KR102196220B1 - Water-based resin composition, coating agent and article - Google Patents

Abstract

An object of the present invention is to provide an aqueous resin composition capable of forming a coating film that is excellent in hydrophilic persistence, chemical resistance, and substrate adhesion, and is capable of preventing deterioration of various substrates. The aqueous resin composition of the present invention contains a urethane resin (A) having a silanol group and/or a hydrolyzable silyl group, a hydrophilic acrylic polymer (B) having a silanol group and/or a hydrolyzable silyl group, and an aqueous medium (C). It is characterized by that. The present invention includes a coating agent containing the aqueous resin composition and an article having a coating film of the coating agent.

Description

Water-based resin composition, coating agent and article

The present invention relates to an aqueous resin composition, a coating agent, and an article having a coating film of the coating agent.

In general, a coating agent capable of forming a coating film capable of preventing deterioration of the surface of various substrates, and imparting design properties to the surface of the substrate is required. In particular, in addition to hydrophilicity and adhesion to the substrate, there is a demand for a coating agent of a level capable of preventing deterioration of the surface of the substrate caused by deterioration of the hydrophilicity caused by adhesion of chemicals such as scale, grease, detergent, etc., or acid rain. Among them, excellent hydrophilic A coating agent capable of forming a coating film with longevity is required by the industry. The coating agent having the above characteristics is in increasing demand in the use of surface treatment of a metal substrate including a steel plate, a glass substrate including a mirror, and a plastic substrate called a non-adhesive substrate.

In addition to the hydrophilic persistence, the coating agent is required to have a high level of substrate followability and a high level of chemical resistance to prevent peeling or cracking of the coating film generated when processing a metal substrate. In particular, the chemical resistance prevents peeling or dissolution of the coating film and deterioration of the metal substrate due to the influence of the cleaning agent in the steel industry in which the surface of the coating film formed on the surface of the metal substrate is frequently cleaned with an alkaline cleaner. This is an important property to prevent.

As a method capable of forming a coating film having excellent hydrophilic persistence, a method of applying hydrophilic particles is known (see, for example, Patent Document 1).

However, with the hydrophilic particles, the adhesion to the metal substrate is low, and the substrate tends to be easily peeled off under a wet condition, and long-term use may be difficult.

Therefore, there has been a demand for a coating agent in which hydrophilic persistence, chemical resistance, and substrate adhesion are compatible.

Japanese Unexamined Patent Application Publication No. Hei 8-3251

The problem to be solved by the present invention is to provide an aqueous resin composition that is excellent in hydrophilic persistence, chemical resistance and substrate adhesion, and capable of forming a coating film capable of preventing deterioration of various substrates.

The present inventors, as a result of intensive research in order to solve the above problems, used an aqueous resin composition containing a urethane resin having a silanol group and/or a hydrolyzable silyl group and a hydrophilic acrylic polymer having a silanol group and/or a hydrolyzable silyl group. The coating agent described above found that a coating film excellent in hydrophilic persistence, chemical resistance, and substrate adhesion could be formed, and the present invention was completed.

That is, the present invention contains a urethane resin (A) having a silanol group and/or a hydrolyzable silyl group, a hydrophilic acrylic polymer (B) having a silanol group and/or a hydrolyzable silyl group, and an aqueous medium (C). It relates to an article having a water-based resin composition, a coating agent, and a coating film of the coating agent.

The aqueous resin composition of the present invention can form a coating film excellent in hydrophilic persistence, chemical resistance and substrate adhesion as a coating agent, and thus can be used for surface protection applications of various substrates. Examples of the substrate to which the coating agent of the present invention can be applied include metal substrates such as galvanized steel plate, aluminum-zinc plated steel plate, aluminum plate, aluminum alloy plate, electronic steel plate, copper plate, stainless steel plate, various plastics and films thereof, and glass. , Paper, and wood. In addition, since the coating agent of the present invention can form a coating film having excellent hydrophilic persistence and chemical resistance that can prevent deterioration of the surface of these substrates, aluminum fins, building members, home appliances, automobile exterior materials, goggles, anti-fog film sheets, anti-fog It can be used for various items such as glass, mirror, and medical equipment.

The aqueous resin composition of the present invention contains a urethane resin (A) having a silanol group and/or a hydrolyzable silyl group, a hydrophilic acrylic polymer (B) having a silanol group and/or a hydrolyzable silyl group, and an aqueous medium (C). Characterized in that.

As the urethane resin (A) having a silanol group and/or a hydrolyzable silyl group, for example, in a urethane prepolymer having an isocyanate group at the terminal, at least one active hydrogen, and at least one silanol group and/or hydrolyzable silyl It can be obtained by reacting a compound having a group. In addition, it can also be obtained by introducing a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, or a (meth)acryloyl group into the urethane prepolymer or a urethane resin having no isocyanate group, and reacting a silane coupling agent.

As the urethane prepolymer, one obtained by reacting a polyol (a1) and a polyisocyanate (a2) is used.

Examples of the polyol (a1) include polyether polyol, polyester polyol, polycarbonate polyol, and polyolefin polyol. Among these, a polyester polyol is preferable because a coating film having excellent substrate adhesion can be formed. Further, these polyols (a1) may be used alone or in combination of two or more.

From the viewpoint of further improving the substrate adhesion, the number average molecular weight of the polyol is preferably 500 or more and 3,000 or less.

Examples of the polyether polyol usable in the polyol (a1) include those obtained by addition polymerization of an alkylene oxide using one or two or more compounds having two or more active hydrogen atoms as initiators. .

As the initiator, for example, ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, etc. A linear diol of; Branched-chain diols such as 1,3-butanediol and neopentyl glycol; Triols such as glycerin, trimethylolethane, trimethylolpropane, and pyrogallol; Sugar alcohols such as sorbitol; Sugars such as sucrose and aconite sugar; Tricarboxylic acids such as aconitic acid, trimellitic acid, and hemimelitic acid; Phosphoric acid; Polyamines per ethylenediamine and diethylenetriamine; Triisopropanolamine; Phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1,2,3-propane trithiol, etc. are mentioned.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

As the polyether polyol, specifically, it is preferable to use polyoxytetramethylene glycol formed by addition polymerization (ring-opening polymerization) of tetrahydrofuran.

As the polyether polyol, since the substrate adhesion can be further improved, it is preferable to use one having a number average molecular weight of 500 to 3,000.

Examples of the polyester polyol include those obtained by esterification reaction of low molecular weight polyols and polycarboxylic acids, polyesters obtained by ring-opening polymerization reactions of cyclic ester compounds such as ε-caprolactone, and copolymerized polyesters thereof. Can be lifted.

As the low molecular weight polyol, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,3- Aliphatic polyols such as butanediol, alicyclic structure-containing polyols such as cyclohexanedimethanol, bisphenol compounds such as bisphenol A and bisphenol F, and aromatic structure-containing polyols such as alkylene oxide adducts thereof.

In addition, examples of the polycarboxylic acid that can be used in the production of the polyester polyol include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and the like. Aromatic polycarboxylic acids, and anhydrides or ester-forming derivatives thereof.

As the polyester polyol, since substrate adhesion can be further improved, it is preferable to use one having a number average molecular weight of 500 to 3,000.

Examples of the polycarbonate polyol include those obtained by reacting a carbonate ester and a polyol, and those obtained by reacting phosgene and bisphenol A.

Examples of the carbonate ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, and diphenyl carbonate.

Examples of the polyol capable of reacting with the carbonate ester include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl- Relatively low molecular weight diols having a molecular weight of 50 to 2,000, such as 1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, and cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, and polyhexamethylene adip Polyester polyols, such as a paint, etc. are mentioned.

As the polycarbonate polyol, since the substrate adhesion can be further improved, it is preferable to use one having a number average molecular weight of 500 to 3,000.

Examples of the polyolefin polyol include polyethylene polyol, polypropylene polyol, polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, and hydrogenated (hydrogenated) polyisoprene polyol.

Further, as the polyol (a1), from the viewpoint of imparting good water dispersion stability to the urethane resin (A), a polyol having a hydrophilic group may be used in combination in addition to the above.

As the polyol having a hydrophilic group, for example, other than the polyol (a1) described above, a polyol having an anionic group, a polyol having a cationic group, and a polyol having a nonionic group can be used. Among these, it is preferable to use a polyol having an anionic group or a polyol having a cationic group.

Examples of the polyol having an anionic group include a polyol having a carboxyl group, a polyol having a sulfonic acid group, and the like.

Examples of the polyol having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid. Among these, 2,2-dimethylolpropionic acid is preferable. Further, a polyester polyol having a carboxyl group obtained by reacting the polyol having a carboxyl group with various polycarboxylic acids may also be used.

When the polyol (a1) contains a polyol having a carboxyl group, the content thereof is preferably 1 part by mass or more, more preferably 2 parts by mass or more, preferably in 100 parts by mass of the total polyol (a1). It is 20 mass parts or less, More preferably, it is 10 mass parts or less.

Examples of the polyol having a sulfonic acid group include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5-(4-sulfophenoxy)isophthalic acid, and their salts and the aromatic structure. Polyester polyols obtained by reacting the low molecular weight polyols exemplified as those usable in the production of polyester polyols having

The polyol having a carboxyl group or a polyol having a sulfonic acid group is preferably used in a range in which the acid value of the urethane resin (A) is 2 to 70 mgKOH/g, more preferably in a range of 10 to 50 mgKOH/g. desirable. In addition, the acid value referred to in the present invention is a theoretical value calculated based on the amount of an acid group-containing compound such as a polyol having a carboxyl group or a sulfonic acid group used in the production of the urethane resin (A).

It is preferable that some or all of the anionic groups are neutralized with a basic compound or the like in order to exhibit good water dispersibility.

Examples of the basic compound that can be used when neutralizing the anionic group include organic amines such as ammonia, triethylamine, morpholine, monoethanolamine, and diethylethanolamine, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. And metal hydroxides to be included. From the viewpoint of improving the water dispersion stability of the urethane resin composition, the basic compound is preferably used in a range of 0.5 to 3.0 (molar ratio) of the basic group/anionic group of the basic compound, and 0.8 to 2.0 (molar ratio) It is more preferable to use in the range of ).

Further, examples of the polyol having a cationic group include a polyol having a tertiary amino group. Specifically, N-methyl-diethanolamine, a polyol obtained by reacting a compound having two epoxy in one molecule with a secondary amine, and the like are mentioned.

It is preferable that a part or all of the tertiary amino group as the cationic group is neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, and phosphoric acid.

Further, it is preferable that a part or all of the tertiary amino group as the cationic group is quaternized. Examples of the quaternizing agent include dimethyl sulfuric acid, diethyl sulfuric acid, methyl chloride and ethyl chloride. Among these, it is preferable to use dimethyl sulfuric acid.

Further, the polyol having a cationic group is preferably used in a range in which the amine value of the urethane resin (A) is 2 to 50 mgKOH/g, and more preferably 5 to 30 mgKOH/g. In addition, the amine value in the present invention is a theoretical value calculated based on the amount of a tertiary amino group-containing compound such as a polyol having a tertiary amino group used in the production of the urethane resin (A).

Further, examples of the polyol having a nonionic group include a polyol having a polyoxyethylene structure.

The polyol having a hydrophilic group is preferably used in the range of 0.3 to 10% by mass in the total amount of the polyol (a1) used for the production of the urethane resin (A).

Further, as the polyol (a1), in addition to the polyol described above, other polyols can be used as necessary.

Examples of the above other polyols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,4 -Relatively low molecular weight polyols such as butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, and cyclohexanedimethanol. have.

Examples of the polyisocyanate (a2) capable of reacting with the polyol (a1) include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and carbodiimide-modified diphenylmethane. Aromatic polyisocyanates such as diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, triene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; And polyisocyanates having an alicyclic structure such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate. These polyisocyanates (a2) may be used alone or in combination of two or more.

The urethane prepolymer (A) having an isocyanate group can be prepared, for example, by mixing and reacting the polyol (a1) and the polyisocyanate (a2) in no solvent or in the presence of an organic solvent.

The reaction between the polyol (a1) and the polyisocyanate (a2) is, for example, the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) [isocyanate group/hydroxyl group] It is preferable to perform in the range of 0.9-3, and it is more preferable to perform in the range of 0.95-2.

The reaction between the polyol (a1) and the polyisocyanate (a2) can be carried out in a temperature range of 50 to 150°C.

The isocyanate group equivalent of the urethane prepolymer (A) obtained by the above reaction is preferably 3,500 to 100,000 g/eq., more preferably 10,000 to 60,000 g/eq., since a coating film having excellent durability can be formed.

Examples of the organic solvent that can be used when producing the urethane prepolymer (A) include ketone solvents such as acetone and methyl ethyl ketone; Ether solvents such as tetrahydrofuran and dioxane; Acetate ester solvents such as ethyl acetate and butyl acetate; Nitrile solvents such as acetonitrile; And amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents may be used alone or in combination of two or more.

In addition, in order to reduce the load on the environment or safety, the organic solvent removes part or all of the organic solvent during or after the production of the urethane resin (A), for example, by distillation under reduced pressure. Also works.

Examples of the silanol group and/or hydrolyzable silyl group-containing compound include γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ- Alkoxysilane compounds containing amino groups such as aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, alkoxysilane compounds containing hydroxyl groups such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane, and mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane.

As the urethane prepolymer not having an isocyanate group, for example, the hydroxyl value of the polyol (a1) reacts in an excessive design with respect to the equivalent ratio of the isocyanate group contained in the polyisocyanate (a2) [isocyanate group/hydroxyl group]. , A urethane prepolymer in which a hydroxyl group remains, and a urethane prepolymer obtained by adding a chain extender to the urethane prepolymer (A). As the chain extender, polyamines, hydrazine compounds, and other active hydrogen atom-containing compounds can be used.

As the polyamine, one or two or more types can be used, for example, ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophorone Diamines such as diamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, and 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; Diethylene triamine, dipropylene triamine, triethylene tetramine, etc. are mentioned.

As the hydrazine compound, one or two or more types may be used, and examples thereof include hydrazine, N,N'-dimethylhydrazine, and 1,6-hexamethylenebishydrazine; Succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide, and the like.

As the above other active hydrogen-containing compounds, one or two or more can be used, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol Glycols such as, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin and sorbitol; Phenols such as bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, and Water, etc. are mentioned, and it can also be used within the range which does not reduce the storage stability of the aqueous resin composition of this invention.

As the hydrolyzable silyl group, for example, an alkoxysilyl group is preferably used because crosslinking property is high and solvent resistance is improved. Particularly, as the alkoxysilyl group, a trimethoxysilyl group and a triethoxysilyl group are preferable because they are excellent in crosslinking properties and improve solvent resistance.

As the silane coupling agent, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyl Epoxy group-containing alkoxysilane compounds such as diethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyl Isocyanato group-containing alkoxysilane compounds such as trichlorosilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-aminopropyltrime Amino group-containing alkoxysilane compounds such as oxysilane and γ-aminopropyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth) (Meth)acryloyl group-containing alkoxysilane compounds such as acryloxypropylmethyldimethoxysilane and γ-(meth)acryloxypropylmethyldiethoxysilane, vinyl group-containing alkoxy such as vinyltrimethoxysilane and vinyltriethoxysilane And styryl group-containing alkoxysilanes such as silane, p-styryltrimethoxysilane, and p-styryltriethoxysilane.

In addition, as the urethane resin (A), a coating film having excellent chemical resistance can be formed, and therefore, it is preferable to use one having an alicyclic structure.

As the alicyclic structure, for example, a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, a cyclooctyl ring, a propylcyclohexyl ring, a tricyclo[5.2.1.0.2.6]decyl skeleton, a bicyclo[ 4.3.0]-nonyl skeleton, tricyclo[5.3.1.1]dodecyl skeleton, propyltricyclo[5.3.1.1]dodecyl skeleton, norbornene skeleton, isobornyl skeleton, dicyclopentanyl skeleton, adamantyl skeleton And the like. Among these, a cyclohexyl ring structure is preferable.

The alicyclic structure is preferably present in the range of 10 to 5000 mmol/kg with respect to the entire urethane resin (A), since it can form a coating film having excellent chemical resistance, and is preferably 1000 to 3000 mmol/kg The range of is more preferable.

The alicyclic structure preferably includes an alicyclic structure derived from a polyisocyanate having an alicyclic structure usable as a polyisocyanate (a2) used when producing the urethane resin (A), but all of them are alicyclic. It does not need to be derived from a polyisocyanate having a structure, and some or all of it may be derived from a polyol containing an alicyclic structure such as cyclohexanedimethanol.

In addition, the ratio of the alicyclic structure contained in the urethane resin (A) to the total of the urethane resin (A) in the present invention is the polyol (a1) used in the production of the urethane resin (A) or It is a value calculated based on the total mass of the power supply material such as polyisocyanate (a2) and the amount of substances having an alicyclic structure in the alicyclic structure-containing compound used in the production of the urethane resin (A).

When the content of silanol groups and/or hydrolyzable silyl groups in the urethane resin (A) is in the range of 0.1 to 5% by mass in the urethane resin (A), a coating film having excellent hydrophilic persistence, chemical resistance and substrate adhesion is formed. Since it can, it is preferable, and the range of 1-3 mass% is more preferable.

As the hydrophilic acrylic polymer (B) having a silanol group and/or a hydrolyzable silyl group, an acrylic monomer (b1-1) having an amide group, an acrylic monomer (b1-2) having an oxyethylene group, and a silanol group and/or hydrolyzable A polymer of a hydrophilic acrylic monomer (b1) containing an acrylic monomer (b1-3) having a silyl group can be used.

In addition, the "hydrophilicity" of the hydrophilic acrylic polymer (B) indicates affinity with water, and specifically, the solubility in 100 g of water (20°C) is preferably 5% by mass or more, and more It is preferably 10% by mass or more, more preferably 20% by mass or more.

In addition, similarly, the "hydrophilicity" of the hydrophilic acrylic monomer (b1) indicates affinity with water, and specifically, the solubility in 100 g of water (20°C), preferably 5% by mass or more, It is more preferably 10% by mass or more, and still more preferably 20% by mass or more.

As the hydrophilic acrylic monomer (b1), if necessary, the acrylic monomer (b1-1) having the above amide group, the acrylic monomer (b1-2) having the oxyethylene group, and the silanol group and/or hydrolyzable silyl In addition to the acrylic monomer (b1-3) having a group having a group, other acrylic monomers can be used.

As the acrylic monomer (b1-1) having an amide group, for example, a compound represented by the following general formula (1) can be used.

(R ¹ in General Formula (1) represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, R ² is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. , -(CH₂)₃-N(CH₃)₂, or the methyl chloride salt of (CH₂)₃-N(CH₃)₂)

As the compound represented by the general formula (1), for example, N-hydroxyethylacrylamide, N-methylolacrylamide, N-methoxyethylacrylamide, N,N-dimethylacrylamide, N,N -Diethylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylacrylamide, methyl chloride salt of N,N-dimethylaminopropylacrylamide, N-isopropylacrylamide, and the like. have. These monomers may be used alone or in combination of two or more.

In addition, as the acrylic monomer (b1-1) having an amide group, for example, a compound represented by the following general formula (2) can be used.

(R ³ and R ⁴ in General Formula (2) represent an alkylene group having 1 to 3 carbon atoms)

As a compound represented by the said general formula (2), N-acryloylmorpholine etc. are mentioned, for example.

As the acrylic monomer (b1-2) having an oxyethylene group, for example, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, polyethylene glycol polypropylene glycol copolymerized (meth) acrylate, methoxy Polyethylene glycol polypropylene glycol copolymerized (meth)acrylate, polyethylene glycol polytetramethylene glycol copolymerized (meth)acrylate, methoxypolyethylene glycol polytetramethylene glycol copolymerized (meth)acrylate, and the like. These monomers may be used alone or in combination of two or more.

As the acrylic monomer (b1-3) having a silanol group and/or a hydrolyzable silyl group, for example, vinyl trimethoxysilane, vinyl triethoxysilane, p-styryltrimethoxysilane, p-styryltri Ethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxy And propylmethyldiethoxysilane. These monomers may be used alone or in combination of two or more.

The total content rate of units derived from the acrylic monomers (b1-1), (b1-2) and (b1-3) is in 100% by mass of the hydrophilic acrylic polymer (B), preferably 70% by mass or more, more It is preferably 80 mass% or more, more preferably 90 mass% or more.

The ratio of the unit derived from the acrylic monomer (b1-1) having an amide group and the unit derived from the acrylic monomer (b1-2) having an oxyethylene group ((b1-1)/(b1-2)) is hydrophilic. From the viewpoint of maintaining the hydrophilic persistence at a high level, on a molar basis, preferably 99/1 or more and 50/50 or less, and from the viewpoint of obtaining even more excellent hydrophilic persistence, more preferably 90/10 or more and 70/30 or less to be.

Examples of the other acrylic monomers described above include, for example, an acrylic monomer having a sulfonic acid group, an acrylic monomer having a quaternary ammonium group, an acrylic monomer having a carboxyl group, an acrylic monomer having an amino group, an acrylic monomer having a cyano group, and an acrylic monomer having a hydroxyl group. , An acrylic monomer having an imide group, and an acrylic monomer having a methoxy group.

Examples of the acrylic monomer having a sulfonic acid group include sodium sulfopropyl (meth)acrylate, sodium 2-sulfoethyl (meth)acrylate, sodium 2-acrylamide-2-methylpropanesulfonate, and the like. . These monomers may be used alone or in combination of two or more.

Examples of the acrylic monomer having a quaternary ammonium group include tetrabutylammonium (meth)acrylate and trimethylbenzylammonium (meth)acrylate. These monomers may be used alone or in combination of two or more.

Examples of the acrylic monomer having a carboxyl group include (meth)acrylic acid, propyl (meth)acrylic acid, isopropyl (meth)acrylic acid, crotonic acid, fumaric acid, and the like. These monomers may be used alone or in combination of two or more.

As the acrylic monomer having an amino group, for example, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, (meth)acryloxyethyl Trimethylammonium chloride, etc. are mentioned. These monomers may be used alone or in combination of two or more.

As the acrylic monomer having a cyano group, for example, acrylonitrile, cyanomethyl acrylate, 2-cyanoethyl acrylate, cyanopropyl acrylate, 1-cyanomethylethyl acrylate, 2-cyano Propyl acrylate, 1-cyanocyclopropyl acrylate, 1-cyanocycloheptyl acrylate, 1,1-dicyanoethyl acrylate, 2-cyanophenyl acrylate, 3-cyanophenyl acrylate, 4- Cyanophenyl acrylate, 3-cyanobenzyl acrylate, 4-cyanobenzyl acrylate, etc. are mentioned. These monomers may be used alone or in combination of two or more.

As the acrylic monomer having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (Meth)acrylate, glycerol mono(meth)acrylate, etc. are mentioned. These monomers may be used alone or in combination of two or more.

Examples of the acrylic monomer having an imide group include (meth)acrylimide, N-methylolmaleimide, N-hydroxyethylmaleimide, N-glycidylmaleimide, and N-4-chloromethylphenylmaleimide. Mid, N-acetoxyethyl maleimide, etc. are mentioned. These monomers may be used alone or in combination of two or more.

As the acrylic monomer having a methoxy group, for example, 3-methoxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-methoxy Butyl (meth)acrylate, etc. are mentioned. These monomers may be used alone or in combination of two or more.

As the total amount of the acrylic monomer (b1-1) having an amide group, the acrylic monomer (b1-2) having an oxyethylene group, and the acrylic monomer (b1-3) having a silanol group and/or a hydrolyzable silyl group, the hydrophilicity It is preferable that it is 70 mass% or more in the acrylic monomer (b1), it is more preferable that it is 80 mass% or more, and it is still more preferable that it is 90 mass% or more.

As the polymerization ratio (molar ratio) of the acrylic monomer (b1-1) having an amide group and the acrylic monomer (b1-2) having an oxyethylene group, since the hydrophilicity and hydrophilic persistence can be maintained at a high level, 99/1 to 50/50 It is preferable that it is the range of, and it is more preferable that it is the range of 90/10-70/30 from the point which further excellent hydrophilic persistence is obtained.

In addition, the average number of moles added of the oxyethylene group of the acrylic monomer (b1-2) having an oxyethylene group is preferably in the range of 5 to 13 moles, more preferably in the range of 8 to 10 moles from the viewpoint of hydrophilicity. desirable.

In the case of producing the hydrophilic acrylic polymer (B), if necessary, radical polymerizable monomers other than the hydrophilic acrylic monomer (b1) may be used in combination.

As the radical polymerizable monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (Meth)acrylate, isobutyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Heptyl(meth)acrylate, n-octyl(meth)acrylate, nonyl(meth)acrylate, dodecyl(meth)acrylate, 3-methylbutyl(meth)acrylate, isooctyl(meth)acrylate, la Uryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, neopentyl (meth) acrylate, hexadecyl (meth) acrylate, isoamyl Aliphatic (meth)acrylates such as (meth)acrylate; Alicyclic (meth)acrylates such as isoboronyl (meth)acrylate, cyclohexyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate; Aromatic (meth)acrylates such as benzyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenyl (meth)acrylate; And vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether. These monomers may be used alone or in combination of two or more.

When the content of the silanol group and/or hydrolyzable silyl group in the hydrophilic acrylic resin (B) is in the range of 0.1 to 10% by mass in the acrylic resin (B), a coating film having excellent hydrophilic persistence and adhesion to the substrate can be formed. Therefore, it is preferable, the range of 0.2-5 mass% is more preferable, and the range of 0.5-3 mass% is more preferable.

As a method for producing the hydrophilic acrylic polymer (B), known radical polymerization can be used, for example, the hydrophilic acrylic monomer (b1), a polymerization initiator, water and/or an organic solvent, and, if necessary, the radical A method of mixing and stirring the polymerizable monomer under a temperature in the range of, for example, 40 to 90°C, and proceeding radical polymerization over, for example, 1 to 10 hours may be mentioned.

Examples of the polymerization initiator include peroxides such as hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate; Organic peroxides such as benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, and cumene hydroperoxide; 2,2'-azobis-(2-aminodipropane) dihydrochloride, 2,2'-azobis-(N,N'-dimethyleneisobutylamidine) dihydrochloride, azobisisobutyronitrile, 2 And azo compounds such as 2'-azobis(2-methylbutyronitrile) and 2,2'-azobis(2,4-dimethylvalerate nitrile). These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used is, for example, in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the monomer as a raw material for the hydrophilic acrylic polymer (B).

As the organic solvent, for example, methanol, ethanol, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylformamide, hexane, acetone, cyclohexanone, 3-pentanone , Acetonitrile, isopropyl alcohol, 1,2-propanediol, 1,3-butanediol, and the like. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent to be used is, for example, in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the monomer that is a raw material for the hydrophilic acrylic polymer (B).

The weight average molecular weight of the hydrophilic acrylic polymer (B) is preferably in the range of 10,000 to 100,000, and more preferably in the range of 15,000 to 50,000, from the viewpoint of affinity with polyurethane (A). Moreover, the weight average molecular weight of the said hydrophilic acrylic polymer (B) shows the value obtained by measuring it under the following conditions by a gel permeation chromatography (GPC) 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 G5000」(7.8㎜I.D.×30cm)×1ea

「TSKgel G4000」(7.8㎜I.D.×30cm)×1ea

「TSKgel G3000」(7.8㎜I.D.×30cm)×1ea

「TSKgel G2000」(7.8㎜I.D.×30cm)×1ea

Detector: RI (differential refractometer)

Column temperature: 40°C

Eluent: Tetrahydrofuran (THF)

Flow rate: 1.0mL/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

Examples of the aqueous medium (C) include water, an organic solvent miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, 1,2-propylene glycol, and 1,3-butylene glycol; Ketone solvents such as acetone and methyl ethyl ketone; Ethylene glycol-n-butyl ether, diethylene glycol-n-butyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene Glycol ether solvents such as glycol-n-butyl ether and tripropylene glycol methyl ether; Lactam solvents such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; Amide solvents, such as N,N-dimethylformamide, etc. are mentioned. These organic solvents to be mixed with water may be used alone or in combination of two or more.

Further, the aqueous medium (C) is preferably only water, or a mixture of water and an organic solvent miscible with water, and more preferably only water in consideration of safety and reduction of the load on the environment.

The aqueous medium (C) is preferably contained in a range of 30 to 80 mass%, and more preferably contained in a range of 50 to 70 mass% in the total amount of the aqueous resin composition of the present invention.

In addition, the aqueous resin composition of the present invention, if necessary, crosslinking agent, plasticizer, antistatic agent, wax, surfactant, light stabilizer, flow regulator, dye, leveling agent, rheology control agent, ultraviolet absorber, antioxidant, photocatalytic properties Various additives, such as compounds, inorganic pigments, organic pigments, and extender pigments, can be used.

By using the crosslinking agent, the durability of the coating film of the aqueous resin composition of the present invention can be further improved. As the crosslinking agent, for example, at least one selected from the group consisting of amino resins, aziridine compounds, melamine compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds and isocyanate compounds can be used.

Further, by using the surfactant, the dispersion stability of the aqueous resin composition of the present invention can be further improved. In the case of using a surfactant, the adhesion to the substrate and water resistance of the resulting coating film can be maintained. Therefore, it is preferable to use it in a range of 20 parts by mass or less with respect to 100 parts by mass of the urethane resin (A). It is desirable.

In the aqueous resin composition of the present invention, a curing agent and a curing catalyst may be used in combination as necessary within the range not impairing the effects of the present invention.

Examples of the curing agent include a compound having a silanol group and/or a hydrolyzable silyl group, a polyepoxy compound, a polyoxazoline compound, and a polyisocyanate.

Among them, it is preferable to use a compound having a silanol group and/or a hydrolyzable silyl group as the curing agent for forming a coating film excellent in corrosion resistance, water resistance and adhesion to a substrate. In particular, when the aqueous resin composition of the present invention is used for a coating agent, the hydrolyzable silyl group or silanol group of the compound improves adhesion to the substrate, and as a result, a coating film having excellent corrosion resistance can be formed.

Examples of the compound having a silanol group and/or a hydrolyzable silyl group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane , Epoxysilane compounds such as γ-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane However, aminosilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldiethoxysilane can be used.

Among them, one selected from the group consisting of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane The use of the above is preferable because the crosslinking density of the coating film is improved and corrosion resistance, water resistance, and substrate adhesion are improved.

The compound having a silanol group and/or a hydrolyzable silyl group forms a coating film having excellent chemical resistance, and obtains the aqueous urethane resin composition of the present invention having excellent storage stability, 0.01% by mass based on the total amount of the urethane resin (A) It is preferable to use in the range of -10 mass%.

In addition, as a curing catalyst usable in the aqueous resin composition of the present invention, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate, Lead octylate, cobalt octylate, zinc octylate, calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di-n-butyltin dilau Rate, di-n-butyltin maleate, p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid, dialkylphosphorous acid, and the like can be used.

In addition, the aqueous resin composition of the present invention may contain an emulsifier, a dispersion stabilizer, or a leveling agent as necessary, but from the viewpoint of suppressing a decrease in the water resistance of the crosslinked coating film, it is preferable not to contain the water-based resin. It is preferable that it is 0.5 mass% or less with respect to the solid content of a composition.

As described above, the aqueous resin composition of the present invention can be used for a coating agent for the purpose of protecting the surface of various substrates and imparting design properties to various substrates.

Examples of the substrate include metals, various plastics, films thereof, glass, paper, and wood.

Examples of the metal base material include galvanized steel sheets, aluminum-zinc plated steel sheets, aluminum sheets, aluminum alloy sheets, electronic steel sheets, copper sheets, stainless steel sheets, etc. used in applications such as automobiles, home appliances, and construction materials. have.

Plastic substrates are generally used in plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, and OA equipment, and include acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC resin), ABS/PC resin, polystyrene resin (PS resin), polymethyl methacrylate resin (PMMA resin), acrylic resin, polypropylene resin, polyethylene resin, etc. are mentioned. As the plastic film base material, polyethylene terephthalate film, polyester Films, polyethylene films, polypropylene films, TAC (triacetylcellulose) films, polycarbonate films, polyvinyl chloride films, and the like can be used.

The aqueous resin composition of the present invention can form a coating film having excellent chemical resistance including acid resistance, alkali resistance, etc. even if the crosslinked coating film has a thickness of about 5 μm. Further, even if the crosslinked coating film has a thickness of about 1 µm, a coating film having excellent chemical resistance including acid resistance, alkali resistance, and the like can be formed.

The aqueous resin composition of the present invention can be coated on a substrate, dried, and cured to form a coating film.

Further, in the above drying step, when water and an organic solvent having a high boiling point are used in combination from water as the aqueous medium (C), after the water in the aqueous resin composition is volatilized, the organic solvent is volatilized. After the volatilization of water, it is composed of an organic solvent, a urethane resin (A) and a hydrophilic acrylic resin (B), and the organic solvent accelerates the fusion of the urethane resin (A) and the hydrophilic acrylic resin (B), thereby preventing defects in the coating film. No good coating film is formed.

Examples of the coating method include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and an immersion method.

The drying may be naturally dried under normal temperature, but may be heated and dried. It is preferable to perform heat-drying normally at 40-250 degreeC over time of about 1 to 600 second.

Further, when the substrate is easily deformed by heat, such as a plastic substrate, it is preferable to adjust the drying temperature of the coating film to approximately 80°C or less.

Examples of articles having a coating film of a coating agent using the water-based resin composition of the present invention include aluminum fins, building members, home appliances, automobile exterior materials, goggles, anti-fog film sheets, anti-fog glass, mirrors, medical instruments, and the like. .

(Example)

(Synthesis Example 1: Synthesis of polyol (1) having a tertiary amino group)

After adding 543 parts by mass of polyethylene glycol-diglycidyl ether (epoxy equivalent 185 g/equivalent) to a 4-neck flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, the inside of the flask was purged with nitrogen. Next, after heating using an oil bath until the temperature in the flask reaches 70°C, 380 parts by mass of di-n-butylamine were added dropwise for 30 minutes using a dropping device, and after completion of the dropwise addition, 10 at 90°C. It was allowed to react for time. After completion of the reaction, using an infrared spectrophotometer ("FT/IR-460Plus" manufactured by Nippon Bunko Co., Ltd.), it was confirmed that the absorption peak in the vicinity of 842 cm ^-1 caused by the epoxy group of the reaction product disappeared, Polyol (1) having a tertiary amino group (amine equivalent 315 g/equivalent, hydroxyl group equivalent 315 g/equivalent) was prepared.

(Preparation Example 1: Preparation of an aqueous dispersion of urethane resin (A-1))

262 parts by mass of polycarbonate polyol (hydroxyl value 56.1 mgKOH/g) obtained using 1,6-hexanediol was added to a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device, and a reduced pressure of 0.095 MPa It dehydrated at 120-130 degreeC at. After dehydration, it cooled to 70 degreeC, added 154 mass parts of methyl ethyl ketone, and it stirred and mixed sufficiently, cooling to 50 degreeC. After stirring and mixing, 69 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4'-H-MDI) and 0.1 parts by mass of stannous octylic acid were added, and reacted at 70° C. for 2 hours.

After the reaction was completed, 18 parts by mass of the polyol (1) having a tertiary amino group obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55°C, and γ-aminopropyltriethoxysilane (Shin-Etsu Chemical After adding 12 parts by mass of "KBE-903" manufactured by Kogyo Co., Ltd. and reacting for 1 hour, 211 parts by mass of methyl ethyl ketone was added to prepare a urethane prepolymer solution having a terminal isocyanate group. Next, to the urethane prepolymer solution, 5 parts by mass of 80% by mass hydrazine hydrate was added, and a chain extension reaction was performed for 1 hour.

Next, 6 parts by mass of an 89% by mass aqueous phosphoric acid solution was added, and after holding at 45°C for 1 hour, the mixture was cooled to 40°C and 1089 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous dispersion of a urethane resin (A-1) having a nonvolatile content of 30% by mass. The ratio of the alicyclic structure per solid content of the water dispersion of the urethane resin (A-1) was 1436 mmol/kg, and the content of the alkoxysilyl group in the urethane resin (A-1) was 2.34% by mass.

(Preparation Example 2: Preparation of an aqueous dispersion of urethane resin (A-2))

262 parts by mass of polycarbonate polyol (hydroxyl value 56.1 mgKOH/g) obtained using 1,6-hexanediol was added to a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device, and a reduced pressure of 0.095 MPa It dehydrated at 120-130 degreeC at. After dehydration, it cooled to 70 degreeC, added 143 mass parts of methyl ethyl ketone, and it stirred and mixed sufficiently, cooling to 50 degreeC. After stirring and mixing, 44 parts by mass of hexamethylene diisocyanate and 0.1 parts by mass of stannous octylate were added, and reacted at 70°C for 2 hours.

After completion of the reaction, 16 parts by mass of the polyol (1) having a tertiary amino group obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55°C, and γ-aminopropyltriethoxysilane (Shin-Etsu Chemical After adding 12 parts by mass of "KBE-903" manufactured by Kogyo Co., Ltd. and reacting for 1 hour, 196 parts by mass of methyl ethyl ketone was added to prepare a urethane prepolymer solution having a terminal isocyanate group. Next, to the urethane prepolymer solution, 5 parts by mass of 80% by mass hydrazine hydrate was added, and a chain extension reaction was performed for 1 hour.

Next, 5 mass parts of an 89 mass% phosphoric acid aqueous solution was added, and after holding|maintaining at 45 degreeC for 1 hour, it cooled to 40 degreeC and added 1012 mass parts of ion-exchanged water to prepare an aqueous dispersion. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous dispersion of a urethane resin (A-2) having a nonvolatile content of 30% by mass. The ratio of the alicyclic structure per solid content of the water dispersion of the urethane resin (A-2) was 0 mmol/kg, and the content of the alkoxysilyl group in the urethane resin (A-2) was 2.52% by mass.

(Preparation Example 3: Preparation of an aqueous dispersion of urethane resin (A-3))

262 parts by mass of polycarbonate polyol (hydroxyl value 56.1 mgKOH/g) obtained using 1,6-hexanediol was added to a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device, and a reduced pressure of 0.095 MPa It dehydrated at 120-130 degreeC at. After dehydration, it cooled to 70 degreeC, 162 mass parts of methyl ethyl ketones were added, and it stirred and mixed sufficiently, cooling to 50 degreeC. After stirring and mixing, 69 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4'-H-MDI) and 0.1 parts by mass of stannous octylic acid were added, and reacted at 70° C. for 2 hours.

After the reaction was completed, 18 parts by mass of the polyol (1) having a tertiary amino group obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55°C, and γ-aminopropyltriethoxysilane (Shin-Etsu Chemical After adding 29 parts by mass of "KBE-903" manufactured by Kogyo Co., Ltd. and reacting for 1 hour, 218 parts by mass of methyl ethyl ketone was added to prepare a urethane prepolymer solution having a terminal isocyanate group. Next, to the urethane prepolymer solution, 2 parts by mass of 80% by mass hydrazine hydrate was added, and a chain extension reaction was performed for 1 hour.

Next, 6 parts by mass of an 89% by mass phosphoric acid aqueous solution was added, and after holding at 45°C for 1 hour, the mixture was cooled to 40°C and 1134 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous dispersion of a urethane resin (A-3) having a nonvolatile content of 30% by mass. The ratio of the alicyclic structure per solid content of the water dispersion of the urethane resin (A-3) was 1376 mmol/kg, and the content of the alkoxysilyl group in the urethane resin (A-3) was 5.63% by mass.

(Preparation Example 4: Preparation of water dispersion of urethane resin (A-4))

262 parts by mass of polycarbonate polyol (hydroxyl value 56.1 mgKOH/g) obtained using 1,6-hexanediol was added to a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device, and a reduced pressure of 0.095 MPa It dehydrated at 120-130 degreeC at. After dehydration, it cooled to 70 degreeC, added 382 mass parts of methyl ethyl ketone, and it stirred and mixed sufficiently, cooling to 50 degreeC. After stirring and mixing, 105 parts of 1,4-cyclohexanedimethanol, 450 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4'-H-MDI) and 0.1 parts by mass of stannous octylate were added, and 70 It was reacted at °C for 2 hours.

After the reaction was completed, 44 parts by mass of the polyol (1) having a tertiary amino group obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55°C, and γ-aminopropyltriethoxysilane (Shin-Etsu Chemical After adding 30 parts by mass of "KBE-903" manufactured by Kogyo Co., Ltd. and reacting for 1 hour, 554 parts by mass of methyl ethyl ketone was added to prepare a urethane prepolymer solution having a terminal isocyanate group. Next, to the urethane prepolymer solution, 45 parts by mass of 80% by mass hydrazine hydrate was added, and a chain extension reaction was performed for 1 hour.

Next, 14 mass parts of an 89 mass% phosphoric acid aqueous solution was added, and after holding|maintaining at 45 degreeC for 1 hour, it cooled to 40 degreeC and added 2795 mass parts of ion-exchanged water to prepare an aqueous dispersion. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous dispersion of a urethane resin (A-4) having a nonvolatile content of 30% by mass. The ratio of the alicyclic structure per solid content of the water dispersion of the urethane resin (A-4) was 4442 mmol/kg, and the content of the alkoxysilyl group in the urethane resin (A-4) was 2.39% by mass.

(Preparation Example 5: Preparation of an aqueous dispersion of urethane resin (A-5))

262 parts by mass of polycarbonate polyol (hydroxyl value 56.1 mgKOH/g) obtained using 1,6-hexanediol was added to a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device, and a reduced pressure of 0.095 MPa It dehydrated at 120-130 degreeC at. After dehydration, it cooled to 70 degreeC, 612 mass parts of methyl ethyl ketones were added, and it stirred and mixed sufficiently, cooling to 50 degreeC. After stirring and mixing, 210 parts of 1,4-cyclohexanedimethanol, 831 parts by mass of 4,4′-dicyclohexylmethane diisocyanate (4,4′-H-MDI) and 0.1 parts by mass of stannous octylic acid were added, and 70 It was reacted at °C for 2 hours.

After completion of the reaction, 70 parts by mass of the polyol (1) having a tertiary amino group obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55°C, and γ-aminopropyltriethoxysilane (Shin-Etsu Chemical After adding 56 parts by mass of "KBE-903" manufactured by Kogyo Co., Ltd. and reacting for 1 hour, 901 parts by mass of methyl ethyl ketone was added to prepare a urethane prepolymer solution having a terminal isocyanate group. Next, 85 mass parts of 80 mass% hydrides were added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

Next, 22 mass parts of an 89 mass% phosphoric acid aqueous solution was added, and after holding|maintaining at 45 degreeC for 1 hour, it cooled to 40 degreeC, and the water dispersion was prepared by adding 4518 mass parts of ion-exchanged water. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous dispersion of a urethane resin (A-5) having a nonvolatile content of 30% by mass. The ratio of the alicyclic structure per solid content of the water dispersion of the urethane resin (A-5) was 5150 mmol/kg, and the content of the alkoxysilyl group in the urethane resin (A-5) was 2.74% by mass.

(Preparation Example 6: Preparation of water dispersion of urethane resin (A-6))

262 parts by mass of polycarbonate polyol (hydroxyl value 56.1 mgKOH/g) obtained using 1,6-hexanediol was added to a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device, and a reduced pressure of 0.095 MPa It dehydrated at 120-130 degreeC at. After dehydration, it cooled to 70 degreeC, 149 mass parts of methyl ethyl ketones were added, and it stirred and mixed sufficiently, cooling to 50 degreeC. After stirring and mixing, 69 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4'-H-MDI) and 0.1 parts by mass of stannous octylic acid were added, and reacted at 70° C. for 2 hours.

After the reaction was completed, 18 parts by mass of the polyol (1) having a tertiary amino group obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55°C, and γ-aminopropyltriethoxysilane (Shin-Etsu Chemical After adding 1 part by mass of "KBE-903" manufactured by Kogyo Co., Ltd. and reacting for 1 hour, 206 parts by mass of methyl ethyl ketone was added to prepare a urethane prepolymer solution having a terminal isocyanate group. Next, to the urethane prepolymer solution, 7 parts by mass of 80% by mass hydrazine was added, and a chain extension reaction was performed for 1 hour.

Next, 6 parts by mass of an 89% by mass aqueous phosphoric acid solution was added, and after holding at 45°C for 1 hour, the mixture was cooled to 40°C and 1061 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous dispersion of a urethane resin (A-6) having a nonvolatile content of 30% by mass. The ratio of the alicyclic structure per solid content of the water dispersion of the urethane resin (A-6) was 1474 mmol/kg, and the content of the alkoxysilyl group in the urethane resin (A-6) was 0.12% by mass.

(Comparative Preparation Example 1: Preparation of an aqueous dispersion of urethane resin (A'-1))

262 parts by mass of polycarbonate polyol (hydroxyl value 56.1 mgKOH/g) obtained using 1,6-hexanediol was added to a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device, and a reduced pressure of 0.095 MPa It dehydrated at 120-130 degreeC at. After dehydration, it cooled to 70 degreeC, 149 mass parts of methyl ethyl ketones were added, and it stirred and mixed sufficiently, cooling to 50 degreeC. After stirring and mixing, 69 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4'-H-MDI) and 0.1 parts by mass of stannous octylic acid were added, and reacted at 70° C. for 2 hours.

After completion of the reaction, 18 parts by mass of the polyol (1) having a tertiary amino group obtained in Synthesis Example 1 was added, followed by reaction for 4 hours, cooled, and 206 parts by mass of methyl ethyl ketone were added to prepare a urethane prepolymer solution having a terminal isocyanate group. did. Next, to the urethane prepolymer solution, 7 parts by mass of 80% by mass hydrazine was added, and a chain extension reaction was performed for 1 hour.

Next, 6 parts by mass of an 89% by mass aqueous phosphoric acid solution was added, and after holding at 45°C for 1 hour, the mixture was cooled to 40°C and 1059 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous dispersion of a urethane resin (A'-1) having a nonvolatile content of 30% by mass. The ratio of the alicyclic structure per solid content of the water dispersion of the urethane resin (A'-1) was 1476 mmol/kg, and the content of the alkoxysilyl group in the urethane resin (A'-1) was 0% by mass.

Table 1 shows the ratio of the alicyclic structure per solid content of the urethane resin aqueous dispersion obtained in Preparation Examples 1 to 6 and Comparative Preparation Example 1, and the content of the alkoxysilyl group.

[Table 1]

(Preparation Example 7: Preparation of hydrophilic acrylic polymer (B-1))

To a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 30 parts by mass of isopropyl alcohol was added, and thereafter, N,N-dimethylacrylamide/methoxypolyethylene glycol acrylate (Shin-Nakamura Chemical "AM-90G" manufactured by Kogyo Corporation, 100 parts by mass of a mixture of oxyethylene group having an average added mole number of 9 moles) = 85/15 (molar ratio) and 2 parts by mass of γ-methacryloxypropyltriethoxysilane A solution obtained by diluting the part with 51 parts by mass of isopropyl alcohol and 20 parts by mass of a 0.5% by mass isopropyl alcohol solution (Azo-based polymerization initiator "V-59" manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a reaction apparatus at 80°C. It dripped over time, and radical polymerization was performed, and the hydrophilic acrylic polymer (B-1) was obtained. The weight average molecular weight of the obtained hydrophilic acrylic polymer (B-1) was 20,000, and the non-volatile content was 50 mass%. In addition, content of the alkoxysilyl group in this hydrophilic acrylic polymer (B-1) was 1.1 mass%.

(Preparation Example 8: Preparation of hydrophilic acrylic polymer (B-2))

To a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 30 parts by mass of isopropyl alcohol was added, and thereafter, N,N-dimethylacrylamide/methoxypolyethylene glycol acrylate (Shin-Nakamura Chemical Kogyo Co., Ltd. "AM-90G", 100 parts by mass of a mixture of oxyethylene group having an average added mole number of 9 moles) = 45/55 (molar ratio), and 2 parts by mass of γ-methacryloxypropyltriethoxysilane A solution obtained by diluting the part with 51 parts by mass of isopropyl alcohol and 20 parts by mass of a 0.5% by mass isopropyl alcohol solution (Azo-based polymerization initiator "V-59" manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a reaction apparatus at 80°C. It dripped over time, and radical polymerization was performed, and the hydrophilic acrylic polymer (B-2) was obtained. The weight average molecular weight of the obtained hydrophilic acrylic polymer (B-2) was 20,000, and the nonvolatile content was 50 mass%. In addition, content of the alkoxysilyl group in this hydrophilic acrylic polymer (B-2) was 1.1 mass%.

(Preparation Example 9: Preparation of hydrophilic acrylic polymer (B-3))

To a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 30 parts by mass of isopropyl alcohol was added, and thereafter, N,N-dimethylacrylamide/methoxypolyethylene glycol acrylate (Shin-Nakamura Chemical Kogyo Co., Ltd. "AM-90G", 100 parts by mass of a mixture of oxyethylene group having an average added mole number of 9 moles) = 85/15 (molar ratio), and 25 parts by mass of γ-methacryloxypropyltriethoxysilane A solution obtained by diluting the part with 63 parts by mass of isopropyl alcohol and 20 parts by mass of a 0.5% by mass isopropyl alcohol solution (Azo-based polymerization initiator "V-59" manufactured by Wako Pure Chemical Industries, Ltd.) were 4 in a reaction apparatus at 80°C. It dripped over time, and radical polymerization was performed, and the hydrophilic acrylic polymer (B-3) was obtained. The weight average molecular weight of the obtained hydrophilic acrylic polymer (B-3) was 20,000, and the non-volatile content was 50 mass%. In addition, content of the alkoxysilyl group in this hydrophilic acrylic polymer (B-3) was 11.24 mass %.

(Preparation Example 10: Preparation of hydrophilic acrylic polymer (B-4))

To a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 30 parts by mass of isopropyl alcohol was added, and thereafter, N,N-dimethylacrylamide/methoxypolyethylene glycol acrylate (Shin-Nakamura Chemical Kogyo Co., Ltd. "AM-90G", 100 parts by mass of a mixture of oxyethylene group having an average added mole number of 9 moles) = 85/15 (molar ratio), and 17 parts by mass of γ-methacryloxypropyltriethoxysilane A solution obtained by diluting the part with 59 parts by mass of isopropyl alcohol and 20 parts by mass of a 0.5% by mass isopropyl alcohol solution (Azo-based polymerization initiator "V-59" manufactured by Wako Pure Chemical Industries, Ltd.) were 4 in a reaction apparatus at 80°C. It dripped over time, and radical polymerization was performed, and the hydrophilic acrylic polymer (B-4) was obtained. The weight average molecular weight of the obtained hydrophilic acrylic polymer (B-4) was 20,000, and the nonvolatile content was 50 mass%. Moreover, the content of the alkoxysilyl group in this hydrophilic acrylic polymer (B-4) was 8.16 mass %.

(Preparation Example 11: Preparation of hydrophilic acrylic polymer (B-5))

To a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 30 parts by mass of isopropyl alcohol was added, and thereafter, N,N-dimethylacrylamide/methoxypolyethylene glycol acrylate (Shin-Nakamura Chemical "AM-90G" manufactured by Kogyo Corporation, 100 parts by mass of a mixture of 9 moles of oxyethylene group added in the average number of moles) = 95/5 (molar ratio), and 2 parts by mass of γ-methacryloxypropyltriethoxysilane A solution obtained by diluting the part with 51 parts by mass of isopropyl alcohol and 20 parts by mass of a 0.5% by mass isopropyl alcohol solution (Azo-based polymerization initiator "V-59" manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a reaction apparatus at 80°C. It dripped over time, and radical polymerization was performed, and the hydrophilic acrylic polymer (B-5) was obtained. The weight average molecular weight of the obtained hydrophilic acrylic polymer (B-5) was 20,000, and the nonvolatile content was 50 mass%. In addition, content of the alkoxysilyl group in this hydrophilic acrylic polymer (B-5) was 1.1 mass %.

(Comparative Preparation Example 2: Preparation of hydrophilic acrylic polymer (B'-1))

To a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 30 parts by mass of isopropyl alcohol was added, and thereafter, N,N-dimethylacrylamide/methoxypolyethylene glycol acrylate (Shin-Nakamura Chemical A solution obtained by diluting 100 parts by mass of a mixture of "AM-90G" manufactured by Kogyo Co., Ltd., with an average added mole number of oxyethylene groups of 9 moles) = 85/15 (molar ratio) with 50 parts by mass of isopropyl alcohol, and Wako Pure Chemicals 20 parts by mass of a 0.5% by mass isopropyl alcohol solution of the azo polymerization initiator “V-59” manufactured by Kogyo Corporation was dripped in a reaction apparatus at 80°C for 4 hours, followed by radical polymerization, and hydrophilic acrylic polymer (B'- 1) was obtained. The weight average molecular weight of the obtained hydrophilic acrylic polymer (B'-1) was 20,000, and the nonvolatile content was 50 mass%. In addition, content of the alkoxysilyl group in this hydrophilic acrylic polymer (B'-1) was 0 mass %.

The molar ratio of the acrylic monomer (b1-1) and the acrylic monomer (b1-2) used in Preparation Examples 7 to 11 and Comparative Preparation Example 2, and the alkoxysilyl of the hydrophilic acrylic polymer obtained in Preparation Examples 7 to 11 and Comparative Preparation Example 2 Table 2 shows the group content.

[Table 2]

The abbreviations in Table 2 will be described.

"DMAA"; N,N-dimethylacrylamide

"AM-90G"; Methoxy polyethylene glycol acrylate (``AM-90G'' manufactured by Shinnakamura Chemical Industry Co., Ltd.)

(Example 1: Preparation of aqueous resin composition (1))

In a 4-neck flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 240 parts by mass of an aqueous dispersion of a urethane resin (A-1) of 30% by mass of the nonvolatile content obtained in Preparation Example 1 (nonvolatile content: 72 parts by mass) And 60 parts by mass (non-volatile content: 30 parts by mass) of the hydrophilic acrylic polymer (B-1) having 50% by mass of the nonvolatile content obtained in Preparation Example 7 and 30 parts by mass of 1,2-propylene glycol and 30 parts by mass of 1,3-butylene glycol. An aqueous dispersion was obtained by adding parts by mass and 30 parts by mass of ion-exchanged water. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (1) having a nonvolatile content of 30% by mass.

(Example 2: Preparation of aqueous resin composition (2))

In a 4-neck flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 240 parts by mass of an aqueous dispersion of a urethane resin (A-1) of 30% by mass of the nonvolatile content obtained in Preparation Example 1 (nonvolatile content: 72 parts by mass) And 60 parts by mass (non-volatile content: 30 parts by mass) of the hydrophilic acrylic polymer (B-2) having 50% by mass of the nonvolatile content obtained in Preparation Example 8, 30 parts by mass of 1,2-propylene glycol and 30 parts by mass of 1,3-butylene glycol An aqueous dispersion was obtained by adding parts by mass and 30 parts by mass of ion-exchanged water. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (2) having a nonvolatile content of 30% by mass.

(Example 3: Preparation of aqueous resin composition (3))

In a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 240 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Preparation Example 1 (non-volatile content: 72 parts by mass) and obtained in Preparation Example 9 60 parts by mass of hydrophilic acrylic polymer (B-3) with 50% by mass of non-volatile content (non-volatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol, 30 parts by mass of 1,3-butylene glycol, and ion-exchanged water 30 parts by mass was added to obtain an aqueous dispersion. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (3) having a nonvolatile content of 30% by mass.

(Example 4: Preparation of aqueous resin composition (4))

In a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device, 240 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Preparation Example 1 (non-volatile content: 72 parts by mass) and obtained in Preparation Example 10 60 parts by mass of hydrophilic acrylic polymer (B-4) with 50% by mass of non-volatile content (non-volatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol, 30 parts by mass of 1,3-butylene glycol, and ion-exchanged water 30 parts by mass was added to obtain an aqueous dispersion. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (4) having a nonvolatile content of 30% by mass.

(Example 5: Preparation of aqueous resin composition (5))

In a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 240 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Preparation Example 1 (non-volatile content: 72 parts by mass) and obtained in Preparation Example 11. 60 parts by mass of hydrophilic acrylic polymer (B-5) with 50% by mass of non-volatile content (non-volatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol, 30 parts by mass of 1,3-butylene glycol, and ion-exchanged water 30 parts by mass was added to obtain an aqueous dispersion. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (5) having a nonvolatile content of 30% by mass.

(Example 6: Preparation of aqueous resin composition (6))

In a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 240 parts by mass of an aqueous dispersion of the urethane resin (A-2) of 30% by mass of the non-volatile content obtained in Preparation Example 2 (non-volatile content: 72 parts by mass) And 60 parts by mass (non-volatile content: 30 parts by mass) of the hydrophilic acrylic polymer (B-1) having 50% by mass of the nonvolatile content obtained in Preparation Example 7 and 30 parts by mass of 1,2-propylene glycol and 30 parts by mass of 1,3-butylene glycol. An aqueous dispersion was obtained by adding parts by mass and 30 parts by mass of ion-exchanged water. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (6) having a nonvolatile content of 30% by mass.

(Example 7: Preparation of aqueous resin composition (7))

In a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 240 parts by mass of an aqueous dispersion of a urethane resin (A-3) of 39% by mass of a non-volatile content obtained in Preparation Example 3 (non-volatile content: 72 parts by mass) And 60 parts by mass (non-volatile content: 30 parts by mass) of the hydrophilic acrylic polymer (B-1) having 50% by mass of the nonvolatile content obtained in Preparation Example 7 and 30 parts by mass of 1,2-propylene glycol and 30 parts by mass of 1,3-butylene glycol. An aqueous dispersion was obtained by adding parts by mass and 30 parts by mass of ion-exchanged water. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (7) having a nonvolatile content of 30% by mass.

(Example 8: Preparation of aqueous resin composition (8))

In a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 240 parts by mass of the aqueous dispersion of the urethane resin (A-4) obtained in Preparation Example 4 (non-volatile content: 72 parts by mass) and the obtained in Preparation Example 7 60 parts by mass of hydrophilic acrylic polymer (B-1) with 50% by mass of non-volatile content (non-volatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol, 30 parts by mass of 1,3-butylene glycol, and ion-exchanged water 30 parts by mass was added to obtain an aqueous dispersion. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (8) having a nonvolatile content of 30% by mass.

(Example 9: Preparation of aqueous resin composition (9))

In a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 240 parts by mass of the aqueous dispersion of the urethane resin (A-5) obtained in Preparation Example 5 (non-volatile content: 72 parts by mass) and the obtained in Preparation Example 7 60 parts by mass of hydrophilic acrylic polymer (B-1) with 50% by mass of non-volatile content (non-volatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol, 30 parts by mass of 1,3-butylene glycol, and ion-exchanged water 30 parts by mass was added to obtain an aqueous dispersion. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (9) having a nonvolatile content of 30% by mass.

(Example 10: Preparation of aqueous resin composition (10))

In a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 240 parts by mass of the aqueous dispersion of the urethane resin (A-6) obtained in Preparation Example 6 (non-volatile content: 72 parts by mass) and obtained in Preparation Example 7 60 parts by mass of hydrophilic acrylic polymer (B-1) with 50% by mass of non-volatile content (non-volatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol, 30 parts by mass of 1,3-butylene glycol, and ion-exchanged water 30 parts by mass was added to obtain an aqueous dispersion. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (10) having a nonvolatile content of 30% by mass.

(Comparative Example 1: Preparation of aqueous resin composition (C1))

In a 4-neck flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 240 parts by mass of an aqueous dispersion of a urethane resin (A-1) of 30% by mass of the nonvolatile content obtained in Preparation Example 1 (nonvolatile content: 72 parts by mass) And 60 parts by mass (non-volatile content: 30 parts by mass) of a hydrophilic acrylic polymer (B'-1) having 50% by mass of a nonvolatile content obtained in Comparative Preparation Example 2, and 30 parts by mass of 1,2-propylene glycol and 1,3-butylene 30 parts by mass of glycol and 30 parts by mass of ion-exchanged water were added to obtain an aqueous dispersion. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (C1) having a nonvolatile content of 30% by mass.

(Comparative Example 2: Preparation of aqueous resin composition (C2))

In a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 240 parts by mass of an aqueous dispersion of a urethane resin (A'-1) of 30% by mass of the nonvolatile content obtained in Comparative Preparation Example 1 (nonvolatile content: 72% by mass) Parts) and 60 parts by mass (non-volatile content: 30 parts by mass) of the hydrophilic acrylic polymer (B-1) having 50% by mass of the nonvolatile content obtained in Preparation Example 7 and 30 parts by mass of 1,2-propylene glycol and 1,3-butylene 30 parts by mass of glycol and 30 parts by mass of ion-exchanged water were added to obtain an aqueous dispersion. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (C2) having a nonvolatile content of 30% by mass.

(Comparative Example 3: Preparation of aqueous resin composition (C3))

To a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device, 240 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Preparation Example 1 (non-volatile content: 72 parts by mass) and 1,2-propylene 30 parts by mass of glycol, 30 parts by mass of 1,3-butylene glycol, and 30 parts by mass of ion-exchanged water were added to obtain an aqueous dispersion. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (C3) having a nonvolatile content of 30% by mass.

(Comparative Example 4: Preparation of aqueous resin composition (C4))

In a four-neck flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 60 parts by mass (non-volatile content: 30 parts by mass) of the hydrophilic acrylic polymer (B-1) of 50% by mass of the nonvolatile content obtained in Preparation Example 7 and An aqueous dispersion was obtained by adding 30 parts by mass of 1,2-propylene glycol, 30 parts by mass of 1,3-butylene glycol, and 30 parts by mass of ion-exchanged water. This aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (C4) having a nonvolatile content of 30% by mass.

[Evaluation method of hydrophilic persistence]

The aqueous resin composition obtained in Examples and Comparative Examples was coated on an aluminum plate treated with phosphoric acid chromate so that the film thickness after drying was about 1 μm using a bar coater, and put in a dryer at an ambient temperature of 200° C. for 30 seconds to dry. , The coating was produced. After that, it was cured at room temperature for 3 days to obtain a specimen.

The specimen was immersed in running water for 240 hours, and the water contact angle after drying at room temperature for 1 day was evaluated according to the following evaluation criteria.

A: The water contact angle of the coating film was less than 20°

B: The water contact angle of the coating film was 20° or more and less than 30°

C: The water contact angle of the coating film was 30° or more and less than 40°

D: The water contact angle of the coating film was 40° or more

[Method of evaluating chemical resistance (alkali resistance)]

The aqueous resin composition obtained in Examples and Comparative Examples was coated on an aluminum plate treated with phosphoric acid chromate so that the film thickness after drying was about 1 μm using a bar coater, and put in a dryer at an ambient temperature of 200° C. for 30 seconds to dry. , The coating was produced. After that, it was cured at room temperature for 3 days to obtain a specimen. Next, a 5 mass% aqueous sodium hydroxide solution was placed as a spot on the coating film, and the deteriorated state of the coating film after standing for 20 minutes was evaluated according to the following evaluation criteria.

A: There was no change in the surface of the coating film

B: Some discoloration was seen on a part of the surface of the coating film, but it was a level that was not a problem in practical use

C: Discoloration was seen on the surface of the coating film

D: The coating film is dissolved and the substrate is exposed

[Evaluation method of substrate adhesion]

The aqueous resin compositions obtained in Examples and Comparative Examples were coated on each of the substrates shown below using a bar coater so that the film thickness after drying was about 1 μm, and for metal substrates, in a dryer at an ambient temperature of 200°C for 30 seconds. It was put and dried, and it dried at 60 degreeC for 30 minutes on a plastic base material, and produced the coating film. After that, it was cured at room temperature for 3 days to obtain a specimen. On the surface of the obtained coating film, in accordance with JIS K-5400, a cell tape (registered trademark) peeling test of 100 substrates per 1 mm was performed. The number of base wood that does not peel was measured and evaluated according to the following evaluation criteria. In addition, the metal substrate used was a phosphoric acid chromate-treated aluminum plate, a 55% by mass aluminum-zinc alloy plated steel plate (GL steel plate), and the plastic substrate used was a substrate made of acrylonitrile-butadiene-styrene resin (ABS resin). , It is a base material made of polycarbonate resin (PC resin).

A: The number of base carpenters without peeling was over 90

B: The number of base carpenters that did not peel was 60 or more and less than 90

C: The number of base carpenters without peeling was 40 or more and less than 60

D: The number of base carpenters without peeling was less than 40

Table 3 shows the evaluation results of the aqueous resin compositions (1) to (10) prepared in Examples 1 to 10, and the evaluation results of the aqueous resin compositions (C1) to (C4) prepared in Comparative Examples 1 to 4.

[Table 3]

Examples 1 to 10 shown in Table 3 are examples using the aqueous resin composition of the present invention. From the evaluation results of Examples 1 to 10, it was confirmed that the coating film obtained by using the aqueous resin composition of the present invention had excellent hydrophilic persistence and chemical resistance, and also had excellent adhesion to various substrates.

On the other hand, Comparative Example 1 is an example in which a hydrophilic acrylic polymer having neither silanol nor hydrolyzable silyl groups was used. It was confirmed that the coating film obtained by using the aqueous resin composition of Comparative Example 1 was remarkably insufficient in all of hydrophilic persistence, chemical resistance, and substrate adhesion.

Comparative Example 2 is an example of using a urethane resin having neither silanol nor hydrolyzable silyl. It was confirmed that the coating film obtained by using the aqueous resin composition of Comparative Example 2 was remarkably insufficient in all of the hydrophilic persistence, chemical resistance, and substrate adhesion.

Comparative Example 3 is an example in which a hydrophilic acrylic polymer having a silanol group and/or a hydrolyzable silyl group is not used. It was confirmed that the coating film obtained by using the aqueous resin composition of Comparative Example 3 was excellent in chemical resistance and substrate adhesion, but the hydrophilic persistence was remarkably insufficient.

Comparative Example 4 is an example in which a urethane resin having a silanol group and/or a hydrolyzable silyl group is not used. It was confirmed that the coating film obtained using the aqueous resin composition of Comparative Example 4 was remarkably insufficient in all of hydrophilic persistence, chemical resistance, and substrate adhesion.

Claims (9)

A urethane resin (A) having a silanol group and/or a hydrolyzable silyl group, a hydrophilic acrylic polymer (B) having a silanol group and/or a hydrolyzable silyl group, and an aqueous medium (C), and the hydrophilic acrylic polymer (B ), the content of the silanol group and/or the hydrolyzable silyl group is in the range of 0.5% by mass or more in the hydrophilic acrylic polymer (B). The method of claim 1,
The hydrophilic acrylic polymer (B) is an acrylic monomer (b1-1) having an amide group, an acrylic monomer (b1-2) having an oxyethylene group, and an acrylic monomer (b1-3) having a silanol group and/or a hydrolyzable silyl group. An aqueous resin composition which is a polymer of a hydrophilic acrylic monomer (b1) containing ). The method of claim 2,
The aqueous resin composition wherein the acrylic monomer (b1-1) having an amide group is represented by the following general formula (1) or the following general formula (2).

(R ¹ in General Formula (1) represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, R ² is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. , -(CH₂)₃-N(CH₃)₂, or the methyl chloride salt of (CH₂)₃-N(CH₃)₂)

(R ³ and R ⁴ in General Formula (2) each independently represent an alkylene group having 1 to 3 carbon atoms) The method of claim 2,
The aqueous resin composition in which the molar ratio of the acrylic monomer (b1-1) having an amide group and the acrylic monomer (b1-2) having an oxyethylene group is in the range of 99/1 to 50/50. The method of claim 1,
The aqueous resin composition wherein the content of the silanol group and/or the hydrolyzable silyl group in the hydrophilic acrylic polymer (B) is in the range of 0.5 to 10% by mass in the hydrophilic acrylic polymer (B). The method of claim 1,
The aqueous resin composition, wherein the urethane resin (A) contains an alicyclic structure in a range of 10 to 5000 mmol/kg. The method of claim 1,
The aqueous resin composition in which the content of the silanol group and/or the hydrolyzable silyl group contained in the urethane resin (A) is in the range of 0.1 to 5% by mass in the urethane resin (A). A coating agent comprising the aqueous resin composition according to any one of claims 1 to 7. An article comprising the coating film of the coating agent according to claim 8.