JPWO2020129669A1 - Urethane resin compositions, surface treatment agents, and articles - Google Patents

Abstract

The present invention is characterized by containing a urethane resin (A), an olefin resin (B), water (C), and an adhesion imparting agent (D) having a number average molecular weight of 300 or more. It provides things. The present invention also provides a surface treatment agent containing the urethane resin composition. The present invention also provides an article characterized by having a layer formed by a surface treatment agent. The adhesion-imparting agent (D) is preferably a polyester having an acid value in the range of 10 to 70 mgKOH / g. The content of the adhesion-imparting agent (D) is preferably in the range of 0.01 to 20% by mass. The article preferably has a layer formed by a surface treatment agent on a thermoplastic olefin sheet.

Description

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

In the manufacturing process of a sheet for automobile interior TPO (thermoplastic olefin) leather, the surface thereof is finished with a surface treatment agent from the viewpoint of imparting durability and design. The mainstream materials used for conventional surface treatment agents are solvent-based resin compositions containing organic solvents, but due to the recent increase in environmental regulations, aqueous surface treatment agents that do not substantially contain organic solvents. Development is in progress.

As the aqueous surface treatment agent, for example, a method of coating two types of urethane resin compositions containing water on top of each other is disclosed (see, for example, Patent Document 1). Although such a method is excellent in wear resistance and the like, the adhesion to TPO is insufficient.

As described above, it has been pointed out that when the surface treatment agent is made water-based, the adhesion to TPO is inferior to that of the conventional solvent-based resin composition.

Japanese Unexamined Patent Publication No. 2006-176615

An object to be solved by the present invention is to provide a urethane resin composition having excellent adhesion to a thermoplastic olefin (TPO) sheet in a urethane resin composition containing water.

The present invention is characterized by containing a urethane resin (A), an olefin resin (B), water (C), and an adhesion imparting agent (D) having a number average molecular weight of 300 or more. It provides things.

The present invention also provides an article characterized by having a surface treatment agent containing the urethane resin composition and a layer formed by the surface treatment agent.

The urethane resin composition of the present invention has excellent adhesion to a TPO sheet (hereinafter, abbreviated as "TPO adhesion"). Further, the urethane resin composition of the present invention contains water and is an environmentally friendly material.

The urethane resin composition of the present invention contains a urethane resin (A), an olefin resin (B), water (C), and a specific adhesion-imparting agent (D).

The urethane resin (A) can be dispersed in water (C), and is, for example, a urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group; forcibly water (with an emulsifier). B) 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 one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group as a raw material.

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

Examples of the compound having a sulfonyl group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, and N- (2-aminoethyl)-. 2-Aminoethyl sulfonic acid and the like can be used. These compounds may be used alone or in combination of two or more.

The carboxyl group and the sulfonyl group may be partially or completely neutralized with a basic compound in the resin composition. As the basic compound, for example, 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 are used. Can be done.

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

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

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

As the compound having an oxyethylene structure, for example, a polyether polyol having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol can be used. These compounds may be used alone or in combination of two or more.

As for the amount of the raw material used for producing the urethane resin having the above hydrophilic groups, urethane is obtained from the viewpoint of obtaining even more excellent 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 raw material of the resin (A).

Examples of the emulsifier that can be used to obtain the urethane resin that is forcibly dispersed in water (C) include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, and polyoxy. Nonionic emulsifiers such as ethylene sorbitol tetraoleate and polyoxyethylene / polyoxypropylene copolymers; fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfates, alkyl sulfosuccinates, naphthalence sulfates, Anionic emulsifiers such as polyoxyethylene alkyl sulfate, alkansulfonate sodium salt, and alkyldiphenyl ether sulfonate sodium salt; cationic emulsifiers such as alkylamine salt, alkyltrimethylammonium salt, and alkyldimethylbenzylammonium salt can be used. can. These emulsifiers may be used alone or in combination of two or more.

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

Examples of the polyisocyanate (a1) include aromatic polyisocyanates such as phenylenediocyanate, 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, dimerate diisocyanate, norbornene diisocyanate and other aliphatic or alicyclic polyisocyanates can be used. 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 more excellent 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 one or more structures directly connected to the ring, it is more preferable to use isophorone diisocyanate and / or dicyclohexylmethane diisocyanate, and isophorone is further improved in processability at the time of stretching. Diamine is more preferred. The amount of the alicyclic polyisocyanate used is preferably 30% by mass or more of the polyisocyanate (a1) from the viewpoint of obtaining even more excellent chemical resistance, abrasion resistance, and weather resistance. , 40% by mass or more is more preferable, and 50% by mass or more is further preferable.

Further, when the urethane resin composition of the present invention is used as a surface treatment agent, when further light resistance and processability at the time of stretching are required, the fat is used as the polyisocyanate (a1). It is preferable to use a cyclic polyisocyanate and an aliphatic polyisocyanate in combination, 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, still 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 more excellent chemical resistance, abrasion resistance, and weather resistance. It is preferably in the range of 15 to 40% by mass, more preferably in the range of 20 to 37% by mass.

As the polyol (a2), for example, a polyether polyol, a polyester polyol, a polyacrylic polyol, a polycarbonate polyol, a polybutadiene polyol, or 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 more excellent chemical resistance, abrasion resistance, and weather resistance.

As the polycarbonate polyol, for example, a reaction product of a carbonic acid 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, and 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, and 1,6 are obtained from the viewpoints 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 −hexanediol, 1,4-cyclohexanedimethanol, 3-methylpentanediol, and 1,10-decanediol, and 1,6-hexanediol is preferable. 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 more excellent chemical resistance, abrasion resistance, and weather resistance. Is more preferable, and 95% by mass or more is further 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 more excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance. It is more preferably in the range of ~ 10,000, and even more preferably in the range of 200 to 2,500. The number average molecular weight of the polycarbonate polyol shows a value measured by a gel permeation column chromatography (GPC) method.

The number average molecular weight of the polyol (a2) other than the polycarbonate polyol is preferably in the range of 500 to 100,000, preferably in the range of 700 to 50,000, from the viewpoint of obtaining even more excellent weather resistance. It is preferably in the range of 800 to 10,000, even more preferably. The number average molecular weight of the polyol (a2) indicates a value measured by a gel permeation column chromatography (GPC) method.

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 preferable.

The chain extender (a3) has, for example, a chain extender having a number average molecular weight in the range of 50 to 450 (excluding the polycarbonate polyol), and specifically, ethylenediamine, 1,2-propanediamine, 1, 6-Hexamethylenediamine, piperazine, 2,5-dimethylpiperazin, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3, Chain extender having an amino group such as 3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine; ethylene glycol, diethylene recall, 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 or trimethylol propane can be used. These chain extenders may be used alone or in combination of two or more.

As the chain extender (a3), a chain extender having an amino group is used because even more excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance can be obtained. Is preferable, piperazine and / or hydrazine is more preferable, and the total amount of piperazine and hydrazine is preferably 30% by mass or more, more preferably 50% by mass or more, and 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 number of functional groups 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 more excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance. The range is preferably from 10% by mass, more preferably from 0.7 to 5% by mass, and even more preferably from 0.9 to 2.3.

As a method for producing the urethane resin (A), for example, the polyisocyanate (a1), the polyol (a2), and the raw material used for producing the urethane resin having a hydrophilic group are reacted to form an isocyanate group. A method of producing a urethane prepolymer having the above, and then reacting the urethane prepolymer with the chain extender (a3); the polyisocyanate (a1), the polyol (a2), and a hydrophilic group. Examples thereof include a raw material used for producing the urethane resin having the above, and a method in which the chain extender (a3) is collectively charged and reacted. These reactions may be carried out, for example, at 50 to 100 ° C. for 3 to 10 hours.

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

When producing the urethane resin (A), it is preferable to inactivate the isocyanate groups remaining in the urethane resin (A). When inactivating 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).

Further, when producing the urethane resin (A), an organic solvent may be used. Examples of the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetate compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; dimethylformamide and N-methylpyrrolidone. An amide compound or the like can be used. These organic solvents may be used alone or in combination of two or more. It is preferable that the organic solvent is finally removed by a distillation method or the like.

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

The urea bond content of the urethane resin (A) is preferably in the range of 315 to 850 mmol / kg from the viewpoint of obtaining even more excellent chemical resistance, abrasion resistance, and weather resistance. The range of 350 to 830 mmol / kg is more preferable, the range of 400 to 800 mmol / kg is further preferable, and the range of 410 to 770 mmol / kg is further preferable. The urea bond content of the urethane resin (A) includes the polyisocyanate (a1), the polyol (a2), the raw material 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 of the urethane resin (A) is in the range of 500 to 3,000 mmol / kg from the viewpoint of obtaining even more excellent chemical resistance, abrasion resistance, and weather resistance. Is preferable, the range of 600 to 2,900 mmol / kg is more preferable, and the range of 700 to 2,700 mmol / kg is further preferable. The content of the alicyclic structure of the urethane resin (A) includes the polyisocyanate (a1), the polyol (a2), the raw material used for producing the urethane resin having a hydrophilic group, and the chain extension. The value calculated from the charge amount of the agent (a3) is shown.

The content of the urethane resin (A) is preferably in the range of 1 to 30% by mass, preferably 2 to 20% by mass, in the urethane resin composition from the viewpoint of coatability, workability and storage stability. The range is more preferred.

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

As the polyolefin compound, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and the like can be used. Further, these olefin compounds may be used alone or in combination of two or more. The polyolefin may be a homopolymer or a copolymer.

As the modified product of the polyolefin, for example, a polyolefin modified with a hydroxyl group, an acid-modified polyolefin, a polyolefin modified with an amino group, or the like can be used. These polyolefins may be used alone or in combination of two or more. Among these, it is preferable to use an acid-modified polyolefin from the viewpoint that the TPO adhesion can be further improved.

As the acid-modified polyolefin, for example, an acid-modified polyolefin without chlorination can be used. For the acid denaturation, a method of reacting with a polyolefin using an unsaturated carboxylic acid or an anhydride thereof is preferable. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, crotonic acid; their anhydrides and the like; half ester of unsaturated carboxylic acid. , Halfamide and the like can be used. 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.

Further, as the acid-modified polyolefin, one having a polyether chain is preferably used from the viewpoint of excellent dispersibility in water, and the polyether chain is a polyethylene chain and / or polypropylene. Chains are preferred, polyethylene chains are more preferred.

The weight average molecular weight of the olefin resin (B) is preferably in the range of 10,000 to 500,000, preferably in the range of 20,000 to 200,000, from the viewpoint of obtaining even more excellent TPO adhesion. Is more preferable. The weight average molecular weight of the olefin resin (B) indicates a value measured by a gel permeation column chromatography (GPC) method.

The content of the olefin resin (B) is preferably in the range of 0.01 to 10% by mass, preferably in the range of 0.1 to 7% by mass, from the viewpoint of obtaining even more excellent TPO adhesion. More preferred.

The amount of the olefin resin (B) used is preferably in the range of 1 to 60 parts by mass, preferably in the range of 2 to 50 parts by mass with respect to 100 parts by mass of the urethane resin (A) (= solid content). Is more preferable.

As the water (C), ion-exchanged water, distilled water, or the like can be used. The content of the water (C) is preferably in the range of 30 to 95% by mass, preferably 40 to 95% by mass, in the urethane resin composition from the viewpoint of coatability, workability and storage stability of the urethane resin composition. The range of 90% by mass is more preferable.

As the adhesion-imparting agent (D), it is essential to use one having a number average molecular weight of 300 or more in order to obtain excellent TPO adhesion. The number average molecular weight of the adhesion-imparting agent is preferably in the range of 400 to 10,000, more preferably in the range of 450 to 4,000, and more preferably 500, from the viewpoint of obtaining even more excellent TPO adhesion. The range of ~ 1,000 is more preferable. The number average molecular weight of the adhesion-imparting agent (D) indicates a value when it can be calculated from a chemical formula, and a value measured by a gel permeation column chromatography (GPC) method in other cases.

As the adhesion-imparting agent (D), for example, a polymer having an acid group, a polymer having an acidic group, a polymer having a functional group, or the like can be used. These adhesion-imparting agents may be used alone or in combination of two or more. Among these, it is preferable to use a polymer having an acid group from the viewpoint of obtaining even more excellent TPO adhesion.

Examples of the polymer having an acid group include polyester having an acid group, acrylic polymer having an acid group, styrene polymer having an acid group, styrene-isoprene polymer having an acid group, and styrene-butadiene polymer having an acid group. Can be used. These polymers may be used alone or in combination of two or more. Among these, it is preferable to use a polyester having an acid group from the viewpoint that the affinity for water (C), the storage stability are good, and even more excellent TPO adhesion can be obtained.

As the polyester having an acid group, for example, a reaction product of a compound having two or more hydroxyl groups and a polybasic acid can be used.

Examples of the compound having two or more hydroxyl groups include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptane. Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1, 3-Butandiol, 2,2-diethyl-1,3-propanediol, 2,2-diethylpropanediol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propane Compounds such as diol, 2-methyl-1,8-octanediol, 2,4-diethyl-1,5-pentanediol, trimethylolethane, trimethylolpropane, and pentaerythritol can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use a compound having 2 to 3 hydroxyl groups, and it is more preferable to use a compound having 3 hydroxyl groups, from the viewpoint of obtaining even more excellent PVC adhesion.

Examples of the polybasic acid include aliphatic polybasic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, dodecanedioic acid, and azelaic acid. A polybasic acid having an unsaturated group such as citraconic acid, itaconic acid, citraconic anhydride, itaconic acid anhydride; aromatic polybasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride and the like can be used. .. These polybasic acids may be used alone or in combination of two or more. Among these, it is preferable to use an aliphatic polybasic acid from the viewpoint of obtaining even more excellent PVC adhesion.

The acid value of the polymer having an acid group is preferably in the range of 10 to 70 mgKOH / g, more preferably in the range of 15 to 40 mgKOH / g, from the viewpoint of obtaining even more excellent TPO adhesion. The acid value of the polymer having an acid group indicates a value measured by a potentiometric titration method based on JISK0070-1992.

The adhesion-imparting agent (D) may contain other components such as a solvent and a neutralizing agent, if necessary. Among these, it is preferable to contain a neutralizing agent from the viewpoint of further improving the affinity for water (C) and the storage stability.

Examples of the solvent include 1-methoxy-2-hydroxypropane, 1-methoxy-2-propyl acetate, dipyrropylene glycol monomethyl ether, and 2,2,4-trimethy-3-hydroxyoentylisobutyrate. , Methanol, ethanol, propanol, butanol, diacetone alcohol, diacetone alcohol, dimethylcarbitol, methyl acetate ester, ethyl acetate ester, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetyl acetone, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, Dimethyl carbonate or the like can be used. These solvents may be used alone or in combination of two or more. Examples of the content when the solvent is used include a range of 1 to 30% by mass in the adhesion-imparting agent (D).

Examples of the neutralizing agent include non-volatile bases such as sodium hydroxide and potassium hydroxide; tertiary amine compounds such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine and triethanol, dimethylamine, diethylamine, dibutylamine and the like. Secondary amine compounds, ethylenediamine, methylamine, ethylamine, butylamine and other primary amine compounds, ammonia and the like can be used. These neutralizers may be used alone or in combination of two or more. Examples of the content when the neutralizing agent is used include the range of 0.001 to 3% by mass in the adhesion-imparting agent (D).

The content of the adhesion-imparting agent (D) is preferably in the range of 0.01 to 20% by mass, preferably 0.1 to 10% by mass, from the viewpoint of obtaining even more excellent TPO adhesion. The range is more preferred.

The amount of the adhesion-imparting agent (D) used with respect to 100 parts by mass of the urethane resin (A) (= solid content) is preferably in the range of 5 to 100 parts by mass, preferably 10 to 70 parts by mass. The range of is more preferable.

The urethane resin composition of the present invention contains the urethane resin (A), the olefin resin (B), the water (C), and the adhesion imparting agent (D) as essential components, but other components are required. Additives may be used.

Examples of the other additives include a filler (E), a cross-linking agent (F), an emulsifier, an antifoaming agent, a leveling agent, a thickener, a viscoelasticity adjusting agent, an antifoaming agent, a wetting agent, a dispersant, and an antiseptic. Agents, plasticizers, penetrants, fragrances, bactericides, acaricides, antifungal agents, UV absorbers, antioxidants, antioxidants, flame retardants, dyes, pigments (eg 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, and when it is used in an application where a matte feeling is required for the coating film, the filler (E) and It is preferable to use a cross-linking agent (F) in order to improve the mechanical strength of the coating film.

Examples of the filler (E) include silica particles, organic beads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, alumina silicate and the like. 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 and the like can be used. Among these, dry silica is preferable because it has a high scattering effect and a wide range of adjusting 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 and the like can be used.

When the filler (E) is used, the amount used can be appropriately determined according to the matte feeling to be applied. For example, 0.1 to 30 parts by mass with respect to 100 parts by mass of the urethane resin (A). The range is preferably in the range, and more preferably in the range of 1 to 10 parts by mass.

As the cross-linking agent (F), for example, an isocyanate cross-linking agent, an epoxy cross-linking agent, a carbodiimide cross-linking agent, an oxazolidine cross-linking agent, an oxazoline cross-linking agent, a melamine cross-linking agent and the like can be used. These cross-linking agents may be used alone or in combination of two or more.

When the cross-linking agent (F) is used, the amount used is preferably in the range of 5 to 40 parts by mass, preferably in the range of 10 to 30 parts by mass with respect to 100 parts by mass of the urethane resin (A). Is more preferable.

As described above, the urethane resin composition of the present invention can obtain excellent TPO adhesion. Therefore, the urethane resin composition of the present invention can be suitably used as a surface treatment agent for TPO leather, and can be particularly preferably used for TPO leather.

Next, the TPO leather surface-treated with the surface treatment agent of the present invention will be described.

Examples of the TPO leather include a method in which the surface treatment agent is applied onto a TPO sheet, dried to form a surface treatment layer, and then stretched.

Examples of the method for applying the surface treatment agent include a method using a bar coater, a roll coater, a spray coater, a knife coater and the like.

Examples of the method of performing the stretching process include a method using a vacuum forming machine. Examples of the stretching include a range of 110 to 150%. In the present invention, by using the surface treatment agent, it is possible to obtain TPO leather which is easy to be stretched and has excellent TPO adhesion by applying the surface treatment agent once.

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

Hereinafter, the present invention will be described in more detail with reference to Examples.

[Synthesis Example 1] Preparation of water dispersion of urethane resin (A-1) 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octylate in a four-necked flask equipped with a stirrer, a thermometer, and a nitrogen recirculation tube. Then, 200 parts by mass of polycarbonate polyol-1 (based on 1,4-butanediol and 1,6-hexanediol, number average molecular weight: 1,000), 2,2-dimethylol propionic 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, 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 emulsify the urethane resin (A-1) in water. Obtained liquid.
Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added to obtain a urethane resin (A-1) aqueous dispersion having a non-volatile content of 30% by mass.
The urethane resin (A-1) obtained 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 water dispersion of urethane resin (A-2) 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octylate in a four-necked flask equipped with a stirrer, a thermometer, and a nitrogen recirculation tube. Then, 220 parts by mass of polycarbonate polyol-3 (based on 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, 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 emulsify the urethane resin (A-2) in water. Obtained liquid.
Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added to obtain a urethane resin (A-2) aqueous dispersion having a non-volatile content of 32% by mass.
The urethane resin (A-2) obtained 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.

[Synthesis Example 3] Preparation of Water Dispersion of Urethane Resin (A-3) 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octylate in a four-necked flask equipped with a stirrer, a thermometer, and a nitrogen recirculation tube. Then, 138 parts by mass of polycarbonate polyol-4 (based on 1,6-hexanediol, number average molecular weight: 2,000) and polycarbonate polyol-5 (based on 1,6-hexanediol) were used as raw materials. 55 parts by mass, 13 parts by mass of 2,2-dimethylol propionic acid, and 100 parts by mass of dicyclohexylmethane diisocyanate were added and reacted at 70 ° C. for 1 hour to prepare a methyl ethyl ketone solution of urethane prepolymer. Obtained.
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 emulsify the urethane resin (A-3) in water. Obtained liquid.
Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added to obtain a urethane resin (A-3) aqueous dispersion having a non-volatile content of 30% by mass.
The urethane resin (A-3) obtained 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]
26 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, acid-modified non-chlorinated polyolefin (“Arrow Base SD-1010” manufactured by Unitica Co., Ltd., non-volatile content: 20.5% by mass, or less (Abbreviated as "POf") 17 parts by mass, carbodiimide compound ("Carbodilite E-04" manufactured by Nisshinbo Chemical Co., Ltd., non-volatile content; 40% by mass) 2.5% by mass, silica ("ACEMATT 3300" manufactured by Ebonic Degusa) , Silica particles produced by a dry method and whose surface is organically treated, average particle size: 9.5 μm) 2% by mass, adhesion-imparting agent (polyolefin having an acid group reacted with adipic acid and trimethylolpropane, number average) Molecular weight: 716, acid value: 30 mgKOH / g, solid content: 80% by mass (other neutralizer: dimethylethanolamine 0.5% by mass, and solvent: 1-methoxy-2-hydroxypropane),. Hereinafter, it is abbreviated as “C-1”.) A urethane resin composition was obtained by mixing 1 part by mass and 51.5% by mass of water.

[Example 2]
A urethane resin composition was obtained in the same manner as in Example 1 except that the amount of C-1 used was changed to 3% by mass and the amount of water used was changed to 49.5% by mass.

[Example 3]
A urethane resin composition was obtained in the same manner as in Example 1 except that the amount of C-1 used was changed to 5% by mass and the amount of water used was changed to 47.5% by mass.

[Example 4]
A urethane resin composition was obtained in the same manner as in Example 3 except that the urethane resin (A-2) aqueous dispersion obtained in Synthesis Example 2 was used instead of the urethane resin (A-1) aqueous dispersion. rice field.

[Example 5]
A urethane resin composition was obtained in the same manner as in Example 3 except that the urethane resin (A-3) aqueous dispersion obtained in Synthesis Example 2 was used instead of the urethane resin (A-1) aqueous dispersion. rice field.

A urethane resin composition was obtained in the same manner as in Example 1 except that the amount of C-1 used was changed to 0% by mass and the amount of water used was changed to 52.5% by mass.

[Measurement method of number average molecular weight]
The number average molecular weight of the polyol and the adhesion imparting agent used in the synthesis example and the weight average molecular weight of the olefin resin were measured by the gel permeation column chromatography (GPC) method under the following conditions. Indicates a value.

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared 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 of preparing sample for evaluation]
After blending the urethane resin compositions obtained in Examples and Comparative Examples, Bar Coater No. After coating the surface on a corona-treated TPO sheet (thickness 0.4 mm) using No. 14, it was dried at 120 ° C. for 1 minute to obtain an evaluation sample.

[Manufacturing vacuum formed products]
The evaluation sample obtained above is vacuum formed using a vacuum forming machine (“Vacuum forming machine forming 300X” manufactured by Seikou Sangyo Co., Ltd.) so that the area ratio is 130%, and a vacuum formed product is obtained. rice field.

[Evaluation of TPO adhesion]
A hot melt tape was adhered to the surface treatment layer of the vacuum formed product obtained above at 180 ° C. for 30 seconds at ^{a pressure of 0.615 kg / cm 2} , and the peel strength at a width of 17 mm was measured and evaluated as follows. bottom.
"T"; 15N / 17mm or more "F"; less than 15N / 17mm

It was found that the urethane resin composition of the present invention has excellent TPO adhesion. Further, in Examples 1 to 3, the stretching process could be smoothly performed.

On the other hand, in Comparative Example 1, although the adhesion-imparting agent (D) was not used, the TPO adhesion was poor.

In Comparative Example 2, instead of the adhesion-imparting agent (D), an adhesion-imparting agent having a number average molecular weight lower than the range specified in the present invention was used, but the TPO adhesion was poor.

Claims (9)

A urethane resin composition comprising a urethane resin (A), an olefin resin (B), water (C), and an adhesion imparting agent (D) having a number average molecular weight of 300 or more. The urethane resin composition according to claim 1, wherein the adhesion-imparting agent (D) has an acid group. The urethane resin composition according to claim 2, wherein the acid value of the adhesion-imparting agent (D) is in the range of 10 to 70 mgKOH / g. The urethane resin composition according to claim 2 or 3, wherein the adhesion-imparting agent (D) is polyester. The urethane resin composition according to any one of claims 1 to 4, wherein the content of the adhesion-imparting agent (D) is in the range of 0.01 to 20% by mass. A surface treatment agent containing the urethane resin composition according to any one of claims 1 to 5. The surface treatment agent according to claim 6, further containing a filler (E). An article characterized by having a layer formed by the surface treatment agent according to claim 6 or 7. The article according to claim 8, which has a layer formed by a surface treatment agent on a thermoplastic olefin sheet.