JP2001172556A - Solvent coating composition and article coated with this - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition for coating which shows an excellent shelf stability and a coated article showing an excellent heat resistance, antifouling property, stain removability, resistance to scuffing, etc. SOLUTION: The curable resin composition comprises an epoxy compound having two or more alicyclic epoxy groups within a molecule and a number average molecular weight of <=2,000, an epoxy group-containing acrylic resin having a number average molecular weight of from 2,000 to 50,000, a hydroxyl equivalent of from 10 to 250 mg KOH/g and an epoxy equivalent of <= 300 and a thermally activated ionic polymerization catalyst which is dissolved and extracted through heating and cooling, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a solvent-based coating composition. More specifically, the present invention relates to a solvent-based coating composition used for coating a vehicle, comprising an epoxy compound having an alicyclic epoxy group, an epoxy group-containing acrylic resin, and a heat-activated ion polymerization catalyst.

[0002]

2. Description of the Related Art Conventionally, in vehicle coating of automobiles and the like, a cationic electrodeposition paint and an intermediate paint are applied to a metal or plastic outer plate, and an opaque paint, a transparent paint and a clear paint are applied as top coats. . If the vehicle is left outdoors, it will be about 50-70 ° C in summer and the coating will soften,
It is easily deteriorated. Accordingly, heat resistance, stain resistance, abrasion resistance and the like are particularly required for the top coat. A solvent-based coating composition comprising a hydroxyl group-containing acrylic resin and a melamine resin is used as the top coating, particularly the clear coating, and the coating has good weather resistance and finished appearance, but has poor acid rain resistance. Not enough. Solvent-based paint (acid-epoxy type paint) containing carboxyl group-containing resin and epoxy group-containing resin as main components as paint with improved acid rain resistance
Is used, but has poor pollution resistance, and is liable to be contaminated by adhesion and penetration of soil, exhaust components, pollutants derived from animals and plants, iron powder, and the like.

On the other hand, ionic polymerizable compositions are known as a method for crosslinking and curing an epoxy compound by ultraviolet light or heat in a short time. However, compositions containing these ion catalysts have poor storage stability, and various methods have been studied. For example, Japanese Unexamined Patent Publication
No. 73163 proposes a method in which organic phosphine is wrapped in a particle shape with a polymer to form microcapsules. There is also a method of achieving one-pack storage by adsorbing on a compound having pores such as zeolite. However, these catalyst systems have insufficient potential to be described later, and are inhomogeneous, so that they cannot be used for a method such as impregnation, and their uses are limited. Further, it has a disadvantage that the cured resin tends to be non-uniform.

On the other hand, a method using a heat latent catalyst, which temporarily suppresses the activity of an acid catalyst and shows the activity again by cleaving it during heat curing, has been widely studied.
Such latent catalysts include, for example, Japanese Patent Publication No. Sho 52
Japanese Patent Application Laid-Open No. 770/770 discloses a method in which active protons are blocked by using an acid-base neutralization reaction, and a method in which active protons are blocked by using an esterification reaction with alcohols. Japanese Patent Application Laid-Open No. 62-192427 discloses a benzylsulfonium salt type and a benzylpyridinium salt type as a latent heat catalyst for generating an active benzyl cation by thermal decomposition of an onium salt. Further, commercially available thermal latent catalysts include a boron trifluoride monoethylamine complex and a boron trifluoride pyridinium complex, which are Lewis acids. However, the acid-
In the case of using a neutralization reaction of a base or an esterification reaction between an acid and an alcohol, a heat-latent acid catalyst having both an appropriate dissociation temperature and the thermal stability of the catalyst itself is obtained. Is difficult. In addition, benzylsulfonium salt type and benzylpyridinium salt type are relatively excellent in storage stability but are not sufficient, and particularly when used for highly reactive alicyclic epoxies, storage stability is poor.

[0005] As described above, when a conventional catalyst is used as a curing catalyst for an epoxy resin, the reaction gradually proceeds immediately after mixing the catalyst with the epoxy resin as a curable resin component even at room temperature. proceed. Therefore, the storage period of the epoxy resin composition is limited, and the epoxy resin composition must be used within that period. On the other hand, Lewis acids such as BF ₃ have been conventionally known as a cationic polymerization catalyst for a cationically polymerizable vinyl compound. However, such a polymerization catalyst has a very poor storage stability due to a reaction even at a temperature of about room temperature. In addition, the degree of polymerization of the obtained resin is small because the polymerization reaction cannot be controlled well. In order to polymerize a vinyl compound, a monomer dissolved in an appropriate solvent is cooled to a predetermined cryogenic temperature, and then a catalyst is added to polymerize. However, performing the polymerization reaction at an extremely low temperature is complicated and expensive. In addition, when a conventional catalyst is used, the epoxy compound or acrylic resin used in the present invention is cured by an ionic reaction. There is a problem that it is greatly reduced. On the other hand, Lewis acids such as BF ₃ are known as cationic polymerization catalysts for cationically polymerizable vinyl compounds. However, such polymerization catalysts cause a reaction even at a temperature of about room temperature and have extremely poor storage stability. It cannot be controlled well and the degree of polymerization is small.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a resin composition for coatings which cures rapidly at a predetermined temperature higher than room temperature and hardly progresses or hardly progresses at about room temperature, and has excellent storage stability. An object of the present invention is to provide a coated article which is excellent in heat resistance, stain resistance, contaminant removal property, scratch resistance and the like using the same.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have developed a specific epoxy compound and an epoxy group-containing acrylic resin, and a special heat-activated ion polymerization catalyst which can be dissolved and precipitated by heating and cooling, respectively. It has been found that such a problem can be solved by using a curable resin composition comprising: and the present invention has been completed.

That is, a first aspect of the present invention is to have two or more alicyclic epoxy groups in one molecule and to have a number average molecular weight of 2,000.
The following epoxy compound (1) having a number average molecular weight of 2,000
0-50,000, hydroxyl value is 10-250mgKOH
/ G and an epoxy group-containing acrylic resin (2) having an epoxy equivalent of 300 or less, and a solvent-based coating composition comprising a heat-activated ion polymerization catalyst (3) capable of being dissolved and precipitated by heating and cooling, respectively. Offer things.
A second aspect of the present invention is that the epoxy group of the epoxy group-containing acrylic resin (2) has an alicyclic epoxy group or glycidyl (meth)
A solvent-based coating composition according to the first aspect of the present invention, which is an acrylate-derived epoxy group. A third aspect of the present invention is the first or second aspect of the present invention, wherein the epoxy compound (1) further contains at least one selected from bisphenol-type epoxy resins, novolak-type epoxy resins, and bromide-type epoxy resins thereof. The present invention provides a solvent-based coating composition as described above. A fourth aspect of the present invention is that the epoxy compound (1) and the epoxy group-containing acrylic resin (2) have an average epoxy equivalent of 30.
The solvent-based coating composition according to any one of the first to third aspects of the present invention, which is 0 or less. A fifth aspect of the present invention is that the heat-activated ionic polymerization catalyst (3) contains at least one selected from the group consisting of a cationic polymerization catalyst (3 ′) and a metal compound (3 ″). The present invention provides a solvent-based coating composition according to any one of the first to fourth aspects.
Is a cationic polymerization catalyst (3 ′) comprising a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms,
The solvent-based coating composition according to the fifth aspect of the present invention, which is a compound having at least one cyclic organic structure having 0 or more substituted or unsubstituted hydrocarbon groups in a molecule. The seventh aspect of the present invention is a cationic polymerization catalyst (3 ′)
Is a sulfonium salt represented by the following general formula (I-1),
An iodonium salt represented by the general formula (I-2), an iron aromatic compound represented by the general formula (I-3), a general formula (I-
4) an organosilicon compound represented by the general formula (I-
The solvent-based coating composition according to any one of the fifth to sixth aspects of the present invention, which is at least one selected from the group consisting of compounds represented by 5).

[0009]

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(In the above general formula, R ¹¹ , R ¹² and R
¹³ may be the same or different and are each a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group or a heteroaromatic group. Note that the molecule has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. X is SbF ₆ , AsF ₆ , PF ₆ ,
BF ₄ , an anion derivative having at least one fluorine atom substituted with a hydroxyl group, CF ₃ SO ₃ , ClO
₄ , an anion selected from the group consisting of a halogen atom, R ¹ —COO, and R ² —SO ₃ . Where R ¹ and R ²
Represents an alkyl group, a halogen atom, a nitro group, a cyano group,
It represents an alkyl group or a phenyl group which may be substituted with an alkoxy group or the like. )

[0011]

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(In the above general formula, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷
May be the same or different, each a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms,
It is a substituted or unsubstituted aromatic or heteroaromatic group. However, a cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in one molecule.
Have more than one. p, q and r are integers from 0 to 3, and p +
q + r is 3 or less. )

[0013]

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(In the above general formula, Ar ¹ is a substituted or unsubstituted aromatic group or a heteroaromatic group, and R ¹⁸ may be the same or different and each has a hydrogen atom and a carbon atom number of 1 to 30. A substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted aromatic group or a heteroaromatic group, provided that a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. Alternatively, the compound has at least one cyclic organic structure having an unsubstituted hydrocarbon group in the molecule, k represents an integer of 1 to 7, and n represents an integer of 1 to 7.) An eighth aspect of the present invention is a metal compound. (3 ″) is at least selected from the group consisting of a compound represented by the following general formula (II-1), a compound represented by (II-2), and a compound represented by (II-3) One of the fifth to seventh aspects of the present invention Providing solvent-based coating composition according to any Re.

[0015]

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(In the above general formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.) However, in one ligand, R ²¹ , R ²² ,
It is assumed that at least one of R ²³ and R ²⁴ having 10 or more carbon atoms is included. M is Al, Ti, C
r, Mn, Fe, Co, Ni, Cu, Zr, Zn, B
It is selected from the group consisting of a, Ca, Ce, Pb, Mg, Sn and V, where n is an integer of 2-4. A ninth aspect of the present invention is that the thermally activated ionic polymerization catalyst (3) comprises a metal compound (3 ″), an organosilane having a hydroxyl group directly bonded to a silicon atom, and an organosiloxane having a hydroxyl group directly bonded to a silicon atom. , Phenolic compounds,
A book comprising: an organosilicon compound having a hydrolyzable group directly bonded to a silicon atom; and at least one selected from the group consisting of a silicon compound capable of generating silanol by light irradiation. A solvent-based coating composition according to any one of the first to eighth aspects of the invention is provided. A tenth aspect of the present invention is a heat-activated ion polymerization catalyst (3).
Contains at least one selected from the group consisting of compounds represented by the following general formulas (III-1 ′) and (III-2). The solvent-based coating composition according to the above.

[0017]

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(In the above formula (III-1 ′), R ¹ , R ² ,
R ³ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, an aromatic group having a substituted or unsubstituted hydrocarbon group, or a heteroaromatic group. is there. However, it has one or more aromatic or heteroaromatic groups having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. )

[0019]

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(In the above general formula (III-2), R ³² ,
R ³³ , R ³⁴ and R ³⁵ may be the same or different,
Each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. However, R ³² , R ³³ , R ³⁴
And at least two of R ³⁵ are a hydrocarbon group having 10 or more carbon atoms. An eleventh aspect of the present invention provides the heat-activated ion polymerization catalyst (3),
The solvent according to any one of the first to fourth aspects of the present invention, comprising at least one selected from the group consisting of compounds represented by the following general formulas (III-1) and (III-2): A coating composition is provided.

[0021]

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(In the general formula (III-1), R ³¹ may be the same or different and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. At least one of R ³¹ has 10 or more carbon atoms, and h, i and j are h + i + j =
3 is an integer satisfying 3, and m is an integer of 1 to 5. )

[0023]

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(In the above formula (III-2), R ³² ,
R ³³ , R ³⁴ and R ³⁵ may be the same or different,
Each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. However, R ³² , R ³³ , R ³⁴
And at least two of R ³⁵ are a hydrocarbon group having 10 or more carbon atoms. A twelfth aspect of the present invention is the solvent according to the eleventh aspect of the present invention, wherein the compound represented by the general formula (III-1) is at least one selected from the following group. A coating composition is provided.

[0025]

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[0026]

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A thirteenth aspect of the present invention is the above-mentioned general formula (III-
The compound represented by 2) provides the solvent-based coating composition according to the tenth or eleventh aspect of the present invention, which is at least one selected from the following group.

[0028]

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According to a fourteenth aspect of the present invention, there is provided the solvent-based coating composition according to any one of the first to thirteenth aspects of the present invention, which is used for coating a vehicle. The fifteenth aspect of the present invention is the first to the first aspects of the present invention.
13. A coated material obtained by coating the substrate with the solvent-based coating composition according to any of 13 and curing the coating.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The solvent-based coating composition of the present invention comprises:
An epoxy compound (1) having two or more alicyclic epoxy groups in the molecule and having a number average molecular weight of 2,000 or less, a number average molecular weight of 2,000 to 50,000, and a hydroxyl value of 10 to 25.
It comprises an epoxy group-containing acrylic resin (2) having 0 mg KOH / g and an epoxy equivalent of 300 or less, and a heat-activated ion polymerization catalyst (3) capable of being dissolved and precipitated by heating and cooling, respectively. The epoxy group-containing acrylic resin (2) has an epoxy group derived from an alicyclic epoxy group or an epoxy group derived from glycidyl (meth) acrylate. Hereinafter, the heat-activated ion polymerization catalyst (3) that can be dissolved and precipitated by heating and cooling is also referred to as a curing catalyst (3). There are two types of curing catalyst (3), a first curing catalyst and a second curing catalyst. The first curing catalyst (3) contains at least one component selected from the group consisting of a cationic polymerization catalyst (3 ′) and a metal compound (3 ″), and at least one of the components of the curing catalyst (3). Can be dissolved and precipitated by heating and cooling.The cationic polymerization catalyst (3 ′) is a sulfonium salt represented by the following general formula (I-1) and a sulfonium salt represented by the following general formula (I-2). Iodonium salt, an iron aromatic compound represented by the general formula (I-3), an organosilicon compound represented by the general formula (I-4),
And a compound represented by the general formula (I-5). The metal compound (3 ″) is selected from the group consisting of compounds represented by the following general formulas (II-1) to (II-3).

[0031]

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(In the above general formula, R ¹¹ , R ¹² and R
¹³ may be the same or different and are each a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group or a heteroaromatic group. Note that the molecule has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. X is SbF ₆ , AsF ₆ , PF ₆ ,
BF ₄ , an anion derivative having at least one fluorine atom substituted with a hydroxyl group, CF ₃ SO ₃ , ClO
₄ , an anion selected from the group consisting of a halogen atom, R ¹ —COO, and R ² —SO ₃ . Where R ¹ and R ²
Represents an alkyl group, a halogen atom, a nitro group, a cyano group,
It represents an alkyl group or a phenyl group which may be substituted with an alkoxy group or the like. )

[0033]

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(In the above formula, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷
May be the same or different, each a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms,
It is a substituted or unsubstituted aromatic or heteroaromatic group. However, a cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in one molecule.
Have more than one. p, q and r are integers from 0 to 3, and p +
q + r is 3 or less. )

[0035]

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(In the above general formula, Ar ¹ is a substituted or unsubstituted aromatic group or a heteroaromatic group, and R ¹⁸ may be the same or different, and each has a hydrogen atom and a C 1-30 carbon atom. A substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted aromatic group or a heteroaromatic group, provided that a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. Alternatively, the compound has at least one cyclic organic structure having an unsubstituted hydrocarbon group in the molecule. K represents an integer of 1 to 7, and n represents an integer of 1 to 7.)

[0037]

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(In the above formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. However, in one ligand, R ²¹ , R ²² ,
It is assumed that at least one of R ²³ and R ²⁴ having 10 or more carbon atoms is included. M is Al, Ti, C
r, Mn, Fe, Co, Ni, Cu, Zr, Zn, B
It is selected from the group consisting of a, Ca, Ce, Pb, Mg, Sn and V, where n is an integer of 2-4. )

The second curing catalyst (3) has the general formula (III-
1 ′), at least one compound selected from the group consisting of compounds represented by (III-1) and (III-2), and at least one of the components of the curing catalyst (3) is heated. Dissolution and precipitation can be performed by cooling.

1. Epoxy compound (1) The epoxy compound (1) used in the present invention has one or more, preferably two to three, alicyclic epoxies in the molecule in consideration of ionic polymerizability, viscosity and the like, and has a number average molecular weight. 2,000 or less, preferably about 100 to 1,500 compounds,
Those having an epoxy equivalent of 30 to 1000, particularly 80 to 400 are preferred. Examples of the epoxy compound (1) include compounds having a terminal epoxy such as glycidyl ether and glycidyl ester, compounds having an internal epoxy, and compounds having an alicyclic epoxy group. The epoxy compound (1) is specifically, CEL-2021P (3,4-
Epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate, epoxy equivalent 128 to
140, viscosity 200-350 cP / 25 ° C), CEL-
2021A (3,4-epoxycyclohexylmethyl 3′4′-epoxycyclohexanecarboxylate,
Epoxy equivalent 130-145, viscosity 200-450 cP
/ 25 ° C), CEL-2000 (1-vinyl-3,4-
Epoxycyclohexane, 1.5 cP / 25 ° C), CE
L-3000 (1,2,8,9-diepoxylimonene,
Epoxy equivalent 93.5 or less, viscosity 5-20 cP / 25
° C), Epolide GT-300, GT-400 series (epoxidized tetrahydrobenzyl alcohol monoester tetrahydrophthalate, epoxidized tetrahydrobenzyl alcohol monoester modified with ε-caprolactone) (all manufactured by Daicel Chemical Industries, Ltd.) Can be In addition, Denacol EX-421,
201 (resorcinol diglycidyl ether), 211
(Neopentyl glycol diglycidyl ether), 9
11 (propylene glycol diglycidyl ether),
701 (diglycidyl adipate) (all manufactured by Nagase Kasei Kogyo Co., Ltd.). In addition, dicyclopentadienedioxide, bis (2,3-epoxycyclopentyl) ether, epoxycyclohexenecarboxylic acid ethylene glycol diester, bis (3,4-
Epoxycyclohexylmethyl) adipate, bis (4,5-epoxy-2-methylcyclohexylmethyl) adipate, ethylene glycol-bis (3,4-
Epoxycyclohexanecarboxylate), 1,2,2
5,6-diepoxy-4,7-methanoperhydroindene, 2- (3,4-epoxycyclohexyl) -3 ',
4'-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxy-bis (3,4
-Epoxycyclohexylmethane), di-2,3-epoxycyclopentyl ether and the like.

The epoxy compound (1) may be used in combination with ionic polymerizable compounds such as vinyl ether and oxetane. When these vinyl ethers or oxetanes are blended, the content is desirably 30% by weight or less based on 100% by weight of the total of the epoxy compound (1), the acrylic resin (2), and the vinyl ethers or oxetanes. The ratio of the compound having an epoxy group in the resin composition comprising the epoxy compound (1) and the acrylic resin (2) is from 20 to 90% by weight, preferably,
40 to 80% by weight. In addition, epoxy compound (1)
For example, a resin having an epoxy group and a reactive silicon group in a molecule, or a mixed resin of an epoxy group-containing resin and a reactive silicon group-containing resin can also be used. The reactive silicon group refers to a silanol group in which a hydroxyl group is directly bonded to a silicon atom, or a group in which a hydrolyzable group is directly bonded to a silicon atom (a group that generates a silanol group by hydrolysis). As the hydrolyzable group directly bonded to the silicon atom, for example,
Examples thereof include an alkoxyl group, an acyloxy group, and a ketoxime group in which the alkyl group has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. Preferred specific examples of the hydrolyzable group include, for example, an alkoxyl group such as a methoxy group, an ethoxy group, and a propoxy group; an acetoxy group, an acyloxy group such as a propionyloxy group, an acetoxime group, and a ketoxime group such as a propionyloxime group. No.
Among these hydrolyzable groups, an alkoxyl group having 1 to 3 carbon atoms, which has excellent effects on storage stability and low-temperature curability, is particularly preferable.

Further, the epoxy compound (1) includes:
Bisphenol-type epoxy compounds, novolak-type epoxy compounds, bromide-type epoxy compounds thereof, and the like can be added. Specifically, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, and ortho-cresol novolak A type epoxy resin, a DPP novolak type epoxy resin, a tris-hydroxyphenylmethane type epoxy resin, other polyfunctional type epoxy resins, a tetrabromobisphenol A type epoxy resin and the like can be used according to the purpose. These epoxy resins are made of an epoxy compound (1)
Can be added in the range of 0 to 70% by weight based on 100% by weight of the above.

2. Epoxy and hydroxyl group-containing acrylic resin (2) The acrylic resin (2) having an epoxy group and a hydroxyl group has a number average molecular weight of 2,000 to 50,000,
An epoxy group-containing acrylic resin having a hydroxyl value of 10 to 250 mgKOH / g and an epoxy equivalent of 300 or less. The acrylic resin (2) has, as constituent components, a monomer having an epoxy group, a monomer having a hydroxyl group, and / or a monomer having an epoxy group and a hydroxyl group, and a monomer copolymerizable therewith.

As the monomer component having an epoxy group, glycidyl ether or a (meth) acrylate having a similar terminal epoxy, and a (meth) acrylate having an alicyclic epoxy can be used. Examples of the monomer include glycidyl (meth) acrylate, 2-methyl-glycidyl methacrylate, allyl glycidyl ether, epoxidized isoprenyl methacrylate, CYM M-100 (3,
4-epoxycyclohexylmethyl methacrylate),
A-200 (3,4-epoxycyclohexylmethyl acrylate), containing a group obtained by ring-opening polymerization of ε-caprolactone between a 3,4-epoxycyclohexylmethyl group and a (meth) acrylate group (all manufactured by Daicel Chemical Industries, Ltd.) ), 2- (1,2-epoxy-4,7-methanoperhydroindene-5 (6) -yl) oxyethyl (meth)
Acrylate, 5,6-epoxy-4,7-methanoperhydroinden-2-yl- (meth) acrylate,
1,2-epoxy-4,7-methanoperhydroinden-5-yl- (meth) acrylate and the like.

Hydroxyl-containing monomer components of the acrylic resin (2) include hydroxyethyl (meth) acrylate, hydroxyethyl acrylate, and PCL-FM obtained by modifying these hydroxyl-containing acrylates with caprolactone.
1, PCL-FM3, PCL-FM10, PCL-FA
1, PCL-FA3 (manufactured by Daicel Chemical Industries, Ltd.), other monoesters of (meth) acrylic acid and a glycol having 3 to 10 carbon atoms, polyether polyols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; ) Monoesters with acrylic acid. The amount of the hydroxyl group in the resin composition comprising the epoxy compound (1) and the acrylic resin (2) is 1 to 300 mgKOH / g, preferably 1.5 to 250 mgKOH / g, as the hydroxyl value.

As the acrylic monomer component of the acrylic resin (2) which can be copolymerized with the acrylic resin, ordinary alkyl acrylate monomers and the like can be used. As the alkyl acrylate monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, etc., have 2 to 10 carbon atoms in the alkyl moiety, preferably 1 to Five alkyl acrylate monomers are included. Other monomer components used in the acrylic resin (2) include styrene, α-methylstyrene, vinyltoluene, vinyl chloride, and the like.
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Carboxy group-containing polymerizable monomers such as maleic acid and fumaric acid; N-methylol (meth) acrylamide, N-
Amide-based polymerizable monomers such as methoxymethyl (meth) acrylamide and N-butoxymethyl (meth) acrylamide; ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether,
Vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, allyl glycidyl ether; vinyl acetate, vinyl propionate, ethylene, propylene, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( (Meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, vinylpyrrolidone and the like can also be used.

Further, a reactive silicon group-containing ethylenically unsaturated monomer or a perfluoroalkyl group or perfluoroalkenyl group-containing ethylenically unsaturated monomer can also be used. Examples of the reactive silicon group-containing ethylenically unsaturated monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) silane Acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, β- (meth) acryloyloxyethylpropyltrimethoxysilane, these and alkoxysilanes (eg, tetraalkoxysilane, trialkoxyalkylsilane, etc.) Of a low-condensation product of a tetracondensed silane with a hydroxyl group-containing ethylenically unsaturated monomer (eg, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc.) Etc. can be mentioned, with these at least one. Here, as the low condensate of the tetraalkoxysilane, the formula alkoxy group is a hydrogen atom, a methyl group, an ethyl group or about 2 to 100-mer obtained by performing a condensation reaction between tetraalkoxysilanes each being a propyl group. And preferably about 2 to 10 mer. Examples of the low-condensate include “Colcoat ES40” (trade name, manufactured by Colcoat, 1 to 10-mer tetraethylsilicate, average about pentamer), and “Colcoat MS51”
(1 to 10-mers of tetramethylsilicate, average about 4-mers) and the like.

An acrylic oligomer can also be used as an acrylic component of the acrylic resin (2) which can be copolymerized with the acrylic resin (2). Specifically, epoxidized oil acrylate, urethane acrylate, polyester urethane acrylate, polyether urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl / acrylate, polyene / thiol, Components such as silicon acrylate, polybutadiene acrylate, polystilethyl methacrylate, and polycarbonate diacrylate can also be used.

When the constituent components of the acrylic resin (2) are polymerized, an initiator can be used. Initiators include potassium persulfate, ammonium persulfate, benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide,
Dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, acetyl peroxide, methyl ethyl ketone peroxide, succinic peroxide, dicetyl Peroxydicarbonate, t-butyl peroxyacetate, AIBN (2,2'-azobisisobutyronitrile), ABN-E (2,2'-azobis (2-methylbutyronitrile)), ABN-V (2,2′-azobis (2,4-dimethylvaleronitrile)), perbutyl O
(T-butylperoxy 2-ethylhexanoate) and the like can be used. The amount of the initiator used is based on 100 parts by weight of the total components of the acrylic resin (2).
It is 1 to 10 parts by weight, preferably 3 to 6 parts by weight. The initiator may be partially charged in advance, or may be added dropwise to the monomer or the like or separately without being added.
Further, after the monomer is charged, an additional initiator may be charged.

The polymerization temperature for synthesizing the acrylic resin (2) is 90 to 130 ° C., preferably 100 to 120 ° C. When the polymerization temperature is higher than 130 ° C., the polymerization becomes unstable and a large amount of high molecular weight compounds are produced.
The reaction time is too long, which is not preferable.

As the solvent used when polymerizing the acrylic resin (2), an epoxy compound (1) or the following solvent having no ordinary ionic polymerizability can be used. Also, after synthesizing the acrylic resin using a normal solvent,
After the solvent is removed, the resin composition can be diluted with the epoxy compound (1) to obtain a resin composition. Examples of the solvent having no ionic polymerizability include aromatic solvents such as toluene and xylene, and methyl ethyl ketone, methyl isobutyl ketone, and methoxypropylene glycol acetate.These may be used alone or in combination. it can.

The content of the epoxy group-containing (meth) acrylate in the acrylic resin (2) is, for example, 1 to 80% by weight as glycidyl methacrylate, preferably
15 to 60% by weight. The oxirane oxygen concentration of the resin composition comprising the epoxy compound (1) and the acrylic resin (2) is 5 to 11% by weight, preferably 7 to 10%.
% By weight.

3. Heat-Activated Ion Polymerization Catalyst (3) The heat-activated ion polymerization catalyst (3) used in the present invention, that is, the curing catalyst (3), comprises a first curing catalyst and / or
Or it is a second curing catalyst. The amount of the first curing catalyst and / or the second curing catalyst described below is based on the total amount of the epoxy compound (1) and the acrylic resin (2) (that is, the one having an epoxy group).

3.1. First Curing Catalyst The first curing catalyst contains at least one component selected from the group consisting of a cationic polymerization catalyst (3 ′) and a metal compound (3 ″). The ingredients of the heating,
It is preferable to have the property that melting and precipitation can be performed reversibly by cooling. The above-mentioned heating means heating from room temperature or more, specifically from 40 ° C. or more to the curing temperature, and cooling means cooling to a curing temperature or less, specifically 80 ° C. or less, preferably 60 ° C. or less. Means to do. The term “precipitation” means that the catalyst takes a form of colloid, micelle, crystal, or the like in the epoxy compound (1) and / or the acrylic resin (2),
It is sufficient that the active site of the catalyst is isolated from the epoxy compound (1) and / or the acrylic resin (2). Furthermore, as long as the thermal activation (latent, thermal latent) of the curing catalyst can be confirmed by a storage stability test or the like, any size may be used, but preferably, the average particle size of the catalyst is 0. What is necessary is to be able to confirm the thing of 1 μm or more. In the present invention, the term “dissolution” means that the curing catalyst (3) having the above-mentioned form may be partially dissolved in the epoxy compound (1) and / or the acrylic resin (2). And / or the curing catalyst precipitated in the acrylic resin (2) is collected together with the resin in a glass plate form, and then observed under a microscope while heating. . Further, the endothermic peak derived from the dissolution of the curing catalyst in the epoxy compound (1) and the acrylic resin (2) is DS
It is even better if it is confirmed in C (differential scanning calorimetry) or the like.

3.1.1. Cationic Polymerization Catalyst (3 ′) Examples of the cationic polymerization catalyst component (3 ′) blended in the first curing catalyst include a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, Alternatively, a compound having at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in a molecule may be used. 1 carbon
6 or more is more preferable. These hydrocarbon group and cyclic organic structure may be present as a substituent or may be present as a part of a ligand. Examples of the cyclic organic structure include aromatic, heteroaromatic, condensed aromatic and condensed heteroaromatics. Examples of the element serving as the cation of the cationic polymerization catalyst component include S, I, Fe, N, O, P,
Examples include Mg, Mn, and Si.

A specific description will be given. Examples of the cationic polymerization catalyst component include a sulfonium salt represented by the following formula (I-1), an iodonium salt represented by the following formula (I-2), and a formula represented by the following formula (I-3). Onium salts such as iron aromatic compounds, organosilicon compounds represented by the following general formula (I-4), and compounds represented by the following general formula (I-5).

3.1.1.1. Onium Salt Catalyst As the onium salt catalyst, the sulfonium salt (I-
1), onium salts (I-3) such as iodonium salts (I-2) and iron aromatic compounds, as well as ammonium salts, diazonium salts, pyrrolium salts, pyrylium salts, quinolium salts,
Anilium salts, pyridium salts, benzylammonium salts, benzothiazolium compound salts, benzylpyridium salts, benzylsulfonium salts, benzylphosphonium salts and the like may be used.

[0058]

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In the above general formula, R ¹¹ , R ¹² and R ¹³ are
They may be the same or different and are each a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group or a heteroaromatic group. However, the compound has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in the molecule. More specifically, a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or
It has at least one aromatic or heteroaromatic group having the above-mentioned substituted or unsubstituted hydrocarbon group. X is Sb
F ₆ , AsF ₆ , PF ₆ , BF ₄ , those anion derivatives in which at least one fluorine atom is substituted with a hydroxyl group, CF ₃ SO ₃ , ClO ₄ , a halogen atom, R ¹ —COO,
An anion selected from the group consisting of R ² -SO _3.
Here, R ¹ and R ² are an alkyl group, a halogen atom,
It represents an alkyl group or a phenyl group which may be substituted with a nitro group, a cyano group, an alkoxy group or the like.

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In the above general formula, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted hydrocarbon group. An unsubstituted aromatic or heteroaromatic group. However, a cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in one molecule.
Have more than one. More specifically, it has at least one aromatic or heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. p, q and r are 0 to
In the integer of 3, p + q + r is 3 or less.

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In the above general formula, Ar ¹ is a substituted or unsubstituted aromatic group or a heteroaromatic group, and R ¹⁸ may be the same or different and each represents a hydrogen atom or a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms. Alternatively, it is an unsubstituted hydrocarbon group, a substituted or unsubstituted aromatic group or a heteroaromatic group. Note that the molecule has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. k represents an integer of 1 to 7, and n represents an integer of 1 to 7, respectively. In the general formula, examples of the hydrocarbon group introduced as R ^{11 to} R ¹⁸ include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, Compounds having a branched or straight-chain substituent such as pentadecane, hexadecane, heptadecane, octadecane, nonadecane, icosane, henyicosane, docosane, trichosane, tetracosane, pentacosane, hexacosane, heoutacosane, octacosane, nonacosane, triacosane or the like, and a steroid skeleton such as cholesterol. Can be used. Further, the above-described hydrocarbon group may contain a hetero atom such as F, Si, O, N, or S.

In the above formula, the substituted or unsubstituted aromatic or heteroaromatic group introduced as R ^{11 to} R ¹⁸ includes, for example, phenyl, benzyl, methylbenzyl, dimethylbenzyl, Two or three benzene rings such as trimethylbenzyl, chlorobenzyl, dichlorobenzyl, trichlorobenzyl, nitrobenzyl, dinitrobenzyl, trinitrobenzyl, naphthylmethyl; naphthyl, anthracenyl and phenanthrenyl Condensed aromatic ring group formed by condensation; furanyl, thiophenyl, pyrrolyl, pyrrolinyl,
Pyrrolidinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, imidazolinyl, imitazolidinyl, pyrazolyl, pyrazolidinyl,
Triazolyl, flazanil, tetrazolyl, pyranyl,
Thiynyl, pyridinyl, piperidinyl, oxazinyl,
Monocyclic heteroaromatic groups such as morpholinyl, thiazinyl, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl and triazinyl groups; benzofuranyl, isobenzofuranyl, benzothiophenyl, indolyl, indolinyl, isoindolyl, benzoxazolyl, benzothiazolyl, indazolyl , Imidazolyl, chromenyl, chromanyl, isochromanyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, dibenzofuranyl, carbazolyl, xanthenyl, acridinyl, phenanthrinyl, phenanthrolinyl, phenazinyl, phenoxinyl, thianthinyl, thianthinyl Fused heterogenes such as quinuclidinyl, naphthyridinyl, prenyl and pteridinyl groups Kowamoto; and hydrogen atoms may include one or more substituent these groups substituted with a group. Examples of the substituent of these substituted aromatic groups or heteroaromatic groups include organic groups having 1 or more carbon atoms. When a plurality of carbon atoms are present, they may be the same or different. Good.

Examples of the sulfonium salt represented by the general formula (I-1) include tris (p-octadecyloxyphenyl) sulfonium hexafluoroantimonate and bis (p-octadecyloxyphenyl) phenylsulfonium hexafluoroantimonate , (P−
Octadecyloxyphenyl) diphenylsulfonium hexafluoroantimonate, tris (p-hexadecyloxyphenyl) sulfonium hexafluoroantimonate, bis (p-hexadecyloxyphenyl)
Phenylsulfonium hexafluoroantimonate,
(P-hexadecyloxyphenyl) diphenylsulfonium hexafluoroantimonate, benzyl-4-
Octadecyloxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-octadecyloxyphenylethylsulfonium hexafluoroantimonate, benzyl-4-octadecyloxyphenylsulfonium hexafluoroantimonate, tris (p-octadecyloxyphenyl) sulfonium hexafluorophosphate, Bis (p-octadecyloxyphenyl) phenylsulfonium hexafluorophosphate, (p-octadecyloxyphenyl) diphenylsulfonium hexafluorophosphate, tris (p-hexadecyloxyphenyl) sulfonium hexafluorophosphate, bis (p-hexadecyloxyphenyl) Phenylsulfonium hexafluorophosphate, (p- Xadecyloxyphenyl) diphenylsulfonium hexafluorophosphate, benzyl-4-octadecyloxyphenylmethylsulfonium hexafluorophosphate, benzyl-4-octadecyloxyphenylethylsulfonium hexafluorophosphate, benzyl-4-octadecyloxyphenylsulfonium hexafluorophosphate, tris (P-octadecyloxyphenyl) sulfonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) phenylsulfonium hexafluoroarsenate, (p-octadecyloxyphenyl) diphenylsulfonium hexafluoroarsenate, tris (p-hexadecyloxyphenyl) ) Sulfonium hexafluoroarsenate, bis ( -Hexadecyloxyphenyl) phenylsulfonium hexafluoroarsenate, (p-hexadecyloxyphenyl) diphenylsulfonium hexafluoroarsenate, benzyl-4-octadecyloxyphenylmethylsulfonium hexafluoroarsenate, benzyl-4-octadecyloxyphenylethyl Sulfonium hexafluoroarsenate, benzyl-4-octadecyloxyphenylsulfonium hexafluoroarsenate, tris (p-octadecyloxyphenyl) sulfonium tetrafluoroborate, bis (p-octadecyloxyphenyl) phenylsulfonium tetrafluoroborate, (p-octadecyl Oxyphenyl) diphenylsulfonium tetrafluoroborate, tris (p-f Xadecyloxyphenyl) sulfonium tetrafluoroborate, bis (p-hexadecyloxyphenyl)
Phenylsulfonium tetrafluoroborate, (p-
(Hexadecyloxyphenyl) diphenylsulfonium tetrafluoroborate, benzyl-4-octadecyloxyphenylmethylsulfonium tetrafluoroborate, benzyl-4-octadecyloxyphenylethylsulfonium tetrafluoroborate, benzyl-4
-Octadecyloxyphenylsulfonium tetrafluoroborate, tris (p-octadecyloxyphenyl) sulfonium trifluoromethanesulfonate, bis (p-octadecyloxyphenyl) phenylsulfonium trifluoromethanesulfonate, (p-octadecyloxyphenyl) diphenylsulfonium trifluoromethanesulfonate, tris (P-hexadecyloxyphenyl) sulfonium trifluoromethanesulfonate, bis (p-hexadecyloxyphenyl) phenylsulfonium trifluoromethanesulfonate,
(P-hexadecyloxyphenyl) diphenylsulfonium trifluoromethanesulfonate, benzyl-4
-Octadecyloxyphenylmethylsulfonium trifluoromethanesulfonate, benzyl-4-octadecyloxyphenylethylsulfonium trifluoromethanesulfonate, benzyl-4-octadecyloxyphenylsulfonium trifluoromethanesulfonate, p-octadecyloxybenzyltetramethylenesulfonium hexafluoroantimonate, (4 -Octadecyloxyphenyl) cinnamylmethylsulfonium hexafluoroantimonate, (4-octadecyloxyphenyl) (3-methyl-2-butenyl) methylsulfonium hexafluoroantimonate, 4-octadecyloxyphenyl- (α-naphthylmethyl) methyl Sulfonium hexafluoroantimonate, 4
-Octadecyloxyphenyl-9-fluorenylmethylsulfonium hexafluoroantimonate, tris (4-octadecyloxyphenylmethyl) sulfonium hexafluoroantimonate, o-nitrobenzyl-4-octadecyloxyphenylmethylsulfonium hexafluoroantimonate, α -Phenylbenzyl-4-octadecyloxyphenylmethylsulfonium hexafluoroantimonate, α-methylbenzyl-4-octadecyloxyphenylmethylsulfonium hexafluoroantimonate, dibenzyl-
4-octadecyloxyphenylsulfonium hexafluoroantimonate, 4-octadecyloxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Hexafluoroantimonate, which forms the anion portion of the above-mentioned sulfonium salt, is obtained by converting hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, these anions having at least one fluorine atom substituted with a hydroxyl group, and trifluoromethanesulfonate; Perchlorate, halogen, R ¹ -CO
A compound converted to an anion selected from the group consisting of O and R ² —SO ₃ can also be used as the curing catalyst component of the present invention. R ¹ and R ² represent an alkyl group, a halogen atom, a nitro group, a cyano group, an alkyl group which may be substituted with an alkoxy group, or a phenyl group.
Further, benzyl-4-octadecyloxyphenylmethylhexafluoroantimonate, benzyl-4-octadecyloxyphenylmethylhexafluoroarsenate, benzyl-4-octadecyloxyphenylmethylhexafluorophosphate, and benzyl-4-octadecyloxyphenylmethyltetrafluorophosphate Borates, benzyl-4-octadecyloxyphenylmethyl trifluoromethanesulfonate, and the like can also be used.

Examples of the iodonium salt represented by the general formula (I-2) include bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, (p-octadecyloxyphenyl) phenyliodonium hexafluoroantimonate, Bis (p-hexadecyloxyphenyl) iodonium hexafluoroantimonate, (p-hexadecyloxyphenyl) phenyliodonium hexafluoroantimonate, benzyl-4-octadecyloxyphenylmethyliodonium hexafluoroantimonate, benzyl-4-octadecyloxy Phenylethyliodonium hexafluoroantimonate, benzyl-4-octadecyloxyphenyliodonium hexafluoroantimonate, bis ( - octadecyloxyphenyl)
Iodonium hexafluorophosphate, (p-octadecyloxyphenyl) phenyliodonium hexafluorophosphate, bis (p-hexadecyloxyphenyl) iodonium hexafluorophosphate,
(P-hexadecyloxyphenyl) phenyliodonium hexafluorophosphate, benzyl-4-octadecyloxyphenylmethyliodonium hexafluorophosphate, benzyl-4-octadecyloxyphenylethyliodonium hexafluorophosphate, benzyl-4-octadecyloxyphenyliodonium hexafluoro Phosphate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, (p-octadecyloxyphenyl) phenyliodonium hexafluoroarsenate, bis (p-hexadecyloxyphenyl) iodonium hexafluoroarsenate, (p-hexadecyl) Oxyphenyl) phenyliodonium hexafluoroarsenate, benzyl-4 Octadecyloxyphenylmethyliodonium hexafluoroarsenate, benzyl-4-octadecyloxyphenylethyliodonium hexafluoroarsenate, benzyl-4-octadecyloxyphenyliodonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) iodonium tetrafluoroborate, (P-octadecyloxyphenyl) phenyliodonium tetrafluoroborate, bis (p-hexadecyloxyphenyl) iodonium tetrafluoroborate, (p-hexadecyloxyphenyl) phenyliodonium tetrafluoroborate, benzyl-4-octadecyloxyphenylmethyliodonium Tetrafluoroborate, benzyl-4-octadecyloxyphenyl Tyliodonium tetrafluoroborate, benzyl-4-octadecyloxyphenyliodonium tetrafluoroborate, bis (p-octadecyloxyphenyl) iodonium trifluoromethylsulfonate, (p-octadecyloxyphenyl) phenyliodonium trifluoromethylsulfonate, bis (p- (Hexadecyloxyphenyl) iodonium trifluoromethylsulfonate, (p-hexadecyloxyphenyl) phenyliodonium trifluoromethylsulfonate, benzyl-
4-octadecyloxyphenylmethyliodonium trifluoromethylsulfonate, benzyl-4-octadecyloxyphenylethyliodonium trifluoromethylsulfonate, benzyl-4-octadecyloxyphenyliodonium trifluoromethylsulfonate, and p-octadecyloxybenzyltetramethyleneiodonium hexafluoro Antimonate, (4
-Octadecyloxyphenyl) cinnamylmethyliodonium hexafluoroantimonate, (4-octadecyloxyphenyl) (3-methyl-2-butenyl) iodonium hexafluoroantimonate, 4
-Octadecyloxyphenyl- (α-naphthylmethyl) iodonium hexafluoroantimonate, 4
-Octadecyloxyphenyl-9-fluorenyliodonium hexafluoroantimonate, bis (4-
Octadecyloxyphenylmethyl) iodonium hexafluoroantimonate, o-nitrobenzyl-4
-Octadecyloxyphenyliodonium hexafluoroantimonate, α-phenylbenzyl-4-octadecyloxyphenyliodonium hexafluoroantimonate, α-methylbenzyl-4-octadecyloxyphenyliodonium hexafluoroantimonate, benzyl-4-octadecyloxyphenyliodonium Hexafluoroantimonate, 4-octadecyloxyphenylmethyliodonium hexafluoroantimonate and the like can be mentioned.

Hexafluoroantimonate which forms the anion part of the above-mentioned iodonium salt is hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, these anions in which at least one fluorine atom is substituted by a hydroxyl group, and trifluoromethanesulfonate; Perchlorate, halogen, R ¹ -CO
A compound converted to an anion selected from the group consisting of O and R ² —SO ₃ can also be used as the curing catalyst component of the present invention. R ¹ and R ² represent an alkyl group, a halogen atom, a nitro group, a cyano group, an alkyl group which may be substituted with an alkoxy group, or a phenyl group.

Further, the following onium salts can be used. Examples of the pyrylium salt include those represented by the following general formula.

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In the above formula, R may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group or a heteroaromatic group. It is. However, an aromatic or heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R also includes a halogen atom, a nitro group, and a cyano group. N is an integer of 1 to 5. X represents SbF ₆ , AsF ₆ , PF ₆ , BF ₄ , an anion derivative having at least one fluorine atom substituted with a hydroxyl group, CF ₃ SO ₃ , ClO ₄ , a halogen atom, R—COO, R—SO ₃ 3 shows anions selected from the group consisting of: Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

The pyrylium salt represented by the above general formula includes 2,6-dimethyl-4-octadecyloxyphenylpyrylium hexafluoroantimonate,
Dimethyl-3- (4-octadecyloxyphenyl) propylpyrylium hexafluoroantimonate and the like can be mentioned. The compounding amount is usually 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the compound (1) and the resin (2). If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use more than 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems. Examples of the benzylphosphonium salt include those represented by the following general formula.

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In the above general formulas, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom,
It is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group or a heteroaromatic group. However, an aromatic or heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R ⁴ also includes halogen atoms, nitro groups, and cyano groups. N is an integer of 1 to 5. X is SbF ₆ , A
sF ₆ , PF ₆ , BF ₄ , an anion derivative having at least one fluorine atom substituted with a hydroxyl group, and CF
₃ SO ₃ , ClO ₄ , halogen atom, R-COO, RS
₃ shows an anion selected from the group consisting of O ₃ . Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

Examples of the benzylphosphonium salt represented by the above general formula include benzyltris (4-octadecyloxyphenyl) phosphonium hexafluoroantimonate, α-phenylbenzyltris (4-octadecyloxyphenyl) phosphonium hexafluoroantimonate and the like. Can be mentioned. Hexafluoroantimonate, which is an anion part of the above-mentioned benzylphosphonium salt, may be at least one of hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate,
These anions in which fluorine atoms have been substituted with hydroxyl groups,
And a compound converted to an anion selected from the group consisting of trifluoromethanesulfonate, perchlorate, halogen, R ¹ —COO, and R ² —SO ₃ can also be used as the curing catalyst component of the present invention. R ¹ and R ² represent an alkyl group, a halogen atom, a nitro group, a cyano group, an alkyl group which may be substituted by an alkoxy group, or a phenyl group. The compounding amount is usually 0.0% based on the epoxy compound (1) and the acrylic resin (2) of the composition.
It is 1 to 20% by weight, preferably 0.1 to 5% by weight.
If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use more than 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

Examples of the benzyl ammonium salt include those represented by the following general formula.

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In the above general formula, R¹, R^Two, R^Three, R^Four, R^Five
And R⁶May be the same or different, each with water
Elemental atoms, substituted or unsubstituted hydrocarbons having 1 to 30 carbon atoms
Group, substituted or unsubstituted aromatic group or heteroaromatic
Group. However, substitution having 10 or more carbon atoms or
Unsubstituted hydrocarbon group or substituted with 10 or more carbon atoms
Or an aromatic group having an unsubstituted hydrocarbon group or
It has one or more aromatic groups. Further, R^Five, R⁶Is both
Both hydrogen atoms, one is a hydrogen atom and the other is an alkyl group
Or a halogen atom or both are alkyl groups
Or it is a halogen atom. R^Five, R⁶Are both hydrogen
In the case of an atom, R¹, R^Two, R^ThreeAt least one of
Is preferably an aromatic or heteroaromatic group.
No. Where R ^FourRepresents a halogen atom, a nitro group, a cyano group
Including. n is an integer of 1 to 5. X is SbF₆, As
F₆, PF₆, BF_FourWherein at least one fluorine atom is water
These anionic derivatives substituted with an acid group, and CF_Three
SO_Three, ClO_Four, Halogen atom, R-COO, R-SO
_Three3 shows anions selected from the group consisting of: Where R
Represents an alkyl group, a halogen atom, a nitro group, a cyano group,
An alkyl group which may be substituted with an alkoxy group, etc.
Is a phenyl group.

The benzyl ammonium salt represented by the above general formula includes N- (p-octadecyloxybenzyl) -N, N-dimethylanilinium hexafluoroantimonate, N- (p-octadecyloxybenzyl) -N, N-dimethylanilinium hexafluorophosphate, N- (p-octadecyloxybenzyl)
-N, N-dimethylanilinium tetrafluoroborate, N- (α-methyl-p-octadecyloxybenzyl) -N, N-dimethylanilinium hexafluoroantimonate, N- (2-hydroxyethyl) -N-
(Α-methyl-p-octadecyloxybenzyl)-
N, N-dimethylammonium hexafluoroantimonate and the like can be mentioned. The compounding amount is usually 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the total amount of the epoxy compound (1) and the acrylic resin (2) in the composition. If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use more than 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.
Among the above benzyl ammonium salts, R ¹ , R ² , R ³
Is an anilium salt represented by a substituted or unsubstituted phenyl group, wherein at least one of the remaining ^{two of} R ¹ , R ² , and R ³ has an alkyl group having a substituent at the β-position carbon atom of the nitrogen atom. What you have is also effective.

Examples of the benzylpyridinium salt include those represented by the following general formula.

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In the above formula, R ¹ , R ² , and R ³ may be the same or different and each represents a hydrogen atom, a carbon number of 1 to 3,
It is 0 substituted or unsubstituted hydrocarbon group, substituted or unsubstituted aromatic group or heteroaromatic group. However, it has one or more aromatic or heteroaromatic groups having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. However, R ^{1 also} includes a cyano group, and R ² also includes a halogen atom, a nitro group, and a cyano group. n is an integer of 1 to 5, m
Is an integer of 1 to 7. X is SbF ₆ , AsF ₆ , P
F ₆ , BF ₄ , these anion derivatives having at least one fluorine atom substituted with a hydroxyl group, CF ₃ SO ₃ , C ₃
lO _4, a halogen atom, R-COO, an anion selected from the group consisting of R-SO _3. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

The benzylpyridinium salt (A) represented by the above general formula includes 1- (p-octadecyloxybenzyl) -4-cyanopyridinium hexafluoroantimonate, 1- (p-octadecyloxybenzyl)
4-cyanopyridinium hexafluorophosphate, 1- (p-octadecyloxybenzyl) -4-cyanopyridinium tetrafluoroborate and the like. Examples of the benzylpyridinium salt (B) represented by the general formula include α-naphthylmethyl- (4-octadecyloxy) pyridinium hexafluoroantimonate, α-naphthylmethyl- (4-octadecyloxy) pyridinium hexafluorophosphate, and α-naphthylmethyl- (4-octadecyloxy) pyridinium hexafluorophosphate.
And naphthylmethyl- (4-octadecyloxy) pyridinium tetrafluoroborate. As the benzylpyridinium salt (C) represented by the above general formula, cinnamyl- (4-octadecyloxy) pyridinium hexafluoroantimonate, 2-butenyl-
(4-octadecyloxy) pyridinium hexafluoroantimonate, cinnamyl- (4-octadecyloxy) pyridinium hexafluorophosphate,
Cinnamyl- (4-octadecyloxy) pyridinium tetrafluoroborate and the like. The compounding amount is
Usually 0.01 to 20% by weight, preferably 0.1 to 20% by weight, based on the total of the epoxy compound (1) and the resin (2) of the composition.
5% by weight. If the amount is less than 0.01% by weight, curing may be insufficient. Also, 20
Although it is possible to use it in an amount exceeding the weight%, it is not preferable because the cost may be high and the decomposition product of the catalyst component may become a problem.

Examples of the benzothiazolium salt include those represented by the following general formula.

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In the above formula, R ¹ , R ² , and R ³ may be the same or different and each represents a hydrogen atom, a carbon number of 1 to 3,
It is 0 substituted or unsubstituted hydrocarbon group, substituted or unsubstituted aromatic group or heteroaromatic group. Note that the compound has one or more aromatic or heteroaromatic groups having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R ¹ and R ² contain a nitro group. R ⁴ is a hydrogen atom, an aromatic group or a heteroaromatic group, n is an integer of 1 to 5, and m is an integer of 1 to 4. The S atom of the thiazolium ring may be substituted with an O atom. X is SbF ₆ , As
F ₆ , PF ₆ , BF ₄ , these anion derivatives having at least one fluorine atom substituted with a hydroxyl group, and CF ₃
SO _3, ClO _4, a halogen atom, R-COO, R-SO
₃ shows an anion selected from the group consisting of ₃ . Where R
Represents an alkyl group, a halogen atom, a nitro group, a cyano group,
An alkyl group or a phenyl group which may be substituted with an alkoxy group or the like.

Further, a compound represented by the following general formula may be used.

[0088]

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In the above formula, R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted group. It is a substituted aromatic or heteroaromatic group. Note that the compound has one or more aromatic or heteroaromatic groups having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R ¹ and R ² contain a nitro group.
n is an integer of 1 to 5, and m is an integer of 1 to 4. The S atom of the thiazolium ring may be substituted with an O atom. X is SbF ₆ , AsF ₆ , PF ₆ , BF ₄ , an anion derivative having at least one fluorine atom substituted with a hydroxyl group,
And CF ₃ SO ₃ , ClO ₄ , halogen atom, R—CO
O, shows the anions selected from the group consisting of R-SO _3. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

The benzothiazolium salt represented by the above general formula includes 3- (p-octadecyloxybenzyl)
Benzothiazolium hexafluoroantimonate, 3
-(P-octadecyloxybenzyl) -2-methylthiobenzothiazolium hexafluoroantimonate,
3- (p-octadecyloxybenzyl) benzothiazolium hexafluorophosphate, 3- (p-octadecyloxybenzyl) benzothiazolium tetrafluoroborate and the like can be mentioned. The compounding amount is usually 0.0% based on the total of the compound (1) and the acrylic resin (2) of the composition.
It is 1 to 20% by weight, preferably 0.1 to 5% by weight.
If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use more than 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

The quinolinium salts include those represented by the following general formula.

[0092]

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In the above formula, R ¹ may be the same or different and each represents a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group. Group or a heteroaromatic group. Note that the compound has one or more aromatic or heteroaromatic groups having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R ² is a group selected from the group consisting of an alkyl group substituted with an aromatic group or a heteroaromatic group and an alkyl group substituted with an unsaturated bond such as ethylene or acetylene. n is an integer of 1 to 7. X is SbF ₆ , AsF ₆ , PF ₆ , BF ₄ , an anion derivative having at least one fluorine atom substituted with a hydroxyl group,
And CF ₃ SO ₃ , ClO ₄ , halogen atom, R—CO
O, shows the anions selected from the group consisting of R-SO _3. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

Examples of the quinolinium salt represented by the above general formula include N-benzyl- (5-octadecyloxy) quinolinium hexafluoroantimonate and N- (1-naphthylmethyl) -5-octadecyloxyquinolinium hexafluoroantimonate. , N-cinnamyl-5
-Octadecyloxyquinolinium hexafluoroantimonate. The compounding amount is usually 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the total amount of the epoxy compound (1) and the acrylic resin (2) in the composition. If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use more than 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

Examples of the pyrrolium salt include those represented by the following general formula.

[0096]

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In the above formula, R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, It is a substituted or unsubstituted aromatic or heteroaromatic group. Note that the compound has one or more aromatic or heteroaromatic groups having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R ⁴ is a hydrogen atom or an alkyl group. n is an integer of 1 to 7. X is S
bF ₆ , AsF ₆ , PF ₆ , BF ₄ , an anion derivative in which at least one fluorine atom is substituted by a hydroxyl group, CF ₃ SO ₃ , ClO ₄ , a halogen atom, R-CO
O, shows the anions selected from the group consisting of R-SO _3. Here, R is an alkyl group or a phenyl group which may be substituted with an alkyl group, a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like.

The pyrrolium salts represented by the above general formula include N- (4-octadecyloxybenzyl-N-methylpyrrolinium) hexafluoroantimonate,
-Benzyl-N-4-octadecyloxyphenylpyrrolinium hexafluoroantimonate, N- (4-
Octadecyloxybenzyl-N-methylpyrrolinium) hexafluorophosphate. The compounding amount is usually 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the epoxy compound (1) and the acrylic resin (2) of the composition. If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use more than 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

3.1.1.2. Organosilicon Compound Catalysts As the organosilicon compounds represented by the general formula (I-4), for example, tris (p-hexadecyloxyphenyl) silanol, tris (p-octadecyloxyphenyl) ) Silanol, tris (p-docosyloxyphenyl) silanol, tris (m-hexadecyloxyphenyl) silanol, tris (m-octadecyloxyphenyl) silanol, tris (m-docosyloxyphenyl) silanol, bis (p- Hexadecyloxyphenyl) silanediol, bis (p-octadecyloxyphenyl) silanediol, bis (p-docosyloxyphenyl) silanediol, bis (m-hexadecyloxyphenyl) silanediol, bis (m-octadecyloxyphenyl) ) Silane Lumpur, bis (m-docosyl oxyphenyl) silane diol, bis (p- Hexadecyloxy) methyl silanol, bis (p-
Hexadecyloxyphenyl) ethylsilanol, bis (p-hexadecyloxyphenyl) propylsilanol, bis (m-hexadecyloxyphenyl) methylsilanol, bis (m-hexadecyloxyphenyl) ethylsilanol, bis (m-hexadecyl) Oxyphenyl) propylsilanol, tris (6-hexadecyloxynaphthyl) silanol, tris (6-octadecyloxynaphthyl) silanol, tris (6-docosyloxynaphthyl) silanol, bis (6-hexadecyloxynaphthyl) silanediol, Bis (6-octadecyloxynaphthyl) silanediol and bis (6
-Docosyloxynaphthyl) silanediol and the like.

Further, the organosilicon compound represented by the above formula (I-4) may be substituted with a hydrolyzable group instead of a hydroxyl group. Alternatively, the above general formula (I-
The organosilicon compound represented by 4) may have a substituent capable of generating silanol upon irradiation with light. In each case, one of the first curing catalysts of the present invention
It can be used as a component. Here, the “hydrolyzable group” is a residue directly bonded to silicon, and a residue that hydrolyzes at a certain temperature or higher in the presence of water to generate a silanol hydroxyl group represented by the following chemical formula. It is.

[0101]

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Examples of such groups include alkoxyl groups having 1 to 5 carbon atoms; aryls such as phenoxy, tolyloxy, paramethoxyphenoxy, paranitrophenoxy, benzyloxy, parachlorophenoxy and the like. Oxy group; acetoxy group, propionyloxy group, butanoyloxy group, benzoyloxy group, phenylacetoxy group, formyloxy group and other acyloxy group; vinyloxy group, allyloxy group and other carbon atoms 2
To 12 alkenyloxy groups; aralkyloxy groups such as a benzyloxy group and a phenethyloxy group; and groups represented by the following formulas.

[0103]

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(Wherein R ′ and R ″ may be the same or different and represent an alkyl group having 1 to 5 carbon atoms)

On the other hand, as the silicon compound having a substituent that generates silanol by light irradiation, a silicon compound having any one of a peroxysilano group, an o-nitrobenzyloxy group, and an α-ketosilyl group is preferable. The silicon compound having a peroxysilano group can be represented by the following general formula (SI-PO).

[0106]

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(Wherein R ⁴¹ , R ⁴² and R ⁴³ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted An aromatic group or a heteroaromatic group, provided that a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or an aromatic group or a heterocyclic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. R ⁴⁴ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group or an aralkyl group, and p, q, r Are each an integer of 0 to 3 and 1 ≦ p + q + r ≦ 3.)

In the above formula, R ⁴¹ , R ⁴² and R
Examples of the substituted or unsubstituted hydrocarbon group, substituted or unsubstituted aromatic group or heteroaromatic group which can be introduced as ⁴³ include those represented by R ¹¹ to R ^{11 in} the above formulas (I-1) to (I-5).
Examples of the group that can be introduced into R ¹⁸ include those listed above. In the above general formula, the halogen atom may be introduced as R ^44, for example, chlorine and bromine atoms, the alkyl group having 1 to 5 carbon atoms, for example, methyl, ethyl, n- propyl, isopropyl, n -Butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl and neopentyl groups having 1 carbon atom
Examples of the alkoxy group of to 5 include methoxy, ethoxy, n-propoxy, n-butoxy, sec-butoxy,
Examples of the tert-butoxy and n-pentyloxy groups, examples of the aryl group include phenyl, naphthyl and anthranyl groups, and examples of the aralkyl group include a benzyl and phenethyl group. These groups may have a substituent such as a halogen atom, a nitro group, a cyano group, and a methoxy group.

Specific examples of the silicon compound having a peroxysilano group include a compound represented by the following formula.

[0110]

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[0111]

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[0112]

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The silicon compound having an o-nitrobenzyloxy group can be represented by the following general formula (SI-NB).

[0114]

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(Wherein R ⁴⁵ , R ⁴⁶ and R ⁴⁷ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted group, Wherein a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or an aromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or 1 heteroaromatic group
Have more than one. R ⁴⁸ represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, a phenyl group or a substituted phenyl group, and R ⁴⁹ , R ⁵⁰ , R ⁵¹ and R ⁵² may be the same or different. Respectively, a hydrogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, a halogen atom, an acetyl group, an allyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, unsubstituted or substituted aryl A group or an aryloxy group,
p, q and r are each an integer of 0 to 3 and 0 ≦ p + q + r ≦ 3. )

In the above formula, R ⁴⁵ , R ⁴⁶ and R
Examples of the substituted or unsubstituted hydrocarbon group, substituted or unsubstituted aromatic group or heteroaromatic group which can be introduced as ⁴⁷ include those represented by R ¹¹ to R ^{11 in} the above general formulas (I-1) to (I-5).
Examples of the group that can be introduced into R ¹⁸ include those listed above. In the above general formula, examples of the unsubstituted or substituted alkyl group having 1 to 10 carbon atoms (or 1 to 5 carbon atoms) include:
Examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, a chloromethyl group, a chloroethyl group, a fluoromethyl group, and a cyanomethyl group, and have 1 to 10 carbon atoms. (Or 1 carbon
Examples of the alkoxy group to 5) include a methoxy group,
Examples include ethoxy, n-propoxy and n-butoxy groups. As an unsubstituted or substituted aryl group,
For example, a phenyl group, a p-methoxyphenyl group, a p-chlorophenyl group and a p-trifluoromethylphenyl group are mentioned, and as the aryloxy group, for example, a phenoxy group is mentioned.

Specific examples of the silicon compound having an o-nitrobenzyloxy group include, for example, tris (p-hexadecyloxyphenyl) (o-nitrobenzyloxy) silane, bis (p-hexadecyloxyphenyl) ) (O-nitrobenzyloxy) methylsilane,
Vinylmethyl (p-hexadecyloxyphenyl) (o
-Nitrobenzyloxy) silane, t-butylmethyl (p-hexadecyloxyphenyl) (o-nitrobenzyloxy) silane, bis (p-hexadecyloxyphenyl) bis (o-nitrobenzyloxy) silane, bis (p- Hexadecyloxyphenyl) bis (o-nitrobenzyloxy) silane, methyl (p-hexadecyloxyphenyl) bis (o-nitrobenzyloxy) silane, t-butyl (p-hexadecyloxyphenyl)
Bis (o-nitrobenzyloxy) silane, tris (p
-Hexadecyloxyphenyl) (3,4,5-trimethoxy-2-nitrobenzyloxy) silane, tris (p-hexadecyloxyphenyl) (4,5,6-trimethoxy-2-nitrobenzyloxy) silane, tris (P-hexadecyloxyphenyl) (5-methyl-
4-methoxy-2-nitrobenzyloxy) silane, tris (p-hexadecyloxyphenyl) (4,5-dimethyl-2-nitrobenzyloxy) silane, and tris (p-hexadecyloxyphenyl) (2,6 -Dinitrobenzyloxy) silane and the like.

The silicon compound having an α-ketosilyl group can be represented by the following general formula (SI-KS).

[0119]

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(Wherein R ⁵³ , R ⁵⁴ and R ⁵⁵ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted An aromatic group or a heteroaromatic group, provided that a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, R ⁵⁶ represents a hydrogen atom, a vinyl group, an allyl group,
Alkyl group having 1 to 10 carbon atoms, 1 to 10 carbon atoms
Represents an alkoxy group, an aryl group or an aryloxy group, wherein p, q, and r are each an integer of 0 to 3,
And 1 ≦ p + q + r ≦ 3. )

In the above general formula, R ⁵³ , R ⁵⁴ and R
Examples of the substituted or unsubstituted hydrocarbon group, substituted or unsubstituted aromatic group or heteroaromatic group which can be introduced as ⁵⁵ include those represented by R ¹¹ to R ^{11 in} the above formulas (I-1) to (I-5).
Examples of the group that can be introduced into R ¹⁸ include those listed above. In the above general formula, examples of the alkyl group having 1 to 10 carbon atoms that can be introduced as R ⁵⁶ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tert-
A butyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group and an n-octyl group, examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group and an n-propoxy group. , N-butoxy group,
a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, an n-hexyloxy group, an n-heptyloxy group and an n-octyloxy group; examples of the aryl group include a phenyl group and a naphthyl group; Examples of the oxy group include a phenoxy group and a naphthyloxy group, respectively. In addition, these groups may be a halogen atom, a nitro group,
It may have a substituent such as a cyano group and a methoxy group.

More specific examples of the silicon compound having an α-ketosilyl group include compounds represented by the following formula.

[0123]

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The silicon compound which generates silanol upon irradiation with light is used alone or as a mixture of two or more kinds in the composition. The compounding amount is usually based on the epoxy compound and the acrylic resin in the composition. It is 0.001 to 20% by weight, preferably 0.1 to 10% by weight. When the amount is less than 0.001% by weight, curing may be insufficient. In addition, although it is possible to use more than 20% by weight, cost increases and decomposition products of the catalyst component are reduced. This can be problematic and is not preferred.

3.1.1.3. Phenol Catalyst Examples of the compound represented by the general formula (I-5) include bis (4-hydroxyphenyl) sulfone monooctadecyl ether and bis (4-hydroxy-3-octadecyloxy). Phenyl) sulfone, bis (4-hydroxyphenyl) sulfide monooctadecyl ether,
(4-hydroxyphenyl) octadecyl sulfone,
4.4'-dihydroxydiphenyl ether monooctadecyl ether, bis (2- (6-hydroxyphenyl)) sulfone monooctadecyl ether, and the like. The above-mentioned compounds are used alone or as a mixture of two or more in the composition. The compounding amount is usually 0.01 to 20% by weight based on the compound (1) and the resin (2) in the composition. , Preferably 0.5 to 10% by weight. If the compounding amount is less than 0.01% by weight, curing may be insufficient, and it is possible to use more than 20% by weight, but the cost is high and the catalyst component adversely affects the physical properties. May give.

Among the above cationic polymerization catalyst components, the organosilicon compound represented by the general formula (I-4) and the compound represented by the general formula (I-5) are represented by the general formula (II-II):
It is used in combination with the metal compounds represented by 1), (II-2) and (II-3). In this case, if at least one of the components is repeatedly dissolved and precipitated reversibly in the heating and cooling processes, Well, the other components are not. Therefore, in this case, in the above general formulas (I-4) and (I-4
-5) a compound represented by general formula (II-1):
Metal compound (3 ″) represented by (II-2) or (II-3)
Does not necessarily have at least one substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or at least one aromatic group or heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. .

Specifically, examples of the organosilicon compound represented by the general formula (I-4) include diphenylsilanediol, triphenylsilanol and the like. Examples of the compound represented by the general formula (I-5) include bis (4-hydroxyphenyl) sulfone, cyanophenol, nitrophenol, 2,2-dihydroxyphenylpropane,
Catechol, p, p'-biphenol, resorcinol and the like. Examples of the iron aromatic compound represented by the general formula (I-3) include those described in the supplementary description after the examples.

Further, the sulfonium salt represented by the general formula (I-1) and the iodonium salt represented by the general formula (I-2) can be obtained by the above-mentioned general formulas (II-1) and (II-2) , (II
-3) can be used in combination with the metal compound (3 ″). In this case, as described above, the metal compound is not necessarily a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, It is not necessary to have one or more aromatic or heteroaromatic groups having 10 or more substituted or unsubstituted hydrocarbon groups.

The sulfonium salt represented by formula (I-1), the iodonium salt represented by (I-2), and the iron aromatic compound represented by (I-3) are as described above. In addition to increasing the activity, it has activity against radiation such as light and electron beams. That is, these sulfonium salts, iodonium salts and iron aromatic compounds excited by heat or an electron beam are curing catalysts for accelerating the polymerization of the ionic polymerizable substance according to the present invention. Is blended to prepare the resin composition of the present invention.

3.1.1.4. Polymerization Reaction of Vinyl Compound with Cationic Polymerization Catalyst (3 ′) In the present invention, when the cationic polymerizable substance is a vinyl compound such as vinyl ether, the polymerization reaction is usually carried out by
A solution polymerization method using an inert solvent for a catalyst, a monomer, or the like is performed, and in some cases, a bulk polymerization method is also performed.
Examples of the solvent include toluene, benzene, aromatic hydrocarbons such as xylene, n-hexane, aliphatic hydrocarbons such as n-heptane, alicyclic hydrocarbons such as cyclohexane, petroleum ether, Hydrocarbon mixtures such as ligroin, halogenated hydrocarbons such as chlorobenzene and dichloroethane can be used, and the polymerization reaction of these vinyl compounds is carried out under normal pressure or pressure, and the reaction temperature is 20 ° C. or higher. , Preferably 60 to 150 ° C, which is industrially easy to heat.

3.1.1.5. Mixing of Cationic Polymerization Catalyst (3 ′) and Curable Resin Component The iodonium salt, sulfonium salt, and iron aromatic compound used as the polymerization catalyst in the present invention include:
Since the cationic polymerization reaction does not start at room temperature, if necessary, the resin composition (also referred to as a curable resin component) and the catalyst can be stored as a single liquid.

The amount of the sulfonium salt, iodonium salt and iron aromatic compound used in the present invention is 0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the epoxy compound. If the amount is less than 0.01 parts by weight, a sufficient polymer cannot be obtained. On the other hand, if the amount exceeds 20 parts by weight, favorable properties are not obtained after polymerization, which is not preferred in terms of cost.

3.1.2. Metal Compound (3 ″) Next, the metal compound (3 ″) which is another component of the first curing catalyst of the present invention will be described in detail. Representative examples of the metal compound (3 ″) that can be blended include compounds represented by the following general formulas (II-1), (II-2), and (II-3).

[0134]

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(In the above formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.) However, in one ligand, R ²¹ , R ²² ,
It is assumed that at least one of R ²³ and R ²⁴ having 10 or more carbon atoms is included. M is Al, Ti, C
r, Mn, Fe, Co, Ni, Cu, Zr, Zn, B
It is selected from the group consisting of a, Ca, Ce, Pb, Mg, Sn, and V, where n is an integer of 2-4. )

The formulas (II-1), (II-2) and (II)
Examples of the compound represented by -3) include tris (octadecyl acetoacetate) aluminum, tris (hexadecyl acetoacetate) aluminum, tris (tetradecyl acetoacetate) aluminum, tris (dodecyl acetoacetate) aluminum, and tris (octyl). Salicylaldehyde) aluminum, tris (3-octadecylacetylacetate) aluminum, and compounds represented by the following chemical formula.

[0137]

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[0138]

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[0139]

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Further, aluminum in the above chemical formula is represented by Ti, Cr, Zr, Mn, Fe, Co, Ni,
A chelate compound changed to a Cu, Zr or Zn atom can also be used as the metal compound (3 ″) component of the first curing catalyst of the present invention. The above-mentioned general formulas (II-1) and (II) In the compounds represented by -2) and (II-3), all the bonds of the metal atom (M) do not need to be bonded to the ligand, and one alkoxy group is used instead of the ligand. , A phenoxy group or an acyloxy group, or all of the bonds may be bonded to these groups.
Seeds or a mixture of two or more kinds are used, and the amount added is
Usually 0.0 to resin such as epoxy compound in the composition.
It is 1 to 20% by weight, preferably 0.5 to 10% by weight. If the amount is less than 0.01% by weight, curing may be insufficient. Although it is possible to use more than 20% by weight, it is not preferable because the cost is high and the catalyst component may adversely affect the physical properties. When these metal compounds (3 ″) are used, ionic substances hardly remain in the cured resin.

3.1.3. Compound usable in combination with metal compound (3 ″) The first curing catalyst of the present invention contains at least one of the above-mentioned cationic polymerization catalyst component and the metal compound (3 ″). In some cases, either component may not be included. For example, the metal compound (3 ") can constitute the first curing catalyst of the present invention in combination with the following other components. As a compound that can be used by mixing with the metal compound (3"), And at least one compound selected from the group consisting of an organosilane having a hydroxyl group directly bonded to a silicon atom, an organosiloxane having a hydroxyl group directly bonded to a silicon atom, and a phenol compound. An organic silicon compound having a hydrolyzable group directly bonded to a silicon atom or a silicon compound capable of generating silanol by light irradiation is also used in combination with the above-described metal compound (3 ″). Here, the “hydrolyzable group” is a residue directly bonded to silicon as described above as a group that can be introduced into the general formula (I-4). And the same groups as mentioned above.

3.1.3.1. An organosilane having a hydroxyl group,
Organosiloxane having a hydroxyl group The organosilane that can be used can be represented by the following general formula (S-1).

[0143]

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(In the formula, R ¹ represents a hydroxyl group or the above-mentioned hydrolyzable group, and X ¹ , X ² and X ³ may be the same or different and each has 1 to 12 carbon atoms. An aryl group such as a phenyl group, a tolyl group, a paramethoxyphenyl group, a parachlorophenyl group, and a paranitrophenyl group; an aralkyl group such as a benzyl group, a phenethyl group, a paramethoxybenzyl group, and a paramethylbenzyl group;
An alkenyl group such as a vinyl group, an allyl group, a propenyl group or a butenyl group; or an acyl group such as an acetyl group, a benzoyl group, or a trifluoroacetyl group, wherein p, q and r are each an integer of 0 to 3, p + q + r is 3 or less)

Specific examples of the organosilanes which are more preferable in the first curing catalyst include diphenylsilanediol, triphenylsilanol, diphenyl (methyl) silanol, phenyl (vinyl) silanediol, and tri (paramethoxyphenyl). Silanol,
Triacetylsilanol, diphenyl (ethyl) silanol, diphenyl (propyl) silanol, tri (paranitrophenyl) silanol, phenyldivinylsilanol, 2-butenyldiphenylsilanol, di (2-pentenyl) phenylsilanol, phenyldipropylsilanol, para Silanols such as methylbenzyldimethylsilanol, triethylsilanol, trimethylsilanol, tripropylsilanol, tributylsilanol and triisobutylsilanol can be mentioned. Specific examples of the organosilane having a hydrolyzable group include triphenyl (methoxy) silane, diphenyldimethoxysilane, triphenyl (ethoxy) silane, diphenyl (methyl) methoxysilane, phenyl (vinyl) (methyl) (methoxy) ) Silane, diphenyldiethoxysilane, tri (paramethoxyphenyl) methoxysilane, triacetyl (methoxy) silane, diphenyl (ethyl) (ethoxy) silane, diphenyl (propyl) (ethoxy) silane, diphenyl (methyl) (acetoxy) silane , Diphenyldipropionyloxysilane, diphenyl (methyl) (triphenylacetoxy) silane, tri (paranitrophenyl) (methoxy)
Silane, triacetyl (methoxy) silane, phenyldivinyl (propoxy) silane, 2-butenyldiphenyl (methoxy) silane, di (2-pentenyl) (phenyl) (ethoxy) silane, phenyldipropyl (methoxy) silane, tri ( Paramethoxyphenyl) (ethoxy) silane, paramethylbenzyltrimethoxysilane,
Trifluoroacetyltrimethoxysilane, di (parachlorophenyl) diethoxysilane, triethyl (methoxy) silane, trimethyl (methoxy) silane, tripropyl (methoxy) silane, tributyl (ethoxy) silane, triisobutyl (acetoxy) silane, and The compound represented by the following chemical formula can be mentioned.

[0146]

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Further, in addition to the above examples, of course, an organosilane having both a hydroxyl group and a hydrolyzable group can also be used.

As described above, the organosilane having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom is
One or more of them may be used in the composition. The compounding amount is usually 0.001 to 20% by weight, preferably 0.01 to 10% by weight, based on the epoxy compound (1) and the acrylic resin (2) in the composition. If the amount is less than 0.001%, curing may be insufficient. Although it is possible to use more than 20 parts by weight, it is not preferable because the cost may be high and the decomposition product of the catalyst component may become a problem.

The organosiloxane that can be suitably used as the first curing catalyst of the present invention is a bifunctional unit represented by the following formula (S-2) and / or the following formula (S-
It is a linear or cyclic siloxane which may have a branch and which comprises a trifunctional unit represented by 3), and may contain a tetrafunctional unit represented by the following formula (S-4) in some cases. Good. Further, this organosiloxane has the following formula (S) when the siloxane chain has a terminal.
It is sealed with a monofunctional unit represented by -5), and in particular, at least one of the structural units contains at least one hydroxyl group or hydrolyzable group.

[0150]

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(Wherein Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ may be the same or different and each is a hydroxyl group or a hydrolyzable group; 12 alkyl groups; aryl groups such as phenyl group, tolyl group, paramethoxyphenyl group, parachlorophenyl group and paracyanophenyl group; aralkyl groups such as benzyl group, phenethyl group, paramethoxybenzyl group and paramethylbenzyl group ;
Alkenyl groups such as vinyl group, allyl group, propenyl group and butenyl group; and acyl groups such as acetyl group, benzoyl group and trifluoroacetyl group)

Of the above-mentioned organosiloxanes, those having a degree of polymerization of 50 or less and an equivalent of hydroxyl group and / or hydrolyzable group of 1,000 or less are more preferred, and those having an equivalent of 50 to 500 are more preferred. Specific examples of such preferred organosiloxanes include those having a hydroxyl group, such as 1,3-dihydroxy-1,3-dimethyl-1,3-diphenyldisiloxane and 1,5-dihydroxy-1,3,5-disiloxane. Trimethyl-1,3,5-triphenyltrisiloxane, 1,7-dihydroxy-1,
3,5,7-tetramethyl-1,3,5,7-tetraphenyltetrasiloxane, 1,3-dihydroxytetraphenyldisiloxane, 1,5-dihydroxyhexaphenyltrisiloxane, 1,7-dihydroxyoctaphenyltetrasiloxane Siloxane, 1,5-dihydroxy-3,
3-dimethyl-1,1,5,5-tetraphenyltrisiloxane, 1,3-dihydroxytetra (dimethylphenyl) disiloxane, 1,5-dihydroxyhexaethyltrisiloxane, 1,7-dihydroxyoctapropyltetrasiloxane, 1,3,5-trihydroxy-3
-Ethyl-1,1,5,5-tetramethyltrisiloxane, 1,5-dihydroxy-1,1,5,5-tetraphenyl-3,3-di-p-tolyltrisiloxane, and represented by the following chemical formula: Compounds.

[0153]

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Further, a silicone resin available under a trade name such as SH6018 (manufactured by Toray Silicone Co., Ltd .: methylphenylpolysiloxane having a hydroxyl equivalent of 400 and a molecular weight of 1,600) can also be used. Generally, a polysiloxane represented by the following general formula can also be used.

[0155]

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(In the above formula, R ⁶¹ , R ⁶² , R ⁶³ ,
R ⁶⁴ , R ⁶⁵ and R ⁶⁶ may be the same or different,
A hydroxyl group or a hydrolyzable group;
12 alkyl groups; aryl groups such as phenyl, tolyl, paramethoxyphenyl, parachlorophenyl, and paracyanophenyl; benzyl, phenethyl,
Aralkyl groups such as paramethoxybenzyl group and paramethylbenzyl group; alkenyl groups such as vinyl group, allyl group, propenyl group and butenyl group; acetyl group, benzoyl group,
Represents an acyl group such as a trifluoroacetyl group. )

The above-mentioned organosiloxane having a hydroxyl group directly bonded to a silicon atom is used alone or in combination of two or more in the composition. The compounding amount is usually 0.001 to 20% by weight, preferably 0.01 to 10% by weight, based on the epoxy compound (1) and the acrylic resin (2) in the composition. 0.001
%, The curing may be insufficient. Although it is possible to use more than 20 parts by weight, it is not preferable because the cost may be high and the decomposition product of the catalyst component may become a problem.

3.1.3.2. Silicon Compound That Can Generate Silanol by Light Irradiation Silicon compounds that can be used to generate silanol by light irradiation include peroxysilano, o-nitrobenzyloxy, and α-ketosilyl groups. Silicon compounds having any of them are preferred. The silicon compound having a peroxysilano group has the general formula (I)
-4) as described in the general formula (SI-P
O). However, in this case,
As R ⁴¹ , R ⁴² and R ⁴³ in the general formula, a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group or an aralkyl group is introduced. . These may be the same or different. Halogen atoms, examples of such alkyl group of 1 to 5 carbon atoms include those listed as the group may be introduced into R ^44.

Specific examples of the silicon compound having a peroxysilano group include a compound represented by the following formula.

[0160]

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[0161]

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[0162]

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The silicon compound having an o-nitrobenzyloxy group is a compound represented by the general formula (SI-NB) as already described in the general formula (I-4). However, in this case, R ⁴⁵ , R ⁴⁶ and R ⁴⁷ represent a hydrogen atom, a halogen atom, a vinyl group, an allyl group,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group, an aryloxy group or a siloxy group is introduced. These may be the same or different. Examples of the halogen atom include a chlorine atom and a bromine atom, and examples of the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tert-butyl group. , N-pentyl group,
Examples thereof include a chloromethyl group, a chloroethyl group, a fluoromethyl group and a cyanomethyl group. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group,
Examples include n-propoxy and n-butoxy groups.
Examples of the unsubstituted or substituted aryl group include a phenyl group, a p-methoxyphenyl group, a p-chlorophenyl group and a p-trifluoromethylphenyl group, and examples of the aryloxy group include a phenoxy group.

Further, the silicon compound having an o-nitrobenzyloxy group may be a compound having an o-nitrobenzyloxy group as a terminal group and a main chain comprising a group represented by the following formula.

[0165]

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[0166] (wherein, s represents an integer of 1 or more, R ⁶⁷
And R ⁶⁸ may be the same or different and represent a hydrogen atom, a halogen atom, a vinyl group, an allyl group,
X ⁴ represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an unsubstituted or substituted aryl group, an aryloxy group or a siloxy group;
Represents an oxygen atom, an alkylene group or an aryldiyl group. )

Specific examples of the silicon compound having an o-nitrobenzyloxy group include trimethyl (o-nitrobenzyloxy group).
Nitrobenzyloxy) silane, dimethylphenyl (o
-Nitrobenzyloxy) silane, diphenylmethyl (o-nitrobenzyloxy) silane, triphenyl (o-nitrobenzyloxy) silane, vinylmethylphenyl (o-nitrobenzyloxy) silane, t-butylmethylphenyl (o-nitro Benzyloxy) silane, triethyl (o-nitrobenzyloxy) silane,
Tri (2-chloroethyl) -o-nitrobenzyloxysilane, tri (p-trifluoromethylphenyl-o-
Nitrobenzyloxy) silane, trimethyl [α- (o
-Nitrophenyl) -o-nitrobenzyloxy] silane, dimethylphenyl [α- (o-nitrophenyl)-
o-nitrobenzyloxy] silane, methylphenyldi [α- (o-nitrophenyl) -o-nitrobenzyloxy] silane, triphenyl (α-ethyl-o-nitrobenzyloxy) silane, trimethyl (3-methyl- 2
-Nitrobenzyloxy) silane, dimethylphenyl (3,4,5-trimethoxy-2-nitrobenzyloxy) silane, triphenyl (4,5,6-trimethoxy-2-nitrobenzyloxy) silane, diphenylmethyl (5- Methyl-4-methoxy-2-nitrobenzyloxy) silane, triphenyl (4,5-dimethyl-2-
Nitrobenzyloxy) silane, vinylmethylphenyl (4,5-dichloro-2-nitrobenzyloxy) silane, triphenyl (2,6-dinitrobenzyloxy)
Silane, diphenylmethyl (2,4-dinitrobenzyloxy) silane, triphenyl (3-methoxy-2-nitrobenzyloxy) silane, vinylmethylphenyl (3,4-dimethoxy-2-nitrobenzyloxy) silane, dimethyldi ( o-nitrobenzyloxy) silane, methylphenyldi (o-nitrobenzyloxy) silane, vinylphenyldi (o-nitrobenzyloxy)
Silane, t-butylphenyldi (o-nitrobenzyloxy) silane, diethyldi (o-nitrobenzyloxy) silane, 2-chloroethylphenyldi (o-nitrobenzyloxy) silane, diphenyldi (o-nitrobenzyloxy) Silane, diphenyldi (3-methoxy-
2-nitrobenzyloxy) silane, diphenyldi (3,4-dimethoxy-2-nitrobenzyloxy) silane, diphenyldi (2,6-dinitrobenzyloxy) silane, diphenyldi (2,4-dinitrobenzyloxy) silane , Methyltri (o-nitrobenzyloxy) silane, phenyltri (o-nitrobenzyloxy) silane, p-bis (o-nitrobenzyloxydimethylsilyl) benzene, 1,1,3,3-tetraphenyl-1,3 -Di (o-nitrobenzyloxy) disiloxane, 1,1,3,3,5,5-hexaphenyl-1,
5-di (o-nitrobenzyloxy) trisiloxane,
And silicon compounds formed by the reaction of a SiCl-containing silicone resin with o-nitrobenzyl alcohol.

The silicon compound having an α-ketosilyl group is a compound represented by the general formula (SI-KS) as already described in the general formula (I-4). However, in this case, R ⁵³ , R ⁵⁴ and R ⁵⁵ in the above general formula represent a hydrogen atom, a vinyl group, an allyl group, a carbon atom 1
An alkyl group having 10 to 10, an alkoxy group having 1 to 10 carbon atoms, an aryl group or an allyloxy group is introduced. These may be the same or different. R ⁵³ , R ⁵⁴
Examples of the alkyl group having 1 to 10 carbon atoms and the alkoxy group having 1 to 10 carbon atoms that can be introduced into R ⁵⁵ include those listed as groups that can be introduced into R ⁵⁶ .

Specific examples of the silicon compound having an α-ketosilyl group include compounds represented by the following chemical formula.

[0170]

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The silicon compound which generates silanol upon irradiation with light as described above may be used alone or in the composition.
More than one kind is used as a mixture, and the compounding amount is usually 0.001 to 20% by weight based on the epoxy compound and the acrylic resin,
Preferably it is 0.01 to 10% by weight. The blending amount is 0.
If it is less than 001% by weight, curing may be insufficient. Although it is possible to use it in an amount exceeding 20% by weight, it is not preferable because high cost and decomposition products of the catalyst component may cause problems.

3.1.3.3. Phenol compound Examples of the phenol compound that can be used include, for example, the following general formula (Ph-1)
Are represented.

[0173]

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(In the general formula (Ph-1), Ar ² represents a substituted or unsubstituted aromatic group or a heteroaromatic group, and n is an integer of 1 to 10.)

In the general formula (Ph-1), Ar^Two
A substituted or unsubstituted aromatic group represented by
As the aromatic group, the above-mentioned general formulas (I-1) to (I-5)
R ¹¹~ R¹⁸Groups as listed as may be introduced into
Can be mentioned. These substituted aromatic groups or
Is a group having 1 or more carbon atoms as a substituent of a heteroaromatic group.
When there are a plurality of bases,
They may be the same or different. Such substituents
Specific examples of the organic groups shown below
Can be.

[0176]

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[0177]

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More specific examples of the compound represented by formula (Ph-1) include the following compounds.

[0179]

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[0180]

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[0181]

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[0182]

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These phenol compounds can be used alone or in combination of two or more.

When the phenolic compound as described above is blended in the first curing catalyst of the present invention, the blending amount is 0.1 to 50% by weight based on the epoxy compound (1) and the acrylic resin (2). % Is preferable.
If the amount is less than 0.1% by weight, it is difficult to sufficiently promote the curing reaction. On the other hand, if it exceeds 50% by weight,
The cost tends to be high and the mechanical strength of the cured product tends to decrease.

3.1.3.4. Organosilicon Compound Having a Hydrolyzable Group Examples of the organosilicon compounds having a hydrolyzable group directly bonded to a silicon atom include an alkoxyl group having 1 to 5 carbon atoms; a phenoxy group and a tolyloxy group. Aryloxy groups such as paramethoxyphenoxy group, paranitrophenoxy group, benzyloxy group and parachlorophenoxy group; acetoxy group, propionyloxy group, butanoyloxy group, benzoyloxy group, phenylacetoxy group and formyloxy group An acyloxy group; an alkenyloxy group having 2 to 12 carbon atoms such as a vinyloxy group and an allyloxy group; an aralkyloxy group such as a benzyloxy group and a phenethyloxy group; and an organosilicon compound having a group represented by the following formula. it can.

[0186]

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(Wherein R ′ and R ″ may be the same or different and represent an alkyl group having 1 to 5 carbon atoms)

The organosilicon compound having a hydrolyzable group directly bonded to a silicon atom as described above is used alone or in combination of two or more in the composition. The compounding amount is usually 0.1 to the epoxy compound and the acrylic resin.
001 to 20% by weight, preferably 0.01 to 10% by weight
It is. If the compounding amount is less than 0.001%, curing may be insufficient, and it is possible to use more than 20 parts by weight, but the cost is high and decomposition products of the catalyst component are problematic. This may be undesirable.

3.2. Second Curing Catalyst Next, the second curing catalyst of the present invention will be described. The second curing catalyst of the present invention contains at least one compound selected from the group consisting of the compounds represented by the general formulas (III-1 ′) and (III-2).

In the general formula (III-1 ′), R ¹ and R
Examples of the hydrocarbon group that can be introduced as ² and R ³ include the groups listed as being able to be introduced into R ^{11 to} R ¹⁸ in the general formulas (I-1) to (I-5).
It is more preferable that R ¹ , R ² , and R ³ each be an aromatic group or a heteroaromatic group having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms.

Specifically, compounds represented by the above general formula (III-1 ′) include bis (p-octadecyloxyphenyl) butylphosphine, bis (m-octadecyloxyphenyl) butylphosphine, and bis (p-octadecyloxyphenyl) butylphosphine. -Octadecyloxyphenyl) decylphosphine, p-octadecyloxyphenyldibutylphosphine, p-octadecyloxyphenyloctadecylphosphine and the like.

As the compound represented by the general formula (III-1 ′), the compound represented by the general formula (III-1) can be used. The general formula (III-1)
And a hydrocarbon group which can be introduced as R ^{31 in the} general formula (III-2), R ³² , R ³³ , R ³⁴ and R ³⁵
Examples of the hydrocarbon group which can be introduced as R 1 include the groups listed as those which can be introduced into R ^{11 to} R ¹⁸ in the general formulas (I-1) to (I-5). Further, such a hydrocarbon group may contain a hetero atom such as F, Si, O, N, or S. Formula (III-1), (I
Examples of the compound represented by II-2) include those described above.

The formula (III-1) or the formula (III-
Examples of the anionic catalyst used in the same manner as in 2) include the following compounds. Specific anionic compounds include linear tertiary amines, piperazine, pyridine, picoline, 1,8-diazabicyclo [5.4.
0] Derivatives such as undecene-1, benzylamine, 2- (aminomethyl) phenol, and 2,4,6-tris (aminomethyl) phenol can be used. These derivatives include a halogen atom, a nitro group, a cyano group, a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, an aromatic group or a heteroaromatic group having a substituted or unsubstituted hydrocarbon group. A substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or 1 carbon atom.
It has at least one aromatic or heteroaromatic group having 0 or more substituted or unsubstituted hydrocarbon groups.

The second curing catalyst of the present invention as described above is blended at a ratio of 0.01 to 20% by weight based on 100% by weight of the total solid content of the epoxy compound (1) and the acrylic resin (2). It is preferable to prepare a resin composition by heating.
If it is less than 0.01%, it is difficult to sufficiently promote the curing reaction, while if it exceeds 20% by weight, the cost tends to be high and the mechanical strength of the cured product tends to decrease.

3.3. Other Features of Heat-Activated Catalyst The first curing catalyst according to the present invention contains at least one of a cationic polymerization catalyst (3 ′) and a metal compound (3 ″), and contains an epoxy compound (1). And / or the acrylic resin (2) can be reversibly dissolved and precipitated by heating and cooling, and the second curing catalyst comprises P and N atoms. It contains at least one atom selected from the group and has the property of being uniformly dissolved by heating in the epoxy compound (1) and / or the acrylic resin (2) and of being precipitated during the cooling process. Precipitation in the case of means that the curing catalyst takes the form of a colloid, micelle, crystal or the like in the epoxy compound (1) and / or the acrylic resin (2). And a N atom,
This shows a state in which the P atom portion is shielded from a reactive site such as an epoxy group, an ester group, or a phenolic hydroxyl group by taking the above-described form. In order to create this state, for example, a compound having a substituted or unsubstituted hydrocarbon group having a large number of carbon atoms is effective. In addition, a hydrocarbon group having a large number of carbon atoms specifically includes a hexadecyl group,
Represents an octadecyl group, a docosyl group or the like.

[0196] 4. Other additives The curable resin composition of the present invention may contain, if necessary, extenders, rust preventive pigments, pigments such as color pigments, reactive diluents, organic solvents, anti-settling agents, sagging agents. , An ordinary paint additive such as a wetting agent, a curing accelerator, an adhesion-imparting agent, a dehydrating agent, an antifoaming agent, and a leveling agent.

[0197] 5. Preparation of Solvent-Based Coating Composition The clear coating used in the present invention comprises an epoxy compound (1), an acrylic resin (2), and a heat-activated catalyst (3).
And the heat-activated catalyst (3) is an epoxy compound (1)
And / or by dissolving or dispersing in the acrylic resin (2) using an organic solvent if necessary. For example, it is possible to prepare a solvent-based coating composition by mixing an epoxy compound (1) and an acrylic resin (2), heating and dissolving the heat-activated catalyst (3) in the mixture, and cooling and precipitating and dispersing the catalyst. it can. Further, after mixing the epoxy compound (1) and the acrylic resin (2) to obtain a resin composition, the resin composition is divided into two parts, and one of the heat-activated catalysts (3) is heated and dissolved in one, and cooled. To disperse the catalyst, dissolve the other type of heat-activated catalyst (3) in the rest, cool and precipitate and disperse the catalyst, and then mix the two liquids to prepare a solvent-based coating composition. Can be. Alternatively, one kind of the heat-activated catalyst (3) is heated and dissolved in the epoxy compound (1), and the catalyst is precipitated and dispersed by cooling, while another kind of the heat-activated catalyst (3) is added to the acrylic resin (2). Is dissolved and cooled to precipitate and disperse the catalyst, and then the two liquids are mixed to prepare a solvent-based coating composition. Examples of the organic solvent include toluene, xylene, ethyl acetate, and a solvent used for polymerizing the acrylic resin (2).
Examples include, but are not limited to, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, methoxypropylene glycol acetate, carbinol acetate, methoxybutyl acetate, cellosolve, cellosolve acetate, and butanol.

6. Coating The solvent-based coating composition of the present invention is used for coating the surface of substrates such as metals such as aluminum, iron, and zinc-treated steel sheets, and resin-lined metal plates such as PET, PBT, polycarbonate, nylon, and vinyl chloride. Further, it can be used for overcoating a coating film made of an oxidative polymerization type coating material such as a melamine hardening coating material, a urethane hardening coating material, or an alkyd used for industrial or general purposes. As the above-mentioned coating method of the paint, conventionally known methods such as roll coating, gravure coating, gravure offset coating, curtain flow coating, reverse coating, screen printing, airless spraying, air spraying, brush coating, and rollers can be adopted. The above paint can be applied so as to have a dry film thickness of 5 to 200 μm. As a method of painting a vehicle or the like, a method of forming a multilayer top coat using an opaque colored paint, a transparent colored paint, and a clear paint is to apply these three kinds of paints all at once and then heat once. Three-coat one-bake method (3C1B) for simultaneously curing three-layer coatings, three-coat two-bake method (3C2B) that employs two heating steps, and three-coat three-bake method (3C3B) for heating each coating film May be performed by any of the methods.

7. Curing Method The curable resin composition of the present invention can be cured by light or heat, or a combination thereof. For example, as a light source for photocuring, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a halogen lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used. In addition, radiation such as an electron beam and γ-ray can be used. As a heat source, curing can be performed by infrared rays, far infrared rays, hot air, high-frequency heating, or the like. Also, these light sources and heat sources can be used in combination.

8. Applications The solvent-based coating resin composition of the present invention is used as a coating for vehicles such as automobiles, motorcycles and trains, a coating for home electric appliances, a coating for building materials and the like, preferably as a top coating. In particular, it is effective as a top coating for automobiles, as a clear coating applied on an opaque coloring coating or a transparent coloring coating, and is excellent in heat resistance, stain resistance, scratch resistance and the like. Further, the solvent-based coating resin composition of the present invention can be used for other surface coatings such as metals and resins requiring lubricity, and can also be used, for example, for coating the outside of a can.

The present invention also relates to a coating method for forming a multi-layer coating film by applying an opaque coloring paint, a transparent coloring paint, and a clear paint on the body surface of a vehicle running on a road such as an automobile or a motorcycle. It is disclosed. Here, the opaque colored paint is a solid color paint, a metallic paint, a light interference fringe paint, and the like, and is a thermosetting paint composed of a resin component, a color pigment, a solvent, and the like, and is first painted on a vehicle body. . The transparent coloring paint is composed of a resin component, a coloring pigment, and a solvent, and is applied to the cured or uncured coating surface of the opaque coloring paint to form a colored transparent coating that is colored so as to be visible through the coating. The clear paint is applied on the cured or uncured surface of the transparent coloring paint, and is usually a paint for forming a transparent coating film. The solvent-based paint resin composition of the present invention is suitably used.

[0202]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Parts and% indicate parts by weight and% by weight, respectively.

The following were used as raw materials for the solvent-based coating resin composition. Component 1-1: CEL-2021P (manufactured by Daicel Chemical Industries, Ltd.) epoxy equivalent 152 Component 1-2: Epode GT-302 (manufactured by Daicel Chemical Industries, Ltd.) epoxy equivalent 235 Component 1-3: Epicoat 806 (hereinafter referred to as Epicoat 806) EP-806, manufactured by Yuka Shell Co.) Epoxy equivalent 177 Epoxy group-containing acrylic resin (2): Synthesis Example 1 (synthesis of component 2-1): 650 parts of glycidyl methacrylate, hydroxyethyl acrylate 116
, 100 parts of N-butyl acrylate and 134 parts of N-butyl methacrylate were subjected to solution polymerization in 1,000 parts of toluene by a conventional method to obtain an acrylic resin solution, and then toluene was distilled off. The obtained acrylic resin has an epoxy equivalent of 21
8, hydroxyl value 56 mgKOH / g, number average molecular weight 15,
Oxirane oxygen was 7.33%. Synthesis Example 2 (Synthesis of Component 2-2): 850 parts of 3,4-epoxycyclohexylmethyl acrylate, 65 parts of hydroxyethyl methacrylate, N-butyl acrylate 8
Five parts of the solution were polymerized in a toluene solution in the same manner as in the case of the component 2-1 to obtain an acrylic resin solution, and then toluene was distilled off. The obtained acrylic resin had an epoxy equivalent of 216, a hydroxyl value of 28 mgKOH / g, a number average molecular weight of 5,000,
Oxirane oxygen was 7.41%.

[Examples 1 to 9] As the epoxy compound, components 1-1 to 1-3 and, if necessary, EP-80
Component No. 6 as epoxy group-containing acrylic resin
Using the components 2-1 to 2-2, and using them in the ratio shown in Table 1, they are mixed uniformly, and the solution of the obtained resin composition is divided into two parts by weight, and one of them is used as a heat-activated catalyst. The following curing catalysts A-1 to A-3, and the other curing catalysts B-1 to B-
4 in the weight ratio shown in Table 1 and separately
Dissolved at ° C. Each solution was stirred while cooling to room temperature to precipitate and disperse the curing catalyst, and then the two solutions were mixed and sufficiently stirred to obtain a solvent-based coating resin composition. Heat activated ion polymerization catalyst (3): curing catalyst A-1 curing catalyst A-2 curing catalyst A-3 curing catalyst B-1 curing catalyst B-2 curing catalyst B-3 curing catalyst B-4

[0205]

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In Examples 7 to 9, the curing agent was
Uban 20SE-60 (butyl etherified melamine resin (solid content: 60% by weight) manufactured by Mitsui Chemicals, Inc.) was used in the ratio shown in Table 1. Table 1 shows the results. In addition, in Table 1, the compounding amount of each component is a solid content weight.

[Comparative Examples 1-2] A solvent-based coating resin composition was prepared in the same manner as in Example 1 except that the conventional onium salt-based curing catalyst or the above-mentioned Uvan 20SE-60 was added in the weight ratio shown in Table 1. I got something. UVI-6974 (manufactured by Union Carbide) was used as a conventional onium salt-based curing catalyst.

[0208]

[Table 1]

(Coating Film Test) The solvent-based coating resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were applied to a cationic electrodeposition coated plate (manufactured by Nippon Test Panel Co.) with an intermediate coating. On the substrate to be cured by heating with a bar coater # 8,
Coated to a cured film thickness of 25 μm, 140 ° C / 15
Cured in minutes.

[0210]

[Table 2]

The evaluation criteria are as follows. (I) Finished appearance: the result of visual evaluation. ：: good gloss and smoothness, etc., Δ: fairly poor gloss and smoothness, ×: extremely poor gloss and smoothness. (Ii) Hardness: Conducted according to JIS K-5400 pencil hardness test. (Iii) Acid resistance: 0.4 ml of 40% sulfuric acid aqueous solution on the coated surface
This is a result of visual evaluation after dripping and heating with a hot air drier at 60 ° C. for 15 minutes and washing with water. ：: No abnormality is recognized, △: Spot trace remains, ×:
Significant spots, whitening or blisters are indicated. (Iv) Pollen resistance: Japanese cedar pollen collected in the field was made into a 0.5% by weight solution with deionized water, and 0.4 ml of the solution was dropped on a coated surface, heated in an oven at 65 ° C. for 30 minutes, and then washed with water. The coated surface was visually evaluated. ：: no contamination was observed at all, Δ: some stains and blemishes were observed, and x: blemishes, blemishes and blisters were remarkably observed. (V) Soil removal: sulfuric acid was added to a mixture of 0.25 parts of carbon black (12 kinds of test dusts, manufactured by Japan Powder Industry Association) and 99.75 parts of deionized water to adjust the pH to 3.0. Spray the test liquid on the coated plate, temperature 20 ℃, humidity 70%
For 17 hours in a hot air dryer at 80 ° C.
Heat for hours. After repeating this for 4 cycles, the painted surface is washed with sponge and the condition of the painted surface is visually evaluated. ：: no contamination was observed at all, 汚染: slight contamination was observed,
X indicates that contamination is remarkably observed.

Specific examples are shown below as supplements to the heat-activated catalyst in the detailed description of the invention.

[0213]

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[0214]

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[0215]

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[0216]

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[0219]

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[0218]

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[0219]

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[0220]

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[0221]

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[0222]

According to the present invention, a resin composition for coatings having excellent storage stability can be obtained, and by using the same, excellent heat resistance, stain resistance, contaminant removal property, scratch resistance, etc. can be obtained. Painted objects,
In particular, a top coat of a car body such as an automobile is obtained.

Claims (15)

[Claims] 1. An epoxy compound (1) having two or more alicyclic epoxy groups in one molecule and having a number average molecular weight of 2,000 or less, a number average molecular weight of 2,000 to 50,000, and a hydroxyl value of An epoxy group-containing acrylic resin (2) having 10 to 250 mgKOH / g and an epoxy equivalent of 300 or less, and a heat-activated ion polymerization catalyst (3) capable of being dissolved and precipitated by heating and cooling, respectively. Solvent-based coating composition. 2. The solvent-based coating composition according to claim 1, wherein the epoxy group of the epoxy group-containing acrylic resin (2) is an alicyclic epoxy group or an epoxy group derived from glycidyl (meth) acrylate. 3. The epoxy compound (1) further comprises a bisphenol type epoxy resin, a novolak type epoxy resin,
The solvent-based coating composition according to claim 1, comprising at least one selected from the group consisting of a bromide-type epoxy resin and a brominated epoxy resin. 4. The solvent-based paint according to claim 1, wherein the oxirane oxygen concentration of the resin composition comprising the epoxy compound (1) and the epoxy group-containing acrylic resin (2) is 5 to 11% by weight. Composition. 5. The heat-activated ionic polymerization catalyst (3) contains at least one member selected from the group consisting of a cationic polymerization catalyst (3 ′) and a metal compound (3 ″). 5. The solvent-based coating composition according to any one of 4. 6. The cationic polymerization catalyst (3 ′) has a cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. The solvent-based coating composition according to claim 5, which is a compound having one or more in a molecule. 7. The cationic polymerization catalyst (3 ′) is a sulfonium salt represented by the following general formula (I-1),
Iodonium salt represented by 2), iron aromatic compound represented by general formula (I-3), organosilicon compound represented by general formula (I-4), and iodonium salt represented by general formula (I-5) The solvent-based coating composition according to any one of claims 5 to 6, which is at least one selected from the group consisting of compounds to be formed. Embedded image (In the above general formula, R ¹¹ , R ¹² and R ¹³ may be the same or different and each represent a hydrogen atom or a carbon atom having 1 to 1 carbon atoms.
30 substituted or unsubstituted hydrocarbon groups, substituted or unsubstituted aromatic groups or heteroaromatic groups. However,
A substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms,
Alternatively, the compound has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in the molecule. X is SbF ₆ , AsF ₆ , PF ₆ , BF ₄ , an anion derivative in which at least one fluorine atom is substituted with a hydroxyl group, CF ₃ SO ₃ , ClO ₄ , a halogen atom,
An anion selected from the group consisting of R ¹ —COO and R ² —SO ₃ is shown. Here, R ¹ and R ² are an alkyl group,
It represents an alkyl group or a phenyl group which may be substituted with a halogen atom, a nitro group, a cyano group, an alkoxy group or the like. ) (In the above general formula, R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ may be the same or different and each represent a hydrogen atom or a carbon atom having 1 to 1 carbon atoms.
30 substituted or unsubstituted hydrocarbon groups, substituted or unsubstituted aromatic groups or heteroaromatic groups. However,
A substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms,
Alternatively, the compound has at least one cyclic organic structure having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms in the molecule. p, q and r are integers from 0 to 3, and p + q + r is 3
It is as follows. ) (In the above general formula, Ar ¹ is a substituted or unsubstituted aromatic group or a heteroaromatic group, and R ¹⁸ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted group having 1 to 30 carbon atoms. A substituted hydrocarbon group, a substituted or unsubstituted aromatic group or a heteroaromatic group, provided that the substituted or unsubstituted hydrocarbon group has 10 or more carbon atoms, or a substituted or unsubstituted group having 10 or more carbon atoms. Has at least one cyclic organic structure having a hydrocarbon group in the molecule, k represents an integer of 1 to 7, and n represents an integer of 1 to 7.) 8. The metal compound (3 ″) has the following general formula (II)
7. The compound according to claim 5, which is at least one selected from the group consisting of a compound represented by -1), a compound represented by (II-2), and a compound represented by (II-3). Or a solvent-based coating composition. Embedded image (In the above general formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and each represent a hydrogen atom,
30 substituted or unsubstituted hydrocarbon groups. However, in one ligand, R ²¹ , R ²² , R ²³ and R
It is assumed that at least one compound having ²⁴ carbon atoms of 10 or more is included. M is Al, Ti, Cr, Mn, F
e, Co, Ni, Cu, Zr, Zn, Ba, Ca, C
It is selected from the group consisting of e, Pb, Mg, Sn and V, where n is an integer of 2-4. ) 9. The heat-activated ionic polymerization catalyst (3) comprises a metal compound (3 ″), an organosilane having a hydroxyl group directly bonded to a silicon atom, an organosiloxane having a hydroxyl group directly bonded to a silicon atom, and a phenol compound. And an organosilicon compound having a hydrolyzable group directly bonded to a silicon atom, and at least one selected from the group consisting of silicon compounds capable of generating silanol by light irradiation. Claims 1 to 8
The solvent-based coating composition according to any one of the above. 10. The heat-activated ion polymerization catalyst (3) contains at least one selected from the group consisting of compounds represented by the following general formulas (III-1 ′) and (III-2). The solvent-based coating composition according to any one of claims 1 to 4, wherein: Embedded image (In the above general formula (III-1 ′), R ¹ , R ² , and R ³ may be the same or different and each represent a hydrogen atom and a carbon number of 1 to 1.
A substituted or unsubstituted hydrocarbon group, an aromatic group or a heteroaromatic group having a substituted or unsubstituted hydrocarbon group; However, it has one or more aromatic or heteroaromatic groups having a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms, or a substituted or unsubstituted hydrocarbon group having 10 or more carbon atoms. ) (In the general formula (III-2), R ³² , R ³³ , R ³⁴ and R ³⁵ may be the same or different and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. However, at least two of R ³² , R ³³ , R ³⁴ and R ³⁵ are a hydrocarbon group having 10 or more carbon atoms.) 11. The heat-activated ion polymerization catalyst (3) contains at least one selected from the group consisting of compounds represented by the following general formulas (III-1) and (III-2). The solvent-based coating composition according to any one of claims 1 to 4. Embedded image (In the above general formula (III-1), R ³¹ may be the same or different and each represents a hydrogen atom or a carbon atom having 1 to 30 carbon atoms.
Is a substituted or unsubstituted hydrocarbon group. However, 1
At least one R ³¹ in the molecule has 10 or more carbon atoms. h, i and j are integers satisfying h + i + j = 3, and m is an integer of 1 to 5. ) (In the general formula (III-2), R ³² , R ³³ , R ³⁴ and R ³⁵ may be the same or different and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. However, at least two of R ³² , R ³³ , R ³⁴ and R ³⁵ are a hydrocarbon group having 10 or more carbon atoms.) 12. The solvent-based coating composition according to claim 11, wherein the compound represented by the general formula (III-1) is at least one selected from the following group. Embedded image Embedded image 13. The solvent-based coating composition according to claim 10, wherein the compound represented by the general formula (III-2) is at least one selected from the group shown below. Embedded image 14. The method according to claim 1, which is used for painting a vehicle.
4. The solvent-based paint / fat composition according to any one of 3. 15. A coated article obtained by coating a substrate with the solvent-based coating composition according to claim 1 and curing the composition.