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WO2016031637A1 - Objet façonné retardateur de flamme comprenant un matériau tissé en 3d et procédé de production - Google Patents

Objet façonné retardateur de flamme comprenant un matériau tissé en 3d et procédé de production Download PDF

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Publication number
WO2016031637A1
WO2016031637A1 PCT/JP2015/073181 JP2015073181W WO2016031637A1 WO 2016031637 A1 WO2016031637 A1 WO 2016031637A1 JP 2015073181 W JP2015073181 W JP 2015073181W WO 2016031637 A1 WO2016031637 A1 WO 2016031637A1
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WO
WIPO (PCT)
Prior art keywords
flame
dimensional fabric
retardant
molded article
fabric according
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/JP2015/073181
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English (en)
Japanese (ja)
Inventor
一雄 堀口
豊 誉田
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.)
International Techtextile Converting Co Ltd
Kepla Inc
Original Assignee
International Techtextile Converting Co Ltd
Kepla 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.)
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Publication date
Application filed by International Techtextile Converting Co Ltd, Kepla Inc filed Critical International Techtextile Converting Co Ltd
Priority to JP2016545452A priority Critical patent/JPWO2016031637A1/ja
Publication of WO2016031637A1 publication Critical patent/WO2016031637A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/24—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least three directions forming a three dimensional structure
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • B32B5/06—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 structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer mechanically connected, e.g. by needling to another layer, e.g. of fibres, of paper
    • 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
    • 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
    • B32B7/05—Interconnection of layers the layers not being connected over the whole surface, e.g. discontinuous connection or patterned connection
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00—Woven fabrics designed to make specified articles
    • D03D1/0035—Protective fabrics
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D11/00—Double or multi-ply fabrics not otherwise provided for
    • D03D11/02—Fabrics formed with pockets, tubes, loops, folds, tucks or flaps
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/242—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
    • D03D15/267—Glass
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/513—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads heat-resistant or fireproof
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B32B2419/00—Buildings or parts thereof
    • 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
    • B32B2605/00—Vehicles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
    • D10B2101/06—Glass
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2403/00—Details of fabric structure established in the fabric forming process
    • D10B2403/02—Cross-sectional features
    • D10B2403/021—Lofty fabric with equidistantly spaced front and back plies, e.g. spacer fabrics

Definitions

  • the present invention relates to an inner wall material or an outer wall material such as a building material or interior of a vehicle that has flame retardancy, requires heat insulation, light weight and high strength.
  • Patent Document 1 discloses a gypsum board that is increased in strength by adding organic fibers, inorganic fibers, or a mixture thereof.
  • lighter weight and higher strength are required for interiors of high-rise buildings and vehicles such as railway vehicles and aircraft.
  • FRP fiber reinforced plastic
  • Patent Document 2 discloses a sandwich structure using a resin foam as a core.
  • the sandwich structure is a plate-like laminated molded product, following the curved surface shape is insufficient.
  • the present invention provides a flame-retardant molded article that has flame retardancy, can be effectively used for building materials and interiors of vehicles that require heat insulation, light weight and high strength, and a manufacturing method. It is aimed.
  • the present invention includes the following aspects.
  • a three-dimensional woven body having a structure in which a plurality of yarns are connected with a third thread is impregnated with a flame retardant and a polymer precursor mixture, and then the polymer precursor mixture is solidified. Flame retardant molded body.
  • ⁇ 2> The flame retardancy using the three-dimensional fabric according to ⁇ 1>, wherein the third yarn forms an angle of 60 degrees to 90 degrees with respect to the fabric forming the flat surface or the curved surface. Molded body.
  • ⁇ 3> The above ⁇ 1> or ⁇ 2>, wherein the third yarn has a structure of connecting two woven fabrics forming the plane or curved surface at a density of 45,000 to 300,000 per square meter.
  • ⁇ 4> A flame-retardant molded article using the three-dimensional fabric according to any one of ⁇ 1> to ⁇ 3>, wherein the three-dimensional fabric is made of inorganic fibers.
  • ⁇ 5> A flame-retardant molded article using the three-dimensional woven fabric according to ⁇ 4>, wherein the inorganic fiber is made of E glass.
  • ⁇ 6> A flame-retardant molded article using the three-dimensional fabric according to any one of ⁇ 1> to ⁇ 5>, wherein the flame retardant is an aluminum hydroxide compound and / or a magnesium hydroxide compound.
  • ⁇ 7> A flame-retardant molded article using the three-dimensional woven fabric according to any one of ⁇ 1> to ⁇ 6>, wherein the flame retardant is an organic phosphorus type.
  • ⁇ 8> A flame-retardant molded article using the three-dimensional fabric according to any one of ⁇ 1> to ⁇ 7>, wherein the polymer precursor includes an acrylic acid derivative and / or a methacrylic acid derivative.
  • ⁇ 9> The flame retardant molded article using the three-dimensional woven fabric according to any one of ⁇ 1> to ⁇ 8>, wherein the polymer precursor includes a polyester compound and / or an epoxy compound.
  • ⁇ 10> A flame-retardant molded article using the three-dimensional woven fabric according to any one of ⁇ 1> to ⁇ 9>, wherein the polymer precursor mixture includes solid particles.
  • ⁇ 11> The flame-retardant molded article using the three-dimensional fabric according to ⁇ 10>, wherein the solid particles are gypsum whose main component is calcium sulfate.
  • ⁇ 12> The three-dimensional fabric according to any one of ⁇ 1> to ⁇ 11>, wherein the three-dimensional fabric is pretreated with a silane compound and impregnated with a flame retardant and a polymer precursor mixture. The flame-retardant molded product used.
  • ⁇ 13> A flame-retardant molded article using the three-dimensional fabric according to any one of ⁇ 1> to ⁇ 12>, wherein a layer composed of another member is disposed on one side or both sides.
  • the present invention it is possible to obtain a flame-retardant molded article that can be effectively used for a lightweight and high-strength building material or vehicle interior that has flame retardancy and is excellent in heat insulation, and can be manufactured. Become. Furthermore, by designing the shape of the two woven fabrics freely, it is possible to obtain the flame retardant molded body having not only a flat plate shape but also a curved surface shape.
  • polymer precursor refers to monomers, oligomers and prepolymers which are raw materials for producing a polymer by reaction.
  • ⁇ Three-dimensional fabric> In the three-dimensional woven fabric according to this embodiment, two woven fabrics that form a plane or curved surface composed of warp and weft yarns are arranged so that their surfaces face each other, and a gap formed by the two woven fabrics is maintained.
  • 1 is a three-dimensional woven body having a structure in which two woven fabrics are connected by a third thread, and the three-dimensional woven body 100 in FIG. 1 or the three-dimensional woven body 102 in FIG. 2 is illustrated as an embodiment. it can.
  • the first woven fabric and the second woven fabric are shown in a planar structure. However, if the first woven fabric and the second woven fabric are composed of warps and wefts, the first woven fabric and / or the second woven fabric are used.
  • the fabric of No. 2 can have a curved surface structure, whereby a flame-retardant molded body using a three-dimensional fabric can be designed to have an arbitrary curved surface shape and can be widely applied to building materials and interiors of vehicles.
  • the weaving method of warp and weft is not particularly limited, and the woven fabric can be obtained by a general method such as plain weaving, oblique weaving, satin weaving, leno weaving, imitation weaving and the like. It is preferable that the third yarn forms an angle of 60 degrees to 90 degrees with respect to the first fabric and the second fabric. In the case of 90 degrees, since the third yarn is perpendicular to the surface of the molded body according to the present embodiment, the strength in the direction perpendicular to the surface of the molded body is maximum, but at less than 60 degrees In some cases, sufficient strength of the molded body cannot be obtained.
  • the third yarn connects two woven fabrics forming the plane or curved surface at a density of 45,000 to 300,000 per square meter.
  • the density of the third yarn does not necessarily need to be uniform, and even if there is a portion that does not partially satisfy the density range, the molded body as a whole satisfies the density range.
  • the desired strength can be expressed.
  • the density of the third yarn is less than 45,000 per square meter, the strength in the direction perpendicular to the surface of the molded body is reduced due to the shortage of the number, and when the density exceeds 300,000, the three-dimensional The weight of the woven body becomes heavy, which is disadvantageous for the weight reduction that is the object of the present invention.
  • the fiber used for the three-dimensional fabric is not particularly limited, and organic fibers and / or inorganic fibers can be used.
  • organic fibers include polyester fibers typified by polyethylene terephthalate fibers, polyolefin fibers such as polypropylene fibers and polyethylene fibers, fibers made of amide bonds such as nylon fibers and aramid fibers, vinylon fibers, and acrylic fibers.
  • inorganic fiber include glass fiber, carbon fiber, basalt, andesite, or rock fiber made from rocks having similar components.
  • glass fiber general glass for fibers, such as E glass which is glass for general purpose fibers, S glass which is glass for high-strength fibers, and C glass which is glass for fibers excellent in acid resistance, depending on the purpose.
  • E glass which is a glass for general-purpose fibers is preferable.
  • the basalt fiber (basalt fiber) which uses basalt as a raw material is preferable.
  • the three-dimensional fabric can be previously treated with a silane compound. Accordingly, in the step of impregnating the flame retardant and the polymer precursor mixture, the wettability of the polymer precursor mixture is improved and the impregnation property is improved. Furthermore, regarding the flame-retardant molded article using the three-dimensional fabric as the final product, the adhesion of the interface between the three-dimensional fabric and the polymer precursor mixture is improved, and the strength of the molded article is increased.
  • the method of treating the three-dimensional fabric with the silane compound is not particularly limited, but any one or all of the warp, weft and third yarn forming the three-dimensional fabric are preliminarily treated, and then the three-dimensional fabric is treated.
  • silane compound used for the treatment of the three-dimensional fabric a general silane coupling agent can be used.
  • vinyltrichlorosilane vinyltris (2-methoxy) silane, ⁇ -glycidoxypropyltri Methoxysilane, methacryloxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyl Triethoxysilane, 3-aminopropylmethyldiethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxy Syrah And its hydrochloride, N- ⁇ - (N-vinylbenzylaminoethyl)
  • Examples of the flame retardant according to this embodiment include phosphorus compounds such as red phosphorus, phosphate esters, and phosphine oxides, melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, nitrogen compounds such as cyanuric acid derivatives and isocyanuric acid derivatives. Containing compounds, phosphorus and nitrogen containing compounds such as cyclophosphazene, aluminum hydroxide, magnesium hydroxide, composite metal hydroxides, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate and other metal elements The compound containing these etc.
  • aluminum hydroxide is preferred from the viewpoint of flame retardancy.
  • the compounding amount of aluminum hydroxide is preferably 50 to 300 parts by mass with respect to 100 parts by mass of the polymer precursor. When it is 50 parts by mass or more, the flame retardancy is improved, and when it is 300 parts by mass or less, the impregnation property to the three-dimensional fabric is improved.
  • As aluminum hydroxide fine and fine aluminum hydroxides B303, B153, B103 (all manufactured by Nippon Light Metal Co., Ltd., trade names) and the like are commercially available.
  • an organic phosphorus flame retardant is preferable, and a phosphate ester compound is particularly preferable.
  • the phosphate ester is not particularly limited as long as it is an ester compound of phosphoric acid and an alcohol compound or a phenol compound.
  • trimethyl phosphate triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate , Xylenyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, and aromatic condensed phosphate.
  • aromatic condensed phosphate esters having a low viscosity are preferable, such as CR-733S and CR-741 (both manufactured by Daihachi Chemical Co., Ltd.). It is available as a commercial product.
  • the amount is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polymer precursor. When it is 10 parts by mass or more, flame retardancy is improved, and when it is 100 parts by mass or less, the strength of the molded body is improved.
  • thermosetting resin precursor As the polymer precursor according to the present embodiment, a general-purpose thermosetting resin precursor or an acrylic resin precursor that is polymerized by heat or light can be used. In consideration of the impregnation property of the three-dimensional fabric, the precursor is preferably liquid at normal temperature or an impregnation temperature.
  • thermosetting resin precursors include precursors such as epoxy resins, phenol resins, urea resins, melamine resins, unsaturated polyester resins, diallyl phthalate resins, vinyl ester resins, silicone resins, and polyurethane resins. Of these, epoxy resins and unsaturated polyester resin precursors are preferred.
  • the unsaturated polyester resin precursor is obtained by a condensation reaction of a dibasic acid such as maleic anhydride, phthalic anhydride, or fumaric acid and a dihydric alcohol such as ethylene glycol, propylene glycol, or bisphenol A alkylene oxide adduct. Further, a mixture of a vinyl monomer for crosslinking such as styrene or methacrylic acid methyl ester can be used.
  • a general radical initiator can be used for curing the unsaturated polyester resin precursor, but in the case of curing at room temperature, a combination of methyl ethyl ketone peroxide and cobalt naphthenate is preferable.
  • t-butylperoxy-2-ethylhexanoate is preferable when cured at 100 ° C. or lower, and benzoyl peroxide, cyclohexanone peroxide, and lauroyl peroxide are preferable when cured at higher temperatures. Can be used alone or in combination of two or more.
  • the epoxy resin is preferably a liquid at normal temperature or an impregnation temperature in consideration of the impregnation property to the three-dimensional fabric.
  • bisphenol A, bisphenol F, bisphenol AD, bisphenol S, hydrogenated bisphenol A, and other diglycidyl ether type epoxy resins, orthocresol novolac type epoxy resins and phenols and aldehydes novolac resins Glycidyl obtained by reaction of epichlorohydrin with epoxidized, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, p-aminophenol, diaminodiphenylmethane, isocyanuric acid and the like
  • Examples include amine type epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, alicyclic epoxy resins, and the like. It can be used in combination of more kinds. Among
  • a curing agent for the curing reaction of the epoxy resin.
  • Aromatic amines such as bis (4-aminophenyl) methane and bis (4-aminophenyl) sulfone.
  • Imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and imidazole derivatives.
  • Carboxylic anhydrides such as hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
  • a polyphenol compound such as a novolak resin, a Lewis acid complex such as a boron trifluoride ethylamine complex, or the like can be used. Among these, it is preferable to use an aliphatic amine having active hydrogen as a curing agent that can be cured at a low temperature.
  • the acrylic resin precursor is an acrylic acid derivative and / or a methacrylic acid derivative, and indicates monomers and oligomers of various acrylic resins.
  • Alkyl (meth) acrylates such as butyl, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate
  • hydroxyl group-containing (meth) acrylate-based monomers such as esters, ethyl ⁇ -hydroxy (meth) acrylate, n-methylolacrylamide, and oligomers obtained by
  • acrylic acid ester copolymer oligomers of these (meth) acrylic acid ester monomers and radical polymerizable monomers such as styrene, vinyl toluene, vinyl acetate, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, ethyl vinyl ether, etc. Etc.
  • acrylic resin precursors can be used alone or in combination of two or more.
  • a polymerization initiator for the curing reaction of the acrylic resin precursor.
  • organic peroxides such as diacyl peroxide compounds, peroxy ester compounds, hydroperoxide compounds, ketone peroxide compounds, alkyl perester compounds, and carbonate compounds in the case of heat curing. Things.
  • photocuring such as ultraviolet rays
  • photopolymerization initiators such as acetophenone, ketone, benzophenone, benzoin, ketal, anthraquinone, disulfide, thioxanthone, thiuram, and fluoroamine are listed. Of these, acetophenone, ketone, and benzophenone are preferred.
  • These polymerization initiators can be used alone or in combination of two or more.
  • the polymer precursor mixture according to the present embodiment can contain solid particles in addition to the flame retardant such as aluminum hydroxide.
  • the flame retardant such as aluminum hydroxide.
  • solid particles include calcium sulfate, calcium silicate, calcium carbonate, fused silica, crystalline silica, alumina, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, fosterite, steatite, spinel, mullite, titania Or powders such as beads, glass fibers and the like.
  • Solid particles have effects of improving strength, reducing linear expansion coefficient, improving thermal conductivity, and reducing hygroscopicity, and among these, gypsum mainly composed of calcium sulfate is preferable.
  • the blending amount of the solid particles is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass with respect to 100 parts by mass of the polymer precursor. When it is 50 parts by mass or more, strength, linear expansion coefficient, thermal conductivity and hygroscopicity are improved, and when it is 300 parts by mass or less, impregnation into a three-dimensional fabric body is improved.
  • Examples of the method for producing a three-dimensional woven fabric according to the present embodiment include a lamination molding method such as hand lay-up and spray-up, a press molding method, an injection molding method, a vacuum or pressure back method, a continuous molding method, and an injection molding method.
  • Known methods such as It is preferable to sufficiently impregnate the three-dimensional fabric body with the polymer precursor mixture at the time of production. However, if the amount of the polymer precursor mixture is too large, it is not possible to secure a void portion which is a feature using the three-dimensional fabric body. A lightweight structure cannot be realized.
  • the weight ratio of the three-dimensional fabric and the polymer precursor mixture is preferably 1.0: 0.8 to 1.6, and more preferably 1.0: 1.0 to 1.4.
  • the polymer precursor mixture is crushed so that voids do not enter the two fabric portions while crushing the third yarn forming the three-dimensional fabric using a defoaming roller.
  • the material is sufficiently impregnated and then hand-laid up so that the third yarn is raised by a defoaming roller.
  • the molding method using a mold there is a method in which the three-dimensional fabric is sufficiently impregnated with the polymer precursor mixture in the first stage, and the mold is opened by a predetermined thickness and cured in the second stage. It is done.
  • the curing conditions for the polymer precursor mixture are preferably in the range of room temperature to 120 ° C., and the curing time is preferably in the range of 1 to 12 hours.
  • the three-dimensional woven fabric according to the present embodiment can be arranged with layers composed of other members on one side or both sides.
  • the other member means a member that is not integrated with the three-dimensional fabric, and the constituent material may be the same as or different from that of the three-dimensional fabric.
  • Specific examples include mats or woven fabrics using organic fibers such as inorganic fibers such as glass fibers and carbon fibers, nylon fibers, polyester fibers, polyimide fibers, and aramid fibers, and prepregs using these.
  • a metal plate made of a metal such as aluminum, copper, iron, or an alloy thereof, or a mat or mesh using a metal fiber may be used.
  • it can be used as a member combined with resin.
  • a metal layer or a layer containing a metal layer is effective as another member, and aluminum, copper, iron, and alloys thereof can be suitably used as the material of the metal layer.
  • the shape is preferably a metal foil, a metal foil having a plurality of through holes in the thickness direction, or a mesh.
  • a structure having a plurality of through holes in the thickness direction including commercially available punching metals and meshes, is preferable.
  • the ratio of the through-holes to the metal layer is preferably 50% or less, more preferably 30% or less by volume.
  • the thickness of these other members is preferably 50 to 500 ⁇ m, and more preferably 100 to 300 ⁇ m, in order to reduce the weight and suppress the occurrence of warpage due to the difference in thermal expansion coefficient from the three-dimensional fabric.
  • the layer including the metal layer is a structure having a non-metal layer on one side or both sides of the metal layer, and has effects of preventing corrosion of the metal layer surface and adjusting the appearance and texture. Examples of the material for the non-metallic layer include glassy inorganic substances and resins.
  • Examples of a method for forming a glassy inorganic substance on the surface of the metal layer include a method in which a silicone compound such as an alkoxysilane compound or a silazane compound is applied, and then a glassy film is formed by heat condensation.
  • a method of curing after applying a thermosetting resin such as epoxy resin, phenol resin, polyester resin, or silicone resin, or curing these resin films after pressure adhesion The method etc. are mentioned.
  • the composition of these resin layers is not particularly limited, but when the three-dimensional fabric of the present invention is applied to a railway vehicle material, it is preferable that the residue of carbide is as small as possible after contact with a flame.
  • a resin composition of 10% or less in terms of the residual carbon content based on Japanese Industrial Standard JIS K 2270-2 is preferable.
  • a silicone compound having a Si—O bond as a main chain and forming a three-dimensional crosslinked structure such as methyl silicone resin and methylphenyl silicone resin, can be preferably used.
  • These silicone compounds are commercially available as silicone resin varnishes such as 804RESIN, 805RESIN, 806ARESIN, 840RESIN, and SR2400 (all are trade names, manufactured by Toray Dow Corning Co., Ltd.).
  • an inorganic filler can be added to the resin layer in order to increase the flame retardancy of the surface and reduce the residual carbon content.
  • the inorganic filler aluminum hydroxide, magnesium hydroxide, composite metal hydroxide, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, etc. that can be used as the above flame retardant
  • the compound containing a metal element etc. are mentioned, These 1 type (s) or 2 or more types can be used together and used.
  • the above-mentioned solid particles which can be added to the above-mentioned polymer precursor mixture as an inorganic filler can be used alone or in combination.
  • Examples of the method for arranging the other member include a method of manufacturing a mat, a woven fabric or a mesh composed of the three-dimensional fabric body and the other member at the time of hand lay-up, a prepreg after forming the three-dimensional fabric body, and a metal plate Alternatively, it is possible to use a method in which a member combined with resin is bonded and integrated by press molding. An image of this structure is shown in FIG.
  • Epoxy resin EPOLAM2500 (Axon) 100 parts by mass and amine curing agent EPOLAM2501 (Axon) 18 parts by mass are mixed uniformly at room temperature, and then aluminum hydroxide B153 (Nippon Light Metal Co., Ltd.) 60 as a flame retardant.
  • the polymer precursor mixture was prepared by mixing the mass parts by hand.
  • the body PG3 (manufactured by Parabeam) is placed on top of each other, and the polymer precursor mixture having a mass of 1.2 times the total mass of these three layers of glass cloth and the three-dimensional fabric is resinized with a defoaming roller. After the impregnation, a 3 mm-thick hand lay-up molded product was produced by causing the third yarn of the three-dimensional fabric body by a defoaming roller so as to be nearly perpendicular to the fabric surface. All the work so far was performed at room temperature. Thereafter, the epoxy resin was cured in two stages of 30 ° C./5 hours and 50 ° C./1 hour in a dryer, and a flame-retardant molded article using a three-dimensional fabric was produced.
  • Example 2 Three-dimensional as in Example 1, except that 20 parts by mass of aromatic condensed phosphate ester CR-733S as a flame retardant was added to the polymer precursor mixture of Example 1 to prepare a polymer precursor mixture. A flame-retardant molded article using a woven fabric was prepared.
  • Example 1 The polymer used in Example 1 with a thickness of about 100 ⁇ m on one side of an aluminum foil of 182 ⁇ 257 ⁇ 0.1 mm (B5 size) in which through holes having a diameter of about 0.5 mm are provided on lattice points at intervals of about 20 mm.
  • a coating film-formed aluminum foil was prepared that was treated with a dryer at 30 ° C. for 5 hours.
  • a 3D woven fabric PG3 (manufactured by Parabeam) of the same size and 3 mm thickness is placed between two sheets of E glass glass cloth WF230 100BX (manufactured by Nitto Boseki Co., Ltd.) having the same size as the aluminum foil
  • the polymer precursor mixture used in Example 1 having a mass 1.2 times the total mass of the three-layer glass cloth and the three-dimensional fabric body was impregnated with a resin by a defoaming roller, and then three-dimensional.
  • a hand lay-up molded product having a thickness of 3 mm was produced by causing the third yarn of the woven fabric to be nearly perpendicular to the woven surface by a defoaming roller.
  • the high-strength gypsum board of the comparative example is nonflammable, but has a large specific gravity and low strength.
  • the glass fiber reinforced epoxy molded body has a high elastic modulus and strength, it has a large specific gravity and is inferior in flame retardancy.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)
  • Moulding By Coating Moulds (AREA)
  • Woven Fabrics (AREA)

Abstract

L'invention concerne un objet façonné retardateur de flamme qui présente des propriétés de retardateur de flamme et d'isolant thermique et qui est léger et solide et qui peut être utilisé en tant que matériau de construction, un habillage intérieur d'un véhicule, etc. ; et un procédé de production correspondant. L'objet façonné 101 retardateur de flamme comprend un matériau tissé en 3D et est obtenu par : l'infiltration d'un mélange d'un retardateur de flamme et d'un précurseur de polymère dans un objet tissé en 3D 100 ayant une structure constituée de deux matériaux tissés pour former des surfaces courbes ou plates, les matériaux tissés étant chacun composés de chaînes 11 et de trames 10 et ayant été disposés de sorte que les matériaux tissés se font face, et d'un troisième fil 12, par lequel les deux matériaux tissés ont été reliés l'un à l'autre en un grand nombre de points de telle sorte qu'un espace est maintenu entre les deux matériaux tissés ; et ensuite la solidification du mélange précurseur de polymère. Selon la présente invention, il est possible d'obtenir un objet façonné retardateur de flamme qui est utilisable, efficacement, comme, par exemple, matériaux de construction, habillages intérieurs d'un véhicule et analogues, qui présentent des propriétés de retardateur de flamme et d'excellentes propriétés d'isolant thermique, qui sont légers et qui présentent une solidité élevée. Ainsi, la production de ceux-ci est rendue possible. Par la conception de la forme des deux matériaux tissés à la demande, l'objet façonné retardateur de flamme est obtenu non seulement dans une forme plate mais également dans une forme incurvée.
PCT/JP2015/073181 2014-08-25 2015-08-19 Objet façonné retardateur de flamme comprenant un matériau tissé en 3d et procédé de production Ceased WO2016031637A1 (fr)

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CN108468159A (zh) * 2018-03-16 2018-08-31 西安工程大学 一种三维面内准各向同性缝合织物的制备方法
US20190382952A1 (en) * 2017-02-09 2019-12-19 Evonik Degussa Gmbh Method for producing a thermally insulating layer
JP2021147522A (ja) * 2020-03-19 2021-09-27 積水化成品工業株式会社 プリプレグ及び繊維強化プラスチック
US11920735B2 (en) 2017-06-09 2024-03-05 Evonik Operations Gmbh Method for thermally insulating an evacuable container
CN118027303A (zh) * 2024-02-03 2024-05-14 惠州市致诚新材料科技有限公司 一种立体织物增强阻燃发泡材料及其制备方法
WO2025028152A1 (fr) * 2023-07-31 2025-02-06 パナソニックＩｐマネジメント株式会社 Composition de résine, matériau de film de résine et carte de circuit imprimé

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JPS61100449A (ja) * 1984-10-23 1986-05-19 株式会社日本触媒 装飾用難燃性積層板
JPS62117842A (ja) * 1985-11-18 1987-05-29 三菱重工業株式会社 複合材の強化部材用又はその芯体用異形織物
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* Cited by examiner, † Cited by third party
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US20190382952A1 (en) * 2017-02-09 2019-12-19 Evonik Degussa Gmbh Method for producing a thermally insulating layer
US11920735B2 (en) 2017-06-09 2024-03-05 Evonik Operations Gmbh Method for thermally insulating an evacuable container
CN108468159A (zh) * 2018-03-16 2018-08-31 西安工程大学 一种三维面内准各向同性缝合织物的制备方法
CN108468159B (zh) * 2018-03-16 2021-03-02 西安工程大学 一种三维面内准各向同性缝合织物的制备方法
JP2021147522A (ja) * 2020-03-19 2021-09-27 積水化成品工業株式会社 プリプレグ及び繊維強化プラスチック
WO2025028152A1 (fr) * 2023-07-31 2025-02-06 パナソニックＩｐマネジメント株式会社 Composition de résine, matériau de film de résine et carte de circuit imprimé
CN118027303A (zh) * 2024-02-03 2024-05-14 惠州市致诚新材料科技有限公司 一种立体织物增强阻燃发泡材料及其制备方法

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