WO2019181476A1 - 接着剤、及び、合成皮革 - Google Patents
接着剤、及び、合成皮革 Download PDFInfo
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- WO2019181476A1 WO2019181476A1 PCT/JP2019/008552 JP2019008552W WO2019181476A1 WO 2019181476 A1 WO2019181476 A1 WO 2019181476A1 JP 2019008552 W JP2019008552 W JP 2019008552W WO 2019181476 A1 WO2019181476 A1 WO 2019181476A1
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- WIPO (PCT)
- Prior art keywords
- urethane resin
- mass
- adhesive
- parts
- anionic urethane
- Prior art date
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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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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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- C08G18/0838—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
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
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- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
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- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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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
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group 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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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- 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
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- 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
- D06N3/145—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
Definitions
- the present invention relates to an adhesive and a synthetic leather obtained using the adhesive.
- a urethane resin composition in which a urethane resin is dispersed in an aqueous medium can reduce the burden on the environment as compared with conventional organic solvent-based urethane resin compositions. Therefore, leather-like sheets such as artificial leather and synthetic leather, gloves In recent years, it has been used favorably as a material for producing coating agents such as curtains and sheets.
- the urethane resin composition in order to impart excellent peel strength and durability, a compound in which a crosslinking agent such as an isocyanate crosslinking agent or an oxazoline crosslinking agent is blended with a main agent containing a urethane resin is used (for example, , See Patent Documents 1 and 2.)
- a crosslinking agent such as an isocyanate crosslinking agent or an oxazoline crosslinking agent is blended with a main agent containing a urethane resin
- the isocyanate cross-linking agent has a short usable time (pot life) of the two-component liquid mixture of the main agent and the cross-linking agent, so it is practically difficult to process stably, and the oxazoline cross-linking agent is
- the hardness of the crosslinked film is weak, and there is a problem that a processed product having sufficient peel strength cannot be obtained.
- the problem to be solved by the present invention is to provide an adhesive that has a long usable time (pot life) and can impart excellent peel strength.
- the present invention comprises an anionic urethane resin (A) having a flow start temperature of 100 ° C. or lower, a neutralizing agent (B), a carbodiimide crosslinking agent (C), and an aqueous medium (D).
- An adhesive is provided.
- the present invention also provides a synthetic leather characterized by having at least a base material (i), an adhesive layer (ii) formed of the adhesive, and a skin layer (iii).
- the adhesive of the present invention has a long pot life and can impart excellent peel strength. Therefore, the adhesive of the present invention can be suitably used for the production of gloves, synthetic leather, curtains, sheets and the like, and can be particularly suitably used for the production of synthetic leather.
- the adhesive of the present invention contains an anionic urethane resin (A) having a flow start temperature of 100 ° C. or lower, a neutralizing agent (B), a carbodiimide crosslinking agent (C), and an aqueous medium (D). is there.
- the anionic urethane resin (A) has a flow start temperature of 100 ° C. or lower, the permeability to the base material and the adhesiveness are improved, so that excellent peel strength can be obtained.
- the flow starting temperature is preferably in the range of 10 to 60 ° C. from the viewpoint of obtaining even better peel strength.
- the type of the polyol (a1) that is a raw material of the urethane resin (A) described later, the amount of the chain extender (a2) used, and The method of adjusting with the kind of polyisocyanate (a3) is mentioned.
- a polyol having high crystallinity such as polycarbonate polyol is used as the polyol (a1), the amount of the chain extender (a2) used is increased, polyisocyanate ( Examples of a3) include the use of polyisocyanates having high crystallinity such as 4,4′-diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate.
- a polyol having low crystallinity such as polyoxypropylene glycol is used as the polyol (a1), and the amount of the chain extender (a2) used is reduced.
- Examples of the polyisocyanate (a3) include using a polyisocyanate having low crystallinity such as toluene diisocyanate and isophorone diisocyanate. Therefore, the flow start temperature of the anionic urethane resin (A) can be adjusted by appropriately selecting these methods. In addition, the measuring method of the flow start temperature of the said anionic urethane resin (A) is described in the Example mentioned later.
- the acid value of the anionic urethane resin (A) is in the range of 1 to 35 mgKOH / g from the viewpoint that the crosslink density is sufficient and the adhesive has high strength and further excellent peel strength can be obtained. Is more preferably in the range of 5 to 30 mg KOH / g, still more preferably 10 to 25.
- Examples of the method for adjusting the acid value include a method for adjusting the amount of a compound having a carboxyl group or a sulfonyl group, which will be described later.
- the measuring method of the acid value of the said anionic urethane resin (A) is described in the Example mentioned later.
- the anionic urethane resin (A) can be dispersed in an aqueous medium (D) to be described later due to its anionic group.
- Examples of the method for obtaining the anionic urethane resin (A) include a method using, as a raw material, one or more compounds selected from the group consisting of a glycol compound having a carboxyl group and a compound having a sulfonyl group.
- glycol compound having a carboxyl group examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, 2,2- Valeric 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-Aminoethylsulfonic acid or the like can be used. These compounds may be used alone or in combination of two or more.
- the acid value of the anionic urethane resin (A) can be easily adjusted, and a further excellent peel strength can be obtained.
- the total amount of the polyol (a1), the raw material used to produce the anionic urethane resin, and the chain extender (a2) is preferably in the range of 0.1 to 8.5% by mass. The range is more preferably 5% by mass, and further preferably 2 to 6% by mass.
- anionic urethane resin (A) reaction of a polyol (a1), the raw material used in order to manufacture an above-described anionic urethane resin, chain extender (a2), and polyisocyanate (a3) Can be used.
- polyether polyol for example, polyether polyol, polyester polyol, polyacryl polyol, polycarbonate polyol, polybutadiene polyol and 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 polyol (a1) is preferably in the range of 500 to 8,000, more preferably in the range of 800 to 4,000, from the viewpoint of the mechanical strength of the resulting film.
- the number average molecular weight of the said polyol (a1) shows the value measured by the gel permeation column chromatography (GPC) method.
- chain extender (a2) those having a number average molecular weight in the range of 50 to 450 can be used.
- the amount of the chain extender (a2) used is easy to adjust the flow start temperature of the obtained anionic urethane resin (A), and more excellent peel strength can be obtained. It is preferably in the range of 0 to 3% by mass, more preferably in the range of 0 to 2.5% by mass, based on the total mass of the raw material and chain extender (a2) used for producing the urethane resin. More preferably, it is in the range of ⁇ 2% by mass.
- polyisocyanate (a3) examples include aromatic polyisocyanates (a3-1) such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate.
- aromatic polyisocyanates (a3-1) such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate.
- Aliphatic polyisocyanates and / or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate Or the like can be used over door (a3-2).
- These polyisocyanates may be used alone or in combination of two or more.
- the amount of the polyisocyanate (a3) used is in the range of 5 to 40% by mass in the total mass of the raw material of the anionic urethane resin (A) from the viewpoint of production stability and mechanical properties of the resulting film. It is preferably 10 to 30% by mass.
- Examples of the method for producing the anionic urethane resin (A) include the polyol (a1), the raw material used for producing the anionic urethane resin, the chain extender (a2), and the polyisocyanate (a3). Can be charged and reacted at once. These reactions can be carried out, for example, at 50 to 100 ° C. for 3 to 10 hours.
- the molar ratio [isocyanate group / (hydroxyl group and amino group)] of the total of hydroxyl groups and amino groups possessed by and the isocyanate group possessed by the polyisocyanate (a4) is in the range of 0.6 to 1.2. Is preferable, and the range of 0.7 to 1.1 is more preferable.
- isocyanate groups remaining in the anionic urethane resin (A) may be deactivated.
- the isocyanate group is deactivated it is preferable to use an alcohol having one hydroxyl group such as methanol.
- the amount of the alcohol used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the anionic 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 finally removed by a distillation method or the like.
- the neutralizing agent (B) neutralizes the carboxyl group and the sulfonyl group of the anionic urethane resin (A).
- non-volatile bases such as sodium hydroxide and potassium hydroxide; trimethylamine, triethylamine, Use tertiary amine compounds such as dimethylethanolamine, methyldiethanolamine, and triethanol; secondary amine compounds such as dimethylamine, diethylamine, and dibutylamine; primary amine compounds such as ethylenediamine, methylamine, ethylamine, and butylamine; and ammonia. it can.
- These neutralizing agents may be used alone or in combination of two or more.
- the neutralizing agent (B) it volatilizes at the temperature (usually 50 to 180 ° C.) when the aqueous medium (D) in the adhesive is dried and disappears from the polyurethane film, and the anionic urethane resin (A)
- the boiling point is preferably 200 ° C. or less from the viewpoint of further improving the reactivity between the carboxyl group of carbodiimide and the carbodiimide cross-linking agent (C) described later, and obtaining even better peel strength, and ⁇ 50 to 180 More preferably, it is in the range of ° C.
- the amount used in the case of using the neutralizing agent (B) is in the range of 0.8 to 1.2 times the number of moles of carboxyl group and sulfonyl group contained in the anionic urethane resin (A). It is preferable.
- carbodiimide crosslinking agent (C) examples include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, N- [3- (dimethyl Amino) propyl] -N′-ethylcarbodiimide, N- [3- (dimethylamino) propyl] -N′-ethylcarbodiimide methiodide, N-tert-butyl-N′-ethylcarbodiimide, N-cyclohexyl-N ′ Carbodiimide compounds such as-(2-morpholinoethyl) carbodiimide meso-p-toluenesulfonate, N, N'-di-tert-butylcarbodiimide, N, N'-di-p-tolylcar
- carbodiimide crosslinking agents may be used alone or in combination of two or more.
- polyisocyanate that is a raw material of the polycarbodiimide crosslinking agent
- examples of the polyisocyanate that is a raw material of the polycarbodiimide crosslinking agent include phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, 1,3- Aromatic polyisocyanates such as bis (1-methyl-1-isocyanatoethyl) benzene and 1,4-bis (1-methyl-1-isocyanatoethyl) benzene; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate , Dicyclohexylmethane di
- polyisocyanates may be used alone or in combination of two or more.
- the pot life is longer and the crosslinking reaction with the anionic urethane resin (A) is moderately slow, a further excellent processability is obtained, and the anionic urethane resin (A) and 1,3-bis (1-methyl-1-isocyanatoethyl) benzene, 1,4 from the point that isourea is formed by the cross-linking reaction, and the film can be made harder and more excellent peel strength can be obtained.
- At least one polyisocyanate selected from the group consisting of -bis (1-methyl-1-isocyanatoethyl) benzene and dicyclohexylmethane diisocyanate, and 1,3-bis (1-methyl-1- It is more preferable to use isocyanatoethyl) benzene and / or 1,4-bis (1-methyl-1-isocyanatoethyl) benzene.
- a carbodiimide cross-linking agent that uses polyalkylene oxide as a raw material in addition to the polyisocyanate from the viewpoint that the solubility in an aqueous medium (D) can be further improved.
- the polyalkylene oxide preferably has at least one group that reacts with the polyisocyanate, and has one group that reacts with the polyisocyanate because the storage stability of the urethane resin composition can be further improved. It is more preferable.
- the alkylene group of the polyalkylene oxide an ethylene group, a propylene group, or a tetramethylene group can be used. Among these, it is preferable that the ethylene group has 50% by mass or more in the alkylene group from the viewpoint of further improving the solubility in the aqueous medium (D).
- the content of the carbodiimide crosslinking agent (C) is in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the anionic urethane resin (A) from the viewpoint that a further excellent peel strength can be obtained.
- the range is 3 to 20 parts by mass, more preferably 5 to 18 parts by mass.
- aqueous medium (D) for example, water, an organic solvent miscible with water, a mixture thereof, or the like can be used.
- organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n- and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycol solvents such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ether solvents: lactam solvents such as N-methyl-2-pyrrolidone and the like can be used.
- These aqueous media may be used alone or in combination of two or more. Among these, it is preferable to use only water or a mixture of water and an organic solvent miscible with water, and more preferable to use only water from the viewpoint of safety and reduction of environmental load.
- the mass ratio [(A) / (D)] of the anionic urethane resin (A) and the aqueous medium (D) is in the range of 10/80 to 70/30 from the viewpoint of workability. A range of 20/80 to 60/40 is more preferable.
- the adhesive of the present invention contains the anionic urethane resin (A), the neutralizing agent (B), the carbodiimide crosslinking agent (C), and the aqueous medium (D) as essential components.
- the additive may be contained.
- additives examples include emulsifiers, thickeners, urethanization catalysts, fillers, foaming agents, pigments, dyes, oil repellents, hollow foams, flame retardants, antifoaming agents, leveling agents, and antiblocking agents. Etc. can be used. These additives may be used alone or in combination of two or more.
- the synthetic leather has at least a base material (i), an adhesive layer (ii) formed of the adhesive, and a skin layer (iii).
- the substrate (i) for example, glass; plastic substrate; wood; non-woven fabric, woven fabric, knitted fabric or other fiber substrate can be used.
- a fiber base material from the viewpoint of obtaining good flexibility.
- polyester fiber, nylon fiber, acrylic fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, blended fiber thereof or the like can be used as the fiber substrate. it can.
- the adhesive layer (ii) is formed of the adhesive, and the thickness thereof is, for example, in the range of 5 to 100 ⁇ m.
- An intermediate layer made of a known material may be provided between the adhesive layer (ii) and the skin layer (iii) as necessary.
- the skin layer (iii) is formed of a known material and has a thickness in the range of, for example, m5 to 100 ⁇ m.
- a surface treatment layer may be provided on the skin layer (iii) as necessary.
- Examples of known materials that can be used to form the intermediate layer, the skin layer (iii), and the surface treatment layer include, for example, a solvent-free urethane resin composition such as a moisture-curable hot melt resin, and a urethane resin in water.
- a solvent-free urethane resin composition such as a moisture-curable hot melt resin
- a urethane resin in water a dispersed aqueous urethane resin composition, an aqueous acrylic resin composition in which an acrylic resin is dispersed in water, a solvent-based urethane resin composition, a solvent-based acrylic resin composition, or the like can be used.
- a resin composition for forming a skin layer is applied on a release paper, dried to form a skin layer (iii), and then the adhesive is applied on the skin layer. And a method of forming the adhesive layer (ii) by drying and bonding the adhesive layer (ii) and the substrate (i).
- Examples of the method of applying the resin composition forming the skin layer and the adhesive include a method using a roll coater, a knife coater, a comma coater, an applicator and the like.
- drying conditions for forming the skin layer (iii) and the adhesive layer (ii) include a method of drying at 40 to 120 ° C. for 10 minutes to 3 days.
- the adhesive of the present invention has a long pot life and can impart excellent peel strength. Therefore, the adhesive of the present invention can be suitably used for the production of gloves, synthetic leather, curtains, sheets and the like, and can be particularly suitably used for the production of synthetic leather.
- Example 1 In the presence of 1,374 parts by weight of methyl ethyl ketone and 0.1 part by weight of stannous octylate, 1,000 parts by weight of polyether polyol ("PTMG1000" manufactured by Mitsubishi Chemical Corporation, number average molecular weight; 1,000), 2 , 2-dimethylolpropionic acid and 317 parts by mass of isophorone diisocyanate were reacted at 70 ° C. until the solution viscosity reached 20,000 mPa ⁇ s, and then the reaction was stopped by adding 3 parts by mass of methanol. A methyl ethyl ketone solution of an anionic urethane resin was obtained.
- PTMG1000 polyether polyol
- urethane resin solution 69 parts by mass of polyoxyethylene distyrenated phenyl ether (Hydrophile-Lipophile Balance (hereinafter abbreviated as “HLB”); 13) and triethylamine (neutralizing agent; boiling point 89.5 ° C.) 38 parts by mass
- HLB Hydrophile Balance
- 2,748 parts by mass of ion-exchanged water was added for phase inversion emulsification to obtain an emulsion in which the anionic urethane resin was dispersed in water.
- a urethane resin composition having a nonvolatile content of 35% by mass was obtained.
- the anionic urethane resin had a flow start temperature of 40 ° C. or lower and an acid value of 17.4 mgKOH / g.
- crosslinking agent (1) 100 parts by mass of the obtained urethane resin composition, 1 part by mass of a thickener (“Borchi Gel 0620” manufactured by Borchers), carbodiimide crosslinking agent (1,3-bis (1-methyl-1-isocyanatoethyl) benzene , And polyalkylene glycol monomethyl ether as a raw material, solid content of 40% by mass, hereinafter abbreviated as “crosslinking agent (1)”.) 9 parts by mass, and stirred for 2 minutes at 2,000 rpm with a mechanical mixer The adhesive was obtained by defoaming with a vacuum defoamer.
- a thickener (“Borchi Gel 0620” manufactured by Borchers)
- carbodiimide crosslinking agent 1,3-bis (1-methyl-1-isocyanatoethyl) benzene
- polyalkylene glycol monomethyl ether solid content of 40% by mass
- Formula A (B ⁇ f ⁇ 5.611) / S (1)
- A is the solid content acid value of the resin (mgKOH / g)
- B is the amount of 0.1 mol / L potassium hydroxide aqueous solution used for titration (mL)
- f is the 0.1 mol / L potassium hydroxide aqueous solution.
- S is the mass (g) of resin particles
- 5.611 is the formula weight of potassium hydroxide (56.11 / 10).
- Example 2 An adhesive was obtained in the same manner as in Example 1 except that the polyether polyol was changed to polycarbonate polyol (“ETERRNACOLL UH-100” manufactured by Ube Industries, Ltd., number average molecular weight: 1,000).
- the anionic urethane resin had a flow start temperature of 40 ° C. or lower and an acid value of 17.2 mg KOH / g.
- Example 3 An adhesive was obtained in the same manner as in Example 1 except that the polyether polyol was changed to a polyester polyol ("Placcel 210" manufactured by Daicel Corporation, number average molecular weight; 1,000).
- the anionic urethane resin had a flow start temperature of 40 ° C. or lower and an acid value of 17.2 mg KOH / g.
- Example 4 In the presence of 1,374 parts by weight of methyl ethyl ketone and 0.1 part by weight of stannous octylate, 1,000 parts by weight of polyether polyol ("PTMG1000" manufactured by Mitsubishi Chemical Corporation, number average molecular weight; 1,000), 2 , 2-dimethylolpropionic acid and 317 parts by mass of isophorone diisocyanate were reacted at 70 ° C. until the solution viscosity reached 20,000 mPa ⁇ s, and then the reaction was stopped by adding 3 parts by mass of methanol. A methyl ethyl ketone solution of an anionic urethane resin was obtained.
- PTMG1000 polyether polyol
- urethane resin solution 69 parts by mass of polyoxyethylene distyrenated phenyl ether (Hydrophile-Lipophile Balance (hereinafter abbreviated as “HLB”); 13) and 61 parts by mass of tripropylamine (neutralizing agent; boiling point 156 ° C.)
- HLB Hydrophile Balance
- tripropylamine neutralizing agent; boiling point 156 ° C.
- 2,748 parts by mass of ion-exchanged water was added for phase inversion emulsification to obtain an emulsion in which the anionic urethane resin was dispersed in water.
- a urethane resin composition having a nonvolatile content of 35% by mass was obtained.
- the anionic urethane resin had a flow start temperature of 40 ° C. or lower and an acid value of 17.4 mgKOH / g.
- Example 5 In the presence of 1,374 parts by weight of methyl ethyl ketone and 0.1 part by weight of stannous octylate, 1,000 parts by weight of polyether polyol ("PTMG1000" manufactured by Mitsubishi Chemical Corporation, number average molecular weight; 1,000), 2 , 2-dimethylolpropionic acid and 317 parts by mass of isophorone diisocyanate were reacted at 70 ° C. until the solution viscosity reached 40,000 mPa ⁇ s, and then the reaction was stopped by adding 3 parts by mass of methanol. A methyl ethyl ketone solution of an anionic urethane resin was obtained.
- PTMG1000 polyether polyol
- urethane resin solution 69 parts by mass of polyoxyethylene distyrenated phenyl ether (Hydrophile-Lipophile Balance (hereinafter abbreviated as “HLB”); 13) and triethylamine (neutralizing agent; boiling point 89.5 ° C.) 38 parts by mass
- HLB Hydrophile Balance
- 2,748 parts by mass of ion-exchanged water was added for phase inversion emulsification to obtain an emulsion in which the anionic urethane resin was dispersed in water.
- a urethane resin composition having a nonvolatile content of 35% by mass was obtained.
- the anionic urethane resin had a flow start temperature of 52 ° C. and an acid value of 17.4 mgKOH / g.
- a thickener (“Borchi Gel 0620” manufactured by Borchers) and 9 parts by mass of a carbodiimide crosslinking agent (1) are added to 100 parts by mass of the obtained urethane resin composition, and 2 parts at 2,000 rpm with a mechanical mixer. The mixture was stirred for minutes and defoamed with a vacuum defoamer to obtain an adhesive.
- Example 6 In the presence of 1,418 parts by weight of methyl ethyl ketone and 0.1 part by weight of stannous octylate, 1,000 parts by weight of polyether polyol ("PTMG1000" manufactured by Mitsubishi Chemical Corporation, number average molecular weight; 1,000), 2 , 2-dimethylolpropionic acid (74 parts by mass) and isophorone diisocyanate (345 parts by mass) were reacted at 70 ° C. until the solution viscosity reached 20,000 mPa ⁇ s, and then 3 parts by mass of methanol was added to stop the reaction. A methyl ethyl ketone solution of an anionic urethane resin was obtained.
- PTMG1000 polyether polyol
- 2-dimethylolpropionic acid 74 parts by mass
- isophorone diisocyanate 345 parts by mass
- urethane resin solution 69 parts by mass of polyoxyethylene distyrenated phenyl ether (Hydrophile-Lipophile Balance (hereinafter abbreviated as “HLB”); 13) and triethylamine (neutralizing agent; boiling point 89.5 ° C.) 38 parts by mass
- HLB Hydrophile Balance
- 2,836 parts by mass of ion-exchanged water was added for phase inversion emulsification to obtain an emulsion in which the anionic urethane resin was dispersed in water.
- a urethane resin composition having a nonvolatile content of 35% by mass was obtained.
- the flow start temperature of the anionic urethane resin was 40 ° C. or lower, and the acid value was 21.8 mgKOH / g.
- urethane resin composition 100 parts by mass of the obtained urethane resin composition, 1 part by mass of a thickener (“Borchi Gel 0620” manufactured by Borchers) and 12 parts by mass of a cross-linking agent (1) are added, and the mechanical mixer is used at 2,000 rpm for 2 minutes. The mixture was stirred and defoamed with a vacuum defoamer to obtain an adhesive.
- a thickener (“Borchi Gel 0620” manufactured by Borchers)
- cross-linking agent (1) 12 parts by mass of a cross-linking agent (1)
- Example 1 In Example 1, an adhesive was obtained in the same manner as in Example 1 except that the carbodiimide crosslinking agent was not used.
- Example 2 an adhesive was obtained in the same manner as in Example 1 except that an oxazoline crosslinking agent (“Epocross WS-700” manufactured by Nippon Shokubai Co., Ltd., solid content: 25% by mass) was used instead of the carbodiimide crosslinking agent. It was.
- an oxazoline crosslinking agent (“Epocross WS-700” manufactured by Nippon Shokubai Co., Ltd., solid content: 25% by mass) was used instead of the carbodiimide crosslinking agent. It was.
- urethane resin solution 69 parts by mass of polyoxyethylene distyrenated phenyl ether (Hydrophile-Lipophile Balance (hereinafter abbreviated as “HLB”); 13) and triethylamine (neutralizing agent; boiling point 89.5 ° C.) 38 parts by mass
- HLB Hydrophile Balance
- triethylamine neutralizing agent; boiling point 89.5 ° C.
- ion-exchanged water was added for phase inversion emulsification to obtain an emulsion in which the anionic urethane resin was dispersed in water.
- a urethane resin composition having a nonvolatile content of 35% by mass was obtained.
- the anionic urethane resin had a flow start temperature of 110 ° C. and an acid value of 17.4 mgKOH / g.
- urethane resin composition 100 parts by mass of the obtained urethane resin composition, 1 part by mass of a thickener (“Borchi Gel 0620” manufactured by Borchers) and 9 parts by mass of a cross-linking agent (1) are added, and the mechanical mixer is used at 2,000 rpm for 2 minutes. The mixture was stirred and defoamed with a vacuum defoamer to obtain an adhesive.
- a thickener (“Borchi Gel 0620” manufactured by Borchers)
- a cross-linking agent (1) 9 parts by mass of a cross-linking agent (1)
- non-woven fabric base material is stacked on the dried product, and thermocompression bonded with a hot roll press (roll temperature 100 ° C., press linear pressure 3 MPa / m 2 , feed rate 1 m / min), and further 70 with a hot air dryer.
- Synthetic leather was obtained by aging at 2 ° C. for 2 days.
- 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.
- the adhesive of the present invention has a long usable time (pot life) and was able to impart excellent peel strength.
- Comparative Example 1 is an embodiment that does not contain a carbodiimide crosslinking agent (C), but the peel strength was insufficient.
- Comparative Example 2 is an embodiment in which an oxazoline crosslinking agent was used instead of the carbodiimide crosslinking agent (C), but the peel strength was insufficient.
- Comparative Example 3 is an embodiment using an anionic urethane resin having a flow start temperature exceeding the range specified in the present invention, but the peel strength was insufficient.
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Abstract
Description
メチルエチルケトン1,374質量部及びオクチル酸第一錫0.1質量部の存在下、ポリエーテルポリオール(三菱化学株式会社製「PTMG1000」、数平均分子量;1,000)1,000質量部と、2,2-ジメチロールプロピオン酸57質量部と、イソホロンジイソシアネート317質量部とを溶液粘度が20,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてアニオン性ウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(Hydrophile-Lipophile Balance(以下、「HLB」と略記する);13)69質量部と、トリエチルアミン(中和剤;沸点89.5℃)38質量部を混合させた後に、イオン交換水2,748質量部を加えて転相乳化させることで前記アニオン性ウレタン樹脂が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、不揮発分35質量%のウレタン樹脂組成物を得た。なお、前記アニオン性ウレタン樹脂の流動開始温度は40℃以下、酸価は17.4mgKOH/gであった。
架橋剤を配合する前のウレタン樹脂組成物を離型紙に塗布し(塗布厚さ150μm)、熱風乾燥機にて70℃、2分間、次いで120℃で2分間乾燥することで乾燥物を得た。この乾燥物を、株式会社島津製作所製フローテスター「CFT-500A」(口径1MM、長さ1MMのダイスを使用、荷重98N、昇温速度3℃/分)を使用して、流動開始温度を測定した。
架橋剤を配合する前のウレタン樹脂組成物を乾燥し、乾燥固化した樹脂粒子の0.05g~0.5gを、300mL三角フラスコに秤量し、次いで、テトラヒドロフランとイオン交換水との質量割合[テトラヒドロフラン/イオン交換水]が80/20の混合溶媒約80mLを加えそれらの混合液を得た。
次いで、前記混合液にフェノールフタレイン指示薬を混合した後、あらかじめ標定された0.1mol/Lの水酸化カリウム水溶液で滴定し、滴定に用いた水酸化カリウム水溶液の量から下記計算式(1)に従い、水性ウレタン樹脂(A)の酸価(mgKOH/g)を求めた。
計算式 A=(B×f×5.611)/S (1)
式中、Aは樹脂の固形分酸価(mgKOH/g)、Bは滴定に用いた0.1mol/L水酸化カリウム水溶液の量(mL)、fは0.1mol/L水酸化カリウム水溶液のファクター、Sは樹脂粒子の質量(g)、5.611は水酸化カリウムの式量(56.11/10)である。
ポリエーテルポリオールをポリカーボネートポリオール(宇部興産株式会社製「ETERNACOLL UH-100」、数平均分子量;1,000)に変更した以外は、実施例1と同様にして、接着剤を得た。なお、前記アニオン性ウレタン樹脂の流動開始温度は40℃以下、酸価は17.2mgKOH/gであった。
ポリエーテルポリオールをポリエステルポリオール(株式会社ダイセル製「プラクセル210」、数平均分子量;1,000)に変更した以外は、実施例1と同様にして、接着剤を得た。なお、前記アニオン性ウレタン樹脂の流動開始温度は40℃以下、酸価は17.2mgKOH/gであった。
メチルエチルケトン1,374質量部及びオクチル酸第一錫0.1質量部の存在下、ポリエーテルポリオール(三菱化学株式会社製「PTMG1000」、数平均分子量;1,000)1,000質量部と、2,2-ジメチロールプロピオン酸57質量部と、イソホロンジイソシアネート317質量部とを溶液粘度が20,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてアニオン性ウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(Hydrophile-Lipophile Balance(以下、「HLB」と略記する);13)69質量部と、トリプロピルアミン(中和剤;沸点156℃)61質量部を混合させた後に、イオン交換水2,748質量部を加えて転相乳化させることで前記アニオン性ウレタン樹脂が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、不揮発分35質量%のウレタン樹脂組成物を得た。なお、前記アニオン性ウレタン樹脂の流動開始温度は40℃以下、酸価は17.4mgKOH/gであった。
メチルエチルケトン1,374質量部及びオクチル酸第一錫0.1質量部の存在下、ポリエーテルポリオール(三菱化学株式会社製「PTMG1000」、数平均分子量;1,000)1,000質量部と、2,2-ジメチロールプロピオン酸57質量部と、イソホロンジイソシアネート317質量部とを溶液粘度が40,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてアニオン性ウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(Hydrophile-Lipophile Balance(以下、「HLB」と略記する);13)69質量部と、トリエチルアミン(中和剤;沸点89.5℃)38質量部を混合させた後に、イオン交換水2,748質量部を加えて転相乳化させることで前記アニオン性ウレタン樹脂が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、不揮発分35質量%のウレタン樹脂組成物を得た。なお、前記アニオン性ウレタン樹脂の流動開始温度は52℃、酸価は17.4mgKOH/gであった。
メチルエチルケトン1,418質量部及びオクチル酸第一錫0.1質量部の存在下、ポリエーテルポリオール(三菱化学株式会社製「PTMG1000」、数平均分子量;1,000)1,000質量部と、2,2-ジメチロールプロピオン酸74質量部と、イソホロンジイソシアネート345質量部とを溶液粘度が20,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてアニオン性ウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(Hydrophile-Lipophile Balance(以下、「HLB」と略記する);13)69質量部と、トリエチルアミン(中和剤;沸点89.5℃)38質量部を混合させた後に、イオン交換水2,836質量部を加えて転相乳化させることで前記アニオン性ウレタン樹脂が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、不揮発分35質量%のウレタン樹脂組成物を得た。なお、前記アニオン性ウレタン樹脂の流動開始温度は40℃以下、酸価は21.8mgKOH/gであった。
実施例1において、カルボジイミド架橋剤を用いなかった以外は実施例1と同様にして接着剤を得た。
実施例1において、カルボジイミド架橋剤に代えて、オキサゾリン架橋剤(日本触媒株式会社製「エポクロスWS-700」、固形分25質量%)を用いた以外は実施例1と同様にして接着剤を得た。
メチルエチルケトン4,121質量部及びオクチル酸第一錫0.1質量部の存在下、ポリエーテルポリオール(三菱化学株式会社製「PTMG1000」、数平均分子量;1,000)1,000質量部と、2,2-ジメチロールプロピオン酸57質量部と、イソホロンジイソシアネート317質量部とを溶液粘度が100,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてアニオン性ウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(Hydrophile-Lipophile Balance(以下、「HLB」と略記する);13)69質量部と、トリエチルアミン(中和剤;沸点89.5℃)38質量部を混合させた後に、イオン交換水5,495質量部を加えて転相乳化させることで前記アニオン性ウレタン樹脂が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、不揮発分35質量%のウレタン樹脂組成物を得た。なお、前記アニオン性ウレタン樹脂の流動開始温度は110℃、酸価は17.4mgKOH/gであった。
エーテル系ウレタンディスパージョン(DIC株式会社製「ハイドランWLS-120AR」100質量部、増粘剤(Borcher社製「Borch Gel ALA」)2質量部、レべリング剤(Evonik社製「TEGO Flow425」)0.2質量部、消泡剤(Evonik社製「TEGO Twin4000」)0.2質量部、黒色顔料(DIC株式会社製「DILAC HS-9550」)5質量部をメカニカルミキサーにて2,000rpm、2分間撹拌し、次いで真空脱泡機を使用して脱泡させて表皮層用配合液を得た。
離型紙(リンテック株式会社製「EK-100D」)上に、表皮層用配合液をナイフコーターにて塗布した後(塗布厚さ150μm)、熱風乾燥機を使用して70℃で2分間、次いで120℃で2分間乾燥させることにより表皮層を得た。更にこの表皮層上に実施例および比較例で得た接着剤をナイフコーターを使用して塗布した後(塗布厚さ150μm)、熱風乾燥機を使用して70℃で6分間乾燥させた。最後に、不織布基材を前記乾燥物上に重ね、熱ロールプレス(ロール温度100℃、プレス線圧3MPa/m2、送り速度1m/min)にて熱圧着させ、さらに熱風乾燥機にて70℃で2日間エージングさせることで合成皮革を得た。
実施例および比較例で用いたポリオール等の数平均分子量は、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」
実施例および比較例において、架橋剤を配合してから10分経過後、および3日経過後の接着剤の粘度を測定し(B型粘度計、10Pコーン、ローター回転数;50rpm)、10分経過後に対する3日経過後粘度上昇率が架橋剤配合前から0.5~2倍以内であるものは「○」と評価し、0.5倍より小さい、または2倍を超えているものは「×」と評価した。
2.5cm幅のホットメルトテープ(サン化成株式会社製「BW-2」)を合成皮革表面に載置し150℃で30秒加熱し、ホットメルトテープを接着した。その後、ホットメルトテープの幅に沿って試料を裁断した。この資料の一部を剥離し、基材とホットメルトテープとをチャックで挟み、張試験機「オートグラフAG-I」(株式会社島津製作所製)を使用して剥離強度を測定した(以下「初期剥離強度」と略記する。)。得られたデータ(n=3)の平均値を求め、1cm幅に換算した(単位;kgf/cm)。
また、実施例および比較例において、架橋剤を配合してから6時間経過してから、合成皮革を作製したものを同様に評価したものを「配合6時間経過後の剥離強度」とした。
Claims (6)
- 流動開始温度が100℃以下であるアニオン性ウレタン樹脂(A)、中和剤(B)、カルボジイミド架橋剤(C)、及び、水性媒体(D)を含有することを特徴とする接着剤。
- 前記アニオン性ウレタン樹脂(A)の酸価が、1~35mgKOH/gの範囲である請求項1記載の接着剤。
- 前記中和剤(B)の沸点が、200℃以下である請求項1又は2記載の接着剤。
- 前記カルボジイミド架橋剤(C)が、1,3-ビス(1-メチル-1-イソシアナトエチル)ベンゼン、1,4-ビス(1-メチル-1-イソシアナトエチル)ベンゼン、及び、ジシクロヘキシルメタンジイソシアネートからなる群より選ばれる1種以上のポリイソシアネートを原料とするものである請求項1~3のいずれか1項記載の接着剤。
- 前記カルボジイミド架橋剤(C)の含有量が、前記アニオン性ウレタン樹脂(A)100質量部に対して、0.5~25質量部の範囲である請求項1~4のいずれか1項記載の接着剤。
- 少なくとも、基材(i)、請求項1~5のいずれか1項記載の接着剤により形成された接着層(ii)、及び、表皮層(iii)を有することを特徴とする合成皮革。
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JP2019545828A JP6620965B1 (ja) | 2018-03-20 | 2019-03-05 | 接着剤、及び、合成皮革 |
CN201980019687.4A CN111868195B (zh) | 2018-03-20 | 2019-03-05 | 粘接剂和合成皮革 |
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US11479908B2 (en) * | 2018-06-07 | 2022-10-25 | Dic Corporation | Synthetic leather |
CN113249080A (zh) * | 2021-05-11 | 2021-08-13 | 广州慧谷化学有限公司 | 一种水分散型热熔胶及其制备方法 |
CN114292598A (zh) * | 2021-12-30 | 2022-04-08 | 广东汇齐新材料有限公司 | 一种高粘着强度的tpu热熔胶膜及其制备方法 |
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KR102356293B1 (ko) | 2022-02-08 |
EP3770229A4 (en) | 2021-11-24 |
EP3770229A1 (en) | 2021-01-27 |
KR20200118182A (ko) | 2020-10-14 |
EP3770229B1 (en) | 2024-06-26 |
JP6620965B1 (ja) | 2019-12-18 |
CN111868195B (zh) | 2022-05-06 |
TWI798376B (zh) | 2023-04-11 |
TW201940637A (zh) | 2019-10-16 |
CN111868195A (zh) | 2020-10-30 |
JPWO2019181476A1 (ja) | 2020-04-30 |
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