JPH09118663A - New sulfonium salt compound, polymerization initiator, curable composition containing the same compound and curing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound excellent in heat and optical activity, capable of curing a cationic polymerizable compound from an extremely thin film to a thick film by heating or irradiation with active energy such as light, electron rays, etc., in a short time, useful as a cationic polymerization initiator, etc. SOLUTION: This compound is shown by formula I R1 and R2 are each a 1-18C alkyl (carbonyl), OH, a 1-18C alkoxy, an aromatic carbonyl, etc.; R<3> is a 1-8C alkyl; R<4> is a 3-20C cycloalkyl [substituted with OH, phenyl, indanyl, etc., (Z-substituted)], a Z-substituted 1-24C alkyl, a 5-24C alkyl, etc.; X is a non-nucleophilic anion residue such as PF6 or SbF6 ; (m) and (n) are each 0-3} such as 2-naphthyl(2-indanyl)methylsulfonium hexafluorophosphate of formula II (X is PF6 ). The compound of formula I is obtained by reacting a compound of formula III with a compound of the formula (R3 O)2 SO2 to give a compound of formula IV (Y<-> is a group of the formula (R3 O)SO3 <-> ] and reacting the compound with a compound of the formula MX (M is a metal alkali).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel sulfonium salt compound, a cationic polymerization initiator containing the compound, a curable composition containing the cationic polymerization initiator, and a curing method, and more specifically, heating or light irradiation. The present invention relates to a cation-curable composition that cures from an extremely thin film to a thick film in a short time by irradiation with active energy rays such as electron beams and X-rays. Since the cured product of the composition has excellent physical properties, it is suitably used as a paint, adhesive, ink, photoresist, photosensitive resin for stereolithography, and the like.

[0002]

2. Description of the Related Art Sulfonium salt compounds similar to the present invention are disclosed in JP-A-50-151997 and JP-A-50-15.
No. 8680 and JP-A No. 2-178303 are known, and it is described that they can be used as an initiator that cures a cationically polymerizable compound such as an epoxy compound by radiation such as light, electron beam, and X-ray.

However, the sulfonium salt compound described in JP-A-50-151997 is known as a photoinitiator having a high photoactivity, but has a wavelength longer than 360 nm which is effective for ultraviolet curing. Since it has almost no absorption, it is effective for photo-curing a transparent composition, but it is not suitable for photo-curing a composition using a long-wavelength laser beam or a composition containing a large amount of pigments. As a solution to this problem, sensitizers have been investigated, and compounds such as phenothiazine, anthracene, and perylene have been found, but they are still insufficient and the problem has not been solved. Further, since it hardly acts as a thermal polymerization initiator, it is difficult to apply it to thick film curing, and the synthesis method is complicated and expensive, and the solubility in monomers is low. On the other hand, the compounds described in JP-A No. 2-178303 and the like act as a thermal polymerization initiator and thus can cure a thick film, but their performance as a photopolymerization initiator is extremely low and the solubility in monomers is also high. Low. Furthermore, an aliphatic sulfonium salt compound [IUPAC MACRO 88 Prepr. 90
(1988)] also acts as a thermal initiator, and thus thick film curing is possible, but the performance as a photoinitiator is extremely low.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of these circumstances, and includes heating, light, electron beam, X-ray.
Sensitive to irradiation of active energy rays, especially 36
A cationic polymerization initiator capable of being exposed to light having a wavelength longer than 0 nm is provided, and it is possible to cure an extremely thin film to a thick film in a short time, and the obtained cured product is excellent. It is an object of the present invention to provide a cationically curable composition having physical properties of a cured product and a curing method.

[0005]

According to the present invention, there is provided a compound represented by the general formula [I]:

[0006]

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[Wherein R ₁ and R ₂ are each a C _1-18 alkyl group, a hydroxy group, a C _1-18 alkoxy group, a C _1-18 alkylcarbonyl group, an aromatic carbonyl group, an aromatic thio group or a halogen. Represents an atom. R ₃ represents a C _1-8 alkyl group. R ₄ is a C _1-24 alkyl group (provided that it is a C _5-24 alkyl group when it is unsubstituted), a C _2-24 alkenyl group or C
_3-20 represents a cycloalkyl group, each as a substituent a hydroxy group, a carbonyl group, a nitrile group, a phenyl group,
It may have an alkoxy group, a phenoxy group, an alkyleneoxy group, a halogen atom, or an indanyl group. m and n
Indicates 0, 1, 2, or 3. X represents a non-nucleophilic anion residue. ] It is a sulfonium salt compound represented by these. Further, a cationic polymerization initiator containing the compound, a curable composition, and a curing method.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula [I], the C _1-18 alkyl group of R ₁ and R ₂ is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group. Group, decyl group, dodecyl group, etc. are C
_{1-18 As the} alkoxy group, a methoxy group, an ethoxy group,
A propyl group, a butoxy group, a hexyloxy group, a decyloxy group, a dodecyloxy group and the like, and a C _1-18 alkylcarbonyl group includes an acetoxy group, a propionyloxy group, a decylcarbonyloxy group, a dodecylcarbonyloxy group, etc. Examples of the carbonyl group include a benzoyloxy group and the like, examples of the aromatic thio group include a phenylthio group, and examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.

Examples of the C _1-8 alkyl group for R ₃ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group and a hexyl group.

The substituent represented by R ₄ includes a pentyl group, a decyl group, a dodecyl group, a 2-phenylethyl group,
2-phenylpropyl group, 2-phenoxyethyl group, 2
-Phenyl-2-hydroxyethyl group, 2-phenyl-
2-acetoxyethyl group, 2-phenyl-2-methoxyethyl group, 2-methoxycarbonylethyl group, 3-hydroxypropyl group, 2-methoxycarbonylpropyl group, cyclohexyl group, 2-hydroxycyclohexyl group, cyclopentyl group, 2- Indanyl group, 1-hydroxy-2-indanyl group, 1-acenaphthenyl group, bicyclononyl group, norbornyl group, coumarinyl group, dihydrobenzofuranyl group, allyl group, 2-butenyl group, cinnamyl group, 1-carboxyethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1
-(N-propoxycarbonyl) ethyl group, 1- (is
o-propoxycarbonyl) ethyl group, 1- (3-chloro-2-hydroxypropoxycarbonyl) ethyl group,
1- (3-acetoxy-2-hydroxypropoxycarbonyl) ethyl group, 1- (3-methacryloyloxy-
2-hydroxypropoxycarbonyl) ethyl group, 1-
(3-benzoyloxy-2-hydroxypropoxycarbonyl) ethyl group, 1- (3-chloro-2-acetoxypropoxycarbonyl) ethyl group, 1- (n-butoxycarbonyl) ethyl group, 1-dodecyloxycarbonylethyl group, 1-phenoxycarbonylethyl group, 1-
Benzyloxycarbonylethyl group, 1- (N-methyl-4-methoxycarbonylanilinocarbonyl) ethyl group, 1-carboxypropyl group, 1-methoxycarbonylpropyl group, 1-ethoxycarbonylpropyl group, 1
-Dodecyloxycarbonylpropyl group, 1-carboxybutyl group, 1-methoxycarbonylbutyl group, 1-ethoxycarbonylbutyl group, 1-dodecyloxycarbonylbutyl group, 1-carboxypentyl group, 1-methoxycarbonylpentyl group, 1- Ethoxycarbonylpentyl group, 1-dodecyloxycarbonylpentyl group, α
-Ethoxycarbonylbenzyl group, phenacyl group, 1-
Examples thereof include a benzoylethyl group, a cyanomethyl group, a 1-cyanoethyl group, an ethoxycarbonylacetylmethyl group, a 2-indanonyl group, a 2-cyclohexanonyl group, a camphor group and a γ-butyrolactonyl group.

The present invention also includes a compound having two sulfonium salt structures represented by the general formula [I] in one molecule, for example, represented by the general formula [II] or the general formula [III]. Sulfonium salt compounds and the like.

[0012]

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[0013]

[Chemical 6]

[Here, Y represents an oxygen or sulfur atom. A represents a cycloalkylene group, a phenylene group, an alkylene group, an alkenylene group, and further, they are a hydroxyl group,
It may have a carbonyl group, an ester and an ether bond. ]

The sulfonium salt compound of the present invention can be produced according to the following reaction formula.

[0016]

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The reaction is carried out at room temperature to 150 ° C. in an organic solvent such as acetonitrile, dioxane or ethanol, if necessary.
C., preferably 40.degree. C. to 90.degree. C., for 1 hour to several tens of hours. After completion of the reaction, water and MX are added to the reaction solution and the mixture is stirred. The precipitated compound is collected by filtration or extracted with an organic solvent to obtain the desired product.

The sulfonium salt compound of the present invention can cure the cationically polymerizable compound not only by heat but also by irradiation with active energy rays such as light, electron beams and X-rays.

Among the compounds represented by the general formula [I] of the present invention, R ₄ of the general formula [I] is a C ₈ -C ₂₄ alkyl group, or an alkyl having an aromatic ring at the β-position carbon as viewed from the sulfur atom. Base,
A sulfonium salt compound which is a cycloalkyl group or an indanyl group is preferable since it has good compatibility with a monomer.

R ₄ is a decyl group, a dodecyl group,
2-phenylethyl group, 2-phenylpropyl group, 2-
Phenoxyethyl group, 2-phenyl-2-hydroxyethyl group, 2-phenyl-2-acetoxyethyl group, 2-
Phenyl-2-methoxyethyl group, cyclohexyl group,
2-hydroxycyclohexyl group, cyclopentyl group,
Examples include 2-indanyl group, 1-hydroxy-2-indanyl group, 1-acenaphthenyl group, bicyclononyl group, norbornyl group, coumarinyl group and dihydrobenzofuranyl group.

Of the compounds represented by the general formula [I] of the present invention, R _{4 of the} general formula [I] is

[0022]

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Or

[0024]

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[Wherein R ₅ is a C _1-24 alkyl group, C _2-24
Represents an alkenyl group or a C _3-20 cycloalkyl group, a C _1-24 alkoxy group, a phenyl group, a naphthyl group, and an amino group, each of which is a hydroxy group, a carbonyl group, a nitrile group, a phenyl group, an alkoxy group, or a phenoxy group as a substituent. It may have an alkyleneoxy group, a halogen atom, or a nitro group. R ₆ and R ₇ represent a hydrogen atom, a C _1-8 alkyl group or a phenyl group. Here, R ₅ and R ₆ may combine to form a ring, and the ring has a hydroxy group, a carbonyl group, a nitrile group, a phenyl group, an alkoxy group, a phenoxy group or an alkyleneoxy group as a substituent. Good. R ₅ and R ₆ may combine to form indanone. Further, when R ₆ is not a hydrogen atom, R ₅ may represent a hydroxyl group. m and n represent 0, 1, 2 or 3. X represents a non-nucleophilic anion residue. The sulfonium salt compound represented by the formula [1] is particularly preferable because it is remarkably improved in photoreactivity when combined with a sensitizer and is suitable for curing a pigment-based curable composition.

R ₅ is hydroxyl group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, 3
-Chloro-2-hydroxypropoxy group, 3-acetoxy-2-hydroxypropoxy group, 3-methacryloyloxy-2-hydroxypropoxy group, 3-benzoyloxy-2-hydroxypropoxy group, 3-chloro-2
-Acetoxypropoxy group, n-butoxy group, 1-dodecyloxy group, phenoxy group, benzyloxy group, N-
Examples include methyl-4-methoxycarbonylanilino group, phenyl group and ethoxycarbonyloxymethyl group.

Preferred examples of the non-nucleophilic anion residue represented by X in the formula include SbF ₆ , AsF ₆ , PF ₆ and BF ₄ .

Representative examples of the sulfonium salt compound of the present invention are shown below. However, X in the formula is SbF ₆ , AsF ₆ ,
A non-nucleophilic anion residue such as PF ₆ or BF ₄ is shown.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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The sulfonium salt compound of the present invention can be used together with a sensitizer, and when the sensitizer is used, it can be cured in a remarkably short time. It is also extremely effective in curing a curable composition containing a pigment such as titanium oxide.

The sensitizer used in the present invention refers to a compound that accelerates the photoreaction of the above sulfonium salt compound. Examples thereof include compounds that readily release hydrogen radicals, radical polymerization inhibitors, compounds that react with a sulfonium salt compound in the photoreaction process of a sulfonium salt compound, and consequently release a proton, and an electron donor. Specifically, compounds that easily release hydrogen radicals such as thiol compounds and hydrocarbon compounds, 4-methoxyphenol, 4-benzyloxyphenol, 4-methoxy-2- (t-butyl) phenol, hydroquinone, 4- Methoxy-1-
Naphthol, phenol derivative such as 2-hydroxydibenzofuran, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1-hydroxyphenanthrene, 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-naphthyl diglycidyl ether, 2,7-di (2-vinyloxyethyl)
Naphthyl ether, 4-methoxy-1-naphthol, E
SN-175 (Epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) or its series, a condensation product of a naphthol derivative and formalin, a radical polymerization inhibitor such as phenothiazine, naphthoquinone, anthraquinone, 2-ethylanthraquinone, 2
Quinone compounds such as -t-butylanthraquinone, 2-hydroxymethylanthraquinone, 2,3-dimethylanthraquinone, naphthacenequinone, 9,10-phenanthrenequinone, camphorquinone, 9,10-dimethoxyanthracene, 2-ethyl-9,10- Dimethoxyanthracene, 2-t-butyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy-10-methylanthracene, 1,4-dimethoxychrysene, 9,10-di Ethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-t-butyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 9-ethoxy-10-methyl Anthracene, 1,4-diet Cyclisene, 9,10-dipropoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-t-butyl-9,10-dipropoxyanthracene, 2,3-dimethyl-9,10-dipropoxyanthracene, 9-isopropoxy-10-methylanthracene, 1,4-dipropoxychrysene,
9,10-Dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2-t-
Butyl-9,10-dibenzyloxyanthracene,
2,3-Dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10-methylanthracene, 1,4-dibenzyloxychrysene, 9,10-di-α-methylbenzyloxyanthracene, 2-ethyl -9,10-Di-α-methylbenzyloxyanthracene, 2-t-butyl-9,10-di-α-methylbenzyloxyanthracene, 2,3-dimethyl-9,10-
Di-α-methylbenzyloxyanthracene, 9- (α
-Methylbenzyloxy) -10-methylanthracene, 1,4-di-α-methylbenzyloxychrysene,
(Thio) such as 9-hydroxyphenanthrene, xanthone, thioxanthone, and 2,4-diethylthioxanthone
A xanthone derivative, a carbazole derivative such as carbazole, N-vinylcarbazole, or N-ethylcarbazole, an aromatic amine compound such as N, N-diphenyl-p-phenylenediamine, or a compound represented by the following general formula [IV] is used. be able to.

[0038]

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[Wherein R ₈ and R ₉ represent the same or different straight-chain or branched C _{1 to} C ₂₀ alkyl groups, and R ₈ and R ₉ may be bonded together. , R
₁₀ represents a hydrogen atom, a lower alkyl group, or a halogen atom, and R ₁₁ represents a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, an optionally substituted phenyl group, or a substituted group. Represents a benzyl group which may be substituted, an alkoxy group which may be substituted, a phenoxy group which may be substituted or a benzyloxy group which may have a substituent]

Examples of the compound represented by the general formula [IV] include p-dimethylaminobenzoic acid, p-dimethylaminobenzaldehyde, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid (2-n -Butoxyethyl), isoamyl p-dimethylaminobenzoate, p-dimethylaminoacetophenone, p-diethylaminobenzoic acid, p-diethylaminobenzaldehyde and the like.

Among these sensitizers, particularly preferable as a combination with a cationic polymerization initiator is phenothiazine, anthraquinone derivative such as 2-ethylanthraquinone, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2 -Ethyl-9,10-dimethoxyanthracene and other 9,10-dialkoxyanthracene derivatives, thioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-isopropylthioxanthone, 2-chlorothioxanthone And the like, carbazole derivatives such as N-ethylcarbazole, and naphthalene derivatives having at least one hydroxyl group or alkoxy group such as 1-naphthol and 2-methoxynaphthalene.

Examples of the cationically polymerizable compound used in the present invention include the following compounds.

(A) As vinyl compounds, methyl vinyl ether, n-butyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-chloroethyl vinyl ether, 2-
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 ethers such as allyl vinyl ether, 2-methacryloyloxyethyl vinyl ether and 2-acryloyloxyethyl vinyl ether. Compounds, aryl vinyl ether compounds such as phenyl vinyl ether and p-methoxyphenyl vinyl ether, cationic polymerizable nitrogen-containing compounds such as N-vinyl carbazole and N-vinyl pyrrolidone, butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexane diol divinyl ether, 1,4-benzenedimethanol divinyl ae Le, hydroquinone divinyl ether, polyfunctional vinyl compounds such as no doubt resorcinol divinyl ether.

(B) As an 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-butadienemonomer Oxide, 1,2-dodecylene oxide, epichlorohydrin, 1,2-epoxydecane, ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethyl cyclohexene oxide, 3-acryloyloxymethyl cyclohexene oxide , 3-vinylcyclohexene oxide, 4-vinylcyclohexene oxide and other monofunctional monomers, 1,1,3-tetradecadienedioxy Ido, limonene oxide, 3,
4-epoxycyclohexylmethyl- (3,4-epoxycyclohexyl) carboxylate, di (3,4-epoxycyclohexyl) adipate, phenylglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, o-, m-, Polyfunctional epoxy compounds such as p-cresol novolac type epoxy resin, phenol novolac type epoxy resin and polyglycidyl ether of polyhydric alcohol.

As (c) bicyclo orthoester compound, 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.

(D) Spiro-orthocarbonate compound, 1,5,7,11-tetraoxaspiro [5,5]
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,
Examples include compounds such as 1,4,6-trioxaspiro [4,5] decane.

These may be used alone or in combination of two or more. In particular, the sulfonium salt compound of the present invention is suitable for curing an alicyclic epoxy compound or vinyl ether compound.

In the present invention, the mixing ratio of the sulfonium salt compound represented by the general formula [I] and the cationically polymerizable compound is 0.01 to 20 parts by weight, preferably 100 to 20 parts by weight of the cationically polymerizable compound. Is 0.1
10 parts. If this sulfonium salt compound is small,
The curability of the cationically polymerizable compound decreases, and when it is excessive, the properties of the cured product deteriorate.

On the other hand, the compounding ratio of the sensitizer and the cationically polymerizable compound is 0.001 to 10 parts, preferably 0.01 to 10 parts of the sensitizer to 100 parts of the cationically polymerizable compound.
It is mixed in a ratio of 5 parts. When the amount of this sensitizer is small, the photoreactivity of the sulfonium salt compound decreases, and when it is excessive, the properties of the composition deteriorate.

The curable composition of the present invention can be easily cured by light. Curing with light has a wavelength of 500n
Light of m or less, especially ultraviolet rays, is preferably used, and therefore, as a light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp or the like is used. Alternatively, laser light such as a semiconductor laser, an argon laser, or a He—Cd laser can be used. In particular, when used in a curable composition containing a pigment such as titanium oxide, a gallium-containing metal halide lamp is preferably used.

The curable composition of the present invention contains α rays, β rays, γ rays.
It can also be easily cured by ionizing radiation such as rays, neutron rays, X rays, and accelerated electron rays. 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.

The curable composition of the present invention can be easily cured by heating. Heating is from 80 ° C to 250 ° C,
It is preferably used in the range of 100 ° C to 200 ° C.
It is also possible to cure by using light, ionizing radiation and heat in combination.

[0053]

EXAMPLES The present invention will now be described in more detail by way of examples, but the present invention is not limited to the following.

Example 1 Synthesis of 2-naphthyl (2-indanyl) methylsulfonium hexafluorophosphonate: 27.64 g of 2-naphthyl (2-indanyl) sulfide and 1 of dimethylsulfate
After mixing 3.24 g and reacting at 50 ° C. for 10 hours,
Dissolve in 100 g of distilled water and add potassium hexafluorophosphate 1
8.41 g was added and vigorously stirred. The precipitated compound was washed with water and dried under reduced pressure at 40 ° C. Yield: 81%

Example 2 Synthesis of 2-naphthyl-2-phenylpropylmethylsulfonium hexafluorophosphonate: 2-naphthyl-2
-27.84 g of phenylpropyl sulfide and 13.24 g of dimethylsulfate were mixed and reacted at 50 ° C for 10 hours, then dissolved in 100 g of distilled water, 18.41 g of potassium hexafluorophosphate was added, and the mixture was vigorously stirred. The precipitated compound was extracted with ethyl acetate, washed with water to remove ethyl acetate, and dried under reduced pressure at 40 ° C. Yield: 86%

Example 3 Synthesis of 2-naphthyldodecylmethylsulfonium hexafluorophosphonate: 32.86 g of 2-naphthyldodecyl sulfide and 13.24 g of dimethylsulfate were mixed to give 8
The reaction was carried out at 0 ° C for 1 hour and then at 50 ° C for 10 hours. The reaction product was dissolved in 100 g of distilled water, 18.41 g of potassium hexafluorophosphate was added, and the mixture was vigorously stirred. The precipitated compound was extracted with ethyl acetate, washed with water, and the ethyl acetate was removed.
It dried under reduced pressure at 0 degreeC. Yield: 93%

Example 4 Synthesis of 2-naphthylethoxycarbonylmethylmethylsulfonium hexafluorophosphonate 2-naphthylethoxycarbonylmethyl sulfide 2
Mix 4.63 g and 13.24 g of dimethylsulfate to obtain 80
The reaction was performed at 10 ° C. for 10 hours. This reaction product is distilled water 300m
1 and 100 ml of ethyl acetate, and after stirring, the aqueous layer was taken out, and 18.41 g of potassium hexafluorophosphate and 300 ml of ethyl acetate were added and stirred. The ethyl acetate layer was washed twice with 100 ml of distilled water, and after removing the water content of the ethyl acetate layer with anhydrous magnesium sulfate, the ethyl acetate was evaporated and further dried at 40 ° C. under reduced pressure to obtain the desired product. Yield: 36.4g

Examples 5 to 27 Manufactured as in the above examples.

Examples of the sulfonium salt compound of the present invention are shown in Table 1.

[0060]

[Table 101]

[0061]

[Table 102]

[0062]

[Table 103]

[0063]

[Table 104]

Test Example 1 (transparent type) (1) Photocuring test ERL-4221 (alicyclic epoxy produced by UCC) was used as a sensitizer with 2,4-diethylthioxanthone (2,4-D).
ETX) and a sulfonium salt compound are dissolved in γ-butyrolactone, the sensitizer is 1.0 part as a pure component, and the sulfonium salt compound is 2.0 parts as a pure component. Was prepared. This formulation was applied to a tin plate to a thickness of 3 μm and photocured under the following conditions. At this time, those in which the composition was cured and tack-free are shown in Table 2, and those in which the tack remains or those not cured are shown in Table 2. UV irradiation equipment: Belt conveyor type UV irradiation equipment Lamp: 2 Kw (80 w / cm) parallel light type high pressure mercury lamp,
Distance 15 cm Conveyor speed: 10 m / min Irradiation frequency: 1 time

(2) Thermosetting test 0.5 g of the above compound was weighed in a sample bottle and
Place in 0 ° C. oven for 30 minutes. At this time, the cured product of the composition is indicated by a circle, and the cured product is indicated by a cross. The results are shown in Table 2.

(3) Storage stability test 100 g of the above compound was weighed in a sample bottle, and stored at 25
Place in oven at 0 ° C for 1 month. At this time, those having a viscosity of the compound which is less than twice the initial viscosity are indicated by a circle, and those having a viscosity more than two times and cured are indicated by a symbol x. The results are shown in Table 2.

[0067]

[Table 2]

Test Example 2 (pigment type) (1) Photocurability test UVR-6110 (alicyclic epoxy made by UCC) 100
Parts and titanium oxide (CR-58 manufactured by Ishihara Sangyo Co., Ltd.), 3 parts of the sulfonium salt compound and 1 part of each sensitizer were dissolved and roll-kneaded to prepare a blend. This formulation was applied to a tin plate to a thickness of 3 μm and photocured under the following conditions. At this time, those in which the composition was cured are shown in Table 3, and those in which it was not cured are shown in Table 3. UV irradiation equipment: HMW-450 lamp manufactured by Oak Manufacturing Co., Ltd .: Water-cooled type 3 kW-ultra high pressure mercury lamp Irradiation amount: 200 mJ / cm ²

(2) Thermosetting test 0.5 g of the above compound was weighed in a sample bottle and
Place in 0 ° C. oven for 30 minutes. At this time, the cured product of the composition is indicated by a circle, and the cured product is indicated by a cross. The results are shown in Table 3.

[0070]

[Table 3]

[0071]

INDUSTRIAL APPLICABILITY The sulfonium salt compound of the present invention is excellent in heat and photoactivity, and contains a cation-polymerizable compound in an extremely thin film to a thick film by heating, light, electron beam,
It can be cured in a short time by irradiation with active energy rays such as X-rays, and when it is used in combination with a sensitizer, photocurability can be further improved. Further, since it can be cured even with light having a wavelength longer than 360 nm, it exhibits high curability even for a composition containing a pigment or the like. Since the cured product of the composition has excellent physical properties, paints, adhesives, inks, photoresists,
It is preferably used as a photosensitive resin for stereolithography.

Claims (13)

[Claims] 1. A compound of the general formula [I] [In the formula, R ₁ and R ₂ each represent a C _1-18 alkyl group, a hydroxy group, a C _1-18 alkoxy group, a C _1-18 alkylcarbonyl group, an aromatic carbonyl group, an aromatic thio group or a halogen atom. . R ₃ represents a C _1-8 alkyl group. R _{4
Represents a} C _1-24 alkyl group (provided that it is a C _5-24 alkyl group when it is unsubstituted), a C _2-24 alkenyl group or a C _3-20 cycloalkyl group, each of which is a hydroxy group, a carbonyl group, Nitrile group, phenyl group, alkoxy group,
It may have a phenoxy group, an alkyleneoxy group, a halogen atom, or an indanyl group. m and n represent 0, 1, 2 or 3. X represents a non-nucleophilic anion residue. ]
A sulfonium salt compound represented by. 2. X in the general formula [I] is SbF ₆ , As.
The sulfonium salt compound according to claim 1, which is one selected from F ₆ , PF ₆ and BF ₄ . 3. A compound represented by the formula [I] wherein R ₄ is a C ₈ -C ₂₄ alkyl group, an alkyl group having an aromatic ring at the β-position carbon as viewed from the sulfur atom, a cycloalkyl group or an indanyl group. 2. The sulfonium salt compound according to item 2. 4. R _{4 of the} general formula [I] is Or [In the formula, R ₅ is a C _1-24 alkyl group, a C _2-24 alkenyl group or a C _3-20 cycloalkyl group, a C _1-24 alkoxy group,
Represents a phenyl group, a naphthyl group, an amino group, each as a substituent a hydroxy group, a carbonyl group, a nitrile group,
It may have a phenyl group, an alkoxy group, a phenoxy group, an alkyleneoxy group, a halogen atom, or a nitro group. R
₆ , R ₇ represents a hydrogen atom, a C _1-8 alkyl group or a phenyl group. Here, R ₅ and R ₆ may combine with each other to form a ring, and in the ring, a hydroxy group, a carbonyl group, a nitrile group,
It may have a phenyl group, an alkoxy group, a phenoxy group or an alkyleneoxy group as a substituent. Also R ₅ and R ₆
May together form an indanone. Also, R
_{When 6} is not a hydrogen atom, R ₅ may represent a hydroxyl group.
m and n represent 0, 1, 2 or 3. X represents a non-nucleophilic anion residue. ] Claim 1 or 2 represented by this
The sulfonium salt compound described. 5. A cationic polymerization initiator containing at least one kind of the sulfonium salt compound according to claim 1. 6. A cationic polymerization initiator composition comprising at least one sulfonium salt compound according to claim 1 and a sensitizer. 7. The cationic polymerization initiator composition according to claim 6, wherein the sensitizer is a naphthalene derivative, a thioxanthone derivative or a 9,10-dialkoxyanthracene derivative having at least one hydroxyl group or an alkoxy group. 8. A curable composition in which the cationically polymerizable compound is an alicyclic epoxy compound or a vinyl ether compound, and the cationic polymerization initiator is at least one of the sulfonium salt compounds according to claim 1. 9. A sensitizer containing at least one selected from naphthalene derivatives, thioxanthone derivatives and 9,10-dialkoxyanthracene derivatives having at least one hydroxyl group or alkoxy group. The curable composition described. 10. The curable composition according to claim 9, which contains a pigment. 11. The curable composition according to claim 10, wherein titanium oxide is used as the pigment. 12. A curable composition comprising the following (1) to (4): (1) Alicyclic epoxy compound or vinyl ether compound as polymerizable compound (2) Pigment (3) Cationic polymerization initiator composition at least one of sulfonium salt compounds according to claim 4 (4) At least one sensitizer At least one selected from naphthalene derivatives, thioxanthone derivatives and 9,10-dialkoxyanthracene derivatives having one hydroxyl group or an alkoxy group 13. A method for curing a cationically polymerizable compound, which comprises photocuring with a gallium-containing lamp for curing the curable composition according to any one of claims 8, 9, 10, 11 and 12.