JP7298608B2 - Urethane resin composition, surface treatment agent, and article - Google Patents

Description

TECHNICAL FIELD The present invention relates to a urethane resin composition, a surface treatment agent, and an article having a layer of the surface treatment agent.

In the manufacturing process of automotive interior leather seats, the surface is finished with a surface treatment agent from the viewpoint of imparting chemical resistance and designability. Solvent-based resin compositions containing organic solvents have been the mainstream materials used for conventional surface treatment agents, but in response to recent heightened environmental regulations, water-based surface treatment agents that do not substantially contain organic solvents are becoming popular. Development is underway.

As the aqueous surface treatment agent, for example, an aqueous surface treatment agent containing a polyurethane having specific mechanical properties, a carbodiimide cross-linking agent, and a filler is disclosed (see, for example, Patent Document 1). However, when the conventional solvent-based resin composition is made water-based, there is a problem that the wear resistance decreases, and the water-based surface treatment agent also has a high surface friction coefficient, and further improvement in wear resistance has been required.

International Publication No. 2015/107933

The problem to be solved by the present invention is to provide a urethane resin composition containing water from which a film having excellent abrasion resistance can be obtained.

The present invention provides a urethane resin composition comprising a urethane resin (A), water (B), and a silicone compound (C) having a number average molecular weight of 150,000 or more and less than 330,000. is.

The present invention also provides a surface-treating agent containing the urethane resin composition, and an article having a layer formed from the surface-treating agent.

The urethane resin composition of the present invention can form a film having excellent chemical resistance. Therefore, the urethane resin composition of the present invention can be suitably used as a surface treatment agent for various articles.

The urethane resin composition of the present invention contains a urethane resin (A), water (B), and a silicone compound (C) having a specific number average molecular weight.

The urethane resin (A) is dispersible 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) A urethane resin or the like dispersed therein 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 compounds having a carboxyl group and compounds having a sulfonyl group.

Examples of compounds having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, and 2,2-dimethylolpropionic acid. Herbal acid or the like can be used. These compounds may be used alone or in combination of two or more.

Examples of compounds 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 and the like can be used. These compounds may be used alone or in combination of two or more.

The carboxyl groups and sulfonyl groups may be partially or wholly 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 containing sodium, potassium, lithium, calcium, and the like. can be done.

Examples of the method for obtaining the urethane resin having a cationic group include a method using one or more compounds having an amino group as raw materials.

Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkyldialkanolamine such as N-methyldiethanolamine and N-ethyldiethanolamine; Compounds having a tertiary amino group such as N-alkyldiaminoalkylamines such as diaminoethylamine and N-ethyldiaminoethylamine can be used. These compounds may be used alone or in combination of two or more.

Examples of the method for obtaining the urethane resin having a nonionic group include a method using one or more compounds having an oxyethylene structure as raw materials.

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.

The amount of the raw material used for producing the urethane resin having the above hydrophilic groups is urethane resin, since it provides even better chemical resistance, abrasion resistance, weather resistance, and hydrolysis resistance. It is preferably in the range of 0.1 to 15% by mass, more preferably in the range of 1 to 10% by mass, and even more preferably in the range of 1.5 to 7% by mass in the starting material of the resin (A).

Examples of emulsifiers that can be used to obtain the urethane resin that is forcibly dispersed in water (B) include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene nonionic emulsifiers such as ethylene sorbitol tetraoleate and polyoxyethylene/polyoxypropylene copolymer; Anionic emulsifiers such as polyoxyethylene alkyl sulfates, alkanesulfonate sodium salts, and alkyldiphenyl ether sulfonate sodium salts; and cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts. can. These emulsifiers may be used alone or in combination of two or more.

Specific examples of the urethane resin (A) include, for example, raw materials used for producing the urethane resin having a hydrophilic group, a polyisocyanate (a1), a polyol (a2), and a chain extender ( The reactants of a3) can be used. A known urethanization reaction can be used for these reactions.

Examples of the polyisocyanate (a1) include aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidated diphenylmethane polyisocyanate; 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.

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

Further, when the urethane resin composition of the present invention is used as a surface treatment agent, when further light resistance is required, the polyisocyanate (a1) may be the alicyclic polyisocyanate and the aliphatic poly It is preferable to use together with isocyanate, and it is preferable to use hexamethylene diisocyanate as the aliphatic polyisocyanate. At this time, the content of the alicyclic polyisocyanate in the polyisocyanate (a1) is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more.

The amount of the polyisocyanate (a1) used is in the range of 5 to 50% by mass in the raw material of the urethane resin (A), from the viewpoint of obtaining even better chemical resistance, abrasion resistance, and weather resistance. It is preferably in the range of 15 to 40% by mass, even more preferably in the range of 20 to 37% by mass.

As the polyol (a2), for example, polyether polyol, polyester polyol, polyacrylic polyol, polycarbonate 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 from the viewpoint of obtaining even better chemical resistance, abrasion resistance, and weather resistance.

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

As the carbonic acid ester, for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate and the like can be used. These compounds may be used alone or in combination of two or more.

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, glycerin and the like can be used. These compounds may be used alone or in combination of two or more. Among these, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -hexanediol, 1,4-cyclohexanedimethanol, 3-methylpentanediol, and one or more compounds selected from the group consisting of 1,10-decanediol is preferably used, and 1,6-hexanediol is more preferred.

The amount of the polycarbonate polyol used is preferably 85% by mass or more, preferably 90% by mass or more, in the polyol (a2) from the viewpoint of obtaining even better chemical resistance, abrasion resistance, and weather resistance. is more preferable, and 95% by mass or more is even more preferable.

The number average molecular weight of the polycarbonate polyol is preferably in the range of 100 to 100,000 from the viewpoint of obtaining even better chemical resistance, mechanical strength, abrasion resistance, and weather resistance. The range of ~10,000 is more preferred, and the range of 200-2,500 is even more preferred. The number average molecular weight of the polycarbonate polyol is a value measured by gel permeation column chromatography (GPC).

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, from the viewpoint of obtaining even better weather resistance. Preferably, the range of 800 to 10,000 is more preferred. The number average molecular weight of the polyol (a2) is the value measured by gel permeation column chromatography (GPC).

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

Examples of the chain extender (a3) include those having a number average molecular weight in the range of 50 to 450 (excluding the polycarbonate polyols). Specific examples 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, Chain extenders having amino groups such as 3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine; 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'-dihydroxy A chain extender having a hydroxyl group such as diphenyl ether and trimethylolpropane can be used. These chain extenders may be used alone or in combination of two or more.

As the chain extender (a3), among the above-described chain extenders, a chain extender having an amino group is used from the viewpoint of obtaining even better chemical resistance, mechanical strength, abrasion resistance, and weather resistance. is preferred, and piperazine and/or hydrazine are more preferred. The total amount of piperazine and hydrazine is preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 60% by mass in the chain extender (a3). The above is more preferable, and 80% by mass or more is particularly preferable. The chain extender (a3) preferably has an average functional group number of less than 3, more preferably less than 2.5. again,

The amount of the chain extender (a3) used is 0.5 in the raw material of the urethane resin (A) from the viewpoint of obtaining even better chemical resistance, mechanical strength, abrasion resistance, and weather resistance. It is preferably in the range of 10 mass %, more preferably in the range of 0.7 to 5 mass %, and even more preferably in the range of 0.9 to 2.3 mass %.

As a method for producing the urethane resin (A), for example, the polyisocyanate (a1), the polyol (a2), and the raw materials used for producing the urethane resin having a hydrophilic group are reacted to obtain an isocyanate group. and then reacting the urethane prepolymer with the chain extender (a3); the polyisocyanate (a1), the polyol (a2), a hydrophilic group A raw material used for producing a urethane resin having and a method of reacting the chain extender (a3) at once. These reactions are carried out, for example, at 50 to 100° C. for 3 to 10 hours.

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

When producing the urethane resin (A), it is preferable to deactivate the isocyanate groups remaining in the urethane resin (A). When deactivating the isocyanate group, 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 urethane resin (A).

Moreover, when manufacturing the said urethane resin (A), you may use an organic solvent. Examples of the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetic ester compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; Amide compounds and the like can be used. These organic solvents may be used alone or in combination of two or more. It is preferable that the organic solvent is finally removed by a distillation method or the like.

The content of urethane bonds in the urethane resin (A) is preferably in the range of 980 to 4,000 mmol/kg from the viewpoint of obtaining even better chemical resistance, abrasion resistance, and weather resistance. ,000 to 3,500 mmol/kg, more preferably 1,100 to 3,000 mmol/kg, even more preferably 1,150 to 2,500 mmol/kg. The urethane bond content of the urethane resin (A) includes the polyisocyanate (a1), the polyol (a2), the raw materials used for producing the urethane resin having a hydrophilic group, and the chain extender (a3 ) shows the value calculated from the charged amount.

The content of the urea bond in the urethane resin (A) is preferably in the range of 315 to 850 mmol/kg from the viewpoint of obtaining even better chemical resistance, abrasion resistance, and weather resistance. The range of 350-830 mmol/kg is more preferred, the range of 400-800 mmol/kg is still more preferred, and the range of 410-770 mmol/kg is even more preferred. The urea bond content of the urethane resin (A) is determined by the polyisocyanate (a1), the polyol (a2), the raw materials used for producing the urethane resin having a hydrophilic group, and the chain extender. The value calculated from the charge amount of (a3) is shown.

The content of the alicyclic structure in the urethane resin (A) is in the range of 500 to 3,000 mmol/kg from the viewpoint of obtaining even better chemical resistance, abrasion resistance, and weather resistance. is preferred, the range of 600 to 2,900 mmol/kg is more preferred, and the range of 700 to 2,700 mmol/kg is even more preferred. In addition, the content of the alicyclic structure of the urethane resin (A) is determined by the polyisocyanate (a1), the polyol (a2), the raw materials used for producing the urethane resin having a hydrophilic group, and the chain elongation The value calculated from the charged amount of the agent (a3) is shown.

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

As the water (B), ion-exchanged water, distilled water, or the like can be used. The content of the water (B) is preferably in the range of 30 to 95% by mass in the urethane resin composition from the viewpoint of coatability, workability and storage stability of the urethane resin composition, and 50 to 95% by mass. A range of 90% by mass is more preferred.

As the silicone compound (C), it is essential to use one having a number average molecular weight of 150,000 or more and less than 330,000 in order to obtain excellent abrasion resistance. By using such a silicone compound having a relatively high molecular weight, a coating film having a high surface strength and a small coefficient of friction can be formed, and excellent abrasion resistance can be obtained. The number average molecular weight of the silicone compound (C) is preferably in the range of 200,000 to 300,000, more preferably in the range of 220,000 to 270,000, from the viewpoint of obtaining even better abrasion resistance. The number-average molecular weight of the silicone compound (C) is a value measured by a gel permeation chromatography (GPC) method, and the specific measurement method is shown in Examples.

Specific examples of the silicone compound (C) include, for example, polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, and polymethylphenylhydrogensiloxane; modified products thereof; can be used. These silicone compounds may be used alone or in combination of two or more. Among these, it is preferable to use polydimethylsiloxane from the viewpoint of obtaining even more excellent abrasion resistance.

From the viewpoint of affinity with water (B), the silicone compound (C) is preferably in the form of an emulsion dispersed in water (B). Further, in such a case, a known surfactant may be contained.

The content of the silicone compound (C) (=silicone compound (C) solid content) is preferably in the range of 0.01 to 10% by mass from the viewpoint of obtaining even better abrasion resistance. A range of 0.1 to 7 mass % is more preferred, and a range of 0.5 to 5 mass % is even more preferred.

The urethane resin composition of the present invention contains the urethane resin (A), water (B), and silicone compound (C) as essential components, but other additives may be used as necessary.

Examples of the other additives include fillers (D), cross-linking agents (E), emulsifiers, antifoaming agents, leveling agents, thickeners, viscoelasticity modifiers, antifoaming agents, wetting agents, dispersing agents, and preservatives. agents, plasticizers, penetrants, fragrances, bactericides, acaricides, fungicides, UV absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments (e.g., titanium white, red iron oxide, phthalocyanine, carbon black, permanent yellow, etc.) can be used. These additives may be used alone or in combination of two or more.

As the other additives, when the urethane resin composition of the present invention is used as a surface treatment agent, a filler (D) for imparting a matte feeling to the coating film, and a mechanical It is preferable to contain a cross-linking agent (E) in order to improve the strength.

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

As the silica particles, for example, dry silica, wet silica, or the like can be used. Among these, dry silica is preferable because it has a high scattering effect and widens the range of adjustment of the gloss value. 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 indicates the particle size (particle size at D50 in the particle size distribution) when the integrated amount occupies 50% in the integrated particle amount curve of the particle size distribution measurement result.

As the organic beads, for example, acrylic beads, urethane beads, silicon beads, olefin beads, etc. can be used.

The amount of the filler (D) to be used can be appropriately determined according to the matte feeling to be imparted. Preferably, the range of 3 to 10 parts by mass is more preferable.

Examples of the cross-linking agent (E) that can be used include isocyanate cross-linking agents, epoxy cross-linking agents, carbodiimide cross-linking agents, oxazolidine cross-linking agents, oxazoline cross-linking agents, and melamine cross-linking agents. These cross-linking agents may be used alone or in combination of two or more.

The amount of the crosslinking agent (E) used is, for example, preferably in the range of 5 to 40 parts by mass, more preferably in the range of 10 to 30 parts by mass, with respect to 100 parts by mass of the urethane resin (A). .

As described above, the urethane resin composition of the present invention can provide a film having excellent chemical resistance. Therefore, the urethane resin composition of the present invention is suitably used as a surface treatment agent for various articles such as synthetic leather, polyvinyl chloride (PVC) leather, thermoplastic olefin resin (TPO) leather, dashboards, and instrument panels. be able to.

The article of the present invention has a layer formed from the surface treatment agent.

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

The thickness of the layer of the surface treatment agent is, for example, in the range of 0.1 to 100 μm.

The present invention will be described in more detail below using examples.

[Synthesis Example 1] Preparation of aqueous dispersion of urethane resin (A-1) 250 parts by mass of methyl ethyl ketone and 0.001 mass of stannous octoate were added to a four-necked flask equipped with a stirrer, thermometer, and nitrogen reflux tube. parts, followed by 200 parts by mass of polycarbonate polyol-1 (made from 1,4-butanediol and 1,6-hexanediol, number average molecular weight: 1,000), 2,2-dimethylolpropionic acid 15 parts by mass, 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 urethane prepolymer.
Next, after mixing 6.8 parts by mass of hydrazine and 15 parts by mass of triethylamine into the methyl ethyl ketone solution of the urethane prepolymer, 820 parts by mass of ion-exchanged water was added to emulsify the urethane resin (A-1) dispersed in water. I got the liquid.
Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was added to obtain an aqueous dispersion of urethane resin (A-1) having a nonvolatile 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.

[Synthesis Example 2] Preparation of aqueous dispersion of urethane resin (A-2) 250 parts by mass of methyl ethyl ketone and 0.001 mass of stannous octoate were added to a four-necked flask equipped with a stirrer, thermometer, and nitrogen reflux tube. 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, dicyclohexylmethane 70 parts by mass of diisocyanate was added and reacted at 70° C. for 1 hour to obtain a methyl ethyl ketone solution of urethane prepolymer.
Next, after mixing 4.5 parts by mass of piperazine and 9 parts by mass of triethylamine with the methyl ethyl ketone solution of the urethane prepolymer, 880 parts by mass of ion-exchanged water was added to emulsify the urethane resin (A-2) dispersed in water. I got the liquid.
Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was added to obtain an aqueous dispersion of urethane resin (A-2) having a non-volatile content of 32% by mass.
The urethane bond content of the obtained urethane resin (A-2) was 1,278 mmol/kg, the urea bond content was 435 mmol/kg, and the alicyclic structure content was 1,713 mmol/kg.

[Synthesis Example 3] Preparation of aqueous dispersion of urethane resin (A-3) 250 parts by mass of methyl ethyl ketone and 0.001 mass of stannous octoate were added to a four-necked flask equipped with a stirrer, thermometer, and nitrogen reflux tube. parts, followed by 138 parts by mass of polycarbonate polyol-4 (made from 1,6-hexanediol, number average molecular weight: 2,000), and polycarbonate polyol-5 (made from 1,6-hexanediol). 55 parts by mass of 500, number average molecular weight: 500), 13 parts by mass of 2,2-dimethylolpropionic acid, and 100 parts by mass of dicyclohexylmethane diisocyanate were added, reacted at 70 ° C. for 1 hour, and a methyl ethyl ketone solution of urethane prepolymer was added. Obtained.
Next, after mixing 5.6 parts by mass of piperazine and 10 parts by mass of triethylamine with the methyl ethyl ketone solution of the urethane prepolymer, 880 parts by mass of ion-exchanged water is added to emulsify the urethane resin (A-3) dispersed in water. I got the liquid.
Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was 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.

[Example 1]
35 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide cross-linking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.), a filler (manufactured by Evonik Degussa “ ACEMATT TS 100", silica particles produced by a dry method, average particle diameter: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 25.5 10) 3 parts by mass and 57 parts by mass of water were mixed to obtain a urethane resin composition.

[Example 2]
35 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide cross-linking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.), a filler (manufactured by Evonik Degussa “ ACEMATT TS 100", silica particles produced by a dry method, average particle diameter: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 25.5 10) A urethane resin composition was obtained by mixing 6 parts by mass and 54 parts by mass of water.

[Example 3]
35 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide cross-linking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd.), a filler (manufactured by Evonik Degussa “ ACEMATT TS 100", silica particles produced by a dry method, average particle diameter: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 25.5 10,000 parts by mass and 59.5 parts by mass of water were mixed to obtain a urethane resin composition.

[Example 4]
35 parts by mass of the urethane resin (A-2) aqueous dispersion obtained in Synthesis Example 1, 3 parts by mass of carbodiimide cross-linking agent "Carbodilite V-02-L2" manufactured by Nisshinbo Chemical Co., Ltd., filler ("ACEMATT" manufactured by Evonik Degussa) TS 100", silica particles produced by a dry method, average particle size: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 200,000) 3 A urethane resin composition was obtained by mixing parts by mass and 57 parts by mass of water.

[Example 5]
Urethane resin (A-3) water dispersion obtained in Synthesis Example 1 35 parts by mass, carbodiimide cross-linking agent Nisshinbo Chemical Co., Ltd. "Carbodilite V-02-L2") 3 parts by mass, filler (Evonik Degussa Co., Ltd. "ACEMATT TS 100", silica particles produced by a dry method, average particle size: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 300,000) 3 A urethane resin composition was obtained by mixing parts by mass and 57 parts by mass of water.

[Comparative Example 1]
A urethane resin composition was obtained in the same manner as in Example 1, except that the polydimethylsiloxane aqueous dispersion was omitted.

[Comparative Example 2]
Urethane resin (A-1) water dispersion obtained in Synthesis Example 1 35 parts by mass, carbodiimide cross-linking agent Nisshinbo Chemical Co., Ltd. "Carbodilite V-02-L2") 3 parts by mass, filler (Evonik Degussa Co., Ltd. "ACEMATT TS 100", silica particles produced by a dry method, average particle size: 10 μm) 2 parts by mass, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 100,000) 3 A urethane resin composition was obtained by mixing parts by mass and 57 parts by mass of water.

[Comparative Example 3]
Urethane resin (A-1) water dispersion obtained in Synthesis Example 1 35 parts by mass, carbodiimide cross-linking agent Nisshinbo Chemical Co., Ltd. "Carbodilite V-02-L2") 3 parts by mass, filler (Evonik Degussa Co., Ltd. "ACEMATT TS 100", silica particles produced by a dry method, average particle diameter: 10 μm) 2 parts by mass, after mixing 57 parts by mass of water, an aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass , number average molecular weight;

[Method for measuring number average molecular weight (1)]
The number average molecular weights of the polyols used in Synthesis Examples are values obtained by measurement under the following conditions by gel permeation column chromatography (GPC).

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8mm 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 Book "TSKgel G2000" (7.8 mm I.D. x 30 cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40°C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was created using the following standard polystyrene.

(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

[Method for measuring number average molecular weight (2)]
The number average molecular weight of the silicone compound (C) is a value obtained by measuring under the following conditions by GPC (gel permeation chromatography) method.

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel GMHXL" (7.8 mm I.D. x 30 cm) x 4 Detector: RI (differential refractometer)
Column temperature: 40°C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL
Concentration: Analysis sample: 4 mg/mL tetrahydrofuran solution Standard substance: 1 mg/mL tetrahydrofuran solution Standard substance: A calibration curve was created using the following polyethylene oxide/polyethylene glycol.

Reference material <Polyethylene oxide>
"TSKgel standard polyethylene oxide SE-70" manufactured by Tosoh Corporation
"TSKgel standard polyethylene oxide SE-30" manufactured by Tosoh Corporation
"TSKgel standard polyethylene oxide SE-15" manufactured by Tosoh Corporation
"TSKgel standard polyethylene oxide SE-8" manufactured by Tosoh Corporation
"TSKgel standard polyethylene oxide SE-5" manufactured by Tosoh Corporation
"TSKgel standard polyethylene oxide SE-2" manufactured by Tosoh Corporation
<Polyethylene glycol>
polyethylene glycol 6,000
polyethylene glycol 3,000
polyethylene glycol 1,000
polyethylene glycol 600

[Abrasion resistance evaluation method]
The urethane resin compositions obtained in Examples and Comparative Examples were coated on release paper using a 50 μm bar coater and dried in a gear oven at 120° C. for 2 minutes to obtain samples for evaluation. This evaluation sample was evaluated using a flat surface abrasion tester (“AR-4S” manufactured by Intec Co., Ltd.) with a load of 2 kg and No. 6 canvas. Specifically, a 4.5 mmφ stainless steel wire, a cushioning material (thickness: 10 mm, compressive stress: 1 N/cm ² ), and a test piece were placed in this order on a flat surface abrasion tester, and were fixed by stretching by 5%. The abrasion state of this sample was observed every 1,000 times, and the number of times until the coating film was torn and the fabric was exposed was measured. In addition, "-" indicates that the wear resistance could not be evaluated.

"PDMSi" in Tables 1 and 2 indicates polydimethylsiloxane.

It was found that the urethane resin composition of the present invention has excellent abrasion resistance.

On the other hand, Comparative Example 1, in which no silicone compound (C) was used, had insufficient wear resistance.

Comparative Example 2 is an embodiment using a silicone compound having a number average molecular weight below the range specified in the present invention instead of the silicone compound (C), but the wear resistance was insufficient.

Comparative Example 3 is an embodiment using a silicone compound having a number-average molecular weight exceeding the range specified in the present invention instead of the silicone compound (C). It was difficult to use as

Claims (4)

3 to 50% by mass of urethane resin (A), 30 to 95% by mass of water (B), and 0.01 to 10% by mass of polydimethylsiloxane having a number average molecular weight of 150,000 or more and less than 330,000. A urethane resin composition characterized by containing A surface treatment agent comprising the urethane resin composition according to claim 1 . 3. The surface treating agent according to claim 2 , further comprising a filler (D). An article comprising a layer formed from the surface treating agent according to claim 2 or 3 .