JPH1036514A - 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 properties, etc., by subjecting a polymer containing both a hydrolyzable silyl group and an acid group and a specific polysiloxane to condensation reaction, neutralizing the reaction product to give a resin and dispersing the resin into water. SOLUTION: (A) A polymer containing both a hydrolyzable silyl group and an acid group and (B) a polysiloxane containing a hydroxyl group bonded to a silicon atom and/or a hydrolyzable group bonded to a silicone atom are subjected to condensation reaction. The reaction product is partially or completely neutralized with a basic compound to give a resin, which is dispersed or dissolved in water to give an aqueous resin excellent in strain resistance by raindrops, acid rain resistance, solvent resistance, chemical resistance and water resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful aqueous resin, a novel and useful production method of the aqueous resin, and a novel and useful aqueous resin containing the aqueous resin as an essential component. And a curable resin composition. More specifically, the present invention relates to a polymer having both a hydrolyzable silyl group and an acid group, or both a hydrolyzable silyl group and an acid group, and a functional group other than these functional groups. Having a polymer,

A polysiloxane having a hydroxyl group bonded to a silicon atom and / or a polysiloxane having a hydrolyzable group bonded to a silicon atom is subjected to a condensation reaction, and then partially or completely neutralized with a basic compound. The resulting resin is obtained by dispersing or dissolving in water, respectively, an aqueous resin,
A method for producing the aqueous resin and containing the aqueous resin as an essential component, an aqueous curable resin composition,

[0003] In particular, a coating film having excellent properties such as so-called durability, solvent resistance, chemical resistance and water resistance, such as gloss retention, rain dripping stain resistance and acid rain resistance. Can be formed, and
It is to provide an aqueous resin having both excellent curability and excellent storage stability, and also to provide a method for producing the aqueous resin, and additionally contains the aqueous resin. The present invention also relates to an invention which provides an aqueous curable resin composition which provides a cured coating film which is excellent in curability and excellent in various properties including durability as described above.

[0004]

2. Description of the Related Art Heretofore, as a water-based curable resin composition for a coating, a vinyl polymer having both a basic group or an acid group and a so-called functional group such as a hydroxyl group has been used.
An aqueous curable composition comprising an aqueous resin obtained by neutralizing with an acidic compound or a basic compound and then dispersing or dissolving in water and various curing agents such as an epoxy resin, an isocyanate resin or an amino resin. Resin compositions are widely used.

[0005] However, the cured coating film obtained from the aqueous curable resin composition based on the aqueous resin as heretofore used has, inter alia, a gloss retention property upon exposure and a resistance to dripping stain. In addition, durability such as acid rain resistance is insufficient, and therefore, in applications where high durability and the like are required, almost completely,
There is a problem that it cannot be used and applied.

[0006]

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

Accordingly, an object of the present invention is to provide a cured product having excellent durability, such as gloss retention, rain dripping stain resistance, and acid rain resistance. Excellent in storage stability and the like, a new and useful aqueous resin, and also to provide a method for producing such an aqueous resin, and in addition, containing such a new and useful aqueous resin, as described above. It is another object of the present invention to provide a highly practical aqueous curable resin composition which is excellent in various properties such as solvent resistance, chemical resistance and water resistance, in addition to such durability.

[0008]

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,

A polymer having both a hydrolyzable silyl group and an acid group, or a polymer having both a hydrolyzable silyl group and an acid group, and a polymer having a functional group other than these functional groups; After a condensation reaction with a polysiloxane having a hydroxyl group bonded to an atom and / or a hydrolyzable group bonded to a silicon atom, a resin obtained by partially or completely neutralizing with a basic compound, Aqueous resin obtained by dispersing or dissolving in water,
It is found that it has excellent curability and storage stability, and establishes a method for producing the aqueous resin,

It has also been found that an aqueous curable resin composition containing the aqueous resin as an essential component has excellent durability, especially gloss retention, acid rain resistance and rain dripping stain resistance. The inventors of the present invention have completed the present invention by convinced that the problem to be solved by the invention as described above can be solved brilliantly.

That is, the present invention basically relates to a polymer (a-1) having both a hydrolyzable silyl group and an acid group.
And a polysiloxane having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom (a-
2) is subjected to a condensation reaction, and then partially or completely neutralized with a basic compound to obtain a resin (A-1).
Is dispersed or dissolved in water to obtain an aqueous resin (AI), a method for producing the aqueous resin (AI), and a form containing the aqueous resin (AI) as an essential component. And further has a functional group that reacts with the aqueous resin (AI) and a functional group contained in the aqueous resin (AI). It is intended to provide an aqueous curable resin composition containing the compound (B) and

In addition, a polymer (a-3) having both a hydrolyzable silyl group and an acid group and a functional group other than both a hydrolyzable silyl group and an acid group, and a silicon atom A polysiloxane (a-2) having a bonded hydroxyl group and / or a hydrolyzable group bonded to a silicon atom is subjected to a condensation reaction and then partially or completely neutralized with a basic compound. An aqueous resin (A-II) obtained by dispersing or dissolving the resin (A-2) in water is provided, and the method for producing the aqueous resin (A-II) and the aqueous resin (A-II) are essential. It is intended to provide an aqueous curable resin composition in a form containing the aqueous resin (A-II) and the aqueous resin (A-
Another object of the present invention is to provide an aqueous curable resin composition containing a compound (B) having a functional group that reacts with the functional group contained in II).

[0013]

DETAILED DESCRIPTION OF THE INVENTION The present invention provides, in part,
Polymer having both a hydrolyzable silyl group and an acid group (a-
After condensation reaction of 1) with a polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, partial neutralization or completeness with a basic compound is performed. (A)
-1) is obtained by dispersing or dissolving in water, and is intended to be a very practical aqueous resin (AI) itself,

The second is a polymer (a-1) having both a hydrolyzable silyl group and an acid group, and a polysiloxane having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. Aqueous resin comprising dispersing or dissolving the resin (A-1) obtained by subjecting (a-2) to a condensation reaction and then partially or completely neutralized with a basic compound, in water. It is intended to claim a new and useful production method of (AI),

The third is a polymer (a-1) having both a hydrolyzable silyl group and an acid group, and a polysiloxane having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. Aqueous resin obtained by dispersing or dissolving the resin (A-1) obtained by subjecting (a-2) to a condensation reaction followed by partial or complete neutralization with a basic compound in water, It is intended to claim an aqueous curable resin composition containing (AI) as an essential component,

Fourth, an aqueous curable composition comprising the aqueous resin (AI) and a compound (B) having a functional group which reacts with a functional group contained in the aqueous resin (AI). It is also intended to claim a resin composition,

Fifth, a polymer (a-3) having both a hydrolyzable silyl group and an acid group and a functional group other than both a hydrolyzable silyl group and an acid group, and silicon A polysiloxane (a-2) having a hydroxyl group bonded to an atom and / or a hydrolyzable group bonded to a silicon atom is subjected to a condensation reaction, and then partially or completely neutralized with a basic compound. It is also intended to claim an extremely practical aqueous resin (A-II) that can be obtained by dispersing or dissolving the obtained resin (A-2) in water,

Sixth, a polymer (a-3) having both a hydrolyzable silyl group and an acid group and a functional group other than both a hydrolyzable silyl group and an acid group, and silicon A polysiloxane (a-2) having a hydroxyl group bonded to an atom and / or a hydrolyzable group bonded to a silicon atom is subjected to a condensation reaction, and then partially or completely neutralized with a basic compound. The resulting resin (A-2) is characterized by dispersing or dissolving the obtained resin (A-2) in water.
II) to seek for a new and useful production method,

Seventh, a polymer (a-3) having both a hydrolyzable silyl group and an acid group and a functional group other than both a hydrolyzable silyl group and an acid group; A polysiloxane (a-2) having a hydroxyl group bonded to an atom and / or a hydrolyzable group bonded to a silicon atom is subjected to a condensation reaction, and then partially or completely neutralized with a basic compound. It is an object of the present invention to provide an aqueous curable resin composition containing, as an essential component, an aqueous resin (A-II) obtained by dispersing or dissolving the obtained resin (A-2) in water,

Eighth, the above-mentioned aqueous resin (A-II)
And a compound (B) having a functional group which reacts with a functional group contained in the aqueous resin (A-II).

In the present invention, the functional group other than the hydrolyzable silyl group and the acid group is a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, and a primary group. Amide group, secondary amide group, carbamate group and the following structural formula (S-I)

[0022]

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

Further, the present invention relates to a method for producing a polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, wherein at least two polysiloxanes per molecule are as follows: It is also intended to claim a specific aqueous resin which is a hydrolyzed condensate or a partially hydrolyzed condensate of a silicon compound containing a silicon compound having a hydrolyzable group bonded to a silicon atom as an essential component. And

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

Further, the above-mentioned silicon compound having at least two hydrolyzable groups bonded to silicon atoms in one molecule is selected from tetraalkoxysilanes, organotrialkoxysilanes, diorganodialkoxysilanes, and the like. It is also intended to claim a specific aqueous resin that is at least one alkoxysilane selected from the group consisting of partial hydrolysis condensates and partial cohydrolysis condensates thereof,

Further, the present invention is directed to a specific aqueous resin in which the hydrolyzable group bonded to the silicon atom is an alkoxy group.

Further, the present invention is also directed to a specific aqueous resin in which the polymer (a-1) or (a-3) is a vinyl polymer, respectively.

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

Further, the present invention provides,
The functional groups other than the hydrolyzable silyl group and the acid group are hydroxyl group, blocked hydroxyl group, tertiary amino group, cyclocarbonate group, epoxy group, primary amide group, secondary amide group, carbamate group and the like. Structural formula (S
-I)

[0031]

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

Further, the present invention relates to a method for producing a polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. It is also intended to claim a specific aqueous resin, which is a hydrolyzed condensate or a partially hydrolyzed condensate of a silicon compound containing a silicon compound having a hydrolyzable group bonded to a silicon atom as an essential component. There is

Further, the present invention is intended to claim a specific method for producing such an aqueous resin, wherein the hydrolyzable silyl group is an alkoxysilyl group,

Further, the above-mentioned silicon compound having at least two hydrolyzable groups bonded to silicon atoms in one molecule may be selected from tetraalkoxysilanes, organotrialkoxysilanes, diorganodialkoxysilanes, and the like. And at least one alkoxysilane selected from the group consisting of partially hydrolyzed condensates and partially hydrolyzed condensates thereof. And

[0036] Alternatively, it is intended to claim a specific method for producing such an aqueous resin, wherein the hydrolyzable group bonded to the silicon atom is an alkoxy group.

Alternatively, it is intended to claim a specific process for producing such an aqueous resin, wherein the polymer (a-1) or (a-3) is a vinyl polymer, respectively. And

It is also an object of the present invention to claim a specific method for producing such an aqueous resin, wherein the vinyl polymer is an acrylic polymer.

Furthermore, the functional groups other than the above-mentioned hydrolyzable silyl group and acid group are hydroxyl group, blocked hydroxyl group, tertiary amino group, cyclocarbonate group, epoxy group, primary amide group. A secondary amide group, a carbamate group and the following structural formula (S-I)

[0040]

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

In addition, the aforementioned polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom contains at least two silicon atoms per molecule. It is also intended to claim a specific aqueous curable resin composition, which is a hydrolyzed condensate or a partially hydrolyzed condensate of a silicon compound having a silicon compound having a hydrolyzable group bonded to the essential component. There is

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

Further, the compound (B) is a compound containing a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, and a compound having an isocyanate group and a silicon atom bonded in one molecule. Compound having both hydrolyzability, compound having both epoxy group and hydrolyzable group bonded to silicon atom in one molecule, polyisocyanate compound, block polyisocyanate compound, polyepoxy compound, polycyclocarbonate compound, amino resin It is also intended to claim a specific aqueous curable resin composition, which is at least one compound selected from the group consisting of a primary or secondary amide group-containing compound, a polycarboxy compound and a polyhydroxy compound. There is

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, it is intended to claim a specific aqueous curable resin composition in which the polymer (a-1) or (a-3) is a vinyl polymer, respectively. And

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.
I will explain.

Here, first, a polymer having both a hydrolyzable silyl group and an acid group, which is used in preparing the above-mentioned resin (A-1) which is a precursor of the aqueous resin according to the present invention. (A-1) refers to a polymer having both a hydrolyzable silyl group and an acid group, and the hydrolyzable silyl group is represented by the following 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, 1 or 2.)

The hydrolyzable silyl group itself is directly bonded to a carbon atom by a covalent bond, as shown in the above formula. It is assumed that the polymer (a-1) is bonded to the polymer (a-1) by bonding to a carbon atom through a siloxane bond.

The term "acid group" as used herein means various free acid groups represented by a carboxyl group, a phosphoric acid group, an acid phosphate group, a phosphite group, a sulfonic acid group or a sulfinic acid group. In addition, an acid anhydride group represented by a carboxylic acid anhydride group, a phosphoric acid anhydride group, a sulfonic acid anhydride group, a carboxylic acid-sulfonic acid mixed acid anhydride group, and the like, further, for example, a silyl ester group, tert-butyl As an ester group or a 1-alkoxyethyl ester group or the like, which is easily converted into a free acid group, a so-called blocked carboxyl group, phosphate group, acid phosphate group, It refers to a blocked acid group such as a phosphite group or a sulfonic acid group.

Among the various acid groups mentioned above, only the particularly desirable ones are exemplified by a carboxyl group, a blocked carboxyl group or a carboxylic anhydride group.

If only typical examples of the polymer (a-1) are given as examples, an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer or an aromatic vinyl polymer may be used. And various kinds of vinyl polymers; or polyester resins, alkyd resins or polyurethane polymers.

Of these, particularly preferred are vinyl polymers and polyurethane polymers, and particularly preferred among vinyl polymers are acrylic polymers.

To prepare the vinyl polymer of the polymer (a-1), for example, (i) a vinyl monomer having a hydrolyzable silyl group, a carboxyl group, Various acid group-containing vinyl monomers such as a blocked monomer having a so-called acid group such as a carboxyl group or a carboxylic acid anhydride group may be co-polymerized with the above-mentioned two types ( Two types) monomers,
It is a method of copolymerizing these monomers and other monomers that can be copolymerized,

(Ii) Various isocyanate group-containing silane compounds, such as 3-isocyanatopropyltriethoxysilane, are reacted with a previously prepared vinyl polymer having both hydroxyl groups and acid groups. That method,

(Iii) A vinyl resin having various acid groups such as a carboxyl group, a blocked carboxyl group or a carboxylic acid anhydride group by using a chain transfer agent having both a mercapto group and a hydrolyzable silyl group. Polymerize so-called acid group-containing vinyl monomers such as monomers, or copolymerize these monomers with other monomers that can be copolymerized with the monomers. It is a method of squeezing,

(Iv) A vinyl monomer containing a hydrolyzable silyl group and a carboxyl group, a blocked carboxyl group or a carboxylic acid are synthesized using a chain transfer agent having both a mercapto group and a hydrolyzable silyl group. Such as vinyl monomers having various acid groups, such as anhydride groups,
It is referred to as copolymerizing a so-called acid group-containing vinyl monomer or copolymerizing the above two types of monomers with other monomers that can be copolymerized with these monomers. Method or

(V) Using a polymerization initiator having a hydrolyzable silyl group, a vinyl monomer having various acid groups such as a carboxyl group, a blocked carboxyl group or a carboxylic acid anhydride group can be used. Such a so-called acid group-containing vinyl monomer is polymerized, or the above two types of monomers are copolymerized with other monomers that can be copolymerized with these monomers. That method,

(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; So-called acid group-containing vinyl monomers, such as vinyl monomers having various acid groups, can be copolymerized or copolymerized with these two types of monomers and these monomers. Possible method of copolymerizing with other monomers

Although various known and commonly used methods such as those described above can be used and applied, among them, the method (i) is particularly simple and can be recommended because it is the simplest. .

The hydrolyzable silyl group-containing vinyl monomer used in preparing the polymer (a-1) includes:
It refers to a monomer having a hydrolyzable silyl group represented by the structural formula (S-I) as described above, and only particularly typical examples of such a monomer are exemplified. If so, 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.

Among the acid group-containing vinyl monomers used for preparing the polymer (a-1), only those particularly typical as vinyl monomers containing 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 monoesters (half esters) of unsaturated dicarboxylic acids such as butyl and saturated monohydric 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. And further include various monomers obtained by performing an addition reaction between the above-mentioned various carboxyl group-containing monomers and lactones.

Among the acid group-containing monomers used in preparing the polymer (a-1), only those particularly representative as monomers having a blocked carboxyl group are exemplified. Such as trimethylsilyl (meth) acrylate, dimethyl-tert-butylsilyl (meth) acrylate or trimethylsilyl crotonate;
Various silyl ester group-containing vinyl monomers as disclosed in JP-A-62-254876;

1-ethoxyethyl (meth) acrylate, 1-n-butoxyethyl (meth) acrylate, 2
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. Containing monomers; or t
tert-butyl (meth) acrylate or tert
And various tert-butyl ester group-containing monomers such as -butyl crotonate.

Of the acid group-containing monomers used in preparing the polymer (a-1), only those particularly typical as carboxylic anhydride group-containing monomers are exemplified.
Anhydrides of various unsaturated polycarboxylic acids, such as maleic anhydride, citraconic anhydride or itaconic anhydride;
Anhydrides of various unsaturated monocarboxylic acids, such as acrylic acid or methacrylic anhydride; or various unsaturated carboxylic acids, such as acrylic acid or methacrylic acid, and acetic acid, propionic acid or benzoic acid. And mixed acid anhydrides with various saturated carboxylic acids.

Further, a hydrolyzable silyl group-containing monomer and an acid group which can be used in preparing the vinyl polymer (a-1) according to the method (i) described above are used. If only other typical vinyl-based monomers that can be copolymerized with the vinyl-based monomer having only typical examples are exemplified,

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
Various 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 or vinyltoluene; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate or benzoate Various carboxylic acid vinyl esters such as vinyl acid;

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

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;

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

Tertiary amide group-containing monomers such as N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine and N-vinylpyrrolidone;

Various polyether-containing monomers such as esters of (meth) acrylic acid with polyethers having one hydroxyl group in one molecule, such as methoxypolyethylene glycol or methoxypolypropylene glycol. And so on.

In order to prepare the vinyl polymer (a-1) using the various monomers listed above,
Various known polymerization methods such as a solution polymerization method, a non-aqueous dispersion polymerization method or a bulk polymerization method can be used and applied. Among them, particularly, the solution radical polymerization in an organic solvent is particularly preferable. It is the easiest to use a law.

As the polymerization initiator which can be used in applying the solution radical polymerization method, various known compounds can be used. Of course, only typical ones are exemplified. If you stop,

Various types such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) or 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 that can be used when applying the solution radical polymerization method, any of known and commonly used organic solvents can be used.
It goes without saying that it may be used alone or in combination of two or more types.

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

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 ;

Alternatively, 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 is too large, gelation often occurs during polymerization, so care must be taken.

To prevent such gelling, 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 above-mentioned solvents.

The desired hydrolysis is carried out by using a monomer, a polymerization initiator and an organic solvent as described above and utilizing a known and common solution radical polymerization method. A vinyl polymer (a-1) having both a reactive silyl group and an acid group can be prepared.

Both a hydrolyzable silyl group and an acid group, which are used when preparing the above-mentioned resin (A-2), which is a precursor of the aqueous resin (A-II) according to the present invention, The polymer (a-3) having both functional groups other than the hydrolyzable silyl group and the acid group is a hydrolyzable silyl group as described above and an acid group as described above. in addition,
The term refers to a polymer containing various known and commonly used functional groups other than the hydrolyzable silyl group and the acid group.

Examples of the acid group to be introduced into the polymer (a-3) include various groups already exemplified as those which can be introduced into the polymer (a-1). However, only particularly desirable ones are exemplified by a carboxyl group, a blocked carboxyl group or a carboxylic anhydride group.

Further, only typical examples of functional groups to be introduced into the polymer (a-3) other than both the hydrolyzable silyl group and the acid group include hydroxyl groups. , Blocked hydroxyl groups, primary amino groups,
Secondary amino group, tertiary amino group, cyclocarbonate group,
A chain carbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group, an oxazoline group, a carbonyl group, an acetoacetyl group, or the following structural formula (S-
I)

[0098]

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.

[0101]

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) And.)

And a functional group represented by the formula:

Further, these functional groups are used for the polymer (a
In -3), only one kind may be contained, or two or more kinds may be contained.

Among the above-mentioned various functional groups other than both the hydrolyzable silyl group and the acid group, only the particularly desirable ones are exemplified as hydroxyl group, blocked hydroxyl group and tertiary amino group. Groups, cyclocarbonate groups, epoxy groups, primary amide groups, secondary amide groups, carbamate groups, and functional groups represented by the aforementioned structural formula (SI).

The polymer having such various functional groups (a
If only typical ones are exemplified as -3), various vinyl polymers such as acrylic polymer, fluoroolefin polymer, vinyl ester polymer or aromatic vinyl polymer can be used. Coalesce; or a polyester resin, alkyd resin, or polyurethane-based polymer.

Of these, particularly preferred are vinyl polymers and polyurethane polymers, and particularly preferred among these vinyl polymers are acrylic polymers. Can be

The vinyl polymer of the polymer (a-3) can be prepared by using various known and commonly used methods. 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 the structural formula (S-
A monomer having at least one functional group selected from the group consisting of various functional groups other than both a hydrolyzable silyl group and an acid group, such as a functional group represented by I),

For example, a method of copolymerizing various vinyl monomers having a hydrolyzable silyl group and various monomers having an acid group, or the above-mentioned three types of functional groups may be used. It is particularly simple to use a method in which, in addition to the monomer having the above, another vinyl monomer copolymerizable therewith is copolymerized.

By these various methods, particularly, the vinyl-based polymer (a-
Particularly representative of the hydrolyzable silyl group-containing vinyl monomer, acid group-containing monomer and other vinyl monomers copolymerizable therewith, which are used in the preparation of 3). If only the above-mentioned ones are exemplified, various monomers and the like as already exemplified for each of the above-mentioned vinyl-based polymers (a-1) may be used. .

Further, if only typical examples of the hydroxyl group-containing vinyl monomer used in preparing the vinyl polymer (a-3) are given,

Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate;
Various hydroxyl-containing vinyl ethers such as hydroxyethyl vinyl ether or 4-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. Monoesters of various polyoxyalkylene glycols obtained from various unsaturated carboxylic acids;

Alternatively, adducts of various hydroxyl group-containing monomers as described above with various lactones, such as ε-caprolactone, or glycidyl (meth) acrylate, etc. 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. Various hydroxyl group-containing monomers such as adducts with various monoepoxy compounds other than the α-olefin epoxide compounds.

If only particularly typical examples of the vinyl monomer having a blocked hydroxyl group used in the preparation of the vinyl polymer (a-3) are given, it is 2 Japanese Patent Application Laid-Open No. 62-62, such as trimethylsiloxyethyl (meth) acrylate, 2-trimethylsiloxypropyl (meth) acrylate, 4-trimethylsiloxybutyl (meth) acrylate, 2-trimethylsiloxyethyl vinyl ether or 4-trimethylsiloxybutyl vinyl ether. Various silyl ether group-containing vinyl monomers as disclosed in JP-A-283163;

2- (1-ethoxy) ethoxyethyl (meth) acrylate, 2- (1-n-butoxy) ethoxyethyl (meth) acrylate, 2- [2- (meth) acryloyloxy] ethoxytetrahydrofuran or 2,2 Various vinyl monomers containing an acetal group or a ketal group, such as -dimethyl-4- (meth) acryloyloxymethyldioxolane, as disclosed in JP-A-4-41515;

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.

If only particularly typical tertiary amino group-containing vinyl monomers used in the preparation of the vinyl polymer (a-3) are exemplified,

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

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;

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;

Various tertiary amino group-containing vinyl ethers such as 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 3-dimethylaminopropyl vinyl ether and 4-dimethylaminobutyl vinyl ether.

If only typical examples of the cyclocarbonate group-containing vinyl monomer used in preparing the vinyl polymer (a-3) 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) A 5-membered cyclocarbonate group-containing vinyl monomer 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-
6-membered cyclocarbonate group-containing vinyl monomers such as dioxan-2-one or 4- (5-ethyl-2-oxo-1,3-dioxan-5-yl) methoxymethylstyrene.

As the epoxy group-containing vinyl monomer used in the preparation of the vinyl polymer (a-3), glycidyl (meth) may be used. Acrylate, methyl glycidyl (meth)
Various compounds such as acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene oxide, glycidyl vinyl ether, methyl glycidyl vinyl ether and allyl glycidyl ether.

Only typical examples of the vinyl monomer having a primary amide group or a secondary amide group used in preparing the vinyl polymer (a-3) are given below. For 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 Various compounds such as (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, and addition products of 2-isocyanatoethyl (meth) acrylate with acetylacetone or acetoacetic esters.

If only typical examples of the carbamate group-containing vinyl monomer used in preparing the vinyl polymer (a-3) 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; Addition product of 2-isocyanatoethyl (meth) acrylate and ethanol; or 2-isocyanatoethyl (meth)
Various compounds such as an addition reaction product of acrylate and methyl ethyl ketoxime.

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

As the vinyl monomer having two or more of the various functional groups as described above, which is used in preparing the vinyl polymer (a-3), If only representative examples are illustrated, mono- (2
-Hydroxyethyl) itaconate or mono- (2,
And various compounds such as (3-carbonatepropyl) itaconate.

The above-mentioned monomer having a hydrolyzable silyl group, an acid group-containing monomer, and a monomer having both a hydrolyzable silyl group and a functional group other than both of the acid group, ,
If necessary, in order to prepare this vinyl polymer (a-3) using these and other monomers that can be copolymerized,

Solvents, a polymerization initiator, and, if necessary, a polymerization initiator as exemplified above as used in preparing the above-mentioned vinyl polymer (a-1). Solution radical polymerization may be carried out by using various hydrolyzable esters as described above for preventing gelation according to various known and commonly used methods.

By using a monomer, a polymerization initiator and an organic solvent as described above, by applying a known and commonly used solution radical polymerization method, the desired hydrolyzable silyl is obtained. A vinyl polymer (a-3) having both a group and an acid group and a functional group other than both a hydrolyzable silyl group and an acid group can be prepared.

The amount of the hydrolyzable silyl group to be introduced into the vinyl polymer (a-1) or (a-3) prepared as described above is determined based on the solid content of each polymer. From about 0.005 to about 3 per 1,000 grams
Molar range is appropriate, preferably 0.01 to
A range of 2 mol is appropriate, and even more preferably, a range of 0.05 to 1 mol is appropriate.

If the amount is less than about 0.005 mol, the vinyl polymer (a-1) or (a-3) must be
The condensation reaction with the polysiloxane (a-2) having a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom becomes difficult to progress, and as a result, the durability of the obtained cured product is reduced. On the other hand, if the amount exceeds about 3 mol and becomes too large, the solution viscosity at the time of the above-mentioned condensation reaction is inevitably increased, which may cause inconvenience such as gelation. Therefore, either case is not preferable.

In addition, these vinyl polymers (a-1)
Or as the amount of acid groups to be introduced into (a-3),
Per 1,000 grams of solids of each polymer,
A range of about 0.05 to about 13.5 moles is suitable, preferably a range of 0.07 to 7.0 moles, and most preferably 0.1 to 2.0 moles. A mole range is appropriate.

Further, a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, and a secondary amide to be introduced into the vinyl polymer (a-3), respectively. Group, carbamate group or at least one of functional groups other than both hydrolyzable silyl group and acid group represented by the functional group represented by the structural formula (S-I). The amount 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-3). Is appropriate, and even more preferably, within a range of 0.3 to 2 mol.

If the amount exceeds about 5 mol and is too large, the cured product, in particular, the water resistance and the chemical resistance, is undesirably deteriorated.

In addition, these vinyl polymers (a-1)
Alternatively, the number average molecular weight of (a-3) is about 500
To about 100,000, preferably 1,
A range of 000 to 50,000 is appropriate, and a range of 1,500 to 30,000 is more preferable.

When the number average molecular weight of the vinyl polymer (a-1) or (a-3) is less than about 500, the curability and the mechanical strength of the cured product are inevitably deteriorated. On the other hand, when it is too high exceeding about 100,000, the nonvolatile content of the aqueous curable resin composition according to the present invention is extremely low,
Either case is not preferable because the coating workability is deteriorated and the appearance of the cured coating film is deteriorated.

As the vinyl polymer (a-1), a polymer having an unsaturated double bond, such as a polyester resin or an alkyd resin, may be used in the presence of a polymer other than the vinyl polymer. A degradable silyl group-containing monomer and a monomer mixture containing an acid group-containing monomer as an essential component are obtained by subjecting the monomer mixture to radical polymerization. It is also possible to use a polyester resin or alkyd resin in the form of a grafted vinyl polymer segment.

As the vinyl polymer (a-3),
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. Monomer and a monomer mixture containing a monomer having a functional group other than these as an essential component, obtained by subjecting the mixture to radical polymerization, both a hydrolyzable silyl group and an acid group, and It is also possible to use a polyester resin or an alkyd resin in the form in which a vinyl polymer segment having the above functional group is grafted.

To prepare a polyurethane resin of the polymer (a-1), a diamine compound having a hydrolyzable silyl group or a hydrolyzable silyl group is added to various dihydroxy compounds and various diisocyanate compounds. JP-A-51-90391 discloses the use of various known and commonly used raw material components such as various acid group-containing dihydroxy compounds such as dimethylolpropionic acid or dimethylolbutanoic acid. JP-A-55-73729 or JP-A-60-73729
What is necessary is just to utilize and apply the method as described in 255817.

To prepare the polyurethane resin of the polymer (a-3), the polyurethane polymer (a)
-1) In addition to the various known and commonly used raw materials listed above as those used in the preparation of -1), various functional groups as described above other than both the hydrolyzable silyl group and the acid group. Using various compounds having one or two groups having an active hydrogen that reacts with an isocyanate group as a raw material component, using various known and commonly used methods, What should I do?

In addition to the hydrolyzable silyl group and the acid group used in preparing the polyurethane polymer (a-3), the polyurethane polymer (a-3) has various functional groups as described above and isocyanate. If only a typical example of a compound having one or two groups having an active hydrogen that reacts with a group is exemplified, 4-hydroxymethyl-1,3-dioxolane-2- Compounds having both various functional groups and hydroxyl groups, such as ON, glycidol, N-methyldiethanolamine, 2-hydroxyethyl carbamate or 2-hydroxypropyl carbamate.

The amount of the hydrolyzable silyl group to be introduced into the polyurethane polymer (a-1) or (a-3) prepared by the above-mentioned method is as follows. For about 1,000 grams of solid content, 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 polyurethane polymer (a-1) or (a-
The condensation reaction between 3) and the polysiloxane (a-2) having a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom does not easily proceed, and as a result,
In particular, the durability etc. will be reduced,
On the other hand, if the amount is more than about 3 mol, the solution viscosity at the time of the above-mentioned condensation reaction increases, and consequently, inconveniences such as causing gelation may be recognized. Therefore, either case is not preferable.

The amount of acid groups to be introduced into the polyurethane polymer (a-1) or (a-3) is about 0.07 per 1,000 g of the solid content of each polymer. From about 5.0 to about 5.0 moles is appropriate, preferably from 0.07 to 2.0 moles, and most preferably from 0.1 to 0.7 moles. Is appropriate.

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

The number average molecular weight of the polyurethane polymer (a-1) or (a-3) is about 500 to 500.
The range of about 100,000 is preferably 1,0.
The range of from 00 to 50,000 is suitable, and the range of from 1,500 to 30,000 is more preferable.

When the number average molecular weight of the polyurethane polymer (a-1) or (a-3) is less than about 500, the curability and the mechanical strength of the cured product are inevitably deteriorated. On the other hand, when it is too high exceeding about 100,000, the non-volatile content of the aqueous curable resin composition according to the present invention is remarkably reduced or the workability of coating becomes inferior. In addition, the appearance of the cured coating film may be degraded, and either case is not preferable.

Resin (A-1) used in the present invention
Or the other component used in the preparation of (A-2), the above-mentioned hydroxyl group bonded to a silicon atom and / or
Alternatively, polysiloxane (a-2) having a hydrolyzable group bonded to a silicon atom refers to a hydroxyl group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, which is generally called a silanol group. It refers to a polysiloxane having a decomposable group.

Here, the hydrolyzable group bonded to the 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 bonded to the silicon atom, respectively. , An aminooxy group, an iminooxy group or an alkenyloxy group, which are hydrolyzed to form a silanol group.

If only typical examples of such polysiloxane (a-2) are given as examples, a silicon compound having at least two hydrolyzable groups bonded to silicon atoms in one molecule may be used. A hydrolyzed condensate of the silicon compound in a form prepared by hydrolytic condensation or a partially hydrolyzed condensate of the silicon compound in a form prepared by partially hydrolyzing and condensing the silicon compound And so on.

The polysiloxane (a-2) used in preparing the resin (A-1) or (A-2)
A hydrolyzed condensate or partial hydrolysis of a silicon compound having at least two hydrolyzable groups bonded to a silicon atom in one molecule, as prepared by the means or formulation as described below. It can be said that a condensate is used.

As described above, at least two of
Having a hydrolyzable group bonded to a silicon atom, which is used when preparing the polysiloxane (a-2) by hydrolyzing or partially hydrolyzing a silicon compound having a hydrolyzable group bonded to a silicon atom. As the silicon compound,
Although various known and commonly used compounds can be used, if only typical ones among them are exemplified, the following general formula (S-IV)

[0160]

Embedded image R ⁵ _b SiR ⁶ _4-b (S-IV)

(Provided that 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 partially hydrolyzed condensate of one of these silicon compounds obtained by partial hydrolytic condensation; or a partial hydrolysis of a mixture of two or more of these silicon compounds A partial cohydrolysis condensate in the form obtained by condensation;

Or

[0164]

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

Or

[0166]

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 silicon compounds represented by the above general formulas, only typical ones are exemplified, and various types of 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-triethoxysilylpropyl vinyl ether,
Various organotrialkoxysilanes, such as 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, 2- (methyldimethoxysilyl) ethyl vinyl ether, 3- ( Various diorganodialkoxysilanes, such as methyldimethoxysilyl) propyl vinyl ether or 3- (meth) acryloyloxypropylmethyldimethoxysilane;

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

Alternatively, tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane,
Various acetoxysilanes such as dimethyldiacetoxysilane or diphenyldiacetoxysilane.

Among these silicon compounds having a hydrolyzable group, only compounds particularly desirable as compounds used in preparing the polysiloxane (a-2) are exemplified, and tetraalkoxysilane, Examples thereof include organotrialkoxysilanes or diorganodialkoxysilanes, partially hydrolyzed condensates thereof, or partially co-hydrolyzed condensates thereof, and further, hydrolyzed condensates of various chlorosilanes.

When a tetrafunctional silicon compound typified by tetraethoxysilane or the like is used as the silicon compound, the polymer (a-1) or (a-3)
To prevent gelation during the condensation reaction between the compound and the polysiloxane (a-2), and to prevent gelation during the neutralization reaction with the basic compound. It is desirable to use them together.

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

By hydrolyzing or partially hydrolyzing and condensing the above-mentioned various silicon compounds, it is possible to obtain a hydrolyzed condensate or a partially hydrolyzed condensate used as polysiloxane (a-2). At this time, a catalyst may or may not be used, and it is preferable to use a catalyst from the viewpoint of facilitating the progress of these condensation reactions.

Here, when 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.

Examples of such catalysts are only typical ones, such as hydrochloric acid, sulfuric acid or 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;

Naphthenates of various metals, such as iron, cobalt, manganese or zinc; various metal carboxylates, such as octylates; or 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 or dimethylbenzylamine or butylamine or octylamine;

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 typical counter anions,
Quaternary ammonium salts having chloride, bromide, carboxylate, hydroxide or the like, respectively.

The amount of such a catalyst to be used is in the range of about 0.000001 to about 10% by weight based on the silicon compound subjected to hydrolysis or partial hydrolysis.
Preferably, the range is 0.000005 to 5% by weight, and particularly preferably, the range is 0.00001 to 1% by weight.

The amount of water used in the above reaction is about 0.05 mol or more per mol of the hydrolyzable group bonded to the silicon atom of the silicon compound.
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. The use of a hydrolyzable group bonded to the compound in an excessive amount with respect to 1 mol of the hydrolyzable group 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 at a time 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, while the reaction may be carried out under any conditions of normal pressure, increased pressure or reduced pressure.

The by-product of such a reaction,
The alcohol and water, respectively, may be used for the subsequent condensation reaction of the polymer (a-1) with the polysiloxane (a-2) and the stability of the resulting aqueous curable resin composition. If there is any problem, it can be removed from the system by means such as distillation, 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 facilitate stirring, etc.
It is desirable to use an organic solvent.

Here, in the case of using such an organic solvent, any of various known and commonly used organic solvents can be used.
It goes without saying that they may be used alone or in combination of two or more.

As the organic solvent to be used in this case, use can be made of any of the above-mentioned organic solvents which can be used for preparing the vinyl polymer (a-1) or (a-3). Can be done.

When preparing the polysiloxane (a-2) using such an organic solvent, a silicon compound having a hydrolyzable group bonded to at least two silicon atoms in one molecule is used. However, the concentration in the organic solvent is desirably about 5% by weight or more.

A commercially available polysiloxane can be used as the polysiloxane (a-2).
To exemplify only typical representative examples of such polysiloxanes, "TSR-160 or 165", which are commercially available as polysiloxanes having a silanol group or a methoxy group bonded to a silicon atom, respectively, are used. ] [Trade name of Toshiba Silicone Co., Ltd.],
Such as "SH-6018" (trade name of Dow Corning Silicone Toray Co., Ltd.) or "GR-100, 908 or 950" (trade name of Showa Denko KK). Hydrolyzed condensate or partially hydrolyzed condensate having a linear, cyclic, branched (branched) or ladder (type) structure.

Among the above-mentioned polysiloxanes, from the viewpoint of the stability of the aqueous resin (AI) or (A-II), all the silicon atoms constituting the polysiloxane (a-2) are considered. Of which, at least 10 mol%, preferably 2 mol%
It is appropriate to use a compound in which a so-called aryl group such as a phenyl group is bonded to 0 mol% or more, more preferably 40 mol% or more of silicon atoms.

The aqueous resin (AI) or (AI)
From the viewpoint of the curability and durability of I), 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol%, of all the silicon atoms constituting the polysiloxane (a-2). Suitably, at least mol% use those derived from so-called trifunctional silane compounds, such as methyltrialkoxysilanes, methyltrichlorosilane, phenyltrialkoxylanes or phenyltrichlorosilane.

Next, the condensation reaction between the polymer (a-1) or (a-3) and the polysiloxane (a-2) will be described.

In conducting the condensation reaction, the polymer (a-1) or (a-3) and the polysiloxane (a-
The usage ratio of 2) is [Polymer (a-1) or (a-
3)]: 5: 95-9 as a weight ratio of (a-2)
The ratio is preferably about 9: 1, preferably 15: 85-9.
5: 5, more preferably from 20:80
It is good to set to 85:15.

If the weight ratio of the polymer (a-1) or (a-3) is set to be less than about 5%, the amount of the polysiloxane (a-2) is too large, and especially In such a case, a cured coating film poor in quality and the like is obtained. On the other hand, when the weight ratio of the polymer (a-1) or (a-3) exceeds about 99% and becomes too large. In any case, the amount of polysiloxane (a-2) is too small, so that it becomes difficult to obtain a cured coating film having high durability and the like.

The polymer (a-1) or (a-
In performing the condensation reaction between 3) and the polysiloxane (a-2), in order to allow this reaction to proceed smoothly,
Although a catalyst can be added, such a catalyst includes:
Various catalysts, such as those already listed as those used in preparing the polysiloxane (a-2), were used as they were.
Can be used.

In the condensation reaction, the catalyst remaining in the polysiloxane (a-2) prepared by the above-described means or formulation can be obtained without adding a catalyst. It is possible to accelerate the condensation reaction.

The amount of the catalyst used may be a polymer (a
-1) or (a-3) and polysiloxane (a-2)
In the range of about 0.0001 to about 10% by weight, preferably in the range of 0.0005 to 3% by weight, particularly preferably in the range of 0.0005 to 1% by weight, based on the total amount of Is appropriate.

The polymer (a-1) or (a-3)
And a polysiloxane (a-2), the polymer (a-1)
Or hydrolysis of a hydrolyzable silyl group contained in (a-3) and hydrolysis of a hydrolyzable group bonded to a silicon atom contained in the polysiloxane (a-2) as the case may be. It is therefore desirable that such condensation reaction be carried out in the presence of water.

In order to obtain a condensate by carrying out the condensation reaction in the presence of water, the polymer (a-1) or (a-3)
And a mixture of polysiloxane (a-2) and water, and a hydrolyzable silyl group contained in polymer (a-1) or (a-3) is added to polysiloxane (a-2). inside,
In some cases, both the hydrolyzable group bonded to the silicon atom contained therein may be hydrolyzed, followed by performing a condensation reaction,

Further, the water remaining in the polysiloxane (a-2) prepared by the above-mentioned means or formulation is used without adding water. Hydrolyzing both a hydrolyzable silyl group contained in the polymer (a-1) and a hydrolyzable group bonded to a silicon atom contained in the polysiloxane (a-2) in some cases. Thereafter, it can be achieved by subsequently performing a condensation reaction.

The amount of water added during the condensation reaction can be appropriately selected, and the method of adding the catalyst and water may be batch addition, divided addition, or addition of catalyst. And water in a mixed form,
Or, of course, they may be added separately.

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

Further, alcohol and water, which are by-products of the condensation reaction, can be removed from the system by means of distillation or the like.
Even if it is left in the system as it is, there is no problem at all.

In the condensation reaction, an organic solvent may or may not be used. However, in order to easily perform stirring or the like, a vinyl polymer ( It is desirable to use various organic solvents, such as those already listed as usable in preparing a-1).

Here, when an organic solvent is used, it is a matter of course that they may be used alone or in combination of two or more.

In the case where the condensation reaction is carried out in the presence of an organic solvent, the polymer (a-1) or (a-3) and the polysiloxane (a-2) are each dissolved in the organic solvent. Is preferably about 5% by weight or more as a total amount of both components.

The polymer (a-
The acid group contained in the condensation reaction product of 1) or (a-3) with polysiloxane (a-2) is partially or completely neutralized with a basic compound. Thereby, the resins (A-1) and (A-2) are prepared, respectively.

As the basic compounds used in the neutralization reaction, particularly only typical ones are exemplified. Methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-butylamine , Tri-n-butylamine, 2-
Amino-2-methylpropanol, 2-aminoethanol
Various organic amine compounds represented by dimethyl or 2-dimethylaminoethanol;

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

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

The amount of the basic compound added is at least as large as the amount of the condensation reaction product of the polymer (a-1) or (a-3) with the polysiloxane (a-2). On the other hand, it is an amount capable of imparting water dispersibility, and is contained in a condensation reaction product of the polymer (a-1) or (a-3) with the polysiloxane (a-2). The ratio of the number of equivalents of the basic compound to the number of equivalents of the acid group contained,

That is, the number of equivalents of the basic compound / [the number of equivalents of acid groups in the condensation reaction product of the polymer (a-1) or (a-3) with the polysiloxane (a-2)] Although an amount such that the equivalent ratio becomes about 0.1 or more is appropriate, an 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. , Most preferably in the range of 0.3-2.

The neutralization reaction may be carried out in the presence of water or in the absence of water. In the absence of water, the above-mentioned polymer (a- The solution at the time of the neutralization reaction depends on the type of the polysiloxane (a-2) or the above-mentioned polysiloxane (a-2) or the composition thereof, and further, the conditions of the neutralization reaction. Attention must be paid to the point where the viscosity increases, and in some cases even gelation may occur.

In the case where such a problem occurs, it is particularly preferable to carry out the neutralization reaction in the coexistence of water, and the amount of water added at this time depends on the amount of the polymer (a
-1) or 100 g or more, preferably 200 g or more, more preferably 500 g or more, based on 1000 g of the solid content of the condensation reaction product of the polysiloxane (a-2) and (a-2). It is appropriate to set the ratio so that it is more than grams.

[0224] The basic compound and water may be added at the time of the neutralization reaction, all at once, in portions, or separately. However, it is most preferable to add it in the form of a mixture of a basic compound and water.

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, and the reaction can be carried out under any of normal pressure and pressurized or reduced pressure.

From the resin (A-1) or (A-2) thus obtained, the aqueous resin (A
To prepare -I) or (A-II), various known and commonly used methods can be applied. For example, water is simply added to the aqueous resin (A-1) or (A-2), or the aqueous resin (A-1)
Or (A-2) is added to water to disperse or dissolve in water, thereby producing aqueous resins (AI) and (A-II), respectively. It can be said.

As described above, when such a neutralization reaction is carried out in the presence of a large amount of water, no additional water is added after the neutralization reaction is completed. In both cases, an aqueous resin can be prepared.

Furthermore, if necessary, the organic solvent contained in the aqueous resin (AI) or (A-II) thus obtained may be partially or partially heated or reduced. By completely removing the aqueous resin (AI) or (A-II), the content of the organic solvent is low or the organic resin does not contain the organic solvent.
Can be prepared.

The aqueous resin thus obtained (A-
The functional group contained in I) includes a silanol group derived from the polymer (a-1) and the polysiloxane (a-2), and a hydrolyzable group bonded to a silicon atom contained in some cases. A free acid group derived from the polymer (a-1) and an acid group neutralized by a basic compound.

Further, the functional group contained in the aqueous resin (A-II) thus obtained is a polymer (a-3)
A silanol group derived from polysiloxane (a-2), a hydrolyzable group bonded to a silicon atom contained in some cases, and a free acid group derived from polymer (a-3). In addition to the acid group neutralized by the basic compound, a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, and a primary amide respectively derived from the polymer (a-3) Group, a secondary amide group, a carbamate group, and / or at least one of the functional groups other than the hydrolyzable silyl group and the acid group among the functional groups represented by the structural formula (SI) described above. Kind of thing.

In the process of preparing the aqueous resin (AI) or (A-II), the polymer (a-1) or (a-2) contained, as an acid group, a blocked acid group or an acid anhydride group. Is used, at least a part of the blocked acid group or acid anhydride group is neutralized by a condensation process with the polysiloxane (a-2) or by a basic compound. In the process, it is converted to a free acid group by hydrolysis, acid-catalyzed decomposition, thermal decomposition or alcoholysis, and functions as a hydrophilic group for aqueous conversion.

If the above-mentioned blocked acid group or acid anhydride group is introduced as the acid group, the amount of free acid group required for aqueous conversion after neutralization with a basic compound is reduced. In the case where is not formed, it is necessary to convert to a free acid group by stricting the reaction conditions in the neutralization step or the condensation step with polysiloxane (a-2).

Further, when preparing the aqueous resin (A-II), a polymer (a-3) having a form in which a blocked hydroxyl group, epoxy group or cyclocarbonate group is introduced is used. Is a step of performing a condensation reaction between the polymer (a-3) and the polysiloxane (a-2),

Further, at the stage of preparing the resin (A-2) by a neutralization reaction using a basic compound performed after the condensation reaction, the resin (A-
At the stage of dispersing or dissolving in 2), at least a part of these functional groups may be converted to free hydroxyl groups by hydrolysis, acid-catalyzed decomposition or alcoholysis.

The type of the blocked hydroxyl group, epoxy group or cyclocarbonate group, or the condensation reaction between the polymer (a-3) and the polysiloxane (a-2), and after the condensation reaction, Depending on the neutralization reaction to be performed and various conditions for dispersing or dissolving in water, such various functional groups may be completely converted to free hydroxyl groups.

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 the aqueous resins (A-II) is used.
(I) and (A-II) are self-curing resins containing the aqueous resin (AI) or (A-II) as an essential component, because they themselves have self-curing properties. It may be a composition,

In the second, the aqueous resin (AI) or (A
-II) and the above-mentioned compound (B) are further blended into these aqueous resins (AI).
Alternatively, an aqueous curable resin composition in which a cross-linking reaction between a functional group contained in (A-II) and a functional group contained in compound (B) is also utilized can be provided.

The compound (B) used in the preparation of the latter aqueous curable resin composition includes the compound (B) contained in the aqueous resin (AI) or (A-II) described above. It refers to various known and commonly used compounds having at least one functional group that reacts with various functional groups as described above.

First, only typical representative examples of such functional groups will be given below.
Blocked isocyanate group, hydroxyl group, blocked 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)

[0240]

Embedded image -C (O) -NH-CH ( OR 3) -COO
R ⁴ (S-III)

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

And the like.

The functional groups contained in the compound (B) are appropriately selected and combined in accordance with the type of the functional group contained in the aqueous resin (AI) or (A-II). I can do it. If only typical examples are exemplified as such combinations, a silanol group-silanol group, a silanol group-alkoxysilyl group,
Examples include an alkoxysilyl group-alkoxysilyl group, a carboxyl group-epoxy group, a carboxyl group-cyclocarbonate group, a tertiary amino group-epoxy group, a hydroxyl group-N-hydroxymethylamino group or a hydroxyl group-isocyanate group.

As the compound (B), 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 that having. Also,
As the compound (B), 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,

Various vinyl polymers such as acrylic resins and fluororesins, and further, polyester resins, alkyd resins, polyurethane resins, epoxy resins and the like. When a class of compounds having two or more of the above-described functional groups is used as the compound (B), a vinyl polymer is used as the compound (B). It is easy to do.

If only a particularly typical example of the compound (B) is exemplified, a compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom; A compound having both an isocyanate group and 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; or an amino group and a silicon atom in one molecule. Including compounds with combined hydrolyzable groups,

Polyisocyanate compounds, blocked polyisocyanate compounds, polyepoxy compounds, polycyclocarbonate compounds, amino resins, compounds containing primary or secondary amide groups, polycarboxy compounds, polyhydroxy compounds, polyaziridine compounds, polyacrylate compounds, Polycarbodiimide compounds, compounds containing blocked hydroxyl groups, polyamine compounds, compounds containing at least two carboxylic anhydride groups or polyoxazoline compounds, and these various compounds can be used alone. Of course, two or more of them may be used in combination.

Among these, particularly desirable compounds are compounds having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom; a hydrolyzable group bonded to an isocyanate group and a silicon atom in one molecule. And a compound having an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule, and a polyisocyanate compound, a blocked polyisocyanate compound, a polyepoxy compound, and a polycyclocarbonate. Examples include compounds, amino resins, compounds containing primary or secondary amide groups, polycarboxy compounds or polyhydroxy compounds.

Among the above-mentioned silicon compounds having a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom, only typical ones are exemplified, and the above-mentioned general formula (S-IV) can be used. A hydrolyzate or a hydrolyzed condensate of these silicon compounds; a partially hydrolyzed condensate obtained by partial hydrolytic condensation of one of these silicon compounds; or 2 of these silicon compounds And partial co-hydrolytic condensates obtained by partial hydrolytic condensation of at least one kind.

Of these, particularly preferred and typical silicon compounds are tetramethoxysilane and tetraethoxysilane, partial hydrolysis condensates thereof, and partial cohydrolysis condensates thereof.

If only the above-mentioned compounds having a isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule are specifically exemplified, only compounds which are particularly typical are described below.

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

Alternatively, various copolymers composed of a vinyl monomer having a hydrolyzable silyl group as described above and a vinyl monomer having an isocyanate group as described later, or both of them. The monomers are copolymerized with (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers, which can be copolymerized with both monomers. Various vinyl copolymers having both an epoxy group and a hydrolyzable silyl group, such as an acrylic copolymer, a vinyl ester copolymer or a fluoroolefin copolymer, obtained by the above method. And so on.

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.

Silicon compounds such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane or 3-glycidoxypropylmethyldiethoxysilane; A partially hydrolyzed condensate obtained by one kind of partial hydrolytic condensation of a silicon compound of the above; or a partial cohydrolyzed condensate obtained by two or more kinds of partial hydrolytic condensation of these silicon compounds;

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

Alternatively, as described above, various copolymers composed of various vinyl monomers having an epoxy group and the above-mentioned vinyl monomers having a hydrolyzable silyl group, or both of these monomers may be used. By copolymerization with (meth) acrylic, vinylester, vinylether, aromatic vinyl or fluoroolefin vinyl monomers, which are copolymerizable with both monomers. And various vinyl copolymers such as acrylic copolymers, vinyl ester copolymers or fluoroolefin copolymers having both an epoxy group and a hydrolyzable silyl group.

As typical examples of the above-mentioned polyisocyanate compounds, only typical ones may be mentioned. 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 various polyisocyanates as described above can be obtained by an addition reaction with polyhydric alcohols.
Prepolymers having isocyanate groups;

Prepolymers having an isocyanurate ring obtained by cyclizing and trimerizing various polyisocyanates as described above;

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

Further, a vinyl monomer having various isocyanate groups such as 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate or (meth) acryloyl isocyanate may be used alone. Coalescence;

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 acrylic copolymer, a vinyl ester copolymer or a fluoroolefin copolymer each containing an isocyanate group can be used.

Among such polyisocyanates, particularly, 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 blocked polyisocyanate compound are given, only various polyisocyanate compounds as described above may be blocked with various blocking agents as described below. Various block polyisocyanate compounds in the form obtained by letting

Examples of the compound include a class of compounds in which isocyanate groups are regenerated by heat, such as compounds containing various uretdione structures in a form obtained by cyclizing and dimerizing isocyanate groups.

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

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

Alternatively, it includes various oximes such as acetone oxime or methyl ethyl ketoxime, and various active methylene compounds such as methyl acetoacetate, ethyl acetoacetate or acetylacetone.

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; aromatic diol derivatives such as ethylene oxide or propylene oxide adducts of aromatic diols as described above. Diglycidyl ethers;

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 Polyglycidyl esters of various aliphatic or aromatic polycarboxylic acids, such as, propanetricarboxylic acid, phthalic acid, terephthalic acid or trimellitic acid;

Various bisepoxides of various hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene or vinylcyclohexene; bis (3,4-epoxycyclohexylmethyl) adipate or 3 , 4
Various cycloaliphatic polyepoxy compounds, such as epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate; or various epoxides 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 the various epoxy group-containing vinyl monomers as described above or these epoxy group-containing vinyl monomers can be copolymerized with the monomers, respectively. ) Acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers and the like, such as obtained by copolymerizing, epoxy group-containing,
Various vinyl copolymers such as an acrylic copolymer, a vinyl ester copolymer or a fluoroolefin copolymer, respectively.

By exemplifying only typical representative examples of the polycyclocarbonate compound, various polyepoxy compounds as described above can be reacted with carbon dioxide in the presence of a catalyst, for example. A polycyclocarbonate compound having a 5-membered cyclocarbonate group obtained by converting this epoxy group into a cyclocarbonate group; or various single polymers of various vinyl monomers having a cyclocarbonate group as described above. Coalescence;

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

If only typical amino resins are exemplified, melamine, benzoguanamine,
A class of alkylol groups, such as those obtained by reacting various amino-containing compounds, such as acetoguanamine, urea or glycouril, with various aldehyde compounds (or aldehyde-supplying substances), such as formaldehyde or acetaldehyde. Various amino resins having;

Alternatively, an amino resin having an alkoxyalkyl group, which is 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 the like. .

Further, if only typical examples of the primary or secondary amide group-containing compound are given as examples, the compounds used for preparing the polymer (a-3) may be used. A homopolymer 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 fluoropolymers having a primary or secondary amide group, such as those obtained by copolymerization with vinyl or fluoroolefin vinyl monomers. Various vinyl copolymers such as olefin copolymers.

Further, only typical examples of polycarboxy compounds are given below, and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, terephthalic acid, Low molecular weight compounds such as isophthalic acid, tartronic acid, malic acid, tartaric acid or citric acid; and

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 to form a (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl, respectively. Various vinyl resins, such as various acrylic copolymers, vinyl ester copolymers or fluoroolefin copolymers, having a carboxyl group, as obtained by copolymerizing with monomers and the like. And copolymers.

As typical polyhydroxy compounds, only typical ones are exemplified by low molecular weight compounds such as ethylene glycol, propylene glycol, butylene glycol and glycerin, and polyethylene glycol or polypropylene glycol. And homopolymers of various vinyl monomers having a hydroxyl group, as already exemplified as those used in preparing the polymer (a-3);

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

The compound (B) was converted to an aqueous resin (AI)
Alternatively, when compound (B) is compounded with (A-II), if compound (B) is water-soluble or has a certain degree of hydrophilicity, compound (B) is Aqueous resin (AI) or (A-II) can be obtained as a composition in the form of being uniformly dissolved or uniformly dispersed.

However, when the hydrophilicity of the compound (B) is low, even when the compound (B) is mixed with the aqueous resin (AI) or (A-2), it is not uniformly dissolved or dispersed. Cannot be obtained. In such a case, the compound (B) may be prepared by various known methods.
By introducing a hydrophilic group or the like into the compound, the hydrophilicity of the compound (B) can be improved, and a uniform composition can be obtained.

When the compound (B) itself is a polymer, the compound (B) may be any of a solvent-free liquid, an organic solvent solution, an aqueous solution or an aqueous dispersion. It can be said that it is used even in the form of. When the compound (B) is a vinyl polymer, it is also preferable to use it as an emulsion polymer.

The aqueous resin (AI) or (A-
In preparing an aqueous curable resin composition comprising II) and the compound (B), the compound (B) is converted into a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. When the compound has the solid content of the aqueous resin (AI) or (A-II), the solid content of the compound (B) is about 0.1 to about 200 wt. Part, preferably within 0.1.
Within the range of 5 to 150 parts by weight, more preferably 1 to 1 part by weight.
This compound (B) is added so as to be within the range of 00 parts by weight.
May be blended.

The compound (B) is a compound having both an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule, a polyisocyanate compound, and a blocked polyisocyanate compound. In such a case, the aqueous resin (AI) or (A-
With respect to one equivalent of a functional group which reacts with an isocyanate group or a blocked isocyanate group contained in II),

The amount of the isocyanate group or the blocked isocyanate group contained in the compound (B) is about 0.1 to
The compound (B) is blended so as to be in a range of about 10 equivalents, preferably in a range of 0.3 to 5 equivalents, and more preferably in a range of 0.5 to 2 equivalents. I just need.

In the case where the compound (B) 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, With respect to one equivalent of a functional group which reacts with an epoxy group or a cyclocarbonate group contained in the aqueous resin (AI) or (A-II),

The total amount of the epoxy groups and / or cyclocarbonate groups contained in the compound (B) 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 (B) may be blended so as to be in a range of 2 equivalents.

Further, when the compound (B) is an amino resin, the compound (B) is added to 100 parts by weight of the solid content of the aqueous resin (AI) or (A-II). In a range of about 5 to about 200 parts by weight, preferably in a range of 10 to 150 parts by weight, and more preferably in a range of 15 to 100 parts by weight. I just need.

When compound (B) is a compound containing a primary or secondary amide group,
1 contained in the aqueous resin (AI) or (A-II)
For one equivalent of a functional group that reacts with a secondary or secondary amide group,

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

Further, when the compound (B) is a polycarboxy compound, the aqueous resin (AI)
Or 1 equivalent of a functional group which reacts with a carboxyl group contained in (A-II),

The amount of the carboxyl group contained in the compound (B) 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 (B) may be blended so as to be in the range of 0.7 to 2 equivalents.

Further, when the compound (B) is a polyhydroxy compound, the aqueous resin (A-
For one equivalent of the functional group that reacts with the hydroxy group contained in I) or (A-II),

The amount of hydroxyl group contained in the compound (B) 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.
The compound (B) may be blended so as to be within the equivalent range.

Each prepared as described above,
The aqueous curable resin composition according to the present invention, which contains the aqueous resin (AI) or (A-II) as an essential component, or the aqueous resin (AI) or (AI)
In the form of compounding compound (B) with compound (B),
The aqueous curable resin composition according to the present invention can be used as a so-called clear composition in a form containing no color pigment, and also contains various commonly used organic or inorganic pigments. It can also be used as a coloring composition.

The aqueous curable resin composition of the present invention may further contain 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 and applied to various uses in a form in which various known and commonly used additives are also blended.

Of these additives, only typical examples of curing catalysts will be given as examples. If they are used in preparing the above-mentioned polysiloxane (a-2), they are already listed. Such various catalysts can be used, and in addition to these already described catalysts,
Tetramethylphosphonium salts, tetraethylphosphonium salts, tetrapropylphosphonium salts, tetrabutylphosphonium salts, trimethyl (2-hydroxypropyl) phosphonium salts, triphenylphosphonium salts, benzylphosphonium salts and the like can be used.

The aqueous curable resin composition according to the present invention thus obtained depends on the type of the aqueous resin (AI) or (A-II) constituting the aqueous resin composition, the presence or absence of the component (B), or ( When the component (B) is added, the optimal curing conditions vary depending on the type and amount of the component, but it is usually dried at room temperature for about 3 to 10 days,

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

The water-based resin according to the present invention contains the water-based resin as an essential component, since the water-based resin according to the present invention gives a cured product having extremely excellent durability and the like. The product can be used and applied mainly for various paints such as paints for automotive top coatings, paints for building exteriors or paints for building materials. Further, it can be used for adhesives, inks, and impregnation of fibers and paper. It can be used and applied to a wide range of uses, such as for agents and surface treatment agents.

[0311] More specifically, automobiles, motorcycles, trains, bicycles, ships or airplanes, or other transportation-related equipment and their various parts; televisions, radios, refrigerators, washing machines, Coolers, cooler outdoor units or computers or other household appliances and their components; various building materials, such as various tiles, metal roofing materials, window frames, doors or interior and exterior wall materials; road,
Road signs, guardrails, bridges, tanks, chimneys or buildings, such as various outdoor structures and the like, respectively, the water-based resin or water-based curable resin composition according to the present invention, respectively, for such applications, It can be used and applied effectively.
Therefore, the substrate to be coated is also in accordance with the above-mentioned application,
It will be clear already.

[0312]

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)] In a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen inlet tube, 470 parts of isopropanol were charged, and nitrogen gas was added. The temperature was raised to 80 ° C. under aeration.

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 of 50 parts of ethylhexanoate with 4 parts of
It was dropped over time.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 16 hours, so that the nonvolatile content was 53.5%.
A solution of the target polymer having a carboxyl group and a trimethoxysilyl group having a number average molecular weight of 12,800 was obtained. 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 thereof were changed as shown in Table 1. As a result, various target polymers (a-1) having properties as shown in the same table were obtained. The polymers are abbreviated as shown in the table.

[0317]

[Table 1]

<< Footnotes in Table 1 >> All numerical values indicating the usage ratios of the raw materials are parts by weight.

"MPTMS" abbreviation for 3-methacryloyloxypropyltrimethoxysilane "TBPOEH" abbreviation for tert-butylperoxy-2-ethylhexanoate

[0320]

[Table 2]

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

Reference Examples 5 to 7 [Preparation Examples of Polymer (a-3)] Except that the types of monomers and polymerization initiators and the amounts used thereof were changed as shown in Table 1, Polymerization was carried out in the same manner as in Reference Example 1 to obtain various target polymers (a-3) having the property values shown in the table. The polymers are abbreviated as shown in the table.

[0323]

[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)

[0327]

[Table 4]

[0328]

[Table 5]

[0329]

[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 the 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 monomers and polymerization initiators and the amounts used thereof are shown in Table 1. Polymerization was performed in the same manner as in Reference Example 1 except that the target polymers (R-1) and (R-2) having the property values shown in the same table were obtained. The polymers are abbreviated as shown in the table.

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

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

REFERENCE EXAMPLE 11 [Preparation Example of Control Resin 2] A reaction vessel equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 1,341 parts of the polymer (R-2). The temperature was raised to ° C.

Next, at the same temperature, 4
9 parts and 1,001 parts of ion-exchanged water
After the dropwise addition over a period of 0 minutes, the solvent-free isopropanol was removed by distillation under reduced pressure 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 shows a preparation example of the aqueous resin (AI).

A reactor equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 354 parts of phenyltrimethoxysilane and 365 parts of isopropanol, and the temperature was raised 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 added to 5 parts After dropwise addition over a period of 4 minutes and stirring at the same temperature for 4 hours, the nuclear magnetic resonance analysis ( ¹ H-NMR) showed that the hydrolysis of phenyltrimethoxysilane was 100%.
% Progress was confirmed.

Thereafter, the polymer (a-1-1) of 1,
480 parts were added, and the mixture was stirred at the same temperature for 4 hours to prepare a condensate of the polysiloxane and the polymer (a-1-1). When this condensate was analyzed by ¹ H-NMR, it was found that the hydrolysis of the trimethoxysilyl group contained in the polymer (a-1-1) had progressed 100%.

Then, at the same temperature, 5
A mixture of 5 parts and 1,485 parts of ion-exchanged water was added to 3 parts
After dropwise addition over 0 minutes, the target aqueous resin having a non-volatile content of 44.9% was obtained by distillation under reduced pressure except for methanol and alcohols such as isopropanol. Hereinafter, this is abbreviated as (AI-1).

Thereafter, the aqueous resin (A-I-1)
Was stored at 40 ° C. for one month. No abnormality such as gelation or precipitation of a precipitate was observed in the aqueous resin after storage, and the aqueous resin (A-I -1)
Was found to be extremely excellent in storage stability.

Embodiments 2 to 10

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

The type and amount of the silicon compound for synthesizing the polysiloxane (a-2) and the amount of the solvent, catalyst and water used, and the type of the polymer (a-1) and its use And the amount of the basic compound used in the neutralization reaction and the amount of water used were changed as shown in Table 2, and the condensation reaction was carried out in the same manner as in Example 1. A neutralization reaction and aqueous conversion were performed to obtain various aqueous resins (AI) having properties as shown in the same table. Those aqueous resins are abbreviated as shown in the table.

[0347]

[Table 7]

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

"PTMS" abbreviation for phenyltrimethoxysilane "DMDMES" abbreviation for dimethyldimethoxysilane

"Storage stability" refers to the storage of each aqueous resin, prepared as described above, at 40.degree.
After storage for one month, the aqueous resin after storage was checked for any so-called abnormalities, such as gelation and precipitation of precipitates, which were not observed before storage. It shows the results.

[0351]

[Table 8]

<< Footnotes to Table 2 >>"MTES": Abbreviation for methyltriethoxysilane "SH-6018": Dow Corning Toray
Product name of silanol group-containing polysiloxane manufactured by Silicone Corporation

[0353]

[Table 9]

Examples 11 to 13

These examples show preparation examples of the aqueous resin (A-II).

The type of the silicon compound for synthesizing the polysiloxane (a-2), the amount thereof and the amount of the solvent, catalyst and water used, and the type of the polymer (a-3) and the The amount used and the amount of water used in the neutralization reaction and the amount of water were changed as shown in Table 2 in the same manner as in Example 1, except that Various aqueous resins (A-II) having properties as shown in the same table were obtained by performing a condensation reaction, a neutralization reaction, and aqueous conversion. Those aqueous resins are abbreviated as shown in the table.

[0357]

[Table 10]

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

"PTMS": Abbreviation for phenyltrimethoxysilane

"Storage stability" refers to the storage of each aqueous resin, prepared as described above, at 40.degree.
After storage for one month, the aqueous resin after storage was checked for any so-called abnormalities, such as gelation and precipitation of precipitates, which were not observed before storage. It shows the results.

Examples 14 to 28 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. By preparing various mill bases having a concentration (PWC) of 60%, then adding the remaining total amount of the aqueous resin (AI) or (A-II) to each mill base and mixing. , Various white bases were prepared.

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

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

[0364] Each of the white paints thus obtained was coated with a polyester / melamine-based paint in advance and baked on a coated steel sheet. Is applied with an applicator so that is about 40 micrometers (μm),
Various cured coating films were obtained under the curing conditions shown in the same table.

It was revealed that each of the coating films obtained using the aqueous curable resin composition according to the present invention was particularly excellent in appearance. Various performances of each coating film were evaluated. The results are summarized in the same table.

Comparative Examples 1 and 2 First, a mixture of a part of the control resin 1 or 2, the pigment, and ethylene glycol monobutyl ether was dispersed using a sand mill, and the pigment weight concentration (PWC) was 60%. Were prepared, and then the entire remaining amount of the control resin 1 or 2 was added to each mill base and mixed to prepare various white bases.

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

The proportions of the control resin 1 or 2, the pigment, ethylene glycol monobutyl ether and the compound (B) used for each white paint prepared as described above are as shown in the table.

Each of the white paints thus obtained was applied in the same manner as in Example 14, and various cured coating films were obtained under the curing conditions shown in the same table.

Each of the coating films obtained using the control aqueous curable resin composition containing the control resin 1 or 2 obtained here was excellent in appearance. Various performances of each coating film were evaluated. The results are summarized in the same table.

[0371]

[Table 11]

<< Footnotes to 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

[0374]

[Table 12]

<< Footnote to Table 3 >>"Weatherresistance" refers to the 60-degree specular reflectance (%) of the coating film after exposure for 2,000 hours using a sunshine weatherometer.
Is divided by the same gloss value of the coating film when not exposed, and multiplied by 100 (gloss retention:
%).

[0376] The higher the value, the better the weather resistance.

[0377] "Stain resistance" indicates the 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 0, the better the stain resistance is.

"Acid resistance" is used as a substitute test for "acid rain resistance". A test plate in which 0.1 ml of a 10% aqueous sulfuric acid 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…: Slightly etched △: Gloss decreased ×: Significant etching

The "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.

[0381]

[Table 13]

<< Footnotes in Table 3 >> All numerical values indicating the usage ratios of the raw materials are parts 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%.

[0384]

[Table 14]

[0385]

[Table 15]

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

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

[0388]

[Table 16]

[0389]

[Table 17]

<< Third Footnote >> Each numerical value indicating the usage ratio of the raw materials is a part by weight.

[0391]

[Table 18]

[0392]

[Table 19]

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

[EX-612] is the same as "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 partially hydrolyzed condensate of 3-glycidoxypropyltrimethoxysilane.

[0396] "EGM-202" is a cyclic polysiloxane made by Dow Corning Toray Silicone Co., Ltd., having both a methoxy group bonded to a silicon atom and a 3-glycidoxypropyl group. Product name.

[0397]

[Table 20]

Embodiment 29

In this example, various water-based resins were evaluated for storage stability, in particular.

The various aqueous resins (AI) and (A-II) obtained in Examples 1 to 13 were heated at 40 ° C.
After storage for one month, Examples 14-28
Various white bases having a PWC of 35% were prepared by preparing various white bases in the same manner as described above, and adding water and, if necessary, the compound (B).

The proportions of the aqueous resins (AI) or (A-II), pigments, ethylene glycol monobutyl ether and compound (B) thus obtained used in each white paint are shown in Table 3. As shown.

Next, in the same manner as in Examples 14 to 28, each white paint was applied on a test coated plate.
Thereafter, the composition was cured under the curing conditions shown in the same table to obtain various cured coating films.

Each of the aqueous curable resin compositions according to the present invention containing a white base prepared from an aqueous resin after being stored at 40 ° C. for one month and obtained at 40 ° C. The coatings are all,
In addition to being excellent in appearance, there were almost no differences in the properties of each coating film from the results shown in the same table.

From these facts, it can be judged that the aqueous resins (AI) and (A-II) are particularly excellent in storage stability.

As described in detail above, the aqueous resin of the present invention is a polymer having both a hydrolyzable silyl group and an acid group; or both a hydrolyzable silyl group and an acid group; After a condensation reaction between a polymer having a functional group other than a hydroxyl group and a polysiloxane having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, the polymer is partially reacted with a basic compound. The resin obtained by neutralizing or completely neutralizing the resin is dispersed or dissolved in water, which is obtained by a novel manufacturing method, and has both excellent curability and excellent storage stability. It is highly practical.

The aqueous curable resin composition according to the present invention, which contains such an aqueous resin as an essential component, has so-called durable properties such as gloss retention, rain dripping stain resistance, and acid rain resistance. It is extremely practical and can form a coating film having excellent properties.

[0407]

The aqueous resin according to the present invention has both excellent curability and excellent storage stability, and the aqueous resin according to the present invention containing such an aqueous resin as an essential component. The aqueous curable resin composition, among others,
It is capable of forming a cured coating film with excellent durability, such as gloss retention during exposure, resistance to rain dripping, and resistance to acid rain, and is particularly highly practical as a coating composition. .

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 13, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

Resin (A-1) used in the present invention
Or the other component used in the preparation of (A-2), the above-mentioned hydroxyl group bonded to a silicon atom and / or
Alternatively, the polysiloxane having a hydrolyzable silyl group bonded to a silicon atom (a-2) is generally referred to as a silanol, a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. It refers to a polysiloxane having a silyl group.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

When the amount is less than 0.5 mol,
Although the rate of hydrolysis becomes extremely slow, which is not desirable in practical use, the amount of water is 5 mol or 10 mol.
There is no problem in using it in a large excess with respect to the mole or the mole of the hydrolyzable group bonded to the silicon atom.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C09D 201/10 PDP C09D 201/10 PDP

Claims (36)

[Claims] 1. A polymer (a-1) having both a hydrolyzable silyl group and an acid group, and a polysiloxane (a-) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. An aqueous resin obtained by dispersing or dissolving the resin (A-1) obtained by subjecting 2) to a condensation reaction followed by partial or complete neutralization with a basic compound, in water. 2. A polymer (a-3) having both a hydrolyzable silyl group and an acid group, a functional group other than the hydrolyzable silyl group and an acid group, and a silicon atom And a polysiloxane (a-2) having a hydrolyzable group bonded to a hydroxyl group and / or a silicon atom, and then partially or completely neutralized with a basic compound. Aqueous resin obtained by dispersing or dissolving the obtained resin (A-2) in water. 3. A functional group other than both the hydrolyzable silyl group and the acid group is a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, A primary amide group, a 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 polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, wherein at least 2
The aqueous resin according to claim 1 or 2, which is a hydrolyzed condensate or a partially hydrolyzed condensate of a silicon compound containing a silicon compound having a hydrolyzable group bonded to a silicon atom as an essential component. 5. The polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, as described above, wherein at least two of the polysiloxanes in one molecule are selected from the group consisting of: A silicon compound having a hydrolyzable group bonded to a silicon atom is selected from the group consisting of tetraalkoxysilanes, organotrialkoxysilanes, diorganodialkoxysilanes, partial hydrolysis condensates thereof, and partial cohydrolysis condensates thereof. Chosen, at least one
The aqueous resin according to any one of claims 1, 2 or 4, which is a kind of alkoxysilane. 6. The polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, wherein the hydrolyzable silyl group is an alkoxysilyl group. Claim 1, wherein
6. The aqueous resin according to any one of 2, 4 and 5. 7. The polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, wherein the hydrolyzable group bonded to a silicon atom is The aqueous resin according to any one of claims 1, 2 or 4 to 6, which is an alkoxy group. 8. The aqueous resin according to claim 1, wherein the polymer (a-1) is a vinyl polymer. 9. The aqueous resin according to claim 2, wherein the polymer (a-3) is a vinyl polymer. 10. The polymer (a-1) described above,
The aqueous resin according to claim 1 or 8, wherein the vinyl polymer is an acrylic polymer. 11. The polymer (a-3) described above,
The aqueous resin according to claim 2 or 9, wherein the vinyl polymer is an acrylic polymer. 12. A polymer (a-1) having both a hydrolyzable silyl group and an acid group, and a polysiloxane (a-) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. Water-soluble resin characterized by dispersing or dissolving the resin (A-1) obtained by subjecting 2) to a condensation reaction and then partially or completely neutralizing with a basic compound, in water. The production method of (AI). 13. A polymer (a-3) having both a hydrolyzable silyl group and an acid group and a functional group other than both a hydrolyzable silyl group and an acid group, and a bond to a silicon atom A resin obtained by subjecting a polysiloxane (a-2) having a hydrolyzable group bonded to a hydroxyl group and / or a silicon atom to a condensation reaction and then partially or completely neutralizing with a basic compound. Aqueous resin (A-I) characterized in that (A-2) is dispersed or dissolved in water.
Production method of I). 14. A functional group other than both the hydrolyzable silyl group and the acid group is a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, A primary amide group, a carbamate group and the following structural formula (S-I): 14. The production method according to claim 13, wherein the production method is at least one kind of a functional group selected from the group consisting of functional groups represented by: 15. The polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom is bonded to at least two silicon atoms in one molecule. The production method according to claim 12 or 13, which is a hydrolyzed condensate or a partially hydrolyzed condensate of a silicon compound containing a silicon compound having a hydrolyzable group as an essential component. 16. The above-mentioned polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, wherein at least two of the polysiloxanes in one molecule are selected from the group consisting of: Silicon compound having a hydrolyzable group bonded to a silicon atom, tetraalkoxysilane,
16. At least one kind of alkoxysilane selected from the group consisting of organotrialkoxysilanes, diorganodialkoxysilanes, partially hydrolyzed condensates thereof, and partially hydrolyzed condensates thereof. The production method according to any one of the above. 17. The polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, wherein the hydrolyzable silyl group is an alkoxysilyl group. Claim 1
The production method according to any one of 2, 13, 15 and 16. 18. The polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, wherein the hydrolyzable group bonded to a silicon atom is The method according to any one of claims 12, 13 or 15 to 17, which is an alkoxy group. 19. The production method according to claim 12, wherein the polymer (a-1) is a vinyl polymer. 20. The method according to claim 13, wherein the polymer (a-3) is a vinyl polymer. 21. The polymer (a-1)
20. The method according to claim 12, wherein the vinyl polymer is an acrylic polymer. 22. The polymer (a-3) as described above,
21. The method according to claim 13, wherein the vinyl polymer is an acrylic polymer. 23. A polymer (a-1) having both a hydrolyzable silyl group and an acid group, and a polysiloxane (a-) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. After the condensation reaction with 2), the resin (A-1) obtained by partially or completely neutralizing with a basic compound is dispersed or dissolved in water to obtain an aqueous resin (A- I) as an essential component,
An aqueous curable resin composition characterized by containing. 24. A polymer (a-1) having both a hydrolyzable silyl group and an acid group, and a polysiloxane (a-) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. After the condensation reaction with 2), the resin (A-1) obtained by partially or completely neutralizing with a basic compound is dispersed or dissolved in water to obtain an aqueous resin (A- I) and the aqueous resin (A-
An aqueous curable resin composition comprising, as an essential component, a compound (B) having a functional group that reacts with the functional group contained in I). 25. A polymer (a-3) having both a hydrolyzable silyl group and an acid group and a functional group other than both a hydrolyzable silyl group and an acid group, and a bond to a silicon atom A resin obtained by subjecting a polysiloxane (a-2) having a hydrolyzable group bonded to a hydroxyl group and / or a silicon atom to a condensation reaction and then partially or completely neutralizing with a basic compound. An aqueous curable resin composition comprising, as an essential component, an aqueous resin (A-II) obtained by dispersing or dissolving (A-2) in water. 26. A polymer (a-3) having both a hydrolyzable silyl group and an acid group and a functional group other than both a hydrolyzable silyl group and an acid group, and a bond to a silicon atom A resin obtained by subjecting a polysiloxane (a-2) having a hydrolyzable group bonded to a hydroxyl group and / or a silicon atom to a condensation reaction and then partially or completely neutralizing with a basic compound. An aqueous resin (A-II) obtained by dispersing or dissolving (A-2) in water, and a compound (B) having a functional group that reacts with a functional group contained in the aqueous resin (A-II). , As an essential component. 27. The functional group other than the hydrolyzable silyl group and the acid group is a hydroxyl group, a blocked hydroxyl group, a tertiary amino group, a cyclocarbonate group, an epoxy group, a primary amide group, A primary amide group, a carbamate group and the following structural formula (S-I): The aqueous curable resin composition according to claim 25 or 26, wherein the aqueous curable resin composition is at least one kind of functional group selected from the group consisting of functional groups represented by 28. The polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom is bonded to at least two silicon atoms in one molecule. 27. A hydrolyzed condensate or partially hydrolyzed condensate of a silicon compound containing a silicon compound having a hydrolyzable group as an essential component.
The aqueous curable resin composition according to any one of the above. 29. The above-mentioned polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, wherein at least two of the polysiloxanes in one molecule are selected from the group consisting of: Silicon compound having a hydrolyzable group bonded to a silicon atom, tetraalkoxysilane,
29. At least one kind of alkoxysilane selected from the group consisting of organotrialkoxysilanes, diorganodialkoxysilanes, partially hydrolyzed condensates thereof, and partially co-hydrolyzed condensates thereof, 29-26 or 28. The aqueous curable resin composition according to any one of the above. 30. The polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, wherein the hydrolyzable silyl group is an alkoxysilyl group. Claim 23.
30. The aqueous curable resin composition according to any one of to 26, 28 or 29. 31. The polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, wherein the hydrolyzable group bonded to a silicon atom is The aqueous curable resin composition according to any one of claims 23 to 26 or 28 to 30, which is an alkoxy group. 32. The aqueous curable resin composition according to claim 24, wherein the polymer (a-1) is a vinyl polymer. 33. The aqueous curable resin composition according to claim 25, wherein the polymer (a-3) is a vinyl polymer. 34. The polymer (a-1) described above,
33. The aqueous curable resin composition according to claim 24, wherein the vinyl polymer is an acrylic polymer. 35. The polymer (a-3) as described above,
34. The aqueous curable resin composition according to claim 25, wherein the vinyl polymer is an acrylic polymer. 36. A compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, wherein the compound (B) is a compound having an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule. A compound having 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, an amino resin,
27. The aqueous curable resin composition according to claim 24, which is at least one compound selected from the group consisting of a primary or secondary amide group-containing compound, a polycarboxy compound and a polyhydroxy compound.