JPH11322900A - Photocurable composition and curing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocuring composition capable of efficiently photocuring photocurable compositions containing a diaryliodonium salt derivative or triarylsulfonium salt derivative as a photocuring catalyst, and to provide a photocurable composition capable of being quickly cured even when containing additives such as a pigment and giving cured products having excellent physical properties. SOLUTION: This photocurable composition comprises a diaryliodonium salt derivative or triarylsulfonium salt derivative acting as a photocation polymerization catalyst, a compound having a cation polymerizable group and a sensitizer accelerating a photocation initiation reaction, a cation polymerizable compound, and a pigment such as titanium dioxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photocurable composition, and more particularly to a sensitized photocationically curable composition. The photocurable composition of the present invention can be cured by irradiating active energy rays such as light, electron beams, and X-rays, and in particular, has excellent characteristics in long-wavelength photosensitivity. , Adhesives, inks and photoresists, and photosensitive resins for stereolithography. Further, the present invention also relates to a photocuring method for the photocurable composition, and a cation polymerizable group and a sensitizing group for promoting a photocation initiation reaction in a molecule used as a sensitizer in the photocurable composition. The present invention relates to a substituted alkoxy polycyclic aromatic compound having a cationically polymerizable group as a substituent on a part of an aromatic ring or an alkoxy group, or a polymer thereof.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open Nos. 50-151997, 50-158680 and 50-15199
No. 6 describes that an arylonium salt compound can be used as a catalyst for curing a cationically polymerizable compound such as an epoxy compound by radiation such as light, electron beam, or X-ray. Since these aryl onium salt compounds have little absorption at wavelengths longer than 360 nm, which is considered to be effective for ultraviolet curing, photocurable compositions using additives such as pigments and stereolithography using laser light of long wavelengths It is known that the curability of a product is significantly reduced. In particular, a photocurable composition containing a large amount of a white pigment such as titanium oxide in which the UV absorption range of the arylonium salt compound overlaps the absorption range has many problems in use. As a solution to this, sensitizers have been studied.For example, various dye derivatives have been reported to be effective as sensitizers for diaryliodonium salts, and thioxanthone derivatives are particularly inexpensive and commonly used. It has been known. However, the photocurability of a photocurable composition using an additive such as a pigment is insufficient with the thioxanthone derivative alone. In addition, general sensitizers are effective at the time of photocuring, but after photocuring, they are merely plasticizers from the viewpoint of the properties of the cured product. It is expected to make it worse.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of these circumstances, and an object of the present invention is to provide a photocurable composition containing a diaryliodonium salt derivative or a triarylsulfonium salt derivative as a photocuring catalyst. The present invention provides a photocurable composition capable of effectively photocuring a product, and is capable of curing in a short time even if the composition contains an additive such as a pigment, and is an excellent cured product. An object of the present invention is to provide a photocurable composition having characteristics.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and found that a photocurable composition containing a diaryliodonium salt derivative or a triarylsulfonium salt derivative as a photocuring catalyst. Compounds having, as a sensitizer, a cationically polymerizable group and a sensitizing group that promotes a photocation initiation reaction in a molecule, particularly a substituted alkoxy group having a cationically polymerizable group as a substituent on a part of an aromatic ring or an alkoxy group The present inventors have found that a photocurable composition that overcomes the above problems can be obtained by using a ring-aromatic compound or a polymer thereof, and has completed the present invention.

That is, the present invention relates to a novel compound,
Compounds having a cationically polymerizable group and a sensitizing group that promotes a photocation initiation reaction in the molecule, or a sensitizing group having a hydroxyl group as a substituent, an optionally substituted aralkyloxy group or an optionally substituted alkoxy group The above compound, which has at least one group and contains a polycyclic aromatic group having a UV absorption spectrum at a wavelength longer than 330 nm, or a sensitizing group having a UV absorption spectrum at a wavelength longer than 330 nm. A compound having a carbazole derivative structure, a compound having a oxirane structure such as an epoxy group having a cation polymerizable group such as an epoxy group having an epoxysilicone structure, or an aromatic ring or an alkoxy group having a cation polymerizable group. A substituted alkoxy polycyclic aromatic compound such as an anthracene derivative or a phenanthrene derivative having a substituent in the moiety, or About polymers (hereinafter these compounds will be referred to as "component compounds of the present invention").

The present invention also relates to a compound having a group functioning as a photocationic polymerization initiator in the molecule, preferably an onium salt compound such as a diaryliodonium salt derivative or a triarylsulfonium salt derivative, which acts as a photocationic polymerization catalyst. A photocurable composition containing the component compound of the present invention, a compound having a group functioning as a photocationic polymerization initiator in the molecule, a component compound of the present invention, and an alicyclic epoxy such as epoxy silicone. A photocurable composition containing a cationically polymerizable compound composed of one or more compounds selected from the group consisting of compounds, vinyl ether compounds and oxetane compounds; and pigments such as titanium dioxide and / or radical polymerizable compounds The present invention relates to the photocurable composition containing a compound or the like.

[0007] The present invention also relates to a method for photocuring the above photocurable composition, which comprises irradiating the photocurable composition containing a pigment with a gallium-containing lamp.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The components of the photocurable composition of the present invention include a compound having a group functioning as a photocationic polymerization initiator in a molecule acting as a photocationic polymerization catalyst, and a cationically polymerizable compound in a molecule. Examples thereof include compounds having a group and a sensitizing group that promotes a photocation initiation reaction, cationically polymerizable compounds, pigments, radically polymerizable compounds, and the like.

The compound having a group functioning as a cationic photopolymerization initiator in the molecule of the present invention can be used without any limitation as long as it acts as a cationic photopolymerization initiator. Is an onium salt,
More preferably, a diaryliodonium salt derivative or a triarylsulfonium salt derivative can be exemplified,
As the diaryliodonium salt derivative, a compound selected from the group consisting of a diphenyliodonium salt derivative, a phenylnaphthyliodonium salt derivative, and a dinaphthyliodonium salt derivative can be exemplified, and specifically, as shown in (Formula 1) Compounds can be mentioned,
In addition, as the triarylsulfonium salt derivative, a compound selected from triphenylsulfonium salt derivatives can be exemplified, and specifically, a compound represented by (Chemical Formula 2) can be exemplified. The counter anion of these derivatives is a non-nucleophilic anion such as Sb
The type is not limited as long as it is F ₆ , AsF ₆ , PF ₆ , BF ₆ , (F ₅ C ₅ ) ₄ B, or the like.

[0010]

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[0011]

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In the present invention, the compound having a cationically polymerizable group and a sensitizing group for accelerating the photocation initiation reaction in the molecule is a novel compound, and these compounds mainly act as sensitizers, Since it has a cationically polymerizable group, it has a feature that it has good compatibility with the cationically polymerizable compound in the photocurable composition, which could not be expected with a conventionally known sensitizer. In addition, since the sensitizer does not remain free in the cured product, the properties of the cured product can be expected not to deteriorate, and the sensitizer does not bleed from the cured product. The effects of toxicity and toxicity due to sensitizers can be minimized.
And the proportion of the cationically polymerizable group in this compound is large, for example, in the case of a chain polymer, the blending ratio of the cationically polymerizable compound in the photocurable composition may be reduced,
In some cases, a cationically polymerizable compound may not be used.

Preferred examples of these compounds include a substituted alkoxy polycyclic aromatic compound having a cationically polymerizable group as a substituent on a part of an aromatic ring or an alkoxy group or a polymer thereof. As the basic skeleton, for example, 9-hydroxyphenanthrene, 9-
Methoxyphenanthrene, 9-ethoxyphenanthrene, 9-benzyloxyphenanthrene, 9,10-dimethoxyphenanthrene, 9,10-diethoxyphenanthrene, 9,10-dipropoxyphenanthrene,
9,10-dibenzyloxyphenanthrene, 9,10
-Di-α-methylbenzyloxyphenanthrene, 9-
Phenanthrene derivative structures such as hydroxy-10-methoxyphenanthrene and 9-hydroxy-10-ethoxyphenanthrene, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene,
2-tbutyl-9,10-dimethoxyanthracene,
2,3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy-10-methylanthracene, 9.1
0-diethoxyanthracene, 2-ethyl-9,10-
Diethoxyanthracene, 2-tbutyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-
Diethoxyanthracene, 9-ethoxy-10-methylanthracene, 9,10-dipropoxyanthracene,
2-ethyl-9,10-dipropoxyanthracene, 2
-Tbutyl-9,10-dipropoxyanthracene,
2,3-dimethyl-9,10-dipropoxyanthracene, 9-isopropoxy-10-methylanthracene,
9,10-dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2-tbutyl-9,10-dibenzyloxyanthracene, 2,
3-dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10-methylanthracene,
9,10-di-α-methylbenzyloxyanthracene, 2-ethyl-9,10-di-α-methylbenzyloxyanthracene, 2-tbutyl-9,10-di-α-
Methylbenzyloxyanthracene, 2,3-dimethyl-9,10-di-α-methylbenzyloxyanthracene, 9- (α-methylbenzyloxy) -10-methylanthracene, 9,10-di (2-hydroxyethoxy) Examples include anthracene derivative structures such as anthracene and 2-ethyl-9,10-di (2-carboxyethoxy) anthracene.

Used as a sensitizer in the present invention;
In the compound having a cationically polymerizable group and a sensitizing group that promotes a photocation initiation reaction in the molecule, the “sensitizing group that promotes a photocation initiation reaction” is one that can enhance photocurable catalytic action. Any one may be used as long as it is present, but it preferably has at least one hydroxyl group, an optionally substituted aralkyloxy group or an optionally substituted alkoxy group, and
Examples include a group containing a polycyclic aromatic group having a UV absorption spectrum at a longer wavelength and a group having a carbazole derivative structure having a UV absorption spectrum at a longer wavelength than 330 nm. The structures of the compounds functioning as sensitizers shown below and the structures of similar compounds thereof can be specifically mentioned as sensitizing groups.

Phenol derivatives such as 4-methoxyphenol, 4-benzyloxyphenol, 4-methoxy-2- (t-butyl) phenol, hydroquinone and 2-hydroxydibenzofuran, 1-naphthol, 2-naphthol and 1-methoxynaphthalene , 2-methoxynaphthalene, glycidyl-1-naphthyl ether, 2- (2-
Naphthoxy) ethyl vinyl ether, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene,
1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,7-dimethoxynaphthalene, 1,
1'-thiobis (2-naphthol), 1,1'-bi-2
-Naphthol, 1,5-naphthyldiglycidyl ether, 2,7-di (2-vinyloxyethyl) naphthyl ether, 4-methoxy-1-naphthol, ES N-
175 (epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) or a series thereof, a condensate of a naphthol derivative and formalin, a condensate of a mixture of a naphthol derivative and a phenol derivative and formalin, and an epoxy compound obtained by reacting them with epichlorohydrin; 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-tbutyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy-10-methyl Anthracene, 9,
10-diethoxyanthracene, 2-ethyl-9,10
-Diethoxyanthracene, 2-tbutyl-9,10-
Diethoxyanthracene, 2,3-dimethyl-9,10
-Diethoxyanthracene, 9-ethoxy-10-methylanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-tbutyl-9,10-dipropoxyanthracene, 2,3 -Dimethyl-9,10-dipropoxyanthracene, 9-isopropoxy-10-methylanthracene, 9,10-dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2-
t-butyl-9,10-dibenzyloxyanthracene,
2,3-dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10-methylanthracene, 9,10-di-α-methylbenzyloxyanthracene, 2-ethyl-9,10-di-α- Methylbenzyloxyanthracene, 2-tbutyl-9,10-di-α
Anthracene derivatives such as -methylbenzyloxyanthracene, 2,3-dimethyl-9,10-di-α-methylbenzyloxyanthracene, 9- (α-methylbenzyloxy) -10-methylanthracene, and 1,4-dimethoxychrysene , 1,4-diethoxychrysene, 1,4
-Chrysene derivatives such as -dipropoxychrysene, 1,4-dimethylbenzyloxychrysene, 1,4-di-α-methylbenzyloxychrysene, 9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-ethoxyphenanthrene, and 9-benzyloxy Phenanthrene, 9.1
0-dimethoxyphenanthrene, 9,10-diethoxyphenanthrene, 9,10-dipropoxyphenanthrene, 9,10-dibenzyloxyphenanthrene, 9,
10-di-α-methylbenzyloxyphenanthrene,
9-hydroxy-10-methoxyphenanthrene, 9-
Phenanthrene derivatives such as hydroxy-10-ethoxyphenanthrene; carbazole derivatives such as carbazole, N-vinylcarbazole and N-ethylcarbazole;

Of these, 2-ethyl-9,10-
9,10-dialkoxyanthracene derivatives such as dimethoxyanthracene, thioxanthone derivatives such as 2,4-diethylthioxanthone, carbazole derivatives such as N-ethylcarbazole, naphthalene derivatives such as 1-naphthol and 2-methoxynaphthalene, 9,10- Phenanthrene derivatives such as dimethoxyphenanthrene are preferred,
Further, by combining a sensitizing group such as a phenanthrene derivative such as 9,10-dimethoxyphenanthrene and a thioxanthone derivative such as 2,4-diethylthioxanthone, the sensitizing effect can be more effectively exerted. Sometimes you can.

The cationically polymerizable group in the component compound of the present invention is a generally known cationically polymerizable compound, for example, the same as the following cationically polymerizable groups of monomers, oligomers and polymers. Although usable, an epoxy compound or an oxetane compound having an oxirane structure is preferable in terms of easiness of synthesis and good cured product characteristics. In particular, compounds having an epoxysilicone structure are generally known to have poor compatibility with sensitizers and cationic photopolymerization initiators, but sensitizers and cationic polymerization initiators are previously introduced into the epoxysilicone structure. This solves the compatibility problem.

(A) Styrene, α-methylstyrene, p-methoxystyrene, p-
styrene compounds such as t-butoxystyrene, methyl vinyl ether, n-butyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-chloroethyl vinyl ether;
-Alkyl vinyl ether compounds such as phenoxyethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, and 2-acetoxyethyl vinyl ether;
Alkenyl vinyl ether compounds such as allyl vinyl ether, 2-methacryloyloxyethyl vinyl ether and 2-acryloyloxyethyl vinyl ether; aryl vinyl ether compounds such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; cationic polymerizable compounds such as N-vinyl carbazole and N-vinyl pyrrolidone Nitrogen-containing compounds, polyfunctional vinyl compounds such as butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, 1,4-benzene dimethanol divinyl ether, hydroquinone divinyl ether, sasolcinol divinyl ether, etc., Journal of Polymer S
science: Part A: Polymer Che
mystry, Vol. 32, 2895 (1994)
Compounds described in the above, Journal
of Polymer Science: Part
A: Polymer Chemistry, Vol. 3
No. 3,2493 (1995), an alkoxyallene compound, Journal of Polymer
Science: Part A: Polymer C
hemistry, Vol. 34, 1015 (199
The vinyl compound described in 6), Journal
of Polymer Science: Part
A: Polymer Chemistry, Vol. 3
And isopropenyl compounds described in U.S. Pat. No. 4,2051 (1996).

(B) As the epoxy compound structure, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-
Ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monoxide, 1,2-dodecylene oxide, epichlorohydrin, 1,2-epoxydecane, ethylene oxide, propylene oxide, Styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-
Monofunctional monomers such as vinylcyclohexene oxide, 1,1,3-tetradecadienedoxide, limonenedoxide, 3,4-epoxycyclohexylmethyl- (3,4-epoxycyclohexyl) carboxylate, di (3,4 -Epoxycyclohexyl) adipate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, o-, m-, p-cresol novolak type epoxy resin, phenol novolak type epoxy resin, polyglycidyl ether of polyhydric alcohol, manufactured by Shin-Etsu Silicone Epoxy silicones such as K-62-722 and UV9300 manufactured by Toshiba Silicone Co., Ltd.
nal of Polymer Science: Pa
rt A: Polymer Chemistry, Vo
l. And polyfunctional epoxy compounds such as the silicone-containing epoxy compounds described in U.S. Pat. No. 28,497 (1990).

(C) The structure of the bicycloorthoester compound is 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1-ethyl-
Examples include compounds such as 4-hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane.

(D) 1,5,7,11-tetraoxaspiro [5,5] undecane, 3,9-dibenzyl-1,5,5
7,11-tetraoxaspiro [5,5] undecane,
1,4,6-trioxaspiro [4,4] nonane, 2-
Examples include compounds such as methyl-1,4,6-trioxaspiro [4,4] nonane and 1,4,6-trioxaspiro [4,5] decane.

(E) As the oxetane compound structure,
3-dimethyloxetane, 3,3-bis (chloromethyl) oxetane, 2-hydroxymethyloxetane, 3
-Methyl-3-oxetanemethanol, 3-methyl-3
Compounds such as -methoxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, resorcinol bis (3-methyl-3-oxetanylethyl) ether, and m-xylylenebis (3-ethyl-3-oxetanylethylether) are exemplified.

Accordingly, compounds having a cationically polymerizable group and a sensitizing group for promoting a photocation initiation reaction in the molecule include, for example, 9-glycidyloxyphenanthrene, 9- (2-vinyloxyethoxy) phenanthrene, and 9-glycidyloxyphenanthrene. -(3-methyl-3-oxetanylmethoxy) phenanthrene, 9- (p-epoxyphenylmethoxy)
Phenanthrene, 9- (p-vinylphenylmethoxy)
Phenanthrene, 9,10-di (glycidyloxy) phenanthrene, 9,10-di (2-vinyloxyethoxy) phenanthrene, 9,10-di (3-methyl-3-
Oxetanylmemethoxy) phenanthrene, 9,10-
Di (p-epoxyphenylmethoxy) phenanthrene,
Phenanthrene derivatives such as 9,10-di (p-vinylphenylmethoxy) phenanthrene, 9,10-di (glycidyloxy) anthracene, 2-ethyl-9,10
-Di (glycidyloxy) anthracene, 2-tbutyl-9,10-di (glycidyloxy) anthracene,
2,3-dimethyl-9,10-di (glycidyloxy)
Anthracene, 9- (glycidyloxy) -10-methylanthracene, 9,10-di (2-vinyloxyethoxy) anthracene, 2-ethyl-9,10-di (2-
Vinyloxyethoxy) anthracene, 2-tbutyl-
9,10-di (2-vinyloxyethoxy) anthracene, 2,3-dimethyl-9,10-di (2-vinyloxyethoxy) anthracene, 9- (2-vinyloxyethoxy) -10-methylanthracene, 9 , 10-Di (3-methyl-3-oxetanylmethoxy) anthracene, 2-ethyl-9,10-di (3-methyl-3-oxetanylmemethoxy) anthracene, 2-tbutyl-
9,10-di (3-methyl-3-oxetanylmemethoxy) anthracene, 2,3-dimethyl-9,10-di (3-methyl-3-oxetanylmemethoxy) anthracene, 9- (3-methyl-3 -Oxetanylmemethoxy) -10-methylanthracene, 9,10-di (p-
Epoxyphenylmethoxy) anthracene, 2-ethyl-9,10-di (p-epoxyphenylmethoxy) anthracene, 2-tbutyl-9,10-di (p-epoxyphenylmethoxy) anthracene, 2,3-dimethyl-
9,10-di (p-epoxyphenylmethoxy) anthracene, 9- (p-epoxyphenylmethoxy) -10
-Methylanthracene, 9,10-di (p-vinylphenylmethoxy) anthracene, 2-ethyl-9,10-
Di (p-vinylphenylmethoxy) anthracene, 2-
t-butyl-9,10-di (p-vinylphenylmethoxy) anthracene, 2,3-dimethyl-9,10-di (p-vinylphenylmethoxy) anthracene, 9-
And anthracene derivatives such as (p-vinylphenylmethoxy) -10-methylanthracene.
The structural formula of a representative one is shown as (Formula 3).

[0024]

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Further, as such polymers, for example,
9- (2-vinyloxyethoxy) phenanthrene, 9- (3-methyl-3-oxetanylmethoxy) phenanthrene, 9- (p-epoxyphenylmethoxy) phenanthrene, 9- (p-vinylphenylmethoxy) phenanthrene as chain polymers Homogenized cationic polymers or cation copolymers and the like, polyaddition products such as dibasic acids such as terephthalic acid and maleic acid, and addition reactants with bifunctional phenolic compounds such as bisphenol A can be mentioned. Its structural formula is shown as (Formula 4).

[0026]

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The method for synthesizing the component compounds of the present invention includes:
A method of synthesizing a compound serving as a substrate, a compound having a cationically polymerizable group, and a compound having a sensitizing group that promotes a photocationic initiation reaction, or a compound having a cationically polymerizable group, and a photocationic initiation reaction Examples thereof include a method of synthesizing the compound by a reaction with a compound having a sensitizing group that promotes a photosensitization initiation reaction having a carboxyl group, an aromatic hydroxyl group, or the like as a functional group. The component of the present invention is reacted with an epoxy group-containing compound or an oxetane group-containing compound such as an epoxy silicone in which at least one or more epoxy groups or oxetane groups remain even when reacted with a sensitizer that promotes a photocation initiation reaction. The method of synthesizing the compound is advantageous in that the synthesis is easy and each group can be controlled. Those skilled in the art can easily synthesize these component compounds of the present invention.

The cationically polymerizable compound used in the present invention can be used without any limitation as long as it is a generally known monomer, oligomer or polymer having a cationically polymerizable group. Can be exemplified. (A) As the vinyl compound, styrene compounds such as styrene, α-methylstyrene, p-methoxystyrene, pt-butoxystyrene, methyl vinyl ether, n-
Butyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether,
Alkyl vinyl ether compounds such as 2-chloroethyl vinyl ether, 2-phenoxyethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, and 2-acetoxyethyl vinyl ether; allyl vinyl ether; 2-methacryloyloxyethyl vinyl ether; Alkenyl vinyl ether compounds such as acryloyloxyethyl vinyl ether; aryl vinyl ether compounds such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; N-vinyl carbazole;
-Polyfunctional such as cationically polymerizable nitrogen-containing compounds such as vinylpyrrolidone, butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, 1,4-benzenedimethanol divinyl ether, hydroquinone divinyl ether, and sasolcinol divinyl ether. Vinyl compound, J
own of PolymerScience:
Part A: Polymer Chemistry,
Vol. 32, 2895 (1994), a Journal of Polym.
er Science: Part A: Polymer
Chemistry, Vol. 33, 2493 (19
95) the alkoxyallene compound described in Jo,
urnal of Polymer Science:
Part A: Polymer Chemistry,
Vol. 34, 1015 (1996), the Journal of Polymer.
Science: Part A: Polymer Ch
chemistry, Vol. 34, 2051 (1996)
And the like.

(B) Epoxy compounds include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene Monooxide, 1,2-dodecylene oxide,
Monofunctional such as epichlorohydrin, 1,2-epoxydecane, ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide monomer,
1,1,3-tetradecadienedoxide, limonenedoxide, 3,4-epoxycyclohexylmethyl- (3,4-epoxycyclohexyl) carboxylate, di (3,4-epoxycyclohexyl) adipate, bisphenol A type epoxy Resin, bisphenol F type epoxy resin, o-, m-, p-cresol novolak type epoxy resin, phenol novolak type epoxy resin, polyglycidyl ether of polyhydric alcohol, K-62-722 manufactured by Shin-Etsu Silicone and Toshiba Silicone Epoxy silicone such as UV9300 manufactured by Journ
al of Polymer Science: Par
tA: Polymer Chemistry, Vo
l. And polyfunctional epoxy compounds such as the silicone-containing epoxy compounds described in U.S. Pat. No. 28,497 (1990).

(C) The bicycloorthoester compounds include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane and 1-ethyl-4
And compounds such as -hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane.

(D) Spiro orthocarbonate compounds include 1,5,7,11-tetraoxaspiro [5,
5] undecane, 3,9-dibenzyl-1,5,7,1
1-tetraoxaspiro [5,5] undecane, 1,
4,6-trioxaspiro [4,4] nonane, 2-methyl-1,4,6-trioxaspiro [4,4] nonane,
Compounds such as 1,4,6-trioxaspiro [4,5] decane can be exemplified.

(E) Oxetane compounds include 3,3
-Dimethyloxetane, 3,3-bis (chloromethyl)
Oxetane, 2-hydroxymethyloxetane, 3-methyl-3-oxetanemethanol, 3-methyl-3-methoxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, resorcinol bis (3-methyl-
Examples thereof include compounds such as 3-oxetanylethyl) ether and m-xylylenebis (3-ethyl-3-oxetanylethylether).

These may be used alone or in combination of two or more. Among these, it is preferable to use one or more compounds selected from the group consisting of alicyclic epoxy compounds, vinyl ether compounds and oxetane compounds. Further, when the component compound of the present invention having a group having an oxirane structure such as an epoxy group having an epoxy silicone structure as a polymerizable group is used as a sensitizer, good compatibility with an alicyclic epoxy compound such as epoxy silicone can be obtained. From the viewpoint of being obtained, the cationic polymerizable compound is preferably an alicyclic epoxy compound such as epoxy silicone.

In the present invention, the compounding ratio of the diaryl iodonium salt derivative or triaryl sulfonium salt derivative acting as a photocationic polymerization initiator and the cationic polymerizable compound is such that the salt derivative is not added to 100 parts by weight of the cationic polymerizable compound. 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight. If the amount of the diaryliodonium salt derivative or triarylsulfonium salt derivative is small, the curability of the cationically polymerizable compound will be reduced, and if it is excessive, the properties of the cured product will be reduced.

On the other hand, a compound having a cationically polymerizable group and a sensitizing group for promoting a photocation initiation reaction in the molecule,
In particular, the compounding ratio of the substituted alkoxy polycyclic aromatic compound or a polymer thereof having a cationic polymerizable group as a substituent on a part of an aromatic ring or an alkoxy group, and the cationic polymerizable compound, In this case, it can be used arbitrarily, depending on the properties of the desired cured product, but is preferably 0.1 to 30 parts by weight per 100 parts by weight of the cationically polymerizable compound, and is preferably a substituted alkoxy polycyclic aromatic. In the case of a compound polymer, the amount is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the cationically polymerizable compound.

The photocurable composition of the present invention can be easily cured by light. As the light source, a low-pressure mercury lamp,
Medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc lamps, etc. are used, and semiconductor lasers, argon lasers, He-
Although laser light such as Cd laser can be used,
In the case of a photocurable composition containing titanium dioxide as a white pigment, 380 to 450 nm without absorption by titanium dioxide
The use of a lamp that emits light efficiently, particularly a gallium-containing lamp, enables effective photo-curing, and is preferable in terms of improving the curing speed, the properties of the cured product, and the thick film curability. Further, the photocurable composition of the present invention comprises α rays, β
It can be easily cured by ionizing radiation such as X-ray, γ-ray, neutron beam, X-ray and accelerating electron beam.

When the photocurable composition of the present invention contains a pigment, it can be used for inks and photoresists. As the pigment used in the present invention, carbon black, acetylene black, orchid black, black pigments such as aniline black, graphite, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navels yellow, Yellow pigments such as naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, tartrazine lake, red mouth lead, molybdenum orange, permanent orange GTR, pyrazolone orange , Vulcan orange, Indaslen brilliant orange RK, Benzidine orange G, Indaslen brilliant orange GK, etc., orange pigments, bengara, cadmium red, lead red, sulfuric acid Mercury cadmium, permanent red 4R, lithol red, pyrazolone red, watching red calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, brilliant carmine 3B
Red pigment, manganese purple, fast violet B, etc.
Purple pigments such as methyl violet lake, navy blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, partially chlorinated phthalocyanine blue, fast sky blue, blue pigments such as indaslen blue BC,
Chrome green, chromium oxide, pigment green B,
Green pigments such as Malachite Green Lake and Fanal Yellow Green G; white pigments such as zinc white, titanium dioxide, antimony white and zinc sulfide; and barite powder, barium carbonate, clay, silica, silica, white carbon, talc, alumina white, etc. An extender can be exemplified.

The effect of the component compound of the present invention in the photocurable composition of the present invention is more excellent than the case where no pigment is used, in that the composition using a white pigment such as zinc white, titanium dioxide, antimony white, and zinc sulfide is more effective. It is more evident in products and is particularly effective when titanium dioxide is used. When a pigment is used, a sensitizer can be separately used.

For controlling the properties, curability and the like of the cured product of the photocurable composition according to the present invention, a radical polymerizable compound can be used. As the radical polymerizable compound used in the present invention, any monomers, oligomers and polymers having radical polymerizability can be used regardless of the kind thereof. As the radical polymerizable monomer, monofunctional or polyfunctional acrylate or methacrylate monomer, etc., as the radical polymerizable oligomer, epoxy acrylate, epoxy methacrylate, polyester acrylate, polyester methacrylate, polyether acrylate, polyether methacrylate, polyurethane acrylate, Polyurethane methacrylate, polybutadiene acrylate, polybutadiene methacrylate, and the like, and radical polymerizable polymers include polyester, polybutadiene, and polyether. , Urethane, each acrylates such as epoxy, the methacrylate compounds, can be exemplified unsaturated polyesters.

Examples of the radically polymerizable reactive diluent include acrylate monomers such as acrylic acid and ethyl acrylate, methacrylate monomers such as methacrylic acid and methyl methacrylate, and styrene.

[0041]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited to these examples. Synthesis Example 1 (Synthesis of 2-ethyl-9,10-diglycidyloxyanthracene) 14.2 g of 2-ethylanthraquinone, 0.4 g of tetrabutylammonium bromide, epichlorohydrin 2
3 g, zinc powder 40 g and dimethylformamide 100 g
And heated at 120 ° C. for 3 hours. Thereafter, 14 g of potassium carbonate was added, and the mixture was further reacted for 8 hours. The obtained solution was poured into 1 liter of water, and then 300 ml of ethyl acetate was added and stirred. The solid was filtered off, the ethyl acetate solution was washed with water, and excess epichlorohydrin, dimethylformamide and ethyl acetate were removed under reduced pressure to obtain 21 g of a solid.

Synthesis Example 2 (Synthesis of polymer of 2-ethyl-9,10-diglycidyloxyanthracene) 35 g of 2-ethyl-9,10-diglycidyloxyanthracene obtained in Synthesis Example 1 and 10 g of succinic anhydride Was dissolved in 100 g of dimethylformamide and reacted at 120 ° C. for 8 hours. The obtained solution was poured into 1 liter of water, and the solid matter was separated by filtration and dried under reduced pressure to obtain 40 g of a solid matter.

Formulation 1 UVR-6110 (alicyclic epoxy manufactured by UCC) 100
Part and titanium oxide (CR-58 manufactured by Ishihara Sangyo Co., Ltd.) in 100 parts, 4,4′-di-tert-butyldiphenyliodonium hexafluorophosphonate and 3 parts of compound (2-ethyl-9,10) synthesized in Synthesis Example 1. -Diglycidyloxyanthracene) was mixed to prepare Formulation 1.

Formulation 2 A compound (2-ethyl-9,10-diglycidyloxyanthracene polymer) synthesized in Synthesis Example 2 in place of 2-ethyl-9,10-diglycidyloxyanthracene synthesized in Synthesis Example 1. ) Was used to prepare Formulation 2 as in Formulation 1.

Formulation 3 A formulation was prepared in the same manner as Formulation 1 except that the compound (2-ethyl-9,10-diglycidyloxyanthracene) synthesized in Synthesis Example 1 was not used.

Photocurability Test Each of the above Formulations 1 to 3 was coated on a tin plate with a bar coater No. 4 and light-cured under the following conditions, Formulation 1 and Formulation 2 had hardened to the inside, but Formulation 3
Did not cure to its interior. UV irradiation equipment: belt conveyor type UV irradiation equipment (manufactured by Eye Graphics Co., Ltd.) Lamp: one condensing type 160 W gallium-containing metal halide lamp Irradiation distance: 10 cm (focal length) Belt conveyor speed: 40 m / min

[0047]

The photocurable composition of the present invention can be cured by irradiating active energy rays such as light, electron beams and X-rays. Furthermore, since the diphenyliodonium salt derivative or the triarylsulfonium salt derivative has no absorption region or can be cured even with light having a wavelength of longer than 330 nm, which has extremely low absorption, the composition containing an additive such as a pigment may be used. Can also be photocured effectively.
Therefore, it is suitably used for a photocurable paint, an adhesive, an ink, a photoresist, a photosensitive resin for stereolithography, and the like.

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Claims (23)

[Claims] 1. A compound having a cationically polymerizable group and a sensitizing group for accelerating a photocation initiation reaction in a molecule. 2. A compound having a cationically polymerizable group and a sensitizing group which promotes a photocation initiation reaction in a molecule, wherein the compound has a cationically polymerizable group as a substituent on a part of an aromatic ring or an alkoxy group. 2. The compound according to claim 1, which is a ring aromatic compound or a polymer thereof. 3. The compound according to claim 2, wherein the substituted alkoxy polycyclic aromatic compound is an anthracene derivative or a phenanthrene derivative. 4. The sensitizing group has at least one of a hydroxyl group, an optionally substituted aralkyloxy group and an optionally substituted alkoxy group, and
The compound according to claim 1, which is a group containing a polycyclic aromatic group having a UV absorption spectrum at a wavelength longer than 30 nm. 5. The method according to claim 1, wherein the sensitizing group has a wavelength longer than 330 nm.
2. The compound according to claim 1, which is a group having a carbazole derivative structure having a V absorption spectrum. 6. The compound according to claim 1, wherein the cationically polymerizable group is a group having an oxirane structure. 7. The compound according to claim 6, wherein the group having an oxirane structure is an epoxy group having an epoxysilicone structure. 8. A composition comprising a compound having a group functioning as a photocationic polymerization initiator in a molecule and a compound having a cationically polymerizable group and a sensitizing group promoting a photocationic initiation reaction in the molecule. Characteristic photocurable composition. 9. A compound having a group that functions as a photocationic polymerization initiator in a molecule, a compound having a cationically polymerizable group and a sensitizing group that promotes a photocationic initiation reaction in a molecule, and a cationically polymerizable compound. And a photocurable composition comprising: 10. The photocurable composition according to claim 8, wherein the compound having a group that functions as a photocationic polymerization initiator in the molecule is an onium salt compound. 11. The photocurable composition according to claim 10, wherein the onium salt compound is a diaryliodonium salt derivative or a triarylsulfonium salt derivative. 12. A compound having a cationically polymerizable group and a sensitizing group for accelerating a photocation initiation reaction in a molecule, wherein the compound has a cationically polymerizable group as a substituent on a part of an aromatic ring or an alkoxy group. The photocurable composition according to any one of claims 8 to 11, which is a ring aromatic compound or a polymer thereof. 13. The substituted alkoxy polycyclic aromatic compound,
The photocurable composition according to claim 12, which is an anthracene derivative or a phenanthrene derivative. 14. The sensitizing group has at least one hydroxyl group, an optionally substituted aralkyloxy group or an optionally substituted alkoxy group as a substituent and absorbs UV light at a wavelength longer than 330 nm. 9. A group containing a polycyclic aromatic group having a spectrum.
14. The photocurable composition according to any one of items 13 to 13. 15. The photocurable composition according to claim 8, wherein the sensitizing group is a group having a carbazole derivative structure having a UV absorption spectrum at a wavelength longer than 330 nm. 16. The photocurable composition according to claim 8, wherein the cationically polymerizable group is a group having an oxirane structure. 17. The photocurable composition according to claim 16, wherein the group having an oxirane structure is an epoxy group having an epoxysilicone structure. 18. The cationic polymerizable compound according to claim 9, wherein the cationically polymerizable compound is one or more compounds selected from the group consisting of an alicyclic epoxy compound, a vinyl ether compound, and an oxetane compound. Or a photocurable composition according to the above. 19. The photocurable composition according to claim 18, wherein the alicyclic epoxy compound is epoxy silicone. 20. The photocurable composition according to claim 8, further comprising a radical polymerizable compound.
The photocurable composition according to any one of the above. 21. The photocurable composition according to claim 8, wherein the photocurable composition further contains a pigment. 22. The photocurable composition according to claim 21, wherein the pigment is titanium dioxide. 23. The photocurable composition according to claim 21,
A photocuring method comprising irradiating a gallium-containing lamp.