JPH1036515A - Aqueous resin, its production and aqueous curable resin composition comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous resin excellent in curing characteristics, storage stability, luster retention, stain resistance by raindrops, acid rain resistance, etc., by subjecting a silicon compound to hydrolytic condensation reaction in the presence of a specific polymer to give a composite resin and dispersing the resin to water. SOLUTION: (B) A silicon containing at least two hydrolyzable groups bonded to silicon atoms in one molecule is subjected to a hydrolytic condensation reaction in the presence of (A) a polymer containing both a hydrolyzable silyl group and an acid group to give a composite resin. Then the resin is partially or completely neutralized with a basic compound and dispersed into or dissolved in water to give an aqueous resin excellent in durability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful aqueous resin, a novel and useful method for producing the aqueous resin, and a novel and useful aqueous resin comprising the aqueous resin as an essential component. The present invention relates to a useful aqueous curable resin composition.

More specifically, the present invention relates to a method for preparing a hydrolyzable silyl group / acid group in the presence of a hydrolyzable silyl group / acid group or a functional group other than these two groups. In the presence of a polymer having

A composite resin obtained by performing a hydrolysis-condensation reaction of a silicon compound having at least two hydrolyzable groups bonded to a silicon atom in one molecule is partially neutralized or neutralized with a basic compound. After completely neutralized, aqueous resin obtained by dispersing or dissolving in water,
A method for producing the aqueous resin and containing the aqueous resin as an essential component, an aqueous curable resin composition,

[0004] In particular, coatings that are excellent in various properties such as solvent resistance, chemical resistance and water resistance as well as so-called durability such as gloss retention, rain dripping stain resistance and acid rain resistance. The present invention relates to an aqueous resin capable of forming a film and having both excellent curability and excellent storage stability, a method for producing the aqueous resin, and, in addition, In particular, an aqueous curable resin composition having extremely high practicability, which is excellent in curability and gives a cured coating film excellent in various properties including durability as described above. About.

[0005]

2. Description of the Related Art Heretofore, aqueous curable resin compositions for paints have been prepared by using a vinyl polymer having both a basic group or an acid group and a so-called functional group such as a hydroxyl group with an acidic compound. Or after neutralizing with a basic compound,
An aqueous curable resin composition in the form of an aqueous resin obtained by dispersing or dissolving in water and various curing agents such as an epoxy resin, an isocyanate resin or an amino resin is widely used.

[0006] However, cured coatings obtained from such aqueous curable resin compositions based on aqueous resins which have hitherto been used are, inter alia, gloss retention upon exposure, resistance to dripping stains and resistance to acids. However, there is a problem that it cannot be used and applied almost completely to applications that require high durability, such as durable rain. Was.

[0007]

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

Accordingly, the problem to be solved by the present invention is to provide a cured product excellent in so-called durability, such as gloss retention, rain dripping stain resistance and acid rain resistance. In addition, it is also to provide a novel and useful aqueous resin having excellent curability and storage stability, and a method for producing such an aqueous resin.In addition, such a novel and useful aqueous resin is also provided. In addition to the above-mentioned durability and the like, it also provides an extremely practical water-curable resin composition which is excellent in various properties such as solvent resistance, chemical resistance and water resistance. There are also things to do.

[0009]

Means for Solving the Problems Accordingly, the present inventors have:
Focusing on the problem to be solved by the invention as described above, as a result of earnest and intensive studies,

In the presence of a polymer having both a hydrolyzable silyl group and an acid group, or a polymer having a hydrolyzable silyl group and an acid group and a functional group other than both of these groups. A composite resin obtained by performing a hydrolysis condensation reaction of at least two silicon compounds having a hydrolyzable group bonded to a silicon atom in one molecule is partially neutralized or neutralized with a basic compound. After completely neutralizing, the aqueous resin obtained by dispersing or dissolving in water is found to be particularly excellent in curability and storage stability. While establishing,

The water-curable resin composition comprising the water-based resin as an essential component has excellent so-called durability, such as gloss retention, acid rain resistance and rain dripping contamination. And, consequently, convinced that the problems to be solved by the invention as described above can be solved brilliantly, and have now completed the present invention.

That is, the present invention basically relates to a method in which at least two silicon atoms are bonded to one molecule in one molecule in the presence of a polymer (a-1) having both a hydrolyzable silyl group and an acid group. Composite resin (A-A) obtained by subjecting a silicon compound (b) having a hydrolyzable group to a hydrolysis-condensation reaction.
1) is to partially or completely neutralize with a basic compound, and then disperse or dissolve in water to provide an aqueous resin (AI) itself,

[0013] The method for producing the aqueous resin (AI) and the aqueous curable resin composition comprising the aqueous resin (AI) as an essential component are further included. And the aqueous resin (A-I) and the aqueous resin (A-
It is another object of the present invention to provide an aqueous curable resin composition comprising a compound (C) having a functional group capable of reacting with a functional group contained in I),

In addition, a polymer (a) having both a hydrolyzable silyl group and an acid group and a functional group other than both groups.
Silicon compound (b) having at least two hydrolyzable groups bonded to silicon atoms in one molecule in the presence of -2)
Aqueous resin (A-2) obtained by partially neutralizing or completely neutralizing a composite resin (A-2) obtained by performing a hydrolysis condensation reaction with a basic compound and then dispersing or dissolving in water. A-II) to provide itself,

Further, the method for producing the aqueous resin (A-II), and the aqueous curable resin composition comprising the aqueous resin (A-II) as an essential component, An aqueous curable resin comprising the aqueous resin (A-II) and a compound (C) having a functional group capable of reacting with a functional group contained in the aqueous resin (A-II). It also seeks to provide a composition.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The present invention provides, in part,
Polymer having both a hydrolyzable silyl group and an acid group (a-
Composite resin (A-1) obtained by performing a hydrolysis-condensation reaction of a silicon compound (b) having at least two hydrolyzable groups bonded to silicon atoms in one molecule in the presence of 1) Is partially neutralized or completely neutralized with a basic compound and then dispersed or dissolved in water to obtain an extremely practical aqueous resin (A-
I)

Second, in the presence of the polymer (a-1) having both a hydrolyzable silyl group and an acid group, at least two hydrolyzable groups bonded to a silicon atom in one molecule are added. The composite resin (A-1) obtained by performing a hydrolysis-condensation reaction of the silicon compound (b) is partially neutralized or completely neutralized with a basic compound, and then dispersed or dissolved in water. A new and useful method for producing the aqueous resin (A-I) comprising:

Third, in the presence of the polymer (a-1) having both a hydrolyzable silyl group and an acid group, at least two hydrolyzable groups bonded to a silicon atom in one molecule are added. The composite resin (A-1) obtained by performing a hydrolysis-condensation reaction of the silicon compound (b) is partially neutralized or completely neutralized with a basic compound, and then dispersed or dissolved in water. It is also intended to claim an extremely practical aqueous curable resin composition comprising an aqueous resin (AI) obtained as an essential component.

Fourth, the above-mentioned aqueous resin (A-I)
And an extremely practical aqueous curable resin composition comprising a compound (C) having a functional group capable of reacting with a functional group contained in the aqueous resin (AI). Is to try and

Fifth, a polymer (a) having both a hydrolyzable silyl group and an acid group and a functional group other than these two groups.
Silicon compound (b) having at least two hydrolyzable groups bonded to silicon atoms in one molecule in the presence of -2)
Is obtained by partially or completely neutralizing the composite resin (A-2) obtained by carrying out the hydrolysis condensation reaction with a basic compound and then dispersing or dissolving it in water. Highly practical aqueous resin (A-
II) as well,

Sixth, a polymer (a) having both a hydrolyzable silyl group and an acid group and a functional group other than these two groups.
Silicon compound (b) having at least two hydrolyzable groups bonded to silicon atoms in one molecule in the presence of -2)
Is obtained by partially neutralizing or completely neutralizing the composite resin (A-2) obtained by performing the hydrolysis-condensation reaction with a basic compound and then dispersing or dissolving the same in water. A new and useful method for producing the aqueous resin (A-II) is also claimed,

Seventh, a polymer (a) having both a hydrolyzable silyl group and an acid group and a functional group other than both of these groups.
Silicon compound (b) having at least two hydrolyzable groups bonded to silicon atoms in one molecule in the presence of -2)
Aqueous resin (A-2) obtained by partially neutralizing or completely neutralizing a composite resin (A-2) obtained by performing a hydrolysis condensation reaction with a basic compound and then dispersing or dissolving in water. A-II) is intended to provide an extremely practical aqueous curable resin composition comprising an essential component,

Eighth, the aqueous resin (A-II)
And a compound (C) having a functional group capable of reacting with a functional group contained in the aqueous resin (A-II). What you want to do.

In the present invention, the functional groups other than the above-mentioned two groups may each be a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide, and a carbamate. And the structural formula (S-I)

[0025]

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It is also intended to claim a specific aqueous resin which is at least one kind of functional group selected from the group consisting of the functional groups represented by

Further, the present invention is directed to a specific aqueous resin wherein the hydrolyzable silyl group is an alkoxysilyl group,

Further, the silicon compound (b) having at least two hydrolyzable groups bonded to silicon atoms in one molecule is a tetraalkoxysilane, an organotrialkoxysilane and a diorganodialkoxysilane. It is intended to claim a specific aqueous resin that is at least one alkoxysilane selected from the group consisting of:

Still another object of the present invention is to claim a specific aqueous resin in which the hydrolyzable group bonded to the silicon atom is an alkoxy group.

Further, it is intended to claim a specific aqueous resin in which each of the polymers (a-1) and (a-2) is a vinyl polymer. ,

Further, the present invention is directed to a specific aqueous resin in which the vinyl polymer is an acrylic polymer.

Further, according to the present invention, a functional group other than the above-mentioned two groups may be a hydroxyl group, a blocked hydroxyl group,
Primary amino group, cyclocarbonate group, epoxy group, primary amide group, secondary amide, carbamate group and the following structural formula (SI)

[0033]

Embedded image

A novel method for producing an aqueous resin in the form of at least one functional group selected from the group consisting of the functional groups represented by

Further, the present invention is intended to claim a novel method for producing an aqueous resin in which the hydrolyzable silyl group is an alkoxysilyl group,

Further, the above-mentioned silicon compound (b) having at least two hydrolyzable groups bonded to silicon atoms in one molecule may be a tetraalkoxysilane, an organotrialkoxysilane and a diorganosilane, respectively. It is intended to claim a novel method for producing an aqueous resin in the form of at least one type of alkoxysilane selected from the group consisting of dialkoxysilanes,

Another object of the present invention is to provide a novel method for producing an aqueous resin in which the hydrolyzable group bonded to the silicon atom is an alkoxy group.

Alternatively, it is intended to claim a novel process for producing an aqueous resin in which both the above-mentioned polymers (a-1) and (a-2) are vinyl polymers. And

It is also an object of the present invention to provide a novel method for producing an aqueous resin in which the vinyl polymer is an acrylic polymer.

Furthermore, the functional groups other than the above-mentioned two groups are respectively a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide, a carbamate group and The following structural formula (S-I)

[0041]

Embedded image

It is also intended to claim a specific aqueous curable resin composition which is at least one kind of functional group selected from the group consisting of functional groups represented by

Further, it is intended to claim a specific aqueous curable resin composition wherein the hydrolyzable silyl group is an alkoxysilyl group,

Further, the above-mentioned compound (C) is a compound having a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom; a compound having an isocyanate group and a silicon atom bonded in one molecule. Compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule; a polyisocyanate compound; a blocked polyisocyanate compound; a polyepoxy compound; a polycyclocarbonate compound; Resins; primary or secondary amide group-containing compounds; and at least one compound selected from the group consisting of polycarboxy compounds and polyhydroxy compounds. And

Further, the present invention is also directed to a specific aqueous curable resin composition wherein the hydrolyzable group bonded to the silicon atom is an alkoxy group,

Further, a specific aqueous curable resin composition in which each of the polymers (a-1) and (a-2) is a vinyl polymer is also claimed. Is the thing,

Further, it is an object of the present invention to provide a specific aqueous curable resin composition in which the vinyl polymer is an acrylic polymer.

Hereinafter, the present invention will be described in further detail.

Here, first, the composite resin (A-A), which is a precursor of the aqueous resin according to the present invention itself, is used.
The polymer (a-1) having both a hydrolyzable silyl group and an acid group, which is used when preparing 1),
It refers to a polymer having both a hydrolyzable silyl group and an acid group, and such a hydrolyzable silyl group is represented by the general formula (S-II)

[0050]

Embedded image

(Wherein R ¹ represents a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R ² represents a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, Represents an amino group, an amide group, an aminooxy group, an iminooxy group or an alkenyloxy group, and a is an integer of 0 or 1 or 2.)

A hydrolyzable silyl group, which is hydrolyzed to form a silanol group as shown in the above, is shared with a carbon atom directly or through a siloxane bond. By joining,
It is assumed that it is bonded to the polymer (a-1).

In addition, only particularly typical examples of the acid group mentioned here are exemplified by a carboxyl group, a phosphoric acid group, an acid phosphate group, a phosphorous acid group, a sulfonic acid group or a sulfinic acid group. In addition to various free acid groups, such as carboxylic acid anhydride groups, phosphoric acid anhydride groups, sulfonic acid anhydride groups or carboxylic acid-sulfonic acid mixed acid anhydride groups. ,

Further, for example, a silyl ester group,
each blocked with an ester group that can be easily converted to a free acid group, such as a tert-butyl ester group or a 1-alkoxyethyl ester group,
Various blocked acid groups such as a carboxyl group, a phosphoric acid group, an acid phosphate group, a phosphite group or a sulfonic acid group.

Among the various acid groups as described above, particularly preferred and representative ones are carboxyl group, blocked carboxyl group and carboxylic anhydride group.

As the polymer (a-1), only typical ones are exemplified, and acrylic polymers, fluoroolefin polymers, vinyl ester polymers or aromatic vinyl polymers are exemplified. And various kinds of vinyl polymers, and further, polyester resins, alkyd resins, polyurethane polymers and the like.

Among these, only typical ones are exemplified, and examples thereof include vinyl-based polymers and polyurethane-based polymers. Among these vinyl polymers, particularly desirable ones include: It is an acrylic polymer.

First, of such a polymer (a-1),
In order to prepare the above-mentioned vinyl polymer, (i) having a hydrolyzable silyl group-containing vinyl monomer and a so-called acid group such as a carboxyl group, a blocked carboxyl group or a carboxylic anhydride group. Various types of acid-containing vinyl monomers, such as vinyl monomers, may be co-polymerized or copolymerized with these two types (two types) of monomers. Copolymerization with other possible monomers;

(Ii) Reaction of a vinyl polymer having both hydroxyl groups and acid groups prepared in advance with various isocyanate group-containing silane compounds such as 3-isocyanatopropyltriethoxysilane. Method;

(Iii) A vinyl monomer having an acid group such as a carboxyl group, a blocked carboxyl group or a carboxylic acid anhydride group using a chain transfer agent having both a mercapto group and a hydrolyzable silyl group. A method of polymerizing various acid group-containing vinyl monomers such as a product, or copolymerizing these monomers with other monomers that can be copolymerized;

(Iv) Using a chain transfer agent having both a mercapto group and a hydrolyzable silyl group, a vinyl monomer containing a hydrolyzable silyl group, a carboxyl group, a blocked carboxyl group or a carboxylic acid Various acid group-containing vinyl monomers such as a vinyl monomer having an acid group such as an anhydride group may be co-polymerized, or the above two types of monomers and these monomers may be used. A method of copolymerizing a compound with another monomer capable of being copolymerized;

(V) Using a polymerization initiator having a hydrolyzable silyl group, various kinds of vinyl monomers having an acid group such as a carboxyl group, a blocked carboxyl group or a carboxylic acid anhydride group can be used. A method of polymerizing an acid group-containing vinyl monomer of the above or copolymerizing these monomers with other monomers that can be copolymerized;
Or

(Vi) Using a polymerization initiator having a hydrolyzable silyl group, a vinyl monomer containing a hydrolyzable silyl group and a carboxyl group, a blocked carboxyl group or a carboxylic acid anhydride group. Various acid group-containing vinyl monomers such as a vinyl monomer having an acid group can be copolymerized or copolymerized with the above two types of monomers and these monomers. It can be applied by using various known and commonly used methods, such as a method of copolymerizing with other monomers.

Among them, the method (i) is the simplest in particular.

The hydrolyzable silyl group-containing vinyl monomer used in preparing the polymer (a-1) includes:
A monomer having a hydrolyzable silyl group as shown in the structural formula (SI) described above, and if only particularly typical examples of such a monomer are given,
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, vinylmethyldimethoxysilane, vinyltris (2-methoxyethoxy) silane, allyltrimethoxysilane, 2-trimethoxysilylethyl vinyl ether, 2-triethoxysilylethyl Vinyl ether, 2- (methyldimethoxysilyl) ethyl vinyl ether, 3-trimethoxysilylpropyl vinyl ether or 3-triethoxysilylpropyl vinyl ether

Or 3- (methyldimethoxysilyl) propyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth)
Acryloyloxypropylmethyldimethoxysilane or 3- (meth) acryloyloxypropylmethyldichlorosilane.

Of the acid group-containing vinyl monomers used in preparing the polymer (a-1), only those particularly typical as vinyl monomers having a free carboxyl group are used. By way of example only, (meth) acrylic acid, 2
Various unsaturated carboxylic acids, such as carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid or fumaric acid;

Monomethyl itaconate, mono-itaconate
n-butyl, monomethyl maleate, mono-maleic acid
n-butyl, monomethyl fumarate, mono-n-fumarate
Various unsaturated dicarboxylic acids, such as butyl, and saturated 1
Monoesters (half esters) with polyhydric alcohols; monovinyl esters of various saturated dicarboxylic acids, such as monovinyl adipate or monovinyl succinate;

Various saturated polycarboxylic acid anhydrides such as succinic anhydride, glutaric anhydride, phthalic anhydride or trimellitic anhydride, and various hydroxyl group-containing vinyl monomers as described below. Addition products with lactones and various carboxyl group-containing monomers as described above.

Among the monomers having an acid group used in preparing the polymer (a-1), only those which are particularly representative as monomers having a blocked carboxyl group are exemplified. To be limited, various silyl ester group-containing vinyls such as trimethylsilyl (meth) acrylate, dimethyl-tert-butylsilyl (meth) acrylate or trimethylsilyl crotonate as disclosed in JP-A-62-254876. System monomers;

1-ethoxyethyl (meth) acrylate, 1-n-butoxyethyl (meth) acrylate, 2
Having various hemiacetal ester groups or hemiketal ester groups such as -methoxy-2- (meth) acryloyloxypropane or 2- (meth) acryloyloxytetrahydrofuran as disclosed in JP-A-5-222134. Monomers; or t
tert-butyl (meth) acrylate or tert
And various tert-butyl ester group-containing monomers such as -butyl crotonate.

Among the monomers having an acid group used for preparing the polymer (a-1), only those particularly representative as monomers having a carboxylic anhydride group will be exemplified. If it stops, various anhydrides of unsaturated polycarboxylic acids, such as maleic anhydride, citraconic anhydride or itaconic anhydride; various unsaturated monocarboxylic acids, such as acrylic acid or methacrylic anhydride. Anhydrides; or mixed acid anhydrides of various unsaturated carboxylic acids such as acrylic acid or methacrylic acid and various saturated carboxylic acids such as acetic acid, propionic acid or benzoic acid.

The hydrolyzable silyl group-containing monomer and the acid group-containing vinyl which can be used in preparing the vinyl polymer (a-1) according to the method (i) described above. If only other typical examples of other vinyl monomers that can be copolymerized with the system monomer are given as examples,

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or lauryl (meth) acrylate Like
Esters of a primary or secondary alkyl alcohol having ₁ to ₂₂ carbon atoms with (meth) acrylic acid;

Benzyl (meth) acrylate or 2
-Various aralkyl (meth) acrylates, such as phenylethyl (meth) acrylate; various cycloalkyl (meth) acrylates, such as cyclohexyl (meth) acrylate or isobornyl (meth) acrylate; 2-methoxyethyl (meth) Various ω-alkoxyalkyl (meth) acrylates, such as acrylate or 4-methoxybutyl (meth) acrylate;

Various aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene and vinyltoluene; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate or benzoate Various carboxylic acid vinyl esters such as vinyl acid;

Various alkyl esters of crotonic acid, such as methyl crotonate or ethyl crotonate;
Such as dimethyl malate, di-n-butyl malate, dimethyl fumarate, di-n-butyl fumarate, dimethyl itaconate or di-n-butyl itaconate;
Various dialkyl esters of unsaturated dibasic acids;

Various cyano group-containing monomers such as (meth) acrylonitrile or crotononitrile; various monomers such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene or hexafluoropropylene. Fluoroolefins;
Various chlorinated olefins, such as vinyl chloride or vinylidene chloride; various α, such as ethylene, propylene, isobutylene, 1-butene or 1-hexene
-Olefins;

Or ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether or n
Various alkyl vinyl ethers, such as hexyl vinyl ether; various cycloalkyl vinyl ethers, such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or 4-methylcyclohexyl vinyl ether;

Alternatively, N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N-
Various tertiary amide group-containing monomers such as (meth) acryloylpyrrolidine or N-vinylpyrrolidone;

Alternatively, various polyether-containing polyethers such as esters of (meth) acrylic acid with polyethers having one hydroxyl group in one molecule such as methoxypolyethylene glycol or methoxypolypropylene glycol. Monomers.

To prepare the vinyl polymer (a-1) using the various monomers listed above, a solution polymerization method, a non-aqueous dispersion polymerization method or a bulk polymerization method may be used. The method can be applied by utilizing various known and commonly used polymerization methods, and among them, the solution radical polymerization method in an organic solvent is most simple.

As the polymerization initiator which can be used when applying by applying such a solution radical polymerization method, it is needless to say that various known and commonly used compounds can be used. To illustrate only

Various types such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2-methylbutyronitrile) Azo compounds;

Or tert-butyl peroxypivalate, tert-butyl peroxybenzoate, te
rt-butylperoxy-2-ethylhexanoate,
Benzoyl peroxide, lauroyl peroxide, acetyl peroxide,

Various peroxides such as di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide or diisopropyl peroxycarbonate.

As the organic solvent which can be used when applying by utilizing such a solution radical polymerization method, any of various known and commonly used organic solvents can be used.
Moreover, they may be used alone or in combination of two or more.

Among these, only typical ones are exemplified, and n-hexane, n-heptane,
various aliphatic or alicyclic hydrocarbons, such as n-octane, cyclohexane, cyclopentane or cyclooctane;

Various aromatic hydrocarbons such as toluene, xylene or ethylbenzene; methyl formate, ethyl formate, ethyl acetate, n-butyl acetate or n-acetate
Various esters such as amyl, ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate;

Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-butanol
Amyl alcohol, i-amyl alcohol or te
rt-amyl alcohol

Or various alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol mono n-butyl ether; various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone or cyclohexanone. ;

Or various ethers such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether or di-n-butyl ether; various chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, trichloroethane or tetrachloroethane. And N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate, and the like.

In preparing the polymer (a-1), if the amount of the acid group-containing monomer used as described above is increased, gelation often occurs during polymerization. Be careful.

In order to prevent such gelation, ethyl orthoacetate, ethyl ortho-n-butylate,
Various hydrolyzable esters such as ethyl orthoformate, ethyl orthopropionate or methyl orthoformate may be used in combination with the organic solvents described above.

By using a monomer, a polymerization initiator and an organic solvent as described above, respectively, by applying a known and common solution radical polymerization method,
The desired vinyl polymer (a-1) having both a hydrolyzable silyl group and an acid group can be prepared.

The hydrolyzable silyl group and acid group used for preparing the above-mentioned composite resin (A-2), which is a precursor of the aqueous resin (A-II) according to the present invention, The polymer (a-2) having both functional groups other than both groups includes the hydrolyzable silyl group as described above and the acid group as described above, as well as known and common groups other than both groups. Is a polymer containing various functional groups.

Examples of the acid group to be introduced into the polymer (a-2) include various groups exemplified as those which can be introduced into the polymer (a-1).
Among them, a carboxyl group, a blocked carboxyl group, a carboxylic acid anhydride group and the like are particularly desirable, and particularly only representative ones are exemplified.

Further, only typical functional groups to be introduced into the polymer (a-2) other than the hydrolyzable silyl group and the acid group are exemplified. Hydroxyl group, blocked hydroxyl group, primary amino group, secondary amino group, tertiary amino group, cyclocarbonate group, chain carbonate group, epoxy group, primary amide group, secondary amide group, carbamate group, oxazoline group ,
Carbonyl group, acetoacetyl group or the following structural formula (S-I)

[0099]

Embedded image

And the like.

The secondary amide group is an N-hydroxymethylamide group, an N-alkoxymethylamide group or a structural formula (S-III) shown below.

[0102]

Embedded image —C (O) —NH—CH (OR ³ ) —COOR ⁴ (S-III)

(Wherein R ³ represents a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and R ⁴ represents an alkyl group or an aryl group having 1 to 8 carbon atoms) Represents a group.)

And the functional group represented by the formula:

Further, these functional groups correspond to the polymer (a-
Only one kind may be contained in 2), or two or more kinds may be contained.

Other than these hydrolyzable silyl groups and acid groups, among the various functional groups described above, only typical ones are exemplified.
A blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group, or various functional groups such as those represented by the structural formula (SI) described above. is there.

The polymers having various functional groups (a-
If only typical examples are exemplified as 2), acrylic polymers, fluoroolefin polymers,
Including various vinyl polymers, such as vinyl ester polymers or aromatic vinyl polymers,
Examples include polyester resin, alkyd resin, and polyurethane-based polymer.

[0108] Of these, only typical ones are exemplified, and examples thereof include vinyl polymers and polyurethane polymers, and further, only typical ones among such vinyl polymers. Is an acrylic polymer.

In order to prepare the vinyl polymer of the polymer (a-2), various known and commonly used methods can be used. For example, a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group or a functional group represented by the structural formula (S-I) described above. A group having at least one functional group selected from the group consisting of various functional groups other than the hydrolyzable silyl group and the acid group,

A method of copolymerizing monomers having so-called three types of functional groups of a hydrolyzable silyl group-containing vinyl monomer and an acid group-containing monomer, or as described above. In addition to the monomers having three types of functional groups, a method of copolymerizing these with other vinyl monomers that can be copolymerized with them is particularly recommended because it is simple.

According to these various methods, a hydrolyzable silyl group-containing vinyl monomer, an acid group-containing monomer, and a hydrolyzable silyl group-containing monomer used in preparing the vinyl polymer (a-2) are used. Particularly typical examples of the other polymerizable vinyl monomers include the vinyl polymer (a-1) described above.
Examples of the compounds used for preparing the compound include various monomers as already exemplified.

In addition, if only particularly typical examples of the vinyl monomer having a hydroxyl group used in preparing the vinyl polymer (a-2) are given,

Various hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate; 2-hydroxyethyl vinyl ether or 4-hydroxyethyl (meth) acrylate
Various hydroxyl-containing vinyl ethers such as hydroxybutyl vinyl ether;

Various hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether; various polyether polyols such as polyethylene glycol; and (meth) acrylic acid. Such as monoesters of various polyoxyalkylene glycols obtained from various unsaturated carboxylic acids,

Or an adduct of various hydroxyl-containing monomers as described above with various lactones such as ε-caprolactone; or glycidyl (meth) acrylate. As represented, various epoxy group-containing unsaturated monomers, as represented by acetic acid and the like, adducts of various acids and the like,

Further, various unsaturated carboxylic acids, such as those represented by (meth) acrylic acid, and “Cardura E” (trade name, manufactured by Shell Co., Netherlands) are represented. And various hydroxyl-containing monomers such as adducts with various monoepoxy compounds other than epoxides of α-olefins.

As typical examples of the vinyl monomer having a blocked hydroxyl group, which is used in preparing the vinyl polymer (a-2), only typical ones can be represented by the following formula: JP-A-62-283163, such as trimethylsiloxyethyl (meth) acrylate, 2-trimethylsiloxypropyl (meth) acrylate, 4-trimethylsiloxybutyl (meth) acrylate, 2-trimethylsiloxyethyl vinyl ether or 4-trimethylsiloxybutyl vinyl ether; Various vinyl monomers containing a silyl ether group, as disclosed in Japanese Patent Publication No.

Or 2- (1-ethoxy) ethoxyethyl (meth) acrylate, 2- (1-n-butoxy) ethoxyethyl (meth) acrylate, 2- [2- (meth) acryloyloxy] ethoxytetrahydrofuran or 2, JP-A-4-4151, such as 2-dimethyl-4- (meth) acryloyloxymethyldioxolane
No. 5, various acetal or ketal group-containing vinyl monomers,

Or 3- [2- (meth) acryloyloxy] ethyloxazolidine, 2,2-dimethyl-3
-[2- (meth) acryloyloxy] ethyloxazolidine or 2-isobutyl-2-methyl-3- [2
-(Meth) acryloyloxy] ethyl oxazolidine, and various oxazolidine group-containing vinyl monomers.

As typical vinyl-based monomers having a tertiary amino group used in preparing the vinyl-based polymer (a-2), only typical ones are exemplified.

2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylamino Various tertiary amino group-containing (meth) acrylates, such as butyl (meth) acrylate or N- [2- (meth) acryloyloxy] ethylmorpholine;

Various tertiary amino group-containing aromatic vinyl monomers such as vinyl pyridine, N-vinyl carbazole or N-vinyl quinoline;

N- (2-dimethylamino) ethyl (meth) acrylamide, N- (2-diethylamino) ethyl (meth) acrylamide, N- (2-di-n-propylamino) ethyl (meth) acrylamide, N- (3-
Dimethylamino) propyl (meth) acrylamide, N
Various (meth) acrylamides containing a tertiary amino group, such as-(4-dimethylamino) butyl (meth) acrylamide or N- [2- (meth) acrylamido] ethylmorpholine;

Or N- (2-dimethylamino) ethylcrotonamide, N- (2-diethylamino) ethylcrotonamide, N- (2-di-n-propylamino) ethylcrotonamide, N- (3 Various tertiary amino group-containing crotonamides, such as -dimethylamino) propylcrotonamide or N- (4-dimethylamino) butylcrotonamide;

Alternatively, 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether,
3-dimethylaminopropyl vinyl ether or 4-
Various types of 3 such as dimethylaminobutyl vinyl ether
And vinyl ethers containing a secondary amino group.

If only typical examples of the vinyl monomer having a cyclocarbonate group used in preparing the vinyl polymer (a-2) are given below,

2,3-carbonatepropyl (meth) acrylate, 2-methyl-2,3-carbonatepropyl (meth) acrylate, 3,4-carbonatebutyl (meth) acrylate, 3-methyl-3,4-carbonatebutyl (Meth) acrylate, 4-methyl-3,4
-Carbonate butyl (meth) acrylate, 4,5-
Carbonate pentyl (meth) acrylate, 6,7-
Carbonate hexyl (meth) acrylate, 5-ethyl-5,6-carbonate hexyl (meth) acrylate or 7,8-carbonate octyl (meth) acrylate, 2,3-carbonate propyl vinyl ether, di (2,3-carbonate propyl) Various 5-membered cyclocarbonate group-containing vinyl monomers, such as malate or di (2,3-carbonatepropyl) itaconate;

Further, [5-N- (meth) acryloylcarbamoyloxy] methyl-5-ethyl-1,3-
Dioxan-2-one, 5- [N- {2- (meth) acryloyloxy} ethylcarbamoyloxy] methyl-
5-ethyl-1,3-dioxan-2-one, 5-ethyl-5- (meth) acryloyloxymethyl-1,3-
Dioxan-2-one or 4- (5-ethyl-2-
Various vinyl monomers containing a 6-membered cyclocarbonate group, such as oxo-1,3-dioxan-5-yl) methoxymethylstyrene.

The glycidyl (meta) may be exemplified by only typical examples of the epoxy group-containing vinyl monomer used in preparing the vinyl polymer (a-2). Acrylates, such as methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene oxide, glycidyl vinyl ether, methyl glycidyl vinyl ether or allyl glycidyl ether;
Various compounds and the like.

The vinyl polymer having a primary or secondary amide group used in the preparation of the vinyl polymer (a-2) is only a typical example. , (Meth) acrylamide, N-isopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-vinylformamide, methyl (meth)
Acrylamide glycolate, methyl (meth) acrylamide glycolate methyl ether, N-methylol (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide or 2-isocyanatoethyl (meth) acrylate, and acetylacetone or acetoacetate And various compounds such as an addition reaction product with

[0131] Only typical representative examples of the vinyl monomer having a carbamate group used in preparing the vinyl polymer (a-2) are given below.

Methyl N- (meth) acryloylcarbamate, ethyl N- (meth) acryloylcarbamate,
Ethyl N- [2-((meth) acryloyloxy] ethylcarbamate, 2-carbamoyloxyethyl (meth) acrylate, 2- (N-methylcarbamoyloxy) ethyl (meth) acrylate, 2- (N-ethylcarbamoyloxy ) Addition products of ethyl (meth) acrylate or 3-isopropenyl-α, α-dimethylbenzyl isocyanate with 2-hydroxypropyl carbamate; addition products of 2-isocyanatoethyl (meth) acrylate with phenol; Various compounds such as an addition reaction product of 2-isocyanatoethyl (meth) acrylate and ethanol; and an addition reaction product of 2-isocyanatoethyl (meth) acrylate and methyl ethyl ketoxime.

Further, a vinyl monomer having a functional group represented by the aforementioned structural formula (SI), which is used when preparing the vinyl polymer (a-2), is particularly typical. By way of example only, vinyl monomers having various isocyanate groups such as 2-isocyanatoethyl (meth) acrylate or 3-isopropenyl-α, α-dimethylbenzyl isocyanate; -Various compounds, such as addition products with various amide compounds, such as caprolactam or γ-butyrolactam.

Further, only the vinyl monomers particularly used as the vinyl polymer (a-2) having two or more of the above functional groups, which are used in preparing the vinyl polymer (a-2), may be used. Examples are various compounds such as a monomer of mono- (2-hydroxyethyl) itaconate or mono- (2,3-carbonatepropyl) itaconate.

As described above, a hydrolyzable silyl group-containing monomer, an acid group-containing monomer, a monomer having a functional group other than these two groups, and, if necessary, The vinyl polymer (a-2) is obtained by using these various monomers and other monomers that can be copolymerized.
To prepare

Solvents, polymerization initiators, and, if necessary, polymerization during the polymerization as exemplified above for use in preparing the above-mentioned vinyl polymer (a-1). In order to prevent gelation, using the various hydrolyzable esters as described above and the like, it is possible to copolymerize by various known and commonly used methods, especially according to a solution radical polymerization method. Good.

By using the above-mentioned monomers, polymerization initiators and organic solvents by utilizing a known and commonly used solution radical polymerization method, the desired hydrolyzable property is obtained. A vinyl polymer (a-2) having both a silyl group and an acid group and a functional group other than both groups can be prepared.

Each prepared as described above,
The amount of the hydrolyzable silyl group to be introduced into the vinyl polymer (a-1) or (a-2) may be about 0.0
A range of from about 0.05 to about 3 moles is suitable, preferably a range of from 0.01 to 2 moles, and even more preferably a range of from 0.05 to 1 mole.

When the amount is less than about 0.005 mol, the cured product obtained from the aqueous curable resin composition according to the present invention, in particular, the durability and the like are reduced. If the amount is too large, the solution viscosity at the time of the above-mentioned hydrolysis-condensation reaction increases, which may cause inconvenience such as gelation.

The amount of acid groups to be introduced into the vinyl polymer (a-1) or (a-2) is preferably about 0.1 per 1,000 g of the solid content of each polymer.
A range of from about 0.5 to about 13.5 moles is suitable, preferably a range of from about 0.07 to 7.0 moles, and most preferably a range of from 0.1 to 2.0 moles. Inside is appropriate.

Further, a hydroxyl group to be introduced into the vinyl polymer (a-2); a blocked hydroxyl group; a tertiary amino group; a cyclocarbonate group; an epoxy group; a primary amide group; A carbamate group; or an amount of at least one kind of a functional group other than a hydrolyzable silyl group and a functional group represented by the functional group represented by the structural formula (SI) described above. Is suitably in the range of about 0.1 to about 5 mol, preferably in the range of 0.2 to 3 mol, per 1,000 g of the solid content of the vinyl polymer (a-2). Is appropriate and
Even more preferably, a range of 0.3 to 2 mol is appropriate.

If the amount is more than about 5 mol, the cured product, especially, the water resistance and the chemical resistance are undesirably deteriorated.

The number average molecular weight of the vinyl polymer (a-1) or (a-2) is in the range of about 500 to about 100,000, preferably 1,000.
A range of from 50,000 to 50,000 is appropriate, and a range of from 1,500 to 30,000 is more preferable.

The vinyl polymer (a-1) or (a-
When the number average molecular weight of 2) is less than about 500, in particular, the curability and the mechanical strength of the cured product become inferior, and on the other hand, it exceeds about 100,000 and is too high. If you do,
The non-volatile content of the aqueous curable resin composition according to the present invention is significantly reduced, or the coating workability is deteriorated, and the cured coating film, in particular, has a reduced appearance, and in any case, Is also not preferred.

As the vinyl polymer (a-1),
In the presence of a polymer other than a vinyl polymer, such as a polyester resin or an alkyd resin, each having a polymerizable unsaturated double bond, a hydrolyzable silyl group-containing monomer and an acid group-containing monomer are contained. Resin or alkyd resin obtained by graft-polymerizing a vinyl polymer segment having both a hydrolyzable silyl group and an acid group, which is obtained by subjecting a monomer mixture containing a monomer to an essential component to radical polymerization. Etc. can also be used.

Further, as a vinyl polymer (a-2), a polymer other than a vinyl polymer having a polymerizable unsaturated double bond, such as a polyester resin or an alkyd resin, is used. By hydrolyzing a monomer mixture containing a hydrolyzable silyl group-containing monomer, an acid group-containing monomer, and a monomer having a functional group other than these two groups as an essential component, It is also possible to use a polyester resin or an alkyd resin obtained by grafting the obtained vinyl polymer segment having a hydrolyzable silyl group and an acid group and a functional group other than both groups.

Of the polymer (a-1), first, to prepare the polyurethane resin (a-1), a hydrolyzable silyl group is added to various dihydroxy compounds and various diisocyanate compounds. Diamine compounds having a monoamine compound having a hydrolyzable silyl group, furthermore, various known and commonly used raw material components such as dihydroxy compounds having various acid groups such as dimethylolpropionic acid or dimethylolbutanoic acid. Use,
JP-A-51-90391 and JP-A-55-7372.
Various methods such as those described in Japanese Patent Application Laid-open No. 9 or Japanese Patent Application Laid-Open No. 60-255817 may be used.

In the polymer (a-2), first,
In preparing the polyurethane resin, in addition to various known and commonly used raw materials listed above as those used in preparing the above-mentioned polyurethane polymer (a-1), hydrolyzable silyl is used. A compound containing one or two groups having active hydrogen that reacts with an isocyanate group, which contains various functional groups as described above, other than both the group and the acid group, is used as a raw material component. use,
What is necessary is just to apply it using various well-known methods.

The polyurethane polymer (a-2)
A group having an active hydrogen that reacts with an isocyanate group, which has various functional groups as described above, other than both of these groups, which are a hydrolyzable silyl group and an acid group, used in the preparation of If only one typical compound is exemplified as a compound having one or two, 4-hydroxymethyl-1,3-dioxolane-
Compounds having both a functional group and a hydroxyl group, such as 2-one, glycidol, N-methyldiethanolamine, 2-hydroxyethyl carbamate or 2-hydroxypropyl carbamate, and the like.

The polyurethane polymer (a-1) or (a-2) prepared by the method described above, respectively.
The amount of the hydrolyzable silyl group to be introduced into the polymer is preferably in the range of about 0.005 to about 3 mol per 1,000 g of the solid content of each polymer,
The range of 0.01 to 2 mol is appropriate, and even more preferably, the range of 0.05 to 1 mol is appropriate.

When the amount is less than about 0.005 mol, the cured product obtained from the aqueous curable resin composition according to the present invention inevitably deteriorates, in particular, the durability and the like. In the case where the molar ratio exceeds the molar ratio, the solution viscosity during the hydrolysis-condensation reaction increases, and thus, there is an inconvenience such that gelation occurs. .

In addition, these polyurethane polymers (a
The amount of the acid group to be introduced into -1) or (a-2) is in the range of about 0.07 to about 5.0 mol per 1,000 g of the solid content of each polymer. It is appropriate, preferably in the range of 0.07 to 2.0 mol, and most preferably in the range of 0.1 to 0.7 mol.

Further, a polyurethane polymer (a-2)
The amount of at least one of the functional groups other than these groups, which are the hydrolyzable silyl group and the acid group, to be introduced into the polymer, may be 1,000% of the solid content of the polyurethane polymer (a-2). A range of about 0.1 to about 5 moles per gram is suitable, preferably a range of 0.2 to 3 moles, and more preferably 0.3 to 2 moles.
A mole range is appropriate.

Further, these polyurethane-based polymers (a
The number average molecular weight of -1) or (a-2) is suitably in the range of about 500 to about 100,000, preferably in the range of 1,000 to 50,000, and more preferably. , 1,500 to 30,000.

When the number average molecular weight of the polyurethane polymer (a-1) or (a-2) is less than about 500, in particular, the curability and the mechanical strength of the cured product are inferior. And on the other hand, about 100,000
If it is too high, the nonvolatile content of the water-based curable resin composition according to the present invention is extremely low, or the coating workability is deteriorated, Either case is not preferred because the film, in particular, its appearance is deteriorated.

The composite resin used in the present invention (A-
The silicon compound (b) having at least two hydrolyzable groups bonded to a silicon atom in one molecule, which is the other component used in preparing 1) and (A-2),
In general, for example, it refers to a silane compound having at least two hydrolyzable groups bonded to a silicon atom in one molecule.

Here, the hydrolyzable group bonded to a silicon atom means a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, and an amide group, respectively, bonded to a silicon atom. , An aminooxy group, an iminooxy group or an alkenyloxy group, which is hydrolyzed to form a silanol group.

As the silicon compound (b), any of the known and commonly used compounds can be used, but if only typical ones among them are exemplified,
The following general formula (S-IV)

[0159]

Embedded image R ⁵ _b SiR ⁶ _(4-b) (S-IV)

(However, R ⁵ in the formula may be an alkyl group, which may or may not have a substituent.
R ⁶ represents a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amide group, an aminooxy group, an iminooxy group. Or b represents an alkenyloxy group, and b is an integer of 0, 1 or 2. )

A monosilane compound represented by the formula:

Or

[0163]

Embedded image (CH ₃ CH ₂ O) ₃ SiCH ₂ CH ₂ Si
(OCH ₂ CH ₃ ) ₃

Or

[0165]

Embedded image (CH ₃ CH ₂ O) ₃ SiCH ₂ CH ₂ CH
₂ Si (OCH ₂ CH ₃ ) ₃

Silicon compounds having two or more hydrolyzable silyl groups in one molecule, such as

As the monosilane compounds represented by the above-mentioned general formula, only typical ones are exemplified, and various tetraalkoxy compounds such as tetraethoxysilane, tetramethoxysilane or tetra-n-butoxysilane may be used. Silanes;

Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane , N-butyltrimethoxysilane or n-butyltriethoxysilane,

Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-butoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, vinyltris (2-methoxyethoxy) silane or allyltrimethoxy Silane or

2-trimethoxysilylethyl vinyl ether, 2-triethoxysilylethyl vinyl ether,
3-trimethoxysilylpropyl vinyl ether, 3-
Various organotrialkoxysilanes such as triethoxysilylpropyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane or 3- (meth) acryloyloxypropyltriethoxysilane;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-butyl Dimethoxysilane or di-n-butyldiethoxysilane or

Diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-butoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, vinylmethyldimethoxysilane,
-(Methyldimethoxysilyl) ethyl vinyl ether,
Various diorganodialkoxysilanes, such as 3- (methyldimethoxysilyl) propyl vinyl ether or 3- (meth) acryloyloxypropylmethyldimethoxysilane;

Alternatively, tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3- (meth) acryloyloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane Various chlorosilanes such as chlorosilane, methylphenyldichlorosilane, vinylmethyldichlorosilane or 3- (meth) acryloyloxypropylmethyldichlorosilane;

Further, there are various acetoxysilanes such as tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane and diphenyldiacetoxysilane.

Among these silicon compounds having a hydrolyzable group, only typical ones used for preparing the composite resins (A-1) and (A-2) will be exemplified. To be more specific, they include alkoxysilanes such as tetraalkoxysilane, organotrialkoxysilane and diorganodialkoxysilane, and various chlorosilanes.

The silicon compound (b) is a so-called 4-ethoxysilane represented by tetraethoxysilane.
When using a functional silicon compound, prevention of gelation during a hydrolysis-condensation reaction in the presence of the polymer (a-1) or (a-2); and prevention of gelation during a neutralization reaction with a basic compound For such reasons, it is desirable to use a bifunctional or trifunctional silicon compound in combination.

In preparing these composite resins (A-1) and (A-2), in addition to the various silicon compounds described above, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane So-called monofunctional having only one hydrolyzable group bonded to a silicon atom in one molecule, such as triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, trimethylchlorosilane, triethylchlorosilane or triphenylchlorosilane. A silicon compound having a property can also be used in combination.

Among the above-mentioned silicon compounds (b), the composite resins (A-1) and (A-2) are preferred in view of the stability of the aqueous resins (AI) and (A-II). At least 10 mol%, preferably at least 20 mol%, more preferably at least 40 mol% of all silicon compounds used in the preparation are aryl, such as phenyltrimethoxysilane or methylphenyldimethoxysilane. Suitably, it is a silicon compound having a silicon atom in which the group and the hydrolyzable group are bonded together.

The aqueous resins (AI) and (AI)
The polymers (A-1) and (A-2) are prepared from the viewpoint of the curability of I) and the cured coating film of the aqueous curable resin composition containing the aqueous resin, particularly from the viewpoint of durability. 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol%, of all the silicon compounds used at this time.
The above is suitably a so-called trifunctional silane compound such as methyltrialkoxysilanes, methyltrichlorosilane, phenyltrialkoxylans or phenyltrichlorosilane.

Next, in the presence of the polymer (a-1) or (a-2), the composite resin (A-
The method for preparing 1) or (A-2) will be described.

The composite resin (A-1) or (A-
In the preparation of 2), the polymer (a-1) or (a-
2) and the silicon compound (b) are used in the ratio [(a-
1) or (a-2)]: (B)
5:95 to 99: 1, preferably 1
5:85 to 95: 5, more preferably 20:80 to
It is preferable to set 85:15.

If the weight ratio of the polymer (a-1) or (a-2) is set to be less than about 5%, since the silicon component derived from the silicon compound (b) is too much, A cured coating film having poor alkali resistance can be obtained, while the polymer (a-1)
Alternatively, when the weight ratio of (a-2) exceeds about 99% and becomes too large, inevitably, the silicon component derived from the silicon compound (b) is too small, resulting in high durability and the like. In any case, it is difficult to obtain a cured coating film having

The polymer (a-1) or (a-
In conducting the hydrolysis-condensation reaction of the silicon compound (b) in the presence of 2), a catalyst may or may not be used, but these hydrolysis-condensation reactions easily proceed. From above, it is desirable to use a catalyst.

In the case where a catalyst is used,
Any of various known and commonly used catalysts can be used, and of course, they may be used alone or in combination of two or more.

If only particularly typical examples of such a catalyst are given, examples thereof include hydrochloric acid, sulfuric acid and phosphoric acid.
Various inorganic acids; various organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate or acetic acid;

Various inorganic bases such as sodium hydroxide or potassium hydroxide; various titanates such as tetraisopropyl titanate or tetrabutyl titanate; various tin carboxylates such as dibutyltin dilaurate or tin octylate Acid salts;

Various metal carboxylate salts such as naphthenate or octylate of various metals such as iron, cobalt, manganese or zinc; Various aluminum compounds such as aluminum trisacetylacetonate;

1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,4-diazabicyclo [2.2 .2] octane (DABCO), tri-n-butylamine, butylamine, octylamine or dimethylbenzylamine or

Various amine compounds such as monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole or 1,4-diethylimidazole;

Tetramethylammonium salt, tetrabutylammonium salt, trimethyl (2-hydroxypropyl) ammonium salt, cyclohexyltrimethylammonium salt, tetrakis (hydroxylmethyl) ammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt or o- Various quaternary ammonium salts, such as trifluoromethylphenyltrimethylammonium salt,

Further, as a typical counter anion,
Quaternary ammonium salts having chloride, bromide, carboxylate, hydroxide or the like, respectively.

The amount of the catalyst to be used is about 0.04 to the silicon compound (b) to be subjected to the hydrolytic condensation reaction.
The range of 00001 to about 10% by weight is preferably
A range of 0.000005 to 5% by weight, particularly preferably a range of 0.00001 to 1% by weight, is appropriate.

The amount of water used in the reaction is preferably about 0.05 mol or more with respect to 1 mol of the hydrolyzable group bonded to the silicon atom of the silicon compound (b). Preferably, 0.1 mol or more is appropriate, and more preferably, 0.2 mol or more is appropriate.

When the amount is less than 0.05 mol, the rate of hydrolysis is extremely slowed down, which is not practically preferable. However, the amount of water is 5 mol, 10 mol or silicon atom. Use in a large excess with respect to 1 mol of the hydrolyzable group bonded to the compound has no problem.

The addition of the catalyst and water is as follows:
It is needless to say that the catalyst and water may be added all at once or separately, and may be added in the form of a mixture of the catalyst and water, or may be added separately.

The reaction temperature of the reaction is from 0 ° C. to 1
About 50 ° C. is appropriate, preferably 20 ° C. to 100 ° C.
C. is appropriate, and the reaction can be carried out under any of normal pressure and increased or reduced pressure.

The by-products of the reaction, such as alcohol and water, are converted into the polymer (A)
If it seems to cause problems with respect to the neutralization reaction with the basic compounds of -1) and (A-2) and the stability of the resulting aqueous curable resin composition, the system may be subjected to distillation or other means. It can be removed outside, and if there is no problem, it can be left in the system as it is without any problem.

In such a reaction, an organic solvent may or may not be used. However, in order to easily perform stirring and the like, an organic solvent is used. It is desirable to do.

Here, when an organic solvent is used, any of the known and commonly used organic solvents can be used, and these may be used alone or in combination of two or more. It is.

As the organic solvent used at this time, there can be used various compounds as described above which can be used for preparing the vinyl polymers (a-1) and (a-2). You can do it. Then, when the hydrolysis condensation reaction of the silicon compound (b) is performed in the presence of the polymer (a-1) or (a-2) using such an organic solvent, the polymer (a- The concentration of 1) or (a-2) and the silicon compound (b) in the organic solvent is preferably about 5% by weight or more based on the total amount of both components.

The composite resin (A) thus prepared
The acid group contained in -1) or (A-2) is partially or completely neutralized with a basic compound, and then dispersed or dissolved in water. Aqueous resins (AI) and (AI)
I) is prepared.

As the above-mentioned basic compounds used in the neutralization reaction, only particularly typical ones are exemplified, and methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n- Butylamine, tri-n-butylamine,
Various organic amine compounds represented by 2-amino-2-methylpropanol, 2-aminoethanol or 2-dimethylaminoethanol;

Various inorganic basic substances represented by sodium hydroxide or potassium hydroxide, such as ammonia; or tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide or trimethylbenzylammonium Various quaternary ammonium hydroxides such as those represented by hydroxides and the like.

Among these various basic compounds, it is particularly desirable to use ammonia and various organic amines.

The amount of the basic compound to be added is such that water dispersibility can be imparted to at least the composite resin (A-1) or (A-2). The composite resin (A-1) or (A-
2) the ratio of the number of equivalents of the basic compound to the number of equivalents of the acid groups contained in

In other words, it is appropriate that the equivalent ratio of the basic compound / [acid group of the composite resin (A-1) or (A-2)] is about 0.1 or more. The amount within a range that does not impair the properties of the coating film is preferably approximately in the range of 0.1 to 3, and most preferably 0.3 to 2.

Such a neutralization reaction may be carried out in the presence of water or in the absence of water, but in the absence of water, the polymer (a-1) In the case where the solution viscosity increases during the neutralization reaction due to the type and composition of the polymer (a-2) or the silicon compound (b), as well as the conditions of the neutralization reaction, and eventually gelation occurs. Be careful as there are some.

When such a problem occurs, it is particularly desirable to carry out the neutralization reaction in the coexistence of water, and the amount of water added at this time depends on the above-mentioned composite resin (A-1) or (A-1). For 1000 g of the solid content of A-2), 10
It is appropriate to set the ratio to 0 g or more, preferably 200 g or more, and more preferably 500 g or more.

[0209] The method of adding the basic compound and water at the time of performing such a neutralization reaction may be batch addition, divided addition, or separate addition.
Needless to say, it is most suitable to add a basic compound and water in a mixed form.

The reaction temperature of such a neutralization reaction is 0
C. to about 150.degree. C. is appropriate, and preferably 20.degree.
100 ° C. is appropriate, while the reaction can be carried out under any conditions of normal pressure and pressure or reduced pressure.

From the neutralized reactants of the composite resin (A-1) or (A-2) thus prepared,
The aqueous resin (AI) or (AI) described above, respectively.
To prepare I), various known and common methods can be used and applied. For example, (A-1) or (A
To the neutralized reactant of -2), water is simply added, or the neutralized reactant of (A-1) or (A-2) is added to water, The aqueous resin (AI) or (A-II) can be produced by dispersing or dissolving, respectively.

As described above, when the neutralization reaction is carried out in the presence of a large amount of water, it is possible to obtain an aqueous resin after the neutralization reaction, particularly without adding water. is there.

Further, if necessary, the organic solvent contained in the aqueous resin (AI) or (A-II) thus prepared may be partially heated and / or reduced in pressure to partially remove the organic solvent. Or by completely removing
An aqueous resin (AI) or (A-II) having a low organic solvent content or containing no organic solvent can be prepared.

The aqueous resin thus prepared (A-
The functional group contained in I) is a silanol group derived from the polymer (a-1) and the silicon compound (b). In some cases, the functional group is included in a hydrolysis bonded to a silicon atom. And a free acid group derived from the polymer (a-1) and an acid group neutralized by a basic compound.

The functional group contained in the aqueous resin (A-II) prepared as described above is a polymer (a-2)
And a silanol group derived from the silicon compound (b);
In addition to a hydrolyzable group bonded to a silicon atom, a free acid group derived from the polymer (a-2), and an acid group neutralized by a basic compound, which may be contained in some cases. A hydroxyl group derived from the polymer (a-2),
A hydroxyl group such as a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group or a functional group represented by the above-mentioned structural formula (SI); It is at least one of functional groups other than these groups, such as a decomposable silyl group and an acid group.

In the process of preparing the aqueous resin (AI) or (A-II), the polymer (a-1) or (a-2)
In the case where a blocked acid group or an acid anhydride group is introduced as an acid group, at least a part of the blocked acid group or the acid anhydride group is
During the hydrolysis and condensation of the silicon compound (b) during the preparation of the composite resin (A-1) or (A-2), or during the neutralization with a basic compound, hydrolysis, acid-catalyzed decomposition, thermal decomposition or It is converted to a free acid group by alcoholysis or the like, and functions as a hydrophilic group for aqueous conversion.

If the above-mentioned blocked acid group or acid anhydride group is introduced as an acid group, an amount of free acid group necessary for aqueous conversion is generated even after the neutralization step with a basic compound. Otherwise, it is converted to a free acid group by taking measures such as stricting the reaction conditions in the neutralization step or the hydrolysis and condensation step of the silicon compound (b) in the preparation of the composite resin (A-2). It is necessary to do so.

In preparing the aqueous resin (A-II), a resin in which a blocked hydroxyl group, epoxy group, cyclocarbonate group or the like is introduced into the polymer (a-2) is used. In such a case, at the stage of the hydrolysis condensation reaction of the silicon compound (b) in the preparation of the composite resin (A-2),

Further, at the stage of the neutralization reaction using a basic compound with respect to the composite resin (A-2), and further at the stage of dispersing or dissolving the neutralization reaction product in water, At least a portion of the functional groups may be converted to free hydroxyl groups by hydrolysis, acid-catalyzed decomposition or alcoholysis.

Then, the kind of the blocked hydroxyl group, epoxy group or cyclocarbonate group, or the silicon compound (b) in the preparation of the composite resin (A-2)
Hydrolytic condensation reaction; a neutralization reaction performed after the hydrolysis / condensation reaction; and depending on the conditions of dispersion or dissolution in water, such various functional groups are completely converted to free hydroxyl groups. There is also.

The aqueous resin (A-
In order to prepare the aqueous curable resin composition according to the present invention from (I) or (A-II), one of these (A-II)
Since both (I) and (A-II) have a so-called self-curing property, a self-curing resin containing (AI) or (A-II) as an essential component is used. It may be a composition,

In the two, (AI) or (A-II)
And further compounding the compound (C) described above,
A functional group contained in (AI) or (A-II),
A curable resin composition in which a so-called cross-linking reaction with a functional group contained in the compound (C) is also used can be provided.

The compound (C) used in the preparation of the curable resin composition in the latter form includes the compound (C) contained in the aqueous resin (AI) or (A-II) described above. At least one functional group that reacts with various functional groups
Species, in the form of having, refers to various known and commonly used compounds, and if only specific examples of such functional groups are given, isocyanate groups, blocked isocyanate groups, hydroxyl groups, Hydroxyl group, carboxyl group, blocked carboxyl group, carboxylic anhydride group, amino group, cyclocarbonate group, chain carbonate group, epoxy group, primary amide group, secondary amide group, carbamate group, oxazoline group,
N-hydroxymethylamino group, N-alkoxymethylamino group, carbonyl group, acetoacetyl group, silanol group, hydrolyzable group bonded to silicon atom, or the following structural formula (S-III)

[0224]

Embedded image —C (O) —NH—CH (OR ³ ) —COOR ⁴ (S-III)

(Wherein R ³ represents a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and R ⁴ represents an alkyl group or an aryl group having 1 to 8 carbon atoms) Shall be represented.)

And the like.

The functional group contained in the compound (C) is appropriately selected according to the type of the functional group contained in the aqueous resin (AI) or (A-II). And only particularly typical examples of such combinations are silanol group-silanol group, silanol group-alkoxysilyl group, alkoxysilyl group-alkoxysilyl group, carboxyl group-
Epoxy group, carboxyl group-cyclocarbonate group,
Examples include a tertiary amino group-epoxy group, a hydroxyl group-N-hydroxymethylamino group or a hydroxyl group-isocyanate group.

As the compound (C), depending on the functional groups contained in the aqueous resin (AI) or (A-II), two or more of the various functional groups described above may be used. It may be in the form of having. Further, as the compound (C), various resins can be used in addition to the compound having a relatively low molecular weight. If only typical examples of such resins are given, examples thereof include various vinyl polymers such as acrylic resins and fluororesins, and further,
Examples include polyester resin, alkyd resin, polyurethane resin, and epoxy resin. When a compound having two or more functional groups as described above is used as the compound (C), a vinyl polymer is used as the compound (C). Is the most convenient.

If only particularly typical examples of the compound (C) are given, examples thereof include a compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom; Compound having both an isocyanate group and a hydrolyzable group bonded to a silicon atom; compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule; bonding to an amino group and a silicon atom in one molecule A polyisocyanate compound; a block polyisocyanate compound; a polyepoxy compound; a polycyclocarbonate compound; an amino resin; a compound containing a primary or secondary amide group; a polycarboxy compound; Polyaziridine compound; polyacrylate compound; polycarbodiimide compound; Compounds having a hydroxyl group; polyamine compounds; and the like compound or polyoxazoline compounds having at least two carboxylic acid anhydride groups, these miscellaneous compounds may be a single use, 2
It goes without saying that more than one kind may be used in combination.

Of these, only typical ones are exemplified. Compounds having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, and an isocyanate group in one molecule. A compound having both a hydrolyzable group bonded to a silicon atom; a compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule; a polyisocyanate compound; a blocked polyisocyanate compound; a polyepoxy compound; Cyclocarbonate compounds; amino resins; compounds containing primary or secondary amide groups; polycarboxy compounds or polyhydroxy compounds.

Of the above-mentioned silicon compounds having a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom, only typical ones are exemplified. In the above-mentioned general formula (S-IV), A silicon compound as shown below; a hydrolyzate or hydrolyzed condensate of these silicon compounds; a partially hydrolyzed condensate obtained by one kind of partial hydrolytic condensation of these silicon compounds; or these silicon compounds And a partial co-hydrolytic condensate obtained by two or more partial hydrolytic condensations.

Among them, tetramethoxysilane or tetraethoxysilane, or a partial hydrolyzate or condensate of these compounds may be used to exemplify only typical silicon compounds. And furthermore, their partial co-hydrolysis condensates.

If only one of the above-mentioned compounds having an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule is specifically exemplified, only the following compounds should be exemplified.

Various silicon compounds such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane or 3-isocyanatopropylmethyldiethoxysilane;

Alternatively, various copolymers obtained from a vinyl monomer having a hydrolyzable silyl group as described above and a vinyl monomer having an isocyanate group as described later or Are copolymerizable with (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers, respectively. Various vinyl resins, such as acrylic copolymers, vinyl ester copolymers or fluoroolefin copolymers, each having both an epoxy group and a hydrolyzable silyl group, as obtained by And copolymers.

If only one of the above-mentioned compounds having a combination of an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule, it is necessary to exemplify only the following compounds.

Various silicon compounds such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane or 3-glycidoxypropylmethyldiethoxysilane A partial hydrolysis condensate of the silicon compound obtained by one kind of partial hydrolysis condensation; or a partial cohydrolysis condensate of the silicon compound obtained by two or more kinds of partial hydrolysis condensation ;

"EGM-202" [trade name of a cyclic polysiloxane having a methoxy group bonded to a silicon atom and 3-glycidoxypropyl, manufactured by Dow Corning Toray Silicone Co., Ltd.] or "KP-392"
[Trade name of partially hydrolyzed condensate of 3-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.];

Alternatively, a vinyl monomer having various epoxy groups as described above and a vinyl monomer as described above may also be used.
Various copolymers obtained from various types of vinyl monomers having a hydrolyzable silyl group or both of these monomers can be copolymerized with both monomers by (meth) acrylic, respectively. Acrylic having both an epoxy group and a hydrolyzable silyl group, such as obtained by copolymerization with a vinyl, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomer, etc. Various vinyl copolymers such as a copolymer, a vinyl ester copolymer, and a fluoroolefin copolymer.

If only typical examples of the above-mentioned polyisocyanate compounds are given as examples, tolylene diisocyanate or diphenylmethane-4,
Various aromatic diisocyanates, such as 4'-diisocyanate;

Meta-xylylene diisocyanate, α,
various aralkyl diisocyanates, such as α, α ′, α′-tetramethyl-meta-xylylene diisocyanate;

Such as hexamethylene diisocyanate, lysine diisocyanate, 1,3-bisisocyanatomethylcyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane or isophorone diisocyanate , Various aliphatic or alicyclic diisocyanates;

The polyisocyanates described above can be obtained by addition reaction with polyhydric alcohols.
Various prepolymers having isocyanate groups;

Various prepolymers having an isocyanurate ring obtained by cyclizing and trimerizing the various polyisocyanates as described above;

Various polyisocyanates having a biuret structure obtained by reacting various polyisocyanates as described above with water;

Further, various vinyl monomers having an isocyanate group, such as 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate or (meth) acryloyl isocyanate, may be used alone. Polymer;

Alternatively, these isocyanate group-containing vinyl monomers can be copolymerized with the monomers to be (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl, or fluoroolefin vinyl, respectively. Obtained by copolymerizing with monomers and the like,

Various vinyl copolymers such as an isocyanate group-containing acrylic copolymer, a vinyl ester copolymer or a fluoroolefin copolymer, respectively.

Among such polyisocyanates, in particular, from the viewpoint of weather resistance and the like, aliphatic or alicyclic diisocyanate compounds, and various prepolymers or isocyanate compounds derived from each of these diisocyanate compounds. The use of a group-containing vinyl polymer or the like is particularly desirable.

If only typical representative examples of the above-mentioned block polyisocyanate compounds are given, only various polyisocyanate compounds as described above may be blocked with various blocking agents as described below. Various block polyisocyanate compounds obtained by letting

Examples of the compound include a class of compounds in which an isocyanate group is regenerated by heat, such as compounds having various uretdione structures obtained by cyclizing and dimerizing an isocyanate group.

When only typical blocking agents used in preparing the blocked polyisocyanate compound are exemplified, various blocking agents such as methanol, ethanol, benzyl alcohol or lactate may be used. Carbinol group-containing compounds;

Various phenolic hydroxyl-containing compounds such as phenol, salicylate or cresol; or various amides such as ε-caprolactam, 2-pyrrolidone or acetanilide;

Alternatively, various oximes such as acetone oxime or methyl ethyl ketoxime, and various active methylene compounds such as methyl acetoacetate, ethyl acetoacetate or acetylacetone may be used.

As the above-mentioned polyepoxy compounds, only typical ones are exemplified, and ethylene glycol, hexanediol, neopentyl glycol,
Polyglycidyl ethers of various aliphatic or cycloaliphatic polyols, such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol or hydrogenated bisphenol A;

Hydroquinone, catechol, resorcinol,
Polyglycidyl ethers of various aromatic diols such as bisphenol A, bisphenol S or bisphenol F; various aromatic diols such as ethylene oxide or propylene oxide adducts of aromatic diols as described above. Diglycidyl ethers of diol derivatives;

Polyglycidyl ethers of various polyether polyols such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; polyglycidyl ethers of tris (2-hydroxyethyl) isocyanurate; adipic acid, butanetetracarboxylic acid Various polyglycidyl esters of aliphatic or aromatic polycarboxylic acids, such as, propanetricarboxylic acid, phthalic acid, terephthalic acid or trimellitic acid;

Various bisepoxides of 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; or various epoxidized products of various diene polymers, such as polybutadiene or polyisoprene;

[EX-612] [Nagase Chemical Industry Co., Ltd.]
Or “EGM-400” [trade name of cyclic polysiloxane having 3-glycidoxypropyl, manufactured by Dow Corning Silicone Toray Co., Ltd.];

Alternatively, various homopolymers of vinyl monomers having various epoxy groups as described above; or these epoxy group-containing vinyl monomers can be copolymerized with the monomers. Epoxy group-containing acrylic copolymers, vinyl esters obtained by copolymerizing with (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers, etc. Various vinyl copolymers such as a copolymer or a fluoroolefin copolymer.

If only typical representative examples of the polycyclocarbonate compound are exemplified, various polyepoxy compounds as described above may be reacted with carbon dioxide in the presence of a catalyst, for example. A polycyclocarbonate compound having various 5-membered cyclocarbonate groups obtained by converting the epoxy group into a cyclocarbonate group; or a vinyl monomer having various cyclocarbonate groups as described above. Various homopolymers;

Alternatively, these cyclocarbonate group-containing vinyl monomers can be copolymerized with the monomers.
(Meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers, etc., and obtained by copolymerizing with a cyclocarbonate group-containing acrylic copolymer, vinyl ester Various vinyl copolymers such as a copolymer or a fluoroolefin copolymer.

If only typical amino resins are exemplified, melamine, benzoguanamine,
Such as acetoguanamine, urea or glycouril,
Various amino resins having an alkylol group, such as those obtained by reacting various amino group-containing compounds with various aldehyde compounds (or aldehyde supply substances) such as formaldehyde or acetaldehyde;

Alternatively, various amino resins having an alkoxyalkyl group obtained by reacting such an amino resin having an alkylol group with various lower alcohols such as methanol, ethanol, n-butanol or i-butanol. And so on.

In addition, if only typical examples of the primary or secondary amide group-containing compound are given, only those which are used in the preparation of the polymer (a-2) are exemplified. Homopolymers of various vinyl monomers having a primary or secondary amide group;

Alternatively, these primary or secondary amide group-containing vinyl monomers can be copolymerized with the monomers, respectively. (Meth) acrylic, vinyl ester, vinyl ether, and aromatic Various acrylic copolymers, vinyl ester copolymers or fluoroolefins having primary or secondary amide groups, such as those obtained by copolymerizing with vinyl or fluoroolefin vinyl monomers, etc. Like copolymers,
Various vinyl copolymers and the like.

Further, as typical examples of polycarboxy compounds, only typical ones may be mentioned.
Various low molecular weight compounds such as malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, tartronic acid, malic acid, tartaric acid or citric acid. ,

Furthermore, homopolymers of various vinyl monomers having a carboxyl group, as already exemplified as those used in preparing the polymer (a-1)

Alternatively, such a carboxyl group-containing vinyl monomer can be copolymerized with the monomer, and can be (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl, respectively. Various vinyl-based polymers such as various acrylic-based copolymers, vinyl ester-based copolymers or fluoroolefin-based copolymers having a carboxyl group, as obtained by copolymerizing with monomers and the like. And copolymers.

As typical polyhydroxy compounds, only typical ones may be mentioned, for example, low molecular weight compounds such as ethylene glycol, propylene glycol, butylene glycol and glycerin;
Such as polyethylene glycol or polypropylene glycol, and further, as already exemplified as those used when preparing the polymer (a-2),
Homopolymers of various vinyl monomers having a hydroxyl group;

Alternatively, these hydroxyl group-containing vinyl monomers are
As can be copolymerized with the monomer, respectively, such as obtained by copolymerizing with (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers, Various vinyl copolymers having a hydroxyl group, such as various acrylic copolymers, vinyl ester copolymers or fluoroolefin copolymers, and the like.

Here, when compound (C) is mixed with aqueous resin (AI) or (A-II), when compound (C) is water-soluble or has a certain degree of hydrophilicity, In this method, a composition in which the compound (C) is uniformly dissolved or uniformly dispersed in the aqueous resin (AI) or (A-II) can be obtained.

However, when the hydrophilicity of the compound (C) is low, even when the compound (C) is mixed with the aqueous resin (AI) or (A-11), the composition is in the form of a uniform solution or dispersion. Cannot be obtained. In such a case, by introducing a hydrophilic group or the like into the compound (C) by various known and common methods, the hydrophilicity of the compound (C) is improved, and a uniform composition is obtained. Can be obtained.

When the compound (C) is a polymer, the compound (C) can be used in any form of a solventless liquid, an organic solvent solution, an aqueous solution or an aqueous dispersion. . And when the said compound (C) is a vinyl polymer especially, it is also suitable to use as an emulsion polymer.

The aqueous resin (AI) or (A-
In order to prepare an aqueous curable resin composition comprising II) and a compound (C), the compound (C) has a hydroxyl group bonded to a silicon atom and / or a compound having a hydrolyzable group bonded to a silicon atom. , The aqueous resin (A
The compound (C) is used in an amount of 0.1 to about 200 parts by weight, preferably 0.5 to 150 parts by weight, based on 100 parts by weight of the solid of (I) or (A-II). Preferably, it may be blended so as to be in the range of 1 to 100 parts by weight.

When the compound (C) is a compound having both an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule, a polyisocyanate compound or a blocked polyisocyanate compound, With respect to one equivalent of a functional group that reacts with an isocyanate group or a blocked isocyanate group contained in the aqueous resin (AI) or (A-II),

The amount of the isocyanate group or the blocked isocyanate group contained in the compound (C) is about 0.1 to about 10 equivalents, preferably 0.3 to 5 equivalents, and more preferably 0.5 to 2 equivalents. The compound (C) may be blended so as to fall within the range.

In the case where the compound (C) is a compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule, a polyepoxy compound or a polycyclocarbonate compound, aqueous Resin (A-
With respect to one equivalent of a functional group that reacts with an epoxy group or a cyclocarbonate group contained in I) and (A-II),

The total amount of the epoxy group and / or cyclocarbonate group contained in the compound (C) is:
Within a range of about 0.2 to about 5.0 equivalents, preferably 0.1 equivalent.
Within the range of 5 to 3.0 equivalents, more preferably 0.7 to
The compound (C) may be blended so as to fall within the range of 2 equivalents.

When the compound (C) is an amino resin, the aqueous resin (AI) or (AI)
The solid content of the compound (C) is about 1 to about 200 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the solid matter of I).
The amount may be 150 parts by weight, more preferably 10 to 100 parts by weight.

In the case where the compound (C) is a compound having a primary or secondary amide group, the primary or secondary compound contained in the aqueous resin (AI) or (A-II) may be used. For one equivalent of a functional group that reacts with a secondary amide group,

Primary or secondary contained in compound (C)
Within the range of about 0.2 to about 5.0 equivalents of the secondary amide group,
Preferably, the compound (C) may be blended so as to be preferably in a range of 0.5 to 3.0 equivalents, more preferably in a range of 0.7 to 2 equivalents.

When compound (C) is a polycarboxy compound, aqueous resin (AI)
Or 1 equivalent of a functional group that reacts with a carboxyl group contained in (A-II),

The amount of the carboxyl group contained in the compound (C) is in the range of about 0.2 to about 5.0 equivalents, preferably in the range of 0.5 to 3.0 equivalents, more preferably,
The compound (C) may be blended so as to be in the range of 0.7 to 2 equivalents.

When compound (C) is a polyhydroxy compound, aqueous resin (AI)
Or 1 equivalent of a functional group that reacts with a hydroxy group contained in (A-II),

The amount of hydroxyl group contained in compound (C) is within the range of about 0.2 to about 5.0 equivalents, preferably 0.5 to about 5.0 equivalents.
To 3.0 equivalents, more preferably 0.7 to 2 equivalents.
What is necessary is just to mix this compound (C) so that it may be in the equivalent range.

The aqueous curable resin composition according to the present invention, which comprises the aqueous resin (AI) or (A-II) as an essential component, prepared as described above,
Alternatively, the aqueous curable resin composition according to the present invention in a form in which the compound (C) is further added to the aqueous resin (AI) or (A-II),
It can be used as a so-called clear composition, or it can also be used as a coloring composition in the form of various known or commonly used organic or inorganic pigments.

The aqueous curable resin composition according to the present invention may further comprise a curing catalyst, a flow regulator, a dye, a leveling agent, a rheology control agent, an ultraviolet absorber, an antioxidant or a plasticizer. It can be used for various purposes in a form in which various known additives are mixed.

Of these various additives, only those particularly typical as curing catalysts are exemplified.
When preparing the above-described composite resins (A-1) and (A-2), various kinds of catalysts already listed as those used for the hydrolysis-condensation reaction of the silicon compound (b) are used. It can be used, and in addition, tetramethylphosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, trimethyl (2-hydroxypropyl) phosphonium salt, triphenylphosphonium salt or benzylphosphonium salt, etc. Can be used.

The thus obtained aqueous curable resin composition according to the present invention comprises an aqueous resin resin (A-
Depending on the type of (I) or (A-II), the presence or absence of the (C) component, or when the (C) component is added, the optimal curing conditions differ depending on the type and amount used, but at room temperature. Let it dry for about 3-10 days,

Alternatively, by performing baking in a temperature range of about 80 to about 250 ° C. for about 30 seconds to about 2 hours, an extremely practical cured product can be obtained.

The aqueous resin according to the present invention comprises the aqueous resin as an essential component, since the aqueous resin according to the present invention gives a cured product having extremely excellent durability and the like. The conductive resin composition can be mainly used and applied for various paints, such as paints for automotive top coatings, paints for building exteriors, or paints for building materials. It can be used and applied to a wide range of applications, such as for textiles, paper impregnating agents and surface treatment agents.

More specifically, a car, a motorcycle, a train, a bicycle, a ship or an airplane, or other transportation-related equipment and their various parts; a television, a radio, a refrigerator, a washing machine, Coolers, cooler outdoor units or computers, or other home appliance related products and their components; various tiles, metal roofing materials,
Various building materials, such as window frames, doors, or interior and exterior wall materials; various outdoor structures, such as roads, road signs, guardrails, bridges, tanks, chimneys or buildings; The aqueous resin or the aqueous curable resin composition according to the invention can be effectively used and applied to such uses. Therefore, the substrate to be coated can be appropriately selected in accordance with the above-mentioned application, and will be already clarified.

[0294]

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

Reference Example 1 [Preparation Example of Polymer (a-1)] First, isopropanol 47 was added to a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel, and a nitrogen inlet tube.
0 parts were charged, and the temperature was raised to 80 ° C. under nitrogen gas flow.

Then, at the same temperature, 100 parts of styrene,
300 parts of methyl methacrylate, 334 parts of n-butyl methacrylate, 186 of n-butyl acrylate
Parts, 30 parts of 3-methacryloyloxypropyltrimethoxysilane and 50 parts of acrylic acid, 450 parts of isopropanol, and tert-butylperoxy-2
A mixture consisting of 50 parts of ethylhexanoate,
It was added dropwise over 4 hours.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 16 hours to provide a carboxyl group and a trimethoxysilyl group having a nonvolatile content of 53.5% and a number average molecular weight of 12,800. To obtain a solution of the target polymer. Hereinafter, this is abbreviated as (a-1-1).

Reference Examples 2 to 4 (same as above) Polymerization was carried out in the same manner as in Reference Example 1, except that the types of monomers and solvents and the amounts used were changed as shown in Table 1. Polymer (a) having property values as shown in the table
-1) was obtained. They are abbreviated as shown in the table.

[0299]

[Table 1]

<< Footnotes in Table 1 >> Each numerical value indicating the usage ratio of raw materials is a part by weight.

"MMB" ... 3-methyl-3
-Methoxybutanol

"MPTMS": abbreviation for 3-methacryloyloxypropyltrimethoxysilane

"TBPOEH": Abbreviation of tert-butylperoxy-2-ethylhexanoate

[0304]

[Table 2]

<< Footnotes to Table 1 >> Each numerical value indicating the number average molecular weight is 1/100, so that the value multiplied by one hundred (ie, “× 100”) is the true value. is there.

Reference Examples 5 to 7 [Preparation Examples of Polymer (a-2)] Except that the types of the monomers and the polymerization initiator and the amounts used were changed as shown in Table 1, Polymerization was carried out in the same manner as in Example 1 to obtain a polymer (a-2) having the property values shown in the same table. They are abbreviated as shown in the table.

[0307]

[Table 3]

<< Footnotes to Table 1 >>"HEMA" abbreviation for 2-hydroxyethyl methacrylate "DMAEMA" abbreviation for 2-dimethylaminoethyl methacrylate

"2,3-CPMA": abbreviation for 2,3-carbonatepropyl methacrylate

"ABMBN": abbreviation of 2,2'-azobis- (2-methylbutyronitrile)

[0311]

[Table 4]

[0312]

[Table 5]

[0313]

[Table 6]

<< Footnotes in Table 1 >>"R-1" refers to Reference Example 8.
Is a polymer used when preparing the control resin 1 obtained in the above.

"R-2" is a polymer obtained in Reference Example 9 and used when preparing Control Resin 2.

Reference Examples 8 and 9 [Preparation Examples of Polymers (R-1) and (R-2)] The types of the monomers and the polymerization initiators and the amounts used were as shown in Table 1. Polymerization was carried out in the same manner as in Reference Example 1 except for the change, to obtain polymers (R-1) and (R-2) having the property values shown in the same table. They are abbreviated as shown in the table.

Reference Example 10 [Preparation Example of Control Resin 1] First, 1,311 parts of the polymer (R-1) was charged into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel. , To 80 ° C.

Then, at the same temperature, 4
9 parts and 1,001 parts of ion-exchanged water
After the dropwise addition over 0 minutes, a solvent-free isopropanol was removed by distillation under reduced pressure to obtain a control aqueous resin having a nonvolatile content of 42.3%. Hereinafter, this is abbreviated as Control Resin 1.

Reference Example 11 [Preparation Example of Control Resin 2]

First, 1,2 of the polymer (R-2) was placed in a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel.
341 parts were charged and the temperature was raised to 80 ° C.

Then, at the same temperature, 4
9 parts and a mixture of 1,001 parts of ion exchanged water
After the dropwise addition over 0 minutes, the solvent-free isopropanol was removed by vacuum distillation to obtain a control aqueous resin having a nonvolatile content of 43.7%. Hereinafter, this is abbreviated as Control Resin 2.

Example 1

This example is intended to show a preparation example of the aqueous resin (AI).

First, 1,480 parts of the polymer (a-1-1), 354 parts of phenyltrimethoxysilane and 365 parts of isopropanol were placed in a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel. It was charged and heated to 80 ° C.

Next, at the same temperature, 2.9 parts of “AP-3” (trade name of isopropyl acid phosphate, manufactured by Daihachi Chemical Industry Co., Ltd.) and 96 parts of ion-exchanged water were mixed with 5 parts. After stirring at the same temperature for 4 hours, the nuclear magnetic resonance analysis (< ¹ > H-NMR) revealed that the tritium contained in the polymer (a-1-1) was It was confirmed that the hydrolysis of the methoxysilyl group and phenyltrimethoxysilane proceeded 100%.

Thereafter, at the same temperature, 55 parts of triethylamine and 1,485 parts of ion-exchanged water were added dropwise over 30 minutes, and then distilled under reduced pressure to remove alcohols such as methanol and isopropanol. Thus, an intended aqueous resin having a nonvolatile content of 43.1% was obtained. Hereinafter, this is abbreviated as (AI-1).

The aqueous resin (AI-1) was heated at 40 ° C.
After storage for one month, no abnormality such as gelation or precipitation of a precipitate was observed in the aqueous resin after storage, and it was found that the aqueous resin was excellent in storage stability.

Examples 2 to 10

These examples are also intended to show preparation examples of the aqueous resin (A-I).

The type and amount of the silicon compound used for preparing the composite resin (A-1) and the amount of the solvent, catalyst and water, and the type of the polymer (a-1) and the amount thereof were And, except that the amount of the basic compound and the amount of water in the neutralization reaction were changed as shown in Table 2,
In the same manner as in Example 1, a condensation reaction, a neutralization reaction, and aqueous conversion were performed to obtain an aqueous resin (AI) having properties shown in the same table. They are abbreviated as shown in the table.

[0331]

[Table 7]

<< Footnotes in Table 2 >> All numerical values indicating the usage ratios of the raw materials are parts by weight.

"PTMS": an abbreviation for phenyltrimethoxysilane "DMDMES": an abbreviation for dimethyldimethoxysilane

The “storage stability” was determined by storing each of the aqueous resins prepared as described above at 40 ° C. for one month.
It is confirmed whether abnormalities such as gelation and precipitation of a precipitate, which were not observed before storage, are observed, and the results are shown.

[0335]

[Table 8]

<< Footnote to Table 2 >>"MTES": Abbreviation for methyltriethoxysilane

Examples 8 to 10

These examples are for showing preparation examples of the aqueous resin (A-II).

The type and amount of the silicon compound for synthesizing the composite resin (A-2) and the amount of the solvent, catalyst and water, and the type of the polymer (a-2) and the amount thereof Further, except that the amount of the basic compound and the amount of water during the neutralization reaction were changed as shown in Table 2,
A condensation reaction, a neutralization reaction and aqueous conversion were carried out in the same manner as in Example 1 to obtain an aqueous resin (A-II) having properties as shown in the same table. They are abbreviated as shown in the table.

[0340]

[Table 9]

<< Footnotes in Table 2 >> All numerical values indicating the usage ratios of the raw materials are parts by weight.

"PTMS": abbreviation for phenyltrimethoxysilane

The “storage stability” was obtained by storing each aqueous resin prepared as described above at 40 ° C. for one month, and in the aqueous resin after storage before storage. It is confirmed whether there is no abnormality such as gelation or precipitation of a precipitate, and the results are shown.

Examples 11 to 22 First, a mixture of a part of the aqueous resin (AI) or (A-II), a pigment and ethylene glycol monobutyl ether was dispersed using a sand mill, and the weight of the pigment was reduced. Various mill bases having a concentration (PWC) of 60% were prepared, and then the aqueous resin (A-
Various white bases were prepared by adding the entire remaining amount of I) or (A-II) and mixing.

Then, for each white base,
Various white paints having a PWC of 35% were prepared by mixing water and, if necessary, compound (C).

The aqueous resin (AI) or (A-I) used for each white paint prepared as described above was used.
The use ratios of II), pigment, ethylene glycol monobutyl ether and compound (C) are as shown in Table 3.

Each of the white paints thus obtained was coated with a polyester / melamine-based paint in advance and baked on a coated steel sheet. The composition was applied with an applicator so as to have a thickness of about 40 micrometers (μm), and various cured coating films were obtained under the curing conditions shown in the same table.

Each of the coating films obtained by using the aqueous curable resin composition according to the present invention thus obtained was particularly excellent in appearance. Various performances of each coating film were evaluated. The results are shown in the same table.

Comparative Examples 1 and 2 First, a mixture of a part of the control resin 1 or 2 with a pigment and ethylene glycol monobutyl ether was mixed by using a sand mill to obtain PW.
Various white bases are prepared by preparing each millbase with a C of 60%, and then adding and dispersing the entire remaining amount of control resin 1 or 2 to this millbase.

Then, for each white base,
Various white paints having a PWC of 35% were prepared by mixing water and compound (C) as required.

The proportions of the control resin 1 or 2, the pigment, ethylene glycol monobutyl ether and the compound (C) used in each white paint thus obtained are as shown in the table.

Next, each of the thus obtained white paints was used in Example 1 in the series consisting of Examples 11 to 22.
Coating was carried out in the same manner as in Example 4, and thereafter, various cured coating films were obtained under the curing conditions shown in the same table.

The control resin 1 or 2 thus obtained
, And all of the coating films using such a curable composition for control were excellent in appearance. Various performances of each coating film were evaluated. The results are shown in the same table.

[0354]

[Table 10]

<< Footnotes in Table 3 >> Each numerical value indicating the usage ratio of raw materials is a part by weight.

"CR-97" is the same as "Taipec CR-
97 ", which is a trade name of rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd. "EGMBE": an abbreviation for ethylene glycol monobutyl ether

[0357]

[Table 11]

<< Footnote to Table 3 >>"Weatherresistance" means the 60-degree specular reflectance (%) of the coating film after exposure for 2,000 hours using a sunshine weatherometer.
The resulting gloss value was divided by the same gloss value of the coating film when not exposed, and multiplied by 100 (gloss retention:
%). The larger the value,
This indicates that the weather resistance is good.

The “stain resistance” indicates a color difference ΔE between a coating film after two months of exposure outdoors and a coating film without exposure. The closer the value is to zero, the better the stain resistance is.

The "acid resistance" is used as a substitute test for the "acid rain resistance". A test plate in which 0.1 ml of a 10% sulfuric acid aqueous solution is placed on the surface of each cured coating film. Was kept in a hot-air dryer at 60 ° C. for 30 minutes, and then the coating film surface was washed with water and dried, and then the state of the surface was visually evaluated and determined. The criteria for the evaluation judgment at that time are as follows.

◎: no etching…: slight etching was observed △: gloss was reduced ×: etching was remarkable

"Alkali resistance" means that each test plate was immersed in a 5% aqueous sodium hydroxide solution at room temperature for 24 hours, and then the coating film surface was washed with water and dried. After that, the surface state was visually evaluated and determined.

[0363]

[Table 12]

<< Footnotes to Table 3 >> Each numerical value indicating the usage ratio of raw materials is a part by weight.

“S-695” is “Watersol S”
−695 ”, a product name of an aqueous solution of methyl etherified methylol melamine resin manufactured by Dainippon Ink and Chemicals, Inc .; nonvolatile content = 66%.

[0366]

[Table 13]

[0367]

[Table 14]

<< Footnotes to Table 3 >> All numerical values indicating the usage ratios of the raw materials are parts by weight.

"GPTMS" abbreviation for 3-glycidoxypropyltrimethoxysilane "Ethylsilicate 40" is a product of Colcoat Co., Ltd.
It is a trade name of a partially hydrolyzed condensate of tetraethoxysilane.

[0370]

[Table 15]

[0371]

[Table 16]

<< Footnotes to Table 3 >> Each numerical value indicating the usage ratio of raw materials is a part by weight.

[EX-612] is "Denacol EX"
-612 ", which is a trade name of sorbitol polyglycidyl ether manufactured by Nagase Kasei Kogyo Co., Ltd.

“KP-392” is a product of Shin-Etsu Chemical Co., Ltd.
Is a trade name of a partially hydrolyzed condensate of 3-glycidoxypropyltrimethoxysilane.

“EGM-202” is a commercial product of a cyclic polysiloxane having a methoxy group bonded to a silicon atom and a 3-glycidoxypropyl group, both manufactured by Dow Corning Toray Silicone Co., Ltd. First name.

[0376]

[Table 17]

Embodiment 23

This example is to verify the performance of the aqueous resin according to the present invention by evaluating the storage stability of the resin.

First, the aqueous resins (AI) and (A-II) prepared in Examples 1 to 10 were separately stored at 40 ° C. for one month. Various white paints having a PWC of 35% were prepared by preparing various white bases in the same manner as in No. 22 and compounding water and, if necessary, compound (C).

The aqueous resin (AI) or (A-II) used for each white paint thus prepared,
The use ratio of the pigment, ethylene glycol monobutyl ether and compound (C) is as shown in Table 3.

Next, in the same manner as in Examples 11 to 22, each of the white paints was applied on a test coated plate and cured under the curing conditions shown in the same table to obtain various cured paints. A membrane was obtained.

Thus, each coating using the aqueous curable resin composition according to the present invention, comprising at 40 ° C. a white base prepared from an aqueous resin after storage for one month. Each of the membranes, inter alia,
The appearance was excellent, and the properties of each coating film were almost the same as the results in the table. Thus, both the aqueous resins (AI) and (A-II) have excellent storage stability.

As described in detail above, the aqueous resin according to the present invention comprises a polymer having both a hydrolyzable silyl group and an acid group, or both a hydrolyzable silyl group and an acid group, In the presence of a polymer having a functional group other than a group, a polymer obtained by performing a hydrolysis-condensation reaction of at least two silicon compounds having a hydrolyzable group bonded to a silicon atom in one molecule. The union is partially or completely neutralized with a basic compound, and then dispersed or dissolved in water, which is obtained by a novel production method.
It has both excellent curability and excellent storage stability.

The aqueous curable resin composition according to the present invention, which comprises such an aqueous resin as an essential component, has properties such as gloss retention, rain dripping resistance and acid rain resistance. It is an extremely practical material that can form a coating film having excellent durability.

[0385]

The aqueous resin according to the present invention has both excellent curability and excellent storage stability, and contains such an aqueous resin as an essential component. The aqueous curable resin composition according to the present invention,
In particular, gloss retention at the time of exposure, such as resistance to rain dripping stain and acid rain, capable of forming a cured film excellent in so-called durability, particularly as a coating composition,
It is extremely practical.

Claims (32)

[Claims] 1. A silicon compound having at least two hydrolyzable groups bonded to silicon atoms in one molecule in the presence of a polymer (a-1) having both a hydrolyzable silyl group and an acid group. The composite resin (A-1) obtained by performing the hydrolysis-condensation reaction of (b) is partially or completely neutralized with a basic compound, and then dispersed or dissolved in water. Aqueous resin. 2. In the presence of a polymer (a-2) having both a hydrolyzable silyl group and an acid group and a functional group other than both groups, at least two silicon atoms per molecule Resin (A-) obtained by performing a hydrolysis-condensation reaction of a silicon compound (b) having a hydrolyzable group bonded to
An aqueous resin obtained by partially or completely neutralizing 2) with a basic compound and then dispersing or dissolving in water. 3. The above-mentioned functional groups other than the hydrolyzable silyl group and the acid group other than both of these groups are a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, and a primary amide. Group, secondary amide, carbamate group and the following structural formula (S-I) The aqueous resin according to claim 2, which is at least one kind of functional group selected from the group consisting of functional groups represented by 4. The aqueous resin according to claim 1, wherein the hydrolyzable silyl group is an alkoxysilyl group. 5. The silicon compound (b) having at least two hydrolyzable groups bonded to silicon atoms in one molecule is formed from tetraalkoxysilane, organotrialkoxysilane and diorganodialkoxysilane. The aqueous resin according to claim 1, wherein the aqueous resin is at least one type of alkoxysilane selected from the group consisting of: 6. The aqueous resin according to claim 1, wherein the hydrolyzable group bonded to the silicon atom is an alkoxy group. 7. The aqueous resin according to claim 1, wherein the polymer (a-1) is a vinyl polymer. 8. The aqueous resin according to claim 2, wherein the polymer (a-2) is a vinyl polymer. 9. The aqueous resin according to claim 1, wherein the vinyl polymer as the polymer (a-1) is an acrylic polymer. 10. The polymer (a-2) described above,
9. The aqueous resin according to claim 2, wherein the vinyl polymer is an acrylic polymer. 11. A silicon compound having at least two hydrolyzable groups bonded to a silicon atom in one molecule in the presence of a polymer (a-1) having both a hydrolyzable silyl group and an acid group. The composite resin (A-1) obtained by performing the hydrolysis-condensation reaction of (b) is partially or completely neutralized with a basic compound and then dispersed or dissolved in water. Aqueous resin (A-
Production method of I). 12. A polymer (a-2) having both a hydrolyzable silyl group and an acid group and a functional group other than both groups.
A compound (A) obtained by performing a hydrolysis-condensation reaction of at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule in the presence of
-2) A method for producing an aqueous resin (A-II), comprising neutralizing partially or completely with a basic compound and then dispersing or dissolving in water. 13. The above-mentioned functional groups other than the hydrolyzable silyl group and the acid group other than both of these groups include a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group,
Epoxy group, primary amide group, secondary amide, carbamate group and the following structural formula (S-I) 13. The production method according to claim 12, which is at least one kind of functional group selected from the group consisting of functional groups represented by 14. The production method according to claim 11, wherein the hydrolyzable silyl group is an alkoxysilyl group. 15. The above-mentioned silicon compound (b) having at least two hydrolyzable groups bonded to silicon atoms in one molecule is formed from tetraalkoxysilane, organotrialkoxysilane and diorganodialkoxysilane. The production method according to claim 11, wherein the production method is at least one type of alkoxysilane selected from the group consisting of: 16. The method according to claim 11, wherein the hydrolyzable group bonded to the silicon atom is an alkoxy group.
5. The production method according to 5. 17. The method according to claim 11, wherein the polymer (a-1) is a vinyl polymer. 18. The production method according to claim 12, wherein the polymer (a-2) is a vinyl polymer. 19. The polymer (a-1) described above,
The method according to claim 11 or 17, wherein the vinyl polymer is an acrylic polymer. 20. The polymer (a-2) as described above,
19. The method according to claim 12, wherein the vinyl polymer is an acrylic polymer. 21. A silicon compound having at least two hydrolyzable groups bonded to a silicon atom in one molecule in the presence of a polymer (a-1) having both a hydrolyzable silyl group and an acid group. The composite resin (A-1) obtained by performing the hydrolysis-condensation reaction of (b) is partially or completely neutralized with a basic compound, and then dispersed or dissolved in water. An aqueous curable resin composition comprising the aqueous resin (AI) as an essential component. 22. A silicon compound having at least two hydrolyzable groups bonded to a silicon atom in one molecule in the presence of a polymer (a-1) having both a hydrolyzable silyl group and an acid group. The composite resin (A-1) obtained by performing the hydrolysis-condensation reaction of (b) is partially or completely neutralized with a basic compound, and then dispersed or dissolved in water. Aqueous curing, characterized by containing, as essential components, an aqueous resin (AI) and a compound (C) having a functional group that reacts with a functional group contained in the aqueous resin (AI). Resin composition. 23. A polymer (a-2) having both a hydrolyzable silyl group and an acid group and a functional group other than both groups.
A compound (A) obtained by performing a hydrolysis-condensation reaction of at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule in the presence of
-2) is partially neutralized or completely neutralized with a basic compound and then dispersed or dissolved in water to obtain an aqueous resin (A-II) as an essential component. An aqueous curable resin composition. 24. A polymer (a-2) having both a hydrolyzable silyl group and an acid group and a functional group other than both groups.
A compound (A) obtained by performing a hydrolysis-condensation reaction of at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule in the presence of
-2) is partially or completely neutralized with a basic compound and, if necessary, dispersed or dissolved in water to obtain an aqueous resin (A-II); An aqueous curable resin composition comprising, as an essential component, a compound (C) having a functional group that reacts with the functional group contained in -II). 25. The above-mentioned functional groups other than the hydrolyzable silyl group and the acid group other than both of these groups are a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group,
Epoxy group, primary amide group, secondary amide, carbamate group and the following structural formula (SI) 23. The aqueous curable resin composition according to claim 22, which is at least one kind of functional group selected from the group consisting of functional groups represented by 26. The method according to claim 21, wherein the hydrolyzable silyl group is an alkoxysilyl group.
5. The aqueous curable resin composition according to 4. 27. The silicon compound (b) having at least two hydrolyzable groups bonded to silicon atoms in one molecule is formed from tetraalkoxysilane, organotrialkoxysilane and diorganodialkoxysilane. 25. The aqueous curable resin composition according to claim 21, which is at least one alkoxysilane selected from the group consisting of: 28. The method according to claim 21, wherein the hydrolyzable group bonded to the silicon atom is an alkoxy group.
28. The aqueous curable resin composition according to 24 or 27. 29. The aqueous curable resin composition according to claim 21, wherein the polymer (a-1) is a vinyl polymer. 30. The aqueous curable resin composition according to claim 23, wherein the polymer (a-2) is a vinyl polymer. 31. The polymer (a-1)
30. The aqueous curable resin composition according to claim 21, wherein the vinyl polymer is an acrylic polymer. 32. The polymer (a-2) described above,
31. The aqueous curable resin composition according to claim 23, 24 or 30, wherein the vinyl polymer is an acrylic polymer.