WO2019235121A1 - 合成皮革 - Google Patents
合成皮革 Download PDFInfo
- Publication number
- WO2019235121A1 WO2019235121A1 PCT/JP2019/018502 JP2019018502W WO2019235121A1 WO 2019235121 A1 WO2019235121 A1 WO 2019235121A1 JP 2019018502 W JP2019018502 W JP 2019018502W WO 2019235121 A1 WO2019235121 A1 WO 2019235121A1
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- WO
- WIPO (PCT)
- Prior art keywords
- urethane resin
- mass
- parts
- synthetic leather
- preferable
- Prior art date
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- 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
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- D—TEXTILES; PAPER
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- 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
- D06N3/145—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 two or more layers of polyurethanes
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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- 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
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- 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
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
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- 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
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- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
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- 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
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- 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
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- 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
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- 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
- D06N3/147—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 isocyanates used
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- D06N2209/00—Properties of the materials
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- D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
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- D06N2211/10—Clothing
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- D06N2211/00—Specially adapted uses
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- D06N2211/26—Vehicles, transportation
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- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Definitions
- the present invention relates to synthetic leather.
- Polyurethane resin is widely used for the production of synthetic leather (including artificial leather) because of its mechanical strength and good texture.
- a solvent-based urethane resin containing N, N-dimethylformamide (DMF) has been mainly used so far.
- DMF N, N-dimethylformamide
- Patent Document 1 a urethane resin composition in which a urethane resin is dispersed in water has been widely studied (for example, see Patent Document 1).
- Patent Document 1 As the skin layer of synthetic leather, although the substitution from the solvent system to the water system is gradually increasing in the market, the water system of the urethane resin for the adhesive layer is still advanced. Not. This is mainly because the peel strength of the urethane resin dispersed in water is insufficient compared to the solvent-based urethane resin. Moreover, the actual situation is that further improvements are required for various performances required for synthetic leather in the skin layer.
- the problem to be solved by the present invention is to provide a synthetic leather excellent in peel strength and chemical resistance.
- the present invention is a synthetic leather having at least a substrate (i), an adhesive layer (ii), and a skin layer (iii), wherein the adhesive layer (ii) is made from an aromatic polyisocyanate (a1).
- the urethane resin (A) and the urethane resin composition containing water (B) are used, and the skin layer (iii) has an anionic group concentration of 0.15 mmol / g.
- the present invention provides a synthetic leather characterized by being formed of a urethane resin composition containing the following anionic urethane resin (X) and water (Y).
- the synthetic leather of the present invention is excellent in peel strength and chemical resistance.
- the synthetic leather of the present invention can be used for various applications, and in particular, has high durability such as automobile interior materials, furniture, sports shoes, etc. that have been difficult to replace from solvent to water. It can be used for required applications.
- the synthetic leather of the present invention has at least a base material (i), an adhesive layer (ii), and a skin layer (iii).
- the adhesive layer (ii) is formed of a urethane resin (A) using aromatic polyisocyanate (a1) as a raw material and a urethane resin composition containing water (B). .
- an excellent peel strength can be obtained by using a urethane resin made from aromatic polyisocyanate (a1) having a high intermolecular interaction.
- the urethane resin (A) can be dispersed in water (B), for example, a urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group; B) Urethane resin or the like dispersed in it can be used.
- B a urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group
- B Urethane resin or the like dispersed in it can be used.
- These urethane resins (A) 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, as a raw material, one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group.
- Examples of the compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, 2,2- Herbic acid or 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-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N- (2-aminoethyl)- 2-aminosulfonic acid, N- (2-aminoethyl) -2-aminoethylsulfonic acid, N-2-aminoethane-2-aminosulfonic acid, N- (2-aminoethyl) - ⁇ -alanine; 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 include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; metal base compounds including sodium, potassium, lithium, calcium, and the like. Can do.
- 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.
- a compound 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 a 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.
- Examples of the compound having an oxyethylene structure include polyether polyols having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol. These compounds may be used alone or in combination of two or more.
- Examples of the emulsifier that can be used for obtaining the urethane resin that is forcibly dispersed in water (B) include polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxy Nonionic emulsifiers such as ethylene sorbitol tetraoleate and polyoxyethylene / polyoxypropylene copolymers; fatty acid salts such as sodium oleate, alkyl sulfate esters, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, Anionic emulsifiers such as polyoxyethylene alkyl sulfate, alkane sulfonate sodium salt, alkyl diphenyl ether sulfonate sodium salt; alkyl amine salt, alkyl trimethyl ammonium Arm salts, cationic
- urethane resin (A) it is preferable to use a urethane resin having an anionic group from the viewpoints of further excellent water dispersion stability, hydrolysis resistance, and light resistance.
- Examples of the urethane resin having an anionic group include raw materials used for producing the urethane resin having an anionic group described above, an aromatic polyisocyanate (a1), a polyol (a2), and chain extension as necessary.
- a reaction product of the agent (a3) can be used.
- the concentration of the anionic group of the urethane resin (A) is adjusted to obtain more excellent hydrolysis resistance and light resistance.
- it is preferably 0.05% by mass or more in the polyol (a2), more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more, It is preferably 10% by mass or less, more preferably 6.2% by mass or less, further preferably 3% by mass or less, particularly preferably 2.7% by mass or less, and in the range of 0.05 to 10% by mass.
- the range of 0.1 to 6.2% by mass is more preferable, the range of 0.5 to 3% by mass is more preferable, and the range of 1 to 2.7% by mass is particularly preferable.
- the aromatic polyisocyanate (a1) has a strong intermolecular force and is an essential component for obtaining an excellent peel strength due to the packing effect.
- Examples of the aromatic polyisocyanate (a1) include phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, and the like. These aromatic polyisocyanates may be used alone or in combination of two or more.
- diphenylmethane diisocyanate and / or toluene diisocyanate it is preferable to use diphenylmethane diisocyanate and / or toluene diisocyanate, and toluene diisocyanate is more preferable from the viewpoint that the crystallinity is moderately weak and a further excellent peel strength can be obtained.
- the amount used when toluene diisocyanate is used as the aromatic polyisocyanate (a1) it is preferably 50% by mass or more in the aromatic polyisocyanate (a1) from the viewpoint that a further excellent peel strength can be obtained. 70 mass% or more is more preferable.
- the aromatic polyisocyanate (a1) may be used in combination with an aliphatic or alicyclic polyisocyanate as long as the effects of the present invention are not hindered.
- aliphatic or alicyclic polyisocyanate examples include fats such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate.
- Aliphatic or alicyclic polyisocyanates can be used. These polyisocyanates may be used alone or in combination of two or more.
- polyether polyol for example, polyether polyol, polyester polyol, polycarbonate polyol, dimer diol, acrylic polyol, polybutadiene polyol and the like can be used. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use polyether polyol and / or polycarbonate polyol from the point that hydrolysis resistance can be further improved.
- the number average molecular weight of the polyol (a2) is preferably in the range of 500 to 10,000 from the viewpoint of obtaining even more excellent peel strength, mechanical strength of the film, and hydrolysis resistance. A range of 800 to 5,000 is more preferable.
- the number average molecular weight of the said polyol (a2) shows the value measured by the gel permeation column chromatography (GPC) method.
- the polyol (a2) may be used in combination with a chain extender (a3) (having no carboxyl group and sulfonyl group, having a molecular weight of 50 or more and less than 500), if necessary.
- a chain extender for example, a chain extender having a hydroxyl group, a chain extender having an amino group, or the like can be used. These may be used alone or in combination of two or more. Among these, it is preferable to use a chain extender having a hydroxyl group from the viewpoint that much more excellent light resistance can be obtained.
- 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, hexamethylene glycol, Aliphatic polyol compounds such as saccharose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc. Aromatic polyol compounds; water and the like can be used. These chain extenders may be used alone or in combination of two or more. Among these, it is preferable to use an aliphatic polyol compound from the viewpoint that discoloration can be easily suppressed and further excellent light resistance can be obtained.
- chain extender having an amino group examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4. '-Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, etc. Can be used. These chain extenders may be used alone or in combination of two or more.
- the amount used in the case of using the chain extender (a3) is 0.5 to 40% by mass in the total mass of each raw material constituting the urethane resin (A) from the viewpoint that the durability of the film can be further improved.
- the range is preferable, and the range of 1 to 20% by mass is more preferable.
- the raw material used in order to manufacture the urethane resin which has the said hydrophilic group, the said aromatic polyisocyanate (a1), a polyol (a2), and as needed for example Examples include a method in which the chain extender (a3) is charged and reacted in a lump. These reactions include, for example, a method in which the reaction is performed at a temperature of 50 to 100 ° C. for 3 to 10 hours.
- the molar ratio [(isocyanate group) / (total of hydroxyl group and amino group)] of the isocyanate group of the polyisocyanate (a1) is preferably in the range of 0.8 to 1.2, preferably 0.9 to A range of 1.1 is more preferred.
- the urethane resin (A) When producing the urethane resin (A), it is preferable to deactivate the isocyanate group remaining in the urethane resin (A). When deactivating the isocyanate group, it is preferable to use an alcohol having a hydroxyl group such as methanol. The amount of alcohol 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 (A).
- 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 Amide compounds and 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 obtaining the urethane resin composition.
- the urethane resin (A) obtained by the above method preferably has an anionic group concentration of 0.35 mmol / g or less from the viewpoint of obtaining further excellent hydrolysis resistance. By being in this range, it is possible to prevent poor hydrolysis resistance derived from the hydrophilic group while maintaining the water dispersibility and peel strength of the urethane resin (A).
- the concentration of the anionic group of the urethane resin (A) is preferably 0.005 mmol / g or more, more preferably 0.01 mmol / g or more, from the viewpoint of obtaining further excellent hydrolysis resistance.
- concentration of the anionic group of the said urethane resin (A) is the number of moles of the anionic group derived from the raw material used in order to manufacture the urethane resin which has the said anionic group, and comprises each urethane resin (A). The value divided by the total mass of the raw materials is shown.
- the concentration of the aromatic ring of the urethane resin (A) is preferably 0.1 mol / kg or more, more preferably 0.3 mol / kg or more, from the point that even more excellent peel strength is obtained.
- 0.4 mol / kg or more is more preferable, 2.5 mol / kg or less is preferable, 2 mol / kg or less is more preferable, 1.5 mol / kg or less is further preferable, and the range is from 0.1 to 2.5 mol / kg.
- the range of 0.3 to 2 mol / kg is more preferable, and the range of 0.4 to 1.5 mol / kg is more preferable.
- the molecular weight of benzene or naphthalene having no substituent is used as the molecular weight of the aromatic ring.
- the weight average molecular weight of the urethane resin (A) is preferably 2,000 or more, more preferably 4,000 or more, and even more preferably 6,000 or more, from the viewpoint of obtaining even better peel strength. 150,000 or less, more preferably 100,000 or less, still more preferably 70,000 or less, preferably in the range of 2,000 to 150,000, more preferably in the range of 4,000 to 100,000. The range of 6,000 to 70,000 is more preferable.
- the weight average molecular weight of the said urethane resin (A) shows the value measured by the gel permeation column chromatography (GPC) method.
- the water (B) for example, ion exchange water, distilled water, tap water and the like can be used. Among these, it is preferable to use ion-exchanged water with few impurities.
- the content of the water (B) is preferably in the range of 20 to 90% by mass in the urethane resin composition from the viewpoint of workability, coating property, and storage stability, and is preferably 40 to 80% by mass. A range is more preferred.
- the urethane resin composition that can be used for the adhesive layer (ii) contains the urethane resin (A) and the aqueous medium (B), but may contain other additives as necessary. Good.
- Examples of the other additives include a urethanization catalyst, a neutralizing agent, a crosslinking agent, a silane coupling agent, a thickening agent, a filler, a thixotropic agent, a tackifier, a wax, a heat stabilizer, and a light resistance 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 absorbent, moisture absorbent, deodorant , Foam stabilizers, antiblocking agents, hydrolysis inhibitors, and the like can be used. These additives may be used alone or in combination of two or more.
- the urethane resin composition that can be used for the skin layer (iii) is a urethane containing an anionic urethane resin (X) having an anionic group concentration of 0.15 mmol / g or less and water (Y). It is essential to use a resin composition. If the concentration of the anionic group is within such a range, since the introduction amount of the hydrophilic group is small, excellent resistance can be obtained even for a highly polar chemical such as ethanol.
- the concentration of the anionic group of the urethane resin (X) is preferably 0.005 mmol / g or more, more preferably 0.01 mmol / g or more, from the viewpoint of obtaining further excellent chemical resistance.
- concentration of the anionic group of the said urethane resin (X) is the number of moles of the anionic group derived from the raw material used in order to manufacture the urethane resin which has the said anionic group, and comprises each urethane resin (X). The value divided by the total mass of the raw materials is shown.
- the method for introducing an anionic group in the urethane resin (X) is the same as that for the urethane resin (A).
- the urethane resin (X) can be emulsified with a small amount of anionic group, has excellent dispersibility in water (Y), and can obtain much better chemical resistance. It is preferable that it is a urethane resin which has a sulfonyl group using the compound which has it as a raw material.
- urethane resin (X) for example, raw materials used for producing the above-described urethane resin having an anionic group, polyisocyanate (x1), polyol (x2), and extender (x3) ) Can be used.
- the amount of the raw material used for producing the urethane resin having an anionic group is preferably 0.05% by mass or more in the polyol (x2) from the viewpoint of obtaining further excellent chemical resistance.
- 1 mass% or more is more preferable, 0.3 mass% or more is further preferable, 0.5 mass% or more is particularly preferable, 10 mass% or less is preferable, 7 mass% or less is more preferable, and 3 mass% or less is more preferable.
- 2 mass% or less is particularly preferred, preferably in the range of 0.05 to 10 mass%, more preferably in the range of 0.1 to 7 mass%, still more preferably in the range of 0.3 to 3 mass%, A range of 0.5 to 2% by mass is particularly preferable.
- polyisocyanate (x1) examples include aliphatics or fats such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate.
- aliphatics or fats such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate.
- Cyclic polyisocyanates aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more.
- aliphatic and / or alicyclic polyisocyanates from the viewpoint of obtaining even better chemical resistance, and selected from the group consisting of isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate. More preferably, one or more polyisocyanates are used.
- polyether polyol for example, polyether polyol, polyester polyol, polycarbonate polyol, dimer diol, acrylic polyol, polybutadiene polyol and the like can be used. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use a polycarbonate polyol and / or a polyester polyol from the viewpoint that a further excellent chemical resistance is obtained, and a preferable amount of the polyol is 20% by mass or more in the polyol (x2). It is preferable that the content is 30% by mass or more.
- polycarbonate polyol it is preferable to use a polycarbonate polyol using hexanediol and / or ⁇ -caprolactone as a raw material from the standpoint of further improving chemical resistance.
- the polyester polyol is a polyester made from one or more compounds selected from the group consisting of butanediol, hexanediol, trimethylolpropane, and neopentylglycol from the standpoint that even better chemical resistance is obtained. It is preferable to use a polyol.
- the number average molecular weight of the polyol (x2) is preferably in the range of 500 to 100,000, and more preferably in the range of 800 to 10,000, from the viewpoint of obtaining further excellent chemical resistance and mechanical strength. A range is more preferred.
- the number average molecular weight of the said polyol (x2) shows the value measured by the gel permeation column chromatography (GPC) method.
- chain extender (x3) for example, a chain extender having a hydroxyl group with a molecular weight of 50 or more and less than 500, a chain extender having an amino group, or the like can be used. These 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, hexamethylene glycol, Aliphatic polyol compounds such as saccharose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc. Aromatic polyol compounds; 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. '-Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, adipine Acid dihydrazide or the like can be used. These chain extenders may be used alone or in combination of two or more.
- chain extender (x3) it is preferable to use a chain extender having an amino group from the viewpoint of obtaining further excellent chemical resistance. From the group consisting of isophoronediamine, hydrazine, and adipic acid dihydrazide It is preferred to use one or more selected chain extenders. The amount of these preferred chain extenders used is preferably 30% by mass or more in the chain extender (x3), more preferably 40% by mass or more, and still more preferably 50% by mass or more.
- the chain extender (x3) is used in an amount of 0.5% in the total mass of raw materials constituting the urethane resin (X) from the viewpoint of further improving the durability, chemical resistance, and light resistance of the film. It is preferably in the range of ⁇ 20% by mass, more preferably in the range of 1 to 10% by mass.
- Examples of the method for producing the urethane resin (X) include reacting the polyisocyanate (x1) and the polyol (x2) to obtain a urethane prepolymer having an isocyanate group, and then a chain extender (x3), and , A method of reacting raw materials used for producing the urethane resin having an anionic group and then adding water (Y). These reactions are preferably performed, for example, at a temperature of 50 to 100 ° C. for 3 to 10 hours.
- chain extender which has a hydroxyl group when using together the chain extender which has a hydroxyl group, and the chain extender which has an amino group as said chain extender (x3), it has the said polyisocyanate (x1), polyol (x2), and a hydroxyl group.
- a urethane prepolymer having an isocyanate group is obtained by reacting a chain extender, and then a chain extender having an amino group and a raw material used for producing the urethane resin having an anionic group are reacted, and then water is added.
- a method of adding (Y) is preferred. It is. These reactions are preferably performed, for example, at a temperature of 50 to 100 ° C. for 3 to 10 hours.
- the molar ratio [(isocyanate group) / (hydroxyl group and amino group)] to the 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 molar ratio [(isocyanate group) / (hydroxyl group and amino group)] is preferably in the range of 1.1 to 3.5, and 1.3 A range of ⁇ 2.5 is more preferred.
- the equivalent ratio of the isocyanate group-reactive group of the chain extender to the free isocyanate group of the urethane prepolymer is preferably in the range of 40 to 100%, more preferably 70 to 100%. It can be made to react so that it may become a range.
- the weight average molecular weight of the urethane resin (X) is preferably 50,000 or more, more preferably 70,000 or more from the viewpoint of further improving the durability, chemical resistance, and light resistance of the film.
- 50,000 or less is preferable, 200,000 or less is more preferable, 50,000 to 250,000 is preferable, and 70,000 to 200,000 is more preferable.
- the weight average molecular weight of the said urethane resin (X) shows the value measured by the gel permeation column chromatography (GPC) method.
- an organic solvent when producing the urethane resin (X), 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 Amide compounds and 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 obtaining the urethane resin composition.
- the same water (B) can be used.
- the content of water (Y) is preferably in the range of 30 to 80% by mass in the urethane resin composition from the viewpoint of workability, coating property, and storage stability, and is preferably 35 to 70% by mass. A range is more preferred.
- the urethane resin composition may contain other additives as necessary in addition to the urethane resin (X) and the water (Y).
- additives examples include, for example, an emulsifier, a coagulant, a urethanization catalyst, a silane coupling agent, a filler, a thixotropic agent, a tackifier, a wax, a heat stabilizer, a light stabilizer, a fluorescent whitening agent, Foaming agent, pigment, dye, conductivity imparting agent, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam, flame retardant, water absorbent, moisture absorbent, deodorant, foam stabilizer, blocking Inhibitors, hydrolysis inhibitors, thickeners and the like can be used. These additives may be used alone or in combination of two or more.
- the synthetic leather of the present invention has at least a base material (i), an adhesive layer (ii), and a skin layer (iii), and specific examples thereof include the following. (1) Substrate (i), adhesive layer (ii), skin layer (iii) (2) Substrate (i), adhesive layer (ii), intermediate layer, skin layer (iii) (3) Substrate (i), porous layer, adhesive layer (ii), skin layer (iii) (4) Substrate (i), porous layer, adhesive layer (ii), intermediate layer, skin layer (iii)
- the substrate (i) examples include polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, glass fiber, carbon fiber, Non-woven fabrics, woven fabrics, knitted fabrics and the like based on these blended fibers; those in which the nonwoven fabric is impregnated with a resin such as polyurethane resin; those in which the nonwoven fabric is further provided with a porous layer; thermoplastic urethane (TPU) A resin base material such as can be used.
- a resin such as polyurethane resin
- TPU thermoplastic urethane
- a solvent-based urethane resin composition formed by a known wet film forming method As the porous layer, a solvent-based urethane resin composition formed by a known wet film forming method; a water-based urethane resin composition made porous by a known method, or the like can be used.
- the material for forming the intermediate layer for example, a known water-based urethane resin, solvent-based urethane resin, solvent-free urethane resin, water-based acrylic resin, silicone resin, polypropylene resin, polyester resin, or the like can be used. These resins may be used alone or in combination of two or more.
- a surface treatment layer may be further provided on the skin layer (iii) to prevent damage.
- a material for forming the surface treatment layer for example, a known water-based urethane resin, solvent-based urethane resin, solvent-free urethane resin, water-based acrylic resin, silicone resin, polypropylene resin, polyester resin, or the like can be used. These resins may be used alone or in combination of two or more.
- a urethane resin composition for forming a skin layer is applied onto a release-treated substrate, and dried and processed to obtain a skin layer (iii).
- the adhesive layer (ii) may be formed by applying a urethane resin composition for forming an adhesive layer on the skin layer (iii), bonding it to the base material (i), and then drying it. .
- Examples of the method for applying the urethane resin composition for forming the skin layer and the adhesive layer include methods using an applicator, roll coater, spray coater, T-die coater, knife coater, comma coater, and the like. It is done.
- Examples of the method for drying the urethane resin composition include a method in which the urethane resin composition is dried at 40 to 130 ° C. for 1 to 10 minutes.
- the thicknesses of the obtained adhesive layer (ii) and skin layer (iii) are appropriately determined according to the use for which the synthetic leather is used, but are, for example, in the range of 0.5 to 100 ⁇ m.
- the synthetic leather After the synthetic leather is produced, it may be aged at 30 to 100 ° C. for 1 to 10 days, if necessary.
- the synthetic leather of the present invention is excellent in peel strength and chemical resistance. Moreover, by using a specific urethane resin for the adhesive layer (ii), in addition to the above effects, a synthetic leather that is further excellent in light resistance and hydrolysis resistance can be obtained.
- the synthetic leather of the present invention can be used for various applications, and in particular, has high durability such as automobile interior materials, furniture, sports shoes, etc. that have been difficult to replace from solvent to water. It can be used for required applications.
- TDI toluene diisocyanate
- 0.1 part by mass of dibutyltin dilaurate was added and reacted at 70 ° C. for about 4 hours.
- 14 parts by mass of 1,3-butanediol was added and reacted at 70 ° C. for about 1 hour to complete the reaction, thereby obtaining a methyl ethyl ketone solution of urethane polymer.
- the urethane resin (A-1) composition for forming an adhesive layer (nonvolatile content: 40% by mass, concentration of anionic group (carboxyl group, the same shall apply hereinafter); 0.11 mmol / g, weight average molecular weight; 29,000, aromatic ring concentration; 0.67 mol / kg).
- the urethane resin (A-2) composition for forming an adhesive layer (nonvolatile content: 40% by mass, weight average molecular weight; 46,000, concentration of anionic group; 0.15 mmol / g, concentration of aromatic ring 0.75 mol / kg).
- an adhesive layer-forming urethane resin (A-3) composition (nonvolatile content: 40% by mass, concentration of anionic group; 0.13 mmol / g, weight average molecular weight; 68, 000, aromatic ring concentration; 0.74 mol / kg).
- urethane prepolymer having isocyanate.
- this urethane prepolymer was cooled to 60 ° C., 928 parts by mass of acetone was added, and the urethane prepolymer was uniformly dissolved.
- a mixed liquid of 191 parts by mass of ion-exchanged water, 30 parts by mass of isophoronediamine and 6 parts by mass of sodium N-2-aminoethane-2-aminosulfonate was added to this urethane prepolymer solution.
- 155 parts by mass of ion-exchanged water was added.
- acetone was distilled off under reduced pressure to obtain a urethane resin (X-1) composition (nonvolatile content: 60% by mass, anionic group concentration: 0.059 mmol / g).
- urethane prepolymer solution a mixed solution of 193 parts by mass of ion exchange water, 30 parts by mass of isophoronediamine and 4 parts by mass of sodium N-2-aminoethane-2-aminosulfonate was added. Next, 172 parts by mass of ion-exchanged water was added. After completion of the reaction, acetone was distilled off under reduced pressure to obtain a urethane resin (X-2) composition (nonvolatile content: 60% by mass, anionic group concentration: 0.039 mmol / g).
- ETERNACOLL UH-200, number average molecular weight; 2,000” and 120 parts by mass of polytetramethylene glycol (number average molecular weight; 2,000) were uniformly mixed at 70 ° C.
- a urethane prepolymer having an isocyanate was obtained by adding 50 parts by mass of isophorone diisocyanate and 38 parts by mass of hexamethylene diisocyanate and reacting at 100 ° C. for 6 hours. Subsequently, this urethane prepolymer was cooled to 60 ° C., and 906 parts by mass of acetone was added and dissolved uniformly.
- urethane prepolymer solution a mixed solution of 90 parts by mass of ion-exchanged water, 11 parts by mass of 80% by mass of hydrazine hydrate, and 5 parts by mass of sodium N-2-aminoethane-2-aminosulfonate was added. Next, 246 parts by mass of ion-exchanged water was added. After completion of the reaction, acetone was distilled off under reduced pressure to obtain a urethane resin (X-3) composition (nonvolatile content: 60% by mass, anionic group concentration: 0.053 mmol / g).
- AR-1 adhesive layer-forming urethane resin
- this urethane prepolymer was cooled to 60 ° C., and 910 parts by mass of acetone was added and dissolved uniformly.
- 910 parts by mass of acetone was added to this urethane prepolymer solution, 18 parts by mass of triethylamine was added to neutralize the carboxyl group, 922 parts by mass of ion-exchanged water was added, and 44 parts by mass of isophoronediamine was added to react.
- acetone was distilled off under reduced pressure to obtain a urethane resin (XR-1) composition (nonvolatile content: 35% by mass, anionic group concentration: 0.36 mmol / g).
- Example 1 ⁇ Manufacture of synthetic leather> 100 parts by mass of the skin layer forming urethane resin (X-1) composition obtained in Synthesis Example 4, 10 parts by mass of a water-dispersible black pigment (“Dilak HS-9530” manufactured by DIC Corporation), associative thickening
- the compounded liquid consisting of 1 part by weight of the agent (“Hydran Assistor T10” manufactured by DIC Corporation) on a flat release paper (“DN-TP-155T” manufactured by Ajinomoto Co., Inc.) so that the film thickness after drying is 30 ⁇ m. It was applied and dried at 70 ° C. for 2 minutes and further at 120 ° C. for 2 minutes.
- Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "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 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 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 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
- Examples 1 to 7 which are the synthetic leather of the present invention were excellent in peel strength, chemical resistance and hydrolysis resistance.
- Comparative Example 1 does not use a urethane resin made of aromatic polyisocyanate as a raw material for the adhesive layer (ii), and further has a urethane layer in which the concentration of anionic groups exceeds the range specified in the present invention in the skin layer (iii). Although it is an embodiment using a resin, the peel strength, chemical resistance and hydrolysis resistance were all poor.
- Comparative Example 2 is an embodiment in which a urethane resin having an anionic group concentration exceeding the range specified in the present invention was used for the skin layer (iii), but the chemical resistance and hydrolysis resistance were poor.
- Comparative Example 3 was an embodiment in which a urethane resin made from aromatic polyisocyanate was not used for the adhesive layer (ii), but the peel strength was poor.
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Abstract
Description
れる。これらの反応は、例えば、50~100℃の温度で3~10時間行うことが好ましい。
(1)基材(i)、接着層(ii)、表皮層(iii)
(2)基材(i)、接着層(ii)、中間層、表皮層(iii)
(3)基材(i)、多孔層、接着層(ii)、表皮層(iii)
(4)基材(i)、多孔層、接着層(ii)、中間層、表皮層(iii)
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、ポリカーボネートジオール(旭化成ケミカルズ株式会社製「DURANOL T5652」数平均分子量:2,000)500質量部、2,2-ジメチロールプロピオン酸(以下「DMPA」と略記する。)8質量部、メチルエチルケトン394質量部を加え、均一に混合した後、トルエンジイソシアネート(以下「TDI」と略記する。)68質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-ブタンジオールを14質量部加え、70℃で約1時間反応させて反応を終了させ、ウレタンポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にトリエチルアミン6質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水886質量部を加えた後、メチルエチルケトンを減圧下留去することによって、接着層形成用ウレタン樹脂(A-1)組成物(不揮発分;40質量%、アニオン性基(カルボキシル基、以下同じ。)の濃度;0.11mmol/g、重量平均分子量;29,000、芳香環の濃度;0.67mol/kg)を得た。
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、ポリテトラメチレングリコール(数平均分子量:2,000)500質量部、エチレングリコール3質量部、DMPA12質量部、メチルエチルケトン403質量部を加え、均一に混合した後、TDI79質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-BGを11質量部加え、70℃で約1時間反応させて反応を終了させ、ウレタンポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にトリエチルアミン9質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水907質量部を加えた後、メチルエチルケトンを減圧下留去することによって、接着層形成用ウレタン樹脂(A-2)組成物(不揮発分;40質量%、重量平均分子量;46,000、アニオン性基の濃度;0.15mmol/g、芳香環の濃度;0.75mol/kg)を得た。
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、ポリプロピレングリコール(数平均分子量:2,000)500質量部、1,4-ブタンジオール9質量部、DMPA10質量部、メチルエチルケトン400質量部を加え、均一に混合した後、TDI78質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-BGを4質量部加え、70℃で約1時間反応させて反応を終了させ、ウレタンポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にN,N-ジメチルエタノールアミン7質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水901質量部を加えた後、メチルエチルケトンを減圧下留去することによって、接着層形成用ウレタン樹脂(A-3)組成物(不揮発分;40質量%、アニオン性基の濃度;0.13mmol/g、重量平均分子量;68,000、芳香環の濃度;0.74mol/kg)を得た。
攪拌機、還流冷却管、温度計、及び、窒素導入管を備えた四つ口フラスコに、窒素気流下、ポリカーボネートポリオール(宇部興産株式会社製「ETERNACOLL UH-200、数平均分子量;2,000」)120質量部、ポリテトラメチレングリコール(数平均分子量;2,000)280質量部を70℃で均一に混合した後、イソホロンジイソシアネート100質量部を加え、100℃で6時間反応させることで、イソシアネートを有するウレタンプレポリマーを得た。次いで、このウレタンプレポリマーを60℃まで冷却し、アセトン928質量部を加え、均一に溶解した。このウレタンプレポリマー溶液に、イオン交換水191質量部、イソホロンジアミン30質量部、及び、N-2-アミノエタン-2-アミノスルホン酸ナトリウム6質量部の混合液を加えた。次いで、イオン交換水155質量部を加えた。反応終了後、アセトンを減圧下留去することで、ウレタン樹脂(X-1)組成物(不揮発分;60質量%、アニオン性基の濃度;0.059mmol/g)を得た。
攪拌機、還流冷却管、温度計、及び、窒素導入管を備えた四つ口フラスコに、窒素気流下、ポリカーボネートポリオール(宇部興産株式会社製「ETERNACOLL UH-200、数平均分子量;2,000」)120質量部、ポリテトラメチレングリコール(数平均分子量;2,000)280質量部、日油株式会社製「ユニルーブ50MB-72」(数平均分子量;3,000)12質量部を70℃で均一に混合した後、イソホロンジイソシアネート101質量部を加え、100℃で6時間反応させることで、イソシアネートを有するウレタンプレポリマーを得た。次いで、このウレタンプレポリマーを60℃まで冷却し、アセトン953質量部を加え、均一に溶解した。このウレタンプレポリマー溶液に、イオン交換水193質量部、イソホロンジアミン30質量部、及び、N-2-アミノエタン-2-アミノスルホン酸ナトリウム4質量部の混合液を加えた。次いで、イオン交換水172質量部を加えた。反応終了後、アセトンを減圧下留去することで、ウレタン樹脂(X-2)組成物(不揮発分;60質量%、アニオン性基の濃度;0.039mmol/g)を得た。
攪拌機、還流冷却管、温度計、及び、窒素導入管を備えた四つ口フラスコに、窒素気流下、ポリカーボネートポリオール(宇部興産株式会社製「ETERNACOLL UH-200、数平均分子量;2,000」)280質量部、ポリテトラメチレングリコール(数平均分子量;2,000)120質量部を70℃で均一に混合した後、イソホロンジイソシアネート50質量部、ヘキサメチレンジイソシアネート38質量部を加え、100℃で6時間反応させることで、イソシアネートを有するウレタンプレポリマーを得た。次いで、このウレタンプレポリマーを60℃まで冷却し、アセトン906質量部を加え、均一に溶解した。このウレタンプレポリマー溶液に、イオン交換水90質量部、80質量%水加ヒドラジン11質量部、及び、N-2-アミノエタン-2-アミノスルホン酸ナトリウム5質量部の混合液を加えた。次いで、イオン交換水246質量部を加えた。反応終了後、アセトンを減圧下留去することで、ウレタン樹脂(X-3)組成物(不揮発分;60質量%、アニオン性基の濃度;0.053mmol/g)を得た。
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、ポリテトラメチレングリコール(数平均分子量;1,000)を500質量部、DMPA15質量部、メチルエチルケトン450質量部を加え、均一に混合した後、イソホロンジイソシアネート(以下「IPDI」と略記する。)149質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-ブタンジオールを11質量部加え、70℃で1時間反応させ、ウレタンプレポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にN,N-ジメチルエタノールアミン10質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水1,012質量部を加えた。反応終了後、メチルエチルケトンを減圧下留去することによって、接着層形成用ウレタン樹脂(AR-1)組成物(不揮発分;40質量%、アニオン性基の濃度;0.16mmol/g、重量平均分子量;28,000、芳香環の濃度;0mol/kg)を得た。
攪拌機、還流冷却管、温度計、及び、窒素導入管を備えた四つ口フラスコに、窒素気流下、ポリカーボネートポリオール(宇部興産株式会社製「ETERNACOLL UH-200、数平均分子量;2,000」)100質量部、ポリテトラメチレングリコール(数平均分子量;2,000)186質量部、DMPA24質量部を70℃で均一に混合した後、IPDI143質量部を加え、100℃で6時間反応させることで、イソシアネートを有するウレタンプレポリマーを得た。次いで、このウレタンプレポリマーを60℃まで冷却し、アセトン910質量部を加え、均一に溶解した。このウレタンプレポリマー溶液に、トリエチルアミン18質量部を加え、カルボキシル基を中和した後、イオン交換水922質量部を加え、イソホロンジアミン44質量部を加え反応した。反応終了後、アセトンを減圧下留去することで、ウレタン樹脂(XR-1)組成物(不揮発分;35質量%、アニオン性基の濃度;0.36mmol/g)を得た。
合成例4で得られた表皮層形成用ウレタン樹脂(X-1)組成物100質量部、水分散性黒色顔料(DIC株式会社製「ダイラックHS-9530」)を10質量部、会合型増粘剤(DIC株式会社製「ハイドラン アシスター T10」)を1質量部からなる配合液をフラット離型紙(味の素株式会社製「DN-TP-155T」)上に乾燥後の膜厚が30μmとなる様に塗布し、70℃で2分間、さらに120℃で2分間乾燥させた。
次いで、合成例1で得られた接着層形成用ウレタン樹脂(A-1)組成物100質量部、会合型増粘剤(DIC株式会社製「ハイドラン アシスター T10」)を1質量部、ポリイソシアネート系架橋剤(DIC株式会社製「ハイドラン アシスター C5」)を9質量部からなる配合液を乾燥後の膜厚が50μmとなるように塗布し、70℃で3分間乾燥させた。乾燥後直ちにポリウレタン含浸不織布を貼り合わせた後、120℃で2分間熱処理し、50℃で2日間熟成させてから離型紙を剥離して合成皮革を得た。
用いる表皮層形成用ウレタン樹脂組成物、接着層形成用ウレタン樹脂組成物の種類を表1~3に変更した以外は、実施例1と同様にして合成皮革を得た。
合成例で用いたポリオールの数平均分子量、及び、合成例で得られたウレタン樹脂の重要平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー(GPC)法により、下記の条件で測定し得られた値を示す。
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度0.4質量%のテトラヒドロフラン溶液)
標準試料:下記の標準ポリスチレンを用いて検量線を作成した。
東ソー株式会社製「TSKgel 標準ポリスチレン A-500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A-2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F-1」
東ソー株式会社製「TSKgel 標準ポリスチレン F-2」
東ソー株式会社製「TSKgel 標準ポリスチレン F-4」
東ソー株式会社製「TSKgel 標準ポリスチレン F-10」
東ソー株式会社製「TSKgel 標準ポリスチレン F-20」
東ソー株式会社製「TSKgel 標準ポリスチレン F-40」
東ソー株式会社製「TSKgel 標準ポリスチレン F-80」
東ソー株式会社製「TSKgel 標準ポリスチレン F-128」
東ソー株式会社製「TSKgel 標準ポリスチレン F-288」
東ソー株式会社製「TSKgel 標準ポリスチレン F-550」
実施例及び比較例で得られた合成皮革を、島津オートグラフ「AG-1」(株式会社島津製作所製)を使用して、フルスケール5kg、ヘッドスピード20mm/分の条件にて剥離強度を測定し、以下のように評価した。
「A」;0.15MPa以上
「B」;0.1MPa以上0.15MPa未満
「C」;0.1MPa未満
実施例及び比較例で得られた合成皮革の表皮層上に、エタノールを10滴滴下し、24時間放置した後の外観を観察し、以下のように評価した。
「A」;外観に異常なし。
「B」;外観に軽度の白化が生じていた。
「C」;外観に大きな黄変が生じていた。
実施例及び比較例で得られた合成皮革を70℃、湿度95%の条件下で5週間放置した。その後の外観観察および指触により、以下のように評価した。
「A」;外観・指触に異常なし。
「B」;外観に艶変化が生じたが、指触では異常は確認されなかった。
「C」;外観に艶変化が生じ、かつ、ベタツキが確認された。
Claims (5)
- 少なくとも、基材(i)、接着層(ii)、及び、表皮層(iii)を有する合成皮革であって、
前記接着層(ii)が、芳香族ポリイソシアネート(a1)を原料とするウレタン樹脂(A)、及び、水(B)を含有するウレタン樹脂組成物により形成されたものであり、かつ、
前記表皮層(iii)が、アニオン性基の濃度が0.15mmol/g以下であるアニオン性ウレタン樹脂(X)、及び、水(Y)を含有するウレタン樹脂組成物により形成されたものであることを特徴とする合成皮革。 - 前記芳香族ポリイソシアネート(a1)が、トルエンジイソシアネートを含むものである請求項1記載の合成皮革。
- 前記ウレタン樹脂(A)中の芳香環の濃度が、0.1~2.5mol/kgの範囲である請求項1又は2記載の合成皮革。
- 前記ウレタン樹脂(A)の重量平均分子量が、2,000~150,000の範囲である請求項1~3のいずれか1項記載の合成皮革。
- 前記アニオン性ウレタン樹脂(X)のアニオン性基が、スルホニル基である請求項1~4のいずれか1項記載の合成皮革。
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KR1020207032703A KR102631671B1 (ko) | 2018-06-07 | 2019-05-09 | 합성 피혁 |
CN201980037444.3A CN112673130B (zh) | 2018-06-07 | 2019-05-09 | 合成皮革 |
EP19815091.4A EP3816344A4 (en) | 2018-06-07 | 2019-05-09 | SYNTHETIC LEATHER |
JP2019562023A JP6683298B1 (ja) | 2018-06-07 | 2019-05-09 | 合成皮革 |
US15/734,595 US11479908B2 (en) | 2018-06-07 | 2019-05-09 | Synthetic leather |
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KR102631668B1 (ko) * | 2018-06-07 | 2024-02-01 | 디아이씨 가부시끼가이샤 | 합성 피혁 |
WO2021084954A1 (ja) * | 2019-10-28 | 2021-05-06 | Dic株式会社 | 繊維基材、及び、人工皮革 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003165950A (ja) * | 2001-11-29 | 2003-06-10 | Mitsui Chemicals Inc | 耐溶剤性に優れる水性塗工材 |
JP2007119749A (ja) | 2005-09-27 | 2007-05-17 | Dai Ichi Kogyo Seiyaku Co Ltd | 繊維積層体表皮層用ポリウレタン樹脂水分散体組成物、繊維積層体の製造方法及び合成皮革 |
CN102618202A (zh) * | 2012-04-01 | 2012-08-01 | 江阴市诺科科技有限公司 | 一种制革用水性聚氨酯复合胶及其制备方法、应用 |
WO2013027489A1 (ja) * | 2011-08-22 | 2013-02-28 | Dic株式会社 | 皮革様シート及びその製造方法 |
WO2017169244A1 (ja) * | 2016-04-01 | 2017-10-05 | Dic株式会社 | 一液型水性樹脂組成物、及び、繊維積層体 |
WO2018110105A1 (ja) * | 2016-12-12 | 2018-06-21 | Dic株式会社 | 水性ウレタン樹脂組成物、及び、合成皮革 |
Family Cites Families (5)
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EP3266930B1 (en) * | 2015-03-03 | 2021-08-18 | DIC Corporation | Method for producing leather-like sheet |
JP6160891B1 (ja) * | 2015-12-16 | 2017-07-12 | Dic株式会社 | 湿気硬化型ウレタンホットメルト樹脂組成物、及び積層体 |
WO2019181476A1 (ja) * | 2018-03-20 | 2019-09-26 | Dic株式会社 | 接着剤、及び、合成皮革 |
KR102522431B1 (ko) * | 2018-06-07 | 2023-04-18 | 디아이씨 가부시끼가이샤 | 합성 피혁 |
KR102631668B1 (ko) * | 2018-06-07 | 2024-02-01 | 디아이씨 가부시끼가이샤 | 합성 피혁 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003165950A (ja) * | 2001-11-29 | 2003-06-10 | Mitsui Chemicals Inc | 耐溶剤性に優れる水性塗工材 |
JP2007119749A (ja) | 2005-09-27 | 2007-05-17 | Dai Ichi Kogyo Seiyaku Co Ltd | 繊維積層体表皮層用ポリウレタン樹脂水分散体組成物、繊維積層体の製造方法及び合成皮革 |
WO2013027489A1 (ja) * | 2011-08-22 | 2013-02-28 | Dic株式会社 | 皮革様シート及びその製造方法 |
CN102618202A (zh) * | 2012-04-01 | 2012-08-01 | 江阴市诺科科技有限公司 | 一种制革用水性聚氨酯复合胶及其制备方法、应用 |
WO2017169244A1 (ja) * | 2016-04-01 | 2017-10-05 | Dic株式会社 | 一液型水性樹脂組成物、及び、繊維積層体 |
WO2018110105A1 (ja) * | 2016-12-12 | 2018-06-21 | Dic株式会社 | 水性ウレタン樹脂組成物、及び、合成皮革 |
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CN112673130A (zh) | 2021-04-16 |
CN112673130B (zh) | 2023-07-25 |
KR20200140898A (ko) | 2020-12-16 |
JPWO2019235121A1 (ja) | 2020-06-25 |
TW202012181A (zh) | 2020-04-01 |
EP3816344A4 (en) | 2021-07-07 |
US20210230797A1 (en) | 2021-07-29 |
US11479908B2 (en) | 2022-10-25 |
KR102631671B1 (ko) | 2024-02-01 |
TWI808185B (zh) | 2023-07-11 |
EP3816344A1 (en) | 2021-05-05 |
JP6683298B1 (ja) | 2020-04-15 |
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