JP2742594B2 - Photopolymerization catalyst and curable composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photopolymerization catalyst and a combination of light or heat and light containing a photopolymerization catalyst and a cationically polymerizable compound and / or a radically polymerizable compound. It relates to a curable curable composition.

(Prior art and problems to be solved by the present invention) At present, even if a catalyst is added in advance to a cationically polymerizable compound, polymerization does not start at room temperature, but starts immediately by light, heat or pressure. Thus, a so-called high potential polymerization catalyst is desired.

Conventional photopolymerization catalysts include, for example, aromatic diazonium salts and the like. This can be rapidly cured by irradiating a cationic polymerizable compound, for example, an epoxy resin with light. However, diazonium salts release nitrogen by photolysis, thereby causing defects in the coating. In addition, the mixture with the resin has poor storage stability as the polymerization proceeds gradually even in a dark place. Further, there is an example of photocuring using a compound that generates a carboxyl group or an amino group by light irradiation as shown in JP-A-48-88197, but the activity of this compound is not sufficient, and carbon dioxide is produced during curing. The release causes defects in the coating.

Investigations have been made to improve the above-mentioned problems.
No. 1997 discloses a photocurable composition containing an aromatic sulfonium salt as described in JP-A No. 1997, and the above-mentioned problems have been improved.However, these aromatic sulfonium salts have poor compatibility with a resin, There are various cationically polymerizable compounds and / or radically polymerizable compounds that do not dissolve the compound, and usable resins are limited. In addition, the synthesis is time-consuming and difficult due to a multi-step reaction.

(Means for Solving the Problems) It has already been reported by Endo et al. That benzyltetrahydrothiophenium hexafluoroantimonate and the like have excellent potential and are effective as a heat polymerization catalyst having activity against heat. (J.Polym.Sci., Polym.Lett.Ed.,
23 , 359 (1985), J. Polym. Sci., Part C: Polym. Lett. 26 , 4
53 (1988), JP-A-58-37003, JP-A-62-192427).
However, it has not been known that when a curable composition containing this composition is irradiated with ultraviolet rays, it can be rapidly cured. This time, the present inventors have conducted intensive studies and found such a novel property. This is something that could not be predicted in the past. Also, aliphatic sulfonium salts are known only as examples of the above-mentioned thermal polymerization catalyst, and there are no examples known as photopolymerization catalysts. Accordingly, the present inventors have conducted intensive studies and found that the use of a sulfonium salt having a specific structure as a catalyst allows a cationically polymerizable compound and / or a radically polymerizable compound to be curable by light or a combination of heat and light. Found that the salt has good compatibility with the polymerizable compound,
The present invention has been completed.

That is, the present invention provides a compound represented by the general formula (I) (Wherein, R represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group, or an alkoxy group, and A represents a hydrogen atom or The, X ^- represents a non-nucleophilic anion. M and n represent 4 or 5. The present invention relates to a photopolymerization catalyst comprising a sulfonium salt represented by the formula (1), and a curable composition containing a photopolymerization catalyst and a cationically polymerizable compound and / or a radically polymerizable compound, which can be cured by a combination of light or heat and light. is there.

R in the above general formula (I) is specifically a halogen atom such as a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group such as a nitro group, methyl and ethyl group, a methoxy group and an ethoxy group. And an alkoxy group of

In the general formula (I), it is preferable that at least one of the positions of the substituent R or A is at the α or γ-position (o or p-position).

As the cation of the sulfonium salt according to the present invention,
Tetrahydrothiophene or tetrahydro 2H-thiopyran and benzyl, o- or p-nitrobenzyl, o- or p-methylbenzyl, o- or p-
Examples include cations obtained by combining substituents such as a methoxybenzyl group, an o- or p-chlorobenzyl group, an o- or p-bromobenzyl group, and a p-xylylene group. X in the general Formulas (I) ^- is a non-nucleophilic anion, specifically _{^{SbF 6 -, AsF 6 -,}} PF 6 -, BF 4 -, ClO 4 - and the like are ^- and CF ₃ SO ₃ . More specific examples of the photopolymerization catalyst according to the present invention include: (1-A) benzyltetrahydrothiophenium hexafluoroantimonate (1-B) benzyltetrahydrothiophenium hexafluorophosphate (1-C) benzyl Tetrahydrothiophenium hexafluoroarsenate (1-O) benzyltetrahydrothiophenium tetrafluoroborate (1-E) benzyltetrahydrothiophenium barchlorate (1-F) benzinetetrahydrothiophenium trifluoromethanesulfonate (2-4) o-chlorobenzyltetrahydrothiophenium hexafluoroantimonate (2-B) o-chlorobenzyltetrahydrothiophenium hexafluorophosphate (3-A) p-chloroben Letetrahydrothiophenium hexafluoroantimonate (3-B) p-chlorobenzyltetrahydrothiophenium hexafluorophosphate (4-A) o-Nitrobenzyltetrahydrothiophenium hexafluoroantimonate (4-B) o- Nitrobenzyltetrahydrothiophenium hexafluorophosphate (5-A) p-nitrobenzyltetrahydrothiophenium hexafluoroantimonate (5-B) p-nitrobenzyltetrahydrothiophenium hexafluorophosphate (6-A) o -Methylbenzyltetrahydrothiophenium hexafluoroantimonate (6-B) o-methylbenzyltetrahydrothiophenium hexafluorophosphate (7-A) p-methylbenzylte Trahydrothiophenium hexafluoroantimonate (7-B) p-methylbenzyltetrahydrothiophenium hexafluorophosphate (7-C) p-methylbenzyltetrahydrothiophenium hexafluoroarsenate (8-A) o- Methoxybenzyltetrahydrothiophenium hexafluoroantimonate (8-B) o-methoxybenzyltetrahydrothiophenium hexafluorophosphate (9-A) p-methoxybenzyltetrahydrothiophenium hexafluoroantimonate (9-B) p -Methoxybenzyltetrahydrothiophenium hexafluorophosphate (9-C) p-methoxybenzyltetrahydrothiophenium tetrafluoroborate (10-A) benzyltetrahydro-2H Thiopyranium hexafluoroantimonate (10-B) benzyltetrahydro-2H-thiopyranium hexafluorophosphate (11-A) o-chlorobenzyltetrahydro-2H-thiopyranium hexafluoroantimonate (11-B) o -Chlorobenzyltetrahydro-2H-thiopyranium hexafluorophosphate (12-A) p-chlorobenzyltetrahydro-2H-thiopyranium hexafluoroantimonate (12-B) p-chlorobenzyltetrahydro-2H-thiopyranium Hexafluorophosphate (13-A) o-nitrobenzyltetrahydro-2H-thiopyranium hexafluoroantimonate (13-B) o-nitrobenzyltetrahydro-2H-thiopyranium hexafluorophosphate (14-A) p -Nitrobe Benzyltetrahydro-2H-thiopyranium hexafluoroantimonate (14-B) p-nitrobenzyltetrahydro-2H-thiopyranium hexafluorophosphate (15-A) o-methylbenzyltetrahydro-2H-thiopyranium hexa Fluoroantimonate (15-B) o-methylbenzyltetrahydro-2H-thiopyranium hexafluorophosphate (16-A) p-methylbenzyltetrahydro-2H-thiopyranium hexafluoroantimonate (16-B) p- Methylbenzyltetrahydro-2H-thiopyranium hexafluorophosphate (17-A) o-methoxybenzyltetrahydro-2H-thiopyranium hexafluoroantimonate (17-B) o-methoxybenzyltetrahydro-2H-thiopyranium hexa Fluoro Phosphate (18-A) p-methoxybenzyltetrahydro-2H-thiopyranium hexafluoroantimonate (18-B) p-methoxybenzyltetrahydro-2H-thiopyranium hexafluorophosphate (19-A) α, α '-Bis [tetrahydrothiophenium] p-xylylenebishexafluoroantimonate (19-B) α, α'-bis [tetrahydrothiophenium] p-xylylenebishexafluorophosphate (20-A) α , Α'-bis [tetrahydro-2H-thiopyranium] p-xylylenebishexafluoroantimonate (20-B) α, α'-bis [tetrahydro-2H-thiopyranium] p-xylylenebishexafluorophosphate These may be used alone or in combination of two or more.

The photopolymerization catalyst of the present invention represented by the general formula (I) can be produced by a known method. For example, after reacting alicyclic sulfides and substituted or unsubstituted benzyl halides in a solvent such as methanol, acetonitrile, N, N-dimethylformamide or in the absence of a solvent at room temperature to the reflux temperature of the solvent. NaMF in water or methanol
It can be easily obtained by anion exchange with ₆ (M = Sb, P, As, B, etc.).

The compound that can be polymerized using the photopolymerization catalyst represented by the general formula (I) of the present invention is not particularly limited, and includes, for example, a cationically polymerizable compound and a radically polymerizable compound. Examples of the cationic polymerizable compound include 1,13-tetradecadienedoxide, limonenedionoxide, 4-vinylcyclohexenedionoxide, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, and di (3 , 4-epoxycyclohexyl)
Epoxy such as adipate, phenylglycidyl ether, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, o-, m-, p-cresol novolak type epoxy resin, phenol novolak type epoxy resin, polyglycidyl ether of polyhydric alcohol Compounds, styrene, α-methylstyrene, styrenes such as p-chloromethylstyrene, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, alkyl vinyl ethers such as hydroxybutyl vinyl ether, allyl vinyl ether, 1-octahydronaphthyl vinyl ether and the like Alkenyl vinyl ethers, ethynyl vinyl ether, 1-methyl-2
Alkynyl vinyl ethers such as propynyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; alkyl divinyl ethers such as butanediol divinyl ether, triethylene glycol divinyl ether and cyclohexanediol divinyl ether; and 1,4-benzene Aralkyl divinyl ethers such as dimethanol divinyl ether, Nm-chlorophenyldiethanolamine divinyl ether, m-phenylene bis (ethylene glycol) divinyl ether, aryl divinyl ethers such as hydroquinone divinyl ether and resorcinol divinyl ether; N-vinyl carbazole; N
-A cationically polymerizable N-containing compound such as vinylpyrrolidone,
Cyclic ether compounds such as tetrahydrofuran, s-trioxane and 3,3-bischloromethyloxetane; 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,
2,2] octane, 1-ethyl-4-hydroxymethyl-
Bicycloorthoester compounds such as 2,6,7-trioxabicyclo [2,2,2] octane, 1,5,7,11-tetraoxaspiro [5,5] undecane, 3,9-dibenzyl-1, 5,7,11−
Spiro orthocarbonate compounds such as tetraoxaspiro [5,5] undecane, 1,4,6-trioxaspiro [4,
4] nonane, 2-methyl-1,4,6-trioxaspiro [4,
4] Nonane, spiroorthoester compounds such as 1,4,6-trioxaspiro [4,5] decane, etc., and these may be used alone or in combination of two or more.

Further, as the radical polymerizable compound, styrene, p
Styrenes such as chloromethylstyrene, monofunctional acrylates such as vinyl pyridines, ethyl acrylate, isopropyl acrylate and hydroxypropyl acrylate, propylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol hydroxypirate Polyfunctional acrylate monomers such as valate diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and oligomers thereof,
Aromatic acrylates such as bisphenol A type acrylate, phenol novolak acrylate, o-cresol novolak acrylate, bisphenol A type epoxy acrylate, phenol novolak epoxy acrylate, o-cresol novolak acrylate, o
-Epoxy acrylates such as cresol novolak epoxy acrylate, urethane acrylates, acrylates containing silyl or silyloxy, phosphate acrylates, amino acrylates, methyl methacrylate,
Hydroxyethyl methacrylate, methacrylates such as isopropyl methacrylate, propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol hydroxypivalate dimethacrylate, trimethylolpropane trimethacrylate,
Polyfunctional methacrylate monomers such as pentaerythritol trimethacrylate and pentaerythritol tetramethacrylate, and oligomers thereof, vinyl chloride, vinylidene chloride, vinyl acetate, butadiene, maleic anhydride, acrylolein, acrylonitrile, methacrylonitrile, and the like. . These may be used alone or in combination of two or more. Further, a mixture of one or more of the above-described cationically polymerizable compounds and one or more of the radically polymerizable compounds in an appropriate ratio may be used.

The curable composition of the present invention can be used, for example, for adhesives, paints, laminates, and the like. Also, because it is photocured,
It can be used as a coating and sealing agent for heat-sensitive electronic materials. Further, by using light and heat together, it is possible to coat and bond a complicated shape.

The curable composition of the present invention may contain an inert solvent, a pigment, a dye, talc, calcium carbonate, glass fiber, a surfactant, and the like.

The polymerization of the cationically polymerizable compound and / or the radically polymerizable compound by the photopolymerization catalyst represented by the general formula (I) of the present invention is carried out in the presence or absence of a solvent in an amount of 0.1 to 15 wt. %, Preferably 0.5-10% by weight, of the photopolymerization catalyst represented by the general formula (I), and irradiation with an active energy ray such as an electron beam or an ultraviolet ray. In addition, it can be carried out by using both light and heat.

Hereinafter, the present invention will be described specifically with reference to examples. In the following description, parts are by weight unless otherwise specified.

Synthesis Example 1 Synthesis of p-nitrobenzyltetrahydrothiophenium hexafluoroantimonate (exemplified compound (5-A)).

After charging 80 ml of acetonitrile and 30.0 g (0.14 mol) of p-nitrobenzyl bromide in a 200 ml four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer,
Heated to 60 ° C. 12.3 g of tetrahydrothiophene there
(0.14 mol) dissolved in 40 ml of acetonitrile
It was dropped over time. After the dropwise addition, the temperature was raised to the reflux temperature and refluxed for 6 hours. The solution was a homogeneous solution during the reflux, but when left to cool to room temperature, colorless crystals precipitated. The crystals were filtered and dried to obtain 27.9 g (yield 66%) of p-nitrobenzyltetrahydrothiophenium bromide. The obtained p-
Of nitrobenzyltetrahydrothiophenium bromide, 15% (48 mmol) was dissolved in 300 g of ion-exchanged water placed in a 500 ml beaker, and 12.9 g (48 mmol) of sodium hexafluoroantimonate was added as a crystal thereto. . Immediately after the addition, the solution became cloudy and became a slurry. Stirring was continued at room temperature for 30 minutes. After filtering the crystals, the crystals were recrystallized from methanol to obtain 18.6 g of p-nitrobenzyltetrahydrothiophenium hexafluoroantimonate (82% yield).

Synthesis Example 2 Synthesis of α, α′-bis [tetrahydrothiophenium] p-xylylenebishexafluoroantimonate (exemplified compound (19-A)) 200 ml of 4 equipped with a stirrer, a reflux condenser, and a thermometer 80 ml of acetonitrile and α, α'-
After charging 10.0 g (38 mmol) of p-xylylene dibromide, the mixture was heated to 60 ° C. There tetrahydrothiophene
A solution of 6.7 g (76 mmol) dissolved in 40 ml of acetonitrile
It was added dropwise over 30 minutes. After the addition, the reaction was further continued at that temperature for 5 hours. During the dropping, white precipitate had already been deposited. After the reaction, the crystals were filtered and dried to obtain 14.2 g (yield 85%) of α,
α′-bis [tetrahydrothiophenium] p-xylylene dibromide was obtained. 10% of this crystal (23mmo
l) was dissolved in 100 g of ion-exchanged water placed in a 200 ml beaker, and 11.8 g (46 mmol) of sodium hexafluoroantimonate was added as crystals as it was. Immediately after the addition, the solution became cloudy and became a slurry. At room temperature
Stirring was continued for 30 minutes. After filtering the crystals, the crystals were recrystallized from methanol to obtain 12.3 g of α, α'-bis [tetrahydrothiophenium] p-xylylenebishexafluoroantimonate (80% yield).

Synthesis Examples 3 to 8 Several kinds of sulfonium salts were synthesized in the same manner as in Synthesis Examples 1 and 2. The results are shown in Table 1.

Example 1 To 100 parts of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co.), 5 parts of p-nitrobenzyltetrahydrothiophenium hexafluoroantimonate (exemplified compound (5-A)) was added, and the mixture was homogenized. A curable composition was obtained. This was coated on a glass plate using a # 8 bar coater, and irradiated with ultraviolet rays from a distance of 20 cm from a 120 W / cm metal halide lamp manufactured by Eye Graphics Co., Ltd., and became tack-free in 10 seconds. .
The pot life at 40 ° C. is 6 months or more, and the potential is very good.

Examples 2 to 8 The sulfonium salts obtained in Synthesis Examples 2 to 8 according to Example 1 were similarly cured by ultraviolet light. Table-
2 is shown.

For comparison, a curable composition containing a diazonium salt (ADEKA ULTRASET PP-33 manufactured by Asahi Denka Co., Ltd.) was similarly cured by ultraviolet light, and bubbles were generated in the cured film. Further, the cured film obtained from the curable composition of the present invention did not have any air bubbles and had no odor. still,
These curable compositions were all homogeneous.

Example 9 To 100 parts of celloxide 2021 ((3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate manufactured by Daicel Chemical Industries, Ltd.) was added p-methylbenzyltetrahydrothiophenium hexafluoroantimonate (exemplified compound ( 7-A)) was added in an amount of 5 parts to obtain a uniform curable composition. This was applied on a glass plate using a # 8 bar coater, and manufactured by Eye Graphics Co., Ltd.
UV irradiation from a distance of 20 cm with a 120 W / cm metal halide lamp resulted in tack-free in one second.

Examples 10-14 According to Example 9, the sulfonium salts shown in Table 3 were similarly cured by ultraviolet rays. These curable compositions were all homogeneous. Table 3 shows the results.

Example 15 50 parts of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy) and UNION CARBIDE ERL
-4299 (Bis [3,4-epoxycyclohexylmethyl] adipate manufactured by Union Carbide Co., Ltd.) was mixed with p-methylbenzyltetrahydrothiophenium hexafluoroantimonate (exemplified compound (7-
A)) was added in an amount of 5 parts to obtain a uniform curable composition. This was applied on a glass plate using a # 8 bar coater and irradiated with ultraviolet rays from a distance of 20 cm from a 120 W / cm metal halide lamp manufactured by Eye Graphics Co., Ltd., and became tack-free in 2 seconds.

Example 16 70 parts of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy) and RAPICURE DVE-3 (G
5 parts of p-methylbenzyltetrahydrothiophenium hexafluoroantimonate (exemplified compound (7-A)) was added to a resin obtained by mixing 30 parts of triethylene glycol divinyl ether manufactured by AF Co. to obtain a uniform curable composition. Obtained. This was coated on a glass plate using a # 24 bar coater, and irradiated with ultraviolet rays from a distance of 20 cm from a 120 W / cm metal halide lamp manufactured by Eye Graphics Co., Ltd., and became tack-free in 1 second or less.

Example 17 80 parts of Epicoat 154 (phenol novolak type epoxy resin manufactured by Yuka Shell Epoxy) and 20 parts of RAPICURE
Three parts of p-methylbenzyltetrahydrothiophenium hexafluoroantimonate (Exemplified Compound (7-A)) is added to a resin mixed with DVE-3 (triethylene glycol divinyl ether manufactured by GAF) to achieve uniform curing. An acidic product was obtained. This was applied on a glass plate using a # 8 bar coater, and 120 W / c manufactured by Eye Graphics Co., Ltd.
When irradiated with ultraviolet rays from a distance of 20 cm with an m-metal halide lamp, tack-free was achieved in less than one second.

Example 18 A homogenous system was prepared by adding 5 parts of p-methylbenzyltetrahydrothiophenium hexafluoroantimonate (exemplified compound (5-A)) to 100 parts of Biscoat 300 (pentaerythritol triacrylate manufactured by Osaka Organic Co., Ltd.). A curable composition was obtained. This was applied on a glass plate using a # 8 bar coater, and the product was
When UV light was irradiated from a distance of 20 cm with a 0 W / cm metal halide lamp, the film became tack-free in 3 seconds.

Example 19 The initiator was p-methylbenzyltetrahydrothiophenium hexafluoroantimonate (exemplified compound (7-
A)) to p-nitrobenzyltetrahydrothiophenium hexafluoroantimonate (exemplified compound (5-
A) The same operation as in Example 18 was performed, except that the procedure was changed to A)).
The result was tack-free in 20 seconds.

Example 20 50 parts of Epikote 828 (bisphenol A type epoxy resin as an oiled shell epoxy resin) and 50 parts of Biscoat 300 (pentaerythritol triacrylate manufactured by Osaka Organic Co., Ltd.)
3 parts of p-methylbenzyltetrahydrothiophenium hexafluoroantimonate (Exemplified Compound (7-A)) was added to the mixed resin to obtain a homogeneous curable composition. This was applied onto a glass plate using a # 8 bar coater, and irradiated with ultraviolet rays from a distance of 20 cm from a 120 W / cm metal halide lamp manufactured by Eye Graphics Co., Ltd., and became tack-free in 5 seconds.

Example 21 p-methylbenzyltetrahydrothiophenium hexafluoroantimonate (Example compound (7-
A)) to p-nitrobenzyltetrahydrothiophenium hexafluoroantimonate (exemplified compound (5-
A) The same operation as in Example 20 was performed, except that the procedure was changed to A)).
The result was tack-free in 25 seconds.

Example 22 A resin obtained by mixing 50 parts of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy) and 50 parts of KAYARAD DPHA (dipentaerythritol hexaacrylate manufactured by Nippon Kayaku) was added to p-methylbenzyl. One part of tetrahydrothiophenium hexafluoroantimonate (exemplified compound (7-A)) was added to obtain a homogeneous curable composition. This was applied on a glass plate using a # 8 bar coater, and was manufactured by Eye Graphics Inc.
UV irradiation from a distance of 20 cm with a / cm metal halide lamp resulted in tack-free in less than 1 second.

Example 23 50 parts of Epicoat 154 (phenol novolak type epoxy resin manufactured by Yuka Shell Epoxy) and 30 parts of UNION C
ARBIDE ERL-4221 (Union Carbide (3,4-
Epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate) and 20 parts of RAPICURE DVE
-3 (triethylene glycol divinyl ether manufactured by GAF) and 2 parts of p-methylbenzyltetrahydrothiophenium hexafluoroantimonate (exemplified compound (7-A)) are added to the resin, and a homogeneous curing is performed. The composition was obtained. This was applied on a glass plate using a # 8 bar coater, and 120 W / cm manufactured by Eye Graphics Co., Ltd.
UV irradiation from a distance of 20 cm with a metal halide lamp resulted in tack-free in less than 1 second.

Example 24 50 parts of Epikote 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy) and 50 parts of 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane 5 parts of p-nitrobenzyltetrahydrothiophenium hexafluoroantimonate (Exemplified Compound (5-A)) was added to a resin obtained by mixing the above and a uniform curable composition was obtained. This was applied on a glass plate using a # 8 bar coater, and 120 W / c manufactured by Eye Graphics Co., Ltd.
When irradiated with ultraviolet rays from a distance of 20 cm with an m-metal halide lamp, tack-free was achieved in 15 seconds.

(Effect of the Invention) As described above, the curable composition containing the photopolymerization catalyst and the cationically polymerizable compound and / or the radically polymerizable compound of the present invention has high photocurability and storage stability. It is very effective as a photo-latent curable composition, and the polymerization catalyst of the present invention has good compatibility with a cationically polymerizable compound and a radically polymerizable compound, and is excellent as a photo-latent catalyst. It is a thing.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ identification symbol FI C07D 335/02 C07D 335/02 (56) References JP-A-59-147001 (JP, A) JP-A-53-124590 (JP) JP-A-54-53181 (JP, A) JP-A-51-56885 (JP, A)

Claims (3)

(57) [Claims] 1. A compound of the general formula (I) (Wherein, R represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group, or an alkoxy group, and A represents a hydrogen atom or The, X ^- represents a non-nucleophilic anion. M and n represent 4 or 5. A photopolymerization catalyst comprising a sulfonium salt represented by the formula: 2. A curable composition comprising the photopolymerization catalyst according to claim 1 and a cationically polymerizable compound and / or a radically polymerizable compound, the composition being curable by light or a combination of heat and light. 3. The sulfonium salt according to claim 1, wherein the sulfonium salt is benzyltetrahydrothiophenium hexafluoroantimonate, benzyltetrahydrothiophenium hexafluorophosphate, p-methylbenzyltetrahydrothiophenium hexafluoroantimonate, p-methylbenzyltetrahydrothiophenium hexafluoroantimonate.
-Methylbenzyltetrahydrothiophenium hexafluorophosphate, p-methoxybenzyltetrahydrothiophenium hexafluoroantimonate, p
-Methoxybenzyltetrahydrothiophenium hexafluorophosphate, o-nitrobenzyltetrahydrothiophenium hexafluoroantimonate, o
A photopolymerization catalyst which is at least one compound selected from the group consisting of -nitrobenzyltetrahydrothiophenium hexafluorophosphate.