JPH09310045A - Curable resin composition for aqueous coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject useful resin composition consisting essentially of an acid group- and/or tertiary amino group-containing resin, a compound having both of an epoxy group and a hydrolyzable silyl group and a polyepoxy compound and excellent in coating workability and curing property, etc. SOLUTION: This resin composition contains (A) an acid group and/or tertiary amino group-containing aqueous resin (preferably an acrylic polymer or a fluoroolefin-based polymer), (B) a compound having both of an epoxy group and a hydrolyzable silyl group and (C) a polyepoxy compound and preferably further, (D) a compound having a hydrolyzable silyl group and/or silanol group, excepting the component B.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful aqueous resin composition for water-based paint. More specifically, the present invention comprises an aqueous resin containing an acid group and / or a tertiary amino group, an epoxy group / hydrolyzable silyl group-containing compound, and a polyepoxy compound as essential components. The present invention relates to a curable resin composition for water-based paints, which is particularly useful for paints, because it gives a hardened product that is excellent in workability and curability, and particularly excellent in stain resistance and weather resistance.

[0002]

2. Description of the Related Art In response to recent demands for environmental protection on a global scale and improvement of the working environment, conventional paints containing organic solvents have been changed from paints containing a small amount of organic solvents to the atmosphere. Needs to be replaced or converted.

In addition, from the viewpoint of energy saving, the advent of a coating resin of a type that crosslinks at room temperature is also desired. Furthermore, the introduction of a novel and extremely highly practical paint resin that has a higher degree of weather resistance and a higher degree of raindrop contamination resistance that reduces maintenance work , Has been desired.

Heretofore, a copolymer composed of an aminoalkyl (meth) acrylate having a primary amino group or a secondary amino group and an ethylenically unsaturated monomer, and an epoxy group-containing silane cup have been used. Although an aqueous emulsion composition composed of a ring agent has been proposed (Japanese Patent Laid-Open No. 61-28543), the cured coating film obtained from such a composition has, inter alia, stain resistance and weather resistance. There was a problem that it was inferior in sex.

Furthermore, the present inventors have proposed a curable resin composition for water-based paints, which contains a tertiary amino group-containing water-based resin and an epoxy group / hydrolyzable silyl group-containing compound as essential components. (Japanese Patent Application No. 6-19043)
No. 0), the cured coating film obtained from such a composition has relatively good raindrop stain resistance, but has not reached the required high level. there were.

[0006]

However, in order to solve the various problems in the conventional technique as described above, and in addition to meet the various demands of the coating industry as described above, the present inventors intend to solve the problems. The research was earnestly started.

[0007] Therefore, the problem to be solved by the present invention is not only excellent in coating workability and curability, but of course, in particular, not only raindrop contamination resistance but also weather resistance, solvent resistance, Compared to conventional organic solvent-based paints, it can give a cured product with excellent chemical resistance and water resistance. It has a low or no organic solvent content and is extremely practical. Another object of the present invention is to provide a curable resin composition for aqueous coating composition.

[0008]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive and intensive studies, focusing on the problems to be solved by the invention as described above, as a result, an aqueous resin containing an acid group and / or a tertiary amino group, and an epoxy group / hydrolyzable silyl group-containing compound And a composition comprising a polyepoxy compound as an essential film-forming component,

[0009] The content of the organic solvent is small, the coating workability and the curability are excellent, and particularly, the raindrop stain resistance and the like are also extremely excellent. Having found to provide a membrane, we have now completed the invention.

By the way, with respect to the curable resin composition for an aqueous coating material according to the present invention in such a form, that is, the acid group and / or tertiary amino group-containing aqueous resin as the base resin component, the curing agent component is added. As described above, by using the compound having both an epoxy group and a hydrolyzable silyl group in combination with the polyepoxy compound, an unexpected effect was obtained.

In other words, the weather resistance, chemical resistance, and curability are improved, in particular, as compared with the case where the use of such a compound having an epoxy group and a hydrolyzable silyl group is completely absent. On the other hand, in comparison with the case where the use of the polyepoxy compound is completely absent, the raindrop contamination resistance and the like are improved.

That is, the present invention basically comprises a compound (B) having an acid group and / or a tertiary amino group-containing aqueous resin (A) having both an epoxy group and a hydrolyzable silyl group, and a polyepoxy. A specific curable resin composition for an aqueous coating composition, which is composed of a compound (C),

Above all, compared with the conventional organic solvent type, which can give a cured product which is excellent in coating workability and curability, and particularly excellent in raindrop stain resistance, etc., It is an object of the present invention to provide a novel curable resin composition for water-based coatings, which has extremely high practicality and contains little or no organic solvent.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the present invention combines an acid group- and / or tertiary amino group-containing aqueous resin (A) with an epoxy group and a hydrolyzable silyl group as essential constituents, respectively. Claiming a curable resin composition for an aqueous coating composition, which comprises the compound (B) having and the polyepoxy compound (C),

Alternatively, as an essential constituent, an acid group- and / or tertiary amino group-containing aqueous resin (A), a compound (B) having both an epoxy group and a hydrolyzable silyl group, and a polyepoxy compound ( C),
A curable resin composition for an aqueous coating composition, which comprises a compound (D) having a hydrolyzable silyl group and / or a silanol group other than the above-mentioned compound (B), is also claimed. ,

Further, as the above-mentioned aqueous resin (A) containing an acid group and / or a tertiary amino group, an emulsion polymer (A-1) obtained by emulsion polymerization of a vinyl monomer in an aqueous medium is contained. It is also said that a curable resin composition for water-based paint in the form of

Further, the above-mentioned acid group and / or 3
As the primary amino group-containing aqueous resin (A), the acid group and / or the tertiary amino group-containing vinyl polymer (I) is allowed to neutralize at least 10% of the acid group or the tertiary amino group, After adding a neutralizing agent, a curable resin composition for water-based paint in the form of containing a hydrate (A-2) obtained by dissolving in water without dispersion is also claimed. ,

Furthermore, the above-mentioned acid group and / or 3
As the primary amino group-containing aqueous resin (A), the acid group and / or the tertiary amino group-containing vinyl polymer (I) is allowed to neutralize at least 10% of the acid group or the tertiary amino group, An aqueous polymer (A-2) obtained by adding a neutralizing agent and then dissolving it in water without dispersion, and an emulsion polymer (A-) obtained by emulsion polymerization of a vinyl monomer in an aqueous medium. 3) and also claims a curable resin composition for water-based paint in the form of containing a mixture consisting of

Further, as the above-mentioned aqueous resin (A) containing an acid group and / or a tertiary amino group, particularly, an emulsion polymer (A in a form prepared by using a vinyl monomer containing a hydroxyl group as an essential component). -1) is used, a specific composition is claimed, and

Further, as the above-mentioned aqueous resin (A) containing an acid group and / or a tertiary amino group, particularly in a form prepared by using a vinyl monomer containing a hydroxyl group as an essential component, an acid group and / or Alternatively, after adding a neutralizing agent to the tertiary amino group-containing vinyl polymer (I) so as to neutralize at least 10% of the acid group or the tertiary amino group,
The specific composition of using the hydrate (A-2) in the form of being dispersed or dissolved in water is also claimed.

Furthermore, when the above-mentioned aqueous resin (A) containing an acid group and / or a tertiary amino group is prepared, a hydroxyl group-containing vinyl monomer is used as an essential component. Claiming a specific composition containing the emulsion polymer (A-3),

Furthermore, the above-mentioned acid group and / or 3
A specific composition in which an emulsion polymer (A-1) in a form prepared by using a cycloalkyl group-containing vinyl monomer as an essential component is used as the primary amino group-containing aqueous resin (A). Is also charged,

Furthermore, as the above-mentioned acid group- and / or tertiary amino group-containing aqueous resin (A), in particular, a form prepared by using a cycloalkyl group-containing vinyl monomer as an essential component, A neutralizing agent is added to the acid group- and / or tertiary amino group-containing vinyl polymer (I) so as to neutralize at least 10% of the acid group or the tertiary amino group, and then dispersed in water. No chemical conversion means to use the hydrated product in the form of a solution (A-2), which also requires a specific composition.

Alternatively, when the above-mentioned aqueous resin (A) containing an acid group and / or a tertiary amino group is prepared, it is particularly prepared by using a cycloalkyl group-containing vinyl monomer as an essential component. Emulsion polymer (A-
3) is also claimed to contain a particular composition,

Alternatively, as the above-mentioned aqueous resin (A) containing an acid group and / or a tertiary amino group, an aqueous resin in the form of being used in combination with an acrylic polymer and a fluoroolefin polymer is used. It means that you also request a specific composition,

Further, as the above-mentioned acid group- and / or tertiary amino group-containing aqueous resin (A), it is particularly preferable to use an aqueous resin in the form of being used in combination with an acrylic polymer or a fluoroolefin polymer. It is also said that the composition of

The emulsion polymer (A-
As 3), it is also claimed that a specific composition is used, in particular in the form of having an acid group and / or a tertiary amino group.

Alternatively, the emulsion polymer (A
As -1), in particular, a specific composition in which a polymer obtained by a soap-free polymerization reaction is used is also claimed.

Further, it is also claimed that a specific composition in which the above-mentioned emulsion polymer (A-3), in particular, a polymer obtained by a soap-free polymerization reaction is used. is there.

Here, first, each component constituting the curable resin composition for water-based paint according to the present invention, and above all, each essential component will be described.

First, an acid group-containing and / or tertiary amino group-containing aqueous resin (A) is used as an essential constituent component of the curable resin composition for aqueous paints of the present invention, that is, as a base resin component. If only representative examples of such resins are given as examples, an acrylic polymer,
Various vinyl-based polymers such as aromatic vinyl-based polymers, vinyl ester-based polymers or fluoroolefin-based polymers, polyester resins, alkyd resins or polyurethane resins, etc., and among these, particularly desirable Examples are various vinyl polymers.

The method for preparing the above-mentioned water-based resin (A), which is a so-called base resin component, which constitutes the curable resin composition for water-based paints according to the present invention, will be described.

First, the emulsion polymer (A-1) having an acid group and / or a tertiary amino group will be described. The emulsion polymer (A-
As typical examples of 1), various vinyl emulsion polymers such as acrylic, fluoroolefin, aromatic vinyl, vinyl ester, etc. are listed.

Among these various vinyl polymers, acrylic and fluoroolefin emulsion polymers are particularly preferable.

The emulsion polymer (A-1) having an acid group and / or a tertiary amino group is, for example, a tertiary amino group-containing emulsion polymer (A-1-).
1), an acid group- and tertiary amino group-containing emulsion polymer (A-1-2), an acid group-containing emulsion polymer (A-1-3), and the like.

Here, each of the tertiary amino group-containing emulsion polymers (A-1-1) is abbreviated as a tertiary amino group-containing vinyl monomer [hereinafter referred to as (a-1). ] And the other monomer copolymerizable with this (a-1) [Hereinafter, this is abbreviated as (a-2). ] Using monomers consisting of

The acid group- and tertiary amino group-containing emulsion polymer (A-1-2) includes the tertiary amino group-containing vinyl monomer (a-1) and the acid group-containing vinyl monomer [hereinafter referred to as , (A-3). ] And other vinyl-based monomer (a-2) copolymerizable with these (a-1) and (a-3),

Acid group-containing emulsion polymer (A-1
-3) is a monomer consisting of the acid group-containing vinyl monomer (a-3) and the other vinyl monomer (a-2) copolymerizable with this (a-3). It can be prepared separately from each other by various known and conventional emulsion polymerization methods.

These emulsion polymers (A-1-1), (A-1-2) and (A-1-3), respectively.
The method for preparing (1) will be described more specifically.

1. First, the method for preparing the tertiary amino group-containing emulsion polymer (A-1-1) will be described. The emulsion polymer (A-1-1)
As a vinyl-based monomer used for preparing 1), first, a tertiary amino group-containing vinyl-based monomer (a-
If we only exemplify the typical ones as 1),
2-dimethylaminoethyl (meth) acrylate, 2-
Diethylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate or 3-
Diethylaminopropyl (meth) acrylate, N-
Various (meth) acrylic acid esters such as [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine or N- [2- (meth) acryloyloxyethyl] morpholine System monomers;

Various aromatic monomers such as 4- (N, N-dimethylamino) styrene, 4- (N, N-diethylamino) styrene or 4-vinylpyridine, and further, Various tertiary amino-containing vinyl ethers such as 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 4-dimethylaminobutyl vinyl ether, 4-diethylaminobutyl vinyl ether or 6-dimethylaminihexyl vinyl ether.

On the other hand, as the other vinyl-based monomer (a-2) copolymerizable with the above-mentioned tertiary amino group-containing vinyl-based monomer (a-1), only typical ones are listed. Non-functional monomers such as alkyl (meth) acrylates, alkyl crotonic acid, dialkyl unsaturated dibasic acid, vinyl monocarboxylic acid esters or vinyl aromatic monomers ;

Or monomers having a non-functional silicon atom such as a monomer having a polysiloxane bond; a fluoroolefin monomer containing a fluorine atom; a monomer having a polyether chain; Or monomers having various functional groups such as amide group, cyano group, hydroxyl group, epoxy group or hydrolyzable silyl group; further, having two or more polymerizable double bonds per molecule, They are so-called polyfunctional vinyl monomers.

Of these monomers, only representative examples of non-functional monomers are given as examples: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl ( (Meth) acrylate, iso
-Propyl (meth) acrylate, n-butyl (meth)
Acrylate, iso-butyl (meth) acrylate,
Various (meth) acrylic acid esters such as tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate. Kind;

Or various crotonic acid esters such as methyl crotonic acid, ethyl crotonic acid or n-butyl crotonic acid; or various unsaturated compounds such as dimethyl maleate, dimethyl fumarate, dibutyl fumarate or dimethyl itaconate. Dibasic acid dialkyl esters; further, vinyl acetate, vinyl cyclohexanecarboxylate, vinyl benzoate, vinyl p-tert-butyl benzoate or "Veova" (vinyl ester of branched monocarboxylic acid manufactured by Ciel Co. of the Netherlands. Various monocarboxylic acid vinyl esters, such as

Alternatively, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-
It is various alkyl ethers or cycloalkyl vinyl ethers such as butyl vinyl ether, iso-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclopentyl vinyl ether, cyclohexyl vinyl ether, and further, styrene, α-methylstyrene, p-tert. -Various aromatic vinyl monomers such as butyl styrene or vinyl toluene.

Only typical examples of monomers having a so-called non-functional silicon atom, such as a monomer having a polysiloxane bond, are given as examples.

[0048]

Embedded image CH ₂ ＣＨCHCOO (CH ₂ ) ₃ [Si (CH
₃ ) ₂ O] _n Si (CH ₃ ) ₃

[0049]

Embedded image CH_Two= C (CH_Three) COOC₆H_Four[Si
(CH_Three)_TwoO]_nSi (CH_Three) _Three

[0050]

Embedded image CH_Two= C (CH_Three) COO (CH_Two)_Three[S
i (CH_Three)_TwoO]_nSi (CH _Three)_Three

[0051]

Embedded image CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ [S
i (CH ₃ ) (C ₆ H ₅ ) O] _n Si (CH ₃ ) ₃

[0052]

Embedded image CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ [S
i (C ₆ H ₅ ) ₂ O] _n Si (CH ₃ ) ₃

(However, n in each formula is 0 or 1 to
It is assumed that the integer is 130. )

Various monomers represented by the above general formula are listed.

As the above-mentioned fluoroolefin monomers, only typical ones are exemplified. Vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, hexafluoropropylene or chlorotritriene. Examples include various fluoroolefins such as fluoroethylene.

As the monomers having a polyether chain as described above, only typical ones are exemplified, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and polytetramethylene. Examples thereof include glycol mono (meth) acrylate, monoalkoxy polyethylene glycol (meth) acrylate, and monoalkoxy polypropylene glycol (meth) acrylate.

Of the monomers having a functional group as described above, first, only the representative examples of the monomer having an amide group are exemplified, and (meth) acrylamide, N, N-dimethyl (meth) acrylamide,
Examples thereof include various carboxylic acid amide group-containing vinyl monomers such as N-alkoxymethyl (meth) acrylamide, diacetone (meth) acrylamide and N-methylol (meth) acrylamide.

Of the monomers having a functional group, only typical examples of the monomer having a hydroxyl group are given. 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) ) Acrylate, 2
-Hydroxybutyl (meth) acrylate or 4-
Various hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate;

2-hydroxyethyl vinyl ether, 4
-Hydroxyl vinyl ethers such as hydroxybutyl vinyl ether or 6-hydroxyhexyl vinyl ether; or allyl ethers containing hydroxyl groups such as 2-hydroxyethoxyallyl ether or 4-hydroxybutoxyallyl ether; And an adduct of ε-caprolactone with the hydroxyl group-containing monomers of

Of the monomers having a functional group, only typical examples of the monomer having a cyano group are acrylonitrile, methacrylonitrile, crotononitrile and the like.

Of the monomers having a functional group, only typical examples of the monomer having an epoxy group will be given below. Glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxyvinyl cyclohexane, di (β-methyl) glycidyl malate or di (β
-Methyl) glycidyl fumarate.

Of the monomers having a functional group, the hydrolyzable silyl group contained in the monomer having a hydrolyzable silyl group is, for example, an alkoxy group, a substituted alkoxy group, a phenoxy group or a halogen. An atomic group containing a silicon atom to which an atom, an isopropenyloxy group, an acyloxy group, an iminooxy group, or the like is bonded, which is easily hydrolyzed to form a silanol group. To do.

The hydrolyzable silyl group constitutes a polysiloxane skeleton, and may be a silicon atom to which various groups described above are bonded. For example, An alkoxysilyl group, a phenoxysilyl group, a halosilyl group, an isopropenyloxysilyl group, a thioalkoxysilyl group, an acyloxysilyl group, an aminoxysilyl group or an iminooxysilyl group represented by the formula [I]. It may be.

[0064]

[Chemical 6]

(Wherein R ₁ is a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, and X ₁ is a halogen atom, an alkoxy group or an acyloxy group. Group, an aminoxy group, a phenoxy group, a thioalkoxy group, an isopropenyloxy group, an iminoxy group and an amino group, and represents a monovalent organic group, and a is 0 or an integer of 1 or 2. There is.)

If only typical vinyl monomers having such a hydrolyzable silyl group are shown, γ
-(Meth) acryloxypropyltrimethoxysilane,
γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltriisopropenyloxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (tris-β-methoxyethoxy) silane, vinyltriacetoxysilane or vinyltrichlorosilane.

Further, as monomers having a functional group,
In addition to the above-mentioned compounds, various silyl esters of carboxyl group-containing monomers such as trimethylsilyl (meth) acrylate or tert-butyldimethylsilyl (meth) acrylate; 1-ethoxyethyl (meth) It has various acetal ester groups in a form obtained by reacting various carboxyl group-containing monomers such as acrylate or 1-isobutoxyethyl (meth) acrylate with α, β-unsaturated ether compounds. Monomers;

Silyl ethers of various monomers having a hydroxyl group such as 2-trimethylsiloxyethyl (meth) acrylate or 2-dimethyl-tert-butylsilyloxyethyl (meth) acrylate;
Various aziridinyl group-containing monomers, such as aziridinylethyl (meth) acrylate; Monomers having various isocyanate groups, such as 2-isocyanatoethyl (meth) acrylate or (meth) acryloyl isocyanate Body type;

Blocked isocyanate group-containing monomers in a form prepared by reacting various isocyanate group-containing monomers as described above with various blocking agents; or 2-isopropenyl- Examples include compounds having various functional groups such as oxazoline group-containing monomers such as 1,3-oxazoline and 2-vinyl-1,3-oxazoline.

If only the representative ones of the above-mentioned polyfunctional vinyl-based monomers are given, ethylene glycol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, allyl (meth) acrylate or Examples include diallyl phthalate and divinylbenzene.

The amount of the tertiary amino group-containing vinyl monomer used when preparing the tertiary amino group-containing emulsion polymer (A-1-1) is the emulsion polymer (A-1-1). In the range of about 0.03 to about 2.5 mol, converted to the amount of the tertiary amino group introduced per 1,000 g of the solid content of the above), it is preferable, and preferably,
An amount within the range of 0.05 to 1.5 mol is suitable, and most preferably, an amount corresponding to within the range of 0.05 to 0.5 mol is suitable.

If the amount of the tertiary amino group-containing monomer used is too large, exceeding the amount corresponding to about 2.5 mol,
A cured coating film containing the emulsion (A-1-1) obtained from the curable resin composition for an aqueous coating composition according to the present invention is unfavorable, especially because the chemical resistance is deteriorated.

This emulsion polymer is prepared by emulsion-polymerizing the above-mentioned monomers containing the tertiary amino group-containing vinyl monomers as an essential monomer component in an aqueous medium. In preparing (A-1-1), various known and conventional emulsion polymerization methods can be applied.

That is, various known and conventional non-reactive emulsifiers such as anionic emulsifiers and nonionic emulsifiers; or known various conventional reactive emulsifiers, dispersion stabilizers, etc. By various conventional methods,
A polymerization reaction may be performed.

Specific examples of the anionic emulsifiers to be used in this case include, but are not limited to, compounds such as alkyl (benzene) sulfonates, alkyl sulfate salts or polyoxyethylene alkylphenol sulfate salts. , Even if they are used alone, 2
It goes without saying that more than one kind may be used in combination.

As used herein, the above-mentioned salts refer to salts of alkali metal hydroxides or salts of various volatile bases such as ammonia or triethylamine.

As the nonionic emulsifiers, only representative ones are given, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether or polyoxyethylene-polyoxypropylene block copolymer; or derivatives thereof. Of course, these may be used alone or in combination of two or more.

Further, among the above-mentioned reactive emulsifiers,
As typical examples of the ionic reactive emulsifiers, various vinyl monomers having a so-called salt structure such as sulfonate group, sulfate group or phosphate group can be given.

Of these, vinyl sulfonic acid, allyl sulfonic acid, 2
-Methylallylsulfonic acid, 4-vinylbenzenesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid Some are obtained by neutralizing vinyl monomers containing a sulfonic acid group with various basic compounds.

As the basic compound used in this case, only typical ones are exemplified by inorganic basic compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide or ammonium hydroxide; methylamine. , Ethylamine, n-butylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tri-n-butylamine, diethanolamine,
Examples thereof include various organic basic compounds such as 2-dimethylaminoethyl alcohol, tetramethylammonium hydroxide or tetra-n-butylammonium hydroxide.

Of the above-mentioned ionic reaction raw emulsifiers, only typical ones as vinyl monomers containing a phosphate group are illustrated, such as mono {2- (meth) acryloyloxyethyl} acid phosphate. Examples thereof include those obtained by neutralizing the phosphoric acid group-containing vinyl monomers with various basic compounds as described above.

Of the above-mentioned ionic reaction raw emulsifiers, only typical examples of vinyl monomers containing a sulfate group are vinyl groups containing a sulfate group such as a sulfate of allyl alcohol. Monomers,
Examples thereof include those obtained by neutralizing with various basic compounds as described above.

Only the typical examples of the commercially available products of the neutralized acid group-containing monomer will be described. As the neutralized sulfonic acid group-containing monomer, , "Latemur S-180 or S-180
A "[Kao's product]," Eleminol JS-2 or RS-30 "[Sanyo Chemical Co., Ltd.], etc.

"Aqualon HS-10" [Daiichi Kogyo Seiyaku Co., Ltd.] and "Adecaria Soap SE-10N" as neutralized sulfate group-containing monomers, respectively.
Asahi Denka Kogyo Co., Ltd., etc., and as a monomer having a phosphoric acid group, "New Frontier A
-229E "[Daiichi Kogyo Seiyaku Co., Ltd. product] and the like.

As the ionic reactive emulsifier among the reactive emulsifiers, the monomers having various polyether chains as described above are used.

Further, as the dispersion stabilizer, for example,
Polyvinyl alcohol, hydroxyethyl cellulose,
Starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid (salt), polyacrylamide,
Examples thereof include synthetic or natural water-soluble or water-dispersible polymer substances such as water-soluble or water-dispersible acrylic resins, and one or a mixture of two or more thereof can be used.

When the emulsion polymer (A-1-1) is prepared by the emulsion polymerization method using various emulsifiers or dispersion stabilizers as described above, the amount of the emulsifier used is the emulsion polymer (A -1) 10% by weight or less, preferably 6% by weight, based on the solid content in
The following are preferable from the viewpoint of water resistance of the cured coating film obtained from the composition of the present invention.

A cured coating film obtained from the composition of the present invention can be obtained by applying a so-called soap-free polymerization method in which polymerization is carried out with a very small amount of the emulsifier used, or polymerization is carried out without using the emulsifier at all. The water resistance of can be further improved.

Examples of the soap-free polymerization method include a method in which a reactive emulsifier as described above is mainly used as an emulsifier species, a polymerization method in the presence of a water-soluble or water-dispersible acrylic resin among the stabilizers, and a reaction. And a water-soluble or water-dispersible acrylic resin are used in combination for polymerization. Of these, or method is particularly preferable.

The amount of the reactive emulsifier used in the soap-free polymerization is the emulsion polymer (A
It is 2% by weight or less, preferably 1% by weight or less based on the solid content in (1-1). The amount of the dispersion stabilizer used is 5 to 70% by weight, preferably 10 to 5% by weight based on the solid content of the emulsion polymer (A-1-1).
It is 0% by weight, and if it is too small, the polymerization stability deteriorates,
If it is too large, the resin viscosity becomes extremely high, and the workability in coating becomes poor.

As the water-soluble or water-dispersible acrylic resin used as a dispersion stabilizer, a tertiary amino group-containing acrylic resin is partially or completely neutralized with an acidic compound to be water-soluble or water-dispersed. It is possible to use an anionic water-soluble or water-dispersible acrylic resin in which a cationic water-soluble acrylic resin or a carboxyl group-containing acrylic resin is partially or completely neutralized with a basic compound to be water-soluble or water-dispersed. it can. Of these, the latter anionic water-soluble or water-dispersible acrylic resin is particularly preferable from the viewpoint of water resistance and adhesiveness.

The anionic water-soluble or water-dispersible acrylic resin used as the dispersion stabilizer is as follows.
It is a resin having a functional group that reacts with the functional group contained in the monomer having a functional group used when preparing the emulsion polymer (A-1-1), or the emulsion polymer (A It is more preferable that the resin has a radically polymerizable unsaturated double bond that can be graft-polymerized during the preparation of (1-1).

The aqueous medium for preparing the emulsion polymer (A-1-1) is not particularly limited, but water alone may be used, or water and a water-soluble solvent may be used. You may use it as a mixed solution. Examples of the water-soluble solvent used here include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, and polar solvents such as N-methylpyrrolidone. Mixtures of two or more can be used. The amount of the water-soluble solvent used when using a mixture of water and a water-soluble solvent can be arbitrarily selected from the viewpoint of stability during polymerization, the risk of ignition of the resulting polymer aqueous dispersion, From the viewpoint of safety and hygiene, it is preferable to use the water-soluble solvent in the smallest possible amount. For these reasons, it is preferable to use water alone.

As a polymerization method for preparing the emulsion polymer (A-1-1), (i) water, a vinyl-based monomer, a polymerization initiator, and an emulsifier and / or a dispersion stabilizer are mixed all together. Polymerization method, (ii) a monomer dropping method of dropping a vinyl monomer, or (iii) water,
Various methods such as a so-called pre-emulsion method in which a mixture of a vinyl-based monomer and an emulsifier is mixed in advance can be applied.

Of these methods, the monomer dropping method or the pre-emulsion method is particularly preferable in terms of stability during polymerization.

It is also possible to add a hydrophilic solvent and a hydrophobic solvent and known additives at the time of polymerization, but the amount of them used is the same as that of the resin for water-based paint of the present invention containing them. It is preferable to control the content within a range that does not adversely affect the performance of the cured coating film obtained by coating.

A radical polymerization initiator is used as a polymerization initiator in the preparation of the emulsion polymer (A-1-1), and only typical ones will be given below.
Inorganic peroxides such as potassium persulfate, ammonium persulfate or hydrogen peroxide; organic peroxides such as tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide or cumene hydroperoxide; , 4,4'-azobis (4-cyanopentanoic acid) or 2,2'-azobis (2-amidinopropane) dihydrochloride.

When the above-mentioned peroxide is used as the polymerization initiator, radical polymerization may be carried out by using only the peroxide, or such peroxide may be reduced with acidic sodium sulfite or sodium thiosulfate. It can also be polymerized by a redox polymerization initiator system in which an agent is used in combination.

Further, various chain transfer agents such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid or α-methylstyrene dimer may be used as a molecular weight modifier. Can be used.

The polymerization temperature at the time of preparing the emulsion polymer (A-1-1) varies depending on the kind of the monomer used and the kind of the polymerization initiator, but the polymerization is carried out in an aqueous medium. In such cases, a temperature range of about 30 to about 90 ° C. is usually suitable.

In preparing the emulsion polymer (A-1-1), the tertiary amino group contained in the polymer (A-1-1) is neutralized with an acid even if it is neutralized. It does not need to be present, but when the polymer (A-1-1) is prepared, stability is poor and a block is generated,
When the storage stability or the stability during use is poor, it can be said that such stability can be improved by neutralizing at least a part of the tertiary amino group with an acid.

In order to prepare such a tertiary amino group-containing polymer (A-1-1) which is at least partially neutralized, a tertiary amino group-containing vinyl monomer is previously added to It is a method of polymerizing after neutralizing with an acidic compound, or a method of neutralizing a tertiary amino group by adding an acidic compound during the polymerization, or the polymer ( After preparing A-1-1), various methods such as a method of adding an acidic compound to neutralize it can be applied.

As the above-mentioned acidic compounds, only typical ones are exemplified by formic acid, acetic acid, propionic acid, butyric acid, 2-methylbutyric acid, isovaleric acid, trimethylacetic acid, glycolic acid or lactic acid. Various carboxylic acids having 1 to 10 carbon atoms, represented by

Various monoesters of phosphoric acid such as phosphoric acid monomethyl ester, phosphoric acid dimethyl ester, phosphoric acid mono-iso-propyl ester, phosphoric acid di-iso-propyl ester, phosphoric acid mono-2-ethylhexyl ester or phosphoric acid di-2-ethylhexyl ester. -Or dialkyl esters;

Methanesulfonic acid, propanesulfonic acid,
Various organic sulfonic acids such as benzenesulfonic acid or dodecylbenzenesulfonic acid; or as represented by hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, etc.
Various inorganic acids and the like are used, and among these, use of carboxylic acids is particularly desirable.

When such an acidic compound is added to improve the stability, the amount used is such that the tertiary amino group contained in the polymer (A-1-1) is used. The ratio of the equivalent number of the acidic compound to the equivalent number of the group,

That is, the acidic compound / polymer (A-1
The equivalent ratio of the tertiary amino group contained in -1) is approximately
An amount of 0.1 or more is suitable, but as an amount within the range that does not impair the coating film performance, preferably,
Generally, the range of 0.1 to 3 is suitable, and the range of 0.1 to 2 is most preferable.

2. Next, the method for preparing the acid group- and tertiary amino group-containing emulsion polymer (A-1-2) will be described.
-2) is prepared by adding an acid group-containing vinyl monomer and 3
It is convenient to use a method such as copolymerizing a vinyl monomer containing a primary amino group with another vinyl monomer that can be copolymerized therewith.

Particularly preferred as the acid group-containing vinyl monomer (a-3) used in preparing the acid group- and tertiary amino group-containing emulsion polymer (A-1-2) by the method as described above. To exemplify only typical ones, in addition to the monomers having a sulfonic acid group, a sulfuric acid group or a phosphoric acid group as described above, various carboxyl group-containing monomers and the like are included.

If only representative examples of such a carboxyl group-containing monomer are given, (meth)
Various unsaturated monobasic acids such as acrylic acid or crotonic acid; various unsaturated dibasic acids such as maleic acid, fumaric acid, itaconic acid or citraconic acid; maleic acid, fumaric acid or itacone as described above Half esters of various unsaturated dibasic acids such as acids and alkyl alcohols having 1 to 10 carbon atoms;

Various carboxyl group-containing aromatic compounds such as 4-vinylbenzoic acid or cinnamic acid; mono-2- (meth) acryloyloxyethyl succinate or mono-2- (meth) acryloyloxyethyl phthalate. Esters such as addition reaction products of various hydroxyl group-containing monomers as described above and saturated dibasic acid anhydrides, and further malonic acid, succinic acid, adipic acid or Examples thereof include monovinyl esters of various polyvalent carboxylic acids such as sebacic acid.

Among the various acid group-containing monomers described above, it is particularly preferable to use the carboxyl group-containing monomer.

When the emulsion polymer (A-1-2) is prepared, the tertiary amino group-containing vinyl monomer may be the tertiary amino group-containing vinyl monomer (a) as described above. -1) may be used, and as the other monomer copolymerizable with the acid group-containing monomer and the tertiary amino group-containing vinyl monomer, respectively. The monomer (a-2) as described above may be appropriately selected and used.

It should be used when preparing the acid group- and tertiary amino group-containing emulsion polymer (A-1-2),
The amount of the tertiary amino group-containing vinyl monomer used is converted to the amount of the tertiary amino group introduced per 1,000 g of the solid content of the emulsion polymer (A-1-2). Then, the range of about 0.03 to about 2.5 mol is suitable, the range of 0.05 to 1.5 mol is suitable, and the most preferable range is 0.05 to 1.5 mol. 0.
An amount corresponding to a range of 5 mol is suitable.

If the amount of the tertiary amino group-containing monomer used is too large, exceeding the amount corresponding to about 2.5 mol,
It is not preferable because the final top-coat coating film has poor chemical resistance, in particular.

On the other hand, acid group-containing vinyl monomer (a-3)
The amount of use of the emulsion polymer (A-1-
The amount is about 0.05 to about 3 mol, preferably about 0.01 to 2.0 mol in terms of the amount of acid groups introduced per 1,000 g of the solid content of 2). However, the most preferable amount is in the range of 0.1 to 0.7 mol.

In order to prepare the emulsion polymer (A-1-2) from the various monomers listed above, various known and conventional emulsion polymerization methods as described above are used. It may be prepared by applying.

In preparing the emulsion polymer (A-1-2), the emulsion polymer (A-
The acid group or tertiary amino group contained in 2) may or may not be neutralized with a neutralizing agent,

When the polymer (A-1-2) is prepared and the stability is poor and blocks occur, or the storage stability or the stability during use is poor, By neutralizing at least a part of the tertiary amino group and / or the acid group with the neutralizing agent with the neutralizing agent, the stability thereof can be improved.

Such a polymer (A-) having an acid group and a tertiary amino group in at least a partially neutralized form.
In order to prepare 1-2), a tertiary amino group-containing vinyl monomer is preliminarily neutralized with an acidic compound and then polymerized, or an acidic compound is added during the polymerization. There is a method of adding it to neutralize the tertiary amino group,

Alternatively, a method in which the polymer (A-1-2) is prepared and then neutralized by adding an acidic compound, or an acid group-containing vinyl monomer is preliminarily added to a basic compound. And then copolymerization, or during polymerization, a basic compound is added to neutralize the acid group, or the polymer (A- After preparing 1-2), various methods such as a method of adding a basic compound to neutralize it can be applied.

As the above-mentioned acidic compound, various compounds as already described can be used as those used for neutralizing the above-mentioned polymer (A-1-1). Of these, the use of carboxylic acids is particularly preferable.

When such an acidic compound is added to improve the stability, the amount of the acidic compound used is 3 contained in the polymer (A-1-2).
The ratio of the number of equivalents of the acidic compound to the number of equivalents of the primary amino group,

That is, the acidic compound / polymer (A-1
-2), the equivalent ratio of the tertiary amino group contained in
An amount of 0.1 or more is suitable, but as an amount in a range that does not impair coating film performance, it is preferably about 0.
The range of 1 to 3 is suitable, and most preferably,
A range of 0.1 to 2 is appropriate.

The basic compound used to neutralize the acid group is an ionic reactive emulsifier,
The compounds as already described are used as being used in preparing the neutralized acid group-containing monomer.

The emulsion film, especially,
When it is desired to further improve the water resistance, among these basic compounds, those basic compounds that are volatilized at room temperature or by heating, such as ammonia or methylamine, dimethylamine or trimethylamine, and so-called It is desirable to use low boiling amines and the like.

When the basic compound neutralizes the acid groups contained in the polymer (A-1-2), the addition amount of the basic compound is the polymer (A-1). -2) with respect to the number of equivalents of acid groups contained in
The ratio of the number of equivalents of this basic compound,

That is, the basic compound / polymer (A-
The equivalent ratio of the acid group contained in 1-2) is about 0.1.
Although the amount as described above is appropriate, as an amount within a range that does not impair the performance of the coating film, preferably, generally,
The range of 0.1 to 3 is suitable, and the range of 0.1 to 2 is most preferable.

3. Subsequently, the method for preparing the acid group-containing emulsion polymer (A-1-3) will be described.

The above-mentioned vinyl emulsion polymer (A-1-3) having an acid group can be easily prepared by various known and conventional methods. However, it is simple, although it is carried out by a method of copolymerizing it with another vinyl-based monomer which can be copolymerized.

The acid group-containing monomer used in the preparation of the acid group-containing vinyl emulsion polymer (A-1-3) by the method as described above is the acid group-containing monomer as described above. The monomer (a-3) may be used, and the acid group-containing monomer (a-
The other vinyl-based monomer copolymerizable with 3) may be appropriately selected and used from the above-mentioned (a-2).

The acid group-containing emulsion polymer (A-1
-3), the amount of the acid group-containing vinyl monomer (a-3) to be used is 1,000 g of the solid content of the emulsion polymer (A-1-3). In terms of the amount of acid groups introduced per unit, about 0.05 to 3 mol, preferably about 0.01 to 2.0 mol is suitable, and most preferably 0.1 to 0 mol. An amount corresponding to a range of 0.7 mol is suitable.

In order to prepare the emulsion polymer (A-1-3) from the various monomers listed above, various known and conventional emulsion polymerization methods as described above are applied. The preparation may be carried out by

In preparing the emulsion polymer (A-1-3), the emulsion polymer (A-1-
The acid group contained in 3) may or may not be neutralized with a basic compound, but the stability is poor when the polymer (A-1-3) is prepared. hand,
In the case of block formation or inferior storage stability or stability during use, basic compounds neutralize at least part of the acid groups to improve their stability. Can be transformed.

In order to prepare the acid group-containing polymer (A-1-3) in such a form that at least a part thereof is neutralized, the acid group-containing vinyl monomer is previously added with a basic monomer. A method of neutralizing with a compound and then copolymerizing, a method of adding a basic compound during the polymerization to neutralize an acid group, or the polymer (A-1)
After preparing -3), various methods such as a method of adding a basic compound to neutralize it can be applied. In that case, it can be said that the above-mentioned basic compound is used as the above-mentioned basic compound.

And, by such a basic compound,
In the case of neutralizing the acid group contained in the polymer (A-1-3), the addition amount of the acid group contained in the polymer (A-1-3) is The ratio of the number of equivalents of the basic compound to the number of equivalents,

That is, the basic compound / polymer (A-
The equivalent ratio of the acid groups contained in 1-3) is about 0.1.
Although the amount as described above is appropriate, as an amount within a range that does not impair the performance of the coating film, preferably, generally,
The range of 0.1 to 3 is suitable, and the range of 0.1 to 2 is most preferable.

Among the monomers having a functional group in the emulsion polymer (A-1) thus prepared, a hydroxyl group-containing monomer is used as one of the copolymerization components. Therefore, when the hydroxyl group is introduced, the emulsion polymer (A-1) is said to be contained,
Aqueous paint for topcoat obtained by using the curable resin composition for water-based paint according to the present invention, in particular, the curability and the like can be further improved, and more excellent solvent resistance, It is possible to obtain a cured coating film having extremely high practicality, which has higher hardness and also has a better appearance.

When the above-mentioned hydroxyl group-containing monomer is copolymerized, the copolymerization amount is based on the amount of the hydroxyl group introduced per 1,000 g of the solid content of the emulsion polymer (A-1). A converted amount of about 0.04 to 2 mol, preferably about 0.08 to 1.2 mol is suitable.

Among the various non-functional monomers as described above, various cycloalkyl group-containing monomers such as cyclohexyl (meth) acrylate are used as a copolymerization component, Polymer (A-
When a cycloalkyl group is introduced into 1),
It is said that the coating film obtained by using the curable resin composition for an aqueous coating material according to the present invention, which contains the polymer (A-1), further improves the weather resistance and the water resistance. You can

Furthermore, by combining the polyepoxy compound (C) and the silane compound (D) respectively, which will be described later, a more excellent coating film appearance and
It can be said that a coating film having more excellent resistance to raindrop contamination is obtained.

In the emulsion polymer (A-1),
When the cycloalkyl group is introduced, the amount of the cycloalkyl group-containing monomer used is the amount of the cycloalkyl group introduced per 1,000 grams of the solid content of the emulsion polymer (A). 0.5 to 5
An amount corresponding to about mole is preferably 1.0 to 4.2.
Amounts equivalent to the molar range are suitable.

The polymer used in the present invention (A
-1) may be one in which the particles are not crosslinked or may be crosslinked, but by internal crosslinking, the cured coating film, in particular, water resistance and weather resistance Etc. can be further improved.

In order to crosslink the inside of the particles of the polymer (A-1), monomers having a hydrolyzable silyl group are used in combination, or each has a functional group capable of reacting with each other. It suffices to use two or more kinds of monomers in combination, and further use polyfunctional monomers in combination with M.

As an example of the formulation for crosslinking the inside of the particles, a hydrolyzable silyl group-containing monomer is used and the polymer (A
In order to crosslink the inside of the particles of -1), the amount of hydrolyzable silyl groups introduced per 1,000 g of the solid content of the emulsion polymer (A-1) is converted to about 1 to 400 mmol. The amount of hydrolyzable silyl group-containing monomers corresponding to 2 to 20 mmol is preferably copolymerized.

The number average molecular weight of the emulsion polymer (A-1) thus prepared is generally 5,000 or more, preferably 30,000.
A value of 0 or more, most preferably 50,000 or more is suitable.

The solid content concentration of the polymer (A-1) is within the range of about 20 to about 70% by weight, and more preferably within the range of 20 to 60% by weight, for the reasons described above. Is appropriate.

That is, by setting the solid content concentration to about 70% by weight or less, an abnormal increase in the viscosity of the system during the polymerization can be suppressed, and the exothermic heat during the polymerization of the monomer can be easily removed. In addition, the emulsion polymer (A) can be easily produced stably. Further, when the solid content concentration is 60% by weight or less, the viscosity of the polymer (A) is desirable because it can be obtained in a range practically required in various applications.

On the other hand, from the viewpoint of productivity, it is desirable that the solid content concentration is about 20% by weight or more.

The particle size of the polymer (A-1) is
Although not particularly limited, the number average particle size is about 3
It is said that the range of 0 to about 1,000 nanometers (nm) is desirable from the viewpoint of the film-forming property of the emulsion film.

The emulsion polymer (A-1) thus prepared has a number average molecular weight of about 5,
000 or more, preferably 30,000 or more, most preferably 50,000 or more is suitable.

Then, a carboxyl group and / or 3
Aqueous solution obtained by adding a neutralizing agent to the vinyl polymer (I) containing a primary amino group so as to neutralize at least 10% of the functional groups as described above, and then dispersing or dissolving it in water. The method for preparing the compound (A-2) will be described.

First, a carboxyl group- and / or tertiary amino group-containing vinyl polymer (I) is used, but if only representative examples of such vinyl polymer are given, the acrylic polymer will be used. And various polymers such as polymers, aromatic vinyl polymers, vinyl ester polymers, fluoroolefin polymers, and the like.

Among these various vinyl polymers, acrylic polymers and fluoroolefin polymers are particularly preferable.

Only specific examples of the vinyl-based polymer (I) will be exemplified. The tertiary amino group-containing vinyl-based polymer (I-1),
Vinyl-based polymer having both carboxyl group and tertiary amino group (I
-2), or a carboxyl group-containing vinyl polymer (I-3).

Then, only specific examples of the hydrated product (A-2) prepared from the vinyl polymer (I) will be given as follows: (a) The vinyl polymer (I)
-1) Aqueous compound (A-2-1) in the form of being obtained by adding an acidic compound as a neutralizing agent, and (a) the vinyl polymer (I-2) as a neutralizing agent. Aqueous product (A-2-2) in the form of being obtained by adding an acidic compound,
(C) A hydrate (A-2-3) in the form of being obtained by adding a basic compound as a neutralizing agent to the vinyl polymer (I-2), and further (D) the vinyl An aqueous product (A-2-4) in the form of being obtained by adding a basic compound as a neutralizing agent to the system polymer (I-3).

4. First, the above-mentioned tertiary amino group-containing vinyl polymer (I-1) is partially neutralized or completely neutralized with an acidic compound, and then obtained by dispersing or dissolving in water. Form of hydrate (A-2
-1) will be described.

The above-mentioned tertiary amino group-containing vinyl polymer (I-1) can be easily prepared by various known and conventional methods.
It can be said to be prepared, for example, by copolymerizing a tertiary amino group-containing vinyl-based monomer with another vinyl-based monomer copolymerizable therewith,

As described in JP-A-59-56243, a vinyl-based polymer containing an acid anhydride group can be used in an amount of 3
For example, a compound having both a primary amino group and a primary amino group is subjected to an addition reaction and then subjected to a dehydration imidization treatment,

Various methods such as the above can be applied. Of these, the above-mentioned method is the most convenient, and the above method is recommended.

The tertiary amino group-containing vinyl monomer used in preparing the tertiary amino group-containing vinyl polymer (I-1) by the above-mentioned method is
Already 1. Monomer (a-1) as described in the section
And so on.

This tertiary amino group-containing vinyl monomer (a
-1), other vinyl-based monomer copolymerizable with
The monomer (a-2) as described above may be appropriately selected and used.

In order to prepare a fluoroolefin polymer among various vinyl polymers, a fluoroolefin and a tertiary amino group-containing monomer are used as essential components and, if necessary, co-polymerized with them. The other polymerizable monomers may be used together.

Specific examples of the fluoroolefins used at that time include, but are not limited to, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene. Examples include various fluoroolefins.

In order to prepare the vinyl polymer (I-1) from various monomers as mentioned above, any one of various known and conventional polymerization methods is applied. Among them, the solution radical polymerization method is particularly recommended because it is the simplest method.

As the solvents to be used at that time, only representative ones are exemplified, and various hydrocarbons such as toluene, xylene, cyclohexane, n-hexane or octane; methanol, ethanol,
various alcohols such as iso-propanol, n-butanol, iso-butanol, sec-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether or ethylene glycol monobutyl ether;

There are various ester types such as methyl acetate, ethyl acetate, -n-butyl acetate or amyl acetate; or various ketone types such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. These are used alone. However, it goes without saying that two or more kinds may be used in combination, and further, water may be used in combination.

A polymerization reaction may be carried out by a conventional method using such a solvent and various known and commonly used radical polymerization initiators such as azo-based or peroxide-based ones. If necessary, it is possible to use the above-mentioned molecular weight modifier.

The amount of the tertiary amino group to be introduced per 1,000 g of the solid content of the tertiary amino group-containing vinyl polymer (I-1) thus prepared is about A range of 0.03 to about 2.5 mol is suitable, a range of 0.05 to 1.5 mol is suitable, and a range of 0.05 to 0.5 mol is most preferred. Within the range, it is appropriate. The number average molecular weight of the polymer (I) is generally about 500 to 100,000, and preferably 1,000 to 30,000.

Further, the emulsion polymer (A-1-1)
For the same reason as described above, the tertiary amino group-containing vinyl polymer (I-1) may be added with a hydroxyl group-containing monomer as one of the other copolymerizable monomers as described above. It is of course possible to introduce a hydroxyl group by using a monomer.

The tertiary amino group-containing vinyl polymer (I
-1), when introducing a hydroxyl group,
The amount of the hydroxyl group introduced is about 0.04 to 2 mol, preferably about 0.08 to 1.2 mol, per 1,000 g of the solid content of the polymer (I-1). is there.

Further, the emulsion polymer (A-
Due to the same reason as in 1-1), the tertiary amino group-containing vinyl polymer (I-1) may be added to various non-functional monomers such as cyclohexyl (meth) as described above. Of course, it is also possible to introduce various cycloalkyl group-containing monomers such as acrylate by using them as copolymerization components.

The tertiary amino group-containing vinyl polymer (I
-1), when the cycloalkyl group is introduced, the amount of the cycloalkyl group introduced is such that the cycloalkyl group introduced per 1,000 g of the solid content of the polymer (I-1). Converted to the amount of alkyl groups,
About 0.5 to 5 mol is preferable, and about 1.0 to 4.2 mol is suitable.

An acidic compound is added as a neutralizing agent to the tertiary amino group-containing vinyl polymer (I-1) thus prepared to partially remove the tertiary amino group in the polymer. Or by completely neutralizing,
That is, a polymer having water dispersibility or water solubility is prepared.

As the above-mentioned acidic compounds used in this case, there are those mentioned above, and of these, it is particularly preferable to use carboxylic acids.

The amount of the acidic compound added is at least an amount that can impart water dispersibility to the vinyl polymer (I-1). The ratio of the equivalent number of the acidic compound to the equivalent number of the tertiary amino group contained in the polymer (I-1),

That is, it is appropriate that the equivalent ratio of the acid group in the acidic compound / the tertiary amino group in the vinyl polymer (I-1) is about 0.1 or more. The amount within the range that does not impair the various properties of the coating film is preferably within the range of 0.1 to 3, and most preferably within the range of 0.1 to 2.

From the neutralized product of the vinyl polymer (I-1) thus prepared, the above-mentioned aqueous product (A-2-
In order to prepare 1), it can be said that various conventionally known methods are applied. For example, water is simply added to the neutralized product, or the neutralized product is added to water. It can be said that this hydrate (A-2-1) can be produced by dispersing or dissolving it in water.

Further, if necessary, the organic solvent used in preparing the vinyl polymer (I-1) can be partially or completely removed by heating and / or reducing pressure. The hydrate (A-2-1) having a low content of the organic solvent or containing no organic solvent can be prepared.

5. Next, an equivalent amount of an acid compound in the vinyl polymer (I-2) having both the acid group and the tertiary amino group, which is an acid group in the acidic compound / the tertiary amino group in the vinyl polymer. The hydrated product (A-2-2) obtained by dispersing or dissolving in water after being added at a ratio of about 0.1 or more will be described.

First, the vinyl polymer (I-2) having both a carboxyl group and a tertiary amino group can be prepared by various known and conventional methods. For example, a tertiary amino group can be prepared. A vinyl monomer containing and a vinyl monomer containing an acid group are subjected to a polymerization reaction of a monomer mixture as an essential component,

As disclosed in JP-A-59-56243, a vinyl polymer containing a carboxylic acid anhydride group is reacted with a compound having both a tertiary amino group and an active hydrogen-containing group.

For example, by reacting a vinyl-based polymer having both a hydroxyl group and a tertiary amino group with a dicarboxylic acid anhydride,

Alternatively, a free acid group such as a trialkylsilyl ester group, a hemiacetal ester group or a tert-butyl ester group is easily generated by the action of an acid, heat or water. A vinyl monomer having a blocked acid group, and 3
A vinyl polymer having both a tertiary amino group and a blocked acid group is prepared by polymerizing a monomer mixture containing a vinyl monomer containing a tertiary amino group as an essential component,

Then, it can be said that a method such as converting a blocked acid group into a free acid group can be applied. Of these, the above method may be particularly recommended because it is the simplest method.

The tertiary amino group-containing vinyl monomer used in preparing the acid group / tertiary amino group-containing vinyl polymer (I-2) by the above-mentioned method is, of course, It can be said that various types of tertiary amino group-containing vinyl monomers (a-1) as described above are used.

The acid group-containing vinyl monomer used in the preparation of the vinyl polymer (I-2) may be the acid group-containing vinyl monomer (a- 3)
Can be used. And among these, the use of carboxyl group-containing monomers is particularly desirable.

Further, as other copolymerizable vinyl-based monomer used when preparing the vinyl-based polymer (I-2), the above-mentioned monomer (a-2) can be used. It can be selected and used from among them.

In order to prepare a fluoroolefin polymer of the vinyl polymer (I-2), the tertiary amino group-containing vinyl polymer (I-1) as described above is prepared.
The fluoroolefin as exemplified above may be used as an essential monomer component for the preparation of the above.

To prepare the vinyl polymer (I-2) from the various monomers listed above, for example, a method similar to that of the vinyl polymer (I-1), and Solvents and initiators can be adopted and applied.

The amount of the tertiary amino group introduced per 1,000 grams of the solid content of the vinyl polymer (I-2) thus prepared is about 0.03 to about 2.
The amount within the range of 5 mol is suitable, and preferably 0.0
The range of 5 to 1.5 mol is suitable, and the range of 0.05 to 0.5 mol is more preferable.

The amount of the acid group is appropriately within the range of about 0.07 to about 5.0 mol, and preferably,
The range of 0.07 to 2.0 mol is suitable, and the range of 0.1 to 0.7 is most preferable.
Further, the number average molecular weight of the vinyl polymer (I-2) is generally in the range of 500 to 100,000, preferably in the range of 1,000 to 30,000.

An acidic compound as a neutralizing agent is added to the thus-prepared vinyl polymer (I-2) having both tertiary amino group and acid group to prepare a polymer in the polymer (I-2). It means that a water-dispersible or water-soluble polymer is prepared by partially or completely neutralizing the tertiary amino group.

The acidic compound used at that time is as follows:
The various compounds described above, such as those used for preparing the above-mentioned aqueous compound (A-2-1), can be used. Among them, the use of carboxylic acid is particularly desirable.

The addition amount of the acidic compound is such that the acid group / vinyl polymer (I-2) in the acidic compound is added.
It is suitable that the equivalent ratio of the tertiary amino group therein is about 0.1 or more, preferably 0.1 to 3, and most preferably 0.1. It is suitable to be within the range.

From the neutralized product of the vinyl polymer (I-2) thus prepared, the above-mentioned aqueous product (A-2-
To prepare 2), for example, a hydrate (A-2-1) is obtained from the neutralized product of the vinyl polymer (I-1) as described above.
The method similar to that for preparing

6. Next, a basic compound is added to the vinyl polymer (I-2) having a tertiary amino group / acid group described above,
The basic group / vinyl polymer (I-
The equivalent ratio represented by the ratio of the equivalent numbers of the acid groups in 2) is 0.1.
Aqueous product (A-2-3) obtained by dispersing or dissolving in water after adding in the above proportions
Will be explained.

First, the tertiary amino group / acid group-containing vinyl polymer (I-2) was prepared from the above-mentioned hydrate (A-2-
It can be prepared by the method already described in the process of 2).

The thus-prepared tertiary amino group
A basic compound as a neutralizing agent is added to the vinyl polymer having an acid group (I-2) to partially or completely neutralize the acid group in the polymer (I-2). By soaking, a water-dispersible or water-soluble polymer is prepared.

[0200] As the basic compounds to be used at that time, only typical ones will be exemplified, and those exemplified as those which can be used when preparing the emulsion polymer (A-1) are mentioned. To be Among these various basic compounds, the use of ammonia and various organic amines is particularly preferable.

The amount of the basic compound added is appropriate such that the equivalent ratio of the basic compound / the acid group in the vinyl polymer (I-2) is 0.1 or more. However, the range of 0.1 to 3 is preferable, and the range of 0.1 to 2 is most preferable.

To prepare the aqueous product (A-2-3) from the mixture of the vinyl polymer (I-2) thus obtained and the basic compound, for example, as described above, It can be prepared from the neutralized product of the vinyl polymer (I) by the method described above in the process for producing the aqueous product (A-2-1).

7. Then, the acid group-containing vinyl polymer (I-3) described above is partially neutralized or completely neutralized with a basic compound, and then dispersed or dissolved in water to obtain an aqueous product ( A-2-4) will be described.

The acid group-containing vinyl polymer (I-
3) can be prepared by various known and conventional methods.

That is, for example, by copolymerizing an acid group-containing vinyl-based monomer with another copolymerizable vinyl-based monomer,

For example, by reacting a hydroxyl group-containing vinyl polymer with a dicarboxylic acid anhydride,

As described above, after the blocked acid group-containing vinyl monomer is copolymerized with another copolymerizable vinyl monomer, the blocked acid group is converted into a free acid group. Various methods such as converting to a base can be applied.

Of these, the above method can be recommended because the above method is the most convenient.

The acid group-containing vinyl monomer used for preparing the acid group-containing vinyl polymer (I-3) by the above-mentioned method is, of course, the above-mentioned tertiary amino group / acid group. Various acid group-containing vinyl monomers as described above, which are used in the preparation of the combined vinyl polymer (I-2), can be used as they are.

Of these acid group-containing vinyl monomers, it is particularly preferable to use a carboxyl group-containing monomer.

Further, as the other copolymerizable vinyl-based monomer used when preparing the vinyl-based polymer (I-3), the vinyl-based polymer (I-1) is of course prepared. Various vinyl-based monomers, such as those mentioned above, which are used in the above case, can be used.

The fluoroolefin polymer of the vinyl polymer (I-3) is prepared by preparing the tertiary amino group-containing vinyl polymer (I-1) as described above. The fluoroolefin as exemplified above may be used as an essential monomer component.

To prepare the vinyl polymer (I-3) from the various monomers listed above, for example, the same vinyl polymer (I-1) as described above can be used. The method, the solvent, the initiator and the like can be directly adopted and applied, or can be used.

The amount of acid groups to be introduced per 1,000 g of solid content of the vinyl polymer (I-3) thus prepared is about 0.07 to about 5.0 mol. The range is appropriately, and preferably 0.3 to
A suitable range is 2.0 moles, and the number average molecular weight of the vinyl polymer (I-3) is generally
Within the range of 500 to 100,000, preferably
The range of 1,000 to 30,000 is suitable.

A basic compound is added to the acid group-containing vinyl polymer (I-3) thus prepared to partially or completely remove the acid groups in the polymer (I-3). By neutralizing, a water-dispersible or water-soluble polymer is prepared.

As the basic compound used at that time, of course, various compounds as described above, which are used when preparing the above-mentioned hydrate (A-2-3), are used. Of these, the use of ammonia or various organic amines is particularly desirable.

The amount of the basic compound added is such that the basic group / vinyl polymer (I-
It is suitable that the equivalent ratio of the acid groups in 3) is about 0.1 or more, preferably 0.1 to 3 and most preferably 0.1. The range of 1-2 is suitable.

To prepare the aqueous product (A-2-4) from the mixture of the vinyl polymer (I-3) thus obtained and the basic compound, for example, the above-mentioned vinyl-based product is used. It may be carried out according to the same method as in the case of preparing the aqueous product (A-2-1) from the neutralized product of the polymer (I-1).

For the same reason as in the emulsion polymer (A-1), the vinyl polymer (I) is used for the same reason.
By using a hydroxyl group-containing monomer as described above, it is of course possible to introduce a hydroxyl group,
It is possible.

In the case where a hydroxyl group is introduced into the vinyl polymer (I), the amount of the hydroxyl group introduced is such that the solid content of the polymer (I) is 1,00.
About 0.04 to 2 moles, preferably about 0.08 to 1.2 moles per 0 gram is suitable.

Further, among such various non-functional monomers as described above, the vinyl-based polymer (I) is added to the emulsion polymer (A-1) for the same reason. For example, it is of course possible to introduce a cycloalkyl group by using various cycloalkyl group-containing monomers such as cyclohexyl methacrylate as a copolymerization component.

In the case of introducing a cycloalkyl group into the vinyl polymer (I), the amount of the cycloalkyl group to be introduced is 1,000 g per solid content of the polymer (I). In terms of the amount of cycloalkyl group to be introduced into the polymer, about 0.5 to 5 mol, preferably about 1.0 to 4.2 mol is suitable.

Next, an emulsion obtained by emulsion-polymerizing the aqueous product (A-2) and the vinyl monomer used as one of the aqueous resin (A) components in an aqueous medium. The mixture with the polymer (A-3) will be described.

The emulsion polymer (A-3) may be an emulsion polymer having an acid group and / or a tertiary amino group, or may be an acid group and a tertiary amino group. It may be an emulsion polymer which does not contain any functional group. When the polymer (A-3) is an emulsion polymer having the former acid group and / or tertiary amino group, the polymer (A-3) is as described above. Emulsion polymers having an acid group and / or a tertiary amino group (A-1-1) and (A-1-
It can be said that 2) or (A-1-3) is used as it is.

When the emulsion polymer (A-3) does not contain any acid group and / or tertiary amino group, the emulsion polymer (A-3) is The vinyl-based monomer component is appropriately selected from the vinyl-based monomers (a-2) as described above, and is subjected to a polymerization reaction by various known and conventional emulsion polymerization methods as described above. Therefore, it can be prepared.

The curable resin composition for water-based paints of the present invention prepared by using a mixture of the emulsion polymer (A-3) and the aqueous product (A-2) as the aqueous resin (A) component. In comparison with the resin composition of the present invention, which is prepared by using only the aqueous product (A-2) as the aqueous resin (A) component, the product is remarkably characterized as a non-Newtonian fluid. To appear in
For example, in the case where both of the above paints are applied to the vertical surface of the base material, the former resin composition is less likely to sag than the latter resin composition, and therefore, when applied with the former resin composition. It means that the appearance of the obtained coating film is much more excellent.

On the other hand, the emulsion polymer (A-3),
The curable resin composition for an aqueous coating material of the present invention prepared by using a mixture with the aqueous product (A-2) as the aqueous resin (A) component is only the emulsion polymer (A-1). Compared with a resin composition prepared by using as a component (A), it is particularly excellent in film-forming property and pigment dispersibility, so that a coating obtained with the former resin composition is obtained. The film, in particular, the appearance and the like, and other properties are further improved.

Thus, the hydrate (A-2) and
When the aqueous resin (A) component is prepared from the mixture with the emulsion polymer (A-3), the aqueous product (A
-2) and the emulsion polymer (A-3) are used in a ratio of resin solid content of the aqueous polymer (A-2) / resin solid content of the emulsion polymer (A-3) of about 2: 1. 2 / about 98 to about 98 / about 2, preferably 5/95 to 95/5, more preferably 15/85 to 85/15.

[0229] Next, if only a typical compound (B) having both an epoxy group and a hydrolyzable silyl group in each molecule is given as an example, both of these compounds will be described. Examples thereof include vinyl polymers having both kinds of reactive groups, silane coupling agents having an epoxy group, and silicone resins having both kinds of reactive groups.

Here, as the hydrolyzable silyl group, the emulsion polymer (A-
As the one that can be used in the preparation of 1), the description has already been given regarding the hydrolyzable silyl group-containing vinyl monomer.

In order to prepare these vinyl polymers having both specific reactive groups as described above, any of various known and conventional methods can be applied, but in particular, they can be recommended. As a method,

(I) The emulsion polymer (A
-1) Various hydrolyzable silyl group-containing vinyl monomers and various epoxy group-containing vinyl monomer as described above as the copolymerizable monomer used in the preparation of It is a method of solution radical copolymerization with the body,

(Ii) As mentioned above, hydrolyzable silyl group-containing vinyl-based monomers, various epoxy group-containing vinyl-based monomers, and other vinyl-based monomers copolymerizable therewith It is a method of copolymerizing a monomer with a solution radical,

(Iii) Various hydrolyzable silyl group-containing groups such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane or γ-mercaptopropyltriisopropenyloxysilane. In the presence of the above chain transfer agent, a method of performing solution radical (co) polymerization of a monomer mixture containing various epoxy group-containing vinyl monomers as essential monomer components as described above. There is

Alternatively, there are various methods such as (iv) a method in which the method (i) or (ii) described above is combined with the method (iii) described above, and the like.

Further, only the representative examples of the above-mentioned epoxy group-containing silane coupling agent will be exemplified. Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, γ-
Glycidoxypropylmethyldiethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane or γ
Various epoxysilane compounds, such as glycidoxypropyltriisopropenyloxysilane;

Addition products of various isocyanate silane compounds such as γ-isocyanatopropyltriisopropenyloxysilane or γ-isocyanatopropyltrimethoxysilane with glycidyl; or γ-aminopropyltrimethoxy Addition products of various aminosilane compounds such as silane with diepoxy compounds; or two or more epoxy groups in one molecule in the form obtained by partial hydrolysis condensation of various epoxysilane compounds described above. For example, a compound having a hydrolyzable silyl group.

Further, to exemplify only a typical silicone resin having both an epoxy group and a hydrolyzable silyl group, a cyclic tetrasiloxane having the following formula [II ] The compound etc. which are shown by these can also be used.

[0239]

[Chemical 7]

(However, Gly represents a 3-glycidoxypropyl group.)

Next, the above-mentioned polyepoxy compound (C), which is one essential component in the present invention, will be explained. The polyepoxy compound referred to herein is at least two per molecule. It refers to a compound having an epoxy group and not containing a hydrolyzable silyl group.

If only typical examples of the epoxy compound are given, ethylene glycol,
Polyethylene of aliphatic or alicyclic polyols such as diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol or hydrogenated bisphenol A. Glycidyl ethers;

Various polyglycidyl ethers of aromatic polyols such as bisphenol A, bisphenol S or bisphenol F or novolac resins; aromatic polyols such as those mentioned above, and various monoglycerides such as ethylene oxide or propylene oxide. Various diglycidyl ethers of aromatic diols in a form obtained by adding an epoxy compound;

Various polyglycidyl ethers of polyether polyols such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; various polyglycidyl ethers of tris (2-hydroxyethyl) isocyanurate; adipic acid, butane tetra Various polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as carboxylic acid, propanetricarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid or trimellitic acid; 4-hydroxybenzoic acid or 4-hydroxyethoxybenzoic acid Various glycidyl ester ethers of hydroxy acids, such as:

Bisepoxides of various hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene or vinylcyclohexene; bis (3,4-epoxycyclohexylmethyl) adipate or 3, Various alicyclic polyepoxy compounds such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate; various epoxidized products of diene polymers such as polybutadiene or polyisoprene;

Alternatively, homopolymers of various epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene oxide or glycidyl vinyl ether, or those listed above. Various epoxy group-containing vinyl monomers can be copolymerized with them, respectively, with (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers. Various epoxy group-containing vinyl copolymers, such as various epoxy group-containing acrylic copolymers, vinyl ester-based copolymers or fluoroolefin-based copolymers in the form of being obtained by hardening Is.

Of these, particularly preferable from the viewpoint of resistance to raindrop contamination, various polyglycidyl ethers of aliphatic polyols, various polyglycidyl ethers of polyether polyols, and the like. .

Here, the above-mentioned aqueous resin containing an acid group and / or a tertiary amino group (A), an epoxy group / hydrolyzable silyl group-containing compound (B), and a polyepoxy compound (C), In order to prepare the curable resin composition for an aqueous coating material of the present invention in the form of containing as an essential resin component, the tertiary resin contained in the acid group- and / or tertiary amino group-containing aqueous resin (A) is used. The ratio is such that the total number of moles of amino groups and acid groups / the total number of moles of epoxy groups contained in compound (B) and compound (C) is in the range of about 0.1 to about 5. Therefore,

The ratio is preferably in the range of 0.3 to 3.0, and most preferably 0.5 to 2.0.
(A) with a ratio such that it falls within the range of
The component, the component (B) and the component (C) are mixed together, and the molar ratio of epoxy group contained in the compound (B) / epoxy group in the compound (C) is about 2 / about 98 to about. Within the range of about 98 / about 2, preferably within the range of 10/90 to 90/10, and most preferably within the range of 20/80 to 80/20, It suffices to set the usage ratio of the component (B) and the component (C).

Further, the epoxy group / hydrolyzable silyl group-containing compound (B) is further removed from the composition comprising the above-mentioned component (A), component (B) and component (C). ,
By adding the compound (D) having a hydrolyzable silyl group and / or silanol group, in particular, in terms of various properties such as weather resistance, corrosion resistance, water resistance, raindrop stain resistance and hardness. A cured coating film that is even more excellent can be obtained.

The compounds (D) having such a hydrolyzable silyl group and / or silanol group are particularly representative, methyl silicate, ethyl silicate, isopropyl silicate or n-.
Various silicate compounds such as butyl silicate; Silicate oligomers in the form obtained by partially hydrolyzing and condensing various silicate compounds as described above;

Various trifunctional silane compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane or isobutyltrimethoxysilane;

Various difunctional silane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane or diphenyldimethoxysilane;

Alternatively, various halosilanes such as methyltrichlorosilane, phenyltrichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane or diphenyldichlorosilane; or various difunctional or trifunctional silane compounds as described above. A so-called low molecular weight silanol compound obtained by hydrolyzing almost completely;

Further, linear or cyclic polysiloxanes having a silanol group in a form obtained by further dehydrating and condensing the silanol compound described above; various bifunctional silanes as described above A linear, branched or cyclic compound having an alkoxysilyl group in a form obtained by partially hydrolyzing and condensing at least one compound selected from the group consisting of a compound, a trifunctional silane compound and a silicate compound. The polysiloxane compound and the like.

To prepare the curable resin composition for an aqueous coating material according to the present invention in the form of containing the component (A), the component (B) and the component (C), and further the component (D). ,
In addition to the composition in the form of being obtained by mixing these three components (A), (B) and (C) in the ratio as described above, the compound (D)
In an amount of about 0.5 to about 200 parts by weight with respect to 100 parts by weight of the total resin solid content of the component (A),
Preferably, it may be blended in a range of 1 to 100 parts by weight.

Furthermore, it is possible to add a curing catalyst (E) to the curable resin composition for water-based paints according to the present invention, if necessary.
By adding the, it is possible to further improve the curability, therefore, it is possible to obtain an extremely highly practical cured coating film in the form of having excellent stain resistance, solvent resistance, hardness, etc. Obtainable.

As the catalyst (E), only typical ones will be exemplified. Various basic compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide or 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 or di-n-
Various metal-containing compounds, such as butyltin maleate;

Further, various acidic compounds such as p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid or dialkylphosphorous acid can be used.

Further, if necessary, various additives such as isopropyl alcohol, sec-butanol, n-butanol, 2-ethylhexanol, 2-propoxyethanol, 2-n may be added to the composition of the present invention.
-Butoxyethanol, 2-n-propoxypropanol, 3-n-propoxypropanol, 2-n-butoxypropanol, 3-n-butoxypropanol,

2-n-butoxyethyl acetate, diethylene glycol monobutyl ether, N-methylpyrrolidone, 2,2,4-trimethyl-1,3-pentanediol monobutyrate, phthalic acid dibutyl ester or butylbenzyl phthalate ester, etc. Such as various film forming aids,

Fillers, organic pigments, inorganic pigments, metallic pigments such as aluminum, pH adjusters, leveling agents, thickeners, water repellents, defoamers, plasticizers, antioxidants, ultraviolet absorbers, cissing prevention It can be said that various conventionally known so-called additives such as an agent, an anti-skinning agent (anti-skinning agent) or a dispersant are appropriately added and used.

The curable resin composition for water-based paints according to the present invention obtained as described above is prepared immediately before use by the compound (B) component having an epoxy group / hydrolyzable silyl group and the polyepoxy compound (C). The component) can be used in a so-called two-component type in which the component is mixed with other components.

Then, after being mixed in this way,
It is desirable to apply within 1 day, preferably within 12 hours. It means that the curability at room temperature will be remarkably reduced when more than one day has passed.

As the base material which can be coated with the curable resin composition for water-based coating composition of the present invention, various known and commonly used base materials are applicable, and any of them are applicable. Particularly, to exemplify only representative ones, iron, nickel, aluminum, copper or lead, or various other metals, and alloys of these various metals;
Among the various metals mentioned above, various surface-treated metals that have been subjected to plating, chemical conversion treatment, etc .; concrete or slate, or other various alkaline inorganic hardened materials;

Polystyrene, polymethylmethacrylate, ABS resin, polyphenylene oxide, polyurethane, polyethylene, polyvinyl chloride, polypropylene, polybutylene terephthalate or 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; and, in addition to fired products of various clays such as tiles, glass, paper or wood Examples include base materials.

Further, even if various kinds of base materials as mentioned above are coated and the deterioration of the coated part is advanced, the water-based composition according to the present invention can be used. It can be said that the curable resin composition for paint is used.

Each of these various types of base material has a plate shape,
Spherical, film-shaped or sheet-shaped materials or products: or large structures or complicated-shaped assemblies, and further, depending on various uses such as various molded products, There is no particular limitation as it is of a type used in various forms.

A cured coating film can be obtained by directly coating and curing the curable resin composition for water-based coating composition of the present invention on various substrates as described above. In this case, the resin composition may be directly coated on various types of substrates, or the resin composition may be coated on the various types of substrates in advance with an undercoat paint. May be applied, or the resin composition may be used as an undercoat paint,
Furthermore, the resin composition may be applied as an undercoat, and then the resin composition may be applied.

To coat the curable resin composition for water-based coating composition of the present invention, brush coating, roller coating, spray coating, dip coating, flow coater coating or roll coater coating is applied on various substrates as mentioned above. For example, various known and commonly used coating means or coating methods may be used.

Then, the substrate coated with the resin composition is allowed to stand at room temperature for about 1 to 10 days or about 4 times.
By heating or heating at a temperature range of 0 to about 250 ° C. for about 1 to 60 minutes,
It can be said that a cured coating film excellent in raindrop stain resistance, weather resistance, solvent resistance, chemical resistance and water resistance can be obtained.

As described above, the curable resin composition for water-based paints according to the present invention is a process for providing a cured coating film excellent in various properties such as weather resistance and raindrop stain resistance. More specific applications of the resin composition include automobiles, motorcycles, trains, bicycles, ships or airplanes or other transportation-related equipment, and parts thereof;

Various building materials such as various roof tiles, roofing materials made of metal, window frames, doors or inner and outer wall materials; roads, road signs,
There are applications where weather resistance and raindrop pollution resistance are required, such as various outdoor structures such as girrails, bridges, tanks, chimneys or buildings.

As other uses, mainly,
There are televisions, radios, refrigerators, washing machines, coolers, cooler outdoor units or computers, or other home electric appliances, and parts thereof, and the curable resin composition for water-based paints of the present invention has various types. Effectively for
It can be used.

[0276]

EXAMPLES Next, the present invention will be explained more specifically by reference examples, examples and comparative examples, but the present invention is by no means limited to these illustrative examples. Not that. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Tertiary Amino Group-Containing Emulsion Polymer (A-1-1)] Deionized water was placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser, a dropping funnel and a nitrogen gas inlet. Of 1,500
Then, 40 parts of "Emulgen 950" (trade name of polyoxyethylene nonylphenyl ether manufactured by Kao Corporation) was added as an emulsifier, and the temperature was raised to 80 ° C with stirring while blowing nitrogen. Warmed to dissolve the emulsifier.

Then, 5 parts of ammonium persulfate (APS) was added, followed by methyl methacrylate (MM
A) 500 parts, n-butyl acrylate (BA) 4
70 parts and 30 parts of 2-dimethylaminoethyl methacrylate (DM), and n-dodecyl mercaptan (L-
A monomer mixture consisting of 1.0 part of SH) was added dropwise over 3 hours for polymerization.

Even after the completion of dropping, stirring was continued at the same temperature for 2 hours. Then, after cooling the contents, the pH is adjusted to 8 or more with ammonia water so that the solid content concentration is 40.0%, and with deionized water. And filtered through a 100 mesh wire mesh.

The emulsion polymer thus obtained is
Solids concentration of 40.0%, pH of 8.1, 25 ℃
And the viscosity measured by a BM type viscometer (the same applies below)
Was 80 cps, and the agglomerates that did not pass through the 100-mesh wire mesh were 0.1% or less (ratio to the aqueous dispersion).

Further, this emulsion polymer contains 0.191 mol of a tertiary amino group in 1,000 g of its solid content. Hereinafter, this emulsion polymer is abbreviated as EM-1.

Reference Example 2 [Preparation Example of Emulsion Polymer Containing Acid Group / Amino Group (A-1-2)] In the same reaction vessel as in Reference Example 1, 1,500 deionized water was used.
4 parts of "Emulgen 950" as an emulsifier
0 parts was added, and with stirring, while blowing nitrogen, 80
The emulsifier was dissolved by raising the temperature to 0 ° C.

Then, 5 parts of APS was added, followed by:
450 of cyclohexyl methacrylate (CHMA)
Part, 2-ethylhexyl methacrylate (2EHMA)
370 parts of 2-ethylhexyl acrylate (2EH
A) 100 parts, 2-hydroxyethyl acrylate (HEMA) 50 parts, methacrylic acid (MAA) 10 parts
And 20 parts of DM and 1.0 part of L-SH were added dropwise over 3 hours for polymerization.

After the dropping was completed, stirring was continued at the same temperature for 2 hours. Then, after cooling the contents, the pH was adjusted to 8.5 with aqueous ammonia and adjusted with deionized water so that the solid content concentration was 40.0%. Filtered.

The emulsion polymer thus obtained is
Solids concentration 40.0%, pH 8.3, viscosity 1
The agglomerates of 80 cps and not passing through the 100-mesh wire net were 0.1% or less (ratio to the aqueous dispersion).

This emulsion polymer contained 0.127 mol of tertiary amino groups and 0.116 mol of carboxyl groups in 1,000 g of its solid content. Hereinafter, this emulsion polymer is abbreviated as EM-2.

Reference Example 3 [Preparation example of acid group-containing emulsion polymer (A-1-3)] 1,500 deionized water was placed in the same reaction vessel as in Reference Example 1.
4 parts of "Emulgen 950" as an emulsifier
0 parts was added, and with stirring, while blowing nitrogen, 80
The emulsifier was dissolved by raising the temperature to 0 ° C.

Then 5 parts of APS was added, followed by:
CHMA 430, 2EHAM 370, 2EHA
Of 100 parts of HEMA, 50 parts of HEMA and 30 parts of MAA, and 1.0 part of L-SH.
The mixture was dropped over a period of time and polymerized.

After the dropping was completed, stirring was continued at the same temperature for 2 hours. Then, after cooling the contents, the pH was adjusted to 8.5 with aqueous ammonia, adjusted with deionized water so that the solid content concentration was 40.0%, and filtered with a 100 mesh wire mesh. did.

The emulsion polymer thus obtained had a solid content concentration of 40.0%, a pH of 8.3, a viscosity of 380 cps, and a 100-mesh wire mesh non-passing aggregate was 0.1. % Or less (to the ratio of the aqueous dispersion).

This emulsion polymer contained 0.349 mol of carboxyl groups in 1,000 g of its solid content. Hereinafter, this emulsion polymer is abbreviated as EM-3.

Reference Example 4 [Preparation Example of Resin for Dispersion Stabilizer (Anionic Water-Soluble Acrylic Resin) and Acid Group Using the Same]
Preparation Example of Amino Group Combined Emulsion Polymer (A-1-2)]

3,000 parts of deionized water was placed in the same reaction vessel as in Reference Example 1, and "Lebenol W" was added as an emulsifier.
Z "[trade name of sodium polyoxyethylene alkylphenyl ether sulfonate manufactured by Kao Corporation; solid content 25%], 20 parts (5 parts in terms of solid content) are added and stirred, While blowing nitrogen, the temperature was raised to 80 ° C. to dissolve the emulsifier.

Then, 5 parts of APS was added, followed by:
3 parts of a monomer mixture consisting of 308 parts of MMA, 660 parts of BA, 30 parts of MAA and 2 parts of mono-2-methacryloxyethyl maleate and 1.0 part of L-SH.
The mixture was added dropwise over a period of time to cause polymerization.

After completion of dropping, the mixture was stirred at the same temperature for 1 hour. Then, after cooling the contents,
The solid content was adjusted to 20.0% with deionized water and filtered through a 100-mesh wire net.

The emulsion polymer thus obtained is
The solid content concentration was 20.0%, the pH was 3.7, the viscosity was 10 cps, and the agglomerates that did not pass through the 100-mesh wire mesh were 0.1% or less (ratio to the aqueous dispersion). It was

Then, in a reaction vessel similar to that of Reference Example 1,
400 parts of deionized water and 1,000 parts of the dispersant resin
0 part (200 parts by solid content) was added, a mixture of 12 parts of 28% ammonia water and 160 parts of deionized water was added over 1 hour, and the pH was adjusted to 6, Then, it heated up to 80 degreeC.

With stirring, 0.4 parts of APS was added, followed by 80 parts of styrene (ST), 281.
A monomer mixture consisting of 5 parts, 320 parts of 2EHMA, 80 parts of 2EHA, 37.5 parts of DM, and 1.0 part of L-SH was added dropwise over 3 hours for polymerization.
After the dropping was completed, stirring was continued for 1 hour at the same temperature.

Thereafter, the contents were cooled and then adjusted so that the solid content concentration became 40.0%. The emulsion polymer thus obtained has a pH of 6.0 and
The viscosity was 30 cps, and the agglomerates that did not pass through the 100-mesh wire net was 4% (ratio to the aqueous dispersion).

In the solid content of 1,000 g of the tertiary amino group-containing emulsion polymer, 0.239 mol of 3 was added.
It contains primary amino groups and 0.358 mol of carboxyl groups. Hereinafter, this emulsion polymer is referred to as EM-
Abbreviated as 4.

Reference Example 5 [Preparation Example of Acid Group / Amino Group-Containing Emulsion Polymer (A-1-2)] In the same reaction vessel as in Reference Example 1, 1,400 deionized water was added.
"Aqualon HS-10" as an emulsifier
2 parts and 3 parts of 25% aqueous ammonia are added, and the temperature is raised to 80 ° C. while stirring and nitrogen is blown in.
The emulsifier was dissolved.

Then 1.0 part of APS was added, followed by 100 parts of n-butyl methacrylate (BMA),
65 parts of BA, 30 parts of MAA and 5 parts of glycidyl methacrylate (GMA), and 1.0 part of L-SH were added dropwise over 1 hour.

After continuing the reaction at the same temperature for 1 hour, 3 parts of 25% aqueous ammonia and 2 parts of APS were added, and MMA of 400 parts was added.
Parts, 120 parts of BMA, 100 parts of BA, 150 parts of ethyl acrylate (EA) and 30 parts of DM, L-
A monomer mixture consisting of 1.0 part of SH and 2 parts of 25% ammonia water was added dropwise over 3 hours to polymerize.

Even after the completion of dropping, stirring was continued at the same temperature for 2 hours. After that, the contents were cooled, adjusted with deionized water so that the solid content concentration was 40.0%, and filtered through a 100-mesh wire net.

The emulsion polymer thus obtained had a solid content concentration of 40.0%, a pH of 6.9, a viscosity of 90 cps, and a 100-mesh wire mesh non-aggregated aggregate was 0. It was 1% or less (ratio to the aqueous dispersion).

In this emulsion polymer, 1,000 g of the solid content contained 0.191 mol of a tertiary amino group and 0.349 mol of a carboxyl group, respectively. It was calculated as a calculated value from the charged amount. Hereinafter, this emulsion polymer is referred to as EM
Abbreviated as -5.

Reference Example 6 [Preparation example of acid group / amino group-containing fluoroolefin emulsion polymer (A-1-2)]

The inside of a 2 liter stainless steel pressure-resistant reaction vessel (autoclave) equipped with a stirrer, a nitrogen inlet tube, a thermometer and a temperature controller was sufficiently replaced with nitrogen gas to obtain ion-exchanged water. 800 parts, 20 parts of sodium dodecylbenzene sulfonate, 20 parts of polyoxyethylene nonyl phenyl ether, and 10 parts of borax as a pH buffer were added and dissolved.

Then, 400 of vinyl neodecanoate was added.
Parts, 15 parts of crotonic acid and 15 parts of dimethylaminoethyl methacrylate, and 500 parts of chlorotrifluoroethylene liquefied and collected were charged, and then ethylene gas was press-fitted until the pressure reached 15 kg / cm ² .

The internal temperature of this autoclave was raised to 65 ° C. At this time, ethylene gas was further adjusted so that the pressure in the system during the reaction was about 30 kg / cm ² .

Then, at the same temperature, 2 parts of 0.05% ferric chloride aqueous solution was added, and further 5 parts of potassium persulfate was dissolved in 100 parts of ion-exchanged water to prepare a catalyst aqueous solution.
5 parts of formaldehyde sodium sulfoxylate and an aqueous reducing agent solution dissolved in 100 parts of ion-exchanged water were adjusted to a reaction temperature of 65 ° C. and press-fitted into the reaction vessel for 3 hours.

After the addition of the aqueous catalyst solution, the temperature was kept at the same temperature for 10 hours to allow the polymerization reaction to proceed. During the reaction, the pressure in the system was lowered as the monomer was consumed, and the pressure of the reaction system was maintained at 30 kg / cm ² by introducing ethylene each time.

After completion of the reaction, after cooling to room temperature,
14% ammonia water was added until the pH reached approximately 7.5, and a 5% aqueous dispersion of "Nopco 8034L" [trade name of silicon-based defoaming agent manufactured by San Nopco Ltd.] was further added. 1.0 part of was added and stirred well. Next, the unreacted gas was gradually taken out of the system, and then the pressure in the system was returned to normal pressure.

Thereafter, the unreacted gas dissolved in the dispersion was distilled off under reduced pressure. The aqueous dispersion thus obtained has a nonvolatile content of 48.5% and a pH of
Was 7.2, the minimum film-forming temperature was 30 ° C., and the average particle size was 0.08 micrometer (μm), which was a white so-called emulsion polymer. Hereinafter, this is abbreviated as EM-6.

The emulsion polymer (EM-6) is
By elemental analysis, ion chromatography analysis, infrared absorption spectrum and composition analysis by pyrolysis gas chromatography (GC), ethylene was 7.2%, fluoroolefin was 48.5%, and vinyl ester monomer was 4%.
The composition was 1.2%, the acid group-containing monomer was 1.5%, and the tertiary amino group-containing monomer was 1.6%.

Reference Example 7 [Preparation example of tertiary amino group-containing vinyl polymer (I) and preparation example of aqueous product obtained therefrom]

A reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet was charged with 660 parts of ethylene glycol monoisopropyl ether and heated to 80 ° C. in a nitrogen atmosphere.

Next, 100 copies of ST, 250 copies of MMA
Parts, 480 parts of BMA, 70 parts of EA and 10 parts of DM
0 part and 8 of azobisisobutyronitrile (AIBN)
Parts and tert-butyl peroxy octoate (T
A mixture consisting of 5 parts of BPO) was added dropwise over 4 hours.

Even after the dropping is completed, the temperature is kept at the same temperature for 10 hours.
And a target 3 having a number average molecular weight of 9,500.
A solution of the vinyl polymer (I) having a tertiary amino group was obtained.

Subsequently, at room temperature, the polymer (I)
To 100 parts of the above solution, 1.0 part of a 88% aqueous solution of formic acid was added, and stirring was continued. The neutralization rate at this time is 50
%Met. Then, 49 parts of water was added thereto, and stirring was continued until the contents became uniform.
%, The desired aqueous product was obtained. Hereinafter, this is abbreviated as aqueous compound (WB-1).

Reference Example 8 [Preparation Example of Vinyl Polymer (II) Having Tertiary Amino Group / Acid Group and Preparation Example of Aqueous Product Obtained therefrom]

Each of the monomers to be used is
ST 100 copies, MMA 250 copies, BMA 440 copies
Parts, 150 parts of EA, 40 parts of DM and 20 parts of acrylic acid (AA), and at the same time 10 parts of TBPO is used as the radical polymerization initiator to be used. In the same manner as in Reference Example 1, except that the nonvolatile content was 60%,
And a target 3 having a number average molecular weight of 8,000
A solution of the vinyl polymer (II) having both a primary amino group and an acid group was obtained.

Subsequently, at room temperature, the polymer (I
After adding 0.8 parts of 88% aqueous solution of formic acid to 100 parts of I) and continuing the stirring, 49.2 parts of water was added and the stirring was continued until uniform. As a result, a target aqueous product having a nonvolatile content of 40% was obtained. Hereinafter, this is abbreviated as aqueous compound (WB-2).

Reference Example 9 [Preparation Example of Vinyl Polymer (II) Having Tertiary Amino Group / Acid Group and Preparation Example of Aqueous Product Obtained therefrom]

The monomers to be used are as follows:
ST 100 copies, MMA 250 copies, BMA 440 copies
Parts, 150 parts of EA, 40 parts of DM and 20 parts of AA are used at the same time, and the radical polymerization initiator to be used is TBPO.
The target tertiary amino group and acid group having a nonvolatile content of 60% and a number average molecular weight of 8,000 are obtained in the same manner as in Reference Example 1 except that 10 parts are used. To obtain a solution of the vinyl polymer (II).

Subsequently, at room temperature, the polymer (I
By adding 1.68 parts of triethylamine to 100 parts of I) and continuing the stirring, 48.3 parts of water was added and the stirring was continued until it became uniform. A target aqueous product having a content of 40% was obtained. Hereinafter, this is abbreviated as aqueous compound (WB-3).

Reference Example 10 [Acid Group-Containing Vinyl Polymer (I
Preparation Example of II) and Preparation Example of Aqueous Product Obtained from It]

As the polymerization solvent to be used, ethylene glycol monoisopropyl ether 6
The monomer to be used was changed to 66 parts, and as the monomers to be used, 150 parts of ST, 500 parts of BMA, EA
150 parts of 2-hydroxyethyl acrylate (HE
A reference example except that a mixture consisting of 100 parts of A) and 100 parts of AA was used, and in addition, 10 parts of TBPO was used as the radical polymerization initiator to be used. In the same manner as in 1, a target solution of the acid group-containing vinyl polymer (III) having a nonvolatile content of 60% and a number average molecular weight of 8,000 was obtained.

Subsequently, this polymer (III)
Of N, N-dimethyloctylamine in 100 parts of
After adding 8 parts and 2.2 parts of triethylamine and continuing the stirring, 96 parts of water was added and the stirring was continued until a uniform dispersion was obtained. To obtain the desired aqueous product having a content of 30%. Hereinafter, this is abbreviated as a water-based product (WB-4).

Reference Example 11 (Preparation example of compound containing hydrolyzable silyl and / or silanol group)

To the same reactor as in Reference Example 1, 1,335 parts of methyltriethoxysilane, 60 parts of phenyltriethoxysilane and 825 parts of n-butanol were added, and the temperature was raised to 80 ° C. .

[AP-3] [Dahachi Chemical Co., Ltd.] at the same temperature
Trade name of isoprohirulic acid phosphate]
Parts and 540 parts of water were added and stirred for 4 hours,
The hydrolysis and condensation reaction were allowed to proceed. After a while, 5
The temperature was lowered to 0 ° C., and water, n-butanol, and ethanol generated by the reaction were removed under reduced pressure to obtain a hydrolyzed condensate having a nonvolatile content of 53%.

Further, n-butanol was added to obtain a hydrolyzed condensate having a nonvolatile content of 49.7% and a Gardner viscosity at 25 ° C. (the same applies below) of A ₄ ² -A ₃ . This product was in the form of containing silanol groups in an amount corresponding to 25 mol% of the ethoxysilyl groups at the time of charging. Hereinafter, this compound is abbreviated as Silicon D-1.

Reference Example 12 (Preparation Example of Pigment Paste for Emulsion) 200.8 parts of "Taipec CR-93" [trade name of titanium oxide manufactured by Ishihara Sangyo Co., Ltd.], "Orotan SG"
-1 "(trade name of pigment dispersant manufactured by Rohm and Haas Company, USA), 3.9 parts of a 10% aqueous solution of sodium tripolyphosphate," Neugen EA-1 "
20 "[trade name of polyoxyethylene nonylphenyl ether emulsifier manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] 1.8
Part, 14.5 parts of ethylene glycol, 0.8 part of "Bestside FX" [trade name of preservative manufactured by Dainippon Ink and Chemicals, Inc.] and "SN Deformer 121" [manufactured by San Nopco Co., Ltd.] 0.6 part of the product name of defoamer] and 5 of water
9.1 parts and 0.4 part of 28% ammonia water were mixed and stirred sufficiently at room temperature. Hereinafter, the solution thus obtained is abbreviated as a pigment paste.

Examples 1 to 18 and Comparative Examples 1 to 4 Various aqueous topcoat paints were prepared with the compounding ratios shown in Table 1. In addition, at the time of coating, it was decided to use each resin composition after diluting it with water so as to obtain a spray viscosity.

[0336]

[Table 1]

<< Footnote of Table 1 >>"TT-935" ... "Primal TT-935"
(Trade name of carboxylic acid group-containing emulsion manufactured by Rohm and Haas Co.), the carboxylic acid group-containing emulsion is triethylamine and has a pH of 8.
Neutralize to 2 and add water until the nonvolatile content is 1.
A shape adjusted to 0% was used.

"Texanol" ......... "TEXANOL
"Ester-Alcohol" (trade name of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate manufactured by Eastman, USA)

“Γ-GPTMS” ... Abbreviation for γ-glycidoxypropyltrimethoxysilane.

"Ex-612" ......... "Denacol E
x-612 ”[trade name of polyglycidyl ether of sorbitol manufactured by Nagase & Co., Ltd .; epoxy equivalent = 17]
0] abbreviation

"DBTDL" ... Abbreviation for dibutyltin dilaurate

[0342]

[Table 2]

<< Footnote in Table 1 >> TSL …………………… “TSL8178” [trade name of silicon compound manufactured by Toshiba Silicon KK] and “T
Abbreviation for a mixture of 2/1 (molar ratio) with "SL8122" (same as above)

[0344]

[Table 3]

<< Footnote of Table 1 >>"Ex-821" ... "Denacol Ex-821"
[Product name of polyethylene glycol glycidyl ether manufactured by Nagase & Co., Ltd .; epoxy epoxy equivalent = 1
95]

[0346]

[Table 4]

<< Footnote of Table 1 >> MAC-2101 ... "MAC-2101" [trade name of silicon compound having epoxy group, alkoxy group and polyalkylene oxide chain, manufactured by Nippon Unicar Co., Ltd.] ]]

[0348]

[Table 5]

[0349]

[Table 6]

Then, each of the aqueous topcoating paints obtained in each of the examples and comparative examples was separately applied onto a predetermined base material by a conventional method and dried under predetermined drying conditions. A coating film was obtained by squeezing.

The items of the evaluation / judgment test of various properties of each coating film after drying are as follows: secondary adhesion after water resistance test; acid resistance; alkali resistance;
And solvent resistance,

Furthermore, the weather resistance after 2 years of outdoor exposure and the contamination after 3 months of outdoor exposure are listed. The results are shown together in the same table.

[0353]

[Table 7]

<< Footnote in Table 2 >> Substrate "1" ...... Slate plate

Drying condition "1": forced drying at 60 ° C for 30 minutes

Solvent resistance: Methyl ethyl ketone was used, and a coating film was subjected to a rubbing test under a load of 1.5 kg, and the coating film was visually evaluated.

Gloss retention rate …………………………………………………………………………………………………………………………………………………………………………………………………………………… ..
It is indicated by the gloss retention rate (%) before and after the exposure.

Contamination property ……………………………………………………………………………………………………………………………………………………………………………… Shows the degree of contamination of the coating film by the ΔL value.

◎ ... ΔL value is 0 or more and less than 5 ○ ... ΔL value is 5 or more and less than 10 Δ ... ΔL value is 10 or more and less than 20, and stains can be easily wiped off. If you can

[0360]

[Table 8]

<< Footnote in Table 2 >> Drying condition "2" ... left at room temperature for one week to dry

[0362]

[Table 9]

<< Footnotes in Table 2 >> Base material "2" ......... untreated mild steel sheet

[0364]

[Table 10]

<< Footnote in Table 2 >> Substrate "3" ... Polycarbonate plate

[0366]

[Table 11]

[0367]

[Table 12]

[0368]

As is clear from the above detailed description, the curable resin composition for aqueous paint according to the present invention is
Above all, it is excellent in weather resistance, rain dripping stain resistance and other performances of other coating films.
It can be said that it is extremely practical.

Claims (16)

[Claims] 1. An aqueous resin (A) containing an acid group and / or a tertiary amino group, a compound (B) having both an epoxy group and a hydrolyzable silyl group, and a polyepoxy compound (C). A curable resin composition for water-based paint, comprising: 2. A compound (B) having both an acid group- and / or tertiary amino group-containing aqueous resin (A), an epoxy group and a hydrolyzable silyl group, a polyepoxy compound (C), and the above compound ( A curable resin composition for water-based paints, which contains a compound (D) having a hydrolyzable silyl group and / or a silanol group, excluding B). 3. An emulsion polymer (A-) obtained by emulsion-polymerizing a vinyl-based monomer in the aqueous resin (A) containing an acid group and / or a tertiary amino group in an aqueous medium.
The composition according to claim 1, which is 1). 4. The above-mentioned aqueous resin containing an acid group and / or a tertiary amino group (A) has the acid group and / or 3
To the vinyl polymer (I) containing a primary amino group, a neutralizing agent is added so as to neutralize at least about 10% of the acid group or the tertiary amino group, and then the polymer is obtained by dissolving in water without dispersion. The composition according to claim 1 or 2, which is an aqueous compound (A-2). 5. The above-mentioned aqueous resin (A) containing an acid group and / or a tertiary amino group is used as the acid group and / or 3
To the vinyl polymer (I) containing a primary amino group, a neutralizing agent is added so as to neutralize at least about 10% of the acid group or the tertiary amino group, and then the polymer is obtained by dissolving in water without dispersion. It is a mixture consisting of the hydrated product (A-2) and the emulsion polymer (A-3) obtained by emulsion polymerization of a vinyl-based monomer in an aqueous medium. The composition as described. 6. The acid group- and / or tertiary amino group-containing aqueous resin (A) is an acrylic polymer.
The composition according to claim 1. 7. The composition according to claim 1, wherein the aqueous resin (A) containing an acid group and / or a tertiary amino group is a fluoroolefin polymer. 8. The acid group and / or tertiary amino group-containing vinyl polymer (I) is prepared by using a hydroxyl group-containing vinyl monomer as an essential component.
The curable resin composition for aqueous paints according to claim 4 or 5. 9. The above-mentioned vinyl polymer (I) containing an acid group and / or a tertiary amino group is prepared by using a vinyl monomer containing a cycloalkyl group as an essential component. The composition according to claim 4 or 5. 10. The emulsion polymer (A-
The composition according to claim 3, wherein 1) is prepared using a hydroxyl group-containing vinyl monomer as an essential component. 11. The emulsion polymer (A-
The composition according to claim 3, wherein 1) is prepared using a cycloalkyl group-containing vinyl monomer as an essential component. 12. The emulsion polymer (A-
The composition according to claim 3, wherein 1) is obtained by soap-free polymerization. 13. The emulsion polymer (A-
The composition according to claim 5, wherein 3) is prepared by using a hydroxyl group-containing vinyl monomer as an essential component. 14. The emulsion polymer (A-
The composition according to claim 5, wherein 3) has an acid group and / or a tertiary amino group. 15. The emulsion polymer (A-
The composition according to claim 5, wherein 3) is prepared using a cycloalkyl group-containing vinyl monomer as an essential component. 16. The emulsion polymer (A-
The composition according to claim 5, wherein 3) is obtained by soap-free polymerization.