JP6544612B2 - Aqueous resin composition, coating agent and article - Google Patents

Description

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

  In general, the coating agent is required to be able to form a coating film capable of preventing the deterioration of the surface of various substrates, to be able to impart design to the surface of the substrate, and the like. In particular, in addition to hydrophilicity and adhesion to a substrate, a coating agent of a level capable of preventing deterioration of the substrate surface caused by the decrease in hydrophilicity due to adhesion of water stains, oil stains, chemicals such as detergents and acid rain In particular, a coating agent capable of forming a coating film having excellent hydrophilic durability is required from the industry. Coating agents having the above-mentioned properties are in increasing demand in the surface treatment applications of metal substrates including steel plates, glass substrates including mirrors, and plastic substrates which are said to be non-adhesive substrates.

  In addition to hydrophilicity, the coating agent is required to have a level of substrate followability capable of preventing peeling and cracking of a coating film generated when processing a metal substrate, and a high level of chemical resistance. Be Particularly in chemical resistance, in the steel industry where the coating film surface formed on the surface of a metal substrate is frequently washed using an alkaline cleaner etc., peeling or dissolution of the coating film due to the influence of the cleaning agent Is an important characteristic to prevent the deterioration of the metal base and the like.

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

  However, the hydrophilic particles have low adhesion to metal substrates, tend to be easily peeled off in wet conditions, and there have been cases where long-term use is difficult.

  Therefore, a coating agent that has both hydrophilic durability, chemical resistance, and substrate adhesion is required.

JP-A-8-3251

  The problem to be solved by the present invention is to provide an aqueous resin composition which is excellent in hydrophilic durability, chemical resistance and substrate adhesion and can form a coating film which can prevent deterioration of various substrates. .

  MEANS TO SOLVE THE PROBLEM As a result of earnestly researching that the present inventors should solve said subject, as a result of the urethane resin which has a silanol group and / or a hydrolysable silyl group, and the hydrophilic acrylic polymer which has a silanol group and / or a hydrolysable silyl group. A coating agent using an aqueous resin composition containing the present invention has been found to be capable of forming a coating film excellent in hydrophilic durability, chemical resistance and substrate adhesion, and completed the present invention.

  That is, according to the present invention, 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), an aqueous resin composition, a coating agent, and an article having a coating of the coating agent.

  The aqueous resin composition of the present invention can be used as a coating agent for surface protection of various substrates because it can form a coating film excellent in hydrophilic durability, chemical resistance and substrate adhesion. 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, electromagnetic steel plate, copper plate, stainless steel plate, various plastics and the like Film, glass, paper, wood and the like can be mentioned. In addition, the coating agent of the present invention can form a coating film excellent in hydrophilic durability and chemical resistance that can prevent deterioration of the surface of these substrates, and therefore aluminum fins, building members, home appliances, automobile exterior materials It can be used for various articles such as goggles, anti-fog film sheet, anti-fog glass, mirrors, medical instruments and the like.

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

  The urethane resin (A) having a silanol group and / or a hydrolyzable silyl group may be, for example, a urethane prepolymer having an isocyanate group at an end, at least one active hydrogen, and at least one silanol group and / or It can be obtained by reacting a compound having a hydrolyzable silyl group. Moreover, functional groups, such as a hydroxyl group, a carboxyl group, an epoxy group, a (meth) acryloyl group, are introduce | transduced with the urethane resin which does not have the said urethane prepolymer or isocyanate group, and it can also obtain by making a silane coupling agent react.

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

Examples of the polyol (a1) include polyether polyols, polyester polyols, polycarbonate polyols, and polyolefin polyols. Among these, polyester polyols are preferable because they can form a coating film having excellent substrate adhesion. These polyols (a1) can 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.

  As said polyether polyol which can be used for the said polyol (a1), what carried out addition polymerization of the alkylene oxide is mentioned, for example using 1 type, or 2 or more types of a compound which has 2 or more of active hydrogen atoms as an initiator. .

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6- Linear diols such as hexanediol; branched diols such as 1,3-butanediol and neopentyl glycol; triols such as glycerin, trimethylolethane, trimethylolpropane and pyrogallol; sugar alcohols such as sorbitol; sucrose, aconit Sugars such as sugars; tricarboxylic acids such as aconitic acid, trimellitic acid and hemimellitic acid; phosphoric acid; polyamines of ethylenediamine and diethylenetriamine sugars; triisopropanolamine; phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; , 3-propanetriol thiols.

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

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

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

  Examples of the polyester polyol include those obtained by esterifying a low molecular weight polyol and a polycarboxylic acid, polyesters obtained by ring-opening polymerization of a cyclic ester compound such as ε-caprolactone, and the like, and these copolymers Polyester etc. are mentioned.

  Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,3-butane having a molecular weight of about 50 to 300, for example. Aliphatic polyols such as diols; alicyclic structure-containing polyols such as cyclohexanedimethanol; bisphenol compounds such as bisphenol A and bisphenol F; and aromatic structure-containing polyols such as their alkylene oxide adducts.

  Moreover, as said polycarboxylic acid which can be used for manufacture of said polyester polyol, Aliphatic polycarboxylic acids, such as a succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, a terephthalic acid, an isophthalic acid, phthalic acid, naphthalene, for example Aromatic polycarboxylic acids such as dicarboxylic acids, and anhydrides or ester-forming derivatives thereof can be mentioned.

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

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

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

  Examples of the polyol that can react with the carbonic ester include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5. Relatively low molecular weight diols having a molecular weight of 50 to 2,000, such as pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, polyhexamethylene adipate, etc. Polyester polyol etc. are mentioned.

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

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

  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 can be used in combination in addition to those described above.

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

  As a polyol which has the said anionic group, the polyol which has a carboxyl group, the polyol which has a sulfonic acid group, etc. are mentioned, for example.

  As a polyol which has the said carboxyl group, 2, 2- dimethylol propionic acid, 2, 2- dimethylol butanoic acid, 2, 2- dimethylol butyric acid, 2, 2- dimethylol valeric acid etc. are mentioned, for example. Among these, 2,2-dimethylol propionic acid is preferable. In addition, polyester polyols having a carboxyl group obtained by reacting a polyol having a carboxyl group with various polycarboxylic acids can also be used.

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

  Examples of the polyol having a sulfonic acid group include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, and salts thereof; The polyester polyol obtained by making it react with the low molecular weight polyol illustrated as what can be used for manufacture of the polyester polyol which has a structure is mentioned.

  It is preferable to use the polyol having a carboxyl group or the polyol having a sulfonic acid group in a range in which the acid value of the urethane resin (A) is 2 to 70 mg KOH / g, and used in a range of 10 to 50 mg KOH / g It is more preferable to do. In addition, the acid value said by this invention is a theoretical value calculated based on the usage-amount of acidic radical containing compounds, such as a polyol which has a carboxyl group and a sulfonic acid group used for manufacture of the said urethane resin (A).

  The anionic group is preferably partially or entirely neutralized by a basic compound or the like in order to express 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 and hydroxide The metal hydroxide etc. which contain lithium etc. are mentioned. From the viewpoint of improving the water dispersion stability of the urethane resin composition, the basic compound is such that the basic group / anionic group of the basic compound is 0.5 to 3.0 (molar ratio). It is preferable to use, and it is more preferable to use in the range which becomes 0.8-2.0 (molar ratio).

  Moreover, as a polyol which has the said cationic group, the polyol etc. which have a tertiary amino group are mentioned, for example. Specific examples thereof include N-methyl-diethanolamine, and a polyol obtained by reacting a compound having two epoxy in one molecule with a secondary amine.

  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 or phosphoric acid Is preferred.

  Moreover, it is preferable that the tertiary amino group as said cationic group is quaternized in part or all. Examples of the quaternizing agent include dimethyl sulfate, diethyl sulfate, methyl chloride and ethyl chloride. Among these, it is preferable to use dimethyl sulfate.

  Moreover, it is preferable to use the polyol which has the said cationic group in the range which will be 2-50 mgKOH / g of the amine values of the said urethane resin (A), and the range of 5-30 mgKOH / g is more preferable. In addition, the amine value said by this invention is a theoretical value calculated based on the usage-amount of tertiary amino group containing compounds, such as a polyol which has a tertiary amino group used for manufacture of the said urethane resin (A).

  Moreover, as a polyol which has the said nonionic group, the polyol etc. which have a polyoxyethylene structure are mentioned, for example.

  It is preferable to use the polyol which has the said hydrophilic group in 0.3-10 mass% in whole quantity of the polyol (a1) used for manufacture of the said urethane resin (A).

  Moreover, as said polyol (a1), other polyols other than the above-mentioned polyol can be used as needed.

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

  Examples of the polyisocyanate (a2) capable of reacting with the polyol (a1) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, triene diisocyanate, Aromatic polyisocyanates such as naphthalene diisocyanate, xylylene diisocyanate and tetramethyl xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; and oils such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate Cyclic structure Such as polyisocyanates with. These polyisocyanates (a2) can be used alone or in combination of two or more.

  The urethane prepolymer (A) having an isocyanate group may be produced, for example, by mixing and reacting the polyol (a1) and the polyisocyanate (a2) in the absence of a solvent or in the presence of an organic solvent. it can.

  In the reaction of the polyol (a1) and the polyisocyanate (a2), the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group possessed by the polyisocyanate (a2) to the hydroxyl group possessed by the polyol (a1) is, for example, It is preferable to carry out in 0.9-3, and it is more preferable to carry out in 0.95-2.

  The reaction of the polyol (a1) with the polyisocyanate (a2) can be carried out usually at a temperature in the range of 50 to 150.degree.

  The isocyanate group equivalent of the urethane prepolymer (A) obtained by the reaction can form 3,500 to 100,000 g / eq. Is preferably 10,000 to 60,000 g / eq. Is more preferred.

  Examples of organic solvents 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; acetonitrile Nitrile solvents such as: Amide solvents such as dimethylformamide, N-methylpyrrolidone and the like. These organic solvents can be used alone or in combination of two or more.

  Further, the organic solvent is partially or entirely removed of the organic solvent, for example, by distillation under reduced pressure during or after the production of the urethane resin (A) in order to reduce the safety and the load on the environment. May be

  Examples of the compound having a silanol group and / or a hydrolyzable silyl group include γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-amino. Amino group-containing alkoxysilane compounds such as propyltrimethoxysilane and γ-aminopropyltriethoxysilane, hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane, γ-mercaptopropyltrimethoxy Mercapto-containing alkoxysilane compounds such as silane and γ-mercaptopropylmethyldimethoxysilane can be mentioned.

  As the urethane prepolymer having no isocyanate group, for example, the hydroxyl group of the polyol (a1) is designed in excess with respect to the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group of the polyisocyanate (a2). Examples thereof include urethane prepolymers which have been reacted and have hydroxyl groups remaining, and urethane prepolymers obtained by adding a chain extender to the urethane prepolymer (A). As the chain extender, polyamines, hydrazine compounds, other active hydrogen atom-containing compounds and the like can be used.

  As said polyamine, 1 type (s) or 2 or more types can be used, For example, ethylenediamine, 1, 2- propane diamine, 1, 6- hexamethylene diamine, piperazine, 2, 5- dimethyl piperazine, isophorone diamine, 4, 4'-Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, diamines such as 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxy Propylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like.

  As the hydrazine compound, one or more kinds can be used. For example, hydrazine, N, N'-dimethylhydrazine, 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.

  The other active hydrogen-containing compounds may be used alone or in combination of two or more, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1 2,4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerol, glycols such as sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, Hydrogenated bisphenol A, phenol such as hydroquinone, water and the like can be mentioned, and the aqueous resin composition of the present invention can also be used within the range in which the storage stability of the composition does not decrease.

  As the hydrolyzable silyl group, for example, it is preferable to use an alkoxysilyl group because the crosslinkability is high and the solvent resistance is improved. In particular, as the alkoxysilyl group, a trimethoxysilyl group and a triethoxysilyl group are preferable because they have excellent crosslinkability and improve the solvent resistance.

  Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. , Epoxy group-containing alkoxysilane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane , Isocyanato group-containing polymers such as γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane and the like Amino groups such as coxysilane compounds, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. Containing alkoxysilane compounds, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyl (Meth) acryloyl group-containing alkoxysilane compounds such as diethoxysilane, vinyltrimethoxysilane, vinyl group-containing alkoxysilanes such as vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, etc. Styryl group-containing alkoxysilane.

  Moreover, as said urethane resin (A), since it can form the coating film excellent in chemical resistance, it is preferable to use what has an alicyclic structure.

  As the alicyclic structure, for example, cyclobutyl ring, cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, cyclooctyl ring, propylcyclohexyl ring, tricyclo [5.2.1.0.2.6] decyl skeleton, 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, Examples include adamantyl skeleton and the like. Among these, a cyclohexyl ring structure is preferable.

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

  The said alicyclic structure is an alicyclic structure derived from polyisocyanate which has an alicyclic structure which can be used as polyisocyanate (a2) used when manufacturing the said urethane resin (A). Although it is preferable that all of them are derived from a polyisocyanate having an alicyclic structure, some or all of them are derived from an alicyclic structure-containing polyol such as cyclohexanedimethanol, Also good.

  In the present invention, the ratio of the alicyclic structure contained in the urethane resin (A) to the entire urethane resin (A) is the polyol (a1) used for the production of the urethane resin (A). And a value calculated based on the total mass of all the raw materials such as polyisocyanate (a2) and the substance of the alicyclic structure possessed by the alicyclic structure-containing compound used for the production of the urethane resin (A).

  The hydrophilic persistence and chemical resistance that the content of the silanol group and / or the hydrolyzable silyl group which the urethane resin (A) has is in the range of 0.1 to 5% by mass in the urethane resin (A) It is preferable from the ability to form the coating film excellent in property and base-material adhesiveness, and the range of 1-3 mass% is more preferable.

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

  In addition, the "hydrophilicity" of the said hydrophilic acrylic polymer (B) shows affinity with water, and, specifically, the solubility to 100 g of water (20 degreeC) is preferable. Represents a substance having a content of 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more.

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

  As the hydrophilic acrylic monomer (b1), if necessary, an acrylic monomer (b1-1) having the above-mentioned amide group, an acrylic monomer (b1-2) having the above-mentioned oxyethylene group, and the above-mentioned silanol group and Other acrylic monomers can be used other than the acrylic monomer (b1-3) having a group having a hydrolyzable silyl group.

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

(In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ² is an alkyl group having 1 to 3 carbon atoms,-(CH ₂ ) _3- Represents a methyl chloride salt of N (CH ₃ ) ₂ or (CH ₂ ) ₃ -N (CH ₃ ) ₂ )

  Examples of the compound represented by the above general formula (1) include N-hydroxyethyl acrylamide, N-methylol acrylamide, N-methoxyethyl acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N, N -Dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl acrylamide, a methyl chloride salt of N, N-dimethylaminopropyl acrylamide, N-isopropyl acrylamide and the like. These monomers may be used alone or in combination of two or more.

  Moreover, as an acryl monomer (b1-1) which has the said amide group, the compound represented by following General formula (2) can be used, for example.

(R ³ and R ⁴ in the general formula (2) represent an alkylene group having 1 to 3 carbon atoms.)

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

  Examples of the acrylic monomer (b1-2) having an oxyethylene group include polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol polypropylene glycol copolymer (meth) acrylate, and methoxy polyethylene glycol polypropylene glycol Polymerized (meth) acrylates, polyethylene glycol polytetramethylene glycol copolymerized (meth) acrylates, methoxypolyethylene glycol polytetramethylene glycol copolymerized (meth) acrylates, etc. may be mentioned. These monomers may be used alone or in combination of two or more.

  Examples of the acrylic monomer (b1-3) having a silanol group and / or a hydrolyzable silyl group include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, and γ -(Meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, etc. Be These monomers may be used alone or in combination of two or more.

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

  The ratio ((b1-1) / (b1-2)) between the unit derived from the acryl monomer (b1-1) having an amide group and the unit derived from the acryl monomer (b1-2) having an oxyethylene group is From the viewpoint of maintaining hydrophilicity and hydrophilic persistence at a high level, preferably from 99/1 to 50/50, more preferably 90/10 on a molar basis. It is above 70/30.

  Examples of the other acrylic monomers include acrylic monomers having a sulfonic acid group, acrylic monomers having a quaternary ammonium group, acrylic monomers having a carboxyl group, acrylic monomers having an amino group, acrylic monomers having a cyano group, and hydroxyl groups. And acrylic monomers having an imide group, acrylic monomers having a methoxy group, and the like.

  Examples of the acrylic monomer having a sulfonic acid group include sodium sulfopropyl (meth) acrylate, sodium 2-sulfoethyl (meth) acrylate, sodium 2-acrylamido-2-methylpropane sulfonate 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 tetrabutyl ammonium (meth) acrylate and trimethylbenzyl ammonium (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.

  Examples of the acrylic monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate, (meth) acryloxyethyl trimethyl ammonium chloride and the like. It can be mentioned. These monomers may be used alone or in combination of two or more.

  Examples of the acrylic monomer having a cyano group include acrylonitrile, cyanomethyl acrylate, 2-cyanoethyl acrylate, cyanopropyl acrylate, 1-cyanomethyl ethyl acrylate, 2-cyanopropyl acrylate, 1-cyanocyclopropyl acrylate, and 1-cyano. Examples include cycloheptyl acrylate, 1,1-dicyanoethyl acrylate, 2-cyanophenyl acrylate, 3-cyanophenyl acrylate, 4-cyanophenyl acrylate, 3-cyanobenzyl acrylate, 4-cyanobenzyl acrylate and the like. 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 ( Meta) 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) acrylic imide, N-methylol maleimide, N-hydroxyethyl maleimide, N-glycidyl maleimide, N-4-chloromethyl phenyl maleimide, N-acetoxyethyl maleimide and the like. It can be 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-methoxybutyl (meth) acrylate and the like It can be mentioned. These monomers may be used alone or in combination of two or more.

  A total of the acrylic monomer (b1-1) having the amide group, the acrylic monomer (b1-2) having the oxyethylene group, and the acrylic monomer (b1-3) having the silanol group and / or the hydrolyzable silyl group The amount is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the hydrophilic acrylic monomer (b1).

  As a polymerization ratio (molar ratio) of the acrylic monomer (b1-1) having an amide group and the acrylic monomer (b1-2) having an oxyethylene group, it is possible to maintain hydrophilicity and hydrophilic persistence at a high level It is preferably in the range of 99/1 to 50/50, and more preferably in the range of 90/10 to 70/30 from the viewpoint of obtaining even more excellent hydrophilic durability.

  The average addition mole number of the oxyethylene group of the acrylic monomer (b1-2) having an oxyethylene group is preferably in the range of 5 to 13 moles, and preferably 8 to 10 moles, from the viewpoint of hydrophilicity maintenance. More preferably, it is in the range of

  When manufacturing the said hydrophilic acryl polymer (B), you may use together radically polymerizable monomers other than the said hydrophilic acryl monomer (b1) as needed.

  Examples of the radical polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate and isobutyl (for example, Meta) acrylate, 2-ethylbutyl (meth) acrylate, n-pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (nonyl (meth) acrylate Meta) acrylate, dodecyl (meth) acrylate, 3-methylbutyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl Aliphatic (meth) acrylates such as (meth) acrylate, isostearyl (meth) acrylate, neopentyl (meth) acrylate, hexadecyl (meth) acrylate and isoamyl (meth) acrylate; isoboronyl (meth) acrylate, cyclohexyl (meth) acrylate, Alicyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, etc. Examples thereof include 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.

  The content of the silanol group and / or the hydrolyzable silyl group which the hydrophilic acrylic resin (B) has is in the range of 0.1 to 10% by mass in the acrylic resin (B). It is preferable from the ability to form the coating film excellent in base-material adhesiveness, the range of 0.2-5 mass% is more preferable, and the range of 0.5-3 mass% is further more preferable.

  As a method for producing the hydrophilic acrylic polymer (B), known radical polymerization can be used, and for example, the hydrophilic acrylic monomer (b1), a polymerization initiator, water and / or an organic solvent, and The method of mixing and stirring the said radically polymerizable monomer, for example under the temperature of the range of 40-90 degreeC as needed, for example, and making a radical polymerization advance in 1 to 10 hours is mentioned.

  Examples of the polymerization initiator include peroxides such as hydrogen peroxide, potassium persulfate, sodium persulfate and ammonium persulfate; benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, cumene hydroperoxide Organic peroxides such as: 2,2'-azobis- (2-aminodipropane) dihydrochloride, 2,2'-azobis- (N, N'-dimethylene isobutylamidine) dihydrochloride, azobisiso Examples include azo compounds such as butyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis (2,4-dimethylvaleric acid nitrile). These polymerization initiators can 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 that is the raw material of the hydrophilic acrylic polymer (B).

  Examples of the organic solvent include methanol, ethanol, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, hexane, acetone, cyclohexanone, 3-pentanone, acetonitrile, isopropyl alcohol, 1,1 Examples thereof include 2-propanediol, 1,3-butanediol and the like. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is, for example, in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the monomer as a raw material of 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 in the range of 15,000 to 50,000, from the viewpoint of affinity with the polyurethane (A). It is more preferable that In addition, the weight average molecular weight of the said hydrophilic acrylic polymer (B) shows the value obtained by measuring on condition of the following by 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 used in series connection.
"TSKgel G5000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 4000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 3000" (7.8 mm ID × 30 cm) × 1 This "TSKgel G2000" (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection 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)
Tosoh Corporation "TSKgel standard polystyrene A-500"
Tosoh Corporation "TSKgel standard polystyrene A-1000"
Tosoh Corporation "TSKgel standard polystyrene A-2500"
Tosoh Corporation "TSKgel standard polystyrene A-5000"
Tosoh Corporation "TSKgel standard polystyrene F-1"
Tosoh Corporation "TSKgel standard polystyrene F-2"
Tosoh Corporation "TSKgel standard polystyrene F-4"
Tosoh Corporation "TSKgel standard polystyrene F-10"
Tosoh Corporation "TSKgel standard polystyrene F-20"
Tosoh Corporation "TSKgel standard polystyrene F-40"
Tosoh Corporation "TSKgel standard polystyrene F-80"
Tosoh Corporation "TSKgel standard polystyrene F-128"
Tosoh Corporation "TSKgel standard polystyrene F-288"
Tosoh Corporation "TSKgel standard polystyrene F-550"

  Examples of the aqueous medium (C) include water, an organic solvent miscible with water, and a mixture 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; 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 n-butyl ether, tripropylene glycol methyl ether, etc. Glycol ether solvent; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone Lactam solvent; N, an amide solvent such as N- dimethylformamide. These organic solvents miscible with water can be used alone or in combination of two or more.

  The aqueous medium (C) is preferably water alone or a mixture of water and an organic solvent miscible with water, and more preferably only water, in consideration of safety and reduction of environmental load.

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

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

  By using the said crosslinking agent, durability of the coating film of the aqueous | water-based resin composition of this invention can be improved more. As said crosslinking agent, 1 or more types of thing selected from the group which consists of an amino resin, an aziridine compound, a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and an isocyanate compound can be used, for example.

  Moreover, the dispersion stability of the aqueous resin composition of the present invention can be further improved by using the surfactant. When a surfactant is used, it can be used in a range of 20 parts by mass or less with respect to 100 parts by mass of the urethane resin (A) because it can maintain the substrate adhesion and water resistance of the obtained coating film. Preferably, it is preferable not to use as much as possible.

  In the aqueous resin composition of the present invention, a curing agent and a curing catalyst may be used in combination as needed, as long as the effects of the present invention are not impaired.

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

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

  Among them, one or more selected from the group consisting of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are used. It is preferable because the crosslink density of the coating film is improved and the corrosion resistance, water resistance and substrate adhesion become good.

  The compound having a silanol group and / or a hydrolyzable silyl group forms a coating film excellent in chemical resistance, and a urethane resin for obtaining the aqueous urethane resin composition of the present invention excellent in storage stability. It is preferable to use in 0.01 mass%-10 mass% with respect to whole quantity of (A).

  Moreover, as a curing catalyst usable for 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 dilaurate, Di-n-butyltin maleate, p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid, dialkyl phosphorous acid and the like can be used.

  In addition, the aqueous resin composition of the present invention may optionally contain an emulsifying agent, a dispersion stabilizer and a leveling agent, but from the viewpoint of suppressing the decrease in water resistance of the crosslinked coating film, it may not be contained as much as possible. It is preferable that it is 0.5 mass% or less with respect to solid content of the said aqueous resin composition.

  Thus, the aqueous resin composition of this invention can be used for the coating agent for the purpose of surface protection of various base materials, and the designability provision to various base materials.

  As said base material, a metal, various plastics, its film, glass, paper, wood etc. are mentioned, for example.

  Examples of the metal substrate include galvanized steel plates, aluminum-galvanized steel plates, aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, stainless steel plates and the like used for applications such as automobiles, home appliances and building materials.

  As a plastic base material, acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC resin) is generally used as a material adopted for plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, OA equipment, etc. And ABS / PC resin, polystyrene resin (PS resin), polymethyl methacrylate resin (PMMA resin), acrylic resin, polypropylene resin, polyethylene resin, etc. As the plastic film substrate, polyethylene terephthalate film, polyester film, A polyethylene film, a polypropylene film, a TAC (triacetyl cellulose) film, a polycarbonate film, a polyvinyl chloride film, etc. can be used.

  The aqueous resin composition of the present invention can form a coating film excellent in chemical resistance including acid resistance, alkali resistance and the like even when the cross-linked coating film has a thickness of about 5 μm. In addition, even if the crosslinked coating film has a thickness of about 1 μm, a coating film excellent in 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.

  In the drying step, when water and an organic solvent having a boiling point higher than water are used in combination as the aqueous medium (C), the water in the aqueous resin composition is volatilized, and then the organic solvent is volatilized. After volatilization of water, it consists of an organic solvent, a urethane resin (A) and a hydrophilic acrylic resin (B), and the organic solvent promotes fusion of the urethane resin (A) and the hydrophilic acrylic resin (B). Thus, a good coating film free of coating film defects 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 natural drying at normal temperature, but may be heat drying. It is preferable to perform heat drying normally at 40-250 degreeC for about 1 to 600 second time.

  In the case where the substrate is a material which is easily deformed by heat, such as a plastic substrate or the like, the drying temperature of the coating film is preferably adjusted to about 80 ° C. or less.

  As an article which has a coating film of a coating agent using the aqueous resin composition of the present invention, for example, aluminum fins, building members, home appliances, automobile exterior materials, goggles, antifogging film sheets, antifogging glass, mirrors, medical Instruments and the like can be mentioned.

Synthesis Example 1: Synthesis of Polyol (1) Having a Tertiary Amino Group
After charging 543 parts by mass of polyethylene glycol diglycidyl ether (epoxy equivalent 185 g / equivalent) into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, the inside of the flask was purged with nitrogen. Then, after heating using an oil bath until the temperature in the flask reaches 70 ° C., 380 parts by mass of di-n-butylamine is dropped over 30 minutes using a dropping device, and after completion of dropping, it is at 90 ° C. It was allowed to react for 10 hours. After completion of the reaction, using an infrared spectrophotometer ("FT / IR-460Plus" manufactured by JASCO Corporation), the disappearance of the absorption peak near 842 cm ^-1 attributed to the epoxy group of the reaction product It confirmed, and prepared polyol (1) (amine equivalent 315g / equivalent, hydroxyl equivalent 315g / equivalent.) Which has a tertiary amino group.

Preparation Example 1 Preparation of Urethane Resin (A-1) Aqueous Dispersion
Polycarbonate polyol (hydroxyl value 56.1 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol is charged into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, and depressurized. Dehydration was carried out at 120 to 130 ° C. at a degree of 0.095 MPa. After dehydration, the mixture was cooled to 70 ° C., 154 parts by mass of methyl ethyl ketone was added, and the mixture was thoroughly mixed while being cooled to 50 ° C. 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 octoate 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 is added, reacted for 4 hours, cooled to 55 ° C., and γ-aminopropyltriethoxysilane (Shin-Etsu Co., Ltd. After 12 parts by mass of “KBE-903” (manufactured by Chemical Industry Co., Ltd.) were added and reacted for 1 hour, 211 parts by mass of methyl ethyl ketone were added to prepare a urethane prepolymer solution having a terminal isocyanate group. Subsequently, 5 mass parts of 80 mass% hydrazine hydrate was added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

  Subsequently, 6 mass parts of 89 mass% phosphoric acid aqueous solution was added, and after maintaining at 45 degreeC for 1 hour, it cooled to 40 degreeC and prepared the aqueous dispersion by adding 1089 mass parts of ion-exchange water. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous dispersion of urethane resin (A-1) having a nonvolatile content of 30% by mass. The ratio of the alicyclic structure per solid content of the urethane resin (A-1) water dispersion is 1436 mmol / kg, and the content of the alkoxysilyl group in the urethane resin (A-1) is 2.34. It was mass%.

Preparation Example 2 Preparation of Urethane Resin (A-2) Water Dispersion
Polycarbonate polyol (hydroxyl value 56.1 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol is charged into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, and depressurized. Dehydration was carried out at 120 to 130 ° C. at a degree of 0.095 MPa. After dehydration, the mixture was cooled to 70 ° C., 143 parts by mass of methyl ethyl ketone was added, and the mixture was sufficiently stirred and mixed while cooling to 50 ° C. After stirring and mixing, 44 parts by mass of hexamethylene diisocyanate and 0.1 parts by mass of stannous octoate 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 is added, reacted for 4 hours, cooled to 55 ° C., γ-aminopropyltriethoxysilane (Shin-Etsu (Shin-Etsu Co., Ltd.) After 12 parts by mass of “KBE-903” (manufactured by Chemical Industry Co., Ltd.) were added and reacted for 1 hour, 196 parts by mass of methyl ethyl ketone were added to prepare a urethane prepolymer solution having terminal isocyanate groups. Subsequently, 5 mass parts of 80 mass% hydrazine hydrate was added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

  Subsequently, 5 mass parts of 89 mass% phosphoric acid aqueous solution was added, and after maintaining at 45 degreeC for 1 hour, it cooled to 40 degreeC and prepared the aqueous dispersion by adding 1012 mass parts of ion-exchange water. The water dispersion was distilled under reduced pressure to obtain a water 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 urethane resin (A-2) water dispersion is 0 mmol / kg, and the content of the alkoxysilyl group in the urethane resin (A-2) is 2.52 It was mass%.

Preparation Example 3 Preparation of Urethane Resin (A-3) Water Dispersion
Polycarbonate polyol (hydroxyl value 56.1 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol is charged into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, and depressurized. Dehydration was carried out at 120 to 130 ° C. at a degree of 0.095 MPa. After dehydration, the mixture was cooled to 70 ° C., 162 parts by mass of methyl ethyl ketone was added, and the mixture was sufficiently stirred and mixed while cooling to 50 ° C. 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 octoate 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 is added, reacted for 4 hours, cooled to 55 ° C., and γ-aminopropyltriethoxysilane (Shin-Etsu Co., Ltd. After 29 parts by mass of "KBE-903" (manufactured by Chemical Industry Co., Ltd.) were added and reacted for 1 hour, 218 parts by mass of methyl ethyl ketone were added to prepare a urethane prepolymer solution having a terminal isocyanate group. Subsequently, 2 mass parts of 80 mass% hydrazine hydrate was added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

  Subsequently, 6 mass parts of 89 mass% phosphoric acid aqueous solution was added, and after maintaining at 45 degreeC for 1 hour, it cooled to 40 degreeC and prepared the water dispersion by adding 1134 mass parts of ion-exchange water. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous dispersion of urethane resin (A-3) having a nonvolatile content of 30% by mass. The ratio of the alicyclic structure per solid content of the urethane resin (A-3) water dispersion is 1376 mmol / kg, and the content of the alkoxysilyl group in the urethane resin (A-3) is 5.63. It was mass%.

Preparation Example 4 Preparation of Urethane Resin (A-4) Water Dispersion
Polycarbonate polyol (hydroxyl value 56.1 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol is charged into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, and depressurized. Dehydration was carried out at 120 to 130 ° C. at a degree of 0.095 MPa. After dehydration, the mixture was cooled to 70 ° C., 382 parts by mass of methyl ethyl ketone was added, and the mixture was thoroughly mixed while being cooled to 50 ° C. 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 octoate are added, The reaction was carried out at 70 ° C. for 2 hours.

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

  Subsequently, 14 mass parts of 89 mass% phosphoric acid aqueous solution was added, and after maintaining at 45 degreeC for 1 hour, it cooled to 40 degreeC and prepared the water dispersion by adding 2795 mass parts of ion-exchange water. The water dispersion was distilled under reduced pressure to obtain a water 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 urethane resin (A-4) water dispersion is 4442 mmol / kg, and the content of the alkoxysilyl group in the urethane resin (A-4) is 2.39. It was mass%.

Preparation Example 5 Preparation of Urethane Resin (A-5) Water Dispersion
Polycarbonate polyol (hydroxyl value 56.1 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol is charged into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, and depressurized. Dehydration was carried out at 120 to 130 ° C. at a degree of 0.095 MPa. After dehydration, the mixture was cooled to 70 ° C., 612 parts by mass of methyl ethyl ketone was added, and the mixture was thoroughly mixed while being cooled to 50 ° C. 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 octoate are added, The reaction was carried out at 70 ° 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 is added, reacted for 4 hours, cooled to 55 ° C., γ-aminopropyltriethoxysilane (Shin-Etsu (Shin-Etsu Co., Ltd.) After 56 parts by mass of “KBE-903” (manufactured by Chemical Industry Co., Ltd.) were added and reacted for 1 hour, 901 parts by mass of methyl ethyl ketone were added to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 85 parts by mass of 80% by mass hydrazine hydrate was added to the urethane prepolymer solution, and a chain elongation reaction was performed for 1 hour.

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

Preparation Example 6 Preparation of Urethane Resin (A-6) Water Dispersion
Polycarbonate polyol (hydroxyl value 56.1 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol is charged into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, and depressurized. Dehydration was carried out at 120 to 130 ° C. at a degree of 0.095 MPa. After dehydration, the mixture was cooled to 70 ° C., 149 parts by mass of methyl ethyl ketone was added, and the mixture was sufficiently stirred and mixed while cooling to 50 ° C. 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 octoate 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 is added, reacted for 4 hours, cooled to 55 ° C., and γ-aminopropyltriethoxysilane (Shin-Etsu Co., Ltd. After 1 part by mass of “KBE-903” manufactured by Chemical Industry Co., Ltd. was added and reacted for 1 hour, 206 parts by mass of methyl ethyl ketone was added to prepare a urethane prepolymer solution having terminal isocyanate group. Subsequently, 7 mass parts of 80 mass% hydrazine hydrate was added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

  Subsequently, 6 mass parts of 89 mass% phosphoric acid aqueous solution was added, and after maintaining at 45 degreeC for 1 hour, it cooled to 40 degreeC and prepared the aqueous dispersion by adding 1061 mass parts of ion-exchange water. The water dispersion was distilled under reduced pressure to obtain a water 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 urethane resin (A-6) water dispersion is 1474 mmol / kg, and the content of the alkoxysilyl group in the urethane resin (A-6) is 0.12 It was mass%.

(Comparative Preparation Example 1: Preparation of Urethane Resin (A'-1) Water Dispersion)
Polycarbonate polyol (hydroxyl value 56.1 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol is charged into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, and depressurized. Dehydration was carried out at 120 to 130 ° C. at a degree of 0.095 MPa. After dehydration, the mixture was cooled to 70 ° C., 149 parts by mass of methyl ethyl ketone was added, and the mixture was thoroughly mixed while being cooled to 50 ° C. 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 octoate 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 is added, reacted for 4 hours, cooled, and 206 parts by mass of methyl ethyl ketone is added to obtain terminal isocyanate group The urethane prepolymer solution was prepared. Subsequently, 7 mass parts of 80 mass% hydrazine hydrate was added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

  Subsequently, 6 mass parts of 89 mass% phosphoric acid aqueous solution was added, and after maintaining at 45 degreeC for 1 hour, it cooled to 40 degreeC and prepared the aqueous dispersion by adding 1059 mass parts of ion-exchange water. The water dispersion was distilled under reduced pressure to obtain a water 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 urethane resin (A'-1) water dispersion is 1476 mmol / kg, and the content of the alkoxysilyl group in the urethane resin (A'-1) is 0. It was mass%.

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

Preparation Example 7 Preparation of Hydrophilic Acrylic Polymer (B-1)
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, 30 parts by mass of isopropyl alcohol is charged, and then N, N-dimethylacrylamide / methoxypolyethylene glycol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 100 parts by mass of a mixture of “AM-90G”, average added mole number of oxyethylene group is 9 mol) = 85/15 (molar ratio), and 2 parts by mass of γ-methacryloxypropyltriethoxysilane in 51 parts of isopropyl alcohol The solution diluted in 1 part and 20 parts by mass of 0.5% by mass isopropyl alcohol solution (azo-based polymerization initiator "V-59" manufactured by Wako Pure Chemical Industries, Ltd.) are dropped in a reactor at 80 ° C for 4 hours. And radical polymerization were performed to obtain a hydrophilic acrylic polymer (B-1). The weight average molecular weight of the obtained hydrophilic acrylic polymer (B-1) was 20,000, and the nonvolatile content was 50% by mass. Moreover, content of the alkoxy silyl group in this hydrophilic acryl polymer (B-1) was 1.1 mass%.

Preparation Example 8 Preparation of Hydrophilic Acrylic Polymer (B-2)
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, 30 parts by mass of isopropyl alcohol is charged, and then N, N-dimethylacrylamide / methoxypolyethylene glycol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 100 parts by mass of a mixture of “AM-90G”, average addition mole number of oxyethylene group is 9 mol) = 45/55 (molar ratio), and 2 parts by mass of γ-methacryloxypropyltriethoxysilane in 51 parts of isopropyl alcohol The solution diluted in 1 part and 20 parts by mass of 0.5% by mass isopropyl alcohol solution (azo-based polymerization initiator "V-59" manufactured by Wako Pure Chemical Industries, Ltd.) are dropped in a reactor at 80 ° C for 4 hours. And radical polymerization were performed to obtain a hydrophilic acrylic polymer (B-2). The weight average molecular weight of the obtained hydrophilic acrylic polymer (B-2) was 20,000, and the nonvolatile content was 50% by mass. Moreover, content of the alkoxy silyl group in this hydrophilic acryl polymer (B-2) was 1.1 mass%.

Preparation Example 9 Preparation of Hydrophilic Acrylic Polymer (B-3)
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, 30 parts by mass of isopropyl alcohol is charged, and then N, N-dimethylacrylamide / methoxypolyethylene glycol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 100 parts by weight of a mixture of “AM-90G”, average added mole number of oxyethylene group is 9 moles) = 85/15 (mole ratio), and 25 parts by weight of γ-methacryloxypropyltriethoxysilane, 63 parts by weight of isopropyl alcohol The solution diluted in 1 part and 20 parts by mass of 0.5% by mass isopropyl alcohol solution (azo-based polymerization initiator "V-59" manufactured by Wako Pure Chemical Industries, Ltd.) are dropped in a reactor at 80 ° C for 4 hours. And radical polymerization were performed to obtain a hydrophilic acrylic polymer (B-3). The weight average molecular weight of the obtained hydrophilic acrylic polymer (B-3) was 20,000, and the nonvolatile content was 50% by mass. Moreover, content of the alkoxy silyl group in this hydrophilic acryl polymer (B-3) was 11.24 mass%.

Preparation Example 10 Preparation of Hydrophilic Acrylic Polymer (B-4)
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, 30 parts by mass of isopropyl alcohol is charged, and then N, N-dimethylacrylamide / methoxypolyethylene glycol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 100 parts by mass of a mixture of “AM-90G”, average added mole number of oxyethylene group is 9 mol) = 85/15 (molar ratio), and 17 parts by mass of γ-methacryloxypropyltriethoxysilane in 59 parts of isopropyl alcohol The solution diluted in 1 part and 20 parts by mass of 0.5% by mass isopropyl alcohol solution (azo-based polymerization initiator "V-59" manufactured by Wako Pure Chemical Industries, Ltd.) are dropped in a reactor at 80 ° C for 4 hours. And radical polymerization were performed to obtain a hydrophilic acrylic polymer (B-4). The weight average molecular weight of the obtained hydrophilic acrylic polymer (B-4) was 20,000, and the nonvolatile content was 50% by mass. Moreover, content of the alkoxy silyl group in this hydrophilic acryl polymer (B-4) was 8.16 mass%.

Preparation Example 11 Preparation of Hydrophilic Acrylic Polymer (B-5)
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, 30 parts by mass of isopropyl alcohol is charged, and then N, N-dimethylacrylamide / methoxypolyethylene glycol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 100 parts by mass of a mixture of “AM-90G”, average addition mole number of oxyethylene group is 9 mol) = 95/5 (molar ratio), and 2 parts by mass of γ-methacryloxypropyltriethoxysilane in 51 parts of isopropyl alcohol The solution diluted in 1 part and 20 parts by mass of 0.5% by mass isopropyl alcohol solution (azo-based polymerization initiator "V-59" manufactured by Wako Pure Chemical Industries, Ltd.) are dropped in a reactor at 80 ° C for 4 hours. And radical polymerization were performed to obtain a hydrophilic acrylic polymer (B-5). The weight average molecular weight of the obtained hydrophilic acrylic polymer (B-5) was 20,000, and the nonvolatile content was 50% by mass. Moreover, content of the alkoxy silyl group in this hydrophilic acryl polymer (B-5) was 1.1 mass%.

Comparative Preparation Example 2: Preparation of Hydrophilic Acrylic Polymer (B'-1)
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, 30 parts by mass of isopropyl alcohol is charged, and then N, N-dimethylacrylamide / methoxypolyethylene glycol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) A solution obtained by diluting 100 parts by mass of a mixture of “AM-90G”, and the average added mole number of oxyethylene group is 9 moles) = 85/15 (molar ratio) with 50 parts by mass of isopropyl alcohol, and Wako Pure Chemical Industries, Ltd. 20 parts by mass of a 0.5 mass% isopropyl alcohol solution of the azo polymerization initiator "V-59" is dropped in a reaction apparatus at 80 ° C for 4 hours, and radical polymerization is performed to obtain a hydrophilic acrylic polymer (B'- I got 1). The weight average molecular weight of the obtained hydrophilic acrylic polymer (B'-1) was 20,000, and the nonvolatile content was 50% by mass. Moreover, content of the alkoxy silyl group in this hydrophilic acryl 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 hydrophilicity obtained in Preparation Examples 7 to 11 and Comparative Preparation Example 2 The content of the alkoxysilyl group of the acrylic polymer is shown in Table 2.

The abbreviations in Table 2 will be described.
“DMAA”; N, N-dimethyl acrylamide “AM-90G”; methoxypolyethylene glycol acrylate (“AM-90G” manufactured by Shin-Nakamura Chemical Co., Ltd.)

Example 1 Preparation of Aqueous Resin Composition (1)
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 240 parts by mass of the urethane resin (A-1) water dispersion having a nonvolatile content of 30% by mass obtained in Preparation Example 1 (nonvolatile content: 60 parts by weight of the hydrophilic acrylic polymer (B-1) having a nonvolatile content of 50% by mass and 72 parts by mass) obtained in Preparation Example 7 (nonvolatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol and 1 An aqueous dispersion was obtained by adding 30 parts by mass of 3-butylene glycol and 30 parts by mass of ion exchange water. The 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 four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 240 parts by mass of the urethane resin (A-1) water dispersion having a nonvolatile content of 30% by mass obtained in Preparation Example 1 (nonvolatile content: 60 parts by weight of the hydrophilic acrylic polymer (B-2) having a nonvolatile content of 50% by mass obtained in Preparation Example 8) and Preparation Example 8 (nonvolatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol and 1 An aqueous dispersion was obtained by adding 30 parts by mass of 3-butylene glycol and 30 parts by mass of ion exchange water. The 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)
Preparation with 240 parts by mass (nonvolatile matter: 72 parts by mass) of the urethane resin (A-1) water dispersion obtained in Preparation Example 1 in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device 60 parts by mass (nonvolatile matter: 30 parts by mass) of 50 parts by mass of a hydrophilic acrylic polymer (B-3) obtained in Example 9 (nonvolatile matter: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol and 1,3-butylene glycol 30 A mass part and 30 mass parts of ion exchange water were added to obtain an aqueous dispersion. The 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)
Preparation with 240 parts by mass (nonvolatile matter: 72 parts by mass) of the urethane resin (A-1) water dispersion obtained in Preparation Example 1 in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device 60 parts by mass (nonvolatile matter: 30 parts by mass) of a 50% by mass hydrophilic acrylic polymer (B-4) obtained in Example 10, 30 parts by mass of 1,2-propylene glycol, and 30 parts by weight of 1,3-butylene glycol A mass part and 30 mass parts of ion exchange water were added to obtain an aqueous dispersion. The 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)
Preparation with 240 parts by mass (nonvolatile matter: 72 parts by mass) of the urethane resin (A-1) water dispersion obtained in Preparation Example 1 in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device 60 parts by mass of the hydrophilic acrylic polymer (B-5) having a nonvolatile content of 50% by mass obtained in Example 11 (nonvolatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol, and 30 parts by mass of 1,3-butylene glycol A mass part and 30 mass parts of ion exchange water were added to obtain an aqueous dispersion. The 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-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 240 parts by mass of the urethane resin (A-2) water dispersion having a nonvolatile content of 30% by mass obtained in Preparation Example 2 (nonvolatile content: 60 parts by weight of the hydrophilic acrylic polymer (B-1) having a nonvolatile content of 50% by mass and 72 parts by mass) obtained in Preparation Example 7 (nonvolatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol and 1 An aqueous dispersion was obtained by adding 30 parts by mass of 3-butylene glycol and 30 parts by mass of ion exchange water. The 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-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 240 parts by mass of the urethane resin (A-3) water dispersion having a nonvolatile content of 39% by mass obtained in Preparation Example 3 (nonvolatile content: 60 parts by weight of the hydrophilic acrylic polymer (B-1) having a nonvolatile content of 50% by mass and 72 parts by mass) obtained in Preparation Example 7 (nonvolatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol and 1 An aqueous dispersion was obtained by adding 30 parts by mass of 3-butylene glycol and 30 parts by mass of ion exchange water. The 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)
Preparation with 240 parts by mass (nonvolatile matter: 72 parts by mass) of the urethane resin (A-4) water dispersion obtained in Preparation Example 4 in a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping unit 60 parts by mass of the hydrophilic acrylic polymer (B-1) having a nonvolatile content of 50% by mass obtained in Example 7 (nonvolatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol, and 30 parts by mass of 1,3-butylene glycol A mass part and 30 mass parts of ion exchange water were added to obtain an aqueous dispersion. The 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 4-neck flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 240 parts by mass (nonvolatile matter: 72 parts by mass) of the urethane resin (A-5) water dispersion obtained in Preparation Example 5 was prepared 60 parts by mass of the hydrophilic acrylic polymer (B-1) having a nonvolatile content of 50% by mass obtained in Example 7 (nonvolatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol, and 30 parts by mass of 1,3-butylene glycol A mass part and 30 mass parts of ion exchange water were added to obtain an aqueous dispersion. The 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-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, 240 parts by mass (nonvolatile matter: 72 parts by mass) of the urethane resin (A-6) water dispersion obtained in Preparation Example 6 was prepared 60 parts by mass of the hydrophilic acrylic polymer (B-1) having a nonvolatile content of 50% by mass obtained in Example 7 (nonvolatile content: 30 parts by mass), 30 parts by mass of 1,2-propylene glycol, and 30 parts by mass of 1,3-butylene glycol A mass part and 30 mass parts of ion exchange water were added to obtain an aqueous dispersion. The 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 four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 240 parts by mass of the urethane resin (A-1) water dispersion having a nonvolatile content of 30% by mass obtained in Preparation Example 1 (nonvolatile content: 60 parts by weight of a hydrophilic acrylic polymer (B'-1) having a nonvolatile content of 50% by mass and 72 parts by mass) obtained in Comparative Preparation Example 2 (nonvolatile content: 30 parts by mass) and 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 exchange water were added to obtain an aqueous dispersion. The 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-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 240 parts by mass of the urethane resin (A'-1) water dispersion having a nonvolatile content of 30 mass% obtained in Comparative Preparation Example 1 (nonvolatile 60 parts by weight of the hydrophilic acrylic polymer (B-1) having a nonvolatile content of 50 parts by mass obtained in Preparation Example 7 with 72 parts by mass) (nonvolatile content: 30 parts by mass) and 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 exchange water were added to obtain an aqueous dispersion. The 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)
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device, 240 parts by mass (nonvolatile matter: 72 parts by mass) of the urethane resin (A-1) aqueous dispersion obtained in Preparation Example 1 and 1 An aqueous dispersion was obtained by adding 30 parts by mass of 2-propylene glycol, 30 parts by mass of 1,3-butylene glycol and 30 parts by mass of ion-exchanged water. The 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-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 60 parts by mass of the hydrophilic acrylic polymer (B-1) having a nonvolatile content of 50% by mass obtained in Preparation Example 7 (nonvolatile content: An aqueous dispersion was obtained by adding 30 parts by mass of 30 parts by mass of 1,2-propylene glycol, 30 parts by mass of 1,3-butylene glycol, and 30 parts by mass of deionized water. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (C4) having a nonvolatile content of 30% by mass.

[Method for evaluating hydrophilicity durability]
The aqueous resin compositions obtained in Examples and Comparative Examples are coated on a phosphate chromate-treated aluminum plate using a bar coater such that the film thickness after drying is about 1 μm, and the ambient temperature is 200 ° C. The film was placed in a dryer for 30 seconds and dried to prepare a coating. Thereafter, it was cured at room temperature for 3 days to make a test piece.
The test piece was immersed in running water for 240 hours, and after being dried at room temperature for 1 day, the water contact angle was evaluated according to the following evaluation criteria.
A: The water contact angle of the coating 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 compositions obtained in Examples and Comparative Examples are coated on a phosphate chromate-treated aluminum plate using a bar coater such that the film thickness after drying is about 1 μm, and the ambient temperature is 200 ° C. The film was placed in a dryer for 30 seconds and dried to prepare a coating. Thereafter, it was cured at room temperature for 3 days to make a test piece. Then, a 5% by mass aqueous solution of sodium hydroxide was spotted on the coating, and the state of deterioration of the coating after standing for 20 minutes was evaluated according to the following evaluation criteria.
A: There was no change on the surface of the coating film.
B: Some discoloration was observed on a part of the surface of the coating, but it was at a level that causes no problem in practical use.
C: Discoloration was observed on the surface of the coating.
D: The coating film was dissolved and the substrate was exposed.

[Method of evaluating adhesion to substrate]
The aqueous resin compositions obtained in Examples and Comparative Examples are coated on respective substrates shown below using a bar coater so that the film thickness after drying becomes about 1 μm, and in the case of metal substrates, the atmosphere is The film was dried by being put in a dryer at a temperature of 200 ° C. for 30 seconds, and dried on a plastic substrate at 60 ° C. for 30 minutes to prepare a coating. Thereafter, it was cured at room temperature for 3 days to make a test piece. The surface of the obtained coating film was subjected to a 1 mm square 100 cross-cut Sellotape (registered trademark) peel test according to JIS K-5400. The number of grids without peeling was measured and evaluated according to the following evaluation criteria. In addition, the metal base used is a phosphoric acid chromate-treated aluminum plate, 55 mass% aluminum-zinc based alloy plated steel sheet (GL steel sheet), and the used plastic base is acrylonitrile-butadiene-styrene resin (ABS And a base material made of polycarbonate resin (PC resin).
A: The number of grids without peeling was 90 or more.
B: The number of grids without peeling was 60 or more and less than 90 C: The number of grids without peeling was 40 or more and less than 60
D: The number of grids 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. Shown in.

  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, the coating film obtained using the aqueous resin composition of the present invention has excellent hydrophilic persistence and chemical resistance, and also has excellent adhesion to various substrates. It could be confirmed that it had sex.

  On the other hand, Comparative Example 1 is an example using a hydrophilic acrylic polymer having neither a silanol group nor a hydrolyzable silyl group. It has been confirmed that the coating obtained using the aqueous resin composition of Comparative Example 1 is extremely insufficient in all of hydrophilic durability, chemical resistance, and substrate adhesion.

  Comparative Example 2 is an example using a urethane resin having neither a silanol group nor a hydrolyzable silyl group. It has been confirmed that the coating obtained using the aqueous resin composition of Comparative Example 2 is extremely insufficient in all of hydrophilic durability, chemical resistance, and substrate adhesion.

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

  The comparative example 4 is an example which did not use the urethane resin which has a silanol group and / or a hydrolysable silyl group. It has been confirmed that the coating obtained using the aqueous resin composition of Comparative Example 4 is extremely insufficient in all of hydrophilic durability, 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) The content of silanol groups and / or hydrolyzable silyl groups in the hydrophilic acrylic polymer (B) is in the range of 0.5% by mass or more in the hydrophilic acrylic polymer (B) Aqueous resin composition characterized by the above.   The said hydrophilic acrylic polymer (B) has an acrylic monomer (b1-1) which has an amide group, an acrylic monomer (b1-2) which has an oxyethylene group, and a silanol group and / or a hydrolysable silyl group. The aqueous resin composition according to claim 1, which is a polymer of a hydrophilic acrylic monomer (b1) containing an acrylic monomer (b1-3). The aqueous resin composition according to claim 2, wherein the acrylic monomer (b1-1) having an amide group is represented by the following general formula (1) or the following general formula (2).

(In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ² represents an alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms It represents a methyl chloride salt of a hydroxyalkyl group, — (CH ₂ ) ₃ —N (CH ₃ ) ₂ , or (CH ₂ ) ₃ —N (CH ₃ ) ₂ ).

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