JPH07173403A - Curable composition - Google Patents

Abstract

(57) [Summary] [Object] To provide a novel curable composition which is suitable for various applications such as paints, adhesives, and sealing agents, and which gives a cured coating film excellent in acid resistance. A curable composition containing as an essential component a polymer (A) having at least one specific substituted methyl ester group and at least one specific substituted acetoxy group in one molecule, or in one molecule A curable composition comprising, as essential components, a compound (B) having at least two said substituted methyl ester groups and a compound (C) having at least two said substituted acetoxy groups in one molecule;
A curable composition, which further comprises a curing catalyst (D).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful curable composition. More specifically, a curable composition centered on a compound having both a specific substituted methyl ester group and a specific substituted acetoxy group, in particular, a curable composition having excellent curability, and moreover, various properties such as acid resistance The present invention relates to a curable composition having extremely high practicality, which gives a cured film having

The curable composition of the present invention is used in a wide variety of fields for coating materials such as metal coatings, adhesives, sealing agents, casting resins and the like.

[0003]

2. Description of the Related Art In recent years, with the deterioration of the global environment, the damage caused by acid rain has become more serious, and the damage to the painted surfaces of outdoor structures and automobiles is beginning to occur. It is desired to develop a composition that forms a cured coating film having excellent properties.

Conventionally, a curable composition consisting of a hydroxyl group-containing acrylic resin or a hydroxyl group-containing alkyd resin and an amino resin has been used as a top coat for automobiles.
A cured coating film obtained from such a class composition generally has insufficient acid resistance, and a great improvement is desired.

As a typical room temperature curable composition for forming a cured coating film having excellent acid resistance, a composition comprising a hydroxyl group-containing acrylic resin and a polyisocyanate compound is used in a wide range of applications. Yes, but
In such a composition, there are safety and health problems due to the polyisocyanate compound.

Because of this, there are no safety and health problems,
In addition, the development of a room temperature curable composition that gives a coating film of extremely high practicality, which is also excellent in acid resistance, has also been desired.

[0007]

However, the inventors of the present invention have proposed a novel composition for forming a cured coating film having excellent acid resistance, especially for baking, and a non-isocyanate curing composition for room temperature curing. In order to develop a composition that gives a coating film excellent in acid resistance and the like, we have earnestly started research.

[0008] Therefore, the problem to be solved by the present invention is to solve the problem, and in particular, to obtain a cured film having various properties such as acid resistance, which is a curable composition having excellent curability. There is an object to provide a curable composition having high practicability.

[0009]

Therefore, the present inventors have
As a result of intensive and thorough investigations, the curability of a compound having both a specific substituted methyl ester group and a specific substituted acetoxy group as the axis is set in accordance with the standards of the problems to be solved by the invention as described above. The present invention has now been completed by finding that the composition has extremely high practicality so as to solve and attain the above-mentioned problems or objects.

That is, the present invention provides, inter alia, at least one substituted methyl ester group represented by the general formula [I] in each molecule,

[0011]

Embedded image —CO ₂ CH ₂ OX [I]

[In the formula, X represents a monovalent organic group. ]

Further, at least one compound represented by the general formula [II] in one molecule

[0014]

Embedded image —O ₂ CCHYCO-Z [II]

[Wherein Y is a hydrogen atom or 1
Represents a monovalent organic group, and Z represents a monovalent organic group. ] The curable composition which contains the polymer (A) which has a substituted acetoxy group shown by these as an essential film-forming component,

Alternatively, at least two in one molecule,
A compound (B) having a substituted methyl ester group represented by the general formula [I], and at least two compounds in one molecule,
A curable composition comprising, as an essential component, a compound (C) having a substituted acetoxy group represented by the above-mentioned general formula [II],

Further, the above-mentioned polymer (A) having at least one substituted methyl ester group and at least one substituted acetoxy group in one molecule, and a curing catalyst (D), As an essential component, a curable composition consisting of containing

Furthermore, at least 2 in one molecule.
A compound (B) having one substituted methyl ester group, a compound (C) having at least two substituted acetoxy groups in one molecule, and a curing catalyst (D) as essential components. It is intended to provide a curable composition comprising

Here, if only typical examples of the monovalent organic group represented by X in the above-mentioned general formula [I] are exemplified, the chain consisting of C ₁ -C ₁₀ A branched or branched alkyl group;

Various cycloalkyl groups such as cyclohexyl group, cyclopentyl group and cyclohexyl group; substituted alkyl groups and substituted cycloalkyl groups substituted with one or more alkyl groups, aryl groups, aralkyl groups, halogen atoms and the like;

Alternatively, various aryl groups such as a phenyl group and a tolyl group; and various aralkyl groups such as a benzyl group and a phenethyl group.

Further, Y in the above general formula [II] is
A hydrogen atom or a monovalent organic group, of which, among these, a monovalent organic group, which is particularly representative as Y, is exemplified, the following general formula [I] Various monovalent organic groups such as those listed for X in the above are included.

Z in the above-mentioned general formula [II]
Are monovalent organic groups, but if only typical ones are exemplified, various monovalent organic groups such as those mentioned above for Y are listed.

Further, the above-mentioned polymer (A) is
A compound having at least one substituted methyl ester group represented by the general formula [I] per molecule and at least one substituted acetoxy group represented by the general formula [II] per molecule is designated. Is something that

Specific examples of the polymer (A) are vinyl polymers, polyester polymers, polyurethane polymers, polyether polymers and alkyd resins. Then

Further, among them, only representative ones of the above vinyl polymers are exemplified, and acrylic polymers, vinyl ester polymers, α
-Olefin-based polymers, fluoroolefin-based polymers, chlorinated olefin-based polymers, and the like.

[0027] Of the polymers (A), first, to prepare the above-mentioned vinyl polymer (A), vinyl monomers having a substituted methyl ester group represented by the general formula [I] are used. And a method of radically copolymerizing a vinyl monomer having a substituted acetoxy group represented by the general formula [II],

It is said that a hydroxyl group in a vinyl polymer having at least one substituted methyl ester group represented by the general formula [I] and a hydroxyl group in one molecule is converted to a substituted acetoxy group. Methods, etc., may be employed as particularly representative.

The substituted methyl ester group-containing vinyl monomers represented by the general formula [I] used in the above-mentioned method include, for example, carboxyl group-containing monomers General formula [III] as posted

[0030]

Embedded image X—O—CH ₂ R [III]

[However, X in the formula is as described above,
In addition, R represents a group represented by WO- (wherein W represents a monovalent organic group which may be the same as X) or a halogen atom. ] And / or the general formula [IV] shown below.

[0032]

Embedded image X—O—CH ₂ OH [IV]

[However, it is assumed that X in the formula is as described above. ] What is obtained by reacting a compound represented by the above is an example of a particularly representative one.

Here, only typical examples of the compounds represented by the above-mentioned general formula [III] will be exemplified. Formaldehyde-dimethyl acetal, -diethyl acetal, -dipropyl acetal,- Various diacetals of formaldehyde, such as dibutyl acetal, -dicyclohexyl acetal or -dibenzyl acetal;

Various halomethyl ethers such as methyl chloromethyl ether, ethyl chloromethyl ether, butyl chloromethyl ether, methyl bromomethyl ether and ethyl bromomethyl ether; hemiacetals obtained from formaldehyde and monohydric alcohol Various carboxylic acid esters, various sulfonic acid esters, various sulfinic acid esters or various mineral acid esters, and the like,

As the compounds represented by the above-mentioned general formula [IV], only typical ones are exemplified. Formaldehyde-methyl acetal, -ethyl acetal, -propyl acetal, -butyl acetal,- Formaldehyde and / or paraformaldehyde, such as cyclohexyl acetal or -benzyl acetal, and

[0037]

Embedded image W-OH

[However, it is assumed that X in the formula is as described above. ] Various formaldehyde acetals and the like obtained from the compound represented by

Such a reaction is carried out by various Lewis compounds represented by, for example, BF ₃ or its ether complex, titanium tetrachloride, tin dichloride, tin tetrachloride, gallium trichloride, aluminum trichloride, zirconium tetrachloride and the like. Acids;

Various metal triflate salts represented by silver trifluoromethane sulfonate, tin trifluoromethane sulfonate, etc .; methanesulfonic acid, propanesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenedisulfonic acid, Various organic sulfonic acids such as trifluoromethanesulfonic acid or trichloromethanesulfonic acid;

Various phosphoric acid esters such as methyl phosphoric acid, isopropyl phosphoric acid, diisopropyl phosphoric acid and tributyl phosphoric acid; various organic sulfonic acids such as butyl methane sulfonate, propyl toluene sulfonate and 2-hydroxycyclohexyl toluene sulfonate, Esters; various inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, metaphosphoric acid;

Various solid acids such as resins having various acid groups such as sulfonic acid groups, sulfuric acid groups or phosphoric acid groups; various acids such as various phosphoric acid anhydrides such as phosphorus pentoxide. In the presence of a catalyst, or in the presence of various base catalysts such as various alkali or organic tertiary amines, etc.

Various compounds represented by the above-mentioned general formulas [III] and / or [IV] are added dropwise to the carboxyl group-containing monomer, and the reaction is carried out for about 1 to about 20 hours. It may be performed by various methods such as urging.

As the solvent used at this time, a carboxyl group-containing monomer, which is a starting material for the reaction, and various compounds and acids represented by the above general formulas [III] and / or [IV] are used. There is no particular limitation as long as it is inert to the catalysts, any compound can be used, and no solvent may be used.

When only a typical solvent is used as a solvent, various kinds of hydrocarbons such as toluene, xylene, cyclohexane, n-hexane or octane; ethyl acetate or butyl acetate can be used. Such as various ester-based compounds; acetone, methyl ethyl ketone or methyl butyl ketone, various ketone-based compounds; or ethylene glycol dimethyl ether or diethylene glycol dimethyl ether, various ether-based compounds, etc. Of course, it may be used in combination.

Such reaction products, that is, the substituted methyl ester group-containing vinyl monomers represented by the above-mentioned general formula [I], particularly, among the compounds obtained by the reaction with methacrylic acid, Particularly, to exemplify only representative ones,

[0047]

Embedded image _{CH 2 = C (CH 3)} CO 2 CH 2 OCH 3 (I-1-1) CH 2 = C (CH 3) CO 2 CH 2 OC 2 H 5 (I-1-2) CH 2 _{= C (CH 3) CO 2} CH 2 OC 3 H 7 (I-1-3) CH 2 = C (CH 3) CO 2 CH 2 O-i-C 3 H 7 (I-1-4) CH 2 _{= C (CH 3) CO 2} CH 2 OC 4 H 9 (I-1-5) CH 2 = C (CH 3) CO 2 CH 2 O-i-C 4 H 9 (I-1-6) CH 2 _{= C (CH 3) CO 2} CH 2 OC 6 H 11 (I-1-7) CH 2 = C (CH 3) CO 2 CH 2 OCH 2 C 6 H 5 (I-1-8) CH 2 = C _{(CH 3) CO 2 CH 2} OC 6 H 5 (I-1-9) or _{CH 2 = C (CH 3)} CO 2 CH 2 OC 6 H 10 -CH 3 (I-1-10) , etc. is there.

The various monomers as listed above are each one of the ester group-containing vinyl monomers for preparing the above-mentioned substituted methyl ester group-containing vinyl polymers. Although they are merely methacrylic acid derivatives, in addition to these, acrylic acid, crotonic acid, or carboxyethyl (meth) acrylates; monovinyl esters of saturated dicarboxylic acids such as succinic acid, adipic acid or sebacic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid; Half-esters of the above-mentioned unsaturated dicarboxylic acids and monohydric alcohols; or a hydroxyl group represented by 2-hydroxyethyl (meth) acrylate Carbohydrates such as addition reaction products of monomers with acid anhydrides such as succinic anhydride or phthalic anhydride. Various substitutions in the form obtained by reacting various compounds such as silyl-containing monomers with various compounds represented by the above-mentioned general formulas [III] and / or [IV] Of course, methyl ester group-containing monomers can also be used.

Next, as the vinyl-based monomer having a substituted acetoxy group represented by the general formula [II], which is used when the vinyl-based polymer (A) is prepared by the above-mentioned method, Hydroxyl group-containing α, β-unsaturated carboxylic acid esters typified by hydroxyethyl (meth) acrylate: Hydroxyl group-containing allyl alcohols typified by allyl alcohol: 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, etc. Hydroxyl group-containing vinyl ethers: 2-hydroxyethyl allyl ether and other hydroxyl group-containing allyl ethers: Furthermore, an adduct obtained by reacting these hydroxyl group-containing vinyl monomers with a lactone compound represented by ε-caprolactone. Etc. of the various hydroxyl group-containing vinyl monomers, Various substituents acetoxy group-containing vinyl was converted to an acetoxy group monomers can be mentioned.

Among these, especially, a hydroxyl group-containing (meta)
As a typical example of the substituted acetoxy compound of acrylic acid ester,

[0051]

CH ₂ ═C (CH ₃ ) CO ₂ CH ₂ CH ₂ OCOCH ₂ COCH ₃ (II-1-1) CH ₂ ═C (CH ₃ ) CO ₂ (CH ₂ ) ₃ OCOCH ₂ COCH ₃ (II _{-1-2) CH 2 = C (CH} 3) CO 2 (CH 2) 4 OCOCH 2 COCH 3 (II-1-3) CH 2 = C (CH 3) CO 2 CH 2 CH 2 OCOCH (CH 3) _{COCH 3 (II-1-4) CH} 2 = C (CH 3) CO 2 CH 2 CH 2 OCOCH 2 COC 2 H 5 (II-1-5) CH 2 = C (CH 3) CO 2 (CH 2) _{3 OCOCH (CH 3) COCH 3} (II-1-6) or _{CH 2 = C (CH 3)} CO 2 (CH 2) 4 OCOCH (CH 3) COCH 3 (II-1-7) , and the like.

As described above, the various monomers are merely the substituted acetoxy compounds of the hydroxyl group-containing methacrylic acid esters among the hydroxyl group-containing α, β-unsaturated carboxylic acid esters, In addition to these, it goes without saying that the substituted acetoxy compounds of the various hydroxyl group-containing vinyl monomers described above can also be used.

Using the substituted methyl ester group-containing vinyl monomer and the substituted acetoxy group-containing vinyl monomer as listed above, or further, if necessary,
As described below, the vinyl-based polymers (A) of the present invention can be prepared by using other monomers copolymerizable with the both monomers, as well. Can be applied.

That is, the desired vinyl polymer (A) is prepared by radical polymerization, ionic polymerization or photopolymerization according to a conventional method such as a solution polymerization method, a solution dispersion polymerization method or a bulk polymerization method. However, the solution radical polymerization method is the simplest method.

Then, only representative examples of the solvents used in the solution radical polymerization method are given below. Toluene, xylene, cyclohexane,
Various hydrocarbon solvents such as n-hexane or octane;

Various ester solvents such as methyl acetate, butyl acetate, amyl acetate, ethyl ethoxypropionate or 2-ethoxyethyl acetate; various ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone solvent;

Alternatively, dibutyl ether, 2-ethoxyethyl ether, 1,2-diethoxyethane, 1,2
-Such as dimethoxyethane or dimethoxymethane,
There are various ether solvents and the like, but it goes without saying that these may be used alone or in combination of two or more kinds.

Furthermore, only typical examples of radical polymerization initiators will be exemplified. Azo-based compounds represented by azobisisobutyronitrile and the like; or peroxides represented by benzoyl peroxide and the like. These are various known and commonly used compounds such as physical initiators.

If necessary, lauryl mercaptan, octyl mercaptan, 2 may be used as a molecular weight modifier.
-Mercaptoethanol, octyl thioglycolate,
Various known and conventional chain transfer agents such as 3-mercaptopropionic acid or α-methylstyrene dimer can also be used.

Then, only specific representative examples of the other copolymerizable monomers used in the above-mentioned copolymerization will be exemplified. Methyl (meth) acrylate, ethyl (meth) acrylate, Such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or lauryl (meth) acrylate,
Various alkyl (meth) acrylates of C _{1 to} C ₂₂ ;

Various alicyclic alkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate or isobornyl (meth) acrylate; various such as benzyl (meth) acrylate or phenethyl (meth) acrylate Aralkyl (meth) acrylates of

Various hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl alcohol, 2-hydroxyethyl vinyl ether or 2-hydroxyethyl allyl ether; methoxyethyl Various alkoxyalkyl (meth) acrylates such as (meth) acrylate or ethoxyethyl (meth) acrylate;

Various alkyl esters of crotonic acid such as methyl crotonic acid or ethyl crotonic acid; various alkyl esters of dimethyl malate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dimethyl itaconate or dibutyl itaconate. Dialkyl esters of unsaturated dicarboxylic acids; styrene, p-tert
Various aromatic vinyl monomers such as -butylstyrene, α-methylstyrene or vinyltoluene;

(Meth) acrylamide or N, N-
Various (meth) acrylamides such as dimethyl (meth) acrylamide, N-methylol (meth) acrylamide and N-butoxymethylmethacrylamide; various cyano group-containing monomers such as (meth) acrylonitrile or crotononitrile Kinds; various haloolefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinyl chloride or vinylidene chloride;

Various α-olefins such as ethylene, propylene, isobutylene or 1-butene; or various carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate or vinyl versatate;

Various unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid or carboxyethyl (meth) acrylates; Monovinyl esters of various saturated dicarboxylic acids such as succinic acid, adipic acid or sebacic acid; Various unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid;

Alternatively, various half esters of unsaturated dicarboxylic acids and monohydric alcohols listed above; hydroxyl group-containing monomers typified by 2-hydroxyethyl (meth) acrylate and the like. And various carboxyl group-containing monomers such as addition reaction products with various acid anhydrides such as succinic anhydride or phthalic anhydride;
Alternatively, various monomers having an acid group other than a carboxyl group, such as 2-phosphoryloxyethyl methacrylate, vinyl sulfonic acid or aryl sulfonic acid;

Further, various alkyl- or cycloalkyl vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether or cyclohexyl vinyl ether are used.

Next, in order to obtain the vinyl polymer (A) by the above-mentioned method, first, a vinyl monomer having a substituted methyl ester group represented by the above-mentioned general formula [I] is used. By the copolymerization of the body and the hydroxyl group-containing vinyl monomer,

Alternatively, a vinyl polymer having both the substituted methyl ester group and the hydroxyl group can be obtained by copolymerization in a form including other vinyl monomers copolymerizable with these both monomers. Then, a substituted acetic acid derivative whose hydroxyl group is represented by the following general formula [V]

[0071]

Embedded image VCOCHYCOZ [V]

[Wherein Y and Z in the formula are the same as described above, and V represents a YO-group. ] To convert the substituted acetoxy group represented by the general formula [II].

Alternatively, when Y and Z in the general formula [II] are both hydrogen atoms, the above hydroxyl group-containing vinyl-based monomer is reacted with diketene to give the monomer. You can get a quantity.

Next, at least one substituted methyl ester group represented by the general formula [I] per molecule and the at least one general formula [I] per molecule are used.
The polymer (A) other than the vinyl polymer having the substituted acetoxy group represented by the formula [I] can be prepared from the carboxyl group-containing polymer.

That is, the carboxyl group-containing polymer is
First, at least one of the carboxyl groups is converted into the substituted methyl ester group by the method described above, and then at least one of the carboxyl groups is converted into

By reacting with an epoxy compound, a polymer having a substituted methyl ester group and a hydroxyl group is obtained. Then, the substituted methyl ester group and the substituted acetoxy group are combined by the same method as in the above case. A polymer having the same can be obtained.

For example, the carboxyl group-containing polyurethane polymer used at that time is prepared from a carboxyl group-containing diol represented by 2,2-dimethylolpropionic acid and the like and a diisocyanate by a known and conventional method. You can get

Alternatively, a hydroxyl group-containing polyurethane resin obtained by a known and commonly used method from diisocyanates and the like and polyols may be mixed with various acid anhydrides such as succinic anhydride, phthalic anhydride or trimellitic anhydride. It can also be obtained by reacting things.

Similarly, the carboxyl group-containing polyester polymer is phthalic acid, hexahydrophthalic acid,
Various polycarboxylic acids represented by isophthalic acid, adipic acid, maleic acid or dimer acid,

Various polyhydric alcohols represented by ethylene glycol, propylene glycol, neopentyl glycol, trimethylol propane, etc. are added to polyhydric alcohols.

It can be obtained by condensation under the condition that the acid component becomes excessive, or by adding an acid anhydride compound such as trimellitic acid to the hydroxyl group of the hydroxyl group-containing polyester resin. Anything can be used.

Thus, as described above, the equivalent ratio of the substituted methyl ester group introduced into the polymer (A) obtained by various methods to the substituted acetoxy group is such as curability. From the aspect, it is appropriate to set within the range of 1: 0.1 to 1:10, and further within the range of 1: 0.2 to 1: 5,

The amount of the functional group introduced is appropriately in the range of about 50 mmol to about 7.6 mol of the total amount of both functional groups per 1,000 g (g) of the polymer solid content. However, the number average molecular weight of the polymers (A) thus obtained is in the range of about 300 to about 300,000, more preferably about 500 to about 100,000. Appropriate.

Next, the above-mentioned compound (B) refers to a compound having at least two substituted methyl ester groups represented by the general formula [I] in one molecule, and
It refers to those having no substituted acetoxy group, and if only representative ones among them are exemplified, various polycarboxylic acids such as dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid are given. Of the substituted methyl ester derivative compound, or 2 per molecule.
A vinyl polymer having at least one substituted methyl ester group,

Further, there are polyurethane-based, polyester-based or polyether-based polymers or alkyd resins each having two or more substituted methyl ester groups in one molecule.

Among the compounds as mentioned above, the compounds corresponding to the case of are prepared by, for example, succinic acid, oxalic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid. , Various dicarboxylic acids such as reaction products of terephthalic acid or dimer acid, maleic anhydride or succinic anhydride, and oxyacid;

Various tricarboxylic acids typified by propanetricarboxylic acid and trimellitic acid; various tetracarboxylic acids typified by butanetetracarboxylic acid and pyromellitic acid, and the like. The compound having two or more carboxyl groups in the molecule may be reacted with the compound represented by the above general formula [III] and / or [IV] in the same manner as described above,

As the compounds thus obtained, only typical ones will be exemplified. Adipic acid bismethoxymethyl ester, succinic acid bisbutoxymethyl ester, propanetricarboxylic acid trisethoxymethyl ester or butanetetracarboxylic acid tetrakis For example, methoxymethyl ester.

Then, in order to prepare a compound corresponding to the above case, it can be obtained by homopolymerizing vinyl monomers having a substituted methyl ester group as described above, or , Can also be obtained by copolymerizing these with other vinyl-based monomers that can be copolymerized,

Furthermore, a vinyl-based polymer having two or more carboxyl groups in one molecule is added to the above-mentioned general formula [I
The compound represented by II] and / or [IV] may be reacted as described above.

Similarly, in order to prepare a compound corresponding to the above-mentioned case, a polyester-based polymer, a polyurethane-based polymer having two or more carboxyl groups in one molecule, For the polyether polymer or alkyd resin, the above-mentioned general formula [II
The compound represented by I] and / or [IV] may be converted to the substituted methyl ester group by reacting as described above.

In the case where two or more compounds (B) having the substituted methyl ester group in one molecule thus obtained are polymers, the introduction amount (introduction ratio) of the functional group. Is suitable, within a range of about 80 millimoles to about 7.6 moles per 1,000 grams (g) of polymer solids,

When the compound (B) having the substituted methyl ester group is a polymer, the number average molecular weight of such a polymer is about 300 to
Within the range of about 300,000, more preferably,
A range of about 500 to about 100,000 is suitable.

Next, the above-mentioned compound (C) having at least two substituted acetoxy groups in one molecule means at least two substituted acetoxy groups represented by the general formula [II] in one molecule. A compound having a group and not having a substituted methyl ester group represented by the general formula [I] is referred to, and if only representative examples of the compound are exemplified, a polyvalent compound These include various low molecular weight compounds and various polymers derived from alcohols.

Of the above compounds (C), only typical examples of the so-called low molecular weight compounds to be used for preparing the so-called low molecular weight compounds from the polyhydric alcohols will be given. , A variety of alkanediols represented by ethylene glycol, propylene glycol, propanediol, butanediol, hexanediol;

Alternatively, various cycloalkane diols such as those represented by cyclohexanediol, methylcyclohexanediol; various aryl type diols such as represented by bisphenol A; various aryl diols such as represented by trimethylolpropane. Triels;

Further, various polyols represented by pentaerythritol and sorbitol;
Furthermore, lactone adducts of these various polyols are also included.

To prepare the compound (C) from such polyhydric alcohols, the above polyhydric alcohols and the substituted acetic acid derivative represented by the above-mentioned general formula [V] are used. It can be prepared by reacting with a compound or diketene.

Further, if only representative ones of the polymers of the compound (C) are exemplified,
Examples thereof include vinyl polymers, polyester resins, polyurethane resins, alkyd resins, epoxy ester resins, and polyether resins.

To prepare a vinyl-based polymer of such polymers, a substituted acetoxy group-containing vinyl-based monomer as described above is (co) polymerized or a hydroxyl group-containing vinyl-based polymer prepared in advance. Can be prepared by converting into a substituted acetoxy group-containing polymer by the method as described above.

In order to prepare polymers other than the vinyl polymer, which belong to the compound (C), the component (C) is prepared from the above-mentioned polyhydric alcohols. In the same manner as described above, various hydroxyl group-containing polymers may be converted into the substituted acetoxy group-containing polymer.

When the compound (C) having two or more substituted acetoxy groups in one molecule thus obtained is a polymer, its number average molecular weight is about 30.
0 to a large range of about 300,000, more preferably about 500 to about 100,000 is suitable,

Furthermore, the amount of the functional group introduced is appropriately in the range of about 50 mmol to about 4.6 mol per 1,000 g (g) of the polymer solid content.

Continuing, each of the above mentioned,
The curable composition of the present invention obtained by using the components (A), (B) and (C) will be described.

First, the component (A) has both a substituted methyl ester group represented by the general formula [I] and a substituted acetoxy group represented by the general formula [II] as functional groups that react with each other. Therefore, the curable composition of the present invention can be formed by using the component (A) alone, which is itself self-curable.

Then, in order to obtain the curable composition of the present invention from the components (B) and (C), these components (B) and (C) are substituted with the substituted methyl ester in the component (B). The equivalent ratio of the group and the substituted acetoxy group in the component (C) is about 1: 0.1.
Within a range of about 1:10, preferably 1:
It may be blended within a range of 0.2 to 1: 5, but when both (B) and (C) are low molecular weight compounds, one is trifunctional or more. There is.

Further, the curable composition of the present invention is a composition composed of both components (A) or (B) and (C) as described above, and a curing catalyst (D). It is also possible to use it in a form in which the following components are mixed.

Among them, first, with the above-mentioned (A),
In order to prepare the curable composition of the present invention from both components (D) and (D), 100 g (g) of the total solid content (total solid content) of component (A) described above is used. The amount of the atomic group or group that exhibits the catalytic effect of the component (D) is about 3
The component (D) may be blended in a proportion such that it is from 00 micromol to a large amount of about 60 mmol, preferably from about 350 micromol to about 50 mmol,

Next, in order to obtain the curable composition of the present invention from the above-mentioned three components (B) and (C) and (D), the components (B) and (C) are required. And, as mentioned above,
An atomic group that exerts the catalytic effect of the component (D) with respect to 100 g (g) of the total solid content (total solid content) of both components (B) and (C) after being mixed. Alternatively, the component (D) may be blended in a ratio such that the amount of the group is about 300 μmol to about 60 mmol, preferably about 350 μmol to about 50 mmol.

As the curing catalyst (D), various curing catalysts such as BF ₃ or its ether complex, titanium tetrachloride, tin dichloride, tin tetrachloride, gallium trichloride, aluminum trichloride and zirconium tetrachloride can be used. Lewis acids;
Various metal triflate salts such as represented by silver trifluoromethanesulfonate, tin trifluoromethanefurphonate;

Methanesulfonic acid, propanesulfonic acid,
Toluene sulfonic acid, dodecylbenzene sulfonic acid,
Various organic sulfonic acids such as naphthalenedisulfonic acid, trifluoromethanesulfonic acid or trichloromethanesulfonic acid; or various phosphoric acid esters such as methylphosphoric acid, isopropylphosphoric acid, diisopropylphosphoric acid, tributylphosphoric acid; butyl methanesulfonate, Propyl toluene sulfonate, toluene sulfonic acid 2
-Esters of various organic sulfonic acids such as those listed above, such as hydroxycyclohexyl;

Alternatively, hydrochloric acid, sulfuric acid, phosphoric acid, metaphosphoric acid,
In addition to various inorganic acids such as pyrophosphoric acid, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 1,5-diazabicyclo [4.3.
0] nonene-5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), triethylamine, N-methylpiperidine, dimethylaminoethanol, diethylamine, aminoethanol, and various other organic amines;

In addition to various salts obtained from the above-listed various acids and the above-listed various bases and various organic amines, BF ₄ ,
PF ₆ , SbF _{6 and the} like as counter anions,
Various types such as tetramethylammonium salt, tetraethylammonium salt, trimethyl (2-hydroxypropyl) ammonium salt, tetrabutylammonium salt, tetrakis (hydroxymethyl) ammonium salt, cyclohexyltrimethylammonium salt, o-trifluoromethylphenyltrimethylammonium salt Quaternary ammonium salts of

Alternatively, a tetramethylphosphonium salt,
Tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, trimethyl (2
Various phosphonium salts such as -hydroxypropyl) phosphonium salt, triphenylammonium salt, benzyltriphenylphosphonium salt;

Alternatively, a benzyldimethylsulfonium salt, a benzyltetramethylenesulfonium salt,
Such as 2-butenyl tetramethylene sulfonium salt,
Examples include various sulfonium salts.

Further, the curable composition of the present invention can be used as it is as a clear composition,
Further, it can be used as a coloring composition in a form in which a pigment is blended.

Furthermore, the composition of the present invention contains, if necessary, various light stabilizers, antioxidants or pigments such as a leveling agent, an ultraviolet absorber and the like, as represented by a hindered amine type light stabilizer. Various well-known and commonly used additives such as a dispersant can also be incorporated.

Furthermore, within a range that does not deviate from the object of the present invention, or within a range that does not impair the features and effects of the present invention, various known curing agents may be included. It is possible to use the curable compositions of the invention.

Any curing agent may be used as the curing agent, as long as it is capable of reacting with the above-mentioned substituted acetoxy group. If you stay,

Various aromatic diisocyanates such as those typified by tolylene diisocyanate; various aliphatic diisocyanates such as typified by hexamethylene diisocyanate; or such as typified by isophorone diisocyanate, Various diisocyanates or polyisocyanates, including various alicyclic (cycloaliphatic) diisocyanates; or various isocyanate prepolymers obtained from these di- or polyisocyanates;

Furthermore, various polyisocyanate compounds such as those di- or polyisocyanates or block isocyanates derived from the above isocyanate prepolymers, etc., Is various amino resins such as melamine resin and urea resin,
Furthermore, it is an epoxy resin or the like.

The curable composition of the present invention thus obtained may be in various forms such as an organic solvent solution type, an organic solvent dispersion type or a solventless solid type depending on its use. , Can be used.

When the curable composition of the present invention thus obtained is used in the form of containing no catalyst,
In the temperature range of about 180 to about 250 ° C., depending on the content of the functional group in each of the components (A) or (B) and (C). By baking for about 30 seconds to about 2 hours, it is possible to provide a fully cured cured film having excellent acid resistance and the like.

On the other hand, when the curable composition of the present invention is used in the form containing the curing catalyst (D),
Depending on the content of the functional group and the amount of catalyst in each of the components (A) and (D),

Further, depending on the content of the functional group and the amount of catalyst in each of the three components of the component (B), the component (C) and the component (D), a temperature of about 60 to about 250 ° C.
By baking in a temperature range of about 30 seconds to about 2 hours, it is possible to provide a fully cured cured film having excellent acid resistance.

Furthermore, it is possible to cure at room temperature by properly selecting the type of catalyst and setting the optimum amount of the catalyst to be used. By drying and curing for about 8 days, it is possible to obtain a coating film which is sufficiently cured and is particularly excellent in acid resistance.

Furthermore, with respect to the component (A), (B)
Even in the case of the composition in which the component or the component (C) is added,
Alternatively, even in the case of a composition in which both components (B) and (C) are added, regardless of the presence or absence of the component (D), the curable composition of the present invention can be successfully used. Of course.

[0128]

EXAMPLES Next, the present invention will be explained more concretely by reference examples, examples and comparative examples, but the present invention is by no means limited to these examples. Absent. In the following, all parts and% are based on weight unless otherwise specified.

Reference Example 1 [Preparation Example of Polymer (A) Containing Substituted Methyl Ester Group and Substituted Acetoxy Group]

In a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas introducing tube, 1 part of xylene was added.
60 parts were charged and the temperature was raised to 105 ° C. under a nitrogen atmosphere.

Then, at the same temperature, 20 parts of styrene, n
-32 parts of butyl methacrylate, 58 parts of n-butyl acrylate, 34 parts of methoxymethyl methacrylate and 56 parts of 2- (acetoacetoxy) ethyl methacrylate, 4 parts of tert-butyl peroxyoctoate (TBO) and tert. -Part of butyl peroxybenzoate (TBZ) and 40 parts of n-butyl acetate.
The mixture consisting of 1 part and 3 parts was added dropwise over 3 hours.

Even after the completion of dropping, the temperature is kept at the same temperature for 15 hours, the nonvolatile content (N.V.) is 53%, and
A solution of the target polymer having a number average molecular weight (Mn) of 6,800 was obtained. Hereinafter, this is abbreviated as a polymer (A-1).

Reference Example 2 (same as above) A reactor similar to that of Reference Example 1 was charged with 160 parts of xylene and heated to 100 ° C. under aeration of nitrogen gas.

Then, at the same temperature, 20 parts of styrene, n
-94 parts of butyl methacrylate, 16 parts of n-butyl acrylate, 34 parts of methoxymethyl methacrylate and 36 parts of 2- (acetoacetoxy) ethyl methacrylate, 4 parts of TBO and 1 part of TBZ, and n-butyl acetate. 40 parts of the above was added dropwise over 3 hours.

After the completion of dropping, the temperature was kept at the same temperature for 15 hours to obtain N.V. V. Is 54% and Mn is 6,7
A solution of the target polymer No. 00 was obtained. Hereinafter, this is abbreviated as a polymer (A-2).

Reference Example 3 (Same as above) A reaction vessel similar to that of Reference Example 1 was charged with 160 parts of xylene and heated to 100 ° C. under aeration of nitrogen gas.

Then, at the same temperature, 20 parts of styrene, n
-50 parts of butyl methacrylate, 56 parts of n-butyl acrylate, 38 parts of ethoxymethyl acrylate and 36 parts of 2- (acetoacetoxy) ethyl methacrylate, 4 parts of TBO and 1 part of TBZ, acetic acid n
-A mixture of 40 parts of butyl was added dropwise over 3 hours.

After the completion of dropping, the temperature was kept at the same temperature for 15 hours to obtain N.V. V. Is 53% and Mn is 6,9
A solution of the target polymer No. 00 was obtained. Hereinafter, this is abbreviated as a polymer (A-3).

Reference Example 4 (Same as above) A reaction vessel similar to that of Reference Example 1 was charged with 160 parts of xylene and heated to 100 ° C. under aeration of nitrogen gas.

Then, at the same temperature, 50 parts of styrene, n
-36 parts of butyl methacrylate, 24 parts of n-butyl acrylate, 54 parts of bismethoxymethyl fumarate and 36 parts of 2- (acetoacetoxy) ethyl methacrylate, 4 parts of TBO and 1 part of TBZ, acetic acid n A mixture of 40 parts of -butyl was added dropwise over 5 hours.

After the completion of dropping, the temperature was kept at the same temperature for 15 hours to obtain N.C. V. Is 52% and Mn is 6,5
A solution of the target polymer of No. 00 was obtained. Hereinafter, this is abbreviated as a polymer (A-4).

Reference Example 5 (same as above) A reaction vessel similar to that of Reference Example 1 was charged with 160 parts of xylene and heated to 100 ° C. under aeration of nitrogen gas.

Then, at the same temperature, 20 parts of styrene, n
-88 parts of butyl methacrylate, 16 parts of n-butyl acrylate, 40 parts of 2- (methoxymethoxycarbonyl) ethyl acrylate and 36 parts of 2- (acetoacetoxy) ethyl methacrylate, 4 parts of TBO and 1 part of TBZ. And 40 parts of n-butyl acetate were added dropwise over 5 hours.

After the completion of dropping, the temperature was kept at the same temperature for 15 hours to obtain N.C. V. Is 53% and Mn is 7,1
A solution of the target polymer of No. 00 was obtained. Hereinafter, this is abbreviated as a polymer (A-5).

Reference Example 6 (Same as above) A reaction vessel similar to that of Reference Example 1 was charged with 160 parts of xylene and heated to 100 ° C. under aeration of nitrogen gas.

Then, at the same temperature, 20 parts of styrene, n
-32 parts of butyl methacrylate, 66 parts of n-butyl acrylate, 34 parts of methoxymethyl methacrylate and 40 parts of 2- (acetoacetoxy) butyl methacrylate, 4 parts of TBO and 1 part of TBZ, and n-butyl acetate. 40 parts of the above was added dropwise over 5 hours.

After the completion of dropping, the temperature was kept at the same temperature for 15 hours to obtain N.V. V. To obtain a solution of the target polymer having a content of 52%. Hereinafter, this is abbreviated as a polymer (A-6).

Reference Example 7 [Preparation Example of Substituted Methyl Ester Group-Containing Polymer (B)] 160 parts of xylene was charged in the same reaction vessel as in Reference Example 1 and heated to 110 ° C. in a nitrogen atmosphere.

Then, at the same temperature, 18 parts of styrene, n
-A mixture of 100 parts of butyl methacrylate, 36 parts of n-butyl acrylate and 46 parts of methoxymethyl methacrylate, 4 parts of TBO and 1 part of TBZ and 40 parts of xylene was added dropwise over 5 hours. did.

After the completion of dropping, the temperature was kept at the same temperature for 15 hours to obtain N.V. V. Is 53% and Mn is 6,6
A solution of the target polymer No. 00 was obtained. Hereinafter, this is abbreviated as a polymer (B-1).

Reference Example 8 (same as above) A reaction vessel similar to that of Reference Example 1 was charged with 280 parts of xylene and heated to 110 ° C. under a nitrogen atmosphere.

Then, at the same temperature, 16 parts of styrene, n
-32 parts of butyl methacrylate, 60 parts of n-butyl acrylate and 9 parts of methoxymethyl methacrylate
A mixture of 2 parts, 12 parts of TBO and 2 parts of TBZ, and 20 parts of xylene was added dropwise over 5 hours.

After the completion of dropping, the temperature was kept at the same temperature for 15 hours to obtain N.V. V. Is 42% and Mn is 3,0
A solution of the target polymer of No. 00 was obtained. Hereinafter, this is abbreviated as a polymer (B-2).

Reference Example 9 (same as above) In a 2 liter autoclave, 184 parts of the compound of the formula [VI],

[0155]

[Chemical 19]

288 parts of ethyl vinyl ether and 480 parts of chlorotrifluoroethylene, 640 parts of methyl isobutyl ketone, and 2,2'-azobis (2,4
-Dimethylvaleronitrile) 19.2 parts,

4-Hydroxy-1,2,2,6,6-pentamethylpiperidine and 19.2 parts of an ester of sebacic acid (molar ratio = 2: 1) were charged, and the mixture was stirred at 60 ° C. for 2 hours.
After carrying out a polymerization reaction for 0 hours, N. V. Is 58%
And a solution of the target polymer having Mn of 22,000 was obtained. Hereinafter, this is abbreviated as a polymer (B-3).

Reference Example 10 [Preparation Example of Substituted Acetoxy Group-Containing Polymer (C)] In a reaction vessel similar to that of Reference Example 1, 160 parts of xylene was charged, and the temperature was raised to 110 ° C. under aeration of nitrogen gas. Warmed.

Then, at the same temperature, 20 parts of styrene, n
-A mixture of 60 parts of butyl methacrylate, 46 parts of n-butyl acrylate and 76 parts of 2- (acetoacetoxy) ethyl methacrylate, 4 parts of TBO and 1 part of TBZ and 40 parts of xylene for 3 hours. It was dripped over.

After the completion of dropping, the temperature was kept at the same temperature for 15 hours to obtain N. V. Is 52% and Mn is 6,8
A solution of the target polymer of No. 00 was obtained. Hereinafter, this is abbreviated as a polymer (C-1).

Reference Example 11 (Same as above) A reaction vessel similar to that of Reference Example 1 was charged with 160 parts of xylene and heated to 110 ° C. under aeration of nitrogen gas.

Then, at the same temperature, 20 parts of styrene, n
A mixture of 50 parts butyl methacrylate, 46 parts n-butyl acrylate and 76 parts 2- (acetoacetoxy) butyl methacrylate, 4 parts TBO and 1 part TBZ and 40 parts xylene for 3 hours. It was dripped over.

After the completion of dropping, the temperature was kept at the same temperature for 15 hours to obtain N.V. V. To obtain a solution of the target polymer having a content of 53%. Hereinafter, this is abbreviated as a polymer (C-2).

Reference Example 12 (Preparation Example of Hydroxyl Group-Containing Polymer for Control) 240 parts of xylene was charged in the same reaction vessel as in Reference Example 1 and heated to 110 ° C. under aeration of nitrogen gas.

Then, at the same temperature, 105 parts of styrene,
580 parts of n-butyl methacrylate, 120 parts of lauryl mecrylate and 243 parts of 2-hydroxyethyl methacrylate, and azobisisobutyronitrile (A
A mixture consisting of 21 parts of IBN) and 210 parts of xylene was added dropwise over 5 hours.

After completion of the dropping, the temperature was kept at the same temperature for 15 hours, and then xylene was added.
N. V. Of 47% and a Gardner viscosity at 25 ° C. of UV was obtained as a target polymer solution. Hereinafter, this is abbreviated as resin (Ref-1).

Examples 1 to 12 Component (A); component (B) and component (C), and component (D) together with thinner were used in the proportions shown in Table 1. , N. by blending in a conventional manner. V. A variety of clear compositions having a content of 47% were prepared.

Incidentally, in Table 1, respectively,
The compounds used as the components (B), (C) and (D) are as follows.

(B-4) ... Adipic acid bis (methoxymethyl) ester (C-3) ... Trimethylolpropane triacetoacetate (D-1) ... Monopropylphosphoric acid (D-2) ……… Dodecylbenzene sulfonic acid

Next, each of the clear compositions thus obtained was coated with a polyester-melamine-based paint in advance, baked, and then water-ground to obtain a coated steel plate. Under the conditions shown in the same table, baking is performed individually to obtain a film thickness of 35.
A cured coating film of micron (μm) was obtained.

After that, the respective coating films thus obtained were compared and examined for various characteristics or various performances. The results are shown together in the same table.

Example 13 A composition prepared by mixing the components (A) and (D) in the proportions shown in Table 1 was coated on the above-mentioned coated steel sheet, and at room temperature, It was allowed to cure for 8 days.
With respect to the coating film thus obtained, various characteristics and various performances were evaluated. The results are shown together in the same table.

Comparative Example 1 Hydroxyl group-containing polymer (Ref-1) obtained in Reference Example 13
Was blended in a conventional manner as shown in Table 1 to prepare a control acrylic melamine-based composition.

Subsequently, a cured coating film was prepared in the same manner as in Examples 1 to 12, and various characteristics and performances were compared and examined. Summarize those results,
Shown in the same table.

[L-117-60] in the table is
It is an abbreviation for "Super Beckamine L-117-60" and is a butyl etherified melamine resin (N.V. = 60%) manufactured by Dainippon Ink and Chemicals, Inc.

[0176]

[Table 1]

<< Footnotes in Table 1 >> 1) "Thinner resistance" ... Xylene rubbing 10
The appearance of the coating film after 10 times (10 reciprocations) was visually determined.

2) "Acid resistance" ... 1 for coating film
Open 0.1 ml of 0% sulfuric acid aqueous solution.
After spotting and heating at 60 ° C. for 30 minutes, the coating film was washed with water, and the appearance of the coating film was visually evaluated.

[0179]

[Table 2]

[0180]

[Table 3]

[0181]

[Table 4]

[0182]

[Table 5]

[0183]

As is clear from the above results, the curable composition of the present invention comprising a polymer obtained by introducing a specific substituted methyl ester group and a specific substituted acetoxy group. In particular, it provides a novel and extremely highly practical cured coating with excellent acid resistance.

Claims (12)

[Claims] 1. In one molecule, at least one compound represented by the general formula [I] -CO ₂ CH ₂ OX [I] [wherein X represents a monovalent organic group] To do. ] And at least one of the general formula [II] -O ₂ CCHYCO-Z [II] [wherein Y is a hydrogen atom or a monovalent organic group] And Z represents a monovalent organic group. ] The curable composition characterized by containing the polymer (A) which also has the substituted acetoxy group shown by these as an essential film-forming component. 2. In one molecule, at least two compounds represented by the general formula [I] embedded image --CO ₂ CH ₂ OX [I] [wherein, X in the formula represents a monovalent organic group. To do. ] The compound (B) having a substituted methyl ester group represented by the formula [I] and at least two compounds represented by the general formula [I]
I] embedded image _{-O 2 CCHYCO-Z [II]} [ However, Y in the formula is intended to represent a hydrogen atom or a monovalent organic group, Z is assumed to represent a monovalent organic group. ] The compound (C) which has a substituted acetoxy group shown by these is contained as an essential film formation component, The curable composition characterized by the above-mentioned. 3. In one molecule, at least one compound represented by the general formula [I]: —CO ₂ CH ₂ OX [I] [wherein, X in the formula represents a monovalent organic group. To do. ] And at least one of the general formula [II] -O ₂ CCHYCO-Z [II] [wherein Y in the formula is a hydrogen atom or a monovalent organic group] And Z represents a monovalent organic group. ] The curable composition characterized by containing the polymer (A) which also has the substituted acetoxy group shown by these, and the curing catalyst (D) as an essential component. 4. In one molecule, at least two compounds represented by the general formula [I]: —CO ₂ CH ₂ OX [I] [wherein, X in the formula represents a monovalent organic group. To do. ] The compound (B) having a substituted methyl ester group represented by the formula [I] and at least two compounds represented by the general formula [I]
I] embedded image _{-O 2 CCHYCO-Z [II]} [ However, Y in the formula is intended to represent a hydrogen atom or a monovalent organic group, Z is assumed to represent a monovalent organic group. ] The compound (C) which has the substituted acetoxy group shown by these, and the curing catalyst (D) are contained as an essential component, Curable composition characterized by the above-mentioned. 5. The above-mentioned general formula [I]: —CO ₂ CH ₂ OX [I] [wherein, X in the formula represents a monovalent organic group. X is a chain, cyclic or branched alkyl group having 1 to 10 carbon atoms.
The curable composition according to any one of to 4. 6. The above-mentioned general formula [II] —O ₂ CCHYCO-Z [II] [wherein Y represents a hydrogen atom or a monovalent organic group, and Z is 1 Shall represent a valent organic group. ], Y is a hydrogen atom or a chain, cyclic or branched alkyl group having 1 to 10 carbon atoms, while Z is a chain having 1 to 10 carbon atoms, 2. A cyclic or branched alkyl group.
The curable composition according to any one of to 4. 7. The curable composition according to claim 1, wherein the substituted acetoxy group is an acetoacetoxy group. 8. The curable composition according to claim 1 or 3, wherein the polymer (A) is a vinyl polymer. 9. The curable composition according to claim 2, wherein the compound (B) is a vinyl polymer. 10. The curable composition according to claim 2, wherein the compound (C) is a vinyl polymer. 11. The curable composition according to claim 8, wherein the vinyl polymer is an acrylic polymer. 12. The curable composition according to claim 8, wherein the vinyl polymer is a fluoroolefin polymer.