JPH06345726A - Novel sulfonium salt compound and its use as initiator for polymerization - Google Patents

Abstract

PURPOSE:To obtain a novel sulfonium salt compound which is useful as an initiator for polymerization, having polymerizing and hardening action on cationic polymerizable compounds in a short period of time. CONSTITUTION:The sulfonium salt compound of formula I or II Where R1 is H, alkyl, halogen, COOH, or alkoxycarbonyl; R2 is alkyl; R3 is (substituted) phenyl or (substituted) naphthyl; X is SbF6, AsF6, PF6, or BF4; R4 is H, alkyl, halogen, OH, alkoxy, COOH, or alkanoyl; R5 is alkyl; and R6 is alkenyl, alpha- alkylbenzyl, fluorenyl, or the like, for example, benzylphenylmethyl-sulfonium hexafluoroantimonate. The compound of the formula I or II can be obtained, for example, by reacting an aromatic sulfide compound with a sulfonic acid alkyl ester, and then by reacting with sodium hexafluoroantimonate and the like compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel sulfonium salt compound and a cationic polymerization initiator containing the same. The cationically polymerizable composition containing the polymerization initiator can be cured in a short time by heating, and the obtained cured product has excellent physical properties and is therefore a molding resin,
It is preferably used as a material for casting resins, paints, adhesives, inks and the like.

[0002]

2. Description of the Related Art Conventionally, as curing agents for epoxy resins, active amine-containing compounds, carboxylic acid anhydrides and mercapto compounds, which are widely used in two-part systems, are available. On the other hand, there is boron fluoride-monoethylamine for curing the epoxy resin as a one-component system. Further, as a thermal latent cationic polymerization initiator and its composition are described,
JP-A-58-37003, JP-A-63-223002
JP-A-56-152833, JP-A-2-1783
No. 19, JP-A-3-17119 and the like are known.

[0003]

In a so-called two-component system in which an epoxy resin is cured by an active amine-containing compound or carboxylic acid anhydride, it is necessary to completely mix the respective components,
It takes several hours to cure. Also, since the reactions occur sequentially even at room temperature, the pot life is short, from hours to days,
There is a problem in handling. On the other hand, a boron fluoride-monoethylamine system capable of curing an epoxy resin as a one-component system is convenient in handling, but the curing temperature is as high as 160 ° C. or higher, and it takes 1 to 8 hours to completely cure. There is a problem of cost. Also, JP-A-58-370
The sulfonium salt-based thermal latent cationic polymerization initiator described in JP-A No. 03 and the pyridinium salt-based thermal latent cationic polymerization initiator described in JP-A-2-178319 must be a one-component system. However, the sulfonium salt system has a problem of odor, and the pyridinium salt system has a problem that the curing temperature is high. Further, these initiators, particularly pyridinium salt-based ones, have almost no photosensing ability and therefore cannot be used as photocuring initiators.

The present invention has been made in view of the above-mentioned circumstances, and it is possible to cure a cationically polymerizable compound in a short time by heating, and a low odor having high photocurability when used together with a sensitizer. Another object is to provide a novel cationic polymerization initiator which is odorless and a cured product having excellent physical properties.

[0005]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object. As a result, by using a polymerization initiator composed of a specific sulfonium salt compound, cationic polymerization can be performed at low temperature and in a short time. The present invention has been completed by finding a novel polymerization initiator capable of curing a polymerizable compound and imparting excellent properties to the cured product. That is,
The present invention is a sulfonium salt compound represented by the following general formula 3 or 4, and a cationic polymerization initiator containing at least one of the compounds.

[0006]

[Chemical 3]

[Wherein R ₁ is a hydrogen atom, an alkyl group,
Represents a halogen atom, a carboxyl group or an alkoxycarbonyl group, R ₂ represents an alkyl group, R ₃ represents an optionally substituted phenyl group or an optionally substituted naphthyl group, X represents SbF ₆ , Represents AsF ₆ , PF ₆ or BF ₄ ]

[0008]

[Chemical 4]

[In the formula, R ₄ is a hydrogen atom, an alkyl group,
Represents a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group or an alkanoyl group, R ₅ represents an alkyl group,
R ₆ is an alkenyl group, α-alkylbenzyl group, α,
represents an α-dialkylbenzyl group, an α-phenylbenzyl group or a fluorenyl group, and X represents SbF ₆ , AsF ₆ , P
Representing F ₆ or BF ₄ ] Hereinafter, the present invention will be described in detail.

The sulfonium salt compound of the present invention is represented by the above formula 3 or formula 4, wherein R ₁ is a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, t. -Alkyl group such as butyl, F,
A halogen atom such as Cl, Br or I, a carboxy group, a methoxycarboxyl group, an alkoxycarbonyl group such as an ethoxycarbonyl group or a phenoxycarbonyl group which may be substituted, and R ₂ is methyl. R is a group selected from the group of alkyl groups such as ethyl, propyl, isopropyl, butyl, t-butyl, and R
₃ is an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl, a halogen atom such as F, Cl, Br and I, an alkoxy group such as a methoxy group and an ethoxy group, a nitro group and a methoxycarbonyl group, It is a group selected from the group consisting of an alkoxycarbonyl group such as an ethoxycarbonyl group and a phenyl group or a naphthyl group which may be substituted with a substituent such as an optionally substituted phenoxycarbonyl group. Further, X is SbF ₆ , AsF ₆ , PF ₆ or BF ₄ , of which SbF ₆ is preferably used.

In the general formula 4, R ₄ is a hydrogen atom, an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl, a halogen atom such as F, Cl, Br and I, a hydroxyl group, Alkoxy group such as methoxy group, ethoxy group, carboxy group, methoxycarbonyl group,
R ₅ is a group selected from the group of alkanoyl groups such as ethoxycarbonyl group and phenoxycarbonyl group, and R ₅ is a group selected from the group of alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl. Yes, R
₆ is an alkenyl group such as a cinnamyl group or a β-methallyl group, an α-alkylbenzyl group such as an α-methylbenzyl group or an α-methylbenzyl group, an α, α-dimethylbenzyl group or an α, α-diethylbenzyl group. And a group selected from the group consisting of α, α-dialkylbenzyl groups, α-phenylbenzyl groups and fluorenyl groups. X is SbF ₆ ,
AsF ₆ , PF ₆ or BF ₄ , of which SbF ₆
Is preferred.

The sulfonium salt compound can be obtained, for example, by the following method. Phenylbenzyl sulfide, 4-hydroxyphenylcinnamyl sulfide, α
-Equimolar amounts of an aromatic sulfide compound such as phenylbenzyl phenyl sulfide and 1-naphthylmethyl phenyl sulfide, and sulfonic acid alkyl ester such as dimethyl sulfate or methyl p-toluene sulfonate, if necessary, methanol, dioxane, acetonitrile, etc. In the presence of the solvent at room temperature to 80 ° C for several hours to 30 days,
Next, the obtained compound is dissolved in water or water-organic solvent system such as water-methanol system, and vigorously stirred by adding sodium hexafluoroantimonate, etc., and after separating the precipitated liquid or solid product, Obtained by drying.

As typical sulfonium salt compounds of the present invention, compounds represented by the following chemical formulas 5 to 7 are exemplified. However, X in the formula is SbF ₆ , AsF ₆ , PF ₆ or BF.
_{Is 4} .

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

In the present invention, the sulfonium salt compound as a polymerization initiator is mixed with a cationically polymerizable compound and used as a cationically polymerized composition. Examples of the cationically polymerizable compound include the following compounds. (A) As a compound having an epoxy group, 1,1,3-
Tetradecadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, (3,4
-Epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, di (3,4-epoxycyclohexyl) adipate, phenylglycidyl ether, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, o-, m-, Epoxy compounds such as p-cresol novolac type epoxy resin, phenol novolac type epoxy resin, polyglycidyl ether of polyhydric alcohol

(B) Styrene and α as vinyl compounds
-Styrenes such as methylstyrene and p-chloromethylstyrene; alkyl vinyl ethers such as n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and hydroxybutyl vinyl ether;
Alkenyl vinyl ethers such as allyl vinyl ether and 1-octahydronaphthyl vinyl ether; alkynyl vinyl ethers such as ethynyl vinyl ether and 1-methyl-2-propenyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; butanediol divinyl ether , Alkyldivinyl ethers such as triethylene glycol vinyl ether and cyclohexanediol divinyl ether; aralkyl dialkyl ethers such as 1,4-benzenedimethanol divinyl ether, N-m-chlorophenyldiethanolamine divinyl ether and m-phenylenebis (ethylene glycol) divinyl ether. Vinyl ethers; hydroquinone divinyl ether, resorcinol divinyl ether Aryl divinyl ethers such as ether; N- vinylcarbazole, N- vinylpyrrolidone and cationic polymerizable nitrogen-containing compounds such

As the (c) bicycloorthoester compound, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1-ethyl-4-
Hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane etc.

(D) As the spiro-orthocarbonate compound, 1,5,7,11-tetraoxaspiro [5,5]
5] Undecane, 3,9-dibenzyl-1,5,7,1
1-tetraoxaspiro [5,5] undecane, etc.
4,6-trioxaspiro [4,4] nonane, 2-methyl-1,4,6-trioxaspiro [4,4] nonane,
Examples thereof include spiro orthoester compounds such as 1,4,6-trioxaspiro [4,5] decane.

These may be used alone or in combination of two or more. Of the compounds (a) to (d), the compound having an epoxy group (a) is preferably used.

In the present invention, the compounding ratio of the sulfonium salt compound and the cationically polymerizable compound is such that the sulfonium salt compound is 0.
It is blended at a ratio of 01 to 20 parts, preferably 0.1 to 10 parts. When the amount of this sulfonium salt compound is small, the curability of the cationically polymerizable compound is lowered, and when it is excessive, the properties of the cured product are lowered.

The cationic polymerization composition containing the sulfonium salt compound of the present invention can be easily cured by heating.
When thermosetting, it is 30 to 200 ° C., preferably 50.
Used in the range of ~ 180 ° C.

The cationic polymerization composition containing the sulfonium salt compound of the present invention contains α rays, β rays, γ rays, neutron rays,
It can be easily cured in a short time by ionizing radiation such as X-rays and accelerated electron beams. In the case of curing by ionizing radiation, a dose range of 0.5-60 Mrad can usually be used, with a range of 1-50 Mrad being preferred. It is also possible to cure by using ionizing radiation and heat in combination.

When a cationic polymerization composition containing the sulfonium salt compound of the present invention is used in combination with a sensitizer such as p-methoxyphenol or phenothiazine, photocuring can be significantly accelerated.

The sulfonium salt compound of the present invention is generally used alone, but can also be used in combination with other cationic polymerization initiators. Further, when the compound having an epoxy group of the above (a) is used, the performance of a curing agent such as a phenolic curing agent or an acid anhydride curing agent that is usually used as a curing agent for an epoxy resin is not impaired. You may use together in the inside.

When the initiator of the present invention is used in combination with the above-mentioned cationically polymerizable compound, a reactive diluent, a curing accelerator, a solvent, a pigment, a dye, a coupling agent, if necessary,
It is used by adding an inorganic filler, carbon fiber glass fiber, surfactant and the like.

[0028]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples. However, the present invention is not limited to these examples.

Example 1 Synthesis of Benzylphenylmethylsulfonium hexafluoroantimonate 8.01 g of benzylphenyl sulfide and 5.05 g of dimethylsulfate were mixed and reacted at 50 ° C. for 25 hours. The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor benzylphenylmethylsulfonium sulfate. Yield :: 99% benzyl phenyl methyl sulfonium sulfate 3.
26 g of distilled water and 5 g of methyl ethyl ketone (hereinafter, ME
It is dissolved in a mixed solution of 2 g (referred to as K), 3.30 g of potassium hexafluoroantimonate is added, and well stirred. Distilled water (45 g) was added to this solution, and the mixture was well stirred and cooled, and after removing the supernatant liquid separated into two layers, it was dried under reduced pressure at 40 ° C.
Yield: 87%

The IR absorption spectrum data of the obtained benzylphenylmethylsulfonium hexafluoroantimonate are as follows. IR (KBr, cm ^-1 ): 3032, 1584, 149
7, 1480, 1450, 1428, 1340, 100
1,750,701,657

Example 2 Synthesis of 4-chlorophenylbenzylmethylsulfonium hexafluoroantimonate 7.04 g of 4-chlorophenylbenzyl sulfide and 3.78 g of dimethylsulfate were dissolved in 4 g of methanol to give 5
The reaction was carried out at 0 ° C for 2 days. The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor 4-chlorophenylbenzylmethylsulfonium sulfate.
Yield: 40% 3.61 g of 4-chlorophenylbenzylmethylsulfonium sulfate was dissolved in 20 g of distilled water, 3.30 g of potassium hexafluoroantimonate was added, and the mixture was well stirred and cooled. The precipitated compound was filtered off and dried under reduced pressure at 40 ° C. Yield: 60%

The IR absorption spectrum data of the obtained 4-chlorophenylbenzylmethylsulfonium hexafluoroantimonate are as follows. IR (KBr, cm ^-1 ): 3036, 1578, 148
2,1425,1398,1098,1000,82
6,750,702,661

(Example 3) Synthesis of 4-methylphenylbenzylmethylsulfonium hexafluoroantimonate 6.43 g of 4-methylphenylbenzyl sulfide and 3.78 g of dimethylsulfate were dissolved in 4 g of methanol to give 5
The reaction was carried out at 0 ° C for 4 days. The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor 4-methylphenylbenzylmethylsulfonium sulfate.
Yield: 99% 4-methylphenylbenzylmethylsulfonium sulfate (3.40 g) was dissolved in distilled water (20 g), potassium hexafluoroantimonate (3.30 g) was added, and the mixture was well stirred and cooled. After separating the precipitated compound, it was dried under reduced pressure at 40 ° C. Yield: 83%

The IR absorption spectrum data of the obtained 4-methylphenylbenzylmethylsulfonium hexafluoroantimonate are as follows. IR (KBr, cm ^-1 ): 3034, 1594, 149
6,1457,1424,810,771,702,6
60

Example 4 Synthesis of vinylbenzyl-4-methylphenylmethylsulfonium hexafluoroantimonate Vinylbenzyl-4-methylphenyl sulfide 7.2
1 g and 3.78 g of dimethylsulfate were dissolved in 4 g of methanol and reacted at 50 ° C. for 3 days. The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor vinylbenzyl-4-methylphenylmethylsulfonium sulfate. Yield: 99% Vinylbenzyl-4-methylphenylmethylsulfonium sulfate (3.66 g) was dissolved in a mixed solvent of distilled water (5 g) and MEK (2 g), potassium hexafluoroantimonate (3.30 g) was added, and the mixture was stirred well. Distilled water 45 in this solution
g was added, the mixture was stirred well and cooled, and after removing the supernatant liquid separated into two layers, it was dried under reduced pressure at 40 ° C. Yield: 77% IR absorption spectrum data of the obtained vinylbenzyl-4-methylphenylmethylsulfonium hexafluoroantimonate was as follows. IR (KBr, cm ^-1 ): 3029, 2932, 159
8, 1494, 1447, 1425, 1090, 99
9,920,809,709,661

Example 5 Synthesis of benzhydrylphenylmethylsulfonium hexafluoroantimonate 8.29 g of benzhydrylphenyl sulfide and 3.78 g of dimethylsulfate were dissolved in 2 g of acetonitrile and 5
The reaction was carried out at 0 ° C for 5 days. The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor benzhydrylphenylmethylsulfonium sulfate. Yield: 73% 4.03 g of benzhydrylphenylmethylsulfonium sulfate was dissolved in a mixed solvent of 5 g of distilled water and 3 g of MEK, 3.30 g of potassium hexafluoroantimonate was added, and well stirred. 45 g of distilled water was added to this solution, and the mixture was stirred well and cooled. After separating the precipitated compound, it was dried under reduced pressure at 40 ° C. Yield: 69%

The IR absorption spectrum data of the obtained benzhydrylphenylmethylsulfonium hexafluoroantimonate are as follows. IR (KBr, cm ^-1 ): 3031, 1662, 151
9, 1496, 1450, 1427, 998, 750,
704,661

(Example 6) Synthesis of cinnamylphenylmethylsulfonium hexafluoroantimonate 8.29 g of cinnamylphenyl sulfide and 3.78 g of dimethylsulfate were dissolved in 2 g of acetonitrile, and the mixture was heated to 50 ° C.
And reacted for 5 days. The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor cinnamylphenylmethylsulfonium sulfate. Yield: 99
% Cinnamylphenylmethylsulfonium sulfate (3.52 g) was dissolved in a mixed solvent of distilled water (5 g) and MEK (2 g), potassium hexafluoroantimonate (3.30 g) was added, and the mixture was stirred well. 45 g of distilled water was added to this solution, and the mixture was stirred well and cooled. After separating the precipitated compound, it was dried under reduced pressure at 40 ° C. Yield: 78% IR absorption spectrum data of the obtained cinnamylphenylmethylsulfonium hexafluoroantimonate was as follows. IR (KBr, cm ^-1 ): 3030, 1598, 149
5,1450,1432,1000,973,750,
702,658

(Example 7) Synthesis of β-methallylphenylmethylsulfonium hexafluoroantimonate 8.29 g of β-methallylphenyl sulfide and 3.78 g of dimethylsulfate were mixed and reacted at 50 ° C. for 5 days.
The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor β-methallylphenylmethylsulfonium sulfate. Yield: 77% 3.52 g of β-methallylphenylmethylsulfonium sulfate was dissolved in a mixed solvent of 5 g of distilled water and 2 g of MEK, 3.30 g of potassium hexafluoroantimonate was added, and the mixture was stirred well. 45 g of distilled water was added to this solution, and the mixture was stirred well and cooled. After separating the precipitated compound, it was dried under reduced pressure at 40 ° C. Yield: 71%

The IR absorption spectrum data of the obtained β-methallylphenylmethylsulfonium hexafluoroantimonate are as follows. IR (KBr, cm ^-1 ): 3039, 1636, 147
3,1451,1432,1001,751,658

(Example 8) Synthesis of 1-naphthylmethylphenylmethylsulfonium hexafluoroantimonate 7.51 g of 1-naphthylmethylphenyl sulfide and 3.78 g of dimethyl sulfate were dissolved in 2 g of acetonitrile and reacted at 50 ° C for 5 days. It was The obtained compound was washed with ether and dried under reduced pressure at 40 ° C to obtain a precursor of 1-naphthylmethylphenylmethylsulfonium sulfate. Yield: 81% 1-naphthylmethylphenylmethylsulfonium sulfate 3.76 g was dissolved in a mixed solvent of 5 g of distilled water and 2 g of MEK to obtain 3.30 g of potassium hexafluoroantimonate.
Was added and stirred well. 45g of distilled water was added to this solution,
Stir well and cool. After separating the precipitated compound, 40
It was dried under reduced pressure at ℃. Yield: 77%

The IR absorption spectrum data of the obtained 1-naphthylmethylphenylmethylsulfonium hexafluoroantimonate is as follows. IR (KBr, cm ^-1 ): 3037, 1596, 144
9,1427,998,798,752,660

Example 9 Synthesis of 4-hydroxyphenylcinnamylmethylsulfonium hexafluoroantimonate 7.01 g of 4-methylthiophenol and 9.85 g of cinnamyl bromide were mixed and reacted at room temperature for 1 hour.
The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor 4-hydroxyphenylcinnamylmethylsulfonium bromide. Yield: 54% 4-Hydroxyphenylcinnamylmethylsulfonium bromide 3.37 g was dissolved in a mixed solvent of 10 g of distilled water and 7 g of MEK, and potassium hexafluoroantimonate 3.
30 g was added and stirred well. Distilled water (40 g) was added to this solution, and the mixture was stirred well and cooled, and after removing the supernatant liquid separated into two layers, it was dried under reduced pressure at 40 ° C. Yield: 96%

I of the obtained 4-hydroxyphenylcinnamylmethylsulfonium hexafluoroantimonate
The R absorption spectrum data were as follows. IR (KBr, cm ^-1 ): 3490, 1600, 158
5,1500,1288,1249,1087,97
9,836,757,702,664

Example 10 Synthesis of 4-hydroxyphenylcrotylmethylsulfonium hexafluoroantimonate 7.01 g of 4-methylthiophenol and 6.78 g of crotyl bromide were dissolved in 3 g of methanol and reacted at 50 ° C. for 21 days. It was The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor 4-hydroxyphenylcrotylmethylsulfonium bromide.
Yield: 49% 4-hydroxyphenyl crotylmethyl sulfonium bromide 2.75 g is dissolved in a mixed solvent of distilled water 5 g and MEK 5 g, and potassium hexafluoroantimonate 3.30 is obtained.
g was added and stirred well. Distilled water (45 g) was added to this solution, and the mixture was well stirred and cooled, and after removing the supernatant liquid separated into two layers, it was dried under reduced pressure at 40 ° C. Yield: 85%

IR of 4-hydroxyphenyl crotylmethyl sulfonium hexafluoroantimonate obtained
The absorption spectrum data was as follows. IR (KBr, cm ^-1 ): 3516, 1603, 158
8, 1503, 1441, 1286, 1220, 109
1,997,842,662

(Example 11) 4-hydroxyphenyl-
Synthesis of β-methallylmethylsulfonium hexafluoroantimonate Dissolve 7.01 g of 4-methylthiophenol and 4.53 g of β-methallyl chloride in 2 g of methanol,
The reaction was carried out at 22 ° C for 22 days. The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor 4-hydroxyphenyl-β-methallylmethylsulfonium chloride. Yield: 37% 4-hydroxyphenyl-β-methallylmethylsulfonium chloride 2.31 g was dissolved in a mixed solvent of distilled water 5 g and MEK 2 g, potassium hexafluoroantimonate 3.30 g was added, and the mixture was stirred well. Distilled water 45 in this solution
g was added, the mixture was stirred well and cooled, and after removing the supernatant liquid separated into two layers, it was dried under reduced pressure at 40 ° C. Yield: 65%

The IR absorption spectrum data of the obtained 4-hydroxyphenyl-β-methallylmethylsulfonium hexafluoroantimonate are as follows. IR (KBr, cm ^-1 ): 3516, 1603, 158
9,1502,1441,1422,1286,121
9,997,842,662

(Example 12) 4-hydroxyphenyl-
Synthesis of α-phenethylethylsulfonium hexafluoroantimonate Mix 6.91 g of α-phenethyl-4-hydroxyphenyl sulfide and 6.24 g of ethyl iodide and mix at room temperature for 6 hours.
Reacted for a month. The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor 4-hydroxyphenyl-α-phenethylethylsulfonium iodide. Yield: 69% 4-hydroxyphenyl-α-phenethylethylsulfonium iodide (3.36 g) was added to distilled water (5 g) and MEK2.
g of a mixed solvent, potassium hexafluoroantimonate (3.30 g) was added, and the mixture was stirred well. Distilled water 4 in this solution
5 g was added, and the mixture was well stirred and cooled, and after removing the supernatant liquid separated into two layers, it was dried under reduced pressure at 40 ° C. Yield: 76%

The IR absorption spectrum data of the obtained 4-hydroxyphenyl-α-phenethylethylsulfonium hexafluoroantimonate are as follows. IR (KBr, cm ^-1 ): 3496, 1599, 158
4,1494, 1451, 1264, 1208, 83
2,702,664

(Example 13) Synthesis of 4-hydroxyphenylbenzhydrylmethylsulfonium hexafluoroantimonate 4-hydroxyphenylbenzhydryl sulfide 8.
77g and 5.05g of dimethyl sulphate are mixed and mixed at 50 ° C
Reacted for days. The obtained compound is washed with ether,
It was dried under reduced pressure at 40 ° C. to obtain a precursor 4-hydroxyphenylbenzhydrylmethylsulfonium sulfate. Yield: 92% 4-hydroxyphenylbenzhydrylmethylsulfonium sulfate 4.19 g, distilled water 5 g and MEK 2 g
Was dissolved in the mixed solvent of, and 3.30 g of potassium hexafluoroantimonate was added, and well stirred. Distilled water 45 in this solution
g was added, the mixture was stirred well and cooled, and after removing the supernatant liquid separated into two layers, it was dried under reduced pressure at 40 ° C. Yield: 75%

The IR absorption spectrum data of the obtained 4-hydroxyphenylbenzhydrylmethylsulfonium hexafluoroantimonate are as follows. IR (KBr, cm ^-1 ): 3470, 1599, 158
6,1495,1451,1421,1293,104
6,748,704,661

(Example 14) 4-hydroxyphenyl-
Synthesis of 9'-fluorenylmethylsulfonium hexafluoroantimonate A mixture of 8.71 g of 4-hydroxyphenyl-9'-fluorenyl sulfide and 5.05 g of dimethylsulfate was added to 50
The reaction was performed at 24 ° C. for 24 hours. The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor 4-hydroxyphenyl-9′-fluorenylmethylsulfonium sulfate. Yield: 76% 4.17 g of 4-hydroxyphenyl-9'-fluorenylmethylsulfonium sulphate, 10 g of distilled water and M
It was dissolved in a mixed solvent of 5 g of EK, 3.30 g of potassium hexafluoroantimonate was added, and well stirred. Distilled water (40 g) was added to this solution, and the mixture was stirred well and cooled, and after removing the supernatant liquid separated into two layers, it was dried under reduced pressure at 40 ° C. yield:
73%

The resulting 4-hydroxyphenyl-9'-
The IR absorption spectrum data of fluorenylmethylsulfonium hexafluoroantimonate are as follows. IR (KBr, cm ^-1 ): 3515, 1603, 158
9,1503,1441,1421,1286,99
7,842,747,662

(Examples 15 to 46) <Curing Performance Test> The compounds synthesized in Examples 1 to 14 were dissolved in propylene carbonate to prepare ERL-4221.
(UCC alicyclic epoxy) and UVR-6410
(Glycidyl type epoxy manufactured by UCC) as a pure component.
A compounding agent was prepared by adding 5 parts to each epoxy resin. DSC and UV-DSC for this formulation
The measurement was performed to determine the top temperature of the exothermic peak in the DSC measurement and the time from the light irradiation to the top peak of the exotherm in the UV-DSC measurement. The DSC measurement conditions and the UV-DSC measurement conditions are as follows, and the measurement results are shown in Tables 1 to 3.

DSC measurement conditions DSC measuring instrument: DSC220C (manufactured by Seiko Denshi Kogyo Co., Ltd.) Atmosphere: Nitrogen gas stream 30 ml / min Temperature rising temperature: 10 ° C./min Sample amount: 0.3-0.8 mg

UV-DSC measurement conditions DSC measurement equipment: DSC220C (manufactured by Seiko Denshi Kogyo Co., Ltd.) UV irradiator: Ultra high pressure mercury lamp atmosphere: Nitrogen gas flow 30 ml / min Measurement temperature: 50 ° C. Sample amount: 0.1 0.3 mg Film thickness: 2-10 μm Illumination: 10 mW / cm ² (365 nm)

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

(Comparative Examples 1 to 6) Benzyl-4-cyanopyridinium hexafluoroantimonate was used as an initiator as a comparison sample 1 of the present invention, and benzyldimethylsulfonium hexafluoroantimonate was used as a comparison sample 2. Was used as the initiator, and the
-4221 (UCC alicyclic epoxy), and UV
2.5 parts each as a pure component was added to R-6410 (UCC glycidyl type epoxy) to prepare a blend, and DS
C and UV-DSC measurements were performed, and the top temperature of the exothermic peak, and in the UV-DSC measurement, the time from the light irradiation to the exothermic top peak was determined. The results are summarized in Tables 1 to 3 above.

[0062]

Since the polymerization initiator of the present invention is a chain polymerization type, it has a function of polymerizing and curing the cationically polymerizable compound in a short time by heating. Further, the combined use with a sensitizer dramatically improves the photopolymerization initiation ability, and the cationically polymerizable compound can be polymerized and cured by light. Furthermore, since the polymerization initiator of the present invention is an aromatic sulfonium salt compound,
The polymerization initiator itself has low odor or no odor, and the decomposition product of the polymerization initiator also has low odor or no odor.

Claims (2)

[Claims] 1. A sulfonium salt compound represented by the general formula 1 or 2. [Chemical 1] [In the formula, R ₁ represents a hydrogen atom, an alkyl group, a halogen atom, a carboxyl group or an alkoxycarbonyl group, R ₂ represents an alkyl group, and R ₃ represents an optionally substituted phenyl group or a substituted phenyl group. Represents a naphthyl group, X represents SbF ₆ , AsF ₆ , PF ₆ or BF _4. ] [In the formula, R ₄ represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group or an alkanoyl group, R ₅ represents an alkyl group, and R ₆ represents an alkenyl group, an α-alkylbenzyl group. , Α, α-dialkylbenzyl group, α-phenylbenzyl group or fluorenyl group, and X is SbF ₆ , AsF ₆ , PF ₆ or B.
Represents F ₄ ] 2. A cationic polymerization initiator comprising at least one of claim 1.