroin-3 (adf-3) [from A raneus diadematus] (Gen Bank accession number AAC 4701 0 (amino acid sequence)). , U 47855 (base sequence) ), fibroin -4 (adf — 4) [from A raneus diadematus] (Gen B ank accession number A AC 4701 1 (amino acid sequence), U 47856 (base rooster sequence) ), draglinesilkproteinsp idroin 1 [from N ephilaclavipes] (Gen Bank Accession No. 880 504 04504 (amino acid sequence)), II 37520 (base ⁇ 02020/175702 28 ⁇ (: 17 2020/008524
  • fibroin whose sequence information is registered in NCB IG en Bank can be further mentioned.
  • DIV ⁇ S ⁇ ⁇ N which includes ⁇ NV, from DEFINITI ON to spidroin, am pullate, fibroin, rs i I k, and po "I y peptide" or "silk and protein" are described as keywords, and the character string of a specific product from CDS ⁇ 2020/175 702 29 ⁇ (:171? 2020 /008524
  • the modified fibroin according to the present embodiment may be modified silk (silk) fibroin (modified amino acid sequence of silk protein produced by silkworm), modified spider silk fibroin (spider produced by spiders). (Amino acid sequence of silk protein is modified).
  • modified spider silk fibroin is preferable because it is superior in flame retardancy.
  • modified fibroin a modified fibroin (first modified fibroin) derived from a large vesicle guideline thread protein produced in the large ampullate gland of a spider, the content of glycine residues is reduced.
  • Modified fibroin having a modified domain sequence (second modified fibroin), (8) Modified fibroin having a reduced sequence of motif content (third modified fibroin), content of glycine residue , And () disregardModified fibroin having a reduced content of motif (fourth modified fibroin), modified fibroin having a domain sequence locally containing a region with a large hydrophobic index (fifth modified fibroin),
  • modified fibroin (sixth modified fibroin) having a domain sequence with a reduced content of glutamine residues can be mentioned.
  • Examples of the first modified fibroin include a protein containing a domain sequence represented by the formula 1: [(8) "motif-[3 ⁇ 4mi].
  • the (8)" motif The number of amino acid residues is preferably 3 to 20 integers, more preferably 4 to 20 integers, even more preferably 8 to 20 integers,
  • the first modified fibroin has the formula 1
  • the number of amino acid residues constituting Minami is preferably 10 to 200 residues, more preferably 10 to 150 residues, and 20 to 100 residues. More preferably, it is still more preferably 20 to 75 residual groups.
  • the first modified fibroin has the formula 1 :[ ( A) The total number of residues of glycine residues, serine residues, and alanine residues contained in the amino acid sequence represented by suddenlymotif-REP] m is 40% or more of the total number of amino acid residues. It is preferably 60% or more, more preferably 70% or more.
  • the first modified fibroin contains a unit of the amino acid sequence represented by the formula 1: [(A) n motif-REP] m , and the C-terminal sequence is an amino acid represented by any of SEQ ID NOs: 1 to 3. It may be a polypeptide which is an amino acid sequence having 90% or more homology to the amino acid sequence shown in the sequence or any of SEQ ID NOs: 1 to 3.
  • amino acid sequence shown in SEQ ID NO: 1 is the same as the amino acid sequence consisting of the amino acids of the C-terminal 50 residues of the amino acid sequence of AD F 3 (GI: 1 263287, NCBI), and SEQ ID NO: 2
  • the amino acid sequence shown in is the same as the amino acid sequence shown in SEQ ID NO: 1 with 20 residues removed from the C-terminus
  • the amino acid sequence shown in SEQ ID NO: 3 is the amino acid sequence shown in SEQ ID NO: 1. It is identical to the amino acid sequence with 29 residues removed from the C-terminus of the sequence.
  • an amino acid sequence represented by (1 _ i) SEQ ID NO: 4 (rec om binantspidersi I kprotein ADF 3 K ai Large NRSH 1), or (1-ii) )
  • a modified fibroin containing an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 4 can be mentioned.
  • the sequence identity is preferably 95% or more.
  • the amino acid sequence represented by SEQ ID NO: 4 has an amino acid sequence (SEQ ID NO: 5) consisting of an initiation codon, a His tag and a recognition site for H RV3C protease (Humanrhinovirus 3 C protease) added to the N-terminus.
  • H RV3C protease Humanrhinovirus 3 C protease
  • the C-terminal amino acid sequence of the amino acid sequence represented by SEQ ID NO: 4 is the same as the amino acid sequence represented by SEQ ID NO: 3. ⁇ 2020/175 702 31 ⁇ (:171? 2020/008524
  • the modified fibroin of (1-I) may consist of the amino acid sequence represented by SEQ ID NO: 4.
  • the second modified fibroin has an amino acid sequence whose domain sequence has a reduced content of glycine residues as compared to naturally occurring fibroin.
  • the second modified fibroin has an amino acid sequence corresponding to at least one glycine residue in at least one amino acid residue substituted with another amino acid residue, as compared with naturally occurring fibroin.
  • the second modified fibroin has a domain sequence that is different from that of naturally occurring fibroin.
  • ⁇ is a glycine residue
  • X is an amino acid residue other than glycine.
  • at least one motif sequence at least one glycine residue in the motif sequence is selected. It may have an amino acid sequence corresponding to substitution of another amino acid residue for a group.
  • the proportion of the motif sequence in which the above-mentioned glycine residue is replaced with another amino acid residue may be 10% or more based on the entire motif sequence.
  • the second modified fibroin contains a domain sequence represented by the formula 1: [(8) "motif-[3 ⁇ 4mi], and from the above-mentioned domain sequence, the (8)" motif is located at the most 0 terminal side.
  • the total number of amino acid residues in the amino acid sequence consisting of (excluding amino acid residues other than glycine) contained in in the sequence excluding the sequence up to the terminus of the above domain sequence is 2, and
  • ⁇ to the ⁇ end of the domain sequence is defined as May have an amino acid sequence of 30% or more, 40% or more, 50% or more, or 50.9% or more.
  • the number of alanine residues with respect to the total number of amino acid residues in the motif may be 83% or more, preferably 86% or more, more preferably 90% or more, 95% or more is more preferable, and 100% or more (composed only of alanine residues ⁇ 2020/175 702 32 ⁇ (:171? 2020 /008524
  • the second modified fibroin is one in which the content ratio of the amino acid sequence consisting of XX is increased by substituting one glycine residue of the X motif for another amino acid residue. Is preferred.
  • the content rate of the amino acid sequence consisting of XX in the domain sequence is preferably 30% or less, more preferably 20% or less, and more preferably 10% or less. Is more preferable, 6% or less is still more preferable, 4% or less is still more preferable, and 2% or less is particularly preferable.
  • the content rate of the amino acid sequence consisting of XX in the domain sequence can be calculated by the same method as the method of calculating the content rate of the amino acid sequence consisting of XX below / ).
  • a fibroin modified fibroin or naturally-occurring fibroin containing a domain sequence represented by [_8]
  • the amino acid sequence consisting of ⁇ ⁇ is extracted from all the sequences included in the sequence, except that the total number of amino acid residues constituting ⁇ ⁇ is 2.
  • the method was confirmed by exemplifying the fibroin whose amino acid sequence information was registered in 1 ⁇ 10 ⁇ ⁇ Gen B ank, and it was confirmed that 6 6 3 types of fibroin (of which spiders Fibroin was extracted (415 kinds). Among all the extracted fibroins, the content of the amino acid sequence consisting of XX is 6% or less in the fibroin, which contains the domain sequence represented by the formula 1: [(8) dominantMotif MIN”]. From the amino acid sequence of naturally-occurring fibroin, by the above calculation method, Was calculated. The results are shown in Figure 6. The horizontal axis of FIG. 6 represents%/% (%), and the vertical axis represents frequency. As is clear from Fig. 6, 2 / in naturally-occurring fibroin was less than 50.9% (the highest was 50.86%).
  • the second modified fibroin It is preferably at least 50.9%, more preferably at least 56.1%, even more preferably at least 58.7%, even more preferably at least 70%, Even more preferably, it is 80% or more.
  • the upper limit of / is not particularly limited, but may be, for example, 95% or less.
  • the second modified fibroin may be obtained, for example, by substituting at least part of the nucleotide sequence encoding a glycine residue from the cloned gene sequence of naturally-occurring fibroin to encode another amino acid residue. It can be obtained by modification.
  • the glycine residue to be modified one glycine residue in the ⁇ and ⁇ ⁇ ⁇ motifs may be selected, or the glycine residue may be substituted so that the ratio / becomes 50.9% or more. May be.
  • an amino acid sequence satisfying the above embodiment from the amino acid sequence of naturally-occurring fibroin and chemically synthesizing a nucleic acid encoding the designed amino acid sequence.
  • one or more amino acid residues were substituted or deleted.
  • the amino acid sequence corresponding to the loss, insertion and/or addition may be modified.
  • the above-mentioned another amino acid residue is an amino acid residue other than a glycine residue. ⁇ 2020/175 702 34 ⁇ (: 171? 2020 /008524
  • V parine
  • a leucine (1_) residue an isoleucine ( ⁇ ) residue, a methionine (IV! residue, a proline () residue, a phenylalanine () residue.
  • hydrophobic amino acid residues glutamine ( ⁇ ) residues, asparagine (1 ⁇ 1) residues, serine (3) residues, lysine ( ⁇ ) residues and glutamic acid (Mitsu) residues Hydrophilic amino acid residues are preferred, and parine (V) residues, leucine (1_) residues, isoleucine (I) residues, phenylalanine () residues and glutamine (0) residues are more preferred. , Glutamine (O) residues are more preferred.
  • the modified fibroin of (2-I) will be described.
  • Amino acid sequence is shown in SEQ ID NO: 6, SEQ ID NO: 1 ⁇ corresponding to fibroin naturally occurring (1 ⁇ / 1 6 All of the amino acids in the amino acid sequence represented by are replaced with ⁇ X.
  • the amino acid sequence represented by SEQ ID NO: 7 is the amino acid sequence represented by SEQ ID NO: 6 with two (8) transitmotifs deleted from the terminal side toward the 0 terminal side, and further before the ⁇ terminal sequence. [(8) ⁇ One motif is included.
  • the amino acid sequence represented by SEQ ID NO: 8 is obtained by inserting two alanine residues at the ⁇ terminal side of each () facedmotif of the amino acid sequence represented by SEQ ID NO: 7, and further adding a part of glutamine ( ⁇ ) residues to serine.
  • the amino acid sequence shown in SEQ ID NO: 9 is obtained by substituting a residue and deleting a part of the amino acid at the ⁇ terminal so that the molecular weight is almost the same as that of SEQ ID NO: 7.
  • Regions of 20 domain sequences present in the amino acid sequence shown by 7 (however, some amino acid residues on the ⁇ 3 terminal side of the region are replaced.) ⁇ 2020/175 702 35 ⁇ (:171? 2020 /008524
  • amino acid sequence represented by SEQ ID NO: 10 (corresponding to naturally occurring fibroin) The value of is 46.8%.
  • the amino acid sequence represented by SEQ ID NO: 6, the amino acid sequence represented by SEQ ID NO: 7, the amino acid sequence represented by SEQ ID NO: 8, and the SEQ ID NO: The values are 58.7%, 70.1%, 66.1% and 7.0%, respectively.
  • the serrated ratio of the amino acid sequences shown in SEQ ID NO: 10, SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 and SEQ ID NO: 9 (described later) 1: 1.8 to 1 1.3 X/V The values of 15.0%, 15.0%, 93.4%, 92.7% and 89.8%, respectively.
  • the modified fibroin of (2-I) may consist of the amino acid sequence shown in SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9.
  • the modified fibroin of (2-II) has SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO:
  • the modified fibroin of (2- ⁇ ) is also a protein containing the domain sequence represented by the formula 1: [(8) "motif [3 ⁇ 4mi].
  • the sequence identity is 95% or more. It is preferable.
  • the modified fibroin of (2-II) has SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO:
  • the second modified fibroin may include a tag sequence at either or both of the 1 ⁇ ! end and the O end. This enables the isolation, immobilization, detection and visualization of the modified fibroin.
  • tag sequence for example, specific affinity with other molecule (binding, affinity ⁇ 2020/175 702 36 ⁇ (:171? 2020 /008524
  • affinity tags using A specific example of the affinity tag is a histidine tag (1 to 1 3 tags).
  • 1 to 1 3 tags are short peptides in which about 4 to 10 histidine residues are lined up, and because they have the property of specifically binding to metal ions such as nickel, metal chelate chromatography
  • tag sequences such as glutathione-3-transferase (03) that specifically binds to glutathione and maltose binding protein (1 ⁇ /1M) that specifically binds to maltose.
  • an "epitope tag” utilizing an antigen-antibody reaction can also be used.
  • a peptide (epitope) showing antigenicity as a tag sequence an antibody against the epitope can be bound.
  • an epitope tag 1 to 18 (influenza virus hemagglutinin peptide sequence) tag, Tags, !_80 tags, etc. can be mentioned.
  • the modified fibroin can be easily purified with high specificity by using the epitope tag.
  • a tag sequence that can be cleaved with a specific protease can also be used.
  • the modified fibroin from which the tag sequence is cleaved can be recovered.
  • modified fibroin containing a tag sequence (2— ⁇ I
  • SEQ ID NO: 1 2 The amino acid sequence represented by SEQ ID NO: 13 (Cho 4 1 0), SEQ ID NO: 14 ([3 ⁇ 4 5 25) or SEQ ID NO: 15 (C D 7 9 9), or (2 — V) SEQ ID No. Examples include modified fibroin containing an amino acid sequence having a sequence identity of 90% or more with the amino acid sequence represented by 12, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15. ⁇ 2020/175 702 37 ⁇ (:171? 2020 /008524
  • SEQ ID NO: 16 ([3 ⁇ 4 3 1 3), SEQ ID NO: 12, SEQ ID NO: 13, SEQ ID NO:
  • SEQ ID NO: 14 and SEQ ID NO: 15 have the amino acid sequences shown in SEQ ID NO: 10 and SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 and SEQ ID NO: 9, respectively.
  • the amino acid sequence shown in 1 is added.
  • the modified fibroin of (2-I I I) may consist of the amino acid sequence shown in SEQ ID NO: 12, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15.
  • the modified fibroin of (2-IV) is an amino acid sequence having a sequence identity of 90% or more with the amino acid sequence represented by SEQ ID NO: 12, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15. Is included.
  • the modified fibroin of (2-V) is also a protein containing a domain sequence represented by the formula 1: [(8) "motif ⁇ ?M]. The above sequence identity is 95% or more. I like that.
  • the modified fibroin of (2-IV) has a sequence identity of 90% or more with the amino acid sequence represented by SEQ ID NO: 12, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15, And the total number of amino acids in the above-mentioned domain sequence is 2, with the total number of amino acid residues in the amino acid sequence consisting of the sequences (where X represents an amino acid residue other than glycine) contained in When the number of residues is Is preferably 50.9% or more.
  • the second modified fibroin may contain a secretory signal for releasing the protein produced in the recombinant protein production system to the outside of the host.
  • the sequence of the secretion signal can be appropriately set depending on the type of host.
  • the domain sequence of the third modified fibroin has (8) an amino acid sequence in which the content of the deliberatelymotif is reduced as compared with naturally-occurring fibroin. Can be said to have an amino acid sequence corresponding to the deletion of at least one or a plurality of (8) motifs as compared with naturally occurring fibroin. ⁇ 2020/175 702 38 ⁇ (: 171? 2020 /008524
  • the third modified fibroin may have an amino acid sequence corresponding to the (8) motif deleted from naturally occurring fibroin by 10 to 40%.
  • the third modified fibroin has a domain sequence at least from the 1 ⁇ 1 terminal side (1 to 3 (8) each toward the 3 terminal side) compared to the naturally occurring fibroin. It may have an amino acid sequence corresponding to the deletion of one (8)* motif.
  • the third modified fibroin has a domain sequence that is at least from the 1 ⁇ 1 terminal side (two consecutive (8) (8)) motifs are missing from the naturally occurring fibroin. It may have an amino acid sequence corresponding to the deletion, and the deletion of one (8)′ motif repeated in this order.
  • the third modified fibroin has an amino acid sequence whose domain sequence corresponds to deletion of at least every two (8) sensiblemotifs from the 1 ⁇ 1 terminal side toward the 0 terminal side. It may be one.
  • the third modified fibroin contains a domain sequence represented by the formula 1: [(8) provokemotif ⁇ ?mi ], and from the 1 ⁇ 1 terminal side (to the 3 terminal side, two adjacent two [ (Eight) The number of amino acid residues in the unit of the unit is sequentially compared, and the number of amino acid residues is small.
  • the ratio of the number of amino acid residues in the other is 1.8 to 11.3
  • the ratio of the two adjacent [(8) provokemotif-[3 ⁇ 4mi] units is X/V is 20% or more, 30% or more, 40% or more, where X is the maximum total value of the total number of amino acid residues and V is the total number of amino acid residues in the domain sequence.
  • the motif may have an amino acid sequence of 50% or more.
  • the number of alanine residues with respect to the total number of amino acid residues in the motif may be 83% or more, but 86% It is preferably not less than 90%, more preferably not less than 90%, still more preferably not less than 95%, and not less than 100% (meaning that it is composed of only alanine residues). Are even more preferred.
  • the 1 ⁇ 1 terminal sequence and the domain sequence excluding the 3 terminal sequence from the modified fibroin are shown.
  • the domain sequence is from the 1 ⁇ 1 terminal side (left side) to (8) Group) 1 (8) concerning the 1 ⁇ 1 terminal side (left side) to (8) Group) 1 (8) concerning the 1 ⁇ 1 terminal side (left side) to (8) Group) 1 (8) concerning the 1 ⁇ 1 terminal side (left side) to (8) Group) 1 (8) concerning the 1 ⁇ 1 terminal side (left side) to (8) Group) 1 (8) concerning the domain sequence is from the 1 ⁇ 1 terminal side (left side) to (8) Group) 1 (8) concerning the domain sequence is from the 1 ⁇ 1 terminal side (left side) to (8) Group) 1 (8) concerning the domain sequence is from the 1 ⁇ 1 terminal side (left side) to (8) Group) 1 (8) concerning the domain sequence is from the 1 ⁇ 1 terminal side (left side) to (8) Group) 1 (8) concerning the domain sequence is from the 1 ⁇ 1 terminal side (left side) to (8) Group) 1 (8) concerning the domain sequence is from the 1
  • the ratio of the number of amino acid residues on the other side is less than 1.8 or more than 11.3 when the one with the smaller number of acid residues is set to 1 [8] perennialMotif-[3 ⁇ 4mi] unit pair is It is indicated by a broken line.
  • V (%) can be calculated.
  • the ratio of father/so is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, It is even more preferably 70% or more, even more preferably 75% or more, and particularly preferably 80% or more.
  • the upper limit of V is not particularly limited and may be, for example, 100% or less.
  • the father/so is 89.6% or more, and when the knurl ratio is 1: 1.8 to 3.4.
  • X/so is preferably 77.1% or more, and when the notched ratio is 1: 1.9 to 8.4, X/V is preferably 75.9% or more,
  • the serrated ratio is 1: 1.9 to 4.
  • the ratio of father/so is preferably 64.2% or more.
  • the father/so has 46. It is preferably at least 4%, more preferably at least 50%, even more preferably at least 55%, even more preferably at least 60%, and at least 70%. It is even more preferred that it is 80% or more, and it is particularly preferred that the upper limit of the father/so is not particularly limited, and may be 100% or less.
  • the method was illustrated by exemplifying the fibroin whose amino acid sequence information is registered in 1 ⁇ 10 ⁇ Gen B ank. 4 1 5 types) were extracted. Of all the extracted fibroins, from the amino acid sequence of naturally-occurring fibroin composed of the domain sequence represented by the formula 1: [(8) perennialMotif Minami”, the father/sodium was calculated by the above-mentioned calculation method. The Giza ratio is 1:
  • Figure 7 shows the results for 1.9 to 4.1.
  • the third modified fibroin is, for example, based on the cloned gene sequence of naturally-occurring fibroin so that the ratio of father/sodium is 64.2% or more (8)
  • an amino acid sequence corresponding to the deletion of one or more (8) transitmotifs so as to be 64.2% or more, and chemically synthesizing a nucleic acid encoding the designed amino acid sequence.
  • one or more amino acid residues were replaced, deleted, inserted and/or Alternatively, the amino acid sequence corresponding to the addition may be modified.
  • amino acid sequence represented by SEQ ID NO: 9 (1 ⁇ /161: -? [3 ⁇ 4 cho 79 9), or (3 — ⁇ ⁇ ) is represented by SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9.
  • a modified fibroin containing an amino acid sequence having 90% or more sequence identity with the amino acid sequence can be mentioned.
  • the amino acid sequence of SEQ ID NO: 10 corresponding to fibroin of natural origin is From the amino acid sequence shown in 1 _ [3 ⁇ 4 3 1 3], delete the motif (every other two (8) toward the 3 terminus side) from the terminal side, and further add [(8 ) One of theticianMotif [3 ⁇ 4” is inserted.
  • the amino acid sequences shown in SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9 are as described in the second modified fibroin.
  • the father/so value of the amino acid sequence represented by SEQ ID NO: 10 (corresponding to naturally occurring fibroin) at the Giza ratio of 1: 1.8 to 1 1.3 is 15.0%.
  • the father/so value in the amino acid sequence represented by SEQ ID NO: 17 and the amino acid sequence represented by SEQ ID NO: 7 is 93.4% in both cases.
  • the X/so value in the amino acid sequence represented by SEQ ID NO: 8 is 92.7%.
  • the father/so value in the amino acid sequence represented by SEQ ID NO: 9 is 89.8%.
  • SEQ ID NO: 10 The values of / in the amino acid sequences shown in SEQ ID NO: 10, SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO: 8 and SEQ ID NO: 9 are 46.8%, 56.2%, and 70.1%, respectively. , 66.1% and 7.0%.
  • the modified fibroin of (3-I) has SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO:
  • It may consist of the amino acid sequence shown in 8 or SEQ ID NO: 9.
  • the modified fibroin of (3-I ⁇ ) has an amino acid sequence having 90% or more sequence identity with the amino acid sequence shown in SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9. It includes.
  • the modified fibroin of (3--) is also a protein containing the domain sequence represented by the formula 1: [(8) "motif [3 ⁇ 4mi]. The sequence identity is 95% or more. Preferably.
  • the modified fibroin of (3-I ⁇ ) has 90% or more sequence identity with the amino acid sequence of SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9, and 1 From ⁇ 1 end side (toward the 3 end side, two adjacent [(8) faced Sequentially comparing the number of amino acid residues in A, the number of amino acid residues in the one with a small number of amino acid residues is 1, and the ratio of the number of amino acid residues in the other is 1.8 to 1 1.
  • the serrated ratio is 1 :1.8 to 1 1.3) ⁇ 2020/175 702 43 ⁇ (: 171? 2020 /008524
  • X be the maximum value of the total sum of the number of amino acid residues of two adjacent [(8) kauMotif-Min] units and V be the total number of amino acid residues of the domain sequence. It is preferably 64.2% or more.
  • the third modified fibroin may include the above-mentioned tag sequence at either or both of the 1 ⁇ 1 end and the O end.
  • modified fibroin containing a tag sequence (3— ⁇ I
  • SEQ ID NO: 18 The amino acid sequence represented by SEQ ID NO: 1 3 (Cho 4 10), SEQ ID No: 14 ([3 ⁇ 4 5 25) or SEQ ID No 15 (Cha 7 9 9), or (3 — V) SEQ ID No.
  • a modified fibroin containing an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by 18, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15 can be mentioned.
  • amino acid sequences represented by SEQ ID NO: 18, SEQ ID NO: 13, SEQ ID NO: 14 and SEQ ID NO: 15 are the amino acids represented by SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO: 8 and SEQ ID NO: 9, respectively.
  • amino acid sequence represented by SEQ ID NO: 11 (including 1 to 1 3 tag sequence and hinge sequence) is added to the 1 ⁇ 1 end of the sequence.
  • the modified fibroin of (3- ⁇ ⁇ ⁇ ) may consist of the amino acid sequence of SEQ ID NO: 18, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15.
  • the modified fibroin of (3-IV) is an amino acid sequence having a sequence identity of 90% or more with the amino acid sequence represented by SEQ ID NO: 18, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15. Is included.
  • the modified fibroin of (3-V) is also a protein containing a domain sequence represented by the formula 1: [(8) "motif ⁇ ?M]. The above sequence identity is 95% or more. I like that.
  • the modified fibroin of (3-IV) has a sequence identity of 90% or more with the amino acid sequence represented by SEQ ID NO: 18, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15, And from the 1 ⁇ ! terminal side (towards the 3 terminal side, the number of amino acid residues of the two adjacent [( ) radicalMochifu 8M] units are sequentially compared, and the amino acid residues are compared. ⁇ 2020/175 702 44 ⁇ (: 171? 2020 /008524
  • the ratio of the number of amino acid residues in the other is 1.8 to 1 1.
  • 3 — F X/so is preferably 64.2% or more, where X is the maximum total value of the total number of amino acid residues in the unit and X is the total number of amino acid residues in the domain sequence.
  • the third modified fibroin may contain a secretory signal for releasing the protein produced in the recombinant protein production system to the outside of the host.
  • the sequence of the secretion signal can be appropriately set depending on the type of host.
  • the fourth modified fibroin its domain sequence had a reduced content of (8) motifs and a reduced content of glycine residues, as compared to naturally-occurring fibroin. It has an amino acid sequence.
  • the domain sequence of the fourth modified fibroin has a deletion of at least one or more (8) transitmotifs as compared with the naturally-occurring fibroin, and at least one or more glycine residues in the mitochondria. It can be said that the group has an amino acid sequence corresponding to the substitution of another amino acid residue, that is, the fourth modified fibroin has the above-mentioned second modified fibroin and the third modified fibroin. It is a modified fibroin having features as well.Specific embodiments are as described in the second modified fibroin and the third modified fibroin.
  • Modified fibroin containing amino acid sequences having 0% or more sequence identity can be mentioned. Modified fibro containing the amino acid sequence of SEQ ID NO: 7, SEQ ID NO: 8, SEQ ID NO: 9, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15 ⁇ 2020/175 702 45 ⁇ (:171? 2020 /008524
  • the fifth modified fibroin has a domain sequence that is comparable to that of naturally-occurring fibroin.
  • An amino acid sequence containing a region with a locally large hydrophobic index which corresponds to the substitution with an amino acid residue and/or the insertion of one or more amino acid residues with a large hydrophobic index into the ridge. May be included.
  • the region where the hydrophobicity index is locally large is preferably composed of consecutive 2 to 4 amino acid residues.
  • amino acid residues having a large hydrophobicity index are isoleucine ( ⁇ ) and valine.
  • it is an amino acid residue selected from (V), leucine (!_), phenylalanine (), cysteine ( ⁇ ), methionine (IV! and alanine (8).
  • the fifth modified fibroin is compared with naturally-derived fibroin, One or more amino acid residues in the amino acid were replaced by amino acid residues with a high hydrophobicity index, and/or one or more amino acid residues with a high hydrophobicity index were inserted into the In addition to the corresponding alterations, there may be further alterations in the amino acid sequence corresponding to substitutions, deletions, insertions and/or additions of one or more amino acid residues as compared to naturally occurring fibrin. Good.
  • the fifth modified fibroin is, for example, one or more hydrophilic amino acid residues (for example, an amino acid residue having a negative hydrophobicity index) in the middle of the cloned gene sequence of naturally-derived fibroin.
  • hydrophilic amino acid residues for example, an amino acid residue having a negative hydrophobicity index
  • hydrophobic amino acid residue for example, an amino acid residue having a positive hydrophobicity index
  • amino acid sequence of naturally occurring fibroin The amino acid sequence corresponding to the substitution of one or more hydrophilic amino acid residues in the hollows with the hydrophobic amino acid residue and/or the insertion of one or more hydrophobic amino acid residues into the hollow It can also be obtained by chemically synthesizing a nucleic acid designed and encoding the designed amino acid sequence.
  • Substitution of one or more hydrophilic amino acid residues in REP with hydrophobic amino acid residues from the amino acid sequence of fibroin derived from nature, and/or insertion of one or more hydrophobic amino acid residues in REP In addition to the corresponding modification, further modification of the amino acid sequence corresponding to substitution, deletion, insertion and/or addition of one or more amino acid residues may be carried out.
  • the fifth modified fibroin contains the domain sequence represented by the formula 1: [(A) "motif-REP] m , and the (A) n motif located closest to the C-terminal side leads to the c-terminal of the above domain sequence.
  • the total number of amino acid residues contained in the region where the average hydrophobicity index of 4 consecutive amino acid residues is 2.6 or more in all REPs contained in the sequence except the above sequences up to the above domain sequence is p
  • the total number of amino acid residues contained in the sequence excluding the sequence from the (A) n motif located closest to the C-terminal to the C-terminus of the above domain sequence is q, then p/ It may have an amino acid sequence in which q is 6.2% or more.
  • sequence 8 From the domain sequence represented by, the sequence (hereinafter referred to as “sequence 8”) excluding the sequence located at the most ⁇ terminal side (8) decisively from the ⁇ end of the domain sequence is used.
  • sequence 8 calculates the average value of the hydrophobicity index of 4 consecutive amino acid residues in all the sequences included in Sequence 8.
  • the average value of the hydrophobicity index is obtained by dividing the sum of 1 to 1 I of each amino acid residue contained in four consecutive amino acid residues by 4 (the number of amino acid residues).
  • the average value of the hydrophobicity index is calculated for all four consecutive amino acid residues (each amino acid residue is used for calculating the average value 1 to 4 times).
  • two "4 consecutive amino acid residues with an average value of the hydrophobicity index of 2.6 or more" are duplicated by 1 amino acid residue, 4 consecutive amino acid residues remain.
  • the fifth modified fibroin it is preferably 6.2% or more, more preferably 7% or more, further preferably 10% or more, and more preferably 20% or more. Even more preferably, it is even more preferably 30% or more.
  • the upper limit of / is not particularly limited, but may be, for example, 45% or less.
  • a fifth modified fibroin is prepared by, for example, changing the amino acid sequence of a cloned naturally-occurring fibroin so as to satisfy the above condition /.
  • hydrophilic amino acid residues for example, amino acid residue with a negative hydrophobicity index
  • hydrophobic amino acid residues for example, amino acid residue with a positive hydrophobicity index
  • a new amino acid residue, and/or one or more amino acid residues having a high hydrophobicity index are inserted into the ridge, and one or more amino acid residues are replaced. , Deletion, insertion and/or addition may be modified.
  • the large amino acid residues of the hydrophobic index in particular, without limitation, isoleucine (I), Pas' phosphorus (V), leucine (! _), Phenylalanine (), cysteine ( ⁇ ) , Methionine (1 ⁇ / ⁇ and alanine (8) are preferred, and parin (V), leucine (!_) and isoleucine (I) are more preferred.
  • Modified fibroin including an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 19, SEQ ID NO: 20 or SEQ ID NO: 21.
  • the modified fibroin of (5-I) is described.
  • the amino acid sequence shown in SEQ ID NO: 19 is the amino acid sequence shown in SEQ ID NO: 7 (1 ⁇ /161: -? , At every other interval, two amino acid sequences (VI-I) each consisting of 3 amino acid residues were inserted, and further some glutamine (0) residues were replaced with serine (3) residues, and It is a partial deletion of amino acids on the terminal side.
  • the amino acid sequence represented by SEQ ID NO: 20 is the amino acid sequence represented by SEQ ID NO: 8 (1 ⁇ /161: -? [3 ⁇ 4 525), Every other pair, every other amino acid sequence (VI-I) consisting of 3 amino acid residues is inserted.
  • the amino acid sequence represented by SEQ ID NO: 21 is the same as the amino acid sequence represented by SEQ ID NO: 8, In each case, every other amino acid sequence (VI-) consisting of 3 amino acid residues is inserted in two places.
  • the modified fibroin of (5-I) may consist of the amino acid sequence shown by SEQ ID NO: 19, SEQ ID NO: 20 or SEQ ID NO: 21.
  • the modified fibroin of (5-I ⁇ ) contains an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 19, SEQ ID NO: 20 or SEQ ID NO: 21. ..
  • the modified fibroin of (5- ⁇ ⁇ ) is also a protein containing the domain sequence represented by the formula 1: [(8) possiblymotif [3 ⁇ 4mi]. The above sequence identity may be 95% or more. Preferred.
  • the modified fibroin of (5-I ⁇ ) has 90% or more sequence identity with the amino acid sequence shown in SEQ ID NO: 19, SEQ ID NO: 20 or SEQ ID NO: 21, and has the most ⁇ 3 terminal. Located on the side (), the average value of the hydrophobicity index of 4 consecutive amino acid residues is 2 in all the sequences included in the sequence excluding the sequence from the motif to the ⁇ 3 end of the domain sequence in the domain sequence. . The total number of amino acid residues contained in the region of 6 or more is defined as ⁇ 2020/175 702 50 ⁇ (:171? 2020 /008524
  • /9 is 6.2% or more when the total number of amino acid residues contained in the sequence excluding the sequence up to the 0 terminal of the domain sequence is excluded from the domain sequence.
  • the fifth modified fibroin may include a tag sequence at either or both of the 1 ⁇ 1 end and the open end.
  • modified fibroin containing the tag sequence (5 — ⁇ ⁇ I) SEQ ID NO: 22 ([3 ⁇ 4 720), SEQ ID NO: 23 ([ 3 ⁇ 4 665) or SEQ ID NO: 24 ([3 ⁇ 4 A modified fibroin containing an amino acid sequence shown in Figure 666), or an amino acid sequence having 90% or more sequence identity with the amino acid sequence shown in (5-V) SEQ ID NO: 22, SEQ ID NO: 23 or SEQ ID NO: 24.
  • 5-V amino acid sequence having 90% or more sequence identity with the amino acid sequence shown in (5-V) SEQ ID NO: 22, SEQ ID NO: 23 or SEQ ID NO: 24.
  • amino acid sequences represented by SEQ ID NO: 22, SEQ ID NO: 23 and SEQ ID NO: 24 are represented by SEQ ID NO: 1 at the 1 ⁇ 1 end of the amino acid sequences represented by SEQ ID NO: 19, SEQ ID NO: 20 and SEQ ID NO: 21, respectively.
  • the amino acid sequence shown by 1 is added.
  • the modified fibroin of (5-II ⁇ ) may consist of the amino acid sequence represented by SEQ ID NO: 22, SEQ ID NO: 23 or SEQ ID NO: 24.
  • the modified fibroin of (5-IV) contains an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 22, SEQ ID NO: 23 or SEQ ID NO: 24.
  • the modified fibroin of (5-V) is also a protein containing the domain sequence represented by the formula 1: [(8) "motif [3 ⁇ 4mi]. The above sequence identity may be 95% or more. Preferred.
  • the modified fibroin of (5-IV) has 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 22, SEQ ID NO: 23 or SEQ ID NO: 24, and is located at the most ⁇ 3 terminal side.
  • the average value of the hydrophobicity index of 4 consecutive amino acid residues is 2.6 or more in all the sequences included in the sequence excluding the sequence from the motif to the ⁇ 3 end of the domain sequence in the domain sequence.
  • the total number of amino acid residues contained in the region is defined as ⁇ 2020/175 702 51 ⁇ (: 171-1? 2020/008524
  • /9 is 6.2% or more when the total number of amino acid residues contained in the sequence excluding the sequence up to the 0 terminal of the domain sequence is excluded from the domain sequence.
  • the fifth modified fibroin may contain a secretory signal for releasing the protein produced in the recombinant protein production system to the outside of the host.
  • the sequence of the secretion signal can be appropriately set depending on the type of host.
  • the sixth modified fibroin has an amino acid sequence with a reduced content of glutamine residues as compared to naturally occurring fibroin.
  • the sixth modified fibroin is It is preferable that the amino acid sequence of Minami contains at least _ motifs selected from the XX and XX motifs.
  • the sixth modified fibroin is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N
  • the content ratio of the motif is usually 1% or more, may be 5% or more, and is preferably 10% or more. ⁇ There is no particular upper limit for the content ratio of the motif, and it may be 50% or less, or 30% or less.
  • XX XX motif content rate is a value calculated by the following method.
  • Formula 1 [(8) n Motif ⁇ _] or Formula 2: [(8) "Motif_ ⁇ ?_M] (8)" Fibroin containing the domain sequence represented by the motif (modified fibroin or naturally derived Fibroin) (8)
  • the number obtained by multiplying the total number of motifs by 3 (that is, equivalent to the total number of ⁇ and ⁇ in the ⁇ ⁇ ⁇ motif) is set to 3, and from the () conductedmost located at the ⁇ 3 terminal side to the ⁇ terminal of the domain sequence.
  • the 0 to 0XX motif content is calculated as 3/1.
  • FIG. 9 is a schematic diagram showing a domain sequence of modified fibroin.
  • the calculation method of the content ratio will be explained in detail.
  • the sixth modified fibroin has a glutamine residue content of preferably 9% or less, more preferably 7% or less, further preferably 4% or less, and 0%. Is particularly preferable.
  • glucose residue content rate is a value calculated by the following method.
  • Formula 1 [(8) n motif- ⁇ mi], or Formula 2: [(8) possiblymotif_ ⁇ ? ⁇ 2020/175 702 53 ⁇ (: 171? 2020 /008524
  • the sixth modified fibroin has a domain sequence that is comparable to that of naturally occurring fibroin. Or may have an amino acid sequence corresponding to substitution with another amino acid residue.
  • the "other amino acid residue” may be any amino acid residue other than the glutamine residue, but is preferably an amino acid residue having a larger hydrophobicity index than the glutamine residue.
  • the hydrophobicity index of amino acid residues is shown in Table 1.
  • isoleucine ( ⁇ ), valine (V), leucine (!_), phenylalanine (), cysteine ( ⁇ ) were used as amino acid residues having a larger hydrophobicity index than glutamine residues.
  • amino acid residues selected from tyrosine ( ⁇ ), proline () and histidine (1 to 1).
  • amino acid residue selected from methionine (1 ⁇ / ⁇ and alanine (8), selected from isoleucine (I), parin (V), leucine (!_) and phenylalanine ()). More preferred is an amino acid residue ⁇ 2020/175 702 54 ⁇ (: 171? 2020 /008524
  • the sixth modified fibroin has a hydrophobicity of preferably not less than 100.8, more preferably not less than 107, more preferably not less than 0, and more preferably not less than 0. It is even more preferably 3 or more, and particularly preferably 0.4 or more. There is no particular upper limit to the hydrophobicity of Tami, 1.
  • It may be 0 or less, and may be 0.7 or less.
  • Formula 1 [(8) n Motif ⁇ ], or Formula 2: [(8) doneMotif _ ⁇ ? ⁇ ”(8) perennialFibroin containing the domain sequence represented by the motif (modified fibroin or naturally derived In the fibroin), it is included in the sequence (sequence corresponding to “region 8” in Figure 9) in which the sequence from the motif (8) motif located at the most ⁇ 3 terminal side to the 0 end of the domain sequence is excluded from the domain sequence. All of In o 9, let V be the sum of the hydrophobicity indices of each amino acid residue in the region, and remove the sequence from the motif located at the 0 end to the 0 end of the domain sequence (8) to the 0 end of the domain sequence.
  • the sixth modified fibroin has a domain sequence that is comparable to that of naturally-occurring fibroin. And/or in addition to the modification corresponding to the substitution of one or more glutamine residues in the amino acid residue with another amino acid residue, in addition to the substitution, deletion, insertion of one or more amino acid residues. And/or there may be amino acid sequence alterations corresponding to the additions.
  • the sixth modified fibroin is obtained by, for example, deleting one or more glutamine residues in the cloned gene sequence of naturally-occurring fibroin. ⁇ 2020/175 702 55 ⁇ (: 171? 2020 /008524
  • one or more glutamine residues in Mami are substituted with other amino acid residues.
  • one or more glutamine residues in the amino acid have been deleted from the amino acid sequence of naturally-occurring fibroin, and/or one or more glutamine residues in the amino acid have been deleted from other amino acid residues. It can also be obtained by designing an amino acid sequence corresponding to the substitution with the above and chemically synthesizing a nucleic acid encoding the designed amino acid sequence.
  • the modified fibroin may be mentioned.
  • the modified fibroin of (6-I) will be described.
  • the amino acid sequence represented by SEQ ID NO: 25 is the amino acid sequence represented by SEQ ID NO: 7 (1 ⁇ /161: -? [3 ⁇ 4 414) with all V!_ substituted for V.
  • the amino acid sequence represented by SEQ ID NO: 26 is obtained by replacing ⁇ 3 ⁇ 3 in the amino acid sequence represented by SEQ ID NO: 7 with all 3's and replacing the remaining ⁇ with 8's.
  • the amino acid sequence represented by SEQ ID NO: 27 is the amino acid sequence represented by SEQ ID NO: 7 in which ⁇ 3 ⁇ 3 are all replaced with V !_, and the remaining ⁇ is replaced with ⁇ .
  • the amino acid sequence represented by SEQ ID NO: 28 is the amino acid sequence represented by SEQ ID NO: 7 in which ⁇ 3 ⁇ 3 are all replaced with V and the remaining ⁇ is replaced with !_.
  • the amino acid sequence shown in SEQ ID NO: 29 is the amino acid sequence shown in SEQ ID NO: 7 with V in all ⁇ 3 ⁇ 3. ⁇ 2020/175 702 56 ⁇ (: 171? 2020 /008524
  • the amino acid sequence represented by SEQ ID NO: 30 is the amino acid sequence represented by SEQ ID NO: 8 (1 ⁇ /161: -? [3 ⁇ 4 525) with all Vs replaced with V !_.
  • the amino acid sequence represented by SEQ ID NO: 31 is the amino acid sequence represented by SEQ ID NO: 8 with all ⁇ replaced with V !_, and the remaining ⁇ replaced with ⁇ .
  • the amino acid sequence represented by SEQ ID NO: 32 is the region of 20 domain sequences present in the amino acid sequence represented by SEQ ID NO: 7 (1 ⁇ /161: -? In the repeated sequence, all ⁇ 30 are replaced with V, and the remaining ⁇ 3 are replaced with I.
  • Amino acid sequence represented by SEQ ID NO: 41 Is the one in which all ⁇ in the amino acid sequence shown in SEQ ID NO: 7 is replaced with !_ ⁇ , and the remaining ⁇ is replaced with V.
  • the amino acid sequence shown in SEQ ID NO: 42 (IV! 6-[3 ⁇ 4 D 028) is the amino acid sequence shown in SEQ ID NO: 7 with all ⁇ replaced with I, and the remaining ⁇ replaced with D. Is.
  • amino acid sequences shown in 9, SEQ ID NO: 30, SEQ ID NO: 31, SEQ ID NO: 32, SEQ ID NO: 41 and SEQ ID NO: 42 all have a glutamine residue content of 9% or less (Table 2).
  • the modified fibroin of (6-I) has SEQ ID NO: 25, SEQ ID NO: 26, SEQ ID NO: ⁇ 2020/175 702 57 ⁇ (:171? 2020 /008524
  • SEQ ID NO: 28 SEQ ID NO: 29, SEQ ID NO: 30, SEQ ID NO: 31, SEQ ID NO: 32, SEQ ID NO: 41 or SEQ ID NO: 42 may be used.
  • the modified fibroin of (6-I ⁇ ) has SEQ ID NO: 25, SEQ ID NO: 26, SEQ ID NO: 27, SEQ ID NO: 28, SEQ ID NO: 29, SEQ ID NO: 30, SEQ ID NO: 31, SEQ ID NO: 32, SEQ ID NO: 41 or an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 42.
  • the modified fibroin of (6- ⁇ I) also has the formula 1: [(8) perennialMotif [3 ⁇ 4mi] ⁇ or the formula 2: [(8) (8) "A protein containing a domain sequence represented by a motif. The above sequence identity is preferably 95% or more.
  • the modified fibroin of (6-I ⁇ ) preferably has a glutamine residue content of 9% or less. Further, it is preferable that the modified fibroin of (6 — ⁇ ⁇ ) has a content of XX X motif of 10% or more.
  • the sixth modified fibroin may include a tag sequence at either one or both of the 1 ⁇ 1 end and the ?-end. This enables the isolation, immobilization, detection and visualization of modified fibroin.
  • modified fibroin containing the tag sequence (6— ⁇ I) SEQ ID NO:33 ([3 ⁇ 4888), SEQ ID NO:34 ([3 ⁇ 4965], SEQ ID NO:35 ([ 3 ⁇ 4 Die 889), SEQ ID NO: 36 (Ding 9 16), SEQ ID NO: 37 ( SEQ ID NO: 38 ([3 ⁇ 4 Ding 699), SEQ ID NO: 39 (Ding 6 98), SEQ ID NO: 40 (Ding 966), SEQ ID NO: 43 (Ding 9 17) or SEQ ID NO: 44 ([3 ⁇ 4 Ding 028])
  • SEQ ID NO: 3 SEQ ID NO: 34, SEQ ID NO: 35, SEQ ID NO: 36, SEQ ID NO: 3
  • amino acid sequences shown are SEQ ID NO: 25, SEQ ID NO: 26, SEQ ID NO: 27, respectively.
  • SEQ ID NO: 28, SEQ ID NO: 29, SEQ ID NO: 30, SEQ ID NO: 31, SEQ ID NO: 32, SEQ ID NO: 41 and SEQ ID NO: 42 are represented by SEQ ID NO: 1 at the 1 ⁇ 1 end of the amino acid sequence.
  • the amino acid sequence shown (including 1 to 1 3 tag sequence and hinge sequence) is added. Since only the tag sequence was added to the 1 ⁇ !
  • SEQ ID NO:33, SEQ ID NO:34, SEQ ID NO:35, SEQ ID NO:36, SEQ ID NO:37 , SEQ ID NO: 38, SEQ ID NO: 39, SEQ ID NO: 40, SEQ ID NO: 43 and SEQ ID NO: 44 all have a glutamine residue content of 9% or less (Table 3).
  • the modified fibroin of (6-II ⁇ ) has SEQ ID NO: 33, SEQ ID NO: 34, SEQ ID NO: 35, SEQ ID NO: 36, SEQ ID NO: 37, SEQ ID NO: 38, SEQ ID NO: 39, It may consist of the amino acid sequence of SEQ ID NO: 40, SEQ ID NO: 43 or SEQ ID NO: 44.
  • the modified fibroin of (6-IV) has the following sequences: SEQ ID NO: 33, SEQ ID NO: 34, SEQ ID NO: 35, SEQ ID NO: 36, SEQ ID NO: 37, SEQ ID NO: 38, SEQ ID NO: 39. It includes an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by No. 40, SEQ ID NO: 43 or SEQ ID NO: 44. (6-V) ⁇ 2020/175 702 59 ⁇ (:171? 2020 /008524
  • the modified fibroin of is also represented by Formula 1: [(8) upsetMotif [3 ⁇ 4mi] ⁇ or Formula 2: [(8) (8) "A protein containing a domain sequence represented by a motif. The above sequence identity is preferably 95% or more.
  • the modified fibroin of (6-IV) preferably has a glutamine residue content of 9% or less.
  • the modified fibroin of (6 — V) preferably has a content of XX X motif of 10% or more.
  • the sixth modified fibroin may contain a secretory signal for releasing the protein produced in the recombinant protein production system to the outside of the host.
  • the sequence of the secretion signal can be appropriately set depending on the type of host.
  • the modified fibroin is the first modified fibroin, the second modified fibroin, the third modified fibroin, the fourth modified fibroin, the fifth modified fibroin, and the sixth modified fibroin having the following characteristics. It may be a modified fibroin having at least two or more characteristics.
  • the modified fibroin may be hydrophilic modified fibroin or hydrophobic modified fibroin.
  • hydrophilic modified fibroin means the sum of hydrophobicity indices (! ⁇ 1 I) of all amino acid residues constituting modified fibroin, and then the sum is calculated as the total number of amino acid residues. It is a modified fibroin whose value (average of 1 to 1) divided by is 0 or less. The hydrophobicity index is shown in Table 1. Further, the “hydrophobic modified fibroin” is a modified fibroin having an average of 1 to 1 over 0. Hydrophilic modified fibroin is particularly excellent in flame retardancy. Hydrophobic modified fibroin is particularly excellent in heat absorption by heat absorption and heat retention. As the modified fibroin, it is preferable to use hydrophobic modified fibroin.
  • hydrophilic modified fibroin examples include amino acid sequence represented by SEQ ID NO: 4, amino acid sequence represented by SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 or amino acid sequence represented by SEQ ID NO: 9, SEQ ID NO: 13, Amino acid sequence represented by SEQ ID NO: 11, SEQ ID NO: 14 or SEQ ID NO: 15; SEQ ID NO: 18; SEQ ID NO: 7; SEQ ID NO: 8 or sequence ⁇ 2020/175 702 60 ⁇ (: 171-1? 2020 /008524
  • amino acid sequence represented by SEQ ID NO: 9, SEQ ID NO: 17, SEQ ID NO: 11, SEQ ID NO: 14 or the amino acid sequence represented by SEQ ID NO: 15 is represented by SEQ ID NO: 19, SEQ ID NO: 20 or SEQ ID NO: 21
  • Examples include modified fibroin containing an amino acid sequence.
  • hydrophobic modified fibroin examples include, for example, SEQ ID NO: 27, SEQ ID NO: 28, SEQ ID NO: 29, SEQ ID NO: 30, SEQ ID NO: 31, SEQ ID NO: 3 2, SEQ ID NO: 3 or SEQ ID NO: 4.
  • the protein according to the present embodiment can be produced by a conventional method using a nucleic acid encoding the protein.
  • the nucleic acid encoding the protein may be chemically synthesized based on the nucleotide sequence information, It may be synthesized using a method or the like.
  • the protein ultrafine fiber or protein fiber is prepared, for example, by dissolving a protein in a solvent capable of dissolving it to obtain a dope solution, which is spun by a known spinning method such as wet spinning, dry spinning, dry wet spinning or melt spinning. Obtainable.
  • the protein ultrafine fibers are preferably obtained by spinning by the electrospinning method described above.
  • Solvents capable of dissolving proteins include, for example, dimethyl sulfoxide 1 ⁇ 1, 1 ⁇ 1-dimethylformamide (0 1 ⁇ /1), formic acid, and hexafluoroisopropanol (1 to 1) are listed.
  • An inorganic salt may be added to the solvent as a dissolution promoter.
  • the waterproof/moisture permeable fabric according to the second embodiment is a waterproof/moisture permeable layer 2 made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less (hereinafter also simply referred to as “non-woven fabric”), and a first water resistance imparting substance. It is joined to the skin layer 1 made of a knitted fabric containing.
  • the skin layer 1 of the waterproof/moisture permeable fabric according to the second embodiment is made of a knitted fabric containing the first water resistance-imparting substance.
  • a knitted fabric is a general term for knitted fabrics and woven fabrics. Knitted fabric ⁇ 2020/175 702 61 ⁇ (:171? 2020 /008524
  • a knitted fabric having a weft knitting structure such as a flat knit or circular knit (also simply referred to as “weft knitted fabric”), a knitted fabric having a warp knitting structure such as tricot, Russell (also simply referred to as “warp knitted fabric”) Any of) may be used.
  • the woven fabric may be a woven fabric having any one of a plain weave, a twill weave, and a Tsumushi weave.
  • the knitted or woven body may be an unprocessed knitted or woven body itself obtained by knitting or weaving, or may be a knitted or woven body subjected to processing such as water repellent after knitting or weaving.
  • the water resistance-imparting substance is a substance capable of improving the water resistance of the waterproof and moisture-permeable fabric.
  • the waterproof/moisture permeable fabric contains a water resistance-imparting substance, for example, the water repellency of the waterproof/moisture permeable fabric is improved, and the contraction of the waterproof/moisture permeable fabric upon contact with water is exerted.
  • the waterproof property of the breathable fabric is further improved.
  • the water resistance-imparting substance include, for example, hydrophobic polymers such as fluorine-based polymers and silicone-based polymers, and modified hydroxyl group-containing polymers in which a hydrophobic functional group is bonded to a hydroxyl group-containing polymer.
  • hydrophobic polymers such as fluorine-based polymers and silicone-based polymers
  • modified hydroxyl group-containing polymers in which a hydrophobic functional group is bonded to a hydroxyl group-containing polymer.
  • first Reactive agent a polyfunctional agent having two or more first reactive groups capable of reacting with a protein to form a bond
  • a protein-binding agent such as a reactive agent having one or more _th reactive group capable of reacting with a protein to form a bond
  • a functional group a polyfunctional agent having two or more first reactive groups capable of reacting with a protein to form a bond
  • the fluorine-based polymer is not particularly limited as long as it is a polymer containing fluorine.
  • the fluorine-based polymer may be, for example, a polymer obtained by polymerizing an olefin containing fluorine.
  • fluoropolymers include polytetrafluoroethylene, polytrifluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyperfluoroalkyl vinyl ether, polyperfluoropropylene, polytetrafluoroethylene-perfluoro.
  • fluorine-based polymer a copolymer obtained by polymerizing two or more kinds of monomers constituting the exemplified polymer (random copolymer, block copolymer or ⁇ 2020/175 702 62 ⁇ (:171? 2020 /008524
  • the silicone-based polymer is not particularly limited as long as it is a polymer having a polysiloxane structure in the main chain.
  • the silicone-based polymer includes, for example, a homopolymer or a copolymer (random copolymer, block copolymer or alternating copolymer) obtained by polymerizing one or more monomers having a siloxane structure unit. ) May be.
  • a copolymer obtained by polymerizing one or more monomers having a siloxane structural unit and one or more monomers having no siloxane structural unit random copolymer, block (Including a copolymer or an alternating copolymer).
  • the modified hydroxyl group-containing polymer is a polymer having a hydrophobic functional group bonded to the hydroxyl group-containing polymer.
  • the modified hydroxyl group-containing polymer can be obtained, for example, by reacting a hydroxyl group-containing polymer with a reactive agent having a hydrophobic functional group.
  • the hydroxyl group-containing polymer can be used without particular limitation as long as it is a polymer compound having a hydroxyl group.
  • Specific examples of the hydroxyl group-containing polymer include, for example, starch, glycogen, cellulose, chitin, agarose, hyaluronic acid, chondroitin sulfate, polysaccharides such as pectin and carrageenan, polyvinyl alcohol (8) and phenol resin. Molecules.
  • the hydroxyl group-containing polymer is preferably a polysaccharide from the viewpoint of biodegradability. Further, as the hydroxyl group-containing polymer, starch is preferable from the viewpoint of high biodegradability and high solubility.
  • the reactive agent having a hydrophobic functional group is a compound having a hydrophobic functional group and further having a binding functional group capable of binding to a hydroxyl group-containing polymer.
  • the binding functional group may be capable of being bonded to the hydroxyl group-containing polymer through a hydrogen bond or a covalent bond, but is preferably a functional group capable of being covalently bonded to the hydroxyl group-containing polymer, and is preferably a hydroxyl group-containing polymer. More preferably, it is a functional group capable of covalently bonding to the hydroxyl group therein.
  • Examples thereof include alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group, aromatic groups such as phenyl group and naphthyl group, and acyl groups such as acetyl group, propanoyl group and benzoyl group. ..
  • Examples of the protein-binding agent include, for example, a polyfunctional reaction agent (first reaction agent) having two or more first reactive groups capable of reacting with a protein to form a bond, a reaction with a protein. And one or more first reactive groups capable of forming a bond, and a reactive agent having a functional group (functional reactive agent).
  • first reaction agent polyfunctional reaction agent having two or more first reactive groups capable of reacting with a protein to form a bond
  • a reaction with a protein a reaction with a protein.
  • a reactive agent having a functional group functional reactive agent
  • the first reactive agent is selected from the group consisting of an amide group, a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxyl group, a thiol group, a selenol group, an imidazolyl group, an indolyl group and a guanidino group contained in a protein. It has a first reactive group capable of reacting with at least _ reactive functional groups to form a bond.
  • Examples of the first reactive group include, for example, the following formulas (81-1), (81-2), (8-3), (81-4), (81-5) or (81-6). )
  • the group represented by is mentioned.
  • the wavy line in each formula represents a bond of each group.
  • X 1 represents an oxygen atom ( ⁇ ) or a sulfur atom (3).
  • X 2 represents a leaving group.
  • X 3 is an oxygen atom ( ⁇ ), a sulfur atom (3), Or
  • a group represented by ([3 ⁇ 4 5 ) 2 _ is shown. May be, for example, a hydrogen atom, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group, an arylsulfonyl group, an alkylsulfonyl group, an acyl group, a power-bamate group. Is an electron-withdrawing group ⁇ 2020/175 702 64 ⁇ (: 171? 2020/008524
  • X 4 represents an oxygen atom ( ⁇ ) or a sulfur atom (3)
  • 1 is a halogen atom, a hydroxyl group, a group represented by, or a group represented by 10 [3 ⁇ 4 6 , Or 10 ⁇ 30 Represents a group represented by. May be, for example, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group.
  • X 5 represents an oxygen atom ( ⁇ ) or a sulfur atom (3)
  • 2 represents a group represented by an oxygen atom ( ⁇ ), a sulfur atom (3) or 7 .
  • the functional reactive agent is a reactive agent having a first reactive agent, a second reactive group (1) capable of reacting with the first reactive group to form a bond, and a functional group. It can be obtained by reacting with (second reaction agent).
  • Examples of the second reactive group include a hydroxyl group, a thiol group, an amino group, and a group represented by the following formula (Minichi 1).
  • X 6 represents an oxygen atom (o) or a sulfur atom (3).
  • Examples of the functional group include a hydrocarbon group such as an alkyl group, an alkenyl group, and an alkynyl group; a group having a ring structure such as an aryl group and a heterocyclic group; a reactive group protected by a protecting group.
  • Examples thereof include an ammonium group.
  • Specific examples of the first reactant include, for example, hexane diisocyanate (1 to 10
  • the water resistance-imparting substance is preferably a fluoropolymer or a silicone polymer from the viewpoint of improving the water repellency of the waterproof/moisture permeable fabric and suppressing the contraction upon contact with water.
  • the knitted or woven body can be obtained by knitting or weaving raw material threads.
  • a knitting method and a weaving method known methods can be used.
  • the knitting machine to be used for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used.
  • the flat knitting machine there are a forming knitting machine, a non-sewn knitting machine, and the like.
  • the non-sewn knitting machine is more preferable.
  • the loom to be used include a hauling loom, and a non-tapping loom such as a gripper loom, a rapier loom, a water jet loom, and an air jet loom.
  • Examples of the method for incorporating the first water resistance-imparting substance into the knitted fabric include, for example, a raw material yarn containing the first water resistance-imparting substance (for example, a raw material yarn mixed with the first water resistance-imparting substance, The raw material yarn to which the first water resistance-imparting substance is bound is used, except that the knitting method or the weaving method described above is used (method), and the first water resistance-imparting substance is not included.
  • a method (method M) of binding the first water resistance-imparting substance to the knitted or woven body can be mentioned.
  • the method Mami includes a step (bonding step) of bonding the first water resistance-imparting substance to the knitted fabric.
  • the first water resistance-imparting substance is brought into contact with the knitted fabric by a means such as coating or crushing, and heating or plasma irradiation is performed as necessary, and the weaving fabric and the first water resistance-imparting substance.
  • the bonding step may include, for example, the first water resistance-imparting substance or the first water resistance-imparting substance on the textile.
  • the precursor of the imparting substance (monomer) was contacted ⁇ 2020/175 702 66 ⁇ (:171? 2020/008524
  • the precursor (monomer) of the first water resistance-imparting substance is used, the precursor (monomer) of the first water resistance-imparting substance is polymerized by the irradiation of plasma to impart the first water resistance-imparting property. Since the substance (hydrophobic polymer such as silicone-based polymer and fluorine-based polymer) is formed, it is possible to obtain a knitted fabric containing the first water resistance imparting substance.
  • the plasma to be irradiated may be appropriately set depending on the kind of the knitted fabric, the first water resistance imparting substance (or its precursor), and the like.
  • the flow rate of the discharge gas is, for example, 0.1 L/rr ⁇ ⁇ It may be within the following range.
  • the plasma density of the generated plasma may be, for example, in the range of 1 ⁇ 1 0 1 3 x 0 1 _ 3 or more and 1 x 1 0 1 5 x _ 3 or less.
  • the discharge gas may be, for example, a rare gas such as helium, neon, or argon, oxygen, nitrogen, or the like. Atmosphere can also be used as the discharge gas.
  • Plasma irradiation can be carried out using a known plasma irradiation device.
  • a plasma irradiation apparatus for example, a plasma processing apparatus manufactured by Minori " ⁇ 333 0! 8" can be used.
  • the raw material yarn of the knitted fabric may be a single yarn, a composite yarn (for example, a mixed yarn, a mixed yarn, a covering yarn, etc.), or may be a combination of these. ..
  • the single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are twisted together.
  • Examples of fibers contained in the raw yarn include protein fibers, synthetic fibers such as nylon, polyester and polytetrafluoroethylene, regenerated fibers such as cupra, rayon and lyocell, and natural fibers such as cotton, hemp and silk. Fibers.
  • the knitted or woven body preferably contains modified fibroin, and more preferably modified spider silk fibroin.
  • modified fibroin preferably modified spider silk fibroin
  • the waterproof and moisture-permeable fabric according to the present embodiment can be further imparted with heat-retaining property, heat-absorption property and/or flame-retardant property. The higher the value as.
  • Modified fibroin is a modified fibroin fiber ⁇ 2020/175 702 67 ⁇ (:171? 2020 /008524
  • Protein fiber may be contained in the knitted fabric.
  • the embodiment described for the waterproof and breathable fabric according to the first invention can be applied.
  • the surface of the knitted or woven body on the side opposite to the side joined to the nonwoven fabric may be water repellent. This makes it possible to obtain a waterproof and moisture-permeable fabric that is more waterproof.
  • the water repellent treatment can be carried out by a conventionally known method such as chemical coating such as plasma processing, physical coating such as coating with a water repellent coating agent, or chemical modification of the surface.
  • the waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the second embodiment is made of a nonwoven fabric containing ultrafine fibers having a fiber diameter of 10 or less (hereinafter, also simply referred to as "nonwoven fabric").
  • the fiber diameter of the ultrafine fibers means the diameter of the smallest circle that surrounds the cross section of the short fibers perpendicular to the longitudinal direction.
  • the fiber diameter of the ultrafine fiber may be 10 (1 0 0 0 0 0 0 n 0 or less, 90 0 or less, 8 0! or less, 7 0! or less, 6 0! or less, 5 or less,
  • the fiber diameters of ultrafine fibers are, for example, 1 0 1!! Or more, 4 0 1 ⁇ ! or more, 5 0 1 ⁇ ! or more, that's all, Or more, 8 0 1 ⁇ ⁇ ! or more, 9 0 1 ⁇ ⁇ ! or more, that's all, that's all,
  • the ultrafine fibers may be formed of any material as long as the fiber diameter condition is satisfied.
  • the ultrafine fibers may be, for example, protein fibers, synthetic fibers such as nylon and polyester, regenerated fibers such as cupra, rayon and lyocell, and natural fibers such as cotton, hemp and silk.
  • the ultrafine fibers preferably include modified fibroin, and more preferably include modified spider silk fibroin.
  • Modified fibroin preferably modified ⁇ 2020/175 702 68 ⁇ (:171? 2020 /008524
  • the waterproof and moisture-permeable fabric according to the present embodiment can be further imparted with heat-retaining properties, heat-absorption properties and/or flame-retardant properties, and its value as a land becomes higher.
  • the modified fibroin may be contained in the ultrafine fibers as modified fibroin fiber (protein fiber).
  • modified fibroin fiber protein fiber
  • the embodiment described in the waterproof and moisture-permeable fabric according to the first invention can be applied.
  • the non-woven fabric may contain only ultrafine fibers, or may contain other fibers (having a fiber diameter of more than 10) in addition to the ultrafine fibers. That is, as the fibers (also referred to as “material yarns”) used for forming the non-woven fabric, a single yarn made of only ultrafine fibers, or a composite yarn made by combining ultrafine fibers with other fibers (having a fiber diameter of more than 10). (For example, blended yarn, blended yarn, covering yarn, etc.) may be used alone or in combination.
  • the single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or filament yarn in which long fibers are twisted together.
  • a filament yarn is preferably used as the single yarn and the composite yarn.
  • the proportion of ultrafine fibers in the non-woven fabric is based on the total mass of the non-woven fabric, for example, 30 mass% or more, 40 mass% or more, 50 mass% or more, It may be 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.
  • the non-woven fabric can be produced by a known production method using, for example, fibers containing at least a portion of ultrafine fibers having a fiber diameter of 10 or less.
  • a web including a single-layer web and a laminated web
  • a dry method is formed by a dry method, a wet method, an air-laid method, or the like from a fiber including at least a part of ultrafine fibers having a fiber diameter of 10 or less.
  • the fibers of the web can be bonded by a chemical bond method (immersion method, spray method, etc.) or a needle punch method to obtain a nonwoven fabric.
  • the nonwoven fabric contains protein ultrafine fibers
  • the following production method can be further exemplified. That is, for example, the protein is dimethyl sulfoxide (mouth! ⁇ /1300) ⁇ 2020/175 702 69 ⁇ (:171? 2020/008524
  • a nonwoven fabric can also be obtained by adding a salt and dissolving it to prepare a dope solution, and spinning the dope solution by an electrospinning method (electrostatic spinning method).
  • the average fiber diameter (average fiber diameter) of protein ultrafine fibers obtained by the electrospinning method is usually 1 0000 n ⁇ ! or less, preferably 1 000 ⁇ 01 or less, and 100 nm to 1 nm. 0000 n 01, 1
  • the fiber diameter of the fibers may vary between 100 ⁇ ⁇ 1 to 1 0000 nm (100 000), preferably 1 00 ⁇ ⁇ ! to 1 0001 ⁇ 111 (1 000).
  • the nonwoven fabric is appropriately set such that the numerical ranges of the fiber density (area weight), the porosity, the bulk density, etc. are within a range in which waterproofness and moisture permeability can be sufficiently ensured.
  • the unit weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of layers.
  • the nonwoven fabric may contain the second water resistance imparting substance.
  • the waterproofness of the waterproof and moisture-permeable fabric according to the present embodiment is further improved.
  • Specific examples of the second water resistance imparting substance include those exemplified for the first water resistance imparting substance.
  • the nonwoven fabric contains the second water resistance-imparting substance, the first and second water resistance-imparting substances may be the same or different.
  • the backing layer 3 of the waterproof/moisture permeable fabric according to the second embodiment is made of a knitted fabric.
  • the backing layer 3 may be provided if necessary. Examples of the preferable embodiment of the backing layer 3 include the embodiments exemplified for the skin layer 1.
  • the skin layer 1 and the backing layer 3 may be knitted fabrics made of the same material, or may be knitted fabrics made of different materials.
  • the backing layer 3 may or may not contain a water resistance-imparting substance. Whether or not it contains a water resistance-imparting substance depends on whether the waterproof/moisture permeable raw material according to the present embodiment. ⁇ 2020/175 702 70 ⁇ (:171? 2020 /008524
  • the waterproof/moisture permeable fabric according to the second embodiment can be obtained by joining a nonwoven fabric (waterproof/moisture permeable layer) and a knitted fabric (skin layer).
  • the method for joining the waterproof moisture-permeable layer and the skin layer can be appropriately selected depending on the materials used for the nonwoven fabric and the knitted fabric.
  • a joining method for example, a method of welding a waterproof moisture-permeable layer and a skin layer with heat or a solvent, a method of bonding the waterproof moisture-permeable layer and a skin layer with an adhesive, a nonwoven fabric and a knitted body A method of irradiating plasma to at least one of the bonding surfaces to form a covalent bond by a radial reaction to bond the waterproof and moisture permeable layer to the skin layer, and the like.
  • both the non-woven fabric and the woven fabric contain a protein (protein ultrafine fiber or protein fiber), a solvent that dissolves the protein in one or both of the joint surfaces of the waterproof moisture-permeable layer and the skin layer (for example, dimethyl sulfoxide ( Mouth 1 ⁇ /1 3 ⁇ ), 1 ⁇ 1, 1 ⁇ 1 _ Dimethylformamide ), formic acid, or an organic solvent such as hexafluoroisopropanol (1 to 1 I), a solution obtained by adding an inorganic salt as a dissolution promoter to them, or water, or an aqueous solution obtained by adding an inorganic salt or the like to water)
  • the waterproof and moisture permeable layer and the epidermis layer are attached to each other, and the solvent is further removed, whereby the waterproof and moisture permeable layer and the epidermis layer can be joined.
  • the waterproof and moisture-permeable layer is formed on the skin layer by a manufacturing method including a waterproof and moisture-permeable layer forming step.
  • a moist dough can be obtained.
  • the waterproof/moisture permeable layer forming step includes the steps of: electrospinning using a dope solution containing a protein to accumulate protein ultrafine fibers on the skin layer to form a nonwoven fabric.
  • a solvent that dissolves the protein may be applied onto the epidermis layer.
  • a nonwoven fabric is formed, and the formed nonwoven fabric and the skin layer are joined together.
  • electrospinning method electrospinning method
  • a voltage is applied between a supply-side electrode (which can also be used as a spinneret) and a collection-side electrode (for example, a metal nozzle or a metal net), and spinning is performed.
  • a supply-side electrode which can also be used as a spinneret
  • a collection-side electrode for example, a metal nozzle or a metal net
  • the applied voltage is usually 5 to 1001 ⁇ V, preferably 10 to 5101 ⁇ V.
  • the distance between the electrodes is It is preferably 2 to 200.
  • FIG. 4 is an explanatory diagram of an electrospinning device 100 according to an embodiment.
  • a voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35.
  • the dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36.
  • a nonwoven fabric 39 containing protein ultrafine fibers can be obtained.
  • a non-woven fabric can also be formed by depositing a protein ultrafine fiber on the skin layer by placing a skin layer (woven body) on the surface of the metal net 38.
  • a skin layer woven body
  • an adhesive or a solvent that dissolves at least one of the knitted fabric and the nonwoven fabric onto the surface of the skin layer (knitted fabric) the formed nonwoven fabric and the knitted fabric are joined together. It can also be done.
  • the resulting non-woven fabric may then be stripped of solvent. Examples of the method for removing the solvent (the solvent in the dope solution, the solvent applied to the knitted fabric or the nonwoven fabric, etc.) include vacuum drying or immersion in a desolvation tank.
  • the method for joining the waterproof moisture-permeable layer and the backing layer is based on the method described above.
  • the waterproof/moisture permeable fabric according to the third embodiment is a waterproof/moisture permeable layer 2 made of a nonwoven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less (hereinafter also simply referred to as “nonwoven fabric”), and a skin layer made of a knitted fabric. 1 is joined.
  • the non-woven fabric forming the waterproof/moisture permeable layer 2 is water-shrinked.
  • a non-woven fabric that is water-condensed may be referred to as a “high-density non-woven fabric”
  • a non-woven fabric before water-shrinkage may be referred to as a “non-woven fabric material”.
  • the waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the third embodiment is a high-density nonwoven fabric (a nonwoven fabric that contains protein ultrafine fibers with a fiber diameter of 10 or less and is water-shrinked). ⁇ 2020/175 702 72 ⁇ (: 171-1? 2020/008524
  • the fiber diameter of a protein ultrafine fiber means the diameter of the smallest circle surrounding a cross section perpendicular to the longitudinal direction of the short fiber.
  • the fiber diameter of the protein ultrafine fiber may be 1001 (1 0 0 0 0 1 ⁇ 111) or less, 9 or less, 8 or less, 7 ⁇ ! or less, 6 ⁇ ! or less, 5 ⁇ ! or less, 4 ⁇ ! or less, 3 or less, 2 ⁇ or less, 1 ⁇ ! (1 0 0 0 1 ⁇ 111) or less, 9 0 0 1 ⁇ or less, 8 0 0 1 ⁇ or less,
  • the fiber diameter of protein ultrafine fiber is, for example, 10 !! 01 or more, 2 0 1 ⁇ 01 or more, that's all,
  • the high-density nonwoven fabric may contain only protein ultrafine fibers, or may contain other fibers such as protein fibers in addition to the proteinaceous ultrafine fibers. That is, as fibers (also referred to as “material threads”) used for forming a high-density nonwoven fabric, other fibers such as a single thread consisting only of protein ultrafine fibers, protein ultrafine fibers and protein fibers (having a fiber diameter of more than 10) are used.
  • the composite yarns for example, mixed yarns, mixed yarns, covering yarns, etc. formed by combining the above fibers with each other may be used alone or in combination.
  • the single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or filament yarn in which long fibers are fired together.
  • a filament yarn is preferably used as the single yarn and the composite yarn.
  • other fibers include protein fibers, synthetic fibers such as nylon and polyester, regenerated fibers such as cupra and rayon, and natural fibers such as cotton and hemp.
  • the proportion of protein ultrafine fibers in the high-density nonwoven fabric is, for example, 30% by mass or more, 40% by mass or more, based on the total mass of the high-density nonwoven fabric. 50 mass% or more, 60 mass% or more, 70 mass% or more, ⁇ 2020/175 702 73 ⁇ (: 171-1? 2020/008524
  • It may be 80% by mass or more, 90% by mass or more, or 95% by mass or more.
  • the fiber density (area weight) of the high-density nonwoven fabric according to the present embodiment is, for example, 0.04
  • the fiber density of the high-density nonwoven fabric is a value defined by the weight per unit area of the nonwoven fabric.
  • the fiber density increase rate is preferably 20% or more, more preferably 30% or more, and further preferably 40% or more, It is even more preferably 50% or more, still more preferably 100% or more.
  • the fiber density increase rate is a value defined by the following formula.
  • Fiber density increase rate ⁇ (fiber density of nonwoven fabric after water shrinkage (high density nonwoven fabric) / fiber density of nonwoven fabric before water shrinkage (raw material nonwoven fabric))-1 ⁇ X 1 ⁇ ⁇ (%) (Equation
  • the high-density non-woven fabric can be obtained by water-shrinking a raw material non-woven fabric (a non-woven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less and before water shrinkage).
  • the high-density non-woven fabric is obtained by a production method including, for example, a step of producing a raw non-woven fabric and a step of contacting the raw non-woven fabric with water to shrink the raw non-woven fabric (hereinafter, also referred to as “shrinking step”). You can
  • the raw material non-woven fabric can be produced by a known production method using, for example, fibers containing at least a portion of protein ultrafine fibers having a fiber diameter of 10 or less.
  • a web single-layer web, laminated web, etc. is prepared by a dry method, a wet method, an air-laid method, or the like from a fiber containing at least a part of a protein ultrafine fiber having a fiber diameter of 10 or less.
  • the raw non-woven fabric also includes, for example, proteins such as dimethyl sulfoxide (mouth 1 ⁇ /1
  • the average fiber diameter (average fiber diameter) of the protein ultrafine fibers obtained by the electrospinning method is usually 1 0000 nm or less, preferably 1 000 doors or less, 100 nm to 1 0000 n ⁇ 1 , 1 00
  • the fiber diameter of the fiber is It may fluctuate between (10), preferably between 100 ⁇ ! and 1 0001 ⁇ 111 (100 ).
  • the raw material non-woven fabric is appropriately set such that the numerical ranges of the fiber density (weight per unit area), the porosity, the bulk density, etc. are within a range in which water proofness and moisture permeability can be sufficiently ensured.
  • the basis weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of laminated layers.
  • the raw material nonwoven fabric is brought into contact with water to shrink the raw material nonwoven fabric. Since the raw material non-woven fabric contains protein ultrafine fibers, it is possible to shrink the protein ultrafine fibers (also referred to as water shrinkage) by contacting with water, without relying on an external force, and to shrink the entire nonwoven fabric. Give rise to.
  • the contraction of the protein ultrafine fibers that does not depend on the external force is considered to occur due to the following reasons, for example. That is, one reason is considered to be due to the secondary structure or the tertiary structure of the protein ultrafine fiber, and another reason is that, for example, in the protein ultrafine fiber having residual stress due to stretching in the manufacturing process, It is considered that the residual stress is relieved by the infiltration of fibers into or between fibers. Therefore, the shrinkage rate of protein ultrafine fibers in the shrinking process depends on, for example, the size of the draw ratio in the process of producing protein ultrafine fibers. ⁇ 2020/175 702 75 ⁇ (:171? 2020/008524
  • the shrinkage rate of the protein microfibers can be controlled by controlling the temperature of water to be contacted, the contact time with water, and the tensile force when contacting with water in the shrinking process. .. Therefore, using a material yarn containing protein ultrafine fibers whose contraction rate upon contact with water is adjusted by adjusting the draw ratio in the production process of protein ultrafine fibers, and the temperature of the water contacted in the shrinking process, By controlling the contact time with water, the tensile force when contacting with water, etc., the shrinkage ratio of the raw material nonwoven fabric due to contact with water can be adjusted arbitrarily. As a result, it is considered that a high-density nonwoven fabric having a desired fiber density can be obtained.
  • the fiber density of the high-density nonwoven fabric can be adjusted by appropriately selecting and combining material threads having different contraction rates upon contact with water. To be done. Further, by limiting the shrinkage amount of the raw material nonwoven fabric due to contact with moisture, the fiber density of the high density nonwoven fabric can be adjusted regardless of the type of material yarn.
  • the method of limiting the amount of shrinkage due to the contact of the raw material nonwoven fabric with water is not particularly limited. Examples of the method of limiting the shrinkage amount include a method of bringing the raw material nonwoven fabric into contact with water to shrink the raw material nonwoven fabric in a fixed state.
  • the non-woven fabric obtained by contacting water with the raw material non-woven fabric in a state where the peripheral edge is free to shrink the maximum amount is smaller than the original size of the raw material non-woven fabric before contacting with water, and the non-woven fabric obtained by contacting water with the raw material non-woven fabric in a state where the peripheral edge is free to shrink the maximum amount.
  • a state in which the peripheral edge of the raw non-woven fabric is fixed over the entire circumference in a frame that is a size larger than the size (a state in which shrinkage is allowed by the difference between the size of the frame and the size of the raw non-woven fabric).
  • the amount of shrinkage can be adjusted by contacting the raw material nonwoven fabric with water.
  • water means water in a liquid or gas state.
  • contact step the method of bringing the moisture into contact with the raw material nonwoven fabric is not particularly limited. ⁇ 2020/175 702 76 ⁇ (: 171? 2020/008524
  • a method of immersing the raw non-woven fabric in water a method of spraying water on the raw non-woven fabric in a state of normal temperature or heated steam, etc., a method of exposing the raw non-woven fabric to a high humidity environment filled with water vapor, etc.
  • the method of immersing the raw material nonwoven fabric in water is preferable because it can effectively shorten the shrinkage time and can simplify the processing equipment.
  • a method for immersing this raw material nonwoven fabric in water specifically, for example, a raw material nonwoven fabric formed using fibers containing protein ultrafine fibers is placed in a container containing water at a predetermined temperature. There is a method of contacting with water.
  • the temperature of the water for contacting the moisture with the raw material nonwoven fabric is not particularly limited, but is preferably lower than the boiling point, for example. At such a temperature, handling and workability in the shrinking process are improved. Further, the upper limit value of the water temperature is preferably 90° or less, more preferably 80° or less. The lower limit of the temperature of the water is preferably at 1 0 ° ⁇ As, more preferably 4 0 ° ⁇ than on, and still more preferably 7 0 ° ⁇ As.
  • the temperature of the water contacted with the raw material nonwoven fabric can be adjusted according to the fibers constituting the raw material nonwoven fabric. In addition, the temperature of the water may be constant while the moisture is in contact with the raw material nonwoven fabric, or the temperature of the water may be changed to reach a predetermined temperature.
  • the time for contacting the raw material nonwoven fabric with water is not particularly limited and may be, for example, 1 minute or more.
  • the time may be 10 minutes or longer, 20 minutes or longer, and 30 minutes or longer.
  • the upper limit of the time is not particularly limited, but it is, for example, 120 minutes or less from the viewpoint of shortening the manufacturing process time and eliminating the risk of hydrolysis of protein fiber. Well, 90 minutes or less, 60 minutes or less.
  • the shrinking step may further include, in addition to the contacting step, contacting the raw material nonwoven fabric with water and then drying (hereinafter, also referred to as "drying step”).
  • drying step ⁇ 2020/175 702 77 ⁇ (:171? 2020/008524
  • the drying method in the drying step is not particularly limited, and may be, for example, natural drying or forced drying using a drying facility.
  • the drying temperature is not particularly limited as long as it is lower than the temperature at which the proteins constituting the nonwoven fabric are thermally damaged, but generally, it is within the range of 20 to 150 ° And preferably in the range of 40 to 120 ° ⁇ ,
  • the temperature is in the range of 60 to 100°. Within such a temperature range, the nonwoven fabric can be dried more quickly and efficiently without causing thermal damage to the protein.
  • the drying time is appropriately selected according to the drying temperature and the like, and for example, the time that can eliminate the influence of overdrying of the protein ultrafine fibers on the quality and physical properties of the nonwoven fabric is used.
  • the skin layer 1 of the waterproof/moisture permeable fabric according to the third embodiment is made of a knitted fabric.
  • a knitted fabric is a generic term for knitted fabrics and woven fabrics.
  • a knitted fabric is a knitted fabric having a weft knitting structure such as a flat knitted fabric or a circular knitted fabric (also simply referred to as a “weft knitted fabric”), a knitted fabric having a warp braided fabric such as tricot, Russell (only Also referred to as ".”.
  • the woven fabric may be a woven fabric having any one of a plain weave, a twill weave, and a Tsumago weave.
  • the knitted or woven body may be an unprocessed knitted or woven body itself obtained by knitting or weaving, or may be a knitted or woven body subjected to a process such as water repellent treatment after knitting or weaving.
  • the knitted or woven body can be obtained by knitting or weaving raw material threads.
  • a knitting method and a weaving method known methods can be used.
  • the knitting machine to be used for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used.
  • the flat knitting machine there are a forming knitting machine, a non-sewn knitting machine, and the like.
  • the non-sewn knitting machine is more preferable.
  • the loom to be used include a hauling loom, and a non-tapping loom such as a gripper loom, a rapier loom, a water jet loom, and an air jet loom.
  • the raw material yarn of the knitted fabric may be a single yarn or a composite yarn (for example, a mixed yarn, a mixed yarn, a covering yarn, etc.), and these may be used in combination. ⁇ 2020/175 702 78 ⁇ (:171? 2020 /008524
  • the single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or may be filament yarn in which long fibers are twisted together.
  • the fibers contained in the raw yarn include, for example, protein fibers (regardless of fiber diameter), synthetic fibers such as nylon, polyester, polytetrafluoroethylene, recycled fibers such as cupra and rayon, cotton, hemp, etc. Examples include natural fibers.
  • the knitted fabric may be water-shrinked, like the high-density nonwoven fabric.
  • the waterproofness can be further improved without impairing the moisture permeability of the waterproof/moisture permeable material according to the present embodiment.
  • the protein fiber has the same properties as the protein ultrafine fiber, the knitted fabric can be water-shrinked by the method described above. The same is true for the preferred mode of contracting water.
  • the surface of the knitted or woven body opposite to the side where it is joined to the high-density nonwoven fabric may be water repellent. This makes it possible to obtain a waterproof and breathable fabric that is more waterproof.
  • the water repellent treatment can be performed by a conventionally known method such as chemical coating such as plasma treatment, physical coating such as application of a water repellent coating agent, or chemical modification of the surface.
  • the waterproof/moisture permeable fabric according to the third embodiment is:
  • a backing layer (textile) may be further bonded to the surface of the (nonwoven fabric) opposite to the surface to which the skin layer (textile) is bonded.
  • Examples of the preferable embodiment of the backing layer include the embodiments exemplified for the skin layer.
  • the skin layer and the backing layer may each be a knitted fabric formed of the same material, or may be a knitted fabric formed of different materials.
  • the method of manufacturing a waterproof moisture-permeable fabric according to the third embodiment includes at least a step of joining a high-density nonwoven fabric to a knitted body (joining step).
  • the manufacturing method is a process of forming a nonwoven fabric by accumulating protein ultrafine fibers having a fiber diameter of 10 or less by electrospinning using a dope solution containing a protein (manufacturing process of a raw material nonwoven fabric).
  • the non-woven fabric (raw material non-woven fabric) may be further provided with a step of contracting by contacting with water (shrinkage step). ⁇ 2020/175 702 79 ⁇ (:171? 2020/008524
  • the high density nonwoven fabric (waterproof and moisture permeable layer) and the knitted fabric (skin layer) are joined.
  • the method for joining the high-density nonwoven fabric and the knitted fabric can be appropriately selected depending on the materials used for the high-density nonwoven fabric and the knitted fabric.
  • a joining method for example, a method of welding a high-density non-woven fabric and a weaving body with heat or a solvent, a method of adhering the high-density non-woven fabric and the weaving body with an adhesive, and a high-density non-woven fabric and a weaving body at least Examples include a method in which one of the bonding surfaces is irradiated with plasma to form a covalent bond by a radical reaction to bond the waterproof moisture-permeable layer and the skin layer.
  • both the high-density nonwoven fabric and the woven body contain proteins (protein ultrafine fibers or protein fibers)
  • a solvent that dissolves the protein in one or both of the bonding surfaces of the high-density nonwoven fabric and the woven body for example, dimethy Organic solvent such as sulphoxide (mouth 1 ⁇ /1300), 1 ⁇ 1, 1 ⁇ 1_ dimethylformamide (0 1 ⁇ /1), formic acid, or hexafluoroisopropanol (1 to 1 I)
  • dimethy Organic solvent such as sulphoxide (mouth 1 ⁇ /1300), 1 ⁇ 1, 1 ⁇ 1_ dimethylformamide (0 1 ⁇ /1), formic acid, or hexafluoroisopropanol (1 to 1 I
  • a solution to which an inorganic salt as a dissolution accelerator is added, or water or an aqueous solution in which inorganic salt or the like is added to water After applying a solution to which an inorganic salt as a dissolution accelerator is added, or water or an aqueous
  • the step of manufacturing the raw material nonwoven fabric and the step of shrinking can be performed according to the method described above.
  • a method for manufacturing a waterproof and moisture-permeable fabric includes a step of preparing a raw material fabric in which a raw material nonwoven fabric and a knitted fabric are joined (preparation step), and contacting the raw material nonwoven fabric with moisture, A step of shrinking with water (shrinking step).
  • the manufacturing method is as follows: electrospinning using a dope containing a protein, a step of accumulating protein ultrafine fibers having a fiber diameter of 10 or less to form a non-woven fabric (manufacturing process of the raw non-woven fabric), a raw non-woven fabric and a woven body It may further be provided with a step of joining the raw material dough by joining (process for producing the raw material dough).
  • the raw material non-woven fabric and the knitted fabric are joined.
  • the joining of the raw material non-woven fabric and the knitted fabric can be performed according to the joining method of the high density non-woven fabric and the knitted fabric. Also, when the raw material nonwoven fabric is formed by electrospinning ⁇ 2020/175 702 80 ⁇ (:171? 2020/008524
  • the raw material nonwoven fabric can be formed by directly accumulating protein ultrafine fibers on the surface of the knitted fabric (skin layer) via an adhesive or the like.
  • electrospinning method electrospinning method
  • a voltage is applied between a supply side electrode (which can also be used as a spinneret) and a collection side electrode (for example, a metal nozzle or a metal net), An electric charge is given to the dope solution extruded from the spinneret and blown to the collecting side electrode. At this time, the dope solution is stretched to form fibers.
  • the applied voltage is normal.
  • the distance between the electrodes is Is.
  • FIG. 4 is an explanatory diagram of an electrospinning device 100 according to an embodiment.
  • a voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35.
  • the dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36.
  • a raw material non-woven fabric 39 containing protein ultrafine fibers can be obtained.
  • a knitted fabric skin layer
  • an adhesive, a solvent or the like that dissolves at least one of the knitted fabric and the nonwoven fabric onto the surface of the knitted fabric (skin layer) the formed raw material nonwoven fabric and the knitted fabric can be obtained. It can also be joined.
  • the resulting raw material nonwoven fabric may then be stripped of the solvent (solvent in the dope solution, solvent applied to the weave or the nonwoven fabric, etc.). Examples of the method for removing the solvent include drying under reduced pressure and immersing in a desolvation tank.
  • the step of bringing the raw material nonwoven fabric into contact with water to shrink it with water can be carried out according to the method described above.
  • the contact between the raw material non-woven fabric and water may be such that only the part of the raw material non-woven fabric in the raw material dough is brought into contact with water, or the raw non-woven fabric and the other part are brought into contact with water. Alternatively, the entire raw material dough may be brought into contact with moisture. ⁇ 2020/175 702 81 ⁇ (:171? 2020/008524
  • the protein as a raw material of the protein ultrafine fibers or protein fibers contained in the nonwoven fabric or knitted fabric, and any protein may be used. You can As the concrete aspect of the protein, the aspect explained in the waterproof and moisture-permeable fabric according to the first invention can be applied.
  • modified fibroin is preferable, and modified spider silk fibroin is more preferable, because it is excellent in heat retention, moisture absorption and heat generation property, and/or flame retardancy in addition to waterproof moisture permeability.
  • the waterproof and moisture-permeable fabric according to the present embodiment has heat-retaining property, moisture-absorbing heat-generating property, and/or flame-retardant property. It is possible to add more sexual character, and it becomes more valuable as a fabric.
  • modified fibroin preferably modified spider silk fibroin
  • the protein according to this embodiment can be produced by a conventional method using a nucleic acid encoding the protein.
  • the nucleic acid encoding the protein may be chemically synthesized based on the nucleotide sequence information, It may be synthesized using a method or the like.
  • the protein ultrafine fiber or protein fiber is prepared by, for example, dissolving a protein in a solvent capable of dissolving it to obtain a dope solution, and spinning the dope by a known spinning method such as wet spinning, dry spinning, dry wet spinning or melt spinning. Obtainable.
  • the protein ultrafine fibers are preferably obtained by spinning by the electrospinning method described above.
  • Solvents capable of dissolving proteins include, for example, dimethyl sulfoxide 1 ⁇ 1, 1 ⁇ 1-dimethylformamide (0 1 ⁇ /1), formic acid, and hexafluoroisopropanol (1 to 1) are listed.
  • An inorganic salt may be added to the solvent as a dissolution promoter.
  • Fig. 13 is an explanatory view schematically showing an example of a spinning apparatus for producing protein fibers.
  • the spinning device 100 shown in FIG. 13 is an example of a spinning device for dry-wet spinning, and includes an extrusion device 101, an undrawn yarn production device 102, and a wet heat drawing device 103. And a drying device 104.
  • a spinning method using the spinning device 100 will be described. First, store in storage tank 107. ⁇ 2020/175 702 82 ⁇ (:171? 2020 /008524
  • the stored dope solution 106 is pushed out of the mouthpiece 109 by the gear pump 108.
  • the dope may be filled in a cylinder and pushed out from a nozzle using a syringe pump.
  • the extruded dope liquid 106 is supplied into the coagulating liquid 111 of the coagulating liquid tank 120 via the air gap 1119, the solvent is removed, the protein is coagulated, and the fiber is A solidified body is formed.
  • the fibrous solidified body is fed into the warm water 1 12 in the stretching bath 1 21 and stretched.
  • the draw ratio is determined by the speed ratio between the feeding nip roller 1 13 and the take-up nip roller 1 14.
  • the stretched fibrous coagulated body is supplied to the drying device 104 and dried in the yarn path 1 22 to obtain the protein fiber 1 36 as a winding body 10 5.
  • 1 1 8 9 is a thread guide.
  • the protein ultrafine fibers or protein fibers according to the present embodiment can be contracted only by bringing them into contact with water to bring them into a wet state.
  • the protein ultrafine fibers or protein fibers according to one embodiment be more highly shrinkable by being brought into contact with water to be in a wet state and then dried.
  • the protein ultrafine fibers or protein fibers according to the present embodiment preferably have a wet shrinkage ratio of 2% or more.
  • the wet shrinkage is more preferably 4% or more, still more preferably 6% or more, even more preferably 8% or more, still more preferably 10% or more, It is particularly preferably 15% or more, particularly preferably 20% or more, particularly preferably 25% or more, and most preferably 30% or more.
  • the upper limit of the wet shrinkage ratio is usually 80% or less.
  • the wet shrinkage ratio is defined by the following formula.
  • the protein ultrafine fiber or protein fiber according to the present embodiment shrinks when dried. ⁇ 2020/175 702 83 ⁇ (:171? 2020 /008524
  • the rate is more than 7%.
  • the dry shrinkage is more preferably 15% or more, further preferably 25% or more, further preferably 32% or more, still more preferably 40% or more,
  • the upper limit of dry shrinkage is usually 80% or less.
  • the dry shrinkage is defined by the following formula.
  • Shrinkage rate during drying ⁇ 1-(length of dried protein ultrafine fibers (or protein fibers) after contacting with water to make them wet / length of protein ultrafine fibers (or protein fiber) before contacting with water) Length)) X 100 (%)
  • the waterproof and moisture-permeable fabric according to the fourth embodiment is a waterproof and moisture-permeable layer 2 made of a nonwoven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less (hereinafter also simply referred to as “nonwoven fabric”), and a skin layer made of a knitted fabric. 1 and are joined together without an intervening layer.
  • the intervening layer is a layer (for example, an adhesive layer, etc.) composed of a material other than the material forming the waterproof/moisture permeable layer 2 and the skin layer 1.
  • the waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the fourth embodiment is made of a nonwoven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less.
  • the protein ultrafine fiber diameter means the diameter of the smallest circle that surrounds the cross section of the short fiber perpendicular to the longitudinal direction.
  • the fiber diameter of the protein ultrafine fiber may be 10 (10000 nm) or less, 9 or less, 8 or less, 7 ⁇ ! or less, 6 ⁇ ! or less, 5 ⁇ ! or less, 4 or less, 3 ⁇ ! or less. , 2 ⁇ ! or less, 1 ⁇ ! (1 0001 ⁇ 111) or less,
  • the fiber diameter of the protein ultrafine fibers is, for example, 1001 or more, 201 ⁇ 01 or more, More than 401 ⁇ !, more than 501 ⁇ !, more than Above, 801 ⁇
  • the non-woven fabric may contain only the protein ultrafine fibers, or may contain other fibers such as protein fibers in addition to the protein ultrafine fibers. That is, as fibers (also referred to as “material threads”) used for forming a non-woven fabric, a single thread consisting only of protein ultrafine fibers, protein ultrafine fibers (fiber diameter of 10 or less), protein fibers of fiber diameter over 10 etc.
  • a composite yarn (for example, a mixed yarn, a mixed yarn, a covering yarn, etc.) formed by combining with other fibers may be used alone or in combination.
  • the single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are twisted together.
  • a filament yarn is preferably used as the single yarn and the composite yarn.
  • the other fibers include protein fibers, synthetic fibers such as nylon and polyester, regenerated fibers such as cubra and rayon, and natural fibers such as cotton and hemp.
  • the percentage of protein ultrafine fibers in the non-woven fabric is based on the total mass of the non-woven fabric, for example, 30 mass% or more, 40 mass% or more, 50 mass% or more. , 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.
  • the non-woven fabric can be produced by a known production method using, for example, fibers containing at least a portion of protein ultrafine fibers having a fiber diameter of 10 or less. Specifically, for example, from a fiber containing at least a part of protein ultrafine fibers having a fiber diameter of 10 or less, a web (a single-layer web and a laminated web are included by a dry method, a wet method and an airlaid method). ) Is formed, and then the fibers of the web are bonded by a chemical bond method (immersion method, spray method, etc.) or a needle punch method to obtain a nonwoven fabric.
  • a chemical bond method immersion method, spray method, etc.
  • Nonwovens also include, for example, proteins such as dimethyl sulfoxide (mouth 1 ⁇ /1300),! ⁇ 1, , ⁇ 1-Dimethylformamide (0 ! ⁇ /!), formic acid, or hexafluoro ⁇ 2020/175 702 85 ⁇ (:171? 2020 /008524
  • the average fiber diameter (average fiber diameter) of protein ultrafine fibers obtained by the electrospinning method is usually 1 0000 nm or less, preferably 1 0001 ⁇ 111 or less, 00001 ⁇ 111, 1 0011111
  • the fiber diameter of protein ultrafine fiber is
  • the protein ultrafine fibers preferably include modified fibroin, more preferably modified spider silk fibroin.
  • modified fibroin preferably the modified spider silk fibroin
  • the waterproof and moisture-permeable fabric according to the present embodiment can be further imparted with heat retention, heat absorption by heat absorption and/or flame retardancy. , More valuable as a fabric.
  • the modified fibroin may be contained in the ultrafine fiber as modified fibroin fiber (protein fiber).
  • the embodiment described in the waterproof and moisture-permeable fabric according to the first invention can be applied.
  • the non-woven fabric is appropriately set such that the numerical values of the fiber density (area weight), porosity, bulk density, etc. are within a range in which waterproofness and moisture permeability can be sufficiently ensured.
  • the unit weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of layers.
  • the skin layer 1 of the waterproof/moisture permeable fabric according to the fourth embodiment is made of a knitted fabric.
  • a knitted fabric is a generic term for knitted fabrics and woven fabrics.
  • a knitted fabric is a knitted fabric having a weft knitting structure such as a flat knitted fabric or a circular knitted fabric (also simply referred to as a “weft knitted fabric”), a knitted fabric having a warp braided fabric such as tricot, Russell (only Also referred to as ".”.
  • the woven fabric is a woven fabric having any one of a plain weave, a twill weave, and a Tsumago weave. ⁇ 2020/175 702 86 ⁇ (:171? 2020 /008524
  • the knitted or woven body may be an unprocessed knitted or woven body itself obtained by knitting or weaving, or may be a knitted or woven body subjected to a process such as water repellent treatment after knitting or weaving.
  • the knitted or woven body can be obtained by knitting or weaving raw material threads.
  • a knitting method and a weaving method known methods can be used.
  • the knitting machine to be used for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used.
  • the flat knitting machine there are a forming knitting machine, a non-sewn knitting machine, and the like.
  • the non-sewn knitting machine is more preferable.
  • the loom to be used include a hauling loom, and a non-tapping loom such as a gripper loom, a rapier loom, a water jet loom, and an air jet loom.
  • the raw material yarn may be a single yarn, a composite yarn (for example, a mixed spun yarn, a mixed fiber yarn, a force burring yarn, etc.), or a combination thereof.
  • the single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are twisted together.
  • the fibers contained in the raw material yarn include protein fibers, synthetic fibers such as nylon, polyester and polytetrafluoroethylene, regenerated fibers such as cupra, rayon and lyocell, and natural fibers such as cotton, hemp and silk. ..
  • fibers that can be dissolved in a solvent that can dissolve the protein ultrafine fibers that make up the non-woven fabric are preferably used. This makes it possible to integrally bond the non-woven fabric and the skin layer by dissolving them with a solvent.
  • the knitted fabric preferably contains protein fibers.
  • the protein fiber preferably contains modified fibroin, more preferably modified spider silk fibroin.
  • modified fibroin preferably modified spider thread fibroin
  • the waterproof and moisture-permeable fabric according to the present embodiment can be further imparted with heat-retaining property, heat-absorption property and/or flame-retardant property, Higher value as a dough.
  • the modified fibroin may be contained as a modified fibroin fiber (protein fiber) in the knitted or woven body. Modified fibroin preference ⁇ 2020/175 702 87 ⁇ (:171? 2020/008524
  • the aspect described in the waterproof and moisture-permeable fabric according to the first invention can be applied.
  • the surface on the side opposite to the side where the nonwoven fabric is joined may be water-repellent. This makes it possible to obtain a waterproof and moisture-permeable fabric that is more waterproof.
  • the water repellent treatment can be carried out by a conventionally known method such as chemical coating such as plasma processing, physical coating such as coating with a water repellent coating agent, or chemical modification of the surface.
  • the waterproof/moisture permeable fabric according to the fourth embodiment is provided with a backing layer (knitted fabric) on the surface of the waterproof/moisture permeable layer opposite to the surface to which the skin layer is bonded, without an intervening layer.
  • the body may be further joined.
  • Preferred embodiments of the backing layer include the embodiments exemplified for the skin layer.
  • the skin layer and the backing layer may be a woven body made of the same material or may be a woven body made of different materials.
  • the waterproof/moisture permeable fabric according to the fourth embodiment can be obtained by joining the waterproof/moisture permeable layer and the skin layer without an intervening layer.
  • the method for joining the waterproof moisture-permeable layer and the skin layer can be appropriately selected depending on the materials used for the nonwoven fabric and the knitted fabric.
  • one or both of the joint surface of the waterproof/moisture permeable layer and the joint surface of the skin layer, which are made of a nonwoven fabric containing protein ultrafine fibers, are dissolved with a solvent to weld both joint surfaces.
  • a step of obtaining a fabric in which the waterproof moisture-permeable layer and the skin layer are joined together is provided.
  • the solvent can be used without particular limitation as long as it can dissolve the material forming the waterproof and moisture permeable layer and/or the skin layer.
  • the epidermal layer contains a protein that is the same as or different from the protein ultrafine fiber that provides the nonwoven fabric (protein fiber)
  • the solvent that dissolves such protein eg, dimethyl sulfoxide (mouth 1 ⁇ /1 3 ⁇ ), 1 ⁇ 1, 1 ⁇ 1-Dimethylformamide (0 1 ⁇ /1 ), formic acid, or organic solvent such as hexafluoroisopropanol (1 to 1 IP), and inorganic salts as a dissolution promoter added to them.
  • Solution, or water, or an aqueous solution obtained by adding an inorganic salt or the like to water) can be used.
  • the solvent a volatile solvent is preferable.
  • the manufacturing method according to the present embodiment includes a waterproof moisture-permeable layer and ⁇ 2020/175 702 88 ⁇ (:171? 2020/008524
  • a step of removing the solvent used may be further provided.
  • the solvent can be removed by, for example, an air drying method, a heating method, or a combination thereof.
  • a manufacturing method is a method for forming a waterproof and moisture-permeable layer by heating and melting one or both of the bonding surface of the waterproof/moisture permeable layer and the bonding surface of the skin layer to weld both bonding surfaces.
  • the method includes a step of obtaining a cloth that is joined to the skin layer.
  • the temperature at the time of heating and melting may be appropriately set depending on the heat-meltable material forming part or all of the waterproof and moisture-permeable layer and the skin layer.
  • a manufacturing method is to irradiate one or both of the joint surface of the waterproof/moisture permeable layer and the joint surface of the skin layer with plasma to form a covalent bond by a radical reaction,
  • the method includes a step of obtaining a cloth in which a waterproof and moisture-permeable layer and a skin layer are joined.
  • the conditions of the plasma to be irradiated may be appropriately set depending on the materials forming the waterproof and moisture permeable layer and the skin layer. For example, when the waterproof and moisture-permeable layer and/or the epidermal layer contains proteins (protein ultrafine fibers or protein fibers), the flow rate of the discharge gas is, for example, 0. It may be within the following range.
  • the plasma density of the generated plasma may be, for example, in the range of 1 ⁇ 1 0 1 3 0 1 _ 3 or more and 1 ⁇ 1 0 1 5 0 1 1 -3 or less.
  • the discharge gas may be, for example, a rare gas such as helium, neon, or argon, oxygen, nitrogen, or the like. Atmosphere can also be used as the discharge gas.
  • Plasma irradiation can be carried out using a known plasma irradiation device. As the plasma irradiation device, for example, a plasma treatment device manufactured by Minori " ⁇ 8 3 01 8" can be used.
  • the waterproof moisture-permeable layer and the skin layer are intervening layers. It is possible to obtain a bonded waterproof breathable fabric without going through.
  • the solvent those mentioned above can be used.
  • electrospinning method electrospinning method
  • a voltage is applied between the supply-side electrode (which can also be used as the spinneret) and the collection-side electrode (for example, a metal nozzle or a metal net) to extrude from the spinneret.
  • the charge is applied to the dope solution and blown off to the collecting side electrode. At this time, the dope solution is stretched to form fibers.
  • the applied voltage is Preferably
  • the distance between the electrodes is usually 1 to 250, and preferably
  • FIG. 4 is an explanatory diagram of an electrospinning device 100 according to an embodiment.
  • a voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35.
  • the dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36.
  • a non-woven fabric containing ultrafine fibers 39 can be obtained.
  • the solvent may be removed from the obtained non-woven fabric.
  • Examples of the method for removing the solvent include vacuum drying or immersion in a desolvation tank.
  • the protein as a raw material of the protein ultrafine fibers or protein fibers contained in the nonwoven fabric or the knitted fabric, and any protein may be used.
  • modified fibroin is preferable because it is excellent in heat retention, moisture absorption and heat generation property and/or flame retardancy in addition to waterproof moisture permeability. ⁇ 2020/175 702 90 ⁇ (:171? 2020 /008524
  • the waterproof and moisture-permeable fabric according to the present embodiment has heat-retaining property, moisture-absorbing heat-generating property, and/or flame-retardant property. It is possible to add more sexual character, and it becomes more valuable as a fabric.
  • the protein according to this embodiment can be produced by a conventional method using a nucleic acid encoding the protein.
  • the nucleic acid encoding the protein may be chemically synthesized based on the nucleotide sequence information, It may be synthesized using a method or the like.
  • the protein ultrafine fiber or protein fiber is prepared by, for example, dissolving a protein in a solvent capable of dissolving it to obtain a dope solution, and spinning it by a known spinning method such as wet spinning, dry spinning, dry wet spinning or melt spinning. Obtainable.
  • the protein ultrafine fibers are preferably obtained by spinning by the electrospinning method described above.
  • Solvents capable of dissolving proteins include, for example, dimethyl sulfoxide 1 ⁇ 1, 1 ⁇ 1-dimethylformamide (0 1 ⁇ /1), formic acid, and hexafluoroisopropanol (1 to 1) are listed.
  • An inorganic salt may be added to the solvent as a dissolution promoter.
  • the waterproof and moisture-permeable fabric according to the fifth embodiment is a nonwoven fabric composed of biodegradable fibers containing biodegradable ultrafine fibers having a fiber diameter of 10 or less (hereinafter, also simply referred to as “nonwoven fabric”) and a biodegradable material. And a weaving body (hereinafter, also simply referred to as “weaving body”).
  • the layer formed of the non-woven fabric has waterproofness and moisture permeability, and can be regarded as the waterproof moisture permeable layer 2.
  • the layer formed by the knitted fabric is located on the surface of the waterproof and moisture-permeable fabric, and can be regarded as the skin layer 1.
  • the skin layer 1 also functions as a shape retaining layer for retaining the shape of the waterproof/moisture permeable material.
  • the waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the fifth embodiment is a nonwoven fabric composed of biodegradable fibers containing biodegradable ultrafine fibers having a fiber diameter of 10 or less (hereinafter, simply referred to as "non-woven fabric"). ⁇ 0 2020/175702 91 ⁇ (: 17 2020/008524
  • the fiber diameter means the diameter of the smallest circle that surrounds the cross section of the short fiber perpendicular to the longitudinal direction.
  • the fiber diameter of the biodegradable ultrafine fiber may be 10 (1 0000 0 0 111) or less, 9 IX 111 or less, 8 or less, 7 or less.
  • the fiber diameter of the biodegradable ultrafine fiber is, for example, 10 or more 111, 2 0 11 111 or more, 3 0 11 111 or more, 4 0 1 ⁇ 111 or more, 5 0 1 ⁇ 111 or more,
  • the biodegradable fiber is a fiber formed of a biodegradable material.
  • Biodegradable materials are materials that are completely consumed by microorganisms and produce only natural byproducts (carbon dioxide, methane, water, biomass, etc.). Specific examples of biodegradable materials include bio-derived raw materials such as cellulose and proteins.
  • the biodegradable fiber is preferably a fiber formed from a bio-derived raw material, and more preferably a fiber formed from cellulose (including regenerated cellulose) and/or protein.
  • the biodegradable fiber is more preferably a fiber formed from a structural protein.
  • the biodegradable fiber is a fiber formed from a structural protein (structural protein fiber)
  • the waterproof moisture-permeable fabric according to the present embodiment is further imparted with heat retention, moisture absorption heat generation and/or flame retardancy. It can be made more valuable as a fabric. From the viewpoint of exerting these effects more significantly, structural proteins are ⁇ 2020/175 702 92 ⁇ (:171? 2020 /008524
  • It may be a fiber formed of one type of biodegradable material or a fiber formed of two or more types of biodegradable materials.
  • the biodegradable fiber may include only biodegradable ultrafine fibers, and in addition to biodegradable ultrafine fibers, other biodegradable fibers (biodegradable with a fiber diameter of more than 10 can be used). Fiber) may be included. That is, as the biodegradable fiber (also referred to as “material yarn”) used for forming a non-woven fabric, a single yarn composed only of biodegradable ultrafine fibers, a combination of biodegradable ultrafine fibers and other biodegradable fibers.
  • the composite yarns for example, mixed yarn, mixed yarn, covering yarn, etc. may be used alone or in combination.
  • the single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or filament yarn in which long fibers are twisted together.
  • a filament yarn is preferably used as the single yarn and the composite yarn.
  • the proportion of biodegradable ultrafine fibers in the nonwoven fabric is based on the total weight of the nonwoven fabric, for example, 30% by mass or more, 40% by mass or more, It may be 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.
  • the nonwoven fabric can be produced, for example, by using the above-mentioned biodegradable fiber by a known production method. Specifically, for example, a web (including a single-layer web and a laminated web) is formed from the above-mentioned biodegradable fiber by a dry method, a wet method, an air-laid method or the like, and then a chemical bond method ( Nonwoven fabric can be obtained by binding the fibers of the web by a dipping method, a spray method, etc.) or a needle punching method.
  • Nonwovens also include, for example, biodegradable materials (eg, proteins) such as dimethyl sulfoxide (mouth 1 ⁇ /1300), 1 ⁇ 1, 1 ⁇ 1 _dimethylformamide (0 1 ⁇ / 1), formic acid, or hexafluoroisopropanol (1 to 1 I), etc. are added, if necessary, together with an inorganic salt as a dissolution accelerator, and dissolved to form a dope solution.
  • biodegradable materials eg, proteins
  • inorganic salt as a dissolution accelerator
  • the average fiber diameter (average fiber diameter) of biodegradable ultrafine fibers (eg, protein ultrafine fibers) obtained by the electrospinning method is usually 1 0000 n 01 or less, preferably 1 000 n 111 or less. Yes, 00001 ⁇ 111, 500011111,
  • the fiber diameter of the biodegradable ultrafine fiber is preferably between 100 nm and 10000 nm (10 ), It may fluctuate between 0001 ⁇ 111 (101).
  • the non-woven fabric is appropriately set such that the numerical value ranges of the fiber density (unit weight), porosity, bulk density, and the like are within a range in which waterproofness and moisture permeability can be sufficiently ensured.
  • the unit weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of layers.
  • the skin layer 1 of the waterproof/moisture permeable fabric according to the fifth embodiment is made of a knitted or woven body made of a biodegradable material.
  • a knitted fabric is a general term for knitted fabrics and woven fabrics.
  • a knitted fabric is a knitted fabric having a weft knitting structure such as a flat knit or a circular knit (also simply referred to as “weft knitted fabric”), a knitted fabric having a warp knitting structure such as tricot, Russell (simply “warp knitted fabric”). Also referred to as “.”).
  • the woven fabric may be a woven fabric having any one of a plain weave, a twill weave, and a Tsumago weave.
  • the knitted or woven body may be an undyed knitted or woven body obtained by knitting or weaving, or may be a knitted or woven body subjected to a process such as water repellent treatment after knitting or weaving.
  • the knitted or woven body can be obtained by knitting or weaving raw material threads.
  • a knitting method and a weaving method known methods can be used.
  • the knitting machine to be used for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used.
  • the flat knitting machine there are a forming knitting machine, a non-sewn knitting machine, and the like.
  • the non-sewn knitting machine is more preferable. Looms used include, for example, corrugated looms and ⁇ 2020/175 702 94 ⁇ (: 171-1? 2020 /008524
  • unwound looms such as gripper looms, rapier looms, water jet looms and air jet looms.
  • the raw yarn may be a single yarn, a composite yarn (for example, a mixed yarn, a mixed yarn, a force burring yarn, etc.), or may be a combination of these.
  • the single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are twisted together.
  • the specific mode of the fiber contained in the raw yarn is the same as the mode of the biodegradable fiber described in the waterproof and moisture-permeable layer.
  • the biodegradable fibers (or biodegradable ultrafine fibers) contained in the waterproof moisture-permeable layer and the epidermis layer may be made of the same biodegradable material, and may have different biodegradability. It may be formed of a material.
  • the surface of the knitted or woven body opposite to the side where it is joined to the nonwoven fabric may be water repellent. This makes it possible to obtain a waterproof and moisture-permeable fabric that is more waterproof.
  • the water repellent treatment can be carried out by a conventionally known method such as applying a vegetable or animal oil or the like on the surface.
  • the waterproof/moisture permeable fabric according to the fifth embodiment is:
  • a backing layer (textile) may be further bonded to the surface of the (nonwoven fabric) opposite to the surface to which the skin layer (textile) is bonded.
  • Examples of the preferable embodiment of the backing layer include the embodiments exemplified for the skin layer.
  • the skin layer and the backing layer may each be a knitted fabric formed of the same material, or may be a knitted fabric formed of different materials.
  • the waterproof moisture-permeable fabric according to the fifth embodiment can be obtained by joining the waterproof moisture-permeable layer and the skin layer.
  • the method for joining the waterproof moisture-permeable layer and the skin layer can be appropriately selected according to the materials used for the nonwoven fabric and the knitted fabric. Examples of the joining method include a method of welding the waterproof/moisture permeable layer and the skin layer with heat or a solvent, a method of bonding the waterproof/moisture permeable layer and the skin layer with an adhesive, and the like.
  • both the non-woven fabric and the knitted fabric contain a protein (protein ultrafine fiber or protein fiber), a solvent that dissolves the protein in one or both of the joint surfaces of the waterproof moisture-permeable layer and the skin layer (eg, dimethyl sulfoxide ( Mouth 1 ⁇ /1300), ⁇ 2020/175 702 95 ⁇ (:171? 2020 /008524
  • a solvent that dissolves the protein in one or both of the joint surfaces of the waterproof moisture-permeable layer and the skin layer eg, dimethyl sulfoxide ( Mouth 1 ⁇ /1300), ⁇ 2020/175 702 95 ⁇ (:171? 2020 /008524
  • Organic solvents such as 1 ⁇ 1, 1 ⁇ 1-dimethylformamide (0 1 ⁇ /1 ), formic acid, or hexafluoroisopropanol (1 to 1 I), to which inorganic salts as a dissolution promoter were added Solution or water, or an aqueous solution in which an inorganic salt or the like is added to water), and then the waterproof/moisture permeable layer and the epidermis layer are bonded together, and the solvent is further removed to bond the waterproof/moisture permeable layer and the epidermis layer. can do.
  • the waterproof and moisture-permeable layer is formed on the surface layer by a manufacturing method including a waterproof and moisture-permeable layer forming step.
  • a moist dough can be obtained.
  • the waterproof/moisture permeable layer forming step includes the steps of: electrospinning using a dope solution containing a protein to accumulate protein ultrafine fibers on the skin layer to form a nonwoven fabric.
  • a solvent that dissolves the protein may be applied onto the epidermis layer.
  • a nonwoven fabric is formed, and the formed nonwoven fabric and the skin layer are joined together.
  • electrospinning method a voltage is applied between a supply-side electrode (which can also be used as a spinneret) and a collection-side electrode (for example, a metal nozzle or a metal net) to perform spinning. An electric charge is given to the dope solution extruded from the die and blown to the collection side electrode. At this time, the dope solution is stretched to form fibers.
  • the applied voltage is usually 5 to 100 V, and preferably 10 to 50 V.
  • the distance between the electrodes is It is preferably 2 to 200.
  • FIG. 4 is an explanatory diagram of an electrospinning device 100 according to an embodiment.
  • a voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35.
  • the dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36.
  • a nonwoven fabric 39 containing protein ultrafine fibers can be obtained.
  • a nonwoven fabric 39 when a nonwoven fabric 39 is thus obtained, by placing a skin layer (textile) on the surface of the metal net 38, the protein ultrafine fibers are accumulated on the skin layer to form a nonwoven fabric.
  • a skin layer textile
  • the resulting non-woven fabric may then be stripped of solvent.
  • the method for removing the solvent include vacuum drying and immersing in a desolvation tank.
  • an adhesive layer or the like made of a predetermined adhesive or a solvent capable of dissolving the protein ultrafine fibers is formed on the surface of the skin layer on the protein ultrafine fiber accumulation side by coating or the like.
  • the nonwoven fabric 39 is formed on the skin layer and at the same time integrally bonded to the skin layer, and the desired waterproof and moisture-permeable fabric can be manufactured advantageously and efficiently.
  • an operation of solidifying the adhesive or an operation of removing the solvent may be added.
  • the structural protein means a protein that forms or retains a structure, morphology, etc. in vivo.
  • structural proteins include fibroin (eg, spider silk fibroin (spider silk), silkworm silk, etc.), keratin, collagen, elastin, resilin, and fragments of these proteins, and proteins derived therefrom (modified fibroin, etc.), etc. Can be mentioned.
  • collagen-derived protein for example, a protein containing a domain sequence represented by the formula 3: [[3 ⁇ 42 2] (wherein, represents an integer of 5 to 300). 3 ⁇ 4 ⁇ 2 shows an amino acid sequence composed of ⁇ ⁇ saw X- ⁇ , where X and ⁇ represent any amino acid residue other than ⁇ I. , Or different amino acid sequences may be used.).
  • Examples of the protein derived from elastin include, for example, 1 ⁇ 10 ⁇ Gen Ban accession numbers 8880 9 8 3 9 5 (human), 1 4 7 0 7 6 (sheep), 7 Examples thereof include proteins having an amino acid sequence such as 8 6 9 6 (bovine). ⁇ 2020/175 702 97 ⁇ (:171? 2020/008524
  • Examples of the protein derived from resilin include, for example, a protein containing the domain sequence represented by the formula 4: [[3 ⁇ 4mi 3] 9 (wherein, in formula 4, is an integer of 4 to 300). [3 ⁇ 4mi 3 represents an amino acid sequence composed of 36 r JJT y "1 ⁇ IV 19 r ⁇ " represents an arbitrary amino acid residue, particularly 3,
  • the amino acid residue is selected from the group consisting of 3 6 "and D".
  • Li represents an arbitrary amino acid residue, and in particular, a group consisting of " ⁇ , 8 ⁇ 3, Ding" and 3 6 ". It is preferable that the amino acid residues selected from among the plurality of existing amino acids 4 have the same amino acid sequence or different amino acid sequences.
  • a protein can be produced by a conventional method using a nucleic acid encoding the protein.
  • the nucleic acid encoding the protein may be chemically synthesized based on the nucleotide sequence information, You may synthesize by utilizing the method etc.
  • the protein ultrafine fiber or protein fiber is prepared by, for example, dissolving a protein in a solvent capable of dissolving it to obtain a dope solution, and spinning the dope by a known spinning method such as wet spinning, dry spinning, dry wet spinning or melt spinning. Obtainable.
  • the protein ultrafine fibers are preferably obtained by spinning by the electrospinning method described above.
  • Solvents capable of dissolving proteins include, for example, dimethyl sulfoxide (0 1 ⁇ /1 300), 1 ⁇ 1, 1 ⁇ 1-dimethylformamide (0 1 ⁇ /1 ), formic acid, and hexafluoro. Examples include isopropanol (1 to 1 g).
  • An inorganic salt may be added to the solvent as a dissolution promoter.
  • the waterproof/moisture permeable fabric according to the sixth embodiment is a waterproof/moisture permeable layer 2 made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less (hereinafter also simply referred to as “non-woven fabric”), and a knitted woven fabric having functionality. It is joined to the epidermis 1 which is the body.
  • the skin layer 1 of the waterproof/moisture permeable fabric according to the sixth embodiment is made of a functionalized fabric.
  • a knitted fabric is a general term for knitted fabrics and woven fabrics.
  • a knitted fabric is a knitted fabric having a weft knitting structure such as a flat knit or a circular knit (also simply referred to as “weft knitted fabric”), a knitted fabric having a warp knitting structure such as tricot and Russell (simply “warp knitted fabric”). Also called.) Any of ⁇ 2020/175 702 98 ⁇ (: 171-1? 2020 /008524
  • the woven fabric may be a woven fabric having any of a plain weave, a twill weave, and a tsubaki weave.
  • the knitted or woven body may be an unprocessed knitted or woven body obtained by knitting or weaving, or may be a knitted or woven body subjected to a process such as water repellent treatment after knitting or weaving.
  • the knitted or woven body can be obtained by knitting or weaving raw material threads.
  • a knitting method and a weaving method known methods can be used.
  • the knitting machine to be used for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used.
  • the flat knitting machine there are a forming knitting machine, a non-sewn knitting machine, and the like.
  • the non-sewn knitting machine is more preferable.
  • the loom to be used include a hauling loom, and a non-tapping loom such as a gripper loom, a rapier loom, a water jet loom, and an air jet loom.
  • the raw yarn may be a single yarn, a composite yarn (for example, a mixed spun yarn, a mixed fiber yarn, a force burring yarn, etc.), or may be a combination of these.
  • the single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are twisted together.
  • the fibers contained in the raw yarn include protein fibers, synthetic fibers such as nylon, polyester and polytetrafluoroethylene, recycled fibers such as Kyupra, rayon and lyocell, and natural fibers such as cotton, hemp and silk.
  • the knitted fabric preferably contains protein fibers.
  • the protein fiber preferably contains modified fibroin, more preferably modified spider silk fibroin.
  • modified fibroin preferably, modified spider thread fibroin
  • the waterproof and moisture-permeable fabric according to the present embodiment can be provided with heat retention, moisture absorption and heat generation properties, and/or flame retardancy, and the value as a fabric becomes higher.
  • the modified fibroin may be contained in the weaving body as modified fibroin fibers (protein fibers).
  • a preferred embodiment of the modified fibroin is the embodiment described in the waterproof and breathable fabric according to the first invention. ⁇ 2020/175 702 99 ⁇ (: 171-1? 2020/008524
  • Examples of a method for imparting functionality to the knitted fabric include a method of including the modified fibroin in the knitted fabric (first method), and a process of including the protein fiber containing a predetermined protein crosslinked body in the knitted fabric.
  • Method (second method) a method of incorporating a modified hydroxyl group-containing polymer in which a functional group is bonded to a hydroxyl group-containing polymer into a knitted fabric (third method), and the like.
  • a protein fiber containing a modified fibroin as a fiber contained in the raw material yarn is used to knit or weave the raw material yarn to obtain a knitted or woven body having functionality. be able to.
  • the modified fibroin it is possible to impart heat retention, moisture absorption and exothermicity and/or flame retardancy to the knitted fabric.
  • the predetermined protein cross-linked product in the second method is a residue of a first peptide having a polypeptide backbone and two or more first reactive groups capable of reacting with a protein to form a bond.
  • the second residue which is the residue of the second reactive agent, which has a first residue that is a group and one second reactive group that can react with the first reactive group to form a bond.
  • a plurality of groups, and at least one of the first residues crosslinks the polypeptide skeleton, and at least one of the first residues binds to the polypeptide skeleton at one end, and It is attached to the second residue at the end.
  • functionality is imparted by knitting or weaving the raw material yarn, for example, by using a protein fiber containing a predetermined protein crosslinked body as a fiber contained in the raw material yarn. It is possible to obtain a knitted woven body.
  • a protein fiber is used as a fiber contained in the raw material yarn, and the raw material yarn is knitted or woven to obtain a knitted fabric (precursor), and a knitted fabric (precursor) is obtained.
  • by reacting the first reaction agent and the second reaction agent to generate a predetermined protein cross-linked product it is possible to obtain a knitted or woven material having a function.
  • the second method is, more specifically, a reaction of a molded body precursor containing a protein with a second reaction of having at least two first reactive groups capable of reacting with the protein to form a bond.
  • the agent is reacted, and the _ step give intermediate, and intermediate, of the _ ⁇ 2020/175 702 100 ⁇ (: 171-1? 2020/008524
  • the molded body in the second method may be, for example, a protein-containing knitted fabric or a protein-containing fiber (protein fiber).
  • the first step is a step of reacting the protein-containing molded body precursor with the first reactant.
  • the first reactive agent is a polyfunctional reactive agent having two or more first reactive groups capable of reacting with a protein to form a bond.
  • the protein is reacted by the first reactive agent. It may be crosslinked.
  • a protein is at least one reactive functional group selected from the group consisting of an amide group, a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxyl group, a thiol group, a selenol group, an imidazolyl group, an indolyl group and a guanidino group.
  • the first reactive group contained in the first reactive agent may be a group capable of reacting with the reactive functional group to form a bond.
  • an electrophilic group is preferable.
  • the first reactive group is an electrophilic group, a bond can be easily formed by an addition reaction with the reactive functional group of the protein.
  • Examples of the first reactive group that is an electrophilic group include, for example, the following formulas (8_1), (81_1), (81_1), (81_1), (81_1). ) Or (81 6) is preferred.
  • the wavy line in each formula represents a bond of each group.
  • X 1 represents an oxygen atom ( ⁇ ) or a sulfur atom (3).
  • X I an oxygen atom is more preferable.
  • X 2 represents a leaving group.
  • the leaving group is not particularly limited as long as it is a group capable of nucleophilic substitution reaction by a reactive functional group of a protein.
  • Examples of the leaving group include a halogen atom (fluorine atom (), chlorine atom ( ⁇ I), bromine) ⁇ 2020/175 702 101 ⁇ (: 171-1? 2020/008524
  • Atom (Mix ⁇ , Iodine atom ( ⁇ ) ), Sulfonate group (_ ⁇ 3 ⁇ 2 [3 ⁇ 4 1 ), Carboxylate group (100 000 [3 ⁇ 4 2 ), Quaternary ammonium group (1 [3 ⁇ 4 3] 3 ) etc.
  • substituents include an alkyl group, an alkenyl group, an aryl group, a halogen atom and the like.
  • X 2 is more preferably a chlorine atom, a bromine atom, an iodine atom, an ester group or a sulfonic acid ester group, and further preferably a bromine atom, an iodine atom or a sulfonic acid ester group.
  • a fluorine atom an alkyl group (in particular, a methyl group, an ethyl group, a benzyl group, an allyl group), a perfluorooroalkyl group (in particular, a trifluoromethyl group, a pentafluoroethyl group), an aryl group (in particular, a phenyl group) , Tolyl group, naphthyl group, fluorophenyl group) and the like are more preferable.
  • alkyl group especially a methyl group, an ethyl group, a benzyl group, an aryl group
  • a perfluorooroalkyl group especially a trifluoromethyl group, a pentafluoroethyl group
  • an aryl group especially a phenyl group, Tolyl group, naphthyl group, fluorophenyl group
  • alkyl group especially a methyl group, an ethyl group, a benzyl group, an aryl group
  • a perfluorooroalkyl group especially a trifluoromethyl group, a pentafluoroethyl group
  • an aryl group especially a phenyl group, Tolyl group, naphthyl group, fluorophenyl group
  • an alkyl group in particular, a methyl group, an ethyl group, a benzyl group, an allyl group
  • an aryl group in particular, a phenyl group, a tolyl group, a naphthyl group, a fluorophenyl group
  • an alkyl group in particular, a methyl group, an ethyl group, a benzyl group, an allyl group
  • an aryl group in particular, a phenyl group, a tolyl group, a naphthyl group, a fluorophenyl group
  • X 3 represents an oxygen atom ( ⁇ ), a sulfur atom (3), a group represented by [3 ⁇ 4 4 -, or a group represented by _ ⁇ 5 ) 2 _ Indicates.
  • it may be a hydrogen atom, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group, an arylsulfonyl group, an alkylsulfonyl group, an acyl group, and a carbamate group.
  • Examples of the electron-withdrawing group include a carbonyl group, a cyano group, an aryl group, an alkenyl group and an alkynyl group. ⁇ 2020/175 702 102 ⁇ (: 171-1? 2020 /008524
  • the two may be the same or different from each other.
  • And 5 may have a substituent.
  • the substituent include an alkyl group, an alkenyl group, an aryl group, a halogen atom and the like.
  • X 3 is more preferably an oxygen atom. More preferred are arylsulfonyl groups, alkylsulfonyl groups, acyl groups, force-bamate groups and the like.
  • X 4 represents an oxygen atom ( ⁇ ) or a sulfur atom (3)
  • 1 represents a halogen atom, a hydroxyl group
  • a group represented by 10 [a group represented by 6 or a 10 ⁇ 3 Represents a group represented by. May be, for example, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group.
  • substituents May have a substituent.
  • substituents include an alkyl group, an alkenyl group, an aryl group, a halogen atom and the like.
  • X 4 is more preferably an oxygen atom.
  • X 5 represents an oxygen atom (o) or a sulfur atom (3)
  • 2 represents a group represented by an oxygen atom (o), a sulfur atom (3) or 7.
  • Show. May be, for example, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a power group, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group.
  • 7 may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, and a halogen atom.
  • X 5 is more preferably an oxygen atom.
  • an oxygen atom is more preferable.
  • 7 is an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a forcebamate group, or the like.
  • the first reactive agent may be a compound having two or more first reactive groups.
  • the number of the first reactive groups contained in the first reactant is not particularly limited and may be, for example, 2 to 100, preferably 2 to 100. ⁇ 2020/175 702 103 ⁇ (:171? 2020/008524
  • the first step may be carried out, for example, by bringing the first reaction liquid containing the first reactant and the precursor of the molded body into contact with each other and heating them.
  • the first reaction liquid may be solvent-free, or may further contain a solvent.
  • the solvent of the first reaction solution is not particularly limited, and for example, it can dissolve the first reaction agent and does not inhibit the reaction between the reactive functional group of the protein and the first reactive group. I wish I had it.
  • the solvent for the first reaction solution may be, for example, 1 ⁇ 1, 1 ⁇ 1-dimethylacetamide, 1 ⁇ 1, 1 ⁇ 1-di- Methylformamide, 1 ⁇ 1_methylpyrrolidone, benzene, toluene, xylene, mesitylene, tetrahydrofuran, dimethylsulfoxide, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and the like can be preferably used.
  • reaction conditions in the first step are not particularly limited as long as the reactive functional group of the protein reacts with the first reactive group.
  • the first step it is preferable that at least a part of the first reactive agent crosslinks the protein and at least a part of the first reactive group remains in the intermediate. That is, in the first step, it is preferable to obtain an intermediate containing a protein cross-linked by the first reactive agent and having a first reactive group.
  • the first reactive agent when the first reactive agent is a compound having two first reactive groups, a part of the first reactive agent cross-links the protein (that is, both of the first reactive groups). May react with the protein). Further, the other part of the first reactive group may be reacted with the protein by only one of the first reactive groups, and at this time, the other first reactive group is unreacted, It may remain in the intermediate.
  • the first reactive agent when the first reactive agent is a compound having three or more first reactive groups, a part of the first reactive agent is a protein having all the first reactive groups. Bridges (ie, all of the first reactive groups react with the protein), and some other of the first reactive agents have some of the first reactive groups react with the protein, Another part of the first reactive group may remain unreacted in the intermediate.
  • the reaction of the first step is to react the reactive functional group of the protein with the first reactive agent. ⁇ 2020/175 702 104 ⁇ (:171? 2020 /008524
  • the origin is a reaction of forming a cross-linked structure or a side chain having a first reactive group.
  • the amount of the crosslinked structure and the side chain can be adjusted by the amount of the first reactant used in the reaction. By reducing the amount of the first reaction agent, there is a tendency for fewer side chains and more crosslinked structures to be formed.By increasing the amount of the first reaction agent, the number of crosslinked structures is reduced. Many side chains tend to be formed.
  • adjustment of the amount of the crosslinked structure and the side chain can be performed, for example, by adding a second reactive group to a part of the first reactive group contained in the first reactive agent prior to performing the first step. It can also be realized by performing a pre-step of reacting the second reactive group contained in the above-mentioned reactant. By appropriately adjusting the amount of the second reactant used in the previous step relative to the first reactant, the first reaction remaining without reacting with the second reactive group in the previous step. The number of sexual groups can be controlled. Thereby, in the first step, the binding amount of the first reactive group with the protein can be easily adjusted, and as a result, the cross-linking structure of the protein and the amount of side chains can be easily controlled. Will be able to.
  • steps may further comprise a pre-reacting a portion of the second reactive group having a second reactant.
  • the water resistance of the molded article for example, the property that the amount of shrinkage due to contact with moisture can be suppressed, the amount of shrinkage after drying after contact with moisture can be suppressed, etc.
  • mechanical strength, heat resistance, etc. tend to improve
  • the functionality imparted to the molded article for example, the texture described later
  • the crosslinked structure and the proportion of side chains may be appropriately adjusted depending on the desired properties.
  • the first step an intermediate containing a reaction product of the protein and the first reactant is obtained.
  • the protein is crosslinked by the first reactive agent, and the unreacted first reactive group may remain. That is, the reaction product was ⁇ 2020/175 702 105 ⁇ (: 171? 2020/008524
  • It may contain a polypeptide skeleton derived from a protein, a cross-linking part that cross-links the polypeptide skeleton, and a side chain part having a first reactive group at the end that is bonded to the polypeptide skeleton. ..
  • the second step is a step of reacting the intermediate obtained in the first step with the second reactant.
  • the second reactive agent has one second reactive group capable of reacting with the first reactive group to form a bond.
  • the second step can also be referred to as a step of reacting the first reactive group remaining in the intermediate with the second reactant.
  • the second reactive group contained in the second reactive agent is not particularly limited and may be appropriately changed depending on the type of the first reactive group.
  • the first reactive group is an electrophilic group
  • the second reactive group is preferably a nucleophilic group.
  • Examples of the second reactive group which is a nucleophilic group include a hydroxyl group, a thiol group, an amino group, and a group represented by the following formula (Minichi 1).
  • X 6 represents an oxygen atom ( ⁇ ) or a sulfur atom (3).
  • Examples of the group represented by the formula (Mimiichi 1) include groups represented by the following formula (Mimiichi 1-1).
  • ⁇ 3 represents a monovalent group.
  • Example 3 is, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkylsulfide group, an arylsulfide group, a monosubstituted amino group, a disubstituted amino group, or the like.
  • ⁇ 2020/175 702 106 ⁇ (:171? 2020/008524
  • the layer 3 may have a substituent.
  • substituents include an alkyl group, an alkenyl group, an aryl group, a halogen atom and the like.
  • the second reactive agent may be a compound having one second reactive group, and the reaction in the second step (reaction between the first reactive group and the second reactive group) It may further have an inactive functional group. With such a second reactive agent, it is possible to easily introduce the functional group into the molded article, starting from the unreacted first reactive group in the intermediate.
  • the functional group is not particularly limited, and may be a group that directly imparts functionality to the molded article or a group that imparts reactivity to the molded article with a further reaction agent.
  • Examples of the functional group include a hydrocarbon group such as an alkyl group, an alkenyl group and an alkynyl group; a group having a ring structure such as an aryl group and a heterocyclic group; a reactive group protected by a protecting group.
  • the texture of the molded article is improved. Therefore, for example, when the molded product is in the form of fiber or cloth, by using the second reactant having an alkyl group as a functional group, a material having an excellent texture and a good texture can be obtained.
  • the second step may be carried out, for example, by bringing the second reaction liquid containing the second reactant and the intermediate into contact with each other and heating them.
  • the second reaction liquid may be solvent-free, or may further contain a solvent.
  • the solvent of the second reaction solution is not particularly limited, and may be, for example, one capable of dissolving the second reaction agent and not inhibiting the reaction between the first reactive group and the second reactive group. Good.
  • the solvent for the second reaction solution is, for example, 1 ⁇ 1, 1 ⁇ 1_dimethylacetate.
  • Amide, 1 ⁇ 1, 1 ⁇ 1_ Dimethylformamide, 1 ⁇ 1_ Methylpyrrolidone, Benzene, Toluene, Xylene, Mesitylene, Tetrahydrofuran, Dimethylsulfoxide, Ethyl acetate, Butyl acetate, Propylene glycol monomethyl ether acetate Etc. can be used suitably.
  • the amount of the second reactant used is not particularly limited.
  • the amount of the second reactant for example, may it amounts der which exceeds the amount of the _ reactive groups intermediates.
  • the second step a part or all of the first reactive group in the intermediate reacts with the second reactive group and is consumed. It is desirable that the first reactive group does not remain in the molded body as much as possible. Therefore, in the second method, it is preferable that all of the first reactive group is consumed by the reaction with the second reactive group or other side reaction.
  • the first residue represents the structure remaining after removing the first reactive group from the first reactant.
  • the second residue represents the structure remaining after removing the second reactive group from the second reactant.
  • the polypeptide skeleton and the first residue form a bond formed by the reaction of the reactive functional group of the protein and the first reactive group (for example, the reactive functional group is an amino group, When the reactive group is an isocyanate group, it is bound by a urea bond). Further, the first residue and the second residue are a bond formed by the reaction of the first reactive group and the second reactive group (for example, the first reactive group is an isocyanato group). ⁇ 2020/175 702 108 ⁇ (:171? 2020 /008524
  • nate group and the second reactive group are hydroxyl groups, they are bonded by a urethane bond).
  • the protein is cross-linked by the first reaction agent, and a molded article excellent in water resistance, mechanical strength, heat resistance and the like can be obtained. Further, in the second method, since the functional group can be added by the second reactive agent starting from the first reactive group remaining in the intermediate, it is possible to easily obtain a molded article having various functionalities. You can
  • the modified hydroxyl group-containing polymer in the third method is a polymer in which a functional group is bonded to the hydroxyl group-containing polymer.
  • the modified hydroxyl group-containing polymer can be obtained, for example, by reacting a hydroxyl group-containing polymer with a reactive agent having a functional functional group.
  • the hydroxyl group-containing polymer can be used without particular limitation as long as it is a polymer compound having a hydroxyl group.
  • Specific examples of the hydroxyl group-containing polymer include, for example, starch, glycogen, cellulose, chitin, agarose, hyaluronic acid, chondroitin sulfate, polysaccharides such as pectin and carrageenan, polyvinyl alcohol (8) and phenol resin. Molecules.
  • the hydroxyl group-containing polymer is preferably a polysaccharide from the viewpoint of having biodegradability.
  • starch is preferred because it has high biosolubility and high solubility.
  • the functional group is a functional group having properties (for example, hydrophobicity and hydrophilicity) corresponding to the desired functionality (for example, water resistance, hydrophilicity, lipophilicity, oil resistance), It can be appropriately selected according to the functionality to be imparted.
  • the reactive agent having a functional functional group is a compound having a functional functional group and further having a binding functional group capable of binding to a hydroxyl group-containing polymer.
  • the binding functional group may be any group that can be bonded to the hydroxyl group-containing polymer through a hydrogen bond or a covalent bond, but is preferably a functional group that can be bonded to the hydroxyl group-containing polymer through a covalent bond, and is preferably a hydroxyl group-containing polymer. More preferably, it is a functional group capable of covalently bonding to the hydroxyl group therein.
  • an isocyanate having a functional functional group and acetic anhydride are preferable because they can be bound to the hydroxyl group in the hydroxyl group-containing polymer by a covalent bond.
  • An isocyanate having a functional functional group is more preferable because it can introduce a functional functional group.
  • the third method for example, knitting or weaving is performed by using a raw material yarn in which fibers and a modified hydroxyl group-containing polymer are mixed to obtain a knitted or woven fabric having functionality.
  • a fiber raw material mixed with a modified hydroxyl group-containing polymer is spun to obtain a fiber containing the modified hydroxyl group-containing polymer, and then the raw material yarn containing the fiber is knitted or woven. By doing so, it is possible to obtain a knitted or woven body having functionality.
  • the content of the modified hydroxyl group-containing polymer contained in the knitted fabric is not particularly limited, and may be appropriately set depending on the functionality to be imparted, the type of fibers contained in the knitted fabric, and the like.
  • the content of the modified hydroxyl group-containing polymer may be, for example, 0.0001 to 70% by mass, or 0.01 to 65% by mass, based on the total amount of the knitted fabric. It may be from 1 to 60 mass %.
  • the modified hydroxyl group-containing polymer and the protein fibers are preferably hydrogen-bonded. This further enhances the functionality. Hydrogen bonding can occur, for example, in modified hydroxyl group-containing polymers. ⁇ 2020/175 702 1 10 ⁇ (:171? 2020/008524
  • It may be a functional group (for example, a hydroxyl group, a functional group in a functional functional group or a binding functional group, etc.) and a functional group in a protein (for example, an amino group, a carboxyl group, etc.). ).
  • a functional group for example, a hydroxyl group, a functional group in a functional functional group or a binding functional group, etc.
  • a functional group in a protein for example, an amino group, a carboxyl group, etc.
  • the knitted fabric may further contain a hydroxyl group-containing polymer.
  • the hydroxyl group-containing polymer is preferably a polymer of the same type as the hydroxyl group-containing polymer which is a raw material of the modified hydroxyl group-containing polymer.
  • the content of the hydroxyl group-containing polymer is 50% by mass or more based on 100% by mass of the total amount of the modified hydroxyl group-containing polymer and the hydroxyl group-containing polymer. It may be 60% by mass or more, 70% by mass or more, or 80% by mass or more. The upper limit may be 90 mass% or less.
  • the waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the sixth embodiment is made of a nonwoven fabric containing ultrafine fibers having a fiber diameter of 10 or less.
  • the fiber diameter means the diameter of the smallest circle that surrounds the cross section of the short fiber perpendicular to the longitudinal direction.
  • the fiber diameter of the ultrafine fibers may be 1 0 0 1 (1 0 0 0 0 1 ⁇ 111) or less, and 9 0! or less, 8 0! or less, 7 or less,
  • the fiber diameter of the ultrafine fibers is, for example, 10 n , 2 0 1 ⁇ ! or more, 3 0 1 ⁇ ! or more, 4 0 1 ⁇ or more, 5 0 1 ⁇ or more, 6 0 or more, 7 0 1 ⁇ ! or more, 8 0 1 ⁇ ! or more, that's all, Above, 2 0 0 n ⁇ ! or above, 3 0 0 1 ⁇ ⁇ ! or above, 4 0 0 1 ⁇ or above, 5 0 0 1 ⁇ or above, Or more, 7 0 0 1 ⁇ ⁇ ! or more, that's all, This may be 1 or more, 2 111 or more, 30! or more, 40! or more, or 50! or more.
  • the ultrafine fibers may be formed of any material as long as the fiber diameter condition is satisfied.
  • Ultrafine fibers include, for example, protein fibers, synthetic fibers such as nylon and polyester, regenerated fibers such as cupra, rayon and lyocell, cotton and hemp. ⁇ 2020/175 702 1 1 1 ⁇ (: 171? 2020 /008524
  • the ultrafine fibers are preferably protein fibers.
  • the protein fiber preferably contains modified fibroin, more preferably modified spider silk fibroin.
  • modified fibroin preferably modified spider silk fibroin
  • the waterproof and moisture-permeable fabric according to the present embodiment can be further imparted with heat retention, moisture absorption and heat generation properties, and/or flame retardant properties. The value of as is higher.
  • the modified fibroin may be contained in the ultrafine fiber as modified fibroin fiber (protein fiber). Preferred embodiments of modified fibroin will be described later.
  • the nonwoven fabric may contain only ultrafine fibers, or may contain other fibers (having a fiber diameter of more than 10) in addition to the ultrafine fibers. That is, as the fibers (also referred to as “material yarns”) used for forming the non-woven fabric, a single yarn made of only ultrafine fibers, or a composite yarn made by combining ultrafine fibers with other fibers (having a fiber diameter of more than 10). (For example, blended yarn, blended yarn, covering yarn, etc.) may be used alone or in combination.
  • the single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or filament yarn in which long fibers are twisted together.
  • a filament yarn is preferably used as the single yarn and the composite yarn.
  • the proportion of ultrafine fibers in the nonwoven fabric is, for example, 30% by mass or more, 40% by mass or more, based on the total mass of the nonwoven fabric. % Or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more.
  • the non-woven fabric can be manufactured by a known manufacturing method using, for example, a fiber containing at least a portion of ultrafine fibers having a fiber diameter of 10 or less.
  • a web including a single-layer web and a laminated web
  • a dry method is formed by a dry method, a wet method, an air-laid method, or the like from a fiber including at least a part of ultrafine fibers having a fiber diameter of 10 or less.
  • the fibers of the web are bonded by the chemical bond method (immersion method, spray method, etc.) and the needle punch method, etc. to obtain a non-woven fabric.
  • the nonwoven fabric contains protein ultrafine fibers
  • the following production method can be further exemplified. That is, for example, the protein is dimethyl sulfoxide (mouth 1 ⁇ /130)
  • the average fiber diameter (average fiber diameter) of the protein ultrafine fibers obtained by the electrospinning method is usually 10000 or less, preferably 1 0001 ⁇ 111 or less, 00001 ⁇ 111,
  • the fiber diameter of protein ultrafine fiber is
  • the non-woven fabric is appropriately set such that the numerical ranges of the fiber density (weight per unit area), the porosity, the bulk density, etc. are within a range in which waterproofness and moisture permeability can be sufficiently ensured.
  • the unit weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of layers.
  • the nonwoven fabric may be a nonwoven fabric provided with functionality. Functionality can be imparted to the nonwoven fabric according to the method for imparting functionality to the knitted or woven body described above.
  • a backing material layer (woven body) is further bonded to the surface of the waterproof/moisture permeable layer opposite to the surface to which the skin layer is bonded. You may stay.
  • Preferred embodiments of the backing layer include the embodiments exemplified for the skin layer.
  • the skin layer and the backing layer may be knitted fabrics made of the same material, or may be knitted fabrics made of different materials.
  • the backing layer may be made of a knitted or woven body having the same functionality as the skin layer. ⁇ 2020/175 702 1 13 ⁇ (:171? 2020/008524
  • It may be composed of a simple knitted body.
  • the waterproof moisture-permeable fabric according to the sixth embodiment can be obtained by joining the waterproof moisture-permeable layer and the skin layer.
  • the method for joining the waterproof moisture-permeable layer and the skin layer can be appropriately selected according to the materials used for the nonwoven fabric and the knitted fabric.
  • a joining method for example, a waterproof moisture-permeable layer and a skin layer are welded together by heat or a solvent, a waterproof moisture-permeable layer and a skin layer are bonded together with an adhesive, and a nonwoven fabric and a knitted fabric are joined.
  • Examples include a method in which at least one of the bonding surfaces is irradiated with plasma to form a covalent bond by a radical reaction, so that the waterproof moisture-permeable layer and the skin layer are bonded.
  • a radical reaction so that the waterproof moisture-permeable layer and the skin layer are bonded.
  • both the non-woven fabric and the woven fabric contain a protein (protein ultrafine fiber or protein fiber), a solvent that dissolves the protein in one or both of the joint surfaces of the waterproof and moisture permeable layer and the epidermis layer (for example, dimethyl sulfoxide).
  • Organic solvents such as 1 ⁇ 1, 1 ⁇ 1-dimethylformamide (0 1 ⁇ /1 ), formic acid, or hexafluoroisopropanol (1 to 1 I), to which inorganic salts as a dissolution promoter were added Solution or water, or an aqueous solution in which an inorganic salt or the like is added to water) is applied, and then the waterproof and moisture permeable layer and the skin layer are bonded together, and the solvent is further removed to bond the waterproof and moisture permeable layer to the skin layer. can do.
  • the waterproof and moisture-permeable fabric can be obtained by a manufacturing method including a waterproof and moisture-permeable layer forming step of forming a waterproof and moisture-permeable layer on the skin layer.
  • the waterproof/moisture permeable layer forming step includes forming ultra-fine fibers on the skin layer to form a nonwoven fabric by electrospinning using a dope solution containing a fiber raw material.
  • electrospinning method a voltage is applied between a supply-side electrode (which can also be used as a spinneret) and a collection-side electrode (for example, a metal nozzle or a metal net) to perform spinning. An electric charge is given to the dope solution extruded from the die and blown to the collection side electrode. At this time, the dope solution is stretched to form fibers.
  • the applied voltage is usually 5 to 100 V, and preferably 10 to 50 V.
  • the distance between the electrodes is It is preferably 2 to 200.
  • FIG. 4 is an explanatory diagram of an electrospinning apparatus 100 according to an embodiment. ⁇ 2020/175 702 1 14 ⁇ (:171? 2020 /008524
  • a voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35.
  • the dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36.
  • a non-woven fabric containing ultrafine fibers 39 can be obtained.
  • a skin layer (woven body) on the surface of the metal net 38, it is possible to accumulate ultrafine fibers on the skin layer to form a non-woven fabric.
  • the formed nonwoven fabric and the knitted fabric are joined. You can also let it.
  • the resulting non-woven fabric may then be stripped of solvent. Examples of the method for removing the solvent (the solvent in the dope solution, the solvent applied to the knitted fabric or the nonwoven fabric, etc.) include vacuum drying or immersion in a desolvation tank.
  • the protein as a raw material of the protein ultrafine fibers or protein fibers contained in the nonwoven fabric or the knitted fabric, and any protein may be used.
  • modified fibroin is preferable, and modified spider silk fibroin is more preferable, because it is excellent in heat retention, moisture absorption and heat generation property, and/or flame retardancy in addition to waterproof moisture permeability.
  • the waterproof and moisture-permeable fabric according to the present embodiment can retain heat, absorb heat and/or flame retardantly. It is possible to add more sexual character, and it becomes more valuable as a fabric.
  • the protein according to the present embodiment can be produced by a conventional method using a nucleic acid encoding the protein.
  • the nucleic acid encoding the protein may be chemically synthesized based on the nucleotide sequence information, It may be synthesized using a method or the like. ⁇ 2020/175 702 1 15 ⁇ (:171? 2020/008524
  • the protein ultrafine fiber or protein fiber is prepared by, for example, dissolving a protein in a solvent capable of dissolving it into a dope solution, and spinning the solution by a known spinning method such as wet spinning, dry spinning, dry wet spinning or melt spinning. Obtainable.
  • the protein ultrafine fibers are preferably obtained by spinning by the electrospinning method described above.
  • Solvents capable of dissolving proteins include, for example, dimethyl sulfoxide 1 ⁇ 1, 1 ⁇ 1-dimethylformamide (0 1 ⁇ /1), formic acid, and hexafluoroisopropanol (1 to 1) are listed.
  • An inorganic salt may be added to the solvent as a dissolution promoter.
  • Modified spider silk fibroin having the amino acid sequence shown in SEQ ID NO: 18 ([3 ⁇ 4 3 9)]
  • Modified spider silk fibroin having the amino acid sequence shown in SEQ ID NO: 12 [3 ⁇ 4 380), SEQ ID NO: Modified spider silk fibroin having the amino acid sequence shown in 13 ([ ⁇ d 10 4), Modified fibroin having the amino acid sequence shown in SEQ ID NO: 37 ([d 9 9]), SEQ ID NO 4
  • a modified fibroin having an amino acid sequence represented by 0 ([ ⁇ 966)] and a modified fibroin having an amino acid sequence represented by SEQ ID NO: 15 ([ ⁇ 7999) were designed.
  • a nucleic acid encoding the designed modified fibroin was synthesized.
  • the nucleic acid contains 6 sites at the 5'end and a sequence at the downstream of the stop codon. Added saisai. This nucleic acid was cloned into a cloning vector (110 1 118). After that, the same nucleic acid was added to 6 After digestion with restriction enzyme treatment and excision, it was recombined into the protein expression vector _22_(+) to obtain the expression vector.
  • the obtained expression vector was used to transform Escherichia coli !_[3 ⁇ 4 (0 £ 3).
  • the transformed Escherichia coli was cultured for 15 hours in 2 !_! culture medium containing ampicillin.
  • the culture solution was added to a seed culture medium containing ampicillin (see Table 1). 4) was added so that 0 600 would be 0.005. Chi holding the culture temperature to 30 ° ⁇ performs flask culture to ⁇ neck 6 hundred becomes 5 (about 1 5 hours), to obtain a seed culture.
  • feed solution glucose 455 g/1 L, Ye ast Extract 1 20 g/1 L
  • feed solution glucose 455 g/1 L, Ye ast Extract 1 20 g/1 L
  • the temperature of the culture solution was kept at 37 °C, and the culture was performed at a constant pH of 6.9. Further, the dissolved oxygen concentration in the culture solution was maintained at 20% of the dissolved oxygen saturated concentration, and the culture was carried out for 20 hours. Then, 1 M isopropyru/S-thiogalactopyranoside ( ⁇ PTG) was added to the culture solution to a final concentration of 1 mM to induce the expression of the modified fibroin.
  • ⁇ PTG isopropyru/S-thiogalactopyranoside
  • the cells collected 2 hours after the addition of I PTG were washed with 2 OmM Tris-HC I buffer (pH 7.4).
  • the washed cells were suspended in 20 mM Tris-HC I buffer (pH 7.4) containing about 1 mM PMS F, and the cells were disrupted with a high-pressure homogenizer (GEANiro Soavi). did.
  • the disrupted cells were centrifuged to obtain a precipitate.
  • the obtained precipitate was washed with 20 mM Tris-HC I buffer (pH 7.4) until it became highly pure.
  • the white aggregated protein obtained after dialysis was recovered by centrifugation, the water was removed using a freeze dryer, and the freeze-dried powder was recovered to obtain the modified fibroin (P RT399, P RT380, P RT410, P RT). 9 18 and P RT 966 and P RT 799) were obtained.
  • PRT 918 and PRT 966 are hydrophobically modified fibroins with an average H> 0.
  • PRT 799 is a hydrophilically modified fibroin with an average H 2 of 0 or less.
  • DMSO dimethylsulfoxide
  • P RT 799 lyophilized powder of modified fibroin
  • the prepared spinning dope was filtered at 90°C with a metal filter having an opening of 5 Mm, ⁇ 2020/175 702 1 18 ⁇ (:171? 2020 /008524
  • a knitted fabric was produced by circular knitting using a circular knitting machine, using the obtained raw material fibers (filament yarns twisted together).
  • the knitted fabric had a thickness of 180 denier and a gauge of 18. 209 pieces were cut out from the obtained knitted fabric to give test pieces.
  • the flammability test complied with the test method for powdery or granular or low melting point synthetic resin of Fire Department Dangerous Goods Regulations No. 50 May 31, 1995, Director, Hazardous Materials Control Division.
  • the test was conducted under the conditions of a temperature of 22°, a relative humidity of 45%, and an atmospheric pressure of 1021II3.
  • Table 6 shows the measurement results (oxygen concentration (%), burning rate (%), converted burning rate (%)).
  • the limit oxygen index (!_ ⁇ ) value of the knitted fabric made of the modified fibroin (Ding 799) fiber was 27.2.
  • the value of !_ ⁇ is above 26, it is considered to be flame retardant. It can be seen that the modified fibroin has excellent flame retardancy.
  • the prepared spinning solution was filtered at 60° with a metal filter having an opening of 5, and then allowed to stand in a stainless syringe of 301_ to be defoamed, and then the diameter of the needle with a diameter of 0.2. It was discharged from the solid nozzle of 100 into a 100 mass% methanol coagulation bath. The discharge temperature was 60 ° . After coagulation, the obtained raw yarn was wound and naturally dried to obtain modified fibroin fiber (raw fiber).
  • a knitted fabric was manufactured by flat knitting using a flat knitting machine.
  • Raw material with fiber The knitted fabric had a thickness of 1/30 (a single yarn of a yarn count) and a gauge number of 18.
  • the knitted fabric using 799 fibers as a raw material fiber has a thickness of 1/30 (a single yarn with a yarn count) and a gauge number of 6].
  • Knitted fabrics using other raw fibers are The thickness and the number of gauges were adjusted so that the cover factor was almost the same as the knitted fabric using the fibers. Specifically, it is as follows.
  • Polyester thickness 1/60 (single yarn), gauge number: 1 4
  • test piece Two pieces of the knitted fabric cut into 100 100 were combined and the four sides were sewn together to form a test piece (sample). After leaving the test piece in a low humidity environment (temperature 20 ⁇ 2 ° ⁇ , relative humidity 40 ⁇ 5%) for 4 hours or more, move it to a high humidity environment (temperature 20 ⁇ 2 ° ⁇ , relative humidity 90 ⁇ 5%). A temperature sensor attached to the center of the inside of the test piece measured the temperature at 1-minute intervals for 30 minutes.
  • Fig. 10 is a graph showing an example of the results of the moisture absorption and exothermicity test.
  • the horizontal axis of the graph indicates the time (minutes) left in the high humidity environment, where the time when the sample was moved from the low humidity environment to the high humidity environment is ⁇ .
  • the vertical axis of the graph shows the temperature (sample temperature) measured by the temperature sensor.
  • the point indicated by IV! corresponds to the maximum sample temperature.
  • Table 7 shows the calculation results of the maximum heat absorption by moisture absorption.
  • the knitted fabric (woven body) knitted with fibers had a higher maximum moisture absorption and exotherm than existing materials, and was superior in moisture absorption and exothermicity. It can be seen that the modified fibroin is excellent in moisture absorption and exothermicity. By knitting or weaving a knitted fabric using fibers containing modified fibroin, a knitted fabric having functionality (heat absorption due to moisture absorption) can be obtained.
  • the prepared spinning dope was filtered at 60° with a metal filter having an opening of 5, and then allowed to stand in a stainless syringe of 301_ to defoam, and then the needle diameter was 0.2. It was discharged from the solid nozzle of 100 into a 100 mass% methanol coagulation bath. The discharge temperature was 60 ° . After coagulation, the obtained raw yarn was wound and naturally dried to obtain modified fibroin fiber (raw fiber).
  • Cotton count 341 ⁇ 1, Number of twists: 2, Number of gauges: 1400, Unit weight: 1 9 4.1 9 / ( ⁇ 2
  • the heat retention property was measured by the dry contact method (using the dry contact method (contact when skin and clothes were in direct contact with dry skin) using a ⁇ 3 3_7 Thermo Lab II tester manufactured by Riki-Tech Co., Ltd. ⁇ 2020/175 702 122 ⁇ (: 171? 2020 /008524
  • One piece of knitted fabric cut into 200,000 was used as a test piece (sample).
  • the heat quantity (3) dissipated through the test piece was obtained under the condition of second.
  • the amount of heat dissipated (sink) was obtained under the same conditions as above, and the heat retention rate (%) was calculated according to the following formula.
  • Insulation rate (%) (1 _ 3 / ⁇ ) X 100
  • Table 8 shows the calculation results of the heat retention index. The higher the heat retention index, the higher the heat retention can be evaluated.
  • the knitted fabric (woven body) knitted with fibers had a higher heat retention index and superior heat retention compared to existing materials. It can be seen that the modified fibroin is excellent in heat retention. By knitting or weaving a knitted fabric using fibers containing modified fibroin, a knitted fabric having functionality (heat retention) can be obtained.
  • the spinning solution was filled in a reserve tank and discharged from a 0.1 or 0.2 diameter monohole nozzle into a 100 mass% methanol coagulation bath using a gear pump. The discharge rate was adjusted to 0. 01 to 0. 08!_/min. After coagulation, washing and stretching were performed in a 100 mass% methanol washing bath. After washing and stretching, it was dried using a dry heat plate, and the obtained raw yarn (modified fibroin fiber) was wound up.
  • a plied yarn was prepared from the obtained modified fibroin fiber.
  • the prepared plied yarn was plain-woven to obtain a woven material.
  • the resulting woven fabric was coated with a fluorine coating monomer, and plasma-treated using a plasma treatment device (Minori " ⁇ 8 3 01 3 Co. Ltd.”.
  • a plasma treatment device Minori " ⁇ 8 3 01 3 Co. Ltd.”
  • As a fluorocarbon coating monomer 3 types of dried I 0 3 1 1 0 (Example 1) and 3 types of ⁇ Dry 1 0 3 1 2 0 (Example 2) (all are manufactured by Minori " ⁇ I 3 3 0! 8 company").
  • a water repellency test was carried out on the woven fabrics of Examples 1 and 2 which were subjected to the plasma treatment, and the woven fabric which was not subjected to the plasma treatment (Comparative Example 1).
  • the water repellency test was carried out according to 340,920:2,012. Visual evaluation was performed according to the following six-level (scores 0 to 5) evaluation criteria. ⁇ 2020/175 702 124 ⁇ (:171? 2020 /008524
  • Score 4 Does not wet the surface, but has water droplets.
  • Score 1 Shows complete wetting in the area hit by water.
  • Score 0 indicates wetness over the entire surface.
  • Example 1 and Example 2 and Comparative Example 1 From the woven fabrics of Example 1 and Example 2 and Comparative Example 1, square test pieces each having a side of 50 were cut out. On one surface of the test piece, the vertices (4 points) of a square with a side of 30 were marked with a pencil. Each test piece was immersed in water at 40° for 10 minutes and then vacuum dried at room temperature, which was repeated for 5 cycles. The vacuum drying was performed for 30 minutes at a set pressure of 10/11 ⁇ 1/3 using a vacuum constant temperature dryer (03_310) (3, manufactured by Tokyo Rikakikai Co., Ltd.). At the end of each cycle, the tactile sensation was sensory evaluated, and the distance between the four marked points was measured to evaluate the shrinkage rate.
  • a vacuum constant temperature dryer 03_310
  • the tactile sensation was evaluated according to the following criteria. The results are shown in Table 10. The woven fabrics of Example 1 and Example 2 which were subjected to the plasma treatment were suppressed in the reduction of tactile sensation as compared with the woven fabric of Comparative Example 1 which was not subjected to the plasma treatment.
  • the shrinkage rate was calculated according to the following formula.
  • the “average length of each side” is the sum of the lengths of the sides of the rectangle marked with 4 points divided by 4.
  • Shrinkage (%) ⁇ 1-(each side Average length of (111 111) / 3 0 ⁇ 1 111) ⁇ XI 0 0
  • the lyophilized powder of the modified fibroin ([ ⁇ 9918) produced above was added to the solvent so that the concentration was 24% by mass. After melting for 1 hour with an aluminum block heater at 90 °C, insoluble materials and bubbles were removed to obtain a spinning solution (dope solution).
  • the spinning solution was filled in a reserve tank and discharged from a 0.1 or 0.2 diameter monohole nozzle into a 100 mass% methanol coagulation bath using a gear pump. The discharge rate was adjusted to 0. 01 to 0. 08!_/min. After coagulation, washing and stretching were performed in a 100 mass% methanol washing bath. After washing and stretching, it was dried using a dry heat plate, and the obtained raw yarn (modified fibroin fiber) was wound up.
  • the modified fibroin fiber obtained was cut to prepare a modified fibroin staple.
  • the modified fibroin staple produced was opened and opened and spun using a known spinning device to obtain spun yarn.
  • a spun yarn obtained, Hall Gar Men Bokuyoko knitting machine (1 ⁇ /! Rei_1 to 1 2 say yes 3, island Seiki) knitting was used to obtain a knitted fabric.
  • the obtained knitted fabric was coated with a fluorine-based coating monomer, and plasma-treated using a plasma treatment device (Minori " ⁇ 8 3 01 3 Co. Ltd.”.
  • a knitted fabric was obtained in which a fluorine-based polymer (water resistance-imparting substance) in which a monomer was polymerized was covalently bonded (Example 3)
  • a monomer for a fluorine-based coating 3 1 ⁇ ⁇ 1 : ⁇ ⁇ 3 1 2 0 (Mitsumi Re " ⁇ I 3 3 0! 8 company) was used.
  • a water repellency test was performed on the knitted fabric of Example 3 that had been subjected to plasma treatment and the knitted fabric that had not been subjected to plasma treatment (Comparative Example 2) in the same manner as in Test Example 4. ..
  • the results are shown in Table 12
  • the knitted fabric of Comparative Example 2 which was not subjected to the plasma treatment had a score of 0, while the knitted fabric of Example 3 which was subjected to the plasma treatment had a score of 5 and was given water resistance (water repellency).
  • ⁇ 2020/175 702 127 ⁇ (: 171-1? 2020/008524
  • Example 3 From the knitted fabrics of Example 3 and Comparative Example 2, square test pieces each having a side of 50 were cut out. On one surface of the test piece, use a pencil to draw 30 Marked the vertices (4 points) of the square. As a pretreatment, each test piece was immersed in 40 ° water for 10 minutes, and then vacuum-dried at room temperature, which was repeated for 5 cycles. The vacuum drying was performed for 30 minutes at a set pressure of 10.11.1 ⁇ /13 using a vacuum constant temperature dryer (03-3_310 (3, manufactured by Tokyo Rikakikai Co., Ltd.)).
  • the preliminarily treated test piece was subjected to 5 cycles of a washing step, a drying step, a water immersion step and a drying step in this order.
  • a washing machine manufactured by Panasonic Corporation 1 0 0 1 _
  • Lion Detergent's detergent Topic Clear Liquid
  • a vacuum constant temperature dryer ( ⁇ 3 _ 310 (3, manufactured by Tokyo Rika Kikai Co., Ltd.) was used to set pressure-0.
  • the test piece was dried at room temperature for 30 minutes.
  • the water immersion step the test piece was immersed in 40 ° water for 10 minutes.
  • the tactile sensation was sensory-evaluated according to the same criteria as in Test Example 4, and the shrinkage rate was evaluated by measuring the distance between the four marked points.
  • Table 13 shows the results of the sensory evaluation of the tactile sensation. “At the start” is the evaluation result after the pretreatment and before the start of the cycle.
  • the knitted fabric of Example 3 which was subjected to the plasma treatment was suppressed in deterioration of the tactile sensation as compared with the knitted fabric of Comparative Example 2 which was not subjected to the plasma treatment. ⁇ 2020/175 702 128 ⁇ (: 171-1? 2020 /008524
  • Freeze-dried powder of the modified fibroin ([ ⁇ n 7 9 9) produced above, using a solution of Lithium Chloride dissolved in 4% by weight of Lithium IV!30 as a solvent, has a concentration of 24% by weight. So added to the solvent. After using the shaker to dissolve the modified fibroin for 3 hours, insoluble materials (dust, etc.) and bubbles in the solution were removed to prepare a spinning solution (dope solution). The solution viscosity of the dope solution was 500 (zero centimeters) at 90 ° .
  • Dry-wet spinning was performed using the obtained dope solution and a known dry-wet spinning device to obtain a monofilament composed of modified fibroin.
  • dry-wet spinning was performed under the following conditions.
  • a spun yarn is manufactured by a known method, and the spun yarn composed of the modified fibroin fiber and a known knitting machine are used to weft-knit 50 A knitted fabric with corners was obtained.
  • the yarn count of the spun yarn made of modified fibroin fiber is 58.
  • the gauge of the knitting machine was 18.
  • the 50,000 square knitted fabric obtained was mixed with hexane diisocyanate.
  • the first reactive agent was immersed in 20 !_.
  • the knitted fabric impregnated with 1 to 10 g was sandwiched between aluminum foils and heated at 130 ° for 30 minutes. After heating, the knitted fabric was taken out, and the knitted fabric was immersed in butanol (Minami 1_1 ⁇ 1 to 1, 2nd reaction agent) 200 1 1 and reacted for 2400 minutes at 100 °C. After the reaction, the knitted fabric was washed with a tray to obtain the knitted fabric of Example 4 to which the water resistance-imparting substance (the _th reactive agent and the second reactive agent) was bound.
  • the knitted fabric of 50,000 squares obtained in (3) was evaluated as the knitted fabric of Comparative Example 3.
  • the 50 square knitted fabric obtained in (3) was immersed in hexanediisocyanate (1 to 10 I, the first reactant) 201 _.
  • the knitted fabric impregnated with 1 to 10 g was sandwiched between aluminum foils and heated at 130 ° for 30 minutes.
  • the knitted fabric was washed with 1 to 1 to obtain a knitted fabric of Comparative Example 4 in which only the first reactant was bound.
  • Example 4 The knitted fabric of Example 4 and the knitted fabrics of Comparative Example 3 and Comparative Example 4 were evaluated for shrinkage.
  • a 30-square square was drawn on each knitted fabric with a pencil to make an evaluation sample.
  • the evaluation sample was washed in the washing mode "house cleaning" of a washing machine (8 _ 1 1 1 0 0 !_) manufactured by Panasonic Corporation. Then, it was dehydrated in the same washing machine for 15 minutes and naturally dried for 120 minutes. The vertical and horizontal lengths of the square before and after washing were measured, and the shrinkage rates in the vertical and horizontal directions were obtained. Repeat the same test 3 times ⁇ 2020/175 702 130 ⁇ (:171? 2020/008524
  • Example 4 The knitted fabrics of Example 4 and the knitted fabrics of Comparative Example 3 and Comparative Example 4 were evaluated in terms of touch in three levels.
  • the texture of the knitted fabric of Comparative Example 3 was used as the standard (Mitsumi), and when the texture was better than that, ⁇ 3 was evaluated when the texture was rough and the texture was poor. The results are shown in Table 15.
  • Fibers containing a water resistance imparting substance were manufactured and evaluated.
  • the fiber containing the water resistance-imparting substance can also be regarded as a fiber having a functional property.
  • the modified fibroin ( 799) freeze-dried powder 3009 was added to the reaction solution and stirred at 90° for 12 hours for dissolution to obtain a transparent spinning solution (dope solution).
  • the content of modified starch in the spinning solution is 17% by mass, based on the total content of modified starch and starch.
  • the prepared spinning solution was filtered at 60° with a metal filter with an opening of 5 and then allowed to stand in a stainless syringe of 301_ to allow it to defoam and then have a diameter of 2 dollars.
  • Nitrogen gas was discharged from the nozzle into a 100 mass% methanol coagulation bath. The discharge temperature is 60 ° and the discharge pressure is 0. Met. After solidification, take-up speed of the obtained yarn 3. It was wound in minutes and air-dried to obtain a fiber containing modified fibroin and a water resistance-imparting substance (modified starch).
  • the length of the obtained fiber is about 10 Length of thread before cutting and dipping in water ) was measured.
  • the yarn was then immersed in a 40 ° water bath for 1 minute. Then, the yarn was taken out from the water bath, vacuum dried at room temperature for 15 minutes, and the length of the dried yarn was measured.
  • the shrinkage rate of the fiber was calculated according to the following formula. The results are shown in Table 16.
  • the modified fibroin Freeze-dried powder 2000 of 9
  • a transparent spinning solution distal solution
  • the content of modified starch in the spinning solution is 17% by mass, based on the total content of modified starch and starch.
  • fibers containing the modified fibroin and the water resistance-imparting substance were obtained by the same procedure as in Example 5.
  • the obtained fiber was subjected to shrinkage evaluation in the same procedure as in Example 5. The results are shown in Table 16.
  • the modified fibroin Freeze-dried powder 2000 of 9
  • a transparent spinning solution distal solution
  • the content of modified starch in the spinning solution is 17% by mass, based on the total content of modified starch and starch.
  • the obtained fiber was subjected to shrinkage evaluation in the same procedure as in Example 5. The results are shown in Table 16.
  • Polyvinyl alcohol (8) (Wako Pure Chemical Industries, Ltd.) 1 2 8 9 Dimethylsulfoxide (0 1 ⁇ /1 3 ⁇ ) containing 4% by weight of 1 _ ⁇ ⁇ , and then phenyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 7 2 9
  • the reaction mixture was added and stirred at 90° for 4 hours for reaction.
  • the hydroxy group of Eight and the phenylisocyanate were reacted to obtain a modified Eight (modified hydroxyl group-containing polymer) in which the phenyl group (functional functional group) was bonded via a urethane bond.
  • the modification ratio (the ratio of conversion of hydroxyl groups to functional functional groups) calculated from the charging ratio was 100%.
  • the modified fibroin Freeze-dried powder 2000 of 9
  • a transparent spinning solution distal solution
  • the content of modified V8 in the spinning solution is 17% by mass, based on the total content of modified V8.
  • fibers containing the modified fibroin and the water resistance-imparting substance (modified?) were obtained by the same procedure as in Example 5.
  • the obtained fiber was subjected to shrinkage evaluation in the same procedure as in Example 5. The results are shown in Table 16.

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Abstract

The present invention relates to a waterproof moisture-permeable fabric that is formed by bonding: a waterproof moisture-permeable layer that comprises a non-woven fabric that includes ultrafine fibers that have a fiber diameter of no more than 10 μm; and a skin layer that comprises a knitted or woven body. The ultrafine fibers include natural fibers and/or naturally-derived fibers.

Description

\¥0 2020/175702 1 卩（：17 2020 /008524 明 細 書 \¥0 2020/175702 1 卩 (: 17 2020 /008524 Clarification

発明の名称 ： 防水透湿性生地、 及びその製造方法 Title of invention: Waterproof and breathable fabric, and method for producing the same

技術分野 Technical field

[0001 ] 本発明は、 防水透湿性生地、 及びその製造方法に関する。 The present invention relates to a waterproof and moisture-permeable fabric, and a method for producing the same.

背景技術 Background technology

[0002] —般に、 各種衣料及びテント、 並びに所定の物品を水等の液体から保護す る被覆シート等の材料に使用される生地には、 外部からの水等の液体の浸入 を防ぐ一方で蒸気を通過させ得る防水透湿性を有することが望まれる。 [0002] In general, a cloth used as a material such as various clothing and tents, and a covering sheet that protects a predetermined article from a liquid such as water prevents the intrusion of a liquid such as water from the outside. It is desired to have a waterproof and moisture-permeable property that allows vapor to pass therethrough.

[0003] 例えば、 特許文献 1 には、 防水性を確保すると共に透湿性を備えた多孔質 フィルムである第 1の層と該第 1の層を補強し所要の形状保持性を具備させ るための織物又は編物である第 2の層を親水性の官能基を含み水分によって 膨潤するが溶解しない親水性接着剤によりラミネートしたことを特徴とする 透湿性の優れた防水材料が開示されている。 [0003] For example, Patent Document 1 discloses that in order to provide a required shape-retaining property by reinforcing a first layer, which is a porous film having waterproofness and moisture permeability, and the first layer. Disclosed is a waterproof material having excellent moisture permeability, characterized in that the second layer, which is a woven or knitted fabric, is laminated with a hydrophilic adhesive which contains a hydrophilic functional group and swells in water but does not dissolve.

[0004] また、 特許文献 2には、 少なくとも布帛の片面に直径が 1 未満の繊維 から成る不織布ウェッブを、 接着剤 を介して積層した積層布帛であって、 該接着剤 が該不織布ウヱッブの厚さ方向に 1 0 %以上含浸しており、 該布 帛と該不織布ウェッブとの剥離強力が 1 2 0〇

Figure imgf000002_0001
以上であることを特 徴とする積層布帛が開示されている。 [0004] Further, Patent Document 2 discloses a laminated fabric in which a non-woven web made of fibers having a diameter of less than 1 is laminated on at least one side of a fabric with an adhesive, and the adhesive has a thickness of the non-woven fabric. It is impregnated with 10% or more in the depth direction, and the peel strength between the fabric and the nonwoven web is 120
Figure imgf000002_0001
A laminated fabric characterized by the above is disclosed.

先行技術文献 Prior art documents

特許文献 Patent literature

[0005] 特許文献 1 :特開昭 5 9 - 1 5 8 2 5 2号公報 [0005] Patent Document 1: Japanese Patent Laid-Open No. 1595-15982

特許文献 2 :特開 2 0 1 0 - 3 0 2 8 9号公報 Patent Document 2: Japanese Unexamined Patent Publication No. 2 0 10 -3 0 2 8 9

発明の概要 Summary of the invention

発明が解決しようとする課題 Problems to be Solved by the Invention

[0006] 特許文献 1 に開示されるような従来の防水透湿性生地では、 防水性と透湿 性のいずれの性能も多孔質フィルムの透孔の径に依存している。 そのため、 透湿性を高めるために孔径を大きくすると防水性が低下し、 場合によっては 〇 2020/175702 2 卩（：171? 2020 /008524 [0006] In the conventional waterproof/moisture permeable fabric as disclosed in Patent Document 1, both the waterproof property and the moisture permeable performance depend on the diameter of the pores of the porous film. Therefore, increasing the pore size to increase the moisture permeability decreases the waterproof property, and in some cases 〇 2020/175702 2 卩(: 171-1? 2020/008524

強度も低下するといった問題が内在していた。 防水性を高めるために多孔フ ィルムの孔径をより小さくする必要があるが、 薄肉フィルムに小径孔を穿設 することは容易ではなかった。 従来の防水透湿性生地では、 防水透湿層の堅 牢性の向上等の目的のために多孔質フィルムの厚さを大きくすると、 それに 応じて多孔質フィルム、 ひいては生地全体の柔軟性及び透湿性が低下する傾 向があった。 加えて、 特許文献 1 に開示されるような従来の防水透湿性生地 では、 第 1層 （多孔質フィルム） と第 2層 （織物又は編物） との接着による 生地全体の透湿性の低下を抑えるために、 親水性の官能基を含み水分によっ て膨潤するが溶解しない親水性接着剤を用いることが提案されている。 しか しながら、 特別な接着剤を準備する必要があるのみならず、 充分な透湿性を 確保するために接着剤の塗布量や塗布箇所をコントロールすることが要求さ れるため、 製造工程が煩雑になる。 しかも、 特許文献 1 に開示されるような 従来の防水透湿性生地は、 防水透湿層が合成樹脂製フィルムであることに加 えて、 編織体も合成樹脂繊維を用いて形成されているため、 近年の脱石油化 による環境負荷低減の要求には到底応えられ得るものではなかった。 加えて 、 防水透湿性生地では、 耐水性等の機能性を更に具備することが求められて いる。 There was an inherent problem that the strength also decreased. Although it is necessary to make the pore size of the porous film smaller in order to improve the waterproofness, it was not easy to make a small size hole in the thin film. In conventional waterproof and breathable fabrics, if the thickness of the porous film is increased for the purpose of improving the rigidity of the waterproof and breathable layer, the flexibility and moisture permeability of the porous film and the fabric as a whole will be correspondingly increased. Tended to decline. In addition, in the conventional waterproof and moisture-permeable fabric as disclosed in Patent Document 1, it is possible to suppress the decrease in the moisture permeability of the entire fabric due to the adhesion between the first layer (porous film) and the second layer (woven or knitted fabric). Therefore, it has been proposed to use a hydrophilic adhesive that contains a hydrophilic functional group and swells with water but does not dissolve. However, not only is it necessary to prepare a special adhesive, but it is also necessary to control the amount and location of the adhesive applied in order to ensure sufficient moisture permeability, which complicates the manufacturing process. Become. Moreover, in the conventional waterproof/moisture permeable fabric as disclosed in Patent Document 1, in addition to the waterproof/moisture permeable layer being a synthetic resin film, the knitted fabric is also formed using synthetic resin fibers, In recent years, it has not been possible to meet the demand for reducing the environmental load due to the removal of petroleum. In addition, waterproof and breathable fabrics are required to have further functionality such as water resistance.

[0007] 特許文献 2に開示される積層布帛は、 高い柔軟性を有する不織布ウェッブ にて構成されているところから、 例えば堅牢性を高めるために不織布ウェッ ブを厚く しても、 積層布帛全体の柔軟性の低下が抑えられ得る。 しかしなが ら、 そのような積層布帛にあっても、 防水性と透湿性とが、 いずれも不織布 ウェッブの繊維密度に依存しているため、 透湿性を高めるために繊維密度を 大きくすると防水性が低下するといった問題が内在していた。 積層布帛にあ っても、 防水性を高めるために繊維密度等を小さくする必要があるが、 その ためには、 不織布を与える繊維をより細径化する等、 面倒な操作を行分けれ ばならなかった。 加えて、 特許文献 2に開示される積層布帛は、 布帛と不織 布ウェッブとが接着剤にて接着されているため、 布帛と不織布ウェッブとの 接着について、 特許文献 1 に開示の防水透湿性生地と同様な問題をも惹起さ 〇 2020/175702 3 卩（：171? 2020 /008524 [0007] Since the laminated fabric disclosed in Patent Document 2 is composed of a nonwoven fabric web having high flexibility, for example, even if the nonwoven fabric web is thickened to enhance the robustness, the entire laminated fabric The decrease in flexibility can be suppressed. However, even with such a laminated fabric, the waterproofness and the moisture permeability are both dependent on the fiber density of the nonwoven web, so if the fiber density is increased to increase the moisture permeability, the waterproofness is increased. There was an inherent problem with the decrease in. Even in the case of laminated fabrics, it is necessary to reduce the fiber density and the like in order to improve waterproofness, but for that purpose, it is necessary to perform troublesome operations such as making the fibers that provide the nonwoven fabrics thinner. There wasn't. In addition, in the laminated fabric disclosed in Patent Document 2, since the fabric and the non-woven fabric web are adhered with an adhesive, the waterproof and moisture-permeable property disclosed in Patent Document 1 regarding the adhesion between the fabric and the non-woven fabric web. Causing the same problems as dough 〇 2020/175 702 3 卩(: 171-1? 2020/008524

れていた。 しかも、 不織布が合成繊維を用いて形成されているため、 環境負 荷低減の実現が不可能であった。 加えて、 そのような積層布帛にあっても、 耐水性等の機能性を更に具備することが望まれている。 It was Moreover, since the non-woven fabric is made of synthetic fibers, it was not possible to reduce the environmental burden. In addition, even such a laminated fabric is desired to further have functionality such as water resistance.

[0008] 上記従来技術の問題点に鑑み、 本発明の第 1の目的は、 透孔の径や繊維密 度等に依らずに充分な透湿性を実現でき、 しかも生地全体の柔軟性及び透湿 性を損なうことなく、 防水透湿層の厚さを容易に変更可能な防水透湿性生地 を提供することである。 本発明はまた、 そのような防水透湿性生地を容易に 製造し得る、 防水透湿性生地の製造方法を提供することを目的とする。 In view of the above-mentioned problems of the prior art, the first object of the present invention is to realize sufficient moisture permeability regardless of the diameter of the through holes, the fiber density, etc., and the flexibility and permeability of the entire fabric. It is an object of the present invention to provide a waterproof breathable fabric whose thickness of the waterproof breathable layer can be easily changed without impairing the wetness. Another object of the present invention is to provide a method for producing a waterproof and breathable fabric, which can easily produce such a waterproof and breathable fabric.

[0009] 本発明の第 2の目的は、 生地全体の柔軟性を損なうことなく、 堅牢性及び 強度を向上させることができ、 しかも充分な防水性を有する防水透湿性生地 を提供することである。 本発明はまた、 そのような防水透湿性生地を容易に 製造し得る、 防水透湿性生地の製造方法を提供することを目的とする。 [0009] A second object of the present invention is to provide a waterproof and moisture-permeable fabric capable of improving robustness and strength without impairing the flexibility of the entire fabric and having sufficient waterproofness. .. Another object of the present invention is to provide a method for producing a waterproof and breathable fabric, which can easily produce such a waterproof and breathable fabric.

[0010] 本発明の第 3の目的は、 生地全体の柔軟性及び透湿性を損なうことなく、 堅牢性及び強度を向上させることができ、 しかも充分な防水性を容易に実現 可能な防水透湿性生地を提供することである。 本発明はまた、 そのような防 水透湿性生地を容易に製造し得る、 防水透湿性生地の製造方法を提供するこ とを目的とする。 [0010] A third object of the present invention is to improve waterproofness and strength without impairing the flexibility and moisture permeability of the entire fabric, and yet to ensure sufficient waterproofness and moisture permeability. Is to provide the dough. It is another object of the present invention to provide a method for producing a waterproof and breathable fabric, which can easily produce such a waterproof and breathable fabric.

[001 1 ] 本発明の第 4の目的は、 透孔の径や繊維密度等に依らずに充分な透湿性を 実現でき、 防水透湿層と表皮層との接合に伴う透湿性の低下を抑制可能な防 水透湿性生地を提供することである。 本発明はまた、 そのような防水透湿性 生地を容易に製造し得る、 防水透湿性生地の製造方法を提供することを目的 とする。 [001 1] A fourth object of the present invention is to achieve sufficient moisture permeability regardless of the diameter of the pores, the fiber density, etc., and to reduce the moisture permeability due to the bonding between the waterproof moisture-permeable layer and the skin layer. It is to provide a water-proof and breathable fabric that can be suppressed. Another object of the present invention is to provide a method for producing a waterproof and breathable fabric, which can easily produce such a waterproof and breathable fabric.

[0012] 本発明の第 5の目的は、 生地全体の柔軟性を損なうことなく、 堅牢性及び 強度を向上させることができ、 しかも脱石油化による環境負荷低減を実現可 能な防水透湿性生地を提供することである。 本発明はまた、 そのような防水 透湿性生地を容易に製造し得る、 防水透湿性生地の製造方法を提供すること を目的とする。 [0012] A fifth object of the present invention is to improve the robustness and strength of the fabric without impairing the flexibility of the fabric as a whole, and to realize a reduction in environmental load by de-oiling the fabric. Is to provide. Another object of the present invention is to provide a method for producing a waterproof and breathable fabric, which can easily produce such a waterproof and breathable fabric.

[0013] 本発明の第 6の目的は、 生地全体の柔軟性を損なうことなく、 堅牢性及び 〇 2020/175702 4 卩（：171? 2020 /008524 [0013] A sixth object of the present invention is to provide robustness and durability without impairing the flexibility of the entire fabric. 〇 2020/175 702 4 卩 (: 171? 2020 /008524

強度を向上させることができ、 しかも耐水性等の機能性を更に具備する防水 透湿性生地を提供することである。 本発明はまた、 そのような防水透湿性生 地を容易に製造し得る、 防水透湿性生地の製造方法を提供することを目的と する。 It is an object of the present invention to provide a waterproof/moisture permeable fabric which can be improved in strength and further has functionality such as water resistance. It is another object of the present invention to provide a method for producing a waterproof and breathable fabric, which can easily produce such a waterproof and breathable material.

課題を解決するための手段 Means for solving the problem

[0014] 上記第 1の目的を達成する本発明 （第 1の発明） は、 例えば、 以下の各発 明に関する。 The present invention (first invention) that achieves the above-mentioned first object relates to the following respective inventions, for example.

[1 - 1 ] [1-1]

繊維径 1 〇 以下の極細繊維を含む不織布からなる防水透湿層と、 編織 体からなる表皮層とが接合されてなり、 上記極細繊維が、 天然繊維及び天然 由来繊維の少なくともいずれか一方を含む極細繊維である、 防水透湿性生地 A waterproof/moisture permeable layer made of a non-woven fabric containing ultrafine fibers with a fiber diameter of 10 or less is bonded to a skin layer made of a weave, and the ultrafine fibers contain at least one of natural fibers and naturally derived fibers. Ultra-thin, waterproof and breathable fabric

[1 -2] [1 -2]

前記極細繊維が、 タンパク質、 セルロース及び再生セルロースからなる群 より選択される少なくとも 1種を含む極細繊維である、 [1 _ 1 ] に記載の 防水透湿性生地。 The waterproof and moisture-permeable fabric according to [1 _ 1], wherein the ultrafine fibers are ultrafine fibers containing at least one selected from the group consisting of protein, cellulose, and regenerated cellulose.

[1 -3] [13]

繊維径 1 0 以下のタンパク質極細繊維を含む不織布からなる防水透湿 層と、 編織体からなる表皮層とが接合されてなる、 防水透湿性生地。 A waterproof/moisture permeable fabric comprising a waterproof/moisture permeable layer made of a non-woven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less and a surface layer made of a knitted fabric.

[1 -4] [14]

上記タンパク質極細繊維が、 改変フイブロインを含む、 [1 —3] に記載 の防水透湿性生地。 The waterproof breathable fabric according to [1-3], wherein the protein ultrafine fibers include modified fibroin.

[1 -5] [1 -5]

上記改変フイブロインが、 改変クモ糸フイブロインである、 [1 —4] に 記載の防水透湿性生地。 The waterproof and moisture-permeable fabric according to [1-4], wherein the modified fibroin is modified spider silk fibroin.

[ 1 — 6 ] [1 — 6]

上記編織体がタンパク質繊維を含む、 [1 - 1 ] 〜 [1 -5] のいずれか に記載の防水透湿性生地。 〇 2020/175702 5 卩（：171? 2020 /008524 The waterproof/moisture permeable fabric according to any one of [1-1] to [1-5], wherein the knitted fabric contains protein fibers. 〇 2020/175702 5 卩(: 171-1? 2020/008524

[1 -7] [1 -7]

上記タンパク質繊維が、 改変フイブロインを含む、 [1 —6] に記載の防 水透湿性生地。 The waterproof/breathable fabric according to [1-6], wherein the protein fiber contains modified fibroin.

[1 -8] [1 -8]

上記改変フイブロインが、 改変クモ糸フイブロインである、 [1 —7] に 記載の防水透湿性生地。 The waterproof/breathable fabric according to [1-7], wherein the modified fibroin is a modified spider silk fibroin.

[1 -9] [1 -9]

繊維径 1 0 以下のタンパク質極細繊維を含む不織布からなる防水透湿 層を編織体からなる表皮層上に形成する防水透湿層形成工程を備え、 上記防水透湿層形成工程は、 タンパク質を含有するドープ液を使用したエ レクトロスピニングにより、 上記表皮層上に上記タンパク質極細繊維を集積 させて不織布を形成させることを含む、 防水透湿性生地の製造方法。 A waterproof/moisture permeable layer forming step of forming a waterproof/moisture permeable layer made of a non-woven fabric containing a protein ultrafine fiber having a fiber diameter of 10 or less on a skin layer made of a knitted woven fabric is provided. A method for producing a waterproof and breathable fabric, which comprises forming the nonwoven fabric by accumulating the protein ultrafine fibers on the skin layer by electrospinning using a dope solution.

[0015] 上記第 2の目的を達成する本発明 （第 2の発明） は、 例えば、 以下の各発 明に関する。 The present invention (second invention) that achieves the above-mentioned second object relates to the following respective inventions, for example.

[2- 1 ] [twenty one ]

繊維径 1 〇 以下の極細繊維を含む不織布からなる防水透湿層と、 第 1 の耐水性付与物質を含有する編織体からなる表皮層とが接合されてなる、 防 水透湿性生地。 A waterproof/moisture permeable fabric comprising a waterproof and moisture permeable layer made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less and a skin layer made of a knitted woven body containing a first water resistance-imparting substance.

[2-2] [2-2]

前記編織体が、 改変フイブロインを含む、 [2 _ 1 ] に記載の防水透湿性 生地。 The waterproof/breathable fabric according to [2 _ 1], wherein the knitted fabric contains a modified fibroin.

[2-3] [2-3]

前記改変フイブロインが、 改変クモ糸フイブロインである、 [2— 2] に 記載の防水透湿性生地。 The waterproof/breathable fabric according to [2-2], wherein the modified fibroin is modified spider silk fibroin.

[2-4] [2-4]

前記改変フイブロインと前記第 1の耐水性付与物質が共有結合している、 The modified fibroin and the first water resistance-imparting substance are covalently bonded,

[2-2] 又は [2_3] に記載の防水透湿性生地。 〇 2020/175702 6 卩（：171? 2020 /008524 The waterproof and breathable fabric according to [2-2] or [2_3]. 〇 2020/175702 6 卩(: 171-1? 2020/008524

前記第 1 の耐水性付与物質が、 シリコーン系ポリマー及びフッ素系ポリマ 一から選ばれる少なくとも 1種である、 ［2— 1 ］ 〜 ［2— 4］ のいずれか に記載の防水透湿性生地。 The waterproof/moisture permeable fabric according to any one of [2-1] to [2-4], wherein the first water resistance-imparting substance is at least one selected from silicone polymers and fluorine polymers.

［ 2— 6］ [2-6]

前記不織布が、 第 2の耐水性付与物質を含有する、 ［ 2 _ 1 ］ 〜 ［ 2 _ 5 ］ のいずれかに記載の防水透湿性生地。 The waterproof/moisture permeable fabric according to any one of [2_1] to [2_5], in which the nonwoven fabric contains a second water resistance-imparting substance.

［2 - 7］ [2-7]

繊維径 1 〇 以下の極細繊維を含む不織布を用意する工程と、 第 1 の耐水性付与物質を含有する編織体を用意する工程と、 A step of preparing a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less, and a step of preparing a knitted fabric containing the first water resistance-imparting substance,

前記不織布と前記編織体を接合する工程と、 を備える、 防水透湿性生地の 製造方法。 A method of manufacturing a waterproof and moisture-permeable fabric, comprising the step of joining the nonwoven fabric and the knitted fabric.

［2-8］ [2-8]

前記編織体が、 改変フイブロインを含む、 ［ 2 _ 7］ に記載の製造方法。 The production method according to [2_7], wherein the knitted fabric contains a modified fibroin.

［2 - 9］ [2-9]

前記改変フイブロインが、 改変クモ糸フイブロインである、 ［2— 8］ に 記載の製造方法。 The production method according to [2-8], wherein the modified fibroin is modified spider silk fibroin.

［2-10］ [2-10]

前記改変フイブロインと前記第 1 の耐水性付与物質が共有結合している、 The modified fibroin and the first water resistance-imparting substance are covalently bonded,

［ 2— 8］ 又は ［2— 9］ に記載の製造方法。 The manufacturing method according to [2-8] or [2-9].

［2- 1 1 ］ [2-1 1]

前記第 1 の耐水性付与物質が、 シリコーン系ポリマー及びフッ素系ポリマ —から選ばれる少なくとも 1種である、 ［2— 8］ 〜 ［2— 1 0］ のいずれ かに記載の製造方法。 The production method according to any one of [2-8] to [2-10], wherein the first water resistance-imparting substance is at least one selected from silicone-based polymers and fluorine-based polymers.

［2- 1 2］ [2-1 2]

前記不織布が、 第 2の耐水性付与物質を含有する、 ［2 _ 8］ 〜 ［2 _ 1 1 ］ のいずれかに記載の製造方法。 The manufacturing method according to any one of [2_8] to [2_11], wherein the nonwoven fabric contains a second water resistance-imparting substance.

［0016］ 上記第 3の目的を達成する本発明 （第 3の発明） は、 例えば、 以下の各発 明に関する。 20/175702 7 卩（：171? 2020 /008524 [0016] The present invention (third invention) that achieves the third object described above, for example, relates to the following respective inventions. 20/175702 7 卩 (: 171? 2020 /008524

［3- 1］ [3-1]

繊維径 1 0 以下のタンパク質極細繊維を含む不織布からなる防水透湿 層と、 編織体からなる表皮層とが接合されてなり、 A waterproof and moisture-permeable layer made of a non-woven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less and a skin layer made of a knitted fabric are joined together,

上記不織布が、 水収縮されている、 防水透湿性生地。 A waterproof and breathable fabric in which the above nonwoven fabric is water-shrinked.

［3-2］ [3-2]

下記式丨で定義される繊維密度増加率が 20%以上である、 ［3 - 1］ に 記載の防水透湿性生地。 The waterproof/moisture permeable fabric according to [3-1], wherein the fiber density increase rate defined by the following formula is 20% or more.

繊維密度増加率 = { （水収縮後の不織布の繊維密度/水収縮前の不織布の 繊維密度） 一 1 } X 1 00 （%） （式 I） Fiber density increase rate = {(fiber density of non-woven fabric after water shrinkage/fiber density of non-woven fabric before water shrinkage) 1 1} X 100 (%) (Formula I)

［3-3］ [3-3]

上記タンパク質極細繊維は、 下記式丨 丨で定義される湿潤時収縮率が 2% 以上である、 ［3 _ 1］ 又は ［3 _ 2］ に記載の防水透湿性生地。 The above protein ultrafine fiber is the waterproof and moisture-permeable fabric according to [3 _ 1] or [3 _ 2], which has a shrinkage ratio when wet defined by the following formula of 2% or more.

湿潤時収縮率 = {1 - （水分に接触させて湿潤状態にしたタンパク質極細 繊維の長さ/水分に接触させる前のタンパク質極細繊維の長さ） ） X 1 00 （%） （式 I I） Shrinkage rate when wet = (1-(length of protein ultrafine fibers wetted by contact with water / length of protein ultrafine fibers before contact with water)) x 100 (%) (Formula I I)

［3-4］ [3-4]

上記タンパク質極細繊維は、 下記式丨 丨 丨で定義される乾燥時収縮率が 7 %超である、 ［3— 1］ 〜 ［3— 3］ のいずれかに記載の防水透湿性生地。 乾燥時収縮率 = { 1 - （水分に接触させて湿潤状態にした後、 乾燥させた タンパク質極細繊維の長さ/水分に接触させる前のタンパク質極細繊維の長 さ） } X 1 00 （%） （式 I I I） The above-mentioned protein ultrafine fiber is the waterproof and moisture-permeable fabric according to any one of [3-1] to [3-3], which has a dry shrinkage rate of more than 7% as defined by the following formula. Shrinkage during drying = {1-(length of dried protein microfibers after contact with water to make them wet/length of protein microfibers before contact with water)} X 100 (%) (Formula III)

［3-5］ [3-5]

上記不織布の繊維密度が 0 049/012以上である、 ［3— 1］ 〜 ［3— 4］ のいずれかに記載の防水透湿性生地。 The waterproof/breathable fabric according to any one of [3-1] to [3-4], wherein the nonwoven fabric has a fiber density of 0 049/01 2 or more.

［ 3— 6］ [3-6]

上記タンパク質極細繊維が、 改変フイブロインを含む、 ［3- 1］ 〜 ［3 The above protein ultrafine fibers contain modified fibroin, [3-1] to [3

-5］ のいずれかに記載の防水透湿性生地。 20/175702 8 卩（：171? 2020 /008524 -5] A waterproof and breathable fabric according to any one of [5]. 20/175702 8 卩 (: 171? 2020 /008524

上記改変フイブロインが、 改変クモ糸フイブロインである、 [3— 6] に 記載の防水透湿性生地。 The waterproof/breathable fabric according to [3-6], wherein the modified fibroin is modified spider silk fibroin.

[3-8] [3-8]

上記編織体は、 上記不織布との接合側とは反対側の表面が撥水加工されて いる、 [3 _ 1 ] 〜 [3 _ 7 ] のいずれかに記載の防水透湿性生地。 The above-mentioned knitted or woven body is the waterproof/moisture permeable fabric according to any one of [3 _ 1] to [3 _ 7], wherein the surface on the side opposite to the side where the nonwoven fabric is joined is treated to be water repellent.

[3-9] [3-9]

上記編織体がタンパク質繊維を含む、 [3- 1 ] 〜 [3-8] のいずれか に記載の防水透湿性生地。 The waterproof/moisture permeable fabric according to any one of [3-1] to [3-8], wherein the knitted fabric contains protein fibers.

[3- 1 0] [3-1 0]

上記タンパク質繊維が、 改変フイブロインを含む、 [3-9] に記載の防 水透湿性生地。 The water-proof and moisture-permeable fabric according to [3-9], wherein the protein fiber contains a modified fibroin.

[3- 1 1 ] [3-1 1]

上記改変フイブロインが、 改変クモ糸フイブロインである、 [3— 1 0] に記載の防水透湿性生地。 The waterproof and breathable fabric according to [3-10], wherein the modified fibroin is modified spider silk fibroin.

[3- 1 2] [3-1 2]

水収縮した不織布を編織体に接合させる接合工程を備え、 Equipped with a joining process to join the water-shrinkable nonwoven fabric to the knitted fabric,

上記水収縮した不織布は、 タンパク質を含有するドープ液を使用したエレ クトロスピニングにより、 繊維径 1 〇 以下のタンパク質極細繊維を集積 させて形成された不織布と、 水分とを接触させることで収縮されたものであ る、 防水透湿性生地の製造方法。 The water-shrinkable non-woven fabric was contracted by contacting moisture with a non-woven fabric formed by accumulating protein ultrafine fibers with a fiber diameter of 10 or less by electrospinning using a dope containing protein. A method of manufacturing a waterproof and breathable fabric.

[3- 1 3] [3-1 3]

タンパク質を含有するドープ液を使用したエレクトロスピニングにより、 繊維径 1 〇 以下のタンパク質極細繊維を集積させて形成された不織布と 、 編織体とが接合してなる原料生地を用意する工程、 及び上記不織布を水分 と接触させて、 水収縮させる工程を備える、 防水透湿性生地の製造方法。 A step of preparing a raw material dough in which a non-woven fabric formed by accumulating protein ultrafine fibers having a fiber diameter of 10 or less by electrospinning using a dope containing a protein, and a knitted fabric are joined, and the above non-woven fabric A method for producing a waterproof and moisture-permeable fabric, comprising the step of bringing water into contact with water to shrink the water.

[3- 1 4] [3-1 4]

下記式丨で定義される繊維密度増加率が 20%以上である、 [3- 1 2] 又は [3— 1 3] に記載の製造方法。 20/175702 9 卩（：171? 2020 /008524 The production method according to [3-1 2] or [3-1 3], wherein the fiber density increase rate defined by the following formula is 20% or more. 20/175702 9 卩 (: 171? 2020 /008524

繊維密度増加率 = { （水収縮後の不織布の繊維密度/水収縮前の不織布の 繊維密度） 一 1 } X 1 00 （%） （式 I） Fiber density increase rate = {(fiber density of non-woven fabric after water shrinkage/fiber density of non-woven fabric before water shrinkage) 1 1} X 100 (%) (Formula I)

［3- 1 5］ [3-1 5]

上記タンパク質極細繊維は、 下記式丨 丨で定義される湿潤時収縮率が 2% 以上である、 ［3- 1 2］ 〜 ［3- 1 4］ のいずれかに記載の製造方法。 湿潤時収縮率 = {1 - （水分に接触させて湿潤状態にしたタンパク質極細 繊維の長さ/水分に接触させる前のタンパク質極細繊維の長さ） ） X 1 00 （%） （式 I I） The production method according to any one of [3-1 2] to [3-1 4], wherein the protein ultrafine fibers have a wet shrinkage rate of 2% or more defined by the following formula. Shrinkage rate when wet = (1-(length of protein ultrafine fibers wetted by contact with water / length of protein ultrafine fibers before contact with water)) x 100 (%) (Formula I I)

［3- 1 6］ [3-1 6]

上記タンパク質極細繊維は、 下記式丨 丨 丨で定義される乾燥時収縮率が 7 %超である、 ［3- 1 2］ 〜 ［3- 1 5］ のいずれかに記載の製造方法。 乾燥時収縮率 = { 1 - （水分に接触させて湿潤状態にした後、 乾燥させた タンパク質極細繊維の長さ/水分に接触させる前のタンパク質極細繊維の長 さ） } X 1 00 （%） （式 I I I） The method for producing a protein ultrafine fiber according to any one of [3-12] to [3-15], wherein the shrinkage factor upon drying defined by the following formula is more than 7%. Shrinkage during drying = {1-(length of dried protein microfibers after contact with water to make them wet/length of protein microfibers before contact with water)} X 100 (%) (Formula III)

［3- 1 7］ [3-1 7]

水収縮後の不織布の繊維密度が〇. 049/〇12以上である、 ［3— 1 2］ 〜 ［3— 1 6］ のいずれかに記載の製造方法。 Fiber density of the nonwoven fabric after the water shrinkage is 〇. 04 9 / Rei_1 2 or more, [3- 1 2] - The process according to any one of [3 1 6].

［3- 1 8］ [3-1 8]

上記タンパク質極細繊維が、 改変フイブロインを含む、 ［3- 1 2］ 〜 ［ 3- 1 7］ のいずれかに記載の製造方法。 The production method according to any one of [3-12] to [3-117], wherein the protein ultrafine fibers contain modified fibroin.

［3- 1 9］ [3-1 9]

上記改変フイブロインが、 改変クモ糸フイブロインである、 ［3— 1 8］ に記載の製造方法。 The modified fibroin is a modified spider silk fibroin production method according to [3-1 8].

［3-20］ [3-20]

上記編織体は、 上記不織布との接合側とは反対側の表面が撥水加工されて いる、 ［3— 1 2］ 〜 ［3— 1 9］ のいずれかに記載の製造方法。 The production method according to any one of [3-12] to [3-19], wherein the surface of the knitted or woven body opposite to the side where the nonwoven fabric is joined is water-repellent.

［3-2 1］ [3-2 1]

上記編織体がタンパク質繊維を含む、 ［3- 1 2］ 〜 ［3-20］ のいず 〇 2020/175702 10 卩（：171? 2020 /008524 Any of [3-1 2] to [3-20], in which the above-mentioned knitted fabric contains protein fibers 〇 2020/175 702 10 卩 (：171? 2020 /008524

れかに記載の製造方法。 Manufacturing method described there.

[3-22] [3-22]

上記タンパク質繊維が、 改変フイブロインを含む、 [3-2 1 ] に記載の 製造方法。 The production method according to [3-21], wherein the protein fiber contains modified fibroin.

[3-23] [3-23]

上記改変フイブロインが、 改変クモ糸フイブロインである、 [3— 22] に記載の製造方法。 The production method according to [3-22], wherein the modified fibroin is a modified spider silk fibroin.

[0017] 上記第 4の目的を達成する本発明 （第 4の発明） は、 例えば、 以下の各発 明に関する。 The present invention (fourth invention) that achieves the above-mentioned fourth object relates to the following respective developments, for example.

[4- 1 ] [4-1]

繊維径 1 0 以下のタンパク質極細繊維を含む不織布からなる防水透湿 層と、 編織体からなる表皮層とが、 介在層を介することなく接合されてなる 、 防水透湿性生地。 A waterproof/moisture permeable fabric comprising a waterproof/moisture permeable layer made of a non-woven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less, and a skin layer made of a knitted fabric, which are joined without an intervening layer.

[4-2] [4-2]

上記タンパク質極細繊維が、 改変フイブロインを含む、 [4 - 1 ] に記載 の防水透湿性生地。 The waterproof and moisture-permeable fabric according to [4-1], wherein the protein ultrafine fibers include modified fibroin.

[4-3] [4-3]

上記改変フイブロインが、 改変クモ糸フイブロインである、 [4— 2] に 記載の防水透湿性生地。 The waterproof/breathable fabric according to [4-2], wherein the modified fibroin is a modified spider silk fibroin.

[4-4] [4-4]

上記編織体が、 タンパク質繊維を含む、 [4- 1 ] 〜 [4-3] のいずれ かに記載の防水透湿性生地。 The waterproof/breathable fabric according to any one of [4-1] to [4-3], wherein the knitted or woven body contains protein fibers.

[4— 5 ] [4-5]

上記タンパク質繊維が、 改変フイブロインを含む、 [4-4] に記載の防 水透湿性生地。 The water-proof and moisture-permeable fabric according to [4-4], wherein the protein fiber contains modified fibroin.

[ 4— 6 ] [4-6]

上記改変フイブロインが、 改変クモ糸フイブロインである、 [4— 5] に 記載の防水透湿性生地。 〇 2020/175702 11 卩（：171? 2020 /008524 The waterproof breathable fabric according to [4-5], wherein the modified fibroin is modified spider silk fibroin. 〇 2020/175702 11 卩(: 171-1?2020/008524

[4-7] [4-7]

繊維径 1 0 以下のタンパク質極細繊維を含む不織布からなる防水透湿 層の接合面、 及び編織体からなる表皮層の接合面の一方又は両方を溶剤で溶 解させて両接合面を溶着させることで、 上記防水透湿層と上記表皮層とが接 合した生地を得る工程を備える、 防水透湿性生地の製造方法。 Dissolve either or both of the joint surface of the waterproof/moisture permeable layer made of non-woven fabric containing protein ultrafine fibers with a fiber diameter of 10 or less, and the joint surface of the skin layer made of the woven fabric, and weld both joint surfaces The method for producing a waterproof and moisture-permeable fabric, comprising the step of obtaining a fabric in which the waterproof and moisture-permeable layer and the skin layer are bonded to each other.

[4-8] [4-8]

上記溶媒が、 上記不織布を構成する繊維に含まれている、 [4_7] に記 載の製造方法。 The production method described in [4_7], in which the solvent is contained in the fibers forming the nonwoven fabric.

[4-9] [4-9]

繊維径 1 0 以下のタンパク質極細繊維を含む不織布からなる防水透湿 層の接合面、 及び編織体からなる表皮層の接合面の一方又は両方にプラズマ を照射して、 ラジカル反応により共有結合を形成させることで、 上記防水透 湿層と上記表皮層とが接合した生地を得る工程を備える、 防水透湿性生地の 製造方法。 A covalent bond is formed by a radical reaction by irradiating plasma to one or both of the joint surface of the waterproof/moisture permeable layer made of non-woven fabric containing protein ultrafine fibers with a fiber diameter of 10 or less, and the joint surface of the skin layer made of the woven fabric. The method for producing a waterproof and moisture-permeable fabric, comprising the step of obtaining a fabric in which the waterproof and moisture-permeable layer is joined to the skin layer.

[4- 1 0] [4-1 0]

編織体からなる表皮層の接合面を溶剤で溶解させた後、 タンパク質繊維原 料を含有するドープ液を使用したエレクトロスピニングにより、 上記表皮層 の接合面上にタンパク質極細繊維を集積させて不織布を形成させることで、 防水透湿層と上記表皮層とが接合した生地を得る工程を備える、 防水透湿性 生地の製造方法。 After dissolving the joint surface of the skin layer made of the woven fabric with a solvent, electrospinning using a dope solution containing the protein fiber raw material is used to accumulate the protein ultrafine fibers on the joint surface of the skin layer to form a nonwoven fabric. A method for producing a waterproof and moisture-permeable fabric, comprising the step of obtaining a fabric in which the waterproof and moisture-permeable layer and the skin layer are joined by forming the fabric.

[4- 1 1 ] [4-1 1]

上記タンパク質極細繊維が、 改変フイブロインを含む、 [4-7] 〜 [4 - 1 0] のいずれかに記載の製造方法。 The production method according to any one of [4-7] to [4-10], wherein the protein ultrafine fibers contain modified fibroin.

[4- 1 2] [4-1 2]

上記改変フイブロインが、 改変クモ糸フイブロインである、 [4— 1 1 ] に記載の製造方法。 The modified fibroin is a modified spider silk fibroin production method according to [4-1 1].

[4- 1 3] [4-1 3]

上記編織体が、 タンパク質繊維を含む、 [4-7] 〜 [4- 1 2] のいず 〇 2020/175702 12 卩（：171? 2020 /008524 Any of [4-7] to [4-112], in which the above-mentioned weaving body contains protein fibers 〇 2020/175 702 12 卩(：171? 2020/008524

れかに記載の製造方法。 Manufacturing method described there.

[4- 1 4] [4-1 4]

上記タンパク質繊維が、 改変フイブロインを含む、 [4- 1 3] に記載の 製造方法。 The production method according to [4-13], wherein the protein fiber contains modified fibroin.

[4- 1 5] [4-1 5]

上記改変フイブロインが、 改変クモ糸フイブロインである、 [4— 1 4] に記載の製造方法。 The production method according to [4-14], wherein the modified fibroin is a modified spider silk fibroin.

[0018] 上記第 5の目的を達成する本発明 （第 5の発明） は、 例えば、 以下の各発 明に関する。 The present invention (fifth invention) that achieves the above fifth object relates to the following respective inventions, for example.

[5- 1 ] [5-1]

繊維径 1 0 以下の生分解性極細繊維を含む生分解性繊維からなる不織 布と、 生分解性材料からなる編織体とが接合されてなる、 防水透湿性生地。 A waterproof and breathable fabric, which is formed by joining a nonwoven fabric made of biodegradable fibers containing biodegradable ultrafine fibers having a fiber diameter of 10 or less and a knitted woven body made of biodegradable material.

[5-2] [5-2]

上記生分解性繊維が、 改変フイブロインを含む、 5 - [1 ] に記載の防水 透湿性生地。 The waterproof and moisture-permeable fabric according to 5-[1], wherein the biodegradable fiber contains modified fibroin.

[5-3] [5-3]

上記改変フイブロインが、 改変クモ糸フイブロインである、 [5— 2] に 記載の防水透湿性生地。 The waterproof/breathable fabric according to [5-2], wherein the modified fibroin is a modified spider silk fibroin.

[ 5— 4 ] [5-4]

上記生分解性材料が、 改変フイブロインを含む、 [ 5 _ 1 ] 〜 [ 5 _ 3 ] のいずれかに記載の防水透湿性生地。 The waterproof and breathable fabric according to any one of [5 _ 1] to [5 _ 3], wherein the biodegradable material contains a modified fibroin.

[ 5— 5 ] [5—5]

上記改変フイブロインが、 改変クモ糸フイブロインである、 [5—4] に 記載の防水透湿性生地。 The waterproof moisture-permeable fabric according to [5-4], wherein the modified fibroin is modified spider silk fibroin.

[0019] 上記第 6の目的を達成する本発明 （第 6の発明） は、 例えば、 以下の各発 明に関する。 The present invention (sixth invention) that achieves the above sixth object relates to the following respective inventions, for example.

[ 6— 1 ] [6—1]

繊維径 1 〇 以下の極細繊維を含む不織布からなる防水透湿層と、 機能 〇 2020/175702 13 卩（：171? 2020 /008524 A waterproof and moisture-permeable layer made of non-woven fabric containing ultrafine fibers with a fiber diameter of 10 or less, and functions 〇 2020/175 702 13 卩(: 171-1? 2020/008524

性が付与された編織体からなる表皮層とが接合されてなる、 防水透湿性生地 A waterproof and breathable fabric that is joined to a skin layer made of a knitted fabric

［ 6— 2］ [6-2]

上記編織体が、 タンパク質繊維を含む、 ［6 - 1］ に記載の防水透湿性生 地。 The waterproof/breathable material according to [6-1], wherein the knitted or woven body contains protein fibers.

［ 6— 3］ [6-3]

上記タンパク質繊維が、 改変フイブロインを含む、 ［6 - 2］ に記載の防 水透湿性生地。 The water-proof and moisture-permeable fabric according to [6-2], wherein the protein fiber contains modified fibroin.

［ 6— 4］ [6-4]

上記改変フイブロインが、 改変クモ糸フイブロインである、 ［6— 3］ に 記載の防水透湿性生地。 The waterproof breathable fabric according to [6-3], wherein the modified fibroin is a modified spider silk fibroin.

［ 6— 5］ [6-5]

上記タンパク質繊維は、 タンパク質架橋体を含有し、 The protein fiber contains a crosslinked protein,

上記タンパク質架橋体が、 ポリペプチド骨格と、 タンパク質と反応して結 合を形成可能な第一の反応性基を 2つ以上有する第一の反応剤の残基である 第一の残基と、 上記第一の反応性基と反応して結合を形成可能な第二の反応 性基を 1つ有する第二の反応剤の残基である第二の残基と、 をそれぞれ複数 有し、 The above-mentioned crosslinked protein is a polypeptide skeleton, a first residue which is a residue of a first reactive agent having two or more first reactive groups capable of reacting with a protein to form a bond, and A second residue, which is a residue of a second reactive agent having one second reactive group capable of reacting with the first reactive group to form a bond, and each having a plurality of

上記第一の残基の少なくとも一つが、 上記ポリべプチド骨格を架橋してお り、 At least one of the first residues crosslinks the polypeptide backbone,

上記第一の残基の少なくとも一つが、 一端でポリべプチド骨格と結合し、 他端で上記第二の残基と結合している、 ［6— 2］ 〜 ［6— 4］ のいずれか に記載の防水透湿性生地。 Any one of [6-2] to [6-4], wherein at least one of the above-mentioned first residues is bound to the polypeptide skeleton at one end and is bound to the above-mentioned second residue at the other end. Waterproof breathable fabric as described in.

［ 6— 6］ [6-6]

上記編織体が、 ヒドロキシル基含有ポリマーに機能性官能基が結合した修 飾ヒドロキシル基含有ポリマーを更に含む、 ［6— 1］ 〜 ［6— 5］ のいず れかに記載の防水透湿性生地。 The waterproof/moisture permeable fabric according to any one of [6-1] to [6-5], wherein the knitted fabric further contains a modified hydroxyl group-containing polymer in which a functional group is bonded to the hydroxyl group-containing polymer. ..

［6 - 7］ 〇 2020/175702 14 卩（：171? 2020 /008524 [6-7] 〇 2020/175 702 14 卩 (：171? 2020 /008524

上記極細繊維が、 タンパク質極細繊維である、 ［6 _ 1］ 〜 ［6 _ 6］ の いずれかに記載の防水透湿性生地。 The waterproof and breathable fabric according to any one of [6 _ 1] to [6 _ 6], wherein the ultrafine fibers are protein ultrafine fibers.

［ 6— 8］ [6-8]

上記タンパク質極細繊維が、 改変フイブロインを含む、 ［6 - 7］ に記載 の防水透湿性生地。 The waterproof and breathable fabric according to [6-7], wherein the protein ultrafine fibers include modified fibroin.

［ 6— 9］ [6-9]

上記改変フイブロインが、 改変クモ糸フイブロインである、 ［6— 8］ に 記載の防水透湿性生地。 The waterproof breathable fabric according to [6-8], wherein the modified fibroin is a modified spider silk fibroin.

［6 - 1 0］ [6-10]

上記タンパク質極細繊維は、 タンパク質架橋体を含有し、 The protein ultrafine fiber contains a protein cross-linked product,

上記タンパク質架橋体が、 ポリペプチド骨格と、 タンパク質と反応して結 合を形成可能な第一の反応性基を 2つ以上有する第一の反応剤の残基である 第一の残基と、 上記第一の反応性基と反応して結合を形成可能な第二の反応 性基を 1つ有する第二の反応剤の残基である第二の残基と、 をそれぞれ複数 有し、 The above-mentioned crosslinked protein is a polypeptide skeleton, a first residue which is a residue of a first reactive agent having two or more first reactive groups capable of reacting with a protein to form a bond, and A second residue, which is a residue of a second reactive agent having one second reactive group capable of reacting with the first reactive group to form a bond, and each having a plurality of

上記第一の残基の少なくとも一つが、 上記ポリべプチド骨格を架橋してお り、 At least one of the first residues crosslinks the polypeptide backbone,

上記第一の残基の少なくとも一つが、 一端でポリべプチド骨格と結合し、 他端で上記第二の残基と結合している、 ［6— 7］ 〜 ［6— 9］ のいずれか に記載の防水透湿性生地。 Any one of [6-7] to [6-9], wherein at least one of the above-mentioned first residues is bound to the polypeptide skeleton at one end and is bound to the above-mentioned second residue at the other end. Waterproof breathable fabric as described in.

［6 - 1 1 ］ [6-11]

上記不織布が、 ヒドロキシル基含有ポリマーに機能性官能基が結合した修 飾ヒドロキシル基含有ポリマーを更に含む、 ［6— 1］ 〜 ［6— 1 0］ のい ずれかに記載の防水透湿性生地。 The waterproof/moisture permeable fabric according to any one of [6-1] to [6-10], wherein the nonwoven fabric further contains a modified hydroxyl group-containing polymer in which a functional group is bonded to the hydroxyl group-containing polymer.

発明の効果 Effect of the invention

［0020］ 第 1の発明に係る防水透湿性生地は、 繊維径 1 〇 以下のタンパク質極 細繊維を含む不織布からなる防水透湿層を備えているため、 透孔の径や繊維 密度等に依らずに充分な透湿性を実現でき、 しかも生地全体の柔軟性及び透 〇 2020/175702 15 卩（：171? 2020 /008524 [0020] The waterproof and moisture-permeable fabric according to the first invention has a waterproof and moisture-permeable layer made of a nonwoven fabric containing protein microfibers having a fiber diameter of 10 or less, and therefore depends on the diameter of the pores and the fiber density. Can achieve sufficient moisture permeability without increasing the flexibility and permeability of the entire fabric. 〇 2020/175 702 15 卩(：171? 2020/008524

湿性を損なうことなく、 防水透湿層の厚さを容易に変更可能である。 防水透 湿層を構成するタンパク質極細繊維は吸湿性を有するため、 水等の液体の侵 入を防ぐ _方で、 繊維自体から蒸気 （気体） を放出することにより、 優れた 透湿性を実現できる。 The thickness of the waterproof breathable layer can be easily changed without impairing the wettability. Protein ultrafine fibers constituting the waterproof moisture-permeable layer to have a hygroscopicity to prevent intrusion of liquid such as water is _ who, by releasing vapor (gas) from the fiber itself, can provide excellent moisture permeability ..

[0021 ] 第 2の発明によれば、 生地全体の柔軟性を損なうことなく、 堅牢性及び強 度を向上させることができ、 しかも充分な防水性を有する防水透湿性生地が 提供可能となる。 第 2の発明に係る防水透湿性生地は、 繊維径 1 〇 以下 の極細繊維を含む不織布からなる防水透湿層を備えているため、 生地全体の 柔軟性及び透湿性を損なうことなく、 防水透湿層の厚さを増すことができ、 堅牢性及び強度を向上させることができる。 また、 第 2の発明に係る防水透 湿性生地は、 編織体 （表皮層） が耐水性付与物質を含有するため、 防水性が 向上している。 [0021] According to the second invention, it is possible to provide a waterproof and moisture-permeable fabric which can improve the robustness and strength without impairing the flexibility of the entire fabric and which has sufficient waterproofness. The waterproof/breathable fabric according to the second invention has a waterproof/breathable layer made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less, so that the waterproof/breathable fabric is not impaired in its flexibility and moisture permeability. The thickness of the wet layer can be increased, and the robustness and strength can be improved. Further, in the waterproof/moisture permeable fabric according to the second invention, the knitted fabric (skin layer) contains the water resistance-imparting substance, so that the waterproof property is improved.

[0022] 第 3の発明に係る防水透湿性生地は、 繊維径 1 〇 以下のタンパク質極 細繊維を含む不織布からなる防水透湿層を備えているため、 透孔の径や繊維 密度等に依らずに充分な透湿性を実現でき、 しかも生地全体の柔軟性及び透 湿性を損なうことなく、 防水透湿層の厚さを容易に変更可能である。 防水透 湿層を構成するタンパク質極細繊維は吸湿性を有するため、 水等の液体の侵 入を防ぐ _方で、 繊維自体から蒸気 （気体） を放出することにより、 優れた 透湿性を実現できる。 また、 第 3の発明に係る防水透湿性生地は、 防水透湿 層として水収縮された不織布を備えているため、 通孔が小径化されており、 防水性が向上している。 したがって、 第 3の発明によれば、 生地全体の柔軟 性及び透湿性を損なうことなく、 堅牢性及び強度を向上させることができ、 しかも充分な防水性を容易に実現可能な防水透湿性生地を提供することが可 能となる。 第 3の発明によればまた、 そのような防水透湿性生地を容易に製 造し得る、 防水透湿性生地の製造方法を提供することが可能となる。 [0022] Since the waterproof/moisture permeable fabric according to the third invention has a waterproof/moisture permeable layer made of a non-woven fabric containing protein fine fibers having a fiber diameter of 10 or less, it depends on the diameter of the pores, the fiber density and the like. It is possible to achieve sufficient moisture vapor permeability without changing the thickness of the waterproof moisture vapor permeable layer without impairing the flexibility and moisture permeability of the entire fabric. Protein ultrafine fibers constituting the waterproof moisture-permeable layer to have a hygroscopicity to prevent intrusion of liquid such as water is _ who, by releasing vapor (gas) from the fiber itself, can provide excellent moisture permeability .. Further, since the waterproof/moisture permeable fabric according to the third aspect of the present invention is provided with a water-shrinkable nonwoven fabric as the waterproof/moisture permeable layer, the diameter of the through hole is reduced and the waterproof property is improved. Therefore, according to the third aspect of the present invention, it is possible to provide a waterproof and moisture-permeable fabric that can improve the robustness and strength without impairing the flexibility and moisture permeability of the entire fabric and that can easily realize sufficient waterproofness. It is possible to provide. According to the third aspect of the invention, it is also possible to provide a method for producing a waterproof and breathable fabric, which can easily produce such a waterproof and breathable fabric.

[0023] 第 4の発明によれば、 透孔の径や繊維密度等に依らずに充分な透湿性を実 現でき、 防水透湿層と表皮層との接合に伴う透湿性の低下を抑制可能な防水 透湿性生地を提供することが可能となる。 第 4の発明に係る防水透湿性生地 〇 2020/175702 16 卩（：171? 2020 /008524 [0023] According to the fourth invention, sufficient moisture permeability can be realized irrespective of the diameter of the pores, the fiber density, etc., and the decrease in moisture permeability due to the joining of the waterproof moisture-permeable layer and the skin layer can be suppressed. It is possible to provide a possible waterproof and breathable fabric. Waterproof and breathable fabric according to the fourth invention 〇 2020/175 702 16 卩(: 171-1? 2020/008524

は、 繊維径 1 0 以下のタンパク質極細繊維を含む不織布からなる防水透 湿層を備えているため、 透孔の径や繊維密度等に依らずに充分な透湿性を実 現できる。 また、 介在層を介すことなく防水透湿層と表皮層とが接合されて いるため、 接合に伴う透湿性の低下を抑制できる。 Has a waterproof/moisture permeable layer made of a non-woven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less, and therefore, sufficient moisture permeability can be realized irrespective of the diameter of the pores and the fiber density. Further, since the waterproof and moisture permeable layer and the skin layer are joined without the intervening layer, it is possible to suppress the decrease in moisture permeability due to the joining.

［0024］ 第 5の発明によれば、 生地全体の柔軟性を損なうことなく、 堅牢性及び強 度を向上させることができ、 しかも脱石油化による環境負荷低減を実現可能 な防水透湿性生地の提供が可能となる。 第 5の発明に係る防水透湿性生地は 、 繊維径 1 〇 以下の生分解性極細繊維を含む生分解性繊維からなる不織 布を備えているため、 生地全体の柔軟性及び透湿性を損なうことなく、 当該 不織布の厚さを増すことができ、 堅牢性及び強度を向上させることができる 。 また、 第 5の発明に係る防水透湿性生地は、 生分解性であるため、 脱石油 化による環境負荷低減を実現可能である。 [0024] According to the fifth invention, a waterproof and moisture-permeable fabric capable of improving robustness and strength without deteriorating the flexibility of the fabric as a whole and realizing reduction of environmental load by de-oiling. It becomes possible to provide. Since the waterproof breathable fabric according to the fifth invention comprises a non-woven fabric made of biodegradable fibers including biodegradable ultrafine fibers having a fiber diameter of 10 or less, the flexibility and moisture permeability of the entire fabric are impaired. Without increasing the thickness of the nonwoven fabric, it is possible to improve the robustness and strength. Further, since the waterproof and moisture-permeable fabric according to the fifth invention is biodegradable, it is possible to reduce the environmental load by removing petroleum.

［0025］ 第 6の発明によれば、 生地全体の柔軟性を損なうことなく、 堅牢性及び強 度を向上させることができ、 しかも耐水性等の機能性を更に具備する防水透 湿性生地を提供することが可能となる。 第 6の発明に係る防水透湿性生地は 、 繊維径 1 〇 以下の極細繊維を含む不織布からなる防水透湿層を備えて いるため、 透生地全体の柔軟性及び透湿性を損なうことなく、 防水透湿層の 厚さを増すことができ、 堅牢性及び強度を向上させることができる。 また、 第 6の発明に係る防水透湿性生地は、 編織体 (表皮層) に任意の機能性 (例 えば、 耐水性) を付与することができる。 [0025] According to the sixth invention, there is provided a waterproof and moisture-permeable fabric which can improve the robustness and strength without impairing the flexibility of the entire fabric and which further has functionality such as water resistance. It becomes possible to do. The waterproof and moisture-permeable fabric according to the sixth invention comprises a waterproof and moisture-permeable layer made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less, so that the waterproof and moisture-permeable fabric does not impair the flexibility and moisture permeability of the entire transparent fabric. The thickness of the moisture permeable layer can be increased, and the robustness and strength can be improved. Further, the waterproof and moisture-permeable fabric according to the sixth aspect of the present invention can impart arbitrary functionality (for example, water resistance) to the knitted fabric (skin layer).

図面の簡単な説明 Brief description of the drawings

［0026］ ［図 1］_実施形態に係る防水透湿性生地の模式図である。 [0026] [Fig. 1] Fig. 1 is a schematic view of a waterproof and moisture-permeable fabric according to an embodiment.

［図 2］_実施形態に係る防水透湿性生地の模式図である。 FIG. 2 is a schematic view of the waterproof/moisture permeable fabric according to the embodiment.

［図 3］_実施形態に係る防水透湿性生地の模式図である。 FIG. 3 is a schematic view of the waterproof/moisture permeable fabric according to the embodiment.

［図 4］_実施形態に係るエレクトロスピニング装置の説明図である。 FIG. 4 is an explanatory diagram of an electrospinning device according to an embodiment.

［図 5］改変フイブロインのドメイン配列の一例を示す模式図である。 FIG. 5 is a schematic diagram showing an example of a modified fibroin domain sequence.

Figure imgf000017_0001
(%) の値の分布を示す図である。 ［図 7］天然由来のフイブロインの /ソ (%) の値の分布を示す図である。 〇 2020/175702 17 卩（：171? 2020 /008524
Figure imgf000017_0001
It is a figure which shows the distribution of the value of (%). [Fig. 7] Fig. 7 is a diagram showing a distribution of /so (%) values of fibroin derived from nature. 〇 2020/175 702 17 卩(：171? 2020/008524

［図 8］改変フィブロインのドメイン配列の一例を示す模式図である。 FIG. 8 is a schematic diagram showing an example of a domain sequence of modified fibroin.

［図 9］改変フィブロインのドメイン配列の一例を示す模式図である。 FIG. 9 is a schematic diagram showing an example of a domain sequence of modified fibroin.

［図 10］吸湿発熱性試験の結果の一例を示すグラフである。 FIG. 10 is a graph showing an example of the results of a moisture absorption and heat generation test.

［図 1 1］試験例 2で得た防水透湿性生地の写真である。 [Fig. 11] This is a photograph of the waterproof breathable fabric obtained in Test Example 2.

［図 12］試験例 2で得た防水透湿性生地の断面写真である。 [FIG. 12] A cross-sectional photograph of the waterproof and moisture-permeable fabric obtained in Test Example 2.

［図 13］タンパク質繊維 （フィラメント） を製造するための紡糸装置の一例を 概略的に示す説明図である。 FIG. 13 is an explanatory view schematically showing an example of a spinning apparatus for producing protein fibers (filaments).

発明を実施するための形態 MODE FOR CARRYING OUT THE INVENTION

［0027］ 以下、 本発明を実施するための形態について図面を参照しながら詳細に説 明する。 便宜上、 実質的に同一の要素には同一の符号を付し、 その説明を省 略する場合がある。 なお、 本発明は以下の実施形態に限定されるものではな い。 [0027] Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. For the sake of convenience, substantially the same elements may be denoted by the same reference numerals, and the description thereof may be omitted. The present invention is not limited to the embodiments below.

［0028］ 〔防水透湿性生地〕 [0028] [Waterproof breathable fabric]

本明細書において、 防水透湿性生地とは、 防水性と透湿性を兼ね備えた生 地を意味し、 例えば、 外部からの水等の液体の浸入を防ぐ一方で蒸気を通過 させ得る生地が含まれる。 In the present specification, the waterproof and moisture-permeable fabric means a material that has both waterproofness and moisture permeability, and includes, for example, a fabric that allows vapor to pass through while preventing liquids such as water from entering from the outside. ..

［0029］ 図 1は、 一実施形態に係る防水透湿性生地の模式図である。 図 1 に示す防 水透湿性生地 1 〇は、 防水透湿層 2と表皮層 1 とが接合されてなるものであ る。 図 1 に示す防水透湿性生地 1 0において、 表皮層 1は、 防水透湿性生地 の形状を保持するための形状保持層としても機能する。 [0029] FIG. 1 is a schematic view of a waterproof and moisture-permeable fabric according to one embodiment. The waterproof/moisture permeable fabric 10 shown in Fig. 1 is formed by joining the waterproof/moisture permeable layer 2 and the skin layer 1. In the waterproof breathable fabric 10 shown in FIG. 1, the skin layer 1 also functions as a shape-retaining layer for holding the shape of the waterproof breathable fabric.

［0030］ 図 2は、 他の実施形態に係る防水透湿性生地の模式図である。 図 2に示す 防水透湿性生地 2 0は、 防水透湿層 2の両面に表皮層 1が接合されてなるも のである。 図 2に示す防水透湿性生地 2 0において、 表皮層 1は、 防水透湿 性生地の形状を保持するための形状保持層としても機能する。 図 2に示す防 水透湿性生地 2 0において、 2つある表皮層 1は、 同種の材料で形成されて いてもよく、 異種の材料で形成されていてもよい。 図 2に示す防水透湿性生 地 2 0において、 2つある表皮層 1のうち一方は裏材層としてもよい。 すな わち、 一実施形態において、 防水透湿性生地 2 0は、 防水透湿層 2と、 防水 〇 2020/175702 18 卩（：171? 2020 /008524 [0030] FIG. 2 is a schematic view of a waterproof and moisture-permeable fabric according to another embodiment. The waterproof/moisture permeable material 20 shown in FIG. 2 is composed of the waterproof/moisture permeable layer 2 and the skin layer 1 bonded to both surfaces thereof. In the waterproof/moisture permeable material 20 shown in FIG. 2, the skin layer 1 also functions as a shape-retaining layer for maintaining the shape of the waterproof/moisture permeable material. In the waterproof/moisture permeable fabric 20 shown in FIG. 2, two skin layers 1 may be formed of the same kind of material or different kinds of materials. In the waterproof/breathable material 20 shown in FIG. 2, one of the two skin layers 1 may be a backing layer. That is, in one embodiment, the waterproof/moisture permeable fabric 20 includes a waterproof/moisture permeable layer 2 and a waterproof/moisture permeable layer 20. 〇 2020/175 702 18 卩 (: 171? 2020 /008524

透湿層 2の一方の面に接合された表皮層 1 と、 防水透湿層 2の表皮層 1が接 合された面の反対側の面に接合された裏材層とを備える。 The water vapor permeable layer (2) is provided with a skin layer (1) joined to one surface thereof, and a backing layer joined to the surface of the waterproof moisture permeable layer (2) opposite to the surface thereof joined.

[0031 ] 図 3は、 他の実施形態に係る防水透湿性生地の模式図である。 図 3に示す 防水透湿性生地 3 0は、 防水透湿層 2の一方の面に表皮層 1が接合され、 更 に防水透湿層 2の表皮層 1が接合されている面とは反対側の面に裏材層 3が 接合されてなるものである。 図 3に示す防水透湿性生地 3 0において、 表皮 層 1及び/又は裏材層 3は、 防水透湿性生地の形状を保持するための形状保 持層としても機能する。 [0031] Fig. 3 is a schematic view of a waterproof and moisture-permeable fabric according to another embodiment. The waterproof/breathable fabric 30 shown in Fig. 3 has the waterproof/moisture permeable layer 2 on one side of which the skin layer 1 is joined, and further on the opposite side of the waterproof/breathable layer 2 to which the skin layer 1 is joined. The backing layer 3 is bonded to the surface of the. In the waterproof breathable fabric 30 shown in FIG. 3, the outer skin layer 1 and/or the backing layer 3 also functions as a shape-retaining layer for retaining the shape of the waterproof breathable fabric.

[0032] 〔第 1の発明に係る防水透湿性生地〕 [Waterproof and breathable fabric according to the first invention]

第 1実施形態に係る防水透湿性生地は、 繊維径 1 〇 以下の極細繊維を 含む不織布 (以下、 単に 「不織布」 ともいう。 ) からなる防水透湿層 2と、 編織体からなる表皮層 1 とが接合されてなる。 極細繊維は、 天然繊維及び天 然由来繊維の少なくともいずれか一方を含む極細繊維である。 The waterproof and moisture-permeable fabric according to the first embodiment includes a waterproof and moisture-permeable layer 2 made of a nonwoven fabric containing ultrafine fibers having a fiber diameter of 10 or less (hereinafter also simply referred to as “nonwoven fabric”), and a skin layer 1 made of a knitted fabric. And are joined. The ultrafine fibers are ultrafine fibers containing at least one of natural fibers and naturally derived fibers.

[0033] 防水透湿層 2は、 繊維径 1 〇 以下のタンパク質極細繊維を含む不織布 からなるものであってよい。 [0033] The waterproof/moisture permeable layer 2 may be made of a nonwoven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less.

[0034] 第 1実施形態に係る防水透湿性生地の防水透湿層 2は、 繊維径 1 0 以 下の極細繊維を含む不織布からなる。 極細繊維の繊維径は、 短繊維の長手方 向に垂直な断面を囲む最小の円の直径を意味する。 極細繊維の繊維径は、 1 The waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the first embodiment is made of a nonwoven fabric containing ultrafine fibers having a fiber diameter of 10 or less. The fiber diameter of the ultrafine fibers means the diameter of the smallest circle that surrounds the cross section of the short fibers perpendicular to the longitudinal direction. The fiber diameter of ultrafine fibers is 1

Figure imgf000019_0006
Figure imgf000019_0006

以下、 又は 2 0 0 n 以下であってよい。 極細繊維の繊維径は、 例えば、 1 0门 以上、 2 0 1^〇!以上、

Figure imgf000019_0001
以上、
Figure imgf000019_0002
以上、 5 0 1^ 以上、Or less, or 200 n or less. The fiber diameter of the ultrafine fiber is, for example, 10 doors or more, 2 0 1 ^ 〇! or more,
Figure imgf000019_0001
that's all,
Figure imgf000019_0002
Or more, 5 0 1^ or more,

6 0 1^〇!以上、 7 0 1^〇!以上、 8 0 1^ 以上、

Figure imgf000019_0003
以上、 1 0 0 111以 上、 2 0 0 1^〇!以上、 3 0 0 1^ 以上、 4 0 0 1^ 以上、 5 0 0 1^ 以上、6 0 1^〇! or above, 7 0 1^〇! or above, 8 0 1^ or above,
Figure imgf000019_0003
Above, 1 0 0 111 or above, 2 0 0 1^〇! or above, 3 0 0 1^ or above, 4 0 0 1^ or above, 5 0 0 1^ or above,

6 0 0 1^〇!以上、

Figure imgf000019_0004
以上、 以上、
Figure imgf000019_0005
以上、 1 111以上、 2 〇!以上、 3 〇!以上、 4 〇!以上又は 5 〇!以上であってよい 〇 2020/175702 19 卩（：171? 2020 /008524 6 0 0 1^〇! or more,
Figure imgf000019_0004
Above, above,
Figure imgf000019_0005
More than 1 111, more than 20!, more than 30!, more than 40! or more than 50! 〇 2020/175 702 19 卩(：171? 2020/008524

[0035] 極細繊維は、 天然繊維及び天然由来繊維の少なくともいずれか一方を含む 極細繊維であればよい。 極細繊維としては、 例えば、 タンパク質、 綿及び麻 等のセルロース、 並びにキュプラ及びレーヨン等の再生セルロースからなる 群より選択される少なくとも一種を含む極細繊維が挙げられる。 [0035] The ultrafine fiber may be an ultrafine fiber containing at least one of a natural fiber and a naturally derived fiber. Examples of the ultrafine fibers include ultrafine fibers containing at least one selected from the group consisting of proteins, cellulose such as cotton and hemp, and regenerated cellulose such as cupra and rayon.

[0036] 不織布は、 天然繊維及び天然由来繊維の少なくともいずれか一方を含む極 細繊維のみを含むものであってもよく、 当該極細繊維に加えてタンパク質繊 維等の他の繊維を含むものであってもよい。 すなわち、 不織布の形成に用い られる繊維 （ 「材料糸」 ともいう。 ） として、 天然繊維及び天然由来繊維の 少なくともいずれか一方を含む極細繊維のみからなる単独糸、 天然繊維及び 天然由来繊維の少なくともいずれか一方を含む極細繊維とタンパク質繊維等 の他の繊維とを組み合わせてなる複合糸 （例えば、 混紡糸、 混繊糸、 カバー リング糸等。 ） が、 それぞれ単独で、 又はそれらが組み合わされて用いられ てもよい。 上記単独糸及び上記複合糸は、 短繊維を撚り合わせたスパン糸で あってもよく、 長繊維を燃り合わせたフィラメント糸であってもよい。 上記 単独糸及び上記複合糸としては、 フィラメント糸が好適に用いられる。 なお 、 他の繊維としては、 タンパク質繊維の他、 例えば、 ナイロン、 ポリエステ ル等の合成繊維、 キュプラ、 レーヨン等の再生繊維、 綿、 麻等の天然繊維が 挙げられる。 他の繊維と組み合わせて使用する場合には、 不織布に占める天 然繊維及び天然由来繊維の少なくともいずれか一方を含む極細繊維の割合は 、 不織布の全質量を基準として、 例えば、 3 0質量％以上、 4 0質量％以上 、 5 0質量％以上、 6 0質量％以上、 7 0質量％以上、 8 0質量％以上、 9 0質量％以上、 又は 9 5質量％以上であってよい。 [0036] The non-woven fabric may contain only ultrafine fibers containing at least one of natural fibers and naturally derived fibers, and may contain other fibers such as protein fibers in addition to the ultrafine fibers. It may be. That is, as the fibers (also referred to as “material yarns”) used for forming the non-woven fabric, a single yarn composed of only ultrafine fibers containing at least one of natural fibers and naturally derived fibers, at least one of natural fibers and naturally derived fibers Composite yarns (for example, blended yarns, blended yarns, covering yarns, etc.) obtained by combining ultrafine fibers containing one or the other with other fibers such as protein fibers are used alone or in combination. May be taken. The single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are fired together. A filament yarn is preferably used as the single yarn and the composite yarn. Examples of other fibers include synthetic fibers such as nylon and polyester, regenerated fibers such as cupra and rayon, and natural fibers such as cotton and hemp, in addition to protein fibers. When used in combination with other fibers, the proportion of ultrafine fibers containing at least one of natural fibers and natural fibers in the nonwoven fabric is, for example, 30% by mass or more based on the total weight of the nonwoven fabric. , 40 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.

[0037] 不織布は、 例えば、 繊維径 1 0 以下の極細繊維を少なくとも一部に含 む繊維を用いて、 公知の製造方法により製造することができる。 具体的には 、 例えば、 繊維径 1 〇 以下の極細繊維を少なくとも一部に含む繊維から 、 乾式法、 湿式法及びエアレイ ド法等でウェブ （単層ウェブ、 及び積層ウェ ブを含む。 ） を形成させた後、 ケミカルボンド法 （浸潰法、 スプレー法等） 〇 2020/175702 20 卩（：171? 2020 /008524 The non-woven fabric can be manufactured by a known manufacturing method using, for example, a fiber containing at least a portion of ultrafine fibers having a fiber diameter of 10 or less. Specifically, for example, a web (including a single-layer web and a laminated web) is formed by a dry method, a wet method, an air-laid method, or the like from a fiber including at least a part of ultrafine fibers having a fiber diameter of 10 or less. After forming, chemical bond method (immersion method, spray method, etc.) 〇 2020/175 702 20 boxes (：171? 2020 /008524

及び二ードルパンチ法等によりウェブの繊維間を結合させて、 不織布を得る ことができる。 Further, the nonwoven fabric can be obtained by binding the fibers of the web together by the needle punch method or the like.

[0038] 不織布はまた、 例えば、 タンパク質を、 ジメチルスルホキシド （口1\/13〇 ） 、 1\1, 1\1 -ジメチルホルムアミ ド （01\/1 ） 、 ギ酸、 又はヘキサフルオロ イソプロパノール （1~1 I ） 等の溶媒に、 必要に応じて、 溶解促進剤とし ての無機塩と共に添加し、 溶解してドープ液を作製した後、 当該ドープ液を 用いてエレクトロスピニング法 （静電紡糸法） により紡糸することにより得 ることもできる。 エレクトロスピニング法で得られるタンパク質極細繊維の 平均繊維径 （繊維径の平均値） は、 通常、 1 0000 n m以下であり、 好ま しくは 1 0001^ 111以下であり、

Figure imgf000021_0001
00001^ 111、 1 0011111[0038] Nonwoven fabrics also include, for example, proteins such as dimethyl sulfoxide (mouth 1\/13〇), 1\1, 1\1-dimethylformamide (01\/1), formic acid, or hexafluoroisopropanol (1 ~ 1 I) etc., if necessary, together with an inorganic salt as a dissolution accelerator, and then dissolved to prepare a dope solution, and then using the dope solution to perform an electrospinning method (electrostatic spinning method). It can also be obtained by spinning with. The average fiber diameter (average fiber diameter) of protein ultrafine fibers obtained by the electrospinning method is usually 1 0000 nm or less, preferably 1 0001^ 111 or less,
Figure imgf000021_0001
00001^111, 1 0011111

〜 50001^ 111、

Figure imgf000021_0002
00011111、 200
Figure imgf000021_0003
90011111、 又 は 300 n m~ 800 n mであってもよい。 タンパク質極細繊維の繊維径は 、
Figure imgf000021_0004
~ 50001^111,
Figure imgf000021_0002
00011111, 200
Figure imgf000021_0003
It may be 90011111 or 300 nm to 800 nm. The fiber diameter of protein ultrafine fiber is
Figure imgf000021_0004

1 0001^ 111 （1 〇〇 の間で変動してもよい。 It may fluctuate between 1 0001^111 (1○).

[0039] 不織布は、 繊維密度 （目付） 、 空隙率、 かさ密度等の数値範囲が、 防水性 と透湿性とを充分に確保し得る範囲となるように適宜設定される。 なお、 そ れら目付、 空隙率、 かさ密度等の調整は、 例えば、 ウェブを構成する繊維量 を増減すること、 積層ウェブの場合は、 積層数を増減することにより行うこ とができる。 [0039] The nonwoven fabric is appropriately set such that the numerical values of the fiber density (area weight), the porosity, the bulk density, etc. are within a range in which waterproofness and moisture permeability can be sufficiently ensured. The unit weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of layers.

[0040] 第 1実施形態に係る防水透湿性生地の表皮層 1は、 編織体からなる。 編織 体とは、 編地及び織地の総称である。 編地は、 横編、 丸編等の緯編組織を有 する編地 （単に 「緯編地」 ともいう。 ） 、 トリコッ ト、 ラッセル等の経編組 織を有する編地 （単に 「経編地」 ともいう。 ） のいずれであってもよい。 織 地は、 平織、 綾織、 又は嬬子織のうちのいずれの組織を有する織地であって もよい。 編織体は、 編成又は織成により得られる未加工の編織体そのもので あってもよいし、 編成又は織成後に撥水加工等の加工を施した編織体であっ てもよい。 [0040] The skin layer 1 of the waterproof/moisture permeable fabric according to the first embodiment is made of a knitted fabric. A knitted fabric is a generic term for knitted fabrics and woven fabrics. A knitted fabric is a knitted fabric having a weft knitting structure such as a flat knitted fabric or a circular knitted fabric (also simply referred to as a “weft knitted fabric”), a knitted fabric having a warp braided fabric such as tricot, Russell (only Also referred to as ".". The woven fabric may be a woven fabric having any one of a plain weave, a twill weave, and a Tsumago weave. The knitted or woven body may be an unprocessed knitted or woven body itself obtained by knitting or weaving, or may be a knitted or woven body subjected to a process such as water repellent treatment after knitting or weaving.

[0041] 編織体は、 原料糸を編成又は織成して得ることができる。 編成方法及び織 〇 2020/175702 21 卩（：171? 2020 /008524 [0041] The knitted or woven body can be obtained by knitting or weaving raw material threads. Knitting method and weaving 〇 2020/175 702 21 卩(: 171? 2020/008524

成方法としては公知の方法を利用することができる。 使用される編機として は、 例えば、 丸編機、 経編機、 横編機などが使用でき、 生産性の観点からは 、 丸編機の使用が好ましい。 横編機としては、 成型編み機、 無縫製編機など があるが、 特に最終製品の形態で編地を製造可能であることから、 無縫製編 機の使用がより好ましい。 使用される織機としては、 例えば、 有抒織機、 及 び、 グリッパー織機、 レピア織機、 ウォータージェッ ト織機、 エアジェッ ト 織機等の無抒織機が挙げられる。 A publicly known method can be used as the method of formation. As the knitting machine to be used, for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used. As the flat knitting machine, there are a forming knitting machine, a non-sewn knitting machine, and the like. However, since the knitted fabric can be manufactured in the form of a final product, the non-sewn knitting machine is more preferable. Examples of the loom to be used include a hauling loom, and a non-tapping loom such as a gripper loom, a rapier loom, a water jet loom, and an air jet loom.

[0042] 編織体の原料糸は、 単独糸であってもよく、 複合糸 （例えば、 混紡糸、 混 繊糸、 カバーリング糸等。 ） であってもよく、 これらを組み合わせて用いて もよい。 単独糸及び複合糸は、 短繊維を撚り合わせたスパン糸であってもよ く、 長繊維を撚り合わせたフィラメント糸であってもよい。 原料糸に含まれ る繊維としては、 例えば、 タンパク質繊維、 ナイロン、 ポリエステル、 ポリ テトラフルオロエチレン等の合成繊維、 キュプラ、 レーヨン及びリヨセル等 の再生繊維、 綿、 麻及び絹等の天然繊維が挙げられる。 [0042] The raw material yarn of the knitted fabric may be a single yarn, a composite yarn (for example, a mixed yarn, a mixed yarn, a covering yarn, etc.), or may be a combination of these. .. The single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or may be filament yarn in which long fibers are twisted together. Examples of the fibers contained in the raw yarn include protein fibers, synthetic fibers such as nylon, polyester and polytetrafluoroethylene, regenerated fibers such as cupra, rayon and lyocell, and natural fibers such as cotton, hemp and silk. ..

[0043] 編織体は、 不織布との接合側とは反対側の表面が撥水加工されていてもよ い。 これにより、 防水性により優れた防水透湿性生地を得ることができる。 撥水加工は、 例えば、 プラズマ加工等の化学コーティングを施す、 撥水コー ティング剤を塗布する等の物理的コーティングを施す、 又は表面を化学修飾 する等の従来公知の方法により行うことができる。 The surface of the knitted or woven body on the side opposite to the side joined to the nonwoven fabric may be water-repellent. This makes it possible to obtain a waterproof and moisture-permeable fabric that is more waterproof. The water repellent treatment can be carried out by a conventionally known method such as chemical coating such as plasma processing, physical coating such as coating with a water repellent coating agent, or chemical modification of the surface.

[0044] 第 1実施形態に係る防水透湿性生地は、 防水透湿層 （不織布） の表皮層 （ 編織体） が接合された面の反対側の面に裏材層 （編織体） が更に接合されて いてもよい。 裏材層の好ましい態様としては、 表皮層で例示した態様が挙げ られる。 表皮層と裏材層は、 それぞれ同一の材料で形成された編織体であっ てもよく、 異なる材料で形成された編織体であってもよい。 [0044] The waterproof/moisture permeable fabric according to the first embodiment further comprises a backing layer (woven body) further bonded to the surface opposite to the surface of the waterproof/moisture permeable layer (nonwoven fabric) bonded to the skin layer (woven body). It may have been done. Preferred embodiments of the backing layer include the embodiments exemplified for the skin layer. The skin layer and the backing layer may be knitted fabrics made of the same material, or may be knitted fabrics made of different materials.

[0045] 第 1実施形態に係る防水透湿性生地は、 防水透湿層と表皮層とを接合して 得ることができる。 防水透湿層と表皮層との接合方法は、 不織布及び編織体 に使用する素材に応じて、 適宜選択することができる。 接合方法として、 例 えば、 防水透湿層と表皮層とを、 熱又は溶剤等により、 溶着する方法、 防水 〇 2020/175702 22 卩（：171? 2020 /008524 The waterproof/moisture permeable fabric according to the first embodiment can be obtained by joining a waterproof/moisture permeable layer and a skin layer. The method for joining the waterproof moisture-permeable layer and the skin layer can be appropriately selected according to the materials used for the nonwoven fabric and the knitted fabric. As a joining method, for example, a method of welding a waterproof moisture-permeable layer and a skin layer with heat or a solvent, and a waterproof method. 〇 2020/175 702 22 卩 (: 171-1? 2020 /008524

透湿層と表皮層とを接着剤を介して接着する方法、 不織布と編織体の少なく ともいずれか一方の接合面にプラズマを照射して、 ラジカル反応により共有 結合を形成させることで、 防水透湿層と表皮層とを接合する方法等が挙げら れる。 例えば、 不織布及び編織体がいずれもタンパク質 （タンパク質極細繊 維又はタンパク質繊維） を含む場合、 防水透湿層及び表皮層の接合面のうち 一方又は両方にタンパク質を溶解する溶媒 （例えば、 ジメチルスルホキシド

Figure imgf000023_0001
1\1 , 1\1 -ジメチルホルムアミ ド （0 1\/1 ） 、 ギ酸、 若しくは ヘキサフルオロイソプロパノール （1~1 I ） 等の有機溶媒、 それらに溶解 促進剤としての無機塩を添加した溶液、 又は水、 若しくは水に無機塩等を添 加した水溶液） を塗布した後、 防水透湿層及び表皮層を貼り合わせ、 更に溶 媒を除去することで防水透湿層と表皮層とを接合することができる。 A method of adhering the moisture-permeable layer and the skin layer with an adhesive, and irradiating plasma to at least one of the bonding surfaces of the nonwoven fabric and the knitted fabric to form a covalent bond by a radical reaction to form a waterproof and transparent layer. Examples include a method of joining the wet layer and the epidermal layer. For example, when both the non-woven fabric and the woven fabric contain a protein (protein ultrafine fiber or protein fiber), a solvent that dissolves the protein in one or both of the joint surfaces of the waterproof and moisture permeable layer and the epidermis layer (for example, dimethyl sulfoxide).
Figure imgf000023_0001
Organic solvent such as 1\1, 1\1-dimethylformamide (0 1\/1 ), formic acid, or hexafluoroisopropanol (1 to 1 I), and a solution prepared by adding an inorganic salt as a dissolution accelerator to them. , Or water, or an aqueous solution in which an inorganic salt or the like is added to water), and then the waterproof moisture-permeable layer and the skin layer are bonded together, and the solvent is further removed to bond the waterproof moisture-permeable layer and the skin layer. can do.

[0046] また、 不織布をエレクトロスピニング法で形成する場合、 防水透湿層を表 皮層上に形成する防水透湿層形成工程を備える製造方法により、 防水透湿性 生地を得ることができる。 防水透湿層形成工程は、 タンパク質を含有するド —プ液を使用したエレクトロスピニングにより、 表皮層上にタンパク質極細 繊維を集積させて不織布を形成させることを含む。 [0046] Further, when the nonwoven fabric is formed by the electrospinning method, the waterproof and moisture-permeable fabric can be obtained by a manufacturing method including a waterproof and moisture-permeable layer forming step of forming a waterproof and moisture-permeable layer on the skin layer. The waterproof/moisture permeable layer forming step includes forming electro-spinning using a dope solution containing a protein to accumulate protein ultrafine fibers on the epidermis layer to form a nonwoven fabric.

[0047] エレクトロスピニング法 （静電紡糸法） は、 供給側電極 （紡糸口金と兼用 できる） と捕集側電極 （例えば、 金属口ール又は金属ネッ ト等） 間に電圧を 印加し、 紡糸口金から押し出したドープ液に電荷を与えて捕集側電極に吹き 飛ばす。 この際にドープ液は伸張されて繊維形成される。 印加電圧は、 通常 5〜 1 0 0 Vであり、 好ましくは 1 〇〜 5 0 Vである。 電極間距離は、

Figure imgf000023_0002
好ましくは 2〜 2 0〇 である。 [0047] The electrospinning method (electrospinning method) is a method in which a voltage is applied between a supply-side electrode (which can also be used as a spinneret) and a collection-side electrode (for example, a metal nozzle or a metal net) to perform spinning. An electric charge is given to the dope solution extruded from the die and blown to the collection side electrode. At this time, the dope solution is stretched to form fibers. The applied voltage is usually 5 to 100 V, and preferably 10 to 50 V. The distance between the electrodes is
Figure imgf000023_0002
It is preferably 2 to 200.

[0048] 図 4は、 一実施形態に係るエレクトロスピニング装置 1 0 0の説明図であ る。 金属製口金ノズル 3 3 （供給側電極） と金属製ネッ ト 3 8 （捕集側電極 ） との間に電源 3 5により電圧をかける。 マイクロシリンジ 3 1内のドープ 液 3 2をシリンジポンプを用いて矢印 方向に移動させ、 金属製口金ノズル 3 3からドープ液 3 2を押し出し、 電荷によってドープ液を伸張し繊維状物 3 6にして金属製ネッ ト 3 8の表面に集積させることで、 タンパク質極細繊 〇 2020/175702 23 卩（：171? 2020 /008524 [0048] FIG. 4 is an explanatory diagram of an electrospinning apparatus 100 according to an embodiment. A voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35. The dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36. By accumulating on the surface of metal net 38, protein fine fibers can be 〇 2020/175702 23 卩(: 171-1? 2020/008524

維を含む不織布 3 9を得ることができる。 得られた不織布は、 次いで溶媒を 離脱してもよい。 溶媒を脱離する方法としては、 例えば、 減圧乾燥又は脱溶 媒槽への浸潰が挙げられる。 また、 かく して不織布 3 9を得る際には、 金属 製ネッ ト 3 8の表面に表皮層 （編織体） を載置することで、 表皮層上にタン パク質極細繊維を集積させて不織布を形成させることもできる。 このとき、 好適には、 表皮層におけるタンパク質極細繊維集積側の面に対して、 所定の 接着剤、 又はタンパク質極細繊維を溶解可能な溶媒からなる接着剤層等が塗 布等により形成される。 そうすることによって、 不織布 3 9が、 表皮層上に 形成されると同時に表皮層に対して一体的に接合され、 目的とする防水透湿 性生地が有利に且つ効率的に製造され得ることとなる。 なお、 表皮層表面上 に接着剤層を形成する場合には、 接着剤を固化させる操作や、 溶媒を除去す る操作が追加されることもある。 A nonwoven fabric 39 containing fibers can be obtained. The solvent may be removed from the obtained non-woven fabric. Examples of the method of removing the solvent include drying under reduced pressure and immersing in a desolvent tank. In addition, when a non-woven fabric 39 is thus obtained, a superficial layer (textile body) is placed on the surface of the metal net 38 so that the ultrafine fibers of the protein are accumulated on the superficial layer. Can also be formed. At this time, preferably, an adhesive layer or the like made of a predetermined adhesive or a solvent capable of dissolving the protein ultrafine fibers is formed on the surface of the skin layer on the protein ultrafine fiber accumulation side by coating or the like. By doing so, the nonwoven fabric 39 is formed on the skin layer and at the same time integrally bonded to the skin layer, and the desired waterproof and moisture-permeable fabric can be manufactured advantageously and efficiently. Become. When the adhesive layer is formed on the surface of the skin layer, an operation of solidifying the adhesive or an operation of removing the solvent may be added.

［0049］ （タンパク質） [0049] (protein)

不織布又は編織体に含まれるタンパク質極細繊維又はタンパク質繊維の原 料となるタンパク質には、 特に制限はなく、 任意のタンパク質を使用するこ とができる。 使用するタンパク質としては、 疎水性タンパク質が好ましい。 本明細書において、 「疎水性タンパク質」 とは、 タンパク質を構成する全て のアミノ酸残基の疎水性指標 （1~1 I） の総和を求め、 次にその総和を全アミ ノ酸残基数で除した値 （平均!· I I） が 0超であるタンパク質を意味する。 一 方、 防水透湿性に加え、 保温性、 吸湿発熱性及び/又は難燃性にも優れると いう観点からは、 タンパク質としては、 改変フイブロインが好ましく、 改変 クモ糸フイブロインがより好ましい。 タンパク質極細繊維及び/又はタンパ ク質繊維が、 改変フイブロイン （好ましくは、 改変クモ糸フイブロイン） を 含むことにより、 本実施形態に係る防水透湿性生地に保温性、 吸湿発熱性及 び/又は難燃性の性質を更に付与することができ、 生地としての価値がより 高くなる。 The protein used as the raw material for the protein ultrafine fibers or protein fibers contained in the nonwoven fabric or the knitted fabric is not particularly limited, and any protein can be used. The protein used is preferably a hydrophobic protein. In the present specification, “hydrophobic protein” means the sum of the hydrophobicity indices (1 to 1 I) of all amino acid residues that compose a protein, and then the sum is expressed as the total number of amino acid residues. Means a protein whose divided value (average! II) is greater than 0. On the other hand, from the viewpoint of being excellent in heat retention, moisture absorption and heat generation and/or flame retardancy in addition to waterproof and moisture permeability, modified fibroin is preferable as the protein, and modified spider silk fibroin is more preferable. By containing the modified fibroin (preferably modified spider silk fibroin) in the protein ultrafine fiber and/or protein fiber, the waterproof and moisture-permeable fabric according to the present embodiment has heat-retaining property, moisture-absorbing heat-generating property, and/or flame-retardant property. It is possible to add more sexual character, and it becomes more valuable as a fabric.

［0050］ 本実施形態に係る改変フイブロインは、 式 1 : ［ （ ） „モチーフー［¾巳 ］ 、 又は式 2 : ［ （八）

Figure imgf000024_0001
一 （八） „モチーフで表され 〇 2020/175702 24 卩（：171? 2020 /008524 [0050] The modified fibroin according to the present embodiment has the formula 1: [( )"Motif [¾mi]" or the formula 2: [(8)
Figure imgf000024_0001
One (eight) „represented by the motif 〇 2020/175 702 24 卩 (: 171? 2020 /008524

るドメイン配列を含むタンパク質である。 改変フィブロインは、 ドメイン配 列の 1\］末端側及び（3末端側のいずれか一方又は両方に更にアミノ酸配列 （ 末端配列及び＜3末端配列） が付加されていてもよい。 1\1末端配列及び（3末端 配列は、 これに限定されるものではないが、 典型的には、 フィブロインに特 徴的なアミノ酸モチーフの反復を有さない領域であり、 1 0 0残基程度のア ミノ酸からなる。 It is a protein containing a domain sequence. The modified fibroin may further have an amino acid sequence (terminal sequence and <3 terminal sequence) added to the 1\] terminal side of the domain sequence and/or both of the 3 terminal side. And (three-terminal sequence is not limited to this, but is typically a region having no repeat of the amino acid motif characteristic of fibroin, and has amino acid residues of about 100 residues. Consists of.

［0051］ 本明細書において 「改変フィブロイン」 とは、 人為的に製造されたフィブ ロイン （人造フィブロイン） を意味する。 改変フィブロインは、 そのドメイ ン配列が、 天然由来のフィブロインのアミノ酸配列とは異なるフィブロイン であってもよく、 天然由来のフィブロインのアミノ酸配列と同一であるフィ ブロインであってもよい。 本明細書でいう 「天然由来のフィブロイン」 もま た、 式 1 : ［ （八） nモチーフー ^巳 ］ 、 又は式 2 : ［ （八） „モチーフー ［¾巳 ］ （八） „モチーフで表されるドメイン配列を含むタンパク質であ る。 [0051] In the present specification, "modified fibroin" means artificially produced fibroin (artificial fibroin). The modified fibroin may be a fibroin whose domain sequence is different from the amino acid sequence of naturally occurring fibroin, or may be the same fibroin as the naturally occurring fibroin. The term "naturally-derived fibroin" as used herein is also represented by the formula 1: [(8) n motif-^mi] or the formula 2: [(8) "motif-[¾mi] (8)" motif. It is a protein containing a domain sequence.

［0052］ 「改変フィブロイン」 は、 天然由来のフィブロインのアミノ酸配列をその まま利用したものであってもよく、 天然由来のフィブロインのアミノ酸配列 に依拠してそのアミノ酸配列を改変したもの （例えば、 クローニングした天 然由来のフィブロインの遺伝子配列を改変することによりアミノ酸配列を改 変したもの） であってもよく、 また天然由来のフィブロインに依らず人工的 に設計及び合成したもの （例えば、 設計したアミノ酸配列をコードする核酸 を化学合成することにより所望のアミノ酸配列を有するもの） であってもよ い。 [0052] The "modified fibroin" may be one that uses the amino acid sequence of naturally occurring fibroin as it is, or one that has its amino acid sequence modified depending on the amino acid sequence of naturally occurring fibroin (for example, cloning Amino acid sequence modified by modifying the gene sequence of naturally-occurring fibroin) or artificially designed and synthesized independently of naturally-occurring fibroin (eg, designed amino acid It may have a desired amino acid sequence by chemically synthesizing a nucleic acid encoding the sequence).

［0053］ 本明細書において 「ドメイン配列」 とは、 フィブロイン特有の結晶領域 （ 典型的には、 アミノ酸配列の （八） „モチーフに相当する。 ） と非晶領域 （典 型的には、 アミノ酸配列の 巳 に相当する。 ） を生じるアミノ酸配列であ り、 式 1 : ［ （八） nモチーフー ^巳 ］ 、 又は式 2 : ［ （八） „モチーフー ［¾巳 ］ 一 （八） „モチーフで表されるアミノ酸配列を意味する。 ここで、 （八） „モチーフは、 アラニン残基を主とするアミノ酸配列を示し、 アミノ酸 残基数は 2〜 27である。 （A） „モチーフのアミノ酸残基数は、 2〜 20、[0053] In the present specification, the "domain sequence" means a crystalline region (typically corresponding to the (8)" motif of an amino acid sequence) and an amorphous region (typically, an amino acid, which are unique to fibroin. Is an amino acid sequence that yields the following formula: [Formula 1: [(8) n Motif ^M]], or Formula 2: [(8) „Motif [¾M] 1 (8)” Motif An amino acid sequence represented by: (8) „Motif indicates an amino acid sequence mainly consisting of alanine residues, The number of residues is 2 to 27. (A) The number of amino acid residues in the „motif is 2 to 20,

4〜 27、 4〜 20、 8〜 20、 1 0〜 20、 4〜 1 6、 8〜 1 6、 又は 1 〇〜 1 6の整数であってよい。 また、 （A） „モチーフ中の全アミノ酸残基数 に対するアラニン残基数の割合は 40%以上であればよく、 60 %以上、 7 0%以上、 80 %以上、 83 %以上、 85 %以上、 86 %以上、 90 %以上 、 95 %以上、 又は 1 00% （アラニン残基のみで構成されることを意味す る。 ） であってもよい。 ドメイン配列中に複数存在する （A） nモチーフは、 少なくとも 7つがアラニン残基のみで構成されてもよい。 R E Pは 2〜 20 0アミノ酸残基から構成されるアミノ酸配列を示す。 R E P 、 1 0〜 20 〇アミノ酸残基から構成されるアミノ酸配列であってもよい。 mは 2〜 30 0の整数を示し、 1 〇〜 300の整数であってもよい。 複数存在する （A） n モチーフは、 互いに同一のアミノ酸配列でもよく、 異なるアミノ酸配列でも よい。 複数存在する R E P 、 互いに同一のアミノ酸配列でもよく、 異なる アミノ酸配列でもよい。 It may be an integer of 4 to 27, 4 to 20, 8 to 20, 10 to 20, 4 to 16, 8 to 16, or 10 to 16. In addition, the ratio of the number of alanine residues to the total number of amino acid residues in the (A) motif may be 40% or more, and is 60% or more, 70% or more, 80% or more, 83% or more, 85% or more. , 86% or more, 90% or more, 95% or more, or 100% (meaning that it is composed of only alanine residues.) Multiple in the domain sequence (A) n At least 7 motifs may be composed of only alanine residues REP represents an amino acid sequence composed of 2 to 200 amino acid residues REP, amino acid composed of 10 to 200 amino acid residues M may be an integer of 2 to 300, or an integer of 10 to 300. Multiple (A) n motifs may have the same amino acid sequence or different amino acids. A plurality of REPs may be the same amino acid sequence or different amino acid sequences.

[0054] 本実施形態に係る改変フィブロインは、 例えば、 クローニングした天然由 来のフィブロインの遺伝子配列に対し、 例えば、 1又は複数のアミノ酸残基 を置換、 欠失、 揷入及び/又は付加したことに相当するアミノ酸配列の改変 を行うことで得ることができる。 アミノ酸残基の置換、 欠失、 挿入及び/又 は付加は、 部分特異的突然変異誘発法等の当業者に周知の方法により行うこ とができる。 具体的には、 N u c l e i c Ac i d R e s. 1 0, 64 87 （1 982） 、 Me t h o d s i n E n z ymo I o g y, 1 00 , 448 （1 983） 等の文献に記載されている方法に準じて行うことがで きる。 [0054] The modified fibroin according to the present embodiment is obtained by, for example, substituting, deleting, inserting and/or adding one or more amino acid residues with respect to the gene sequence of the cloned naturally-occurring fibroin. It can be obtained by modifying the amino acid sequence corresponding to. Substitution, deletion, insertion and/or addition of amino acid residues can be performed by a method known to those skilled in the art, such as a partial directed mutagenesis method. Specifically, according to the method described in the literature such as Nucleic Acid Res. 1 0, 64 87 (1 982), Me thodsin E nz ymo I ogy, 1 00, 448 (1 983). Can be done.

[0055] 天然由来のフィブロインは、 式 1 : [ （A） „モチーフーR E P] m、 又は 式 2 : [ （ A） nモチ—フ—R E P] m— （A） nモチ—フで表されるドメイン 配列を含むタンパク質であり、 具体的には、 例えば、 昆虫又はクモ類が産生 するフィブロインが挙げられる。 [0055] A naturally-derived fibroin is represented by the formula 1: [(A) „motif-REP] m or the formula 2: [(A) n motif-REP] m — (A) n motif. A protein containing a domain sequence, and specific examples thereof include fibroin produced by insects or arachnids.

[0056] 昆虫が産生するフィブロインとしては、 例えば、 ボンビックス ·モリ （ B om b y x mo r i） 、 クワコ （B om b y x m a n d a r i n a） 、 天奎 （A n t h e r a e a y am am a i） 、 ネ乍奎 （A n t e r a e a p e r n y i） 、 楓奎 （E r i o g y n a p y r e t o r u m） 、 蓖奎 （ P i l o s am i a C y n t h i a r i c i n i） 、 樗奎 （S am i a c y n t h i a） 、 栗虫 （C a l i g u r a j a p o n i c a） 、 チュ ッサー奎 （A n t h e r a e a m y l i t t a） 、 ムガ奎 （A n t h e r a e a a s s a m a） 等のカイコが産生する絹タンパク質、 及びスズメバ チ （Ve s p a s i m i I I i m a x a n t h o p t e r a） の幼虫が 吐出するホーネッ トシルクタンパク質が挙げられる。 [0056] Examples of fibroin produced by insects include Bombix mori (B om byx mo ri), mulberry (B om byxmandarina), 天奎 (A ntheraeay am am ai), Ne 乍奎(A nteraeapernyi), Silk proteins produced by silkworms such as sam iacynthia, chestnuts (C aligurajaponica), chusser syrup (A ntheraeamylitta), stag beetle (A ntheraeaassama), and vespid (Ve spasimi II imaxanthoptera) This includes hornet silk protein.

[0057] 昆虫が産生するフィブロインのより具体的な例としては、 例えば、 カイコ フィブロイン L鎖 （Ge n B a n kアクセッション番号 M 76430 （塩 基配列） 、 及び AAA 27840. 1 （アミノ酸配列） ） が挙げられる。 [0057] More specific examples of fibroin produced by insects include, for example, silkworm fibroin L chain (Gen Bank accession number M76430 (salt sequence), and AAA 27840.1 (amino acid sequence)). Can be mentioned.

[0058] クモ類が産生するフィブロインとしては、 例えば、 クモ目 （ A r a n e a e） に属するクモが産生するスパイダーシルクタンパク質が挙げられる。 よ り具体的には、 オニグモ、 ニワオニグモ、 アカオニグモ、 アオオニグモ及び マメオニグモ等のオニグモ属 （A r a n e u s属） に属するクモ、 ヤマシロ オニグモ、 イエオニグモ、 ドヨウオニグモ及びサツマノミダマシ等のヒメオ ニグモ属 （N e o s c o n a属） に属するクモ、 コオニグモモドキ等のコオ ニグモモドキ属 （P r o n u s属） に属するクモ、 トリノフンダマシ及び才 オトリノフンダマシ等のトリノフンダマシ属 （C y r t a r a c h n e属） に属するクモ、 トゲグモ及びチブサトゲグモ等のトゲグモ属 （G a s t e r a c a n t h a属） に属するクモ、 マメイタイセキグモ及びムツトゲイセキ グモ等のイセキグモ属 （〇 r d g a r i u s属） に属するクモ、 コガネグモ 、 コガタコガネグモ及びナガコガネグモ等のコガネグモ属 （A r g i 〇 p e 属） に属するクモ、 キジロオヒキグモ等のオヒキグモ属 （A r a c h n u r a属） に属するクモ、 ハツリグモ等のハツリグモ属 （Ac u s i I a s属） に属するクモ、 スズミグモ、 キヌアミグモ及びハラビロスズミグモ等のスズ ミグモ属 （C y t 〇 p h〇 r a属） に属するクモ、 ゲホウグモ等のゲホウグ モ属 （P o 丨 t y s属） に属するクモ、 ゴミグモ、 ヨツデゴミグモ、 マルゴ ミグモ及びカラスゴミグモ等のゴミグモ属 （C y c 丨 o s a属） に属するク モ、 及びヤマトカナエグモ等のカナエグモ属 （C h o r i z o p e s属） に 属するクモが産生するスパイダーシルクタンパク質、 並びにアシナガグモ、 ヤサガタアシナガグモ、 ハラビロアシダカグモ及びウロコアシナガグモ等の アシナガグモ属 （T e t r a g n a t h a属） に属するクモ、 オオシロカネ グモ、 チュウガタシロカネグモ及びコシロカネグモ等のシロカネグモ属 （L e u c a u g e属） に属するクモ、 ジョロウグモ及びオオジョロウグモ等の ジョロウグモ属 （N e p h i 丨 a属） に属するクモ、 キンヨウグモ等のアズ ミグモ属 （Me n o s i r a属） に属するクモ、 ヒメアシナガグモ等のヒメ アシナガグモ属 （D y s c h i r i o g n a t h a属） に属するクモ、 クロ ゴケグモ、 セアカゴケグモ、 ハイイロゴケグモ及びジュウサンボシゴケグモ 等のゴケグモ属 （L a t r o d e c t u s属） に属するクモ、 及びユープロ ステノプス属 （E u p r o s t h e n o p s属） に属するクモ等のアシナガ グモ科 （T e t r a g n a t h i d a e科） に属するクモが産生するスパイ ダーシルクタンパク質が挙げられる。 スパイダーシルクタンパク質としては 、 例えば、 M a S p （M a S p 1及び M a S p 2） 、 A D F （A D F 3及び A D F 4） 等の牽引糸タンパク質、 M i S p （M i S p 1及び M i S p 2）[0058] Examples of fibroin produced by arachnids include spider silk proteins produced by arachnids belonging to the order Aranea. More specifically, spiders belonging to the genus Araneus (Araneus spp.), such as Onigumo, Ani spider, Red-bellied spider, Blue-headed spider, and Araneus spider, etc. Spiders that belong to the genus Cronata, such as spiders and spiders belonging to the genus P ronus, spiders that belong to the genus Cyrtarachne, such as genus Cyrtarachne, and spiders that belong to the genus Cyrtarachne. Spiders belonging to the genus (genus G asteracantha), Spiders belonging to the genus Grace (○ rdgarius) such as Mamei Taiseki spider and Mutsugai spider, Genus Argiosus (Argi) belonging to the genus Argio (Argi genus). Spiders belonging to the genus A rachnura such as spiders and white-breasted spiders, spiders belonging to the genus Acusi I as such as spiders such as ant spiders, spiders such as spiders, brown spiders and dwarf spiders (C yt 〇 ph 〇 ra) Spiders belonging to the genus) Spiders belonging to the genus Pho tys, spiders belonging to the genus Cyc osa, such as spiders, wolf spiders, marsupial spiders, and black spiders, and genus C horizopes, such as Yamato kana spiders Spider silk proteins produced by spiders belonging to the genus T. sp., spider silk spiders belonging to the genus Tetragnatha, such as the spider spider, the herring spider, the spider duck spider Spiders belonging to the genus L eucauge, spiders belonging to the genus Nephila (genus N ephi 丨a) such as Nephila and Nephila spp. Spiders belonging to the genus D yschiriognatha, black spiders, black-backed spiders, black-spotted spiders and spiders belonging to the genus Latrodectus and spiders belonging to the genus E uprosthenops. Spider silk proteins produced by spiders belonging to the family (T etragnathidae). Examples of spider silk proteins include dragline proteins such as M a S p (M a S p 1 and M a S p 2) and ADF (ADF 3 and ADF 4), and M i S p (M i S p 1). And M i S p 2)

、 Ac S p、 P yS p、 F I a g等が挙げられる。 , Ac S p, P yS p, F I a g and the like.

[0059] クモ類が産生するスパイダーシルクタンパク質のより具体的な例としては 、 例えば、 f i b r o i n— 3 （a d f — 3） [A r a n e u s d i a d e m a t u s由来] （Ge n B a n kアクセッション番号 A A C 4701 0 （アミノ酸配列） 、 U 47855 （塩基配列） ） 、 f i b r o i n -4 （a d f — 4） [A r a n e u s d i a d e m a t u s由来] （ G e n B a n kアクセッション番号 A AC 4701 1 （アミノ酸配列） 、 U 47856 （ 塩基酉己列） ） 、 d r a g l i n e s i l k p r o t e i n s p i d r o i n 1 [N e p h i l a c l a v i p e s由来] （Ge n B a n kア クセッション番号八八〇 04504 （アミノ酸配列） 、 II 37520 （塩基 \¥02020/175702 28 卩（：17 2020 /008524 [0059] More specific examples of spider silk proteins produced by arachnids include, for example, fibroin-3 (adf-3) [from A raneus diadematus] (Gen Bank accession number AAC 4701 0 (amino acid sequence)). , U 47855 (base sequence) ), fibroin -4 (adf — 4) [from A raneus diadematus] (Gen B ank accession number A AC 4701 1 (amino acid sequence), U 47856 (base rooster sequence) ), draglinesilkproteinsp idroin 1 [from N ephilaclavipes] (Gen Bank Accession No. 880 504 04504 (amino acid sequence)), II 37520 (base \¥02020/175702 28 卩(: 17 2020/008524

酉己列） ） 、 m a j o r am p u l l a t e s p i d r o i n 1 [L a t r o d e c t u s h e s p e r u s由来] （Ge n B a n kアクセッシ ョン番号 A B R 68856 （アミノ酸配列） 、 E F 595246 （塩基配列 ） ） 、 d r a g l i n e s i l k p r o t e i n s p i d r o i n 2 [ N e p h i l a c l a v a t a由来] （Ge n B a n kアクセッショ ン番号 AAL 32472 （アミノ酸配列） 、 A F 44 1 245 （塩基配列） ） 、 m a j o r am p u l l a t e s p i d r o i n 1 [ E u p r o s t h e n o p s a u s t r a l i s由来] （Ge n B a n kアクセッシ ョン番号 C A J 00428 （アミノ酸配列） 、 A J 973 1 55 （塩基配列 ） J 、 及び m a j o r am p u l l a t e s p i d r o i n 2 [ E u p r o s t h e n o p s a u s t r a I i s ] （Ge n B a n kアクセッ ション番号 CAM 32249. 1 （アミノ酸配列） 、 AM 4901 69 （塩 基酉己列） ） 、 m i n o r am p u l l a t e s i l k p r o t e i n 1 [N e p h i I a c l a v i p e s] （Ge n B a n kアクセッショ ン番号 A A C 1 4589. 1 （アミノ酸配列） ） 、 m i n o r am p u l l a t e s i l k p r o t e i n 2 [ N e p h i l a c l a v i p e s ] （Ge n B a n kアクセッション番号 A A C 1 459 1. 1 （アミノ 酸酉己列） ） 、 m i n o r am p u l l a t e s p i d r o i n— I i k e p r o t e i n [N e p h i l e n g y s c r u e n t a t a] （G e n B a n kアクセッション番号 A B R 37278. 1 （アミノ酸配列） 等 が挙げられる。 Rooster self)), major am pullatespidroin 1 [from Latrodectus hesperus] (Gen n Accession number ABR 68856 (amino acid sequence), EF 595246 (base sequence)), draglinesilkproteinsp idroin 2 [from Nephilaclavata] (Ge n Ban accession number AAL 32472 (amino acid sequence), AF 44 1 245 (base sequence)), major am pullatespidroin 1 [from E uprosthenopsaustralis] (Gen Bank accession number CAJ 00428 (amino acid sequence), AJ 973 1 55 (base sequence) J, and major am pullatespidroin 2 [E uprosthenopsaustra I is] (Gen Bank accession number CAM 32249. 1 (amino acid sequence), AM 4901 69 (salt group)), minor am pullatesilkprotein 1 [N ephi I aclavipes] (Gen n Bank accession number AAC 1 4589. 1 (amino acid sequence)), minor am pullatesilkprotein 2 [N ephilaclavipes] (Gen n Bank accession number AAC 1 459 1.1 (amino acid sequence) Acid rooster row) )), minor am pullatespidroin— I ikeprotein [N e p h i l e n g y s c r u e n t a t a] (G e n B a n k Accession number A B R 37278. 1 (amino acid sequence)) and the like.

[0060] 天然由来のフイブロインのより具体的な例としては、 更に、 NCB I G e n B a n kに配列情報が登録されているフイブロインを挙げることができ る。 例えば、 NCB I Ge n B a n kに登録されている配列情報のうち D I V 丨 S 丨 〇 Nとして 丨 N Vを含む配列の中から、 D E F I N I T I ONに s p i d r o i n、 am p u l l a t e、 f i b r o i n、 rs i I k及ひ p o I y p e p t i d e」 、 又は 「s i l k及び p r o t e i n」 がキーワ —ドとして記載されている配列、 CDSから特定の p r o d u c tの文字列 〇 2020/175702 29 卩（：171? 2020 /008524 [0060] As a more specific example of naturally-occurring fibroin, fibroin whose sequence information is registered in NCB IG en Bank can be further mentioned. For example, among the sequence information registered in NCB I Gen B ank, DIV 丨 S 丨 〇 N, which includes 丨 NV, from DEFINITI ON to spidroin, am pullate, fibroin, rs i I k, and po "I y peptide" or "silk and protein" are described as keywords, and the character string of a specific product from CDS 〇 2020/175 702 29 卩 (：171? 2020 /008524

、 3〇 II

Figure imgf000030_0001
巳から丁 丨 3 3 II巳 丁丫 巳に特定の文字列の記載された配 列を抽出することにより確認することができる。 , 30 II
Figure imgf000030_0001
This can be confirmed by extracting the sequence in which a specific character string is written from the Tami to Mita 3 3 II Tami Toma.

［0061］ 本実施形態に係る改変フィブロインは、 改変絹 （シルク） フィブロイン （ カイコが産生する絹タンパク質のアミノ酸配列を改変したもの） であっても よく、 改変クモ糸フィブロイン （クモ類が産生するスパイダーシルクタンパ ク質のアミノ酸配列を改変したもの） であってもよい。 改変フィブロインと しては、 難燃性により優れることから、 改変クモ糸フィブロインが好ましい [0061] The modified fibroin according to the present embodiment may be modified silk (silk) fibroin (modified amino acid sequence of silk protein produced by silkworm), modified spider silk fibroin (spider produced by spiders). (Amino acid sequence of silk protein is modified). As modified fibroin, modified spider silk fibroin is preferable because it is superior in flame retardancy.

［0062］ 改変フィブロインの具体的な例として、 クモの大瓶状腺で産生される大吐 糸管しおり糸タンパク質に由来する改変フィブロイン （第 1の改変フィブロ イン） 、 グリシン残基の含有量が低減されたドメイン配列を有する改変フィ ブロイン （第 2の改変フィブロイン） 、 （八） „モチーフの含有量が低減され たドメイン配列を有する改変フィブロイン （第 3の改変フィブロイン） 、 グ リシン残基の含有量、 及び （ ） „モチーフの含有量が低減された改変フィブ ロイン （第 4の改変フィブロイン） 、 局所的に疎水性指標の大きい領域を含 むドメイン配列を有する改変フィブロイン （第 5の改変フィブロイン） 、 並 びにグルタミン残基の含有量が低減されたドメイン配列を有する改変フィブ ロイン （第 6の改変フィブロイン） が挙げられる。 [0062] As a specific example of the modified fibroin, a modified fibroin (first modified fibroin) derived from a large vesicle guideline thread protein produced in the large ampullate gland of a spider, the content of glycine residues is reduced. Modified fibroin having a modified domain sequence (second modified fibroin), (8) Modified fibroin having a reduced sequence of motif content (third modified fibroin), content of glycine residue , And () „Modified fibroin having a reduced content of motif (fourth modified fibroin), modified fibroin having a domain sequence locally containing a region with a large hydrophobic index (fifth modified fibroin), In addition, modified fibroin (sixth modified fibroin) having a domain sequence with a reduced content of glutamine residues can be mentioned.

［0063］ 第 1の改変フィブロインとしては、 式 1 : ［ （八） „モチーフー［¾巳 ］ で表されるドメイン配列を含むタンパク質が挙げられる。 第 1の改変フィブ ロインにおいて、 （八） „モチーフのアミノ酸残基数は、 3〜 2 0の整数が好 ましく、 4〜 2 0の整数がより好ましく、 8〜 2 0の整数が更に好ましく、 [0063] Examples of the first modified fibroin include a protein containing a domain sequence represented by the formula 1: [(8) "motif-[¾mi]. In the first modified fibroin, the (8)" motif The number of amino acid residues is preferably 3 to 20 integers, more preferably 4 to 20 integers, even more preferably 8 to 20 integers,

1 〇〜 2 0の整数が更により好ましく、 4〜 1 6の整数が更によりまた好ま しく、 8〜 1 6の整数が特に好ましく、 1 0〜 1 6の整数が最も好ましい。 第 1の改変フィブロインは、 式 1中、

Figure imgf000030_0002
巳 を構成するアミノ酸残基の数は 、 1 0〜 2 0 0残基であることが好ましく、 1 0〜 1 5 0残基であることが より好ましく、 2 0〜 1 0 0残基であることが更に好ましく、 2 0〜 7 5残 基であることが更により好ましい。 第 1の改変フィブロインは、 式 1 : ［ （ A） „モチーフーR E P] mで表されるアミノ酸配列中に含まれるグリシン残 基、 セリン残基及びアラニン残基の合計残基数がアミノ酸残基数全体に対し て、 40 %以上であることが好ましく、 60 %以上であることがより好まし く、 70%以上であることが更に好ましい。 An integer of 10 to 20 is even more preferred, an integer of 4 to 16 is even more preferred, an integer of 8 to 16 is particularly preferred, and an integer of 10 to 16 is most preferred. The first modified fibroin has the formula 1
Figure imgf000030_0002
The number of amino acid residues constituting Minami is preferably 10 to 200 residues, more preferably 10 to 150 residues, and 20 to 100 residues. More preferably, it is still more preferably 20 to 75 residual groups. The first modified fibroin has the formula 1 :[ ( A) The total number of residues of glycine residues, serine residues, and alanine residues contained in the amino acid sequence represented by „motif-REP] m is 40% or more of the total number of amino acid residues. It is preferably 60% or more, more preferably 70% or more.

[0064] 第 1の改変フイブロインは、 式 1 : [ （A） nモチーフーR E P] mで表さ れるアミノ酸配列の単位を含み、 かつ C末端配列が配列番号 1〜 3のいずれ かに示されるアミノ酸配列又は配列番号 1〜 3のいずれかに示されるアミノ 酸配列と 90 %以上の相同性を有するアミノ酸配列であるポリべプチドであ ってもよい。 [0064] The first modified fibroin contains a unit of the amino acid sequence represented by the formula 1: [(A) n motif-REP] m , and the C-terminal sequence is an amino acid represented by any of SEQ ID NOs: 1 to 3. It may be a polypeptide which is an amino acid sequence having 90% or more homology to the amino acid sequence shown in the sequence or any of SEQ ID NOs: 1 to 3.

[0065] 配列番号 1 に示されるアミノ酸配列は、 AD F 3 （G I : 1 263287 、 NCB I） のアミノ酸配列の C末端の 50残基のアミノ酸からなるアミノ 酸配列と同一であり、 配列番号 2に示されるアミノ酸配列は、 配列番号 1 に 示されるアミノ酸配列の C末端から 20残基取り除いたアミノ酸配列と同一 であり、 配列番号 3に示されるアミノ酸配列は、 配列番号 1 に示されるアミ ノ酸配列の C末端から 29残基取り除いたアミノ酸配列と同一である。 [0065] The amino acid sequence shown in SEQ ID NO: 1 is the same as the amino acid sequence consisting of the amino acids of the C-terminal 50 residues of the amino acid sequence of AD F 3 (GI: 1 263287, NCBI), and SEQ ID NO: 2 The amino acid sequence shown in is the same as the amino acid sequence shown in SEQ ID NO: 1 with 20 residues removed from the C-terminus, and the amino acid sequence shown in SEQ ID NO: 3 is the amino acid sequence shown in SEQ ID NO: 1. It is identical to the amino acid sequence with 29 residues removed from the C-terminus of the sequence.

[0066] 第 1の改変フイブロインのより具体的な例として、 （ 1 _ i） 配列番号 4 （ r e c om b i n a n t s p i d e r s i I k p r o t e i n A D F 3 K a i L a r g e N R S H 1） で示されるアミノ酸配列、 又は （ 1 - i i） 配列番号 4で示されるアミノ酸配列と 90%以上の配列同一性を有す るアミノ酸配列を含む、 改変フイブロインを挙げることができる。 配列同一 性は、 95 %以上であることが好ましい。 [0066] As a more specific example of the first modified fibroin, an amino acid sequence represented by (1 _ i) SEQ ID NO: 4 (rec om binantspidersi I kprotein ADF 3 K ai Large NRSH 1), or (1-ii) ) A modified fibroin containing an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 4 can be mentioned. The sequence identity is preferably 95% or more.

[0067] 配列番号 4で示されるアミノ酸配列は、 N末端に開始コドン、 H i s 1 0 タグ及び H RV3Cプロテアーゼ （H u m a n r h i n o v i r u s 3 Cプロテアーゼ） 認識サイ トからなるアミノ酸配列 （配列番号 5） を付加し た A D F 3のアミノ酸配列において、 第 1〜 1 3番目の反復領域をおよそ 2 倍になるように増やすとともに、 翻訳が第 1 1 54番目アミノ酸残基で終止 するように変異させたものである。 配列番号 4で示されるアミノ酸配列の C 末端のアミノ酸配列は、 配列番号 3で示されるアミノ酸配列と同一である。 〇 2020/175702 31 卩（：171? 2020 /008524 [0067] The amino acid sequence represented by SEQ ID NO: 4 has an amino acid sequence (SEQ ID NO: 5) consisting of an initiation codon, a His tag and a recognition site for H RV3C protease (Humanrhinovirus 3 C protease) added to the N-terminus. In addition, in the amino acid sequence of ADF3, the 1st to 13th repeat regions were increased to approximately double and the translation was mutated to terminate at the 1154th amino acid residue. The C-terminal amino acid sequence of the amino acid sequence represented by SEQ ID NO: 4 is the same as the amino acid sequence represented by SEQ ID NO: 3. 〇 2020/175 702 31 卩(：171? 2020/008524

[0068] （ 1 - I） の改変フイブロインは、 配列番号 4で示されるアミノ酸配列か らなるものであってもよい。 The modified fibroin of (1-I) may consist of the amino acid sequence represented by SEQ ID NO: 4.

[0069] 第 2の改変フイブロインは、 そのドメイン配列が、 天然由来のフイブロイ ンと比較して、 グリシン残基の含有量が低減されたアミノ酸配列を有する。 第 2の改変フイブロインは、 天然由来のフイブロインと比較して、 少なくと も 巳 中の 1又は複数のグリシン残基が別のアミノ酸残基に置換されたこ とに相当するアミノ酸配列を有するものということができる。 [0069] The second modified fibroin has an amino acid sequence whose domain sequence has a reduced content of glycine residues as compared to naturally occurring fibroin. The second modified fibroin has an amino acid sequence corresponding to at least one glycine residue in at least one amino acid residue substituted with another amino acid residue, as compared with naturally occurring fibroin. You can

[0070] 第 2の改変フイブロインは、 そのドメイン配列が、 天然由来のフイブロイ ンと比較して、

Figure imgf000032_0001
（但し、 ◦はグリシン残基 、 はプロリン残基、 Xはグリシン以外のアミノ酸残基を示す。 ） から選ば れる少なくとも一つのモチーフ配列において、 少なくとも 1又は複数の当該 モチーフ配列中の 1つのグリシン残基が別のアミノ酸残基に置換されたこと に相当するアミノ酸配列を有するものであってもよい。 [0070] The second modified fibroin has a domain sequence that is different from that of naturally occurring fibroin.
Figure imgf000032_0001
(However, ◦ is a glycine residue, is a proline residue, and X is an amino acid residue other than glycine.) In at least one motif sequence, at least one glycine residue in the motif sequence is selected. It may have an amino acid sequence corresponding to substitution of another amino acid residue for a group.

[0071 ] 第 2の改変フイブロインは、 上述のグリシン残基が別のアミノ酸残基に置 換されたモチーフ配列の割合が、 全モチーフ配列に対して、 1 0 %以上であ ってもよい。 [0071] In the second modified fibroin, the proportion of the motif sequence in which the above-mentioned glycine residue is replaced with another amino acid residue may be 10% or more based on the entire motif sequence.

[0072] 第 2の改変フイブロインは、 式 1 : [ （八） „モチーフー [¾巳 ] で表さ れるドメイン配列を含み、 上記ドメイン配列から、 最も 0末端側に位置する （八） „モチーフから上記ドメイン配列の〇末端までの配列を除いた配列中の に含まれる乂〇乂 （但し、 Xはグリシン以外のアミノ酸残基を示す 。 ） からなるアミノ酸配列の総アミノ酸残基数を 2とし、 上記ドメイン配列 から、 最も〇末端側に位置する （八） „モチーフから上記ドメイン配列の〇末 端までの配列を除いた配列中の総アミノ酸残基数を としたときに、

Figure imgf000032_0002
が 3 0 %以上、 4 0 %以上、 5 0 %以上又は 5 0 . 9 %以上であるアミノ酸 配列を有するものであってもよい。 （八） „モチーフ中の全アミノ酸残基数に 対するアラニン残基数は 8 3 %以上であってよいが、 8 6 %以上であること が好ましく、 9 0 %以上であることがより好ましく、 9 5 %以上であること が更に好ましく、 1 0 0 %であること （アラニン残基のみで構成されること 〇 2020/175702 32 卩（：171? 2020 /008524 [0072] The second modified fibroin contains a domain sequence represented by the formula 1: [(8) "motif-[¾mi], and from the above-mentioned domain sequence, the (8)" motif is located at the most 0 terminal side. The total number of amino acid residues in the amino acid sequence consisting of (excluding amino acid residues other than glycine) contained in in the sequence excluding the sequence up to the terminus of the above domain sequence is 2, and When the total number of amino acid residues in the sequence excluding the sequence located from the domain sequence at the most 〇 terminal side (8) □ to the 〇 end of the domain sequence is defined as
Figure imgf000032_0002
May have an amino acid sequence of 30% or more, 40% or more, 50% or more, or 50.9% or more. (8) “The number of alanine residues with respect to the total number of amino acid residues in the motif may be 83% or more, preferably 86% or more, more preferably 90% or more, 95% or more is more preferable, and 100% or more (composed only of alanine residues 〇 2020/175 702 32 卩 (：171? 2020 /008524

を意味する） が更により好ましい。 Is more preferable.

[0073] 第 2の改変フイブロインは、 〇〇乂モチーフの 1つのグリシン残基を別の アミノ酸残基に置換することにより、 乂〇乂からなるアミノ酸配列の含有割 合を高めたものであることが好ましい。 第 2の改変フイブロインは、 ドメイ ン配列中の〇〇乂からなるアミノ酸配列の含有割合が 3 0 %以下であること が好ましく、 2 0 %以下であることがより好ましく、 1 0 %以下であること が更に好ましく、 6 %以下であることが更により好ましく、 4 %以下である ことが更によりまた好ましく、 2 %以下であることが特に好ましい。 ドメイ ン配列中の〇〇乂からなるアミノ酸配列の含有割合は、 下記乂〇乂からなる アミノ酸配列の含有割合 / ） の算出方法と同様の方法で算出すること ができる。 [0073] The second modified fibroin is one in which the content ratio of the amino acid sequence consisting of XX is increased by substituting one glycine residue of the X motif for another amino acid residue. Is preferred. In the second modified fibroin, the content rate of the amino acid sequence consisting of XX in the domain sequence is preferably 30% or less, more preferably 20% or less, and more preferably 10% or less. Is more preferable, 6% or less is still more preferable, 4% or less is still more preferable, and 2% or less is particularly preferable. The content rate of the amino acid sequence consisting of XX in the domain sequence can be calculated by the same method as the method of calculating the content rate of the amino acid sequence consisting of XX below / ).

[0074] の算出方法を更に詳細に説明する。 まず、 式 1 : [ （八） „モチーフ [0074] The calculation method of will be described in more detail. First, formula 1: [(8) „motif

_ 8巳 ] で表されるドメイン配列を含むフイブロイン （改変フイブロイン 又は天然由来のフイブロイン） において、 ドメイン配列から、 最も <3末端側 に位置する （八） „モチーフからドメイン配列の〇末端までの配列を除いた配 列に含まれる全ての 巳 から、 乂〇乂からなるアミノ酸配列を抽出する。 乂〇乂を構成するアミノ酸残基の総数が 2である。 例えば、 乂〇乂からなる アミノ酸配列が 5 0個抽出された場合 （重複はなし） 、 2は 5 0 X 3 = 1 5 0である。 また、 例えば、 乂〇乂〇乂からなるアミノ酸配列の場合のように 2つの乂〇乂に含まれる X （中央の X） が存在する場合は、 重複分を控除し て計算する （乂〇乂〇乂の場合は 5アミノ酸残基である） 。 は、 ドメイン 配列から、 最も 0末端側に位置する （八） モチーフからドメイン配列の〇末 端までの配列を除いた配列に含まれる総アミノ酸残基数である。 例えば、 図 5に示したドメイン配列の場合、 は 4 + 5 0 + 4 + 1 0 0 + 4 + 1 0 + 4 + 2 0 + 4 + 3 0 = 2 3 0である （最も〇末端側に位置する （八） „モチーフ は除いている。 ） 。 次に、 åを で除すことによって、

Figure imgf000033_0001
（%） を算出 することができる。 In a fibroin (modified fibroin or naturally-occurring fibroin) containing a domain sequence represented by [_8], the sequence from the domain sequence to the most <3 terminal side (8) The amino acid sequence consisting of 乂 乂 is extracted from all the sequences included in the sequence, except that the total number of amino acid residues constituting 乂 〇 is 2. For example, the amino acid sequence consisting of When 50 pieces are extracted (no duplication), 2 is 5 0 X 3 = 1 50. Also, for example, it is included in two pairs as in the case of an amino acid sequence consisting of 乂 〇 乂 〇 乂. If there is an X (central X), it is calculated by subtracting the overlap (in the case of 乂 〇 乂 〇, it is 5 amino acid residues). is located at the 0-most position from the domain sequence. (8) The total number of amino acid residues contained in the sequence excluding the sequence from the motif to the end of the domain sequence.For example, in the case of the domain sequence shown in Fig. 5, is 4 + 5 0 + 4 + 1 0 0 + 4 + 1 0 + 4 + 2 0 + 4 + 3 0 = 2 3 0 ((8) „most located on the terminal side is excluded.). Then by dividing by
Figure imgf000033_0001
(%) can be calculated.

[0075] ここで、 天然由来のフイブロインにおける

Figure imgf000033_0002
について説明する。 まず 〇 2020/175702 33 卩（：171? 2020 /008524 [0075] Here, in the naturally-derived fibroin
Figure imgf000033_0002
Will be described. First 〇 2020/175 702 33 卩(：171? 2020/008524

、 上述のように、 1\1〇巳 丨 G e n B a n kにアミノ酸配列情報が登録され ているフィブロインを例示した方法により確認したところ、 6 6 3種類のフ ィブロイン （このうち、 クモ類由来のフィブロインは 4 1 5種類） が抽出さ れた。 抽出された全てのフィブロインのうち、 式 1 : ［ （八） „モチーフー 巳 ］ で表されるドメイン配列を含み、 フィブロイン中の〇〇乂からなるア ミノ酸配列の含有割合が 6 %以下である天然由来のフィブロインのアミノ酸 配列から、 上述の算出方法により、

Figure imgf000034_0001
を算出した。 その結果を図 6に示 す。 図 6の横軸は å /% （%） を示し、 縦軸は頻度を示す。 図 6から明らか なとおり、 天然由来のフィブロインにおける 2 / は、 いずれも 5〇. 9 % 未満である （最も高いもので、 5 0 . 8 6 %） 。 , As mentioned above, the method was confirmed by exemplifying the fibroin whose amino acid sequence information was registered in 1\10 跳 丨 Gen B ank, and it was confirmed that 6 6 3 types of fibroin (of which spiders Fibroin was extracted (415 kinds). Among all the extracted fibroins, the content of the amino acid sequence consisting of XX is 6% or less in the fibroin, which contains the domain sequence represented by the formula 1: [(8) „Motif MIN”]. From the amino acid sequence of naturally-occurring fibroin, by the above calculation method,
Figure imgf000034_0001
Was calculated. The results are shown in Figure 6. The horizontal axis of FIG. 6 represents%/% (%), and the vertical axis represents frequency. As is clear from Fig. 6, 2 / in naturally-occurring fibroin was less than 50.9% (the highest was 50.86%).

［0076］ 第 2の改変フィブロインにおいて、

Figure imgf000034_0002
5〇. 9 %以上であること が好ましく、 5 6 . 1 %以上であることがより好ましく、 5 8 . 7 %以上で あることが更に好ましく、 7 0 %以上であることが更により好ましく、 8 0 %以上であることが更によりまた好ましい。 å / の上限に特に制限はない が、 例えば、 9 5 %以下であってもよい。 [0076] In the second modified fibroin,
Figure imgf000034_0002
It is preferably at least 50.9%, more preferably at least 56.1%, even more preferably at least 58.7%, even more preferably at least 70%, Even more preferably, it is 80% or more. The upper limit of / is not particularly limited, but may be, for example, 95% or less.

［0077］ 第 2の改変フィブロインは、 例えば、 クローニングした天然由来のフィブ ロインの遺伝子配列から、 グリシン残基をコードする塩基配列の少なくとも —部を置換して別のアミノ酸残基をコードするように改変することにより得 ることができる。 このとき、 改変するグリシン残基として、 〇〇乂モチーフ 及び◦ 〇乂乂モチーフにおける 1つのグリシン残基を選択してもよいし、 また å / が 5 0 . 9 %以上になるように置換してもよい。 また、 例えば、 天然由来のフィブロインのアミノ酸配列から上記態様を満たすアミノ酸配列 を設計し、 設計したアミノ酸配列をコードする核酸を化学合成することによ り得ることもできる。 いずれの場合においても、 天然由来のフィブロインの アミノ酸配列から 巳 中のグリシン残基を別のアミノ酸残基に置換したこ とに相当する改変に加え、 更に 1又は複数のアミノ酸残基を置換、 欠失、 揷 入及び/又は付加したことに相当するアミノ酸配列の改変を行ってもよい。 [0077] The second modified fibroin may be obtained, for example, by substituting at least part of the nucleotide sequence encoding a glycine residue from the cloned gene sequence of naturally-occurring fibroin to encode another amino acid residue. It can be obtained by modification. At this time, as the glycine residue to be modified, one glycine residue in the ◯◯ and ◯ ◯ 乂乂 motifs may be selected, or the glycine residue may be substituted so that the ratio / becomes 50.9% or more. May be. Alternatively, it can be obtained, for example, by designing an amino acid sequence satisfying the above embodiment from the amino acid sequence of naturally-occurring fibroin and chemically synthesizing a nucleic acid encoding the designed amino acid sequence. In each case, in addition to the modification corresponding to the substitution of the glycine residue in the amino acid sequence with another amino acid residue from the amino acid sequence of naturally-occurring fibroin, one or more amino acid residues were substituted or deleted. The amino acid sequence corresponding to the loss, insertion and/or addition may be modified.

［0078］ 上記の別のアミノ酸残基としては、 グリシン残基以外のアミノ酸残基であ 〇 2020/175702 34 卩（：171? 2020 /008524 [0078] The above-mentioned another amino acid residue is an amino acid residue other than a glycine residue. 〇 2020/175 702 34 卩 (: 171? 2020 /008524

れば特に制限はないが、 パリン （V） 残基、 ロイシン （1_） 残基、 イソロイ シン （丨） 残基、 メチオニン （IV!） 残基、 プロリン （ ） 残基、 フヱニルア ラニン （ ） 残基及びトリブトファン ） 残基等の疎水性アミノ酸残基、 グルタミン （〇） 残基、 アスパラギン （1\1） 残基、 セリン （3） 残基、 リシ ン （<） 残基及びグルタミン酸 （巳） 残基等の親水性アミノ酸残基が好まし く、 パリン （V） 残基、 ロイシン （1_） 残基、 イソロイシン （ I） 残基、 フ エニルアラニン （ ） 残基及びグルタミン （0） 残基がより好ましく、 グル タミン （〇） 残基が更に好ましい。 There is no particular limitation as long as it is a parine (V) residue, a leucine (1_) residue, an isoleucine (丨) residue, a methionine (IV!) residue, a proline () residue, a phenylalanine () residue. And tributophan) residues, etc., hydrophobic amino acid residues, glutamine (〇) residues, asparagine (1\1) residues, serine (3) residues, lysine (<) residues and glutamic acid (Mitsu) residues Hydrophilic amino acid residues are preferred, and parine (V) residues, leucine (1_) residues, isoleucine (I) residues, phenylalanine () residues and glutamine (0) residues are more preferred. , Glutamine (O) residues are more preferred.

[0079] 第 2の改変フィブロインのより具体的な例として、 （2_ 丨） 配列番号 6 （1\/161： -? [¾丁380） 、 配列番号 7 （1\/161： -? [¾丁4 1 0） 、 配列番 号 8 （1\/161： -? [¾丁 525） 若しくは配列番号 9 （1\/161： -? [¾丁 799 ） で示されるアミノ酸配列、 又は （2— 丨 丨） 配列番号 6、 配列番号 7、 配 列番号 8若しくは配列番号 9で示されるアミノ酸配列と 90 %以上の配列同 —性を有するアミノ酸配列を含む、 改変フィブロインを挙げることができる [0079] As a more specific example of the second modified fibroin, (2_丨) SEQ ID NO: 6 (1\/161: -? [¾ 380), SEQ ID NO: 7 (1\/161: -? [¾ Ding 4 10), SEQ ID NO: 8 (1\/161: -? [¾ 525) or SEQ ID NO: 9 (1\/161: -? [¾ 799), or (2—丨 丨) Modified fibroin containing an amino acid sequence having 90% or more sequence homology with the amino acid sequence shown by SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9 can be mentioned.

[0080] （2 - I） の改変フィブロインについて説明する。 配列番号 6で示される アミノ酸配列は、 天然由来のフィブロインに相当する配列番号 1 〇 （1\/16

Figure imgf000035_0001
で示されるアミノ酸配列の 巳 中の全ての〇〇乂を◦〇 Xに置換したものである。 配列番号 7で示されるアミノ酸配列は、 配列番号 6で示されるアミノ酸配列から、 末端側から 0末端側に向かって 2つおき に （八） „モチーフを欠失させ、 更に〇末端配列の手前に [ （八） „モチーフ を 1つ揷入したものである。 配列番号 8で示されるアミノ酸配列 は、 配列番号 7で示されるアミノ酸配列の各 （ ） „モチーフの〇末端側に 2 つのアラニン残基を挿入し、 更に一部のグルタミン （〇） 残基をセリン （3 ） 残基に置換し、 配列番号 7の分子量とほぼ同じとなるように〇末端側の一 部のアミノ酸を欠失させたものである。 配列番号 9で示されるアミノ酸配列 は、 配列番号 7で示されるアミノ酸配列中に存在する 20個のドメイン配列 の領域 （但し、 当該領域の <3末端側の数アミノ酸残基が置換されている。 ） 〇 2020/175702 35 卩（：171? 2020 /008524 [0080] The modified fibroin of (2-I) will be described. Amino acid sequence is shown in SEQ ID NO: 6, SEQ ID NO: 1 〇 corresponding to fibroin naturally occurring (1 \ / 1 6
Figure imgf000035_0001
All of the amino acids in the amino acid sequence represented by are replaced with ◯○X. The amino acid sequence represented by SEQ ID NO: 7 is the amino acid sequence represented by SEQ ID NO: 6 with two (8) „motifs deleted from the terminal side toward the 0 terminal side, and further before the 〇 terminal sequence. [(8) □ One motif is included. The amino acid sequence represented by SEQ ID NO: 8 is obtained by inserting two alanine residues at the 〇 terminal side of each () „motif of the amino acid sequence represented by SEQ ID NO: 7, and further adding a part of glutamine (〇) residues to serine. (3) The amino acid sequence shown in SEQ ID NO: 9 is obtained by substituting a residue and deleting a part of the amino acid at the 〇 terminal so that the molecular weight is almost the same as that of SEQ ID NO: 7. Regions of 20 domain sequences present in the amino acid sequence shown by 7 (however, some amino acid residues on the <3 terminal side of the region are replaced.) 〇 2020/175 702 35 卩 (：171? 2020 /008524

を 4回繰り返した配列の〇末端に所定のヒンジ配列と 1~1 丨 3タグ配列が付加 されたものである。 It is a sequence in which a predetermined hinge sequence and 1 to 1 to 3 tag sequences are added to the O-terminal of the sequence repeated 4 times.

[0081] 配列番号 1 0で示されるアミノ酸配列 （天然由来のフイブロインに相当） における

Figure imgf000036_0001
の値は、 46. 8%である。 配列番号 6で示されるアミノ酸 配列、 配列番号 7で示されるアミノ酸配列、 配列番号 8で示されるアミノ酸 配列、 及び配列番号
Figure imgf000036_0002
の値は、 それ それ 58. 7%、 7〇. 1 %、 66. 1 %及び 7〇. 0%である。 また、 配 列番号 1 〇、 配列番号 6、 配列番号 7、 配列番号 8及び配列番号 9で示され るアミノ酸配列のギザ比率 （後述する） 1 : 1. 8〜 1 1. 3における X/ Vの値は、 それぞれ 1 5. 0%、 1 5. 0%、 93. 4%、 92. 7 %及び 89. 8%である。 [0081] In the amino acid sequence represented by SEQ ID NO: 10 (corresponding to naturally occurring fibroin)
Figure imgf000036_0001
The value of is 46.8%. The amino acid sequence represented by SEQ ID NO: 6, the amino acid sequence represented by SEQ ID NO: 7, the amino acid sequence represented by SEQ ID NO: 8, and the SEQ ID NO:
Figure imgf000036_0002
The values are 58.7%, 70.1%, 66.1% and 7.0%, respectively. In addition, the serrated ratio of the amino acid sequences shown in SEQ ID NO: 10, SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 and SEQ ID NO: 9 (described later) 1: 1.8 to 1 1.3 X/V The values of 15.0%, 15.0%, 93.4%, 92.7% and 89.8%, respectively.

[0082] （2 - I） の改変フイブロインは、 配列番号 6、 配列番号 7、 配列番号 8 又は配列番号 9で示されるアミノ酸配列からなるものであってもよい。 The modified fibroin of (2-I) may consist of the amino acid sequence shown in SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9.

[0083] （2 - I I） の改変フイブロインは、 配列番号 6、 配列番号 7、 配列番号 [0083] The modified fibroin of (2-II) has SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO:

8又は配列番号 9で示されるアミノ酸配列と 90%以上の配列同一性を有す るアミノ酸配列を含むものである。 （2- 丨 丨） の改変フイブロインもまた 、 式 1 : [ （八） „モチーフー [¾巳 ] で表されるドメイン配列を含むタン パク質である。 上記配列同一性は、 95%以上であることが好ましい。 8 or an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 9. The modified fibroin of (2-丨丨) is also a protein containing the domain sequence represented by the formula 1: [(8) "motif [¾mi]. The sequence identity is 95% or more. It is preferable.

[0084] （2 - I I） の改変フイブロインは、 配列番号 6、 配列番号 7、 配列番号 [0084] The modified fibroin of (2-II) has SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO:

8又は配列番号 9で示されるアミノ酸配列と 90%以上の配列同一性を有し 、 かつ 巳 中に含まれる乂〇乂 （但し、 Xはグリシン以外のアミノ酸残基 を示す。 ） からなるアミノ酸配列の総アミノ酸残基数を 2とし、 上記ドメイ ン配列中の 巳 の総アミノ酸残基数を としたときに、

Figure imgf000036_0003
が 50. 9 %以上であることが好ましい。 8 or an amino acid sequence having a sequence identity of 90% or more with the amino acid sequence represented by SEQ ID NO: 9 and consisting of ##STR3## (where X represents an amino acid residue other than glycine). If the total number of amino acid residues in is 2 and the total number of amino acid residues in the above domain is,
Figure imgf000036_0003
Is preferably 50.9% or more.

[0085] 第 2の改変フイブロインは、 1\!末端及び◦末端のいずれか一方又は両方に タグ配列を含んでいてもよい。 これにより、 改変フイブロインの単離、 固定 化、 検出及び可視化等が可能となる。 [0085] The second modified fibroin may include a tag sequence at either or both of the 1\! end and the O end. This enables the isolation, immobilization, detection and visualization of the modified fibroin.

[0086] タグ配列として、 例えば、 他の分子との特異的親和性 （結合性、 アフイニ 〇 2020/175702 36 卩（：171? 2020 /008524 [0086] As the tag sequence, for example, specific affinity with other molecule (binding, affinity 〇 2020/175 702 36 卩 (：171? 2020 /008524

ティ） を利用したアフィニティタグを挙げることができる。 アフィニティタ グの具体例として、 ヒスチジンタグ （1~1 丨 3タグ） を挙げることができる。Affinity tags using A specific example of the affinity tag is a histidine tag (1 to 1 3 tags).

1~1 丨 3タグは、 ヒスチジン残基が 4から 1 0個程度並んだ短いペプチドで、 ニッケル等の金属イオンと特異的に結合する性質があるため、 金属キレート クロマトグラフィー

Figure imgf000037_0001
1 to 1 3 tags are short peptides in which about 4 to 10 histidine residues are lined up, and because they have the property of specifically binding to metal ions such as nickel, metal chelate chromatography
Figure imgf000037_0001

9

Figure imgf000037_0002
による改変フィブロインの単離に利用することができる。 夕 グ配列の具体例として、 例えば、 配列番号 1 1で示されるアミノ酸配列 （ ! !9
Figure imgf000037_0002
Can be used for isolation of modified fibroin. As a specific example of the coding sequence, for example, the amino acid sequence (!!

） タグ配列及びヒンジ配列を含むアミノ酸配列） が挙げられる。 ) Amino acid sequence including tag sequence and hinge sequence).

[0087] また、 グルタチオンに特異的に結合するグルタチオンー 3 -トランスフエ ラーゼ （0 3丁） 、 マルトースに特異的に結合するマルトース結合タンパク 質 （1\/1巳 ） 等のタグ配列を利用することもできる。 [0087] Further, use of tag sequences such as glutathione-3-transferase (03) that specifically binds to glutathione and maltose binding protein (1\/1M) that specifically binds to maltose. Can also

[0088] さらに、 抗原抗体反応を利用した 「エピトープタグ」 を利用することもで きる。 抗原性を示すペプチド （エピトープ） をタグ配列として付加すること により、 当該エピトープに対する抗体を結合させることができる。 エピトー プタグとして、 1~1八 （インフルエンザウイルスのへマグルチニンのペプチド 配列） タグ、

Figure imgf000037_0003
タグ、 !_八〇タグ等を挙げることができる。 エピトー プタグを利用することにより、 高い特異性で容易に改変フィブロインを精製 することができる。 [0088] Furthermore, an "epitope tag" utilizing an antigen-antibody reaction can also be used. By adding a peptide (epitope) showing antigenicity as a tag sequence, an antibody against the epitope can be bound. As an epitope tag, 1 to 18 (influenza virus hemagglutinin peptide sequence) tag,
Figure imgf000037_0003
Tags, !_80 tags, etc. can be mentioned. The modified fibroin can be easily purified with high specificity by using the epitope tag.

[0089] さらにタグ配列を特定のプロテアーゼで切り離せるようにしたものも使用 することができる。 当該タグ配列を介して吸着したタンパク質をプロテアー ゼ処理することにより、 タグ配列を切り離した改変フィブロインを回収する こともできる。 [0089] Furthermore, a tag sequence that can be cleaved with a specific protease can also be used. By treating the protein adsorbed via the tag sequence with a protease, the modified fibroin from which the tag sequence is cleaved can be recovered.

[0090] タグ配列を含む改変フィブロインのより具体的な例として、 （2— 丨 丨 I [0090] As a more specific example of modified fibroin containing a tag sequence, (2—丨丨I

） 配列番号 1 2

Figure imgf000037_0004
配列番号 1 3 （ 丁 4 1 0） 、 配列番 号 1 4 （ [¾丁 5 2 5） 若しくは配列番号 1 5 （ 丁 7 9 9） で示される アミノ酸配列、 又は （2— 丨 V） 配列番号 1 2、 配列番号 1 3、 配列番号 1 4若しくは配列番号 1 5で示されるアミノ酸配列と 9 0 %以上の配列同一性 を有するアミノ酸配列を含む、 改変フィブロインを挙げることができる。 〇 2020/175702 37 卩（：171? 2020 /008524 ) SEQ ID NO: 1 2
Figure imgf000037_0004
The amino acid sequence represented by SEQ ID NO: 13 (Cho 4 1 0), SEQ ID NO: 14 ([¾ 5 25) or SEQ ID NO: 15 (C D 7 9 9), or (2 — V) SEQ ID No. Examples include modified fibroin containing an amino acid sequence having a sequence identity of 90% or more with the amino acid sequence represented by 12, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15. 〇 2020/175 702 37 卩 (：171? 2020 /008524

[0091 ] 配列番号 1 6 （ [¾丁3 1 3） 、 配列番号 1 2、 配列番号 1 3、 配列番号 [0091] SEQ ID NO: 16 ([¾ 3 1 3), SEQ ID NO: 12, SEQ ID NO: 13, SEQ ID NO:

1 4及び配列番号 1 5で示されるアミノ酸配列は、 それぞれ配列番号 1 0、 配列番号 6、 配列番号 7、 配列番号 8及び配列番号 9で示されるアミノ酸配 列の 1\1末端に配列番号 1 1で示されるアミノ酸配列 （1~1 丨 3タグ配列及びヒ ンジ配列を含む） を付加したものである。 14 and SEQ ID NO: 15 have the amino acid sequences shown in SEQ ID NO: 10 and SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 and SEQ ID NO: 9, respectively. The amino acid sequence shown in 1 (including 1 to 1 3 tag sequences and hinge sequences) is added.

[0092] （2 - I I I） の改変フィブロインは、 配列番号 1 2、 配列番号 1 3、 配 列番号 1 4又は配列番号 1 5で示されるアミノ酸配列からなるものであって もよい。 The modified fibroin of (2-I I I) may consist of the amino acid sequence shown in SEQ ID NO: 12, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15.

[0093] （2 - I V） の改変フィブロインは、 配列番号 1 2、 配列番号 1 3、 配列 番号 1 4又は配列番号 1 5で示されるアミノ酸配列と 9 0 %以上の配列同一 性を有するアミノ酸配列を含むものである。 （2 - 丨 V） の改変フィブロイ ンもまた、 式 1 : [ （八） „モチーフー^?巳 ] で表されるドメイン配列を 含むタンパク質である。 上記配列同一性は、 9 5 %以上であることが好まし い。 [0093] The modified fibroin of (2-IV) is an amino acid sequence having a sequence identity of 90% or more with the amino acid sequence represented by SEQ ID NO: 12, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15. Is included. The modified fibroin of (2-V) is also a protein containing a domain sequence represented by the formula 1: [(8) "motif ^?M]. The above sequence identity is 95% or more. I like that.

[0094] （2 - I V） の改変フィブロインは、 配列番号 1 2、 配列番号 1 3、 配列 番号 1 4又は配列番号 1 5で示されるアミノ酸配列と 9 0 %以上の配列同一 性を有し、 かつ 巳 中に含まれる乂〇乂 （但し、 Xはグリシン以外のアミ ノ酸残基を示す。 ） からなるアミノ酸配列の総アミノ酸残基数を 2とし、 上 記ドメイン配列中の 巳 の総アミノ酸残基数を としたときに、

Figure imgf000038_0001
が 5 0 . 9 %以上であることが好ましい。 [0094] The modified fibroin of (2-IV) has a sequence identity of 90% or more with the amino acid sequence represented by SEQ ID NO: 12, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15, And the total number of amino acids in the above-mentioned domain sequence is 2, with the total number of amino acid residues in the amino acid sequence consisting of the sequences (where X represents an amino acid residue other than glycine) contained in When the number of residues is
Figure imgf000038_0001
Is preferably 50.9% or more.

[0095] 第 2の改変フィブロインは、 組換えタンパク質生産系において生産された タンパク質を宿主の外部に放出するための分泌シグナルを含んでいてもよい 。 分泌シグナルの配列は、 宿主の種類に応じて適宜設定することができる。 [0095] The second modified fibroin may contain a secretory signal for releasing the protein produced in the recombinant protein production system to the outside of the host. The sequence of the secretion signal can be appropriately set depending on the type of host.

[0096] 第 3の改変フィブロインは、 そのドメイン配列が、 天然由来のフィブロイ ンと比較して、 （八） „モチーフの含有量が低減されたアミノ酸配列を有する 。 第 3の改変フィブロインのドメイン配列は、 天然由来のフィブロインと比 較して、 少なくとも 1又は複数の （八） モチーフが欠失したことに相当する アミノ酸配列を有するものということができる。 〇 2020/175702 38 卩（：171? 2020 /008524 [0096] The domain sequence of the third modified fibroin has (8) an amino acid sequence in which the content of the „motif is reduced as compared with naturally-occurring fibroin. Can be said to have an amino acid sequence corresponding to the deletion of at least one or a plurality of (8) motifs as compared with naturally occurring fibroin. 〇 2020/175 702 38 卩 (: 171? 2020 /008524

［0097］ 第 3の改変フイブロインは、 天然由来のフイブロインから （八） モチーフ を 1 0〜 4 0 %欠失させたことに相当するアミノ酸配列を有するものであっ てもよい。 [0097] The third modified fibroin may have an amino acid sequence corresponding to the (8) motif deleted from naturally occurring fibroin by 10 to 40%.

［0098］ 第 3の改変フイブロインは、 そのドメイン配列が、 天然由来のフイブロイ ンと比較して、 少なくとも 1\1末端側から（3末端側に向かって 1〜 3つの （八 ） „モチーフ毎に 1つの （八） „モチーフが欠失したことに相当するアミノ酸 配列を有するものであってもよい。 [0098] The third modified fibroin has a domain sequence at least from the 1\1 terminal side (1 to 3 (8) each toward the 3 terminal side) compared to the naturally occurring fibroin. It may have an amino acid sequence corresponding to the deletion of one (8)* motif.

［0099］ 第 3の改変フイブロインは、 そのドメイン配列が、 天然由来のフイブロイ ンと比較して、 少なくとも 1\1末端側から（3末端側に向かって 2つ連続した （ 八） „モチーフの欠失、 及び 1つの （八） „モチーフの欠失がこの順に繰り返 されたことに相当するアミノ酸配列を有するものであってもよい。 [0099] The third modified fibroin has a domain sequence that is at least from the 1\1 terminal side (two consecutive (8) (8)) motifs are missing from the naturally occurring fibroin. It may have an amino acid sequence corresponding to the deletion, and the deletion of one (8)′ motif repeated in this order.

［0100］ 第 3の改変フイブロインは、 そのドメイン配列が、 少なくとも 1\1末端側か ら〇末端側に向かって 2つおきに （八） „モチーフが欠失したことに相当する アミノ酸配列を有するものであってもよい。 [0100] The third modified fibroin has an amino acid sequence whose domain sequence corresponds to deletion of at least every two (8) „motifs from the 1\1 terminal side toward the 0 terminal side. It may be one.

［0101］ 第 3の改変フイブロインは、 式 1 : ［ （八） „モチーフー^?巳 ］ で表さ れるドメイン配列を含み、 1\1末端側から（3末端側に向かって、 隣合う 2つの ［ （八）

Figure imgf000039_0001
ユニッ トの 巳 のアミノ酸残基数を順次比較 して、 アミノ酸残基数が少ない
Figure imgf000039_0002
のアミノ酸残基数を 1 としたとき、 他 方の 巳 のアミノ酸残基数の比が 1 . 8〜 1 1 . 3となる隣合う 2つの ［ （八） „モチーフー［¾巳 ］ ユニッ トのアミノ酸残基数を足し合わせた合計値 の最大値を Xとし、 ドメイン配列の総アミノ酸残基数を Vとしたときに、 X / Vが 2 0 %以上、 3 0 %以上、 4 0 %以上又は 5 0 %以上であるアミノ酸 配列を有するものであってもよい。 （八） „モチーフ中の全アミノ酸残基数に 対するアラニン残基数は 8 3 %以上であってよいが、 8 6 %以上であること が好ましく、 9 0 %以上であることがより好ましく、 9 5 %以上であること が更に好ましく、 1 0 0 %であること （アラニン残基のみで構成されること を意味する） が更により好ましい。 [0101] The third modified fibroin contains a domain sequence represented by the formula 1: [(8) „motif ^?mi ], and from the 1\1 terminal side (to the 3 terminal side, two adjacent two [ (Eight)
Figure imgf000039_0001
The number of amino acid residues in the unit of the unit is sequentially compared, and the number of amino acid residues is small.
Figure imgf000039_0002
When the number of amino acid residues in the other is 1, the ratio of the number of amino acid residues in the other is 1.8 to 11.3, and the ratio of the two adjacent [(8) „motif-[¾mi] units is X/V is 20% or more, 30% or more, 40% or more, where X is the maximum total value of the total number of amino acid residues and V is the total number of amino acid residues in the domain sequence. Alternatively, it may have an amino acid sequence of 50% or more.(8) “The number of alanine residues with respect to the total number of amino acid residues in the motif may be 83% or more, but 86% It is preferably not less than 90%, more preferably not less than 90%, still more preferably not less than 95%, and not less than 100% (meaning that it is composed of only alanine residues). Are even more preferred.

［0102］ 父/ソの算出方法を図 5を参照しながら更に詳細に説明する。 図 5には、 〇 2020/175702 39 卩（：171? 2020 /008524 [0102] The father/so calculation method will be described in more detail with reference to FIG. In Figure 5, 〇 2020/175 702 39 卩 (: 171-1? 2020 /008524

改変フィブロインから 1\1末端配列及び（3末端配列を除いたドメイン配列を示 す。 当該ドメイン配列は、 1\1末端側 （左側） から （八） „モチーフー第 1の 巳 （5 0アミノ酸残基） 一 （八） „モチーフー第 2の 巳 （ 1 0 0アミノ 酸残基） 一 （八）

Figure imgf000040_0001
（1 0アミノ酸残基） 一 （八） „ モチーフー第
Figure imgf000040_0002
（ 2 0アミノ酸残基） 一 （八） „モチ—フー第 5の 巳 （3 0アミノ酸残基） 一 （八） nモチーフという配列を有する。 The 1\1 terminal sequence and the domain sequence excluding the 3 terminal sequence from the modified fibroin are shown. The domain sequence is from the 1\1 terminal side (left side) to (8) Group) 1 (8) „Motif-second mine (100 amino acid residue) 1 (8)
Figure imgf000040_0001
(10 amino acid residues) 1 (8) „Motif-No.
Figure imgf000040_0002
(20 amino acid residues) 1 (8) „Mochi-Fu 5th Min (30 amino acid residues) 1 (8) n Motif has a sequence.

［0103］ 隣合う 2つの ［ （八） „モチーフー［¾巳 ］ ユニッ トは、 重複がないように 、 1\1末端側から（3末端側に向かって、 順次選択する。 このとき、 選択されな い ［ （八） „モチーフー ^巳 ］ ユニッ トが存在してもよい。 図 5には、 パタ —ン 1 （第 1の 巳 と第 2の 巳 の比較、 及び第

Figure imgf000040_0003
[0103] Two adjacent [(8) „Motifs [¾mi] units are selected sequentially from the 1\1 end side (towards the 3 end side so that they do not overlap. At this time, they are selected. There may be a [(8) „Motif^Mimi” unit. In Fig. 5, pattern 1 (comparison of 1st and 2nd Min, and
Figure imgf000040_0003

巳 の比較） 、 パターン 2

Figure imgf000040_0004
及び第 4 の 巳 と第 5の 巳 の比較） 、 バターン 3
Figure imgf000040_0005
Comparison of Mami), pattern 2
Figure imgf000040_0004
And comparison of the 4th and the 5th), Bataan 3
Figure imgf000040_0005

の比較、 及び第 4の 巳 と第 5の 巳 の比較） 、 バターン 4 （第 1の 巳 と第 2の 巳 の比較） を示した。 なお、 これ以外にも選択方法は存 在する。 And Bataan 4 (comparison between 1st and 2nd Mitsumi), and 4th and 5th Mitsumi). There are other selection methods besides this.

［0104］ 次に各パターンについて、 選択した隣合う 2つの ［ （八） „モチーフー ^巳 ］ ユニッ ト中の各 巳 のアミノ酸残基数を比較する。 比較は、 よりアミ ノ酸残基数の少ない方を 1 としたときの、 他方のアミノ酸残基数の比を求め ることによって行う。 例えば、

Figure imgf000040_0006
（5 0アミノ酸残基） と第 2の 合、 よりアミノ酸残基数の少ない
Figure imgf000040_0007
のアミノ酸残基数の比は、 1 0 0 / 5 0 = 2である。 同様に、
Figure imgf000040_0008
（2 0アミノ酸残基） と第 5の 合、 よりアミノ酸残基数の少ない第
Figure imgf000040_0009
のアミノ酸残基数の比は、 3 0 /[0104] Next, for each pattern, the number of amino acid residues in each of the two adjacent [(8) „Motif ^^] units selected is compared. This is done by finding the ratio of the number of amino acid residues of the other when the smaller one is 1. For example:
Figure imgf000040_0006
(50 amino acid residues) and the second, the number of amino acid residues is smaller
Figure imgf000040_0007
The ratio of the number of amino acid residues in is 100/50=2. Similarly,
Figure imgf000040_0008
(20 amino acid residues) and the fifth, the number of amino acid residues with a smaller number
Figure imgf000040_0009
The ratio of the number of amino acid residues in

2 0 = 1 . 5である。 20 = 1.5.

［0105］ 図 5中、 よりアミノ酸残基数の少ない方を 1 としたときに、 他方のアミノ 酸残基数の比が 1 . 8〜 1 1 . 3となる ［ （八） „モチーフー［¾巳 ］ ユニッ 卜の組を実線で示した。 本明細書中、 この比をギザ比率と呼ぶ。 よりアミノ 〇 2020/175702 40 卩（：171? 2020 /008524 [0105] In FIG. 5, when the number of amino acid residues is smaller, the ratio of the number of amino acid residues on the other side is 1.8 to 11.3 [(8) "Motif-[¾ Min]] A set of units is shown by a solid line.In the present specification, this ratio is called a "giza ratio". 〇 2020/175 702 40 卩 (：171? 2020 /008524

酸残基数の少ない方を 1 としたときに、 他方のアミノ酸残基数の比が 1 . 8 未満又は 1 1 . 3超となる ［ （八） „モチーフー［¾巳 ］ ユニッ トの組は破線 で示した。 The ratio of the number of amino acid residues on the other side is less than 1.8 or more than 11.3 when the one with the smaller number of acid residues is set to 1 [8] „Motif-[¾mi] unit pair is It is indicated by a broken line.

［0106］ 各バターンにおいて、 実線で示した隣合う 2つの ［ （八） „モチーフー［¾巳 ］ ユニッ トの全てのアミノ酸残基数を足し合わせる （［¾巳 のみではなく 、 （八） „モチーフのアミノ酸残基数もである。 ） 。 そして、 足し合わせた合 計値を比較して、 当該合計値が最大となるパターンの合計値 （合計値の最大 値） を Xとする。 図 5に示した例では、 バターン 1の合計値が最大である。 [0106] In each pattern, the total number of amino acid residues in the two adjacent [(8) "motifs-[¾mi] units indicated by the solid line is added together ([not only in (¾mi, (8)" motifs Is also the number of amino acid residues. Then, the sum of the added values is compared, and the total value of the pattern with the maximum total value (maximum total value) is set as X. In the example shown in Fig. 5, the total value of pattern 1 is the maximum.

［0107］ 次に、 Xをドメイン配列の総アミノ酸残基数ソで除すことによって、 X / [0107] Then, by dividing X by the total number of amino acid residues in the domain sequence, X /

V （%） を算出することができる。 V (%) can be calculated.

［0108］ 第 3の改変フィブロインにおいて、 父/ソは、 5 0 %以上であることが好 ましく、 6 0 %以上であることがより好ましく、 6 5 %以上であることが更 に好ましく、 7 0 %以上であることが更により好ましく、 7 5 %以上である ことが更によりまた好ましく、 8 0 %以上であることが特に好ましい。 X / [0108] In the third modified fibroin, the ratio of father/so is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, It is even more preferably 70% or more, even more preferably 75% or more, and particularly preferably 80% or more. X /

Vの上限に特に制限はなく、 例えば、 1 0 0 %以下であってよい。 ギザ比率 が 1 : 1 . 9〜 1 1 . 3の場合には、 父/ソは8 9 . 6 %以上であることが 好ましく、 ギザ比率が 1 : 1 . 8〜 3 . 4の場合には、 X /ソは 7 7 . 1 % 以上であることが好ましく、 ギザ比率が 1 : 1 . 9〜 8 . 4の場合には、 X / Vは 7 5 . 9 %以上であることが好ましく、 ギザ比率が 1 : 1 . 9〜 4 .The upper limit of V is not particularly limited and may be, for example, 100% or less. When the knurl ratio is 1: 1.9 to 11.3, it is preferable that the father/so is 89.6% or more, and when the knurl ratio is 1: 1.8 to 3.4. , X/so is preferably 77.1% or more, and when the notched ratio is 1: 1.9 to 8.4, X/V is preferably 75.9% or more, The serrated ratio is 1: 1.9 to 4.

1の場合には、 父/ソは6 4 . 2 %以上であることが好ましい。 In the case of 1, the ratio of father/so is preferably 64.2% or more.

［0109］ 第 3の改変フィブロインが、 ドメイン配列中に複数存在する （八） „モチー フの少なくとも 7つがアラニン残基のみで構成される改変フィブロインであ る場合、 父/ソは、 4 6 . 4 %以上であることが好ましく、 5 0 %以上であ ることがより好ましく、 5 5 %以上であることが更に好ましく、 6 0 %以上 であることが更により好ましく、 7 0 %以上であることが更によりまた好ま しく、 8 0 %以上であることが特に好ましい。 父/ソの上限に特に制限はな く、 1 0 0 %以下であればよい。 [0109] When the third modified fibroin is present in the domain sequence more than once, (8) when at least seven of the motifs are modified fibroins composed only of alanine residues, the father/so has 46. It is preferably at least 4%, more preferably at least 50%, even more preferably at least 55%, even more preferably at least 60%, and at least 70%. It is even more preferred that it is 80% or more, and it is particularly preferred that the upper limit of the father/so is not particularly limited, and may be 100% or less.

［01 10］ ここで、 天然由来のフィブロインにおける父/ソについて説明する。 まず 〇 2020/175702 41 卩（：171? 2020 /008524 [01 10] Here, the father/so of naturally-occurring fibroin will be described. First 〇 2020/175 702 41 卩 (：171? 2020 /008524

、 上述のように、 1\1〇巳 丨 Ge n B a n kにアミノ酸配列情報が登録され ているフィブロインを例示した方法により確認したところ、 663種類のフ ィブロイン （このうち、 クモ類由来のフィブロインは 4 1 5種類） が抽出さ れた。 抽出された全てのフィブロインのうち、 式 1 : [ （八） „モチーフー 巳 ] で表されるドメイン配列で構成される天然由来のフィブロインのアミ ノ酸配列から、 上述の算出方法により、 父/ソを算出した。 ギザ比率が 1 :, As described above, the method was illustrated by exemplifying the fibroin whose amino acid sequence information is registered in 1\10 跳丨Gen B ank. 4 1 5 types) were extracted. Of all the extracted fibroins, from the amino acid sequence of naturally-occurring fibroin composed of the domain sequence represented by the formula 1: [(8) „Motif Minami”, the father/sodium was calculated by the above-mentioned calculation method. The Giza ratio is 1:

1. 9〜 4. 1の場合の結果を図 7に示す。 Figure 7 shows the results for 1.9 to 4.1.

[0111]

Figure imgf000042_0001
（%） を示し、 縦軸は頻度を示す。 図 7から明らかな とおり、 天然由来のフィブロインにおける父/ソは、 いずれも 64. 2%未 満である （最も高いもので、 64. 1 4%） 。 [0111]
Figure imgf000042_0001
(%), and the vertical axis shows frequency. As is clear from Fig. 7, 64.2% of the fathers/so of the naturally-occurring fibroin were both unsatisfied (the highest was 64.1%).

[0112] 第 3の改変フィブロインは、 例えば、 クローニングした天然由来のフィブ ロインの遺伝子配列から、 父/ソが64. 2%以上になるように （八） „モチ [0112] The third modified fibroin is, for example, based on the cloned gene sequence of naturally-occurring fibroin so that the ratio of father/sodium is 64.2% or more (8)

—フをコードする配列の 1又は複数を欠失させることにより得ることができ る。 また、 例えば、 天然由来のフィブロインのアミノ酸配列から、 ハが— It can be obtained by deleting one or more of the sequences coding for In addition, for example, from the amino acid sequence of naturally-derived fibroin,

64. 2%以上になるように 1又は複数の （八） „モチーフが欠失したことに 相当するアミノ酸配列を設計し、 設計したアミノ酸配列をコードする核酸を 化学合成することにより得ることもできる。 いずれの場合においても、 天然 由来のフィブロインのアミノ酸配列から （八） „モチーフが欠失したことに相 当する改変に加え、 更に 1又は複数のアミノ酸残基を置換、 欠失、 挿入及び /又は付加したことに相当するアミノ酸配列の改変を行つてもよい。 It can also be obtained by designing an amino acid sequence corresponding to the deletion of one or more (8) „motifs so as to be 64.2% or more, and chemically synthesizing a nucleic acid encoding the designed amino acid sequence. In each case, in addition to the modification corresponding to the deletion of the (8) „motif in the amino acid sequence of naturally-occurring fibroin, one or more amino acid residues were replaced, deleted, inserted and/or Alternatively, the amino acid sequence corresponding to the addition may be modified.

[0113] 第 3の改変フィブロインのより具体的な例として、 （3- 丨） 配列番号 1 [0113] As a more specific example of the third modified fibroin, (3-丨) SEQ ID NO: 1

7 （1\/161： -? [¾丁399） 、 配列番号 7 （1\/161： -? [¾丁4 1 0） 、 配列 番号 8 （1\/161： -? [¾丁 525） 若しくは配列番号 9 （1\/161： -? [¾丁 79 9） で示されるアミノ酸配列、 又は （3— 丨 丨） 配列番号 1 7、 配列番号 7 、 配列番号 8若しくは配列番号 9で示されるアミノ酸配列と 90 %以上の配 列同一性を有するアミノ酸配列を含む、 改変フィブロインを挙げることがで きる。 7 (1\/161: -? [¾ 399), SEQ ID NO: 7 (1\/161: -? [¾ 410), SEQ ID 8 (1\/161: -? [¾ 525) Alternatively, the amino acid sequence represented by SEQ ID NO: 9 (1\/161: -? [¾ cho 79 9), or (3 — 丨 丨) is represented by SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9. A modified fibroin containing an amino acid sequence having 90% or more sequence identity with the amino acid sequence can be mentioned.

[0114] （3 - I） の改変フィブロインについて説明する。 配列番号 1 7で示され 〇 2020/175702 42 卩（：171? 2020 /008524 [0114] The modified fibroin of (3-I) will be described. SEQ ID NO: 1 7 〇 2020/175 702 42 卩 (: 171? 2020 /008524

るアミノ酸配列は、 天然由来のフイブロインに相当する配列番号 1 〇

Figure imgf000043_0001
1 _ ［¾丁3 1 3） で示されるアミノ酸配列から、 末端側から（3末端側に 向かって 2つおきに （八） „モチーフを欠失させ、 更に 0末端配列の手前に ［ （八） „モチーフー［¾巳 ］ を 1つ揷入したものである。 配列番号 7、 配列番 号 8又は配列番号 9で示されるアミノ酸配列は、 第 2の改変フイブロインで 説明したとおりである。 The amino acid sequence of SEQ ID NO: 10 corresponding to fibroin of natural origin is
Figure imgf000043_0001
From the amino acid sequence shown in 1 _ [¾ 3 1 3], delete the motif (every other two (8) toward the 3 terminus side) from the terminal side, and further add [(8 ) One of the „Motif [¾” is inserted. The amino acid sequences shown in SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9 are as described in the second modified fibroin.

［0115］ 配列番号 1 0で示されるアミノ酸配列 （天然由来のフイブロインに相当） のギザ比率 1 : 1. 8〜 1 1. 3における父/ソの値は 1 5. 0%である。 配列番号 1 7で示されるアミノ酸配列、 及び配列番号 7で示されるアミノ酸 配列における父/ソの値は、 いずれも 93. 4%である。 配列番号 8で示さ れるアミノ酸配列における X /ソの値は、 92. 7%である。 配列番号 9で 示されるアミノ酸配列における父/ソの値は、 89. 8%である。 配列番号 1 0、 配列番号 1 7、 配列番号 7、 配列番号 8及び配列番号 9で示されるア ミノ酸配列における å / の値は、 それぞれ 46. 8%、 56. 2%、 70 . 1 %、 66. 1 %及び 7〇. 0%である。 [0115] The father/so value of the amino acid sequence represented by SEQ ID NO: 10 (corresponding to naturally occurring fibroin) at the Giza ratio of 1: 1.8 to 1 1.3 is 15.0%. The father/so value in the amino acid sequence represented by SEQ ID NO: 17 and the amino acid sequence represented by SEQ ID NO: 7 is 93.4% in both cases. The X/so value in the amino acid sequence represented by SEQ ID NO: 8 is 92.7%. The father/so value in the amino acid sequence represented by SEQ ID NO: 9 is 89.8%. The values of / in the amino acid sequences shown in SEQ ID NO: 10, SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO: 8 and SEQ ID NO: 9 are 46.8%, 56.2%, and 70.1%, respectively. , 66.1% and 7.0%.

［0116］ （3- I） の改変フイブロインは、 配列番号 1 7、 配列番号 7、 配列番号 [0116] The modified fibroin of (3-I) has SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO:

8又は配列番号 9で示されるアミノ酸配列からなるものであってもよい。 It may consist of the amino acid sequence shown in 8 or SEQ ID NO: 9.

［0117］ （3- I \） の改変フイブロインは、 配列番号 1 7、 配列番号 7、 配列番 号 8又は配列番号 9で示されるアミノ酸配列と 90%以上の配列同一性を有 するアミノ酸配列を含むものである。 （3- 丨 丨） の改変フイブロインもま た、 式 1 : ［ （八） „モチーフー［¾巳 ］ で表されるドメイン配列を含む夕 ンパク質である。 上記配列同一性は、 95%以上であることが好ましい。[0117] The modified fibroin of (3-I \) has an amino acid sequence having 90% or more sequence identity with the amino acid sequence shown in SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9. It includes. The modified fibroin of (3--) is also a protein containing the domain sequence represented by the formula 1: [(8) "motif [¾mi]. The sequence identity is 95% or more. Preferably.

［0118］ （3- I \） の改変フイブロインは、 配列番号 1 7、 配列番号 7、 配列番 号 8又は配列番号 9で示されるアミノ酸配列と 90%以上の配列同一性を有 し、 かつ 1\1末端側から（3末端側に向かって、 隣合う 2つの ［ （八） „モチーフ

Figure imgf000043_0002
のアミノ酸残基数を順次比較して、 アミノ酸残 基数が少ない 巳 のアミノ酸残基数を 1 としたとき、 他方の 巳 のアミ ノ酸残基数の比が 1. 8〜 1 1. 3 （ギザ比率が 1 : 1. 8〜 1 1. 3） と 〇 2020/175702 43 卩（：171? 2020 /008524 [0118] The modified fibroin of (3-I\) has 90% or more sequence identity with the amino acid sequence of SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9, and 1 From \1 end side (toward the 3 end side, two adjacent [(8) „motifs
Figure imgf000043_0002
Sequentially comparing the number of amino acid residues in A, the number of amino acid residues in the one with a small number of amino acid residues is 1, and the ratio of the number of amino acid residues in the other is 1.8 to 1 1. The serrated ratio is 1 :1.8 to 1 1.3) 〇 2020/175 702 43 卩 (: 171? 2020 /008524

なる隣合う 2つの [ （八） „モチーフー 巳 ] ユニッ トのアミノ酸残基数を 足し合わせた合計値の最大値を Xとし、 ドメイン配列の総アミノ酸残基数を Vとしたときに、 父/ソが6 4 . 2 %以上であることが好ましい。 Let X be the maximum value of the total sum of the number of amino acid residues of two adjacent [(8) „Motif-Min] units and V be the total number of amino acid residues of the domain sequence. It is preferably 64.2% or more.

[01 19] 第 3の改変フィブロインは、 1\1末端及び〇末端のいずれか一方又は両方に 上述したタグ配列を含んでいてもよい。 [0119] The third modified fibroin may include the above-mentioned tag sequence at either or both of the 1\1 end and the O end.

[0120] タグ配列を含む改変フィブロインのより具体的な例として、 （3— 丨 丨 I [0120] As a more specific example of modified fibroin containing a tag sequence, (3—丨丨I

） 配列番号 1 8

Figure imgf000044_0001
配列番号 1 3 （ 丁 4 1 0） 、 配列番 号 1 4 （ [¾丁 5 2 5） 若しくは配列番号 1 5 （ 丁 7 9 9） で示される アミノ酸配列、 又は （3— 丨 V） 配列番号 1 8、 配列番号 1 3、 配列番号 1 4若しくは配列番号 1 5で示されるアミノ酸配列と 9 0 %以上の配列同一性 を有するアミノ酸配列を含む、 改変フィブロインを挙げることができる。 ) SEQ ID NO: 18
Figure imgf000044_0001
The amino acid sequence represented by SEQ ID NO: 1 3 (Cho 4 10), SEQ ID No: 14 ([¾ 5 25) or SEQ ID No 15 (Cha 7 9 9), or (3 — V) SEQ ID No. A modified fibroin containing an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by 18, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15 can be mentioned.

[0121 ] 配列番号 1 8、 配列番号 1 3、 配列番号 1 4及び配列番号 1 5で示される アミノ酸配列は、 それぞれ配列番号 1 7、 配列番号 7、 配列番号 8及び配列 番号 9で示されるアミノ酸配列の 1\1末端に配列番号 1 1で示されるアミノ酸 配列 （1~1 丨 3タグ配列及びヒンジ配列を含む） を付加したものである。 [0121] The amino acid sequences represented by SEQ ID NO: 18, SEQ ID NO: 13, SEQ ID NO: 14 and SEQ ID NO: 15 are the amino acids represented by SEQ ID NO: 17, SEQ ID NO: 7, SEQ ID NO: 8 and SEQ ID NO: 9, respectively. The amino acid sequence represented by SEQ ID NO: 11 (including 1 to 1 3 tag sequence and hinge sequence) is added to the 1\1 end of the sequence.

[0122] （3 - \ \ \） の改変フィブロインは、 配列番号 1 8、 配列番号 1 3、 配 列番号 1 4又は配列番号 1 5で示されるアミノ酸配列からなるものであって もよい。 [0122] The modified fibroin of (3-\ \ \) may consist of the amino acid sequence of SEQ ID NO: 18, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15.

[0123] （3 - I V） の改変フィブロインは、 配列番号 1 8、 配列番号 1 3、 配列 番号 1 4又は配列番号 1 5で示されるアミノ酸配列と 9 0 %以上の配列同一 性を有するアミノ酸配列を含むものである。 （3 - 丨 V） の改変フィブロイ ンもまた、 式 1 : [ （八） „モチーフー^?巳 ] で表されるドメイン配列を 含むタンパク質である。 上記配列同一性は、 9 5 %以上であることが好まし い。 [0123] The modified fibroin of (3-IV) is an amino acid sequence having a sequence identity of 90% or more with the amino acid sequence represented by SEQ ID NO: 18, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15. Is included. The modified fibroin of (3-V) is also a protein containing a domain sequence represented by the formula 1: [(8) "motif ^?M]. The above sequence identity is 95% or more. I like that.

[0124] （3 - I V） の改変フィブロインは、 配列番号 1 8、 配列番号 1 3、 配列 番号 1 4又は配列番号 1 5で示されるアミノ酸配列と 9 0 %以上の配列同一 性を有し、 かつ 1\!末端側から（3末端側に向かって、 隣合う 2つの [ （ ） „モ チーフー 8巳 ] ユニッ トの 巳 のアミノ酸残基数を順次比較して、 アミ 〇 2020/175702 44 卩（：171? 2020 /008524 [0124] The modified fibroin of (3-IV) has a sequence identity of 90% or more with the amino acid sequence represented by SEQ ID NO: 18, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15, And from the 1\! terminal side (towards the 3 terminal side, the number of amino acid residues of the two adjacent [( )„Mochifu 8M] units are sequentially compared, and the amino acid residues are compared. 〇 2020/175 702 44 卩 (: 171? 2020 /008524

ノ酸残基数が少ない 巳 のアミノ酸残基数を 1 としたとき、 他方の 巳 のアミノ酸残基数の比が 1. 8〜 1 1. 3となる隣合う 2つの [ （八） „モチ —フ

Figure imgf000045_0001
ユニッ トのアミノ酸残基数を足し合わせた合計値の最大値を Xとし、 ドメイン配列の総アミノ酸残基数をソとしたときに、 X /ソが 64 . 2 %以上であることが好ましい。 When the number of amino acid residues in the one with a small number of amino acid residues is 1, the ratio of the number of amino acid residues in the other is 1.8 to 1 1. 3 — F
Figure imgf000045_0001
X/so is preferably 64.2% or more, where X is the maximum total value of the total number of amino acid residues in the unit and X is the total number of amino acid residues in the domain sequence.

[0125] 第 3の改変フイブロインは、 組換えタンパク質生産系において生産された タンパク質を宿主の外部に放出するための分泌シグナルを含んでいてもよい 。 分泌シグナルの配列は、 宿主の種類に応じて適宜設定することができる。 [0125] The third modified fibroin may contain a secretory signal for releasing the protein produced in the recombinant protein production system to the outside of the host. The sequence of the secretion signal can be appropriately set depending on the type of host.

[0126] 第 4の改変フイブロインは、 そのドメイン配列が、 天然由来のフイブロイ ンと比較して、 （八） モチーフの含有量が低減されたことに加え、 グリシン 残基の含有量が低減されたアミノ酸配列を有するものである。 第 4の改変フ イブロインのドメイン配列は、 天然由来のフイブロインと比較して、 少なく とも 1又は複数の （八） „モチーフが欠失したことに加え、 更に少なくとも 巳 中の 1又は複数のグリシン残基が別のアミノ酸残基に置換されたことに 相当するアミノ酸配列を有するものということができる。 すなわち、 第 4の 改変フイブロインは、 上述した第 2の改変フイブロインと、 第 3の改変フイ ブロインの特徴を併せ持つ改変フイブロインである。 具体的な態様等は、 第 2の改変フイブロイン、 及び第 3の改変フイブロインで説明したとおりであ る。 [0126] In the fourth modified fibroin, its domain sequence had a reduced content of (8) motifs and a reduced content of glycine residues, as compared to naturally-occurring fibroin. It has an amino acid sequence. The domain sequence of the fourth modified fibroin has a deletion of at least one or more (8) „motifs as compared with the naturally-occurring fibroin, and at least one or more glycine residues in the mitochondria. It can be said that the group has an amino acid sequence corresponding to the substitution of another amino acid residue, that is, the fourth modified fibroin has the above-mentioned second modified fibroin and the third modified fibroin. It is a modified fibroin having features as well.Specific embodiments are as described in the second modified fibroin and the third modified fibroin.

[0127] 第 4の改変フイブロインのより具体的な例として、 （4_ 丨） 配列番号 7 （1\/161： -? [¾丁4 1 0） 、 配列番号 8 （1\/161： -? [¾丁 525） 、 配列番 号 9 （1\/161： -? [¾丁 799） 、 配列番号 1 3 （ 丁 4 1 0） 、 配列番号 1 4 （ 丁 525） 若しくは配列番号 1 5 （ 丁 799） で示されるア ミノ酸配列、 又は （4— 丨 丨） 配列番号 7、 配列番号 8、 配列番号 9、 配列 番号 1 3、 配列番号 1 4若しくは配列番号 1 5で示されるアミノ酸配列と 9 0%以上の配列同一性を有するアミノ酸配列を含む、 改変フイブロインを挙 げることができる。 配列番号 7、 配列番号 8、 配列番号 9、 配列番号 1 3、 配列番号 1 4又は配列番号 1 5で示されるアミノ酸配列を含む改変フイブロ 〇 2020/175702 45 卩（：171? 2020 /008524 [0127] As a more specific example of the fourth modified fibroin, (4_ 丨) SEQ ID NO: 7 (1\/161: -? [¾ D 4 10), SEQ ID NO: 8 (1\/161: -? [¾ 525], Sequence No. 9 (1\/161: -? [¾ 799), Sequence No. 13 (Cho 414), Sequence No. 14 (Cho 525) or Sequence No. 15 (Cho) 799), or (4 — 丨 丨) SEQ ID NO: 7, SEQ ID NO: 8, SEQ ID NO: 9, SEQ ID NO: 13, SEQ ID NO: 14 or the amino acid sequence of SEQ ID NO: 15 and 9 Modified fibroin containing amino acid sequences having 0% or more sequence identity can be mentioned. Modified fibro containing the amino acid sequence of SEQ ID NO: 7, SEQ ID NO: 8, SEQ ID NO: 9, SEQ ID NO: 13, SEQ ID NO: 14 or SEQ ID NO: 15 〇 2020/175 702 45 卩 (：171? 2020 /008524

インの具体的な態様は上述のとおりである。 Specific aspects of the in have been described above.

[0128] 第 5の改変フィブロインは、 そのドメイン配列が、 天然由来のフィブロイ ンと比較して、

Figure imgf000046_0001
[0128] The fifth modified fibroin has a domain sequence that is comparable to that of naturally-occurring fibroin.
Figure imgf000046_0001

アミノ酸残基に置換されたこと、 及び/又は 巳 中に 1又は複数の疎水性 指標の大きいアミノ酸残基が挿入されたことに相当する、 局所的に疎水性指 標の大きい領域を含むアミノ酸配列を有するものであってよい。 An amino acid sequence containing a region with a locally large hydrophobic index, which corresponds to the substitution with an amino acid residue and/or the insertion of one or more amino acid residues with a large hydrophobic index into the ridge. May be included.

[0129] 局所的に疎水性指標の大きい領域は、 連続する 2〜 4アミノ酸残基で構成 されていることが好ましい。 [0129] The region where the hydrophobicity index is locally large is preferably composed of consecutive 2 to 4 amino acid residues.

[0130] 上述の疎水性指標の大きいアミノ酸残基は、 イソロイシン （丨） 、 バリン [0130] The above-mentioned amino acid residues having a large hydrophobicity index are isoleucine (丨) and valine.

（V） 、 ロイシン （!_） 、 フエニルアラニン （ ） 、 システイン （〇） 、 メ チオニン （IV!） 及びアラニン （八） から選ばれるアミノ酸残基であることが より好ましい。 More preferably, it is an amino acid residue selected from (V), leucine (!_), phenylalanine (), cysteine (○), methionine (IV!) and alanine (8).

[0131 ] 第 5の改変フィブロインは、 天然由来のフィブロインと比較して、

Figure imgf000046_0002
中の 1又は複数のアミノ酸残基が疎水性指標の大きいアミノ酸残基に置換さ れたこと、 及び/又は 巳 中に 1又は複数の疎水性指標の大きいアミノ酸 残基が揷入されたことに相当する改変に加え、 更に、 天然由来のフィブロイ ンと比較して、 1又は複数のアミノ酸残基を置換、 欠失、 挿入及び/又は付 加したことに相当するアミノ酸配列の改変があってもよい。 [0131] The fifth modified fibroin is compared with naturally-derived fibroin,
Figure imgf000046_0002
One or more amino acid residues in the amino acid were replaced by amino acid residues with a high hydrophobicity index, and/or one or more amino acid residues with a high hydrophobicity index were inserted into the In addition to the corresponding alterations, there may be further alterations in the amino acid sequence corresponding to substitutions, deletions, insertions and/or additions of one or more amino acid residues as compared to naturally occurring fibrin. Good.

[0132] 第 5の改変フィブロインは、 例えば、 クローニングした天然由来のフィブ ロインの遺伝子配列から 巳 中の 1又は複数の親水性アミノ酸残基 （例え ば、 疎水性指標がマイナスであるアミノ酸残基） を疎水性アミノ酸残基 （例 えば、 疎水性指標がプラスであるアミノ酸残基） に置換すること、 及び/又 は 巳 中に 1又は複数の疎水性アミノ酸残基を揷入することにより得るこ とができる。 また、 例えば、 天然由来のフィブロインのアミノ酸配列から

Figure imgf000046_0003
巳 中の 1又は複数の親水性アミノ酸残基を疎水性アミノ酸残基に置換した こと、 及び/又は 巳 中に 1又は複数の疎水性アミノ酸残基を揷入したこ とに相当するアミノ酸配列を設計し、 設計したアミノ酸配列をコードする核 酸を化学合成することにより得ることもできる。 いずれの場合においても、 天然由来のフイブロインのアミノ酸配列から R E P中の 1又は複数の親水性 アミノ酸残基を疎水性アミノ酸残基に置換したこと、 及び/又は R E P中に 1又は複数の疎水性アミノ酸残基を揷入したことに相当する改変に加え、 更 に 1又は複数のアミノ酸残基を置換、 欠失、 揷入及び/又は付加したことに 相当するアミノ酸配列の改変を行ってもよい。 [0132] The fifth modified fibroin is, for example, one or more hydrophilic amino acid residues (for example, an amino acid residue having a negative hydrophobicity index) in the middle of the cloned gene sequence of naturally-derived fibroin. To a hydrophobic amino acid residue (for example, an amino acid residue having a positive hydrophobicity index) and/or by inserting one or more hydrophobic amino acid residues into the cavity. You can In addition, for example, from the amino acid sequence of naturally occurring fibroin
Figure imgf000046_0003
The amino acid sequence corresponding to the substitution of one or more hydrophilic amino acid residues in the hollows with the hydrophobic amino acid residue and/or the insertion of one or more hydrophobic amino acid residues into the hollow It can also be obtained by chemically synthesizing a nucleic acid designed and encoding the designed amino acid sequence. In any case, Substitution of one or more hydrophilic amino acid residues in REP with hydrophobic amino acid residues from the amino acid sequence of fibroin derived from nature, and/or insertion of one or more hydrophobic amino acid residues in REP In addition to the corresponding modification, further modification of the amino acid sequence corresponding to substitution, deletion, insertion and/or addition of one or more amino acid residues may be carried out.

[0133] 第 5の改変フイブロインは、 式 1 : [ （A） „モチーフーR E P] mで表さ れるドメイン配列を含み、 最も C末端側に位置する （A） nモチーフから上記 ドメイン配列の c末端までの配列を上記ドメイン配列から除いた配列に含ま れる全ての R E Pにおいて、 連続する 4アミノ酸残基の疎水性指標の平均値 が 2. 6以上となる領域に含まれるアミノ酸残基の総数を pとし、 最も C末 端側に位置する （A） nモチーフから上記ドメイン配列の C末端までの配列を 上記ドメイン配列から除いた配列に含まれるアミノ酸残基の総数を qとした ときに、 p/qが 6. 2 %以上であるアミノ酸配列を有してもよい。 [0133] The fifth modified fibroin contains the domain sequence represented by the formula 1: [(A) "motif-REP] m , and the (A) n motif located closest to the C-terminal side leads to the c-terminal of the above domain sequence. The total number of amino acid residues contained in the region where the average hydrophobicity index of 4 consecutive amino acid residues is 2.6 or more in all REPs contained in the sequence except the above sequences up to the above domain sequence is p And the total number of amino acid residues contained in the sequence excluding the sequence from the (A) n motif located closest to the C-terminal to the C-terminus of the above domain sequence is q, then p/ It may have an amino acid sequence in which q is 6.2% or more.

[0134] アミノ酸残基の疎水性指標については、 公知の指標 （H y d r〇 p a t h y i n d e x : K y t e J , &D o o l i t t l e R （1 982） “ [0134] Regarding the hydrophobicity index of amino acid residues, a known index (H y d r 〇 p a t h y i n d e x :K y t e J ,&D o o l i t t l e R (1 982) “

A s i m p l e me t h o d f o r d i s p l a y i n g t h e h y d r o p a t h i c c h a r a c t e r o f a p r o t e i n” ， J . Mo l . B i o l . , 1 57, p p. 1 05 - 1 32） を使用す る。 具体的には、 各アミノ酸の疎水性指標 （ハイ ドロパシー ·インデックス 、 以下 「H I」 とも記す。 ） は、 下記表 1 に示すとおりである。 A simple me thodfordisplaying theh ydropathiccharacterof aprotein”, J. Mol. B iol., 1 57, p p. 1 05-1 32).Specifically, the hydrophobicity index of each amino acid (Hydropathic index) is used. , Hereafter referred to as “HI.”) is as shown in Table 1 below.

[0135] [表 1] [0135] [Table 1]

Figure imgf000047_0001
〇 2020/175702 47 卩（：171? 2020 /008524
Figure imgf000047_0001
〇 2020/175 702 47 卩 (：171? 2020 /008524

[0136] の算出方法を更に詳細に説明する。 算出には、 式 1 : [ （八） „モチThe calculation method of [0136] will be described in more detail. To calculate, use the formula 1: [(8)

—フ

Figure imgf000048_0001
で表されるドメイン配列から、 最も〇末端側に位置する （八 ） „モチーフからドメイン配列の〇末端までの配列を除いた配列 （以下、 「配 列八」 とする） を用いる。 まず、 配列八に含まれる全ての 巳 において、 連続する 4アミノ酸残基の疎水性指標の平均値を算出する。 疎水性指標の平 均値は、 連続する 4アミノ酸残基に含まれる各アミノ酸残基の 1~1 Iの総和を 4 （アミノ酸残基数） で除して求める。 疎水性指標の平均値は、 全ての連続 する 4アミノ酸残基について求める （各アミノ酸残基は、 1〜 4回平均値の 算出に用いられる。 ） 。 次いで、 連続する 4アミノ酸残基の疎水性指標の平 均値が 2. 6以上となる領域を特定する。 あるアミノ酸残基が、 複数の 「疎 水性指標の平均値が 2. 6以上となる連続する 4アミノ酸残基」 に該当する 場合であっても、 領域中には 1 アミノ酸残基として含まれることになる。 そ して、 当該領域に含まれるアミノ酸残基の総数が である。 また、 配列八に 含まれるアミノ酸残基の総数が である。 — F
Figure imgf000048_0001
From the domain sequence represented by, the sequence (hereinafter referred to as “sequence 8”) excluding the sequence located at the most 〇 terminal side (8) „motif from the 〇 end of the domain sequence is used. First, calculate the average value of the hydrophobicity index of 4 consecutive amino acid residues in all the sequences included in Sequence 8. The average value of the hydrophobicity index is obtained by dividing the sum of 1 to 1 I of each amino acid residue contained in four consecutive amino acid residues by 4 (the number of amino acid residues). The average value of the hydrophobicity index is calculated for all four consecutive amino acid residues (each amino acid residue is used for calculating the average value 1 to 4 times). Next, identify the region where the average hydrophobicity index of 4 consecutive amino acid residues is 2.6 or more. Even if a certain amino acid residue corresponds to multiple "4 consecutive amino acid residues whose average hydrophobicity index is 2.6 or more", it must be included as 1 amino acid residue in the region. become. Then, the total number of amino acid residues contained in the region is. The total number of amino acid residues contained in Sequence 8 is.

[0137] 例えば、 「疎水性指標の平均値が 2. 6以上となる連続する 4アミノ酸残 基」 が 20力所抽出された場合 （重複はなし） 、 連続する 4アミノ酸残基の 疎水性指標の平均値が 2. 6以上となる領域には、 連続する 4アミノ酸残基 （重複はなし） が 20含まれることになり、 は 20X4 = 80である。 ま た、 例えば、 2つの 「疎水性指標の平均値が 2. 6以上となる連続する 4ア ミノ酸残基」 が 1 アミノ酸残基だけ重複して存在する場合、 連続する 4アミ ノ酸残基の疎水性指標の平均値が 2. 6以上となる領域には、 7アミノ酸残 基含まれることになる （ = 2 4— 1 =7。 「一 1」 は重複分の控除であ る。 ） 。 例えば、 図 8に示したドメイン配列の場合、 「疎水性指標の平均値 が 2. 6以上となる連続する 4アミノ酸残基」 が重複せずに 7つ存在するた め、 は 7 X4 = 28となる。 また、 例えば、 図 8に示したドメイン配列の 場合、 は 4 + 50 + 4 + 40 + 4+ 1 0 + 4 + 20 + 4 + 30= 1 70で ある （＜3末端側の最後に存在する （ ） „モチーフは含めない） 。 次に、 を で除すことによって、 / （%） を算出することができる。 図 8の場合 〇 2020/175702 48 卩（：171? 2020 /008524 [0137] For example, when "consecutive 4 amino acid residues having an average hydrophobicity index of 2.6 or more" was extracted at 20 power points (no duplication), the hydrophobicity index of 4 consecutive amino acid residues was A region with an average value of 2.6 or more contains 20 consecutive 4 amino acid residues (no overlap), and is 20X4 = 80. In addition, for example, if two "4 consecutive amino acid residues with an average value of the hydrophobicity index of 2.6 or more" are duplicated by 1 amino acid residue, 4 consecutive amino acid residues remain. The region where the average value of the hydrophobicity index of the group is 2.6 or more contains 7 amino acid residues (=2 4 — 1 =7. “One 1” is a deduction for duplicates). ). For example, in the case of the domain sequence shown in Fig. 8, there are 7 "4 consecutive amino acid residues with an average hydrophobicity index of 2.6 or more" that do not overlap, so 7 X4 = 28 Becomes For example, in the case of the domain sequence shown in Fig. 8, is 4 + 50 + 4 + 40 + 4+ 1 0 + 4 + 20 + 4 + 30 = 1 70 (<3 is present at the end of the end) () „Motif is not included.) Next, / can be calculated by dividing by. 〇 2020/175 702 48 卩 (：171? 2020 /008524

28/1 70= 1 6. 47%となる。 28/1 70= 1 6.47%.

[0138] 第 5の改変フィブロインにおいて、 6. 2%以上であることが 好ましく、 7 %以上であることがより好ましく、 1 0 %以上であることが更 に好ましく、 20%以上であることが更により好ましく、 30%以上である ことが更によりまた好ましい。 / の上限は、 特に制限されないが、 例え ば、 45 %以下であってもよい。 [0138] In the fifth modified fibroin, it is preferably 6.2% or more, more preferably 7% or more, further preferably 10% or more, and more preferably 20% or more. Even more preferably, it is even more preferably 30% or more. The upper limit of / is not particularly limited, but may be, for example, 45% or less.

[0139] 第 5の改変フィブロインは、 例えば、 クローニングした天然由来のフィブ ロインのアミノ酸配列を、 上記の / の条件を満たすように、

Figure imgf000049_0001
中の 1又は複数の親水性アミノ酸残基 （例えば、 疎水性指標がマイナスであるア ミノ酸残基） を疎水性アミノ酸残基 （例えば、 疎水性指標がプラスであるア ミノ酸残基） に置換すること、 及び/又は 巳 中に 1又は複数の疎水性ア ミノ酸残基を挿入することにより、 局所的に疎水性指標の大きい領域を含む アミノ酸配列に改変することにより得ることができる。 また、 例えば、 天然 由来のフィブロインのアミノ酸配列から上記の / の条件を満たすアミノ 酸配列を設計し、 設計したアミノ酸配列をコードする核酸を化学合成するこ とにより得ることもできる。 いずれの場合においても、 天然由来のフィブロ インと比較して、
Figure imgf000049_0002
[0139] A fifth modified fibroin is prepared by, for example, changing the amino acid sequence of a cloned naturally-occurring fibroin so as to satisfy the above condition /.
Figure imgf000049_0001
To one or more hydrophilic amino acid residues (for example, amino acid residue with a negative hydrophobicity index) to hydrophobic amino acid residues (for example, amino acid residue with a positive hydrophobicity index) It can be obtained by substituting, and/or inserting one or more hydrophobic amino acid residues in the pit, to locally modify the amino acid sequence to include a region having a large hydrophobic index. It can also be obtained by, for example, designing an amino acid sequence satisfying the above condition / from the amino acid sequence of naturally-derived fibroin and chemically synthesizing a nucleic acid encoding the designed amino acid sequence. In each case, compared to naturally occurring fibroin,
Figure imgf000049_0002

いアミノ酸残基に置換されたこと、 及び/又は 巳 中に 1又は複数の疎水 性指標の大きいアミノ酸残基が挿入されたことに相当する改変に加え、 更に 1又は複数のアミノ酸残基を置換、 欠失、 揷入及び/又は付加したことに相 当する改変を行ってもよい。 A new amino acid residue, and/or one or more amino acid residues having a high hydrophobicity index are inserted into the ridge, and one or more amino acid residues are replaced. , Deletion, insertion and/or addition may be modified.

[0140] 疎水性指標の大きいアミノ酸残基としては、 特に制限はないが、 イソロイ シン （ I） 、 パ'リン （V） 、 ロイシン （!_） 、 フエニルアラニン （ ） 、 シ ステイン （〇） 、 メチオニン （1\/〇 及びアラニン （八） が好ましく、 パリン （V） 、 ロイシン （!_） 及びイソロイシン （ I） がより好ましい。 [0140] The large amino acid residues of the hydrophobic index, in particular, without limitation, isoleucine (I), Pas' phosphorus (V), leucine (! _), Phenylalanine (), cysteine (〇) , Methionine (1\/○ and alanine (8) are preferred, and parin (V), leucine (!_) and isoleucine (I) are more preferred.

[0141] 第 5の改変フィブロインのより具体的な例として、 （5- 丨） 配列番号 1 [0141] As a more specific example of the fifth modified fibroin, (5-丨) SEQ ID NO: 1

9 （1\/161： -? [¾丁 720） 、 配列番号 20 （1\/161： -? [¾丁 665） 若し くは配列番号 2 1 （1\/161： -? [¾丁 666） で示されるアミノ酸配列、 又は 〇 2020/175702 49 卩（：171? 2020 /008524 9 (1\/161: -? [¾ 720), SEQ ID NO: 20 (1\/161: -? [¾ 665) or SEQ ID NO: 2 1 (1\/161: -? [¾ 666), or 〇 2020/175 702 49 卩 (：171? 2020 /008524

（5- 1 \） 配列番号 1 9、 配列番号 20若しくは配列番号 2 1で示される アミノ酸配列と 90 %以上の配列同一性を有するアミノ酸配列を含む、 改変 フィブロインを挙げることができる。 (5-1 \) Modified fibroin including an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 19, SEQ ID NO: 20 or SEQ ID NO: 21.

[0142] （5 - I） の改変フィブロインについて説明する。 配列番号 1 9で示され るアミノ酸配列は、 配列番号 7 （1\/161： -? [¾丁4 1 0） で示されるアミノ 酸配列に対し、 〇末端側の端末のドメイン配列を除いて、

Figure imgf000050_0001
巳 一つ置きに それぞれ 3アミノ酸残基からなるアミノ酸配列 （VI- I） を 2力所揷入し、 更に一部のグルタミン （0） 残基をセリン （3） 残基に置換し、 かつ〇末端 側の一部のアミノ酸を欠失させたものである。 配列番号 20で示されるアミ ノ酸配列は、 配列番号 8 （1\/161： -? [¾丁 525） で示されるアミノ酸配列 に対し、
Figure imgf000050_0002
巳 一つ置きにそれぞれ 3アミノ酸残基からなるアミノ酸配列 （ VI- I） を 1力所揷入したものである。 配列番号 2 1で示されるアミノ酸配 列は、 配列番号 8で示されるアミノ酸配列に対し、
Figure imgf000050_0003
巳 一つ置きにそれぞ れ 3アミノ酸残基からなるアミノ酸配列 （VI- 丨） を 2力所揷入したもので ある。 [0142] The modified fibroin of (5-I) is described. The amino acid sequence shown in SEQ ID NO: 19 is the amino acid sequence shown in SEQ ID NO: 7 (1\/161: -? ,
Figure imgf000050_0001
At every other interval, two amino acid sequences (VI-I) each consisting of 3 amino acid residues were inserted, and further some glutamine (0) residues were replaced with serine (3) residues, and It is a partial deletion of amino acids on the terminal side. The amino acid sequence represented by SEQ ID NO: 20 is the amino acid sequence represented by SEQ ID NO: 8 (1\/161: -? [¾ 525),
Figure imgf000050_0002
Every other pair, every other amino acid sequence (VI-I) consisting of 3 amino acid residues is inserted. The amino acid sequence represented by SEQ ID NO: 21 is the same as the amino acid sequence represented by SEQ ID NO: 8,
Figure imgf000050_0003
In each case, every other amino acid sequence (VI-) consisting of 3 amino acid residues is inserted in two places.

[0143] （5 - I） の改変フィブロインは、 配列番号 1 9、 配列番号 20又は配列 番号 2 1で示されるアミノ酸配列からなるものであってもよい。 [0143] The modified fibroin of (5-I) may consist of the amino acid sequence shown by SEQ ID NO: 19, SEQ ID NO: 20 or SEQ ID NO: 21.

[0144] （5 - I \） の改変フィブロインは、 配列番号 1 9、 配列番号 20又は配 列番号 2 1で示されるアミノ酸配列と 90%以上の配列同一性を有するアミ ノ酸配列を含むものである。 （5 - 丨 丨） の改変フィブロインもまた、 式 1 : [ （八） „モチーフー [¾巳 ] で表されるドメイン配列を含むタンパク質 である。 上記配列同一性は、 95 %以上であることが好ましい。 [0144] The modified fibroin of (5-I \) contains an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 19, SEQ ID NO: 20 or SEQ ID NO: 21. .. The modified fibroin of (5-丨 丨) is also a protein containing the domain sequence represented by the formula 1: [(8) „motif [¾mi]. The above sequence identity may be 95% or more. Preferred.

[0145] （5 - I \） の改変フィブロインは、 配列番号 1 9、 配列番号 20又は配 列番号 2 1で示されるアミノ酸配列と 90%以上の配列同一性を有し、 かつ 最も <3末端側に位置する （ ） „モチーフからドメイン配列の <3末端までの配 列をドメイン配列から除いた配列に含まれる全ての 巳 において、 連続す る 4アミノ酸残基の疎水性指標の平均値が 2. 6以上となる領域に含まれる アミノ酸残基の総数を とし、 最も <3末端側に位置する （/\） „モチーフから 〇 2020/175702 50 卩（：171? 2020 /008524 [0145] The modified fibroin of (5-I \) has 90% or more sequence identity with the amino acid sequence shown in SEQ ID NO: 19, SEQ ID NO: 20 or SEQ ID NO: 21, and has the most <3 terminal. Located on the side (), the average value of the hydrophobicity index of 4 consecutive amino acid residues is 2 in all the sequences included in the sequence excluding the sequence from the motif to the <3 end of the domain sequence in the domain sequence. . The total number of amino acid residues contained in the region of 6 or more is defined as 〇 2020/175 702 50 卩 (：171? 2020 /008524

ドメイン配列の〇末端までの配列をドメイン配列から除いた配列に含まれる アミノ酸残基の総数を としたときに、 / 9が 6. 2 %以上であることが 好ましい。 It is preferable that /9 is 6.2% or more when the total number of amino acid residues contained in the sequence excluding the sequence up to the 0 terminal of the domain sequence is excluded from the domain sequence.

[0146] 第 5の改変フイブロインは、 1\1末端及び◦末端のいずれか一方又は両方に タグ配列を含んでいてもよい。 [0146] The fifth modified fibroin may include a tag sequence at either or both of the 1\1 end and the open end.

[0147] タグ配列を含む改変フイブロインのより具体的な例として、 （5— 丨 丨 I ） 配列番号 22 （ [¾丁 720） 、 配列番号 23 （ [¾丁 665） 若しくは 配列番号 24 （ [¾丁 666） で示されるアミノ酸配列、 又は （ 5 - 丨 V） 配列番号 22、 配列番号 23若しくは配列番号 24で示されるアミノ酸配列 と 90%以上の配列同一性を有するアミノ酸配列を含む、 改変フイブロイン を挙げることができる。 [0147] As more specific examples of the modified fibroin containing the tag sequence, (5 — 丨 丨 I) SEQ ID NO: 22 ([¾ 720), SEQ ID NO: 23 ([ ¾ 665) or SEQ ID NO: 24 ([¾ A modified fibroin containing an amino acid sequence shown in Figure 666), or an amino acid sequence having 90% or more sequence identity with the amino acid sequence shown in (5-V) SEQ ID NO: 22, SEQ ID NO: 23 or SEQ ID NO: 24. Can be mentioned.

[0148] 配列番号 22、 配列番号 23及び配列番号 24で示されるアミノ酸配列は 、 それぞれ配列番号 1 9、 配列番号 20及び配列番号 2 1で示されるアミノ 酸配列の 1\1末端に配列番号 1 1で示されるアミノ酸配列 （1~1 丨 3タグ配列及 びヒンジ配列を含む） を付加したものである。 [0148] The amino acid sequences represented by SEQ ID NO: 22, SEQ ID NO: 23 and SEQ ID NO: 24 are represented by SEQ ID NO: 1 at the 1\1 end of the amino acid sequences represented by SEQ ID NO: 19, SEQ ID NO: 20 and SEQ ID NO: 21, respectively. The amino acid sequence shown by 1 (including 1 to 1 3 tag sequence and hinge sequence) is added.

[0149] （5 - I I \） の改変フイブロインは、 配列番号 22、 配列番号 23又は 配列番号 24で示されるアミノ酸配列からなるものであってもよい。 [0149] The modified fibroin of (5-II\) may consist of the amino acid sequence represented by SEQ ID NO: 22, SEQ ID NO: 23 or SEQ ID NO: 24.

[0150] （5 - I V） の改変フイブロインは、 配列番号 22、 配列番号 23又は配 列番号 24で示されるアミノ酸配列と 90%以上の配列同一性を有するアミ ノ酸配列を含むものである。 （5 - 丨 V） の改変フイブロインもまた、 式 1 : [ （八） „モチーフー [¾巳 ] で表されるドメイン配列を含むタンパク質 である。 上記配列同一性は、 95 %以上であることが好ましい。 [0150] The modified fibroin of (5-IV) contains an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 22, SEQ ID NO: 23 or SEQ ID NO: 24. The modified fibroin of (5-V) is also a protein containing the domain sequence represented by the formula 1: [(8) "motif [¾mi]. The above sequence identity may be 95% or more. Preferred.

[0151] （5 - I V） の改変フイブロインは、 配列番号 22、 配列番号 23又は配 列番号 24で示されるアミノ酸配列と 90%以上の配列同一性を有し、 かつ 最も <3末端側に位置する （ ） „モチーフからドメイン配列の <3末端までの配 列をドメイン配列から除いた配列に含まれる全ての 巳 において、 連続す る 4アミノ酸残基の疎水性指標の平均値が 2. 6以上となる領域に含まれる アミノ酸残基の総数を とし、 最も <3末端側に位置する （/\） „モチーフから 〇 2020/175702 51 卩（：171? 2020 /008524 [0151] The modified fibroin of (5-IV) has 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 22, SEQ ID NO: 23 or SEQ ID NO: 24, and is located at the most <3 terminal side. () The average value of the hydrophobicity index of 4 consecutive amino acid residues is 2.6 or more in all the sequences included in the sequence excluding the sequence from the motif to the <3 end of the domain sequence in the domain sequence. The total number of amino acid residues contained in the region is defined as 〇 2020/175 702 51 卩(: 171-1? 2020/008524

ドメイン配列の〇末端までの配列をドメイン配列から除いた配列に含まれる アミノ酸残基の総数を としたときに、 / 9が 6 . 2 %以上であることが 好ましい。 It is preferable that /9 is 6.2% or more when the total number of amino acid residues contained in the sequence excluding the sequence up to the 0 terminal of the domain sequence is excluded from the domain sequence.

［0152］ 第 5の改変フィブロインは、 組換えタンパク質生産系において生産された タンパク質を宿主の外部に放出するための分泌シグナルを含んでいてもよい 。 分泌シグナルの配列は、 宿主の種類に応じて適宜設定することができる。 [0152] The fifth modified fibroin may contain a secretory signal for releasing the protein produced in the recombinant protein production system to the outside of the host. The sequence of the secretion signal can be appropriately set depending on the type of host.

［0153］ 第 6の改変フィブロインは、 天然由来のフィブロインと比較して、 グルタ ミン残基の含有量が低減されたアミノ酸配列を有する。 [0153] The sixth modified fibroin has an amino acid sequence with a reduced content of glutamine residues as compared to naturally occurring fibroin.

［0154］ 第 6の改変フィブロインは、

Figure imgf000052_0001
巳 のアミノ酸配列中に、 〇〇乂モチーフ 及び◦ 〇乂乂モチーフから選ばれる少なくとも _つのモチーフが含まれて いることが好ましい。 [0154] The sixth modified fibroin is
Figure imgf000052_0001
It is preferable that the amino acid sequence of Minami contains at least _ motifs selected from the XX and XX motifs.

［0155］ 第 6の改変フィブロインが、

Figure imgf000052_0002
[0155] The sixth modified fibroin is
Figure imgf000052_0002

◦ 〇乂乂モチーフ含有率は、 通常 1 %以上であり、 5 %以上であってもよ く、 1 0 %以上であるのが好ましい。 ◦ 〇乂乂モチーフ含有率の上限に特 に制限はなく、 5 0 %以下であってよく、 3 0 %以下であってもよい。 ◯ The content ratio of the motif is usually 1% or more, may be 5% or more, and is preferably 10% or more. ○ There is no particular upper limit for the content ratio of the motif, and it may be 50% or less, or 30% or less.

［0156］ 本明細書において、 「〇 〇 X Xモチーフ含有率」 は、 以下の方法により 算出される値である。 [0156] In the present specification, "XX XX motif content rate" is a value calculated by the following method.

式 1 : ［ （八） nモチーフー ^巳 ］ 、 又は式 2 : ［ （八） „モチーフ_ ^? 巳 ］ （八） „モチーフで表されるドメイン配列を含むフィブロイン （改 変フィブロイン又は天然由来のフィブロイン） において、 最も <3末端側に位 置する （八） „モチーフからドメイン配列の〇末端までの配列をドメイン配列 から除いた配列に含まれる全ての 巳 において、 その領域に含まれる◦ ◦ X Xモチーフの個数の総数を 3倍した数 （即ち、 〇 〇乂乂モチーフ中の ◦及び の総数に相当） を 3とし、 最も <3末端側に位置する （ ） „モチーフ からドメイン配列の〇末端までの配列をドメイン配列から除き、 更に （八） „ モチーフを除いた全 巳 のアミノ酸残基の総数を 1:としたときに、 0 ? 0 X Xモチーフ含有率は 3 / 1として算出される。 Formula 1: [(8) n Motif ^_] or Formula 2: [(8) "Motif_^?_M] (8)" Fibroin containing the domain sequence represented by the motif (modified fibroin or naturally derived Fibroin) (8) The region that is located in the most <3 terminal side (8), except for the sequence from the „motif to the 0 end of the domain sequence, is included in that region in all the sequences included in the sequence ◦ ◦ XX The number obtained by multiplying the total number of motifs by 3 (that is, equivalent to the total number of ◦ and ◯ in the ◯ 〇 乂乂 motif) is set to 3, and from the () „most located at the <3 terminal side to the 〇 terminal of the domain sequence. (8) When the total number of amino acid residues excluding the motif is set to 1:, the 0 to 0XX motif content is calculated as 3/1.

［0157］ ◦ 〇乂乂モチーフ含有率の算出において、 「最も <3末端側に位置する （ 〇 2020/175702 52 卩（：171? 2020 /008524 八） „モチーフからドメイン配列の〇末端までの配列をドメイン配列から除い た配列」 を対象としているのは、 「最も <3末端側に位置する （ ） „モチーフ からドメイン配列の〇末端までの配列」 （?¾巳 に相当する配列） には、 フ ィブロインに特徴的な配列と相関性の低い配列が含まれることがあり、 01が 小さい場合 （つまり、 ドメイン配列が短い場合） 、 〇 〇乂乂モチーフ含有 率の算出結果に影響するので、 この影響を排除するためである。 なお、 ［¾巳 の（3末端に 「〇 〇 X Xモチーフ」 が位置する場合、 「X X」 が例えば 「 八八」 の場合であっても、 「〇 〇乂乂モチーフ」 として扱う。 [0157] ◦ In the calculation of the content ratio of the customary motif, “most located at the <3 end side ( 〇 2020/175702 52 卩 (：171? 2020/008524 VIII) “A sequence in which the sequence from the motif to the 〇 end of the domain sequence is removed from the domain sequence” is targeted at “most located at the <3 end side () "The sequence from the motif to the end of the domain sequence" (the sequence corresponding to ?¾mi) may contain a sequence that has a low correlation with the sequence characteristic of fibroin, and when 01 is small. This is to eliminate this influence (that is, when the domain sequence is short), because it affects the calculation result of the content of the ____________ motif. In addition, in the case of the case where the “XX XX motif” is located at the 3 terminal of ¾, even if the “XX” is, for example, “88”, it is treated as a “XX motif”.

［0158］ 図 9は、 改変フィブロインのドメイン配列を示す模式図である。 図 9を参 照しながら◦ 〇乂乂モチーフ含有率の算出方法を具体的に説明する。 まず 、 図 9に示した改変フィブロインのドメイン配列 （ 「 ［ （八） „モチーフー 巳 ］ 一 （八） „モチーフ」 タイプである。 ） では、 全ての

Figure imgf000053_0001
「最も 〇末端側に位置する （八） „モチーフからドメイン配列の〇末端までの配列を ドメイン配列から除いた配列」 （図 9中、 「領域八」 で示した配列。 ） に含 まれているため、 3を算出するための◦ 〇乂乂モチーフの個数は 7であり 、 3は 7 X 3 = 2 1 となる。 同様に、 全ての
Figure imgf000053_0002
が 「最も〇末端側に位置 する （八） モチーフからドメイン配列の〇末端までの配列をドメイン配列か ら除いた配列」 （図 9中、 「領域八」 で示した配列。 ） に含まれているため 、 当該配列から更に （八） „モチーフを除いた全 巳 のアミノ酸残基の総数 1:は 5 0 + 4 0 + 1 0 + 2 0 + 3 0 = 1 5 0である。 次に、 3を で除すこ とによって、 3 / （%） を算出することができ、 図 9の改変フィブロイン の場合 2 1 / 1 5 0 = 1 4 . 0 %となる。 [0158] FIG. 9 is a schematic diagram showing a domain sequence of modified fibroin. With reference to Fig. 9, the calculation method of the content ratio will be explained in detail. First, in the modified fibroin domain sequence shown in FIG. 9 (“[(8) ”Motif-Min] 1 (8) ”Motif” type.)
Figure imgf000053_0001
It is included in “(8) the most-positioned position (8) ”A sequence obtained by removing the sequence from the motif to the 0 end of the domain sequence from the domain sequence” (the sequence shown as “Region 8” in FIG. 9 ). Therefore, the number of ◯ ◯ 乂乂 motifs for calculating 3 is 7, and 3 is 7 X 3 = 21. Similarly, all
Figure imgf000053_0002
Is included in the “sequence that excludes the sequence from the (8) motif located at the most 0 terminal side to the 0 terminal of the domain sequence from the domain sequence” (the sequence shown as “Region 8” in FIG. 9 ). Therefore, the total number of amino acid residues 1: (8) except for the □ motif is 50+40+1+0+2+0+30=150. By dividing 3 by, 3 / (%) can be calculated, which is 2 1/1 5 0 = 1 4.0% for the modified fibroin in Fig. 9.

［0159］ 第 6の改変フィブロインは、 グルタミン残基含有率が 9 %以下であること が好ましく、 7 %以下であることがより好ましく、 4 %以下であることが更 に好ましく、 0 %であることが特に好ましい。 [0159] The sixth modified fibroin has a glutamine residue content of preferably 9% or less, more preferably 7% or less, further preferably 4% or less, and 0%. Is particularly preferable.

［0160］ 本明細書において、 「グルタミン残基含有率」 は、 以下の方法により算出 される値である。 [0160] In the present specification, the "glutamine residue content rate" is a value calculated by the following method.

式 1 : ［ （八） nモチーフー ^巳 ］ 、 又は式 2 : ［ （八） „モチーフ_ ^? 〇 2020/175702 53 卩（：171? 2020 /008524 Formula 1: [(8) n motif-^mi], or Formula 2: [(8) „motif_^? 〇 2020/175 702 53 卩 (: 171? 2020 /008524

巳 ] 111 - （八） „モチーフで表されるドメイン配列を含むフィブロイン （改 変フィブロイン又は天然由来のフィブロイン） において、 最も <3末端側に位 置する （八） „モチーフからドメイン配列の〇末端までの配列をドメイン配列 から除いた配列 （図 9の 「領域八」 に相当する配列。 ） に含まれる全ての

Figure imgf000054_0001
巳 において、 その領域に含まれるグルタミン残基の総数をリとし、 最も〇 末端側に位置する （八） モチーフからドメイン配列の〇末端までの配列をド メイン配列から除き、 更に （八） „モチーフを除いた全 巳 のアミノ酸残基 の総数を 1:としたときに、 グルタミン残基含有率はリ/ として算出される 。 グルタミン残基含有率の算出において、 「最も <3末端側に位置する （八） „ モチーフからドメイン配列の〇末端までの配列をドメイン配列から除いた配 列」 を対象としている理由は、 上述した理由と同様である。 [ 111 ] (8) „In a fibroin containing a domain sequence represented by a motif (modified fibroin or naturally-occurring fibroin), it is located at the most <3 terminal side (8) All sequences included in the sequence obtained by removing the sequences up to the domain sequence (the sequence corresponding to "Region 8" in Fig. 9)
Figure imgf000054_0001
In Minami, the total number of glutamine residues contained in that region is re-defined, and the sequence from the most 0-terminal (8) motif to the 0-terminal of the domain sequence is excluded from the domain sequence. The glutamine residue content is calculated as r/ when the total number of amino acid residues in all except for is 1:. (8) The reason why "a sequence in which the sequence from the motif to the 0 terminal of the domain sequence is removed from the domain sequence" is targeted is the same as the reason described above.

[0161 ] 第 6の改変フィブロインは、 そのドメイン配列が、 天然由来のフィブロイ ンと比較して、

Figure imgf000054_0002
したこと、 又 は他のアミノ酸残基に置換したことに相当するアミノ酸配列を有するもので あってよい。 [0161] The sixth modified fibroin has a domain sequence that is comparable to that of naturally occurring fibroin.
Figure imgf000054_0002
Or may have an amino acid sequence corresponding to substitution with another amino acid residue.

[0162] 「他のアミノ酸残基」 は、 グルタミン残基以外のアミノ酸残基であればよ いが、 グルタミン残基よりも疎水性指標の大きいアミノ酸残基であることが 好ましい。 アミノ酸残基の疎水性指標は表 1 に示すとおりである。 [0162] The "other amino acid residue" may be any amino acid residue other than the glutamine residue, but is preferably an amino acid residue having a larger hydrophobicity index than the glutamine residue. The hydrophobicity index of amino acid residues is shown in Table 1.

[0163] 表 1 に示すとおり、 グルタミン残基よりも疎水性指標の大きいアミノ酸残 基としては、 イソロイシン （丨） 、 バリン （V） 、 ロイシン （!_） 、 フエニ ルアラニン （ ） 、 システイン （〇） 、 メチオニン （1\/〇 アラニン （八） 、 グリシン （◦） 、 スレオニン （丁） 、 セリン （3） 、 トリブトファン （ ） [0163] As shown in Table 1, isoleucine (丨), valine (V), leucine (!_), phenylalanine (), cysteine (○) were used as amino acid residues having a larger hydrophobicity index than glutamine residues. , Methionine (1\/〇 alanine (8), glycine (◦), threonine (Ding), serine (3), tribtophan ()

、 チロシン （丫） 、 プロリン （ ） 及びヒスチジン （1~1） から選ばれるアミ ノ酸残基を挙げることができる。 これらの中でも、 イソロイシン （丨） 、 バ リン （V） 、 ロイシン （!_） 、 フエニルアラニン （ ） 、 システイン （〇）Examples thereof include amino acid residues selected from tyrosine (丫), proline () and histidine (1 to 1). Among these, isoleucine (丨), valine (V), leucine (!_), phenylalanine (), cysteine (○)

、 メチオニン （1\/〇 及びアラニン （八） から選ばれるアミノ酸残基であるこ とがより好ましく、 イソロイシン （ I） 、 パリン （V） 、 ロイシン （!_） 及 びフエニルアラニン （ ） から選ばれるアミノ酸残基であることが更に好ま 〇 2020/175702 54 卩（：171? 2020 /008524 More preferably, it is an amino acid residue selected from methionine (1\/〇 and alanine (8), selected from isoleucine (I), parin (V), leucine (!_) and phenylalanine ()). More preferred is an amino acid residue 〇 2020/175 702 54 卩 (: 171? 2020 /008524

しい。 Good

［0164］ 第 6の改変フィブロインは、 の疎水性度が、 一〇. 8以上であるこ とが好ましく、 一〇. 7以上であることがより好ましく、 0以上であること が更に好ましく、 〇. 3以上であることが更により好ましく、 〇. 4以上で あることが特に好ましい。

Figure imgf000055_0001
巳 の疎水性度の上限に特に制限はなく、 1 .[0164] The sixth modified fibroin has a hydrophobicity of preferably not less than 100.8, more preferably not less than 107, more preferably not less than 0, and more preferably not less than 0. It is even more preferably 3 or more, and particularly preferably 0.4 or more.
Figure imgf000055_0001
There is no particular upper limit to the hydrophobicity of Tami, 1.

0以下であってよく、 〇. 7以下であってもよい。 It may be 0 or less, and may be 0.7 or less.

［0165］ 本明細書において、 「［¾巳 の疎水性度」 は、 以下の方法により算出され る値である。 [0165] In the present specification, "[hydrophobicity of 辳]" is a value calculated by the following method.

式 1 : ［ （八） nモチーフー ^巳 ］ 、 又は式 2 : ［ （八） „モチーフ_ ^? 巳 ］ （八） „モチーフで表される ドメイン配列を含むフィブロイン （改 変フィブロイン又は天然由来のフィブロイン） において、 最も <3末端側に位 置する （八） モチーフからドメイン配列の〇末端までの配列をドメイン配列 から除いた配列 （図 9の 「領域八」 に相当する配列。 ） に含まれる全ての

Figure imgf000055_0002
º 9において、 その領域の各アミノ酸残基の疎水性指標の総和を Vとし、 最 も〇末端側に位置する （八） „モチーフからドメイン配列の〇末端までの配列 をドメイン配列から除き、 更に （八） „モチーフを除いた全 巳 のアミノ酸 残基の総数を 1： としたときに、
Figure imgf000055_0003
巳 の疎水性度は / として算出される 。 巳 の疎水性度の算出において、 「最も <3末端側に位置する （ ） „モチ —フからドメイン配列の〇末端までの配列をドメイン配列から除いた配列」 を対象としている理由は、 上述した理由と同様である。 Formula 1: [(8) n Motif ^^], or Formula 2: [(8) „Motif _ ^?^ ”(8) „Fibroin containing the domain sequence represented by the motif (modified fibroin or naturally derived In the fibroin), it is included in the sequence (sequence corresponding to “region 8” in Figure 9) in which the sequence from the motif (8) motif located at the most <3 terminal side to the 0 end of the domain sequence is excluded from the domain sequence. All of
Figure imgf000055_0002
In º 9, let V be the sum of the hydrophobicity indices of each amino acid residue in the region, and remove the sequence from the motif located at the 0 end to the 0 end of the domain sequence (8) to the 0 end of the domain sequence. (8) When the total number of all amino acid residues excluding the motif is 1:
Figure imgf000055_0003
The degree of hydrophobicity of Minami is calculated as /. In the calculation of the hydrophobicity of Mami, the reason why "the sequence that is located at the most <3 end side () except the sequence from the motif to the 0 end of the domain sequence is excluded from the domain sequence" is the above-mentioned reason. The reason is the same.

［0166］ 第 6の改変フィブロインは、 そのドメイン配列が、 天然由来のフィブロイ ンと比較して、

Figure imgf000055_0004
したこと、 及 び/又は 巳 中の 1又は複数のグルタミン残基を他のアミノ酸残基に置換 したことに相当する改変に加え、 更に 1又は複数のアミノ酸残基を置換、 欠 失、 揷入及び/又は付加したことに相当するアミノ酸配列の改変があっても よい。 [0166] The sixth modified fibroin has a domain sequence that is comparable to that of naturally-occurring fibroin.
Figure imgf000055_0004
And/or in addition to the modification corresponding to the substitution of one or more glutamine residues in the amino acid residue with another amino acid residue, in addition to the substitution, deletion, insertion of one or more amino acid residues. And/or there may be amino acid sequence alterations corresponding to the additions.

［0167］ 第 6の改変フィブロインは、 例えば、 クローニングした天然由来のフィブ ロインの遺伝子配列から 巳 中の 1又は複数のグルタミン残基を欠失させ 〇 2020/175702 55 卩（：171? 2020 /008524 [0167] The sixth modified fibroin is obtained by, for example, deleting one or more glutamine residues in the cloned gene sequence of naturally-occurring fibroin. 〇 2020/175 702 55 卩 (: 171? 2020 /008524

ること、 及び/又は 巳 中の 1又は複数のグルタミン残基を他のアミノ酸 残基に置換することにより得ることができる。 また、 例えば、 天然由来のフ イブロインのアミノ酸配列から 巳 中の 1又は複数のグルタミン残基を欠 失したこと、 及び/又は 巳 中の 1又は複数のグルタミン残基を他のアミ ノ酸残基に置換したことに相当するアミノ酸配列を設計し、 設計したアミノ 酸配列をコードする核酸を化学合成することにより得ることもできる。 And/or by substituting one or more glutamine residues in Mami with other amino acid residues. In addition, for example, one or more glutamine residues in the amino acid have been deleted from the amino acid sequence of naturally-occurring fibroin, and/or one or more glutamine residues in the amino acid have been deleted from other amino acid residues. It can also be obtained by designing an amino acid sequence corresponding to the substitution with the above and chemically synthesizing a nucleic acid encoding the designed amino acid sequence.

[0168] 第 6の改変フイブロインのより具体的な例として、 （6_ 丨） 配列番号 2 [0168] As a more specific example of the sixth modified fibroin, (6__) SEQ ID NO: 2

5 （1\/161: -? [¾丁888） 、 配列番号 26 （1\/161: -? [¾丁 965） 、 配 列番号 27 （1\/161： -? [¾丁889） 、 配列番号 28 （1\/161： -? [¾丁 9 1 6） 、 配列番号 29 （1\/161： -? [¾丁 9 1 8） 、 配列番号 30 （IV! 61: -

Figure imgf000056_0001
配列番号 3 1 （1\/161： -? [¾丁 698） 、 配列番号 32 （IV! 61： -? [¾丁 966） 、 配列番号 4 1 （1\/161： -? [¾丁 9 1 7） 若しくは配 列番号 42 （1\/161： -? [¾丁 1 028） で示されるアミノ酸配列を含む改変 フイブロイン、 又は （6— 丨 丨） 配列番号 25、 配列番号 26、 配列番号 2 7、 配列番号 28、 配列番号 29、 配列番号 30、 配列番号 3 1、 配列番号 32、 配列番号 4 1若しくは配列番号 42で示されるアミノ酸配列と 90% 以上の配列同一性を有するアミノ酸配列を含む改変フイブロインを挙げるこ とができる。 5 (1\/161: -? [¾ 888), SEQ ID NO: 26 (1\/161: -? [¾ 965), Sequence number 27 (1\/161: -? [¾ 889), SEQ ID NO: 28 (1\/161: -? [¾ 9 16 6), SEQ ID NO: 29 (1\/161: -? [¾ 9 8), SEQ ID NO: 30 (IV! 61:-
Figure imgf000056_0001
SEQ ID NO: 3 1 (1\/161: -? [¾ 698), SEQ ID NO: 32 (IV! 61: -? [¾ 966), SEQ ID NO: 4 1 (1\/161: -? [¾ 9 1 7) or modified fibroin containing the amino acid sequence shown in SEQ ID NO: 42 (1\/161: -? [¾ D 028), or (6 — 丨 丨) SEQ ID NO: 25, SEQ ID NO: 26, SEQ ID NO: 2 7, SEQ ID NO: 28, SEQ ID NO: 29, SEQ ID NO: 30, SEQ ID NO: 31, SEQ ID NO: 32, including an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 41 or SEQ ID NO: 42 The modified fibroin may be mentioned.

[0169] （6 - I） の改変フイブロインについて説明する。 配列番号 25で示され るアミノ酸配列は、 配列番号 7で示されるアミノ酸配列 （1\/161： -? [¾丁4 1 0） 中の〇〇を全て V !_に置換したものである。 配列番号 26で示される アミノ酸配列は、 配列番号 7で示されるアミノ酸配列中の <3 <3を全て丁 3に 置換し、 かつ残りの〇を八に置換したものである。 配列番号 27で示される アミノ酸配列は、 配列番号 7で示されるアミノ酸配列中の <3 <3を全て V !_に 置換し、 かつ残りの〇を 丨 に置換したものである。 配列番号 28で示される アミノ酸配列は、 配列番号 7で示されるアミノ酸配列中の <3 <3を全て V 丨 に 置換し、 かつ残りの〇を !_に置換したものである。 配列番号 29で示される アミノ酸配列は、 配列番号 7で示されるアミノ酸配列中の <3 <3を全て V に 〇 2020/175702 56 卩(：171? 2020 /008524 [0169] The modified fibroin of (6-I) will be described. The amino acid sequence represented by SEQ ID NO: 25 is the amino acid sequence represented by SEQ ID NO: 7 (1\/161: -? [¾ 414) with all V!_ substituted for V. The amino acid sequence represented by SEQ ID NO: 26 is obtained by replacing <3 <3 in the amino acid sequence represented by SEQ ID NO: 7 with all 3's and replacing the remaining ◯ with 8's. The amino acid sequence represented by SEQ ID NO: 27 is the amino acid sequence represented by SEQ ID NO: 7 in which <3 <3 are all replaced with V !_, and the remaining ◯ is replaced with 丨. The amino acid sequence represented by SEQ ID NO: 28 is the amino acid sequence represented by SEQ ID NO: 7 in which <3 <3 are all replaced with V and the remaining ◯ is replaced with !_. The amino acid sequence shown in SEQ ID NO: 29 is the amino acid sequence shown in SEQ ID NO: 7 with V in all <3 <3. 〇 2020/175 702 56 卩 (: 171? 2020 /008524

置換し、 かつ残りの〇を 丨 に置換したものである。 It replaces, and replaces the remaining ◯ with 丨.

[0170] 配列番号 30で示されるアミノ酸配列は、 配列番号 8で示されるアミノ酸 配列 （1\/161： -? [¾丁 525） 中の〇〇を全て V !_に置換したものである。 配列番号 3 1で示されるアミノ酸配列は、 配列番号 8で示されるアミノ酸配 列中の〇〇を全て V !_に置換し、 かつ残りの〇を 丨 に置換したものである。 [0170] The amino acid sequence represented by SEQ ID NO: 30 is the amino acid sequence represented by SEQ ID NO: 8 (1\/161: -? [¾ 525) with all Vs replaced with V !_. The amino acid sequence represented by SEQ ID NO: 31 is the amino acid sequence represented by SEQ ID NO: 8 with all ◯◯ replaced with V !_, and the remaining ◯ replaced with 丨.

[0171] 配列番号 32で示されるアミノ酸配列は、 配列番号 7で示されるアミノ酸 配列 （1\/161： -? [¾丁4 1 0） 中に存在する 20個のドメイン配列の領域を 2回繰り返した配列中の <30を全て V に置換し、 かつ残りの <3を I に置換 したものである。 [0171] The amino acid sequence represented by SEQ ID NO: 32 is the region of 20 domain sequences present in the amino acid sequence represented by SEQ ID NO: 7 (1\/161: -? In the repeated sequence, all <30 are replaced with V, and the remaining <3 are replaced with I.

[0172] 配列番号 4 1で示されるアミノ酸配列

Figure imgf000057_0001
は、 配列 番号 7で示されるアミノ酸配列中の〇〇を全て !_ 丨 に置換し、 かつ残りの〇 を Vに置換したものである。 配列番号 42で示されるアミノ酸配列 （IV! 6 - [¾丁 1 028） は、 配列番号 7で示されるアミノ酸配列中の〇〇を全て I に置換し、 かつ残りの〇を丁に置換したものである。 [0172] Amino acid sequence represented by SEQ ID NO: 41
Figure imgf000057_0001
Is the one in which all ◯ in the amino acid sequence shown in SEQ ID NO: 7 is replaced with !_ 丨, and the remaining ◯ is replaced with V. The amino acid sequence shown in SEQ ID NO: 42 (IV! 6-[¾ D 028) is the amino acid sequence shown in SEQ ID NO: 7 with all ◯ replaced with I, and the remaining ◯ replaced with D. Is.

[0173] 配列番号 25、 配列番号 26、 配列番号 27、 配列番号 28、 配列番号 2 [0173] SEQ ID NO:25, SEQ ID NO:26, SEQ ID NO:27, SEQ ID NO:28, SEQ ID NO:2

9、 配列番号 30、 配列番号 3 1、 配列番号 32、 配列番号 4 1及び配列番 号 42で示されるアミノ酸配列は、 いずれもグルタミン残基含有率は 9%以 下である （表 2） 。 The amino acid sequences shown in 9, SEQ ID NO: 30, SEQ ID NO: 31, SEQ ID NO: 32, SEQ ID NO: 41 and SEQ ID NO: 42 all have a glutamine residue content of 9% or less (Table 2).

[0174] [表 2] [0174] [Table 2]

Figure imgf000057_0002
Figure imgf000057_0002

[0175] （6- I） の改変フイブロインは、 配列番号 25、 配列番号 26、 配列番 〇 2020/175702 57 卩（：171? 2020 /008524 [0175] The modified fibroin of (6-I) has SEQ ID NO: 25, SEQ ID NO: 26, SEQ ID NO: 〇 2020/175 702 57 卩 (：171? 2020 /008524

号 27、 配列番号 28、 配列番号 29、 配列番号 30、 配列番号 3 1、 配列 番号 32、 配列番号 4 1又は配列番号 42で示されるアミノ酸配列からなる ものであつてもよい。 No. 27, SEQ ID NO: 28, SEQ ID NO: 29, SEQ ID NO: 30, SEQ ID NO: 31, SEQ ID NO: 32, SEQ ID NO: 41 or SEQ ID NO: 42 may be used.

［0176］ （6 - I \） の改変フィブロインは、 配列番号 25、 配列番号 26、 配列 番号 27、 配列番号 28、 配列番号 29、 配列番号 30、 配列番号 3 1、 配 列番号 32、 配列番号 4 1又は配列番号 42で示されるアミノ酸配列と 90 %以上の配列同一性を有するアミノ酸配列を含むものである。 （6 - 丨 I） の改変フィブロインもまた、 式 1 : ［ （八） „モチーフー［¾巳 ］ ^ 又は式 2 : ［ （八）

Figure imgf000058_0001
一 （八） „モチ—フで表されるドメイン配 列を含むタンパク質である。 上記配列同一性は、 95%以上であることが好 ましい。 [0176] The modified fibroin of (6-I \) has SEQ ID NO: 25, SEQ ID NO: 26, SEQ ID NO: 27, SEQ ID NO: 28, SEQ ID NO: 29, SEQ ID NO: 30, SEQ ID NO: 31, SEQ ID NO: 32, SEQ ID NO: 41 or an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 42. The modified fibroin of (6-丨 I) also has the formula 1: [(8) „Motif [¾mi] ^ or the formula 2: [(8)
Figure imgf000058_0001
(8) "A protein containing a domain sequence represented by a motif. The above sequence identity is preferably 95% or more.

［0177］ （6 - I \） の改変フィブロインは、 グルタミン残基含有率が 9 %以下で あることが好ましい。 また、 （6— 丨 丨） の改変フィブロインは、 〇 〇乂 Xモチーフ含有率が 1 0%以上であることが好ましい。 [0177] The modified fibroin of (6-I\) preferably has a glutamine residue content of 9% or less. Further, it is preferable that the modified fibroin of (6 — 丨 丨) has a content of XX X motif of 10% or more.

［0178］ 第 6の改変フィブロインは、 1\1末端及び◦末端のいずれか一方又は両方に タグ配列を含んでいてもよい。 これにより、 改変フィブロインの単離、 固定 化、 検出及び可視化等が可能となる。 [0178] The sixth modified fibroin may include a tag sequence at either one or both of the 1\1 end and the ?-end. This enables the isolation, immobilization, detection and visualization of modified fibroin.

［0179］ タグ配列を含む改変フィブロインのより具体的な例として、 （6— 丨 丨 I ） 配列番号 33 （ ［¾丁888） 、 配列番号 34 （ ［¾丁 965） 、 配列番 号 35 （ ［¾丁889） 、 配列番号 36 （ 丁 9 1 6） 、 配列番号 37 （

Figure imgf000058_0002
配列番号 38 （ ［¾丁 699） 、 配列番号 39 （ 丁 6 98） 、 配列番号 40 （ 丁 966） 、 配列番号 43 （ 丁 9 1 7） 若 しくは配列番号 44 （ ［¾丁 1 028） で示されるアミノ酸配列を含む改変 フィブロイン、 又は （6— 丨 V） 配列番号 33、 配列番号 34、 配列番号 3 5、 配列番号 36、 配列番号 37、 配列番号 38、 配列番号 39、 配列番号 40、 配列番号 43若しくは配列番号 44で示されるアミノ酸配列と 90% 以上の配列同一性を有するアミノ酸配列を含む改変フィブロインを挙げるこ とができる。 〇 2020/175702 58 卩（：171? 2020 /008524 [0179] As a more specific example of the modified fibroin containing the tag sequence, (6—丨丨I) SEQ ID NO:33 ([¾888), SEQ ID NO:34 ([¾965], SEQ ID NO:35 ([ ¾ Die 889), SEQ ID NO: 36 (Ding 9 16), SEQ ID NO: 37 (
Figure imgf000058_0002
SEQ ID NO: 38 ([¾ Ding 699), SEQ ID NO: 39 (Ding 6 98), SEQ ID NO: 40 (Ding 966), SEQ ID NO: 43 (Ding 9 17) or SEQ ID NO: 44 ([¾ Ding 028]) A modified fibroin containing the amino acid sequence shown, or (6 — V) SEQ ID NO: 33, SEQ ID NO: 34, SEQ ID NO: 35, SEQ ID NO: 36, SEQ ID NO: 37, SEQ ID NO: 38, SEQ ID NO: 39, SEQ ID NO: 40, sequence A modified fibroin containing an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by SEQ ID NO: 43 or SEQ ID NO: 44 can be mentioned. 〇 2020/175 702 58 卩 (：171? 2020 /008524

[0180] 配列番号 3 3、 配列番号 3 4、 配列番号 3 5、 配列番号 3 6、 配列番号 3 [0180] SEQ ID NO: 3 3, SEQ ID NO: 34, SEQ ID NO: 35, SEQ ID NO: 36, SEQ ID NO: 3

7、 配列番号 3 8、 配列番号 3 9、 配列番号 4 0、 配列番号 4 3及び配列番 号 4 4で示されるアミノ酸配列は、 それぞれ配列番号 2 5、 配列番号 2 6、 配列番号 2 7、 配列番号 2 8、 配列番号 2 9、 配列番号 3 0、 配列番号 3 1 、 配列番号 3 2、 配列番号 4 1及び配列番号 4 2で示されるアミノ酸配列の 1\1末端に配列番号 1 1で示されるアミノ酸配列 （1~1 丨 3タグ配列及びヒンジ 配列を含む） を付加したものである。 1\!末端にタグ配列を付加しただけであ るため、 グルタミン残基含有率に変化はなく、 配列番号 3 3、 配列番号 3 4 、 配列番号 3 5、 配列番号 3 6、 配列番号 3 7、 配列番号 3 8、 配列番号 3 9、 配列番号 4 0、 配列番号 4 3及び配列番号 4 4で示されるアミノ酸配列 は、 いずれもグルタミン残基含有率が 9 %以下である （表 3） 。 7, SEQ ID NO: 38, SEQ ID NO: 39, SEQ ID NO: 40, SEQ ID NO: 43 and SEQ ID NO: 4 4, the amino acid sequences shown are SEQ ID NO: 25, SEQ ID NO: 26, SEQ ID NO: 27, respectively. SEQ ID NO: 28, SEQ ID NO: 29, SEQ ID NO: 30, SEQ ID NO: 31, SEQ ID NO: 32, SEQ ID NO: 41 and SEQ ID NO: 42 are represented by SEQ ID NO: 1 at the 1\1 end of the amino acid sequence. The amino acid sequence shown (including 1 to 1 3 tag sequence and hinge sequence) is added. Since only the tag sequence was added to the 1\! end, there was no change in the glutamine residue content, and SEQ ID NO:33, SEQ ID NO:34, SEQ ID NO:35, SEQ ID NO:36, SEQ ID NO:37 , SEQ ID NO: 38, SEQ ID NO: 39, SEQ ID NO: 40, SEQ ID NO: 43 and SEQ ID NO: 44 all have a glutamine residue content of 9% or less (Table 3).

[0181 ] [表 3] [0181] [Table 3]

Figure imgf000059_0001
Figure imgf000059_0001

[0182] （6 - I I \ ） の改変フイブロインは、 配列番号 3 3、 配列番号 3 4、 配 列番号 3 5、 配列番号 3 6、 配列番号 3 7、 配列番号 3 8、 配列番号 3 9、 配列番号 4 0、 配列番号 4 3又は配列番号 4 4で示されるアミノ酸配列から なるものであってもよい。 [0182] The modified fibroin of (6-II \) has SEQ ID NO: 33, SEQ ID NO: 34, SEQ ID NO: 35, SEQ ID NO: 36, SEQ ID NO: 37, SEQ ID NO: 38, SEQ ID NO: 39, It may consist of the amino acid sequence of SEQ ID NO: 40, SEQ ID NO: 43 or SEQ ID NO: 44.

[0183] （6 - I V） の改変フイブロインは、 配列番号 3 3、 配列番号 3 4、 配列 番号 3 5、 配列番号 3 6、 配列番号 3 7、 配列番号 3 8、 配列番号 3 9、 配 列番号 4 0、 配列番号 4 3又は配列番号 4 4で示されるアミノ酸配列と 9 0 %以上の配列同一性を有するアミノ酸配列を含むものである。 （6 - 丨 V） 〇 2020/175702 59 卩（：171? 2020 /008524 [0183] The modified fibroin of (6-IV) has the following sequences: SEQ ID NO: 33, SEQ ID NO: 34, SEQ ID NO: 35, SEQ ID NO: 36, SEQ ID NO: 37, SEQ ID NO: 38, SEQ ID NO: 39. It includes an amino acid sequence having 90% or more sequence identity with the amino acid sequence represented by No. 40, SEQ ID NO: 43 or SEQ ID NO: 44. (6-V) 〇 2020/175 702 59 卩 (：171? 2020 /008524

の改変フィブロインもまた、 式 1 : ［ （八） „モチーフー［¾巳 ］ ^ 又は式 2 : ［ （八）

Figure imgf000060_0001
一 （八） „モチ—フで表されるドメイン配 列を含むタンパク質である。 上記配列同一性は、 9 5 %以上であることが好 ましい。 The modified fibroin of is also represented by Formula 1: [(8) „Motif [¾mi] ^ or Formula 2: [(8)
Figure imgf000060_0001
(8) "A protein containing a domain sequence represented by a motif. The above sequence identity is preferably 95% or more.

［0184］ （6 - I V） の改変フィブロインは、 グルタミン残基含有率が 9 %以下で あることが好ましい。 また、 （6— 丨 V） の改変フィブロインは、 〇 〇乂 Xモチーフ含有率が 1 0 %以上であることが好ましい。 [0184] The modified fibroin of (6-IV) preferably has a glutamine residue content of 9% or less. In addition, the modified fibroin of (6 — V) preferably has a content of XX X motif of 10% or more.

［0185］ 第 6の改変フィブロインは、 組換えタンパク質生産系において生産された タンパク質を宿主の外部に放出するための分泌シグナルを含んでいてもよい 。 分泌シグナルの配列は、 宿主の種類に応じて適宜設定することができる。 [0185] The sixth modified fibroin may contain a secretory signal for releasing the protein produced in the recombinant protein production system to the outside of the host. The sequence of the secretion signal can be appropriately set depending on the type of host.

［0186］ 改変フィブロインは、 第 1の改変フィブロイン、 第 2の改変フィブロイン 、 第 3の改変フィブロイン、 第 4の改変フィブロイン、 第 5の改変フィブロ イン、 及び第 6の改変フィブロインが有する特徴のうち、 少なくとも 2つ以 上の特徴を併せ持つ改変フィブロインであってもよい。 [0186] The modified fibroin is the first modified fibroin, the second modified fibroin, the third modified fibroin, the fourth modified fibroin, the fifth modified fibroin, and the sixth modified fibroin having the following characteristics. It may be a modified fibroin having at least two or more characteristics.

［0187］ 改変フィブロインとしては、 親水性改変フィブロインであってもよく、 疎 水性改変フィブロインであってもよい。 本明細書において、 「親水性改変フ ィブロイン」 とは、 改変フィブロインを構成する全てのアミノ酸残基の疎水 性指標 （!~1 I） の総和を求め、 次にその総和を全アミノ酸残基数で除した値 （平均 1~1 丨） が 0以下である改変フィブロインである。 疎水性指標は表 1 に 示したとおりである。 また、 「疎水性改変フィブロイン」 とは、 平均 1~1 丨が 0超である改変フィブロインである。 親水性改変フィブロインは、 特に難燃 性に優れている。 疎水性改変フィブロインは、 特に吸湿発熱性及び保温性に 優れている。 改変フィブロインとしては、 疎水性改変フィブロインを使用す るのが好ましい。 [0187] The modified fibroin may be hydrophilic modified fibroin or hydrophobic modified fibroin. In the present specification, “hydrophilic modified fibroin” means the sum of hydrophobicity indices (! ~ 1 I) of all amino acid residues constituting modified fibroin, and then the sum is calculated as the total number of amino acid residues. It is a modified fibroin whose value (average of 1 to 1) divided by is 0 or less. The hydrophobicity index is shown in Table 1. Further, the “hydrophobic modified fibroin” is a modified fibroin having an average of 1 to 1 over 0. Hydrophilic modified fibroin is particularly excellent in flame retardancy. Hydrophobic modified fibroin is particularly excellent in heat absorption by heat absorption and heat retention. As the modified fibroin, it is preferable to use hydrophobic modified fibroin.

［0188］ 親水性改変フィブロインとしては、 例えば、 配列番号 4で示されるアミノ 酸配列、 配列番号 6、 配列番号 7、 配列番号 8又は配列番号 9で示されるア ミノ酸配列、 配列番号 1 3、 配列番号 1 1、 配列番号 1 4又は配列番号 1 5 で示されるアミノ酸配列、 配列番号 1 8、 配列番号 7、 配列番号 8又は配列 〇 2020/175702 60 卩（：171? 2020 /008524 [0188] Examples of the hydrophilic modified fibroin include amino acid sequence represented by SEQ ID NO: 4, amino acid sequence represented by SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 or amino acid sequence represented by SEQ ID NO: 9, SEQ ID NO: 13, Amino acid sequence represented by SEQ ID NO: 11, SEQ ID NO: 14 or SEQ ID NO: 15; SEQ ID NO: 18; SEQ ID NO: 7; SEQ ID NO: 8 or sequence 〇 2020/175 702 60 卩 (: 171-1? 2020 /008524

番号 9で示されるアミノ酸配列、 配列番号 1 7、 配列番号 1 1、 配列番号 1 4又は配列番号 1 5で示されるアミノ酸配列、 配列番号 1 9、 配列番号 2 0 又は配列番号 2 1で示されるアミノ酸配列を含む改変フイブロインが挙げら れる。 The amino acid sequence represented by SEQ ID NO: 9, SEQ ID NO: 17, SEQ ID NO: 11, SEQ ID NO: 14 or the amino acid sequence represented by SEQ ID NO: 15 is represented by SEQ ID NO: 19, SEQ ID NO: 20 or SEQ ID NO: 21 Examples include modified fibroin containing an amino acid sequence.

[0189] 疎水性改変フイブロインとしては、 例えば、 配列番号 2 7、 配列番号 2 8 、 配列番号 2 9、 配列番号 3 0、 配列番号 3 1、 配列番号 3 2、 配列番号 3 3又は配列番号 4 3で示されるアミノ酸配列、 配列番号 3 5、 配列番号 3 7 、 配列番号 3 8、 配列番号 3 9、 配列番号 4 0、 配列番号 4 1又は配列番号 4 4で示されるアミノ酸配列を含む改変フイブロインが挙げられる。 [0189] Examples of the hydrophobic modified fibroin include, for example, SEQ ID NO: 27, SEQ ID NO: 28, SEQ ID NO: 29, SEQ ID NO: 30, SEQ ID NO: 31, SEQ ID NO: 3 2, SEQ ID NO: 3 or SEQ ID NO: 4. Modified fibroin containing the amino acid sequence represented by SEQ ID NO:3, SEQ ID NO:35, SEQ ID NO:37, SEQ ID NO:38, SEQ ID NO:39, SEQ ID NO:40, SEQ ID NO:41 or SEQ ID NO:44. Is mentioned.

[0190] 本実施形態に係るタンパク質は、 当該タンパク質をコードする核酸を使用 して、 常法により製造することができる。 当該タンパク質をコードする核酸 は、 塩基配列情報に基づいて、 化学合成してもよく、

Figure imgf000061_0001
法等を利用して 合成してもよい。 [0190] The protein according to the present embodiment can be produced by a conventional method using a nucleic acid encoding the protein. The nucleic acid encoding the protein may be chemically synthesized based on the nucleotide sequence information,
Figure imgf000061_0001
It may be synthesized using a method or the like.

[0191 ] タンパク質極細繊維又はタンパク質繊維は、 例えば、 タンパク質を溶解可 能な溶媒で溶解させてドープ液とし、 湿式紡糸、 乾式紡糸、 乾湿式紡糸又は 溶融紡糸等の公知の紡糸方法により紡糸して得ることができる。 タンパク質 極細繊維は、 上述したエレクトロスピニング法により紡糸して得ることが好 ましい。 タンパク質を溶解可能な溶媒としては、 例えば、 ジメチルスルホキ シド

Figure imgf000061_0002
1\1 , 1\1 -ジメチルホルムアミ ド （0 1\/1 ） 、 ギ酸、 及び ヘキサフルオロイソプロパノール （1~1 丨 ） 等が挙げられる。 当該溶媒に は、 溶解促進剤として無機塩を添加してもよい。 [0191] The protein ultrafine fiber or protein fiber is prepared, for example, by dissolving a protein in a solvent capable of dissolving it to obtain a dope solution, which is spun by a known spinning method such as wet spinning, dry spinning, dry wet spinning or melt spinning. Obtainable. The protein ultrafine fibers are preferably obtained by spinning by the electrospinning method described above. Solvents capable of dissolving proteins include, for example, dimethyl sulfoxide
Figure imgf000061_0002
1\1, 1\1-dimethylformamide (0 1\/1), formic acid, and hexafluoroisopropanol (1 to 1) are listed. An inorganic salt may be added to the solvent as a dissolution promoter.

[0192] 〔第 2の発明に係る防水透湿性生地〕 [0192] [Waterproof and breathable fabric according to the second invention]

第 2実施形態に係る防水透湿性生地は、 繊維径 1 〇 以下の極細繊維を 含む不織布 （以下、 単に 「不織布」 ともいう。 ） からなる防水透湿層 2と、 第 1の耐水性付与物質を含有する編織体からなる表皮層 1 とが接合されてな る。 The waterproof/moisture permeable fabric according to the second embodiment is a waterproof/moisture permeable layer 2 made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less (hereinafter also simply referred to as “non-woven fabric”), and a first water resistance imparting substance. It is joined to the skin layer 1 made of a knitted fabric containing.

[0193] 第 2実施形態に係る防水透湿性生地の表皮層 1は、 第 1の耐水性付与物質 を含有する編織体からなる。 編織体とは、 編地及び織地の総称である。 編地 〇 2020/175702 61 卩（：171? 2020 /008524 [0193] The skin layer 1 of the waterproof/moisture permeable fabric according to the second embodiment is made of a knitted fabric containing the first water resistance-imparting substance. A knitted fabric is a general term for knitted fabrics and woven fabrics. Knitted fabric 〇 2020/175 702 61 卩 (：171? 2020 /008524

は、 横編、 丸編等の緯編組織を有する編地 （単に 「緯編地」 ともいう。 ） 、 トリコッ ト、 ラッセル等の経編組織を有する編地 （単に 「経編地」 ともいう 。 ） のいずれであってもよい。 織地は、 平織、 綾織、 又は嬬子織のうちのい ずれの組織を有する織地であってもよい。 編織体は、 編成又は織成により得 られる未加工の編織体そのものであってもよいし、 編成又は織成後に撥水加 エ等の加工を施した編織体であってもよい。 Is a knitted fabric having a weft knitting structure such as a flat knit or circular knit (also simply referred to as “weft knitted fabric”), a knitted fabric having a warp knitting structure such as tricot, Russell (also simply referred to as “warp knitted fabric”) Any of) may be used. The woven fabric may be a woven fabric having any one of a plain weave, a twill weave, and a Tsumushi weave. The knitted or woven body may be an unprocessed knitted or woven body itself obtained by knitting or weaving, or may be a knitted or woven body subjected to processing such as water repellent after knitting or weaving.

[0194] 耐水性付与物質は、 防水透湿性生地の耐水性を向上させ得る物質である。 [0194] The water resistance-imparting substance is a substance capable of improving the water resistance of the waterproof and moisture-permeable fabric.

防水透湿性生地が耐水性付与物質を含むことにより、 例えば、 防水透湿性生 地の撥水性が向上する、 防水透湿性生地の水接触時の収縮が抑制される等の 効果が発揮され、 防水透湿性生地の防水性がより一層向上することになる。 When the waterproof/moisture permeable fabric contains a water resistance-imparting substance, for example, the water repellency of the waterproof/moisture permeable fabric is improved, and the contraction of the waterproof/moisture permeable fabric upon contact with water is exerted. The waterproof property of the breathable fabric is further improved.

[0195] 耐水性付与物質の具体例としては、 例えば、 フッ素系ポリマー及びシリコ —ン系ポリマー、 並びにヒドロキシル基含有ポリマーに疎水性官能基が結合 した修飾ヒドロキシル基含有ポリマー等の疏水性ポリマーが挙げられる。 表 皮層 1がタンパク質繊維を含む場合、 耐水性付与物質の更なる具体例として 、 タンパク質と反応して結合を形成可能な第一の反応性基を 2つ以上有する 多官能反応剤 （第一の反応剤） 、 タンパク質と反応して結合を形成可能な第 _の反応性基を 1つ以上、 及び機能性基を有する反応剤等のタンパク質結合 剤を挙げることができる。 [0195] Specific examples of the water resistance-imparting substance include, for example, hydrophobic polymers such as fluorine-based polymers and silicone-based polymers, and modified hydroxyl group-containing polymers in which a hydrophobic functional group is bonded to a hydroxyl group-containing polymer. To be When the skin layer 1 contains a protein fiber, as a further specific example of the water resistance-imparting substance, a polyfunctional agent having two or more first reactive groups capable of reacting with a protein to form a bond (first Reactive agent), a protein-binding agent such as a reactive agent having one or more _th reactive group capable of reacting with a protein to form a bond, and a functional group.

[0196] フッ素系ポリマーとしては、 フッ素を含むポリマーであれば特に制限され ない。 フッ素系ポリマーは、 例えば、 フッ素を含むオレフィンを重合して得 られるポリマーであってよい。 フッ素系ポリマーとしては、 例えば、 ポリテ トラフルオロエチレン、 ポリ トリフルオロエチレン、 ポリクロロトリフルオ ロエチレン、 ポリフッ化ビニル、 ポリフッ化ビニリデン、 ポリパーフルオロ アルキルビニルエーテル、 ポリパーフルオロプロピレン、 ポリテトラフルオ ロエチレンーパーフルオロプロピレン共重合体、 テトラフルオロエチレンー エチレン共重合体、 及びポリフッ化ビニルーエチレン共重合体が挙げられる 。 フッ素系ポリマーとしては、 例示したポリマーを構成するモノマー 2種以 上を重合して得られる共重合体 （ランダム共重合体、 ブロック共重合体又は 〇 2020/175702 62 卩（：171? 2020 /008524 [0196] The fluorine-based polymer is not particularly limited as long as it is a polymer containing fluorine. The fluorine-based polymer may be, for example, a polymer obtained by polymerizing an olefin containing fluorine. Examples of fluoropolymers include polytetrafluoroethylene, polytrifluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyperfluoroalkyl vinyl ether, polyperfluoropropylene, polytetrafluoroethylene-perfluoro. Propylene copolymers, tetrafluoroethylene-ethylene copolymers, and polyvinyl fluoride-ethylene copolymers. As the fluorine-based polymer, a copolymer obtained by polymerizing two or more kinds of monomers constituting the exemplified polymer (random copolymer, block copolymer or 〇 2020/175 702 62 卩 (：171? 2020 /008524

交互共重合体を含む。 ） であってもよい。 Includes alternating copolymers. ) May be.

[0197] シリコーン系ポリマーとしては、 主鎖にポリシロキサン構造を有するポリ マーであれば特に制限されない。 シリコーン系ポリマーは、 例えば、 シロキ サン構造単位を有するモノマー 1種又は 2種以上を重合して得られる単独重 合体又は共重合体 （ランダム共重合体、 ブロック共重合体又は交互共重合体 を含む。 ） であってよい。 シリコーン系ポリマーとしては、 シロキサン構造 単位を有するモノマー 1種又は 2種以上と、 シロキサン構造単位を有しない モノマー 1種又は 2種以上とを重合して得られる共重合体 （ランダム共重合 体、 ブロック共重合体又は交互共重合体を含む。 ） であってもよい。 [0197] The silicone-based polymer is not particularly limited as long as it is a polymer having a polysiloxane structure in the main chain. The silicone-based polymer includes, for example, a homopolymer or a copolymer (random copolymer, block copolymer or alternating copolymer) obtained by polymerizing one or more monomers having a siloxane structure unit. ) May be. As the silicone polymer, a copolymer obtained by polymerizing one or more monomers having a siloxane structural unit and one or more monomers having no siloxane structural unit (random copolymer, block (Including a copolymer or an alternating copolymer).

[0198] 修飾ヒドロキシル基含有ポリマーは、 ヒドロキシル基含有ポリマーに疏水 性官能基が結合したポリマーである。 修飾ヒドロキシル基含有ポリマーは、 例えば、 ヒドロキシル基含有ポリマーと、 疎水性官能基を有する反応剤とを 反応させることで得ることができる。 [0198] The modified hydroxyl group-containing polymer is a polymer having a hydrophobic functional group bonded to the hydroxyl group-containing polymer. The modified hydroxyl group-containing polymer can be obtained, for example, by reacting a hydroxyl group-containing polymer with a reactive agent having a hydrophobic functional group.

[0199] ヒドロキシル基含有ポリマーは、 ヒドロキシル基を有する高分子化合物で あれば、 特に制限なく使用することができる。 ヒドロキシル基含有ポリマー の具体例としては、 例えば、 デンプン、 グリコーゲン、 セルロース、 キチン 、 アガロース、 ヒアルロン酸、 コンドロイチン硫酸、 ぺクチン及びカラギー ナン等の多糖類、 ポリビニルアルコール （ 八） 及びフエノール樹脂等の 合成高分子が挙げられる。 ヒドロキシル基含有ポリマーとしては、 生分解性 を有するという観点からは、 多糖類が好ましい。 また、 ヒドロキシル基含有 ポリマーとしては、 生分解性を有することに加え溶解性が高いという観点か らは、 デンプンが好ましい。 [0199] The hydroxyl group-containing polymer can be used without particular limitation as long as it is a polymer compound having a hydroxyl group. Specific examples of the hydroxyl group-containing polymer include, for example, starch, glycogen, cellulose, chitin, agarose, hyaluronic acid, chondroitin sulfate, polysaccharides such as pectin and carrageenan, polyvinyl alcohol (8) and phenol resin. Molecules. The hydroxyl group-containing polymer is preferably a polysaccharide from the viewpoint of biodegradability. Further, as the hydroxyl group-containing polymer, starch is preferable from the viewpoint of high biodegradability and high solubility.

[0200] 疎水性官能基を有する反応剤は、 疎水性官能基を有し、 更にヒドロキシル 基含有ポリマーと結合可能な結合性官能基を有する化合物である。 結合性官 能基は、 ヒドロキシル基含有ポリマーと、 水素結合又は共有結合で結合可能 であればよいが、 ヒドロキシル基含有ポリマーと共有結合で結合可能な官能 基であることが好ましく、 ヒドロキシル基含有ポリマー中のヒドロキシル基 と共有結合で結合可能な官能基であることがより好ましい。 疎水性官能基と 〇 2020/175702 63 卩（：171? 2020 /008524 [0200] The reactive agent having a hydrophobic functional group is a compound having a hydrophobic functional group and further having a binding functional group capable of binding to a hydroxyl group-containing polymer. The binding functional group may be capable of being bonded to the hydroxyl group-containing polymer through a hydrogen bond or a covalent bond, but is preferably a functional group capable of being covalently bonded to the hydroxyl group-containing polymer, and is preferably a hydroxyl group-containing polymer. More preferably, it is a functional group capable of covalently bonding to the hydroxyl group therein. With hydrophobic functional groups 〇 2020/175 702 63 卩 (：171? 2020 /008524

しては、 例えば、 メチル基、 エチル基、 门ープロピル基、 イソプロピル基等 のアルキル基、 フエニル基、 ナフチル基等の芳香族基、 並びにアセチル基、 プロパノイル基、 ベンゾイル基等のアシル基が挙げられる。 疎水性官能基を 有する反応剤としては、 例えば、 疎水性官能基を有するイソシアネート ^

Figure imgf000064_0001
は疎水性官能基） 、 酸無水物 （［¾_◦ （=〇） -0-0 （ =〇） 一［¾ :
Figure imgf000064_0002
は疎水性官能基） 、 エポキシド、 アジリジン及びアルキルハ ライ ド等が挙げられる。 Examples thereof include alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group, aromatic groups such as phenyl group and naphthyl group, and acyl groups such as acetyl group, propanoyl group and benzoyl group. .. Examples of the reactive agent having a hydrophobic functional group include isocyanate having a hydrophobic functional group ^
Figure imgf000064_0001
Is a hydrophobic functional group), an acid anhydride ([¾_ ◦ (= 〇) -0-0 (= 〇) 1 [¾:
Figure imgf000064_0002
Is a hydrophobic functional group), epoxide, aziridine, alkyl halide, and the like.

［0201］ タンパク質結合剤としては、 例えば、 タンパク質と反応して結合を形成可 能な第一の反応性基を 2つ以上有する多官能反応剤 （第一の反応剤） 、 タン パク質と反応して結合を形成可能な第一の反応性基を 1つ以上、 及び機能性 基を有する反応剤 （機能性反応剤） を挙げることができる。 [0201] Examples of the protein-binding agent include, for example, a polyfunctional reaction agent (first reaction agent) having two or more first reactive groups capable of reacting with a protein to form a bond, a reaction with a protein. And one or more first reactive groups capable of forming a bond, and a reactive agent having a functional group (functional reactive agent).

［0202］ 第一の反応剤は、 タンパク質に含まれるアミ ド基、 ヒドロキシル基、 フエ ノール性水酸基、 アミノ基、 カルボキシル基、 チオール基、 セレノール基、 イミダゾリル基、 インドリル基及びグアニジノ基からなる群より少なくとも _種の反応性官能基と反応して結合を形成可能な第一の反応性基を有する。 [0202] The first reactive agent is selected from the group consisting of an amide group, a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxyl group, a thiol group, a selenol group, an imidazolyl group, an indolyl group and a guanidino group contained in a protein. It has a first reactive group capable of reacting with at least _ reactive functional groups to form a bond.

［0203］ 第一の反応性基としては、 例えば、 下記式 （八一 1） 、 （八一2） 、 （八 — 3） 、 （八一 4） 、 （八一 5） 又は （八一 6） で表される基が挙げられる 。 各式中の波線は、 各基の結合手を示す。 [0203] Examples of the first reactive group include, for example, the following formulas (81-1), (81-2), (8-3), (81-4), (81-5) or (81-6). ) The group represented by is mentioned. The wavy line in each formula represents a bond of each group.

［化 1］

Figure imgf000064_0003
[Chemical 1]
Figure imgf000064_0003

（八- 1） （ 2） （ 3） （ 4） （ 5） （ 6） (8-1) (2) (3) (4) (5) (6)

［0204］ 式 （八一 1） 中、 X1は酸素原子 （〇） 又は硫黄原子 （3） を示す。 式 （八 -3） 中、 X 2は脱離基を示す。 式 （八一4） 中、 X3は酸素原子 （〇） 、 硫 黄原子 （3） 、

Figure imgf000064_0005
又は、
Figure imgf000064_0004
（［¾5） 2_で表される基 を示す。
Figure imgf000064_0006
は、 例えば、 水素原子、 アルキル基、 アリール基、 ハロゲン化ア ルキル基又はハロゲン化アリール基、 アリールスルホニル基、 アルキルスル ホニル基、 アシル基、 力ーバメート基であってよい。
Figure imgf000064_0007
は、 電子求引性基を 〇 2020/175702 64 卩(：171? 2020 /008524 [0204] In the formula (81), X 1 represents an oxygen atom (○) or a sulfur atom (3). In formula (8 -3), X 2 represents a leaving group. In the formula (81), X 3 is an oxygen atom (○), a sulfur atom (3),
Figure imgf000064_0005
Or
Figure imgf000064_0004
A group represented by ([¾ 5 ) 2 _ is shown.
Figure imgf000064_0006
May be, for example, a hydrogen atom, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group, an arylsulfonyl group, an alkylsulfonyl group, an acyl group, a power-bamate group.
Figure imgf000064_0007
Is an electron-withdrawing group 〇 2020/175 702 64 卩(: 171? 2020/008524

示す。 式 （八一 5） 中、 X 4は酸素原子 （〇） 又は硫黄原子 （3） を示し、 丫 1はハロゲン原子、 ヒドロキシル基、 で表される基、 一〇［¾ 6で表される 基、 又は、 一〇＜3〇

Figure imgf000065_0001
で表される基を示す。
Figure imgf000065_0002
は、 例えば、 アルキル基、 アリール基、 ハロゲン化アルキル基又はハロゲン化アリール基であってよい 。 式 （八一 6） 中、 X 5は酸素原子 （〇） 又は硫黄原子 （3） を示し、 丫2は 酸素原子 （〇） 、 硫黄原子 （3） 又は 7で表される基を示す。
Figure imgf000065_0003
は例え ば、 アルキルスルホニル基、 アリールスルホニル基、 アシル基、 力ーバメー 卜基、 アルキル基、 アリール基、 ハロゲン化アルキル基又はハロゲン化アリ —ル基であってよい。 Show. In the formula (81 5), X 4 represents an oxygen atom (○) or a sulfur atom (3), and 1 is a halogen atom, a hydroxyl group, a group represented by, or a group represented by 10 [¾ 6 , Or 10 <30
Figure imgf000065_0001
Represents a group represented by.
Figure imgf000065_0002
May be, for example, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group. In the formula (81 6), X 5 represents an oxygen atom (○) or a sulfur atom (3), and 2 represents a group represented by an oxygen atom (○), a sulfur atom (3) or 7 .
Figure imgf000065_0003
May be, for example, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a power group, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group.

［0205］ 機能性反応剤は、 第一の反応剤と、 第一の反応性基と反応して結合を形成 可能な第二の反応性基 （1つ） 、 及び機能性基を有する反応剤 （第二の反応 剤） とを反応させて得ることができる。 [0205] The functional reactive agent is a reactive agent having a first reactive agent, a second reactive group (1) capable of reacting with the first reactive group to form a bond, and a functional group. It can be obtained by reacting with (second reaction agent).

［0206］ 第二の反応性基としては、 例えば、 ヒドロキシル基、 チオール基、 アミノ 基、 下記式 （巳一 1） で表される基等が挙げられる。 [0206] Examples of the second reactive group include a hydroxyl group, a thiol group, an amino group, and a group represented by the following formula (Minichi 1).

［化 2］ [Chemical 2]

Figure imgf000065_0004
Figure imgf000065_0004

［0207］ 式 （巳一 1） 中、 X 6は酸素原子 （〇） 又は硫黄原子 （3） を示す。 [0207] In the formula (Miichi 1), X 6 represents an oxygen atom (o) or a sulfur atom (3).

［0208］ 機能性基としては、 例えば、 アルキル基、 アルケニル基、 アルキニル基等 の炭化水素基； アリ _ル基、 複素環基等の環構造を有する基；保護基で保護 された反応性基 （ヒドロキシ基、 アミノ基、 チオール基等） ；カルボニル基 （- 0 （=〇） 一） 、 エーテル結合 （一〇一） 、 アミ ド結合 （＞1\1〇 （=〇 ） -） 、 ウレタン結合 （＞!\1〇 （=〇） 〇一） 、 ウレア結合 （＞ （0 = 0 ） N 0 、 力ーボネート結合 （_〇〇 （=〇） 0 -） 等の構造を有する基； アルコキシシリル基、 スルホニル基 （一 3 （=〇） _） 、 カルボキシル基 （ - 0 （=〇） 〇!~1） 、 スルホン酸基 （一 3 （=〇） 2〇1~1） 、 及び、 第四級ア 〇 2020/175702 65 卩（：171? 2020 /008524 [0208] Examples of the functional group include a hydrocarbon group such as an alkyl group, an alkenyl group, and an alkynyl group; a group having a ring structure such as an aryl group and a heterocyclic group; a reactive group protected by a protecting group. (Hydroxy group, amino group, thiol group, etc.); Carbonyl group (-0 (= 〇) one), ether bond (101), amide bond (>1\1 〇 (= 〇) -), urethane bond (>!\1 〇 (= 〇) 〇 1), Urea bond (> (0 = 0) N 0, Force-bonate bond (_ 〇 〇 (= 〇) 0 -), etc.; Alkoxysilyl group , a sulfonyl group (one 3 (= 〇) _), a carboxyl group (- 0 (= 〇) 〇 to 1), a sulfonic acid group (one 3 (= 〇) 2 Rei_1 to 1), and, quaternary A 〇 2020/175 702 65 卩 (：171? 2020 /008524

ンモニウム基等が挙げられる。 Examples thereof include an ammonium group.

[0209] 第一の反応剤の具体例としては、 例えば、 ヘキサンジイソアネート （1~1 0 [0209] Specific examples of the first reactant include, for example, hexane diisocyanate (1 to 10

I） を挙げることができる。 第二の反応剤の具体例としては、 例えば、 ブタ ノール （巳 1_1〇1~1） を挙げることができる。 I) can be mentioned. As a specific example of the second reaction agent, for example, butanol (Mimi 1_1 0 1 to 1) can be mentioned.

[0210] 耐水性付与物質は、 防水透湿性生地の撥水性が向上すると共に水接触時の 収縮も抑制できるという観点から、 フッ素系ポリマー及びシリコーン系ポリ マーが好ましい。 [0210] The water resistance-imparting substance is preferably a fluoropolymer or a silicone polymer from the viewpoint of improving the water repellency of the waterproof/moisture permeable fabric and suppressing the contraction upon contact with water.

[021 1 ] 編織体は、 原料糸を編成又は織成して得ることができる。 編成方法及び織 成方法としては公知の方法を利用することができる。 使用される編機として は、 例えば、 丸編機、 経編機、 横編機などが使用でき、 生産性の観点からは 、 丸編機の使用が好ましい。 横編機としては、 成型編み機、 無縫製編機など があるが、 特に最終製品の形態で編地を製造可能であることから、 無縫製編 機の使用がより好ましい。 使用される織機としては、 例えば、 有抒織機、 及 び、 グリッパー織機、 レピア織機、 ゥォータージェッ ト織機、 エアジェッ ト 織機等の無抒織機が挙げられる。 [021 1] The knitted or woven body can be obtained by knitting or weaving raw material threads. As a knitting method and a weaving method, known methods can be used. As the knitting machine to be used, for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used. As the flat knitting machine, there are a forming knitting machine, a non-sewn knitting machine, and the like. However, since the knitted fabric can be manufactured in the form of a final product, the non-sewn knitting machine is more preferable. Examples of the loom to be used include a hauling loom, and a non-tapping loom such as a gripper loom, a rapier loom, a water jet loom, and an air jet loom.

[0212] 編織体に第 1の耐水性付与物質を含有させる方法としては、 例えば、 第 1 の耐水性付与物質を含有する原料糸 （例えば、 第 1の耐水性付与物質を混合 した原料糸、 第 1の耐水性付与物質が結合した原料糸） を用いる他は、 上述 の編成方法又は織成方法で編成又は織成する方法 （方法 ） 、 第 1の耐水性 付与物質を含まずに製造した編織体に対して、 第 1の耐水性付与物質を結合 させる方法 （方法巳） が挙げられる。 [0212] Examples of the method for incorporating the first water resistance-imparting substance into the knitted fabric include, for example, a raw material yarn containing the first water resistance-imparting substance (for example, a raw material yarn mixed with the first water resistance-imparting substance, The raw material yarn to which the first water resistance-imparting substance is bound is used, except that the knitting method or the weaving method described above is used (method), and the first water resistance-imparting substance is not included. A method (method M) of binding the first water resistance-imparting substance to the knitted or woven body can be mentioned.

[0213] 方法巳は、 編織体に第 1の耐水性付与物質を結合させる工程 （結合工程） を含む。 結合工程は、 例えば、 編織体に第 1の耐水性付与物質を塗布又は浸 潰等の手段により接触させ、 必要に応じて加熱又はプラズマ照射等を行い、 編織体と第 1の耐水性付与物質を結合させることで実施することができる。 第 1の耐水性付与物質が、 例えば、 シリコン系ポリマー及びフッ素系ポリマ 一等の疎水性ポリマーである場合、 結合工程は、 例えば、 編織体に第 1の耐 水性付与物質又は第 1の耐水性付与物質の前駆体 （モノマー） を接触させた 〇 2020/175702 66 卩（：171? 2020 /008524 [0213] The method Mami includes a step (bonding step) of bonding the first water resistance-imparting substance to the knitted fabric. In the binding step, for example, the first water resistance-imparting substance is brought into contact with the knitted fabric by a means such as coating or crushing, and heating or plasma irradiation is performed as necessary, and the weaving fabric and the first water resistance-imparting substance. Can be carried out by combining When the first water resistance-imparting substance is, for example, a hydrophobic polymer such as a silicon-based polymer and a fluorine-based polymer, the bonding step may include, for example, the first water resistance-imparting substance or the first water resistance-imparting substance on the textile. The precursor of the imparting substance (monomer) was contacted 〇 2020/175 702 66 卩(：171? 2020/008524

状態でプラズマを照射して、 編織体と第 1の耐水性付与物質とを共有結合さ せる工程であってよい。 第 1の耐水性付与物質の前駆体 （モノマー） を使用 した場合であっても、 プラズマの照射により、 第 1の耐水性付与物質の前駆 体 （モノマー） が重合して第 1の耐水性付与物質 （シリコン系ポリマー及び フッ素系ポリマー等の疎水性ポリマー） が形成されるため、 第 1の耐水性付 与物質を含む編織体を得ることができる。 It may be a step of irradiating plasma in the state to covalently bond the knitted fabric and the first water resistance imparting substance. Even when the precursor (monomer) of the first water resistance-imparting substance is used, the precursor (monomer) of the first water resistance-imparting substance is polymerized by the irradiation of plasma to impart the first water resistance-imparting property. Since the substance (hydrophobic polymer such as silicone-based polymer and fluorine-based polymer) is formed, it is possible to obtain a knitted fabric containing the first water resistance imparting substance.

[0214] 照射するプラズマは、 編織体、 及び第 1の耐水性付与物質 （又はその前駆 体） の種類等に応じて、 適宜設定してよい。 放電ガスの流量は、 例えば、 0 . 1 L / rr\ \

Figure imgf000067_0001
以下の範囲内であってよい。 発生させる プラズマのプラズマ密度は、 例えば、 1 X 1 0 1 3〇〇1 _ 3以上 1 X 1 0 1 5〇 _ 3以下の範囲内であってよい。 放電ガスは、 例えば、 ヘリウム、 ネオン、 ア ルゴン等の希ガス、 酸素、 窒素等であってよい。 放電ガスとして、 大気を使 用することもできる。 [0214] The plasma to be irradiated may be appropriately set depending on the kind of the knitted fabric, the first water resistance imparting substance (or its precursor), and the like. The flow rate of the discharge gas is, for example, 0.1 L/rr\ \
Figure imgf000067_0001
It may be within the following range. The plasma density of the generated plasma may be, for example, in the range of 1×1 0 1 3 x 0 1 _ 3 or more and 1 x 1 0 1 5 x _ 3 or less. The discharge gas may be, for example, a rare gas such as helium, neon, or argon, oxygen, nitrogen, or the like. Atmosphere can also be used as the discharge gas.

[0215] プラズマ照射は、 公知のプラズマ照射装置を使用して実施することができ る。 プラズマ照射装置としては、 例えば、 巳リ 「〇 丨 3 3〇! 8社製のプラ ズマ処理装置を使用することができる。 [0215] Plasma irradiation can be carried out using a known plasma irradiation device. As the plasma irradiation apparatus, for example, a plasma processing apparatus manufactured by Minori "○ 333 0! 8" can be used.

[0216] 編織体の原料糸は、 単独糸であってもよく、 複合糸 （例えば、 混紡糸、 混 繊糸、 カバーリング糸等。 ） であってもよく、 これらを組み合わせて用いて もよい。 単独糸及び複合糸は、 短繊維を撚り合わせたスパン糸であってもよ く、 長繊維を撚り合わせたフイラメント糸であってもよい。 [0216] The raw material yarn of the knitted fabric may be a single yarn, a composite yarn (for example, a mixed yarn, a mixed yarn, a covering yarn, etc.), or may be a combination of these. .. The single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are twisted together.

[0217] 原料糸に含まれる繊維としては、 例えば、 タンパク質繊維、 ナイロン、 ポ リエステル及びポリテトラフルオロエチレン等の合成繊維、 キュプラ、 レー ヨン及びリヨセル等の再生繊維、 綿、 麻及び絹等の天然繊維が挙げられる。 [0217] Examples of fibers contained in the raw yarn include protein fibers, synthetic fibers such as nylon, polyester and polytetrafluoroethylene, regenerated fibers such as cupra, rayon and lyocell, and natural fibers such as cotton, hemp and silk. Fibers.

[0218] 編織体は、 改変フイブロインを含むことが好ましく、 改変クモ糸フイブロ インを含むことがより好ましい。 改変フイブロイン （好ましくは、 改変クモ 糸フイブロイン） を含むことにより、 本実施形態に係る防水透湿性生地に保 温性、 吸湿発熱性及び/又は難燃性の性質を更に付与することができ、 生地 としての価値がより高くなる。 改変フイブロインは、 改変フイブロイン繊維 〇 2020/175702 67 卩（：171? 2020 /008524 [0218] The knitted or woven body preferably contains modified fibroin, and more preferably modified spider silk fibroin. By containing the modified fibroin (preferably modified spider silk fibroin), the waterproof and moisture-permeable fabric according to the present embodiment can be further imparted with heat-retaining property, heat-absorption property and/or flame-retardant property. The higher the value as. Modified fibroin is a modified fibroin fiber 〇 2020/175 702 67 卩 (：171? 2020 /008524

（タンパク質繊維） として編織体に含まれていてもよい。 改変フィブロイン の好ましい態様は、 第 1の発明に係る防水透湿性生地で説明した態様を適用 できる。 (Protein fiber) may be contained in the knitted fabric. As a preferred embodiment of the modified fibroin, the embodiment described for the waterproof and breathable fabric according to the first invention can be applied.

[0219] 編織体は、 不織布との接合側とは反対側の表面が撥水加工されていてもよ い。 これにより、 防水性により優れた防水透湿性生地を得ることができる。 撥水加工は、 例えば、 プラズマ加工等の化学コーティングを施す、 撥水コー ティング剤を塗布する等の物理的コーティングを施す、 又は表面を化学修飾 する等の従来公知の方法により行うことができる。 [0219] The surface of the knitted or woven body on the side opposite to the side joined to the nonwoven fabric may be water repellent. This makes it possible to obtain a waterproof and moisture-permeable fabric that is more waterproof. The water repellent treatment can be carried out by a conventionally known method such as chemical coating such as plasma processing, physical coating such as coating with a water repellent coating agent, or chemical modification of the surface.

[0220] 第 2実施形態に係る防水透湿性生地の防水透湿層 2は、 繊維径 1 〇 以 下の極細繊維を含む不織布 （以下、 単に 「不織布」 ともいう。 ） からなる。 極細繊維の繊維径は、 短繊維の長手方向に垂直な断面を囲む最小の円の直径 を意味する。 極細繊維の繊維径は、 1 〇 （1 0 0 0 0 n〇〇 以下であれ ばよく、 9 〇!以下、 8 〇!以下、 7 〇!以下、 6 〇!以下、 5 以下、 [0220] The waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the second embodiment is made of a nonwoven fabric containing ultrafine fibers having a fiber diameter of 10 or less (hereinafter, also simply referred to as "nonwoven fabric"). The fiber diameter of the ultrafine fibers means the diameter of the smallest circle that surrounds the cross section of the short fibers perpendicular to the longitudinal direction. The fiber diameter of the ultrafine fiber may be 10 (1 0 0 0 0 0 n 0 0 or less, 90 0 or less, 8 0! or less, 7 0! or less, 6 0! or less, 5 or less,

4 〇!以下、 3 〇!以下、 2 〇!以下、 1 〇!

Figure imgf000068_0001
以下、 9 04 〇 or less, 3 〇! or less, 2 〇! or less, 1 〇!
Figure imgf000068_0001
Below, 90

0 〇!以下、 8 0 0 1^〇!以下、 7 0 0 1^ 以下、 6 0 0 1^ 以下、 5 0 0 1^ 111以下、 4 0 0 1^〇!以下、

Figure imgf000068_0002
以下、 又は 2 0 0 1^ 以下であってよ い。 極細繊維の繊維径は、 例えば、 1 0 1·!〇!以上、 2 0 1^〇!以上、
Figure imgf000068_0003
以上、 4 0 1^〇!以上、 5 0 1^〇!以上、
Figure imgf000068_0004
以上、
Figure imgf000068_0005
以上、 8 0 1^ 〇!以上、 9 0 1^〇!以上、
Figure imgf000068_0006
以上、
Figure imgf000068_0007
以上、
Figure imgf000068_0008
0 〇 or less, 8 0 0 1^ 〇! or less, 7 0 0 1^ or less, 6 0 0 1^ or less, 5 0 0 1^ 111 or less, 4 0 0 1^ 〇! or less,
Figure imgf000068_0002
Below, or below 2 0 0 1^. The fiber diameters of ultrafine fibers are, for example, 1 0 1!!
Figure imgf000068_0003
Or more, 4 0 1^〇! or more, 5 0 1^〇! or more,
Figure imgf000068_0004
that's all,
Figure imgf000068_0005
Or more, 8 0 1^ 〇! or more, 9 0 1^ 〇! or more,
Figure imgf000068_0006
that's all,
Figure imgf000068_0007
that's all,
Figure imgf000068_0008

、 4 0 0 1^〇!以上、 5 0 0 1^ 以上、 6 0 0 1^ 以上、 7 0 0 1^ 以上、 8 0 0 〇!以上、 9 0 0 1^〇!以上、 1 以上、 2 以上、 3 以上、 4 111以上又は 5 〇!以上であつてよい。 , 4 0 0 1^〇! or above, 5 0 0 1^ or above, 6 0 0 1^ or above, 7 0 0 1^ or above, 8 0 0 0 〇! or above, 9 0 0 1^ 〇! or above, 1 or above, It may be 2 or more, 3 or more, 4 111 or more, or 50! or more.

[0221 ] 極細繊維は、 繊維径の条件を満たす限り、 任意の材料で形成されたもので あってよい。 極細繊維は、 例えば、 タンパク質繊維、 ナイロン及びポリエス テル等の合成繊維、 キュプラ、 レーヨン及びリヨセル等の再生繊維、 綿、 麻 及び絹等の天然繊維であってよい。 [0221] The ultrafine fibers may be formed of any material as long as the fiber diameter condition is satisfied. The ultrafine fibers may be, for example, protein fibers, synthetic fibers such as nylon and polyester, regenerated fibers such as cupra, rayon and lyocell, and natural fibers such as cotton, hemp and silk.

[0222] 極細繊維は、 改変フィブロインを含むことが好ましく、 改変クモ糸フィブ ロインを含むことがより好ましい。 改変フィブロイン （好ましくは、 改変ク 〇 2020/175702 68 卩（：171? 2020 /008524 [0222] The ultrafine fibers preferably include modified fibroin, and more preferably include modified spider silk fibroin. Modified fibroin (preferably modified 〇 2020/175 702 68 卩 (：171? 2020 /008524

モ糸フィブロイン） を含むことにより、 本実施形態に係る防水透湿性生地に 保温性、 吸湿発熱性及び/又は難燃性の性質を更に付与することができ、 生 地としての価値がより高くなる。 改変フィブロインは、 改変フィブロイン繊 維 （タンパク質繊維） として極細繊維に含まれていてもよい。 改変フィブロ インの好ましい態様は、 第 1の発明に係る防水透湿性生地で説明した態様を 適用できる。 By including moist fiber fibroin), the waterproof and moisture-permeable fabric according to the present embodiment can be further imparted with heat-retaining properties, heat-absorption properties and/or flame-retardant properties, and its value as a land becomes higher. .. The modified fibroin may be contained in the ultrafine fibers as modified fibroin fiber (protein fiber). As a preferred embodiment of the modified fibroin, the embodiment described in the waterproof and moisture-permeable fabric according to the first invention can be applied.

[0223] 不織布は、 極細繊維のみを含むものであってもよく、 極細繊維に加えて他 の繊維 （繊維径 1 〇 超のもの） を含むものであってもよい。 すなわち、 不織布の形成に用いられる繊維 （ 「材料糸」 ともいう。 ） として、 極細繊維 のみからなる単独糸、 極細繊維と他の繊維 （繊維径 1 〇 超のもの） とを 組み合わせてなる複合糸 （例えば、 混紡糸、 混繊糸、 カバーリング糸等。 ） が、 それぞれ単独で、 又はそれらが組み合わされて用いられてもよい。 上記 単独糸及び上記複合糸は、 短繊維を撚り合わせたスパン糸であってもよく、 長繊維を撚り合わせたフィラメント糸であってもよい。 上記単独糸及び上記 複合糸としては、 フィラメント糸が好適に用いられる。 他の繊維と組み合わ せて使用する場合には、 不織布に占める極細繊維の割合は、 不織布の全質量 を基準として、 例えば、 3 0質量％以上、 4 0質量％以上、 5 0質量％以上 、 6 0質量％以上、 7 0質量％以上、 8 0質量％以上、 9 0質量％以上、 又 は 9 5質量％以上であってよい。 [0223] The non-woven fabric may contain only ultrafine fibers, or may contain other fibers (having a fiber diameter of more than 10) in addition to the ultrafine fibers. That is, as the fibers (also referred to as “material yarns”) used for forming the non-woven fabric, a single yarn made of only ultrafine fibers, or a composite yarn made by combining ultrafine fibers with other fibers (having a fiber diameter of more than 10). (For example, blended yarn, blended yarn, covering yarn, etc.) may be used alone or in combination. The single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or filament yarn in which long fibers are twisted together. A filament yarn is preferably used as the single yarn and the composite yarn. When used in combination with other fibers, the proportion of ultrafine fibers in the non-woven fabric is based on the total mass of the non-woven fabric, for example, 30 mass% or more, 40 mass% or more, 50 mass% or more, It may be 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.

[0224] 不織布は、 例えば、 繊維径 1 0 以下の極細繊維を少なくとも一部に含 む繊維を用いて、 公知の製造方法により製造することができる。 具体的には 、 例えば、 繊維径 1 〇 以下の極細繊維を少なくとも一部に含む繊維から 、 乾式法、 湿式法及びエアレイ ド法等でウェブ （単層ウェブ、 及び積層ウェ ブを含む。 ） を形成させた後、 ケミカルボンド法 （浸潰法、 スプレー法等） 及び二ードルパンチ法等によりウェブの繊維間を結合させて、 不織布を得る ことができる。 [0224] The non-woven fabric can be produced by a known production method using, for example, fibers containing at least a portion of ultrafine fibers having a fiber diameter of 10 or less. Specifically, for example, a web (including a single-layer web and a laminated web) is formed by a dry method, a wet method, an air-laid method, or the like from a fiber including at least a part of ultrafine fibers having a fiber diameter of 10 or less. After being formed, the fibers of the web can be bonded by a chemical bond method (immersion method, spray method, etc.) or a needle punch method to obtain a nonwoven fabric.

[0225] 不織布がタンパク質極細繊維を含む場合、 更に以下の製造方法を例示でき る。 すなわち、 例えば、 タンパク質を、 ジメチルスルホキシド （口!\/1 3〇） 〇 2020/175702 69 卩（：171? 2020 /008524 [0225] When the nonwoven fabric contains protein ultrafine fibers, the following production method can be further exemplified. That is, for example, the protein is dimethyl sulfoxide (mouth!\/1300) 〇 2020/175 702 69 卩(：171? 2020/008524

、 1\1, 1\1 -ジメチルホルムアミ ド （01\/1 ） 、 ギ酸、 又はヘキサフルオロイ ソプロパノール （1~1 I ） 等の溶媒に、 必要に応じて、 溶解促進剤として の無機塩と共に添加し、 溶解してドープ液を作製した後、 当該ドープ液を用 いてエレクトロスピニング法 （静電紡糸法） により紡糸することにより、 不 織布を得ることもできる。 エレクトロスピニング法で得られるタンパク質極 細繊維の平均繊維径 （繊維径の平均値） は、 通常、 1 0000 n〇!以下であ り、 好ましくは 1 000门 01以下であり、 1 00 n m~ 1 0000 n 01、 1 , 1\1, 1\1-Dimethylformamide (01\/1 ), formic acid, or hexafluoroisopropanol (1 to 1 I) as a solvent, if necessary, as an inorganic A nonwoven fabric can also be obtained by adding a salt and dissolving it to prepare a dope solution, and spinning the dope solution by an electrospinning method (electrostatic spinning method). The average fiber diameter (average fiber diameter) of protein ultrafine fibers obtained by the electrospinning method is usually 1 0000 n 〇! or less, preferably 1 000 门 01 or less, and 100 nm to 1 nm. 0000 n 01, 1

900

Figure imgf000070_0001
繊維の 繊維径は、 1 00门〇1~ 1 0000 n m （1 0 〇〇 の間、 好ましくは 1 0 〇门〇!〜 1 0001^ 111 （1 〇〇 の間で変動してもよい。 900
Figure imgf000070_0001
The fiber diameter of the fibers may vary between 100 门 〇 1 to 1 0000 nm (100 000), preferably 1 00 门 〇! to 1 0001^111 (1 000).

[0226] 不織布は、 繊維密度 （目付） 、 空隙率、 かさ密度等の数値範囲が、 防水性 と透湿性とを充分に確保し得る範囲となるように適宜設定される。 なお、 そ れら目付、 空隙率、 かさ密度等の調整は、 例えば、 ウェブを構成する繊維量 を増減すること、 積層ウェブの場合は、 積層数を増減することにより行うこ とができる。 [0226] The nonwoven fabric is appropriately set such that the numerical ranges of the fiber density (area weight), the porosity, the bulk density, etc. are within a range in which waterproofness and moisture permeability can be sufficiently ensured. The unit weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of layers.

[0227] 不織布は、 第 2の耐水性付与物質を含有するものであってもよい。 これに より、 本実施形態に係る防水透湿性生地の防水性がより一層向上する。 第 2 の耐水性付与物質の具体例としては、 第 1の耐水性付与物質で例示したもの が挙げられる。 不織布が第 2の耐水性付与物質を含有する場合、 第 1及び第 2の耐水性付与物質は、 同一であってもよく、 異なっていてもよい。 [0227] The nonwoven fabric may contain the second water resistance imparting substance. Thereby, the waterproofness of the waterproof and moisture-permeable fabric according to the present embodiment is further improved. Specific examples of the second water resistance imparting substance include those exemplified for the first water resistance imparting substance. When the nonwoven fabric contains the second water resistance-imparting substance, the first and second water resistance-imparting substances may be the same or different.

[0228] 第 2実施形態に係る防水透湿性生地の裏材層 3は、 編織体からなる。 裏材 層 3は、 必要に応じて設けてもよい。 裏材層 3の好ましい態様としては、 表 皮層 1で例示した態様が挙げられる。 表皮層 1 と裏材層 3は、 それぞれ同一 の材料で形成された編織体であってもよく、 異なる材料で形成された編織体 であつてもよい。 [0228] The backing layer 3 of the waterproof/moisture permeable fabric according to the second embodiment is made of a knitted fabric. The backing layer 3 may be provided if necessary. Examples of the preferable embodiment of the backing layer 3 include the embodiments exemplified for the skin layer 1. The skin layer 1 and the backing layer 3 may be knitted fabrics made of the same material, or may be knitted fabrics made of different materials.

[0229] 裏材層 3は、 耐水性付与物質を含有していてもよく、 含有していなくても よい。 耐水性付与物質を含有するか否かは、 本実施形態に係る防水透湿性生 〇 2020/175702 70 卩（：171? 2020 /008524 [0229] The backing layer 3 may or may not contain a water resistance-imparting substance. Whether or not it contains a water resistance-imparting substance depends on whether the waterproof/moisture permeable raw material according to the present embodiment. 〇 2020/175 702 70 卩 (：171? 2020 /008524

地の用途等に応じて、 適宜設定してよい。 It may be appropriately set depending on the use of the ground.

[0230] 第 2実施形態に係る防水透湿性生地は、 不織布 （防水透湿層） と編織体 （ 表皮層） とを接合して得ることができる。 防水透湿層と表皮層との接合方法 は、 不織布及び編織体に使用する素材に応じて、 適宜選択することができる 。 接合方法として、 例えば、 防水透湿層と表皮層とを、 熱又は溶剤等により 、 溶着する方法、 防水透湿層と表皮層とを接着剤を介して接着する方法、 不 織布と編織体の少なくともいずれか一方の接合面にプラズマを照射して、 ラ ジカル反応により共有結合を形成させることで、 防水透湿層と表皮層とを接 合する方法等が挙げられる。 例えば、 不織布及び編織体がいずれもタンパク 質 （タンパク質極細繊維又はタンパク質繊維） を含む場合、 防水透湿層及び 表皮層の接合面のうち一方又は両方にタンパク質を溶解する溶媒 （例えば、 ジメチルスルホキシド （口1\/1 3〇） 、 1\1 , 1\1 _ジメチルホルムアミ ド

Figure imgf000071_0001
） 、 ギ酸、 又はヘキサフルオロイソプロパノール （1~1 I ） 等の有機溶 媒、 それらに溶解促進剤としての無機塩を添加した溶液、 又は水、 若しくは 水に無機塩等を添加した水溶液） を塗布した後、 防水透湿層及び表皮層を貼 り合わせ、 更に溶媒を除去することで防水透湿層と表皮層とを接合すること ができる。 [0230] The waterproof/moisture permeable fabric according to the second embodiment can be obtained by joining a nonwoven fabric (waterproof/moisture permeable layer) and a knitted fabric (skin layer). The method for joining the waterproof moisture-permeable layer and the skin layer can be appropriately selected depending on the materials used for the nonwoven fabric and the knitted fabric. As a joining method, for example, a method of welding a waterproof moisture-permeable layer and a skin layer with heat or a solvent, a method of bonding the waterproof moisture-permeable layer and a skin layer with an adhesive, a nonwoven fabric and a knitted body A method of irradiating plasma to at least one of the bonding surfaces to form a covalent bond by a radial reaction to bond the waterproof and moisture permeable layer to the skin layer, and the like. For example, when both the non-woven fabric and the woven fabric contain a protein (protein ultrafine fiber or protein fiber), a solvent that dissolves the protein in one or both of the joint surfaces of the waterproof moisture-permeable layer and the skin layer (for example, dimethyl sulfoxide ( Mouth 1\/1 3 〇), 1\1, 1\1 _ Dimethylformamide
Figure imgf000071_0001
), formic acid, or an organic solvent such as hexafluoroisopropanol (1 to 1 I), a solution obtained by adding an inorganic salt as a dissolution promoter to them, or water, or an aqueous solution obtained by adding an inorganic salt or the like to water) After that, the waterproof and moisture permeable layer and the epidermis layer are attached to each other, and the solvent is further removed, whereby the waterproof and moisture permeable layer and the epidermis layer can be joined.

[0231 ] また、 不織布がタンパク質極細繊維を含み、 不織布をエレクトロスピニン グ法で形成する場合、 防水透湿層を表皮層上に形成する防水透湿層形成工程 を備える製造方法により、 防水透湿性生地を得ることができる。 防水透湿層 形成工程は、 タンパク質を含有するドープ液を使用したエレクトロスピニン グにより、 表皮層上にタンパク質極細繊維を集積させて不織布を形成させる ことを含む。 このとき、 表皮層上にタンパク質を溶解する溶媒を塗布してお いてもよい。 これにより、 不織布が形成されると共に、 形成された不織布と 表皮層が接合する。 [0231] When the nonwoven fabric contains protein ultrafine fibers and the nonwoven fabric is formed by the electrospinning method, the waterproof and moisture-permeable layer is formed on the skin layer by a manufacturing method including a waterproof and moisture-permeable layer forming step. A moist dough can be obtained. The waterproof/moisture permeable layer forming step includes the steps of: electrospinning using a dope solution containing a protein to accumulate protein ultrafine fibers on the skin layer to form a nonwoven fabric. At this time, a solvent that dissolves the protein may be applied onto the epidermis layer. As a result, a nonwoven fabric is formed, and the formed nonwoven fabric and the skin layer are joined together.

[0232] エレクトロスピニング法 （静電紡糸法） は、 供給側電極 （紡糸口金と兼用 できる） と捕集側電極 （例えば、 金属口ール又は金属ネッ ト等） 間に電圧を 印加し、 紡糸口金から押し出したドープ液に電荷を与えて捕集側電極に吹き 〇 2020/175702 71 卩（：171? 2020 /008524 [0232] In the electrospinning method (electrospinning method), a voltage is applied between a supply-side electrode (which can also be used as a spinneret) and a collection-side electrode (for example, a metal nozzle or a metal net), and spinning is performed. Charge the dope solution extruded from the die and blow it onto the collection side electrode. 〇 2020/175 702 71 卩(: 171-1? 2020/008524

飛ばす。 この際にドープ液は伸張されて繊維形成される。 印加電圧は、 通常 5〜 1 0 0 1< Vであり、 好ましくは 1 〇〜 5 0 1< Vである。 電極間距離は、

Figure imgf000072_0001
好ましくは 2〜 2 0〇 である。 Fly. At this time, the dope solution is stretched to form fibers. The applied voltage is usually 5 to 1001<V, preferably 10 to 5101<V. The distance between the electrodes is
Figure imgf000072_0001
It is preferably 2 to 200.

[0233] 図 4は、 一実施形態に係るエレクトロスピニング装置 1 0 0の説明図であ る。 金属製口金ノズル 3 3 （供給側電極） と金属製ネッ ト 3 8 （捕集側電極 ） との間に電源 3 5により電圧をかける。 マイクロシリンジ 3 1内のドープ 液 3 2をシリンジポンプを用いて矢印 方向に移動させ、 金属製口金ノズル 3 3からドープ液 3 2を押し出し、 電荷によってドープ液を伸張し繊維状物 3 6にして金属製ネッ ト 3 8の表面に集積させることで、 タンパク質極細繊 維を含む不織布 3 9を得ることができる。 また、 このとき、 金属製ネッ ト 3 8の表面に表皮層 （編織体） を載置することで、 表皮層上にタンパク質極細 繊維を集積させて不織布を形成させることもできる。 また、 表皮層 （編織体 ） の面上に接着剤、 又は編織体と不織布の少なくともいずれか一方を溶解さ せる溶媒等を塗布しておくことで、 形成された不織布と、 編織体とを接合さ せることもできる。 得られた不織布は、 次いで溶媒を離脱してもよい。 溶媒 （ドープ液中の溶媒、 編織体又は不織布に塗布された溶媒等） を脱離する方 法としては、 例えば、 減圧乾燥又は脱溶媒槽への浸潰が挙げられる。 [0233] FIG. 4 is an explanatory diagram of an electrospinning device 100 according to an embodiment. A voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35. The dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36. By accumulating on the surface of the metallic net 38, a nonwoven fabric 39 containing protein ultrafine fibers can be obtained. At this time, a non-woven fabric can also be formed by depositing a protein ultrafine fiber on the skin layer by placing a skin layer (woven body) on the surface of the metal net 38. In addition, by bonding an adhesive or a solvent that dissolves at least one of the knitted fabric and the nonwoven fabric onto the surface of the skin layer (knitted fabric), the formed nonwoven fabric and the knitted fabric are joined together. It can also be done. The resulting non-woven fabric may then be stripped of solvent. Examples of the method for removing the solvent (the solvent in the dope solution, the solvent applied to the knitted fabric or the nonwoven fabric, etc.) include vacuum drying or immersion in a desolvation tank.

[0234] 第 2実施形態に係る防水透湿性生地が裏材層を有する場合、 防水透湿層と 裏材層との接合方法は、 上述した方法に準ずる。 [0234] When the waterproof moisture-permeable fabric according to the second embodiment has a backing layer, the method for joining the waterproof moisture-permeable layer and the backing layer is based on the method described above.

[0235] 〔第 3の発明に係る防水透湿性生地〕 [0235] [Waterproof and breathable fabric according to the third invention]

第 3実施形態に係る防水透湿性生地は、 繊維径 1 〇 以下のタンパク質 極細繊維を含む不織布 （以下、 単に 「不織布」 ともいう。 ） からなる防水透 湿層 2と、 編織体からなる表皮層 1 とが接合されてなる。 防水透湿層 2を構 成する不織布は、 水収縮されているものである。 以下の説明において、 水収 縮されている不織布を 「高密度不織布」 と、 水収縮前の不織布を 「原料不織 布」 と呼ぶことがある。 The waterproof/moisture permeable fabric according to the third embodiment is a waterproof/moisture permeable layer 2 made of a nonwoven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less (hereinafter also simply referred to as “nonwoven fabric”), and a skin layer made of a knitted fabric. 1 is joined. The non-woven fabric forming the waterproof/moisture permeable layer 2 is water-shrinked. In the following description, a non-woven fabric that is water-condensed may be referred to as a “high-density non-woven fabric”, and a non-woven fabric before water-shrinkage may be referred to as a “non-woven fabric material”.

[0236] 第 3実施形態に係る防水透湿性生地の防水透湿層 2は、 高密度不織布 （織 維径 1 0 以下のタンパク質極細繊維を含み、 水収縮されている不織布） 〇 2020/175702 72 卩（：171? 2020 /008524 [0236] The waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the third embodiment is a high-density nonwoven fabric (a nonwoven fabric that contains protein ultrafine fibers with a fiber diameter of 10 or less and is water-shrinked). 〇 2020/175 702 72 卩(: 171-1? 2020/008524

からなるものである。 タンパク質極細繊維の繊維径は、 短繊維の長手方向に 垂直な断面を囲む最小の円の直径を意味する。 タンパク質極細繊維の繊維径 は、 1 0 01 （1 0 0 0 0 1^ 111） 以下であればよく、 9 以下、 8 以 下、 7 〇!以下、 6 〇!以下、 5 〇!以下、 4 〇!以下、 3 以下、 2 ^ 以下、 1 〇! （1 0 0 0 1^ 111） 以下、 9 0 0 1^ 以下、 8 0 0 1^ 以下、It consists of The fiber diameter of a protein ultrafine fiber means the diameter of the smallest circle surrounding a cross section perpendicular to the longitudinal direction of the short fiber. The fiber diameter of the protein ultrafine fiber may be 1001 (1 0 0 0 0 1^111) or less, 9 or less, 8 or less, 7 〇! or less, 6 〇! or less, 5 〇! or less, 4 ○! or less, 3 or less, 2 ^ or less, 1 ○! (1 0 0 0 1^ 111) or less, 9 0 0 1^ or less, 8 0 0 1^ or less,

7 0 0 1^〇!以下、

Figure imgf000073_0001
以下、
Figure imgf000073_0002
以下、
Figure imgf000073_0003
以下、 3 0 〇门 以下、 又は 2 0 0 n
Figure imgf000073_0004
以下であってよい。 タンパク質極細繊維の繊維 径は、 例えば、 1 0 !! 01以上、 2 0 1^ 01以上、
Figure imgf000073_0005
以上、
Figure imgf000073_0006
7 0 0 1^〇 or less,
Figure imgf000073_0001
Less than,
Figure imgf000073_0002
Less than,
Figure imgf000073_0003
Or less, 300 or less, or 200 or less
Figure imgf000073_0004
May be: The fiber diameter of protein ultrafine fiber is, for example, 10 !! 01 or more, 2 0 1^ 01 or more,
Figure imgf000073_0005
that's all,
Figure imgf000073_0006

、 5 0 1^〇!以上、 6 0 1^〇!以上、 7 0 1^ 以上、 8 0 1^ 以上、 9 0 111以 上、 1 0 0 〇!以上、 2 0 0 1^〇!以上、 3 0 0 1^ 以上、 4 0 0 1^ 以上、 , 5 0 1^〇! or higher, 6 0 1^〇! or higher, 7 0 1^ or higher, 8 0 1^ or higher, 9 0 111 or higher, 1 0 0 0! or higher, 2 0 0 1^〇! or higher , 3 0 0 1^ or more, 4 0 0 1^ or more,

5 0 0 1^〇!以上、

Figure imgf000073_0007
以上、
Figure imgf000073_0008
以上、
Figure imgf000073_0009
以上、 9 0 0门〇!以上、 1 以上、 2 〇!以上、 3 〇!以上、 4 以上又は
Figure imgf000073_0010
以上であってよい。 5 0 0 1^〇 or more,
Figure imgf000073_0007
that's all,
Figure imgf000073_0008
that's all,
Figure imgf000073_0009
Or more, 900 or more!, 1 or more, 2! or more, 30! or more, 4 or more or
Figure imgf000073_0010
It may be the above.

[0237] 高密度不織布は、 タンパク質極細繊維のみを含むものであってもよく、 夕 ンパク質極細繊維に加えてタンパク質繊維等の他の繊維を含むものであって もよい。 すなわち、 高密度不織布の形成に用いられる繊維 （ 「材料糸」 とも いう。 ） として、 タンパク質極細繊維のみからなる単独糸、 タンパク質極細 繊維と、 タンパク質繊維 （繊維径 1 〇 超のもの） 等の他の繊維とを組み 合わせてなる複合糸 （例えば、 混紡糸、 混繊糸、 カバーリング糸等。 ） が、 それぞれ単独で、 又はそれらが組み合わされて用いられてもよい。 上記単独 糸及び上記複合糸は、 短繊維を撚り合わせたスパン糸であってもよく、 長繊 維を燃り合わせたフィラメント糸であってもよい。 上記単独糸及び上記複合 糸としては、 フィラメント糸が好適に用いられる。 なお、 他の繊維としては 、 タンパク質繊維の他、 例えば、 ナイロン、 ポリエステル等の合成繊維、 キ ュプラ、 レーヨン等の再生繊維、 綿、 麻等の天然繊維が挙げられる。 他の繊 維と組み合わせて使用する場合には、 高密度不織布に占めるタンパク質極細 繊維の割合は、 高密度不織布の全質量を基準として、 例えば、 3 0質量％以 上、 4 0質量％以上、 5 0質量％以上、 6 0質量％以上、 7 0質量％以上、 〇 2020/175702 73 卩（：171? 2020 /008524 [0237] The high-density nonwoven fabric may contain only protein ultrafine fibers, or may contain other fibers such as protein fibers in addition to the proteinaceous ultrafine fibers. That is, as fibers (also referred to as “material threads”) used for forming a high-density nonwoven fabric, other fibers such as a single thread consisting only of protein ultrafine fibers, protein ultrafine fibers and protein fibers (having a fiber diameter of more than 10) are used. The composite yarns (for example, mixed yarns, mixed yarns, covering yarns, etc.) formed by combining the above fibers with each other may be used alone or in combination. The single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or filament yarn in which long fibers are fired together. A filament yarn is preferably used as the single yarn and the composite yarn. Examples of other fibers include protein fibers, synthetic fibers such as nylon and polyester, regenerated fibers such as cupra and rayon, and natural fibers such as cotton and hemp. When used in combination with other fibers, the proportion of protein ultrafine fibers in the high-density nonwoven fabric is, for example, 30% by mass or more, 40% by mass or more, based on the total mass of the high-density nonwoven fabric. 50 mass% or more, 60 mass% or more, 70 mass% or more, 〇 2020/175 702 73 卩(: 171-1? 2020/008524

8 0質量％以上、 9 0質量％以上、 又は 9 5質量％以上であってよい。 It may be 80% by mass or more, 90% by mass or more, or 95% by mass or more.

[0238] 本実施形態に係る高密度不織布の繊維密度 （目付） は、 例えば、 0 . 0 4

Figure imgf000074_0001
[0238] The fiber density (area weight) of the high-density nonwoven fabric according to the present embodiment is, for example, 0.04
Figure imgf000074_0001

く、 〇. 0 5 9 /〇 01 2以上であることがより好ましく、 〇. 0 5 5 9 /〇 111 2以上であることが更に好ましい。 高密度不織布の繊維密度の上限に特に制限 はなく、 十分な防水性が確保可能な範囲において適宜に決定される。 繊維密 度 （目付） は、 不織布の単位面積当たりの重量で定義される値である。 Ku, 0.0 more preferably 5 9 / 〇 01 is 2 or more, 0.0 5 and still more preferably 5 to 9 / 〇 111 2 or more. There is no particular upper limit to the fiber density of the high-density nonwoven fabric, and the fiber density is appropriately determined within the range in which sufficient waterproofness can be secured. The fiber density (area weight) is a value defined by the weight per unit area of the nonwoven fabric.

[0239] 本実施形態に係る高密度不織布は、 繊維密度増加率が 2 0 %以上であるこ とが好ましく、 3 0 %以上であることがより好ましく、 4 0 %以上であるこ とが更に好ましく、 5 0 %以上であることが更により好ましく、 1 0 0 %以 上であることが更によりまた好ましい。 繊維密度増加率は、 下記式丨で定義 される値である。 [0239] In the high-density nonwoven fabric according to the present embodiment, the fiber density increase rate is preferably 20% or more, more preferably 30% or more, and further preferably 40% or more, It is even more preferably 50% or more, still more preferably 100% or more. The fiber density increase rate is a value defined by the following formula.

繊維密度増加率 = { （水収縮後の不織布 （高密度不織布） の繊維密度/水 収縮前の不織布 （原料不織布） の繊維密度） - 1 } X 1 〇〇 （%） （式 Fiber density increase rate = {(fiber density of nonwoven fabric after water shrinkage (high density nonwoven fabric) / fiber density of nonwoven fabric before water shrinkage (raw material nonwoven fabric))-1} X 1 〇 〇 (%) (Equation

I） I)

[0240] 高密度不織布は、 原料不織布 （繊維径 1 〇 以下のタンパク質極細繊維 を含み、 水収縮前の不織布） を水収縮させることで得ることができる。 高密 度不織布は、 例えば、 原料不織布を製造する工程と、 原料不織布を水分と接 触させて、 原料不織布を収縮させる工程 （以下、 「収縮工程」 ともいう。 ） とを備える製造方法により得ることができる。 [0240] The high-density non-woven fabric can be obtained by water-shrinking a raw material non-woven fabric (a non-woven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less and before water shrinkage). The high-density non-woven fabric is obtained by a production method including, for example, a step of producing a raw non-woven fabric and a step of contacting the raw non-woven fabric with water to shrink the raw non-woven fabric (hereinafter, also referred to as “shrinking step”). You can

[0241 ] 原料不織布を製造する工程において、 原料不織布は、 例えば、 繊維径 1 0 以下のタンパク質極細繊維を少なくとも一部に含む繊維を用いて、 公知 の製造方法により製造することができる。 具体的には、 例えば、 繊維径 1 0 以下のタンパク質極細繊維を少なくとも一部に含む繊維から、 乾式法、 湿式法及びエアレイ ド法等でウェブ （単層ウェブ、 及び積層ウェブを含む。 [0241] In the step of producing the raw material non-woven fabric, the raw material non-woven fabric can be produced by a known production method using, for example, fibers containing at least a portion of protein ultrafine fibers having a fiber diameter of 10 or less. Specifically, for example, a web (single-layer web, laminated web, etc.) is prepared by a dry method, a wet method, an air-laid method, or the like from a fiber containing at least a part of a protein ultrafine fiber having a fiber diameter of 10 or less.

） を形成させた後、 ケミカルボンド法 （浸漬法、 スプレー法等） 及び二ード ルパンチ法等によりウェブの繊維間を結合させて、 原料不織布を得ることが できる。 〇 2020/175702 74 卩（：171? 2020 /008524 ) Is formed and then the fibers of the web are bonded by a chemical bond method (dipping method, spray method, etc.), a double punch method, etc. to obtain a raw material nonwoven fabric. 〇 2020/175 702 74 卩(：171? 2020/008524

[0242] 原料不織布はまた、 例えば、 タンパク質を、 ジメチルスルホキシド （口1\/1 [0242] The raw non-woven fabric also includes, for example, proteins such as dimethyl sulfoxide (mouth 1\/1

3〇） 、 1\1, 1\1 -ジメチルホルムアミ ド （01\/1 ） 、 ギ酸、 又はへキサフル オロイソプロパノール （1~1 I ） 等の溶媒に、 必要に応じて、 溶解促進剤 としての無機塩と共に添加し、 溶解してドープ液を作製した後、 当該ドープ 液を用いてエレクトロスピニング法 （静電紡糸法） により紡糸することによ り得ることもできる。 エレクトロスピニング法で得られるタンパク質極細繊 維の平均繊維径 （繊維径の平均値） は、 通常、 1 0000 n m以下であり、 好ましくは 1 000门 以下であり、 1 00 n m~ 1 0000 n〇1、 1 00 30), 1\1, 1\1-dimethylformamide (01\/1), formic acid, or hexafluoroisopropanol (1 to 1 I) as a solvent, if necessary, as a dissolution promoter It can also be obtained by adding together with the above inorganic salt, dissolving it to prepare a dope solution, and then spinning using the dope solution by an electrospinning method (electrostatic spinning method). The average fiber diameter (average fiber diameter) of the protein ultrafine fibers obtained by the electrospinning method is usually 1 0000 nm or less, preferably 1 000 doors or less, 100 nm to 1 0000 n 〇 1 , 1 00

90011111 90011111

、

Figure imgf000075_0001
繊維の繊維 径は、
Figure imgf000075_0002
（ 1 0 ） の間、 好ましくは 1 00门 〇!〜 1 0001^ 111 （1 〇〇 の間で変動してもよい。 ,
Figure imgf000075_0001
The fiber diameter of the fiber is
Figure imgf000075_0002
It may fluctuate between (10), preferably between 100 ◯! and 1 0001^111 (100 ).

[0243] 原料不織布は、 繊維密度 （目付） 、 空隙率、 かさ密度等の数値範囲が、 防 水性と透湿性とを充分に確保し得る範囲となるように適宜設定される。 なお 、 それら目付、 空隙率、 かさ密度等の調整は、 例えば、 ウェブを構成する繊 維量を増減すること、 積層ウェブの場合は、 積層数を増減することにより行 うことができる。 [0243] The raw material non-woven fabric is appropriately set such that the numerical ranges of the fiber density (weight per unit area), the porosity, the bulk density, etc. are within a range in which water proofness and moisture permeability can be sufficiently ensured. The basis weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of laminated layers.

[0244] 収縮工程では、 原料不織布を水分と接触させて、 原料不織布を収縮させる 。 原料不織布は、 タンパク質極細繊維を含むものであるため、 水分と接触さ せることで、 外力によらずに、 タンパク質極細繊維を収縮させる （水収縮さ せるともいう。 ） ことができ、 不織布全体の収縮を生じさせる。 [0244] In the shrinking step, the raw material nonwoven fabric is brought into contact with water to shrink the raw material nonwoven fabric. Since the raw material non-woven fabric contains protein ultrafine fibers, it is possible to shrink the protein ultrafine fibers (also referred to as water shrinkage) by contacting with water, without relying on an external force, and to shrink the entire nonwoven fabric. Give rise to.

[0245] タンパク質極細繊維の外力によらない収縮は、 例えば、 以下の理由により 生ずると考えられる。 すなわち、 一つの理由は、 タンパク質極細繊維の二次 構造又は三次構造に起因すると考えられ、 また別の一つの理由は、 例えば、 製造工程での延伸等によって残留応力を有するタンパク質極細繊維において 、 水分が繊維間又は繊維内へ浸入することにより、 残留応力が緩和されるこ とで生ずると考えられる。 それ故、 収縮工程でのタンパク質極細繊維の収縮 率は、 例えば、 タンパク質極細繊維の製造過程での延伸倍率の大きさに応じ 〇 2020/175702 75 卩（：171? 2020 /008524 [0245] The contraction of the protein ultrafine fibers that does not depend on the external force is considered to occur due to the following reasons, for example. That is, one reason is considered to be due to the secondary structure or the tertiary structure of the protein ultrafine fiber, and another reason is that, for example, in the protein ultrafine fiber having residual stress due to stretching in the manufacturing process, It is considered that the residual stress is relieved by the infiltration of fibers into or between fibers. Therefore, the shrinkage rate of protein ultrafine fibers in the shrinking process depends on, for example, the size of the draw ratio in the process of producing protein ultrafine fibers. 〇 2020/175 702 75 卩(：171? 2020/008524

て任意にコントロールすることもできると考えられる。 また、 タンパク質極 細繊維の収縮率は、 例えば、 収縮工程における、 接触させる水分の温度、 水 分との接触時間、 水分と接触させるときの引張力を制御することでコントロ —ルすることができる。 したがって、 タンパク質極細繊維の製造過程におけ る延伸倍率の調節等により水分との接触時の収縮率が調整されたタンパク質 極細繊維を含む材料糸を用いること、 及び収縮工程で接触させる水分の温度 、 水分との接触時間、 水分と接触させるときの引張力等を制御すること等に より、 原料不織布の水分との接触による収縮率を任意に調整することができ る。 その結果、 所望の繊維密度を有する高密度不織布が得られるようになる と考えられる。 It is thought that it can be controlled arbitrarily. In addition, the shrinkage rate of the protein microfibers can be controlled by controlling the temperature of water to be contacted, the contact time with water, and the tensile force when contacting with water in the shrinking process. .. Therefore, using a material yarn containing protein ultrafine fibers whose contraction rate upon contact with water is adjusted by adjusting the draw ratio in the production process of protein ultrafine fibers, and the temperature of the water contacted in the shrinking process, By controlling the contact time with water, the tensile force when contacting with water, etc., the shrinkage ratio of the raw material nonwoven fabric due to contact with water can be adjusted arbitrarily. As a result, it is considered that a high-density nonwoven fabric having a desired fiber density can be obtained.

[0246] また、 水分との接触時の収縮率が互いに異なる材料糸の中から適当なもの を適宜に選択し組み合わせて用いることによっても、 高密度不織布の繊維密 度の調整が可能になると期待される。 さらに、 水分との接触による原料不織 布の収縮量を制限することにより、 材料糸の種類等に関わらず、 高密度不織 布の繊維密度を調整することもできる。 原料不織布の水分との接触による収 縮量を制限する方法は、 特に限定されない。 収縮量を制限する方法としては 、 例えば、 原料不織布の周端部を固定した状態で水分と接触させて収縮させ る方法などが挙げられる。 より具体的には、 水分との接触前の原料不織布の 元のサイズよりも小さく、 且つ周端部を自由にした状態で水分と原料不織布 とを接触させて最大量収縮させて得られる不織布のサイズよりも所定寸法だ け大きなサイズの枠体等に、 原料不織布の周端部を全周において固定した状 態 （枠体のサイズと、 原料不織布のサイズとの差分だけ収縮が許容された状 態） で、 原料不織布を水分に接触させることで、 収縮量の調整が可能である 。 そのような枠体のサイズを種々調節することにより、 高密度不織布の繊維 密度を任意に調整することが可能となる。 [0246] Further, it is expected that the fiber density of the high-density nonwoven fabric can be adjusted by appropriately selecting and combining material threads having different contraction rates upon contact with water. To be done. Further, by limiting the shrinkage amount of the raw material nonwoven fabric due to contact with moisture, the fiber density of the high density nonwoven fabric can be adjusted regardless of the type of material yarn. The method of limiting the amount of shrinkage due to the contact of the raw material nonwoven fabric with water is not particularly limited. Examples of the method of limiting the shrinkage amount include a method of bringing the raw material nonwoven fabric into contact with water to shrink the raw material nonwoven fabric in a fixed state. More specifically, it is smaller than the original size of the raw material non-woven fabric before contacting with water, and the non-woven fabric obtained by contacting water with the raw material non-woven fabric in a state where the peripheral edge is free to shrink the maximum amount. A state in which the peripheral edge of the raw non-woven fabric is fixed over the entire circumference in a frame that is a size larger than the size (a state in which shrinkage is allowed by the difference between the size of the frame and the size of the raw non-woven fabric). In this case, the amount of shrinkage can be adjusted by contacting the raw material nonwoven fabric with water. By adjusting various sizes of such a frame, it becomes possible to arbitrarily adjust the fiber density of the high-density nonwoven fabric.

[0247] 本明細書において 「水分」 とは、 液体、 気体のいずれの状態の水をも意味 する。 原料不織布を水分と接触させるステップ （以下、 「接触ステップ」 と もいう。 ） において、 水分を原料不織布に接触させる方法も、 特に限定され 〇 2020/175702 76 卩（：171? 2020 /008524 [0247] In the present specification, "water" means water in a liquid or gas state. In the step of bringing the raw material nonwoven fabric into contact with water (hereinafter, also referred to as “contact step”), the method of bringing the moisture into contact with the raw material nonwoven fabric is not particularly limited. 〇 2020/175 702 76 卩(: 171? 2020/008524

ない。 例えば、 原料不織布を水中に浸潰する方法、 原料不織布に対して、 水 を常温又は加温したスチーム等の状態で噴霧する方法、 原料不織布を水蒸気 が充満した高湿度環境下に暴露する方法等が挙げられる。 これらの方法の中 でも、 収縮時間の短縮化が効果的に図れると共に、 加工設備の簡素化等が実 現できることから、 原料不織布を水中に浸潰する方法が好ましい。 この原料 不織布の水中への浸漬方法としては、 具体的には、 例えば、 タンパク質極細 繊維を含む繊維を用いて形成される原料不織布を、 所定の温度の水が収容さ れた容器内に投入して、 水と接触させる方法等がある。 Absent. For example, a method of immersing the raw non-woven fabric in water, a method of spraying water on the raw non-woven fabric in a state of normal temperature or heated steam, etc., a method of exposing the raw non-woven fabric to a high humidity environment filled with water vapor, etc. Is mentioned. Among these methods, the method of immersing the raw material nonwoven fabric in water is preferable because it can effectively shorten the shrinkage time and can simplify the processing equipment. As a method for immersing this raw material nonwoven fabric in water, specifically, for example, a raw material nonwoven fabric formed using fibers containing protein ultrafine fibers is placed in a container containing water at a predetermined temperature. There is a method of contacting with water.

[0248] 接触ステップにおいて、 水分を原料不織布に接触させる際の水の温度は、 特に限定されないが、 例えば沸点未満であることが好ましい。 このような温 度であれば、 取扱性及び収縮工程の作業性等が向上する。 また水の温度の上 限値は、 9 0 °〇以下であることが好ましく、 8 0 °〇以下であることがより好 ましい。 水の温度の下限値は、 1 0 °〇以上であることが好ましく、 4 0 °〇以 上であることがより好ましく、 7 0 °〇以上であることが更に好ましい。 原料 不織布に接触させる水の温度は、 原料不織布を構成する繊維に応じて調整す ることができる。 また、 水分を原料不織布に接触させている間、 水の温度は 一定であってもよく、 水の温度を所定の温度になるように変動させてもよい [0248] In the contacting step, the temperature of the water for contacting the moisture with the raw material nonwoven fabric is not particularly limited, but is preferably lower than the boiling point, for example. At such a temperature, handling and workability in the shrinking process are improved. Further, the upper limit value of the water temperature is preferably 90° or less, more preferably 80° or less. The lower limit of the temperature of the water is preferably at 1 0 ° ● As, more preferably 4 0 ° 〇 than on, and still more preferably 7 0 ° ● As. The temperature of the water contacted with the raw material nonwoven fabric can be adjusted according to the fibers constituting the raw material nonwoven fabric. In addition, the temperature of the water may be constant while the moisture is in contact with the raw material nonwoven fabric, or the temperature of the water may be changed to reach a predetermined temperature.

[0249] 接触ステップにおいて、 水分を原料不織布に接触させる時間は、 特に制限 されず、 例えば、 1分以上であってよい。 当該時間は、 1 0分以上であって よく、 2 0分以上であってよく、 3 0分以上であってもよい。 また、 当該時 間の上限に特に制限はないが、 製造工程の時間を短縮するという観点、 及び タンパク質繊維の加水分解のおそれを排除する等の観点から、 例えば、 1 2 〇分以下であってよく、 9 0分以下であってよく、 6 0分以下であってもよ い。 [0249] In the contacting step, the time for contacting the raw material nonwoven fabric with water is not particularly limited and may be, for example, 1 minute or more. The time may be 10 minutes or longer, 20 minutes or longer, and 30 minutes or longer. The upper limit of the time is not particularly limited, but it is, for example, 120 minutes or less from the viewpoint of shortening the manufacturing process time and eliminating the risk of hydrolysis of protein fiber. Well, 90 minutes or less, 60 minutes or less.

[0250] 収縮工程は、 接触ステップに加えて、 原料不織布を水分と接触させた後に 、 乾燥させること （以下、 「乾燥ステップ」 ともいう。 ） を更に含むもので あってもよい。 〇 2020/175702 77 卩（：171? 2020 /008524 [0250] The shrinking step may further include, in addition to the contacting step, contacting the raw material nonwoven fabric with water and then drying (hereinafter, also referred to as "drying step"). 〇 2020/175 702 77 卩(：171? 2020/008524

[0251 ] 乾燥ステップにおける乾燥方法は、 特に限定されず、 例えば、 自然乾燥で もよく、 乾燥設備を使用して強制的に乾燥させてもよい。 乾燥温度としては 、 不織布を構成するタンパク質が熱的損傷を受けたりする温度より低い温度 であれば何ら限定されるものではないが、 一般的には、 2 0 ~ 1 5 0 °〇の範 囲内の温度であり、 4 0〜 1 2 0 °〇の範囲内の温度であることが好ましく、[0251] The drying method in the drying step is not particularly limited, and may be, for example, natural drying or forced drying using a drying facility. The drying temperature is not particularly limited as long as it is lower than the temperature at which the proteins constituting the nonwoven fabric are thermally damaged, but generally, it is within the range of 20 to 150 ° And preferably in the range of 40 to 120 ° 〇,

6 0 ~ 1 0 0 °〇の範囲内の温度であることがより好ましい。 このような温度 範囲内であれば、 タンパク質の熱的損傷等を生ずることなく、 不織布を、 よ り迅速かつ効率的に乾燥させることができる。 乾燥時間は、 乾燥温度等に応 じて適宜選択され、 例えば、 タンパク質極細繊維の過乾燥による不織布の品 質及び物性等への影響が排除されうる時間が採用される。 It is more preferable that the temperature is in the range of 60 to 100°. Within such a temperature range, the nonwoven fabric can be dried more quickly and efficiently without causing thermal damage to the protein. The drying time is appropriately selected according to the drying temperature and the like, and for example, the time that can eliminate the influence of overdrying of the protein ultrafine fibers on the quality and physical properties of the nonwoven fabric is used.

[0252] 第 3実施形態に係る防水透湿性生地の表皮層 1は、 編織体からなる。 編織 体とは、 編地及び織地の総称である。 編地は、 横編、 丸編等の緯編組織を有 する編地 （単に 「緯編地」 ともいう。 ） 、 トリコッ ト、 ラッセル等の経編組 織を有する編地 （単に 「経編地」 ともいう。 ） のいずれであってもよい。 織 地は、 平織、 綾織、 又は嬬子織のうちのいずれの組織を有する織地であって もよい。 編織体は、 編成又は織成により得られる未加工の編織体そのもので あってもよいし、 編成又は織成後に撥水加工等の加工を施した編織体であっ てもよい。 [0252] The skin layer 1 of the waterproof/moisture permeable fabric according to the third embodiment is made of a knitted fabric. A knitted fabric is a generic term for knitted fabrics and woven fabrics. A knitted fabric is a knitted fabric having a weft knitting structure such as a flat knitted fabric or a circular knitted fabric (also simply referred to as a “weft knitted fabric”), a knitted fabric having a warp braided fabric such as tricot, Russell (only Also referred to as ".". The woven fabric may be a woven fabric having any one of a plain weave, a twill weave, and a Tsumago weave. The knitted or woven body may be an unprocessed knitted or woven body itself obtained by knitting or weaving, or may be a knitted or woven body subjected to a process such as water repellent treatment after knitting or weaving.

[0253] 編織体は、 原料糸を編成又は織成して得ることができる。 編成方法及び織 成方法としては公知の方法を利用することができる。 使用される編機として は、 例えば、 丸編機、 経編機、 横編機などが使用でき、 生産性の観点からは 、 丸編機の使用が好ましい。 横編機としては、 成型編み機、 無縫製編機など があるが、 特に最終製品の形態で編地を製造可能であることから、 無縫製編 機の使用がより好ましい。 使用される織機としては、 例えば、 有抒織機、 及 び、 グリッパー織機、 レピア織機、 ゥォータージェッ ト織機、 エアジェッ ト 織機等の無抒織機が挙げられる。 [0253] The knitted or woven body can be obtained by knitting or weaving raw material threads. As a knitting method and a weaving method, known methods can be used. As the knitting machine to be used, for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used. As the flat knitting machine, there are a forming knitting machine, a non-sewn knitting machine, and the like. However, since the knitted fabric can be manufactured in the form of a final product, the non-sewn knitting machine is more preferable. Examples of the loom to be used include a hauling loom, and a non-tapping loom such as a gripper loom, a rapier loom, a water jet loom, and an air jet loom.

[0254] 編織体の原料糸は、 単独糸であってもよく、 複合糸 （例えば、 混紡糸、 混 繊糸、 カバーリング糸等。 ） であってもよく、 これらを組み合わせて用いて 〇 2020/175702 78 卩（：171? 2020 /008524 [0254] The raw material yarn of the knitted fabric may be a single yarn or a composite yarn (for example, a mixed yarn, a mixed yarn, a covering yarn, etc.), and these may be used in combination. 〇 2020/175 702 78 卩 (：171? 2020 /008524

もよい。 単独糸及び複合糸は、 短繊維を撚り合わせたスパン糸であってもよ く、 長繊維を撚り合わせたフィラメント糸であってもよい。 原料糸に含まれ る繊維としては、 例えば、 タンパク質繊維 （繊維径は問わない） 、 ナイロン 、 ポリエステル、 ポリテトラフルオロエチレン等の合成繊維、 キュプラ、 レ —ヨン等の再生繊維、 綿、 麻等の天然繊維が挙げられる。 Good. The single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or may be filament yarn in which long fibers are twisted together. The fibers contained in the raw yarn include, for example, protein fibers (regardless of fiber diameter), synthetic fibers such as nylon, polyester, polytetrafluoroethylene, recycled fibers such as cupra and rayon, cotton, hemp, etc. Examples include natural fibers.

[0255] 編織体がタンパク質繊維を含む場合、 編織体は、 高密度不織布と同様に、 水収縮したものであってよい。 これにより、 本実施形態に係る防水透湿性生 地の透湿性を損なうことなく、 防水性をより一層向上させることができる。 タンパク質繊維は、 タンパク質極細繊維と同様の性質を有するため、 上述し た方法により編織体を水収縮させることができる。 水収縮させる際の好まし い態様も同様である。 [0255] When the knitted fabric contains protein fibers, the knitted fabric may be water-shrinked, like the high-density nonwoven fabric. As a result, the waterproofness can be further improved without impairing the moisture permeability of the waterproof/moisture permeable material according to the present embodiment. Since the protein fiber has the same properties as the protein ultrafine fiber, the knitted fabric can be water-shrinked by the method described above. The same is true for the preferred mode of contracting water.

[0256] 編織体は、 高密度不織布との接合側とは反対側の表面が撥水加工されてい てもよい。 これにより、 防水性により優れた防水透湿性生地を得ることがで きる。 撥水加工は、 例えば、 プラズマ加工等の化学コーティングを施す、 撥 水コーティング剤を塗布する等の物理的コーティングを施す、 又は表面を化 学修飾する等の従来公知の方法により行うことができる。 [0256] The surface of the knitted or woven body opposite to the side where it is joined to the high-density nonwoven fabric may be water repellent. This makes it possible to obtain a waterproof and breathable fabric that is more waterproof. The water repellent treatment can be performed by a conventionally known method such as chemical coating such as plasma treatment, physical coating such as application of a water repellent coating agent, or chemical modification of the surface.

[0257] _実施形態において、 第 3実施形態に係る防水透湿性生地は、 防水透湿層 [0257] In the embodiment, the waterproof/moisture permeable fabric according to the third embodiment is:

（不織布） の表皮層 （編織体） が接合された面の反対側の面に裏材層 （編織 体） が更に接合されていてもよい。 裏材層の好ましい態様としては、 表皮層 で例示した態様が挙げられる。 表皮層と裏材層は、 それぞれ同一の材料で形 成された編織体であってもよく、 異なる材料で形成された編織体であっても よい。 A backing layer (textile) may be further bonded to the surface of the (nonwoven fabric) opposite to the surface to which the skin layer (textile) is bonded. Examples of the preferable embodiment of the backing layer include the embodiments exemplified for the skin layer. The skin layer and the backing layer may each be a knitted fabric formed of the same material, or may be a knitted fabric formed of different materials.

[0258] 第 3実施形態に係る防水透湿性生地の製造方法は、 少なくとも高密度不織 布を編織体に接合させる工程 （接合工程） を備える。 当該製造方法は、 タン パク質を含有するドープ液を使用したエレクトロスピニングにより、 繊維径 1 〇 以下のタンパク質極細繊維を集積させて不織布を形成する工程 （原 料不織布の製造工程） 、 形成された不織布 （原料不織布） を水分と接触させ て、 収縮させる工程 （収縮工程） を更に備えるものであってもよい。 〇 2020/175702 79 卩（：171? 2020 /008524 [0258] The method of manufacturing a waterproof moisture-permeable fabric according to the third embodiment includes at least a step of joining a high-density nonwoven fabric to a knitted body (joining step). The manufacturing method is a process of forming a nonwoven fabric by accumulating protein ultrafine fibers having a fiber diameter of 10 or less by electrospinning using a dope solution containing a protein (manufacturing process of a raw material nonwoven fabric). The non-woven fabric (raw material non-woven fabric) may be further provided with a step of contracting by contacting with water (shrinkage step). 〇 2020/175 702 79 卩(：171? 2020/008524

[0259] 接合工程では、 高密度不織布 （防水透湿層） と編織体 （表皮層） とを接合 する。 高密度不織布と編織体との接合方法は、 高密度不織布及び編織体に使 用する素材に応じて、 適宜選択することができる。 接合方法として、 例えば 、 高密度不織布と編織体とを、 熱又は溶剤等により、 溶着する方法、 高密度 不織布と編織体とを接着剤を介して接着する方法、 高密度不織布と編織体の 少なくともいずれか一方の接合面にプラズマを照射して、 ラジカル反応によ り共有結合を形成させることで、 防水透湿層と表皮層とを接合する方法等が 挙げられる。 例えば、 高密度不織布及び編織体がいずれもタンパク質 （タン パク質極細繊維又はタンパク質繊維） を含む場合、 高密度不織布及び編織体 の接合面のうち一方又は両方にタンパク質を溶解する溶媒 （例えば、 ジメチ ルスルホキシド （口1\/1 3〇） 、 1\1 , 1\1 _ジメチルホルムアミ ド （0 1\/1 ） 、 ギ酸、 又はヘキサフルオロイソプロパノール （1~1 I ） 等の有機溶媒、 そ れらに溶解促進剤としての無機塩を添加した溶液、 又は水、 若しくは水に無 機塩等を添加した水溶液） を塗布した後、 高密度不織布及び編織体を貼り合 わせ、 更に溶媒を除去することで高密度不織布と編織体とを接合することが できる。 [0259] In the joining step, the high density nonwoven fabric (waterproof and moisture permeable layer) and the knitted fabric (skin layer) are joined. The method for joining the high-density nonwoven fabric and the knitted fabric can be appropriately selected depending on the materials used for the high-density nonwoven fabric and the knitted fabric. As a joining method, for example, a method of welding a high-density non-woven fabric and a weaving body with heat or a solvent, a method of adhering the high-density non-woven fabric and the weaving body with an adhesive, and a high-density non-woven fabric and a weaving body at least Examples include a method in which one of the bonding surfaces is irradiated with plasma to form a covalent bond by a radical reaction to bond the waterproof moisture-permeable layer and the skin layer. For example, when both the high-density nonwoven fabric and the woven body contain proteins (protein ultrafine fibers or protein fibers), a solvent that dissolves the protein in one or both of the bonding surfaces of the high-density nonwoven fabric and the woven body (for example, dimethy Organic solvent such as sulphoxide (mouth 1\/1300), 1\1, 1\1_ dimethylformamide (0 1\/1), formic acid, or hexafluoroisopropanol (1 to 1 I) After applying a solution to which an inorganic salt as a dissolution accelerator is added, or water or an aqueous solution in which inorganic salt or the like is added to water), a high-density nonwoven fabric and a woven fabric are attached, and the solvent is further removed. By doing so, the high-density nonwoven fabric and the knitted fabric can be joined.

[0260] 原料不織布の製造工程、 及び収縮工程は、 上述した方法に従って実施する ことができる。 [0260] The step of manufacturing the raw material nonwoven fabric and the step of shrinking can be performed according to the method described above.

[0261 ] 他の実施形態に係る防水透湿性生地の製造方法は、 原料不織布と編織体と が接合してなる原料生地を用意する工程 （用意工程） と、 原料不織布を水分 と接触させて、 水収縮させる工程 （収縮工程） とを備える。 当該製造方法は 、 タンパク質を含有するドープ液を使用したエレクトロスピニングにより、 繊維径 1 0 以下のタンパク質極細繊維を集積させて不織布を形成するエ 程 （原料不織布の製造工程） 、 原料不織布と編織体とを接合して原料生地を 得る工程 （原料生地の製造工程） を更に備えるものであってもよい。 [0261] A method for manufacturing a waterproof and moisture-permeable fabric according to another embodiment includes a step of preparing a raw material fabric in which a raw material nonwoven fabric and a knitted fabric are joined (preparation step), and contacting the raw material nonwoven fabric with moisture, A step of shrinking with water (shrinking step). The manufacturing method is as follows: electrospinning using a dope containing a protein, a step of accumulating protein ultrafine fibers having a fiber diameter of 10 or less to form a non-woven fabric (manufacturing process of the raw non-woven fabric), a raw non-woven fabric and a woven body It may further be provided with a step of joining the raw material dough by joining (process for producing the raw material dough).

[0262] 原料生地の製造工程では、 原料不織布と編織体とを接合する。 原料不織布 と編織体との接合は、 高密度不織布と編織体との接合方法に準じて実施する ことができる。 また、 原料不織布をエレクトロスピニング法で形成する場合 〇 2020/175702 80 卩（：171? 2020 /008524 [0262] In the raw material dough manufacturing process, the raw material non-woven fabric and the knitted fabric are joined. The joining of the raw material non-woven fabric and the knitted fabric can be performed according to the joining method of the high density non-woven fabric and the knitted fabric. Also, when the raw material nonwoven fabric is formed by electrospinning 〇 2020/175 702 80 卩(：171? 2020/008524

、 接着剤等を介して編織体 （表皮層） の面上にタンパク質極細繊維を直接集 積させて原料不織布を形成させることもできる。 Alternatively, the raw material nonwoven fabric can be formed by directly accumulating protein ultrafine fibers on the surface of the knitted fabric (skin layer) via an adhesive or the like.

[0263] エレクトロスピニング法 （静電紡糸法） では、 供給側電極 （紡糸口金と兼 用できる） と捕集側電極 （例えば、 金属口ール又は金属ネッ ト等） 間に電圧 を印加し、 紡糸口金から押し出したドープ液に電荷を与えて捕集側電極に吹 き飛ばす。 この際にドープ液は伸張されて繊維形成される。 印加電圧は、 通 である。 電極間距離は

Figure imgf000081_0001
である。 [0263] In the electrospinning method (electrospinning method), a voltage is applied between a supply side electrode (which can also be used as a spinneret) and a collection side electrode (for example, a metal nozzle or a metal net), An electric charge is given to the dope solution extruded from the spinneret and blown to the collecting side electrode. At this time, the dope solution is stretched to form fibers. The applied voltage is normal. The distance between the electrodes is
Figure imgf000081_0001
Is.

[0264] 図 4は、 一実施形態に係るエレクトロスピニング装置 1 0 0の説明図であ る。 金属製口金ノズル 3 3 （供給側電極） と金属製ネッ ト 3 8 （捕集側電極 ） との間に電源 3 5により電圧をかける。 マイクロシリンジ 3 1内のドープ 液 3 2をシリンジポンプを用いて矢印 方向に移動させ、 金属製口金ノズル 3 3からドープ液 3 2を押し出し、 電荷によってドープ液を伸張し繊維状物 3 6にして金属製ネッ ト 3 8の表面に集積させることで、 タンパク質極細繊 維を含む原料不織布 3 9を得ることができる。 また、 このとき、 金属製ネッ 卜 3 8の表面に編織体 （表皮層） を載置することで、 表皮層上にタンパク質 極細繊維を直接集積させて原料不織布を形成させることもできる。 また、 編 織体 （表皮層） の面上に接着剤、 又は編織体と不織布の少なくともいずれか 一方を溶解させる溶媒等を塗布しておくことで、 形成された原料不織布と、 編織体とを接合させることもできる。 得られた原料不織布は、 次いで溶媒 （ ドープ液中の溶媒、 編織体又は不織布に塗布された溶媒等） を離脱してもよ い。 溶媒を脱離する方法としては、 例えば、 減圧乾燥又は脱溶媒槽への浸潰 が挙げられる。 [0264] FIG. 4 is an explanatory diagram of an electrospinning device 100 according to an embodiment. A voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35. The dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36. By accumulating on the surface of the metal net 38, a raw material non-woven fabric 39 containing protein ultrafine fibers can be obtained. At this time, by placing a knitted fabric (skin layer) on the surface of the metallic net 38, it is possible to directly accumulate the protein ultrafine fibers on the skin layer to form a raw material nonwoven fabric. In addition, by applying an adhesive, a solvent or the like that dissolves at least one of the knitted fabric and the nonwoven fabric onto the surface of the knitted fabric (skin layer), the formed raw material nonwoven fabric and the knitted fabric can be obtained. It can also be joined. The resulting raw material nonwoven fabric may then be stripped of the solvent (solvent in the dope solution, solvent applied to the weave or the nonwoven fabric, etc.). Examples of the method for removing the solvent include drying under reduced pressure and immersing in a desolvation tank.

[0265] 原料不織布を水分と接触させて、 水収縮させる工程 （収縮工程） は、 上述 した方法に従って実施することができる。 なお、 原料不織布と水分との接触 は、 原料生地中の原料不織布の部分のみを水分と接触させるものであっても よく、 原料不織布とそれ以外の部分を水分と接触させるものであってもよく 、 原料生地全体を水分と接触させるものであってもよい。 〇 2020/175702 81 卩（：171? 2020 /008524 [0265] The step of bringing the raw material nonwoven fabric into contact with water to shrink it with water (shrinking step) can be carried out according to the method described above. The contact between the raw material non-woven fabric and water may be such that only the part of the raw material non-woven fabric in the raw material dough is brought into contact with water, or the raw non-woven fabric and the other part are brought into contact with water. Alternatively, the entire raw material dough may be brought into contact with moisture. 〇 2020/175 702 81 卩(：171? 2020/008524

[0266] 第 3実施形態に係る防水透湿性生地において、 不織布又は編織体に含まれ るタンパク質極細繊維又はタンパク質繊維の原料となるタンパク質には、 特 に制限はなく、 任意のタンパク質を使用することができる。 タンパク質の具 体的な態様は、 第 1の発明に係る防水透湿性生地で説明した態様を適用でき る。 使用するタンパク質としては、 防水透湿性に加え、 保温性、 吸湿発熱性 及び/又は難燃性にも優れることから、 改変フイブロインが好ましく、 改変 クモ糸フイブロインがより好ましい。 タンパク質極細繊維及び/又はタンパ ク質繊維が、 改変フイブロイン （好ましくは、 改変クモ糸フイブロイン） を 含むことにより、 本実施形態に係る防水透湿性生地に保温性、 吸湿発熱性及 び/又は難燃性の性質を更に付与することができ、 生地としての価値がより 高くなる。 [0266] In the waterproof and moisture-permeable fabric according to the third embodiment, there is no particular limitation on the protein as a raw material of the protein ultrafine fibers or protein fibers contained in the nonwoven fabric or knitted fabric, and any protein may be used. You can As the concrete aspect of the protein, the aspect explained in the waterproof and moisture-permeable fabric according to the first invention can be applied. As the protein to be used, modified fibroin is preferable, and modified spider silk fibroin is more preferable, because it is excellent in heat retention, moisture absorption and heat generation property, and/or flame retardancy in addition to waterproof moisture permeability. By including the modified fibroin (preferably modified spider silk fibroin) in the protein ultrafine fiber and/or protein fiber, the waterproof and moisture-permeable fabric according to the present embodiment has heat-retaining property, moisture-absorbing heat-generating property, and/or flame-retardant property. It is possible to add more sexual character, and it becomes more valuable as a fabric.

[0267] 本実施形態に係るタンパク質は、 当該タンパク質をコードする核酸を使用 して、 常法により製造することができる。 当該タンパク質をコードする核酸 は、 塩基配列情報に基づいて、 化学合成してもよく、

Figure imgf000082_0001
法等を利用して 合成してもよい。 [0267] The protein according to this embodiment can be produced by a conventional method using a nucleic acid encoding the protein. The nucleic acid encoding the protein may be chemically synthesized based on the nucleotide sequence information,
Figure imgf000082_0001
It may be synthesized using a method or the like.

[0268] タンパク質極細繊維又はタンパク質繊維は、 例えば、 タンパク質を溶解可 能な溶媒で溶解させてドープ液とし、 湿式紡糸、 乾式紡糸、 乾湿式紡糸又は 溶融紡糸等の公知の紡糸方法により紡糸して得ることができる。 タンパク質 極細繊維は、 上述したエレクトロスピニング法により紡糸して得ることが好 ましい。 タンパク質を溶解可能な溶媒としては、 例えば、 ジメチルスルホキ シド

Figure imgf000082_0002
1\1 , 1\1 -ジメチルホルムアミ ド （0 1\/1 ） 、 ギ酸、 及び ヘキサフルオロイソプロパノール （1~1 丨 ） 等が挙げられる。 当該溶媒に は、 溶解促進剤として無機塩を添加してもよい。 [0268] The protein ultrafine fiber or protein fiber is prepared by, for example, dissolving a protein in a solvent capable of dissolving it to obtain a dope solution, and spinning the dope by a known spinning method such as wet spinning, dry spinning, dry wet spinning or melt spinning. Obtainable. The protein ultrafine fibers are preferably obtained by spinning by the electrospinning method described above. Solvents capable of dissolving proteins include, for example, dimethyl sulfoxide
Figure imgf000082_0002
1\1, 1\1-dimethylformamide (0 1\/1), formic acid, and hexafluoroisopropanol (1 to 1) are listed. An inorganic salt may be added to the solvent as a dissolution promoter.

[0269] 図 1 3は、 タンパク質繊維を製造するための紡糸装置の一例を概略的に示 す説明図である。 図 1 3に示す紡糸装置 1 0 0 0は、 乾湿式紡糸用の紡糸装 置の一例であり、 押出し装置 1 0 1 と、 未延伸糸製造装置 1 0 2と、 湿熱延 伸装置 1 0 3と、 乾燥装置 1 0 4とを有している。 [0269] Fig. 13 is an explanatory view schematically showing an example of a spinning apparatus for producing protein fibers. The spinning device 100 shown in FIG. 13 is an example of a spinning device for dry-wet spinning, and includes an extrusion device 101, an undrawn yarn production device 102, and a wet heat drawing device 103. And a drying device 104.

[0270] 紡糸装置 1 0 0 0を使用した紡糸方法を説明する。 まず、 貯槽 1 0 7に貯 〇 2020/175702 82 卩（：171? 2020 /008524 [0270] A spinning method using the spinning device 100 will be described. First, store in storage tank 107. 〇 2020/175 702 82 卩 (：171? 2020 /008524

蔵されたドープ液 1 0 6が、 ギアポンプ 1 0 8により口金 1 0 9から押し出 される。 ラボスケールにおいては、 ドープ液をシリンダーに充填し、 シリン ジポンプを用いてノズルから押し出してもよい。 次いで、 押し出されたドー プ液 1 0 6は、 エアギャップ 1 1 9を経て、 凝固液槽 1 2 0の凝固液 1 1 1 内に供給され、 溶媒が除去されて、 タンパク質が凝固し、 繊維状凝固体が形 成される。 次いで、 繊維状凝固体が、 延伸浴槽 1 2 1内の温水 1 1 2中に供 給されて、 延伸される。 延伸倍率は供給ニップローラ 1 1 3と引き取りニッ プローラ 1 1 4との速度比によって決まる。 その後、 延伸された繊維状凝固 体が、 乾燥装置 1 0 4に供給され、 糸道 1 2 2内で乾燥されて、 タンパク質 繊維 1 3 6が、 卷糸体 1 0 5として得られる。 1

Figure imgf000083_0001
1 8 9は糸ガイ ドである。 The stored dope solution 106 is pushed out of the mouthpiece 109 by the gear pump 108. In the lab scale, the dope may be filled in a cylinder and pushed out from a nozzle using a syringe pump. Next, the extruded dope liquid 106 is supplied into the coagulating liquid 111 of the coagulating liquid tank 120 via the air gap 1119, the solvent is removed, the protein is coagulated, and the fiber is A solidified body is formed. Next, the fibrous solidified body is fed into the warm water 1 12 in the stretching bath 1 21 and stretched. The draw ratio is determined by the speed ratio between the feeding nip roller 1 13 and the take-up nip roller 1 14. After that, the stretched fibrous coagulated body is supplied to the drying device 104 and dried in the yarn path 1 22 to obtain the protein fiber 1 36 as a winding body 10 5. 1
Figure imgf000083_0001
1 8 9 is a thread guide.

[0271 ] 本実施形態に係るタンパク質極細繊維又はタンパク質繊維は、 水分に接触 させて湿潤状態にするだけで収縮可能であることが好ましい。 また、 一実施 形態に係るタンパク質極細繊維又はタンパク質繊維は、 水分に接触させて湿 潤状態にし、 その後乾燥させることで、 より高度に収縮可能であることが好 ましい。 [0271] It is preferable that the protein ultrafine fibers or protein fibers according to the present embodiment can be contracted only by bringing them into contact with water to bring them into a wet state. In addition, it is preferable that the protein ultrafine fibers or protein fibers according to one embodiment be more highly shrinkable by being brought into contact with water to be in a wet state and then dried.

[0272] 本実施形態に係るタンパク質極細繊維又はタンパク質繊維は、 湿潤時収縮 率が 2 %以上であることが好ましい。 湿潤時収縮率は、 4 %以上であること がより好ましく、 6 %以上であることが更に好ましく、 8 %以上であること が更により好ましく、 1 〇 %以上であることが更によりまた好ましく、 1 5 %以上であることが特に好ましく、 2 0 %以上であることが特により好まし く、 2 5 %以上であることが特によりまた好ましく、 3 0 %以上であること が最も好ましい。 湿潤時収縮率の上限は、 通常、 8 0 %以下である。 なお、 湿潤時収縮率は、 下記式丨 丨で定義される。 [0272] The protein ultrafine fibers or protein fibers according to the present embodiment preferably have a wet shrinkage ratio of 2% or more. The wet shrinkage is more preferably 4% or more, still more preferably 6% or more, even more preferably 8% or more, still more preferably 10% or more, It is particularly preferably 15% or more, particularly preferably 20% or more, particularly preferably 25% or more, and most preferably 30% or more. The upper limit of the wet shrinkage ratio is usually 80% or less. The wet shrinkage ratio is defined by the following formula.

湿潤時収縮率 = { 1 - （水分に接触させて湿潤状態にしたタンパク質極細 繊維 （又はタンパク質繊維） の長さ/水分に接触させる前のタンパク質極細 繊維 （又はタンパク質繊維） の長さ） } X 1 0 0 （%） （式 I I） Shrinkage rate when wet = {1-(length of protein ultrafine fiber (or protein fiber) wetted by contact with water / length of protein ultrafine fiber (or protein fiber) before contact with water)} X 100 (%) (Formula II)

[0273] 本実施形態に係るタンパク質極細繊維又はタンパク質繊維は、 乾燥時収縮 〇 2020/175702 83 卩（：171? 2020 /008524 [0273] The protein ultrafine fiber or protein fiber according to the present embodiment shrinks when dried. 〇 2020/175 702 83 卩 (：171? 2020 /008524

率が 7%超であることが好ましい。 乾燥時収縮率は、 1 5%以上であること がより好ましく、 25 %以上であることが更に好ましく、 32 %以上である ことが更により好ましく、 40 %以上であることが更によりまた好ましく、It is preferable that the rate is more than 7%. The dry shrinkage is more preferably 15% or more, further preferably 25% or more, further preferably 32% or more, still more preferably 40% or more,

48%以上であることが特に好ましく、 56%以上であることが特により好 ましく、 64 %以上であることが特によりまた好ましく、 72 %以上である ことが最も好ましい。 乾燥時収縮率の上限は、 通常、 80%以下である。 な お、 乾燥時収縮率は、 下記式丨 丨 丨で定義される。 It is particularly preferably 48% or more, particularly preferably 56% or more, particularly preferably 64% or more, and most preferably 72% or more. The upper limit of dry shrinkage is usually 80% or less. The dry shrinkage is defined by the following formula.

乾燥時収縮率 = { 1 - （水分に接触させて湿潤状態にした後、 乾燥させた タンパク質極細繊維 （又はタンパク質繊維） の長さ/水分に接触させる前の タンパク質極細繊維 （又はタンパク質繊維） の長さ） ） X 1 00 （%） Shrinkage rate during drying = {1-(length of dried protein ultrafine fibers (or protein fibers) after contacting with water to make them wet / length of protein ultrafine fibers (or protein fiber) before contacting with water) Length)) X 100 (%)

（式丨 丨 丨） (Shiki 丨 丨)

[0274] 〔第 4の発明に係る防水透湿性生地〕 [0274] [Waterproof and breathable fabric according to the fourth invention]

第 4実施形態に係る防水透湿性生地は、 繊維径 1 〇 以下のタンパク質 極細繊維を含む不織布 （以下、 単に 「不織布」 ともいう。 ） からなる防水透 湿層 2と、 編織体からなる表皮層 1 とが、 介在層を介することなく接合され てなる。 なお、 介在層は、 防水透湿層 2及び表皮層 1 を構成する材料以外の 材料で構成される層 （例えば、 接着剤層等） である。 The waterproof and moisture-permeable fabric according to the fourth embodiment is a waterproof and moisture-permeable layer 2 made of a nonwoven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less (hereinafter also simply referred to as “nonwoven fabric”), and a skin layer made of a knitted fabric. 1 and are joined together without an intervening layer. The intervening layer is a layer (for example, an adhesive layer, etc.) composed of a material other than the material forming the waterproof/moisture permeable layer 2 and the skin layer 1.

[0275] 第 4実施形態に係る防水透湿性生地の防水透湿層 2は、 繊維径 1 〇 以 下のタンパク質極細繊維を含む不織布からなる。 タンパク質極細繊維径は、 短繊維の長手方向に垂直な断面を囲む最小の円の直径を意味する。 タンパク 質極細繊維の繊維径は、 1 0 （1 0000 n m） 以下であればよく、 9 以下、 8 以下、 7 〇!以下、 6 〇!以下、 5 〇!以下、 4 以下 、 3 〇!以下、 2 〇!以下、 1 〇! （1 0001^ 111） 以下、

Figure imgf000084_0001
[0275] The waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the fourth embodiment is made of a nonwoven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less. The protein ultrafine fiber diameter means the diameter of the smallest circle that surrounds the cross section of the short fiber perpendicular to the longitudinal direction. The fiber diameter of the protein ultrafine fiber may be 10 (10000 nm) or less, 9 or less, 8 or less, 7 〇! or less, 6 〇! or less, 5 〇! or less, 4 or less, 3 〇! or less. , 2 〇! or less, 1 〇! (1 0001^111) or less,
Figure imgf000084_0001

、 8001^〇!以下、 7001^ 以下、 6001^ 以下、 5001^ 以下、 4 , 8001^〇! or less, 7001^ or less, 6001^ or less, 5001^ or less, 4

00 〇!以下、 300 〇!以下、

Figure imgf000084_0002
以下であってよい。 タンパ ク質極細繊維の繊維径は、 例えば、 1 〇 01以上、 201^ 01以上、
Figure imgf000084_0003
以上、 401^〇!以上、 501^〇!以上、 以上、
Figure imgf000084_0004
以上、 801^00 〇! or less, 300 〇! or less,
Figure imgf000084_0002
May be: The fiber diameter of the protein ultrafine fibers is, for example, 1001 or more, 201^ 01 or more,
Figure imgf000084_0003
More than 401^〇!, more than 501^〇!, more than
Figure imgf000084_0004
Above, 801^

〇!以上、 901^〇!以上、 以上、

Figure imgf000084_0005
以上、 〇 2020/175702 84 卩（：171? 2020 /008524 More than 〇!, more than 901^〇!, more than
Figure imgf000084_0005
that's all, 〇 2020/175 702 84 卩 (: 171? 2020 /008524

、 4 0 0 1^〇!以上、 5 0 0 1^ 以上、 6 0 0 1^ 以上、 7 0 0 1^ 以上、 8 0 0 〇!以上、 9 0 0 1^〇!以上、 1 以上、 2 以上、 3 以上、 4 111以上又は 5 〇!以上であつてよい。 , 4 0 0 1^〇! or above, 5 0 0 1^ or above, 6 0 0 1^ or above, 7 0 0 1^ or above, 8 0 0 0 〇! or above, 9 0 0 1^ 〇! or above, 1 or above, It may be 2 or more, 3 or more, 4 111 or more, or 50! or more.

[0276] 不織布は、 タンパク質極細繊維のみを含むものであってもよく、 タンパク 質極細繊維に加えてタンパク質繊維等の他の繊維を含むものであってもよい 。 すなわち、 不織布の形成に用いられる繊維 （ 「材料糸」 ともいう。 ） とし て、 タンパク質極細繊維のみからなる単独糸、 タンパク質極細繊維 （繊維径 1 〇 以下） 繊維径 1 0 超のタンパク質繊維等の他の繊維とを組み合 わせてなる複合糸 （例えば、 混紡糸、 混繊糸、 カバーリング糸等。 ） が、 そ れぞれ単独で、 又はそれらが組み合わされて用いられてもよい。 上記単独糸 及び上記複合糸は、 短繊維を撚り合わせたスパン糸であってもよく、 長繊維 を撚り合わせたフィラメント糸であってもよい。 上記単独糸及び上記複合糸 としては、 フィラメント糸が好適に用いられる。 なお、 他の繊維としては、 タンパク質繊維の他、 例えば、 ナイロン、 ポリエステル等の合成繊維、 キュ ブラ、 レーヨン等の再生繊維、 綿、 麻等の天然繊維が挙げられる。 他の繊維 と組み合わせて使用する場合には、 不織布に占めるタンパク質極細繊維の割 合は、 不織布の全質量を基準として、 例えば、 3 0質量％以上、 4 0質量％ 以上、 5 0質量％以上、 6 0質量％以上、 7 0質量％以上、 8 0質量％以上 、 9 0質量％以上、 又は 9 5質量％以上であってよい。 [0276] The non-woven fabric may contain only the protein ultrafine fibers, or may contain other fibers such as protein fibers in addition to the protein ultrafine fibers. That is, as fibers (also referred to as “material threads”) used for forming a non-woven fabric, a single thread consisting only of protein ultrafine fibers, protein ultrafine fibers (fiber diameter of 10 or less), protein fibers of fiber diameter over 10 etc. A composite yarn (for example, a mixed yarn, a mixed yarn, a covering yarn, etc.) formed by combining with other fibers may be used alone or in combination. The single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are twisted together. A filament yarn is preferably used as the single yarn and the composite yarn. Examples of the other fibers include protein fibers, synthetic fibers such as nylon and polyester, regenerated fibers such as cubra and rayon, and natural fibers such as cotton and hemp. When used in combination with other fibers, the percentage of protein ultrafine fibers in the non-woven fabric is based on the total mass of the non-woven fabric, for example, 30 mass% or more, 40 mass% or more, 50 mass% or more. , 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.

[0277] 不織布は、 例えば、 繊維径 1 0 以下のタンパク質極細繊維を少なくと も一部に含む繊維を用いて、 公知の製造方法により製造することができる。 具体的には、 例えば、 繊維径 1 〇 以下のタンパク質極細繊維を少なくと も一部に含む繊維から、 乾式法、 湿式法及びエアレイ ド法等でウェブ （単層 ウェブ、 及び積層ウェブを含む。 ） を形成させた後、 ケミカルボンド法 （浸 潰法、 スプレー法等） 及び二ードルパンチ法等によりウェブの繊維間を結合 させて、 不織布を得ることができる。 [0277] The non-woven fabric can be produced by a known production method using, for example, fibers containing at least a portion of protein ultrafine fibers having a fiber diameter of 10 or less. Specifically, for example, from a fiber containing at least a part of protein ultrafine fibers having a fiber diameter of 10 or less, a web (a single-layer web and a laminated web are included by a dry method, a wet method and an airlaid method). ) Is formed, and then the fibers of the web are bonded by a chemical bond method (immersion method, spray method, etc.) or a needle punch method to obtain a nonwoven fabric.

[0278] 不織布はまた、 例えば、 タンパク質を、 ジメチルスルホキシド （口1\/1 3〇 ） 、 ！\1 , !\1 -ジメチルホルムアミ ド （0 !\/! ） 、 ギ酸、 又はヘキサフルオロ 〇 2020/175702 85 卩（：171? 2020 /008524 [0278] Nonwovens also include, for example, proteins such as dimethyl sulfoxide (mouth 1\/1300),! \1, ,\\1-Dimethylformamide (0 !\/!), formic acid, or hexafluoro 〇 2020/175 702 85 卩 (：171? 2020 /008524

イソプロパノール （1~1 I ） 等の溶媒に、 必要に応じて、 溶解促進剤とし ての無機塩と共に添加し、 溶解してドープ液を作製した後、 当該ドープ液を 用いてエレクトロスピニング法 （静電紡糸法） により紡糸することにより得 ることもできる。 エレクトロスピニング法で得られるタンパク質極細繊維の 平均繊維径 （繊維径の平均値） は、 通常、 1 0000 n m以下であり、 好ま しくは 1 0001^ 111以下であり、

Figure imgf000086_0001
00001^ 111、 1 0011111If necessary, it is added to a solvent such as isopropanol (1 to 1 I) together with an inorganic salt as a dissolution accelerator, and dissolved to prepare a dope solution, which is then subjected to electrospinning method (static It can also be obtained by spinning by the electrospinning method). The average fiber diameter (average fiber diameter) of protein ultrafine fibers obtained by the electrospinning method is usually 1 0000 nm or less, preferably 1 0001^ 111 or less,
Figure imgf000086_0001
00001^111, 1 0011111

〜 50001^ 111、

Figure imgf000086_0002
00011111、 200
Figure imgf000086_0003
90011111、 又 は 300 n m~ 800 n mであってもよい。 タンパク質極細繊維の繊維径は 、
Figure imgf000086_0004
~ 50001^111,
Figure imgf000086_0002
00011111, 200
Figure imgf000086_0003
It may be 90011111 or 300 nm to 800 nm. The fiber diameter of protein ultrafine fiber is
Figure imgf000086_0004

1 0001^ 111 （1 〇〇 の間で変動してもよい。 It may fluctuate between 1 0001^111 (1○).

[0279] タンパク質極細繊維としては、 改変フイブロインを含むことが好ましく、 改変クモ糸フイブロインを含むことがより好ましい。 改変フイブロイン （好 ましくは、 改変クモ糸フイブロイン） を含むことにより、 本実施形態に係る 防水透湿性生地に保温性、 吸湿発熱性及び/又は難燃性の性質を更に付与す ることができ、 生地としての価値がより高くなる。 改変フイブロインは、 改 変フイブロイン繊維 （タンパク質繊維） として極細繊維に含まれていてもよ い。 改変フイブロインの好ましい態様は、 第 1の発明に係る防水透湿性生地 で説明した態様を適用できる。 [0279] The protein ultrafine fibers preferably include modified fibroin, more preferably modified spider silk fibroin. By including the modified fibroin (preferably the modified spider silk fibroin), the waterproof and moisture-permeable fabric according to the present embodiment can be further imparted with heat retention, heat absorption by heat absorption and/or flame retardancy. , More valuable as a fabric. The modified fibroin may be contained in the ultrafine fiber as modified fibroin fiber (protein fiber). As a preferred embodiment of the modified fibroin, the embodiment described in the waterproof and moisture-permeable fabric according to the first invention can be applied.

[0280] 不織布は、 繊維密度 （目付） 、 空隙率、 かさ密度等の数値範囲が、 防水性 と透湿性とを充分に確保し得る範囲となるように適宜設定される。 なお、 そ れら目付、 空隙率、 かさ密度等の調整は、 例えば、 ウェブを構成する繊維量 を増減すること、 積層ウェブの場合は、 積層数を増減することにより行うこ とができる。 [0280] The non-woven fabric is appropriately set such that the numerical values of the fiber density (area weight), porosity, bulk density, etc. are within a range in which waterproofness and moisture permeability can be sufficiently ensured. The unit weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of layers.

[0281] 第 4実施形態に係る防水透湿性生地の表皮層 1は、 編織体からなる。 編織 体とは、 編地及び織地の総称である。 編地は、 横編、 丸編等の緯編組織を有 する編地 （単に 「緯編地」 ともいう。 ） 、 トリコッ ト、 ラッセル等の経編組 織を有する編地 （単に 「経編地」 ともいう。 ） のいずれであってもよい。 織 地は、 平織、 綾織、 又は嬬子織のうちのいずれの組織を有する織地であって 〇 2020/175702 86 卩（：171? 2020 /008524 [0281] The skin layer 1 of the waterproof/moisture permeable fabric according to the fourth embodiment is made of a knitted fabric. A knitted fabric is a generic term for knitted fabrics and woven fabrics. A knitted fabric is a knitted fabric having a weft knitting structure such as a flat knitted fabric or a circular knitted fabric (also simply referred to as a “weft knitted fabric”), a knitted fabric having a warp braided fabric such as tricot, Russell (only Also referred to as ".". The woven fabric is a woven fabric having any one of a plain weave, a twill weave, and a Tsumago weave. 〇 2020/175 702 86 卩 (：171? 2020 /008524

もよい。 編織体は、 編成又は織成により得られる未加工の編織体そのもので あってもよいし、 編成又は織成後に撥水加工等の加工を施した編織体であっ てもよい。 Good. The knitted or woven body may be an unprocessed knitted or woven body itself obtained by knitting or weaving, or may be a knitted or woven body subjected to a process such as water repellent treatment after knitting or weaving.

[0282] 編織体は、 原料糸を編成又は織成して得ることができる。 編成方法及び織 成方法としては公知の方法を利用することができる。 使用される編機として は、 例えば、 丸編機、 経編機、 横編機などが使用でき、 生産性の観点からは 、 丸編機の使用が好ましい。 横編機としては、 成型編み機、 無縫製編機など があるが、 特に最終製品の形態で編地を製造可能であることから、 無縫製編 機の使用がより好ましい。 使用される織機としては、 例えば、 有抒織機、 及 び、 グリッパー織機、 レピア織機、 ウォータージェッ ト織機、 エアジェッ ト 織機等の無抒織機が挙げられる。 [0282] The knitted or woven body can be obtained by knitting or weaving raw material threads. As a knitting method and a weaving method, known methods can be used. As the knitting machine to be used, for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used. As the flat knitting machine, there are a forming knitting machine, a non-sewn knitting machine, and the like. However, since the knitted fabric can be manufactured in the form of a final product, the non-sewn knitting machine is more preferable. Examples of the loom to be used include a hauling loom, and a non-tapping loom such as a gripper loom, a rapier loom, a water jet loom, and an air jet loom.

[0283] 原料糸は、 単独糸であってもよく、 複合糸 （例えば、 混紡糸、 混繊糸、 力 バーリング糸等。 ） であってもよく、 これらを組み合わせて用いてもよい。 単独糸及び複合糸は、 短繊維を撚り合わせたスパン糸であってもよく、 長繊 維を撚り合わせたフィラメント糸であってもよい。 原料糸に含まれる繊維と しては、 例えば、 タンパク質繊維、 ナイロン、 ポリエステル、 ポリテトラフ ルオロエチレン等の合成繊維、 キュプラ、 レーヨン及びリヨセル等の再生繊 維、 綿、 麻及び絹等の天然繊維が挙げられる。 また、 原料糸としては、 不織 布を構成するタンパク質極細繊維を溶解し得る溶媒に溶解可能な繊維が好適 に用いられる。 これによって、 不織布と表皮層との溶媒を用いた溶解による 一体接合が可能となる。 [0283] The raw material yarn may be a single yarn, a composite yarn (for example, a mixed spun yarn, a mixed fiber yarn, a force burring yarn, etc.), or a combination thereof. The single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are twisted together. Examples of the fibers contained in the raw material yarn include protein fibers, synthetic fibers such as nylon, polyester and polytetrafluoroethylene, regenerated fibers such as cupra, rayon and lyocell, and natural fibers such as cotton, hemp and silk. .. Further, as the raw material yarn, fibers that can be dissolved in a solvent that can dissolve the protein ultrafine fibers that make up the non-woven fabric are preferably used. This makes it possible to integrally bond the non-woven fabric and the skin layer by dissolving them with a solvent.

[0284] 編織体は、 タンパク質繊維を含むことが好ましい。 タンパク質繊維として は、 改変フィブロインを含むことが好ましく、 改変クモ糸フィブロインを含 むことがより好ましい。 改変フィブロイン （好ましくは、 改変クモ糸フィブ ロイン） を含むことにより、 本実施形態に係る防水透湿性生地に保温性、 吸 湿発熱性及び/又は難燃性の性質を更に付与することができ、 生地としての 価値がより高くなる。 改変フィブロインは、 改変フィブロイン繊維 （タンパ ク質繊維） として編織体に含まれていてもよい。 改変フィブロインの好まし 〇 2020/175702 87 卩（：171? 2020 /008524 [0284] The knitted fabric preferably contains protein fibers. The protein fiber preferably contains modified fibroin, more preferably modified spider silk fibroin. By including the modified fibroin (preferably modified spider thread fibroin), the waterproof and moisture-permeable fabric according to the present embodiment can be further imparted with heat-retaining property, heat-absorption property and/or flame-retardant property, Higher value as a dough. The modified fibroin may be contained as a modified fibroin fiber (protein fiber) in the knitted or woven body. Modified fibroin preference 〇 2020/175 702 87 卩(：171? 2020/008524

い態様は、 第 1の発明に係る防水透湿性生地で説明した態様を適用できる。 As the other aspect, the aspect described in the waterproof and moisture-permeable fabric according to the first invention can be applied.

[0285] 編織体は、 不織布との接合側とは反対側の表面が撥水加工されていてもよ い。 これにより、 防水性により優れた防水透湿性生地を得ることができる。 撥水加工は、 例えば、 プラズマ加工等の化学コーティングを施す、 撥水コー ティング剤を塗布する等の物理的コーティングを施す、 又は表面を化学修飾 する等の従来公知の方法により行うことができる。 [0285] In the knitted fabric, the surface on the side opposite to the side where the nonwoven fabric is joined may be water-repellent. This makes it possible to obtain a waterproof and moisture-permeable fabric that is more waterproof. The water repellent treatment can be carried out by a conventionally known method such as chemical coating such as plasma processing, physical coating such as coating with a water repellent coating agent, or chemical modification of the surface.

[0286] _実施形態において、 第 4実施形態に係る防水透湿性生地は、 防水透湿層 の表皮層が接合された面の反対側の面に、 介在層を介することなく裏材層 （ 編織体） が更に接合されていてもよい。 裏材層の好ましい態様としては、 表 皮層で例示した態様が挙げられる。 表皮層と裏材層は、 それぞれ同一の材料 で形成された編織体であってもよく、 異なる材料で形成された編織体であっ てもよい。 [0286] In the embodiment, the waterproof/moisture permeable fabric according to the fourth embodiment is provided with a backing layer (knitted fabric) on the surface of the waterproof/moisture permeable layer opposite to the surface to which the skin layer is bonded, without an intervening layer. The body) may be further joined. Preferred embodiments of the backing layer include the embodiments exemplified for the skin layer. The skin layer and the backing layer may be a woven body made of the same material or may be a woven body made of different materials.

[0287] 第 4実施形態に係る防水透湿性生地は、 防水透湿層と表皮層とを、 介在層 を介することなく接合して得ることができる。 防水透湿層と表皮層との接合 方法は、 不織布及び編織体に使用する素材に応じて、 適宜選択することがで きる。 [0287] The waterproof/moisture permeable fabric according to the fourth embodiment can be obtained by joining the waterproof/moisture permeable layer and the skin layer without an intervening layer. The method for joining the waterproof moisture-permeable layer and the skin layer can be appropriately selected depending on the materials used for the nonwoven fabric and the knitted fabric.

[0288] _実施形態に係る製造方法は、 タンパク質極細繊維を含む不織布からなる 防水透湿層の接合面、 及び表皮層の接合面の一方又は両方を溶剤で溶解させ て両接合面を溶着させることで、 防水透湿層と表皮層とが接合した生地を得 る工程を備える。 溶剤は、 防水透湿層及び/又は表皮層を構成する材料を溶 解できるものであれば、 特に制限なく使用することができる。 例えば、 表皮 層が、 不織布を与えるタンパク質極細繊維と同一又は異なるタンパク質 （夕 ンパク質繊維） を含む場合、 溶剤として、 そのようなタンパク質を溶解する 溶媒 （例えば、 ジメチルスルホキシド （口1\/1 3〇） 、 1\1 , 1\1 -ジメチルホル ムアミ ド （0 1\/1 ） 、 ギ酸、 又はヘキサフルオロイソプロパノール （1~1 I P） 等の有機溶媒、 それらに溶解促進剤としての無機塩を添加した溶液、 又 は水、 若しくは水に無機塩等を添加した水溶液） を使用できる。 溶剤として は、 揮発性の溶剤が好ましい。 本実施形態に係る製造方法は、 防水透湿層と 〇 2020/175702 88 卩（：171? 2020 /008524 [0288] In the manufacturing method according to the embodiment, one or both of the joint surface of the waterproof/moisture permeable layer and the joint surface of the skin layer, which are made of a nonwoven fabric containing protein ultrafine fibers, are dissolved with a solvent to weld both joint surfaces. Thus, a step of obtaining a fabric in which the waterproof moisture-permeable layer and the skin layer are joined together is provided. The solvent can be used without particular limitation as long as it can dissolve the material forming the waterproof and moisture permeable layer and/or the skin layer. For example, when the epidermal layer contains a protein that is the same as or different from the protein ultrafine fiber that provides the nonwoven fabric (protein fiber), the solvent that dissolves such protein (eg, dimethyl sulfoxide (mouth 1\/1 3 〇), 1\1, 1\1-Dimethylformamide (0 1\/1 ), formic acid, or organic solvent such as hexafluoroisopropanol (1 to 1 IP), and inorganic salts as a dissolution promoter added to them. Solution, or water, or an aqueous solution obtained by adding an inorganic salt or the like to water) can be used. As the solvent, a volatile solvent is preferable. The manufacturing method according to the present embodiment includes a waterproof moisture-permeable layer and 〇 2020/175 702 88 卩(：171? 2020/008524

表皮層とが接合した生地を得る工程の後、 使用した溶剤を除去する工程を更 に備えていてもよい。 溶剤の除去は、 例えば、 風乾する方法、 加熱する方法 、 及びこれらを組み合わせた方法等により行うことができる。 本実施形態に 係る製造方法により、 防水透湿層と表皮層が介在層を介すことなく接合され た防水透湿性生地を得ることができる。 After the step of obtaining the dough bonded to the skin layer, a step of removing the solvent used may be further provided. The solvent can be removed by, for example, an air drying method, a heating method, or a combination thereof. By the manufacturing method according to the present embodiment, it is possible to obtain a waterproof and moisture-permeable fabric in which a waterproof and moisture-permeable layer and a skin layer are joined without an intervening layer.

[0289] 他の実施形態に係る製造方法は、 防水透湿層の接合面、 及び表皮層の接合 面の一方又は両方を加熱溶融させて両接合面を溶着させることで、 防水透湿 層と表皮層とが接合した生地を得る工程を備える。 加熱溶融させる際の温度 は、 防水透湿層及び表皮層の一部又は全部を構成する加熱溶融可能な材料に 応じて適宜設定してよい。 本実施形態に係る製造方法により、 防水透湿層と 表皮層が介在層を介すことなく接合された防水透湿性生地を得ることができ る。 [0289] A manufacturing method according to another embodiment is a method for forming a waterproof and moisture-permeable layer by heating and melting one or both of the bonding surface of the waterproof/moisture permeable layer and the bonding surface of the skin layer to weld both bonding surfaces. The method includes a step of obtaining a cloth that is joined to the skin layer. The temperature at the time of heating and melting may be appropriately set depending on the heat-meltable material forming part or all of the waterproof and moisture-permeable layer and the skin layer. By the manufacturing method according to the present embodiment, it is possible to obtain a waterproof and moisture-permeable fabric in which a waterproof and moisture-permeable layer and a skin layer are joined without an intervening layer.

[0290] 他の実施形態に係る製造方法は、 防水透湿層の接合面、 及び表皮層の接合 面の一方又は両方にブラズマを照射して、 ラジカル反応により共有結合を形 成させることで、 防水透湿層と表皮層とが接合した生地を得る工程を備える 。 照射するプラズマの条件は、 防水透湿層及び表皮層を構成する材料に応じ て適宜設定してよい。 例えば、 防水透湿層及び/又は表皮層がタンパク質 （ タンパク質極細繊維又はタンパク質繊維） を含む場合、 放電ガスの流量は、 例えば、 0 .

Figure imgf000089_0001
以下の範囲内であってよい。 発生させるプラズマのプラズマ密度は、 例えば、 1 X 1 0 1 3〇〇1 _ 3以上 1 X 1 0 1 5〇 01 - 3以下の範囲内であってよい。 放電ガスは、 例えば、 ヘリウム、 ネオン、 アルゴン等の希ガス、 酸素、 窒素等であってよい。 放電ガスとして 、 大気を使用することもできる。 プラズマ照射は、 公知のプラズマ照射装置 を使用して実施することができる。 プラズマ照射装置としては、 例えば、 巳 リ 「〇 丨 8 3 01 8社製のプラズマ処理装置を使用することができる。 本実 施形態に係る製造方法により、 防水透湿層と表皮層が介在層を介すことなく 接合された防水透湿性生地を得ることができる。 [0290] A manufacturing method according to another embodiment is to irradiate one or both of the joint surface of the waterproof/moisture permeable layer and the joint surface of the skin layer with plasma to form a covalent bond by a radical reaction, The method includes a step of obtaining a cloth in which a waterproof and moisture-permeable layer and a skin layer are joined. The conditions of the plasma to be irradiated may be appropriately set depending on the materials forming the waterproof and moisture permeable layer and the skin layer. For example, when the waterproof and moisture-permeable layer and/or the epidermal layer contains proteins (protein ultrafine fibers or protein fibers), the flow rate of the discharge gas is, for example, 0.
Figure imgf000089_0001
It may be within the following range. The plasma density of the generated plasma may be, for example, in the range of 1×1 0 1 3 0 1 _ 3 or more and 1×1 0 1 5 0 1 1 -3 or less. The discharge gas may be, for example, a rare gas such as helium, neon, or argon, oxygen, nitrogen, or the like. Atmosphere can also be used as the discharge gas. Plasma irradiation can be carried out using a known plasma irradiation device. As the plasma irradiation device, for example, a plasma treatment device manufactured by Minori "○丨 8 3 01 8" can be used. By the manufacturing method according to the present embodiment, the waterproof moisture-permeable layer and the skin layer are intervening layers. It is possible to obtain a bonded waterproof breathable fabric without going through.

[0291 ] 他の実施形態に係る製造方法は、 表皮層の接合面を溶剤で溶解させた後、 〇 2020/175702 89 卩（：171? 2020 /008524 [0291] In a manufacturing method according to another embodiment, after dissolving the joint surface of the skin layer with a solvent, 〇 2020/175 702 89 卩(：171? 2020/008524

繊維原料を含有するドープ液を使用したエレクトロスピニングにより、 表皮 層の接合面上にタンパク質極細繊維を集積させて不織布を形成させることで 、 防水透湿層と表皮層とが接合した生地を得る工程を備える。 溶剤は、 上述 したものを使用できる。 エレクトロスピニング法 （静電紡糸法） は、 供給側 電極 （紡糸口金と兼用できる） と捕集側電極 （例えば、 金属口ール又は金属 ネッ ト等） 間に電圧を印加し、 紡糸口金から押し出したドープ液に電荷を与 えて捕集側電極に吹き飛ばす。 この際にドープ液は伸張されて繊維形成され る。 印加電圧は、

Figure imgf000090_0001
好ましくは
Figure imgf000090_0002
A process to obtain a fabric in which a waterproof and moisture-permeable layer and a skin layer are joined by electrospinning using a dope containing a fiber raw material to form a nonwoven fabric by accumulating protein ultrafine fibers on the joint surface of the skin layer. Equipped with. As the solvent, those mentioned above can be used. In the electrospinning method (electrospinning method), a voltage is applied between the supply-side electrode (which can also be used as the spinneret) and the collection-side electrode (for example, a metal nozzle or a metal net) to extrude from the spinneret. The charge is applied to the dope solution and blown off to the collecting side electrode. At this time, the dope solution is stretched to form fibers. The applied voltage is
Figure imgf000090_0001
Preferably
Figure imgf000090_0002

ある。 電極間距離は、 通常 1〜 2 5〇 であり、 好ましくは

Figure imgf000090_0003
is there. The distance between the electrodes is usually 1 to 250, and preferably
Figure imgf000090_0003

ある。 本実施形態に係る製造方法により、 防水透湿層と表皮層が介在層を介 すことなく接合された防水透湿性生地を得ることができる。 is there. By the manufacturing method according to the present embodiment, it is possible to obtain a waterproof and moisture-permeable fabric in which a waterproof and moisture-permeable layer and a skin layer are joined without an intervening layer.

[0292] 図 4は、 一実施形態に係るエレクトロスピニング装置 1 0 0の説明図であ る。 金属製口金ノズル 3 3 （供給側電極） と金属製ネッ ト 3 8 （捕集側電極 ） との間に電源 3 5により電圧をかける。 マイクロシリンジ 3 1内のドープ 液 3 2をシリンジポンプを用いて矢印 方向に移動させ、 金属製口金ノズル 3 3からドープ液 3 2を押し出し、 電荷によってドープ液を伸張し繊維状物 3 6にして金属製ネッ ト 3 8の表面に集積させることで、 極細繊維を含む不 織布 3 9を得ることができる。 また、 このとき、 金属製ネッ ト 3 8の表面に 表皮層 （編織体） を載置することで、 表皮層上に極細繊維を集積させて不織 布を形成させることもできる。 得られた不織布は、 次いで溶媒を離脱しても よい。 溶媒を脱離する方法としては、 例えば、 減圧乾燥又は脱溶媒槽への浸 潰が挙げられる。 [0292] FIG. 4 is an explanatory diagram of an electrospinning device 100 according to an embodiment. A voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35. The dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36. By accumulating on the surface of the metal net 38, a non-woven fabric containing ultrafine fibers 39 can be obtained. Further, at this time, by placing a skin layer (woven body) on the surface of the metal net 38, it is possible to accumulate ultrafine fibers on the skin layer to form a non-woven fabric. The solvent may be removed from the obtained non-woven fabric. Examples of the method for removing the solvent include vacuum drying or immersion in a desolvation tank.

[0293] 第 4実施形態に係る防水透湿性生地において、 不織布又は編織体に含まれ るタンパク質極細繊維又はタンパク質繊維の原料となるタンパク質には、 特 に制限はなく、 任意のタンパク質を使用することができる。 タンパク質の具 体的な態様は、 第 1の発明に係る防水透湿性生地で説明した態様を適用でき る。 使用するタンパク質としては、 防水透湿性に加え、 保温性、 吸湿発熱性 及び/又は難燃性にも優れることから、 改変フィブロインが好ましく、 改変 〇 2020/175702 90 卩（：171? 2020 /008524 [0293] In the waterproof and moisture-permeable fabric according to the fourth embodiment, there is no particular limitation on the protein as a raw material of the protein ultrafine fibers or protein fibers contained in the nonwoven fabric or the knitted fabric, and any protein may be used. You can As the concrete aspect of the protein, the aspect explained in the waterproof and moisture-permeable fabric according to the first invention can be applied. As the protein to be used, modified fibroin is preferable because it is excellent in heat retention, moisture absorption and heat generation property and/or flame retardancy in addition to waterproof moisture permeability. 〇 2020/175 702 90 卩 (：171? 2020 /008524

クモ糸フイブロインがより好ましい。 タンパク質極細繊維及び/又はタンパ ク質繊維が、 改変フイブロイン （好ましくは、 改変クモ糸フイブロイン） を 含むことにより、 本実施形態に係る防水透湿性生地に保温性、 吸湿発熱性及 び/又は難燃性の性質を更に付与することができ、 生地としての価値がより 高くなる。 More preferred is spider silk fibroin. By including the modified fibroin (preferably modified spider silk fibroin) in the protein ultrafine fiber and/or protein fiber, the waterproof and moisture-permeable fabric according to the present embodiment has heat-retaining property, moisture-absorbing heat-generating property, and/or flame-retardant property. It is possible to add more sexual character, and it becomes more valuable as a fabric.

[0294] 本実施形態に係るタンパク質は、 当該タンパク質をコードする核酸を使用 して、 常法により製造することができる。 当該タンパク質をコードする核酸 は、 塩基配列情報に基づいて、 化学合成してもよく、

Figure imgf000091_0001
法等を利用して 合成してもよい。 [0294] The protein according to this embodiment can be produced by a conventional method using a nucleic acid encoding the protein. The nucleic acid encoding the protein may be chemically synthesized based on the nucleotide sequence information,
Figure imgf000091_0001
It may be synthesized using a method or the like.

[0295] タンパク質極細繊維又はタンパク質繊維は、 例えば、 タンパク質を溶解可 能な溶媒で溶解させてドープ液とし、 湿式紡糸、 乾式紡糸、 乾湿式紡糸又は 溶融紡糸等の公知の紡糸方法により紡糸して得ることができる。 タンパク質 極細繊維は、 上述したエレクトロスピニング法により紡糸して得ることが好 ましい。 タンパク質を溶解可能な溶媒としては、 例えば、 ジメチルスルホキ シド

Figure imgf000091_0002
1\1 , 1\1 -ジメチルホルムアミ ド （0 1\/1 ） 、 ギ酸、 及び ヘキサフルオロイソプロパノール （1~1 丨 ） 等が挙げられる。 当該溶媒に は、 溶解促進剤として無機塩を添加してもよい。 [0295] The protein ultrafine fiber or protein fiber is prepared by, for example, dissolving a protein in a solvent capable of dissolving it to obtain a dope solution, and spinning it by a known spinning method such as wet spinning, dry spinning, dry wet spinning or melt spinning. Obtainable. The protein ultrafine fibers are preferably obtained by spinning by the electrospinning method described above. Solvents capable of dissolving proteins include, for example, dimethyl sulfoxide
Figure imgf000091_0002
1\1, 1\1-dimethylformamide (0 1\/1), formic acid, and hexafluoroisopropanol (1 to 1) are listed. An inorganic salt may be added to the solvent as a dissolution promoter.

[0296] 〔第 5の発明に係る防水透湿性生地〕 [0296] [Waterproof and breathable fabric according to fifth invention]

第 5実施形態に係る防水透湿性生地は、 繊維径 1 0 以下の生分解性極 細繊維を含む生分解性繊維からなる不織布 （以下、 単に 「不織布」 ともいう 。 ） と、 生分解性材料からなる編織体 （以下、 単に 「編織体」 ともいう。 ） とが接合されてなる。 不織布で形成される層は、 防水性及び透湿性を有する ものであり、 防水透湿層 2と捉えることもできる。 編織体で形成される層は 、 防水透湿性生地の表面に位置するものであり、 表皮層 1 と捉えることもで きる。 なお、 表皮層 1は、 防水透湿性生地の形状を保持するための形状保持 層としても機能する。 The waterproof and moisture-permeable fabric according to the fifth embodiment is a nonwoven fabric composed of biodegradable fibers containing biodegradable ultrafine fibers having a fiber diameter of 10 or less (hereinafter, also simply referred to as “nonwoven fabric”) and a biodegradable material. And a weaving body (hereinafter, also simply referred to as “weaving body”). The layer formed of the non-woven fabric has waterproofness and moisture permeability, and can be regarded as the waterproof moisture permeable layer 2. The layer formed by the knitted fabric is located on the surface of the waterproof and moisture-permeable fabric, and can be regarded as the skin layer 1. The skin layer 1 also functions as a shape retaining layer for retaining the shape of the waterproof/moisture permeable material.

[0297] 第 5実施形態に係る防水透湿性生地の防水透湿層 2は、 繊維径 1 〇 以 下の生分解性極細繊維を含む生分解性繊維からなる不織布 （以下、 単に 「不 \¥0 2020/175702 91 卩（：17 2020 /008524 [0297] The waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the fifth embodiment is a nonwoven fabric composed of biodegradable fibers containing biodegradable ultrafine fibers having a fiber diameter of 10 or less (hereinafter, simply referred to as "non-woven fabric"). \¥0 2020/175702 91 卩(: 17 2020/008524

織布」 ともいう。 ） からなる。 繊維径は、 短繊維の長手方向に垂直な断面を 囲む最小の円の直径を意味する。 生分解性極細繊維の繊維径は、 1 〇 （ 1 〇〇 0 0 111） 以下であればよく、 9 IX 111以下、 8 以下、 7 以下

Figure imgf000092_0001
Also called "woven cloth". ) Consists of. The fiber diameter means the diameter of the smallest circle that surrounds the cross section of the short fiber perpendicular to the longitudinal direction. The fiber diameter of the biodegradable ultrafine fiber may be 10 (1 0000 0 0 111) or less, 9 IX 111 or less, 8 or less, 7 or less.
Figure imgf000092_0001

（1 0 0 0门 ） 以下、 9 0 0门 111以下、 8 0 0门 111以下、 7 0 0门 111以下 、 6 0 0门 111以下、 5 0 0门 111以下、 4 0 0门 111以下、 3 0 0门 111以下、 又 は 2 0 0 n 以下であってよい。 生分解性極細繊維の繊維径は、 例えば、 1 〇门 111以上、 2 0 11 111以上、 3 0 11 111以上、 4 0 1^ 111以上、 5 0 1^ 111以上、 (1 00 0 doors) or less, 900 0 doors 111 or less, 800 0 doors 111 or less, 7 0 0 doors 111 or less, 600 0 doors 111 or less, 5 0 0 doors 111 or less, 4 0 0 doors 111 or less , 300 or less 111 or less than or equal to 200 n. The fiber diameter of the biodegradable ultrafine fiber is, for example, 10 or more 111, 2 0 11 111 or more, 3 0 11 111 or more, 4 0 1^ 111 or more, 5 0 1^ 111 or more,

6 0 11 111以上、 7 0 11 111以上、 8 0 1^ 111以上、 9 0 1^ 111以上、 1 0 0 111以 上、 2 0 0 11 111以上、 3 0 0 11 111以上、 4 0 0 1^ 111以上、 5 0 0 1^ 111以上、6 0 11 111 or higher, 7 0 11 111 or higher, 8 0 1^ 111 or higher, 9 0 1^ 111 or higher, 1 0 0 111 or higher, 2 0 0 11 111 or higher, 3 0 0 11 111 or higher, 4 0 0 1^111 or more, 5 0 0 1^111 or more,

6 0 0 11 111以上、 7 0 0 11 111以上、 8 0 0 1^ 111以上、 9 0 0 1^ 111以上、 1 111以上、 2 111以上、 3 111以上、 4 以上又は 5 以上であってよい 6 0 0 11 111 or more, 7 0 0 11 111 or more, 8 0 0 1^ 111 or more, 9 0 0 1^ 111 or more, 1 111 or more, 2 111 or more, 3 111 or more, 4 or more or 5 or more Good

[0298] 生分解性繊維は、 生分解性材料から形成された繊維である。 生分解性材料 は、 微生物によって完全に消費され自然的副産物 （炭酸ガス、 メタン、 水、 バイオマスなど） のみを生じる材料である。 生分解性材料の具体例としては 、 セルロース及びタンパク質等のバイオ由来原料が挙げられる。 生分解性繊 維としては、 バイオ由来原料から形成された繊維であることが好ましく、 セ ルロース （再生セルロースを含む） 及び/又はタンパク質から形成された繊 維であることがより好ましい。 セルロース及び/又はタンパク質から形成さ れた繊維を用いれば、 合成繊維にはない、 それらの繊維特有の吸湿性により 、 水等の液体の侵入を防ぐ一方で、 繊維自体から蒸気 （気体） を放出するこ とにより、 優れた透湿性を実現できる。 また、 生分解性繊維としては、 構造 タンパク質から形成された繊維であることが更に好ましい。 生分解性繊維が 構造タンパク質から形成された繊維 （構造タンパク質繊維） であると、 本実 施形態に係る防水透湿性生地に保温性、 吸湿発熱性及び/又は難燃性の性質 を更に付与することができ、 生地としての価値がより高くなる。 これらの効 果をより顕著に発揮するという観点から、 構造タンパク質は、 改変フィブロ 〇 2020/175702 92 卩（：171? 2020 /008524 [0298] The biodegradable fiber is a fiber formed of a biodegradable material. Biodegradable materials are materials that are completely consumed by microorganisms and produce only natural byproducts (carbon dioxide, methane, water, biomass, etc.). Specific examples of biodegradable materials include bio-derived raw materials such as cellulose and proteins. The biodegradable fiber is preferably a fiber formed from a bio-derived raw material, and more preferably a fiber formed from cellulose (including regenerated cellulose) and/or protein. When fibers made of cellulose and/or protein are used, vapors (gases) are emitted from the fibers themselves while preventing the ingress of liquids such as water due to the hygroscopicity that is unique to those fibers that synthetic fibers do not have. By doing so, excellent moisture permeability can be realized. Further, the biodegradable fiber is more preferably a fiber formed from a structural protein. When the biodegradable fiber is a fiber formed from a structural protein (structural protein fiber), the waterproof moisture-permeable fabric according to the present embodiment is further imparted with heat retention, moisture absorption heat generation and/or flame retardancy. It can be made more valuable as a fabric. From the viewpoint of exerting these effects more significantly, structural proteins are 〇 2020/175 702 92 卩 (：171? 2020 /008524

インであることが好ましく、 改変クモ糸フイブロインであることがより好ま しい。 構造タンパク質のより具体的な態様は、 後述する。 生分解性繊維は、In, preferably modified spider silk fibroin. A more specific embodiment of the structural protein will be described later. Biodegradable fiber,

1種の生分解性材料から形成された繊維であってもよく、 2種以上の生分解 性材料から形成された繊維であってもよい。 It may be a fiber formed of one type of biodegradable material or a fiber formed of two or more types of biodegradable materials.

[0299] 生分解性繊維は、 生分解性極細繊維のみを含むものであってもよく、 生分 解性極細繊維に加えて他の生分解性繊維 （繊維径が 1 〇 超の生分解性繊 維） を含むものであってもよい。 すなわち、 不織布の形成に用いられる生分 解性繊維 （ 「材料糸」 ともいう。 ） として、 生分解性極細繊維のみからなる 単独糸、 生分解性極細繊維と他の生分解性繊維とを組み合わせてなる複合糸 （例えば、 混紡糸、 混繊糸、 カバーリング糸等。 ） が、 それぞれ単独で、 又 はそれらが組み合わされて用いられてもよい。 上記単独糸及び上記複合糸は 、 短繊維を撚り合わせたスパン糸であってもよく、 長繊維を撚り合わせたフ イラメント糸であってもよい。 上記単独糸及び上記複合糸としては、 フイラ メント糸が好適に用いられる。 他の生分解性繊維と組み合わせて使用する場 合には、 不織布に占める生分解性極細繊維の割合は、 不織布の全質量を基準 として、 例えば、 3 0質量％以上、 4 0質量％以上、 5 0質量％以上、 6 0 質量％以上、 7 0質量％以上、 8 0質量％以上、 9 0質量％以上、 又は 9 5 質量％以上であってよい。 [0299] The biodegradable fiber may include only biodegradable ultrafine fibers, and in addition to biodegradable ultrafine fibers, other biodegradable fibers (biodegradable with a fiber diameter of more than 10 can be used). Fiber) may be included. That is, as the biodegradable fiber (also referred to as “material yarn”) used for forming a non-woven fabric, a single yarn composed only of biodegradable ultrafine fibers, a combination of biodegradable ultrafine fibers and other biodegradable fibers. The composite yarns (for example, mixed yarn, mixed yarn, covering yarn, etc.) may be used alone or in combination. The single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or filament yarn in which long fibers are twisted together. A filament yarn is preferably used as the single yarn and the composite yarn. When used in combination with other biodegradable fibers, the proportion of biodegradable ultrafine fibers in the nonwoven fabric is based on the total weight of the nonwoven fabric, for example, 30% by mass or more, 40% by mass or more, It may be 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.

[0300] 不織布は、 例えば、 上述の生分解性繊維を用いて、 公知の製造方法により 製造することができる。 具体的には、 例えば、 上述の生分解性繊維から、 乾 式法、 湿式法及びエアレイ ド法等でウェブ （単層ウェブ、 及び積層ウェブを 含む。 ） を形成させた後、 ケミカルボンド法 （浸潰法、 スプレー法等） 及び 二ードルパンチ法等によりウェブの繊維間を結合させて、 不織布を得ること ができる。 [0300] The nonwoven fabric can be produced, for example, by using the above-mentioned biodegradable fiber by a known production method. Specifically, for example, a web (including a single-layer web and a laminated web) is formed from the above-mentioned biodegradable fiber by a dry method, a wet method, an air-laid method or the like, and then a chemical bond method ( Nonwoven fabric can be obtained by binding the fibers of the web by a dipping method, a spray method, etc.) or a needle punching method.

[0301 ] 不織布はまた、 例えば、 生分解性材料 （例えば、 タンパク質） を、 ジメチ ルスルホキシド （口1\/1 3〇） 、 1\1 , 1\1 _ジメチルホルムアミ ド （0 1\/1 ） 、 ギ酸、 又はヘキサフルオロイソプロパノール （1~1 I ） 等の溶媒に、 必要 に応じて、 溶解促進剤としての無機塩と共に添加し、 溶解してドープ液を作 〇 2020/175702 93 卩（：171? 2020 /008524 [0301] Nonwovens also include, for example, biodegradable materials (eg, proteins) such as dimethyl sulfoxide (mouth 1\/1300), 1\1, 1\1 _dimethylformamide (0 1\/ 1), formic acid, or hexafluoroisopropanol (1 to 1 I), etc. are added, if necessary, together with an inorganic salt as a dissolution accelerator, and dissolved to form a dope solution. 〇 2020/175 702 93 卩(: 171-1? 2020/008524

製した後、 当該ドープ液を用いてエレクトロスピニング法 （静電紡糸法） に より紡糸することにより得ることもできる。 エレクトロスピニング法で得ら れる生分解性極細繊維 （例えば、 タンパク質極細繊維） の平均繊維径 （繊維 径の平均値） は、 通常、 1 0000 n 01以下であり、 好ましくは 1 000 n 111以下であり、

Figure imgf000094_0001
00001^ 111、
Figure imgf000094_0002
500011111、
Figure imgf000094_0003
It can also be obtained by spinning the product using the dope solution by an electrospinning method (electrostatic spinning method). The average fiber diameter (average fiber diameter) of biodegradable ultrafine fibers (eg, protein ultrafine fibers) obtained by the electrospinning method is usually 1 0000 n 01 or less, preferably 1 000 n 111 or less. Yes,
Figure imgf000094_0001
00001^111,
Figure imgf000094_0002
500011111,
Figure imgf000094_0003

00 n mであってもよい。 生分解性極細繊維 （例えば、 タンパク質極細繊維 ） の繊維径は、 1 00 n m~ 1 0000 n m （1 0 ） の間、 好ましくは

Figure imgf000094_0004
0001^ 111 （1 〇1） の間で変動してもよい。 It may be 00 nm . The fiber diameter of the biodegradable ultrafine fiber (eg, protein ultrafine fiber) is preferably between 100 nm and 10000 nm (10 ),
Figure imgf000094_0004
It may fluctuate between 0001^111 (101).

[0302] 不織布は、 繊維密度 （目付） 、 空隙率、 かさ密度等の数値範囲が、 防水性 と透湿性とを充分に確保し得る範囲となるように適宜設定される。 なお、 そ れら目付、 空隙率、 かさ密度等の調整は、 例えば、 ウェブを構成する繊維量 を増減すること、 積層ウェブの場合は、 積層数を増減することにより行うこ とができる。 [0302] The non-woven fabric is appropriately set such that the numerical value ranges of the fiber density (unit weight), porosity, bulk density, and the like are within a range in which waterproofness and moisture permeability can be sufficiently ensured. The unit weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of layers.

[0303] 第 5実施形態に係る防水透湿性生地の表皮層 1は、 生分解性材料からなる 編織体からなる。 編織体とは、 編地及び織地の総称である。 編地は、 横編、 丸編等の緯編組織を有する編地 （単に 「緯編地」 ともいう。 ） 、 トリコッ ト 、 ラッセル等の経編組織を有する編地 （単に 「経編地」 ともいう。 ） のいず れであってもよい。 織地は、 平織、 綾織、 又は嬬子織のうちのいずれの組織 を有する織地であってもよい。 編織体は、 編成又は織成により得られる未加 エの編織体そのものであってもよいし、 編成又は織成後に撥水加工等の加工 を施した編織体であってもよい。 [0303] The skin layer 1 of the waterproof/moisture permeable fabric according to the fifth embodiment is made of a knitted or woven body made of a biodegradable material. A knitted fabric is a general term for knitted fabrics and woven fabrics. A knitted fabric is a knitted fabric having a weft knitting structure such as a flat knit or a circular knit (also simply referred to as “weft knitted fabric”), a knitted fabric having a warp knitting structure such as tricot, Russell (simply “warp knitted fabric”). Also referred to as “.”). The woven fabric may be a woven fabric having any one of a plain weave, a twill weave, and a Tsumago weave. The knitted or woven body may be an undyed knitted or woven body obtained by knitting or weaving, or may be a knitted or woven body subjected to a process such as water repellent treatment after knitting or weaving.

[0304] 編織体は、 原料糸を編成又は織成して得ることができる。 編成方法及び織 成方法としては公知の方法を利用することができる。 使用される編機として は、 例えば、 丸編機、 経編機、 横編機などが使用でき、 生産性の観点からは 、 丸編機の使用が好ましい。 横編機としては、 成型編み機、 無縫製編機など があるが、 特に最終製品の形態で編地を製造可能であることから、 無縫製編 機の使用がより好ましい。 使用される織機としては、 例えば、 有抒織機、 及 〇 2020/175702 94 卩（：171? 2020 /008524 [0304] The knitted or woven body can be obtained by knitting or weaving raw material threads. As a knitting method and a weaving method, known methods can be used. As the knitting machine to be used, for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used. As the flat knitting machine, there are a forming knitting machine, a non-sewn knitting machine, and the like. However, since the knitted fabric can be manufactured in the form of a final product, the use of the non-sewn knitting machine is more preferable. Looms used include, for example, corrugated looms and 〇 2020/175 702 94 卩 (: 171-1? 2020 /008524

び、 グリッパー織機、 レピア織機、 ゥォータージェッ ト織機、 エアジェッ ト 織機等の無抒織機が挙げられる。 There are also unwound looms such as gripper looms, rapier looms, water jet looms and air jet looms.

[0305] 原料糸は、 単独糸であってもよく、 複合糸 （例えば、 混紡糸、 混繊糸、 力 バーリング糸等。 ） であってもよく、 これらを組み合わせて用いてもよい。 単独糸及び複合糸は、 短繊維を撚り合わせたスパン糸であってもよく、 長繊 維を撚り合わせたフィラメント糸であってもよい。 原料糸に含まれる繊維の 具体的な態様は、 防水透湿層で説明した生分解性繊維の態様と同様である。 なお、 防水透湿層及び表皮層に含まれる生分解性繊維 （乃至生分解性極細繊 維） は、 それぞれ同一の生分解性材料で形成されたものであってもよく、 異 なる生分解性材料で形成されたものであってもよい。 [0305] The raw yarn may be a single yarn, a composite yarn (for example, a mixed yarn, a mixed yarn, a force burring yarn, etc.), or may be a combination of these. The single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are twisted together. The specific mode of the fiber contained in the raw yarn is the same as the mode of the biodegradable fiber described in the waterproof and moisture-permeable layer. The biodegradable fibers (or biodegradable ultrafine fibers) contained in the waterproof moisture-permeable layer and the epidermis layer may be made of the same biodegradable material, and may have different biodegradability. It may be formed of a material.

[0306] 編織体は、 不織布との接合側とは反対側の表面が撥水加工されていてもよ い。 これにより、 防水性により優れた防水透湿性生地を得ることができる。 撥水加工は、 例えば、 植物性又は動物性の油剤等を表面に塗布する等の従来 公知の方法により行うことができる。 [0306] The surface of the knitted or woven body opposite to the side where it is joined to the nonwoven fabric may be water repellent. This makes it possible to obtain a waterproof and moisture-permeable fabric that is more waterproof. The water repellent treatment can be carried out by a conventionally known method such as applying a vegetable or animal oil or the like on the surface.

[0307] _実施形態において、 第 5実施形態に係る防水透湿性生地は、 防水透湿層 [0307] In the embodiment, the waterproof/moisture permeable fabric according to the fifth embodiment is:

（不織布） の表皮層 （編織体） が接合された面の反対側の面に裏材層 （編織 体） が更に接合されていてもよい。 裏材層の好ましい態様としては、 表皮層 で例示した態様が挙げられる。 表皮層と裏材層は、 それぞれ同一の材料で形 成された編織体であってもよく、 異なる材料で形成された編織体であっても よい。 A backing layer (textile) may be further bonded to the surface of the (nonwoven fabric) opposite to the surface to which the skin layer (textile) is bonded. Examples of the preferable embodiment of the backing layer include the embodiments exemplified for the skin layer. The skin layer and the backing layer may each be a knitted fabric formed of the same material, or may be a knitted fabric formed of different materials.

[0308] 第 5実施形態に係る防水透湿性生地は、 防水透湿層と表皮層とを接合して 得ることができる。 防水透湿層と表皮層との接合方法は、 不織布及び編織体 に使用する素材に応じて、 適宜選択することができる。 接合方法として、 例 えば、 防水透湿層と表皮層とを、 熱又は溶剤等により、 溶着する方法、 防水 透湿層と表皮層とを接着剤を介して接着する方法等が挙げられる。 例えば、 不織布及び編織体がいずれもタンパク質 （タンパク質極細繊維又はタンパク 質繊維） を含む場合、 防水透湿層及び表皮層の接合面のうち一方又は両方に タンパク質を溶解する溶媒 （例えば、 ジメチルスルホキシド （口1\/1 3〇） 、 〇 2020/175702 95 卩（：171? 2020 /008524 [0308] The waterproof moisture-permeable fabric according to the fifth embodiment can be obtained by joining the waterproof moisture-permeable layer and the skin layer. The method for joining the waterproof moisture-permeable layer and the skin layer can be appropriately selected according to the materials used for the nonwoven fabric and the knitted fabric. Examples of the joining method include a method of welding the waterproof/moisture permeable layer and the skin layer with heat or a solvent, a method of bonding the waterproof/moisture permeable layer and the skin layer with an adhesive, and the like. For example, when both the non-woven fabric and the knitted fabric contain a protein (protein ultrafine fiber or protein fiber), a solvent that dissolves the protein in one or both of the joint surfaces of the waterproof moisture-permeable layer and the skin layer (eg, dimethyl sulfoxide ( Mouth 1\/1300), 〇 2020/175 702 95 卩 (：171? 2020 /008524

1\1 , 1\1 -ジメチルホルムアミ ド （0 1\/1 ） 、 ギ酸、 又はヘキサフルオロイソ プロパノール （1~1 I ） 等の有機溶媒、 それらに溶解促進剤としての無機 塩を添加した溶液、 又は水、 若しくは水に無機塩等を添加した水溶液） を塗 布した後、 防水透湿層及び表皮層を貼り合わせ、 更に溶媒を除去することで 防水透湿層と表皮層とを接合することができる。 Organic solvents such as 1\1, 1\1-dimethylformamide (0 1\/1 ), formic acid, or hexafluoroisopropanol (1 to 1 I), to which inorganic salts as a dissolution promoter were added Solution or water, or an aqueous solution in which an inorganic salt or the like is added to water), and then the waterproof/moisture permeable layer and the epidermis layer are bonded together, and the solvent is further removed to bond the waterproof/moisture permeable layer and the epidermis layer. can do.

[0309] また、 不織布がタンパク質極細繊維を含み、 不織布をエレクトロスピニン グ法で形成する場合、 防水透湿層を表皮層上に形成する防水透湿層形成工程 を備える製造方法により、 防水透湿性生地を得ることができる。 防水透湿層 形成工程は、 タンパク質を含有するドープ液を使用したエレクトロスピニン グにより、 表皮層上にタンパク質極細繊維を集積させて不織布を形成させる ことを含む。 このとき、 表皮層上にタンパク質を溶解する溶媒を塗布してお いてもよい。 これにより、 不織布が形成されると共に、 形成された不織布と 表皮層が接合する。 [0309] In addition, when the non-woven fabric contains protein ultrafine fibers and the non-woven fabric is formed by the electrospinning method, the waterproof and moisture-permeable layer is formed on the surface layer by a manufacturing method including a waterproof and moisture-permeable layer forming step. A moist dough can be obtained. The waterproof/moisture permeable layer forming step includes the steps of: electrospinning using a dope solution containing a protein to accumulate protein ultrafine fibers on the skin layer to form a nonwoven fabric. At this time, a solvent that dissolves the protein may be applied onto the epidermis layer. As a result, a nonwoven fabric is formed, and the formed nonwoven fabric and the skin layer are joined together.

[0310] エレクトロスピニング法 （静電紡糸法） は、 供給側電極 （紡糸口金と兼用 できる） と捕集側電極 （例えば、 金属口ール又は金属ネッ ト等） 間に電圧を 印加し、 紡糸口金から押し出したドープ液に電荷を与えて捕集側電極に吹き 飛ばす。 この際にドープ液は伸張されて繊維形成される。 印加電圧は、 通常 5〜 1 0 0 Vであり、 好ましくは 1 〇〜 5 0 Vである。 電極間距離は、

Figure imgf000096_0001
好ましくは 2〜 2 0〇 である。 [0310] In the electrospinning method (electrospinning method), a voltage is applied between a supply-side electrode (which can also be used as a spinneret) and a collection-side electrode (for example, a metal nozzle or a metal net) to perform spinning. An electric charge is given to the dope solution extruded from the die and blown to the collection side electrode. At this time, the dope solution is stretched to form fibers. The applied voltage is usually 5 to 100 V, and preferably 10 to 50 V. The distance between the electrodes is
Figure imgf000096_0001
It is preferably 2 to 200.

[031 1 ] 図 4は、 一実施形態に係るエレクトロスピニング装置 1 0 0の説明図であ る。 金属製口金ノズル 3 3 （供給側電極） と金属製ネッ ト 3 8 （捕集側電極 ） との間に電源 3 5により電圧をかける。 マイクロシリンジ 3 1内のドープ 液 3 2をシリンジポンプを用いて矢印 方向に移動させ、 金属製口金ノズル 3 3からドープ液 3 2を押し出し、 電荷によってドープ液を伸張し繊維状物 3 6にして金属製ネッ ト 3 8の表面に集積させることで、 タンパク質極細繊 維を含む不織布 3 9を得ることができる。 また、 かく して不織布 3 9を得る 際には、 金属製ネッ ト 3 8の表面に表皮層 （編織体） を載置することで、 表 皮層上にタンパク質極細繊維を集積させて不織布を形成させることもできる 〇 2020/175702 96 卩（：171? 2020 /008524 [031 1] FIG. 4 is an explanatory diagram of an electrospinning device 100 according to an embodiment. A voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35. The dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36. By accumulating on the surface of the metallic net 38, a nonwoven fabric 39 containing protein ultrafine fibers can be obtained. In addition, when a nonwoven fabric 39 is thus obtained, by placing a skin layer (textile) on the surface of the metal net 38, the protein ultrafine fibers are accumulated on the skin layer to form a nonwoven fabric. Can also be 〇 2020/175 702 96 卩(：171? 2020/008524

。 得られた不織布は、 次いで溶媒を離脱してもよい。 溶媒を脱離する方法と しては、 例えば、 減圧乾燥又は脱溶媒槽への浸潰が挙げられる。 このとき、 好適には、 表皮層におけるタンパク質極細繊維集積側の面に対して、 所定の 接着剤、 又はタンパク質極細繊維を溶解可能な溶媒からなる接着剤層等が塗 布等により形成される。 そうすることによって、 不織布 3 9が、 表皮層上に 形成されると同時に表皮層に対して一体的に接合され、 目的とする防水透湿 性生地が有利に且つ効率的に製造され得ることとなる。 なお、 表皮層表面上 に接着剤層を形成する場合には、 接着剤を固化させる操作や、 溶媒を除去す る操作が追加されることもある。 .. The resulting non-woven fabric may then be stripped of solvent. Examples of the method for removing the solvent include vacuum drying and immersing in a desolvation tank. At this time, preferably, an adhesive layer or the like made of a predetermined adhesive or a solvent capable of dissolving the protein ultrafine fibers is formed on the surface of the skin layer on the protein ultrafine fiber accumulation side by coating or the like. By doing so, the nonwoven fabric 39 is formed on the skin layer and at the same time integrally bonded to the skin layer, and the desired waterproof and moisture-permeable fabric can be manufactured advantageously and efficiently. Become. When the adhesive layer is formed on the surface of the skin layer, an operation of solidifying the adhesive or an operation of removing the solvent may be added.

[0312] 構造タンパク質とは、 生体内で構造、 形態等を形成又は保持するタンパク 質を意味する。 構造タンパク質の具体例としては、 フィブロイン （例えば、 クモ糸フィブロイン （スパイダーシルク） 、 カイコシルク等） 、 ケラチン、 コラーゲン、 エラスチン、 レシリン、 及びこれらタンパク質の断片、 並びに これら由来のタンパク質 （改変フィブロイン等） 等を挙げることができる。 [0312] The structural protein means a protein that forms or retains a structure, morphology, etc. in vivo. Specific examples of structural proteins include fibroin (eg, spider silk fibroin (spider silk), silkworm silk, etc.), keratin, collagen, elastin, resilin, and fragments of these proteins, and proteins derived therefrom (modified fibroin, etc.), etc. Can be mentioned.

[0313] 改変フィブロインの具体的な態様は、 第 1の発明に係る防水透湿性生地で 説明した態様を適用できる。 [0313] As a specific aspect of the modified fibroin, the aspect described in the waterproof and moisture-permeable fabric according to the first invention can be applied.

[0314] ケラチン由来のタンパク質として、 例えば、 カプラ · ヒルクス （〇 3 「 [0314] As a protein derived from keratin, for example, Capra hirux (〇 3 “

^ 1 「〇リ 3） のタイプ丨 ケラチン等を挙げることができる。 ^ 1 "Type 3" type keratin and the like can be mentioned.

[0315] コラーゲン由来のタンパク質としては、 例えば、 式 3 : [ [¾巳 2 ] で表 されるドメイン配列を含むタンパク質 （ここで、 式 3中、 は 5〜 3 0 0の 整数を示す。 [¾巳 2は、 ◦ 丨 ソー X—丫から構成されるアミノ酸配列を示 し、 X及び丫は〇 I ソ以外の任意のアミノ酸残基を示す。 複数存在する 巳 2は、 互いに同一のアミノ酸配列でもよく、 異なるアミノ酸配列でもよい 。 ） を挙げることができる。 [0315] As the collagen-derived protein, for example, a protein containing a domain sequence represented by the formula 3: [[¾2 2] (wherein, represents an integer of 5 to 300). ¾ 跳 2 shows an amino acid sequence composed of ◦ 丨 saw X-丫, where X and 伫 represent any amino acid residue other than 〇I. , Or different amino acid sequences may be used.).

[0316] エラスチン由来のタンパク質としては、 例えば、 1\1〇巳 丨の G e n B a n のアクセッション番号八八〇 9 8 3 9 5 （ヒト） 、 1 4 7 0 7 6 （ヒツジ ） 、 7 8 6 9 6 6 （ウシ） 等のアミノ酸配列を有するタンパク質を挙げ ることができる。 〇 2020/175702 97 卩（：171? 2020 /008524 [0316] Examples of the protein derived from elastin include, for example, 1\10 跳丨 Gen Ban accession numbers 8880 9 8 3 9 5 (human), 1 4 7 0 7 6 (sheep), 7 Examples thereof include proteins having an amino acid sequence such as 8 6 9 6 (bovine). 〇 2020/175 702 97 卩(：171? 2020/008524

[0317] レシリン由来のタンパク質としては、 例えば、 式 4 : [ [¾巳 3 ] 9で表さ れるドメイン配列を含むタンパク質 （ここで、 式 4中、 は 4〜 3 0 0の整 数を示す。 [¾巳 3は3 6 r J J T y 「一◦ I V 1 9 r〇から構 成されるアミノ酸配列を示す。 」は任意アミノ酸残基を示し、 特に 3 、[0317] Examples of the protein derived from resilin include, for example, a protein containing the domain sequence represented by the formula 4: [[¾mi 3] 9 (wherein, in formula 4, is an integer of 4 to 300). [¾mi 3 represents an amino acid sequence composed of 36 r JJT y "1 ◦ IV 19 r 〇" represents an arbitrary amino acid residue, particularly 3,

3 6 「及び丁 「からなる群から選ばれるアミノ酸残基であることが好まし い。 リは任意のアミノ酸残基を示し、 特に 「〇、 八 丨 3、 丁 「及び3 6 「からなる群から選ばれるアミノ酸残基であることが好ましい。 複数存在す る 巳 4は、 互いに同一のアミノ酸配列でもよく、 異なるアミノ酸配列で もよい。 ） を挙げることができる。 It is preferable that the amino acid residue is selected from the group consisting of 3 6 "and D". Li represents an arbitrary amino acid residue, and in particular, a group consisting of "○, 8 丨 3, Ding" and 3 6 ". It is preferable that the amino acid residues selected from among the plurality of existing amino acids 4 have the same amino acid sequence or different amino acid sequences.

[0318] タンパク質は、 当該タンパク質をコードする核酸を使用して、 常法により 製造することができる。 当該タンパク質をコードする核酸は、 塩基配列情報 に基づいて、 化学合成してもよく、

Figure imgf000098_0001
法等を利用して合成してもよい。 [0318] A protein can be produced by a conventional method using a nucleic acid encoding the protein. The nucleic acid encoding the protein may be chemically synthesized based on the nucleotide sequence information,
Figure imgf000098_0001
You may synthesize by utilizing the method etc.

[0319] タンパク質極細繊維又はタンパク質繊維は、 例えば、 タンパク質を溶解可 能な溶媒で溶解させてドープ液とし、 湿式紡糸、 乾式紡糸、 乾湿式紡糸又は 溶融紡糸等の公知の紡糸方法により紡糸して得ることができる。 タンパク質 極細繊維は、 上述したエレクトロスピニング法により紡糸して得ることが好 ましい。 タンパク質を溶解可能な溶媒としては、 例えば、 ジメチルスルホキ シド （0 1\/1 3〇） 、 1\1 , 1\1 -ジメチルホルムアミ ド （0 1\/1 ） 、 ギ酸、 及び ヘキサフルオロイソプロパノール （1~1 丨 ） 等が挙げられる。 当該溶媒に は、 溶解促進剤として無機塩を添加してもよい。 [0319] The protein ultrafine fiber or protein fiber is prepared by, for example, dissolving a protein in a solvent capable of dissolving it to obtain a dope solution, and spinning the dope by a known spinning method such as wet spinning, dry spinning, dry wet spinning or melt spinning. Obtainable. The protein ultrafine fibers are preferably obtained by spinning by the electrospinning method described above. Solvents capable of dissolving proteins include, for example, dimethyl sulfoxide (0 1\/1 300), 1\1, 1\1-dimethylformamide (0 1\/1 ), formic acid, and hexafluoro. Examples include isopropanol (1 to 1 g). An inorganic salt may be added to the solvent as a dissolution promoter.

[0320] 〔第 6の発明に係る防水透湿性生地〕 [0320] [Waterproof and breathable fabric according to sixth invention]

第 6実施形態に係る防水透湿性生地は、 繊維径 1 〇 以下の極細繊維を 含む不織布 （以下、 単に 「不織布」 ともいう。 ） からなる防水透湿層 2と、 機能性が付与された編織体からなる表皮層 1 とが接合されてなる。 The waterproof/moisture permeable fabric according to the sixth embodiment is a waterproof/moisture permeable layer 2 made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less (hereinafter also simply referred to as “non-woven fabric”), and a knitted woven fabric having functionality. It is joined to the epidermis 1 which is the body.

[0321 ] 第 6実施形態に係る防水透湿性生地の表皮層 1は、 機能性が付与された編 織体からなる。 編織体とは、 編地及び織地の総称である。 編地は、 横編、 丸 編等の緯編組織を有する編地 （単に 「緯編地」 ともいう。 ） 、 トリコッ ト、 ラッセル等の経編組織を有する編地 （単に 「経編地」 ともいう。 ） のいずれ 〇 2020/175702 98 卩（：171? 2020 /008524 [0321] The skin layer 1 of the waterproof/moisture permeable fabric according to the sixth embodiment is made of a functionalized fabric. A knitted fabric is a general term for knitted fabrics and woven fabrics. A knitted fabric is a knitted fabric having a weft knitting structure such as a flat knit or a circular knit (also simply referred to as “weft knitted fabric”), a knitted fabric having a warp knitting structure such as tricot and Russell (simply “warp knitted fabric”). Also called.) Any of 〇 2020/175 702 98 卩 (: 171-1? 2020 /008524

であってもよい。 織地は、 平織、 綾織、 又は嬬子織のうちのいずれの組織を 有する織地であってもよい。 編織体は、 編成又は織成により得られる未加工 の編織体そのものであってもよいし、 編成又は織成後に撥水加工等の加工を 施した編織体であってもよい。 May be The woven fabric may be a woven fabric having any of a plain weave, a twill weave, and a tsubaki weave. The knitted or woven body may be an unprocessed knitted or woven body obtained by knitting or weaving, or may be a knitted or woven body subjected to a process such as water repellent treatment after knitting or weaving.

[0322] 編織体は、 原料糸を編成又は織成して得ることができる。 編成方法及び織 成方法としては公知の方法を利用することができる。 使用される編機として は、 例えば、 丸編機、 経編機、 横編機などが使用でき、 生産性の観点からは 、 丸編機の使用が好ましい。 横編機としては、 成型編み機、 無縫製編機など があるが、 特に最終製品の形態で編地を製造可能であることから、 無縫製編 機の使用がより好ましい。 使用される織機としては、 例えば、 有抒織機、 及 び、 グリッパー織機、 レピア織機、 ゥォータージェッ ト織機、 エアジェッ ト 織機等の無抒織機が挙げられる。 [0322] The knitted or woven body can be obtained by knitting or weaving raw material threads. As a knitting method and a weaving method, known methods can be used. As the knitting machine to be used, for example, a circular knitting machine, a warp knitting machine, a flat knitting machine or the like can be used, and from the viewpoint of productivity, the circular knitting machine is preferably used. As the flat knitting machine, there are a forming knitting machine, a non-sewn knitting machine, and the like. However, since the knitted fabric can be manufactured in the form of a final product, the non-sewn knitting machine is more preferable. Examples of the loom to be used include a hauling loom, and a non-tapping loom such as a gripper loom, a rapier loom, a water jet loom, and an air jet loom.

[0323] 原料糸は、 単独糸であってもよく、 複合糸 （例えば、 混紡糸、 混繊糸、 力 バーリング糸等。 ） であってもよく、 これらを組み合わせて用いてもよい。 単独糸及び複合糸は、 短繊維を撚り合わせたスパン糸であってもよく、 長繊 維を撚り合わせたフィラメント糸であってもよい。 原料糸に含まれる繊維と しては、 例えば、 タンパク質繊維、 ナイロン、 ポリエステル、 ポリテトラフ ルオロエチレン等の合成繊維、 キユプラ、 レーヨン、 リヨセル等の再生繊維 、 綿、 麻、 絹等の天然繊維が挙げられる。 [0323] The raw yarn may be a single yarn, a composite yarn (for example, a mixed spun yarn, a mixed fiber yarn, a force burring yarn, etc.), or may be a combination of these. The single yarn and the composite yarn may be spun yarns in which short fibers are twisted together, or filament yarns in which long fibers are twisted together. Examples of the fibers contained in the raw yarn include protein fibers, synthetic fibers such as nylon, polyester and polytetrafluoroethylene, recycled fibers such as Kyupra, rayon and lyocell, and natural fibers such as cotton, hemp and silk.

[0324] 編織体は、 タンパク質繊維を含むことが好ましい。 タンパク質繊維として は、 改変フィブロインを含むことが好ましく、 改変クモ糸フィブロインを含 むことがより好ましい。 改変フィブロイン （好ましくは、 改変クモ糸フィブ ロイン） を含むことにより、 編織体に保温性、 吸湿発熱性及び/又は難燃性 の機能性を付与することができる。 ひいては、 本実施形態に係る防水透湿性 生地に保温性、 吸湿発熱性及び/又は難燃性の機能性を付与することができ 、 生地としての価値がより高くなる。 改変フィブロインは、 改変フィブロイ ン繊維 （タンパク質繊維） として編織体に含まれていてもよい。 改変フィブ ロインの好ましい態様は、 第 1の発明に係る防水透湿性生地で説明した態様 〇 2020/175702 99 卩（：171? 2020 /008524 [0324] The knitted fabric preferably contains protein fibers. The protein fiber preferably contains modified fibroin, more preferably modified spider silk fibroin. By including the modified fibroin (preferably, modified spider thread fibroin), it is possible to impart heat retention, moisture absorption and exothermicity and/or flame retardancy to the knitted fabric. As a result, the waterproof and moisture-permeable fabric according to the present embodiment can be provided with heat retention, moisture absorption and heat generation properties, and/or flame retardancy, and the value as a fabric becomes higher. The modified fibroin may be contained in the weaving body as modified fibroin fibers (protein fibers). A preferred embodiment of the modified fibroin is the embodiment described in the waterproof and breathable fabric according to the first invention. 〇 2020/175 702 99 卩(: 171-1? 2020/008524

を適用できる。 Can be applied.

[0325] 編織体に機能性を付与する方法としては、 例えば、 編織体に改変フイブロ インを含ませる方法 （第 1の方法） 、 編織体に所定のタンパク質架橋体を含 有するタンパク質繊維を含ませる方法 （第 2の方法） 、 編織体にヒドロキシ ル基含有ポリマーに機能性官能基が結合した修飾ヒドロキシル基含有ポリマ 一を含ませる方法 （第 3の方法） 等が挙げられる。 [0325] Examples of a method for imparting functionality to the knitted fabric include a method of including the modified fibroin in the knitted fabric (first method), and a process of including the protein fiber containing a predetermined protein crosslinked body in the knitted fabric. Method (second method), a method of incorporating a modified hydroxyl group-containing polymer in which a functional group is bonded to a hydroxyl group-containing polymer into a knitted fabric (third method), and the like.

[0326] 第 1の方法では、 例えば、 原料糸に含まれる繊維として改変フイブロイン を含むタンパク質繊維を使用して、 原料糸を編成又は織成することで、 機能 性が付与された編織体を得ることができる。 改変フイブロインを含むことに よって、 編織体に保温性、 吸湿発熱性及び/又は難燃性の機能性を付与する ことができる。 [0326] In the first method, for example, a protein fiber containing a modified fibroin as a fiber contained in the raw material yarn is used to knit or weave the raw material yarn to obtain a knitted or woven body having functionality. be able to. By including the modified fibroin, it is possible to impart heat retention, moisture absorption and exothermicity and/or flame retardancy to the knitted fabric.

[0327] 第 2の方法における所定のタンパク質架橋体とは、 ポリべプチド骨格と、 タンパク質と反応して結合を形成可能な第一の反応性基を 2つ以上有する第 一の反応剤の残基である第一の残基と、 第一の反応性基と反応して結合を形 成可能な第二の反応性基を 1つ有する第二の反応剤の残基である第二の残基 と、 をそれぞれ複数有し、 第一の残基の少なくとも一つが、 ポリペプチド骨 格を架橋しており、 第一の残基の少なくとも一つが、 一端でポリペプチド骨 格と結合し、 他端で第二の残基と結合しているものである。 [0327] The predetermined protein cross-linked product in the second method is a residue of a first peptide having a polypeptide backbone and two or more first reactive groups capable of reacting with a protein to form a bond. The second residue, which is the residue of the second reactive agent, which has a first residue that is a group and one second reactive group that can react with the first reactive group to form a bond. And a plurality of groups, and at least one of the first residues crosslinks the polypeptide skeleton, and at least one of the first residues binds to the polypeptide skeleton at one end, and It is attached to the second residue at the end.

[0328] 第 2の方法では、 例えば、 原料糸に含まれる繊維として所定のタンパク質 架橋体を含有するタンパク質繊維を使用して、 原料糸を編成又は織成するこ とで、 機能性が付与された編織体を得ることができる。 第 2の方法ではまた 、 例えば、 原料糸に含まれる繊維としてタンパク質繊維を使用して、 原料糸 を編成又は織成することで編織体 （前駆体） を得て、 編織体 （前駆体） に対 して、 第一の反応剤及び第二の反応剤を反応させることで所定のタンパク質 架橋体を生成させることで、 能性が付与された編織体を得ることができる。 [0328] In the second method, functionality is imparted by knitting or weaving the raw material yarn, for example, by using a protein fiber containing a predetermined protein crosslinked body as a fiber contained in the raw material yarn. It is possible to obtain a knitted woven body. In the second method, for example, a protein fiber is used as a fiber contained in the raw material yarn, and the raw material yarn is knitted or woven to obtain a knitted fabric (precursor), and a knitted fabric (precursor) is obtained. On the other hand, by reacting the first reaction agent and the second reaction agent to generate a predetermined protein cross-linked product, it is possible to obtain a knitted or woven material having a function.

[0329] 第 2の方法は、 より具体的には、 タンパク質を含有する成形体前駆体と、 タンパク質と反応して結合を形成可能な第一の反応性基を 2つ以上有する第 _の反応剤とを反応させて、 中間体を得る第 _の工程と、 中間体と、 第 _の 〇 2020/175702 100 卩（：171? 2020 /008524 [0329] The second method is, more specifically, a reaction of a molded body precursor containing a protein with a second reaction of having at least two first reactive groups capable of reacting with the protein to form a bond. the agent is reacted, and the _ step give intermediate, and intermediate, of the _ 〇 2020/175 702 100 卩(: 171-1? 2020/008524

反応性基と反応して結合を形成可能な第二の反応性基を 1 つ有する第二の反 応剤とを反応させて、 成形体を得る第二の工程と、 を備える。 第 2の方法に おける成形体としては、 例えば、 タンパク質を含有する編織体、 タンパク質 を含有する繊維 （タンパク質繊維） であってよい。 A second step of reacting with a reactive group and a second reaction agent having one second reactive group capable of forming a bond to obtain a molded article. The molded body in the second method may be, for example, a protein-containing knitted fabric or a protein-containing fiber (protein fiber).

[0330] 第一の工程は、 タンパク質を含有する成形体前駆体と第一の反応剤とを反 応させる工程である。 第一の反応剤は、 タンパク質と反応して結合を形成可 能な第一の反応性基を 2つ以上有する多官能反応剤であり、 第一の工程では 、 第一の反応剤によりタンパク質が架橋されてよい。 [0330] The first step is a step of reacting the protein-containing molded body precursor with the first reactant. The first reactive agent is a polyfunctional reactive agent having two or more first reactive groups capable of reacting with a protein to form a bond. In the first step, the protein is reacted by the first reactive agent. It may be crosslinked.

[0331 ] タンパク質は、 アミ ド基、 ヒ ドロキシル基、 フエノール性水酸基、 アミノ 基、 カルボキシル基、 チオール基、 セレノール基、 イミダゾリル基、 インド リル基及びグアニジノ基からなる群より少なくとも一種の反応性官能基を有 している。 第一の反応剤が有する第一の反応性基は、 上記反応性官能基と反 応して結合を形成可能な基であってよい。 [0331] A protein is at least one reactive functional group selected from the group consisting of an amide group, a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxyl group, a thiol group, a selenol group, an imidazolyl group, an indolyl group and a guanidino group. have. The first reactive group contained in the first reactive agent may be a group capable of reacting with the reactive functional group to form a bond.

[0332] 第一の反応性基としては、 求電子性基が好ましい。 第一の反応性基が求電 子性基であると、 タンパク質の反応性官能基と付加反応によって容易に結合 を形成できる。 [0332] As the first reactive group, an electrophilic group is preferable. When the first reactive group is an electrophilic group, a bond can be easily formed by an addition reaction with the reactive functional group of the protein.

[0333] 求電子性基である第一の反応性基としては、 例えば、 下記式 （八_ 1 ） 、 （八一 2） 、 （八一 3） 、 （八一 4） 、 （八一 5） 又は （八一 6） で表され る基が好ましい。 なお、 各式中の波線は、 各基の結合手を示す。 [0333] Examples of the first reactive group that is an electrophilic group include, for example, the following formulas (8_1), (81_1), (81_1), (81_1), (81_1). ) Or (81 6) is preferred. The wavy line in each formula represents a bond of each group.

[0334] [化 3]

Figure imgf000101_0001
[0334] [Chemical 3]
Figure imgf000101_0001

（八- 1） （八- 2） （八- 3） （八-4） （八- 5） （八 -6） (8-1) (8-2) (8-3) (8-4) (8-5) (8-6)

[0335] 式 （八一 1 ） 中、 X 1は酸素原子 （〇） 又は硫黄原子 （3） を示す。 X Iと しては、 酸素原子がより好ましい。 [0335] In the formula (81), X 1 represents an oxygen atom (○) or a sulfur atom (3). As X I , an oxygen atom is more preferable.

[0336] 式 （八_ 3） 中、 X 2は脱離基を示す。 脱離基は特に限定されず、 タンパク 質の反応性官能基による求核置換反応が可能な基であればよい。 脱離基とし ては、 例えば、 ハロゲン原子 （フッ素原子 （ ） 、 塩素原子 （〇 I ） 、 臭素 〇 2020/175702 101 卩（：171? 2020 /008524 [0336] In formula (8_3), X 2 represents a leaving group. The leaving group is not particularly limited as long as it is a group capable of nucleophilic substitution reaction by a reactive functional group of a protein. Examples of the leaving group include a halogen atom (fluorine atom (), chlorine atom (〇I), bromine) 〇 2020/175 702 101 卩(: 171-1? 2020/008524

原子 （巳 〇 、 ヨウ素原子 （丨） ） 、 スルホン酸エステル基 （_〇3〇2 [¾ 1 ） 、 カルボン酸エステル基 （一〇〇〇[¾ 2） 、 四級アンモニウム基 （一 [¾ 3 3 ） 等が挙げられる。 は、 例えば、 フッ素原子、 アルキル基、 アリール基、 ハロゲン化アルキル基又はハロゲン化アリール基であってよい。

Figure imgf000102_0001
は、 例え ば、 アルキル基、 アリール基、 ハロゲン化アルキル基又はハロゲン化アリー ル基であってよい。
Figure imgf000102_0002
は、 例えば、 アルキル基、 アリール基、 ハロゲン化ア ルキル基又はハロゲン化アリール基であってよい。
Figure imgf000102_0003
及び は置換基 を有していてもよい。 当該置換基としては、 例えば、 アルキル基、 アルケニ ル基、 アリール基、 ハロゲン原子等が挙げられる。 Atom (Mix 〇, Iodine atom (丨) ), Sulfonate group (_ 〇 3 〇 2 [¾ 1 ), Carboxylate group (100 000 [¾ 2 ), Quaternary ammonium group (1 [¾ 3] 3 ) etc. May be, for example, a fluorine atom, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group.
Figure imgf000102_0001
May be, for example, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group.
Figure imgf000102_0002
May be, for example, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group.
Figure imgf000102_0003
And may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a halogen atom and the like.

[0337] X 2としては、 塩素原子、 臭素原子、 ヨウ素原子、 エステル基及びスルホン 酸エステル基がより好ましく、 臭素原子、 ヨウ素原子、 スルホン酸エステル 基が更に好ましい。 としては、 フッ素原子、 アルキル基 （特に、 メチル基 、 エチル基、 ベンジル基、 アリル基） 、 パーフルオロオロアルキル基 （特に 、 トリフルオロメチル基、 ペンタフルオロエチル基） 、 アリール基 （特に、 フエニル基、 トリル基、 ナフチル基、 フルオロフエニル基） 等がより好まし い。 としては、 アルキル基 （特に、 メチル基、 エチル基、 ベンジル基、 ア リル基） 、 パーフルオロオロアルキル基 （特に、 トリフルオロメチル基、 ぺ ンタフルオロエチル基） 、 アリール基 （特に、 フエニル基、 トリル基、 ナフ チル基、 フルオロフエニル基） 等がより好ましい。

Figure imgf000102_0004
としては、 アルキル基 （特に、 メチル基、 エチル基、 ベンジル基、 アリル基） 、 アリール基 （特に 、 フエニル基、 トリル基、 ナフチル基、 フルオロフエニル基） 等がより好ま しい。 [0337] X 2 is more preferably a chlorine atom, a bromine atom, an iodine atom, an ester group or a sulfonic acid ester group, and further preferably a bromine atom, an iodine atom or a sulfonic acid ester group. Are a fluorine atom, an alkyl group (in particular, a methyl group, an ethyl group, a benzyl group, an allyl group), a perfluorooroalkyl group (in particular, a trifluoromethyl group, a pentafluoroethyl group), an aryl group (in particular, a phenyl group) , Tolyl group, naphthyl group, fluorophenyl group) and the like are more preferable. Are an alkyl group (especially a methyl group, an ethyl group, a benzyl group, an aryl group), a perfluorooroalkyl group (especially a trifluoromethyl group, a pentafluoroethyl group), an aryl group (especially a phenyl group, Tolyl group, naphthyl group, fluorophenyl group) and the like are more preferable.
Figure imgf000102_0004
As the above, an alkyl group (in particular, a methyl group, an ethyl group, a benzyl group, an allyl group), an aryl group (in particular, a phenyl group, a tolyl group, a naphthyl group, a fluorophenyl group) and the like are more preferable.

[0338] 式 （八一4） 中、 X 3は酸素原子 （〇） 、 硫黄原子 （3） 、 一 [¾ 4 -で表 される基、 又は、 _〇 5） 2 _で表される基を示す。

Figure imgf000102_0005
例えば、 水素 原子、 アルキル基、 アリール基、 ハロゲン化アルキル基又はハロゲン化アリ —ル基、 アリールスルホニル基、 アルキルスルホニル基、 アシル基、 カーバ メート基であってよい。 は、 電子求引性基を示す。 電子求引性基としては 、 例えば、 カルボニル基、 シアノ基、 アリール基、 アルケニル基、 アルキニ 〇 2020/175702 102 卩（：171? 2020 /008524 [0338] In the formula (81), X 3 represents an oxygen atom (○), a sulfur atom (3), a group represented by [¾ 4 -, or a group represented by _○ 5 ) 2 _ Indicates.
Figure imgf000102_0005
For example, it may be a hydrogen atom, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group, an arylsulfonyl group, an alkylsulfonyl group, an acyl group, and a carbamate group. Represents an electron-withdrawing group. Examples of the electron-withdrawing group include a carbonyl group, a cyano group, an aryl group, an alkenyl group and an alkynyl group. 〇 2020/175 702 102 卩 (: 171-1? 2020 /008524

ル基等が挙げられる。 2つの は互いに同一でも異なっていてもよい。

Figure imgf000103_0001
及び 5は置換基を有していてもよい。 当該置換基としては、 例えば、 アルキ ル基、 アルケニル基、 アリール基、 ハロゲン原子等が挙げられる。 And the like. The two may be the same or different from each other.
Figure imgf000103_0001
And 5 may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a halogen atom and the like.

[0339] X 3としては、 酸素原子がより好ましい。

Figure imgf000103_0002
としては、 アリールスルホニ ル基、 アルキルスルホニル基、 アシル基、 力ーバメート基等がより好ましい [0339] X 3 is more preferably an oxygen atom.
Figure imgf000103_0002
More preferred are arylsulfonyl groups, alkylsulfonyl groups, acyl groups, force-bamate groups and the like.

[0340] 式 （八一 5） 中、 X 4は酸素原子 （〇） 又は硫黄原子 （3） を示し、 丫1は ハロゲン原子、 ヒドロキシル基、 一

Figure imgf000103_0003
で表される基、 一〇[¾ 6で表される基 、 又は、 一〇＜3
Figure imgf000103_0004
で表される基を示す。
Figure imgf000103_0005
は、 例えば、 アルキル基、 ア リール基、 ハロゲン化アルキル基又はハロゲン化アリール基であってよい。 [0340] In the formula (81 5), X 4 represents an oxygen atom (○) or a sulfur atom (3), and 1 represents a halogen atom, a hydroxyl group,
Figure imgf000103_0003
A group represented by 10 [a group represented by 6 or a 10 <3
Figure imgf000103_0004
Represents a group represented by.
Figure imgf000103_0005
May be, for example, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group.

は置換基を有していてもよい。 当該置換基としては、 例えば、 アルキル基 、 アルケニル基、 アリール基、 ハロゲン原子等が挙げられる。 May have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a halogen atom and the like.

[0341 ] X 4としては、 酸素原子がより好ましい。 丫1としては、 ハロゲン原子、 _ 〇[¾ 6で表される基、 又は、 一〇〇〇[¾ 6で表される基等がより好ましい。

Figure imgf000103_0006
としては、 アルキル基、 アリール基等がより好ましい。 [0341] X 4 is more preferably an oxygen atom. The丫1, a halogen atom, _ 〇 [group represented by ¾ 6, or the like group represented by one thousand [¾ 6 is more preferable.
Figure imgf000103_0006
Of these, an alkyl group, an aryl group and the like are more preferable.

[0342] 式 （八一 6） 中、 X 5は酸素原子 （〇） 又は硫黄原子 （3） を示し、 丫2は 酸素原子 （〇） 、 硫黄原子 （3） 又は 7で表される基を示す。

Figure imgf000103_0007
は例え ば、 アルキルスルホニル基、 アリールスルホニル基、 アシル基、 力ーバメー 卜基、 アルキル基、 アリール基、 ハロゲン化アルキル基又はハロゲン化アリ —ル基であってよい。
Figure imgf000103_0008
7は置換基を有していてもよい。 当該置換基としては 、 例えば、 アルキル基、 アルケニル基、 アリール基、 ハロゲン原子等が挙げ られる。 [0342] In the formula (81 6), X 5 represents an oxygen atom (o) or a sulfur atom (3), and 2 represents a group represented by an oxygen atom (o), a sulfur atom (3) or 7. Show.
Figure imgf000103_0007
May be, for example, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a power group, an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group.
Figure imgf000103_0008
7 may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, and a halogen atom.

[0343] X 5としては、 酸素原子がより好ましい。 丫2としては、 酸素原子がより好 ましい。

Figure imgf000103_0009
7としては、 アルキルスルホニル基、 アリールスルホニル基、 アシ ル基、 力ーバメート基等がより好ましい。 [0343] X 5 is more preferably an oxygen atom. As the second layer , an oxygen atom is more preferable.
Figure imgf000103_0009
More preferably, 7 is an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a forcebamate group, or the like.

[0344] 第一の反応剤は、 第一の反応性基を 2以上有する化合物であればよい。 第 一の反応剤が有する第一の反応性基の数は、 特に限定されず、 例えば 2〜 1 0 0 0 0であってよく、 好ましくは 2〜 1 0 0 0である。 〇 2020/175702 103 卩（：171? 2020 /008524 [0344] The first reactive agent may be a compound having two or more first reactive groups. The number of the first reactive groups contained in the first reactant is not particularly limited and may be, for example, 2 to 100, preferably 2 to 100. 〇 2020/175 702 103 卩(：171? 2020/008524

[0345] 第一の工程は、 例えば、 第一の反応剤を含有する第一の反応液と、 成形体 前駆体とを接触させて加熱することで実施してよい。 [0345] The first step may be carried out, for example, by bringing the first reaction liquid containing the first reactant and the precursor of the molded body into contact with each other and heating them.

[0346] 第一の反応液は、 無溶媒であってよく、 溶媒を更に含有していてもよい。 [0346] The first reaction liquid may be solvent-free, or may further contain a solvent.

第一の反応液の溶媒は特に限定されず、 例えば、 第一の反応剤を溶解可能で あり、 且つ、 タンパク質の反応性官能基と第一の反応性基との反応を阻害し ないものであればよい。 第一の反応性基が求電子性基である場合、 第一の反 応液の溶媒としては、 例えば、 1\1 , 1\1 -ジメチルアセトアミ ド、 1\1 , 1\1 -ジ メチルホルムアミ ド、 1\1 _メチルピロリ ドン、 ベンゼン、 トルエン、 キシレ ン、 メシチレン、 テトラヒドロフラン、 ジメチルスルホキシド、 酢酸エチル 、 酢酸プチル、 プロピレングリコールモノメチルェーテルアセテート等を好 適に用いることができる。 The solvent of the first reaction solution is not particularly limited, and for example, it can dissolve the first reaction agent and does not inhibit the reaction between the reactive functional group of the protein and the first reactive group. I wish I had it. When the first reactive group is an electrophilic group, the solvent for the first reaction solution may be, for example, 1\1, 1\1-dimethylacetamide, 1\1, 1\1-di- Methylformamide, 1\1_methylpyrrolidone, benzene, toluene, xylene, mesitylene, tetrahydrofuran, dimethylsulfoxide, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and the like can be preferably used.

[0347] 第一の工程における反応条件は特に限定されず、 タンパク質の反応性官能 基と第一の反応性基とが反応する条件であればよい。 [0347] The reaction conditions in the first step are not particularly limited as long as the reactive functional group of the protein reacts with the first reactive group.

[0348] 第一の工程では、 第一の反応剤の少なくとも一部がタンパク質を架橋し、 且つ、 第一の反応性基の少なくとも一部が中間体中に残存することが好まし い。 すなわち、 第一の工程では、 第一の反応剤により架橋されたタンパク質 を含み、 且つ、 第一の反応性基を有する中間体が得られることが好ましい。 [0348] In the first step, it is preferable that at least a part of the first reactive agent crosslinks the protein and at least a part of the first reactive group remains in the intermediate. That is, in the first step, it is preferable to obtain an intermediate containing a protein cross-linked by the first reactive agent and having a first reactive group.

[0349] 例えば、 第一の反応剤が第一の反応性基を 2つ有する化合物であるとき、 第一の反応剤の一部は、 タンパク質を架橋 （すなわち、 第一の反応性基の両 方がタンパク質と反応） していてよい。 また、 第一の反応性基の他の一部は 、 第一の反応性基の一方のみでタンパク質と反応していてよく、 このとき、 もう一方の第一の反応性基は未反応で、 中間体中に残存していてよい。 [0349] For example, when the first reactive agent is a compound having two first reactive groups, a part of the first reactive agent cross-links the protein (that is, both of the first reactive groups). May react with the protein). Further, the other part of the first reactive group may be reacted with the protein by only one of the first reactive groups, and at this time, the other first reactive group is unreacted, It may remain in the intermediate.

[0350] また、 例えば、 第一の反応剤が第一の反応性基を 3つ以上有する化合物で あるとき、 第一の反応剤の一部は、 全ての第一の反応性基でタンパク質を架 橋 （すなわち、 第一の反応性基の全てがタンパク質と反応） していてよく、 第一の反応剤の他の一部は、 一部の第一の反応性基がタンパク質と反応し、 他の一部の第一の反応性基が未反応で中間体中に残存していてもよい。 [0350] In addition, for example, when the first reactive agent is a compound having three or more first reactive groups, a part of the first reactive agent is a protein having all the first reactive groups. Bridges (ie, all of the first reactive groups react with the protein), and some other of the first reactive agents have some of the first reactive groups react with the protein, Another part of the first reactive group may remain unreacted in the intermediate.

[0351 ] 第一の工程の反応は、 第一の反応剤により、 タンパク質の反応性官能基を 〇 2020/175702 104 卩（：171? 2020 /008524 [0351] The reaction of the first step is to react the reactive functional group of the protein with the first reactive agent. 〇 2020/175 702 104 卩 (：171? 2020 /008524

起点として、 架橋構造、 又は、 第一の反応性基を有する側鎖を形成する反応 ということもできる。 架橋構造及び側鎖の量は、 反応に用いる第一の反応剤 の量によって調節することができる。 第一の反応剤の使用量を少なくするこ とで、 側鎖が少なく、 架橋構造が多く形成される傾向があり、 第一の反応剤 の使用量を多くすることで、 架橋構造が少なく、 側鎖が多く形成される傾向 がある。 It can also be said that the origin is a reaction of forming a cross-linked structure or a side chain having a first reactive group. The amount of the crosslinked structure and the side chain can be adjusted by the amount of the first reactant used in the reaction. By reducing the amount of the first reaction agent, there is a tendency for fewer side chains and more crosslinked structures to be formed.By increasing the amount of the first reaction agent, the number of crosslinked structures is reduced. Many side chains tend to be formed.

[0352] なお、 架橋構造及び側鎖の量の調節は、 例えば、 第一の工程の実施に先立 って、 第一の反応剤が有する第一の反応性基の一部に、 第二の反応剤が有す る第二の反応性基を反応させる前工程を行うことによっても実現できる。 こ のような前工程で用いる第二の反応剤の第一の反応剤に対する量等を適宜に 調整することで、 前工程で第二の反応性基と反応せずに残存する第一の反応 性基の数をコントロールすることができる。 それによって、 第一の工程で、 第一の反応性基のタンパク質との結合量を容易に調節することが可能となり 、 その結果として、 タンパク質の架橋構造及び側鎖の量を容易にコントロー ルすることができるようになる。 [0352] Note that adjustment of the amount of the crosslinked structure and the side chain can be performed, for example, by adding a second reactive group to a part of the first reactive group contained in the first reactive agent prior to performing the first step. It can also be realized by performing a pre-step of reacting the second reactive group contained in the above-mentioned reactant. By appropriately adjusting the amount of the second reactant used in the previous step relative to the first reactant, the first reaction remaining without reacting with the second reactive group in the previous step. The number of sexual groups can be controlled. Thereby, in the first step, the binding amount of the first reactive group with the protein can be easily adjusted, and as a result, the cross-linking structure of the protein and the amount of side chains can be easily controlled. Will be able to.

[0353] すなわち、 第 2の方法は、 第一の工程の前に、 第一の反応剤の一部と第二 の反応剤の _部とを反応させて、 第 _の反応剤が有する第 _の反応性基の _ 部と、 第二の反応剤が有する第二の反応性基の一部とを反応させる前工程を 更に備えていてよい。 [0353] That is, the second method, before the first step, is reacted with a portion of the first reactant and a _ part of the second reactant, the first having a _ of the reactant and _ Department of _ reactive group, steps may further comprise a pre-reacting a portion of the second reactive group having a second reactant.

[0354] 架橋構造を多く形成することで、 成形体の耐水性 （例えば、 水分との接触 による収縮量を抑制可能な特性、 水分との接触後の乾燥時における収縮量を 抑制可能な特性等） 、 機械的強度、 耐熱性等が向上する傾向があり、 側鎖を 多く形成することで、 成形体に付与される機能性 （例えば、 後述の質感） が 向上する傾向がある。 第 2の方法では、 所望の特性に応じて、 架橋構造及び 側鎖の割合を適宜調節してよい。 [0354] By forming a large number of crosslinked structures, the water resistance of the molded article (for example, the property that the amount of shrinkage due to contact with moisture can be suppressed, the amount of shrinkage after drying after contact with moisture can be suppressed, etc.) ), mechanical strength, heat resistance, etc. tend to improve, and by forming a large number of side chains, the functionality imparted to the molded article (for example, the texture described later) tends to improve. In the second method, the crosslinked structure and the proportion of side chains may be appropriately adjusted depending on the desired properties.

[0355] 第一の工程では、 タンパク質と第一の反応剤との反応物を含む中間体が得 られる。 当該反応物中、 タンパク質は第一の反応剤により架橋されており、 未反応の第一の反応性基が残存していてよい。 すなわち、 上記反応物は、 夕 〇 2020/175702 105 卩(：171? 2020 /008524 [0355] In the first step, an intermediate containing a reaction product of the protein and the first reactant is obtained. In the reaction product, the protein is crosslinked by the first reactive agent, and the unreacted first reactive group may remain. That is, the reaction product was 〇 2020/175 702 105 卩(: 171? 2020/008524

ンパク質に由来するポリべプチド骨格と、 ポリべプチド骨格を架橋する架橋 部と、 ポリペプチド骨格に結合し、 末端に第一の反応性基を有する側鎖部と 、 を含有していてよい。 It may contain a polypeptide skeleton derived from a protein, a cross-linking part that cross-links the polypeptide skeleton, and a side chain part having a first reactive group at the end that is bonded to the polypeptide skeleton. ..

[0356] 第二の工程は、 第一の工程で得られた中間体と、 第二の反応剤とを反応さ せる工程である。 第二の反応剤は、 第一の反応性基と反応して結合を形成可 能な第二の反応性基を 1つ有している。 第二の工程は、 中間体中に残存する 第一の反応性基を、 第二の反応剤と反応させる工程ということもできる。 [0356] The second step is a step of reacting the intermediate obtained in the first step with the second reactant. The second reactive agent has one second reactive group capable of reacting with the first reactive group to form a bond. The second step can also be referred to as a step of reacting the first reactive group remaining in the intermediate with the second reactant.

[0357] 第二の反応剤が有する第二の反応性基は特に限定されず、 第一の反応性基 の種類に応じて適宜変更してよい。 例えば、 第一の反応性基が求電子性基で ある場合、 第二の反応性基は求核性基であることが好ましい。 [0357] The second reactive group contained in the second reactive agent is not particularly limited and may be appropriately changed depending on the type of the first reactive group. For example, when the first reactive group is an electrophilic group, the second reactive group is preferably a nucleophilic group.

[0358] 求核性基である第二の反応性基としては、 例えば、 ヒドロキシル基、 チオ —ル基、 アミノ基、 下記式 （巳一 1） で表される基等が挙げられる。 [0358] Examples of the second reactive group which is a nucleophilic group include a hydroxyl group, a thiol group, an amino group, and a group represented by the following formula (Minichi 1).

[0359] [化 4] [0359] [Chemical 4]

Figure imgf000106_0001
Figure imgf000106_0001

[0360] 式 （巳一 1） 中、 X 6は酸素原子 （〇） 又は硫黄原子 （3） を示す。 [0360] In the formula (Michiichi 1), X 6 represents an oxygen atom (○) or a sulfur atom (3).

[0361 ] 式 （巳一 1） で表される基としては、 例えば、 下記式 （巳一 1 - 1） で表 される基が挙げられる。 [0361] Examples of the group represented by the formula (Mimiichi 1) include groups represented by the following formula (Mimiichi 1-1).

[0362] [化 5] [0362] [Chemical 5]

Figure imgf000106_0002
Figure imgf000106_0002

[0363] 式 （巳_ 1 _ 1 ） 中、 丫3は一価の基を示す。 丫3は、 例えば、 アルキル基 、 アルケニル基、 アルキニル基、 アリール基、 アルコキシ基、 アルキルスル フイ ド基、 アリールスルフイ ド基、 1置換アミノ基、 2置換アミノ基等であ 〇 2020/175702 106 卩（：171? 2020 /008524 [0363] In the formula (__ 1 _ 1), 丫3 represents a monovalent group. Example 3 is, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkylsulfide group, an arylsulfide group, a monosubstituted amino group, a disubstituted amino group, or the like. 〇 2020/175 702 106 卩(：171? 2020/008524

ってよく、 好ましくはアルキル基、 アリール基、 アルコキシ基、 1置換アミ ノ基である。 丫3は置換基を有していてもよい。 当該置換基としては、 例えば 、 アルキル基、 アルケニル基、 アリール基、 ハロゲン原子等が挙げられる。 And preferably an alkyl group, an aryl group, an alkoxy group, or a mono-substituted amino group. The layer 3 may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a halogen atom and the like.

[0364] 第二の反応剤は、 第二の反応性基を 1つ有する化合物であればよく、 第二 の工程の反応 （第一の反応性基と第二の反応性基との反応） に不活性な機能 性基を更に有していてよい。 このような第二の反応剤によれば、 中間体中の 未反応の第一の反応性基を起点として、 容易に成形体に機能性基を導入する ことができる。 [0364] The second reactive agent may be a compound having one second reactive group, and the reaction in the second step (reaction between the first reactive group and the second reactive group) It may further have an inactive functional group. With such a second reactive agent, it is possible to easily introduce the functional group into the molded article, starting from the unreacted first reactive group in the intermediate.

[0365] 機能性基は特に限定されず、 成形体に直接的に機能性を付与する基であっ てよく、 成形体に更なる反応剤との反応性を付与する基であってもよい。 [0365] The functional group is not particularly limited, and may be a group that directly imparts functionality to the molded article or a group that imparts reactivity to the molded article with a further reaction agent.

[0366] 機能性基としては、 例えば、 アルキル基、 アルケニル基、 アルキニル基等 の炭化水素基； アリ _ル基、 複素環基等の環構造を有する基；保護基で保護 された反応性基 （ヒドロキシ基、 アミノ基、 チオール基等） ；カルボニル基 （- 0 （=〇） 一） 、 エーテル結合 （一〇一） 、 アミ ド結合 （＞1\1〇 （=〇 ） -） 、 ウレタン結合 （＞!\1〇 （=〇） 〇一） 、 ウレア結合 （＞ （0 = 0 ） N 0 力ーボネート結合 （_〇〇 （=〇） 0 -） 等の構造を有する基； ア ルコキシシリル基、 スルホニル基 （_ 3 （=〇） _） 、 カルボキシル基 （_ [0366] Examples of the functional group include a hydrocarbon group such as an alkyl group, an alkenyl group and an alkynyl group; a group having a ring structure such as an aryl group and a heterocyclic group; a reactive group protected by a protecting group. (Hydroxy group, amino group, thiol group, etc.); Carbonyl group (-0 (= 〇) one), ether bond (101), amide bond (>1\1 〇 (= 〇) -), urethane bond (>!\1 〇 (= 〇) 〇 1), a group having a structure such as a urea bond (> (0 = 0) N 0 force-bonate bond (_ 〇 〇 (= 〇) 0 -); an alkoxysilyl group, Sulfonyl group (_ 3 (= ○) _), carboxyl group (_

0 （=〇） 〇1~1） 、 スルホン酸基 （一 3 （=〇） 2〇1~1） 、 及び、 第四級アン モニウム基等が挙げられる。 0 (= 〇) 〇 1 to 1), a sulfonic acid group (1 3 (= 〇) 2 0 1 to 1), and a quaternary ammonium group.

[0367] 例えば、 機能性基がアルキル基であると、 成形体の質感が向上する。 この ため、 例えば、 成形体が繊維状又は布状である場合、 機能性基としてアルキ ル基を有する第二の反応剤を用いることで、 質感に優れ、 風合いの良い素材 を得ることができる。 [0367] For example, when the functional group is an alkyl group, the texture of the molded article is improved. Therefore, for example, when the molded product is in the form of fiber or cloth, by using the second reactant having an alkyl group as a functional group, a material having an excellent texture and a good texture can be obtained.

[0368] 従来のタンパク質素材は、 架橋によって耐水性や強度の向上を図ると、 素 材の手触りが悪化して、 人肌に触れる用途に使用しにくくなる場合があった 。 しかし、 第 2の方法によれば、 架橋による耐水性及び機械的強度を維持し つつ、 機能性基によって優れた質感及び風合いが得られ、 人肌に触れる用途 に好適に使用可能な素材を得ることができる。 〇 2020/175702 107 卩（：171? 2020 /008524 [0368] When conventional water-based materials are improved in water resistance and strength by cross-linking, the hand feeling of the materials may be deteriorated, and it may be difficult to use them for applications where human skin is touched. However, according to the second method, while maintaining water resistance and mechanical strength due to crosslinking, excellent texture and texture can be obtained by the functional group, and a material suitable for use in contact with human skin can be obtained. be able to. 〇 2020/175 702 107 卩(：171? 2020/008524

[0369] 第二の工程は、 例えば、 第二の反応剤を含有する第二の反応液と、 中間体 とを接触させて加熱することで実施してよい。 [0369] The second step may be carried out, for example, by bringing the second reaction liquid containing the second reactant and the intermediate into contact with each other and heating them.

[0370] 第二の反応液は、 無溶媒であってよく、 溶媒を更に含有していてもよい。 [0370] The second reaction liquid may be solvent-free, or may further contain a solvent.

第二の反応液の溶媒は特に限定されず、 例えば、 第二の反応剤を溶解可能で あり、 且つ、 第一の反応性基と第二の反応性基との反応を阻害しないもので あればよい。 第一の反応性基が求電子性基、 第二の反応性基が求核性基であ る場合、 第二の反応液の溶媒としては、 例えば、 1\1 , 1\1 _ジメチルアセトア ミ ド、 1\1 , 1\1 _ジメチルホルムアミ ド、 1\1 _メチルピロリ ドン、 ベンゼン、 トルエン、 キシレン、 メシチレン、 テトラヒドロフラン、 ジメチルスルホキ シド、 酢酸エチル、 酢酸プチル、 プロピレングリコールモノメチルエーテル アセテート等を好適に用いることができる。 The solvent of the second reaction solution is not particularly limited, and may be, for example, one capable of dissolving the second reaction agent and not inhibiting the reaction between the first reactive group and the second reactive group. Good. When the first reactive group is an electrophilic group and the second reactive group is a nucleophilic group, the solvent for the second reaction solution is, for example, 1\1, 1\1_dimethylacetate. Amide, 1\1, 1\1_ Dimethylformamide, 1\1_ Methylpyrrolidone, Benzene, Toluene, Xylene, Mesitylene, Tetrahydrofuran, Dimethylsulfoxide, Ethyl acetate, Butyl acetate, Propylene glycol monomethyl ether acetate Etc. can be used suitably.

[0371 ] 第二の工程において、 第二の反応剤の使用量は特に限定されない。 第二の 反応剤の使用量は、 例えば、 中間体中の第 _の反応性基の量を超える量であ ってよい。 [0371] In the second step, the amount of the second reactant used is not particularly limited. The amount of the second reactant, for example, may it amounts der which exceeds the amount of the _ reactive groups intermediates.

[0372] 第二の工程では、 中間体中の第一の反応性基の一部又は全部が第二の反応 性基と反応して消費される。 成形体中には、 可能な限り、 第一の反応性基が 残存しないことが望ましい。 このため、 第 2の方法では、 第一の反応性基の 全部が第二の反応性基との反応又は他の副反応により消費されることが好ま しい。 [0372] In the second step, a part or all of the first reactive group in the intermediate reacts with the second reactive group and is consumed. It is desirable that the first reactive group does not remain in the molded body as much as possible. Therefore, in the second method, it is preferable that all of the first reactive group is consumed by the reaction with the second reactive group or other side reaction.

[0373] 第二の工程により、 タンパク質架橋体を含有する成形体が得られる。 [0373] By the second step, a molded product containing a crosslinked protein is obtained.

[0374] 第 2の方法の説明において、 第一の残基は、 第一の反応剤から、 第一の反 応性基を除いた残りの構造を示す。 また、 第二の残基は、 第二の反応剤から 、 第二の反応性基を除いた残りの構造を示す。 [0374] In the description of the second method, the first residue represents the structure remaining after removing the first reactive group from the first reactant. The second residue represents the structure remaining after removing the second reactive group from the second reactant.

[0375] ポリべプチド骨格と第一の残基とは、 タンパク質の反応性官能基及び第一 の反応性基の反応により形成される結合 （例えば、 反応性官能基がアミノ基 、 第一の反応性基がイソシアネート基の場合は、 ウレア結合） によって結合 している。 また、 第一の残基と第二の残基とは、 第一の反応性基及び第二の 反応性基の反応により形成される結合 （例えば、 第一の反応性基がイソシア 〇 2020/175702 108 卩（：171? 2020 /008524 [0375] The polypeptide skeleton and the first residue form a bond formed by the reaction of the reactive functional group of the protein and the first reactive group (for example, the reactive functional group is an amino group, When the reactive group is an isocyanate group, it is bound by a urea bond). Further, the first residue and the second residue are a bond formed by the reaction of the first reactive group and the second reactive group (for example, the first reactive group is an isocyanato group). 〇 2020/175 702 108 卩 (：171? 2020 /008524

ネート基、 第二の反応性基がヒドロキシル基の場合は、 ウレタン結合） によ って結合している。 When the nate group and the second reactive group are hydroxyl groups, they are bonded by a urethane bond).

[0376] 第 2の方法では、 第一の反応剤によってタンパク質が架橋され、 耐水性、 機械的強度、 耐熱性等に優れた成形体が得られる。 また、 第 2の方法では、 中間体中に残存する第一の反応性基を起点として第二の反応剤により機能性 基を付与できるため、 様々な機能性を有する成形体を容易に得ることができ る。 [0376] In the second method, the protein is cross-linked by the first reaction agent, and a molded article excellent in water resistance, mechanical strength, heat resistance and the like can be obtained. Further, in the second method, since the functional group can be added by the second reactive agent starting from the first reactive group remaining in the intermediate, it is possible to easily obtain a molded article having various functionalities. You can

[0377] 第 3の方法における修飾ヒドロキシル基含有ポリマーは、 ヒドロキシル基 含有ポリマーに機能性官能基が結合したポリマーである。 修飾ヒドロキシル 基含有ポリマーは、 例えば、 ヒドロキシル基含有ポリマーと、 機能性官能基 を有する反応剤とを反応させることで得ることができる。 [0377] The modified hydroxyl group-containing polymer in the third method is a polymer in which a functional group is bonded to the hydroxyl group-containing polymer. The modified hydroxyl group-containing polymer can be obtained, for example, by reacting a hydroxyl group-containing polymer with a reactive agent having a functional functional group.

[0378] ヒドロキシル基含有ポリマーは、 ヒドロキシル基を有する高分子化合物で あれば、 特に制限なく使用することができる。 ヒドロキシル基含有ポリマー の具体例としては、 例えば、 デンプン、 グリコーゲン、 セルロース、 キチン 、 アガロース、 ヒアルロン酸、 コンドロイチン硫酸、 ぺクチン及びカラギー ナン等の多糖類、 ポリビニルアルコール （ 八） 及びフエノール樹脂等の 合成高分子が挙げられる。 [0378] The hydroxyl group-containing polymer can be used without particular limitation as long as it is a polymer compound having a hydroxyl group. Specific examples of the hydroxyl group-containing polymer include, for example, starch, glycogen, cellulose, chitin, agarose, hyaluronic acid, chondroitin sulfate, polysaccharides such as pectin and carrageenan, polyvinyl alcohol (8) and phenol resin. Molecules.

[0379] ヒドロキシル基含有ポリマーとしては、 生分解性を有するという観点から は、 多糖類が好ましい。 また、 ヒドロキシル基含有ポリマーとしては、 生分 解性を有することに加え溶解性が高いという観点からは、 デンプンが好まし い。 [0379] The hydroxyl group-containing polymer is preferably a polysaccharide from the viewpoint of having biodegradability. As the hydroxyl group-containing polymer, starch is preferred because it has high biosolubility and high solubility.

[0380] 機能性官能基とは、 付与したい機能性 （例えば、 耐水性、 親水性、 親油性 、 耐油性） に対応した特性 （例えば、 疎水性、 親水性） を有する官能基であ り、 付与したい機能性に応じて、 適宜選択することができる。 [0380] The functional group is a functional group having properties (for example, hydrophobicity and hydrophilicity) corresponding to the desired functionality (for example, water resistance, hydrophilicity, lipophilicity, oil resistance), It can be appropriately selected according to the functionality to be imparted.

[0381 ] 例えば、 耐水性を向上したい場合は、 機能性官能基として、 例えば、 メチ ル基、 エチル基、

Figure imgf000109_0001
プロピル基、 イソプロピル基等のアルキル基、 フエニ ル基、 ナフチル基等の芳香族基、 並びにアセチル基、 プロパノイル基、 ベン ゾイル基等のアシル基といった疎水性官能基を使用することができる。 〇 2020/175702 109 卩（：171? 2020 /008524 [0381] For example, when it is desired to improve water resistance, functional groups such as a methyl group, an ethyl group,
Figure imgf000109_0001
It is possible to use an alkyl group such as a propyl group and an isopropyl group, an aromatic group such as a phenyl group and a naphthyl group, and a hydrophobic functional group such as an acyl group such as an acetyl group, a propanoyl group and a benzoyl group. 〇 2020/175 702 109 卩 (: 171-1? 2020 /008524

［0382］ 機能性官能基を有する反応剤は、 機能性官能基を有し、 更にヒドロキシル 基含有ポリマーと結合可能な結合性官能基を有する化合物である。 結合性官 能基は、 ヒドロキシル基含有ポリマーと、 水素結合又は共有結合で結合可能 であればよいが、 ヒドロキシル基含有ポリマーと共有結合で結合可能な官能 基であることが好ましく、 ヒドロキシル基含有ポリマー中のヒドロキシル基 と共有結合で結合可能な官能基であることがより好ましい。 [0382] The reactive agent having a functional functional group is a compound having a functional functional group and further having a binding functional group capable of binding to a hydroxyl group-containing polymer. The binding functional group may be any group that can be bonded to the hydroxyl group-containing polymer through a hydrogen bond or a covalent bond, but is preferably a functional group that can be bonded to the hydroxyl group-containing polymer through a covalent bond, and is preferably a hydroxyl group-containing polymer. More preferably, it is a functional group capable of covalently bonding to the hydroxyl group therein.

［0383］ 機能性官能基を有する反応剤としては、 例えば、 機能性官能基を有するイ ソシアネート

Figure imgf000110_0001
は機能性官能基） 、 酸無水物 （［¾ _〇 （ =〇） - 0 - 0 （=〇） 一［¾ : は機能性官能基） 、 エポキシド、 アジリジ ン及びアルキルハライ ド等が挙げられる。 機能性官能基を有する反応剤とし ては、 ヒドロキシル基含有ポリマー中のヒドロキシル基と共有結合で結合可 能であることから、 機能性官能基を有するイソシアネート及び無水酢酸が好 ましく、 更に任意の機能性官能基を導入可能であることから、 機能性官能基 を有するイソシアネートがより好ましい。 [0383] Examples of the reactive agent having a functional functional group include an isocyanate having a functional functional group.
Figure imgf000110_0001
Is a functional functional group), an acid anhydride ([¾ _ 〇 (= 〇)-0-0 (= 〇)-1 [¾: is a functional functional group], epoxide, aziridin, alkyl halide, etc. .. As the reactive agent having a functional functional group, an isocyanate having a functional functional group and acetic anhydride are preferable because they can be bound to the hydroxyl group in the hydroxyl group-containing polymer by a covalent bond. An isocyanate having a functional functional group is more preferable because it can introduce a functional functional group.

［0384］ 第 3の方法では、 例えば、 繊維と修飾ヒドロキシル基含有ポリマーを混合 した原料糸を使用して、 編成又は織成することで、 機能性が付与された編織 体を得ることができる。 第 3の方法ではまた、 例えば、 修飾ヒドロキシル基 含有ポリマーを混合した繊維原料を紡糸して、 修飾ヒドロキシル基含有ポリ マーを含有する繊維を得た後、 当該繊維を含む原料糸を編成又は織成するこ とで、 機能性が付与された編織体を得ることができる。 [0384] In the third method, for example, knitting or weaving is performed by using a raw material yarn in which fibers and a modified hydroxyl group-containing polymer are mixed to obtain a knitted or woven fabric having functionality. In the third method, for example, a fiber raw material mixed with a modified hydroxyl group-containing polymer is spun to obtain a fiber containing the modified hydroxyl group-containing polymer, and then the raw material yarn containing the fiber is knitted or woven. By doing so, it is possible to obtain a knitted or woven body having functionality.

［0385］ 編織体に含まれる修飾ヒドロキシル基含有ポリマーの含有量は特に制限は なく、 付与したい機能性、 編織体に含まれる繊維の種類等に応じて適宜設定 してよい。 修飾ヒドロキシル基含有ポリマーの含有量は、 例えば、 編織体全 量を基準として、 0 . 0 0 1〜 7 0質量％であってよく、 0 . 0 1〜 6 5質量 %であってよく、 0 . 1〜 6 0質量％であってよい。 [0385] The content of the modified hydroxyl group-containing polymer contained in the knitted fabric is not particularly limited, and may be appropriately set depending on the functionality to be imparted, the type of fibers contained in the knitted fabric, and the like. The content of the modified hydroxyl group-containing polymer may be, for example, 0.0001 to 70% by mass, or 0.01 to 65% by mass, based on the total amount of the knitted fabric. It may be from 1 to 60 mass %.

［0386］ 編織体がタンパク質繊維を含む場合、 修飾ヒドロキシル基含有ポリマーと タンパク質繊維が水素結合していることが好ましい。 これにより、 機能性が より向上する。 水素結合は、 例えば、 修飾ヒドロキシル基含有ポリマー中の 〇 2020/175702 1 10 卩（：171? 2020 /008524 [0386] When the knitted fabric contains protein fibers, the modified hydroxyl group-containing polymer and the protein fibers are preferably hydrogen-bonded. This further enhances the functionality. Hydrogen bonding can occur, for example, in modified hydroxyl group-containing polymers. 〇 2020/175 702 1 10 卩(：171? 2020/008524

官能基 (例えば、 ヒドロキシル基、 機能性官能基又は結合性官能基中の官能 基等であってよい。 ) と、 タンパク質中の官能基 (例えば、 アミノ基、 カル ボキシル基等であってよい。 ) との間で形成させることができる。 It may be a functional group (for example, a hydroxyl group, a functional group in a functional functional group or a binding functional group, etc.) and a functional group in a protein (for example, an amino group, a carboxyl group, etc.). ).

[0387] 第 3の方法では、 編織体は、 更にヒドロキシル基含有ポリマーを含むもの であってもよい。 当該ヒドロキシル基含有ポリマーは、 修飾ヒドロキシル基 含有ポリマーの原料であるヒドロキシル基含有ポリマーと同種のポリマーで あることが好ましい。 編織体がヒドロキシル基含有ポリマーを含む場合、 ヒ ドロキシル基含有ポリマーの含有量は、 修飾ヒドロキシル基含有ポリマーと ヒドロキシル基含有ポリマーの総量 1 0 0質量％に対して、 5 0質量％以上 であってよく、 6 0質量％以上であってよく、 7 0質量％以上であってもよ く、 8 0質量％以上であってもよい。 また上限としては、 9 0質量％以下で あってよい。 [0387] In the third method, the knitted fabric may further contain a hydroxyl group-containing polymer. The hydroxyl group-containing polymer is preferably a polymer of the same type as the hydroxyl group-containing polymer which is a raw material of the modified hydroxyl group-containing polymer. When the textile fabric contains a hydroxyl group-containing polymer, the content of the hydroxyl group-containing polymer is 50% by mass or more based on 100% by mass of the total amount of the modified hydroxyl group-containing polymer and the hydroxyl group-containing polymer. It may be 60% by mass or more, 70% by mass or more, or 80% by mass or more. The upper limit may be 90 mass% or less.

[0388] 第 6実施形態に係る防水透湿性生地の防水透湿層 2は、 繊維径 1 〇 以 下の極細繊維を含む不織布からなる。 繊維径は、 短繊維の長手方向に垂直な 断面を囲む最小の円の直径を意味する。 極細繊維の繊維径は、 1 0 〇1 ( 1 0 0 0 0 1^ 111 ) 以下であればよく、 9 〇!以下、 8 〇!以下、 7 以下、

Figure imgf000111_0001
[0388] The waterproof/moisture permeable layer 2 of the waterproof/moisture permeable fabric according to the sixth embodiment is made of a nonwoven fabric containing ultrafine fibers having a fiber diameter of 10 or less. The fiber diameter means the diameter of the smallest circle that surrounds the cross section of the short fiber perpendicular to the longitudinal direction. The fiber diameter of the ultrafine fibers may be 1 0 0 1 (1 0 0 0 0 1^111) or less, and 9 0! or less, 8 0! or less, 7 or less,
Figure imgf000111_0001

6 0 0 1^〇!以下、

Figure imgf000111_0002
以下、
Figure imgf000111_0003
以下、
Figure imgf000111_0004
以下、 又は6 0 0 1^〇 or less,
Figure imgf000111_0002
Less than,
Figure imgf000111_0003
Less than,
Figure imgf000111_0004
Below, or

2 0 0^ 以下であってよい。 極細繊維の繊維径は、 例えば、 1 0 n

Figure imgf000111_0005
、 2 0 1^〇!以上、 3 0 1^〇!以上、 4 0 1^ 以上、 5 0 1^ 以上、 6 0 以 上、 7 0 1^〇!以上、 8 0 1^〇!以上、
Figure imgf000111_0006
以上、
Figure imgf000111_0007
以上、 2 0 0 n〇!以上、 3 0 0 1^〇!以上、 4 0 0 1^ 以上、 5 0 0 1^ 以上、
Figure imgf000111_0008
以上、 7 0 0 1^〇!以上、
Figure imgf000111_0009
以上、
Figure imgf000111_0010
以上、 1 以上、 2 111以上、 3 〇!以上、 4 〇!以上又は 5 〇!以上であってよい。 It may be less than 200^. The fiber diameter of the ultrafine fibers is, for example, 10 n
Figure imgf000111_0005
, 2 0 1^〇! or more, 3 0 1^〇! or more, 4 0 1^ or more, 5 0 1^ or more, 6 0 or more, 7 0 1^〇! or more, 8 0 1^〇! or more,
Figure imgf000111_0006
that's all,
Figure imgf000111_0007
Above, 2 0 0 n 〇! or above, 3 0 0 1^ 〇! or above, 4 0 0 1^ or above, 5 0 0 1^ or above,
Figure imgf000111_0008
Or more, 7 0 0 1^ 〇! or more,
Figure imgf000111_0009
that's all,
Figure imgf000111_0010
This may be 1 or more, 2 111 or more, 30! or more, 40! or more, or 50! or more.

[0389] 極細繊維は、 繊維径の条件を満たす限り、 任意の材料で形成されたもので あってよい。 極細繊維は、 例えば、 タンパク質繊維、 ナイロン及びポリエス テル等の合成繊維、 キュプラ、 レーヨン及びリヨセル等の再生繊維、 綿、 麻 〇 2020/175702 1 1 1 卩（：171? 2020 /008524 [0389] The ultrafine fibers may be formed of any material as long as the fiber diameter condition is satisfied. Ultrafine fibers include, for example, protein fibers, synthetic fibers such as nylon and polyester, regenerated fibers such as cupra, rayon and lyocell, cotton and hemp. 〇 2020/175 702 1 1 1 卩 (: 171? 2020 /008524

及び絹等の天然繊維であってよい。 And natural fibers such as silk.

[0390] 極細繊維は、 タンパク質繊維であることが好ましい。 タンパク質繊維とし ては、 改変フィブロインを含むことが好ましく、 改変クモ糸フィブロインを 含むことがより好ましい。 改変フィブロイン （好ましくは、 改変クモ糸フィ ブロイン） を含むことにより、 本実施形態に係る防水透湿性生地に保温性、 吸湿発熱性及び/又は難燃性の性質を更に付与することができ、 生地として の価値がより高くなる。 改変フィブロインは、 改変フィブロイン繊維 （タン パク質繊維） として極細繊維に含まれていてもよい。 改変フィブロインの好 ましい態様は後述する。 [0390] The ultrafine fibers are preferably protein fibers. The protein fiber preferably contains modified fibroin, more preferably modified spider silk fibroin. By containing the modified fibroin (preferably modified spider silk fibroin), the waterproof and moisture-permeable fabric according to the present embodiment can be further imparted with heat retention, moisture absorption and heat generation properties, and/or flame retardant properties. The value of as is higher. The modified fibroin may be contained in the ultrafine fiber as modified fibroin fiber (protein fiber). Preferred embodiments of modified fibroin will be described later.

[0391 ] 不織布は、 極細繊維のみを含むものであってもよく、 極細繊維に加えて他 の繊維 （繊維径 1 〇 超のもの） を含むものであってもよい。 すなわち、 不織布の形成に用いられる繊維 （ 「材料糸」 ともいう。 ） として、 極細繊維 のみからなる単独糸、 極細繊維と他の繊維 （繊維径 1 〇 超のもの） とを 組み合わせてなる複合糸 （例えば、 混紡糸、 混繊糸、 カバーリング糸等。 ） が、 それぞれ単独で、 又はそれらが組み合わされて用いられてもよい。 上記 単独糸及び上記複合糸は、 短繊維を撚り合わせたスパン糸であってもよく、 長繊維を撚り合わせたフィラメント糸であってもよい。 上記単独糸及び上記 複合糸としては、 フィラメント糸が好適に用いられる。 他の繊維 （繊維径 1 〇 超のもの） と組み合わせて使用する場合には、 不織布に占める極細繊 維の割合は、 不織布の全質量を基準として、 例えば、 3 0質量％以上、 4 0 質量％以上、 5 0質量％以上、 6 0質量％以上、 7 0質量％以上、 8 0質量 %以上、 9 0質量％以上、 又は 9 5質量％以上であってよい。 [0391] The nonwoven fabric may contain only ultrafine fibers, or may contain other fibers (having a fiber diameter of more than 10) in addition to the ultrafine fibers. That is, as the fibers (also referred to as “material yarns”) used for forming the non-woven fabric, a single yarn made of only ultrafine fibers, or a composite yarn made by combining ultrafine fibers with other fibers (having a fiber diameter of more than 10). (For example, blended yarn, blended yarn, covering yarn, etc.) may be used alone or in combination. The single yarn and the composite yarn may be spun yarn in which short fibers are twisted together, or filament yarn in which long fibers are twisted together. A filament yarn is preferably used as the single yarn and the composite yarn. When used in combination with other fibers (having a fiber diameter of more than 10), the proportion of ultrafine fibers in the nonwoven fabric is, for example, 30% by mass or more, 40% by mass or more, based on the total mass of the nonwoven fabric. % Or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more.

[0392] 不織布は、 例えば、 繊維径 1 〇 以下の極細繊維を少なくとも一部に含 む繊維を用いて、 公知の製造方法により製造することができる。 具体的には 、 例えば、 繊維径 1 〇 以下の極細繊維を少なくとも一部に含む繊維から 、 乾式法、 湿式法及びエアレイ ド法等でウェブ （単層ウェブ、 及び積層ウェ ブを含む。 ） を形成させた後、 ケミカルボンド法 （浸潰法、 スプレー法等） 及び二ードルパンチ法等によりウェブの繊維間を結合させて、 不織布を得る 〇 2020/175702 112 卩（：171? 2020 /008524 [0392] The non-woven fabric can be manufactured by a known manufacturing method using, for example, a fiber containing at least a portion of ultrafine fibers having a fiber diameter of 10 or less. Specifically, for example, a web (including a single-layer web and a laminated web) is formed by a dry method, a wet method, an air-laid method, or the like from a fiber including at least a part of ultrafine fibers having a fiber diameter of 10 or less. After forming, the fibers of the web are bonded by the chemical bond method (immersion method, spray method, etc.) and the needle punch method, etc. to obtain a non-woven fabric. 〇 2020/175 702 112 卩 (: 171-1? 2020 /008524

ことができる。 be able to.

[0393] 不織布がタンパク質極細繊維を含む場合、 更に以下の製造方法を例示でき る。 すなわち、 例えば、 タンパク質を、 ジメチルスルホキシド （口1\/13〇） [0393] In the case where the nonwoven fabric contains protein ultrafine fibers, the following production method can be further exemplified. That is, for example, the protein is dimethyl sulfoxide (mouth 1\/130)

、 1\1, 1\1 -ジメチルホルムアミ ド （01\/1 ） 、 ギ酸、 又はヘキサフルオロイ ソプロパノール （1~1 I ） 等の溶媒に、 必要に応じて、 溶解促進剤として の無機塩と共に添加し、 溶解してドープ液を作製した後、 当該ドープ液を用 いてエレクトロスピニング法 （静電紡糸法） により紡糸することにより得る こともできる。 エレクトロスピニング法で得られるタンパク質極細繊維の平 均繊維径 （繊維径の平均値） は、 通常、 1 0000门 以下であり、 好まし くは 1 0001^ 111以下であり、

Figure imgf000113_0001
00001^ 111、
Figure imgf000113_0002
, 1\1, 1\1-Dimethylformamide (01\/1 ), formic acid, or hexafluoroisopropanol (1 to 1 I) as a solvent, if necessary, as an inorganic It can also be obtained by adding a salt and dissolving it to prepare a dope solution, and spinning the dope solution by an electrospinning method (electrostatic spinning method). The average fiber diameter (average fiber diameter) of the protein ultrafine fibers obtained by the electrospinning method is usually 10000 or less, preferably 1 0001^111 or less,
Figure imgf000113_0001
00001^111,
Figure imgf000113_0002

50001^ 111、

Figure imgf000113_0003
00011111、 200
Figure imgf000113_0004
90011111、 又は 300 n m~ 800 n mであってもよい。 タンパク質極細繊維の繊維径は、
Figure imgf000113_0005
50001^111,
Figure imgf000113_0003
00011111, 200
Figure imgf000113_0004
It may be 90011111, or 300 nm to 800 nm. The fiber diameter of protein ultrafine fiber is
Figure imgf000113_0005

0001^ 111 （1 〇〇 の間で変動してもよい。 It may vary between 0001^111 (100).

[0394] 不織布は、 繊維密度 （目付） 、 空隙率、 かさ密度等の数値範囲が、 防水性 と透湿性とを充分に確保し得る範囲となるように適宜設定される。 なお、 そ れら目付、 空隙率、 かさ密度等の調整は、 例えば、 ウェブを構成する繊維量 を増減すること、 積層ウェブの場合は、 積層数を増減することにより行うこ とができる。 [0394] The non-woven fabric is appropriately set such that the numerical ranges of the fiber density (weight per unit area), the porosity, the bulk density, etc. are within a range in which waterproofness and moisture permeability can be sufficiently ensured. The unit weight, porosity, bulk density and the like can be adjusted, for example, by increasing or decreasing the amount of fibers constituting the web, and in the case of a laminated web, increasing or decreasing the number of layers.

[0395] 不織布は、 機能性が付与された不織布であってもよい。 不織布への機能性 の付与は、 上述した編織体に機能性を付与する方法に準じて実施することが できる。 [0395] The nonwoven fabric may be a nonwoven fabric provided with functionality. Functionality can be imparted to the nonwoven fabric according to the method for imparting functionality to the knitted or woven body described above.

[0396] _実施形態において、 第 6実施形態に係る防水透湿性生地は、 防水透湿層 の表皮層が接合された面の反対側の面に裏材層 （編織体） が更に接合されて いてもよい。 裏材層の好ましい態様としては、 表皮層で例示した態様が挙げ られる。 表皮層と裏材層は、 それぞれ同一の材料で形成された編織体であっ てもよく、 異なる材料で形成された編織体であってもよい。 なお、 裏材層は 、 表皮層と同様に機能性が付与された編織体からなるものであってもよいし 〇 2020/175702 1 13 卩（：171? 2020 /008524 [0396] In the embodiment, in the waterproof/moisture permeable fabric according to the sixth embodiment, a backing material layer (woven body) is further bonded to the surface of the waterproof/moisture permeable layer opposite to the surface to which the skin layer is bonded. You may stay. Preferred embodiments of the backing layer include the embodiments exemplified for the skin layer. The skin layer and the backing layer may be knitted fabrics made of the same material, or may be knitted fabrics made of different materials. The backing layer may be made of a knitted or woven body having the same functionality as the skin layer. 〇 2020/175 702 1 13 卩(：171? 2020/008524

、 単なる編織体からなるものであってもよい。 It may be composed of a simple knitted body.

[0397] 第 6実施形態に係る防水透湿性生地は、 防水透湿層と表皮層とを接合して 得ることができる。 防水透湿層と表皮層との接合方法は、 不織布及び編織体 に使用する素材に応じて、 適宜選択することができる。 接合方法として、 例 えば、 防水透湿層と表皮層とを、 熱又は溶剤等により、 溶着する方法、 防水 透湿層と表皮層とを接着剤を介して接着する方法、 不織布と編織体の少なく ともいずれか一方の接合面にプラズマを照射して、 ラジカル反応により共有 結合を形成させることで、 防水透湿層と表皮層とを接合する方法等が挙げら れる。 例えば、 不織布及び編織体がいずれもタンパク質 （タンパク質極細繊 維又はタンパク質繊維） を含む場合、 防水透湿層及び表皮層の接合面のうち 一方又は両方にタンパク質を溶解する溶媒 （例えば、 ジメチルスルホキシド

Figure imgf000114_0001
1\1 , 1\1 -ジメチルホルムアミ ド （0 1\/1 ） 、 ギ酸、 又はヘキ サフルオロイソプロパノール （1~1 I ） 等の有機溶媒、 それらに溶解促進 剤としての無機塩を添加した溶液、 又は水、 若しくは水に無機塩等を添加し た水溶液） を塗布した後、 防水透湿層及び表皮層を貼り合わせ、 更に溶媒を 除去することで防水透湿層と表皮層とを接合することができる。 [0397] The waterproof moisture-permeable fabric according to the sixth embodiment can be obtained by joining the waterproof moisture-permeable layer and the skin layer. The method for joining the waterproof moisture-permeable layer and the skin layer can be appropriately selected according to the materials used for the nonwoven fabric and the knitted fabric. As a joining method, for example, a waterproof moisture-permeable layer and a skin layer are welded together by heat or a solvent, a waterproof moisture-permeable layer and a skin layer are bonded together with an adhesive, and a nonwoven fabric and a knitted fabric are joined. Examples include a method in which at least one of the bonding surfaces is irradiated with plasma to form a covalent bond by a radical reaction, so that the waterproof moisture-permeable layer and the skin layer are bonded. For example, when both the non-woven fabric and the woven fabric contain a protein (protein ultrafine fiber or protein fiber), a solvent that dissolves the protein in one or both of the joint surfaces of the waterproof and moisture permeable layer and the epidermis layer (for example, dimethyl sulfoxide).
Figure imgf000114_0001
Organic solvents such as 1\1, 1\1-dimethylformamide (0 1\/1 ), formic acid, or hexafluoroisopropanol (1 to 1 I), to which inorganic salts as a dissolution promoter were added Solution or water, or an aqueous solution in which an inorganic salt or the like is added to water) is applied, and then the waterproof and moisture permeable layer and the skin layer are bonded together, and the solvent is further removed to bond the waterproof and moisture permeable layer to the skin layer. can do.

[0398] また、 不織布をエレクトロスピニング法で形成する場合、 防水透湿層を表 皮層上に形成する防水透湿層形成工程を備える製造方法により、 防水透湿性 生地を得ることができる。 防水透湿層形成工程は、 繊維原料を含有するドー プ液を使用したエレクトロスピニングにより、 表皮層上に極細繊維を集積さ せて不織布を形成させることを含む。 [0398] Further, when the nonwoven fabric is formed by the electrospinning method, the waterproof and moisture-permeable fabric can be obtained by a manufacturing method including a waterproof and moisture-permeable layer forming step of forming a waterproof and moisture-permeable layer on the skin layer. The waterproof/moisture permeable layer forming step includes forming ultra-fine fibers on the skin layer to form a nonwoven fabric by electrospinning using a dope solution containing a fiber raw material.

[0399] エレクトロスピニング法 （静電紡糸法） は、 供給側電極 （紡糸口金と兼用 できる） と捕集側電極 （例えば、 金属口ール又は金属ネッ ト等） 間に電圧を 印加し、 紡糸口金から押し出したドープ液に電荷を与えて捕集側電極に吹き 飛ばす。 この際にドープ液は伸張されて繊維形成される。 印加電圧は、 通常 5〜 1 0 0 Vであり、 好ましくは 1 〇〜 5 0 Vである。 電極間距離は、

Figure imgf000114_0002
好ましくは 2〜 2 0〇 である。 [0399] In the electrospinning method (electrospinning method), a voltage is applied between a supply-side electrode (which can also be used as a spinneret) and a collection-side electrode (for example, a metal nozzle or a metal net) to perform spinning. An electric charge is given to the dope solution extruded from the die and blown to the collection side electrode. At this time, the dope solution is stretched to form fibers. The applied voltage is usually 5 to 100 V, and preferably 10 to 50 V. The distance between the electrodes is
Figure imgf000114_0002
It is preferably 2 to 200.

[0400] 図 4は、 一実施形態に係るエレクトロスピニング装置 1 0 0の説明図であ 〇 2020/175702 1 14 卩（：171? 2020 /008524 [0400] FIG. 4 is an explanatory diagram of an electrospinning apparatus 100 according to an embodiment. 〇 2020/175 702 1 14 卩 (：171? 2020 /008524

る。 金属製口金ノズル 3 3 （供給側電極） と金属製ネッ ト 3 8 （捕集側電極 ） との間に電源 3 5により電圧をかける。 マイクロシリンジ 3 1内のドープ 液 3 2をシリンジポンプを用いて矢印 方向に移動させ、 金属製口金ノズル 3 3からドープ液 3 2を押し出し、 電荷によってドープ液を伸張し繊維状物 3 6にして金属製ネッ ト 3 8の表面に集積させることで、 極細繊維を含む不 織布 3 9を得ることができる。 また、 このとき、 金属製ネッ ト 3 8の表面に 表皮層 （編織体） を載置することで、 表皮層上に極細繊維を集積させて不織 布を形成させることもできる。 また、 表皮層 （編織体） の面上に接着剤、 又 は編織体と不織布の少なくともいずれか一方を溶解させる溶媒等を塗布して おくことで、 形成された不織布と、 編織体とを接合させることもできる。 得 られた不織布は、 次いで溶媒を離脱してもよい。 溶媒 （ドープ液中の溶媒や 編織体又は不織布に塗布された溶媒等） を脱離する方法としては、 例えば、 減圧乾燥又は脱溶媒槽への浸潰が挙げられる。 It A voltage is applied between the metal nozzle 3 3 (supply side electrode) and the metal net 3 8 (collection side electrode) by the power supply 35. The dope solution 32 in the microsyringe 31 is moved in the direction of the arrow using a syringe pump, the dope solution 32 is extruded from the metal die nozzle 33, and the dope solution is expanded by the electric charge to form the fibrous material 36. By accumulating on the surface of the metal net 38, a non-woven fabric containing ultrafine fibers 39 can be obtained. Further, at this time, by placing a skin layer (woven body) on the surface of the metal net 38, it is possible to accumulate ultrafine fibers on the skin layer to form a non-woven fabric. In addition, by bonding an adhesive agent or a solvent that dissolves at least one of the knitted fabric and the nonwoven fabric onto the surface of the skin layer (knitted fabric), the formed nonwoven fabric and the knitted fabric are joined. You can also let it. The resulting non-woven fabric may then be stripped of solvent. Examples of the method for removing the solvent (the solvent in the dope solution, the solvent applied to the knitted fabric or the nonwoven fabric, etc.) include vacuum drying or immersion in a desolvation tank.

[0401 ] 第 6実施形態に係る防水透湿性生地において、 不織布又は編織体に含まれ るタンパク質極細繊維又はタンパク質繊維の原料となるタンパク質には、 特 に制限はなく、 任意のタンパク質を使用することができる。 タンパク質の具 体的な態様は、 第 1の発明に係る防水透湿性生地で説明した態様を適用でき る。 使用するタンパク質としては、 防水透湿性に加え、 保温性、 吸湿発熱性 及び/又は難燃性にも優れることから、 改変フィブロインが好ましく、 改変 クモ糸フィブロインがより好ましい。 タンパク質極細繊維及び/又はタンパ ク質繊維が、 改変フィブロイン （好ましくは、 改変クモ糸フィブロイン） を 含むことにより、 本実施形態に係る防水透湿性生地に保温性、 吸湿発熱性及 び/又は難燃性の性質を更に付与することができ、 生地としての価値がより 高くなる。 [0401] In the waterproof and moisture-permeable fabric according to the sixth embodiment, there is no particular limitation on the protein as a raw material of the protein ultrafine fibers or protein fibers contained in the nonwoven fabric or the knitted fabric, and any protein may be used. You can As the concrete aspect of the protein, the aspect explained in the waterproof and moisture-permeable fabric according to the first invention can be applied. As the protein to be used, modified fibroin is preferable, and modified spider silk fibroin is more preferable, because it is excellent in heat retention, moisture absorption and heat generation property, and/or flame retardancy in addition to waterproof moisture permeability. By containing the modified fibroin (preferably the modified spider silk fibroin) in the protein ultrafine fiber and/or protein fiber, the waterproof and moisture-permeable fabric according to the present embodiment can retain heat, absorb heat and/or flame retardantly. It is possible to add more sexual character, and it becomes more valuable as a fabric.

[0402] 本実施形態に係るタンパク質は、 当該タンパク質をコードする核酸を使用 して、 常法により製造することができる。 当該タンパク質をコードする核酸 は、 塩基配列情報に基づいて、 化学合成してもよく、

Figure imgf000115_0001
法等を利用して 合成してもよい。 〇 2020/175702 1 15 卩（：171? 2020 /008524 [0402] The protein according to the present embodiment can be produced by a conventional method using a nucleic acid encoding the protein. The nucleic acid encoding the protein may be chemically synthesized based on the nucleotide sequence information,
Figure imgf000115_0001
It may be synthesized using a method or the like. 〇 2020/175 702 1 15 卩(：171? 2020/008524

［0403］ タンパク質極細繊維又はタンパク質繊維は、 例えば、 タンパク質を溶解可 能な溶媒で溶解させてドープ液とし、 湿式紡糸、 乾式紡糸、 乾湿式紡糸又は 溶融紡糸等の公知の紡糸方法により紡糸して得ることができる。 タンパク質 極細繊維は、 上述したエレクトロスピニング法により紡糸して得ることが好 ましい。 タンパク質を溶解可能な溶媒としては、 例えば、 ジメチルスルホキ シド

Figure imgf000116_0001
1\1 , 1\1 -ジメチルホルムアミ ド （0 1\/1 ） 、 ギ酸、 及び ヘキサフルオロイソプロパノール （1~1 丨 ） 等が挙げられる。 当該溶媒に は、 溶解促進剤として無機塩を添加してもよい。 [0403] The protein ultrafine fiber or protein fiber is prepared by, for example, dissolving a protein in a solvent capable of dissolving it into a dope solution, and spinning the solution by a known spinning method such as wet spinning, dry spinning, dry wet spinning or melt spinning. Obtainable. The protein ultrafine fibers are preferably obtained by spinning by the electrospinning method described above. Solvents capable of dissolving proteins include, for example, dimethyl sulfoxide
Figure imgf000116_0001
1\1, 1\1-dimethylformamide (0 1\/1), formic acid, and hexafluoroisopropanol (1 to 1) are listed. An inorganic salt may be added to the solvent as a dissolution promoter.

実施例 Example

［0404］ 以下、 試験例等に基づいて本発明をより具体的に説明する。 ただし、 本発 明は以下の試験例に限定されるものではない。 [0404] Hereinafter, the present invention will be described more specifically based on test examples and the like. However, the present invention is not limited to the following test examples.

［0405］ 〔参考例 1 :改変フイブロインの製造〕 [0405] [Reference Example 1: Production of modified fibroin]

配列番号 1 8で示されるアミノ酸配列を有する改変クモ糸フイブロイン （ ［¾丁 3 9 9） 、 配列番号 1 2で示されるアミノ酸配列を有する改変クモ糸 フイブロイン （ ［¾丁3 8 0） 、 配列番号 1 3で示されるアミノ酸配列を有 する改変クモ糸フイブロイン （ ［¾丁4 1 0） 、 配列番号 3 7で示されるア ミノ酸配列を有する改変フイブロイン （ ［¾丁 9 1 8） 、 配列番号 4 0で示 されるアミノ酸配列を有する改変フイブロイン （ ［¾丁 9 6 6） 、 及び配列 番号 1 5で示されるアミノ酸配列を有する改変フイブロイン （ ［¾丁 7 9 9 ） を設計した。 設計した改変フイブロインをコードする核酸を合成した。 当 該核酸には、 5’ 末端に 6 丨サイ ト、 終止コドン下流に巳〇〇

Figure imgf000116_0002
丨サイ 卜を付加した。 この核酸をクローニングベクター （ 11〇 1 1 8） にクロー ニングした。 その後、 同核酸を 6 丨及び巳〇〇
Figure imgf000116_0003
丨で制限酵素処理して 切り出した後、 タンパク質発現べクター 巳丁_ 2 2匕 （+） に組換えて発 現べクターを得た。 Modified spider silk fibroin having the amino acid sequence shown in SEQ ID NO: 18 ([¾ 3 9)], Modified spider silk fibroin having the amino acid sequence shown in SEQ ID NO: 12 ([¾ 380), SEQ ID NO: Modified spider silk fibroin having the amino acid sequence shown in 13 ([¸d 10 4), Modified fibroin having the amino acid sequence shown in SEQ ID NO: 37 ([d 9 9]), SEQ ID NO 4 A modified fibroin having an amino acid sequence represented by 0 ([¸966)] and a modified fibroin having an amino acid sequence represented by SEQ ID NO: 15 ([¸7999) were designed. A nucleic acid encoding the designed modified fibroin was synthesized. The nucleic acid contains 6 sites at the 5'end and a sequence at the downstream of the stop codon.
Figure imgf000116_0002
Added saisai. This nucleic acid was cloned into a cloning vector (110 1 118). After that, the same nucleic acid was added to 6
Figure imgf000116_0003
After digestion with restriction enzyme treatment and excision, it was recombined into the protein expression vector _22_(+) to obtain the expression vector.

［0406］ 得られた発現べクターで、 大腸菌巳 !_［¾ （0 £ 3） を形質転換した。 当該 形質転換大腸菌を、 アンピシリンを含む 2 !_の !_巳培地で 1 5時間培養し た。 当該培養液を、 アンピシリンを含む 1 〇〇 !_のシード培養用培地 （表 4） に〇0600が〇. 005となるように添加した。 培養液温度を 30°〇に保 ち、 〇口 6〇〇が 5になるまでフラスコ培養を行い （約 1 5時間） 、 シード培養 液を得た。 [0406] The obtained expression vector was used to transform Escherichia coli !_[¾ (0 £ 3). The transformed Escherichia coli was cultured for 15 hours in 2 !_! culture medium containing ampicillin. The culture solution was added to a seed culture medium containing ampicillin (see Table 1). 4) was added so that 0 600 would be 0.005. Chi holding the culture temperature to 30 ° 〇 performs flask culture to 〇 neck 6 hundred becomes 5 (about 1 5 hours), to obtain a seed culture.

[0407] [表 4] [0407] [Table 4]

シード培養用培地

Figure imgf000117_0001
Seed culture medium
Figure imgf000117_0001

[0408] 当該シード培養液を 500 !_の生産培地 （表 5） を添加したジャーファ —メンターに〇0600が〇. 05となるように添加した。 培養液温度を 37°〇 に保ち、 1~16. 9で一定に制御して培養した。 また培養液中の溶存酸素濃 度を、 溶存酸素飽和濃度の 20 %に維持するようにした。 Was Rei_0 to mentor 600 is added to a 〇 05 - [0408] Jafa said that the seed culture solution was added to 500 _ of production medium (Table 5)!.. The temperature of the culture solution was kept at 37 ° and the culture was carried out while controlling the culture temperature at 1 to 16.9. In addition, the dissolved oxygen concentration in the culture solution was maintained at 20% of the dissolved oxygen saturation concentration.

[0409] [表 5] [0409] [Table 5]

生産培地 Production medium

Figure imgf000117_0002
Figure imgf000117_0002

[0410] 生産培地中のグルコースが完全に消費された直後に、 フイード液 （グルコ —ス 455 g/1 L、 Ye a s t E x t r a c t 1 20 g/1 L） を 1 m L/分の速度で添加した。 培養液温度を 37 °Cに保ち、 p H 6. 9で一定 に制御して培養した。 また培養液中の溶存酸素濃度を、 溶存酸素飽和濃度の 20%に維持するようにし、 20時間培養を行った。 その後、 1 Mのイソプ ロピルー/ S—チオガラクトピラノシド （丨 PTG） を培養液に対して終濃度 1 mMになるよう添加し、 改変フイブロインを発現誘導させた。 丨 PTG添 加後 20時間経過した時点で、 培養液を遠心分離し、 菌体を回収した。 丨 P TG添加前と I PTG添加後の培養液から調製した菌体を用いて S DS— P AGEを行い、 丨 PTG添加に依存した目的とする改変フィブロインサイズ のバンドの出現により、 目的とする改変フィブロインの発現を確認した。 [0410] Immediately after the glucose in the production medium was completely consumed, feed solution (glucose 455 g/1 L, Ye ast Extract 1 20 g/1 L) was added at a rate of 1 mL/min. did. The temperature of the culture solution was kept at 37 °C, and the culture was performed at a constant pH of 6.9. Further, the dissolved oxygen concentration in the culture solution was maintained at 20% of the dissolved oxygen saturated concentration, and the culture was carried out for 20 hours. Then, 1 M isopropyru/S-thiogalactopyranoside (丨 PTG) was added to the culture solution to a final concentration of 1 mM to induce the expression of the modified fibroin. At 20 hours after adding PTG, the culture was centrifuged to collect the cells.丨 P SDS-PAGE was performed using cells prepared from the culture medium before TG addition and after I PTG addition, and the appearance of the desired modified fibroin size band depending on the addition of PTG resulted in the desired modified fibroin. The expression was confirmed.

[0411] I PTGを添加してから 2時間後に回収した菌体を 2 OmM T r i s - HC I b u f f e r （p H 7. 4） で洗浄した。 洗浄後の菌体を約 1 m M の PMS Fを含む 20mM T r i s— HC I緩衝液 （ p H 7. 4） に懸濁 させ、 高圧ホモジナイザー （GEA N i r o S o a v i社製） で細胞を 破砕した。 破砕した細胞を遠心分離し、 沈殿物を得た。 得られた沈殿物を、 高純度になるまで 20 mM T r i s -HC I緩衝液 （ p H 7. 4） で洗浄 した。 洗浄後の沈殿物を 1 00m g/mLの濃度になるように 8M グアニ ジン緩衝液 （ 8 M グアニジン塩酸塩、 1 0 m M リン酸二水素ナトリウム 、 20 mM N aC I、 1 mM T r i s -HC I、 p H 7. 0） で懸濁し 、 60°Cで 30分間、 スターラーで撹拌し、 溶解させた。 溶解後、 透析チユ —ブ （三光純薬株式会社製のセルロースチユーブ 36/32） を用いて水で 透析を行った。 透析後に得られた白色の凝集タンパク質を遠心分離により回 収し、 凍結乾燥機で水分を除き、 凍結乾燥粉末を回収することにより、 改変 フイブロイン （P RT399、 P RT380、 P RT4 1 0、 P RT 9 1 8 、 P RT 966及び P RT 799） を得た。 [0411] The cells collected 2 hours after the addition of I PTG were washed with 2 OmM Tris-HC I buffer (pH 7.4). The washed cells were suspended in 20 mM Tris-HC I buffer (pH 7.4) containing about 1 mM PMS F, and the cells were disrupted with a high-pressure homogenizer (GEANiro Soavi). did. The disrupted cells were centrifuged to obtain a precipitate. The obtained precipitate was washed with 20 mM Tris-HC I buffer (pH 7.4) until it became highly pure. Adjust the washed precipitate to a concentration of 100 mg/mL with 8 M guanidine buffer (8 M guanidine hydrochloride, 10 mM sodium dihydrogen phosphate, 20 mM NaCI, 1 mM Tris- HCI, pH 7.0), and stirred at 60 ° C for 30 minutes with a stirrer to dissolve. After the dissolution, dialysis was performed with water using a dialysis tube (Cellulose tube 36/32 manufactured by Sanko Junyaku Co., Ltd.). The white aggregated protein obtained after dialysis was recovered by centrifugation, the water was removed using a freeze dryer, and the freeze-dried powder was recovered to obtain the modified fibroin (P RT399, P RT380, P RT410, P RT). 9 18 and P RT 966 and P RT 799) were obtained.

[0412] P R T 9 1 8及び P R T 966は、 平均 H 丨が 0超である疎水性改変フィ ブロインである。 P R T 799は、 平均 H 丨が 0以下である親水性改変フィ ブロインである。 [0412] PRT 918 and PRT 966 are hydrophobically modified fibroins with an average H> 0. PRT 799 is a hydrophilically modified fibroin with an average H 2 of 0 or less.

[0413] 〔試験例 1 :改変フィブロインを含む編織体の製造及び難燃性評価〕 [0413] [Test Example 1: Production of a knitted fabric containing modified fibroin and evaluation of flame retardancy]

4. 0質量％になるように L i C I を溶解させたジメチルスルホキシド （ DMSO） を溶媒として用意し、 そこに改変フィブロイン （P RT 799） の凍結乾燥粉末を、 濃度 24質量％となるよう添加し、 シエーカーを使用し て 3時間溶解させた。 その後、 不溶物と泡を取り除き、 改変フィブロイン溶 液 （紡糸原液） を得た。 Prepare dimethylsulfoxide (DMSO) in which LiCI was dissolved to 4.0 mass% as a solvent, and add lyophilized powder of modified fibroin (P RT 799) to a concentration of 24 mass%. Then, it was dissolved for 3 hours using a shaker. Then, the insoluble matter and bubbles were removed to obtain a modified fibroin solution (spinning stock solution).

[0414] 調製した紡糸原液を 90°Cにて目開き 5 Mmの金属フィルターで濾過し、 〇 2020/175702 1 18 卩（：171? 2020 /008524 [0414] The prepared spinning dope was filtered at 90°C with a metal filter having an opening of 5 Mm, 〇 2020/175 702 1 18 卩 (：171? 2020 /008524

次いで 3 0 1_のステンレスシリンジ内で静置し、 脱泡させた後に、 二ード ル径〇.

Figure imgf000119_0001
ドノズルから 1 0 0質量％メタノール凝固浴槽中へ 吐出させた。 吐出温度は 9 0 °〇であった。 凝固後、 得られた原糸を巻き取り 、 自然乾燥させて改変フィブロイン繊維 （原料繊維） を得た。 Then, let it stand still in a stainless steel syringe of 301_1 to defoam, and then double needle diameter ○.
Figure imgf000119_0001
It was discharged from a nozzle into a 100 mass% methanol coagulation bath. The discharge temperature was 90 ° . After coagulation, the obtained raw yarn was wound and naturally dried to obtain modified fibroin fiber (raw fiber).

[0415] 得られた原料繊維 （撚り合せたフィラメント糸） を使用して、 丸編機を使 用した丸編みで編地を製造した。 編地は、 太さ 1 8 0デニール、 ゲージ数 1 8とした。 得られた編地から 2 0 9切り出して試験片とした。 [0415] A knitted fabric was produced by circular knitting using a circular knitting machine, using the obtained raw material fibers (filament yarns twisted together). The knitted fabric had a thickness of 180 denier and a gauge of 18. 209 pieces were cut out from the obtained knitted fabric to give test pieces.

[0416] 燃焼性試験は、 消防庁危険物規制課長 消防危 5 0号平成 7年 5月 3 1 日 の粉粒状又は融点の低い合成樹脂の試験方法に準拠した。 試験は、 温度 2 2 °〇、 相対湿度 4 5 %、 気圧 1 0 2 1 II 3の条件下で実施した。 測定結果 （ 酸素濃度 （％） 、 燃焼率 （％） 、 換算燃焼率 （％） ） を表 6に示す。 [0416] The flammability test complied with the test method for powdery or granular or low melting point synthetic resin of Fire Department Dangerous Goods Regulations No. 50 May 31, 1995, Director, Hazardous Materials Control Division. The test was conducted under the conditions of a temperature of 22°, a relative humidity of 45%, and an atmospheric pressure of 1021II3. Table 6 shows the measurement results (oxygen concentration (%), burning rate (%), converted burning rate (%)).

[表 6] [Table 6]

Figure imgf000119_0002
Figure imgf000119_0002

[0417] 難燃性試験の結果、 改変フイブロイン （ 丁 7 9 9） 繊維で編んだ編地 の限界酸素指数 （!_〇 丨） 値は 2 7 . 2であった。 一般に !_〇 丨値が 2 6以 上あれば難燃性があるとされる。 改変フイブロインは、 難燃性に優れている ことが分かる。 改変フイブロインを含む繊維を使用して編織体を編成又は織 成することで、 機能性 （難燃性） を有する編織体を得ることができる。 [0417] As a result of the flame retardancy test, the limit oxygen index (!_〇丨) value of the knitted fabric made of the modified fibroin (Ding 799) fiber was 27.2. Generally, if the value of !_○ is above 26, it is considered to be flame retardant. It can be seen that the modified fibroin has excellent flame retardancy. By knitting or weaving a knitted fabric using fibers containing modified fibroin, a knitted fabric having functionality (flame retardancy) can be obtained.

[0418] 〔試験例 2 :改変フイブロインを含む編織体の製造及び吸湿発熱性評価〕 [0418] [Test Example 2: Production of a knitted fabric containing modified fibroin and evaluation of heat absorption by moisture absorption]

4 . 0質量％になるように !_ 丨 〇 I を溶解させたジメチルスルホキシド （ を溶媒として用意し、 そこに改変フイブロインの凍結乾燥粉末を 、 濃度 2 4質量％となるよう添加し、 シエーカーを使用して 3時間溶解させ 〇 2020/175702 119 卩（：171? 2020 /008524 Prepare dimethyl sulfoxide () in which !_ 〇I is dissolved to a concentration of 4.0% by mass as a solvent, add lyophilized powder of modified fibroin to the concentration of 24% by mass, and add a shaker. Use and dissolve for 3 hours 〇 2020/175 702 119 卩(: 171-1? 2020/008524

た。 その後、 不溶物と泡を取り除き、 改変フィブロイン溶液 （紡糸原液） を 得た。 It was Then, the insoluble matter and bubbles were removed to obtain a modified fibroin solution (spinning stock solution).

[0419] 調製した紡糸原液を 60°〇にて目開き 5 の金属フィルターで濾過し、 次いで 30 1_のステンレスシリンジ内で静置し、 脱泡させた後に、 二ード ル径〇. 2

Figure imgf000120_0001
のソリッ ドノズルから 1 00質量％メタノール凝固浴槽中へ 吐出させた。 吐出温度は 60°〇であった。 凝固後、 得られた原糸を巻き取り 、 自然乾燥させて改変フィブロイン繊維 （原料繊維） を得た。 [0419] The prepared spinning solution was filtered at 60° with a metal filter having an opening of 5, and then allowed to stand in a stainless syringe of 301_ to be defoamed, and then the diameter of the needle with a diameter of 0.2.
Figure imgf000120_0001
It was discharged from the solid nozzle of 100 into a 100 mass% methanol coagulation bath. The discharge temperature was 60 ° . After coagulation, the obtained raw yarn was wound and naturally dried to obtain modified fibroin fiber (raw fiber).

[0420] 比較のため、 原料繊維として、 市販されているウール繊維、 コッ トン繊維 、 テンセル繊維、 レーヨン繊維及びポリエステル繊維を用意した。 [0420] For comparison, commercially available wool fibers, cotton fibers, tencel fibers, rayon fibers and polyester fibers were prepared as raw fibers.

[0421] 各原料繊維を使用して、 横編機を使用した横編みで編地を製造した。 原料 繊維と

Figure imgf000120_0002
した編地は、 太さ ： 1 /30 （毛番手 単糸） 、 ゲージ数： 1 8とした。 原料繊維として 丁 799繊維を使用し た編地は、 太さ ： 1 /30 （毛番手単糸） 、 ゲージ数： 】 6とした。 その 他の原料繊維を使用した編地は、
Figure imgf000120_0003
繊維を 使用した編地とほぼ同一のカバーファクターとなるように太さ及びゲージ数 を調整した。 具体的には、 以下のとおりである。 [0421] Using each raw material fiber, a knitted fabric was manufactured by flat knitting using a flat knitting machine. Raw material with fiber
Figure imgf000120_0002
The knitted fabric had a thickness of 1/30 (a single yarn of a yarn count) and a gauge number of 18. The knitted fabric using 799 fibers as a raw material fiber has a thickness of 1/30 (a single yarn with a yarn count) and a gauge number of 6]. Knitted fabrics using other raw fibers are
Figure imgf000120_0003
The thickness and the number of gauges were adjusted so that the cover factor was almost the same as the knitted fabric using the fibers. Specifically, it is as follows.

ウール 太さ ： 2/30 （双糸） 、 ゲージ数： 1 4 Wool thickness: 2/30 (twisted yarn), gauge: 1 4

コッ トン 太さ ： 2/34 （双糸） 、 ゲージ数： 1 4 Cotton thickness: 2/34 (twisted yarn), gauge: 1 4

テンセル 太さ ： 2/3〇 （双糸） 、 ゲージ数： 1 5 Tencel thickness: 2/3 〇 (twisted yarn), number of gauges: 15

レーヨン 太さ ： 1 /38 （単糸） 、 ゲージ数： 1 4 Rayon Thickness: 1/38 (single yarn), gauge: 1 4

ポリエステル 太さ ·· 1 /60 （単糸） 、 ゲージ数： 1 4 Polyester thickness·· 1/60 (single yarn), gauge number: 1 4

[0422] 1 0〇 1 0〇 に裁断した編地を 2枚合わせにし、 四辺を縫い合わせ て試験片 （試料） とした。 試験片を低湿度環境 （温度 20±2°〇、 相対湿度 40±5%） で 4時間以上放置した後、 高湿度環境 （温度 20±2°〇、 相対 湿度 90±5%） に移し、 試験片内部中央に取り付けた温度センサーにより 30分間、 1分間隔で温度の測定を行った。 [0422] Two pieces of the knitted fabric cut into 100 100 were combined and the four sides were sewn together to form a test piece (sample). After leaving the test piece in a low humidity environment (temperature 20 ± 2 ° 〇, relative humidity 40 ± 5%) for 4 hours or more, move it to a high humidity environment (temperature 20 ± 2 ° 〇, relative humidity 90 ± 5%). A temperature sensor attached to the center of the inside of the test piece measured the temperature at 1-minute intervals for 30 minutes.

[0423] 測定結果から、 下記式八に従って、 最高吸湿発熱度を求めた。 [0423] From the measurement results, the maximum moisture absorption exothermic degree was determined according to the following equation 8.

式八 ：最高吸湿発熱度 = ｛ （試料を、 試料温度が平衡に達するまで低湿度 〇 2020/175702 120 卩（：171? 2020 /008524 Formula 8: Maximum moisture absorption exotherm = {( Sample is low humidity until sample temperature reaches equilibrium 〇 2020/175 702 120 卩(：171? 2020/008524

環境下に置いた後、 高湿度環境下に移したときの試料温度の最高値） 一 （試 料を、 試料温度が平衡に達するまで低湿度環境下に置いた後、 高湿度環境下 に移すときの試料温度） ｝ （°0 /試料重量 （9） Maximum value of sample temperature when placed in high-humidity environment after being placed in the environment) 1 (Place sample in low-humidity environment until sample temperature reaches equilibrium and then in high-humidity environment Sample temperature when)} ( ° 0 / sample weight (9)

[0424] 図 1 0は、 吸湿発熱性試験の結果の一例を示すグラフである。 グラフの横 軸は、 試料を低湿度環境から高湿度環境に移した時点を〇とし、 高湿度環境 での放置時間 （分） を示す。 グラフの縦軸は、 温度センサーで測定した温度 （試料温度） を示す。 図 1 0に示したグラフ中、 IV!で示した点が、 試料温度 の最高値に対応している。 [0424] Fig. 10 is a graph showing an example of the results of the moisture absorption and exothermicity test. The horizontal axis of the graph indicates the time (minutes) left in the high humidity environment, where the time when the sample was moved from the low humidity environment to the high humidity environment is ◯. The vertical axis of the graph shows the temperature (sample temperature) measured by the temperature sensor. In the graph shown in Fig. 10, the point indicated by IV! corresponds to the maximum sample temperature.

[0425] 最高吸湿発熱度の算出結果を表 7に示す。 [0425] Table 7 shows the calculation results of the maximum heat absorption by moisture absorption.

[表 7] [Table 7]

Figure imgf000121_0002
Figure imgf000121_0002

[0426] 表 7に示すとおり、 改変フイブロイン

Figure imgf000121_0001
[0426] As shown in Table 7, modified fibroin
Figure imgf000121_0001

繊維で編んだ編地 （編織体） は、 既存の材料と比べて、 最高吸湿発熱度が高 く、 吸湿発熱性に優れていた。 改変フイブロインは、 吸湿発熱性に優れてい ることが分かる。 改変フイブロインを含む繊維を使用して編織体を編成又は 織成することで、 機能性 （吸湿発熱性） を有する編織体を得ることができる The knitted fabric (woven body) knitted with fibers had a higher maximum moisture absorption and exotherm than existing materials, and was superior in moisture absorption and exothermicity. It can be seen that the modified fibroin is excellent in moisture absorption and exothermicity. By knitting or weaving a knitted fabric using fibers containing modified fibroin, a knitted fabric having functionality (heat absorption due to moisture absorption) can be obtained.

[0427] 〔試験例 3 :改変フイブロインを含む編織体の製造及び保温性評価〕 [0427] [Test Example 3: Production and thermal insulation evaluation of knitted fabric containing modified fibroin]

4 . 0質量％になるように !_ 丨 〇 I を溶解させたジメチルスルホキシド （ を溶媒として用意し、 そこに改変フイブロインの凍結乾燥粉末を 、 濃度 2 4質量％となるよう添加し、 シエーカーを使用して 3時間溶解させ た。 その後、 不溶物と泡を取り除き、 改変フイブロイン溶液 （紡糸原液） を 〇 2020/175702 121 卩（：171? 2020 /008524 Prepare dimethyl sulfoxide () in which !_ 〇I is dissolved to a concentration of 4.0% by mass as a solvent, and add lyophilized powder of modified fibroin to the concentration of 24% by mass, and add a shaker. Dissolve for 3 hours, then remove insolubles and bubbles and add modified fibroin solution (stock solution for spinning). 〇 2020/175 702 121 卩 (: 171? 2020 /008524

得た。 Obtained.

[0428] 調製した紡糸原液を 60°〇にて目開き 5 の金属フィルターで濾過し、 次いで 30 1_のステンレスシリンジ内で静置し、 脱泡させた後に、 二ード ル径〇. 2

Figure imgf000122_0001
のソリッ ドノズルから 1 00質量％メタノール凝固浴槽中へ 吐出させた。 吐出温度は 60°〇であった。 凝固後、 得られた原糸を巻き取り 、 自然乾燥させて改変フィブロイン繊維 （原料繊維） を得た。 [0428] The prepared spinning dope was filtered at 60° with a metal filter having an opening of 5, and then allowed to stand in a stainless syringe of 301_ to defoam, and then the needle diameter was 0.2.
Figure imgf000122_0001
It was discharged from the solid nozzle of 100 into a 100 mass% methanol coagulation bath. The discharge temperature was 60 ° . After coagulation, the obtained raw yarn was wound and naturally dried to obtain modified fibroin fiber (raw fiber).

[0429] 比較のため、 原料繊維として、 市販されているウール繊維、 シルク繊維、 綿繊維、 レーヨン繊維及びポリエステル繊維を用意した。 [0429] For comparison, commercially available wool fibers, silk fibers, cotton fibers, rayon fibers and polyester fibers were prepared as raw material fibers.

[0430] 各原料繊維を使用して、 横編機を使用した横編みで編地を製造した。 原料 繊維として [¾丁 966繊維を使用した編地は、 番手： 301\1 、 撚り本数 : 1、 ゲージ数： 1 800、 目付け = 90.

Figure imgf000122_0002
した。 原料繊維とし て [¾丁 799繊維を使用した編地は、 番手： 301\1 、 撚り本数： 1、 ゲ[0430] Using each raw material fiber, a knitted fabric was manufactured by flat knitting using a flat knitting machine. Knitted fabrics using [¾ 966 fiber as raw material fiber, count: 301\1, twist number: 1, gauge number: 1800, basis weight = 90.
Figure imgf000122_0002
did. As the raw material fiber, the knitted fabric using [¾ 799 fiber has a count: 301\1, the number of twists: 1,

2とした。 その他の原料繊維を

Figure imgf000122_0003
、 丁 799繊維を使用した編地と ほぼ同一のカバーファクターとなるように太さ及びゲージ数を調整した。 具 体的には、 以下のとおりである。 It was 2. Other raw fibers
Figure imgf000122_0003
The thickness and the number of gauges were adjusted so that the cover factor was almost the same as that of the knitted fabric using 799 fibers. Specifically, it is as follows.

ウール 番手： 301\1 、 撚り本数： 2、 ゲージ数： 1 400、 目付け： 242. 69 /〇! 2 Wool count: 301\1, number of twists: 2, gauge: 1400, basis weight: 242. 69 / 〇! 2

シルク 番手： 601\1 、 撚り本数： 2、 ゲージ数： 1 400、 目付け：

Figure imgf000122_0004
Silk count: 601\1, number of twists: 2, gauge: 1400, basis weight:
Figure imgf000122_0004

綿 番手： 341\1 、 撚り本数： 2、 ゲージ数： 1 400、 目付け： 1 9 4. 1 9 /（^2 Cotton count: 341\1, Number of twists: 2, Number of gauges: 1400, Unit weight: 1 9 4.1 9 / (^ 2

レーヨン 番手： 381\1 、 撚り本数： 1、 ゲージ数： 1 400、 目付け : 1 81. 82 /^2 Rayon count: 381\1, number of twists: 1, gauge: 1400, basis weight: 1 81. 82 /^ 2

ポリエステル 番手： 601\1 、 撚り本数： 1、 ゲージ数：

Figure imgf000122_0005
目 付け： 1 84.
Figure imgf000122_0006
Polyester count: 601\1, Number of twists: 1, Number of gauges:
Figure imgf000122_0005
Unit weight: 1 84.
Figure imgf000122_0006

[0431] 保温性は、 力卜ーテック株式会社製の <巳 3 _ 7サーモラボ I I試験機 を使用し、 ドライコンタクト法 （皮膚と衣服が乾燥状態で直接触れた時を想 〇 2020/175702 122 卩（：171? 2020 /008524 [0431] The heat retention property was measured by the dry contact method (using the dry contact method (contact when skin and clothes were in direct contact with dry skin) using a <3 3_7 Thermo Lab II tester manufactured by Riki-Tech Co., Ltd. 〇 2020/175 702 122 卩 (: 171? 2020 /008524

定した方法） を用いて評価した。 2 0〇 2 0〇 に裁断した編地 1枚を 試験片 （試料） とした。 試験片を、 一定温度 （3 0 °〇） に設定した熱板にセ ツ トし、 風洞内風速 3 0

Figure imgf000123_0001
秒の条件で、 試験片を介して放散された熱量 （3） を求めた。 試験片をセツ トしない状態で、 上記同様の条件で放散され た熱量 （匕） を求め、 下記の式に従い保温率 （％） を算出した。 Method). One piece of knitted fabric cut into 200,000 was used as a test piece (sample). Set the test piece on a hot plate set to a constant temperature (30 ° 〇), and set the wind speed in the wind tunnel to 30 °.
Figure imgf000123_0001
The heat quantity (3) dissipated through the test piece was obtained under the condition of second. With the test piece not set, the amount of heat dissipated (sink) was obtained under the same conditions as above, and the heat retention rate (%) was calculated according to the following formula.

保温率 （％） = （ 1 _ 3 /匕） X 1 0 0 Insulation rate (%) = (1 _ 3 / 匕) X 100

[0432] 測定結果から、 下記式巳に従って、 保温性指数を求めた。 [0432] From the measurement results, the heat retention index was calculated according to the following formula.

式巳 ：保温性指数 =保温率 （％） /試料の目付け

Figure imgf000123_0002
Formula: Thermal insulation index = Thermal insulation rate (%) / Sample weight
Figure imgf000123_0002

[0433] 保温性指数の算出結果を表 8に示す。 保温性指数が高いほど、 保温性に優 れる材料と評価することができる。 [0433] Table 8 shows the calculation results of the heat retention index. The higher the heat retention index, the higher the heat retention can be evaluated.

[0434] [表 8] [0434] [Table 8]

Figure imgf000123_0004
Figure imgf000123_0004

[0435] 表 8に示すとおり、 改変フイブロイン

Figure imgf000123_0003
[0435] As shown in Table 8, modified fibroin
Figure imgf000123_0003

繊維で編んだ編地 （編織体） は、 既存の材料と比べて、 保温性指数が高く、 保温性に優れていた。 改変フイブロインは、 保温性に優れていることが分か る。 改変フイブロインを含む繊維を使用して編織体を編成又は織成すること で、 機能性 （保温性） を有する編織体を得ることができる。 The knitted fabric (woven body) knitted with fibers had a higher heat retention index and superior heat retention compared to existing materials. It can be seen that the modified fibroin is excellent in heat retention. By knitting or weaving a knitted fabric using fibers containing modified fibroin, a knitted fabric having functionality (heat retention) can be obtained.

[0436] 〔試験例 4 :耐水性付与物質を含有する編織体 （織生地） の製造及び評価〕 耐水性付与物質を含有する編織体 （織生地） を製造し、 その評価を行った 。 なお、 耐水性付与物質を含有する編織体 （織生地） は、 機能性が付与され た編織体 （織生地） と捉えることもできる。 [Test Example 4: Production and Evaluation of Knitted Woven Body (Woven Dough) Containing Water Resistance-Providing Substance] A knitted woven fabric (woven fabric) containing a water resistance-providing substance was produced and evaluated. The knitted fabric (woven fabric) containing the water resistance-imparting substance can also be regarded as a knitted fabric (woven fabric) having added functionality.

[0437] （ 1） 紡糸液 （ドープ液） の調製 〇 2020/175702 123 卩（：171? 2020 /008524 [0437] (1) Preparation of spinning solution (dope solution) 〇 2020/175 702 123 卩(: 171-1? 2020/008524

4質量％になるように塩化リチウムを溶解した口 IV! 3〇を溶媒として用い 、 上記で製造した改変フィブロイン （ [¾丁 7 9 9） の凍結乾燥粉末を、 濃 度 2 4質量％となるように溶媒に添加した。 9 0 °〇のアルミブロックヒータ 一で 1時間溶解させた後、 不溶物と泡を取り除き、 紡糸液 （ドープ液） とし た。 The concentration of the freeze-dried powder of the modified fibroin ([¾d 7 9 9) produced above, using the mouth IV! So added to the solvent. After melting for 1 hour with an aluminum block heater at 90 °C, insoluble materials and bubbles were removed to obtain a spinning solution (dope solution).

[0438] （2） 紡糸 [0438] (2) Spinning

紡糸液をリザーブタンクに充填し、 〇. 1又は〇. 2 径のモノホール ノズルからギアポンプを用い 1 0 0質量％メタノール凝固浴槽中へ吐出させ た。 吐出量は〇. 0 1〜〇. 〇 8 !_ /分に調整した。 凝固後、 1 0 0質量 %メタノール洗浄浴槽で洗浄及び延伸を行った。 洗浄及び延伸後、 乾熱板を 用いて乾燥させ、 得られた原糸 （改変フィブロイン繊維） を巻き取った。 The spinning solution was filled in a reserve tank and discharged from a 0.1 or 0.2 diameter monohole nozzle into a 100 mass% methanol coagulation bath using a gear pump. The discharge rate was adjusted to 0. 01 to 0. 08!_/min. After coagulation, washing and stretching were performed in a 100 mass% methanol washing bath. After washing and stretching, it was dried using a dry heat plate, and the obtained raw yarn (modified fibroin fiber) was wound up.

[0439] （3） 織生地の製造 [0439] (3) Manufacture of woven fabrics

得られた改変フィブロイン繊維から諸撚糸を作製した。 作製した諸撚糸を 平織りして織生地を得た。 A plied yarn was prepared from the obtained modified fibroin fiber. The prepared plied yarn was plain-woven to obtain a woven material.

[0440] （4） 織生地への耐水性付与物質の結合 [0440] (4) Bonding of water resistance-imparting substance to woven fabric

得られた織生地にフッ素系コーティング用モノマーを塗布し、 プラズマ処 理装置 （巳リ 「〇 丨 8 3 01 3社製） を用いてプラズマ処理を施した。 プラ ズマ処理により、 フッ素系コーティング用モノマーが重合したフッ素系ポリ マー （耐水性付与物質） が共有結合した織生地を得た。 フッ素系コーティン グ用モノマーとして、 3门〇干 I 〇 3 1 1 0 （実施例 1） 及び 3门〇干 1 0 3 1 2 0 （実施例 2） （いずれも巳リ 「〇 I 3 3〇! 8社製） を使用し た。 The resulting woven fabric was coated with a fluorine coating monomer, and plasma-treated using a plasma treatment device (Minori "○丨 8 3 01 3 Co. Ltd.". We obtained a woven fabric with covalently bonded fluoropolymer (water resistance-imparting substance) in which the monomers were polymerized.3 As a fluorocarbon coating monomer, 3 types of dried I 0 3 1 1 0 (Example 1) and 3 types of 〇 Dry 1 0 3 1 2 0 (Example 2) (all are manufactured by Minori "○ I 3 3 0! 8 company").

[0441 ] （5） 撥水性評価 [0441] (5) Water repellency evaluation

プラズマ処理を施した実施例 1及び実施例 2の織生地、 並びにプラズマ処 理を施していない織生地 （比較例 1） について、 撥水度試験 （スプレー試験 ） を実施した。 撥水度試験 （スプレー試験） は、 丨 3 0 4 9 2 0 : 2 0 1 2 に準じて実施した。 以下に示す 6段階 （スコア〇〜 5） の評価基準に従い、 目視で判定を実施した。 〇 2020/175702 124 卩（：171? 2020 /008524 A water repellency test (spray test) was carried out on the woven fabrics of Examples 1 and 2 which were subjected to the plasma treatment, and the woven fabric which was not subjected to the plasma treatment (Comparative Example 1). The water repellency test (spray test) was carried out according to 340,920:2,012. Visual evaluation was performed according to the following six-level (scores 0 to 5) evaluation criteria. 〇 2020/175 702 124 卩 (：171? 2020 /008524

スコア 5 :表面に湿潤及び水滴の付着がない。 Score 5: There is no wetting and no water droplets on the surface.

スコア 4 :表面に湿潤しないが， 水滴の付着がある。 Score 4: Does not wet the surface, but has water droplets.

スコア 3 :表面に小さな湿潤がある。 Score 3: There is little wetting on the surface.

スコア 2 :湿潤が広がり， いくつかは互いに接続している。 Score 2: Moisture spreads, some connected to each other.

スコア 1 :水が当たった部分に完全な湿潤を示す。 Score 1: Shows complete wetting in the area hit by water.

スコア 0 :表面全体に湿潤を示す。 Score 0: indicates wetness over the entire surface.

[0442] 結果を表 9に示す。 プラズマ処理を施していない比較例 1の織生地はスコ ア〇であったのに対し、 プラズマ処理を施した実施例 1及び実施例 2の織生 地はいずれもスコア 4であり、 耐水性 （撥水性） が付与されていた。 [0442] The results are shown in Table 9. The woven fabric of Comparative Example 1 which was not subjected to the plasma treatment was score ◯, whereas the woven fabrics of Example 1 and Example 2 which were subjected to the plasma treatment each had a score of 4, and the water resistance ( Water repellency) was added.

[0443] [表 9] [0443] [Table 9]

Figure imgf000125_0001
Figure imgf000125_0001

[0444] （6） 触感評価及び収縮性評価 [0444] (6) Tactile evaluation and shrinkage evaluation

実施例 1及び実施例 2並びに比較例 1の織生地から、 一辺 5〇 の正方形 状の試験片をそれぞれ切り出した。 試験片の一方の表面に、 鉛筆で一辺 3 0 の正方形の頂点 （4点） をマークした。 各試験片を 4 0 °〇の水に 1 0分 間浸潰した後、 次いで室温で真空乾燥させる工程を 5サイクル繰り返した。 真空乾燥は、 真空定温乾燥機 （ 0 3 _ 3 1 0（3 , 東京理化器械 （株） 製） を用いて、 設定圧力一〇. 1 1\/1 3で 3 0分間行った。 また、 各サイクル終 了時に、 触感を官能評価すると共に、 マークした 4点間の距離を測定して収 縮率を評価した。 From the woven fabrics of Example 1 and Example 2 and Comparative Example 1, square test pieces each having a side of 50 were cut out. On one surface of the test piece, the vertices (4 points) of a square with a side of 30 were marked with a pencil. Each test piece was immersed in water at 40° for 10 minutes and then vacuum dried at room temperature, which was repeated for 5 cycles. The vacuum drying was performed for 30 minutes at a set pressure of 10/11\ 1/3 using a vacuum constant temperature dryer (03_310) (3, manufactured by Tokyo Rikakikai Co., Ltd.). At the end of each cycle, the tactile sensation was sensory evaluated, and the distance between the four marked points was measured to evaluate the shrinkage rate.

[0445] 触感は、 以下の基準に従って判定した。 結果を表 1 0に示す。 プラズマ処 理を施した実施例 1及び実施例 2の織生地はいずれもブラズマ処理を施して いない比較例 1の織生地と比べて触感の低下が抑制されていた。 [0445] The tactile sensation was evaluated according to the following criteria. The results are shown in Table 10. The woven fabrics of Example 1 and Example 2 which were subjected to the plasma treatment were suppressed in the reduction of tactile sensation as compared with the woven fabric of Comparative Example 1 which was not subjected to the plasma treatment.

評点 5 :オリジナルと同様に良好である。 Score 5: As good as the original.

評点 4 :良好であるが、 オリジナルと比べて若干劣る。 〇 2020/175702 125 卩（：171? 2020 /008524 Rating 4: Good, but slightly inferior to the original. 〇 2020/175 702 125 卩 (：171? 2020 /008524

評点 3 :悪くはないが、 やや堅い。 Score 3: Not bad, but rather firm.

評点 2 :悪く、 かつ堅いが、 曲げられる。 Score 2: Bad and stiff, but bendable.

評点 1 : とても悪く、 堅く、 かつ曲げられない。 Score 1: Very bad, stiff, and inflexible.

[0446] [表 10] [0446] [Table 10]

Figure imgf000126_0001
Figure imgf000126_0001

[0447] 収縮率は、 下記式に従って算出した。 なお、 「各辺の長さの平均値」 は、 マークした 4点で作られる四角形の各辺の長さの総和を 4で割った値である 収縮率 （％） = { 1 - （各辺の長さの平均値 （111 111） / 3 0〇1 111） } X I 0 0 [0447] The shrinkage rate was calculated according to the following formula. The “average length of each side” is the sum of the lengths of the sides of the rectangle marked with 4 points divided by 4. Shrinkage (%) = {1-(each side Average length of (111 111) / 3 0 ○ 1 111)} XI 0 0

結果を表 1 1 に示す。 プラズマ処理を施した実施例 1及び実施例 2の織生 地はいずれもプラズマ処理を施していない比較例 1の織生地と比べて収縮率 が小さかった。 The results are shown in Table 11. The shrinkage rates of the woven fabrics of Example 1 and Example 2 which were subjected to the plasma treatment were smaller than those of the woven fabric of Comparative Example 1 which was not subjected to the plasma treatment.

[0448] [表 1 1 ] [0448] [Table 1 1]

Figure imgf000126_0002
Figure imgf000126_0002

[0449] 〔試験例 5 :耐水性付与物質を含有する編織体 （編生地） の製造及び評価〕 耐水性付与物質を含有する編織体 （織生地） を製造し、 その評価を行った 。 なお、 耐水性付与物質を含有する編織体 （織生地） は、 機能性が付与され た編織体 （織生地） と捉えることもできる。 [Test Example 5: Production and Evaluation of Knitted Woven Body (Knitted Fabric) Containing Water Resistance-Providing Substance] A knitted fabric (woven fabric) containing the water resistance-imparting substance was produced and evaluated. The knitted fabric (woven fabric) containing the water resistance-imparting substance can also be regarded as a knitted fabric (woven fabric) having added functionality.

[0450] （ 1） 紡糸液 （ドープ液） の調製 [0450] (1) Preparation of spinning solution (dope solution)

4質量％になるように塩化リチウムを溶解した口 IV! 3〇を溶媒として用い 〇 2020/175702 126 卩（：171? 2020 /008524 Use the mouth IV!30 that dissolves lithium chloride to 4% by mass as the solvent. 〇 2020/175 702 126 卩 (：171? 2020 /008524

、 上記で製造した改変フィブロイン （ [¾丁 9 1 8） の凍結乾燥粉末を、 濃 度 2 4質量％となるように溶媒に添加した。 9 0 °〇のアルミブロックヒータ 一で 1時間溶解させた後、 不溶物と泡を取り除き、 紡糸液 （ドープ液） とし た。 The lyophilized powder of the modified fibroin ([¸9918) produced above was added to the solvent so that the concentration was 24% by mass. After melting for 1 hour with an aluminum block heater at 90 °C, insoluble materials and bubbles were removed to obtain a spinning solution (dope solution).

[0451 ] （2） 紡糸 [0451] (2) Spinning

紡糸液をリザーブタンクに充填し、 〇. 1又は〇. 2 径のモノホール ノズルからギアポンプを用い 1 0 0質量％メタノール凝固浴槽中へ吐出させ た。 吐出量は〇. 0 1〜〇. 〇 8 !_ /分に調整した。 凝固後、 1 0 0質量 %メタノール洗浄浴槽で洗浄及び延伸を行った。 洗浄及び延伸後、 乾熱板を 用いて乾燥させ、 得られた原糸 （改変フィブロイン繊維） を巻き取った。 The spinning solution was filled in a reserve tank and discharged from a 0.1 or 0.2 diameter monohole nozzle into a 100 mass% methanol coagulation bath using a gear pump. The discharge rate was adjusted to 0. 01 to 0. 08!_/min. After coagulation, washing and stretching were performed in a 100 mass% methanol washing bath. After washing and stretching, it was dried using a dry heat plate, and the obtained raw yarn (modified fibroin fiber) was wound up.

[0452] （3） 編生地の製造 [0452] (3) Manufacturing of knitted fabric

得られた改変フィブロイン繊維を裁断して改変フィブロインステープルを 作製した。 作製した改変フィブロインステープルを開繊開毛した後、 公知の 紡績装置により紡績し、 紡績糸を得た。 得られた紡績糸を、 ホールガーメン 卜横編機 （1\/! 〇1~1 2乂3 , 島精機製） を使用して編み、 編生地を得た。 The modified fibroin fiber obtained was cut to prepare a modified fibroin staple. The modified fibroin staple produced was opened and opened and spun using a known spinning device to obtain spun yarn. A spun yarn obtained, Hall Gar Men Bokuyoko knitting machine (1 \ /! Rei_1 to 1 2 say yes 3, island Seiki) knitting was used to obtain a knitted fabric.

[0453] （4） 編生地への耐水性付与物質の結合 [0453] (4) Binding of water resistance-imparting substance to knitted fabric

得られた編生地にフッ素系コーティング用モノマーを塗布し、 プラズマ処 理装置 （巳リ 「〇 丨 8 3 01 3社製） を用いてプラズマ処理を施した。 プラ ズマ処理により、 フッ素系コーティング用モノマーが重合したフッ素系ポリ マー （耐水性付与物質） が共有結合した編生地を得た （実施例 3） 。 フッ素 系コーティング用モノマーとして、 3 1^〇 1: 丨 〇 3 1 2 0 （巳リ 「〇 I 3 3〇! 8社製） を使用した。 The obtained knitted fabric was coated with a fluorine-based coating monomer, and plasma-treated using a plasma treatment device (Minori "○丨 8 3 01 3 Co. Ltd.". A knitted fabric was obtained in which a fluorine-based polymer (water resistance-imparting substance) in which a monomer was polymerized was covalently bonded (Example 3) As a monomer for a fluorine-based coating, 3 1 ^ 〇 1 :丨 〇 3 1 2 0 (Mitsumi Re "○ I 3 3 0! 8 company) was used.

[0454] （5） 撥水性評価 [0454] (5) Water repellency evaluation

プラズマ処理を施した実施例 3の編生地、 及びプラズマ処理を施していな い編生地 （比較例 2） について、 試験例 4と同様の方法で、 撥水度試験 （ス プレー試験） を実施した。 結果を表 1 2に示す。 プラズマ処理を施していな い比較例 2の編生地はスコア 0であったのに対し、 プラズマ処理を施した実 施例 3の編生地はスコア 5であり、 耐水性 （撥水性） が付与されていた。 〇 2020/175702 127 卩（：171? 2020 /008524 A water repellency test (spray test) was performed on the knitted fabric of Example 3 that had been subjected to plasma treatment and the knitted fabric that had not been subjected to plasma treatment (Comparative Example 2) in the same manner as in Test Example 4. .. The results are shown in Table 12 The knitted fabric of Comparative Example 2 which was not subjected to the plasma treatment had a score of 0, while the knitted fabric of Example 3 which was subjected to the plasma treatment had a score of 5 and was given water resistance (water repellency). Was there. 〇 2020/175 702 127 卩(: 171-1? 2020/008524

[表 12]

Figure imgf000128_0004
[Table 12]
Figure imgf000128_0004

[0455] （6） 触感評価及び収縮性評価 [0455] (6) Tactile evaluation and shrinkage evaluation

実施例 3及び比較例 2の編生地から、 一辺 5〇 の正方形状の試験片をそ れぞれ切り出した。 試験片の一方の表面に、 鉛筆で一辺 3 0

Figure imgf000128_0001
の正方形の 頂点 （4点） をマークした。 予備処理として、 各試験片を 4 0 °〇の水に 1 0 分間浸潰した後、 次いで室温で真空乾燥させる工程を 5サイクル繰り返した 。 真空乾燥は、 真空定温乾燥機 （ 〇3 _ 3 1 0（3 , 東京理化器械 （株） 製 ） を用いて、 設定圧力一〇. 1 1\/1 3で 3 0分間行った。 From the knitted fabrics of Example 3 and Comparative Example 2, square test pieces each having a side of 50 were cut out. On one surface of the test piece, use a pencil to draw 30
Figure imgf000128_0001
Marked the vertices (4 points) of the square. As a pretreatment, each test piece was immersed in 40 ° water for 10 minutes, and then vacuum-dried at room temperature, which was repeated for 5 cycles. The vacuum drying was performed for 30 minutes at a set pressure of 10.11.1\/13 using a vacuum constant temperature dryer (03-3_310 (3, manufactured by Tokyo Rikakikai Co., Ltd.)).

[0456] 次いで、 予備処理を経た試験片に対し、 洗浄工程、 乾燥工程、 浸水工程及 び乾燥工程をこの順に 5サイクル繰り返した。 洗浄工程では、 パナソニック （株） 製洗濯機

Figure imgf000128_0002
1 0 0 1 _） を使用し、 ライオン （株） 製洗剤 （トップクリアリキッ ド） を用いて、 試験片に対して、 洗浄を 5分間行った 後、 すすぎを 2回行い、 次いで脱水 1分間を行った。 乾燥工程では、 真空定 温乾燥機 （ 〇3 _ 3 1 0（3 , 東京理化器械 （株） 製） を用いて、 設定圧力 - 0 .
Figure imgf000128_0003
で 3 0分間、 室温で試験片の乾燥を行った。 浸水工程では、 試験片を 4 0 °〇の水に 1 0分間浸潰した。 各サイクル終了時に、 試験例 4と 同様の基準で、 触感を官能評価すると共に、 マークした 4点間の距離を測定 して収縮率を評価した。 [0456] Next, the preliminarily treated test piece was subjected to 5 cycles of a washing step, a drying step, a water immersion step and a drying step in this order. In the washing process, a washing machine manufactured by Panasonic Corporation
Figure imgf000128_0002
1 0 0 1 _) and using Lion Detergent's detergent (Top Clear Liquid), wash the test piece for 5 minutes, then rinse twice, and then dehydrate for 1 minute. I went. In the drying process, a vacuum constant temperature dryer (○ 3 _ 310 (3, manufactured by Tokyo Rika Kikai Co., Ltd.) was used to set pressure-0.
Figure imgf000128_0003
The test piece was dried at room temperature for 30 minutes. In the water immersion step, the test piece was immersed in 40 ° water for 10 minutes. At the end of each cycle, the tactile sensation was sensory-evaluated according to the same criteria as in Test Example 4, and the shrinkage rate was evaluated by measuring the distance between the four marked points.

[0457] 触感の官能評価結果を表 1 3に示す。 なお、 「開始時」 は、 予備処理後、 サイクルを開始する前の評価結果である。 プラズマ処理を施した実施例 3の 編生地は、 プラズマ処理を施していない比較例 2の編生地と比べて触感の低 下が抑制されていた。 〇 2020/175702 128 卩（：171? 2020 /008524 [0457] Table 13 shows the results of the sensory evaluation of the tactile sensation. “At the start” is the evaluation result after the pretreatment and before the start of the cycle. The knitted fabric of Example 3 which was subjected to the plasma treatment was suppressed in deterioration of the tactile sensation as compared with the knitted fabric of Comparative Example 2 which was not subjected to the plasma treatment. 〇 2020/175 702 128 卩 (: 171-1? 2020 /008524

[表 13] [Table 13]

Figure imgf000129_0001
Figure imgf000129_0001

［0458］ 収縮率の評価結果を表 1 4に示す。 プラズマ処理を施した実施例 3の編生 地は、 プラズマ処理を施していない比較例 2の編生地と比べて収縮率が小さ かった。 [0458] The results of evaluation of shrinkage are shown in Table 14. The knitted fabric of Example 3 which was subjected to the plasma treatment had a smaller shrinkage rate than the knitted fabric of Comparative Example 2 which was not subjected to the plasma treatment.

［表 14］ [Table 14]

Figure imgf000129_0002
Figure imgf000129_0002

［0459］ 〔試験例 6 :耐水性付与物質を含有する編織体 （編生地） の製造及び評価〕 耐水性付与物質を含有する編織体 （織生地） を製造し、 その評価を行った 。 なお、 耐水性付与物質を含有する編織体 （織生地） は、 機能性が付与され た編織体 （織生地） と捉えることもできる。 [0459] [Test Example 6: Production and Evaluation of Knitted Woven Body (Knitted Fabric) Containing Water Resistance-Providing Substance] A knitted fabric (woven fabric) containing a water resistance-imparting substance was produced and evaluated. The knitted fabric (woven fabric) containing the water resistance-imparting substance can also be regarded as a knitted fabric (woven fabric) having added functionality.

［0460］ （ 1） 紡糸液 （ドープ液） の調製 [0460] (1) Preparation of spinning solution (dope solution)

4質量％になるように塩化リチウムを溶解した口 IV! 3〇を溶媒として用い 、 上記で製造した改変フィブロイン （ ［¾丁 7 9 9） の凍結乾燥粉末を、 濃 度 2 4質量％となるように溶媒に添加した。 シエーカーを使用して、 改変フ ィブロインを 3時間かけて溶解させた後、 溶液中の不溶物 （ゴミ等） と泡を 取り除き、 紡糸液 （ドープ液） とした。 ドープ液の溶液粘度は 9 0 °〇におい て 5 0 0 0〇 （センチボアズ） であった。 Freeze-dried powder of the modified fibroin ([¸n 7 9 9) produced above, using a solution of Lithium Chloride dissolved in 4% by weight of Lithium IV!30 as a solvent, has a concentration of 24% by weight. So added to the solvent. After using the shaker to dissolve the modified fibroin for 3 hours, insoluble materials (dust, etc.) and bubbles in the solution were removed to prepare a spinning solution (dope solution). The solution viscosity of the dope solution was 500 (zero centimeters) at 90 ° .

［0461］ （2） 紡糸 [0461] (2) Spinning

得られたドープ液と公知の乾湿式紡糸装置とを用いて乾湿式紡糸を行って 、 改変フィブロインからなるモノフィラメントを得た。 なお、 ここでは、 乾 湿式紡糸を下記の条件で行った。 Dry-wet spinning was performed using the obtained dope solution and a known dry-wet spinning device to obtain a monofilament composed of modified fibroin. Here, dry-wet spinning was performed under the following conditions.

凝固液 （メタノール） の温度： 5〜 1 0 °〇 〇 2020/175702 129 卩（：171? 2020 /008524 Temperature of coagulation liquid (methanol): 5 to 10 ° 〇 〇 2020/175 702 129 卩 (: 171? 2020 /008524

延伸倍率： 6倍 Draw ratio: 6 times

乾燥温度： 8 0 °0 Drying temperature: 80 ° 0

[0462] （3） 編生地の製造 [0462] (3) Manufacturing of knitted fabric

上記のようにして得た改変フイブロイン繊維を用いて公知の方法により紡 績糸を製造し、 この改変フイブロイン繊維からなる紡績糸と公知の編機とを 用いて、 横編みにより 5〇

Figure imgf000130_0001
角の編生地を得た。 なお、 改変フイブロイン繊 維からなる紡績糸の番手は 5 8 .
Figure imgf000130_0002
編機のゲージ数は 1 8であ った。 Using the modified fibroin fiber obtained as described above, a spun yarn is manufactured by a known method, and the spun yarn composed of the modified fibroin fiber and a known knitting machine are used to weft-knit 50
Figure imgf000130_0001
A knitted fabric with corners was obtained. The yarn count of the spun yarn made of modified fibroin fiber is 58.
Figure imgf000130_0002
The gauge of the knitting machine was 18.

[0463] （4） 編生地への耐水性付与物質の結合 [0463] (4) Bonding of water resistance-imparting substance to knitted fabric

得られた 5〇 角の編生地を、 ヘキサンジイソアネート

Figure imgf000130_0003
第一の 反応剤） 2 0 !_中に浸潰した。 次いで、 1~1 0 丨が含浸した編生地をアルミ ホイルに挟み、 1 3 0 °〇で 3 0分加熱した。 加熱後、 編生地を取り出し、 ブ タノール （巳 1_1〇1~1 , 第二の反応剤） 2 0〇1 丨 中に浸潰し、 1 0 0 °〇で 2 4 〇分反応させた。 反応後の編生地を丁 ! ! で洗浄して、 耐水性付与物質 （第 _の反応剤及び第二の反応剤） が結合した、 実施例 4の編生地を得た。 The 50,000 square knitted fabric obtained was mixed with hexane diisocyanate.
Figure imgf000130_0003
The first reactive agent) was immersed in 20 !_. Next, the knitted fabric impregnated with 1 to 10 g was sandwiched between aluminum foils and heated at 130 ° for 30 minutes. After heating, the knitted fabric was taken out, and the knitted fabric was immersed in butanol (Minami 1_1○ 1 to 1, 2nd reaction agent) 200 1 1 and reacted for 2400 minutes at 100 °C. After the reaction, the knitted fabric was washed with a tray to obtain the knitted fabric of Example 4 to which the water resistance-imparting substance (the _th reactive agent and the second reactive agent) was bound.

（3） で得られた 5〇〇!角の編生地を、 比較例 3の編生地として評価した The knitted fabric of 50,000 squares obtained in (3) was evaluated as the knitted fabric of Comparative Example 3.

（3） で得られた 5〇 角の編生地を、 ヘキサンジイソアネート （1~1 0 I , 第一の反応剤） 2 0 1_中に浸潰した。 次いで、 1~1 0 丨が含浸した編生地 をアルミホイルに挟み、 1 3 0 °〇で 3 0分加熱した。 その後、 編生地を丁1~1 で洗浄して、 第一の反応剤のみが結合した、 比較例 4の編生地を得た。 The 50 square knitted fabric obtained in (3) was immersed in hexanediisocyanate (1 to 10 I, the first reactant) 201 _. Next, the knitted fabric impregnated with 1 to 10 g was sandwiched between aluminum foils and heated at 130 ° for 30 minutes. Then, the knitted fabric was washed with 1 to 1 to obtain a knitted fabric of Comparative Example 4 in which only the first reactant was bound.

[0464] （5） 収縮性評価 [0464] (5) Shrinkage evaluation

実施例 4の編生地、 並びに比較例 3及び比較例 4の編生地について、 収縮 性を評価した。 各編生地に鉛筆で 3〇 角の正方形を描き、 評価サンプルと した。 評価サンプルをパナソニック （株） 製洗濯機 （ 八ー 〇 1 1 0 0 !_ ） の洗濯モード 「お家クリーニング」 で洗濯した。 次いで、 同じ洗濯機で 1 5分脱水し、 1 2 0分自然乾燥させた。 洗濯前後の正方形の縦横の長さをそ れぞれ測定し、 縦向及び横方向の収縮率を求めた。 同じ試験を 3回行い、 3 〇 2020/175702 130 卩（：171? 2020 /008524 The knitted fabric of Example 4 and the knitted fabrics of Comparative Example 3 and Comparative Example 4 were evaluated for shrinkage. A 30-square square was drawn on each knitted fabric with a pencil to make an evaluation sample. The evaluation sample was washed in the washing mode "house cleaning" of a washing machine (8 _ 1 1 1 0 0 !_) manufactured by Panasonic Corporation. Then, it was dehydrated in the same washing machine for 15 minutes and naturally dried for 120 minutes. The vertical and horizontal lengths of the square before and after washing were measured, and the shrinkage rates in the vertical and horizontal directions were obtained. Repeat the same test 3 times 〇 2020/175 702 130 卩(：171? 2020/008524

回の平均値を評価結果とした。 結果を表 1 5に示す。 The average value of the times was used as the evaluation result. The results are shown in Table 15.

[0465] （6） 質感評価 [0465] (6) Texture evaluation

実施例 4の編生地、 並びに比較例 3及び比較例 4の編生地について、 肌触 りを三段階で評価した。 比較例 3の編生地の肌触りを基準 （巳） とし、 それ より風合いに優れる場合を 、 肌触りが荒く風合いに劣る場合を <3として評 価した。 結果を表 1 5に示す。 The knitted fabrics of Example 4 and the knitted fabrics of Comparative Example 3 and Comparative Example 4 were evaluated in terms of touch in three levels. The texture of the knitted fabric of Comparative Example 3 was used as the standard (Mitsumi), and when the texture was better than that, <3 was evaluated when the texture was rough and the texture was poor. The results are shown in Table 15.

[0466] [表 15] [0466] [Table 15]

Figure imgf000131_0003
Figure imgf000131_0003

[0467] 〔試験例 7 :耐水性付与物質を含む繊維 （改変フィブロイン繊維） の製造及 び評価〕 [0467] [Test Example 7: Production and evaluation of fiber containing modified water resistance substance (modified fibroin fiber)]

耐水性付与物質を含む繊維 （改変フィブロイン繊維） を製造し、 その評価 を行った。 なお、 耐水性付与物質を含む繊維は、 機能性が付与された繊維と 捉えることもできる。 Fibers containing a water resistance imparting substance (modified fibroin fibers) were manufactured and evaluated. The fiber containing the water resistance-imparting substance can also be regarded as a fiber having a functional property.

[0468] <実施例 5 > [0468] <Example 5>

（ 1） 紡糸液 （ドープ液） の調製 (1) Preparation of spinning solution (dope solution)

デンプン （和光純薬工業株式会社製） 2 0

Figure imgf000131_0001
の溶媒 （4重量％の 1_ 丨 〇 丨 を含むジメチルスルホキシド
Figure imgf000131_0002
） に溶解さ せた後、 これにフエニルイソシアネート （東京化成工業株式会社製） 4 0 0 9を添加し、 9 0 °〇で 4時間撹拌して反応させた。 これにより、 デンプン のヒドロキシル基とフエニルイソシアネートのイソシアネート基とが反応し て、 フエニル基 （機能性官能基） が、 ウレタン結合を介して結合した修飾デ ンプン （修飾ヒドロキシル基含有ポリマー） を得た。 修飾デンプンは、 仕込 み比から求めた修飾率 （ヒドロキシル基が機能性官能基に変換された割合） が 1 0 0 %であった。 〇 2020/175702 131 卩（：171? 2020 /008524 Starch (Wako Pure Chemical Industries, Ltd.) 20
Figure imgf000131_0001
Solvent (4% by weight of 1 _ 丨 dimethyl sulfoxide
Figure imgf000131_0002
), phenylisocyanate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 409 was added thereto, and the mixture was reacted by stirring at 90° for 4 hours. As a result, the hydroxyl group of starch and the isocyanate group of phenylisocyanate were reacted to give a modified starch (polymer containing hydroxyl group) in which the phenyl group (functional functional group) was bonded via the urethane bond. .. The modified starch had a modification ratio (the ratio of conversion of hydroxyl groups to functional functional groups) of 100%, which was determined from the charging ratio. 〇 2020/175 702 131 卩(: 171-1? 2020/008524

[0469] 反応液を室温まで冷却した後、 改変フィブロイン （

Figure imgf000132_0001
丁 799） の凍結 乾燥粉末 300 9を反応液に添加し、 90°〇で 1 2時間撹拌して溶解させ 、 透明な紡糸液 （ドープ液） を得た。 紡糸液中の修飾デンプンの含有量は、 修飾デンプンとデンプンの総含有量を基準として、 1 7質量％である。 [0469] After cooling the reaction solution to room temperature, the modified fibroin (
Figure imgf000132_0001
799) freeze-dried powder 3009 was added to the reaction solution and stirred at 90° for 12 hours for dissolution to obtain a transparent spinning solution (dope solution). The content of modified starch in the spinning solution is 17% by mass, based on the total content of modified starch and starch.

[0470] （2） 改変フィブロインと耐水性付与物質を含む繊維の製造 [0470] (2) Production of fibers containing modified fibroin and a water resistance-imparting substance

調製した紡糸液を 60°〇にて目開き 5 の金属フィルターで濾過し、 次 いで 30 1_のステンレスシリンジ内で静置し、 脱泡させた後に、 二ードル 径〇.

Figure imgf000132_0002
ドノズルから窒素ガスを用い 1 00質量％メタノール 凝固浴槽中へ吐出させた。 吐出温度は 60°〇であり、 吐出圧は〇.
Figure imgf000132_0003
であった。 凝固後、 得られた原糸を巻き取り速度 3.
Figure imgf000132_0004
分で巻き取り 、 自然乾燥させて、 改変フィブロインと耐水性付与物質 （修飾デンプン） を 含む繊維を得た。 The prepared spinning solution was filtered at 60° with a metal filter with an opening of 5 and then allowed to stand in a stainless syringe of 301_ to allow it to defoam and then have a diameter of 2 dollars.
Figure imgf000132_0002
Nitrogen gas was discharged from the nozzle into a 100 mass% methanol coagulation bath. The discharge temperature is 60 ° and the discharge pressure is 0.
Figure imgf000132_0003
Met. After solidification, take-up speed of the obtained yarn 3.
Figure imgf000132_0004
It was wound in minutes and air-dried to obtain a fiber containing modified fibroin and a water resistance-imparting substance (modified starch).

[0471] （3） 収縮性評価 [0471] (3) Shrinkage evaluation

得られた繊維を長さ約 1 0

Figure imgf000132_0006
に切断し、 水への浸漬前の糸の長さ
Figure imgf000132_0005
） を測定した。 次いで、 糸を 40°〇の水浴に 1分間浸潰した。 その後、 糸を 水浴から取り出して、 1 5分間室温で真空乾燥させた後、 乾燥後の糸の長さ を測定した。 繊維の収縮率を以下の式に従って算出した。 結果を表 1 6に示 す。 The length of the obtained fiber is about 10
Figure imgf000132_0006
Length of thread before cutting and dipping in water
Figure imgf000132_0005
) Was measured. The yarn was then immersed in a 40 ° water bath for 1 minute. Then, the yarn was taken out from the water bath, vacuum dried at room temperature for 15 minutes, and the length of the dried yarn was measured. The shrinkage rate of the fiber was calculated according to the following formula. The results are shown in Table 16.

収縮率 （％） = { （浸漬前の長さ/浸潰 ·乾燥後の長さ） _ 1 } X 1 00 [0472] <実施例 6> Shrinkage (%) = {(length before immersion/immersion-length after drying) _ 1 }X 100 [0472] <Example 6>

（ 1） 紡糸液 （ドープ液） の調製 (1) Preparation of spinning solution (dope solution)

デンプン （和光純薬工業株式会社製） 253〇19を 7600

Figure imgf000132_0007
の溶媒 （ 4重量％の 1_ 丨 〇 丨 を含むジメチルスルホキシド
Figure imgf000132_0008
） に溶解させ た後、 これに無水酢酸 （和光純薬工業株式会社製）
Figure imgf000132_0009
を添加し、 9 0°〇で 4時間撹拌して反応させた。 これにより、 デンプンのヒドロキシル基 と無水酢酸とが反応して、 ァセチル基 （機能性官能基） が結合した修飾デン プン （修飾ヒドロキシル基含有ポリマー） を得た。 修飾デンプンは、 仕込み 比から求めた修飾率 （ヒドロキシル基が機能性官能基に変換された割合） が 〇 2020/175702 132 卩（：171? 2020 /008524 Starch (manufactured by Wako Pure Chemical Industries, Ltd.) 253 〇 19 to 7600
Figure imgf000132_0007
Solvent (4% by weight of 1 _ 丨 containing dimethyl sulfoxide
Figure imgf000132_0008
) Is dissolved in acetic anhydride (Wako Pure Chemical Industries, Ltd.)
Figure imgf000132_0009
Was added, and the mixture was stirred at 90° and reacted for 4 hours. As a result, a hydroxyl group of starch and acetic anhydride were reacted to obtain a modified starch (modified hydroxyl group-containing polymer) having an acetyl group (functional functional group) bonded thereto. The modified starch has a modification rate (the rate of conversion of hydroxyl groups to functional functional groups) calculated from the charging ratio. 〇 2020/175 702 132 卩 (: 171? 2020 /008524

1 0 0 %であった。 It was 100%.

[0473] 反応液を室温まで冷却した後、 改変フイブロイン （

Figure imgf000133_0001
丁 7 9 9） の凍結 乾燥粉末 2 0 0 0 9を反応液に添加し、 9 0 °◦で 1 2時間撹拌して溶解さ せ、 透明な紡糸液 （ドープ液） を得た。 紡糸液中の修飾デンプンの含有量は 、 修飾デンプンとデンプンの総含有量を基準として、 1 7質量％である。 [0473] After the reaction solution was cooled to room temperature, the modified fibroin (
Figure imgf000133_0001
Freeze-dried powder 2000 of 9) was added to the reaction solution and dissolved by stirring at 90°° for 12 hours to obtain a transparent spinning solution (dope solution). The content of modified starch in the spinning solution is 17% by mass, based on the total content of modified starch and starch.

[0474] （2） 改変フイブロインと耐水性付与物質を含む繊維の製造 [0474] (2) Production of fiber containing modified fibroin and water resistance-imparting substance

調製した紡糸液を使用して、 実施例 5と同様の手順で改変フイブロインと 耐水性付与物質 （修飾デンプン） を含む繊維を得た。 Using the prepared spinning solution, fibers containing the modified fibroin and the water resistance-imparting substance (modified starch) were obtained by the same procedure as in Example 5.

[0475] （3） 収縮性評価 [0475] (3) Shrinkage evaluation

得られた繊維について、 実施例 5と同様の手順で収縮性評価を実施した。 結果を表 1 6に示す。 The obtained fiber was subjected to shrinkage evaluation in the same procedure as in Example 5. The results are shown in Table 16.

[0476] <実施例 7 > [0476] <Example 7>

（ 1） 紡糸液 （ドープ液） の調製 (1) Preparation of spinning solution (dope solution)

デンプン （和光純薬工業株式会社製） 2 1

Figure imgf000133_0002
の溶媒 （ 4重量％の 1_ 丨 〇 丨 を含むジメチルスルホキシド
Figure imgf000133_0003
） に溶解させ た後、 これに無水酢酸 （和光純薬工業株式会社製） 1 8 5〇! 9を添加し、 9 0 °〇で 4時間撹拌して反応させた。 これにより、 デンプンのヒドロキシル基 と無水酢酸とが反応して、 アセチル基 （機能性官能基） が結合した修飾デン プン （修飾ヒドロキシル基含有ポリマー） を得た。 修飾デンプンは、 仕込み 比から求めた修飾率 （ヒドロキシル基が機能性官能基に変換された割合） が 5 0 %であった。 Starch (Wako Pure Chemical Industries, Ltd.) 2 1
Figure imgf000133_0002
Solvent (4% by weight of 1 _ 丨 containing dimethyl sulfoxide
Figure imgf000133_0003
), acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 1850! 9 was added thereto, and the mixture was reacted at 90° for 4 hours with stirring. As a result, a hydroxyl group of starch and acetic anhydride were reacted to obtain a modified starch (modified hydroxyl group-containing polymer) having an acetyl group (functional functional group) bonded thereto. The modified starch had a modification ratio (ratio of conversion of hydroxyl groups to functional functional groups) of 50%, which was determined from the charging ratio.

[0477] 反応液を室温まで冷却した後、 改変フイブロイン （

Figure imgf000133_0004
丁 7 9 9） の凍結 乾燥粉末 2 0 0 0 9を反応液に添加し、 9 0 °◦で 1 2時間撹拌して溶解さ せ、 透明な紡糸液 （ドープ液） を得た。 紡糸液中の修飾デンプンの含有量は 、 修飾デンプンとデンプンの総含有量を基準として、 1 7質量％である。 [0477] After the reaction solution was cooled to room temperature, the modified fibroin (
Figure imgf000133_0004
Freeze-dried powder 2000 of 9) was added to the reaction solution and dissolved by stirring at 90°° for 12 hours to obtain a transparent spinning solution (dope solution). The content of modified starch in the spinning solution is 17% by mass, based on the total content of modified starch and starch.

[0478] （2） 改変フイブロインと耐水性付与物質を含む繊維の製造 [0478] (2) Production of fiber containing modified fibroin and water resistance-imparting substance

調製した紡糸液を使用して、 実施例 5と同様の手順で改変フイブロインと 耐水性付与物質 （修飾デンプン） を含む繊維を得た。 〇 2020/175702 133 卩（：171? 2020 /008524 Using the prepared spinning solution, fibers containing the modified fibroin and the water resistance-imparting substance (modified starch) were obtained by the same procedure as in Example 5. 〇 2020/175 702 133 卩 (: 171-1? 2020 /008524

[0479] （3） 収縮性評価 [0479] (3) Shrinkage evaluation

得られた繊維について、 実施例 5と同様の手順で収縮性評価を実施した。 結果を表 1 6に示す。 The obtained fiber was subjected to shrinkage evaluation in the same procedure as in Example 5. The results are shown in Table 16.

[0480] <実施例 8 > [0480] <Example 8>

（ 1） 紡糸液 （ドープ液） の調製 (1) Preparation of spinning solution (dope solution)

ポリビニルアルコール （ 八） （和光純薬工業株式会社製） 1 2 8 9

Figure imgf000134_0001
の溶媒 （4重量％の 1_ 丨 〇 丨 を含むジメチルスルホキシド （ 0 1\/1 3〇） ） に溶解させた後、 これにフエニルイソシアネート （東京化成エ 業株式会社製） 2 7 2 9を添加し、 9 0 °〇で 4時間撹拌して反応させた。 これにより、 八のヒ ドロキシル基とフエニルイソシアネートとが反応し て、 フエニル基 （機能性官能基） が、 ウレタン結合を介して結合した修飾 八 （修飾ヒドロキシル基含有ポリマー） を得た。 修飾 は、 仕込み比 から求めた修飾率 （ヒドロキシル基が機能性官能基に変換された割合） が 1 0 0 %であった。 Polyvinyl alcohol (8) (Wako Pure Chemical Industries, Ltd.) 1 2 8 9
Figure imgf000134_0001
Dimethylsulfoxide (0 1\/1 3 〇) containing 4% by weight of 1 _ 丨 丨, and then phenyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 7 2 9 The reaction mixture was added and stirred at 90° for 4 hours for reaction. As a result, the hydroxy group of Eight and the phenylisocyanate were reacted to obtain a modified Eight (modified hydroxyl group-containing polymer) in which the phenyl group (functional functional group) was bonded via a urethane bond. As for the modification, the modification ratio (the ratio of conversion of hydroxyl groups to functional functional groups) calculated from the charging ratio was 100%.

[0481 ] 反応液を室温まで冷却した後、 改変フィブロイン （

Figure imgf000134_0002
丁 7 9 9） の凍結 乾燥粉末 2 0 0 0 9を反応液に添加し、 9 0 °◦で 1 2時間撹拌して溶解さ せ、 透明な紡糸液 （ドープ液） を得た。 紡糸液中の修飾 V八の含有量は、 修飾 と の総含有量を基準として、 1 7質量％である。 [0481] After cooling the reaction solution to room temperature, the modified fibroin (
Figure imgf000134_0002
Freeze-dried powder 2000 of 9) was added to the reaction solution and dissolved by stirring at 90°° for 12 hours to obtain a transparent spinning solution (dope solution). The content of modified V8 in the spinning solution is 17% by mass, based on the total content of modified V8.

[0482] （2） 改変フィブロインと耐水性付与物質を含む繊維の製造 [0482] (2) Production of fibers containing modified fibroin and water resistance-imparting substance

調製した紡糸液を使用して、 実施例 5と同様の手順で改変フィブロインと 耐水性付与物質 （修飾？ ） を含む繊維を得た。 Using the prepared spinning solution, fibers containing the modified fibroin and the water resistance-imparting substance (modified?) were obtained by the same procedure as in Example 5.

[0483] （3） 収縮性評価 [0483] (3) Shrinkage evaluation

得られた繊維について、 実施例 5と同様の手順で収縮性評価を実施した。 結果を表 1 6に示す。 The obtained fiber was subjected to shrinkage evaluation in the same procedure as in Example 5. The results are shown in Table 16.

[0484] <実施例 9 > [0484] <Example 9>

（ 1） 紡糸液 （ドープ液） の調製 (1) Preparation of spinning solution (dope solution)

ポリビニルアルコール （ 八） （和光純薬工業株式会社製） 1 9 3〇1 9

Figure imgf000134_0003
の溶媒 （4重量％の 1_ 丨 〇 丨 を含むジメチルスルホキシド （ 〇 2020/175702 134 卩（：171? 2020 /008524 Polyvinyl alcohol (eight) (manufactured by Wako Pure Chemical Industries, Ltd.) 1 9 3 0 19
Figure imgf000134_0003
Solvent (containing 4% by weight of 1 _ 丨 dimethyl sulfoxide ( 〇 2020/175 702 134 卩(: 171-1? 2020/008524

0 1\/1 3〇） ） に溶解させた後、 これにフエニルイソシアネート （東京化成エ 業株式会社製） 2 0 7 9を添加し、 9 0 °〇で 4時間撹拌して反応させた。 これにより、 八のヒ ドロキシル基とフエニルイソシアネートとが反応し て、 フエニル基 （機能性官能基） が、 ウレタン結合を介して結合した修飾 八 （修飾ヒドロキシル基含有ポリマー） を得た。 修飾 は、 仕込み比 から求めた修飾率 （ヒドロキシル基が機能性官能基に変換された割合） が 5 0 %であった。 (0 1\/1 30))), phenylisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) 207 9 was added to this, and the mixture was reacted by stirring at 90° 〇 for 4 hours. .. As a result, the hydroxy group of Eight and the phenylisocyanate were reacted to obtain a modified Eight (modified hydroxyl group-containing polymer) in which the phenyl group (functional functional group) was bonded via a urethane bond. For the modification, the modification ratio (the ratio of conversion of hydroxyl group to functional functional group) calculated from the charging ratio was 50%.

[0485] 反応液を室温まで冷却した後、 改変フィブロイン （

Figure imgf000135_0001
丁 7 9 9） の凍結 乾燥粉末 2 0 0 0 9を反応液に添加し、 9 0 °◦で 1 2時間撹拌して溶解さ せ、 透明な紡糸液 （ドープ液） を得た。 紡糸液中の修飾 V八の含有量は、 修飾 と の総含有量を基準として、 1 7質量％である。 [0485] After the reaction solution was cooled to room temperature, the modified fibroin (
Figure imgf000135_0001
Freeze-dried powder 2000 of 9) was added to the reaction solution and dissolved by stirring at 90°° for 12 hours to obtain a transparent spinning solution (dope solution). The content of modified V8 in the spinning solution is 17% by mass, based on the total content of modified V8.

[0486] （2） 改変フィブロインと耐水性付与物質を含む繊維の製造 [0486] (2) Production of fibers containing modified fibroin and a water resistance-imparting substance

調製した紡糸液を使用して、 実施例 5と同様の手順で改変フィブロインと 耐水性付与物質 （修飾？ ） を含む繊維を得た。 Using the prepared spinning solution, fibers containing the modified fibroin and the water resistance-imparting substance (modified?) were obtained by the same procedure as in Example 5.

[0487] （3） 収縮性評価 [0487] (3) Contractility evaluation

得られた繊維について、 実施例 5と同様の手順で収縮性評価を実施した。 結果を表 1 6に示す。 The obtained fiber was subjected to shrinkage evaluation in the same procedure as in Example 5. The results are shown in Table 16.

[0488] <比較例 5 > [0488] <Comparative example 5>

（ 1） 紡糸液 （ドープ液） の調製 (1) Preparation of spinning solution (dope solution)

改変フィブロイン （ [¾丁 7 9 9） の凍結乾燥粉末 1 2 0〇 9を溶媒 （ 4重量％の !_ 丨 〇 丨 を含むジメチルスルホキシド （0 1\/1 3〇） ） に添加し、 Freeze-dried powder of modified fibroin ([¾ 7 9 9) 1 2 0 0 9 was added to the solvent (dimethyl sulfoxide (0 1\/1 3 0) containing 4 wt% !_ 丨 〇 丨),

9 0 °〇で 1 2時間撹拌して溶解させ、 透明な紡糸液 （ドープ液） を得た。 The mixture was stirred for 12 hours at 90° and dissolved to obtain a transparent spinning solution (dope solution).

[0489] （2） 繊維の製造 [0489] (2) Fiber production

調製した紡糸液を使用して、 実施例 5と同様の手順で繊維を得た。 Using the prepared spinning solution, fibers were obtained by the same procedure as in Example 5.

[0490] （3） 収縮性評価 [0490] (3) Shrinkage evaluation

得られた繊維について、 実施例 5と同様の手順で収縮性評価を実施した。 結果を表 1 6に示す。 The obtained fiber was subjected to shrinkage evaluation in the same procedure as in Example 5. The results are shown in Table 16.

[0491 ] <比較例 6 > 〇 2020/175702 135 卩（：171? 2020 /008524 [0491] <Comparative example 6> 〇 2020/175 702 135 卩(：171? 2020/008524

（ 1） 紡糸液 （ドープ液） の調製 (1) Preparation of spinning solution (dope solution)

改変フイブロイン （ 丁 7 9 9） の凍結乾燥粉末 3 0 0 0 9、 及びデ ンプン （和光純薬工業株式会社製） 6 0 0〇! 9を溶媒 （4重量％の !_ 丨 〇 丨 を含むジメチルスルホキシド （口1\/1 3〇） ） に添加し、 9 0 °〇で 1 2時間撹 拌して溶解させ、 透明な紡糸液 （ドープ液） を得た。 Freeze-dried powder of modified fibroin (799) 309, and Dampung (manufactured by Wako Pure Chemical Industries, Ltd.) 600 0! 9 as solvent (4% by weight !_ 丨 〇 丨 included Dimethylsulfoxide (mouth 1\/130) was added and dissolved by stirring at 90 ° for 12 hours to obtain a transparent spinning solution (dope solution).

[0492] （2） 繊維の製造 [0492] (2) Manufacture of fibers

調製した紡糸液を使用して、 実施例 5と同様の手順で繊維を得た。 Using the prepared spinning solution, fibers were obtained by the same procedure as in Example 5.

[0493] （3） 収縮性評価 [0493] (3) Shrinkage evaluation

得られた繊維について、 実施例 5と同様の手順で収縮性評価を実施した。 結果を表 1 6に示す。 The obtained fiber was subjected to shrinkage evaluation in the same procedure as in Example 5. The results are shown in Table 16.

[0494] [表 16] [0494] [Table 16]

Figure imgf000136_0001
Figure imgf000136_0001

（修飾ヒド'ロキシル基含有ポリマーの含有量/修飾ヒドロキシル基含有ポリマー体とヒドロキシル基含有ポリマーの総含有量） 100(Content / modifying polymers containing hydroxyl groups thereof and the total content of the hydroxyl group-containing polymer of the modified hydrate 'Rokishiru group-containing polymer) 100

[0495] 改変フイブロインと、 耐水性付与物質 （ヒドロキシル基含有ポリマー （修 飾デンプン又は修飾 ） ） を含む繊維は、 耐水性付与物質を含まない繊 維と比べて、 収縮率が低減されていた。 なお、 この結果は、 機能性官能基と して疎水性の官能基 （フエニル基又はアセチル基） が結合した修飾ヒドロキ シル基含有ポリマー （修飾デンプン又は修飾 ） と、 タンパク質 （改変 フイブロイン） とを含む紡糸原液を用いてタンパク質繊維を製造することに より （実施例 5〜 9） 、 タンパク質のみを含む紡糸原液を用いた場合 （比較 例 5） 、 及びタンパク質と修飾されていないヒドロキシル基含有ポリマーと を含む紡糸原液を用いた場合 （比較例 6） と比べて、 水収縮率が低減され、 耐水性を有するタンパク質繊維が得られたことを示している。 これらのタン 〇 2020/175702 136 卩（：171? 2020 /008524 [0495] The fiber containing the modified fibroin and the water resistance-imparting substance (hydroxyl group-containing polymer (decorative starch or modified)) had a reduced shrinkage rate as compared to the fiber containing no water resistance-imparting substance. The results include a modified hydroxyl group-containing polymer (modified starch or modified) having a hydrophobic functional group (phenyl group or acetyl group) bonded as a functional functional group, and a protein (modified fibroin). By producing a protein fiber using a spinning dope (Examples 5 to 9), a spinning dope containing only a protein was used (Comparative Example 5), and a protein and an unmodified hydroxyl group-containing polymer were used. Compared with the case of using the spinning dope containing water (Comparative Example 6), the water shrinkage rate was reduced, and it was shown that a protein fiber having water resistance was obtained. These tans 〇 2020/175 702 136 卩(: 171-1? 2020/008524

パク質繊維を使用して編織体を編成又は織成することで、 機能性 （耐水性） を有する編織体を得ることができる。 A knitted or woven body having functionality (water resistance) can be obtained by knitting or weaving the knitted or woven body using the puffy fibers.

[0496] 〔試験例 8 :改変フイブロイン繊維の製造及び収縮性評価〕 [0496] [Test Example 8: Production of modified fibroin fiber and evaluation of shrinkability]

4 . 0質量％になるように 1_ 丨 〇 I を溶解させたジメチルスルホキシド （ を溶媒として用意し、 そこに改変フイブロイン （ [¾丁 3 9 9、 [¾丁3 8 0、 [¾丁4 1 0又は [¾丁 7 9 9） の凍結乾燥粉末を、 濃度 1 8質量％又は 2 4質量％となるよう添加し、 シエーカーを使用して 3時間溶 解させた。 その後、 不溶物と泡を取り除き、 改変フイブロイン溶液を得た。 Prepare dimethyl sulfoxide (, which is prepared by dissolving 1_ 丨 〇I so as to be 4.0% by mass, as a solvent, and add the modified fibroin ([¾ 3 9 9, [¾ 3 8 0, [¾ 4 1 Freeze-dried powder of 0 or [9, 799] was added so that the concentration was 18% by mass or 24% by mass, and the mixture was dissolved for 3 hours by using a shaker. After removal, a modified fibroin solution was obtained.

[0497] 得られた改変フイブロイン溶液をドープ液 （紡糸原液） とし、 図 1 3に示 す紡糸装置 1 〇〇〇に準じた紡糸装置を用いた乾湿式紡糸によって、 紡糸及 び延伸された改変クモ糸フイブロイン繊維を製造した。 用いた紡糸装置は、 図 1 3に示す紡糸装置 1 0 0 0において、 未延伸糸製造装置 1 0 2 （第 1浴 ） 及び湿熱延伸装置 1 0 3 （第 3浴） の間に、 更に第 2の未延伸糸製造装置 （第 2浴） を備えるものである。 乾湿式紡糸の条件は以下のとおりである。 押出しノズル直径： 〇.

Figure imgf000137_0001
[0497] The modified fibroin solution thus obtained was used as a dope solution (spinning stock solution), and modified by spinning and stretching by dry-wet spinning using a spinning device according to the spinning device 100 shown in Fig. 13. Spider fiber fibroin fiber was produced. The spinning device used is the spinning device 100 shown in FIG. 13 in which an unstretched yarn producing device 10 2 (first bath) and a wet heat stretching device 10 3 (third bath) are used. It is equipped with 2 undrawn yarn manufacturing devices (second bath). The conditions of dry-wet spinning are as follows. Extrusion nozzle diameter: 〇.
Figure imgf000137_0001

凝固浴温度： 2〜 1 5 °0 Coagulation bath temperature: 2 to 15 ° 0

総延伸倍率： 1〜 4倍 Total draw ratio: 1 to 4 times

乾燥温度： 6 0 °0 Drying temperature: 60 ° 0

[0498] （収縮率評価） [0498] (Evaluation of shrinkage rate)

得られた改変フイブロイン繊維 （製造例 1〜 1 9） について、 収縮率を評 価した。 すなわち、 各改変フイブロイン繊維に対して、 水に接触させて湿潤 状態にし （接触ステップ） 、 その後乾燥させる （乾燥ステップ） 収縮工程を 実施し、 湿潤状態にした改変フイブロイン繊維の収縮率、 並びに湿潤状態に した後、 乾燥させた改変フイブロイン繊維の収縮率を求めた。 The obtained modified fibroin fibers (Production Examples 1 to 19) were evaluated for shrinkage. That is, each modified fibroin fiber is brought into a wet state by contacting it with water (contact step), and then dried (drying step). A shrinking step is performed to shrink the modified fibroin fiber in a wet state and a wet state. After that, the shrinkage ratio of the dried modified fibroin fiber was determined.

[0499] ＜接触ステップ＞ [0499] <Contact step>

各改変フイブロイン繊維の巻回物から、 それぞれ、 長さ 3 0

Figure imgf000137_0002
の複数本 の試験用の改変フイブロイン繊維を切り出した。 それら複数本の改変フイブ ロイン繊維を束ねて、 繊度 1 5 0デニールの改変フイブロイン繊維束を得た 〇 2020/175702 137 卩（：171? 2020 /008524 From each modified fibroin fiber roll, a length of 30
Figure imgf000137_0002
A plurality of modified fibroin fibers for testing were cut out. A bundle of these modified fibroin fibers was bundled to obtain a modified fibroin fiber bundle with a fineness of 150 denier. 〇 2020/175 702 137 卩(: 171-1? 2020/008524

。 各改変フイブロイン繊維束に〇. 8 9の鉛錘を取り付け、 その状態で各改 変フイブロイン繊維束を表 1 7〜 2 0に示す温度の水に 1 0分間浸潰した。 その後、 水中で各改変フイブロイン繊維束の長さを測定した。 測定は、 改変 フイブロイン繊維束の縮れを無くすために、 改変フイブロイン繊維束に〇... Each modified Fuiburoin fiber bundles fitted with 〇. 8 9 plumb, each modified variable Fuiburoin fiber bundle mashed immersed for 10 minutes in water at a temperature shown in Table 1 7-2 0 in this state. Then, the length of each modified fibroin fiber bundle was measured in water. The measurement was carried out on the modified fibroin fiber bundle in order to eliminate the crimping of the modified fibroin fiber bundle.

8 9の鉛錘を取り付けたまま実施した。 次いで、 湿潤状態にした改変フイブ ロイン繊維の収縮率 （湿潤時収縮率） を、 下記式 Vに従って算出した。 式 V 中、 ！_ 0は水に浸漬する前の改変フイブロイン繊維束の長さ （3 0〇〇〇 を 示し、 1_ は水に浸潰して湿潤状態にした改変フイブロイン繊維束の長さを 示す。 It was carried out with the 89 lead weights attached. Then, the shrinkage ratio (wet shrinkage ratio) of the modified fibroin fiber in a wet state was calculated according to the following formula V. During Formula V,! _ 0 represents the length of the modified fibroin fiber bundle before being immersed in water (30000), and 1_ represents the length of the modified fibroin fiber bundle that was immersed in water to be in a wet state.

湿潤時収縮率 （％） = { 1 - （!_ %/ !_ 0） ） X 1 0 0 （式 V） Wet shrinkage (%) = {1-(!_ %/ !_ 0)) X 100 (Formula V)

[0500] ＜乾燥ステップ＞ [0500] <Drying step>

接触ステップの後、 改変フイブロイン繊維束を水中から取り出した。 取り 出した改変フイブロイン繊維束を、 〇. 8 9の鉛錘を取り付けたまま、 室温 で 2時間おいて乾燥させた。 乾燥後、 各改変フイブロイン繊維束の長さを測 定した。 次いで、 湿潤状態にした後、 乾燥させた改変フイブロイン繊維の収 縮率 （乾燥時収縮率） を、 下記式 V I に従って算出した。 式 V I 中、 ！_ 0は 水に浸漬する前の改変フイブロイン繊維束の長さ （3 0〇〇1） を示し、

Figure imgf000138_0001
は水に浸潰して湿潤状態にした後、 乾燥させた改変フイブロイン繊維束の 長さを示す。 After the contacting step, the modified fibroin fiber bundle was removed from the water. The modified fibroin fiber bundle taken out was dried at room temperature for 2 hours with the lead weight of 0.89 attached. After drying, the length of each modified fibroin fiber bundle was measured. Then, after the wet state, the modified fibroin fiber dried was subjected to a shrinkage ratio (dry shrinkage ratio) calculated according to the following formula VI. In formula VI,! _ 0 represents the length of the modified fibroin fiber bundle before being immersed in water (300 001),
Figure imgf000138_0001
Indicates the length of the modified fibroin fiber bundle that was dried by immersing it in water to make it wet.

乾燥時収縮率 （％） = { 1 -

Figure imgf000138_0002
} X 1 0 0 （%） （式Dry shrinkage (%) = {1-
Figure imgf000138_0002
} X 100 (%) (expression

V I） V I)

[0501 ] 結果を表 1 7〜 2 0に示す。 なお、 表 1 7〜 2 0中、 「総延伸倍率」 は、 紡糸工程における総延伸倍率を示す。 [0501] The results are shown in Tables 17 to 20. In Tables 17 to 20, “total draw ratio” indicates the total draw ratio in the spinning process.

[0502] \¥0 2020/175702 138 卩（：17 2020 /008524[0502] \¥0 2020/175 702 138 卩 (: 17 2020 /008524

[表 17]

Figure imgf000139_0001
[Table 17]
Figure imgf000139_0001

[0503] [表 18] [0503] [Table 18]

Figure imgf000139_0002
Figure imgf000139_0002

[0504] 〇 2020/175702 139 卩（：171? 2020 /008524 [0504] 〇 2020/175 702 139 卩 (: 171? 2020 /008524

[表 1 9] [Table 19]

Figure imgf000140_0001
Figure imgf000140_0001

[0505] [表 20] [0505] [Table 20]

Figure imgf000140_0002
Figure imgf000140_0002

[0506] 以上の結果から、 改変フイブロイン繊維は、 充分に高い収縮率を有するこ とが分かる。 したがって、 改変フイブロイン繊維から形成した原料不織布も 充分に高い収縮率を有することが認識される。 また、 改変フイブロイン繊維 及びそれから形成した原料不織布の収縮率は、 例えば、 改変フイブロイン繊 維の延伸倍率、 接触させる水の温度、 水との接触時間、 水と接触させるとき の引張力を制御することでコントロールすることができることも理解できる [0506] From the above results, it can be seen that the modified fibroin fiber has a sufficiently high shrinkage ratio. Therefore, it is recognized that the raw material nonwoven fabric formed from the modified fibroin fiber also has a sufficiently high shrinkage ratio. Further, the shrinkage ratio of the modified fibroin fiber and the raw material nonwoven fabric formed from it can be controlled, for example, by controlling the draw ratio of the modified fibroin fiber, the temperature of water to be contacted, the contact time with water, and the tensile force when contacting with water. Understand that you can control with

[0507] 〔試験例 9 :高収縮不織布の製造及び評価〕 〇 2020/175702 140 卩（：171? 2020 /008524 [0507] [Test Example 9: Production and evaluation of highly shrinkable nonwoven fabric] 〇 2020/175 702 140 卩(: 171-1? 2020/008524

（ 1） 原料不織布の製造 (1) Manufacture of raw material nonwoven fabric

4 . 0質量％になるように !_ 丨 〇 I を溶解させたジメチルスルホキシド （ Dimethylsulfoxide (!I) dissolved in dimethyl sulfoxide (

〇） を溶媒として用意し、 そこに改変フィブロイン （ [¾丁 7 9 9） の凍結乾燥粉末を、 濃度 2 4質量％となるよう添加し、 シェーカーを使用し て 3時間溶解させた。 その後、 不溶物と泡を取り除き、 改変フィブロイン溶 液を得た。 ◯) was prepared as a solvent, and a freeze-dried powder of modified fibroin ([¾799) was added thereto to a concentration of 24% by mass and dissolved for 3 hours using a shaker. Then, insoluble matter and bubbles were removed to obtain a modified fibroin solution.

[0508] 得られた改変フィブロイン溶液をドープ液 （紡糸原液） とし、 図 1 3に示 す紡糸装置 1 〇〇〇に準じた紡糸装置を用いて乾湿式紡糸を行い、 改変フィ ブロイン繊維 （2 4本のマルチフィラメント） を得た。 乾湿式紡糸の条件は 以下のとおりである。 [0508] The obtained modified fibroin solution was used as a dope solution (spinning stock solution), and dry-wet spinning was performed using a spinning device similar to the spinning device 100 shown in Fig. 13 to obtain modified fibroin fibers (2 4 multifilaments) were obtained. The dry-wet spinning conditions are as follows.

凝固液 （メタノール） の温度： 5〜 1 0 °〇 Temperature of coagulation liquid (methanol): 5 to 10 ° 〇

延伸倍率： 5倍 Draw ratio: 5 times

乾燥温度： 8 0 °0 Drying temperature: 80 ° 0

[0509] 得られた改変フィブロイン繊維 （2 4本のマルチフィラメント） を所定長 さにカツ トして短繊維化した。 その後、 公知の力ード機にて力ーディングを 行って、 短繊維が交絡してなるウェブを複数枚得た。 [0509] The obtained modified fibroin fiber (24 multifilaments) was cut into a predetermined length to shorten the fiber. After that, it was subjected to force-bonding with a known force machine to obtain a plurality of webs in which short fibers were entangled.

[0510] 次いで、 得られたウェブ 1枚を公知の二ードルパンチ機でパンチして原料 不織布 1 を得た。 この原料不織布 1の繊維密度 （目付） は 3 .

Figure imgf000141_0001
[0510] Next, one piece of the obtained web was punched with a known needle punch machine to obtain a raw material nonwoven fabric 1. The fiber density (area weight) of this raw material nonwoven fabric is 3.
Figure imgf000141_0001

った。 It was.

[051 1 ] また、 得られたウェブ 3枚を 0度、 4 5度及び 9 0度の角度に傾けた状態 で積層して積層ウェブを得た後、 この積層ウェブを公知の二ードルパンチ機 で 2回パンチして原料不織布 2を得た。 原料不織布 2の繊維密度 （目付） は 5 . 3 9 / 01 2であった。 [051 1] Further, after the three obtained webs were laminated at a tilt angle of 0°, 45° and 90° to obtain a laminated web, the laminated web was cut by a known needle punch machine. Raw material nonwoven fabric 2 was obtained by punching twice. The raw material nonwoven fabric 2 had a fiber density (weight per unit area) of 53.9/01 2 .

[0512] （2） 高収縮不織布の製造及び評価 [0512] (2) Manufacture and evaluation of highly shrinkable nonwoven fabric

原料不織布 1及び 2から、

Figure imgf000141_0002
の寸法で試験片をそれぞ れ切り出し、 重量を測定した。 試験片それぞれを 4 0 °〇の水に 1 0分間浸漬 した後、 室温で 1 2時間乾燥して、 繊維密度が互いに異なる 2種類の高収縮 不織布 1及び 2を得た。 〇 2020/175702 141 卩（：171? 2020 /008524 From raw material nonwoven fabric 1 and 2,
Figure imgf000141_0002
Each of the test pieces was cut out with the dimensions of, and the weight was measured. Each of the test pieces was immersed in 40 ° water for 10 minutes and then dried at room temperature for 12 hours to obtain two types of highly shrinkable nonwoven fabrics 1 and 2 having different fiber densities. 〇 2020/175 702 141 卩(: 171-1? 2020/008524

［0513］ 得られた高収縮不織布 1及び 2の縦及び横の長さ、 並びに重量を測定した 。 次いで、 高収縮不織布 1及び 2の収縮率、 繊維密度及び繊維密度増加率を それぞれ算出した = 3の平均値） 。 結果を表 2 1 に示した。 なお、 収縮 率及び繊維密度増加率は、 それぞれ下記式 V I I及び式 I に従って算出した 収縮率 = { 1 （高収縮不織布の縦 （横） の長さ/原料不織布の縦 （横） の長さ） ） X 1 0 0 （%） （式 V I I） [0513] The length and width of the obtained high shrinkage nonwoven fabrics 1 and 2 and the weight thereof were measured. Next, the shrinkage rate, the fiber density, and the fiber density increase rate of the high shrinkage nonwoven fabrics 1 and 2 were calculated = the average value of 3). The results are shown in Table 21. The shrinkage rate and the fiber density increase rate were calculated according to the following equations VII and I, respectively: Shrinkage rate = (1 (length of high shrinkage nonwoven fabric (length) / length of raw material nonwoven fabric (width))) ) X 100 (%) (Formula VII)

繊維密度増加率 = { （高密度不織布の繊維密度/原料不織布の繊維密度） — 1 } X 1 0 0 （%） （式丨） Fiber density increase rate = {(fiber density of high-density non-woven fabric/fiber density of raw non-woven fabric) — 1} X 100 (%) (Equation)

［0514］ ［表 21］ [0514] [Table 21]

Figure imgf000142_0002
Figure imgf000142_0002

［0515］ 原料不織布を水分と接触させるという簡便な工程のみで高密度不織布が得 られることが理解される。 また、 得られる高密度不織布は、 原料である繊維 （改変フイブロイン繊維） から常法に従って得られる不織布 （原料不織布に 相当） で実現可能な繊維密度の最大値を超える繊維密度を達成することがで きることも理解される。 [0515] It is understood that the high density nonwoven fabric can be obtained only by a simple process of contacting the raw nonwoven fabric with moisture. In addition, the obtained high-density nonwoven fabric can achieve a fiber density that exceeds the maximum value of the fiber density that can be achieved with a non-woven fabric (corresponding to a raw non-woven fabric) obtained from a raw material fiber (modified fibroin fiber) by a conventional method. It is also understood that it can be done.

［0516］ 〔試験例 1 0 :改変フイブロイン不織布の製造及び評価〕 [0516] [Test Example 10: Production and evaluation of modified fibroin nonwoven fabric]

改変フイブロインからなる不織布を製造し、 防水性及び透湿性を評価した A nonwoven fabric made of modified fibroin was manufactured and evaluated for waterproofness and moisture permeability.

［0517］ （ 1） 改変フイブロイン不織布の製造 [0517] (1) Manufacture of modified fibroin nonwoven fabric

改変フイブロイン （ ［¾丁 9 6 6） の凍結乾燥粉末を、 1~1 I に濃度 5 質量％となるように添加し、 シエーカーを使用して〇. 5時間溶解させ、 改 変フイブロイン （ ［¾丁 9 6 6） 溶液を得た。 Lyophilized powder of modified fibroin ([¾ 966) was added to 1 to 1 I at a concentration of 5% by mass and dissolved using a shaker for 0.5 hours to prepare modified fibroin ([¾ Ding 966) A solution was obtained.

［0518］ 得られた改変フイブロイン （ ［¾丁 9 6 6） 溶液を紡糸原液として、 電界 紡糸装置 （丨

Figure imgf000142_0001
1 9 7型， 株式会社井元製作所製） を用いてエレクト 〇 2020/175702 142 卩（：171? 2020 /008524 [0518] Using the obtained modified fibroin ([¾ Ding 966] solution as a spinning stock solution, an electrospinning apparatus (
Figure imgf000142_0001
1 9 7 type, manufactured by Imoto Manufacturing Co., Ltd.) 〇 2020/175 702 142 卩(: 171-1? 2020/008524

ロスピニングを行い、 改変フイブロイン不織布 （繊維直径： 6 、 不織布 の厚み： 〇. 2 8〇1〇〇 を形成した。 エレクトロスピニングの条件は以下の とおりである。 A modified fibroin non-woven fabric (fiber diameter: 6 and non-woven fabric thickness: 0.280100) was formed by performing loss-spinning. The conditions of electrospinning are as follows.

印可電圧： 2 0 1< V Applied voltage: 2 0 1< V

スピニング距離：

Figure imgf000143_0001
Spinning distance:
Figure imgf000143_0001

吐出量： 2〇!し /分 Discharge rate: 20!/min

[0519] （2） 防水性の評価 [0519] (2) Evaluation of waterproofness

水を添加した遠沈管の入口を、 （ 1） で得られた改変フイブロイン不織布 で包んだ。 次いで、 遠沈管を逆向きにして、 改変フイブロイン不織布を水に 接触させた。 この状態で 5分間保持したが、 改変フイブロイン不織布は水に 濡れなかった。 この結果から、 水は改変フイブロイン不織布を透過しないこ と、 すなわち改変フイブロイン不織布は防水性を備えていることが理解でき る。 なお、 エレクトロスピニングの条件を変更 （スピニング距離を 1 5〇

Figure imgf000143_0002
から 2 0〇〇!に変更） して形成した改変フイブロイン不織布 （繊維直径： 1 . 3 / x m s 不織布の厚み： 〇. 3 2 111 111） に対して同様の評価を実施したと ころ、 同様に改変フイブロイン不織布は水に濡れなかった。 The inlet of the centrifuge tube containing water was wrapped with the modified fibroin non-woven fabric obtained in (1). Then, the centrifuge tube was turned upside down to bring the modified fibroin nonwoven fabric into contact with water. This state was maintained for 5 minutes, but the modified fibroin nonwoven fabric did not get wet with water. From this result, it can be understood that water does not permeate the modified fibroin nonwoven fabric, that is, the modified fibroin nonwoven fabric is waterproof. The electrospinning conditions were changed (spinning distance was set to 150
Figure imgf000143_0002
! 2 0_Rei_rei vary) and was formed by modifying Fuiburoin nonwoven (fiber diameter:. 1 3 / xm s nonwoven thickness:. 〇 3 2 111 111) and was conducted the same evaluation with respect to time, similar The modified fibroin nonwoven fabric was not wet with water.

[0520] （3） 透湿性の評価 [0520] (3) Evaluation of moisture permeability

水を添加した遠沈管の入口を、 （ 1） で得られた改変フイブロイン不織布 で包んだ。 次いで、 遠沈管を逆向きにして、 改変フイブロイン不織布を水に 接触させた。 この状態で、 エアダスターを使用して遠沈管の入口から空気を 吹き込んだところ、 水の中から泡が浮かび上がることが観察された。 この結 果から、 空気は改変フイブロイン不織布を透過すること、 すなわち改変フイ ブロイン不織布は透湿性を備えていることが理解できる。 なお、 エレクトロ スピニングの条件を変更 （スピニング距離を 1 5〇 から 2 0〇 に変更） して形成した改変フイブロイン不織布 （繊維直径： 1 . 3 、 不織布の厚 み： 〇. 3 2〇1〇〇 に対して同様の評価を実施したところ、 同様に水の中か ら泡が浮かび上がることが観察された。 The inlet of the centrifuge tube containing water was wrapped with the modified fibroin non-woven fabric obtained in (1). Then, the centrifuge tube was turned upside down to bring the modified fibroin nonwoven fabric into contact with water. In this state, when air was blown in from the inlet of the centrifuge tube using an air duster, it was observed that bubbles emerged from the water. From this result, it can be understood that air permeates the modified fibroin nonwoven fabric, that is, the modified fibroin nonwoven fabric has moisture permeability. The modified fibroin non-woven fabric (fiber diameter: 1.3, non-woven fabric thickness: 0.32 210 100) was formed by changing the electrospinning conditions (spinning distance was changed from 150 to 200). When the same evaluation was performed for the same, it was observed that bubbles similarly emerged from the water.

[0521 ] 〔試験例 1 1 :防水透湿性生地の製造及び評価〕 改変フイブロイン (P RT 799) の凍結乾燥粉末を、 ギ酸に濃度 24質 量％となるよう添加し、 シエーカーを使用して 3時間溶解させた。 その後、 不溶物と泡を取り除き、 改変フイブロイン (P RT 799) 溶液 (紡糸原液 ) を得た。 得られた改変フイブロイン (P RT 799) 溶液をドープ液 (紡 糸原液) とし、 公知の乾湿式紡糸装置を用いた乾湿式紡糸によって、 紡糸及 び延伸された改変フイブロイン (P RT 799) 繊維を製造した。 乾湿式紡 糸の条件は以下のとおりである。 [0521] [Test Example 11: Production and evaluation of waterproof breathable fabric] Freeze-dried powder of modified fibroin (P RT 799) was added to formic acid to a concentration of 24% by mass and dissolved using a shaker for 3 hours. Then, the insoluble matter and bubbles were removed to obtain a modified fibroin (P RT 799) solution (spinning stock solution). Using the obtained modified fibroin (P RT 799) solution as a dope solution (spinning stock solution), the modified fibroin (P RT 799) fibers spun and stretched were subjected to dry-wet spinning using a known dry-wet spinning device. Manufactured. The dry-wet spinning conditions are as follows.

凝固浴温度： 2〜 1 5°C Coagulation bath temperature: 2 to 15 ° C

総延伸倍率： 1〜 4倍 Total draw ratio: 1 to 4 times

乾燥温度： 60°C Drying temperature: 60 ° C

[0522] 上記のようして得られた改変フイブロイン (P RT 799) 繊維から公知 の方法により撚糸を製造した後、 この撚糸をレピア織機 (E v e r g r e e n A u t om a t i c S am p l i n g L o om : CC I製) により 平織して、 基布 (表皮層 1 ) を織成した。 [0522] A twisted yarn was produced from the modified fibroin (P RT 799) fiber obtained as described above by a known method, and this twisted yarn was used. The base fabric (skin layer 1) was woven into a plain fabric.

[0523] 次いで、 得られた基布を水に浸潰した後、 水滴がしたたり落ちない程度に 水気を取り除いた。 その後、 電界紡糸装置 (丨 MC- 1 9 F 7型， 株式会社 井元製作所製) を用い、 濡れた基布を電界紡糸装置のコレクターに張り付け てセツ トした。 [0523] Next, the obtained base cloth was soaked in water, and then the water was removed to the extent that water droplets did not drip or drop. Then, using an electrospinning apparatus (CMC- 19 F 7 type, manufactured by Imoto Machinery Co., Ltd.), the wet base cloth was attached to the collector of the electrospinning apparatus and set.

[0524] 改変フイブロイン ( P R T 966 ) の凍結乾燥粉末を、 H F I Pに濃度 5 質量％となるよう添加し、 シエーカーを使用して 3時間溶解させた。 その後 、 不溶物と泡を取り除き、 改変フイブロイン ( P R T 966 ) 溶液 (紡糸原 液) を得た。 [0524] Freeze-dried powder of modified fibroin (PRT966) was added to HFIPP at a concentration of 5% by mass, and dissolved using a shaker for 3 hours. Then, the insoluble matter and bubbles were removed to obtain a modified fibroin (PRT966) solution (spinning stock solution).

[0525] 次に、 得られた改変フイブロイン (P RT 966) 溶液と、 基布をセッ ト した上記の電界紡糸装置とを用いてエレクトロスピニングを行い、 基布上に 改変フイブロイン ( P R T 966 ) 極細繊維を吹き付けて不織布 (防水透湿 層 2) を形成した。 このとき、 不織布は、 水によって表面の一部が溶解した 基布に対して一体的に接合した。 これによって、 目的とする防水透湿性生地 を得た。 なお、 得られた防水透湿性生地は自然乾燥させた。 また、 エレクト \¥02020/175702 144 卩（：17 2020 /008524 [0525] Next, electrospinning was performed using the obtained modified fibroin (PRT 966) solution and the electrospinning apparatus described above in which the base cloth was set, and the modified fibroin (PRT 966) extra fine The fibers were sprayed to form a nonwoven fabric (waterproof and moisture permeable layer 2). At this time, the non-woven fabric was integrally bonded to the base fabric whose surface was partially dissolved by water. As a result, the desired waterproof and breathable fabric was obtained. The obtained waterproof and breathable fabric was naturally dried. Also, Elect \¥02020/175702 144 卩(: 17 2020/008524

ロスピニングの条件は以下の通りである。 印加電圧： 201＜ 、 スピニング 距離： 1 5〇 、 吐出量： 2 !_/ 、 二ードル径： 250 （内径〇 25 111111） The conditions of losspinning are as follows. Applied voltage: 201<, Spinning distance: 150, Discharge rate: 2 !_/, Needle diameter: 250 (inside diameter 25 11111)

[0526] 図 1 1は、 得られた防水透湿性生地の写真である。 図 1 2は、 得られた防 水透湿性生地の断面写真である。 [0526] Fig. 11 is a photograph of the obtained waterproof and breathable fabric. Figure 12 is a cross-sectional photograph of the obtained water-proof and moisture-permeable fabric.

符号の説明 Explanation of symbols

[0527] 1 表皮層、 2 防水透湿層、 3 裏材層、 3 1 マイクロシリンジ、 3 [0527] 1 skin layer, 2 waterproof breathable layer, 3 backing layer, 3 1 micro syringe, 3

2 ドープ液、 33 金属製口金ノズル、 35 電源、 36 繊維状物、 3 8 金属製ネッ ト、 39 不織布、 1 0, 20 防水透湿性生地、 1 00 エレクトロスピニング装置。 2 Dope solution, 33 metal nozzle, 35 power supply, 36 fibrous material, 3 8 metal net, 39 non-woven fabric, 10 and 20 waterproof and breathable fabric, 100 electro spinning device.

Claims

\¥0 2020/175702 145 卩（：17 2020 /008524 請求の範囲 \¥0 2020/175 702 145 卩(: 17 2020/008524 Claims [請求項 1 ] 繊維径 1 〇 以下の極細繊維を含む不織布からなる防水透湿層と [Claim 1] A waterproof and moisture-permeable layer made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less 、 編織体からなる表皮層とが接合されてなり、 上記極細繊維が、 天然 繊維及び天然由来繊維の少なくともいずれか一方を含む極細繊維であ る、 防水透湿性生地。 A waterproof/moisture permeable fabric, wherein the superfine fibers are joined to a skin layer made of a knitted fabric, and the ultrafine fibers are ultrafine fibers containing at least one of natural fibers and naturally derived fibers. [請求項 2] 繊維径 1 〇 以下のタンパク質極細繊維を含む不織布からなる防 水透湿層と、 編織体からなる表皮層とが接合されてなる、 防水透湿性 生地。 [Claim 2] A waterproof and moisture-permeable fabric, comprising a moisture-proof and moisture-permeable layer made of a non-woven fabric containing a protein ultrafine fiber having a fiber diameter of 10 or less, and a skin layer made of a knitted fabric. [請求項 3] 前記極細繊維又はタンパク質極細繊維が、 改変フイブロインを含む [Claim 3] The ultrafine fibers or protein ultrafine fibers include modified fibroin. 、 請求項 1又は 2に記載の防水透湿性生地。 The waterproof/breathable fabric according to claim 1 or 2. [請求項 4] 繊維径 1 〇 以下の極細繊維を含む不織布からなる防水透湿層と [Claim 4] A waterproof and moisture-permeable layer comprising a nonwoven fabric containing ultrafine fibers having a fiber diameter of 10 or less 、 第 1の耐水性付与物質を含有する編織体からなる表皮層とが接合さ れてなる、 防水透湿性生地。 A waterproof/moisture permeable fabric, which is joined to a skin layer made of a knitted fabric containing the first water resistance-imparting substance. [請求項 5] 前記編織体が、 改変フイブロインを含む、 請求項 4に記載の防水透 湿性生地。 5. The waterproof/moisture permeable fabric according to claim 4, wherein the knitted fabric includes a modified fibroin. [請求項 6] 前記第 1の耐水性付与物質が、 シリコーン系ポリマー及びフツ素系 ポリマーから選ばれる少なくとも 1種である、 請求項 4又は 5に記載 の防水透湿性生地。 6. The waterproof and moisture-permeable fabric according to claim 4 or 5, wherein the first water resistance-imparting substance is at least one selected from silicone-based polymers and fluorine-based polymers. [請求項 7] 繊維径 1 〇 以下のタンパク質極細繊維を含む不織布からなる防 水透湿層と、 編織体からなる表皮層とが接合されてなり、 [Claim 7] A moisture-proof and moisture-permeable layer made of a non-woven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less and a skin layer made of a knitted fabric are joined, 上記不織布が、 水収縮されている、 防水透湿性生地。 A waterproof and breathable fabric in which the above nonwoven fabric is water-shrinked. [請求項 8] 下記式丨で定義される繊維密度増加率が 2 0 %以上である、 請求項 [Claim 8] The fiber density increase rate defined by the following formula is 20% or more, 7に記載の防水透湿性生地。 Waterproof breathable fabric according to 7. 繊維密度増加率 = { （水収縮後の不織布の繊維密度/水収縮前の不 織布の繊維密度） 一 1 } X 1 0 0 （%） （式 I） Fiber density increase rate = {(fiber density of non-woven fabric after water shrinkage/fiber density of non-woven fabric before water shrinkage) 1 1} X 100 (%) (Formula I) [請求項 9] 前記不織布の繊維密度が〇. 0 4
Figure imgf000146_0001
以上である、 請求項 7又 は 8に記載の防水透湿性生地。 [Claim 9] The fiber density of the non-woven fabric is 0.04.
Figure imgf000146_0001
The waterproof/breathable fabric according to claim 7 or 8, which is the above. [請求項 10] 前記タンパク質極細繊維が、 改変フイブロインを含む、 請求項 7〜 〇 2020/175702 146 卩（：171? 2020 /008524 [Claim 10] The protein ultrafine fiber comprises a modified fibroin. 〇 2020/175 702 146 卩 (: 171? 2020 /008524 9のいずれか一項に記載の防水透湿性生地。 9. The waterproof breathable fabric according to any one of 9 above. [請求項 1 1 ] 繊維径 1 0 以下のタンパク質極細繊維を含む不織布からなる防 水透湿層と、 編織体からなる表皮層とが、 介在層を介することなく接 合されてなる、 防水透湿性生地。 [Claim 11] A waterproof and moisture-permeable layer comprising a water-permeable and moisture-permeable layer made of a non-woven fabric containing protein ultrafine fibers having a fiber diameter of 10 or less, and a skin layer made of a knitted fabric, without an intervening layer. Wet fabric. [請求項 12] 前記タンパク質極細繊維が、 改変フイブロインを含む、 請求項 1 1 に記載の防水透湿性生地。 12. The waterproof and moisture-permeable fabric according to claim 11, wherein the protein ultrafine fibers contain modified fibroin. [請求項 13] 繊維径 1 0 以下の生分解性極細繊維を含む生分解性繊維からな る不織布と、 生分解性材料からなる編織体とが接合されてなる、 防水 透湿性生地。 [Claim 13] A waterproof and moisture-permeable fabric, comprising a nonwoven fabric made of biodegradable fibers containing biodegradable ultrafine fibers having a fiber diameter of 10 or less and a knitted fabric made of a biodegradable material, which are joined together. [請求項 14] 前記生分解性繊維が、 改変フイブロインを含む、 請求項 1 3に記載 の防水透湿性生地。 14. The waterproof and moisture-permeable fabric according to claim 13, wherein the biodegradable fiber contains modified fibroin. [請求項 15] 繊維径 1 0 以下の極細繊維を含む不織布からなる防水透湿層と 、 機能性が付与された編織体からなる表皮層とが接合されてなる、 防 水透湿性生地。 [Claim 15] A waterproof/moisture permeable fabric, comprising a waterproof/moisture permeable layer made of a non-woven fabric containing ultrafine fibers having a fiber diameter of 10 or less and a surface layer made of a functionalized knitted fabric. [請求項 16] 前記編織体が、 タンパク質繊維を含む、 請求項 1 5に記載の防水透 湿性生地。 16. The waterproof and moisture-permeable fabric according to claim 15, wherein the knitted fabric includes a protein fiber. [請求項 17] 前記タンパク質繊維が、 改変フイブロインを含む、 請求項 1 6に記 載の防水透湿性生地。 17. The waterproof and moisture-permeable fabric according to claim 16, wherein the protein fiber contains modified fibroin.
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JP2017222074A (en) * 2016-06-15 2017-12-21 富山県 Composite base fabric and method for producing the same
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