Classifications

• • 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
  • 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
  • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
  • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
  • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
  • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
• • 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
• • 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
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/3228—Polyamines acyclic
  • C08G18/3231—Hydrazine or derivatives thereof
• • 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
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/3234—Polyamines cycloaliphatic
• • 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
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters
• • 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
  • D06N3/04—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 by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N3/06—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 by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
• • 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
  • D06N3/04—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 by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N3/06—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 by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
  • D06N3/08—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 by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products with a finishing layer consisting of polyacrylates, polyamides or polyurethanes or polyester
• • 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
• • 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
  • D06N3/146—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 characterised by the macromolecular diols used
• • 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
  • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials

Definitions

• the present invention relates to a laminated body and synthetic leather.
• Urethane resin compositions containing urethane resin are widely used for surface treatment of synthetic leather, artificial leather, films, sheets, adhesives, sheet-like materials, and the like. Among these, higher durability is required when used for long-term use members such as synthetic leather for interior materials for vehicles.
• An object to be solved by the present invention is to provide a urethane resin composition excellent in adhesion between a thermoplastic resin layer and a film formed by a urethane resin composition and suppression of bleeding of a plasticizer.
• the present invention has a thermoplastic resin layer and a film formed of a urethane resin composition containing a urethane resin having a structure derived from a polycarbonate polyol made from glycol having 8 to 12 carbon atoms as a raw material. It provides a characteristic laminate.
• the present invention provides synthetic leather characterized by further having a surface treatment layer.
• the laminate of the present invention has excellent adhesion between the thermoplastic resin layer and the film formed of the urethane resin composition (hereinafter, abbreviated as “adhesion"), and suppresses bleeding of the plastic agent (hereinafter, abbreviated as “adhesion”). , Abbreviated as “bleed resistance”).
• the laminate of the present invention has a thermoplastic resin layer and a film formed of a urethane resin composition containing a urethane resin using a specific raw material.
• thermoplastic resin layer for example, one formed of known polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polystyrene or the like can be used. In the present invention, even when polyvinyl chloride is used as the thermoplastic resin, it has excellent bleed resistance.
• the film is formed of a urethane resin composition containing a urethane resin having a structure derived from a polycarbonate polyol made of glycol having a carbon atom number of 8 to 12 as a raw material.
• the urethane resin has a structure derived from a polycarbonate polyol made from glycol having 8 to 12 carbon atoms. It is presumed that excellent adhesion and bleed resistance can be obtained by using a non-polar polycarbonate polyol as the polycarbonate polyol.
• urethane resin for example, a solvent-based urethane resin composition containing an organic solvent; an aqueous urethane resin composition containing water, or the like can be used.
• a water-based urethane resin composition is preferable from the viewpoint of reducing the environmental load.
• Examples of the solvent-based urethane resin composition include urethane resins and those containing an organic solvent.
• a polyol (a1-1) containing a polycarbonate polyol made of a glycol having a carbon atom number of 8 to 12 as a raw material, and a reaction product of a polyisocyanate (a2-1) can be used. ..
• glycol having 8 to 11 carbon atoms which is the raw material of the polycarbonate polyol, include 2,4-dimethyl-1,5-pentanediol, 2,3-dimethyl-1,5-pentanediol, and 2-ethyl.
• glycols having 8 to 9 carbon atoms and carbon atoms have the same number of carbon atoms because excellent adhesion, bleed resistance, low temperature bending property, and mechanical strength can be obtained. It is preferable to use a glycol having 10 to 11 carbon atoms in combination, and more preferably to use a glycol having 9 carbon atoms and a glycol having 10 carbon atoms in combination.
• the molar ratio [C8-9 / C10-11] of the two is even more excellent.
• the range is preferably 5/95 to 50/50, and more preferably 10/90 to 40/60.
• polycarbonate diol one obtained by reacting the glycol having 8 to 11 carbon atoms with a carbonic acid ester and / or phosgene by a known method can be used.
• carbonic acid ester for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate and the like can be used. These compounds may be used alone or in combination of two or more.
• the number average molecular weight of the polycarbonate diol is preferably in the range of 1,500 to 3,500 from the viewpoint of obtaining even more excellent mechanical strength, bleed resistance, adhesion, and low temperature bending property.
• the number average molecular weight of the polycarbonate polyol is a value measured by a gel permeation chromatography (GPC) method.
• the amount of the polycarbonate polyol used is preferably 30% by mass or more in the polyol (a1-1) from the viewpoint of obtaining further excellent mechanical strength, bleed resistance, adhesion, and low temperature flexibility, and is preferably 50. By mass or more is preferable, and 70% by mass or more is more preferable.
• polyol (a1-1) other polyols can be used.
• other polyol for example, a polyester polyol, a polyether polyol, a polycarbonate polyol other than the polycarbonate polyol, or the like can be used. These polyols may be used alone or in combination of two or more.
• the number average molecular weight of the other polyol is preferably in the range of 500 to 10,000, more preferably in the range of 700 to 8,000, from the viewpoint of the mechanical properties of the film and the bleed resistance.
• the number average molecular weight of the other polyols is a value measured by a gel permeation chromatography (GPC) method.
• a chain extender (a'1-1) having a molecular weight of less than 500 may be used in combination with the polyol (a1-1).
• a chain extender (a'1-1) for example, a chain extender having a hydroxyl group, a chain extender having an amino group, or the like can be used.
• These chain extenders (a'1-1) may be used alone or in combination of two or more.
• chain extender having a hydroxyl group examples include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and hexamethylene glycol.
• Aliphatic polyol compounds such as saccharose, methylene glycol, glycerin, and sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc.
• Aromatic polyol compound; water and the like can be used. These chain extenders may be used alone or in combination of two or more.
• chain extender having an amino group examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4.
• chain extender (a'1-1) a chain extender having an amino group is preferable from the viewpoint of obtaining even better adhesion and bleed resistance, and piperazine, hydrazine, isophoronediamine, and the chain extender are preferable. It is more preferable to use one or more compounds selected from the group consisting of 4,4'-dicyclohexylmethanediamine.
• the amount used is 0.1 to 80 in the polyol (a1-1) from the viewpoint of obtaining even better adhesion and bleed resistance.
• the range of% by mass is preferable, and the range of 1 to 60% by mass is more preferable.
• polyisocyanate (a2-1) examples include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylenediisocyanate, toluenediisocyanate, naphthalenediocyanate, and xylylene diisocyanate.
• Aromatic polyisocyanate such as tetramethylxylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexanediisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, aliphatic polyisocyanate such as dicyclohexylmethane diisocyanate and the like can be used. These polyisocyanates may be used alone or in combination of two or more.
• aliphatic polyisocyanates are preferable from the viewpoint of obtaining even better adhesion and bleed resistance, and one or more selected from the group consisting of hexamethylene diisocyanate, isophorone diamine, and dicyclohexylmethane diisocyanate.
• Polyisocyanate is preferred.
• the content of the aliphatic polyisocyanate in the polyisocyanate (a2-1) is preferably 30% by mass or more, preferably 50% by mass, from the viewpoint of obtaining even better adhesion and bleed resistance. More preferred.
• the polyol (a1-1), the polyisocyanate (a2-1) and, if necessary, the chain extender (a'1-1) are charged and reacted.
• a method of manufacturing by. These reactions are preferably carried out at a temperature of 50 to 100 ° C. for about 3 to 10 hours. Further, the reaction may be carried out in an organic solvent described later.
• the isocyanate group) / (hydroxyl group and amino group)] is preferably in the range of 0.8 to 1.2, and more preferably in the range of 0.9 to 1.1.
• the weight average molecular weight of the urethane resin is preferably in the range of 5,000 to 1,000,000 from the viewpoint of mechanical properties, adhesion, and bleed resistance of the film, and is preferably 10,000 to 500. A range of 000 is more preferred.
• the weight average molecular weight of the urethane resin indicates a value obtained by measuring in the same manner as the number average molecular weight of the polyol (a1-1).
• the content of the urethane resin may be, for example, in the range of 10 to 90 parts by mass in the solvent-based urethane resin composition.
• organic solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N, 2-trimethylpropionamide, N, N-dimethylacrylamide, N, N-dimethylpropion.
• Amides, N, N-diethylacetamide, N, N-diethylacrylamide, N-ethylpyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like can be used. These organic solvents may be used alone or in combination of two or more.
• an organic solvent such as ethyl acetate, methyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, isobutanol, sec-butanol, and tertiary butanol may be used in combination. good.
• the content of the organic solvent may be, for example, in the range of 10 to 90% by mass in the solvent-based urethane resin composition.
• water-based urethane resin composition examples include urethane resin and those containing water.
• the urethane resin can be dispersed in water, and for example, a urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group; a urethane resin forcibly dispersed in water with an emulsifier, or the like. Can be used. These urethane resins may be used alone or in combination of two or more.
• Examples of the method for obtaining the urethane resin having an anionic group include a method using one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group as a raw material.
• Examples of the compound having a carboxyl group include 2,2-dimethylol propionic acid, 2,2-dimethylol butyric acid, 2,2-dimethylol butyric acid, 2,2-dimethylol propionic acid, and 2,2-valeric acid. Valeric acid and the like can be used. These compounds may be used alone or in combination of two or more.
• Examples of the compound having a sulfonyl group include 3,4-diaminobutane sulfonic acid, 3,6-diamino-2-toluene sulfonic acid, 2,6-diaminobenzene sulfonic acid, and N- (2-aminoethyl)-.
• 2-Aminosulfonic acid, N- (2-aminoethyl) -2-aminoethylsulfonic acid and the like can be used. These compounds may be used alone or in combination of two or more.
• the carboxyl group and the sulfonyl group may be partially or completely neutralized with a basic compound in the urethane resin composition.
• a basic compound for example, organic amines such as ammonia, triethylamine, pyridine, and morpholin; alkanolamines such as monoethanolamine and dimethylethanolamine; and metal base compounds containing sodium, potassium, lithium, calcium and the like are used. Can be done.
• Examples of the method for obtaining the urethane resin having a cationic group include a method using one or more compounds having an amino group as a raw material.
• Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-methyl.
• Compounds having a tertiary amino group such as N-alkyldiaminoalkylamine such as diaminoethylamine and N-ethyldiaminoethylamine can be used. These compounds may be used alone or in combination of two or more.
• Examples of the method for obtaining the urethane resin having a nonionic group include a method using one or more compounds having an oxyethylene structure as a raw material.
• a polyether polyol having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol can be used. These compounds may be used alone or in combination of two or more.
• Examples of the emulsifier that can be used to obtain the urethane resin that is forcibly dispersed in water include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, and polyoxyethylene sorbitol tetraole.
• Nonionic emulsifiers such as ate, polyoxyethylene / polyoxypropylene copolymer; fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalensulphonate, polyoxyethylene alkyl Anionic emulsifiers such as sulfates, alkansulfonate sodium salts and alkyldiphenyl ether sulfonate sodium salts; cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts and alkyldimethylbenzylammonium salts can be used. These emulsifiers may be used alone or in combination of two or more.
• urethane resin a urethane resin having an anionic group and a urethane resin having an anionic group can be obtained from the viewpoints of further excellent water dispersion stability, hydrolysis resistance, peel strength, immediate peeling property, bleeding resistance, and light resistance. / Or, a urethane resin having a nonionic group is preferable.
• the concentration of the hydrophilic group of the urethane resin is adjusted to further improve the water dispersion stability, hydrolysis resistance, and peel strength. From the viewpoint of immediate peeling property, bleeding resistance, and light resistance, the range of 0.01 to 10% by mass is preferable, and the range of 0.1 to 5% by mass is more preferable in the raw materials constituting the urethane resin. preferable.
• the urethane resin examples include a polyol (a1-2) containing a polycarbonate polyol made from a glycol having 8 to 12 carbon atoms as a raw material, a polyisocyanate (a2-2), and the hydrophilic resin.
• a1-2 a polycarbonate polyol made from a glycol having 8 to 12 carbon atoms as a raw material
• a2-2 polyisocyanate
• hydrophilic resin examples include reaction products of raw materials used for producing urethane resins having a sex group.
• polyol (a1-2) containing the polycarbonate polyol the same polyol as the polyol (a1-1) can be used.
• a chain extender (a'1-2) having a molecular weight of less than 500 may be used in combination with the polyol (a1-2).
• the chain extender (a'1-2) the same one as the chain extender (a'1-1) can be used, and even more excellent adhesion and bleed resistance can be obtained.
• a chain extender having an amino group is preferable, and it is more preferable to use one or more compounds selected from the group consisting of piperazine, hydrazine, isophoronediamine, and 4,4'-dicyclohexylmethanediamine.
• the amount used is 0.1 to 80 in the polyol (a1-2) from the viewpoint of obtaining even better adhesion and bleed resistance.
• the range of% by mass is preferable, and the range of 1 to 60% by mass is more preferable.
• polyisocyanate (a2-2) the same one as the polyisocyanate (a2-1) can be used, and an alicyclic type can be obtained from the viewpoint of obtaining further excellent adhesion and bleed resistance.
• Polyisocyanates are preferred, isophorone diamines and / or dicyclohexylmethane diisocyanates are preferred.
• the content of the alicyclic polyisocyanate in the polyisocyanate (a2-2) is preferably 30% by mass or more, more preferably 50% by mass, from the viewpoint of obtaining even more excellent bleed resistance.
• the raw material used for producing the urethane resin having a hydrophilic group for example, the raw material used for producing the urethane resin having a hydrophilic group, the polyisocyanate (a2-2), the polyol (a1-2), and if necessary, the above.
• examples thereof include a method in which a chain extender (a'1-2) is charged in a batch and reacted.
• examples thereof include a method in which these reactions are carried out at a temperature of 50 to 100 ° C. for 3 to 10 hours.
• the molar ratio [(isocyanate group) / (total of hydroxyl groups and amino groups)] of the total to the isocyanate group of the aromatic polyisocyanate (a2-2) is in the range of 0.8 to 1.2. It is preferable, and the range of 0.9 to 1.1 is more preferable.
• the urethane resin When producing the urethane resin, it is preferable to inactivate the isocyanate groups remaining in the urethane resin. When inactivating the isocyanate group, it is preferable to use an alcohol having a hydroxyl group such as methanol. When the alcohol is used, the amount used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the urethane resin.
• an organic solvent when producing the urethane resin, an organic solvent may be used.
• the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetate compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; dimethylformamide and N-methylpyrrolidone.
• An amide compound or the like can be used.
• These organic solvents may be used alone or in combination of two or more. The organic solvent is preferably removed by a distillation method or the like when the urethane resin composition is obtained.
• the water for example, ion-exchanged water, distilled water, tap water, or the like can be used. Among these, it is preferable to use ion-exchanged water having few impurities.
• the content of the water (B) is preferably in the range of 20 to 90% by mass, preferably in the range of 40 to 80% by mass in the water-based urethane resin composition from the viewpoint of workability, coatability, and storage stability. More preferred.
• the urethane resin composition of the present invention may contain other additives, if necessary, in either the solvent-based urethane resin composition or the water-based urethane resin composition.
• Examples of the other additives include a urethanization catalyst, a neutralizing agent, a cross-linking agent, a silane coupling agent, a thickener, a filler, a thixo-imparting agent, a tackifier, a wax, a heat stabilizer, and a light-resistant stabilizer.
• Fluorescent whitening agent, foaming agent, pigment, dye, conductivity imparting agent, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam, flame retardant, water absorbing agent, moisture absorbing agent, deodorant , Anti-foaming agent, anti-blocking agent, anti-hydrolysis agent and the like can be used. These additives may be used alone or in combination of two or more.
• film swelling rate The swelling rate of the film after immersing the film cut into a thickness of 30 ⁇ m, a length of 3 cm, and a width of 3 cm in a plasticizer for 24 hours (hereinafter, abbreviated as “film swelling rate”). Is preferably 10% or more, more preferably 10 to 40%, still more preferably 10 to 25%, in order to obtain even better bleed resistance.
• plasticizer examples include phthalates such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate and dibutyl phthalate; adiponic acid esters such as dioctyl adipate and diisononyl adipate; trimellitic acid esters such as trioctyl trimertate; Phosphoric acid esters such as tricresyl phosphate; citrate esters such as acetyltributyl citrate; epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; sevacinic acid ester; azelaic acid ester; maleic acid ester; benzoic acid ester; In addition, polyester or the like can be used. These plasticizers may be used alone or in combination of two or more. In the present invention, it also has excellent bleed resistance against phthalates often used for polyvinyl chloride.
• the laminate of the present invention is excellent in adhesion and bleed resistance.
• Examples of the synthetic leather include those having a base material, a thermoplastic resin layer, the film, and a surface treatment layer in sequence.
• the base material examples include polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, linen, silk, wool, glass fiber, carbon fiber, and a blend thereof.
• Non-woven fabrics made of fibers, woven fabrics, knitting and the like can be used.
• the surface treatment layer for example, a layer formed of a known solvent-based urethane resin, water-based urethane resin, solvent-based acrylic resin, water-based acrylic resin, or the like can be used.
• Example 1 ⁇ Preparation of water-based urethane resin composition (1)> Polypolypolyol (1,9-nonanediol and 2-methyl-1,8-octanediol) are used as raw materials in a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer and a nitrogen blowing tube under a nitrogen stream. , Number average molecular weight: 2,000) 340 parts by mass, methyl ethyl ketone 300 parts by mass, dimethylol propionic acid 11 parts by mass, mixed uniformly, then 90 parts by mass of dicyclohexylmethane diisocyanate was added, and then bismuth carboxylate 0.
• the aqueous urethane resin composition (1) is coated on a PVC base material (manufactured by Engineering Test Service Co., Ltd.) so that the thickness after drying is 10 ⁇ m, and dried at 120 ° C. for 2 minutes to form a laminate. Obtained.
• Example 2 ⁇ Preparation of water-based urethane resin composition (2)> An aqueous urethane resin composition (2) and a laminate were obtained in the same manner as in Example 1 except that 90 parts by mass of dicyclohexylmethane diisocyanate was changed to 76 parts by mass of isophorone diisocyanate.
• Example 3 ⁇ Preparation of water-based urethane resin composition (3)> An aqueous urethane resin composition (3) and a laminate were obtained in the same manner as in Example 1 except that 6.8 parts by mass of piperazine was changed to 4.9 parts by mass of hydrazine.
• Example 4 ⁇ Preparation of water-based urethane resin composition (4)> An aqueous urethane resin composition (4) and a laminate were obtained in the same manner as in Example 1 except that 6.8 parts by mass of piperazine was changed to 13.4 parts by mass of isophorone diamine.
• Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: A calibration curve was prepared using the following standard polystyrene.
• EK-100D manufactured by Lintec Corporation
• the bleed resistance was evaluated as follows. " ⁇ ”; 10% or more. "X”; less than 10%.
• Examples 1 to 4 which are the laminated bodies of the present invention, are excellent in adhesion and bleed resistance.
• Comparative Example 1 is an embodiment in which another polycarbonate polyol is used instead of the specific polycarbonate polyol, but the bleed resistance is poor.
• Comparative Example 2 is an embodiment in which another polytetramethylene glycol is used instead of the specific polycarbonate polyol, but the adhesion is insufficient.

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• 2021
  • 2021-07-29 JP JP2022519727A patent/JP7205666B2/ja active Active
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