JPH04332768A - Curable coating composition - Google Patents

Abstract

PURPOSE:To provide a curable coating composition having good curability and comprising a (meth)acryloyloxy group-containing polymerizable compound, a specific polyether polyol, and a polymer having one or more polymerizable unsaturated double bonds in a constant ratio. CONSTITUTION:The objective composition containing as main components (A) 30-90wt.% of a polymerizable compound having three or more (meth)acryloyloxy groups in the molecule, such as a polyol poly(meth)acrylate, (B) 5-50wt.% of a polyether polyene of the formula [R<1> is the active hydrogen-removed residue of an active hydrogen-containing compound consisting of an alcohol, a thiol, a carboxylic acid (amide) and/or an amine and has a mol. wt. of >=2000 in the R<1> part; n is 1-10; R<2> is H, 2-10C organic radical; m is 1 or larger], and (C) 5-6wt.% (the total amount of the components A, B and C is 100wt.%) of a polymer having one or more polymerizable unsaturated double bonds, such as a polymer having one or more methacryloyl groups, and giving coating films having excellent coating appearance, abrasion resistance, water resistance, heat resistance, etc.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention has excellent abrasion resistance, water resistance, heat resistance, solvent resistance, chemical resistance, adhesion to substrates, etc. by heating or ultraviolet irradiation in an air atmosphere at room temperature. The present invention relates to a curable coating composition capable of forming a crosslinked cured coating.

0002

[Prior Art] Synthetic resin molded products made from ABS resin, polypropylene resin, polyester resin, polymethyl methacrylate resin, polycarbonate resin, etc. are not only lightweight and have excellent impact resistance, but are also inexpensive and easy to mold. Due to its various advantages, it has been used in many fields.

However, these synthetic resin molded products generally have poor surface wear resistance, so they are susceptible to contact with other hard materials, friction,
The surface is easily damaged by scratching, etc. This surface damage significantly reduces the commercial value or causes the product to become unusable in a short period of time. From this point of view, there has been a desire to improve the abrasion resistance on the surface of synthetic resin molded products. In addition, various types of furniture such as tables, desks, chairs, chests of drawers, and mirror stands are usually finished with amino resin paint or urethane paint, but this paint also has the disadvantage that the surface is easily scratched, which cannot be improved. It was wanted.

Various methods have been known to improve the abrasion resistance of the surfaces of such synthetic resin molded products, furniture, etc., by forming coatings on their surfaces. For example, there is a method in which a coating material made of a silicone-based, melamine-based, etc. resin composition is applied to the surface of a synthetic resin molded article, and a crosslinked film is formed by heat condensation. Further, for example, there is a method in which an ultraviolet curable coating mainly composed of a polyfunctional acrylate such as pentaerythritol tetraacrylate is applied onto the surface of a synthetic resin molded article, and the coating film is crosslinked and cured by radical polymerization by ultraviolet irradiation.

However, the former method requires heating at a high temperature for a long period of time to form a film, so it is difficult to apply to plastic molded products with low heat resistance. In addition, the latter method can be applied to synthetic resin molded products that are sensitive to heat, and although the cured film has excellent physical properties such as durability, chemical resistance, and heat resistance, it cannot be applied to molded products with complex shapes. When applied, there are areas where it is difficult or not exposed to light, which causes problems such as those areas not being sufficiently cured and remaining sticky or emitting a monomer odor.

[0006]

[Problems to be Solved by the Invention] The present invention has been made to solve the above-mentioned problems.The purpose of the present invention is to solve the problems described above. It is a curable coating composition that can be cured satisfactorily even when the coating is applied. The object of the present invention is to provide a curable coating composition capable of forming a coating film having excellent various physical properties.

[0007]

[Means for Solving the Problems] The present invention provides (a) 30 to 90% by weight of a polymerizable compound having three or more (meth)acryloyloxy groups in one molecule; (b) the following general formula (1); Polyether polyene represented by 5 to 40% by weight,

[0008]

[Chemical formula 2] (However, R1 is alcohol, thiol, carboxylic acid,
R represents a residue excluding an active hydrogen atom of an active hydrogen-containing compound selected from the group consisting of carboxylic acid amides and amines.
The molecular weight of 1 part is 2000 or less, n represents an integer of 1 to 10, R2 represents hydrogen or an organic radical having 2 to 10 carbon atoms, and m represents an integer of 1 or more. ), and (c) a polymer having a polymerizable unsaturated double bond 5
This is a curable coating composition comprising as a main component 65% by weight (however, the total amount of components (a) to (c) is 100% by weight).

In the present invention, "(meth)acryloyloxy" refers to acryloyloxy and/or methacryloyloxy.

Polymerizable compound (a) having three or more (meth)acryloyloxy groups in one molecule used in the present invention
For example, polyol poly(meth)acrylate, polyester poly(meth)acrylate, epoxy poly(meth)acrylate, polyurethane poly(meth)acrylate
A poly(meth)acrylate such as acrylate, polyacrylic poly(meth)acrylate, polysiloxane poly(meth)acrylate, polyamide poly(meth)acrylate, aminopoly(meth)acrylate, or aminopolyamide(meth)acrylate, which has one molecule. Polymerizable compounds having three or more (meth)acryloyloxy groups therein can fully function in the present invention. Furthermore, from the viewpoint of wear resistance, the molecular weight per polymerizable double bond equivalent (meth)acryloyloxy group of the polymerizable compound (a) is preferably 450 or less.

More specific examples of the polymerizable compound (a) include the following compounds (1) to (2).

[0012]■. Trivalent or higher polyhydric alcohol or its modified compound (e.g. modified polyhydric alcohol such as ethylene oxide, propylene oxide, tetrahydrofuran, γ-caprolactone), acrylic acid, methacrylic acid or chloride or ester of these acids. (meth)acrylate obtained by reacting.

Examples of the trivalent or higher polyhydric alcohol used to synthesize the above-mentioned (meth)acrylate ① include trimethylolmethane, polytrimethylolmethane, trimethylolethane, polytrimethylolethane,
Trimethylolpropane, polytrimethylolpropane, glycerin, polyglycerin, pentaerythritol, polypentaerythritol, petriol, tris(
Examples include 2-hydroxyethyl) isocyanurate, sorbitol, mannitol, and the like.

[0014]■. The following general formula (2) obtained by reacting a trivalent or higher polyhydric alcohol, a polybasic acid, and (meth)acrylic acid

[0015]

[Chemical formula 3] X: Trivalent or higher polyhydric alcohol residue Y: polybasic acid residue A: (meth)acryloyloxy group m: integer greater than or equal to 1 n: an integer of 3 or more Polyester poly(meth)acrylate represented by.

[0016] Specific examples of polyhydric alcohols having a valence of 3 or more to be used for synthesizing the above-mentioned polyester poly(meth)acrylate (■) include those similar to the polyhydric alcohols having a valence of 3 or more in (meth)acrylate (■). can be mentioned.

Examples of the polybasic acids used to synthesize the above-mentioned polyester poly(meth)acrylate (1) include oxalic acid, succinic acid, malonic acid, methylsuccinic acid,
2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid , 3,3-diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, 1,2-hexahydrophthalic acid, 1,3 -hexahydrophthalic acid, 1,4-
Examples include hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, and anhydrides of these acids.

[0018]■. Trivalent or higher epoxy resin and (meth)
Epoxy poly(meth)acrylate obtained by reacting with acrylic acid or a (meth)acrylic acid monomer having a carboxyl group.

The trivalent or higher valence epoxy resins used to synthesize the above-mentioned epoxy poly(meth)acrylate (■) include sorbitol triglycidyl ether, sorbitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, tris(2-glycidyloxyethyl ) isocyanurate, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerin polyglycidyl ether,
Examples include phenol novolac type epoxy resin, cresol novolac type epoxy resin, reduced maltose polyglycidyl ether, and tris(glycidyloxyphenyl)methane.

The (meth)acrylic acid monomer having a carboxyl group used for synthesizing the above-mentioned epoxy poly(meth)acrylate (2) is represented by the following general formula (3).

[0021]

[C4] R3: H or CH3 R4: Hydrocarbon group having 2 to 4 carbon atoms R5: Dibasic acid anhydride residue Examples include monomers represented by:

Examples of the dibasic acid anhydride used to synthesize the above-mentioned epoxy poly(meth)acrylate (■) include maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, Examples include methyl succinic anhydride, 2,2-dimethyl succinic anhydride, 2,3-dimethyl succinic anhydride, hexyl succinic anhydride, and the like.

[0023]■. The following general formula (4) synthesized from a trivalent or higher polyhydric alcohol, a polyisocyanate, and a hydroxyl group-containing (meth)acrylate

[0024]

embedded image X: polyhydric alcohol residue Y: polyisocyanate residue A: hydroxyl group-containing (meth)acrylate residue m: 2 or 3 n: urethane poly(meth)acrylate represented by an integer of 3 or more.

[0025] As the trihydric or higher polyhydric alcohol used for synthesizing the above-mentioned urethane poly(meth)acrylate (■), the same ones as in the above-mentioned (meth)acrylate (■) can be mentioned. .

Examples of the polyisocyanate used to synthesize the above-mentioned urethane poly(meth)acrylate (1) include tolylene diisocyanate, ethylene diisocyanate, 1,2-diisocyanatopropane, and 1,3-diisocyanate.
-diisocyanatopropane, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4
′-methylenebis(cyclohexyl isocyanate),
Methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,
Examples include 3-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and the like.

The hydroxyl group-containing (meth)acrylate used to synthesize the above-mentioned urethane poly(meth)acrylate (■) is represented by the following general formula (5) or (6).

002
8]

[C6] R6: H or CH3 R7: Hydrocarbon residue having 2 to 6 carbon atoms

[0029]

[Formula 7] R8: H or CH3 R9: Trivalent or higher polyhydric alcohol residue n: 2-5
Examples include monomers represented by an integer of .

Specific examples of polyhydric alcohols having a valence of 3 or more in the monomer represented by the above general formula (6) include the same examples as the polyhydric alcohols having a valence of 3 or more in the (meth)acrylate ■ mentioned above. I can list things.

[0031]■. General formula (7) below

[0032]

embedded image (X represents an alkoxymethylated melamine residue, an alkoxymethylated benzoguanamine residue, or an alkoxymethylated acetoguanamine residue, R10 represents a methyl group, an ethyl group, a propyl group, or a butyl group, and n represents a Aminopoly(meth)acrylate obtained by reacting an alkoxymethylated amino resin represented by (2 or 3) with a hydroxyl group-containing (meth)acrylate represented by the above general formula (5) or (6); Aminopoly(meth)acrylate obtained by reacting an alkoxymethylated amino resin represented by formula (7) with a (meth)acrylic acid monomer having a carboxyl group; or an alkoxymethylated amino resin represented by the above general formula (7) Aminopoly(meth)acrylamide obtained by the reaction of and (meth)acrylamide.

[0033]■. An acrylic polymer having a functional group such as a hydroxyl group, a carboxyl group, a glycidyl group, or an isocyanate group, and an acrylic acid that reacts with the functional group, for example, 2
- Polyacrylic poly(meth)acrylate obtained by reacting with a monomer such as hydroxyethyl acrylate.

The content of the polymerizable compound (a) used in the present invention is 30 to 90% by weight. This content is 30% by weight
If it is less than that, it will not be possible to obtain the excellent physical properties of wear resistance that are the object of the present invention. Moreover, if this content exceeds 90% by weight, the adhesiveness with the base material will decrease.

Polyether polyene used in the present invention (
b) is the following general formula (1)

[0036]

[Formula 9] (where R1 is alcohol, thiol, carboxylic acid,
Represents a residue excluding an active hydrogen atom of an active hydrogen-containing compound with a molecular weight of 2000 or less selected from the group consisting of carboxylic acid amides and amines, n represents an integer of 1 to 10, R2
represents hydrogen or an organic radical having 2 to 10 carbon atoms,
m represents an integer of 1 or more. ) is a compound represented by

The polyether polyene (b) comprises allyl glycidyl ether and an active compound selected from alcohols, thiols, carboxylic acids, carboxylic acid amides and amines (primary or secondary amines). It can be synthesized by reacting with a hydrogen-containing compound using a Lewis acid or base catalyst. The active hydrogen atom of these active hydrogen-containing compounds is removed by the above reaction, and the residue constitutes the skeleton R1 in the above general formula (1). This skeleton R1 has a structure such as hydrocarbon, polyether, polyester, polyamide, polyurethane, etc., and R1
The molecular weight of is 2000 or less. Further, the number of active hydrogens in the active hydrogen-containing compound is 1 to 10, corresponding to n in general formula (1). Moreover, m in general formula (1) is an integer of 1 or more.

Examples of active hydrogen-containing compounds include ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, Alcohols such as trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, trimethylolpropane trithioglycolate, trimethylol Synthesized from thiols, polyhydric alcohols, and polybasic acids such as propane trithiopropionate, pentaerythritol tetrathioglycolate, and pentaerythritol tetrathiopropionate. Polyester polyols such as polyester polyols and polycaprolactol polyols, succinic acid, adipic acid, maleic acid, fumaric acid, phthalic acid,
Carboxylic acid compounds such as carboxyl group-containing polyesters synthesized from polyhydric alcohols and polybasic acids, carboxylic acid amide compounds synthesized from polybasic acids and polyvalent amine compounds, ethylenediamine, diethylenetriamine, phenylenediamine, diaminophenyl Mention may be made of primary or secondary amine compounds such as methane.

R2 is hydrogen or a saturated or unsaturated organic radical having 2 to 10 carbon atoms, such as a hydrocarbon group, an acyl group such as acetyl or acryloyl, or a 1,2-epoxy group such as glycidyl.

The content of polyether polyene (b) is 5
~40% by weight. If the content is less than 5% by weight, curing properties at room temperature or under heat in an air atmosphere will be poor. If the content exceeds 40% by weight, copolymerizability will be poor and various physical properties will significantly deteriorate.

This polyether polyene (b) is an essential compound for curing the composition of the present invention in air at room temperature or by heating. Not only is it effective in improving the appearance of the paint, but surprisingly it is also effective in significantly improving the appearance of the paint.

Examples of the polymer (c) having a polymerizable unsaturated double bond used in the present invention include those whose main chain is formed by vinyl polymerization and which has a polymerizable unsaturated double bond in its side chain; is formed by condensation polymerization and has a polymerizable unsaturated double bond in its side chain, the main chain is formed by condensation polymerization and has a polymerizable unsaturated double bond in the main chain, Examples include embodiments in which the polymer is formed and has a polymerizable unsaturated double bond in its side chain.

The weight average molecular weight of the polymer (c) is 3,
Approximately 000 to 500,000 is suitable. If the molecular weight is lower than this range, the apparent curing, that is, the tack-free time will be longer, while if the molecular weight is higher than this range, the apparent curing will be faster, but problems will tend to occur in workability, appearance, etc. In addition, due to the presence of polymerizable double bonds in the polymer, when this polymer is used, various physical properties, especially surface hardness,
There is no deterioration in abrasion resistance, chemical resistance, or stain resistance, and since curing progresses quickly, it maintains a good appearance even on sloped surfaces without causing defects such as running patterns on the surface. can get. The content of polymerizable double bonds is preferably 0.2 or more per 1000 molecular weight. If the amount is less than this, deterioration of physical properties may be observed.

Polymer having a polymerizable unsaturated double bond (
The content of c) is 5-65% by weight. If it is less than 5% by weight, the tack-free time will be longer, while if it is less than 65% by weight.
Naturally, the higher the amount, the lower the content ratio of the polymerizable compound (a) and polyether polyene (b), which lowers the surface hardness and abrasion resistance, and worsens the curability in air. So I don't like it.

The polymers (c) having polymerizable unsaturated double bonds in the embodiments exemplified above can be obtained by the following methods. (1) A polymer whose main chain is formed by vinyl polymerization and has a polymerizable unsaturated double bond in its side chain can be obtained by any of the following methods. (a) A vinyl monomer and a vinyl monomer having a hydroxyl group are copolymerized, and a vinyl monomer having an isocyanate group is reacted therewith. (b) A vinyl monomer and a vinyl monomer having an isocyanate group are copolymerized, and this is reacted with a vinyl monomer having a hydroxyl group. (c) A vinyl monomer and a vinyl monomer having an epoxy group are copolymerized, and a vinyl monomer having a carboxyl group is reacted therewith. (d) A vinyl monomer and a vinyl monomer having a carboxyl group are copolymerized, and a vinyl monomer having an epoxy group is reacted with the copolymerization. (e) A vinyl monomer and a vinyl monomer having a hydroxyl group are copolymerized, and a vinyl monomer having a carboxyl group is reacted therewith. (f) A vinyl monomer and a vinyl monomer having a carboxyl group are copolymerized, and a vinyl monomer having a hydroxyl group is reacted therewith.

The monomers used in each of these methods (a) to (f) include the following.

Examples of vinyl monomers include styrene, vinyltoluene, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. , tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl meth(acrylate),
Cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, ( meth) dimethylaminoethyl acrylate, (
meth)diethyl amylethyl acrylate, vinyl acetate,
Examples include vinyl propionate and vinyl versatate.

The vinyl monomer having a hydroxyl group used in methods (a), (e), and (f) has the following general formula (8).
) or 2 of this monomer
Examples include a mer, a trimer, a vinyl monomer represented by the following general formula (9), and the like.

[0049]

[Chemical formula 10] R11:H or CH3 R12: Hydrocarbon residue having 2 to 6 carbon atoms

[0050]

[Chemical formula 11] R13: H or CH3 R14: Hydrocarbon residue having 2 to 6 carbon atoms n: Integer from 1 to 4 The vinyl monomer having an isocyanate group used in methods (a) and (b) is 2-methacryloyloxy Ethyl isocyanate, m-isopropenyl-α,α
Examples include -dimethylbenzylisocyanate, a reaction product of 1 mole of diisocyanate among those exemplified as polyisocyanates in the synthesis of urethane poly(meth)acrylate (1) and 1 mole of the above-mentioned vinyl monomer having a hydroxyl group.

The vinyl monomer having an epoxy group used in methods (c) and (d) has the following general formula (1).
Compounds represented by 0) to (13),

[0052]

[Chemical formula 12] R15: H or CH3 R16: Hydrocarbon residue having 1 to 6 carbon atoms R17: H or CH3 Or, bisphenol A diglycidyl ether, triethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcindi Examples include monoester compounds produced by reacting equivalent moles of a diepoxy compound such as glycidyl ether with a vinyl monomer having a carboxyl group such as (meth)acrylic acid.

As the vinyl monomer having a carboxyl group used in methods (c), (d), (e) and (f), (
meth)acrylic acid and its dimers and trimers, monomers having a hydroxyl group represented by the above general formula (5) or (6), and dibasic anhydrides such as succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Examples include monoester compounds produced by reaction of equimolar amounts with acids.

(2) A polymer whose main chain is formed by condensation polymerization and has a polymerizable unsaturated double bond in its side chain is obtained by condensation polymerization of a dibasic acid, a trivalent or higher polyol, and a diol. A polyester having a hydroxyl group in its side chain,
It can be obtained by reaction with a vinyl monomer having an isocyanate group as exemplified above. Specific examples of the dibasic acids include phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid. There is. Specific examples of diols include ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol, 3,3,5-trimethyl- 2,4-pentanediol, diethylene glycol, dipropylene glycol, hydrogenated bisphenol A, bisphenol A
Examples include ethylene oxide adducts. Examples of polyols having a valence of 3 or more include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

(3) A polymer whose main chain is formed by condensation polymerization and has a polymerizable unsaturated double bond in the main chain is a so-called unsaturated polyester, and is composed of the above-mentioned dibasic acids and trimerite anhydrides. It is obtained by the reaction of a saturated polybasic acid such as an acid, an unsaturated dibasic acid such as maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, and the above-mentioned polyol.

(4) A polymer formed by addition polymerization of the main chain and having a polymerizable unsaturated double bond in its side chain is, for example, a polymer formed by the above-mentioned diisocyanate and 2-isocyanatoethyl-2,6- 3 such as diisocyanatohexanoate
A polyurethane having an isocyanate group in the side chain is obtained by reacting a polyvalent isocyanate with the above-mentioned diol, and this is obtained by reacting this with the above-mentioned vinyl monomer having a hydroxyl group. For example, a polyurethane having a hydroxyl group in the side chain is obtained by reacting the above-mentioned diisocyanate, a diol, and a polyol with a valence of 3 or more, and a vinyl monomer having the above-mentioned isocyanate group or a carboxyl group is obtained. It can also be obtained by reaction with vinyl monomers.

The composition of the present invention contains each of the above-mentioned components (a
) to (c) as main components. That is, the composition of the present invention may be a composition consisting only of components (a) to (c), or other optional components may be added within a range that does not impair the purpose of the present invention. . Particularly preferred optional components to be added are a polymerization initiator (d) and a metal dryer (e).

Free radical polymerization initiators are suitable as the polymerization initiator (d) used in the present invention, and specific examples thereof include:
Peroxides such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile)
, 2,2-azobis(2-methylpropane) and other azo compounds. The blending amount of the polymerization initiator is determined by the component (
It is preferably 10 parts by weight or less based on a total of 100 parts by weight of a) to (c). If it exceeds 10 parts by weight, the stability of the coating composition decreases, which is not preferable.

When the composition of the present invention is used for curing by ultraviolet irradiation, a polymerization initiator (
It is preferable to incorporate a photopolymerization initiator as d). The blending amount is 0.01 to 10 parts by weight. Specific examples include benzophenone, benzoin isobutyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2,
2-dibutoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1-
[4-(methylthio)phenyl]-2-morpholino-
Propanone-1,2-benzyl-2-dimethylamino-
1-(4-morpholinophenyl)-butanone-1-
Methylphenylglyoxylate, ethylphenylglyoxylate, 2-chlorothioxatone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxane, 2,4,6-trimethylbenzoyldiphenoylphosphine oxide etc. can be mentioned.

The metal dryer (e) used in the present invention is:
It is effective in significantly accelerating the curing of the coating composition of the present invention. Specific examples of metal dryers (e) include metals such as cobalt, manganese, barium, cerium, lead, zinc, calcium, titanium, zirconium, iron, copper, and tin, acetylic acid, naphthenic acid, octylic acid, and tall oil. Examples include salts with carboxylic acids such as fatty acids. The amount of metal dryer (e) added is the amount of components (a) to (c).
It is preferably 1 part by weight or less based on a total of 100 parts by weight. If it exceeds 1 part by weight, problems such as coloring and fading may occur. The metal dryer (e) is usually added as a solution in a suitable solvent in order to disperse it throughout the composition.

The composition of the present invention contains each of the above-mentioned components (a
) to (e), other components can be added according to various purposes as long as they do not impair the purpose of the present invention. Examples of other components include (meth)acrylic oligomers and monomers that are copolymerizable with components (a) to (c) and different from components (a) and (b). Specific examples of this oligomer include polyol poly(meth)acrylate such as neopentyl glycol diacrylate and tetraethylene glycol diacrylate;
Polyester poly(meth) obtained by the reaction of polybasic acids such as phthalic acid and adipic acid, polyhydric alcohols such as ethylene glycol and butanediol, and (meth)acrylic acid.
Acrylate oligomers, epoxy poly(meth)acrylates obtained by the reaction of epoxy resins and (meth)acrylic acid, urethane poly(meth)acrylates obtained by the reaction of polyols, polyisocyanates, and hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate Oligomers such as meth)acrylate, polysiloxane poly(meth)acrylate obtained by the reaction of polysiloxane and a (meth)acrylic acid compound, and polyamide poly(meth)acrylate obtained by the reaction of polyamide and a (meth)acrylic acid compound. can be mentioned. Specific examples of this monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and t-(meth)acrylate. Butyl, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylic acid -2-
Dicyclopentenoxyethyl, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, ( Tetrahydrofurfuryl meth)acrylate, 2-hydroxyethyl (meth)acrylate, (
2-hydroxypropyl acrylate (meth)acrylate, (meth)
(Meth)acrylic acid monomers such as 4-hydroxybutyl acrylate, (meth)acrylic acid, (meth)acryloylmorpholine, N-vinyl-2-pyrrolidone, N-vinylimidazole, N-vinylcaprolactam, styrene, α- Examples include methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, and vinyl benzoate.

[0062] As other additives, various thermoplastic resins can be added to the composition of the present invention within a range that does not impair wear resistance. Examples include cellulose derivatives such as nitrocellulose, acetylcellulose, acetylbutyrylcellulose, ethylcellulose, methylcellulose, polyvinyl chloride, polyvinylidene chloride,
Polyvinyl acetate, vinyl chloride/vinyl acetate copolymer, polyvinyl alcohol, polyvinyl ether, acrylic resin, styrene resin, polyamide resin, fluororesin, petroleum resin, alkyd resin, polyester resin, rosin ester, chlorinated rubber, cyclized rubber, etc. can be mentioned.

Furthermore, the composition of the present invention may contain a leveling agent, a slip agent, an antifoaming agent, an anti-repellent agent, a wetting agent, a dispersing agent, an anti-settling agent, an anti-sagging agent, an ultraviolet absorber, an oxidizing agent, etc., as necessary. Various additives such as inhibitors, polymerization inhibitors, coupling agents, and volatile organic solvents can be added to adjust the viscosity. Furthermore, dyes, pigments, etc. can also be added for the purpose of coloring.

The coating composition of the present invention can be easily produced by simply mixing or dispersing the various components described above. Further, when coating a substrate with the coating composition of the present invention, general coating methods such as spray coating, curtain flow coating, roll coating, dipping coating, spin coating, gravure coating, and screen coating may be used.

The composition of the present invention can be cured by simply leaving it in the air at room temperature after being coated on the object to be coated, or the curing can be accelerated by heating.
Low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, extra high pressure mercury lamps,
It can also be rapidly cured by irradiation with ultraviolet light such as a xenon lamp, gallium lamp, metal halide lamp, or sunlight.

[0066]

[Examples] The present invention will be explained in more detail below with reference to Examples.

<Production Example 1 of polyether polyene (b)
>Into a reaction vessel equipped with a stirrer and a condenser, 416 parts by weight of ethylene glycol and 50 parts by weight of boron trifluoride ethyl ether as a catalyst were charged, and the internal temperature was brought to 7.
Raise the temperature to 7-78°C, and allyl glycidyl ether 856
0 parts by weight was added dropwise over 2 hours, and then the mixture was cooled to 20°C and 30 parts by weight of catalyst was added. After this, increase the internal temperature to 77-7 again.
Raise the temperature to 8℃ and add allyl glycidyl ether 8560 again.
Parts by weight were added dropwise over 2 hours, reacted at 78 to 80°C for 30 minutes, and then cooled to room temperature. After adding ether and further adding 100 parts by weight of 10% sodium hydroxide aqueous solution to deactivate the catalyst, dry ice was added to neutralize excess sodium hydroxide, and the aqueous layer was removed. Sodium sulfate was added to the ether layer for dehydration. Thereafter, the solvent was removed by evaporation to obtain 17,360 parts by weight of the desired polyether polyene (b-1).

<Production example 2 of polyether polyene (b)
>Into the same reaction vessel as in Production Example 1 above, 911 parts by weight of anhydrous powdered sorbitol and 30 parts by weight of boron trifluoride ethyl ether as a catalyst were charged, and the temperature was gradually raised to 95°C.
Sorbitol was dissolved. 17,180 parts by weight of allyl glycidyl ether was gradually added dropwise to this, and when the reaction layer became transparent, the reaction temperature was gradually lowered to 80°C, and 1/
When about 3 parts were dropped, the reaction temperature was cooled to room temperature, and 20 parts by weight of the catalyst was added. After this addition, the reaction temperature was increased to 80
°C and resumed dropping allyl glycidyl ether.
When about 2/3 of the total amount was dropped, the same operation was repeated again, and finally the entire amount of allyl glycidyl ether was dropped over 5 hours. Thereafter, the reaction was continued for 30 minutes and then cooled. Thereafter, 18,200 parts by weight of the desired polyether polyene (b-2) was obtained in the same manner as in Production Example 1.

<Production Example 3 of polyether polyene (b)
> Molecular weight 1 instead of 416 parts by weight of ethylene glycol
The reaction was carried out in the same manner as in Production Example 1, except that 50 parts by weight of polytetramethylene glycol 000 and 114 parts by weight were used instead of 17,120 parts by weight of allyl glycidyl ether to obtain a polyether having the desired polyether skeleton. 147 parts by weight of polyene (b-3) was obtained.

<Production Example 4 of polyether polyene (b)
> Instead of 416 parts by weight of ethylene glycol, 50 parts by weight of polyester diol with a molecular weight of about 1000 obtained by reacting 5 moles of succinic acid and 6 moles of neopentyl glycol was used, and in place of 17,120 parts by weight of allyl glycidyl ether, 114 parts by weight were used. The reaction was carried out in the same manner as in Production Example 1 except that the desired polyether polyene (b-4) having a polyester skeleton was obtained.

<Production Example 1 of Polymer (c) Having Polymerizable Unsaturated Double Bonds> 100 parts by weight of toluene was placed in a flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel, and the temperature inside the flask was raised to 80°C. After raising the temperature to ℃, 0% of azobisisobutyronitrile was added to a monomer mixture consisting of 35 parts by weight of n-butyl methacrylate, 35 parts by weight of methyl methacrylate, and 30 parts by weight of glycidyl methacrylate.
．． A solution containing 5 parts by weight of azobisisobutyronitrile was added dropwise from the dropping funnel over 4 hours, and 0.1 parts by weight of azobisisobutyronitrile was added 4 times every hour to complete the polymerization.

Next, 15.2 parts by weight of acrylic acid, 1 part by weight of triethylamine, 0.1 part by weight of hydroquinone, and 15.2 parts by weight of toluene were added to this and reacted at 90° C. for 8 hours, resulting in a weight average molecular weight of about 78,000. and 1
A polymer (c-1) having about 1.8 acryloyl groups per 1,000 molecular weight was obtained.

<Production Example 2 of Polymer (c) Having Polymerizable Unsaturated Double Bonds> 100 parts by weight of toluene was placed in the same reaction vessel as in Production Example 1 above, and the temperature inside the flask was raised to 80°C. A solution obtained by dissolving 0.5 parts by weight of azobisisobutyronitrile in a monomer mixture consisting of 40 parts by weight of styrene, 40 parts by weight of methyl methacrylate, and 20 parts by weight of 2-hydroxyethyl methacrylate was added through a dropping funnel. The mixture was added dropwise over 4 hours, and 0.1 part by weight of azobisisobutyronitrile was added four times every hour to complete the polymerization.

Next, to this was added 23.8 parts by weight of isocyanatoethyl methacrylate and 0.1 parts by weight of dibutyltin dilaurate.
parts by weight, 0.1 parts by weight of hydroquinone, 23 parts by weight.
8 parts by weight was added and the reaction was carried out at 60°C for 6 hours, and the weight average molecular weight was about 50,000, which was about 1% per 1,000 molecular weight.
．． Polymer having two methacryloyl groups (c-2)
I got it.

<Production Example 3 of Polymer (c) Having a Polymerizable Unsaturated Double Bond> Polymer solution 200 polymerized using the same monomer composition, same solvent, and same method as in Production Example 2 above
The weight part was placed in a flask equipped with a stirrer, a thermometer, and a decanter, and 22 parts by weight of acrylic acid, 1 part by weight of concentrated sulfuric acid, 0.2 parts by weight of hydroquinone, and 100 parts by weight of toluene were added thereto, and the mixture was heated at 100°C. The reaction was carried out until no water of condensation was produced. After the reaction, excess acrylic acid and sulfuric acid of the catalyst were neutralized and removed with an aqueous sodium hydroxide solution, and after washing several times with deionized water, part of the toluene was removed by distillation.The solid content was adjusted to 50%, and the weight A polymer (c-3) having an average molecular weight of 48,000 and approximately 1.3 acryloyl groups per 1,000 molecular weight was obtained.

<Production Example 4 of Polymer (c) Having Polymerizable Unsaturated Double Bonds> 166 parts by weight of isophthalic acid and 66.1 parts by weight of ethylene glycol were placed in a reaction vessel equipped with a stirrer, a thermometer, and a distillation column. Parts by weight, 16.1 parts by weight of trimethylolpropane, and 0.1 parts by weight of antimony trioxide are added, and the temperature inside the reaction vessel is raised to 260°C, causing condensed water to flow out of the reaction system, so that water no longer flows out. The esterification reaction was carried out for about 3 hours.

[0077] Thereafter, the reaction temperature was maintained at 245°C, and the pressure inside the reaction system was reduced to 2 mmHg, and ethylene glycol was flowed out from the reaction system to carry out a condensation reaction. Approximately 3 hours after ethylene glycol had flowed out, the pressure of the reaction system was returned to normal pressure to complete the reaction. Then, the resin was taken out from the reaction vessel and cooled to obtain a pale yellow solid polyester resin. The hydroxyl value of this resin was 84.

Next, 130 parts by weight of methyl ethyl ketone was placed in a flask equipped with a stirrer, a thermometer, and a condenser.
Add 100 parts by weight of the above polyester resin while stirring and completely dissolve it. To this were added 30 parts by weight of an equivalent reaction product of tolylene diisocyanate and 2-hydroxyethyl acrylate, 0.1 part by weight of dibutyltin dilaurate, and 0.1 part by weight of hydroquinone, and the reaction was carried out at 60°C for 6 hours to give a weight average A polymer (c-4) having a molecular weight of about 5000 and about 0.7 acryloyl groups per 1000 molecular weight was obtained.

<Production Example 5 of Polymer (c) Having Polymerizable Unsaturated Double Bonds> In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 735 parts by weight of maleic anhydride and 1110 parts by weight of phthalic anhydride were added. parts, propylene glycol 1368 parts by weight, tert-butylhydroquinone 2 parts
．． 5 parts by weight was added, the temperature of the reaction vessel was raised to 210° C., and while blowing nitrogen gas, condensed water was allowed to flow out of the reaction system, and the reaction was carried out for about 10 hours until no more water flowed out.

After the reaction was completed, the mixture was cooled to 110° C. and 3,213 parts by weight of toluene was added to obtain the desired resin. The weight average molecular weight of this product is about 4000, and the polymer (c-5
) was obtained.

<Example 1> 60 parts by weight of pentaerythritol tetraacrylate, polyurethane polyene (b-
1) 30 parts by weight, 10 parts by weight of polymerizable polymer (c-1) (using 20 parts by weight of a 50% toluene solution of polymerizable polymer), 0.4 parts by weight of a 12% cyclohexane solution of cobalt 2-ethylhexylate, Benzoyl peroxide 2
A coating composition consisting of parts by weight was applied to an ABS resin board to a film thickness of 30%.
After applying it evenly to a thickness of μm and leaving it for 10 minutes at room temperature,
When heated at 70° C. for 30 minutes at an angle of 45° with respect to a flat surface, the coating film was completely cured. Table 1 shows the compounding ratio, and Table 2 shows the results of evaluating the coating film performance of the coated board.

<Example 2> Urethane polyacrylate having an average of three acryloyloxy groups in one molecule was synthesized from hexamethylene diisocyanate trimer and 3 moles of 2-hydroxyethyl acrylate. 30 parts by weight of this urethane polyacrylate, 20 parts by weight of pentaerythritol triacrylate, polyurethane polyene (b
-2) 10 parts by weight, 20 parts by weight of polymerizable polymer (c-2) (using 40 parts by weight of 50% toluene solution of polymerizable polymer), 20 parts by weight of neopentyl glycol, 3 parts by weight of benzoyl peroxide, 2 - A coating composition consisting of 0.2 parts by weight of a 12% solution of cobalt ethylhexylate in cyclohexane was uniformly applied to a methacrylic resin plate to a film thickness of 40 μm, left at room temperature for 10 minutes, and then tilted at 45° with respect to the flat surface. When heated at 90° C. for 30 minutes, the coating film was completely cured. Table 1 shows the compounding ratio, and Table 2 shows the results of evaluating the coating film performance of the coated board.

<Example 3> Using 1 mole of hexakismethoxymelamine and 4 moles of 2-hydroxyethyl acrylate as raw materials, using p-toluenesulfonic acid as a catalyst, 1
A melamine polyacrylate having an average of four acryloyloxy groups in its molecule was synthesized. 30 parts by weight of this melamine polyacrylate, 20 parts by weight of dipentaerythritol hexaacrylate, polyurethane polyene (b-
3) 15 parts by weight, 35 parts by weight of polymerizable polymer (c-3) (using 70 parts by weight of a 50% toluene solution of polymerizable polymer), 0.4 parts by weight of a 12% cyclohexane solution of cobalt 2-ethylhexylate, t-Butylperoxy-2-
A coating composition consisting of 4 parts by weight of ethylhexanoate
Apply it evenly to the S resin plate to a film thickness of 40 μm,
After being left at room temperature for 10 minutes, the coating film was heated at 80° C. for 60 minutes at an angle of 45° with respect to the flat surface, and the coating film was completely cured. Table 1 shows the compounding ratio, and Table 2 shows the results of evaluating the coating film performance of the coated board.

Example 4 A polyester polyacrylate having an average of four acryloyloxy groups in one molecule was synthesized using 2 moles of trimethylolpropane, 1 mole of isophthalic acid, and 4 moles of acrylic acid as raw materials. 50 parts by weight of this polyester polyacrylate, 20 parts by weight of polyether polyene (b-4), polymerizable polymer (c-4)
20 parts by weight (4 parts of 50% toluene solution of polymerizable polymer)
0 parts by weight used), 10 parts by weight of neopentyl glycol diacrylate, 12% of cobalt 2-ethylhexylate.
A coating composition consisting of 0.6 parts by weight of cyclohexane solution and 1 part by weight of cyclohexanone peroxide was uniformly applied to a polyester resin plate to a film thickness of 40 μm, left at room temperature for 10 minutes, and then tilted at 45° with respect to a flat surface. 7 in condition
When heated at 0° C. for 60 minutes, the coating film was completely cured. Table 1 shows the compounding ratio, and Table 2 shows the results of evaluating the coating film performance of the coated board.

<Example 5> 25 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of tris(2-acryloyloxyethyl)isocyanurate, 20 parts by weight of polyether polyene (b-1), polymerizable polymer (
c-5) Coating composition consisting of 45 parts by weight (using 90 parts by weight of a 50% toluene solution of polymerizable polymer), 0.4 parts by weight of a 12% cyclohexane solution of cobalt 2-ethylhexylate, and 2 parts by weight of benzoyl peroxide. ABS things
Coat the resin plate uniformly to a film thickness of 40 μm, leave it at room temperature for 10 minutes, and then tilt it at a 45° angle to a flat surface for 7 minutes.
When heated at 0° C. for 60 minutes, the coating was completely cured. Table 1 shows the compounding ratio, and Table 2 shows the results of evaluating the coating film performance of the coated board.

<Comparative Examples 1 to 4> Coating compositions were prepared according to the formulations shown in Table 3, and each coating composition was coated on an ABS resin plate with a film thickness of 30 μm.
The coating was applied uniformly so that the coating was applied uniformly, and after being left at room temperature for 10 minutes, it was heated at 70° C. for 45 minutes at an angle of 45° with respect to a flat surface. Table 4 shows the state of the coating film and the performance evaluation results at that time.

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

[Table 3]

[0090]

[Table 4]

[0091]

As explained above, the curable coating composition of the present invention can be cured satisfactorily in an air atmosphere at room temperature, depending on the application, by heating, irradiating ultraviolet rays, or leaving it at room temperature. Furthermore, it is possible to form a film that is excellent in various physical properties required of a cured film, such as painted appearance, abrasion resistance, water resistance, heat resistance, solvent resistance, chemical resistance, and adhesion to substrates.

Claims (3)

[Claims] Claim 1: (a) 3 or more (meta) in one molecule
Polymerizable compound having acryloyloxy group 30~
90% by weight, (b) 5-40% by weight of polyether polyene represented by the following general formula (1), [Chemical formula 1] (However, R1 is alcohol, thiol, carboxylic acid,
R represents a residue excluding an active hydrogen atom of an active hydrogen-containing compound selected from the group consisting of carboxylic acid amides and amines.
The molecular weight of 1 part is 2000 or less, n represents an integer of 1 to 10, R2 represents hydrogen or an organic radical having 2 to 10 carbon atoms, and m represents an integer of 1 or more. ), and (c) a polymer having a polymerizable unsaturated double bond 5
-65% by weight (however, the total amount of components (a) to (c) is 100% by weight) as a main component. 2. The curable coating composition according to claim 1, comprising 10 parts by weight or less of (d) a polymerization initiator based on a total of 100 parts by weight of components (a) to (c). 3. The curable coating composition according to claim 1, which comprises (e) not more than 1 part by weight of a metal dryer, based on a total of 100 parts by weight of components (a) to (c).