Urethane resin composition, surface treatment agent, and article

Abstract

To provide an urethane resin composition containing water which is excellent in ethanol resistance.SOLUTION: There is provided an urethane resin composition which contains an urethane resin (A), an olefin resin (B), water (C), and a carbodiimide compound (D) having a carbodiimide equivalent of 340 or more. There are provided a surface treatment agent which contains the urethane resin composition, and an article which has a layer formed by the surface treatment agent. The urethane resin composition is suitably usable as, especially, a surface treatment agent of a TPO (thermoplastic olefin resin) leather.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a urethane resin composition, a surface treatment agent, and an article having a layer formed with the surface treatment agent. [Background technology]

[0002] In the manufacturing process of leather seats for automobile interiors, the surface is finished with a surface treatment agent from the viewpoint of chemical resistance and design. Conventional materials used for surface treatment agents have mainly been solvent-based resin compositions containing organic solvents, but in response to the recent tightening of environmental regulations, water-based surface treatment agents that are substantially free of organic solvents are being developed.

[0003] As the aqueous surface treatment agent, for example, a method of overpainting two types of urethane resin compositions containing water has been disclosed (see, for example, Patent Document 1). Although this method provides excellent adhesion to the base and abrasion resistance, it has insufficient ethanol resistance.

[0004] It has been pointed out that when surface treatment agents are made water-based, the chemical resistance, particularly the ethanol resistance, is inferior to that of conventional solvent-based resin compositions. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2006-176615 A Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a water-containing urethane resin composition that has excellent ethanol resistance. [Means for solving the problem]

[0007] The present invention provides a urethane resin composition comprising a urethane resin (A), an olefin resin (B), water (C), and a carbodiimide compound (D) having a carbodiimide equivalent of 340 or more.

[0008] The present invention also provides a surface treatment agent containing the urethane resin composition, and an article having a layer formed from the surface treatment agent. Effect of the Invention

[0009] The urethane resin composition of the present invention has excellent ethanol resistance. In addition, the urethane resin composition of the present invention contains water and is therefore an environmentally friendly material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The urethane resin composition of the present invention contains a urethane resin (A), an olefin resin (B), water (C), and a specific carbodiimide compound (D).

[0011] The urethane resin (A) is dispersible in water (C), and examples of the urethane resin that can be used include urethane resins having hydrophilic groups such as anionic groups, cationic groups, and nonionic groups; urethane resins forcibly dispersed in water (B) using an emulsifier, etc. These urethane resins (A) may be used alone or in combination of two or more kinds.

[0012] The method for obtaining the urethane resin having an anionic group may, for example, be a method using, as a raw material, one or more compounds selected from the group consisting of compounds having a carboxyl group and compounds having a sulfonyl group.

[0013] Examples of the compound having a carboxyl group that can be used include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, 2,2-valeric acid, etc. These compounds may be used alone or in combination of two or more.

[0014] Examples of the compound having a sulfonyl group that can be used include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N-(2-aminoethyl)-2-aminoethylsulfonic acid, etc. These compounds may be used alone or in combination of two or more.

[0015] The carboxyl group and sulfonyl group may be partially or completely neutralized with a basic compound in the resin composition. Examples of the basic compound include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; and metal base compounds including sodium, potassium, lithium, and calcium.

[0016] The urethane resin having a cationic group can be obtained, for example, by using one or more compounds having an amino group as a raw material.

[0017] Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine, compounds having a tertiary amino group such as N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-alkyldiaminoalkylamines such as N-methyldiaminoethylamine and N-ethyldiaminoethylamine, etc. These compounds may be used alone or in combination of two or more.

[0018] The method for obtaining the urethane resin having a nonionic group may, for example, be a method using one or more compounds having an oxyethylene structure as a raw material.

[0019] Examples of the compound having an oxyethylene structure that can be used include polyether polyols having an oxyethylene structure, such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, etc. These compounds may be used alone or in combination of two or more.

[0020] The amount of the raw materials used to produce the above-mentioned urethane resin having a hydrophilic group is preferably in the range of 0.1 to 15 mass % of the raw materials for the urethane resin (A), more preferably in the range of 1 to 10 mass %, and even more preferably in the range of 1.5 to 7 mass %, in order to obtain even better chemical resistance, abrasion resistance, weather resistance, and hydrolysis resistance.

[0021] Examples of emulsifiers that can be used when obtaining the urethane resin that is forcibly dispersed in water (C) include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene-polyoxypropylene copolymers; anionic emulsifiers such as fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, sodium alkanesulfonates, and sodium alkyldiphenyl ether sulfonates; and cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts. These emulsifiers may be used alone or in combination of two or more.

[0022] Specifically, the urethane resin (A) may be, for example, a reaction product of the raw materials used for producing the urethane resin having a hydrophilic group, that is, polyisocyanate (a1), polyol (a2), and chain extender (a3). These reactions may be performed by known urethane reactions.

[0023] Examples of the polyisocyanate (a1) include aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate; and aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

[0024] As the polyisocyanate (a1), it is preferable to use an alicyclic polyisocyanate, more preferably a polyisocyanate having at least one structure in which a nitrogen atom of an isocyanate group is directly linked to a cyclohexane ring, and even more preferably isophorone diisocyanate and / or dicyclohexylmethane diisocyanate. In addition, the amount of the alicyclic polyisocyanate used is preferably 30% by mass or more in the polyisocyanate (a1), more preferably 40% by mass or more, and even more preferably 50% by mass or more, in order to obtain even better chemical resistance, abrasion resistance, and weather resistance.

[0025] In addition, when the urethane resin composition of the present invention is used as a surface treatment agent and even higher light resistance is required, it is preferable to use the alicyclic polyisocyanate and the aliphatic polyisocyanate in combination as the polyisocyanate (a1), and it is preferable to use hexamethylene diisocyanate as the aliphatic polyisocyanate. In this case, the content of the alicyclic polyisocyanate in the polyisocyanate (a1) is preferably 30 mass% or more, more preferably 40 mass% or more, and even more preferably 50 mass% or more.

[0026] The amount of the polyisocyanate (a1) used is preferably within a range from 5 to 50 mass % in the raw material of the urethane resin (A), more preferably within a range from 15 to 40 mass %, and even more preferably within a range from 20 to 37 mass %, in order to obtain even better chemical resistance, abrasion resistance, and weather resistance.

[0027] As the polyol (a2), for example, polyether polyol, polyester polyol, polyacrylic polyol, polycarbonate polyol, polybutadiene polyol, etc. can be used. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use polycarbonate polyol because it provides better chemical resistance, abrasion resistance, and weather resistance.

[0028] As the polycarbonate polyol, for example, a reaction product of a carbonate ester and / or phosgene with a compound having two or more hydroxyl groups can be used.

[0029] Examples of the carbonate ester that can be used include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. These compounds may be used alone or in combination of two or more kinds.

[0030] Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, 3-methylpentanediol, neopentyl glycol, trimethylolethane, and glycerin. These compounds may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining even more excellent chemical resistance, abrasion resistance, and weather resistance, it is preferable to use one or more compounds selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methylpentanediol, and 1,10-decanediol, and 1,6-hexanediol is more preferable.

[0031] The amount of the polycarbonate polyol used is preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, of the polyol (a2), in order to obtain even better chemical resistance, abrasion resistance, and weather resistance.

[0032] The number average molecular weight of the polycarbonate polyol is preferably in the range of 100 to 100,000, more preferably in the range of 150 to 10,000, and further preferably in the range of 200 to 2,500, in order to obtain even better chemical resistance, mechanical strength, abrasion resistance, and weather resistance. The number average molecular weight of the polycarbonate polyol is a value measured by gel permeation column chromatography (GPC).

[0033] The number average molecular weight of the polyol (a2) other than the polycarbonate polyol is preferably in the range of 500 to 100,000, more preferably in the range of 700 to 50,000, and further preferably in the range of 800 to 10,000, in terms of obtaining even better weather resistance. The number average molecular weight of the polyol (a2) is a value measured by gel permeation column chromatography (GPC).

[0034] The amount of the polyol (a2) used is preferably within a range from 30 to 80% by mass, more preferably from 40 to 75% by mass, and even more preferably from 50 to 70% by mass, in the raw material of the urethane resin (A).

[0035] The chain extender (a3) ​​is, for example, one having a number average molecular weight in the range of 50 to 450 (excluding the polycarbonate polyols). Specific examples of the chain extender (a3) ​​include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethane ... Chain extenders having an amino group such as Sandiamine and hydrazine, and chain extenders having a hydroxyl group such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, and trimethylolpropane can be used. These chain extenders can be used alone or in combination of two or more.

[0036] As the chain extender (a3), among the above, it is preferable to use a chain extender having an amino group, and more preferably piperazine and / or hydrazine, from the viewpoint of obtaining even better chemical resistance, mechanical strength, abrasion resistance, and weather resistance, and the total amount of piperazine and hydrazine in the chain extender (a3) ​​is preferably 30 mass% or more, more preferably 50 mass% or more, even more preferably 60 mass% or more, and particularly preferably 80 mass% or more. In addition, the chain extender (a3) ​​preferably has an average functional group number of less than 3, more preferably less than 2.5. In addition,

[0037] The amount of the chain extender (a3) ​​used is preferably within a range from 0.5 to 10 mass % in the raw material of the urethane resin (A), more preferably within a range from 0.7 to 5 mass %, and even more preferably within a range from 0.9 to 2.3, in order to obtain even better chemical resistance, mechanical strength, abrasion resistance, and weather resistance.

[0038] Examples of the method for producing the urethane resin (A) include a method in which the polyisocyanate (a1), the polyol (a2), and the raw materials used for producing the urethane resin having a hydrophilic group are reacted to produce a urethane prepolymer having an isocyanate group, and then the urethane prepolymer is reacted with the chain extender (a3); a method in which the polyisocyanate (a1), the polyol (a2), the raw materials used for producing the urethane resin having a hydrophilic group, and the chain extender (a3) ​​are charged at once and reacted, etc. These reactions can be carried out, for example, at 50 to 100°C for 3 to 10 hours.

[0039] The molar ratio of the sum of the hydroxyl groups in the raw materials used for producing the urethane resin having a hydrophilic group, the hydroxyl groups in the polyol (a2), and the hydroxyl groups and amino groups in the chain extender (a3) ​​to the isocyanate groups in the polyisocyanate (a1) [(isocyanate groups) / (hydroxyl groups and amino groups)] is preferably in the range of 0.8 to 1.2, and more preferably in the range of 0.9 to 1.1.

[0040] When producing the urethane resin (A), it is preferable to deactivate the isocyanate groups remaining in the urethane resin (A). When deactivating the isocyanate groups, 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 per 100 parts by mass of the urethane resin (A).

[0041] In addition, when producing the urethane resin (A), an organic solvent may be used. As the organic solvent, for example, 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; amide compounds such as dimethylformamide and N-methylpyrrolidone, etc. may be used. These organic solvents may be used alone or in combination of two or more kinds. It is preferable that the organic solvent is finally removed by a distillation method or the like.

[0042] The content of the urethane bond in the urethane resin (A) is preferably in the range of 980 to 4,000 mmol / kg, more preferably in the range of 1,000 to 3,500 mmol / kg, further preferably in the range of 1,100 to 3,000 mmol / kg, and particularly preferably in the range of 1,150 to 2,500 mmol / kg, in order to obtain even better chemical resistance, abrasion resistance, and weather resistance. The content of the urethane bond in the urethane resin (A) is a value calculated from the amounts of the polyisocyanate (a1), polyol (a2), raw materials used for producing the urethane resin having a hydrophilic group, and chain extender (a3) ​​charged.

[0043] The content of the urea bond in the urethane resin (A) is preferably in the range of 315 to 850 mmol / kg, more preferably in the range of 350 to 830 mmol / kg, further preferably in the range of 400 to 800 mmol / kg, and further preferably in the range of 410 to 770 mmol / kg, from the viewpoint of obtaining even more excellent chemical resistance, abrasion resistance, and weather resistance. Note that the content of the urea bond in the urethane resin (A) is a value calculated from the charged amounts of the polyisocyanate (a1), the polyol (a2), the raw materials used for producing the urethane resin having a hydrophilic group, and the chain extender (a3).

[0044] The content of the alicyclic structure in the urethane resin (A) is preferably in the range of 500 to 3,000 mmol / kg, more preferably in the range of 600 to 2,900 mmol / kg, and even more preferably in the range of 700 to 2,700 mmol / kg, from the viewpoint of obtaining even better chemical resistance, abrasion resistance, and weather resistance. The content of the alicyclic structure in the urethane resin (A) is a value calculated from the charged amounts of the polyisocyanate (a1), the polyol (a2), the raw materials used for producing the urethane resin having a hydrophilic group, and the chain extender (a3).

[0045] The content of the urethane resin (A) is preferably in the range of 3 to 50% by mass, and more preferably in the range of 5 to 30% by mass, in the urethane resin composition from the viewpoints of coatability, workability and storage stability.

[0046] The olefin resin (B) is used for the purpose of improving adhesion to the base. As the olefin resin (B), for example, polyolefin obtained by polymerizing a polyolefin compound; natural rubber, ethylene-vinyl acetate copolymer, synthetic isopropylene rubber; modified products thereof, etc. can be used. These olefin resins may be used alone or in combination of two or more kinds.

[0047] As the polyolefin compound, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, etc. can be used. These olefin compounds can be used alone or in combination of two or more. The polyolefin can be a homopolymer or a copolymer.

[0048] The modified polyolefin may be, for example, a polyolefin modified with a hydroxyl group, an acid modified polyolefin, or an amino modified polyolefin. These polyolefins may be used alone or in combination of two or more. Among these, it is preferable to use an acid modified polyolefin, since it can further improve the adhesion to the substrate (especially to thermoplastic olefin resin (TPO) leather).

[0049] The acid-modified polyolefin may be, for example, a polyolefin that has been acid-modified without chlorination. The acid modification is preferably carried out by reacting an unsaturated carboxylic acid or an anhydride thereof with a polyolefin. The unsaturated carboxylic acid may be, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, crotonic acid; anhydrides thereof; half esters and half amides of unsaturated carboxylic acids. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use one or more selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, and maleic anhydride.

[0050] In addition, as the acid-modified polyolefin, it is preferable to use one having a polyether chain because it has excellent dispersibility in water. The polyether chain is preferably a polyethylene chain and / or a polypropylene chain, and more preferably a polyethylene chain.

[0051] The weight average molecular weight of the olefin resin (B) is preferably in the range of 10,000 to 500,000, more preferably in the range of 20,000 to 200,000, in order to obtain even better adhesion to the substrate (particularly TPO leather). The weight average molecular weight of the olefin resin (B) is a value measured by gel permeation column chromatography (GPC).

[0052] The content of the olefin resin (B) is preferably in the range of 0.01 to 10 mass %, more preferably in the range of 0.1 to 7 mass %, in order to obtain even better adhesion to the base (particularly TPO leather).

[0053] The amount of the olefin resin (B) used per 100 parts by mass of the urethane resin (A) (=solid content) is preferably in the range of 1 to 60 parts by mass, more preferably in the range of 2 to 50 parts by mass.

[0054] The water (C) may be ion-exchanged water, distilled water, etc. The content of the water (C) in the urethane resin composition is preferably in the range of 30 to 95% by mass, more preferably in the range of 50 to 90% by mass, from the viewpoints of the coatability, workability, and storage stability of the urethane resin composition.

[0055] In order to obtain excellent ethanol resistance, it is essential that the carbodiimide compound (D) used has a carbodiimide equivalent of 340 or more. In order to obtain even better ethanol resistance, the carbodiimide equivalent of the carbodiimide compound (D) is preferably in the range of 360 to 1,000. The formula weight per 1 mole of the carbodiimide group is shown.

[0056] Specific examples of the carbodiimide compound (D) that can be used include carbodiimide compounds such as N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-[3-(dimethylamino)propyl]-N'-ethylcarbodiimide, N-[3-(dimethylamino)propyl]-N'-ethylcarbodiimide methiodide, N-tert-butyl-N'-ethylcarbodiimide, N-cyclohexyl-N'-(2-morpholinoethyl)carbodiimide meso-p-toluenesulfonate, N,N'-di-tert-butylcarbodiimide, and N,N'-di-p-tolylcarbodiimide; carbodiimide compounds obtained by a known condensation reaction of polyisocyanate in the presence of a carbodiimidization catalyst; and carbodiimide compounds using polyisocyanate and polyalkylene oxide as raw materials. These carbodiimide compounds may be used alone or in combination of two or more kinds.

[0057] The preferred carbodiimide compound (D) is commercially available as, for example, "Carbodilite V-02", "Carbodilite V-02-L2", "Carbodilite SV-02", "Carbodilite V-10", "Carbodilite SW-12G", "Carbodilite E-02", "Carbodilite E-03A", "Carbodilite E-05", etc., manufactured by Nisshinbo Chemical Inc.

[0058] The content of the carbodiimide compound (D) is preferably in the range of 0.01 to 20 mass %, more preferably in the range of 0.1 to 10 mass %, and even more preferably in the range of 0.2 to 5 mass %, in order to obtain even better ethanol resistance.

[0059] The amount of the carbodiimide compound (D) used relative to 100 parts by mass of the urethane resin (A) (=solid content) is preferably in the range of 1 to 40 parts by mass, more preferably in the range of 2 to 35 parts by mass.

[0060] The urethane resin composition of the present invention contains the urethane resin (A), the olefin resin (B), the water (C), and the carbodiimide compound (D) as essential components, but may contain other additives as necessary.

[0061] Examples of the other additives that can be used include fillers (E), emulsifiers, antifoaming agents, leveling agents, thickeners, viscoelasticity regulators, antifoaming agents, wetting agents, dispersants, preservatives, plasticizers, penetrants, fragrances, bactericides, miticides, fungicides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments (e.g., titanium white, red iron oxide, phthalocyanine, carbon black, permanent yellow, etc.), etc. These additives may be used alone or in combination of two or more.

[0062] As the other additives, when the urethane resin composition of the present invention is used as a surface treatment agent, or when it is used in an application requiring a matte finish in the coating film, it is preferable that it contains a filler (E).

[0063] Examples of the filler (E) that can be used include silica particles, organic beads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, alumina silicate, etc. These fillers may be used alone or in combination of two or more.

[0064] As the silica particles, for example, dry silica, wet silica, etc. can be used. Among these, dry silica is preferred because it has a high scattering effect and a wide range of gloss adjustment. The average particle size of these silica particles is preferably in the range of 2 to 14 μm, more preferably in the range of 3 to 12 μm. The average particle size of the silica particles refers to the particle size when the cumulative amount in the cumulative particle amount curve of the particle size distribution measurement result is 50% (particle size at D50 in the particle size distribution).

[0065] Examples of the organic beads that can be used include acrylic beads, urethane beads, silicon beads, and olefin beads.

[0066] When the filler (E) is used, the amount used can be appropriately determined depending on the matte feel to be imparted. For example, the amount is preferably in the range of 0.1 to 30 parts by mass, and more preferably in the range of 1 to 10 parts by mass, per 100 parts by mass of the urethane resin (A).

[0067] As described above, the urethane resin composition of the present invention has excellent ethanol resistance, and therefore can be suitably used as a surface treatment agent for various articles such as synthetic leather, polyvinyl chloride (PVC) leather, thermoplastic olefin resin (TPO) leather, dashboards, instrument panels, etc., and can be particularly suitably used for TPO leather.

[0068] The article of the present invention has a layer formed from the above-mentioned surface treatment agent.

[0069] Specific examples of the articles include synthetic leather, artificial leather, natural leather, and polyvinyl chloride (PVC) leather used in automobile interior seats, sports shoes, clothing, furniture, thermoplastic olefin (TPO) leather, dashboards, and instrument panels.

[0070] The thickness of the layer formed by the surface treatment agent is, for example, in the range of 0.1 to 100 μm. EXAMPLES

[0071] The present invention will now be described in more detail with reference to examples.

[0072] [Synthesis Example 1] Preparation of aqueous dispersion of urethane resin (A-1) A four-neck flask equipped with a stirrer, a thermometer, and a nitrogen reflux tube was charged with 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octoate, and then 200 parts by mass of polycarbonate polyol-1 (made from 1,4-butanediol and 1,6-hexanediol, number average molecular weight: 1,000), 15 parts by mass of 2,2-dimethylolpropionic acid, 49 parts by mass of isophorone diisocyanate, and 34 parts by mass of hexamethylene diisocyanate were added and reacted at 70°C for 1 hour to obtain a methyl ethyl ketone solution of a urethane prepolymer. Next, 6.8 parts by mass of hydrazine and 15 parts by mass of triethylamine were mixed with the methyl ethyl ketone solution of this urethane prepolymer, and then 820 parts by mass of ion-exchanged water was added to obtain an emulsion in which the urethane resin (A-1) was dispersed in water. Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added to obtain an aqueous dispersion of urethane resin (A-1) having a non-volatile content of 30% by mass. The resulting urethane resin (A-1) had a urethane bond content of 2,052 mmol / kg, a urea bond content of 698 mmol / kg, and an alicyclic structure content of 715 mmol / kg.

[0073] [Synthesis Example 2] Preparation of aqueous dispersion of urethane resin (A-2) A four-neck flask equipped with a stirrer, a thermometer, and a nitrogen reflux tube was charged with 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octoate, and then 220 parts by mass of polycarbonate polyol-3 (made from 1,6-hexanediol, number average molecular weight: 2,000), 12 parts by mass of 2,2-dimethylolpropionic acid, and 70 parts by mass of dicyclohexylmethane diisocyanate were added and reacted at 70°C for 1 hour to obtain a methyl ethyl ketone solution of a urethane prepolymer. Next, 4.5 parts by mass of piperazine and 9 parts by mass of triethylamine were mixed with the methyl ethyl ketone solution of this urethane prepolymer, and then 880 parts by mass of ion-exchanged water was added to obtain an emulsion in which the urethane resin (A-2) was dispersed in water. Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added to obtain an aqueous dispersion of urethane resin (A-2) having a nonvolatile content of 32% by mass. The resulting urethane resin (A-2) had a urethane bond content of 1,278 mmol / kg, a urea bond content of 435 mmol / kg, and an alicyclic structure content of 1,713 mmol / kg.

[0074] [Synthesis Example 3] Preparation of aqueous dispersion of urethane resin (A-3) A four-neck flask equipped with a stirrer, a thermometer, and a nitrogen reflux tube was charged with 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octoate, followed by 138 parts by mass of polycarbonate polyol-4 (made from 1,6-hexanediol, number average molecular weight: 2,000), 55 parts by mass of polycarbonate polyol-5 (made from 1,6-hexanediol, number average molecular weight: 500), 13 parts by mass of 2,2-dimethylolpropionic acid, and 100 parts by mass of dicyclohexylmethane diisocyanate, and the reaction was carried out at 70° C. for 1 hour to obtain a methyl ethyl ketone solution of a urethane prepolymer. Next, 5.6 parts by mass of piperazine and 10 parts by mass of triethylamine were mixed with the methyl ethyl ketone solution of this urethane prepolymer, and then 880 parts by mass of ion-exchanged water was added to obtain an emulsion in which the urethane resin (A-3) was dispersed in water. Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added to obtain an aqueous dispersion of urethane resin (A-3) having a nonvolatile content of 30% by mass. The resulting urethane resin (A-3) had a urethane bond content of 1,747 mmol / kg, a urea bond content of 576 mmol / kg, and an alicyclic structure content of 2,341 mmol / kg.

[0075] [Example 1] A urethane resin composition was obtained by mixing 40 parts by mass of the aqueous dispersion of urethane resin (A-1) obtained in Synthesis Example 1, 7 parts by mass of acid-modified non-chlorinated polyolefin ("Arrowbase SD-1010" manufactured by Unitika Ltd., non-volatile content: 20.5% by mass, hereinafter abbreviated as "POf"), 53 parts by mass of water, and 2.5 parts by mass of a carbodiimide compound ("Carbodilite V-02" manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 590, non-volatile content: 40% by mass, hereinafter abbreviated as "NCN(1)").

[0076] [Example 2] A urethane resin composition was obtained by mixing 42 parts by mass of the aqueous dispersion of urethane resin (A-1) obtained in Synthesis Example 1, 6 parts by mass of POf, 3 parts by mass of a filler ("ACEMATT TS 100" manufactured by Evonik Degussa, silica particles produced by a dry method, average particle diameter: 10 μm, hereinafter abbreviated as "silica"), 49 parts by mass of water, and 3.5 parts by mass of NCN (1).

[0077] [Example 3] A urethane resin composition was obtained in the same manner as in Example 1, except that the type of carbodiimide compound was changed to "Carbodilite V-02-L2" manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 385, non-volatile content: 40 mass%, hereinafter abbreviated as "NCN(2)".

[0078] [Example 4] A urethane resin composition was obtained in the same manner as in Example 2, except that the type of carbodiimide compound was changed to NCN(2).

[0079] [Example 5] A urethane resin composition was obtained in the same manner as in Example 1, except that the type of carbodiimide compound was changed to "Carbodilite SV-02" manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 430, non-volatile content: 40 mass%, hereinafter abbreviated as "NCN(3)".

[0080] [Example 6] A urethane resin composition was obtained in the same manner as in Example 2, except that the type of carbodiimide compound was changed to NCN (3).

[0081] [Example 7] A urethane resin composition was obtained in the same manner as in Example 1, except that the type of carbodiimide compound was changed to "Carbodilite V-10" manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 410, non-volatile content: 40 mass%, hereinafter abbreviated as "NCN(4)".

[0082] [Example 8] A urethane resin composition was obtained in the same manner as in Example 2, except that the type of carbodiimide compound was changed to NCN(4).

[0083] [Example 9] A urethane resin composition was obtained in the same manner as in Example 1, except that the type of carbodiimide compound was changed to "Carbodilite SW-12G" manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 465, non-volatile content: 40 mass%, hereinafter abbreviated as "NCN(5)".

[0084] [Example 10] A urethane resin composition was obtained in the same manner as in Example 2, except that the type of carbodiimide compound was changed to NCN(5).

[0085] [Example 11] A urethane resin composition was obtained in the same manner as in Example 1, except that the aqueous dispersion of urethane resin (A-1) was changed to the aqueous dispersion of urethane resin (A-2) obtained in Synthesis Example 2.

[0086] [Example 12] A urethane resin composition was obtained in the same manner as in Example 1, except that the aqueous dispersion of urethane resin (A-1) was changed to the aqueous dispersion of urethane resin (A-3) obtained in Synthesis Example 3.

[0087] [Comparative Example 1] A urethane resin composition was obtained in the same manner as in Example 1, except that the type of carbodiimide compound was changed to "V-04" manufactured by Nisshinbo Chemical Inc. (carbodiimide equivalent: 335, hereinafter abbreviated as "NCN-R(1)").

[0088] [Comparative Example 2] A urethane resin composition was obtained in the same manner as in Example 2, except that the type of carbodiimide compound was changed to NCN-R(1).

[0089] [Method for measuring number average molecular weight] The number average molecular weight of the polyols and the weight average molecular weight of the olefin resins used in the synthesis examples and the like are values ​​measured by gel permeation column chromatography (GPC) under the following conditions.

[0090] Measurement equipment: High-speed GPC equipment (Tosoh Corporation "HLC-8220GPC") Column: The following columns manufactured by Tosoh Corporation were used, connected in series. "TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mmI.D. x 30cm) x 1 Detector: RI (differential refractometer) Column temperature: 40℃ Eluent: tetrahydrofuran (THF) Flow rate: 1.0mL / min Injection volume: 100 μL (sample concentration 0.4% by mass in tetrahydrofuran solution) Standard sample: A calibration curve was prepared using the following standard polystyrene.

[0091] (Standard polystyrene) "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0092] [Method for evaluating ethanol resistance] The urethane resin compositions obtained in the Examples and Comparative Examples were blended, and then coated using a bar coater onto a TPO sheet (thickness 0.4 mm) whose surface had been corona-treated using Bar Coater No. 14, and then dried at 120°C for 1 minute to obtain a sample for evaluation. The obtained evaluation sample surface was rubbed with a cotton cloth soaked in a 30% by mass ethanol aqueous solution under a load of 500 g using a Gakushin friction tester ("RT-200" manufactured by Daiei Scientific Instruments Co., Ltd.), and the coating condition was observed and evaluated as follows. "T": No peeling of the coating is observed for 100 or more times. "F": Peeling of the coating was observed after less than 100 cycles.

[0093] [Table 1]

[0094] [Table 2]

[0095] [Table 3]

[0096] [Table 4]

[0097] It was found that the urethane resin composition of the present invention has excellent ethanol resistance.

[0098] On the other hand, Comparative Examples 1 and 2 are embodiments in which carbodiimide compounds having carbodiimide equivalents below the range specified in the present invention were used, and both had poor ethanol resistance.

Claims

1. The composition contains a urethane resin (A), an olefin resin (B), water (C), and a carbodiimide compound (D) having a carbodiimide equivalent of 340 or more, the urethane resin (A) is a reaction product of hexamethylene diisocyanate, the content of the carbodiimide compound (D) is in the range of 0.2 to 5 mass% in the urethane resin composition, A urethane resin composition, characterized in that the olefin resin (B) is an acid-modified non-chlorinated polyolefin, and its content in the urethane resin composition is in the range of 0.1 to 7 mass%.

2. Furthermore, the urethane resin described in Claim 1, wherein the urethane resin (A) is a reaction product of isophorone diisocyanate.

3. A urethane resin described in claim 1 or 2, wherein the urethane bond content of the urethane resin (A) is in the range of 980 to 4,000 mmol / kg.

4. A urethane resin composition described in any one of claims 1 to 3, wherein the content of the alicyclic structure of the urethane resin (A) is in the range of 500 to 3,000 mmol / kg.

5. A surface treatment agent comprising the urethane resin composition according to any one of claims 1 to 3.

6. An article having a layer formed from the surface treatment agent according to claim 5.