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WO2013027489A1 - Feuille en simili cuir et procédé pour sa fabrication - Google Patents

Feuille en simili cuir et procédé pour sa fabrication Download PDF

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Publication number
WO2013027489A1
WO2013027489A1 PCT/JP2012/066690 JP2012066690W WO2013027489A1 WO 2013027489 A1 WO2013027489 A1 WO 2013027489A1 JP 2012066690 W JP2012066690 W JP 2012066690W WO 2013027489 A1 WO2013027489 A1 WO 2013027489A1
Authority
WO
WIPO (PCT)
Prior art keywords
urethane resin
skin layer
leather
sheet
resin composition
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/JP2012/066690
Other languages
English (en)
Japanese (ja)
Inventor
智博 鉄井
直孝 後藤
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.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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 DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2012546286A priority Critical patent/JP5196088B1/ja
Priority to CN201280040939.XA priority patent/CN103764899B/zh
Priority to US14/239,669 priority patent/US20140212676A1/en
Publication of WO2013027489A1 publication Critical patent/WO2013027489A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B5/022—Non-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
    • 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
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0292—Polyurethane 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • 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
    • B32B2437/00—Clothing
    • B32B2437/02—Gloves, shoes
    • 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
    • B32B2479/00—Furniture
    • 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
    • B32B2605/003—Interior finishings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/145—Oleophobic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31554—Next to second layer of polyamidoester

Definitions

  • the present invention relates to a leather-like sheet such as synthetic leather or artificial leather.
  • leather-like sheets such as synthetic leather and artificial leather have excellent textures comparable to natural leather, so they are used in various fields including clothing, furniture, vehicle interior materials, shoes, bags, etc. Yes.
  • an intermediate layer such as a porous layer is laminated on the surface of a support such as a fibrous base material, and a skin layer made of urethane resin or the like is further laminated on the surface.
  • a support such as a fibrous base material
  • a skin layer made of urethane resin or the like is further laminated on the surface.
  • each layer is required to have its own characteristics. Specifically, the intermediate layer is required to have a soft texture, and the skin layer is often required to have durability such as sweat resistance and oil resistance in addition to the flexibility.
  • the durability such as sweat resistance required for the skin layer is not limited to the use of the leather-like sheet, even when sweat or oil components adhere to the surface of the skin layer. This is a characteristic that is particularly regarded as important in maintaining high quality over a long period of time without causing changes in the appearance or deterioration of the film and a decrease in the adhesion of the skin layer to the support.
  • a fiber laminate manufacturing method in which a fiber base material and a skin layer formed of a synthetic resin film are bonded by a dry laminating method using an adhesive.
  • a manufacturing method is known (for example, refer to Patent Document 1).
  • the skin layer used for the production of the fiber laminate when exposed to sweat or oil components for a long time, the skin layer may cause swelling or cracking of the skin layer and a significant decrease in adhesive strength. In some cases, the appearance of the leather-like sheet is poor, or the peeling from the support with time is caused.
  • the problem to be solved by the present invention is, for example, a level of resistance that does not cause poor appearance of the leather-like sheet or time-lapse peeling from the support even when sweat or oil components adhere to it.
  • An object of the present invention is to provide a leather-like sheet having a skin layer excellent in durability such as sweat resistance and oil resistance.
  • the inventors have found that the above-mentioned problems can be solved by using a urethane resin in which two or more hydroxyl groups are present at the terminals present in the urethane resin, in order to solve the above-mentioned problems. .
  • the present invention relates to a skin layer (C) formed using a urethane resin composition containing at least one hydroxyl group at a terminal and a urethane resin composition containing an aqueous medium (B).
  • the present invention relates to a leather-like sheet having an adhesive layer (D) and a support layer (E).
  • the leather-like sheet of the present invention is a level that does not cause poor appearance of the leather-like sheet or peeling over time from the support even when sweat, oil, solvent, etc. adhere to the skin layer. Therefore, it can be used for manufacturing clothing, furniture, vehicle interior materials, shoes, bags, and the like.
  • the leather-like sheet of the present invention comprises a skin layer (C) formed using a urethane resin composition containing a urethane resin (A) having two or more hydroxyl groups at at least one end and an aqueous medium (B). And an adhesive layer (D) and a support layer (E).
  • Examples of the urethane resin composition that can be used to form the skin layer (C) include a urethane resin (A) having two or more hydroxyl groups at the terminal, an aqueous medium (B), and other additives as necessary. The thing containing etc. can be used.
  • the urethane resin (A) has two or more hydroxyl groups at at least one terminal among two or more resin terminals that may exist in the urethane resin.
  • the urethane resin is obtained by reacting a diol and diisocyanate and has two ends in the urethane resin, it has two or more hydroxyl groups at at least one of the ends. Is. Two or more hydroxyl groups may be present at each of the two ends.
  • the urethane resin has a multi-branched structure and has three or more terminals, it has two or more hydroxyl groups at least at one terminal.
  • a skin layer having excellent durability such as sweat resistance and oil resistance is formed.
  • the appearance of the leather-like sheet may be poor, and the skin layer (C) may be peeled off from the adhesive layer (D) or the support (E).
  • the urethane resin (A) when a urethane resin bonded to the urethane main chain is used instead of a terminal hydroxyl group, a skin layer having excellent durability such as sweat resistance and oil resistance is formed.
  • the appearance of the leather-like sheet may be poor, and the skin layer (C) may be peeled off from the adhesive layer (D) or the support (E).
  • the number of hydroxyl groups that can be present in the urethane resin (A) is preferably 2 to 3 and more preferably 2 with respect to one end. Further, two or more hydroxyl groups may be present at each of all terminals present in the urethane resin (A).
  • the urethane resin (A) preferably has a hydroxyl value in the range of 10-50.
  • urethane resin (A) for example, a so-called linear urethane resin obtained by using a diol as the polyol (a1) and a diisocyanate as the polyisocyanate (a2) is used.
  • a so-called linear urethane resin obtained by using a diol as the polyol (a1) and a diisocyanate as the polyisocyanate (a2) is used.
  • Using at least two, preferably two, hydroxyl groups at each of the ends is particularly flexible without impairing durability such as heat resistance (water), sweat resistance, and oil resistance. It is preferable because an excellent skin layer (C) can be formed.
  • the urethane resin (A) preferably has a hydrophilic group for stable dispersion in the aqueous medium (B).
  • hydrophilic group for example, an anionic group, a cationic group, or a nonionic group can be used.
  • an anionic group when forming the skin layer (C), it is more preferable to use an anionic group in order to quickly increase the viscosity of the urethane resin composition used in the present invention.
  • anionic group for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group and the like can be used.
  • a carboxylate group partially or wholly neutralized with a basic compound or the like
  • Use of a sulfonate group is preferable in producing a composite resin having good water dispersibility.
  • Examples of basic compounds that can be used for neutralizing the anionic group include organic amines such as ammonia, triethylamine, pyridine, and morpholine, alkanolamines such as monoethanolamine, sodium, potassium, lithium, and calcium.
  • organic amines such as ammonia, triethylamine, pyridine, and morpholine
  • alkanolamines such as monoethanolamine, sodium, potassium, lithium, and calcium.
  • a metal base compound etc. are mentioned.
  • a carboxylate group or a sulfonate group is used as the anionic group, they are present in the range of 50 mmol / kg to 1,000 mmol / kg of the entire urethane resin (A). It is preferable for maintaining good water dispersion stability.
  • a tertiary amino group etc. can be used, for example.
  • the acid that can be used for neutralizing a part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid, sulfonic acid, methanesulfonic acid, and the like.
  • Organic sulfonic acids and inorganic acids such as hydrochloric acid, sulfuric acid, orthophosphoric acid and orthophosphorous acid may be used alone or in combination of two or more.
  • Examples of the quaternizing agent that can be used for quaternizing a part or all of the tertiary amino group include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, methyl chloride, and ethyl chloride.
  • Alkyl halides such as benzyl chloride, alkyls such as methyl methanesulfonate and methyl paratoluenesulfonate, and epoxies such as ethylene oxide, propylene oxide, and epichlorohydrin may be used alone or in combination of two or more.
  • nonionic group examples include polyoxyalkylene groups such as polyoxyethylene group, polyoxypropylene group, polyoxybutylene group, poly (oxyethylene-oxypropylene) group, and polyoxyethylene-polyoxypropylene group. Can be used. Among these, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.
  • urethane resin (A) used in the present invention one having a weight average molecular weight in the range of 10,000 to 50,000 is used from the viewpoint of forming a skin layer having excellent durability such as sweat resistance. It is preferable to use 20,000 to 50,000.
  • the urethane resin (A) is, for example, a step of producing a urethane prepolymer having an isocyanate group at a terminal by reacting the polyol (a1), the polyisocyanate (a2), and a chain extender (a3) as necessary. (Step 1) and the step of reacting the urethane prepolymer and polyalkanolamine (Step 2) can be used.
  • step 1 is a process of manufacturing the urethane prepolymer which has an isocyanate group at the terminal by making the said polyol (a1), polyisocyanate (a2), and the chain extender (a3) react as needed.
  • the polyol (a1), the polyisocyanate (a2) and, if necessary, the chain extender (a3) are mixed in the absence of a solvent or in the presence of an organic solvent, and the mixture is mixed at 50 ° C. to 100 ° C. It can be produced by reacting for about 3 to 10 hours.
  • the reactant and the chain extender (a3) are mixed and further reacted to achieve the purpose. It is also possible to produce a urethane prepolymer having an isocyanate group at the terminal.
  • polystyrene polyol (a1) usable in the step 1 for example, polycarbonate polyol, polyester polyol, polyether polyol and the like can be used. Of these, the use of polycarbonate polyol is preferable for further improving the sweat resistance of the skin layer (C).
  • polycarbonate polyol for example, a product obtained by reacting a carbonate with a low molecular weight polyol of about 100 to about 500 can be used.
  • carbonate ester methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, or the like can be used.
  • Examples of the low molecular weight polyol that can react with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1, 3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7 -Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol
  • the polycarbonate polyol preferably has a number average molecular weight of 500 to 3,000.
  • a polycarbonate polyol having a number average molecular weight of 500 to 1,500 it is preferable to use.
  • the skin layer (C) is preferably A polycarbonate polyol having a number average molecular weight of 1,500 to 3,000, more preferably 1,600 to 2,500 can be used.
  • the polycarbonate polyol is preferably used in the range of 20% by mass to 95% by mass with respect to the total amount of the polyol (a1).
  • polyester polyol for example, those obtained by esterifying a low molecular weight polyol of about 100 to 500 and a polycarboxylic acid can be used.
  • low molecular weight polyol examples include 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1 , 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3- Aliphatic polyols such as propanediol, cyclobutaned
  • polycarboxylic acid examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, and fumaric acid.
  • Aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, and anhydrides or ester-forming derivatives thereof can be used.
  • polyether polyol for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.
  • the initiator examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolethane, Trimethylolpropane and the like can be used.
  • alkylene oxide for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or the like can be used.
  • polyol (a1) it is preferable to use a polyol having a hydrophilic group from the viewpoint of introducing a hydrophilic group into the urethane resin (A).
  • polyol having a hydrophilic group examples include carboxyls such as 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, and 2,2′-dimethylolvaleric acid.
  • a polyol having a sulfonic acid group such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid can be used.
  • polyol having a hydrophilic group examples include a polyester polyol having a hydrophilic group obtained by reacting the above-described polyol having a low molecular weight hydrophilic group with various polycarboxylic acids such as adipic acid. It can also be used.
  • the polyol having a hydrophilic group is preferably used in a range of 0.5% by mass to 10% by mass with respect to the total amount of the polyol (a1), and is used in a range of 1% by mass to 5% by mass. It is more preferable.
  • polyisocyanate (a2) that can react with the polyol (a1) examples include aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate.
  • aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate.
  • Polyisocyanates having aliphatic or aliphatic cyclic structures such as isocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate Etc. Alone in combination with the above use or two or may be used.
  • a polyisocyanate having an aliphatic cyclic structure it is preferable to use a polyisocyanate having an aliphatic cyclic structure, and it is more preferable to use isophorone diisocyanate or dicyclohexylmethane diisocyanate in order to prevent yellowing of the skin layer (C) over time. .
  • the equivalent ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polyol (a1) and the isocyanate group of the polyisocyanate (a2) is 1.0. Is preferably in the range of ⁇ 2.0, more preferably 1.1 to 1.9.
  • chain extender (a3) examples include polyamines and hydroxyl group-containing compounds.
  • polyamines examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, Diamines containing one primary amino group and one secondary amino group such as N-methylaminopropylamine; polyamines such as diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, Hydrazines such as N, N'-dimethylhydrazine and 1,6-hexamethylenebishydrazine; Dihydrazides
  • hydroxyl group-containing compound examples include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene Glycols such as glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, and the like; Water or the like can be used alone or in combination of two or more within a range in which the storage stability of the urethane resin composition used in the present invention does not deteriorate.
  • the chain extender (a3) introduces a urea bond into the formed skin layer, and as a result, the urethane resin (A ) Is preferably used in the range of 1% by mass to 10% by mass, and more preferably in the range of 1% by mass to 5% by mass, based on the total amount of the raw materials used for the production of the above.
  • Examples of the organic solvent that can be used when the polyol (a1) and the polyisocyanate (a2) are reacted with the chain extender (a3) as necessary in the step 1 include ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran and dioxane; acetates such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as dimethylformamide and N-methylpyrrolidone may be used alone or in combination of two or more. it can.
  • the urethane prepolymer obtained in Step 1 preferably has a functional group capable of reacting with the amino group of the polyalkanolamine in Step 2 at the molecular end.
  • the functional group is preferably an isocyanate group.
  • the urethane prepolymer obtained in Step 1 may be a solvent-free type, but is preferably a type dissolved in the organic solvent from the viewpoint of imparting good handleability.
  • Step 2 is a process in which the isocyanate group-containing urethane prepolymer obtained in Step 1 or an organic solvent solution thereof is mixed with polyalkanolamine and reacted to cause one or more urethane resins (A) to be obtained. In this step, two or more hydroxyl groups are introduced into the terminal.
  • the desired urethane resin (A) is prepared by mixing the isocyanate group-containing urethane prepolymer or an organic solvent solution thereof or an aqueous dispersion thereof with polyalkanolamine and reacting the mixture at a room temperature of 25 ° C., for example. Can be manufactured. In that case, the amount of hydroxyl groups introduced into the urethane resin (A) to be obtained can be adjusted by adjusting the amount of polyalkanolamine used.
  • polyalkanolamine (a4) examples include diethanolamine, 2-amino-1,3-propanediol, (R) -3-amino-1,2-propanediol, tris (hydroxymethyl) aminoethane, and 1-amino.
  • An amine having a plurality of hydroxyl groups with respect to one amino group such as 1-deoxy-D-glucitol is used alone within a range in which the storage stability of the urethane resin composition used in the present invention is not lowered.
  • 2 or more types can be used together.
  • the urethane resin composition for forming the skin layer used in the present invention may be a solventless type containing the urethane resin (A), from the viewpoint of imparting good coating workability, etc. It is preferable that it contains a solvent.
  • a solvent an aqueous medium or various organic solvents can be used.
  • a urethane resin (A) or an aqueous medium (B) as a urethane resin composition for said skin layer formation, according to the said process 1 and the process 2, a urethane resin (A) or After producing the organic solvent solution and then neutralizing hydrophilic groups such as anionic groups in the urethane resin as necessary, an aqueous medium is supplied, and the urethane resin (A ) Is preferably dispersed.
  • a machine such as a homogenizer may be used as necessary.
  • Examples of the aqueous medium (B) include water, organic solvents miscible with water, and mixtures thereof.
  • the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; lactams such as N-methyl-2-pyrrolidone, and the like.
  • only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
  • the aqueous medium (B) is preferably used in a range of 40% by mass to 85% by mass, and in a range of 50% by mass to 80% by mass with respect to the total amount of the urethane resin composition for forming the skin layer. More preferably it is used.
  • organic solvent examples include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetates such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; dimethylformamide, N-methylpyrrolidone and the like.
  • ketones such as acetone and methyl ethyl ketone
  • ethers such as tetrahydrofuran and dioxane
  • acetates such as ethyl acetate and butyl acetate
  • nitriles such as acetonitrile
  • the amides can be used.
  • the urethane resin composition for forming the skin layer used in the present invention preferably contains the urethane resin (A) in the range of 10% by mass to 50% by mass with respect to the total amount of the urethane resin composition.
  • the content of 20% by mass to 50% by mass is preferable for improving the coating workability.
  • a crosslinking agent can be used in combination.
  • crosslinking agent conventionally known ones such as carbodiimide crosslinking agents, oxazoline crosslinking agents, epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents and the like can be used, and among them, carbodiimide crosslinking agents and oxazolines. It is preferable to use a crosslinking agent.
  • the crosslinking agent may be used in an amount of 1 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A) to improve durability such as heat resistance (water) resistance, sweat resistance and oil resistance. It is preferable in order to improve.
  • the urethane resin composition for forming the skin layer used in the present invention may contain various additives in addition to the above-described ones.
  • additives such as associative thickeners, urethanization catalysts, silane coupling agents, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light resistance stabilizers, fluorescent whitening agents, foaming agents, Thermoplastic resin, thermosetting resin, pigment, dye, conductivity imparting agent, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam, crystal water-containing compound, flame retardant, water absorbing agent, moisture absorption Agents, deodorants, foam stabilizers, antifoaming agents, antifungal agents, antiseptics, algaeproofing agents, pigment dispersants, antiblocking agents, and hydrolysis inhibitors can be used in combination.
  • the associative thickener for example, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylate, polyvinyl pyrrolidone, urethane, polyether, and the like can be used. Especially, since it has favorable compatibility with the said urethane resin (A), it is preferable to use a urethane type association type thickener.
  • the associative thickener is preferably used in the range of 0.5% by mass to 5% by mass with respect to the total amount of the urethane resin (A).
  • the urethane resin composition is capable of forming a film having a sweat resistance level that does not cause poor appearance of leather-like sheets or peeling over time with respect to the support even when sweat or the like adheres. Therefore, it can be suitably used as a coating agent for forming a top coat layer of various substrates. In particular, it can be suitably used for forming the skin layer (C) constituting the leather-like sheet.
  • the urethane resin composition for forming the skin layer can be used as a material for forming the skin layer (C) constituting the leather-like sheet.
  • the leather-like sheet generally has a skin layer (C) laminated on the surface of a support layer (E) made of a fibrous base material impregnated with a resin as necessary via an adhesive layer (D).
  • the urethane resin composition used in the present invention can be suitably used for forming the skin layer (C).
  • the leather-like sheet may have a porous layer (foamed layer) for the purpose of imparting flexibility and the like, and the adhesive layer (D) is foamed and substantially corresponds to the porous layer. You may do.
  • a nonwoven fabric, a woven fabric, a knitted fabric, or the like can be used as the support that can be used for forming the support layer (E).
  • a nonwoven fabric, a woven fabric, a knitted fabric, or the like can be used as the material constituting the base material.
  • polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, blended fiber thereof or the like is used. can do.
  • the surface of the support may be subjected to antistatic processing, mold release processing, water repellent processing, water absorption processing, antibacterial deodorization processing, antibacterial processing, ultraviolet blocking processing, and the like as necessary.
  • the leather-like sheet in which the skin layer (C) is laminated on the surface of the support via the adhesive layer (D) is, for example, a urethane resin composition for forming the skin layer on a sheet subjected to a release treatment.
  • the skin layer (C) is formed by applying and drying, and then the support is laminated on the skin layer (C) using an adhesive (d) or the like.
  • Examples of the method of applying the urethane resin composition on the sheet include a gravure coater method, a knife coater method, a pipe coater method, and a comma coater method. Further, as a method for drying and curing the urethane resin composition applied by the above method, for example, it is allowed to stand for 1 to 10 days at room temperature, or heated at a temperature of 50 to 250 ° C. for 1 to 600 seconds. The method of doing is mentioned.
  • Examples of the adhesive (d) used for bonding the skin layer (C) and the support layer (E) include a compound (d-1) having a hydroxyl group and a compound (d-2) having an isocyanate group. It is preferable to use the contained adhesive.
  • the adhesive (d) it is preferable to use an adhesive containing the compound (d-2) having an isocyanate group in excess relative to the compound (d-1) having a hydroxyl group.
  • the hydroxyl group of the compound (d-1) and the isocyanate group of the compound (d-2) react to form an adhesive layer (D), and the compound (d- 2)
  • the isocyanate group of 2) reacts with part or all of the hydroxyl groups of the urethane resin (A) forming the skin layer (C), so that even if sweat or the like adheres, the appearance is poor.
  • the isocyanate group of the compound (d-2) contained in the adhesive (d) and the compound (d-1) The equivalent ratio with the hydroxyl group [isocyanate group / hydroxyl group] is preferably in the range exceeding 1.0.
  • the adhesive (d) specifically, a two-component adhesive containing a urethane resin having a hydroxyl group and a crosslinking agent having an isocyanate group can be used.
  • Examples of the urethane resin having a hydroxyl group that can be used for the adhesive (d) include the polyol (a1), polyisocyanate (a2), and chain extender (a3) exemplified as those usable for the production of the urethane resin (A). ) And the like, and those obtained by reacting them can be used.
  • the isocyanate group of the polyisocyanate used for the production and the hydroxyl group of the polyol It is preferable to use a product obtained by mixing and reacting the polyisocyanate and the polyol within the range where the equivalent ratio [isocyanate group / hydroxyl group] is less than 1.0.
  • the urethane resin having a hydroxyl group obtained above preferably has a weight average molecular weight of about 10,000 to 50,000 in order to exhibit excellent adhesive strength.
  • a two-component adhesive containing a polyol and a polyisocyanate can be used in addition to those described above.
  • the two-component adhesive can form an adhesive layer (D) in which urethane bonds are formed by mixing the polyol and polyisocyanate and then quickly applying the mixture onto the support surface.
  • the same polyols (a1) exemplified as those that can be used when the urethane resin (A) is produced can be used.
  • polycarbonate polyol or the like can be used.
  • polyisocyanate which can be used for the two-component adhesive
  • the same polyisocyanate (a2) exemplified as that usable when the urethane resin (A) is produced may be used. it can.
  • the two-component adhesive reacts with the hydroxyl group of the urethane resin (A) forming the skin layer (C), and even when sweat or the like adheres to it, the appearance or support of the leather-like sheet is poor.
  • a urethane resin having a hydroxyl group as described above, a crosslinking agent having an isocyanate group, or a curing component such as polyol or polyisocyanate dispersed or dissolved in a solvent such as water or a solvent is used. It is possible to use a solvent-free type.
  • the adhesive (d) can be applied to the surface of the support (C) or the skin layer (C) by a method such as a gravure coater method, a knife coater method, a pipe coater method, or a comma coater method.
  • a method such as a gravure coater method, a knife coater method, a pipe coater method, or a comma coater method.
  • the porous layer is formed by applying a method generally referred to as a mechanical foaming method, a microballoon, foaming, or the like when the adhesive (d) is applied to the support surface. It can form by making it foam by adding additives, such as an agent.
  • the adhesive layer (D) and the skin layer (C) are coated with the adhesive (d) and the skin layer (C) by heating them under the condition of 40 ° C. to 120 ° C. Even if the isocyanate group present in the adhesive (d) reacts with the hydroxyl group present in the skin layer (C) at the interface with (C) and sweat or the like adheres, It is possible to obtain a leather-like sheet having an outer skin layer having durability such as sweat resistance and oil resistance at a level that does not cause poor appearance of the leather-like sheet and peeling over time with respect to the support.
  • an intermediate layer such as a porous layer is provided as the leather-like sheet in addition to the adhesive layer (D), for example, the urethane resin composition for forming the skin layer on a sheet subjected to a release treatment.
  • a skin layer (C) is formed by coating and drying, and then a porous layer forming resin composition foamed by a conventionally known mechanical foaming method or water foaming method on the skin layer (C). It can be obtained by forming a porous layer by coating and curing, and then laminating the support (C) on the porous layer using the adhesive (d).
  • the thickness of the skin layer (C) constituting the leather-like sheet obtained above is preferably in the range of about 10 ⁇ m to 300 ⁇ m.
  • the adhesive layer (D) preferably has a thickness of 10 ⁇ m to 300 ⁇ m.
  • the leather-like sheet obtained by the above method is excellent in bending resistance, including durability such as sweat resistance and oil resistance, and is used for various applications such as bags, shoes, clothes, and vehicle interior materials. It is possible.
  • urethane resin composition [d1-1-1] obtained above 100 g of the urethane resin composition [d1-1-1] obtained above, 0.2 g of silicone leveling agent, 0.1 g of silicone antifoaming agent, 1.0 g of urethane associative thickener, isocyanate crosslinking agent 5.0 g was added, stirred at 2000 rpm for 2 minutes using a mechanical mixer, and then defoamed using a vacuum defoamer to obtain an aqueous adhesive (d1-1).
  • Example 1 Preparation of leather-like sheet In the presence of 710 g of methyl ethyl ketone and 0.1 g of stannous octylate, 1000 g of polycarbonate diol (Niporan N981; Nippon Polyurethane Industry Co., Ltd .: number average molecular weight 1000) and dimethylolpropionic acid 67 g and 590 g of dicyclohexylmethane diisocyanate (HMDI) are reacted at 70 ° C. until the NCO% reaches 2.7% by mass to obtain a methyl ethyl ketone solution of the terminal isocyanate group-containing urethane prepolymer (A′-1). It was.
  • the NCO% is the ratio of the mass of isocyanate groups possessed by polyisocyanate to the total mass of raw materials used in the production of the polyurethane.
  • the resulting emulsion was supplied with 1310 g of a chain extender aqueous solution containing 36 g of ethylenediamine and 95 g of diethanolamine, and mixed to cause a chain elongation reaction.
  • urethane resin composition [I] obtained above 100 g of the urethane resin composition [I] obtained above, 0.2 g of the silicone leveling agent, 0.1 g of the silicone antifoaming agent, and 1.0 g of the urethane-based associative thickener are added, and 2000 rpm using a mechanical mixer. The mixture was stirred for 2 minutes and then defoamed using a vacuum defoamer to obtain a urethane resin composition [I-1] for forming a skin layer.
  • urethane resin composition [I-1] for forming the skin layer 100 parts by mass of the urethane resin composition [I-1] for forming the skin layer was applied on a release paper (155T Flat Flat Nihon Printing Co., Ltd.) so that the film thickness after application was 150 ⁇ m. .
  • a support made of a polyester fiber nonwoven fabric was placed on the coated surface of the adhesive (d1-1), pressure-bonded using a roll adjusted to 120 ° C., and then aged at 80 ° C. for 24 hours. After the aging, the release paper was removed to obtain a leather-like sheet [I-2].
  • Example 2 Production of leather-like sheet
  • 100 parts by mass of the urethane resin composition [I-1] for forming the skin layer used in Example 1 above was separated from release paper (155T Flat Dai Nippon Printing Co., Ltd.).
  • the film thickness after application was 150 ⁇ m.
  • Example 3 Preparation of leather-like sheet In the presence of 710 g of methyl ethyl ketone and 0.1 g of stannous octylate, 1000 g of polyester diol (Placcel 210, Daicel Chemical Industries, Ltd. molecular weight of about 1000), 67 g of dimethylolpropionic acid, By reacting 590 g of dicyclohexylmethane diisocyanate (HMDI) at 70 ° C. until NCO% reached 2.7% by mass, a methyl ethyl ketone solution of the terminal isocyanate group-containing urethane prepolymer (A′-2) was obtained.
  • HMDI dicyclohexylmethane diisocyanate
  • the resulting emulsion was supplied with 1310 g of a chain extender aqueous solution containing 36 g of ethylenediamine and 95 g of diethanolamine, and mixed to cause a chain elongation reaction.
  • urethane resin composition [II] 100 g of the urethane resin composition [II] obtained above, 0.2 g of silicone leveling agent, 0.1 g of silicone antifoaming agent and 1.0 g of urethane associative thickener are added, and 2000 rpm using a mechanical mixer. The mixture was stirred for 2 minutes and then defoamed using a vacuum defoamer to obtain a urethane resin composition [II-2] for forming a skin layer.
  • Example 1 except that 100 parts by mass of the urethane resin composition for skin layer formation [II-1] was used instead of the urethane resin composition for skin layer formation [I-1].
  • the leather-like sheet [III-2] was obtained by this method.
  • Example 4 Production of leather-like sheet In the presence of 710 g of methyl ethyl ketone and 0.1 g of stannous octylate, 1000 g of polycarbonate diol (Niporan N981; Nippon Polyurethane Industry Co., Ltd .: number average molecular weight 1000) and polyethylene glycol (PEG1000) , NOF Corporation) 50 g, polyethylene glycol monomethyl ether (Uniox M1000: NOF Corporation) 50 g, and dicyclohexylmethane diisocyanate (HMDI) 590 g until NCO% reaches 2.7% by mass.
  • a methyl ethyl ketone solution of the terminal isocyanate group-containing urethane prepolymer (A'-3) was obtained by reacting at 0 ° C.
  • the resulting emulsion was supplied with 1310 g of a chain extender aqueous solution containing 36 g of ethylenediamine and 95 g of diethanolamine, and mixed to cause a chain elongation reaction.
  • urethane resin composition [III] 100 g of the urethane resin composition [III] obtained above, 0.2 g of silicone leveling agent, 0.1 g of silicone antifoaming agent and 1.0 g of urethane associative thickener are added, and 2000 rpm using a mechanical mixer. The mixture was stirred for 2 minutes and then defoamed using a vacuum defoamer to obtain a urethane resin composition [III-1] for forming a skin layer.
  • Example 1 except that 100 parts by mass of the urethane resin composition for forming the skin layer [III-1] is used instead of the urethane resin composition for forming the skin layer [I-1].
  • a leather-like sheet [IV-2] was obtained.
  • Example 5 Production of leather-like sheet In the presence of 630 g of methyl ethyl ketone and 0.1 g of stannous octylate, 1000 g of polycarbonate diol (Niporan N980R; Nippon Polyurethane Industry Co., Ltd .: number average molecular weight 2000) and dimethylolpropionic acid
  • HMDI dicyclohexylmethane diisocyanate
  • the obtained emulsion was supplied with 770 g of a chain extender aqueous solution containing 24 g of ethylenediamine and 53 g of diethanolamine, and mixed to cause a chain elongation reaction.
  • urethane resin composition [IV] weight average molecular weight 42000, hydroxyl value 36.8 having a nonvolatile content of 35% by mass.
  • urethane resin composition [IV] 100 g of the urethane resin composition [IV] obtained above, 0.2 g of a silicone leveling agent, 0.1 g of a silicone antifoaming agent, and 1.0 g of a urethane-based associative thickener are added, and 2000 rpm using a mechanical mixer. By stirring for 2 minutes and then defoaming using a vacuum defoamer, a urethane resin composition [IV-1] for forming the skin layer was obtained.
  • Urethane resin composition for forming the skin layer [I- A leather-like sheet [V-2] was obtained in the same manner as in Example 1 except that 100 parts by mass of the urethane resin composition [IV-1] for forming the skin layer was used instead of 1]. .
  • Example 6 Production of leather-like sheet In the presence of 710 g of methyl ethyl ketone and 0.1 g of stannous octylate, 1000 g of polycarbonate diol (Niporan N981; Nippon Polyurethane Industry Co., Ltd .: number average molecular weight 1000) and dimethylolpropionic acid 67 g and 590 g of dicyclohexylmethane diisocyanate (HMDI) are reacted at 70 ° C. until the NCO% reaches 2.7% by mass to obtain a methyl ethyl ketone solution of the terminal isocyanate group-containing urethane prepolymer (A′-1). It was.
  • polycarbonate diol Niporan N981; Nippon Polyurethane Industry Co., Ltd .: number average molecular weight 1000
  • HMDI dicyclohexylmethane diisocyanate
  • the resulting emulsion was supplied with 530 g of a chain extender solution containing 42 g of ethylenediamine and 11 g of diethanolamine, and mixed to cause a chain extension reaction.
  • urethane resin composition [V] 100 g of the urethane resin composition [V] obtained above, 0.2 g of the silicone leveling agent, 0.1 g of the silicone antifoaming agent, and 1.0 g of the urethane associative thickener are added, and 2000 rpm using a mechanical mixer. By stirring for 2 minutes and then defoaming using a vacuum defoamer, a urethane resin composition [V-1] for forming the skin layer was obtained.
  • Urethane resin composition for forming the skin layer [I- A leather-like sheet [V-2] was obtained in the same manner as in Example 1 except that 100 parts by mass of the urethane resin composition for forming a skin layer [V-1] was used instead of 1]. .
  • the obtained emulsion was supplied with 910 g of a chain extender aqueous solution containing 36 g of ethylenediamine and 55 g of monoethanolamine, and mixed to cause a chain extension reaction.
  • urethane resin composition [I ′] obtained above, 0.2 g of silicone leveling agent, 0.1 g of silicone antifoaming agent, and 1.0 g of urethane associative thickener, and use a mechanical mixer. By stirring at 2000 rpm for 2 minutes and then defoaming using a vacuum defoamer, a urethane resin composition [I′-1] for forming a skin layer was obtained.
  • Example 1 except that 100 parts by mass of the urethane resin composition [I′-1] for forming the skin layer was used instead of the urethane resin composition [I-1] for forming the skin layer.
  • a leather-like sheet [I'-2] was obtained by the method described above.
  • the obtained emulsion was supplied with 520 g of a chain extender aqueous solution containing 21 g of N- (aminoethyl) ethanolamine and 31 g of monoethanolamine, and mixed to cause a chain elongation reaction.
  • urethane resin composition [II ′] obtained above, 0.2 g of silicone leveling agent, 0.1 g of silicone antifoaming agent, and 1.0 g of urethane associative thickener, and use a mechanical mixer. By stirring at 2000 rpm for 2 minutes and then defoaming using a vacuum defoamer, a urethane resin composition [II′-1] for forming a skin layer was obtained.
  • Example 1 except that 100 parts by mass of the urethane resin composition for forming the skin layer [II′-1] is used instead of the urethane resin composition for forming the skin layer [I-1].
  • a leather-like sheet [II′-2] was obtained by the method described above.
  • the obtained emulsion was supplied with 1400 g of an aqueous chain extender solution containing 36 g of ethylenediamine and 116 g of dibutylamine, and mixed to cause a chain extension reaction.
  • Example 1 except that 100 parts by mass of the urethane resin composition for forming the skin layer [III′-1] is used instead of the urethane resin composition for forming the skin layer [I-1].
  • a leather-like sheet [III'-2] was obtained by the method described above.
  • the surface of the skin layer after wiping was visually observed and evaluated according to the following evaluation criteria.
  • the gauze was removed, and the oleic acid adhering to the surface of the epidermis layer was wiped off with waste cloth.
  • the leather-like sheet after wiping is dried in an environment of 90 ° C. for 1 hour, the leather-like sheet is fixed horizontally, a canvas is placed on the surface of the skin layer, and a weight of 500 g is applied. Then, the surface of the skin layer was repeatedly rubbed.
  • Evaluation was performed according to the following evaluation criteria based on the number of frictions during the rubbing and the appearance of the skin layer.
  • a material having the above evaluation of “C” or higher is practically preferable, and is preferably “B” or higher.
  • the specific number of frictions is unknown. (For checking every 1000 times) A: The number of friction was 5000 times, and the skin layer of the leather-like sheet was not peeled off. B: The skin layer of the leather-like sheet was peeled off when the number of friction was 5000, and the base material was exposed. C: The skin layer of the leather-like sheet was peeled off when the number of frictions was 4000, and the base material was exposed. D: The skin layer of the leather-like sheet was peeled off when the number of frictions was 3000, and the base material was exposed. E: The skin layer of the leather-like sheet was peeled off and the substrate was exposed before rubbing or within 5 times of rubbing.
  • the filter paper was removed, and the sun oil adhering to the surface of the skin layer was wiped off with a waste cloth.
  • the surface of the skin layer after wiping was visually observed and evaluated according to the following evaluation criteria.
  • A Compared with before the sun oil was adhered, the appearance was not changed at all, and the skin layer was not peeled off.
  • B Slight swelling (swelling of the skin layer) was observed in a small part of the appearance compared to before the sun oil was applied, but this was a practically acceptable level and peeling of the skin layer was also observed. There wasn't.
  • C Although swelling (swelling of the skin layer) that can be clearly confirmed was observed in appearance as compared with before the sun oil was adhered, peeling of the skin layer was not observed.
  • D Swelling (swelling of the skin layer) that can be clearly confirmed in appearance was observed and partial peeling of the skin layer was observed as compared to before the sun oil was adhered.
  • E Most of the epidermis layer peeled or dissolved.
  • the specific number of flexions is unknown. (For checking every specified number of times) A: Cracks did not occur on the surface of the leather-like sheet when the number of bendings was 100,000. B: Cracks occurred on the surface of the leather-like sheet when the number of flexions was 75,000. C: Cracks occurred on the surface of the leather-like sheet when the number of flexing was 50000 times. D: Cracks occurred on the surface of the leather-like sheet when the number of flexing was 25000 times. E: Cracks occurred on the surface of the leather-like sheet when the number of bendings was 10,000.
  • the leather-like sheets obtained in Examples 1 and 2 each had a skin layer excellent in sweat resistance and oil resistance, and did not cause cracking even when bent. Further, the leather-like sheets obtained in Example 3 and Example 4 did not contain a polycarbonate structure, or the ratio of the polycarbonate structure was small. As well as excellent oil resistance and bending resistance. Further, the leather-like sheet obtained in Example 5 had good sweat resistance, oil resistance, and flex resistance, although the hydroxyl value of the urethane resin constituting the skin layer was slightly reduced. .
  • the leather-like sheet obtained in Comparative Examples 1 and 2 is an example in which a urethane resin having one hydroxyl group at one end is used as the urethane resin constituting the skin layer, and is sweat and oil resistant. Caused a significant decline.
  • the leather-like sheet obtained in Comparative Example 3 is an example in which a urethane resin having no hydroxyl group at the terminal is used as the urethane resin constituting the skin layer, and the sweat resistance and oil resistance are significantly reduced. Caused.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'objectif de la présente invention est de proposer une composition de résine d'uréthane pour former une couche peau superficielle d'une feuille en simili cuir, ladite composition de résine d'uréthane permettant la formation de la couche peau superficielle qui présente une excellente durabilité, telle qu'une résistance à la perspiration et une résistance à l'huile, dans une mesure telle que la feuille en simili cuir ne présente ni détérioration d'apparence ni décollage à partir d'un substrat avec le temps même lorsque, par exemple, de la transpiration, de l'huile, ou analogue, colle à ladite feuille. La solution proposée consiste en une feuille en simili cuir qui est caractérisée en ce qu'elle comprend : une couche peau superficielle (C) formée en utilisant une composition de résine d'uréthane qui comprend une résine d'uréthane (A) au moins à une extrémité de laquelle se trouvent deux, ou plus, groupes hydroxyle, et un milieu aqueux (B) ; une couche adhésive (D) ; et une couche substrat (E).
PCT/JP2012/066690 2011-08-22 2012-06-29 Feuille en simili cuir et procédé pour sa fabrication Ceased WO2013027489A1 (fr)

Priority Applications (3)

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JP2012546286A JP5196088B1 (ja) 2011-08-22 2012-06-29 皮革様シート及びその製造方法
CN201280040939.XA CN103764899B (zh) 2011-08-22 2012-06-29 皮革样片材及其制造方法
US14/239,669 US20140212676A1 (en) 2011-08-22 2012-06-29 Leather-like sheet and method for manufacturing the same

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JP2011180491 2011-08-22
JP2011-180491 2011-08-22

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JP5196088B1 (ja) 2013-05-15
CN103764899B (zh) 2016-07-06
TWI547618B (zh) 2016-09-01
JPWO2013027489A1 (ja) 2015-03-19
CN103764899A (zh) 2014-04-30
US20140212676A1 (en) 2014-07-31

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