JPH11209475A - Production of water-base fluororesin, and water-base curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a novel useful water-base resin which is excellent in storage stability and can give a cured article excellent in gloss retention and resistance to raindrop stain and to provide a water-base curable resin compsn. which contains a fluororesin obtd. by this process and is practically very useful. SOLUTION: This process for producing a water-base fluororesin comprises condensing a fluoropolymer (a-1) having hydrolyzable silyl groups and acid groups with a polysiloxane (a-2) having Si-bonded hydroxyl groups and/or Si- bonded hydrolyzable groups, partly or completely neutralizing the condensate with a basic compd., and dispersing or dissolving the resultant fluororesin (A-1) in water. The water-base curable resin compsn. is prepd. by using the water-base fluororesin obtd. by this process as the essential ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful process for producing a new and useful aqueous fluororesin, and a new and useful aqueous curable resin containing the aqueous fluororesin as an essential component. Composition.

More specifically, the present invention relates to a fluorine-containing copolymer having both a hydrolyzable silyl group and an acid group, or both a hydrolyzable silyl group and an acid group, and a hydrolyzable silyl group and an acid group. After a condensation reaction of a fluorine copolymer having both functional groups other than both acid groups and a polysiloxane having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, A method for producing an aqueous fluororesin, which comprises dispersing or dissolving a resin obtained by partially or completely neutralizing with a hydrophilic compound in water, and an aqueous curable resin composition containing the aqueous fluororesin as an essential component About things

[0003] In particular, an object of the present invention is to provide an aqueous fluororesin capable of forming a coating film having excellent gloss retention and resistance to rain dripping contamination and having excellent storage stability. A water-curable resin composition which provides a method for producing a resin, and additionally provides a cured coating film containing the aqueous fluororesin and having excellent gloss retention and rain dripping resistance as described above. To the invention that also provides.

[0004]

2. Description of the Related Art As a fluororesin containing a hydrolyzable silyl group, there have been known hydrolyzable silyl group-containing chain transfer agents as described in JP-B-6-99655. Copolymerization of a fluorine-containing resin obtained by copolymerizing a fluorine-containing vinyl monomer with another vinyl monomer, or a vinyl monomer containing a hydrolyzable silyl group under a fluorine-containing vinyl monomer. For example, a fluororesin having a hydrolyzable silyl group introduced into a polymer main chain is known.

[0005] However, the hydrolyzable silyl group-containing fluororesin thus obtained is based on an organic solvent solution, and an aqueous material containing the functional group is not known. Furthermore, the composition described in Japanese Patent Publication No. 6-99655 has a high degree of weather resistance, but at the present time does not have a satisfactory level of resistance to rain dripping contamination.

[0006]

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

[0007] Therefore, the problem to be solved by the present invention is to provide a cured product excellent in gloss retention and rain dripping stain resistance, and also excellent in storage stability and new and useful. Another object of the present invention is to provide a method for producing an aqueous fluororesin, and to provide an extremely practical aqueous curable resin composition containing such a novel and useful aqueous fluororesin. .

[0008]

Means for Solving the Problems Accordingly, the present inventors have:
Focusing on the problems to be solved by the invention as described above, as a result of diligent and intensive studies, a fluorine copolymer having both a hydrolyzable silyl group and an acid group, or a hydrolyzable silyl group and an acid group And a fluorine copolymer having both functional groups other than the hydrolyzable silyl group and the acid group, and a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. Aqueous fluororesin obtained by dispersing or dissolving in water water a fluororesin obtained by subjecting a polysiloxane to have a condensation reaction and then partially or completely neutralized with a basic compound is particularly storage-stable. Water-curable resin composition containing the water-based fluororesin as an essential component is particularly excellent in gloss retention and rain dripping contamination. The inventors have found that the above-mentioned problems to be solved by the invention can be brilliantly solved, and have now completed the present invention. .

That is, the present invention relates to (1) a fluorine-containing copolymer 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 method for producing an aqueous fluororesin, which comprises dispersing or dissolving the fluororesin (A-1) obtained by neutralizing the aqueous fluororesin in water,

(2) The fluorine copolymer (a-
The production method according to the above (1), wherein 1) is a fluorocopolymer containing a fluoroolefin as an essential component,

(3) The fluorine copolymer (a-
The above (1), wherein 1) is a fluorocopolymer containing at least one fluoroolefin as an essential component selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and vinylidene fluoride. Described manufacturing method,

(4) A fluorine-containing copolymer (a-) having both a hydrolyzable silyl group and an acid group and a functional group other than the hydrolyzable silyl group and the acid group.
3) and a polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom (a-2), and then partially neutralized or completely neutralized with a basic compound. A process for producing an aqueous fluororesin, which comprises dispersing or dissolving the fluororesin (A-2) obtained by neutralizing the aqueous fluororesin in water,

(5) The fluorine copolymer (a-
(3) The production method according to the above (4), wherein the fluorocopolymer contains a fluoroolefin as an essential component.

(6) The fluorine copolymer (a-
The above (4), wherein 3) is a fluorine copolymer containing at least one fluoroolefin as an essential component selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and vinylidene fluoride. Described manufacturing method,

(7) A 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, Amide group, carbamate group and the following structural formula (S-I)

[0016]

Embedded image

(4) and (5), which are at least one kind of functional group selected from the group consisting of functional groups represented by
Or the production method according to (6),

(8) 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 polysiloxanes per molecule. (1) to (1) which are hydrolyzed condensates or partially hydrolyzed condensates of silicon compounds containing a silicon compound having a bonded hydrolyzable group as an essential component.
(7) The production method according to any one of (1),

(9) The silicon compound having at least two hydrolyzable groups bonded to a silicon atom in one molecule is tetraalkoxysilane, organotrialkoxysilane, diorganodialkoxysilane, The production method according to the above (8), wherein at least one kind of alkoxysilane is selected from the group consisting of a partial hydrolysis condensate and a partial cohydrolysis condensate thereof,

(10) In the polysiloxane (a-2) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, the hydrolyzable group bonded to a silicon atom is: The production method according to any one of the above (1) to (9), which is an alkoxy group bonded to a silicon atom,

(11) The fluorine copolymer (a-
The production method according to any one of the above (1) to (10), wherein the hydrolyzable silyl group in 1) is an alkoxysilyl group,

(12) An aqueous curable resin composition comprising, as an essential component, an aqueous fluororesin obtained by the production method according to any one of (1) to (11) above,

(13) An aqueous fluororesin obtained by the production method according to any one of the above (1) to (11), and a compound having a functional group which reacts with a functional group contained in the aqueous fluororesin ( And B) as an essential component, and an aqueous curable resin composition,

(14) 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 silicon atom bonded in one molecule. Compound having an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule, polyisocyanate compound, block polyisocyanate compound, polyepoxy compound, polycyclocarbonate compound, amino resin (13) 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.
It is intended to provide the aqueous curable resin composition described above.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The fluorine copolymer (a-1) having both a hydrolyzable silyl group and an acid group, which is used when preparing the fluororesin (A-1), is a hydrolyzable silyl group and an acid group. The term "polymer" refers to a polymer having both groups. The hydrolyzable silyl group is represented by the following general formula (S-II)

[0027]

Embedded image

(Wherein R ¹ is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R ² is a halogen atom, an alkoxy group, an alkoxyalkoxy group, an acyloxy group, a phenoxy group, an aryloxy group ,
Mercapto group, amino group, amide group, aminooxy group,
It represents an iminooxy group or an alkenyloxy group, and a is an integer of 0, 1 or 2. ), Which refers to a group which is hydrolyzed to form a silanol group, and furthermore, the hydrolyzable silyl group itself is directly covalently bonded to a carbon atom. Or by covalently bonding to a carbon atom through a siloxane bond,
It is assumed that the compound is bonded to the fluorine copolymer (a-1).

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.

The fluorine-containing copolymer (a-1) refers to a copolymer containing a fluorine-containing vinyl monomer as an essential constituent unit. If only what is illustrated, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene,
Fluoroolefins represented by various fluorine-containing α-olefins and fluorine-containing β-olefins, such as hexafluoropropylene, 3,3,3-trifluoropropene or perfluoro-2-methyl-2-pentene Kind;

Or various perfluoroalkyl perfluorovinyl ethers such as trifluoromethyltrifluorovinylether, trifluoromethylvinylether, pentafluoroethyltrifluorovinylether, pentafluoroethylvinylether, heptafluoropropyltrifluorovinylether or heptafluoropropylvinylether And (per) fluoroalkyl vinyl ethers;

Or various kinds of resins such as β-trifluoromethyl acrylate, β-trifluoromethyl methacrylate, β-pentafluoroethyl acrylate, β-pentafluoroethyl methacrylate, β-heptafluoropropyl acrylate or β-heptafluoropropyl methacrylate. -Fluoroalkyl acrylates, perfluoroalkyl methacrylates, fluoroalkyl acrylates and fluoroalkyl methacrylates;

Or β-trifluoromethylethyl acrylate, β-trifluoromethylethyl methacrylate, β-pentafluoroethylethyl acrylate, β
-Pentafluoroethylethyl methacrylate, β-heptafluoropropylethyl acrylate or β-
Such as heptafluoropropylethyl methacrylate,
Various perfluoroalkyl alkyl acrylates, perfluoroalkyl methacrylates, fluoroalkyl alkyl acrylates and fluoroalkyl methacrylates are included.

Of these, the fluoroolefins described above, more preferably tetrafluoroethylene, chlorotrifluoroethylene, are preferred as the fluorine-containing vinyl monomer, especially in view of high gloss retention after long-term exposure. , Hexafluoroethylene, vinylidene fluoride are suitable.

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

To prepare such a fluorocopolymer (a-1), for example, (i) a vinyl monomer having a hydrolyzable silyl group, a carboxyl group, a blocked carboxyl group or a carboxylic acid Various acid group-containing vinyl monomers such as vinyl monomers having an acid group such as an anhydride group and a fluorine-containing vinyl monomer may be copolymerized, or these monomers may be used. And the method of copolymerizing other monomers that can be copolymerized with the monomer,

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

(Iii) Using a chain transfer agent having both a mercapto group and a hydrolyzable silyl group, a vinyl compound having various acid groups such as a carboxyl group, a blocked carboxyl group or a carboxylic acid anhydride group. It is possible to copolymerize a so-called acid group-containing vinyl monomer such as a monomer and a fluorine-containing vinyl monomer, or to copolymerize these monomers with the monomer. It is a method of copolymerizing with other monomers,

(Iv) Using a chain transfer agent having both a mercapto group and a hydrolyzable silyl group, a vinyl monomer containing a hydrolyzable silyl group, a carboxyl group, a blocked carboxyl group or a carboxylic acid So-called acid group-containing vinyl monomers such as vinyl monomers having various acid groups, such as anhydride groups, and fluorinated vinyl monomers can be copolymerized, or these monomers can be used. And, it is a method of copolymerizing the monomer and other monomers that can be copolymerized,

(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 and a fluorine-containing vinyl monomer can be copolymerized, or these monomers and other monomers capable of copolymerizing with the monomer can be used. It is a method of copolymerizing with the body,

(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, and copolymerizing fluorine-containing vinyl monomers,
A method of copolymerizing these monomers and other monomers copolymerizable with the monomers.

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

The hydrolyzable silyl group-containing vinyl monomer used in preparing the fluorocopolymer (a-1) is represented by the structural formula (S-II) described above. The term "monomer having a hydrolyzable silyl group" refers to a monomer having a hydrolyzable silyl group. If only typical examples of such a monomer are given, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, -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, 3-
Triethoxysilylpropyl vinyl ether or 3
-(Methyldimethoxysilyl) propyl vinyl ether,

Or 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane or 3- (meth) acryloyloxypropylmethyldimethoxysilane Chlorosilane and the like.

Among these, as described above, when a fluoroolefin is used as a fluorine monomer for the purpose of securing a high gloss retention after long-term exposure, vinyltrimethoxysilane is used. , Vinyltriethoxysilane, vinyltri-n-butoxysilane, vinylmethyldimethoxysilane, vinyltris (2-methoxyethoxy) silane, allyltrimethoxysilane, 2-trimethoxysilylethyl vinyl ether, 2-triethoxysilylethyl vinyl ether, 2- Use of (methyldimethoxysilyl) ethyl vinyl ether, 3-trimethoxysilylpropyl vinyl ether, 3-triethoxysilylpropyl vinyl ether or 3- (methyldimethoxysilyl) propyl vinyl ether is preferred.

Among the acid group-containing vinyl monomers used for preparing the fluorocopolymer (a-1), those which are particularly typical as vinyl monomers containing a free carboxyl group To illustrate only

Various unsaturated carboxylic acids such as (meth) acrylic acid, 2-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
Polymerizable unsaturated dicarboxylic acids such as butyl and saturated 1
Various monoesters (half esters) with polyhydric alcohols; monovinyl esters of various saturated dicarboxylic acids, such as monovinyl adipate or monovinyl succinate;

Various saturated polycarboxylic acid anhydrides such as succinic anhydride, glutaric anhydride, phthalic anhydride or trimellitic anhydride, and various hydroxyl group-containing vinyl monomers as described below. And further include various monomers obtained by performing an addition reaction between the various carboxyl group-containing monomers described above and lactones.

Among them, as described above, when fluoroolefins are used as the fluorine monomer for the purpose of securing a high gloss retention after long-term exposure, crotonic acid and It is preferable to use various monoesters (half esters) of saturated dicarboxylic acids and saturated monohydric alcohols and monovinyl esters of saturated dicarboxylic acids.

Among the acid group-containing monomers used for preparing the fluorocopolymer (a-1), only those particularly representative as monomers having a blocked carboxyl group will be exemplified. If you stop,

Trimethylsilyl (meth) acrylate,
Such as dimethyl-tert-butylsilyl (meth) acrylate or trimethylsilylcrotonate, as disclosed in JP-A-62-254876;
Various silyl ester group-containing vinyl monomers;

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
There are various tert-butyl ester group-containing monomers such as -butyl crotonate.

Of these, as described above, in order to ensure a high gloss retention after long-term exposure, trimethylsilyl crotonate and tertiary silicone are particularly preferred.
t-butyl crotonate and the like.

Among the acid group-containing monomers used in preparing the fluorocopolymer (a-1), only typical carboxylic acid anhydride group-containing monomers are exemplified. For example, 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 a mixed acid anhydride of various unsaturated carboxylic acids such as acrylic acid or methacrylic acid and various saturated carboxylic acids such as acetic acid, propionic acid or benzoic acid.

Among these, as described above, in order to ensure a high gloss retention after long-term exposure, it is particularly preferable to use a polymer such as maleic anhydride, citraconic anhydride or itaconic anhydride. And anhydrides of unsaturated polycarboxylic acids.

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

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 alkyl esters of crotonic acid, such as methyl crotonate or ethyl crotonate; dimethyl maleate, di-n-butyl maleate, 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 chlorinated olefins such as vinyl chloride or vinylidene chloride; ethylene, propylene, isobutylene,
Various α-olefins, such as 1-butene or 1-hexene;

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;

Various (cyclo) alkyl allyl ethers, such as methyl allyl ether, ethyl allyl ether or cyclohexyl allyl ether;

An ester of (meth) acrylic acid with a polyether having one hydroxyl group in one molecule such as methoxypolyethylene glycol or methoxypolypropylene glycol, or a mixture of the polyether with vinyl alcohol or the like There are various polyether-containing monomers such as vinyl ethers such as dehydration condensates, or allyl ethers of the polyethers with allyl groups.

Among these, as described above, when fluoroolefins are used as the fluorine monomer for the purpose of securing a high gloss retention after long-term exposure, vinyl carboxylate is used. , Α-olefins,
(Cyclo) alkyl vinyl ethers, (cyclo) alkyl allyl ethers, polyethers having one hydroxyl group in one molecule, and vinyl ethers with vinyl groups, or allyl ethers with the polyethers and allyl groups It is preferable to select and use monomers generally having good copolymerizability with fluoroolefins.

In order to prepare the fluorocopolymer (a-1) using various monomers as listed above,
Although it can be applied using various polymerization methods, such as a solution polymerization method, a non-aqueous dispersion polymerization method or a bulk polymerization method,
Among them, the simplest method is a solution radical polymerization method in an organic solvent.

As a polymerization initiator that can be used when applying this solution radical polymerization method, various compounds can be used, of course, but only typical ones among them can be used. ,

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 are included.

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.

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

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

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

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

Alternatively, dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether, di-n
-Various ethers such as butyl ether or methylene glycol dimethyl ether; various chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, trichloroethane or tetrachloroethane, and further, N-methylpyrrolidone, Examples include dimethylformamide, dimethylacetamide or ethylene carbonate.

In preparing the fluorocopolymer (a-1), if the amount of the acid group-containing monomer used is large, gelation often occurs during the polymerization, so care must be taken.

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

By applying the above-described monomer radicals, polymerization initiators and organic solvents using a solution radical polymerization method under normal pressure or pressure conditions, respectively. Thus, a desired fluorocopolymer (a-1) having both a hydrolyzable silyl group and an acid group can be prepared.

[0082] Both the hydrolyzable silyl group and the acid group and the functional groups other than the hydrolyzable silyl group and the acid group used in preparing the above-mentioned fluororesin (A-2) are used. The fluorine copolymer (a-3) having both a group and
In addition to the hydrolyzable silyl group as described above and the acid group as described above, the polymer also contains various functional groups other than the hydrolyzable silyl group and the acid group. It refers to coalescence.

Examples of the acid group to be introduced into the fluorocopolymer (a-3) include the various groups already exemplified as those which can be introduced into the fluorocopolymer (a-1). Among them, a carboxyl group, a blocked carboxyl group, a carboxylic acid anhydride group, and the like are exemplified only when it is particularly desirable.

Further, only typical representative functional groups other than the hydrolyzable silyl group and the acid group to be introduced into the fluorocopolymer (a-3) will be described. Hydroxyl group, blocked hydroxyl group, primary amino group, secondary amino group, tertiary amino group, cyclocarbonate group, chain carbonate group, epoxy group, primary amide group, secondary amide group, carbamate group, oxazoline group ,
Carbonyl group, acetoacetyl group or the following structural formula (S-I)

[0085]

Embedded image

And the like.

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

[0088]

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

(Where 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) ) Are included.

These functional groups may be included in the fluorocopolymer (a-3) alone, or two or more of them may be included. it can.

Among the above-mentioned various functional groups other than both the hydrolyzable silyl group and the acid group, only desirable ones are exemplified as hydroxyl group, blocked hydroxyl group and tertiary amino group. , A cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group, or a functional group represented by the aforementioned structural formula (S-I). More preferred are pigment dispersibility And hydroxyl groups, blocked hydroxyl groups, tertiary amino groups, epoxy groups, and the like.

The fluorine copolymer (a-3) having various functional groups refers to a copolymer containing the above-mentioned fluorine-containing vinyl monomer as an essential constituent unit.

The fluorocopolymer (a-3) can be prepared by using various methods. Among them, a hydroxyl group, a blocked hydroxyl group and a tertiary amino group can be used. , A cyclocarbonate group, an epoxy group, a primary amide group, a secondary amide group, a carbamate group or a hydrolyzable silyl group and an acid group such as a functional group represented by the aforementioned structural formula (SI). A monomer having at least one functional group selected from the group consisting of various functional groups other than a group, various vinyl monomers having a hydrolyzable silyl group, and various monomers having an acid group Body and
It is a method such as copolymerizing a fluorine-containing vinyl monomer,

Alternatively, in addition to the above-mentioned four types of monomers, a method of copolymerizing these with other vinyl monomers which can be copolymerized is particularly simple.

By these various methods, the hydrolyzable silyl group-containing vinyl monomer, acid group-containing monomer, and the like used in preparing the fluorocopolymer (a-3). Only other typical examples of the other copolymerizable vinyl monomers are given below. Examples of the vinyl monomers used in preparing the above-mentioned fluorine copolymer (a-1) include: For each, there are various monomers as exemplified above.

In addition, if only typical examples of the hydroxyl group-containing vinyl monomer used in preparing the fluorocopolymer (a-3) are given below,

Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate;
Various hydroxyl group-containing vinyl ethers represented by hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, monovinyl ether of polyoxyalkylene glycol, and the like;

Various hydroxyl-containing allyl ethers represented by 2-hydroxyethyl allyl ether or monoallyl ether of polyoxyalkylene glycol; various kinds of allyl ethers represented by polyethylene glycol; A polyether polyol,
Monoesters of various polyoxyalkylene glycols obtained from various unsaturated carboxylic acids such as represented by (meth) acrylic acid;

Alternatively, adducts of various hydroxyl group-containing monomers as described above with various lactones such as ε-caprolactone; or glycidyl (meth) acrylate, allyl glycidyl ether As represented by, for example, various epoxy group-containing unsaturated monomers, as represented by acetic acid and the like, there are 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, The Netherlands), and the like. There are various hydroxyl group-containing monomers such as adducts with various monoepoxy compounds other than the α-olefin epoxide compounds.

If only typical vinyl monomers having a blocked hydroxyl group to be used in preparing the fluorine copolymer (a-3) are exemplified, only

2-trimethylsiloxyethyl (meth) acrylate, 2-trimethylsiloxypropyl (meth)
Acrylate, 4-trimethylsiloxybutyl (meth)
Various silyl ether group-containing vinyl monomers, such as acrylate, 2-trimethylsiloxyethyl vinyl ether or 4-trimethylsiloxybutyl vinyl ether, as disclosed in JP-A-62-283163;

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] ethyloxazoline, 2,2-dimethyl-3-
[2- (meth) acryloyloxy] ethyloxazoline or 2-isobutyl-2-methyl-3- [2-
There are various oxazoline group-containing vinyl monomers such as (meth) acryloyloxy] ethyloxazoline.

If only particularly typical tertiary amino group-containing vinyl monomers used in preparing this fluorine copolymer (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 vinylpyridine, N-vinylcarbazole or N-vinylquinoline;

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;

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

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 are included.

If only typical examples of the cyclocarbonate group-containing vinyl monomer used for preparing the fluorine copolymer (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-
There are 6-membered cyclocarbonate group-containing vinyl monomers such as dioxan-2-one or 4- (5-ethyl-2-oxo-1,3-dioxan-5-yl) methoxymethylstyrene.

If only typical examples of the epoxy group-containing vinyl monomer used in preparing the fluorocopolymer (a-3) are given, glycidyl (meth) Acrylate, methyl glycidyl (meth)
There are various compounds such as acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene oxide, glycidyl vinyl ether, methyl glycidyl vinyl ether or allyl glycidyl ether.

Only typical examples of the vinyl monomer containing a primary amide group or a secondary amide group used in preparing the fluorocopolymer (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 There are 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 carbamate group-containing vinyl monomers used in preparing the fluorine copolymer (a-3) are exemplified, N
Methyl- (meth) acryloylcarbamate, ethyl N- (meth) acryloylcarbamate, N- [2-
Ethyl ((meth) acryloyloxy] ethylcarbamate, 2-carbamoyloxyethyl (meth) acrylate, 2- (N-methylcarbamoyloxy) ethyl (meth) acrylate, 2- (N-ethylcarbamoyloxy) ethyl (meth) Addition product of acrylate or 3-isopropenyl-α, α-dimethylbenzyl isocyanate with 2-hydroxypropyl carbamate; Addition product of 2-isocyanatoethyl (meth) acrylate with phenol; 2-isocyanatoethyl There are various compounds such as an addition reaction product of (meth) acrylate and ethanol; or an addition reaction product of 2-isocyanatoethyl (meth) acrylate and methyl ethyl ketoxime.

The vinyl copolymer monomer having a functional group represented by the aforementioned structural formula (S-I) used in preparing the fluorocopolymer (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,
There are various compounds such as addition products with various amide compounds.

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

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, the fluorine copolymer (a-3) can be prepared by using these and other copolymerizable monomers to prepare the fluorine copolymer (a- Solvents, polymerization initiators, and further, if necessary, as described above for preventing gelation during polymerization, as already exemplified as those used in preparing 1). The solution radical polymerization may be performed using various hydrolyzable esters according to various methods.

When a fluoroolefin is used as the fluorine-containing vinyl monomer, it is preferable to use a monomer having good copolymerizability with the fluoroolefin, as described above.

By applying the above-described monomers, polymerization initiators, and organic solvents by utilizing the solution radical polymerization method, the objective compound can be obtained under the normal pressure or the pressurized condition. A fluorine copolymer (a-3) having both a hydrolyzable silyl group and an acid group and a functional group other than both the hydrolyzable silyl group and the acid group can be prepared.

The amount of the hydrolyzable silyl group to be introduced into the fluorocopolymer (a-1) or (a-3) prepared as described above is determined based on the solid content of each polymer. The range of 0.005 to 10 mol per 1,000 g is appropriate, preferably 0.01 to 2 mol, and more preferably 0.05 to 1 mol.

When the amount is less than 0.005 mol, the fluorine copolymer (a-1) or (a-3) and the polysiloxane (H) having a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom must be used. The condensation reaction with a-2) becomes difficult to progress, and eventually the durability and the like of the obtained cured product are reduced. On the other hand, if it exceeds 10 mol and becomes too large, The solution viscosity at the time of the above-mentioned condensation reaction is increased, which may cause inconvenience such as gelation.

Further, these fluorine copolymers (a-1)
Or as the amount of acid groups to be introduced into (a-3),
Per 1,000 grams of solids of each polymer,
The range of 0.005 to 13.5 mol is appropriate,
Preferably it is in the range of 0.07 to 7.0 mol, most preferably in the range of 0.1 to 2.0 mol.

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 fluorocopolymer (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 appropriately in the range of 0.01 to 20 mol, preferably in the range of 0.2 to 3 mol, per 1,000 g of the solid content of the fluorocopolymer (a-3). More preferably, it is in the range of 0.3 to 2 mol. If the amount exceeds 20 moles and becomes too large, the cured product, in particular, the water resistance and the chemical resistance, etc., will necessarily decrease.

In order to obtain a high gloss retention which is a feature of the present invention, the following composition is preferable. That is, the required amount of the hydrolyzable silyl group and the acid group and, if necessary, at least one type of functional group other than both the hydrolyzable silyl group and the acid group is within the range described above, and The amount of the fluorinated vinyl monomer is from 5 to 95% by weight, preferably from 10 to 90% by weight, more preferably from 20 to 80% by weight, and comprises vinyl ethers, vinyl esters and allyl ethers. The amount of at least one vinyl monomer selected from the group is from 5 to 5;
95% by weight, preferably 10-90% by weight, even more preferably 20-80% by weight, the amount of α-olefins is 0-80% by weight, preferably 0.1-50% by weight, even more Preferably, the content is 0.5 to 20% by weight.

Further, these fluorine copolymers (a-1)
Alternatively, the number average molecular weight of (a-3) is 500 to 1
The range of 00000 is appropriate, preferably 1,
000 to 50,000, more preferably 1,
It is in the range of 500 to 30,000.

When the number average molecular weight of these fluorocopolymers (a-1) or (a-3) is less than 500,
Inevitably, the curability and the mechanical strength of the cured product will be inferior. On the other hand, if it exceeds 100,000 and becomes too high, the nonvolatile curable resin composition according to the present invention must be cured. In addition, the content becomes extremely low, the coating workability and the like become poor, and the appearance of the cured coating film deteriorates.

The fluorine copolymer (a-1) or (a-
As 3), a hydrolyzable silyl group-containing monomer in the presence of a polymer other than a fluorocopolymer, such as an acrylic resin, a polyester resin, or an alkyd resin, each having a polymerizable unsaturated double bond. And a monomer mixture containing an acid group-containing monomer as an essential component, obtained by subjecting to radical polymerization, a fluorine copolymer segment having both a hydrolyzable silyl group and an acid group. An acrylic resin, a polyester resin, an alkyd resin or the like in a grafted form can also be used.

The fluororesin (A) used in the present invention
-1) or polysiloxane (a) having the other component used in preparing (A-2), which has a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. -2) refers to a polysiloxane having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, which is generally called a silanol group.

Here, the hydrolyzable group bonded to a silicon atom means a halogen atom, an alkoxy group, a substituted alkoxy group, an alkoxyalkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group bonded to a silicon atom, respectively. It refers to various groups, such as groups, amide groups, aminooxy groups, iminooxy groups or alkenyloxy groups, which are hydrolyzed to form silanol groups.

If only typical examples of such polysiloxane (a-2) are given as examples, silicon compounds 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) used in preparing the fluororesin (A-1) or (A-2)
As -2), a hydrolyzed condensate or a silicon compound having at least two hydrolyzable groups bonded to a silicon atom in one molecule, as prepared by the means or formulation described later, or It can be said that a partially hydrolyzed condensate is used.

As described above, at least two of one molecule
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 any of various compounds can be used, if only typical ones are exemplified, the following general formula (S-IV)

[0136]

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

(However, R ⁵ in the formula may be a monovalent organic group such as an alkyl group, an aryl group, an aralkyl group or an alkenyl group, which may or may not have a substituent. ⁶ is a halogen atom, an alkoxy group, an alkoxyalkoxy 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 an alkenyloxy group, and b is 0 or 1 or 2
Be an integer. A) a silicon compound represented by the formula:

A partial hydrolysis condensate of the type obtained by partial hydrolysis and condensation of one of these silicon compounds; or a partial hydrolysis and condensation of a mixture obtained by partial hydrolysis and condensation of a mixture of two or more of these silicon compounds Hydrolysis condensate; or

[0139]

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

Or

[0141]

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

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

If only typical typical examples of the silicon compound represented by the above general formula are given below,

Various tetraalkoxysilanes such as tetraethoxysilane, tetramethoxysilane or tetra-n-butoxysilane;

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;

Or tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane,
There are various acetoxysilanes such as dimethyldiacetoxysilane or diphenyldiacetoxysilane.

Among these silicon compounds having a hydrolyzable group, only those particularly desirable as compounds used for preparing the polysiloxane (a-2) are exemplified, and tetraalkoxysilane, Examples thereof include organotrialkoxysilanes and diorganodialkoxysilanes, partial hydrolysis condensates thereof and partial cohydrolysis condensates thereof, and further, hydrolysis condensates of various chlorosilanes.

When a tetrafunctional silicon compound such as tetraethoxysilane is used as the silicon compound, a fluorine copolymer (a-1) or (a-3) and In order to prevent gelation during the condensation reaction with the siloxane (a-2) and prevent gelation during the neutralization reaction with the basic compound, 2 or 3
It is desirable to use a functional silicon compound in combination.

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 various silicon compounds as described above, 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 catalysts can be used, and of course, they may be used alone or in combination of two or more.

As typical examples of such catalysts, only typical ones may be mentioned, 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 carboxylic acids, such as dibutyltin dilaurate or tin octylate Acid salts;

Naphthenates of various metals such as iron, cobalt, manganese or zinc; various metal carboxylate salts such as octylate; 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 the catalyst used is in the range of 0.000001 to 10% by weight, preferably 0.000005 to 5% by weight, based on the silicon compound subjected to hydrolysis or partial hydrolysis. %, Particularly preferably 0.00001 to 1% by weight.

The amount of water used in the above-mentioned reaction is preferably 0.05 mol or more, more preferably 0.1 mol, per 1 mol of the hydrolyzable group bonded to the silicon atom of the silicon compound. 1 mol or more, 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, but the amount of water is 5 mol, 10 mol, or the amount of water bonded to silicon atoms. To be used in an excessive amount with respect to 1 mol of the decomposable group,
There is no problem.

The addition of these catalysts 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
50 ° C., preferably 20 ° C. to 100 ° C. is appropriate,
On the other hand, it can be said that the reaction is carried out under any conditions of normal pressure, increased pressure or reduced pressure.

The by-product of such a reaction,
Alcohol, water, and the like are respectively mixed with a fluorine copolymer (a-1) and a polysiloxane (a-
If a problem is caused due to the condensation reaction with 2) or the stability of the resulting aqueous curable resin composition, it can be removed from the system by means such as distillation, and there is no problem. If it exists in the system as it is, there is no problem at all.

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

In the case where such an organic solvent is used, any of various known and commonly used organic solvents can be used, and these can be used alone or in combination of two or more. Of course, it may be.

As the organic solvent to be used in this case, use can be made of the various solvents already listed as those which can be used in preparing the fluorocopolymer (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 such an organic solvent is desirably 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 polysiloxanes, from the viewpoint of the stability of the aqueous fluororesin, etc., one out of all the silicon atoms constituting the polysiloxane (a-2) is used.
0 mol% or more, preferably 20 mol% or more, more preferably 40 mol% or more of silicon atoms have a phenyl group, cyclohexyl group, isopropyl group, isobutyl group, t-butyl group and / or a carbon atom having a length of 3 or more. It is appropriate to use a compound having a group having a group which is relatively bulkier than an ethyl group, such as a chain alkyl group, alone or in combination.

From the viewpoint of the curability and durability of the aqueous fluororesin, 10 mol% or more, preferably 20 mol% or more, of all the silicon atoms constituting the polysiloxane (a-2). Preferably, 30 mol% or more is derived from a so-called trifunctional silane compound such as methyltrialkoxysilanes, methyltrichlorosilane, phenyltrialkoxylans or phenyltrichlorosilane. It is.

Next, the fluorine copolymer (a-
1) or (a-3) and the above-mentioned polysiloxane (a
-2) will be described.

In carrying out the condensation reaction, the ratio of the fluorine copolymer (a-1) or (a-3) and the polysiloxane (a-2) used was as follows: [fluorine copolymer (a-1)
Or (a-3)]: as a weight ratio of (a-2),
5:95 to 99: 1, preferably 15: 8
5: 95: 5, more preferably 20: 8.
It is preferable to set the value to be 0 to 85:15.

Fluorine copolymer (a-1) or (a-
If the weight ratio of 3) is set to be less than 5%, a cured coating film having poor alkali resistance or the like will be obtained due to too much polysiloxane (a-2). On the other hand, a fluorine copolymer (a-
If the weight ratio of 1) or (a-3) exceeds 99% and becomes too large, it is inevitable that the amount of the polysiloxane (a-2) is too small, so that the cured coating having the resistance to rain dripping contamination. It becomes difficult to obtain a film.

In carrying out the condensation reaction between the fluorine copolymer (a-1) or (a-3) and the polysiloxane (a-2), a catalyst was added in order to allow the reaction to proceed smoothly. However, as such a catalyst, various catalysts already listed as those used in preparing the polysiloxane (a-2) can be used as they are.

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

The amount of the catalyst used is from 0.0001 to 10% by weight based on the total amount of the fluorocopolymer (a-1) or (a-3) and the polysiloxane (a-2). The range is preferably from 0.0005 to 3% by weight, and particularly preferably from 0.0005 to 1% by weight.

Further, in order for the condensation reaction between the fluorine copolymer (a-1) or (a-3) and the polysiloxane (a-2) to proceed smoothly, the fluorine copolymer (a) a-1) or hydrolysis of a hydrolyzable silyl group contained in (a-3) and polysiloxane (a-
It is desirable that the hydrolysis of the hydrolyzable group bonded to the silicon atom contained in the case 2) proceed smoothly, and it is particularly preferable that such a condensation reaction be carried out in the presence of water. desirable.

In order to obtain the condensate by conducting the condensation reaction in the presence of water, the fluorocopolymer (a-1) or (a-
Water is added to a mixture of 3) and polysiloxane (a-2), and a hydrolyzable silyl group contained in fluorine copolymer (a-1) or (a-3) and polysiloxane ( a
-2) if necessary, by hydrolyzing both the hydrolyzable group bonded to the silicon atom and the subsequent condensation reaction,

Further, in particular, the water remaining in the polysiloxane (a-2) prepared by the above-mentioned means or formulation is utilized without adding water. , A hydrolyzable silyl group contained in a fluorine-co-fluorinated copolymer (a-1) and a polysiloxane (a-
In some cases, it can also be achieved by hydrolyzing both the hydrolyzable group bonded to the silicon atom contained in 2) and then performing a subsequent 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
To 150 ° C. is appropriate, and preferably 20 to 100 ° C. On the other hand, the pressure of the condensation reaction can be performed under any conditions of normal pressure and pressurized or reduced pressure.

Alcohol and water, which are by-products of the condensation reaction, can be removed from the system by means of distillation or the like.
There is no problem even if it is left in the system as it is.

Further, in the condensation reaction, an organic solvent may or may not be used. However, in order to easily perform stirring or the like, a fluorine-co-fluorine copolymer is used. It is desirable to use various organic solvents, such as those already listed as those that can be used when preparing the coalescence (a-1).

Here, when using organic solvents, 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 respective fluorine copolymers (a
-1) or (a-3) and polysiloxane (a-2)
The concentration in the organic solvent is desirably 5% by weight or more as a total amount of both components.

The thus prepared fluorocopolymer (a-1) or (a-3) and polysiloxane (a
-2) by partially or completely neutralizing the acid groups contained in the product of the condensation reaction with the basic compound with a basic compound, whereby each of the fluororesins (A
-1) and (A-2) are prepared.

As the basic compounds used in the neutralization reaction, 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;

Various inorganic basic substances such as ammonia, and further represented by sodium hydroxide or potassium hydroxide; or tetramethylammonium hydroxide, tetra-n-
There are 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 to be added is at least as large as the above-mentioned fluorine copolymer (a-1)
Or (a-3) and the polysiloxane (a-
This is an amount capable of imparting water dispersibility to the condensation reaction product of 2). These fluorine copolymer (a-1) or (a-3) and polysiloxane (a-
The ratio of the number of equivalents of the basic compound to the number of equivalents of acid groups contained in the condensation reaction product with 2), that is, the number of equivalents of the basic compound / [the fluorine copolymer (a-1) or (A-3) and an equivalent number of acid groups in the condensation reaction product of the polysiloxane (a-2)] is appropriate. The amount within a range that does not impair the performance is preferably within a range of 0.1 to 3, and most preferably within a range of 0.3 to 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 fluorine-containing copolymer ( a-1) or (a-3) or the type of the polysiloxane (a-2) and the composition thereof, and further, depending on the conditions of the neutralization reaction, etc. Attention must be paid to the point where the viscosity of the solution in the step (1) rises, and in some cases even gelation may occur.

In the case where such a problem arises, it is particularly desirable to carry out the neutralization reaction in the presence of water, and the amount of water added at this time depends on the amount of the fluorine copolymer (a- 1) or (a-3) and the solid content of the condensation reaction product of the above-mentioned polysiloxane (a-2): 1000
100 grams or more, preferably 200 grams per gram
It is appropriate to set the ratio so that the ratio is at least gram, more preferably at least 500 gram.

The method of adding the basic compound and water in carrying out the neutralization reaction may, of course, be batch addition, divided addition, or separate addition. Most preferably, it is added in the form of a mixture of a basic compound and water.

The reaction temperature of such a neutralization reaction is 0
About 150 ° C. is appropriate, preferably 20 to 10 ° C.
0 ° C. is appropriate, and the reaction can be carried out under any of normal pressure and increased or reduced pressure.

The fluororesin (A-
Various methods can be applied to prepare the above-mentioned aqueous fluororesin from 1) or (A-2), respectively. For example, water is simply added to the fluororesin (A-1) or (A-2), or the fluororesin (A-1) or (A-2) is added to water. By dispersing or dissolving in water, an aqueous fluororesin (AI) is obtained from the fluororesin (A-1) and an aqueous fluororesin (A-2) is obtained from the fluororesin (A-2). Fluororesin (A-
II) can be manufactured respectively.

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

Further, if necessary, the aqueous fluororesin (AI) or (A-II) thus obtained may be used.
By partially or completely removing the organic solvent contained in the aqueous fluororesin by heating and / or reduced pressure, so that the content of the organic solvent is low or the aqueous fluororesin containing no organic solvent (A -I) or (A)
-II) can be prepared.

The functional group contained in the aqueous fluororesin (A-I) thus obtained is a fluorine-containing copolymer (a
-1), a silanol group derived from polysiloxane (a-2), a hydrolyzable group bonded to a silicon atom contained in some cases, and a free radical derived from fluorine copolymer (a-1). And an acid group neutralized by a basic compound.

The functional group contained in the aqueous fluororesin (A-II) thus obtained is a silanol derived from the fluorocopolymer (a-3) and the polysiloxane (a-2). Group, a hydrolyzable group bonded to a silicon atom contained in some cases, a free acid group derived from the fluorocopolymer (a-3), and an acid group neutralized by a basic compound. In addition, 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 and a hydroxyl group, respectively, derived from the fluorine copolymer (a-3) 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.

The aqueous fluororesin (AI) or (AI)
In the process of preparing I), a case where a blocked acid group or an acid anhydride group is introduced as an acid group in the fluorocopolymer (a-1) or (a-2) is used. Means that at least a part of the blocked acid groups or acid anhydride groups is condensed with the polysiloxane (a-2) or neutralized with a basic compound,
It is converted into 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).

In preparing the aqueous fluororesin (A-II), a fluorocopolymer (a-3) having a blocked hydroxyl group, epoxy group or cyclocarbonate group introduced thereinto is used. In this case, the condensation reaction between the fluorine copolymer (a-3) and the polysiloxane (a-2) is carried out. At the stage of preparing the fluorofluororesin (A-2) by the summation reaction, and in addition, at the stage of dispersing or dissolving the fluorofluororesin (A-2) in water, at least a part of these functional groups is By hydrolysis, acid catalyzed decomposition or alcoholysis, etc.
Sometimes converted to free hydroxyl groups.

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

In order to prepare the aqueous curable resin composition according to the present invention from the aqueous fluororesin (AI) or (A-II) thus obtained, one of the aqueous fluororesin ( A-I) and (A-II) are self-curable in a form containing these aqueous fluororesins (AI) or (A-II) as an essential component because they themselves have self-curability. The above-mentioned compound (B) may be further added to the aqueous fluororesin (AI) or (A-II). Aqueous curing in which a crosslinking reaction between a functional group contained in the aqueous fluororesin (AI) or (A-II) and a functional group contained in the compound (B) is also used. It can also be made into a hydrophilic resin composition.

The compound (B) used in preparing the latter aqueous curable resin composition is contained in the above-mentioned aqueous fluororesin (AI) or (A-II). And various compounds having at least one functional group that reacts with the 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 a silicon atom, or the following structural formula (S-III)

[0213]

Embedded image —C (O) —NH—CH (OR ³ ) —COOR 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 group contained in the compound (B) is selected from the group consisting of the aqueous fluororesin (AI) and (A-II)
They can be appropriately selected and combined according to the type of the functional group contained therein. Only typical examples of such combinations are silanol group-silanol group, silanol group-alkoxysilyl group, alkoxysilyl group-alkoxysilyl group, carboxyl group-epoxy group, carboxyl group-cyclocarbonate group. And 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 fluororesin (AI) or (A-II), two or more of the various functional groups described above may be used. May be provided. Further, 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, fluororesins, acrylic resins,
Examples include polyester resin, alkyd resin, polyurethane resin, and epoxy resin.

If only typical examples of such a compound (B) are given, examples thereof include a compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom; 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 a compound having 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, There are 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 include 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. Silicon compounds represented by the following: hydrolysates or hydrolysis condensates of these silicon compounds;
There are a partial hydrolytic condensate obtained by one kind of partial hydrolytic condensation of these silicon compounds; and a partial cohydrolytic condensate obtained by two or more kinds of partial hydrolytic condensation of these silicon compounds.

Of these, particularly desirable and typical silicon compounds are tetramethoxysilane and tetraethoxysilane, their partially hydrolyzed condensates or their partially co-hydrolyzed condensates.

If only the above-mentioned compounds which are particularly typical as compounds having both an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule are to be exemplified,

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 an isocyanate group-containing vinyl monomer 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 the above-mentioned compounds which are particularly typical as compounds having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule are to be mentioned only,

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 Silicone Toray Co., Ltd.); "KP-392" [Partially hydrolyzed condensate of 3-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.];

Alternatively, various copolymers comprising the above-mentioned vinyl monomer having an epoxy group and the above-mentioned vinyl monomer having a hydrolyzable silyl group, or both monomers, 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 and fluoroolefin copolymers having both an epoxy group and a hydrolyzable silyl group.

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

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

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

The polyisocyanates as described above can be obtained by 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, respectively, of (meth) acrylic type, vinyl ester type, vinyl ether type, aromatic vinyl type or fluoroolefin type. Obtained by copolymerizing with vinyl monomers, etc.

There are various vinyl copolymers such as acrylic copolymers, vinyl ester copolymers and fluoroolefin copolymers each containing an isocyanate group.

Among these polyisocyanates, in particular, from the viewpoint of weather resistance and the like, aliphatic or alicyclic diisocyanate compounds, 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

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

[0241] If only typical representative examples of the blocking agent used in preparing the blocked polyisocyanate compound are given, various kinds of blocking agents such as methanol, ethanol, benzyl alcohol or 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, there are various oximes such as acetone oxime or methyl ethyl ketoxime, and further, 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 Kasei Kogyo Co., Ltd.]
Or “EGM-400” (trade name of cyclic polysiloxane having 3-glycidoxypropyl, manufactured by Dow Corning Toray Silicone 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, obtained by copolymerization, such as epoxy group-containing,
There are various vinyl copolymers such as acrylic copolymer, vinyl ester copolymer or 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. There are various vinyl copolymers such as a polymer, a vinyl ester copolymer or a fluoroolefin copolymer.

As typical amino resins, only typical ones are exemplified, and 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, there is an amino resin having an alkoxyalkyl group obtained by reacting such an amino resin having an alkylol group with various lower alcohols such as methanol, ethanol, n-butanol or i-butanol. .

Further, if only typical examples of the primary or secondary amide group-containing compound are given, only those which are used when preparing the fluorocopolymer (a-3) are exemplified. Homopolymers of various vinyl monomers having a primary or secondary amide group as described above;

Alternatively, the primary or secondary amide group-containing vinyl monomer can be copolymerized with the monomer, and can be (meth) acrylic, vinyl ester, vinyl ether, or aromatic vinyl, respectively. Or various acrylic copolymers, vinyl ester-based copolymers or fluoroolefin-based copolymers having a primary or secondary amide group, such as obtained by copolymerizing with a fluoroolefin-based vinyl monomer or the like. There are various vinyl copolymers such as copolymers.

In addition, only typical representative examples of the polycarboxy compounds include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, terephthalic acid, and the like. 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 fluorocopolymer (a-1);

Alternatively, these carboxyl group-containing vinyl monomers can be copolymerized with the monomers to be (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. Further, as already exemplified as those used in preparing the fluorocopolymer (a-3),
Homopolymers of various vinyl monomers having a hydroxyl group;

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. ,
There are various vinyl copolymers such as various acrylic copolymers, vinyl ester copolymers and fluoroolefin copolymers having a hydroxyl group.

The compound (B) was converted to an aqueous fluororesin (A
When compound (B) is water-soluble or has a certain degree of hydrophilicity when compounded in (I) or (A-II), the compound (B) B) is an aqueous fluororesin (AI) or (A-II)
In the form of a composition which is uniformly dissolved or uniformly dispersed.

However, when the hydrophilicity of the compound (B) is low, the aqueous fluororesin (A-
Even when mixed with (I) or (A-II), it is not possible to obtain a composition which is not uniformly dissolved or dispersed. In such a case, by introducing a hydrophilic group or the like into the compound (B) by various methods,
Improve the hydrophilicity of the compound (B), 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.

In preparing an aqueous curable resin composition comprising the above-mentioned aqueous fluororesin (AI) or (A-II) and the compound (B), the compound (B)
Is a compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, 100 weight parts of the solid content of the aqueous fluororesin (AI) or (A-II) Parts by weight, the solid content of compound (B) is in the range of 0.1 to 200 parts by weight, preferably in the range of 0.5 to 150 parts by weight, more preferably 1 to 200 parts by weight.
The compound (B) may be blended so as to be in the range of 100 parts by weight.

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 compound (B) is added to one equivalent of the functional group that reacts with the isocyanate group or the blocked isocyanate group contained in the aqueous fluororesin (AI) or (A-II). So that the amount of isocyanate groups or blocked isocyanate groups contained in the above is within the range of 0.1 to 10 equivalents, preferably within the range of 0.3 to 5 equivalents, more preferably within the range of 0.5 to 2 equivalents. What is necessary is just to mix this compound (B).

Further, when 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, One of the functional groups that react with the epoxy group or the cyclocarbonate group contained in the aqueous fluororesin (AI) or (A-II)
The total amount of the epoxy group and / or the cyclocarbonate group contained in the compound (B) is in the range of 0.2 to 5.0 equivalents, preferably 0.5 equivalent to the equivalent.
The compound (B) may be blended so as to be in a range of ３3.0 equivalents, more preferably in a range of 0.7 to 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 fluororesin (AI) or (A-II). ) Is in the range of 5 to 200 parts by weight,
The compound may be blended so as to be preferably in the range of 10 to 150 parts by weight, more preferably in the range of 15 to 100 parts by weight.

When compound (B) is a compound containing a primary or secondary amide group,
With respect to one equivalent of the functional group which reacts with the primary or secondary amide group contained in the aqueous fluororesin (AI) or (A-II), the primary or secondary functional group contained in the compound (B) is used.
The amount of the primary amide group is adjusted so as to be in the range of 0.2 to 5.0 equivalents, preferably in the range of 0.5 to 3.0 equivalents, and more preferably in the range of 0.7 to 2 equivalents. Compound (B) may be added.

Further, when the compound (B) is a polycarboxy compound, the aqueous fluororesin (A
The range in which the amount of the carboxyl group contained in the compound (B) is 0.2 to 5.0 equivalents relative to 1 equivalent of the functional group which reacts with the carboxyl group contained in -I) or (A-II). The compound (B) may be blended so as to be within the range, preferably within the range of 0.5 to 3.0 equivalents, and more preferably within the range of 0.7 to 2 equivalents.

Further, in the case where the compound (B) is a polyhydroxy compound, one of the functional groups reactive with the hydroxy group contained in the aqueous fluororesin (AI) or (A-II) may be used. The amount of the hydroxyl group contained in the compound (B) is within the range of 0.2 to 5.0 equivalents with respect to the equivalent.
The compound (B) may be blended so as to be preferably in the range of 0.5 to 3.0 equivalents, more preferably in the range of 0.7 to 2 equivalents.

Prepared as described above, each
The aqueous curable resin composition according to the present invention, which contains the aqueous fluororesin (AI) or (A-II) as an essential component, or the aqueous fluororesin (AI) or (A-II) ), The aqueous curable resin composition according to the present invention, in which the compound (B) is further compounded, can be used as a so-called clear composition containing no coloring pigment, It can also be used as a coloring composition containing various organic or inorganic pigments.

The aqueous curable resin composition of the present invention further comprises a curing catalyst, a flow regulator, a dye, a leveling agent, a thickener, a rheology control agent, a film-forming auxiliary, an ultraviolet absorber, an antioxidant, Various additives such as an agent or a plasticizer may be used in various applications in a blended form.

Of these additives, only typical examples of the curing catalyst are given below. If they are used when preparing the above-mentioned polysiloxane (a-2), they may be used. 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 thus obtained aqueous curable resin composition according to the present invention comprises an aqueous fluororesin (A-
Depending on the type of (I) or (A-II), the presence or absence of the (B) component, or when the (B) component is added, the optimum curing conditions differ depending on the type and amount thereof. Dry at room temperature for about 3 to 10 days, or in a temperature range of 80 to 250 ° C. for 3 days.
By performing baking for 0 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 mainly used and applied to various paints such as a paint for automotive top coating, a paint for PCM, a paint for building exterior or a paint for building material. Particularly, it is most suitable as a top coat for wall materials or roof materials for applications requiring high weather resistance. Furthermore, it can also be used and applied to a wide range of applications, such as for adhesives, inks, impregnating agents for fibers and paper, and surface treatment agents.

[0276]

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 Fluorocopolymer (a-1)] In a stainless steel autoclave having an inner volume of 3 liters and having been replaced with nitrogen gas, 910 parts of isopropanol (IPA) were added. 10 parts of methyl orthoformate, 68 parts of monobutyl maleate (MBM), 120 parts of vinyl acetate, 352 parts of ethyl vinyl ether (EVE), and 60 parts of vinyl tris (β-methoxyethoxy) silane (VTMES). And 50 parts of tert-butyl peroxy-2-ethylhexanoate (TBPOEH) as a polymerization initiator were charged.

Next, 400 parts of liquefied and collected chlorotrifluoroethylene (CTFE) was press-fitted therein. By continuing the reaction at 60 ° C. for 15 hours with stirring, the nonvolatile content becomes 51.2%, which has both a carboxyl group and a trimethoxysilyl group.
A solution of the desired fluorocopolymer was obtained. Hereinafter, this fluorine copolymer is abbreviated as (a-1-1).

Thereafter, the solution of the fluorocopolymer (a-1-1) thus obtained was charged into heptane,
The copolymer was precipitated, and the precipitated fluorocopolymer was subsequently dried under reduced pressure. The yield calculated from the ratio of the weight of the obtained fluorocopolymer to the total weight of the monomers charged before the reaction was 96%.

The fluorine copolymer (a-1-1)
The number average molecular weight in terms of polystyrene was 10,000, and the fluorine content was measured by the alizarin complexon method. As a result, it was confirmed to be 19.6%.

Reference Example 2 [Preparation Example of Fluorocopolymer (a-3)] Table 1 (1-
Except for changing as shown in 1), polymerization was carried out in the same manner as in Reference Example 1, and the desired fluorocopolymer (a-3) having property values as shown in Table 1 (1-2) I got These polymers are abbreviated as shown in Table 1 (1-2).

[0282]

[Table 1]

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

MEF: Monoethyl fumarate VPv: Vinyl pivalate EVE: Ethyl vinyl ether HBVE: Hydroxybutyl vinyl ether VTMES: Vinyl tris (β-methoxyethoxy) silane HFP: Hexafluoropropylene TBPOEH: tert-butylperoxy-2-ethylhexano Eat

[0285]

[Table 2]

Reference Example 3 (same as above) In a stainless steel autoclave having a 3 liter internal volume purged with nitrogen gas, 920 parts of isopropanol (IPA) and 100 parts of hydroxybutyl vinyl ether (HBVE) were added. 140 parts of ethyl vinyl ether (EVE), 150 parts of cyclohexyl vinyl ether (CHVE), 60 parts of vinyltrimethoxysilane (VTMS), and tert-
Butylperoxy-2-ethylhexanoate (TBP
OEH).

Next, 550 parts of liquefied and collected chlorotrifluoroethylene (CTFE) was press-fitted therein. The reaction was continued at 60 ° C. for 15 hours with stirring to obtain a solution of a trimethoxysilyl group-containing fluorocopolymer having a nonvolatile content of 51.2%. To 1000 g of the fluorocopolymer solution, 9 g of succinic anhydride was added, and 1 g of triethylbenzylammonium chloride was further added. While stirring
The reaction was continued at 110 ° C. for 2 hours to obtain a solution of the desired fluorocopolymer having a carboxyl group and a trimethoxysilyl group and having a non-volatile content of 52.0%. Hereinafter, this fluorine copolymer is referred to as (a-3).
-2).

Thereafter, the solution of the fluorocopolymer (a-3-2) thus obtained was charged into heptane,
The copolymer was precipitated, and the precipitated fluorocopolymer was subsequently dried under reduced pressure. The yield calculated from the ratio of the weight of the thus obtained fluorocopolymer to the total weight of the monomers charged before the reaction was 95%.

The fluorine copolymer (a-3-2)
Has a number average molecular weight in terms of polystyrene of 11,000, and the fluorine content is measured by the alizarin complexon method. As a result, it was confirmed to be 26.5% by weight.

Reference Examples 4 and 5 [Preparation Examples of Polymers (R-1) and (R-2)] The types of monomers and the amounts used thereof are shown in Table 1 (2-
Polymerization was carried out in the same manner as in Reference Example 1 except for the change as shown in 1), to obtain polymers (R-1) and (R-2) having property values as shown in Table 1 (2-2). ) Got. These polymers (R-1) and (R-2) are used when preparing a comparative resin.

[0291]

[Table 3]

<< Footnotes to Table (2-1) >> MBM: monobutyl maleate EVE: ethyl vinyl ether CTFE: chlorotrifluoroethylene CHVE: cyclohexyl vinyl ether HBVE: hydroxybutyl vinyl ether TBPOEH: tert-butylperoxy-2-ethyl Hexanoate

[0293]

[Table 4]

Reference Example 6 [Preparation Example of Comparative Control Resin] 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 dropping over a period of 0 minutes, the non-volatile content was 42.3% by distillation under reduced pressure except for isopropanol as a solvent.
An aqueous fluororesin containing no hydrolyzable silyl group for comparison was obtained. Hereinafter, this is abbreviated as Control Resin 1.

Reference Example 7 (same as above) The polymer (R-2) was diluted with toluene,
A 3.0% solvent-based fluororesin containing no hydrolyzable silyl group and no acid group was obtained as a control. Hereinafter, this is abbreviated as Control Resin 2.

Example 1 This example shows a preparation example of the aqueous fluororesin (A-I). In a reaction vessel equipped with a thermometer, reflux condenser, stirrer and dropping funnel, 35 phenyltrimethoxysilane was added.
4 parts and 365 parts of isopropanol were charged to give 8 parts.
The temperature was raised to 0 ° C.

Next, at the same temperature, 2.9 parts of “AP-3” (trade name of isopropyl acid phosphate, manufactured by Daihachi Chemical Industry Co., Ltd.) and 96 parts of ion-exchanged water were mixed with 5 parts of After dropping over a period of 4 minutes and stirring at the same temperature for 4 hours, 100% hydrolysis of phenyltrimethoxysilane was determined by nuclear magnetic resonance analysis ( ¹ H-NMR).
I confirmed that it was progressing.

Thereafter, the fluorocopolymer (a-1-
1,480 parts of 1) was added, and the mixture was stirred at the same temperature for 4 hours to obtain a condensate of polysiloxane (hydrolyzate of phenyltrimethoxysilane) and fluorine copolymer (a-1-1). Was prepared. When this condensate was analyzed by ¹ H-NMR, the hydrolysis of the tris (β-methoxyethoxy) silyl group contained in the fluorocopolymer (a-1-1) proceeded 100%. Turned out to be.

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 the dropwise addition over 0 minutes, the target aqueous resin having a non-volatile content of 44.9% was obtained by removing the alcohols such as methanol and isopropanol by distillation under reduced pressure. Hereinafter, this is abbreviated as (AI-1).

Thereafter, the aqueous fluororesin (AI)
-1) was stored at 40 ° C. for one month, but no abnormality such as gelation or precipitation of a precipitate was observed in the aqueous fluororesin after storage. AI-1) was found to be extremely excellent in storage stability.

Examples 2 to 4 These examples also show preparation examples of the aqueous fluororesin (A-I). The kind and amount of the silicon compound for synthesizing the polysiloxane (a-2) and the amounts of the solvent, the catalyst and the water were determined, and the fluorine copolymer (a-
The amount of the basic compound and the amount of water used in the neutralization reaction are determined in the second
Except for the change as shown in Table (1-1), a condensation reaction, a neutralization reaction and aqueous conversion were carried out in the same manner as in Example 1,
Various aqueous fluororesins (AI) having the property values shown in the same table were obtained. The aqueous fluororesins are abbreviated as shown in the table.

[0303]

[Table 5]

<< Footnotes to Table 2 (1-1) >> Each numerical value indicating the usage ratio of raw materials is a part by weight.

PTMS: phenyltrimethoxysilane DMDMES: dimethyldimethoxysilane MTES: methyltriethoxysilane SH-6018: trade name of silanol group-containing polysiloxane manufactured by Toray Dow Corning Silicone Co., Ltd.

The “storage stability” means that each aqueous fluororesin prepared as described above was stored at 40 ° C. for one month, and
The results are shown to confirm that there was no so-called abnormality such as gelation or precipitation of a precipitate, which was not observed before storage.

Examples 5 and 6 These examples show preparation examples of the aqueous fluororesin (A-II). The kind of the silicon compound for synthesizing the polysiloxane (a-2), its use amount, and a solvent;
The amount of the catalyst and water used, the type of the fluorocopolymer (a-3) and the amount used, and the amount of the basic compound used in the neutralization reaction and the amount of water Except that the amount used was changed as shown in Table 2 (1-2), the condensation reaction, neutralization reaction and aqueous conversion were carried out in the same manner as in Example 1 to obtain properties as shown in the same table. Various aqueous fluororesins (A-II) having different values were obtained. Those aqueous resins are abbreviated as shown in the table.

[0308]

[Table 6]

<< Footnotes to Table 2 (1-2) >> Each numerical value indicating the usage ratio of raw materials is a part by weight.

PTMS: phenyltrimethoxysilane

The “storage stability” means that each aqueous fluororesin prepared as described above was stored at 40 ° C. for one month,
The results are shown to confirm that there was no so-called abnormality such as gelation or precipitation of a precipitate, which was not observed before storage.

Examples 7-14 and Comparative Examples 1-2 First, aqueous fluororesin (AI) and aqueous fluororesin (A
-II), a part of control resin 1 or control resin 2, a pigment, and ethylene glycol monobutyl ether (EGMB).
The mixture with E) is dispersed using a sand mill,
Various mill bases having a pigment weight concentration (PWC) of 60% are prepared, and then, the remaining amount of the aqueous fluororesin (AI) or (A-II) is added to each mill base and mixed. Thus, 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).

Aqueous fluororesin (AI), aqueous fluororesin (A-II), control resin 1 or control resin 2, pigment, ethylene used in each white paint prepared as described above. Glycol monobutyl ether (EGMB
The use ratio of E) and compound (B) is shown in Table 3 (1-
1), as shown in Table 3 (2-1) or Table 3 (3-1).

Each of the white paints thus obtained was previously coated with a chlorinated polyolefin paint,
It is applied on a sufficiently dried slate plate by an applicator so that a dry film thickness is about 40 micrometers (μm), and is applied to Table 3 (1-2), Table 3 (2-2) or Various cured coating films were obtained under the curing conditions shown in Table 3 (3-2).

The coatings obtained using the aqueous curable resin composition of the present invention obtained here were evaluated for various properties. The results are collectively shown in Table 3 (1-2), Table 3 (2-2) or Table 3 (3-2).

[0317]

[Table 7]

<< Footnotes of Table 3 (1-1) >> All numerical values indicating the usage ratios of the raw materials are parts by weight.

CR-97: "Taipec CR-97"
Is a trade name of rutile-type titanium oxide manufactured by Ishihara Sangyo Co., Ltd. EGMBE: Ethylene glycol monobutyl ether

[0320]

[Table 8]

<< Footnote to Table 3 (1-2) >>"Weatherresistance"
Is 4,000 by Sunshine Weatherometer
After a 0 hour exposure, the gloss value of the coating at 60 ° specular reflectance (%) is divided by the same gloss value of the coating at the time of non-exposure, which is taken as 100 This is a value obtained by multiplying (gloss retention:%). The larger the value, the better the weather resistance.

“Stain resistance” indicates the color difference ΔE between a coating film after exposure for 6 months outdoors and a coating film without exposure. The closer the value is to 0, the better the stain resistance is.

[0323]

[Table 9]

<< Footnotes in Table 3 (2-1) >> Each numerical value indicating the usage ratio of raw materials is a part by weight.

DN-950: "Barnock DN-95
"0" is a trade name of isocyanate prepolymer manufactured by Dainippon Ink and Chemicals, Inc.

[0326]

[Table 10]

[0327]

[Table 11]

<< Footnotes in Table 3 (3-1) >> All numerical values indicating the usage ratios of the raw materials are parts by weight.

[0329] S-695: "c _o Tazoru S-
695 ”, which is Dainippon Ink and Chemicals, Inc.
KP-392: a partially hydrolyzed condensate of 3-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.

[0330]

[Table 12]

Examples 15 to 22 This example relates to various kinds of aqueous fluororesins,
The storage stability was evaluated. Various aqueous fluororesins (A) obtained in Examples 1 to 6
After storing (I) and (A-II) at 40 ° C. for one month, various white bases were prepared in the same manner as in Examples 7-14, and water was further required. Various white paints having a PWC of 35% were prepared by incorporating the compound (B) according to the formula (1).

Next, in the same manner as in Examples 7 to 14, each white paint was applied on a test coated plate, and then cured under the curing conditions shown in the same table. Various cured coatings were obtained.

Each of the aqueous curable resin compositions according to the present invention containing a white base prepared from an aqueous fluororesin obtained here and stored for one month at 40 ° C. Each of the coating films has various properties as shown in Table 3 (1-2), Table 3 (2-2) or
Almost no difference was observed from the results of Examples 7 to 14 shown in Table (3-2).

From these facts, it can be seen that the aqueous fluororesin (A-
It is judged that I) and (A-II) are particularly excellent in storage stability.

[0335]

The aqueous fluororesin obtained by the production method of the present invention has, in particular, excellent storage stability, and contains the aqueous fluororesin as an essential component. The water-soluble resin composition is capable of forming a cured coating film having excellent gloss retention upon exposure and excellent resistance to rain dripping, and is particularly highly practical as a coating composition.

Claims (14)

[Claims] 1. A fluorine copolymer (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 fluororesin (A-1) which is dispersed or dissolved in water. A method for producing an aqueous fluororesin. 2. The fluorine copolymer (a-1) described above,
2. The method according to claim 1, wherein the fluorocopolymer contains a fluoroolefin as an essential component. 3. The fluorine copolymer (a-1) described above,
2. The process according to claim 1, wherein the fluorocopolymer is at least one fluoroolefin selected as an essential component and selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and vinylidene fluoride. 4. A fluorine copolymer (a-3) having both a hydrolyzable silyl group and an acid group, and a functional group other than the hydrolyzable silyl group and the acid group.
Polysiloxane having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom (a-2)
And then partially or completely neutralized with a basic compound to obtain a fluororesin (A-
2. A method for producing an aqueous fluororesin, wherein 2) is dispersed or dissolved in water. 5. The fluorine copolymer (a-3) described above,
The method according to claim 4, which is a fluorocopolymer containing a fluoroolefin as an essential component. 6. The fluorine copolymer (a-3) described above,
The production method according to claim 4, wherein the production method is a fluorine copolymer containing at least one kind of fluoroolefin selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and vinylidene fluoride as an essential component. 7. 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, and a secondary group. An amide group, a carbamate group and the following structural formula (S-I) The method according to claim 4, wherein the at least one functional group is selected from the group consisting of functional groups represented by the formula: 8. 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
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. Manufacturing method. 9. The above-mentioned silicon compound having at least two hydrolyzable groups bonded to a silicon atom in one molecule is a tetraalkoxysilane, an organotrialkoxysilane, a diorganodialkoxysilane, or a portion thereof. 9. The production method according to claim 8, wherein the production method is at least one alkoxysilane selected from the group consisting of a hydrolysis condensate and a partial cohydrolysis condensate thereof. 10. 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 silicon. The method according to any one of claims 1 to 9, which is an alkoxy group bonded to an atom. 11. The method according to claim 1, wherein the hydrolyzable silyl group in the fluorocopolymer (a-1) is an alkoxysilyl group. 12. An aqueous curable resin composition comprising, as an essential component, an aqueous fluororesin obtained by the production method according to claim 1. Description: 13. An aqueous fluororesin obtained by the production method according to claim 1 and a compound (B) having a functional group that reacts with a functional group contained in the aqueous fluororesin. An aqueous curable resin composition, which is contained as an essential component. 14. 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) has a hydrolyzable group bonded to an isocyanate group and 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,
The aqueous curable resin composition according to claim 13, 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.