JPH10147608A - Photocatalyst composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To cure a cationic polymerizable compound containing an additive such as pigment in a short time by including a specific sensitizer in a photocatalyst composition. SOLUTION: This photocatalyst composition comprises (A) one or more kinds of sensitizer compounds selected from a polycyclic aromatic compound (e.g. a naphthalene derivative, an anthracene derivative, a chrysene derivative or a phenanthrene derivative) having at least one or more substituent groups among hydroxyl group, (substituted)aralkyloxy group and (substituted)alkoxy group) as substituent groups and a carbazole derivative and having UV spectrum absorption at a wavelength higher than 330nm and (B) one or more kinds of arylonium salt compounds selected from a diphenylsalkylsulfonium salt compound, dinaphthylalkylsulfonium salt compound, triphenylsulfonium salt compound, diphenyliodonium salt compound, phenylnaphthyliodonium compound and a dinaphthyliodonium salt compound acting as a photocationic polymerization catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sensitized cationic photopolymerization catalyst composition, and more particularly to a photocationic polymerization catalyst composition for a photocurable cationically polymerizable compound. The photocatalyst composition of the present invention can be cured by mixing with a cationic polymerizable compound and irradiating with active energy rays such as light, an electron beam, and X-rays. It is suitably used for photocurable paints, adhesives, inks, photoresists, and photosensitive resins for stereolithography.

[0002]

2. Description of the Related Art As examples of arylonium salt compounds that can be used in the present invention, JP-A-50-151997 and JP-A-50-158680
No., JP-A-50-151996 is known, light, electron beam,
It describes that it can be used as a catalyst for curing a cationically polymerizable compound such as an epoxy compound by radiation such as X-rays. 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, the photocurable composition containing a large amount of a white pigment such as titanium oxide, in which the UV absorption of the arylonium salt compound and the absorption overlap, has many problems. As a solution to this, sensitizers have been studied, and compounds such as phenothiazine, anthracene, and perylene have been reported to be effective. However, with these sensitizers, the photocurability of a photocurable composition using an additive such as a pigment is insufficient.

Further, in the case of aryliodonium salt compounds represented by diphenyliodonium salts, when the counter anion other than SbF6 and B (C6F5) anions, such as PF6, is used as a photocuring agent even when used in a clear paint. Is known to be significantly worse.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it has been found that an aryliodonium salt compound represented by a diphenyliodonium salt having a counter anion such as PF6 can be cured well. Cationic photopolymerization catalyst composition capable of being cured, and can be cured in a short time even with a composition containing an additive such as a pigment, and have excellent cured physical properties. It is intended to provide things.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and found a photocatalyst composition which can overcome the above-mentioned problems by using a specific sensitizer. The invention has been completed.

Hereinafter, the present invention will be described in detail. The present invention is a compound selected from the group consisting of a hydroxyl group or an aralkyloxy group which may be substituted as a substituent, a polycyclic aromatic compound having at least one alkoxy group and a carbazole derivative, and A photocatalyst composition characterized by containing at least one compound having UV spectrum absorption at a long wavelength, more specifically, a hydroxyl group or an optionally substituted aralkyloxy group, an alkoxy group as a substituent. A compound selected from the group consisting of a polycyclic aromatic compound having at least one or more and a carbazole derivative, and at least one compound having UV spectrum absorption at a wavelength longer than 330 nm, and diphenyl acting as a photocationic polymerization catalyst Alkylsulfonium salt compound, dinaphthyl al Rusuruhonimu salt compounds, triphenyl sulfonium salt compounds, diphenyliodonium salt compound,
A photocatalyst composition comprising at least one of an arylonium salt compound selected from a phenylnaphthyliodonium salt compound and a dinaphthyliodonium salt compound.

The compound of the present invention is selected from the group consisting of a polycyclic aromatic compound having at least one aralkyloxy group or an optionally substituted aralkyloxy group or an alkoxy group as a substituent and a carbazole derivative, and Compounds having UV spectral absorption at wavelengths longer than 330 nm mainly act as sensitizers for cationic photopolymerization catalysts.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The arylonium salt compounds usable in the present invention are described in JP-A-50-151997 and JP-A-50-1997.
No. 158680, those described in JP-A-50-151996 and the like can be exemplified, in particular, diphenylalkylsulfonium salt, dinaphthylalkylsulfonium salt, triphenylsulfonium salt, diphenyliodonium salt, A phenylnaphthyliodonium salt, a dinaphthyliodonium salt compound or a derivative thereof is preferred.

The counter anion is not limited to its kind as long as it is a non-nucleophilic anion. The following compounds can be exemplified as the sulfonium salt compounds. In the formula, X represents an anion residue, and B (C ₆ F ₅ ), SbF ₆ , AsF
₆ , PF ₆ , BF _{4 and the} like.

[0010]

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Particularly, a diaryliodonium salt compound has a remarkable sensitizing effect when combined with the photocatalyst composition of the present invention.

Examples of the diaryliodonium salt compound include diphenyliodonium salt, phenylnaphthyliodonium salt and dinaphthyliodonium salt compound, and include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl. An alkyl group such as a pentyl group, a hexyl group and a decyl group, a cycloalkyl group such as a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, an alkoxy group such as a decyloxy group and a dodecyloxy group, and fluorine. Having a phenyl group or a naphthyl group which may be substituted with a halogen atom such as chlorine, bromine or iodine, a carbonyl group such as a benzoyl group, a phenyl group or a nitro group; As the counter anion, B
(C ₆ F ₅ ), SbF ₆ , AsF ₆ , PF ₆ , BF _{4 and the} like can be exemplified.

The following can be exemplified as the diallyliodonium salt compound. In the formula, X represents an anion residue, and B (C ₆ F ₅ ), SbF ₆ , AsF ₆ , P
F ₆ and BF ₄ can be exemplified.

[0014]

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The sensitizer used in the present invention has a wavelength of 330 nm.
It is a compound that has UV spectrum absorption at longer wavelength than
A polycyclic aromatic compound or a carbazole derivative having at least one hydroxyl group, an optionally substituted aralkyloxy group, or an alkoxy group as a substituent.

As the polycyclic aromatic compound, naphthalene derivatives, anthracene derivatives, chrysene derivatives and phenanthrene derivatives are preferred. The alkoxy group as a substituent preferably has 1 to 18 carbon atoms, and particularly preferably has 1 to 8 carbon atoms. The aralkyloxy group preferably has 7 to 10 carbon atoms, and particularly preferably has 7 to 10 carbon atoms.
And a benzyloxy group and a phenethyloxy group of 8 are preferable.

Illustrative sensitizers that can be used in the present invention are:
Carbazole derivatives such as carbazole, N-ethylcarbazole, N-vinylcarbazole, N-phenylcarbazole, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 1-stearyloxynaphthalene, 2-methoxynaphthalene, 2-dodecyloxynaphthalene , 4
-Methoxy-1-naphthol, glycidyl-1-naphthyl ether, 2- (2-naphthoxy) ethyl vinyl ether, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxy Naphthalene, 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, ESN-175 (epoxy resin manufactured by Nippon Steel Chemical) or a series thereof, naphthalene derivatives such as condensates of naphthol derivatives and formalin, 9,10
-Dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-tbutyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy-10-methylanthracene, 9 ,Ten
-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-methylbenzyloxyanthracene, 2,3-dimethyl-9,10-di-α-methylbenzyloxyanthracene, 9- (α-methylbenzyloxy) -10-methylanthracene 9,10-di (2-hydroxyethoxy) anthracene, anthracene derivatives such as 2-ethyl-9,10-di (2-carboxyethoxy) anthracene, 1,4-dimethoxychrysene, 1,4-diethoxychrysene, Chrysene derivatives such as 1,4-dipropoxychrysene, 1,4-dibenzyloxychrysene, 1,4-di-α-methylbenzyloxychrysene, 9-hydroxyphenanthrene, 9,10-dimethoxyphenanthrene, 9,10-
Phenanthrene derivatives such as diethoxyphenanthrene can be exemplified. Among these derivatives, a 9,10-dialkoxyanthracene derivative which may have an alkyl group having 1 to 4 carbon atoms as a substituent is particularly preferable, and a methoxy group or an ethoxy group is preferable as the alkoxy group.

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. Are exemplified.

(A) As the vinyl compound, styrene, α
Styrene compounds such as -methylstyrene, p-methoxystyrene, pt-butoxystyrene, methyl vinyl ether, n-butyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-chloroethyl vinyl ether, 2-phenoxyethyl vinyl ether, -Hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether,
Stearyl vinyl ether, alkyl vinyl ether compounds such as 2-acetoxyethyl vinyl ether, allyl vinyl ether, alkenyl vinyl ether compounds such as 2-methacryloyloxyethyl vinyl ether, 2-acryloyloxyethyl vinyl ether, phenyl vinyl ether, aryl vinyl ether compounds such as p-methoxyphenyl vinyl ether, N-vinyl carbazole, cationically polymerizable nitrogen-containing compounds such as N-vinyl pyrrolidone, butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, 1,4-benzenedimethanol divinyl ether, hydroquinone divinyl ether,
And polyfunctional vinyl compounds such as sasolcinol divinyl ether.

(B) As the epoxy compound, 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 mono Oxide, 1,2-dodecylene oxide, epichlorohydrin, 1,2-epoxydecane, ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide Monofunctional monomers such as, 3-vinylcyclohexene oxide,
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 And polyfunctional epoxy compounds such as polyepoxy resin and polyglycidyl ether of polyhydric alcohol.

(C) As bicycloorthoester compounds, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1-ethyl-4-
Compounds such as hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane are exemplified.

(D) As the spiro orthocarbonate compound, 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 are exemplified.

(E) As the oxetane compound, 3,3-
Dimethyl oxetane, 3,3-bis (chloromethyl) oxetane, 2-hydroxymethyl oxetane, 3-methyl-3-oxetane methanol, 3-methyl-3-methoxymethyl oxetane, 3-ethyl-3-phenoxymethyl oxetane, resorcinol Bis (3-methyl-3
-Oxetanylethyl) ether and m-xylylenebis (3-ethyl-3-oxetanylethyl ether).

These may be used alone or in combination of two or more.

In the present invention, the mixing ratio of the arylonium salt compound and the sensitizer can be arbitrarily set, but the weight ratio of the arylonium salt compound to the sensitizer is 0.1 to 0.1.
-10, preferably 0.3-5. If the ratio of the sensitizer to the arylonium salt compound is small, the sensitizing effect decreases, and if it is excessive, the properties of the cured product deteriorate. However,
The sensitizer having a reactive group such as an epoxy group or a vinyl ether group such as ESN-175 (epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) or 2- (2-naphthoxy) ethyl vinyl ether is not limited to this.

In the present invention, the combination of the arylonium salt compound and the sensitizer is preferably a 9,10-dialkoxyanthracene derivative as the sensitizer when the arylonium salt compound is a sulfonium salt compound.
On the other hand, when the arylonium salt compound is an iodonium salt compound, the clear compound is a carbazole derivative, a naphthol derivative, an alkoxynaphthalene derivative,
Phenanthrene derivatives are preferred, and 9,10-dialkoxyanthracene derivatives are preferred for pigment-based formulations.

The curable composition using the catalyst composition of the present invention can be easily cured by light. As a light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, or the like is used. Further, laser light such as a semiconductor laser, an argon laser, and a He-Cd laser can be used. In particular, a gallium-containing metal halide lamp is preferably used when used for thick film curing or a pigment-containing photocurable composition such as titanium oxide.

The curable composition using the catalyst composition of the present invention can be easily cured by ionizing radiation such as α-ray, β-ray, γ-ray, neutron beam, X-ray, and accelerating electron beam. it can.

[0029]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only the following Examples.

Example 1 (Photocuring test I (clear system)) 100 parts of UVR-6110 (alicyclic epoxy manufactured by UCC) were mixed with 1 part of an arylonium salt compound and 1 part of a sensitizer as pure components. To prepare a formulation. This composition was applied to a tin plate at a thickness of 5 μm and photocured under the following conditions. At this time, those having no tack in the cured film were shown in Table 1 by ○, and those having tack were shown in Table 1 by x. UV irradiation equipment: belt conveyor type UV irradiation equipment (manufactured by Eye Graphics Co., Ltd.) Lamp: 1 condensing 80W high-pressure mercury lamp Irradiation distance: 10 cm (focal length)

[0031]

[Table 1]

Example 2 (Photocuring test II (pigment type)) 100 parts of UVR-6110 (alicyclic epoxy manufactured by UCC) and 100 parts of titanium oxide (CR-58 manufactured by Ishihara Sangyo) were used as pure components. A mixture was prepared by mixing 3 parts of the arylonium salt compound and 1 part of the sensitizer. Add this composition to a tin plate
It was applied so as to have a thickness of 5 μm, and was photocured under the following conditions.
At this time, those which were cured to the inside of the compound were indicated by ○, and those not cured were indicated by × in Table-2. UV irradiation equipment: belt conveyor type UV irradiation equipment (manufactured by Eye Graphics Co., Ltd.) Lamp: condensing type 160W gallium-containing metaharatampu 1
Light Irradiation distance: 10cm (focal length) Belt conveyor speed: 30m / min

[0033]

[Table 2]

[0034]

The photocatalyst composition of the present invention can be cured by mixing it with a cationically polymerizable compound and irradiating it with an active energy ray such as light, an electron beam, or an X-ray. Further, the triphenylsulfonium salt compound and the diphenyliodonium salt compound have no absorption region or extremely low absorption.
Since curing can be performed even with light having a wavelength longer than 30 nm, the curing speed of the clear composition can be remarkably accelerated, and even a composition containing an additive such as a pigment can be effectively photocured. Therefore, light-curing paints,
It can be suitably used for adhesives, inks, photoresists, photosensitive resins for stereolithography, and the like.

Claims (13)

[Claims] 1. A compound selected from the group consisting of a polycyclic aromatic compound having at least one hydroxyl group or an optionally substituted aralkyloxy group or an alkoxy group as a substituent and a carbazole derivative, and 330
A photocatalyst composition comprising at least one compound having UV spectrum absorption at a wavelength longer than nm. 2. A compound selected from the group consisting of a polycyclic aromatic compound having at least one hydroxyl group or an optionally substituted aralkyloxy group or an alkoxy group as a substituent and a carbazole derivative, and 330
at least one compound having a UV spectrum absorption at a wavelength longer than nm, and a diphenylalkylsulfonium salt compound, a dinaphthylalkylsulfonium salt compound, a triphenylsulfonium salt compound, a diphenyliodonium salt compound acting as a photocationic polymerization catalyst And at least one arylonium salt compound selected from a phenylnaphthyliodonium salt compound and a dinaphthyliodonium salt compound.
The photocatalyst composition according to any one of the preceding claims. 3. The polycyclic aromatic compound is a naphthalene derivative,
3. The photocatalyst composition according to claim 1, which is an anthracene derivative, a chrysene derivative or a phenanthrene derivative. 4. The photocatalyst composition according to claim 2, wherein the polycyclic aromatic compound is a 9,10-dialkoxyanthracene derivative or a 9,10-diaralkyloxyanthracene derivative. 5. The photocatalyst composition according to claim 2, wherein the polycyclic aromatic compound is a 1-naphthol derivative, a 2-naphthol derivative, a 1-alkoxynaphthalene derivative, or a 2-alkoxynaphthalene derivative. 6. A compound in which the alkoxy group of the 9,10-dialkoxyanthracene derivative is an alkoxy having 1 to 8 carbon atoms, or the aralkyloxy group of the 9,10-diaralkyloxyanthracene derivative is an aralkyloxy having 7 to 8 carbon atoms. 5. The photocatalyst composition according to claim 4, wherein the compound is used as a polycyclic aromatic compound. 7. The polycyclic aromatic compound is 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene,
The photocatalyst composition according to claim 6, which is at least one selected from 9,10-dibenzylanthracene and a derivative thereof. 8. A photocurable composition comprising the photocatalyst composition according to claim 6, a cationically polymerizable compound, and a pigment which can be practically used for cationic photopolymerization. 9. A photocurable composition wherein the pigment according to claim 8 is titanium oxide. 10. A photocurable composition wherein the cationically polymerizable compound according to claim 8 is an alicyclic epoxy compound, a vinyl ether compound or an oxetane compound. 11. A photocurable composition comprising the photocatalyst composition according to claim 5, and a cationically polymerizable compound. 12. A photocurable composition wherein the cationically polymerizable compound according to claim 11 is an alicyclic epoxy compound, a vinyl ether compound or an oxetane compound. 13. A curing method, wherein the photocurable composition according to claim 7 or 10 is photocured with a gallium-containing lamp.