JP2000344986A - Aqueous curable resin composition and coated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous curable resin composition excellent in disperse stability and curability and a coated material coated with the aqueous curable resin composition, excellent in water resistance, weather resistance and stain resistance and having high practicality. SOLUTION: This aqueous curable resin composition comprises (A) an aqueous material obtained by dispersing or dissolving a copolymer (a) obtained by copolymerizing an amino group-containing vinyl monomer, a carbonyl group- containing vinyl monomer and a fluoroolefin which are essential components with copolymerizable vinyl monomers as other components in the presence or absence of an emulsifying agent and/or a disperse stability into water, (B) a compound having a compound having two or more epoxy groups in one molecule or a compound having both of epoxy group and hydrolyzable silyl group in one molecule and (C) a compound having hydrazino group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful aqueous curable resin composition, and an object coated with the aqueous curable resin composition, more specifically, an emulsifier and / or a dispersant. In the presence or absence of a stabilizer, an amino group-containing vinyl monomer, a carbonyl group-containing vinyl monomer and a fluoroolefin, or a nonionic reactive macromonomer, an amino group-containing vinyl monomer, and a carbonyl group-containing An aqueous product (A) obtained by dispersing or dissolving a copolymer obtained by polymerizing a vinyl monomer and a fluoroolefin as essential components and other copolymerizable vinyl monomers in water; A compound having two or more epoxy groups therein or a compound (B) having both an epoxy group and a hydrolyzable silyl group in one molecule; and a compound having a hydrazino group An aqueous curable resin composition comprising the compound (C) and having excellent dispersion stability and curability of the aqueous compound (A), and a coating of the aqueous curable resin composition. The present invention relates to a highly practical coated object excellent in water resistance, weather resistance, and stain resistance.

[0002]

2. Description of the Related Art The purpose of coating the surface of a so-called alkaline inorganic cured product such as cement, metal, wood or plastic is mainly to improve the so-called durability such as water resistance, chemical resistance or weather resistance of a substrate. For this reason, the coated object coated with these coating agents is required to be protected for a long period of time.

[0003] In response to recent demands for environmental protection and work environment improvement on a global scale, conventional organic solvent-based paints have been replaced or converted to water-based paints that emit a small amount of organic solvents into the atmosphere. Is becoming necessary. In addition, from the viewpoint of resource saving, a resin composition having a longer life cycle and requiring no maintenance is urgently desired.

Although there has been reported a technique for crosslinking an aqueous fluororesin by using a compound having a hydrazide group as a curing agent (JP-A-2-214756, JP-A-7-97497, JP-A-7-97497, 7-2682
73, JP-A-8-295841 and JP-A-8-319450), in each case, crosslinking is insufficient, and a coating film that satisfies stain resistance over a long period of time has not been obtained. .

Although there is a report on a technique for crosslinking an aqueous fluororesin by using a compound having an isocyanate group as a curing agent (JP-A-8-151551 and JP-A-8-193178), there is a view from the viewpoint of harmfulness. Therefore, it is not preferable to use an isocyanate compound.

Further, there is a report on a technique of crosslinking an aqueous fluororesin using a melamine compound as a curing agent (Japanese Patent Application Laid-Open Nos. Hei 2-28939 and Hei 7-179).
809 and JP-A-8-193178),
Since cross-linking requires heat baking, painting on site is impossible, and line painting in a factory is economically disadvantageous.

[0007]

SUMMARY OF THE INVENTION However, the present inventors have enthusiastically started research in order to solve various problems in the conventional technology as described above.

[0008] Accordingly, the problem to be solved by the present invention is, inter alia, an aqueous curable resin composition having excellent dispersion stability and curability, and a water-resistant, coated water-curable resin composition. An object of the present invention is to provide a highly practical coated object excellent in weather resistance and stain resistance.

[0009]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of diligent and intensive studies, aiming at the problems to be solved by the invention as described above, amino group-containing vinyl monomers and carbonyls were obtained in the presence or absence of emulsifiers and / or dispersion stabilizers. A group-containing vinyl monomer and a fluoroolefin, preferably a macromonomer having reactivity with these monomers (hereinafter abbreviated as “reactive macromonomer”) as essential constituents, and other copolymers. An aqueous product (A) obtained by dispersing or dissolving a copolymer (a) obtained by polymerizing with a possible vinyl monomer in water, and a compound or a compound having two or more epoxy groups in one molecule. An aqueous curable resin composition comprising: a compound (B) having both an epoxy group and a hydrolyzable silyl group in a molecule; and a compound (C) having a hydrazino group, In particular, it is excellent in dispersion stability and curability, and moreover, the coated object coated with this aqueous curable resin composition is excellent in water resistance, weather resistance and stain resistance, as a reactive macromonomer. Is preferably a nonionic reactive macromonomer, as the carbonyl group-containing vinyl monomer, a carbonyl group-containing vinyl monomer contained in ketones or aldehydes, among which acetoacetyl group-containing vinyl monomer As the aqueous compound (A), the aqueous compound obtained by neutralizing the amino group in the copolymer (a) with an acid and dispersing or dissolving it in water is preferable. To
The present invention has been completed.

That is, the present invention provides: (1) an amino group-containing vinyl monomer, a carbonyl group-containing vinyl monomer and a fluoroolefin in the presence or absence of an emulsifier and / or a dispersion stabilizer; And an aqueous product (A) obtained by dispersing or dissolving a copolymer (a) obtained by polymerizing with a copolymerizable vinyl monomer in water, and two or more epoxy groups in one molecule. Or a compound (B) having both an epoxy group and a hydrolyzable silyl group in one molecule [hereinafter, abbreviated as "compound (B) having an epoxy group". ] And a compound having a hydrazino group (C),

(2) The copolymer (a) comprises a reactive macromonomer as an essential component together with an amino group-containing vinyl monomer, a carbonyl group-containing vinyl monomer and a fluoroolefin, and other copolymerizable vinyl. The aqueous curable resin composition according to the above (1), which is a copolymer obtained by polymerization with a monomer,

(3) The aqueous curable resin composition according to the above (2), wherein the reactive macromonomer is a nonionic reactive macromonomer.

(4) The above (1), (2) or (3), wherein the carbonyl group-containing vinyl monomer is a carbonyl group-containing vinyl monomer contained in ketones or aldehydes. Aqueous curable resin composition,

(5) The carbonyl group-containing vinyl monomer is an acetoacetyl group-containing vinyl monomer.
The aqueous curable resin composition according to (1), (2) or (3),

(6) The aqueous compound (A) is an aqueous compound obtained by neutralizing an amino group in the copolymer (a) with an acid and dispersing or dissolving it in water. An aqueous curable resin composition according to any one of (1) to (3), and a coating object coated with the aqueous curable resin composition according to any one of (1) to (6) above. Things.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As the copolymer (a) used when preparing the above-mentioned aqueous compound (A), a vinyl monomer containing an amino group, a vinyl monomer containing a carbonyl group, a fluoroolefin, and preferably further a reaction Copolymers obtained by copolymerizing a hydrophilic macromonomer and a copolymerizable vinyl monomer in an aqueous medium or an organic solvent.

As typical examples of such amino group-containing vinyl monomers, 2-aminoethyl (meth) acrylate, 2-methylaminoethyl (meth) acrylate, 2-dimethylaminoethyl (Meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, N- [2- (meth) acryloyloxyethyl] piperidine, N Various (meth) acrylate monomers such as-[2- (meth) acryloyloxyethyl] pyrrolidine and N- [2- (meth) acryloyloxyethyl] morpholine; 4- (N, N
Various aromatic monomers such as -dimethylamino) styrene, 4- (N, N-diethylamino) styrene and 4-vinylpyridine; 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether,
Various vinyl ethers such as -aminopropyl vinyl ether, 3-methylaminopropyl vinyl ether, 4-dimethylaminobutyl vinyl ether, 4-diethylaminobutyl vinyl ether, 6-dimethylaminohexyl vinyl ether; 2-dimethylaminoethyl allyl ether, 2-amino Various allyl ethers such as ethyl allyl ether; various allyl amines such as N, N-dimethylallylamine and allylamine.

Of these, the use of a vinyl monomer having a tertiary amino group is preferred, especially in consideration of the reactivity with the epoxy group.

These amino group-containing vinyl monomers may be used alone or in combination of two or more.

Next, examples of the carbonyl group of the carbonyl group-containing vinyl monomer include carbonyl groups contained in esters, ketones, aldehydes, amides and the like. Among these, the use of ketones or aldehydes having high crosslinking reactivity is preferred. Hereinafter, a carbonyl group contained in a ketone or an aldehyde is referred to as a crosslinkable carbonyl group.

As the above-mentioned cross-linkable carbonyl group-containing vinyl monomers, only typical ones are exemplified. Acrolein, diacetone acrylamide, formylstyrene, vinyl ethyl ketone, vinyl propyl ketone, crotonaldehyde Acrylamide pivalinaldehyde, diacetone (meth) acrylate, acetonyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate acetyl acetate, butanediol (meth) acrylate acetyl acetate, represented by the following general formulas (1) and (2) And vinyl monomers.

[0022]

Embedded image R ¹ CH = CR ² (CH ₂ ) _m —O— (C ＝ O) _n — (CH ₂ ) _o — (O) _p — (C ＝ O) _q — (CH ₂ ) _r − (C = O) - (CH 2) -CH 3 ‥‥ (1)

(Wherein, R ¹ and R ² are hydrogen atoms or methyl groups; m and n are 0 or 1; o is 0 or an integer of 1 to 20; p and q are 0 or 1; r is 1 to 20) Integer; s is 0
Or, represents an integer of 1 to 20. )

[0024]

Embedded image R ³ CH = CR ⁴ (CH ₂ ) _m -O- (C = O) _n -R ^5- (O) _p- (C = O) _q- (CH ₂ ) _r- (C = O )-(CH ₂ ) -CH ₃ ‥‥ (2)

(Wherein, R ³ and R ⁴ are hydrogen atoms or methyl groups; m and n are 0 or 1; R ⁵ is a divalent alicyclic hydrocarbon group; p and q are 0 or 1; An integer from 1 to 20; s is 0
Or, represents an integer of 1 to 20. )

Of these, diacetone acrylamide, crotonaldehyde, and vinyl monomers represented by the general formulas (1) and (2) are preferable, especially in view of copolymerizability with fluoroolefin. Considering the storage stability of the monomer, it is preferable to use diacetone acrylamide and an acetoacetyl group-containing vinyl monomer represented by the general formulas (1) and (2).

Of course, these carbonyl group-containing vinyl monomers may be used alone or in combination of two or more.

Next, as typical examples of fluoroolefins, only typical ones are exemplified, and vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, Pentafluoropropylene,
Examples include various fluorine-containing α-olefins and fluorine-containing β-olefins such as hexafluoropropylene, 3,3,3-trifluoropropene, and perfluoro-2-methyl-2-pentene.

Of these, use of chlorotrifluoroethylene, hexafluoropropylene or vinylidene fluoride is particularly preferred from the viewpoint of reaction control during polymerization.

Of course, these fluoroolefins may be used alone or in combination of two or more.

Here, in order to improve the dispersion stability of the aqueous compound (A), it is preferable to use a reactive macromonomer when synthesizing the copolymer (a). As the reactive macromonomer, any type of anionic, nonionic or cationic can be used,
Among these, in view of long-term dispersion stability, use of nonionic or cationic is preferable, and further,
Considering coloring, the use of nonionic properties is even more preferred.

Examples of the nonionic reactive macromonomer include various types of polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid esters of polyoxyethylene, and polyoxyethylene-polyoxypropylene block copolymers. Examples thereof include vinyl esters having an ether chain in a side chain, vinyl ethers, allyl ethers and (meth) acrylates.

Of these, the use of vinyl esters, vinyl ethers or allyl ethers having a polyether chain in the side chain is preferred from the viewpoint of copolymerizability with fluoroolefins.

Of course, these nonionic reactive macromonomers may be used alone or in combination of two or more.

As the above-mentioned amino-containing vinyl monomer, carbonyl-containing vinyl monomer and vinyl monomer copolymerizable with fluoroolefin, only typical ones are exemplified. Various (halogen-substituted other than fluorine atoms) olefins such as vinyl chloride, vinylidene chloride, propylene and butene-1; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, versatic Vinyl acrylate (vinyl neononanoate or vinyl neodecanoate), vinyl laurate, vinyl stearate,
Vinyl esters of various carboxylic acids, such as vinyl cyclohexanecarboxylate, vinyl pt-butylbenzoate, and "Veoba" (vinyl ester manufactured by Shell); alkyl vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; cyclopentyl Various (alkyl-substituted) cyclic alkyl group-containing vinyl ethers such as vinyl ether, cyclohexyl vinyl ether, and methylcyclohexyl vinyl ether; various aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether;

Of these, the carboxylic acid in the vinyl ester of carboxylic acid is a straight-chain, branched, or cyclic carboxylic acid having 5 or more carbon atoms, and is required to improve the weather resistance of the film. In order to increase the carbon content, those having more carbon atoms are more preferable.

Further, the following various monomers such as acid group-containing monomers, hydroxyl group-containing monomers, fluorine atom-containing monomers other than fluoroolefins, and other monomers are also included. And can be used as a copolymerizable vinyl monomer.

Examples of the acid group-containing monomers include various acid anhydride groups such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride and itaconic anhydride. Carboxyl group-containing monomers and dicarboxylic acids typified by unsaturated group-containing hydroxyalkyl ester monocarboxylic acids such as adducts of monomers and glycols; various kinds of monomers such as maleic anhydride; Polycarboxylic acid anhydride group-containing monomers; various sulfonic acid group-containing monomers such as 2-acrylamido-2-methylpropanesulfonic acid.

Of these, the use of crotonic acid or itaconic acid is preferred from the viewpoint of copolymerizability. The purpose of introducing the acid group-containing monomers is to improve the adhesion to the substrate in the final use.

Examples of the hydroxyl group-containing monomers include hydroxyl group-containing vinyl ethers such as various hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth)
Acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3
-Chloro-2-hydroxypropyl (meth) acryle-
And various hydroxyalkyl esters of (meth) acrylic acid, such as polyethylene glycol mono (meth) acrylate. Of these, use of hydroxyl group-containing vinyl ethers is preferred from the viewpoint of copolymerizability.

The fluorine atom-containing monomers other than the fluoroolefin include trifluoromethyl vinyl ether, 1,1,1-trifluoroethyl vinyl ether,
2,2-difluoroethyl vinyl ether, tetrafluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorobutyl vinyl ether, perfluorohexyl vinyl ether, perfluorooctyl vinyl ether, perfluorododecyl vinyl ether, 2,2,3,3-tetrafluoropropyl vinyl ether 2,2,3,3,4,4,5,5-octafluoropentyl vinyl ether, 2,2,3,3,4
4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl vinyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether, perfluoro Various (per) fluoroalkyl vinyl ethers such as cyclohexyl vinyl ether; vinyl ethers having a fluoroalkyl group having 3 to 12 carbon atoms in which a part of hydrogen atoms has been replaced by fluorine atoms;

"Viscoat 8F, 8FM, 3F or 3FM" [Fluorine-containing (meta) manufactured by Osaka Organic Chemical Co., Ltd.
Acrylic monomers], various (per) fluoroalkyl group-containing alcohols such as perfluorocyclohexyl (meth) acrylate, Ni-propylperfluorooctanesulfonamidoethyl (meth) acrylate, and (meth) (Meth) acrylic esters obtained by an esterification reaction with acrylic acid;

Various (per) fluoroalkyl group-containing vinyl esters, such as vinyl trifluoroacetate and diperfluorocyclohexyl fumarate, may be mentioned.

Other monomers include (meth)
Carboxamide group-containing monomers represented by acrylamide, N, N-dimethyl (meth) acrylamide, N-alkoxymethylated (meth) acrylamide, N-methylol (meth) acrylamide, and the like;

P-styrenesulfonamide, N-methyl-p-styrenesulfonamide, N, N-dimethyl-p
-Various sulfonic acid amide group-containing monomers represented by styrene sulfonamide and the like;

Cyano group-containing monomers represented by (meth) acrylonitrile; hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids, such as hydroxyalkyl (meth) acrylates; , Obtained by a condensation reaction with phosphoric esters,
Various phosphate group-containing monomers; methyl (meth)
Linear having 1 to 9 carbon atoms, such as acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate Or various alkyl (meth) acrylates having a branched or cyclic alkyl group;

Styrene, α-methylstyrene, p-te
represented by styrene or derivatives thereof, such as rt-butyl-styrene or p-methylstyrene;
Various aromatic vinyl compounds; various (substituted) aromatic nucleus-containing (meth) acrylic esters represented by benzyl (meth) acrylate; etc .; represented by maleic acid, fumaric acid, itaconic acid, etc. Examples include diesters of various unsaturated dicarboxylic acids and monohydric alcohols.

These monomers are appropriately selected and used in order to adjust the glass transition point of the finally obtained copolymer and the minimum film forming temperature.
Of course, more than one type may be used in combination.

The copolymer (a) obtained by polymerizing an amino group-containing vinyl monomer, a carbonyl group-containing vinyl monomer and a fluoroolefin with a copolymerizable vinyl monomer as an essential component is as described above. It can be easily obtained by polymerizing various monomers as described above by solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization or the like. Among these, solution polymerization in an organic solvent is preferred from the viewpoint of controlling the reactivity.

Next, a preparation example as a preferred embodiment will be described. The monomers are dropped into the reaction vessel all at once, divided or continuously, and in the presence of a polymerization initiator, a gauge pressure of about 1 to 10
The polymerization may be carried out at 0 kg / cm ^{2 at} a reaction temperature of about 50 to 150 ° C. In some cases, the polymerization may be carried out under a higher pressure or a lower temperature condition. The non-volatile content at the time of polymerization is 1 to 90% by weight, preferably 4% by weight.
It should be set in the range of 0-80% by weight.

The organic solvent is not particularly limited, and any general-purpose organic solvent can be used. Among them, only typical ones are exemplified. For example, ketone organic solvents such as acetone, methyl ethyl ketone and methyl amyl ketone;
Ester organic solvents such as ethyl acetate and butyl acetate; aromatic hydrocarbon organic solvents such as benzene, toluene and xylene; aliphatic hydrocarbon organic solvents such as hexane and heptane; methanol, ethanol, isopropanol,
Alcoholic organic solvents such as butanol; carbon tetrachloride,
Halogen-containing organic solvents, such as methylene dichloride and hexafluoroisopropanol, including chlorofluorocarbon-based solvents.

Of these, those having a boiling point of 100 ° C. or less are preferably used in combination because the solvent can be easily removed after dispersing in water. Of course, these solvents may be used alone or in combination of two or more.

The polymerization initiator is not particularly limited as long as it is a commonly used one, but if only typical ones are exemplified, cumene hydroperoxide may be used. And various organic peroxides such as tert-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, benzoyl peroxide and t-butyl hydroperoxide; azobisisobutyronitrile, azobiscyano Examples include various azo initiators such as valeric acid, and these may be used alone or in combination of two or more.

The amount of the polymerization initiator used is suitably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the monomers.

The copolymer (a) thus prepared
When dispersing or dissolving in water, an emulsifier and / or
Alternatively, dispersion stabilizers can be used.

As a method for obtaining the above-mentioned aqueous compound (A), the following methods can be exemplified. (1) A method in which a mixture of an emulsifier and / or a dispersion stabilizer and a copolymer and water are simultaneously mixed and stirred. (2) A method in which water is added at once, dividedly or dropwise while stirring a mixture of an emulsifier and / or a dispersion stabilizer and a copolymer. (3) A method in which a mixture of an emulsifier and / or a dispersion stabilizer and a copolymer is added all at once, dividedly or dropwise while stirring water. (4) A method of simultaneously mixing and stirring a mixture of an emulsifier and / or a dispersion stabilizer with water and a copolymer. (5) A method in which the copolymer is added at once, dividedly or dropwise while stirring a mixture of the emulsifier and / or dispersion stabilizer and water. (6) A method in which a mixture of an emulsifier and / or a dispersion stabilizer and water is added all at once, dividedly or dropwise while stirring the copolymer.

The step of dispersing or dissolving in water may be performed at room temperature or under heating, but it is preferable that the temperature under heating is 70 ° C. or lower in order to avoid skinning of the liquid surface.

As described above, when the copolymer is dispersed or dissolved in water, the amino group of the copolymer (a) is neutralized with an acid to obtain a more stable aqueous compound (A). Can be. This neutralization step may be performed before, during, or after the step of dispersing or dissolving in water.

[0059] Furthermore, the mechanical dispersion is preferably utilizing the apparatus such as de _Lee spar, a homomixer or multi kneading extruder at the time of dispersion.

As the above-mentioned emulsifier, various emulsifiers such as an ionic emulsifier and a nonionic (nonionic) emulsifier can be used, and the water resistance of the cured coating film obtained from the composition of the present invention can be used. From a viewpoint, a nonionic emulsifier is preferable.

Of these, only typical representative examples of anionic emulsifiers are exemplified, and alkyl (benzene) sulfonate, alkyl sulfate salt,
Examples thereof include polyoxyethylene alkylphenol sulfate salts, styrene sulfonate salts, vinyl sulfate salts, and derivatives thereof.

The term "salt" as used herein refers to salts derived from alkali metal hydroxides; salts derived from volatile bases such as ammonia and triethylamine. Among these, selected from the group consisting of (substituted) alkyl (benzene) sulfonates and vinyl sulfonates,
It is desirable to use at least one or more compounds.

As typical examples of the cationic emulsifier, only typical ones may be mentioned, such as lauryltrimethylammonium chloride, didecyldimethylammonium chloride and lauryldimethylbenzylammonium chloride.

As nonionic emulsifiers, only typical ones are exemplified. Polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, ethylene oxide-propylene oxide block copolymer Or derivatives thereof, and these may be used alone or in combination of two or more. Of these, polyoxyethylene (substituted)
Use of an alkyl (phenyl) ether is desirable from the viewpoint of physical properties of the finally obtained film.

In addition, various fluorine-containing emulsifiers such as perfluorooctanoates and various fluorine-containing emulsifiers such as fluoroalkyl sulfates can be used in combination.

The amount of the emulsifier to be used is preferably within a range of 10 parts by weight or less based on 100 parts by weight of the total resin solid content from the viewpoint of the water resistance of the cured coating film obtained from the composition of the present invention. It is appropriate, and especially, the range of 0.1 to 5 parts by weight is preferable.

Examples of the dispersion stabilizer include various water-soluble oligomers selected from the group consisting of polycarboxylic acids and sulfonates, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, maleated alkyd resins, Various synthetic or natural water-soluble or water-dispersible water-soluble polymer substances such as polyacrylic acid (salt), polyacrylamide, water-soluble or water-dispersible acrylic resin, and one or more kinds of these. Can be used.

From the viewpoint of the water resistance of the cured coating film obtained from the composition of the present invention, the amount of the dispersion stabilizer used is preferably not more than 10 parts by weight based on 100 parts by weight of the total resin solids. Is appropriate, especially 0.1 to 5
It is preferably within the range of parts by weight.

The compound (B) having an epoxy group is a compound having two or more epoxy groups in one molecule or a compound having both an epoxy group and a hydrolyzable silyl group in one molecule. . Of these, particularly representative ones are only examples, and diglycidyl ethers of glycols, polyglycidyl ethers of polyols, and dicarboxylic acids of dicarboxylic acids as represented by "Denacol" [Nagase Sangyo Products]. Compounds having at least two or more epoxy groups in one molecule such as glycidyl esters; bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin,
Urethane-modified epoxy resin;

Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, γ-glycidoxypropyl Various epoxy silane compounds such as triisopropenyloxysilane; various isocyanate silane compounds such as γ-isocyanatopropyltriisopropenyloxysilane and γ-isocyanatopropyltrimethoxysilane; and glycidol. Adducts with various aminosilane compounds such as γ-aminopropyltrimethoxysilane and diepoxy compounds; adducts obtained by partially hydrolyzing and condensing various epoxysilane compounds as described above. Two or more epoxy groups and water in the molecule Such compounds can be mentioned having both gender silyl group, they may be used alone or in combination.

Further, a compound (B) having an epoxy group
Examples thereof include a silicone resin having both an epoxy group and a hydrolyzable silyl group. Of these silicone resins, only typical ones are exemplified, and cyclic tetrasiloxanes such as compounds represented by the following general formula (3) can also be used.

[0072]

Embedded image

(Wherein Gly represents a 3-glycidoxypropyl group)

As the above-mentioned compound (C) having a hydrazino group, only typical ones are exemplified. , Adipic dihydrazide, sebacic dihydrazide, dodecane diacid dihydrazide, various aliphatic dicarboxylic dihydrazides; phthalic dihydrazide, isophthalic dihydrazide, terephthalic dihydrazide, various aromatic dicarboxylic dihydrazides; maleic diacid; Various unsaturated dicarboxylic acid dihydrazides such as fumaric dihydrazide and itaconic dihydrazide are exemplified.

Further, as the compound (C) having a hydrazino group, an aliphatic polycarboxylic acid polyhydrazide or aromatic polycarboxylic acid polyhydrazide having three or more hydrazino groups in one molecule can be used.

These can be used as one kind or as a mixture of two or more kinds.

Here, in order to prepare the aqueous curable resin composition of the present invention, the number of moles of amino groups contained in the aqueous compound (A) / the number of moles of epoxy groups contained in the compound (B) The ratio [molar ratio of (amino group / epoxy group)] is in the range of 0.1 to 5, and the number of moles of carbonyl group / compound contained in the aqueous compound (A). Ratio of the number of moles of hydrazino groups contained in (C) [molar ratio of (carbonyl group / hydrazino group)]
Is preferably in the range of 0.1 to 5, preferably in the ratio of 0.3 to 3.0, and 0.3 to 3 in the latter. 0.0, and most preferably, the former is in the range of 0.5 to 2.0, and the latter is in the range of 0.5 to 2.0.
The components (A), (B) and (C) may be mixed at such a ratio as to fall within the range of (1).

Furthermore, a curing catalyst can be added to the aqueous curable resin composition according to the present invention, if necessary. By adding such a curing catalyst, more curability can be obtained. Thus, it is possible to obtain a highly practical cured coating film having better stain resistance, solvent resistance, hardness and the like.

As typical examples of such catalysts, only typical ones are exemplified, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and sodium methylate.
Various basic compounds; tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, zinc naphthenate, cobalt naphthenate, di-n- Various metal-containing compounds such as butyltin diacetate, di-n-butyltin dioctoate, di-n-butyltin dilaurate, di-n-butyltin maleate; p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid,
Various acidic compounds such as monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid and dialkylphosphorous acid are exemplified.

Further, if necessary, the composition of the present invention may contain various additives such as isopropyl alcohol, sec-butanol, n-butanol, 2-ethylhexanol, 2-propoxyethanol, and 2-n
-Butoxyethanol, 2-n-propoxypropanol, 3-n-propoxypropanol, 2-n-butoxypropanol, 3-n-butoxypropanol, 2-
Such as n-butoxyethyl acetate, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, N-methylpyrrolidone, 2,2,4-trimethyl-1,3-pentanediol monobutyrate, dibutyl phthalate, and butyl benzyl phthalate In addition to various film-forming aids, fillers,
Organic pigments, inorganic pigments, metal pigments such as aluminum, p
Such as H adjusters, leveling agents, thickeners, water repellents, defoamers, plasticizers, antioxidants, ultraviolet absorbers, cissing inhibitors, anti-skinning agents (anti-burrs) or dispersants What
It can be said that various commonly used so-called additives are appropriately added and used.

The aqueous curable resin composition according to the present invention obtained as described above has a so-called two-component type in which the compound (B) having an epoxy group is mixed with other components immediately before use. It can be used in liquid form.

The compound (C) having a hydrazino group may be previously mixed with the aqueous compound (A), or may be mixed with the compound (B) having an epoxy group.

The hydrazino group may be partially or entirely neutralized with an acid in advance.

Then, after being mixed in this way,
It is desirable to apply the coating within one day, preferably within 12 hours. After one day or more, the curability at room temperature starts to decrease.

As the substrate that can be used to obtain a substrate coated with the aqueous curable resin composition according to the present invention, various known and commonly used substrates can be used. , Iron, nickel, aluminum, copper,
Lead or other various metals and alloys of these various metals; various metals as described above, which have been subjected to plating, chemical conversion treatment, etc., various surface-treated metals; concrete, Slate or other various kinds of cured alkaline inorganic materials; polystyrene, polymethyl methacrylate, ABS resin, polyphenylene oxide, polyurethane, polyethylene, polyvinyl chloride, polypropylene, polybutylene terephthalate, polyethylene terephthalate, or other various thermoplastic resins; Unsaturated polyester molded products, phenolic resin molded products or crosslinked polyurethane molded products, or other thermosetting resin molded products; including tiles, fired products of various clays, glass, paper, and wood-based substrates No.

In addition, even if the above-mentioned various substrates are coated, and the class of the substrate in which the coated part is deteriorated is advanced, the aqueous material according to the present invention can be used. It can be said that the curable resin composition is used.

The coating (coating) may be various organic coatings such as acrylic, acrylic urethane, urethane, epoxy or alkyd, and various coatings such as cement or silicon. Inorganic coating film. Further, these coatings may be microelastic or elastic, and may be a single layer or multiple layers.

Each of these various substrates is in the form of a plate,
Various materials or products such as spheres, films, sheets, etc .: Large structures, assemblies with complex shapes, etc.
Furthermore, it is a class used in various forms according to various uses such as various molded products, and there is no particular limitation.

A cured coating film can be obtained by directly applying and curing the aqueous curable resin composition according to the present invention on the various substrates as described above. Is the resin composition, on various substrates,
It may be directly applied, or in advance, on various substrates, after applying an undercoat, the resin composition may be applied, or the resin composition, The resin composition may be used as an undercoat, or the resin composition may be used as an undercoat, and then the resin composition may be applied.

The aqueous curable resin composition of the present invention can be applied on various substrates as described above by brush coating, roller coating, spray coating, dip coating, flow coater coating, roll coater coating, or the like. The coating may be performed by various known and commonly used coating means or coating methods.

Then, the base material coated with the resin composition is allowed to stand at room temperature for about 1 to 20 days,
By heating at a temperature range of 250 ° C. for about 1 to 60 minutes, it is possible to obtain a cured coating film having excellent hardness, weather resistance and stain resistance.

As described above, the water-based curable resin composition according to the present invention is particularly useful for providing a cured coating film having good curability and dispersion stability and excellent weatherability and stain resistance. Further specific examples of the use of the resin composition include automobiles, motorcycles, trains, bicycles, ships, airplanes, and other transportation-related equipment and parts thereof; Roofing materials, window frames,
Various building materials, such as doors, interior and exterior wall materials; requirements for weather resistance and pollution resistance, such as roads, road signs, gart rails, bridges, tanks, chimneys, buildings, and various outdoor structures. There are applications such as

As other uses, mainly
There are TVs, radios, refrigerators, washing machines, coolers, cooler outdoor units, computers, and other home appliances and their parts, and the water-based curable resin composition of the present invention is effectively used for these various applications. It can be used.

[0094]

EXAMPLES Next, the present invention will be described more specifically with reference examples, examples, and comparative examples, but the present invention is in no way limited to only these illustrative examples. Not something. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Aqueous Product (A) of Fluorine Copolymer Having Amino Group and Carbonyl Group] Acetic acid was placed in a stainless steel autoclave having an internal volume of 3 liters in which the inside was replaced with nitrogen gas. Ethyl 608
Parts, methyl ethyl ketone 200 parts, hydroxybutyl vinyl ether 216 parts, vinyl acetate 204 parts, dimethylaminoethyl methacrylate 72 parts, diacetone acrylamide 72 parts, the end is capped with a methyl group,
Further, 72 parts of allyl ether having a side chain of polyethylene oxide having an addition mole number of 23 mol and 50 parts of t-butyl peroxy-2-ethylhexanoate as a polymerization initiator were charged.

Next, 564 parts of liquefied and collected chlorotrifluoroethylene was injected into the reactor. The reaction was continued at 60 ° C. for 15 hours with stirring to obtain a fluorine copolymer having an amino group and a carbonyl group in the side chain, having a nonvolatile content of 57.5%.

Into a resin solution obtained by neutralizing 100 parts of the thus obtained fluorocopolymer with 1 part of acetic acid, 1.5 parts of "Emulgen 911" (an emulsifier of Kao Corporation) and 1.5 parts of "Emal NC" [ An aqueous solution obtained by dissolving 0.5 part of an emulsifier of Kao Corporation in 70 parts of deionized water was added. Then, by using the de _Lee spar 10 minutes at room temperature, 5000 r
Stirring at pm gave an aqueous dispersion.

Next, the aqueous dispersion thus obtained was heated to 50 ° C. in a flask, and the solvent was removed under reduced pressure. Thereafter, after cooling the content, the solid content concentration becomes 45.
The mixture was adjusted to 0% with deionized water, and filtered through a 100 mesh wire mesh. The resulting aqueous product has a pH of 5.8.
And the viscosity was 85 cps, and the amount of agglomerates that did not pass through a 100-mesh wire mesh was 0.1% or less (ratio to aqueous compound). Hereinafter, this aqueous product is abbreviated as (A-1).

Reference Examples 2 to 3 (same as above) The same procedure as in Reference Example 1 was carried out except that the charged composition was changed as shown in Tables 1 and 2, to obtain a fluorine-containing copolymer having an amino group and a carbonyl group. Aqueous compound (A-2)-
(A-3) was obtained. The analytical values of the obtained aqueous compound are also shown in the table.

Reference Example 5 [Preparation Example of Aqueous Product of Fluorine Copolymer Having Amino Group] An amino acid was prepared in the same manner as in Reference Example 1 except that the charged composition was changed as shown in Tables 1 and 2. An aqueous product (R-1) of a fluorine copolymer having a group was obtained. The analytical values of the obtained aqueous compound are also shown in the table.

Reference Example 5 [Example of preparing aqueous fluorinated copolymer having no amino group and / or carbonyl group] Reference Example 1 except that the charged composition was changed as shown in Tables 1 and 2. In the same manner as described above, the aqueous fluorinated copolymer (R) having no amino group and / or carbonyl group (R
-2) was obtained. The analytical values of the obtained aqueous compound are also shown in the table.

[0102]

[Table 1] Table 1

[0103]

[Table 2] Table 2

(Footnote to Table 1) EtAc: ethyl acetate MEK: methyl ethyl ketone MeOH: methanol CTFE: chlorotrifluoroethylene HFP: hexafluoropropylene VAc: vinyl acetate VV-10: vinyl ester of versatic acid having 10 carbon atoms HBVE : Hydroxybutyl vinyl ether BVE: Butyl vinyl ether DMAEMA: N, N-dimethylaminoethyl methacrylate APVE: Aminopropyl vinyl ether DMAA: N, N-dimethylallylamine DAAM: Diacetone acrylamide NMM: The end is capped with a methyl group and the mole added Allyl ether having 50 moles of polyethylene oxide in the side chain Initiator: t-butylperoxy-2-ethylhexanoate

(Footnote to Table 2) NC: "Emal NC" [Emulsifier from Kao Corporation] EM911: "Emulgen 911" [Emulsifier from Kao Corporation] PVAL: "Kurarepovar PVA-205" [(Co., Ltd.) )
Kuraray's polyvinyl alcohol] NV: Non-volatile content (%) VIS: Viscosity (cps) Filtration residue: Agglomerate that does not pass through a 100 mesh wire mesh (ratio to water-based compound) Thereafter, the dispersion state of the aqueous compound (A) was observed and evaluated according to the following criteria. A: No change such as precipitation was observed. ；: Some water floating was observed in the upper layer, but redispersion was possible by stirring. Δ: Some water floating was observed in the upper layer, and a precipitate was formed, but redispersion was possible by stirring. ×: A precipitate is formed and cannot be redispersed even by stirring.

Reference Example 6 [Preparation example of pigment paste] "Taipec CR-93" (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) 200.8 parts, "Orotan SG-1" (Rohm & Haas Company, USA) Pigment dispersant) 5.
2. 9 parts of a 10% aqueous solution of sodium tripolyphosphate
9 parts, "Neugen EA-120" [Daiichi Kogyo Pharmaceutical Co., Ltd.
1.8 parts of polyoxyethylene nonyl phenyl ether-based emulsifier, 14.5 parts of ethylene glycol, "Best Side FX" [preservative manufactured by Dainippon Ink Co., Ltd.]
8, SN Deformer 121 [San Nopco Co., Ltd.
0.6 parts of water, 59.1 parts of water, and 28 parts
% Ammonia water and stirred at room temperature. Hereinafter, the solution thus obtained is abbreviated as a pigment paste.

Examples 1 to 5 Aqueous products (A-1) to (A-) obtained in Reference Examples 1 to 3
3), a curing agent [compound (B) having an epoxy group and compound (C) having a hydrazino group], Texanol, and, if necessary, a pigment paste and a curing catalyst,
It was blended with the blending composition shown in Table 3 to obtain an aqueous curable resin composition. In addition, in making the aqueous curable resin composition into a paint, "SN thickener A-806" is used as a thickener.
Thickness was increased using [polyether-based viscoelasticity modifier manufactured by San Nopco Co., Ltd.] to obtain a paint having a stoma viscosity of 85 KU.

The water-based paint was applied on a glass plate with a 3 mil applicator and dried under the drying conditions shown in Table 3 and the results of various tests are shown in the same table.

Comparative Examples 1 to 3 Aqueous products (A-1) obtained in Reference Examples 1, 4 and 5
(R-1) and (R-2), Texanol, and, if necessary, a curing agent [compound (B) having an epoxy group and compound (C) having a hydrazino group], a pigment paste, and a curing catalyst Was blended according to the formulation shown in Table 3 to obtain an aqueous resin composition. In addition, in making the aqueous curable resin composition into a paint, "SN thickener A-
806 "to obtain a paint having a Stomer viscosity of 85 KU.

The water-based paint was applied on a glass plate with a 3 mil applicator and dried under the drying conditions shown in Table 3 and the results of various tests are shown in the same table.

[0111]

[Table 3] Table 3

(Footnote to Table 3) A-187: "γ-glycidoxypropyltrimethoxysilane" [Epoxysilane manufactured by Nippon Unicar Co., Ltd.] HDE: 1,6-hexanediol diglycidyl ether CDH: Carbo Dihydrazide texanol: “TEXANOL Ester-Alcoho
l "[organic solvent 2, manufactured by Eastman Chemical Company, USA
2,4-trimethyl-1,3-pentanediol monoisobutyrate] Curing catalyst: p-toluenesulfonic acid Drying conditions: A (dry at room temperature for 5 days) B (at 50 ° C. × 10 minutes, then at room temperature for 5 days) Drying) Kale Fraction: The dried film obtained on the glass plate was peeled off, immersed in acetone for 24 hours, and the gel content of the film remaining without dissolving in acetone was weighed, and the percentage of the initial dry film weight was calculated. Indicated by Entities hardness: One soft value of pencil hardness when scratches are observed when scratching the surface of a coating film with a Mitsubishi uni pencil. Accelerated weathering resistance: After a 5000-hour test with a dual panel light control weather meter, the appearance of each coating film was visually judged according to the following criteria. A: No abnormalities such as discoloration and peeling were observed in the film. ；: Blister or peeling was slightly observed. Δ: Blister or peeling was partially observed. ×: Blisters are generated over the entire surface and markedly deteriorated. Stain resistance: On a dry film obtained on a glass plate,
Place a 1cm x 1cm carbon paper, put a glass plate on it, put a 2kg weight on it, then put it in a dryer at 80 ° C and let it stand for 20 minutes. The stained state of the paper was observed and evaluated according to the following evaluation criteria. A: No dirt. ；: Slight stain is observed. Δ: A part is stained. X: The whole surface is stained.

Reference Example 7 [Preparation Example of Aqueous Product (A) of Fluorine Copolymer Having Amino Group and Carbonyl Group] After obtaining a fluorine copolymer in the same manner as in Reference Example 2, the obtained fluorine copolymer was obtained. In a resin solution obtained by neutralizing 100 parts of the combined with 1 part of acetic acid, "Kurarepovar PVA-20" was previously added.
5 "[Polyvinyl alcohol from Kuraray Co., Ltd.] 2.0 parts was dissolved in 70 parts of deionized water. Then, by using the de _Lee spar 10 minutes at room temperature, 5000
The mixture was stirred at rpm to obtain an aqueous dispersion.

Next, the thus obtained aqueous dispersion was heated to 50 ° C. in a flask, and the solvent was removed under reduced pressure. Thereafter, after cooling the content, the solid content concentration becomes 45.
The mixture was adjusted to 0% with deionized water, and filtered through a 100 mesh wire mesh. The obtained aqueous product has a pH of 6.0.
And the viscosity is 102 cps, the aggregates that do not pass through a 100 mesh wire mesh are 0.1% or less (ratio to aqueous compound), and after 3 months at room temperature, the dispersion state shows changes such as precipitation. Was good. Hereinafter, this aqueous compound is referred to as (A
Abbreviated as -5).

Reference Example 8 [Preparation Example of Acrylic Copolymer Emulsion] A monomer mixture comprising 120 parts of styrene, 245 parts of butyl acrylate, 117.5 parts of ethyl acrylate, 10 parts of N-methylolacrylamide, and 7.5 parts of methacrylic acid. This mixture was emulsified in 130 parts of ion-exchanged water using 10 parts of AQUALON HS-10 (a sodium vinyl sulfonate emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) to prepare a pre-emulsion.

1 L equipped with a stirrer, thermometer and cooler
355 parts of ion-exchanged water was charged into the reaction vessel, and the inside of the reaction vessel was heated to 70 ° C. while stirring while inserting nitrogen gas. After the temperature was raised, 15 parts of the pre-emulsion was charged into a reaction vessel, and then 1 part of a 0.75% ferric chloride aqueous solution, 0.3 part of ammonium persulfate, and 0.2 part of sodium pyrosulfite were added. The remaining pre-emulsion, 1.2 parts of ammonium persulfate dissolved in 50 parts of ion-exchanged water, and 0.8 part of sodium pyrosulfite dissolved in 50 parts of ion-exchanged water were each dropped using a dropping funnel. And polymerized. The dropping time was 3 hours, and the temperature in the flask was maintained at 70 ° C. during this time. After completion of the dropwise addition, the mixture was further kept at 70 ° C. for 2 hours, cooled, adjusted to a pH of about 7.5 with 10% aqueous ammonia, and filtered through a 100-mesh filter cloth to obtain an acrylic copolymer emulsion (R-
3) was obtained.

REFERENCE EXAMPLE 9 [Blending of Aqueous Curable Resin Composition] The aqueous compound (A-5) obtained in Reference Example 7, a curing agent (the above-mentioned compound (C) having a hydrazino group), texanol, and a pigment paste And the curing catalyst was blended according to the formulation shown in Table 3 to obtain an aqueous curable resin composition. The aqueous resin composition was formed into a paint by thickening using "SN thickener A-806" (trade name of a polyether-based viscoelasticity modifier manufactured by San Nopco) as a thickener, and then increasing the Stomer viscosity. Of 85 KU was obtained.

Reference Example 10 [Blending of aqueous resin composition] 100 parts of the emulsion (R-3) obtained in Reference Example 8,
An aqueous resin composition was obtained by mixing 6 parts of Texanol and 50 parts of a pigment paste. In addition, in making this aqueous resin composition into a paint, "SN thickener A-80" is used as a thickener.
6 "[a polyether-based viscoelasticity modifier manufactured by San Nopco]
To obtain a paint having a Stomer viscosity of 85 KU.

Examples 6 to 10 The coating obtained in Example 1 [hereinafter referred to as (P-1)
Was abbreviated as described in Table 4 above, and applied to an undercoated slate plate described in Table 4 with a 6 mil applicator, and dried under the drying conditions described in the table.

Comparative Examples 4 and 5 The paint obtained in Reference Example 9 [hereinafter referred to as (P-2)
And the paint obtained in Reference Example 10 [hereinafter, referred to as
This paint is abbreviated as (P-3)] on a slate plate previously coated with an undercoat as shown in Table 4 using a 6 mil applicator, and dried under the drying conditions shown in the same table. It is described in the same table.

[0121]

[Table 4] Table 4

(Footnote to Table 4) SV: "Silvia Surf" [Nippon Special Paint Co., Ltd.
EP: Epicuron 853 with EPICURE 853
6MY60 ”[polyamideamine manufactured by Yuka Shell Epoxy Co., Ltd.] is blended so that epoxy group / amino group = 1/1. Drying conditions: A (dried at room temperature for 5 days) B (50 ° C. × After drying for 10 minutes, drying at room temperature for 5 days. C (old coating film exposed outdoors for 3 years) Water resistance: After dipping in water at room temperature for 30 days, the appearance of each coating film was visually judged. A: Blister-free. ；: Blister generation was slightly observed. Δ: Blister generation was partially observed. X: The occurrence of finister was observed on the entire surface. Accelerated weathering resistance: Same as above. Stain resistance: Same as above.

Examples 11 to 14 The paint (P-1) obtained in Example 1 was applied to various undercoated base materials shown in Table 5 with a 6 mil applicator, and the results were described in the same table. The results of various tests dried under the above drying conditions are shown in the same table.

[0124]

[Table 5] Table 5

[0125]

The aqueous curable resin composition obtained according to the present invention has, in particular, excellent dispersion stability and curability. It is excellent in water resistance, weather resistance, and stain resistance, and is extremely practical as an object to be coated.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/02 C08L 101/02 C09D 127/12 C09D 127/12 // C08F 290/06 C08F 290/06 F Terms (Reference) 4J002 BC12W BD12W BD13W BD14W BD15W BD16W BE00W BE04W BF01W BG07W BG10W BG13W CD01X CD11X CD13X CD19X CP05X EQ027 EQ037 EX066 FD146 FD147 FD150 FD200 HA06 4J027 AC01 BA02 ACO3 GA13 GA17 JA01 4J038 CC091 CD091 CD101 CD111 CD121 CD131 CE051 CG141 CG161 CG171 CH111 CH201 CR071 DB032 DB062 DB072 DB092 DB482 DL052 GA06 GA09 GA12 JB17 JC34 JC35 KA03 KA04 KA08 MA08 MA10 NA03 PC04 PC03 P04 PC05

Claims (7)

[Claims] 1. An amino group-containing vinyl monomer, a carbonyl group-containing vinyl monomer and a fluoroolefin as essential constituents in the presence or absence of an emulsifier and / or a dispersion stabilizer. An aqueous product (A) obtained by dispersing or dissolving a copolymer (a) obtained by polymerizing with a vinyl monomer in water, a compound having two or more epoxy groups in one molecule, or a compound in one molecule (B) having an epoxy group and a hydrolyzable silyl group together
And a compound having a hydrazino group (C). 2. A copolymer (a) comprising, together with an amino group-containing vinyl monomer, a carbonyl group-containing vinyl monomer and a fluoroolefin, a macromonomer having reactivity with these monomers (hereinafter, referred to as “a”). The aqueous curable resin composition according to claim 1, wherein the aqueous curable resin composition is a copolymer obtained by polymerizing a reactive macromonomer) as an essential constituent and other copolymerizable vinyl monomers. 3. The aqueous curable resin composition according to claim 2, wherein the reactive macromonomer is a nonionic reactive macromonomer. 4. The aqueous curable resin composition according to claim 1, wherein the carbonyl group-containing vinyl monomer is a carbonyl group-containing vinyl monomer contained in ketones or aldehydes. object. 5. The aqueous curable resin composition according to claim 1, wherein the carbonyl group-containing vinyl monomer is an acetoacetyl group-containing vinyl monomer. 6. The aqueous compound (A) according to claim 1, wherein the aqueous compound (A) is obtained by neutralizing an amino group in the copolymer (a) with an acid and dispersing or dissolving in water. The aqueous curable resin composition according to any one of the above. 7. A coated object coated with the aqueous curable resin composition according to claim 1.