JPH1045993A - Curable resin composition and paint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the weather resistance of a curable acrylic resin composition and a paint having a Michael addition reaction as a crosslinking mechanism. SOLUTION: (a) a component having a plurality of α, β-unsaturated carbonyl groups in the molecule, (b) an acrylic polymer having a plurality of pendant malonic ester groups in the molecule, and (c) a Michael reaction. Curable resin compositions and paints containing a promoting catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION The Michael addition reaction in which an active methylene group is added to a polarized double bond such as an α, β-unsaturated carbonyl group does not generate a reaction by-product, and a newly formed bond is formed. Since it is a chemically stable carbon-carbon bond, it has been applied to a crosslinking reaction of a curable resin composition such as a paint. Representative prior art includes the following patent documents. U.S. Pat. No. 4,408,018 U.S. Pat. No. 4,602,061 U.S. Pat. No. 5,017,649 U.S. Pat. No. 5,084,536 EP-A-0448154 JP-A-1-121341 (corresponding to EP0310011) JP-A-1-204919 (corresponding to EP0326723)

[0002] Active methylene compounds which can be used in the Michael addition reaction are derivatives of acetoacetic acid, cyanoacetic acid and malonic acid. In order to use the Michael addition reaction for a crosslinking reaction of a resin, a compound or polymer having a plurality of active methylene groups in a molecule must be used. The acrylic monomer having an acetoacetyl group is 2-acrylic.
Hydroxyethyl acrylate (HEA), and 2-
Active methylene group-containing acrylic polymers used in many prior arts can be prepared relatively easily by reacting diketene with a hydroxylalkyl (meth) acrylate such as hydroxyethyl methacrylate (HEMA). A polymer of an acrylic monomer containing these acetoacetoxy groups or a modified acrylic polyol obtained by reacting an acrylic polyol with diketene in the same manner.

[0003] However, it has been found that the use of an acrylic polymer having a malonate group instead of an acetoacetoxy group in a coating material significantly improves the weather resistance of the coating film.

Since malonic acid is a dibasic acid, it can be incorporated into the polyester main chain and crosslinked by Michael reaction. U.S. Pat. No. 4,602,061 discloses a polyurethane, polyester, polyacrylate, epoxy, polyamide or polyvinyl resin having a malonate group in a main chain and / or a side chain, and an .alpha.,. Beta.-ethylenically unsaturated carbonyl group-containing component. And a two-part cured resin composition containing a strong basic catalyst. However, there is a specific disclosure of a malonate group-containing polyacrylate in addition to an acrylic-modified polyester obtained by reacting a polyester containing malonic acid as an acid component with HEA or a diisocyanate compound added with HEMA by reaction with one isocyanate group. There is no.

JP-A-3-206012 discloses a malonate group-containing acrylic monomer and a polymer thereof as a dental material having low odor, low stimulus and low water absorption of the polymer. However, as is clear from the fact that they do not contain a catalyst and that monomers containing homologs such as succinic acid and adipic acid can be used for the same purpose, these monomers and polymers have an activity of Michael reaction. It is not intended to be used as a methylene component.

Accordingly, there is a need for a curable resin composition and a coating material utilizing the Michael reaction in which the active methylene component is an acrylic polymer having excellent weather resistance.

Disclosed in the present invention is an acrylic polymer having a plurality of pendant groups containing a malonate group in a molecule instead of an acrylic polymer having a plurality of pendant groups containing a plurality of acetoacetyl groups in a molecule. By using the resin composition as an active methylene component, a curable resin composition and a paint having excellent weather resistance can be provided.

Accordingly, the present invention provides (a) a component having a plurality of α, β-unsaturated carbonyl groups in the molecule, (b) an acrylic polymer having a plurality of malonic ester pendant groups in the molecule, and (c) A) providing a curable resin composition comprising a catalyst that promotes the Michael reaction;

The present invention also provides a paint containing the curable resin composition as a vehicle.

Preferred Embodiment (a) Component (a) The component (a) is a compound or polymer having a plurality of alkenecarbonyl bonds having a double bond between the α and β carbons in the molecule. Typical examples of such compounds are (meth) acrylates of polyhydric alcohols, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, peritaerythritol tetra (meth) acrylate and polyester acrylate resins.

Α, β- such as fumaric acid and maleic acid
Unsaturated polyesters containing unsaturated dicarboxylic acids can also be used as component (a). Unsaturated polyesters are used in large quantities as molding resins such as FRP, and as is well known, α, β-unsaturated dicarboxylic acids such as maleic anhydride and fumaric acid, and optionally phthalic anhydride, isophthalic acid, terephthalic acid and the like. Acid components consisting of other polycarboxylic acids such as acid, adipic acid, sebacic acid and trimellitic acid, and ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, It is synthesized by a polycondensation reaction with a polyhydric alcohol such as methylolpropane, glycerin, and pentaerythritol.

An example of another resin which can be used as the component (a) is an epoxy acrylate resin. This can be synthesized by, for example, ring-opening addition of an epoxy ring of an epoxy resin such as a bisphenol type or a novolak type by reaction with (meth) acrylic acid. As another example, a hydroxy group-containing acrylic resin is obtained by an addition reaction of a polyisocyanate compound such as isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate or a urethane prepolymer thereof with 2-hydroxyethyl (meth) acrylate. There is a urethane acrylate resin.

The acrylic resin containing an α, β-unsaturated carbonyl group can be used to open the epoxy ring with (meth) acrylic acid,
It can be synthesized using a reaction such as acylation of a hydroxyl group with (meth) acrylic acid. For example, an epoxy group-containing acrylic resin obtained by copolymerization of an epoxy group-containing acrylic monomer such as glycidyl (meth) acrylate with another acrylic monomer and / or a non-acrylic ethylenically unsaturated monomer may be used as (meth) It can be synthesized by reacting acrylic acid. Acrylic monomers that can be used for copolymerization include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, 2-ethylhexyl, lauryl, phenyl, benzyl and 2-hydroxyethyl of acrylic acid or methacrylic acid. Acrylamide, methylenebisacrylamide, acrylonitrile, and the like, and non-acrylic resins, 2-hydroxypropyl ester, PCL-FM-1 (addition product of 2-hydroxyethyl methacrylate and polycaprolactone, manufactured by Daicel Chemical Industries, Ltd.), and the like. Examples of the system monomer include styrene, α-methylstyrene, itaconic acid, maleic acid, and vinyl acetate.

The carboxy group-containing acrylic resin may be reacted with an epoxy group-containing acrylic monomer such as glycidyl (meth) acrylate. The carboxy group-containing acrylic resin can be synthesized by copolymerizing a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, and itaconic acid with the above-mentioned acrylic monomer and, if necessary, a non-acrylic monomer.

Acrylic polyols can be subjected to α, β-acylation by acrylic acid or methacrylic acid or a reactive derivative thereof (such as chloride), or by transesterification with acrylic or methacrylic lower alkyl esters such as methyl esters. Unsaturated carbonyl groups can be introduced. Acrylic polyol is
Hydroxyl-containing acrylic monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, PLCFM-1 and / or other acrylic monomers and / or
Alternatively, it can be synthesized by copolymerizing with a non-acrylic monomer.

Other components (a) which can be used include polyether acrylate resins such as polyethylene glycol di (meth) acrylate, and poly (organosiloxanes such as polydiorganosiloxanes having 3-methacryloyloxypropyl groups at both ends. ) An acryloyl group-containing silicone oligomer and an α, β-unsaturated carbonyl-containing fluororesin.

When the above compound or resin is used as the component (a), the molecular weight is 400 to 100,000, preferably 600 to 10,000, and the double bond equivalent is 80 to 1
0000, preferably 100 to 1,000. In addition, in this specification, equivalent means the molecular weight per functional group.

Component (b) The component (b) is obtained by copolymerizing an acrylic monomer bonded with a malonic ester with the acrylic monomer and / or non-acrylic monomer described above for the acrylic resin of the component (a). Can be manufactured.

The acrylic monomer bonded to the malonic ester may be a monomer disclosed in JP-A-3-206012, but is not limited thereto. The malonic ester-bonded acrylic monomer that can be used can be represented by the following formula.

[0020]

Embedded image

In the formula, R ¹ is hydrogen or a methyl group, R ² is an alkylene group having 2 to 6 carbon atoms, R ³ is an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 10. Preferred monomers are those in the above formula where R ² = —CH ₂ CH ₂ —, n =
A monomer in which 1, R ⁴ = alkyl. These monomers can be produced by a transesterification reaction between a hydroxyalkyl (meth) acrylate such as HEA or HEMA and a dialkyl malonate.

Further, an acrylic monomer obtained by transesterification of the mono (meth) acrylate of polyoxyalkylene glycol obtained by ring-opening addition polymerization of ethylene oxide or propylene oxide or tetrahydrofuran with the above-mentioned dialkyl malonate ( n> 1) can be used.

The acrylic monomers that can be used in the copolymerization include acrylic acid or methacrylic acid methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, and the like.
2-ethylhexyl, lauryl, phenyl, benzyl,
Examples include 2-hydroxyethyl, 2-hydroxypropyl ester, acrylamide, methylenebisacrylamide, and acrylonitrile, and non-acrylic monomers include styrene, α-methylstyrene, itaconic acid, maleic acid, and vinyl acetate.

The polymer of the malonic ester-bonded acrylic monomer has a number average molecular weight of 1,000 to 50,000, especially 1,000 to 10,000, and an active hydrogen equivalent of an active methylene group of 100 to 10,000, especially 150 to 10,000. 5,000
It is preferable to have

Component (c) As is well known, in the Michael reaction, two carbonyl groups adjacent to methylene increase the acidity of the methylene proton and usually require the presence of a strong base to form an enolate anion. I do. In the present invention, of course, a strong base can be used as a catalyst.

Strong base catalysts include alkali metal hydroxide compounds (eg, sodium hydroxide, potassium hydroxide, etc.), alkali metal alkoxides (eg, sodium methoxide, potassium ethoxide, etc.), and quaternary ammonium hydroxides (eg, tetrabutyl hydroxide). Ammonium hydroxide, benzyltrimethylammonium hydroxide, etc.), quaternary ammonium carbonates (eg, tetrabutylammonium carbonate, benzyltrimethylammonium carbonate, etc.), tertiary amines (eg, diazabicyclooctane, also known as DABCO), guanidines and amidines ( For example, tetramethylguanidine, 1,8-diazabicyclo [5.4.0]
Undecene-7, diazabicyclo [4.3.0] nonene-5, and the like, and tertiary phosphine (such as triphenylphosphine). Two or more of these strong base catalysts may be used in combination.

Of the quaternary ammonium salts, those whose counter anion is fluorine or tetrahydroborate
Tertiary ammonium salts such as tetrabutylammonium fluoride, benzyltrimethylammonium fluoride and the corresponding tetrahydroborate, as well as strong bases, are themselves catalysts for the Michael reaction and can of course be used in the present invention.

The strong bases and quaternary ammonium fluorides described above have catalytic activity by themselves, and may impair storage stability when incorporated into a one-part composition. If you want a neutral composition,
As disclosed in P-A-0448154, strong base catalysts that are volatile with carboxylic acids or that undergo a decarboxylation reaction under curing conditions may be used.

As disclosed in JP-A-7-173262 of the present applicant, one-pack compositions having storage stability include (i) quaternary ammonium salts which themselves have no catalytic activity at room temperature, A combination of a quaternary phosphonium salt or a tertiary sulfonium salt and (ii) an epoxy compound can be used. The epoxy compound may be added as an independent compound, or (a)
It may be carried on the component or the component (b).

Although quaternary ammonium salts having various cationic moieties can be used, tetraalkylammonium salts and trialkylaralkylammonium salts are easily available. A quaternary ammonium salt of a nitrogen-containing heterocyclic compound such as pyridine, piperidine, piperazine, and morpholine may be used. Specifically, tetrabutylammonium, tetramethylammonium, tetraethylammonium, trimethylbenzylammonium, tetrapropylammonium, tetrahexylammonium, tetraoctylammonium, tetradecylammonium, tetrahexadecylammonium, triethylhexylammonium, 2-hydroxyethyltrimethylammonium (Choline), methyltrioctylammonium, cetyltrimethylammonium, 2-chloroethyltrimethylammonium, methylpyridinium and the like.

The counter anion of the ammonium salt is selected from those which form a stable salt with the cation moiety,
Halides except fluoride, carboxylate, sulfonate, sulfate, phosphate and the like. Specifically, acetate, laurate, glycolate, benzoate, salicylate, maleate, phthalate, fluoride, chloride, bromide, iodide, methanesulfonate, p-toluenesulfonate, dodecylbenzenesulfonate, triflate, nitrate,
Sulfate, metsulfate, phosphate, di-
t-butyl phosphate and the like.

Quaternary phosphonium salts such as tetrabutylphosphonium bromide, and tertiary sulfonium salts such as trimethylsulfonium iodide can be used as well as quaternary ammonium salts.

Among these onium salts, aromatic carboxylic acids whose anions have a phenolic hydroxyl group such as salicylic acid, polybasic carboxylic acids such as oxalic acid, maleic acid, fumaric acid and phthalic acid, nitric acid, phosphoric acid, Onium salts that are anions of sulfuric acid, sulfurous acid, acidic phosphoric acid ester, or sulfonic acid alone have no catalytic activity for the Michael addition reaction, but by heating under baking conditions usually used in the presence of an epoxy group. Demonstrates satisfactory catalytic activity. On the other hand, it has excellent storage stability.

When the composition of the present invention is applied as a clear top coat wet-on-wet and baked simultaneously, such as in a two coat / one bake coating of an automobile, the catalyst migrates to the base coat. In some cases, the curability of the clear coat decreases.
In such a case, the transfer of the catalyst to the base coat can be avoided by using a quaternary ammonium salt having a functional group capable of covalently bonding to the component (a) or the component (b).

For example, when the component (a) or the component (b) has a free carboxyl group by copolymerizing acrylic acid or methacrylic acid, a quaternary ammonium salt having a glycidyl group, for example, glycidyl trimethyl Ammonium chloride or bromide can be chemically bonded to component (a) or component (b) by a covalent bond. These may be bonded to the component (a) or the component (b) having a carboxyl group in advance, or may be independently added to the composition.

As another method, an ammonium salt having an acryloyl group or a methacryloyl group, for example, 2-
There is a method using (methacryloyloxy) ethyltrimethylammonium chloride or bromide. These quaternary ammonium monomers can be chemically bonded to the component (a) or the component (b) by copolymerization. In addition, even when independently added to the composition, it reacts with the active methylene group of the component (a), and migration to the base coat layer during baking is reduced.

When added as an independent compound, preferred epoxy compounds are glycidyl ethers (eg, phenylglycidyl ether, bisphenol type epoxy resin, reaction product of epichlorohydrin with polyhydric alcohol), glycidyl esters (eg, glycidyl benzoate, (Glycidyl (meth) acrylate and polymer), alicyclic epoxy compounds (for example, 4- (3,4-
Epoxycyclohexyl) methoxycarbonyl-1,2
-Epoxycyclohexane, (meth) acrylate of 3,4-epoxycyclohexanemethanol and polymers thereof), and α-olefin epoxides (eg, epoxyhexadecane).

When the above compound or resin is used as the epoxy compound, the molecular weight is 400 to 100,000, particularly 400 to 10,000, and the epoxy equivalent is 200 to 100.
000, particularly preferably 200 to 5,000.

The epoxy compound is covalently bonded to (a)
As a method of loading on the component or the component (b),
(A) a method in which less than a stoichiometric amount of (meth) acrylic acid is allowed to react with the epoxy resin or the epoxy group-containing acrylic resin to leave a part of the epoxy group, and in the synthesis of the (b) component acrylic resin. There is a method using glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, or 3,4-epoxycyclohexanemethanol (meth) acrylate as a copolymer monomer.

Curable Resin Composition The curable resin component of the present invention relates to the double bond and the active hydrogen atom to be added thereto, and the components (a) and (b) are preferably 2: 1 to 1: 2, more preferably 2: 1 to 1: 2. Are 1.5: 1 to 1: 1.
Should be included in an equivalent ratio of 5. Component (c) is 0.1 to 10.0 equivalent% based on the total of components (a) and (b),
Preferably, 0.2 to 5.0 equivalent% is added.

These components are dissolved or dispersed in a conventional organic solvent for paint. Examples of solvents that can be used are aliphatic hydrocarbons such as hexane, heptane; aromatic hydrocarbons such as toluene and xylene; various petroleum fractions having a suitable boiling range; butyl acetate, ethylene glycol diacetate and Esters such as 2-ethylhexyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dibutyl ether; butanol and methoxypropanol And mixtures of these solvents.

When the composition of the present invention is prepared into a paint, it may contain a conventional paint additive such as an extender, a coloring pigment, an anti-sagging agent and an ultraviolet absorber. After coating, leave the coating film at room temperature or apply 100-200
When heated to ℃, especially 120 to 150 ℃, it is cured by a crosslinking reaction to form a hard coating film.

The present invention will be illustrated below by way of Synthesis Examples, Examples and Comparative Examples. In these, "part" and "%"
Is based on weight.

Synthesis Example 1 A monomer and an initiator shown in Table 1 were mixed, and a decanter
In a four-necked flask equipped with a condenser, a stirring rod and a dropping funnel, 360 parts of xylene was charged at 110 ° C.
It was dropped over time. Thereafter, aging was performed at 110 ° C. for 0.5 hour. Further, 2 parts of Kayaester O (t-butylperoxyoctate) and 40 parts of xylene were mixed, added dropwise at 110 ° C. over 0.5 hours, and then aged for 1.5 hours. The obtained acrylic resin solution had a nonvolatile content of 49.4%, a number average molecular weight of about 5400 by GPC, and an active methylene equivalent of 200.
Met.

Synthesis Examples 2 to 10 The monomers and initiators shown in Tables 1 and 2 were mixed, and 360 parts of xylene was charged into a four-necked flask equipped with a decanter, a condenser, a stirring rod, and a dropping funnel.
It was added dropwise at 10 ° C. over 3 hours. Then at 110 ° C.
Aged for 5 hours. Further, 2 parts of Kayaester O (t-butyl peroxyoctate) and 40 parts of xylene were mixed,
The solution was dropped at 110 ° C. over 0.5 hours, and then aged for 1.5 hours. The obtained acrylic resin solution contains non-volatile components and GP
The number average molecular weight, active methylene equivalent and epoxy equivalent by C are shown in Tables 1 and 2.

Synthesis Examples 11 to 15 (for Comparative Examples) The monomers and initiators shown in Table 3 were mixed, and the mixture was decanted.
In a four-necked flask equipped with a condenser, a stirring rod and a dropping funnel, 360 parts of xylene was charged at 110 ° C.
It was dropped over time. Thereafter, aging was performed at 110 ° C. for 0.5 hour. Further, 2 parts of Kayaester O (t-butylperoxyoctate) and 40 parts of xylene were mixed, added dropwise at 110 ° C. over 0.5 hours, and then aged for 1.5 hours. Table 3 shows the nonvolatile content of the obtained acrylic resin solution, the number average molecular weight determined by GPC, the active methylene equivalent, and the epoxy equivalent.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

Example 1 405 parts of the resin solution synthesized in Synthesis Example 1 (resin solid content 20
0 parts), 50 parts of pentaerythritol triacrylate (hereinafter abbreviated as PETA), 2 parts of tetrabutylammonium bromide (TBABr), 10 parts of an ultraviolet absorber (Tinuvin T-384 manufactured by Ciba Geigy), a light stabilizer (Sanol manufactured by Ciba Geigy) LS-440) was mixed and uniformly dissolved. This solution was applied on a tin plate using a # 40 bar coater, and dried at 140 ° C. for 20 minutes in a drier.
Minutes. The gel fraction was determined by using acetone /
It was calculated from the weight change before and after immersion in a mixed solvent of methanol = 1/1 at normal temperature for 48 hours. The yellowing state of the coating film after 5 cycles of the S-UV test was visually evaluated according to the following criteria. ◎: No abnormality ：: Slight yellowing is observed Δ: Yellowing is observed ×: Yellowing is remarkable The results are shown in Table 4.

Examples 2 to 30 Table 4 shows the composition of the components (a), (b) and (c).
Example 1 was followed except for the following changes:
The results are shown in Tables 4-9.

[0052]

[Table 4]

[0053]

[Table 5]

[0054]

[Table 6]

[0055]

[Table 7]

[0056]

[Table 8]

[0057]

[Table 9]

Comparative Examples 1 to 20 Table 1 shows the composition of the components (a), (b) and (c).
Example 1 was followed except for the changes 0-13. These correspond to Examples 1 to 20. Table 10 shows the results.
~ 12.

[0059]

[Table 10]

[0060]

[Table 11]

[0061]

[Table 12]

[0062]

[Table 13]

Example 31 A dull steel sheet having a thickness of 0.8 mm treated with zinc phosphate was coated with a cationic electrodeposition paint (Powertop PU-5 manufactured by Nippon Paint Co., Ltd.).
0) was electrodeposited to a dry film thickness of about 25 μm, and an intermediate coating (Nippon Paint Co., Ltd. Olga P-2 sealer) was air-sprayed to a dry film thickness of about 40 μm and baked at 140 ° C. for 30 minutes. . Next, a high solid base paint having the following composition was applied by air spray so as to have a dry film thickness of about 16 μm, and set for about 7 minutes.

[0064] Composition of the base coating formulation ALPASTE 7160N (Toyo Aluminum Co., Ltd. Aluminum flake 10 parts paste, 65% aluminum flake content) acrylic resin varnish (nonvolatile content 80%, OH value 100, acid 50 parts number 80, Mn1800) Cymel 202 (Melamine resin manufactured by Mitsui Cytec Co., Ltd., non-volatile 10 parts, emission 80%) Cymel 327 (same as above, nonvolatile content 90%) 10 parts Isopropyl alcohol 7 parts

Next, the viscosity of the clear paint of Example 1 was adjusted with a Ford cup # 4 for 30 seconds, and the dry film thickness was about 40 μm.
m, applied electrostatically by wet-on-wet, set for about 7 minutes, baked at 140 ° C. for 25 minutes, and formed a composite coating with two coats and one bake.

Comparative Example 21 A composite coating film was formed by two coats and one bake in the same manner as in Example 31 except that the clear paint was changed to the clear paint of Comparative Example 1.

Weather resistance test With respect to the composite coating films prepared in Example 31 and Comparative Example 21, the yellowing state of the coating film after 5 cycles of the S-UV test was observed in the same manner as in Example 1. The coating film of Example 31 is Comparative Example 2.
The degree of yellowing was clearly smaller than that of the coating film No. 1.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08L 83/07 C08L 83/07 101/02 101/02 C09D 133/14 C09D 133/14 167/06 167/06 171/02 171/02 175/04 175/04 183/07 183/07 // C08F 8/00 C08F 8/00 C08G 61/00 C08G 61/00 C09D 4/02 C09D 4/02

Claims (10)

[Claims] 1. A component having a plurality of α, β-unsaturated carbonyl groups in a molecule, (b) an acrylic polymer having a plurality of pendant malonic ester groups in a molecule, and (c) a Michael reaction A curable resin composition comprising a catalyst for accelerating the reaction. 2. The method according to claim 1, wherein the component (a) is a (meth) acrylate ester of a polyhydric alcohol, an unsaturated polyester resin,
Polyester acrylate resin, epoxy acrylate resin, urethane acrylate resin, α, β-unsaturated carbonyl group-containing acrylic resin, polyether acrylate resin, (meth) acryloyl group-containing silicone oligomer or α, β-unsaturated carbonyl-containing fluorine-containing resin The composition of claim 1. 3. The component (b) wherein one of the carboxyl groups of malonic acid is hydroxyalkyl (meth) acrylate or polyoxyalkylene glycol mono (meth).
2. The composition according to claim 1, wherein the composition is a polymer of an acrylic monomer esterified with acrylate and the other carboxyl group is alkylesterified. 4. The composition according to claim 1, wherein said component (c) is a strong base catalyst, quaternary ammonium fluoride or quaternary ammonium tetrahydroborate. 5. The strong base catalyst is selected from hydroxides and alkoxides of alkali metals, quaternary ammonium hydroxides and carbonates, tertiary amines, guanidines, amidines, tertiary phosphines, and mixtures thereof. Composition. 6. The component (c) comprises: (i) an onium salt selected from quaternary ammonium salts, quaternary phosphonium salts and tertiary sulfonium salts having no catalytic activity per se; and (ii) 2. The composition of claim 1 which is a combination with an epoxy compound independently added or covalently supported on component (a) or component (b). 7. The cation of the onium salt is a tetraalkylammonium, trialkylaralkylammonium, alkylpyridinium, tetraalkylphosphonium or trialkylsulfonium cation, and the anion of the onium salt is a halide anion other than fluorine, The composition according to claim 6, which is an anion derived from a basic carboxylic acid, polybasic carboxylic acid, nitric acid, sulfonic acid, sulfuric acid, acid sulfate, sulfurous acid, phosphoric acid or acid phosphate. 8. The composition according to claim 6, wherein the epoxy group of the epoxy compound is a glycidyl group, an alicyclic epoxy group, or an α-olefin epoxide. 9. The quaternary ammonium salt according to (a)
The composition according to claim 6, which is a reactive quaternary ammonium salt having a functional group capable of reacting and covalently bonding with the component (b). 10. A paint containing the curable resin composition according to claim 1 as a vehicle.