WO2011016425A1

WO2011016425A1 - Photoacid generator, photocurable composition and cured product of same

Info

Publication number: WO2011016425A1
Application number: PCT/JP2010/063035
Authority: WO
Inventors: 一生鈴木; 秀基木村
Original assignee: サンアプロ株式会社
Priority date: 2009-08-03
Filing date: 2010-08-02
Publication date: 2011-02-10
Also published as: JPWO2011016425A1; JP5699080B2

Abstract

Disclosed is an acid generator which contains a sulfonium salt having high i-line photosensitivity, excellent compatibility with cationically polymerizable compounds and excellent post-formulation storage stability. A photoacid generator comprises formula (1) and formula (2). (R¹-R⁹ represent an alkyl, a hydroxyl, an alkoxyl, an alkylcarbonyl, an arylcarbonyl, an alkoxycarbonyl, an aryloxycarbonyl, an arylthiocarbonyl, an acyloxy, an arylthio, an alkylthio, an aryl, a heterocyclic hydrocarbon group, an aryloxy, an alkylsulfinyl, an arylsulfinyl, an alkylsulfonyl, an arylsulfonyl, a hydroxy(poly)alkyleneoxy, an optionally substituted amino, a cyano, a nitro, or a halogen, m¹-m⁹ each represent the number of groups R¹-R⁹, A₁ represents S or SO, and X¯ represents a monovalent polyatomic anion.)

Description

Photoacid generator, photocurable composition, and cured product thereof

The present invention relates to a photoacid generator, a curable composition, and a cured product thereof. More specifically, the present invention relates to a photoacid generator containing a specific sulfonium salt suitable for curing a cationically polymerizable compound by acting an active energy ray such as light, electron beam or X-ray, The present invention relates to a curable composition containing a generator and a cured product obtained by curing the curable composition.

Conventionally, as a photoacid generator for use in curing a cationically polymerizable compound such as an epoxy compound by applying an active energy ray such as light, electron beam or X-ray, a triarylsulfonium salt (Patent Document 1), naphthalene Phenacylsulfonium salts having a skeleton (Patent Document 2), dialkylbenzylsulfonium salts (Patent Document 3), sulfonium salts having a thioxanthone skeleton (Patent Document 4), and sulfonium salts having a polyarylsulfide skeleton (Patent Document 5) )It has been known.

Currently, i-line having a wavelength of 365 nm is widely used as exposure light in a photolithography process using a photoresist. For this reason, an inexpensive medium-pressure / high-pressure mercury lamp that exhibits good emission intensity can be used as an irradiation light source, and LED lamps having an emission wavelength in the i-line region (360 nm to 390 nm) have recently become widespread. It can also be mentioned. Therefore, the need for a photoacid generator exhibiting high sensitivity to i-line is expected to increase further in the future.
However, among existing photoacid generators, triarylsulfonium salts (Patent Document 1), phenacylsulfonium salts having a naphthalene skeleton (Patent Document 2) and dialkylbenzylsulfonium salts (Patent Document 3) are sensitive to i-line. Because of its low nature, it is necessary to use a sensitizer together to increase sensitivity. In addition, the sulfonium salt having a thioxanthone skeleton introduced therein (Patent Document 4) has a problem that the absorption rate is too large for i-line, and therefore, light curing does not pass to the deep part during thick film curing, resulting in a problem of poor curing. Moreover, although the sulfonium salt (Patent Document 5) having a polyarylsulfide skeleton is described as being effective as a photoacid generator for mercury lamp irradiation, it is not disclosed for sensitivity to i-line.

Japanese Patent Laid-Open No. 50-151997 JP-A-9-118663 JP-A-2-178303 JP-A-8-165290 JP-A-61-100557

In the above background, the object of the present invention is to provide a compound with a cationically polymerizable compound such as an epoxy compound having high photosensitivity to i-line and high compatibility with a cationically polymerizable compound such as an epoxy compound. It is an object of the present invention to provide a new acid generator comprising a sulfonium salt having excellent storage stability.

The present inventor has found that a mixture of a specific sulfonium salt is suitable for the above purpose, and has further studied and completed the present invention. That is, the present invention provides a sulfonium salt represented by the following formula (1) and a sulfonium salt represented by the following formula (2).

[In the formulas (1) and (2), R ¹ to R ⁹ are independently of each other an alkyl group (including a “cycloalkyl group” in this specification), a hydroxyl group, an alkoxyl group, an alkylcarbonyl group. Group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group , An alkylsulfonyl group, an arylsulfonyl group, a hydroxy (poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m ¹ to m ⁹ are R ¹ to R ⁹ , respectively. Represents the number, m ⁴ , m ⁶ , m ⁷ and m ⁹ are integers from 0 to 5 , M ¹ , m ² , m ³ , m ⁵ and m ⁸ represent an integer of 0 to 4, A ₁ represents S or SO, and X ⁻ represents a monovalent polyatomic anion. ]

The present invention also provides a photoacid generator characterized by containing a sulfonium salt represented by the above formula (1) and a sulfonium salt represented by the formula (2).

The present invention also provides an energy beam curable composition comprising the photoacid generator and a cationically polymerizable compound.

Furthermore, the present invention also provides a cured product obtained by curing the energy beam curable composition.

The sulfonium salt of the present invention has excellent photosensitivity to active energy rays such as visible light, ultraviolet rays, electron beams and X-rays, has high compatibility with cationically polymerizable compounds such as epoxy compounds, and cationic polymerization of epoxy compounds and the like. Storage stability is excellent in a blend with a functional compound.
The photoacid generator of the present invention is excellent in curability by the action of ultraviolet light, particularly i-ray, when used for curing a cationically polymerizable compound, and cures a cationically polymerizable compound without using a sensitizer. Can be made. The photoacid generator of the present invention is also excellent in thick film curability.
Since the energy beam curable composition of the present invention contains the above-mentioned photoacid generator, it can be cured with ultraviolet light. In addition, the energy ray-curable composition of the present invention has high storage stability and does not require the use of a sensitizer, and thus is excellent in cost and workability.
Since the cured product of the present invention can be obtained without using a sensitizer, there is no problem of coloring or deterioration caused by the remaining sensitizer.

Therefore, the sulfonium salt of the present invention is used for paints, coating agents, various coating materials (hard coat, anti-fouling coating materials, anti-fogging coating materials, touch-proof coating materials, optical fibers, etc.), back surface treatment agents for adhesive tapes, and adhesive labels. Release coating materials for release sheets (release paper, release plastic films, release metal foils, etc.), printing plates, dental materials (dental compounds, dental composites, etc.), inks, inkjet inks, positive resists (circuit boards, Used for connection terminals and wiring pattern formation in the manufacture of electronic components such as CSP and MEMS elements), resist films, liquid resists, negative resists (permanent films such as surface protective films for semiconductor elements, interlayer insulating films, planarization films, etc.) Used for forming), MEMS resist, positive photosensitive material, negative photosensitive material, various adhesives (temporary fixing agent for various electronic components, DD adhesive, pickup lens adhesive, FPD functional film (deflection plate, antireflection film, etc.), holographic resin, FPD material (color filter, black matrix, partition material, photospacer, Rib, formation of alignment film for liquid crystal, and sealant for FPD), optical member, molding material (for building materials, optical parts, lenses, etc.), casting material, putty, glass fiber impregnating agent, sealing material It is suitable as a photoacid generator for use in sealing materials, sealing materials, optical semiconductor (LED) sealing materials, optical waveguide materials, nanoimprint materials, photofabrication materials, and micro stereolithography materials. Moreover, the energy beam curable composition and the cured product of the present invention are suitable for the above applications.

In the formulas (1) and (2), among R ¹ to R ⁹ , the alkyl group is a linear alkyl group having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), a branched alkyl group having 3 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, Isopentyl, neopentyl, tert-pentyl, isohexyl and isooctadecyl), and cycloalkyl groups having 3 to 18 carbon atoms (such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 4-decylcyclohexyl). Of these, a methyl group is particularly preferred.

Among R ¹ to R ⁹ , the alkoxyl group includes a straight-chain alkoxyl group having 1 to 18 carbon atoms or a branched alkoxyl group having 3 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec -Butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, octadecyloxy, etc.). Of these, a methoxy group is particularly preferred.

Among R ¹ to R ⁹ , the alkylcarbonyl group includes a linear alkylcarbonyl group having 2 to 18 carbon atoms or a branched alkylcarbonyl group having 4 to 18 carbon atoms (acetyl, propionyl, butanoyl, 2-methylpropionyl, Heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, etc.). Of these, an acetyl group is particularly preferred.

Among R ¹ to R ⁹ , examples of the arylcarbonyl group include arylcarbonyl groups having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

Among R ¹ to R ⁹ , the alkoxycarbonyl group is a straight-chain alkoxycarbonyl group having 2 to 19 carbon atoms or a branched alkoxycarbonyl group having 4 to 19 carbon atoms (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxy Carbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc.).

Among R ¹ to R ⁹ , examples of the aryloxycarbonyl group include aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

Among R ¹ to R ⁹ , examples of the arylthiocarbonyl group include arylthiocarbonyl groups having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

Among R ¹ to R ⁹ , the acyloxy group includes a straight-chain acyloxy group having 2 to 19 carbon atoms or a branched acyloxy group having 4 to 19 carbon atoms (acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, Butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy and the like.

Among R ¹ to R ⁹ , the arylthio group is an arylthio group having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenyl. Thio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4 -Hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4 -[4- (Phenylthio) phenyl Phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthio Phenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) phenylthio, 4- (p-ethylbenzoyl) phenylthio 4- (p-isopropylbenzoyl) Phenylthio and 4- (p-tert-butylbenzoyl) phenylthio) and the like.

Among R ¹ to R ⁹ , the alkylthio group includes a linear alkylthio group having 1 to 18 carbon atoms or a branched alkylthio group having 3 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, isooctadecylthio and the like.

Among R ¹ to R ⁹ , examples of the aryl group include aryl groups having 6 to 10 carbon atoms (such as phenyl, tolyl, dimethylphenyl, and naphthyl).

Among R ¹ to R ⁹ , the heterocyclic hydrocarbon group includes a heterocyclic hydrocarbon group having 4 to 20 carbon atoms (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, Benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, etc. Is mentioned.

Among R ¹ to R ⁹ , examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

Among R ¹ to R ⁹ , the alkylsulfinyl group is a linear alkylsulfinyl group having 1 to 18 carbon atoms or a branched alkylsulfinyl group having 3 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl). , Butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, isooctadecylsulfinyl and the like.

Among R ¹ to R ⁹ , examples of the arylsulfinyl group include arylsulfinyl groups having 6 to 10 carbon atoms (such as phenylsulfinyl, tolylsulfinyl and naphthylsulfinyl).

Among R ¹ to R ⁹ , the alkylsulfonyl group is a straight-chain alkylsulfonyl group having 1 to 18 carbon atoms or a branched alkylsulfonyl group having 3 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl). , Butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, octadecylsulfonyl and the like.

Among R ¹ to R ⁹ , examples of the arylsulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms (phenylsulfonyl, tolylsulfonyl (tosyl group), naphthylsulfonyl, etc.) and the like.

Among R ¹ to R ⁹ , examples of the hydroxy (poly) alkyleneoxy group include a hydroxy (poly) alkyleneoxy group represented by the formula (3).

[AO represents an ethyleneoxy group and / or propyleneoxy group, and q represents an integer of 1 to 5. ]

Among R ¹ to R ^9, the optionally substituted amino group includes an amino group (—NH ₂ ) and a hydrocarbon group substituent having 1 to 15 carbon atoms, which may include a saturated hydrocarbon group or an aromatic group. A substituted amino group substituted with (methylamino, dimethylamino, ethylamino, methylethylamino, diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, Isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenylamino, ethylphenylamino, n-propylphenylamino, isopropylphenylamino, etc.).

Among R ¹ to R ⁹ , examples of the halogen atom group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ¹ to R ⁹ are independent of each other, and therefore may be the same as or different from each other.

m ¹ to m ⁹ represent the numbers of R ¹ to R ⁹ , respectively, and m ⁴ , m ⁶ , m ⁷ and m ⁹ are integers of 0 to 5, preferably 0 to 3, more preferably 0 to 2. , Particularly preferably 0 or 1, and m ¹ , m ² , m ³ , m ⁵ and m ⁸ are integers of 0 to 4, preferably 0 to 3, more preferably 0 to 2, particularly preferably. Is 0 or 1. When m ¹ to m ⁶ are in these preferred ranges, the photosensitivity of the sulfonium salt is further improved.

A ₁ represents S (sulfur atom) or SO (sulfoxide). Each A ₁ may be the same or different. If A ₁ is S, preferably the light sensitive sulfonium salt is further improved.

Among the sulfoniums of the present invention, those having the following structures are particularly preferred from the viewpoint of photosensitivity.

In Formula (1) and Formula (2), X ⁻ corresponds to an acid (HX) generated by irradiating the sulfonium salt of the present invention with active energy rays (visible light, ultraviolet rays, electron beams, X-rays, etc.). An anion. X ⁻ is not limited except that it is a monovalent polyatomic anion, but MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ¹⁰ _c BY _4-c ⁻ , R ¹⁰ _c GaY _{4 ^{^{_{^{-c -, R 11 SO 3 -}}}}} , (R 11 SO 2) 3 C - or ^{_{_{(R 11 SO 2) 2 N}}} - anion represented by are preferred.

M represents a phosphorus atom, a boron atom, or an antimony atom.
Y represents a halogen atom (a fluorine atom is preferred).

Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms. Examples of the alkyl group to be converted into Rf by fluorine substitution include linear alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl and octyl), branched chain alkyl groups (such as isopropyl, isobutyl, sec-butyl and tert-butyl) and And cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and the like. The ratio of hydrogen atoms of these alkyl groups substituted by fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90%, based on the number of moles of hydrogen atoms that the original alkyl group had. % Or more, particularly preferably 100%. When the substitution ratio by fluorine atoms is within these preferable ranges, the photosensitivity of the sulfonium salt is further improved. Particularly preferable Rf is CF _3- , CF ₃ CF _2- , (CF ₃ ) ₂ CF-, CF ₃ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF _2- , (CF ₃ ) ₂ CFCF _2-. , CF ₃ CF ₂ (CF ₃ ) CF— and (CF ₃ ) ₃ C—. The b Rf's are independent of each other, and therefore may be the same as or different from each other.

P represents a phosphorus atom, and F represents a fluorine atom.

R ¹⁰ represents a phenyl group in which a part of hydrogen atoms is substituted with at least one element or electron withdrawing group. Examples of such one element include a halogen atom, and include a fluorine atom, a chlorine atom and a bromine atom. Examples of the electron withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group. Of these, a phenyl group in which one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable. c number of R ¹⁰ is independently from each other, therefore, it may be the same or different from each other.

B represents a boron atom, and Ga represents a gallium atom.

R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group and the perfluoroalkyl group are linear or branched. Alternatively, the aryl group may be unsubstituted or may have a substituent.

S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom.
a represents an integer of 4 to 6.
b is preferably an integer of 1 to 5, more preferably 2 to 4, and particularly preferably 2 or 3.
c is preferably an integer of 1 to 4, more preferably 4.

Examples of the anion represented _{^{_{^{by, SbF 6 - - MY a,}}}} PF 6 - or BF ₄ ^-, and the like.

Examples of the anion represented by (Rf) _b PF _6-b ^— include (CF ₃ CF ₂ ) ₂ PF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₂ PF ₄ ⁻ , ((CF ₃ ) ₂ CF) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ^— or (CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ^— It is done. Of these, (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₂ PF ₄ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^— or ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^— is preferred.

Examples of the anion represented by R ¹⁰ _c BY _4-c ^— include (C ₆ F ₅ ) ₄ B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ^{_{_{_{-, (C 6 F 5)}}}} 2 BF 2 -, C 6 F 5 BF 3 - or _{_{_{_{(C 6 H 3 F 2)}}}} 4 B - , and the like. Of these, (C ₆ F ₅ ) ₄ B ^— or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^— is preferred.

Examples of the anion represented by R ¹⁰ _c GaY _4-c ^— include (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ , (CF ₃ C ₆ H ₄ ) ₄ Ga ^{_{_{_{-, (C 6 F 5)}}}} 2 GaF 2 -, C 6 F 5 GaF 3 - or _{_{_{_{(C 6 H 3 F 2)}}}} 4 Ga - , and the like. Of these, (C ₆ F ₅ ) ₄ Ga ^- or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^- is preferred.

Examples of the anion represented by R ¹¹ SO ₃ ^— include trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nonafluorobutanesulfonate anion, pentafluorophenylsulfonate anion, p-toluenesulfone. Examples include an acid anion, benzene sulfonate anion, naphthalene sulfonate anion, anthracene sulfonate anion, camphor sulfonate anion, methane sulfonate anion, ethane sulfonate anion, propane sulfonate anion and butane sulfonate anion. Of these, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, benzenesulfonate anion or p-toluenesulfonate anion is preferred.

Examples of the anion represented by (R ¹¹ SO ₂ ) ₃ C ^— include (CF ₃ SO ₂ ) ₃ C ⁻ , (C ₂ F ₅ SO ₂ ) ₃ C ⁻ , (C ₃ F ₇ SO ₂ ) ₃ C ⁻ or (C ₄ F ₉ SO ₂ ) ₃ C ^{— and the} like.

Examples of the anion represented by (R ¹¹ SO ₂ ) ₂ N ⁻ include (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (C ₃ F ₇ SO ₂ ) ₂ N ⁻ or (C ₄ F ₉ SO ₂ ) ₂ N ^{— and the} like.

The monovalent polyatomic anions include MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ¹⁰ _c BY _4-c ⁻ , R ¹⁰ _c GaY _4-c ⁻ , R ¹¹ SO ₃ ⁻ , (R ¹¹ In addition to the anion represented by SO ₂ ) ₃ C ^— or (R ¹¹ SO ₂ ) ₂ N ^— , perhalogenate ions (ClO ₄ ⁻ , BrO ₄ ^— etc.), halogenated sulfonate ions (FSO ₃ ⁻ , ClSO ₃₎ ^- etc.), sulfate ion _{_{^{_{(CH 3 SO 4 -, CF}}}} 3 SO 4 -, HSO 4 - , etc.), carbonate ions _{^{_{(HCO 3 -, CH 3 CO}}} 3 - , etc.), aluminate ions (AlCl ₄ ^-, AlF ₄ ^- etc.), hexafluoro bismuthate ions (BiF ₆ ^-), carboxylate ion _{^{_{^{(CH 3 COO -, CF 3}}}} COO -, C 6 H 5 COO -, CH 3 C 6 H 4 COO -, C 6 F ₅ COO ⁻ , CF ₃ C ₆ H ₄ COO ^{− and the} like), aryl borate ions (B (C ₆ H ₅ ) ₄ ⁻ , CH ₃ CH ₂ CH ₂ CH ₂ B (C ₆ H ₅ ) ₃ ^{− and the} like), Thiocyanate ions (SCN ⁻ ), nitrate ions (NO ₃ ⁻ ) and the like can be used.

Among these anions X, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ¹⁰ _c BY _4-c ⁻ , R ¹⁰ _c GaY _4-c ⁻ , R ¹¹ SO ₃ are included in terms of cationic polymerization performance. ^{^{_{_{-, (R 11 SO 2)}}}} 3 C - or ^{_{_{(R 11 SO 2) 2 N}}} - anion is preferably represented _{^{_{_{^{by, MY a -, (Rf)}}}}} b PF 6-b -, R 10 c bY 4-c - ^{_{_{, R 10 c GaY 4-c}}} - or ^{_{_{(R 11 SO 2) 3 C}}} - more _{^{_{^{_{preferably, SbF 6 -, PF 6 -}}}}} , (CF 3 CF 2) 3 PF 3 -, (C 6 F 5) 4 B ^{_{_{_{-, ((CF 3) 2}}}} C 6 H 3) 4 B -, (C 6 F 5) 4 Ga -, ((CF 3) 2 C 6 H 3) 4 Ga - or _(CF ₃ SO ₂₎ 3 C ^- is particularly preferred.

Of the total amount (100 mol%) of the sulfonium salt represented by formula (1) and the sulfonium salt represented by formula (2) contained in the photoacid generator, the proportion of the sulfonium salt represented by formula (1) is at least It is preferably 50 mol%, more preferably at least 70 mol%, and even more preferably at least 80 mol%. This is because if the ratio of the sulfonium salt of the formula (1) is less than 50 mol%, the thermal stability of the sulfonium salt is lowered, and the storage stability when blended with a cationic polymerizable compound is deteriorated. The sulfonium salt of formula (2) works to enhance the photocuring performance, but there is no particular lower limit to the blending ratio, and it may be 0.5 mol% or more, 1 mol% or more, 5 mol% or more, etc. . Therefore, for example, of the total amount of both, the sulfonium salt represented by the formula (1) can be 50 to 99.5 mol%, 50 to 99 mol%, 50 to 95 mol%, and the like.

The sulfonium salt mixture of the present invention can be produced, for example, by the production method (1) described below.

<Manufacturing method (1)>
The method represented by the following reaction formula (for example, 4th edition, Experimental Chemistry Course Vol. 24, 1992, published by Maruzen Co., Ltd., page 376, JP-A-7-329399, JP-A-8-165290, JP-A-10- No. 212286 or JP-A-10-7680).

In the above reaction formulas, R ¹ to R ⁹ , S, O, A ₁ , X ⁻ , m ¹ to m ⁹ are the same as defined in the formulas (1) and (2). H represents a hydrogen atom.
HX ′ represents a conjugate acid of a monovalent polyatomic anion. HX ′ is preferably methanesulfonic acid, perfluoromethanesulfonic acid and sulfuric acid from the viewpoints of availability, acid stability and reaction yield.
The dehydrating agent represents, for example, phosphoric anhydride and acetic anhydride.
The monovalent polyatomic anion (X ′ ⁻ ) can be exchanged for another anion (X ⁻ ) of the present invention by, for example, a side decomposition reaction as described above.
DX represents an alkali metal (lithium, sodium, potassium, etc.) cation and another anion of the present invention (eg, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ¹⁰ _c BY _4-c ⁻ , R ¹⁰ _c An anion represented by GaY _4-c ⁻ , R ¹¹ SO ₃ ⁻ , (R ¹¹ SO ₂ ) ₃ C ⁻ , R ¹¹ SO ₂ ) ₂ N ^{− and the} like.
DX ′ represents a salt of an alkali metal (such as lithium, sodium and potassium) cation and a monovalent polyatomic anion (preferably a methanesulfonate anion, a perfluoromethanesulfonate anion and a hydrogen sulfate anion).

The ratio of <G5 (G3)> and <G6 (G4)>, which are the sulfonium salts of the present invention, can be adjusted by the ratio of sulfide <G1> and sulfoxide <G2> as raw materials, and the molar ratio of sulfoxide to sulfide can be adjusted. When it is excessive, the production ratio of <G6 (G4)> increases, and when the molar ratio of sulfoxide to sulfide is decreased, the production ratio of <G5 (G3)> increases.

In the above reaction formula, the first-stage reaction may be carried out in the absence of a solvent or, if necessary, in an organic solvent (acetonitrile, tetrahydrofuran, dioxane, ethanol, acetone, etc.). The reaction temperature is about 20 to 105 ° C. The reaction time is about 1 to several tens of hours.

The reaction in the second stage may be performed subsequent to the reaction in the first stage, or may be performed after the reaction intermediates (G3) and (G4) are isolated (purified as necessary). . The reaction intermediates (G3) and (G4) and an aqueous solution of the salt (MX) of an alkali metal cation and an anion of the present invention are mixed and stirred to perform a metathesis reaction, and the precipitated solid is filtered off, Alternatively, by extracting the separated oily substance with an organic solvent and removing the organic solvent, the sulfonium salt of the present invention is obtained as a solid or viscous liquid. The obtained solid or viscous liquid can be washed with an appropriate organic solvent, if necessary, or purified by recrystallization or column chromatography (the same applies hereinafter).

<Manufacturing method (2)>
<G2> can be synthesized by the oxidation reaction described in the 4th edition, Experimental Chemistry Course Vol. 23 (1991, Maruzen), pages 276 to 277, etc. as shown in the following reaction formula.

In the reaction formula, R ⁴ to R ⁶ , S, O, A ₁ , and m ⁴ to m ⁶ are the same as defined in the formulas (1) and (2).
The oxidizing agent represents an oxidizing agent (hydrogen peroxide or the like).

The chemical structure of the sulfonium salt of the present invention can be determined by a general analytical method (for example, ¹ H-, ¹¹ B-, ¹³ C-, ¹⁹ F-, ³¹ P-nuclear magnetic resonance spectrum, infrared absorption spectrum and / or element). Analysis).

The sulfonium salt mixture of the present invention is suitable as a photoacid generator.
A photoacid generator is an acid generator that decomposes its chemical structure when irradiated with light. The generated acid can be applied as a catalyst for the curing reaction of epoxides.
As the photoacid generator of the present invention, the mixture of the present invention may be used as it is, or another photoacid generator may be contained in this mixture.

When other photoacid generator is contained, the content (mol%) of the other photoacid generator is preferably 1 to 100, more preferably 5 to 50, based on the total number of moles of the sulfonium salt in the mixture. It is.

Other photoacid generators include conventionally known ones such as salts of onium ions (sulfonium, iodonium, selenium, ammonium, phosphonium, etc.) or transition metal complex ions with anions.

As anions, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ¹⁰ _c BY _4−c ⁻ , R ¹⁰ _c GaY _4-c ⁻ , R ¹¹ SO ₃ ⁻ , (R ¹¹ SO ₂ ) ₃ C ^In addition to the anion represented by ^— or (R ¹¹ SO ₂ ) ₂ N ^— , perhalogenate ions (ClO ₄ ⁻ , BrO ₄ ^— etc.), halogenated sulfonate ions (FSO ₃ ⁻ , ClSO ₃ ^— etc.), sulfuric acid Ion (CH ₃ SO ₄ ⁻ , CF ₃ SO ₄ ⁻ , HSO ₄ ⁻ etc.), carbonate ion (HCO ₃ ⁻ , CH ₃ CO ₃ ⁻ etc.), aluminate ion (AlCl ₄ ⁻ , AlF ₄ ⁻ etc.), hexa Fluorobismate ion (BiF ₆ ⁻ ), carboxylate ion (CH ₃ COO ⁻ , CF ₃ COO ⁻ , C ₆ H ₅ COO ⁻ , CH ₃ C ₆ H ₄ COO ⁻ , C ₆ F ₅ COO ^{_{_{_{-, CF 3 C 6 H 4}}}} COO - , etc.), an aryl boronic acid ions _{_{_{^{_{(B (C 6 H 5)}}}}} 4 -, CH 3 CH 2 CH 2 CH 2 B (C 6 H 5) 3 - , etc.), thiocyanate ion (SCN ⁻ ), nitrate ions (NO ₃ ⁻ ) and the like can be used.
Here, M represents a phosphorus atom, a boron atom, or an antimony atom.

Examples of sulfonium ions include triarylsulfonium, diarylsulfonium, monoarylsulfonium, and trialkylsulfonium.

Examples of triarylsulfonium include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris (4-fluoro Phenyl) sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (p-tolylthio) phenyldi-p-tolylsulfonium, 4- (4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (phenyl) Thio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxy Ethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulfonio] phenyl} sulfide, bis {4- [Bis (4-methoxyphenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenyl Sulfonium, 4- (4- Nzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi -P-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) ) Sulfonio] thioxanthone, 2-{[4- (phenylthio) phenyl] phenylsulfonio} thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- ( 4-tert-butylbenzoyl) Phenylthio] phenyldiphenylsulfonium, 4- [4- (benzoylphenylthio)] phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrhenium , 5-phenylthiaanthrhenium, 5-tolylthiaanthrhenium, 5- (4-ethoxyphenyl) thiaanthrhenium, 5- (2,4,6-trimethylphenyl) thiaanthrhenium, etc. No. 4,231,951, U.S. Pat. No. 4,256,828, JP-A-61-100557, JP-A-7-61964, JP-A-7-10914, JP-A-7-25922, JP-A-8-27208, JP-A-8-27209. No. 1, JP-A-8-165290, JP-A-8-30 No. 991, JP-A-9-143212, JP-A-9-278813, JP-A-10-7680, JP-A-10-212286, JP-A-10-287463, JP-A-10-245378, JP-A-8-157510 JP-A-10-204083, JP-A-8-245556, JP-A-8-157451, JP-A-7-324069, JP-A-9-268205, JP-A-9-278935, JP-A-2001-288205. JP-A-11-80118, JP-A-10-182825, JP-A-10-330353, JP-A-10-152495, JP-A-5-239213, JP-A-7-333834, JP-A-9-12537, JP-A-9-12537. No. 8-325259, JP-A-8-160606, JP-A-2000-186071 (US Pat. No. 636) 769 No.), JP-T-2005-501040, JP 2005-530698, JP 2006-104185, JP-T-2006-518332 and JP 2007-254454 No., etc.).

Examples of the diarylsulfonium include diphenylphenacylsulfonium, diphenyl4-nitrophenacylsulfonium, diphenylbenzylsulfonium and diphenylmethylsulfonium (Japanese Patent Laid-Open Nos. 7-300504, 64-45357 and 64-64). 29419 etc.).

Examples of monoarylsulfonium include phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl (1 -Ethoxycarbonyl) ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium and 9-anthracenylmethylphenacyl Examples include ruthenium (Japanese Patent Laid-Open No. 6-345726, Japanese Patent Laid-Open No. 8-325225, Japanese Patent Laid-Open No. 9-118663 (US Pat. No. 6,097,753), Japanese Patent Laid-Open No. 2-196812, Japanese Patent Laid-Open No. 2-1470, Japanese Patent Laid-Open No. 2-196812, JP-A-3-237107, JP-A-3-17101, JP-A-6-228086, JP-A-10-152469, JP-A-7-300505, JP-A-2000-39706, JP-A-2003. -277353 and JP-A-2003-277352).

Examples of the trialkylsulfonium include dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium (Japanese Patent Laid-Open Nos. 4-308563 and 5-140210). JP, 5-140209, JP 5-230189, JP 6-271532, JP 58-37003, JP 2-178303, JP 10-338688, JP 9-328506. No. 11, JP-A-11-228534, JP-A-8-27102, JP-A-7-333834, JP-A-5-222167, JP-A-11-21307, JP-A-11-35613, US Pat. No. 6,031,014, etc. ).

Examples of the iodonium ion include diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxyphenyl) ) Iodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, isobutylphenyl (p-tolyl) iodonium, etc. (Macromolecules, 10, 1307 (1977), JP-A-6-184170, US Pat. No. 4,256,828, US Pat. No. 4,351,708, JP-A-56-135519, JP-A-58-38350, JP-A-10-195117 JP 2001-139539, JP 2000-510516 and JP 2000-119306 No., etc.).

Selenium ions include triaryl selenium (triphenyl selenium, tri-p-tolyl selenium, tri-o-tolyl selenium, tris (4-methoxyphenyl) selenium, 1-naphthyldiphenyl selenium, tris (4-fluorophenyl) selenium , Tri-1-naphthyl selenium, tri-2-naphthyl selenium, tris (4-hydroxyphenyl) selenium, 4- (phenylthio) phenyldiphenyl selenium and 4- (p-tolylthio) phenyldi-p-tolyl selenium), diaryl Selenium (diphenylphenacyl selenium, diphenyl benzyl selenium, diphenylmethyl selenium, etc.), monoaryl selenium (phenylmethyl benzyl selenium, 4-hydroxyphenyl methanium) Rubenzyl selenium, phenylmethylphenacyl selenium, 4-hydroxyphenylmethyl phenacyl selenium, 4-methoxyphenylmethyl phenacyl selenium, etc.) and trialkyl selenium (dimethyl phenacyl selenium, phenacyl tetrahydroselenophenium, dimethyl benzyl selenium, Benzyltetrahydroselenophenium, octadecylmethylphenacyl selenium, etc.) (Japanese Patent Laid-Open Nos. 50-151997, 50-151976, 53-22597, etc.).

Examples of ammonium ions include tetraalkylammonium (tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethyl-n-propylammonium, trimethylisopropylammonium, trimethyl-n-butylammonium, trimethylisobutylammonium, Trimethyl-t-butylammonium, trimethyl-n-hexylammonium, dimethyldi-n-propylammonium, dimethyldiisopropylammonium, dimethyl-n-propylisopropylammonium, methyltri-n-propylammonium and methyltriisopropylammonium), pyrrolidinium (N , N-Dimethylpyrrolidinium N-ethyl-N-methylpyrrolidinium and N, N-diethylpyrrolidinium, etc.), imidazolinium (N, N'-dimethylimidazolinium, N, N'-diethylimidazolinium, N-ethyl- N'-methylimidazolinium, 1,2,3-trimethylimidazolinium, 1,3,4-trimethylimidazolinium, 1,3-diethyl-2-methylimidazolinium, 1,3-diethyl-4 -Methylimidazolinium and 1,2,3,4-tetramethylimidazolinium, etc.), tetrahydropyrimidinium (N, N'-dimethyltetrahydropyrimidinium, N, N'-diethyltetrahydropyrimidinium, N -Ethyl-N'-methyltetrahydropyrimidinium and 1,2,3-trimethyltetrahydropyrimidinium, etc.), mol Linium (N, N'-dimethylmorpholinium, N-ethyl-N-methylmorpholinium, N, N-diethylmorpholinium, etc.), piperidinium (N, N-dimethylpiperidinium, N-ethyl-N) '-Methylpiperidinium and N, N'-diethylpiperidinium, etc.), pyridinium (N-methylpyridinium, N-ethylpyridinium, Nn-propylpyridinium, N-isopropylpyridinium, Nn-butylpyridinium, N-benzylpyridinium and N-phenacylpyridinium), imidazolium (N, N'-dimethylimidazolium, N-ethyl-N-methylimidazolium, N, N'-diethylimidazolium, 1,2-diethyl) -3-Methylimidazolium, 1,3-diethyl-2-methylimidazolium and 1-methyl-3-n-propyl-2,4-dimethylimidazolium, etc.), quinolium (N-methylquinolium, N-ethylquinolium, Nn-propylquinolium, N-isopropylquinolium, N -N-butyl quinolium, N-benzyl quinolium, N-phenacyl quinolium, etc.), isoquinolium (N-methylisoquinolium, N-ethylisoquinolium, Nn-propylisoquinolium, N-isopropyl Isoquinolium, Nn-butylisoquinolium, N-benzylisoquinolium, N-phenacylisoquinolium, etc.), thiazonium (benzylbenzothiazonium, phenacylbenzothiazonium, etc.), and alridinium ( And the like (US Pat. No. 406). No. 055, Japanese Patent Publication No. 2519480, Japanese Patent Application Laid-Open No. 5-222112, Japanese Patent Application Laid-Open No. 5-222111, Japanese Patent Application Laid-Open No. 5-262613, Japanese Patent Application Laid-Open No. 5-255256, Japanese Patent Application Laid-Open No. 7-109303, Japanese Patent Application Laid-Open No. JP-A-2-268173, JP-A-9-328507, JP-A-5-132461, JP-A-9-221652, JP-A-7-43854, JP-A-7-43901, JP-A-5-262813, JP-A-4-327574, JP-A-2-43202, JP-A-60-203628, JP-A-57-209931, JP-A-9-221652, etc.).

Examples of phosphonium ions include tetraarylphosphonium (tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, tetrakis (4-methoxyphenyl) phosphonium, etc.), tria Reel phosphonium (triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, triphenylbutylphosphonium, etc.) and tetraalkylphosphonium (triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethyl Phenacylphosphonium and tributylphenacylphos Honiumu etc.) and the like (JP-A-6-157624, JP-A-5-105692, JP-A-7-82283 and JP-A 9-202873 Patent etc.).

Transition metal complex ions include chromium complex cations {(η5-cyclopentadienyl) (η6-toluene) Cr ⁺ , (η5-cyclopentadienyl) (η6-xylene) Cr ⁺ , (η5-cyclopentadienyl) ) (Η6-1-methylnaphthalene) Cr ⁺ , (η5-cyclopentadienyl) (η6-cumene) Cr ⁺ , (η5-cyclopentadienyl) (η6-mesitylene) Cr ⁺ , (η5-cyclopentadiene) Enyl) (η6-pyrene) Cr ⁺ , (η5-fluorenyl) (η6-cumene) Cr ⁺ , (η5-indenyl) (η6-cumene) Cr ⁺ , bis (η6-mesitylene) Cr ²⁺ , bis (η6-xylene) ) ^{Cr 2+,} bis (Ita6- cumene) ^{Cr 2+,} bis (Ita6- toluene) ^{Cr 2+,} (η6- toluene) (η6- xylene) ^{Cr 2+,} (η6 Cumene) (η6- naphthalene) ^{Cr 2+,} bis (eta. @ 5-cyclopentadienyl) Cr ^+, bis (eta. @ 5-indenyl) ^Cr +, (η5- cyclopentadienyl) (eta. @ 5 fluorenyl) Cr ⁺ and (eta. @ 5 Cyclopentadienyl) (η5-indenyl) Cr ⁺ etc}, and iron complex cation {(η5-cyclopentadienyl) (η6-toluene) Fe ⁺ , (η5-cyclopentadienyl) (η6-xylene) Fe ⁺ , (Η5-cyclopentadienyl) (η6-1-methylnaphthalene) Fe ⁺ , (η5-cyclopentadienyl) (η6-cumene) Fe ⁺ , (η5-cyclopentadienyl) (η6-mesitylene) Fe ^+, (η5- cyclopentadienyl) (η6- pyrene) ^Fe +, ^(η5- fluorenyl) (η6- cumene) ^Fe +, ^(η5- Indeni ) (Ita6- cumene) Fe ^+, bis (Ita6- mesitylene) ^{Fe 2+,} bis (Ita6- xylene) ^{Fe 2+,} bis (Ita6- cumene) ^{Fe 2+,} bis (Ita6- toluene) ^{Fe 2+,} (η6- toluene) (Η6-xylene) Fe ²⁺ , (η6-cumene) (η6-naphthalene) Fe ²⁺ , bis (η5-cyclopentadienyl) Fe ⁺ , bis (η5-indenyl) Fe ⁺ , (η5-cyclopentadienyl) (Η5-fluorenyl) Fe ⁺ and (η5-cyclopentadienyl) (η5-indenyl) Fe ⁺ etc.} (wherein Cr represents a chromium atom and Fe represents an iron atom) (Macromol. Chem. 81,86 (1965), Angew. Makromol.
Chem., 50, 9 (1976), Macromol. Chem., 153, 229 (1972), J. Polym. Sci., Polym. Chem. Edn., 14, 1547 (1976), Chem. Ztg., 108, 345 (1984), J. Imaging. Sci.,
30, 174 (1986), J. Photochem. Photobiol. A: Chem., 77 (1994), J. Rad. Curing., 26 (1986), Adv. Polym. Sci., 78,
61 (1986), U.S. Pat. Nos. 4,973,722, 4,992,572, 3,895,954, European Patent Publication Nos. 203829, 354181, 94914, 109851, 94949 Kaihei 58-210904 (US Pat. No. 4,868,288), JP-A-59-108003, JP-A-2000-226396, JP-A-2-284903, and the like.

The photoacid generator of the present invention may be dissolved in advance in a solvent that does not inhibit cationic polymerization in order to facilitate dissolution in a cationically polymerizable compound.

Solvents include carbonates (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate); esters (ethyl acetate, ethyl lactate, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ -Valerolactone and ε-caprolactone, etc.); ethers (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.); and ether esters ( Ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate And diethylene glycol monobutyl ether acetate, etc.) and the like.

When a solvent is used, the proportion of the solvent used is preferably 15 to 1000 parts by weight, more preferably 30 to 500 parts by weight with respect to 100 parts by weight of the photoacid generator of the present invention. The solvent to be used may be used independently or may use 2 or more types together.

The energy beam curable composition of the present invention is composed of the above-mentioned photoacid generator and a cationically polymerizable compound.

Examples of cationically polymerizable compounds include cyclic ethers (epoxides and oxetanes), ethylenically unsaturated compounds (vinyl ether and styrene, etc.), bicycloorthoesters, spiroorthocarbonates and spiroorthoesters (Japanese Patent Laid-Open No. 11-060996). JP-A 09-302269, JP-A 2003-026993, JP-A 2002-206017, JP-A 11-349895, JP-A 10-212343, JP-A 2000-119306, JP-A 10-67812, JP 2000-186071, JP 08-85775, JP 08-134405, JP 2008-20838, JP 2008-20839, JP 2008-20841, JP 2008-26660, JP 2008-26644. , JP 007-277327, photopolymer social gathering “Photopolymer Handbook” (1989, Industrial Research Committee), General Technology Center “UV / EB Curing Technology” (1982, General Technology Center), Radtech Study Group “UV. "EB Curing Material" (1992, CMC), Technical Information Association, "Hardening Failure / Inhibition Causes in UV Curing and Countermeasures" (2003, Technical Information Association), Coloring Materials, 68, (5), 286-293 (1995), fine chemicals, 29, (19), 5-14 (2000), etc.).

As the epoxide, known ones can be used, and aromatic epoxides, alicyclic epoxides and aliphatic epoxides are included.

Aromatic epoxides include monovalent or polyvalent phenols having at least one aromatic ring (phenol, biphenol, bisphenol A, bisphenol F, phenol novolac, cresol novolac and brominated products thereof or alkylene oxide adducts thereof. A glycidyl ether of a compound) and a glycidyl ester (such as diglycidyl phthalate and diglycidyl-3-methyl phthalate) of a monovalent or polyvalent carboxylic acid (such as phthalic acid and 3-methylphthalic acid) having at least one aromatic ring Can be mentioned.

As the alicyclic epoxide, a compound obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3, 4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4 -Epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- ( 3, -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanemetadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis (3,4 -Epoxycyclohexane), dicyclopentadiene diepoxide and ethylene bis (3,4-epoxycyclohexanecarboxylate)).

Aliphatic epoxides include aliphatic polyhydric alcohols or polyglycidyl ethers of this alkylene oxide adduct (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, Triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol and hexaglycidyl ether of dipentaerythritol), polyglycidyl ester of aliphatic polybasic acid (diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate) And diglycidyl hexahydro-3-methylphthalate), epoxidized products of long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.) , Glycidyl group-containing polymers (such as homopolymers of glycidyl (meth) acrylate or copolymers thereof with other unsaturated monomers), and polyfunctional epoxides having a dimethylsiloxane skeleton (Journal of Polym. Sci., Part A, Polym. Chem., Vol. 28, 497 (1990))

As oxetane, known ones can be used, such as 3-ethyl-3-hydroxymethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] Phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2- Ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3- ethyl- -Oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanyl) Methyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ) Ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, Tabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3'- (1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2 -Bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) Ether, dicyclopentenyl bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3 -Ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3 -Ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3- Ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl) -3-Oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-phenoxymethyloxetane , 3-ethyl-3- (4-methylphenoxy) methyloxetane, 3-ethyl-3- (4-fluorophenoxy) methyloxetane, 3-ethyl-3- (1-naphthoxy) methyloxetane, 3-ethyl-3 -(2-naphthoxy) methyloxetane, 3-ethyl-3-{[3- (ethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxetane, phenol novolac oxetane and the like.

As the ethylenically unsaturated compound, known cationically polymerizable monomers and the like can be used, and include aliphatic monovinyl ether, aromatic monovinyl ether, polyfunctional vinyl ether, styrene, and cationically polymerizable nitrogen-containing monomers.

Aliphatic monovinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, 2-acetoxyethyl vinyl ether, diethylene glycol Examples thereof include monovinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, allyl vinyl ether, 2-methacryloyloxyethyl vinyl ether, and 2-acryloyloxyethyl vinyl ether.

Examples of the aromatic monovinyl ether include 2-phenoxyethyl vinyl ether, phenyl vinyl ether and p-methoxyphenyl vinyl ether.

Polyfunctional vinyl ethers include butanediol-1,4-divinyl ether, triethylene glycol divinyl ether, 1,4-benzene divinyl ether, hydroquinone divinyl ether, cyclohexanedimethanol divinyl ether (1,4-bis [(vinyloxy) methyl Cyclohexane), diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, and the like.

Examples of styrene include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

Examples of the cationic polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.

Bicycloorthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2.2.2] octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo. -[2.2.2] octane and the like.

Examples of spiro orthocarbonates include 1,5,7,11-tetraoxaspiro [5.5] undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5.5] undecane. It is done.

Spiro orthoesters include 1,4,6-trioxaspiro [4.4] nonane, 2-methyl-1,4,6-trioxaspiro [4.4] nonane and 1,4,6-trioxas. Examples include pyro [4.5] decane.

Among these cationically polymerizable compounds, epoxides, oxetanes and vinyl ethers are preferable, epoxides and oxetanes are more preferable, and alicyclic epoxides and oxetanes are particularly preferable. In addition, these cationically polymerizable compounds may be used alone or in combination of two or more.

The content of the photoacid generator of the present invention in the energy ray curable composition is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts of the cationic polymerizable compound. is there. Within this range, the cationically polymerizable compound is further sufficiently polymerized, and the physical properties of the cured product are further improved. This content is determined by considering various factors such as the nature of the cationic polymerizable compound, the type and energy dose of the energy ray, temperature, curing time, humidity, and coating thickness, and is limited to the above range. Not.

In the energy ray curable composition of the present invention, a known additive (sensitizer, pigment, filler, antistatic agent, flame retardant, antifoaming agent, flow control agent, light stabilizer, Antioxidants, adhesion-imparting agents, ion scavengers, solvents, non-reactive resins, radical polymerizable compounds, and the like).

The energy beam curable composition of the present invention basically does not require a sensitizer, but may contain a sensitizer as necessary to supplement the curability. As such a sensitizer, known sensitizers (Japanese Patent Laid-Open Nos. 11-279212 and 09-183960) can be used, and anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10 -Dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-tert-butyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9 -Methoxy-10-methylanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2,3-dimethyl-9, 10-diethoxyanthracene, 9-ethoxy-10-methylanthracene, , 10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-tert-butyl-9,10-dipropoxyanthracene, 2,3-dimethyl-9,10-dipropoxyanthracene, 9-isopropoxy-10-methylanthracene, 9,10-dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2-tert- 9,10-dibenzyloxyanthracene, 2,3-dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10-methylanthracene, 9,10-di-α-methylbenzyloxyanthracene, 2-ethyl -9,10-di-α-methylbenzyloxy Nthracene, 2-tert-9,10-di-α-methylbenzyloxyanthracene, 2,3-dimethyl-9,10-di-α-methylbenzyloxyanthracene, 9- (α-methylbenzyloxy) -10- Methyl anthracene, 9,10-diphenylanthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-methylanthracene, 9-bromoanthracene, 9-methylthioanthracene, 9-ethylthioanthracene, etc.}; pyrene; 1,2-benz Anthracene; perylene; tetracene; coronene; thioxanthone {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.}; phenothiazine Xanthone; naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 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), 4-methoxy-1-naphthol, etc.}; ketone {dimethoxyacetophenone, diethoxyacetophenone , 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2- Dimethoxy-1,2-diphenylethane-1-one, p-di Methylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin- n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4 , 4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone and 4-benzoyl-4′-methyldiphenyl sulfide, etc.]; carbazole {N Phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole and the like}; chrysene {1,4-dimethoxychrysene, 1,4-diethoxychrysene, 1,4-dipropoxychrysene, 1,4 -Dibenzyloxychrysene and 1,4-di-α-methylbenzyloxychrysene, etc.}; phenanthrene {9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-ethoxyphenanthrene, 9-benzyloxyphenanthrene, 9,10-dimethoxyphenanthrene , 9,10-diethoxyphenanthrene, 9,10-dipropoxyphenanthrene, 9,10-dibenzyloxyphenanthrene, 9,10-di-α-methylbenzyloxyphenanthrene, 9-hydroxy-10-methoxyphen Nantoren and 9-hydroxy-10-ethoxy phenanthrene and the like}.

When a sensitizer is contained, the content of the sensitizer is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, with respect to 100 parts of the photoacid generator.

As the pigment, known pigments and the like can be used, and inorganic pigments (such as titanium oxide, iron oxide, and carbon black) and organic pigments (such as azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments) can be used.

When a pigment is contained, the content of the pigment is preferably 0.5 to 400,000 parts by weight, more preferably 10 to 150,000 parts by weight with respect to 100 parts of the photoacid generator.

Known fillers can be used as fillers, such as fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate and lithium aluminum silicate. Can be mentioned.

When the filler is contained, the content of the filler is preferably 50 to 600000 parts by weight, more preferably 300 to 200000 parts by weight with respect to 100 parts of the photoacid generator.

As the antistatic agent, known antistatic agents can be used, and nonionic antistatic agents {glycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, N, N-bis (2-hydroxyethyl) ) Alkylamine, polyoxyethylene alkylamine, polyoxyethylene alkylamine fatty acid ester, alkyldiethanolamide, etc.}; anionic antistatic agent {alkyl sulfonate, alkylbenzene sulfonate, alkyl phosphate, etc.}; cationic charge Inhibitor {tetraalkylammonium salt and trialkylbenzylammonium salt, etc.}; amphoteric antistatic agent {alkylbetaine and alkylimidazolium betaine etc.}; polymer antistatic agent {quaternary ammo-containing styrene- (medium ) Acrylate copolymer, quaternary ammonio-containing styrene-acrylonitrile-maleimide copolymer, polyoxyethylene glycol, polyether ester amide, polyether amide imide, ethylene oxide-epichlorohydrin copolymer and methoxy polyoxyethylene glycol (Meth) acrylate copolymer, etc.}.

When the antistatic agent is contained, the content of the antistatic agent is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight, with respect to 100 parts of the photoacid generator.

As the flame retardant, known flame retardants can be used. Inorganic flame retardant {antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide , Magnesium hydroxide, calcium aluminate, etc.}; bromine flame retardant {tetrabromophthalic anhydride, hexabromobenzene, decabromobiphenyl ether, etc.}; and phosphate ester flame retardant {tris (tribromophenyl) phosphate, etc.} It is done.

When the flame retardant is contained, the content of the flame retardant is preferably 0.5 to 40000 parts by weight, more preferably 5 to 10000 parts by weight with respect to 100 parts of the photoacid generator.

As the antifoaming agent, known antifoaming agents can be used, alcohol defoaming agents {isopropanol, n-butanol, octaethyl alcohol, hexadecyl alcohol, etc.}; metal soap defoaming agents {calcium stearate, aluminum stearate, etc. }; Phosphate ester defoamers {tributyl phosphate, etc.}; Fatty acid ester defoamers {glycerin monolaurate, etc.}; Polyether defoamers {polyalkylene glycol, etc.}; Silicone defoamers {dimethylsilicone oil and silica Silicone compound and the like}; and mineral oil defoaming agent {mineral oil in which silica powder is dispersed} and the like.

When the antifoaming agent is contained, the content of the antifoaming agent is preferably 0.1 to 20000 parts by weight, more preferably 0.5 to 5000 parts by weight with respect to 100 parts of the photoacid generator.

As the flow control agent, known flow control agents can be used, and examples thereof include hydrogenated castor oil, polyethylene oxide, organic bentonite, colloidal silica, amide wax, metal soap, and acrylate polymer.

When the fluidity modifier is contained, the content of the fluidity modifier is preferably 0.1 to 20000 parts by weight, more preferably 0.5 to 5000 parts by weight with respect to 100 parts of the photoacid generator. .

As the light stabilizer, known light stabilizers and the like can be used. Ultraviolet absorbing stabilizers {benzotriazole, benzophenone, salicylate, cyanoacrylate and derivatives thereof}; radical scavenging stabilizers {hindered amine, etc.}; and quenching And a type stabilizer {nickel complex etc.}.

When the light stabilizer is contained, the content of the light stabilizer is preferably 0.05 to 40,000 parts by weight, more preferably 0.5 to 10,000 parts by weight with respect to 100 parts of the photoacid generator.

As antioxidants, known antioxidants can be used, such as phenolic antioxidants (monophenolic, bisphenolic and polymeric phenolic), sulfur antioxidants and phosphorus antioxidants. It is done.

When the antioxidant is contained, the content of the antioxidant is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight with respect to 100 parts of the photoacid generator.

As the adhesion-imparting agent, a known adhesion-imparting agent can be used, and examples thereof include a coupling agent, a silane coupling agent, and a titanium coupling agent.

When the adhesiveness-imparting agent is contained, the content of the adhesiveness-imparting agent is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight with respect to 100 parts of the adhesiveness-imparting agent. .

As the ion scavenger, known ion scavengers can be used, and organic aluminum (alkoxyaluminum, phenoxyaluminum, etc.) and the like can be mentioned.

In the case of containing an ion scavenger, the content of the ion scavenger is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight with respect to 100 parts of the photoacid generator.

The solvent is not limited as long as it can be used for dissolving a cationically polymerizable compound or adjusting the viscosity of an energy ray-curable composition. In addition to those that can be used as a solvent for the photoacid generator, for example, ether {anisole, diethyl Ether, tetrahydrofuran, 1,4-dioxane and ethyl-tert-butyl ether, etc.}; aromatic hydrocarbon {toluene, xylene, cumene, ethylbenzene, mesitylene, etc.}; ketone {acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc.}; alcohol { Methanol, ethanol, isopropyl alcohol, tert-butanol and the like}; nitrile {acetonitrile and the like} and the like.

In the case of containing a solvent, the content of the solvent is preferably 50 to 2,000,000 parts by weight, more preferably 200 to 500,000 parts by weight with respect to 100 parts of the photoacid generator.

Non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, hydrogenated styrene butadiene block copolymer, and (meth) acrylic ester co-polymer. Examples include coalescence and polyurethane. The number average molecular weight of these resins is preferably 1,000 to 500,000, more preferably 5000 to 100,000 (the number average molecular weight is a value measured by a general method such as GPC).

When the non-reactive resin is contained, the content of the non-reactive resin is preferably 5 to 400000 parts by weight, more preferably 50 to 150,000 parts by weight with respect to 100 parts of the photoacid generator.

When a non-reactive resin is included, it is desirable to dissolve the non-reactive resin in a solvent in advance so that the non-reactive resin can be easily dissolved with the cationic polymerizable compound.

As radically polymerizable compounds, known {photopolymer social gathering edition “Photopolymer Handbook” (1989, Industrial Research Committee), General Technology Center “UV / EB Curing Technology” (1982, General Technology Center), Radtech Research The radical-polymerizable compounds in the “UV / EB Curing Materials” edition (1992, CMC) and the “Technical Information Association”, “Hardening Failure / Inhibition Causes in UV Curing and Countermeasures” (2003, Technical Information Association)} Monofunctional monomers, bifunctional monomers, polyfunctional monomers, epoxy (meth) acrylates, polyester (meth) acrylates and urethane (meth) acrylates can be used.

Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 1,6-hexanediol mono (meta) ) Acrylate, styrene, vinylcyclohexene, isobutylene and butadiene.

Bifunctional monomers include dihydric alcohols or di (meth) acrylates of these alkylene oxide adducts {dihydric alcohols (ethylene hydride, propylene glycol, bisphenol A, bisphenol A hydrides and their alkylene oxide adducts, etc.) Di (meth) acrylate} and divinylbenzene.

As the polyfunctional monomer, a monomer other than the bifunctional monomer can be used, and examples thereof include (meth) acrylates of polyhydric alcohols (trimethylolpropane, glycerin, pentaerythritol, and adducts thereof with an alkylene oxide).

Examples of the epoxy (meth) acrylate include epoxy (meth) acrylate obtained by reacting epoxide {aromatic epoxide, alicyclic epoxide, aliphatic epoxide, etc.} with (meth) acrylic acid.

Polyester (meth) acrylates include aromatic polybasic acids (phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) or aliphatic polybasic acids (succinic acid, adipic acid, sebacic acid, etc.) , Polyhydric alcohol (ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, polytetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6- Esterification of a hydroxy-terminated polyester obtained from hexanediol, trimethylolpropane, glycerin, pentaerythritol, bisphenol and their alkylene oxide adducts) with (meth) acrylic acid. The polyester (meth) acrylate obtained.

Urethane (meth) acrylates include polyfunctional isocyanates {alicyclic isocyanates (such as isophorone diisocyanate and dicyclohexylmethane diisocyanate), aliphatic isocyanates (such as tetramethylene diisocyanate and hexamethylene diisocyanate), aromatic isocyanates (toluene diisocyanate, phenylene diisocyanate and Diphenylmethane diisocyanate etc.) and polyhydric alcohol {ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, polytetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 1 , 6-hexanediol, trimethylolpropane, glycerin, pe An isocyanate-terminated prepolymer obtained from taerythritol, bisphenol, hydrogenated bisphenol, polycaprolactone diol, polyester diol, polycarbonate diol, etc.} is converted into a hydroxyl group-containing (meth) acrylate {2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and pentaerythritol with tri (meth) acrylate, etc.} are urethane (meth) acrylates obtained by urethanization reaction.

When the radical polymerizable compound is contained, the content of the radical polymerizable compound is preferably 5 to 400000 parts by weight, more preferably 50 to 150,000 parts by weight with respect to 100 parts of the photoacid generator.

When a radical polymerizable compound is contained, it is preferable to use a radical polymerization initiator that initiates polymerization by heat or light in order to increase the molecular weight by radical polymerization.

As the radical polymerization initiator, a known radical polymerization initiator or the like can be used, and a thermal radical polymerization initiator and a photo radical polymerization initiator are included.

As thermal radical polymerization initiators, organic peroxides {ketone peroxides (such as methyl ethyl ketone peroxide and cyclohexanone peroxide), peroxyketals (2,2-bis (tert-butylperoxy) butane and 1,1-bis (Tert-butylperoxy) cyclohexane, etc.), hydroperoxides (such as tert-butylhydroperoxide and cumene hydroperoxide), dialkyl peroxides (such as di-tert-butylperoxide), diacyl peroxides (isobutyryl peroxide) Oxide, lauroyl peroxide and benzoyl peroxide), peroxydicarbonate (diisopropyl peroxydicarbonate, etc.), peroxyester (tert-butylperoxyisobutyrate and 2,5-dimethyl) -2,5-di (benzoylperoxy) hexane, etc.)}, and azo compounds {1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobisisobutyronitrile, 2 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [2-methyl-N- (2 -Propenyl) propionamidine] dihydrochloride, 2,2'-azobis (2-methylpropionamide), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2 ' -Azobis (2-methylpropane), 2,2'-azobis (2,4,4-trimethylpentane) and dimethyl 2,2'-azobis (2-methylpropyl) Pioneto) and the like}.

Examples of photo radical polymerization initiators include acetophenone initiators {acetophenone, p-tert-butyltrichloroacetophenone and 2,2-diethoxyacetophenone, etc.}, benzophenone initiators {benzophenone, methyl o-benzoylbenzoate and 4-benzoyl-4 '-Methyldiphenyl sulfide, etc.}, Michler's ketone initiator {4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone, etc.}, benzoin initiator {benzoin, benzoin methyl ether, etc.}, thioxanthone Initiators {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.} and acyl phosphines Initiator {mono acyl phosphine oxides and bisacylphosphine oxides and the like}.

When the radical polymerization initiator is contained, the content of the radical polymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts of the radical polymerizable compound. .

The energy ray-curable composition of the present invention comprises a cationically polymerizable compound, a photoacid generator, and, if necessary, a uniform additive at room temperature (about 20 to 30 ° C.) or optionally heated (about 40 to 90 ° C.). Can be prepared by kneading with three rolls or the like.

The energy ray-curable composition of the present invention can be cured by irradiating energy rays to obtain a cured product.
As the energy ray, any energy ray may be used as long as it has energy that induces the decomposition of the sulfonium salt of the present invention, but low pressure, medium pressure, high pressure or ultrahigh pressure mercury lamp, metal halide lamp, LED lamp, xenon lamp, carbon arc lamp, Energy rays in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from a fluorescent lamp, a semiconductor solid state laser, an argon laser, a He—Cd laser, a KrF excimer laser, an ArF excimer laser, or an F ₂ laser are preferable. In addition, the radiation which has high energy, such as an electron beam or an X-ray, can also be used for an energy beam.

The irradiation time of the energy beam is affected by the energy beam intensity and the energy beam permeability to the energy beam curable composition, but about 0.1 to 10 seconds is sufficient at room temperature (about 20 to 30 ° C). It is. However, it may be preferable to spend more time when energy beam permeability is low or when the energy beam curable composition is thick. Most energy ray-curable compositions are cured by cationic polymerization within 0.1 seconds to several minutes after irradiation with energy rays, but if necessary, after irradiation with energy rays, room temperature (about 20 to 30 ° C.) to 150 It is also possible to carry out after-curing by heating at a temperature of several seconds to several hours.

Specific applications of the energy ray-curable composition of the present invention include paints, coating agents, various coating materials (hard coat, anti-stain coating, anti-fogging coating, touch-resistant coating, optical fiber, etc.), adhesive tape Back surface treatment agent, Release coating material for adhesive labels (release paper, release plastic film, release metal foil, etc.), printing plate, dental materials (dental compound, dental composite, etc.), ink, inkjet ink , Positive resist (used for forming connection terminals and wiring patterns for manufacturing electronic parts such as circuit boards, CSPs, MEMS elements, etc.), resist films, liquid resists, negative resists (surface protective films for semiconductor elements, interlayer insulation films) ), MEMS resist, positive photosensitive material, negative photosensitive material, various adhesives (electrical materials) Temporary fixing agent for parts, HDD adhesive, pickup lens adhesive, FPD functional film (deflection plate, antireflection film, etc.), holographic resin, FPD material (color filter, black matrix, (Partition materials, photo spacers, ribs, alignment films for liquid crystals, etc. and FPD sealants), optical members, molding materials (for building materials, optical components, lenses, etc.), casting materials, putty, glass fiber Examples thereof include an impregnating agent, a sealing material, a sealing material, a sealing material, an optical semiconductor (LED) sealing material, an optical waveguide material, a nanoimprint material, an optical fabrication material, and a micro stereolithography material.

Since the sulfonium salt of the present invention generates a strong acid upon irradiation with light, light for chemically amplified resist materials known in the art (JP 2003-267968, JP 2003-261529, JP 2002-193925, etc.) is used. It can also be used as an acid generator.

Chemically amplified resist materials include: (1) a two-component chemically amplified positive resist containing, as essential components, a resin that is soluble in an alkali developer by the action of an acid and a photoacid generator; and (2) an alkali developer. Soluble resin, a three-component chemical amplification type positive resist containing, as essential components, a dissolution inhibitor and a photoacid generator that are soluble in an alkali developer by the action of an acid, and (3) suitable for an alkali developer. A chemically amplified negative resist containing a crosslinking agent that crosslinks the resin by heat treatment in the presence of a soluble resin and an acid and makes the resin insoluble in an alkaline developer and a photoacid generator as an essential component is included.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not intended to be limited thereto. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

(Production Example 1) Production of a mixture of [4- (phenylthio) phenyl] phenyl sulfide and [4- (phenylthio) phenyl] phenyl sulfoxide-1
[4- (Phenylthio) phenyl] phenyl sulfide 10.0 parts, 40.0 parts of acetonitrile, 0.17 parts of sulfuric acid were charged and mixed uniformly, then heated to 50 ° C. and 2.31 parts of 30% aqueous hydrogen peroxide solution Was added dropwise over 10 minutes. Thereafter, the mixture was reacted at 65 ° C. for 3 hours. After cooling the reaction solution to room temperature (about 25 ° C.), 120 parts of dichloromethane was added and washed with 200 parts of distilled water until the pH became neutral. By transferring the dichloromethane layer to a rotary evaporator and distilling off the solvent, 38.7% of [4- (phenylthio) phenyl] phenyl sulfide and 61.3% of [4- (phenylthio) phenyl] phenyl sulfoxide were obtained. 9.8 parts of a mixture containing were obtained. ¹ H-NMR data of [4- (phenylthio) phenyl] phenyl sulfoxide: {d6-dimethyl sulfoxide, δ (ppm) 7.59-7.70 (4H, m), 7.40-7.55 (8H, m), 7.25-7.35 (2H, m)}. The content was calculated from the peak area ratio by HPLC analysis of the mixture.

Production Example 2 Production of a mixture of [4- (phenylthio) phenyl] phenyl sulfide and [4- (phenylthio) phenyl] phenyl sulfoxide-2
A brown liquid [4- (phenylthio) phenyl] phenyl sulfide was obtained in an amount of 37.3% and [4] in the same manner as in Production Example 1, except that 2.31 parts of 30% hydrogen peroxide aqueous solution was changed to 2.37 parts. 9.8 parts of a mixture containing 62.7% of-(phenylthio) phenyl] phenyl sulfoxide was obtained.

Production Example 3 Production of a mixture of [4- (phenylthio) phenyl] phenyl sulfide and [4- (phenylthio) phenyl] phenyl sulfoxide-3
The brown liquid [4- (phenylthio) phenyl] phenyl sulfide was changed to 42.2% and [4] in the same manner as in Production Example 1, except that 2.31 parts of 30% hydrogen peroxide aqueous solution was changed to 2.18 parts. 9.8 parts of a mixture containing 57.8% of-(phenylthio) phenyl] phenyl sulfoxide was obtained.

(Production Example 4) Production of a mixture of [4- (phenylthio) phenyl] phenyl sulfide and [4- (phenylthio) phenyl] phenyl sulfoxide-4
46.3% of brownish liquid [4- (phenylthio) phenyl] phenyl sulfide was obtained in the same manner as in Production Example 1 except that 2.31 parts of 30% hydrogen peroxide aqueous solution was changed to 2.02 parts. 9.7 parts of a mixture containing 53.7% of-(phenylthio) phenyl] phenyl sulfoxide was obtained.

Production Example 5 Production of a mixture of [4-[(2-methyl) phenylthio] phenyl] (2-methylphenyl) sulfide and [4-[(2-methyl) phenylthio] phenyl] (2-methylphenyl) sulfoxide 1. 30 parts of a 30% aqueous hydrogen peroxide solution with 10.0 parts of [4- (phenylthio) phenyl] phenyl sulfide and 11.0 parts of [4-[(2-methyl) phenylthio] phenyl] (2-methylphenyl) sulfide The amount of brown liquid [4-[(2-methyl) phenylthio] phenyl] (2-methylphenyl) sulfide was 42.3% as in Production Example 1, except that 31 parts were changed to 2.18 parts. 10.7 parts of a mixture containing 57.7% of [4-[(2-methyl) phenylthio] phenyl] (2-methylphenyl) sulfoxide was obtained. ¹ H-NMR data of [4-[(2-methyl) phenylthio] phenyl] (2-methylphenyl) sulfoxide: {d6-dimethylsulfoxide, δ (ppm) 7.40-7.65 (5H, m), 7.10-7.45 (7H, m), 2.30-2.40 (6H, d)}. The content of each compound was calculated from the peak area ratio by HPLC analysis of the mixture.

Production Example 6 Production of a mixture of [4-[(2-methoxy) phenylthio] phenyl] (2-methoxyphenyl) sulfide and [4-[(2-methoxy) phenylthio] phenyl] (2-methoxyphenyl) sulfoxide 1. 30 parts of a 30% aqueous hydrogen peroxide solution with 10.0 parts of [4- (phenylthio) phenyl] phenyl sulfide and 12.0 parts of [4-[(2-methoxy) phenylthio] phenyl] (2-methoxyphenyl) sulfide The amount of brown liquid [4-[(2-methoxy) phenylthio] phenyl] (2-methoxyphenyl) sulfide was 42.4% as in Production Example 1, except that 31 parts were changed to 2.18 parts. 11.7 parts of a mixture containing 57.6% of [4-[(2-methoxy) phenylthio] phenyl] (2-methoxyphenyl) sulfoxide was obtained. It was. ¹ H-NMR data of [4-[(2-methoxy) phenylthio] phenyl] (2-methoxyphenyl) sulfoxide: {d6-dimethylsulfoxide, δ (ppm) 7.35-7.45 (5H, m), 7.00-7.35 (7H, m), 3.60-3.75 (6H, d)}. The content of each compound was calculated from the peak area ratio by HPLC analysis of the mixture.

(Production Example 7) Synthesis of 2- (phenylthio) thioxanthone 11.0 parts of 2-chlorothioxanthone, 4.9 parts of thiophenol, 2.5 parts of potassium hydroxide and 162 parts of N, N-dimethylformamide were uniformly mixed. After reacting at 130 ° C. for 9 hours, the reaction solution was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. The product was purified by column chromatography (eluent: toluene / hexane = 1/1: volume ratio) to give 2- (phenylthio) thioxanthone in a yield of 45%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.43 (1H, d), 8.25 (1H, s), 7.75-7.90 (3H, m ), 7.66 (1H, d), 7.60 (1H, t), 7.42-7.46 (5H, m)}.

[Example 1]
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tris (pentafluoroethyl) trifluorophosphate [compound (a)] and 1,4-bis {4-[[4- (phenylthio)] Preparation of a mixture of phenylphenyl] sulfonio] phenylthio} benzene bis [tris (pentafluoroethyl) trifluorophosphate] [compound (b)]-1

Mixture prepared in Preparation Example 1 [mixture containing 39% of [4- (phenylthio) phenyl] phenyl sulfide and 61% of [4- (phenylthio) phenyl] phenyl sulfoxide], 2.8 parts of acetic anhydride, and 16.5 parts of acetonitrile was charged and mixed uniformly, and 1.6 parts of trifluoromethanesulfonic acid was added dropwise at room temperature. Thereafter, the reaction is carried out at 60 ° C. for 2 hours, the reaction solution is cooled to room temperature (about 25 ° C.), poured into 100 parts of distilled water, extracted with 80 parts of dichloromethane, and until the pH of the aqueous layer becomes neutral. Washed with water. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a brown liquid product. After adding 5 parts of ethyl acetate and dissolving in a 60 ° C water bath, adding 50 parts of hexane and stirring, let stand for 30 minutes in a refrigerator (about 5 ° C) and then remove the supernatant twice. And the product was washed. By transferring the residue to a rotary evaporator and distilling off the solvent, phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium triflate (triflate = trifluoromethanesulfonic acid anion) and 1,4 4.9 parts of a mixture of -bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] phenylthio} benzene bis (triflate) was obtained.

The above triflate is dissolved in 75 parts of dichloromethane, charged into 52.7 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate, and stirred at room temperature (about 25 ° C.) for 3 hours. After liquid separation, washing with water three times, transferring the organic layer to a rotary evaporator and distilling off the solvent, phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tris (pentafluoro Ethyl) trifluorophosphate [compound (a)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] phenylthio} benzene bis [tris (pentafluoroethyl) trifluorophosphate] [compound ( b)] [mole of compound (a) and compound (b) The ratio was 50 mol% and 50 mol%, respectively]. 7.2 parts were obtained. The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethyl sulfoxide; δ (ppm) 7.6 to 8.0 (m), 7.3 to 7.6 (m). IR (KBr tablet method: CF bond characteristic absorption; around 1200 cm ^−1. LC-MS: molecular ion peak of compound (a); 588, molecular ion peak of compound (b); 441}, and ratio of the mixture (Mole%) was calculated from the peak area ratio by HPLC analysis.

[Example 2]
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tris (pentafluoroethyl) trifluorophosphate [compound (a)] and 1,4-bis {4-[[4- (phenylthio)] Preparation of a mixture of phenylphenyl] sulfonio] phenylthio} benzene bis [tris (pentafluoroethyl) trifluorophosphate] [compound (b)]-2
4.6 parts of a mixture containing 39% of [4- (phenylthio) phenyl] phenylsulfide prepared in Preparation Example 1 and 61% of [4- (phenylthio) phenyl] phenylsulfoxide was prepared in Preparation Example 2 [4- In the same manner as in Example 1, except that the mixture was changed to 4.5 parts of a mixture containing 37% of (phenylthio) phenyl] phenyl sulfide and 63% of [4- (phenylthio) phenyl] phenyl sulfoxide, phenyl [4- (4 -Phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tris (pentafluoroethyl) trifluorophosphate [compound (a)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] phenylthio } Benzene bis [tris (pentafluoroethyl) trifluorophosphate 7.1 parts of a mixture of [sulfate] [compound (b)] (molar ratios of compound (a) and compound (b) were 40 mol% and 60 mol%, respectively) were obtained.

Example 3
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tris (pentafluoroethyl) trifluorophosphate [compound (a)] and 1,4-bis {4-[[4- (phenylthio)] Phenylphenyl] sulfonio] phenylthio} benzene Preparation of a mixture of bis [tris (pentafluoroethyl) trifluorophosphate] [compound (b)]-3
4.6 parts of a mixture containing 39% of [4- (phenylthio) phenyl] phenylsulfide prepared in Preparation Example 1 and 61 of [4- (phenylthio) phenyl] phenylsulfoxide was prepared in Preparation Example 3. In the same manner as in Example 1, except that the mixture was changed to 4.9 parts of a mixture containing 42% of phenylthio) phenyl] phenyl sulfide and 58% of [4- (phenylthio) phenyl] phenyl sulfoxide. Phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium Tris (pentafluoroethyl) trifluorophosphate [compound (a)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] phenylthio} Benzene bis [tris (pentafluoroethyl) trifluorophos 7.4 parts of a mixture of [fate] [compound (b)] (molar ratios of compound (a) and compound (b) were 70 mol% and 30 mol%, respectively) were obtained.

Example 4
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tris (pentafluoroethyl) trifluorophosphate [compound (a)] and 1,4-bis {4-[[4- (phenylthio)] Phenylphenyl] sulfonio] phenylthio} benzene Preparation of a mixture of bis [tris (pentafluoroethyl) trifluorophosphate] [compound (b)]-4
4.6 parts of a mixture containing 39% of [4- (phenylthio) phenyl] phenyl sulfide prepared in Preparation Example 1 and 61% of [4- (phenylthio) phenyl] phenyl sulfoxide was prepared in Preparation Example 4. In the same manner as in Example 1, except that the mixture was changed to 5.2 parts of a mixture containing 46% (phenylthio) phenyl] phenylsulfide and 54% [4- (phenylthio) phenyl] phenylsulfoxide, phenyl [4- (4 -Phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tris (pentafluoroethyl) trifluorophosphate [compound (a)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] phenylthio } Benzene bis [tris (pentafluoroethyl) trifluorophosphate 7.8 parts of a mixture of [sulfate] [compound (b)] (molar ratios of compound (a) and compound (b) were 90 mol% and 10 mol%, respectively) were obtained.

Example 5
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (c)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl Sulphonio] phenylthio} benzene Preparation of a mixture of bis [tetrakis (pentafluorophenyl) borate] [compound (d)]-1

Except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 52.7 parts” was changed to “10% tetrakis (pentafluorophenyl) lithium borate aqueous solution 74.6 parts”, the same procedure as in Example 1 was performed. Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (c)] and 1,4-bis {4-[[4- (phenylthio)] Phenylphenyl] sulfonio] phenylthio} benzene mixture of bis [tetrakis (pentafluorophenyl) borate] [compound (d)] [molar ratios of compound (c) and compound (d) are 50 mol% and 50 mol%, respectively. 9.0 parts were obtained. The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethyl sulfoxide; δ (ppm) 7.6 to 8.0 (m), 7.3 to 7.6 (m). IR (KBr tablet method): BC bond characteristic absorption; near 980 cm ⁻¹ . LC-MS: molecular ion peak of compound (c); 588, molecular ion peak of compound (d); 441}. The ratio (mol%) of the mixture was calculated from the peak area ratio by HPLC analysis.

Example 6
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (c)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl Sulphonio] phenylthio} benzene Preparation of a mixture of bis [tetrakis (pentafluorophenyl) borate] [compound (d)]-2
Except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 52.7 parts” was changed to “10% tetrakis (pentafluorophenyl) lithium borate aqueous solution 74.6 parts”, the same procedure as in Example 2 was performed. Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (c)] and 1,4-bis {4-[[4- (phenylthio)] Phenylphenyl] sulfonio] phenylthio} benzene A mixture of bis [tetrakis (pentafluorophenyl) borate] [compound (d)] [molar ratios of compound (c) and compound (d) are 40 mol% and 60 mol%, respectively. 8.9 parts were obtained.

Example 7
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (c)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl Sulphonio] phenylthio} benzene Preparation of a mixture of bis [tetrakis (pentafluorophenyl) borate] [compound (d)]-3
Except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 52.7 parts” was changed to “10% tetrakis (pentafluorophenyl) lithium borate aqueous solution 74.6 parts”, the same procedure as in Example 3 was performed. Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (c)] and 1,4-bis {4-[[4- (phenylthio)] Phenylphenyl] sulfonio] phenylthio} benzene Mixture of bis [tetrakis (pentafluorophenyl) borate] [compound (d)] [molar ratios of compound (c) and compound (d) are 70 mol% and 30 mol%, respectively. 9.2 parts were obtained.

Example 8
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (c)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl Sulphonio] phenylthio} benzene Preparation of a mixture of bis [tetrakis (pentafluorophenyl) borate] [compound (d)]-4
Except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 52.7 parts” was changed to “10% tetrakis (pentafluorophenyl) lithium borate aqueous solution 74.6 parts”, the same procedure as in Example 4 was performed. Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (c)] and 1,4-bis {4-[[4- (phenylthio)] Phenylphenyl] sulfonio] phenylthio} benzene A mixture of bis [tetrakis (pentafluorophenyl) borate] [compound (d)] [molar ratios of compound (c) and compound (d) are 90 mol% and 10 mol%, respectively. 9.6 parts were obtained.

Example 9
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium hexafluoroantimonate [compound (e)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] Preparation of a mixture of phenylthio} benzene bis [hexafluoroantimonate] [compound (f)]

In the same manner as in Example 3 except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 52.7 parts” was changed to “5% potassium hexafluoroantimonate aqueous solution 59.8 parts”, phenyl [ 4- (4-Phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium hexafluoroantimonate [compound (e)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] phenylthio} 5.8 parts of a mixture of benzene bis [hexafluoroantimonate] [compound (f)] (molar ratios of compound (e) and compound (f) were 70 mol% and 30 mol%, respectively) were obtained. .
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethyl sulfoxide; δ (ppm) 7.6 to 8.0 (m), 7.3 to 7.6 (m). IR (KBr tablet method): Sb—F bond characteristic absorption; around 650 cm ⁻¹ . LC-MS: molecular ion peak of compound (e); 588, molecular ion peak of compound (f); 441}. The ratio (mol%) of the mixture was calculated from the peak area ratio by HPLC analysis.

Example 10
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium hexafluorophosphate [compound (g)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] phenylthio } Production of a mixture of benzene bis [hexafluorophosphate] [compound (h)]

In the same manner as in Example 3 except that “52.7 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate” was changed to “40.1 parts of 5% aqueous potassium hexafluorophosphate”, phenyl [ 4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium hexafluorophosphate [compound (g)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] phenylthio} benzene 5.2 parts of a mixture of bis [hexafluorophosphate] [compound (h)] [molar ratios of compound (g) and compound (h) were 70 mol% and 30 mol%, respectively] were obtained.
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethyl sulfoxide; δ (ppm) 7.6 to 8.0 (m), 7.3 to 7.6 (m). IR (KBr tablet method): PF bond characteristic absorption; around 840 cm ⁻¹ . LC-MS: molecular ion peak of compound (g); 588, molecular ion peak of compound (h); 441}. The ratio (mol%) of the mixture was calculated from the peak area ratio by HPLC analysis.

Example 11
(2-methyl) phenyl {[4- [4- (2-methyl) phenylthio] phenylthio] -3-methyl-phenyl} [4- (2-methyl) phenylthio] phenylsulfonium tris (pentafluoroethyl) trifluorophosphate [Compound (i)] and 1,4-bis {4-[[4-((2-methyl) phenylthio) phenyl (2-methyl) phenyl] sulfonio] -2- (methyl) phenylthio} benzene bis [tris ( Preparation of a mixture of (pentafluoroethyl) trifluorophosphate] [compound (j)]

4.6 parts of a mixture containing 39% of [4- (phenylthio) phenyl] phenyl sulfide prepared in Preparation Example 1 and 61% of [4- (phenylthio) phenyl] phenyl sulfoxide was prepared in Preparation Example 5. A mixture containing 42% [(2-methyl) phenylthio] phenyl] (2-methylphenyl) sulfide and 58% [4-[(2-methyl) phenylthio] phenyl] (2-methylphenyl) sulfoxide 5.3 (2-Methyl) phenyl [4- [4- (2-methyl) phenylthio] phenylthio] phenyl [4- (2-methyl) phenylthio] phenylsulfonium tris () Pentafluoroethyl) trifluorophosphate [compound (i)] and 1,4-bis {4-[[4-((2-methyl) phenyl] Nylthio) phenyl (2-methyl) phenyl] sulfonio] -2- (methyl) phenylthio} benzene A mixture of bis [tris (pentafluoroethyl) trifluorophosphate] [compound (j)] [compound (i) and compound (j) ) Was 70 mol% and 30 mol%, respectively].
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethyl sulfoxide; δ (ppm) 7.6 to 8.0 (m), 7.3 to 7.6 (m), 2.3 to 2.4 (m). IR (KBr tablet method): CF bond characteristic absorption; around 1200 cm ⁻¹ . LC-MS: molecular ion peak of compound (i); 644, molecular ion peak of compound (j); 483}. The ratio (mol%) of the mixture was calculated from the peak area ratio by HPLC analysis.

Example 12
(2-methyl) phenyl {[4- [4- (2-methyl) phenylthio] phenylthio] -3-methyl-phenyl} [4- (2-methyl) phenylthio] phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (K)] and 1,4-bis {4-[[4-((2-methyl) phenylthio) phenyl (2-methyl) phenyl] sulfonio] -2- (methyl) phenylthio} benzene bis [tetrakis (pentafluoro Of phenyl) borate] [compound (m)]

4.6 parts of a mixture containing 39% of [4- (phenylthio) phenyl] phenyl sulfide prepared in Preparation Example 1 and 61% of [4- (phenylthio) phenyl] phenyl sulfoxide was prepared in Preparation Example 5. A mixture containing 42% [(2-methyl) phenylthio] phenyl] (2-methylphenyl) sulfide and 58% [4-[(2-methyl) phenylthio] phenyl] (2-methylphenyl) sulfoxide 5.3 Except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 52.7 parts” was changed to “10% tetrakis (pentafluorophenyl) lithium borate aqueous solution 74.6 parts”. In the same manner as in Example 1, (2-methyl) phenyl [4- [4- (2-methyl) phenylthio] phenylthio] phen [4- (2-methyl) phenylthio] phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (k)] and 1,4-bis {4-[[4-((2-methyl) phenylthio) phenyl (2 -Methyl) phenyl] sulfonio] -2- (methyl) phenylthio} benzene A mixture of bis [tetrakis (pentafluorophenyl) borate] [compound (m)] [molar ratio of compound (k) and compound (m) is 9.6 parts were obtained.
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethyl sulfoxide; δ (ppm) 7.6 to 8.0 (m), 7.3 to 7.6 (m), 2.3 to 2.4 (m). IR (KBr tablet method): BC bond characteristic absorption; near 980 cm ⁻¹ . LC-MS: molecular ion peak of compound (k); 644, molecular ion peak of compound (m); 483}. The ratio (mol%) of the mixture was calculated from the peak area ratio by HPLC analysis.

Example 13
(2-methoxy) phenyl {[4- [4- (2-methoxy) phenylthio] phenylthio] -3-methoxy-phenyl} [4- (2-methoxy) phenylthio] phenylsulfonium tris (pentafluoroethyl) trifluorophosphate [Compound (n)] and 1,4-bis {4-[[4-((2-methoxy) phenylthio) phenyl (2-methoxy) phenyl] sulfonio] -2- (methoxy) phenylthio} benzene bis [tris ( Preparation of a mixture of (pentafluoroethyl) trifluorophosphate] [compound (o)]

4.6 parts of a mixture containing 39% of [4- (phenylthio) phenyl] phenylsulfide prepared in Preparation Example 1 and 61% of [4- (phenylthio) phenyl] phenylsulfoxide was prepared in Preparation Example 6 [4- A mixture of 42% [(2-methoxy) phenylthio] phenyl] (2-methoxyphenyl) sulfide and 58% [4-[(2-methoxy) phenylthio] phenyl] (2-methoxyphenyl) sulfoxide 5.8 (2-methoxy) phenyl [4- [4- (2-methoxy) phenylthio] phenylthio] phenyl [4- (2-methoxy) phenylthio] phenylsulfonium tris (Example 1) Pentafluoroethyl) trifluorophosphate [compound (n)] and 1,4-bis {4-[[4-(( -Methoxy) phenylthio) phenyl (2-methoxy) phenyl] sulfonio] -2- (methoxy) phenylthio} benzene mixture of bis [tris (pentafluoroethyl) trifluorophosphate] [compound (o)] [compound (n) and The molar ratios of the compound (o) were 70 mol% and 30 mol%, respectively.] 8.3 parts were obtained.
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethyl sulfoxide; δ (ppm) 7.6 to 8.0 (m), 7.3 to 7.6 (m), 3.6 to 3.75 (m). IR (KBr tablet method): CF bond characteristic absorption; around 1200 cm ⁻¹ . LC-MS: molecular ion peak of compound (n); 710, molecular ion peak of compound (o); 531}. The ratio (mol%) of the mixture was calculated from the peak area ratio by HPLC analysis.

Example 14
(2-methoxy) phenyl {[4- [4- (2-methoxy) phenylthio] phenylthio] -3-methoxy-phenyl} [4- (2-methoxy) phenylthio] phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (P)] and 1,4-bis {4-[[4-((2-methoxy) phenylthio) phenyl (2-methoxy) phenyl] sulfonio] -2- (methoxy) phenylthio} benzene bis [tetrakis (pentafluoro Synthesis of a mixture of [phenyl] borate] [compound (q)]

4.6 parts of a mixture containing 39% of [4- (phenylthio) phenyl] phenyl sulfide prepared in Preparation Example 1 and 61% of [4- (phenylthio) phenyl] phenyl sulfoxide was prepared in Preparation Example 6 [4- A mixture of 42% [(2-methoxy) phenylthio] phenyl] (2-methoxyphenyl) sulfide and 58% [4-[(2-methoxy) phenylthio] phenyl] (2-methoxyphenyl) sulfoxide 5.8 Except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 52.7 parts” was changed to “10% tetrakis (pentafluorophenyl) lithium borate aqueous solution 74.6 parts”. In the same manner as in Example 1, (2-methoxy) phenyl [4- [4- (2-methoxy) phenylthio] phenyl Thio] phenyl [4- (2-methoxy) phenylthio] phenylsulfonium tetrakis (pentafluorophenyl) borate [compound (p)] and 1,4-bis {4-[[4-((2-methoxy) phenylthio) phenyl (2-Methoxy) phenyl] sulfonio] -2- (methoxy) phenylthio} benzene A mixture of bis [tetrakis (pentafluorophenyl) borate] [compound (q)] [molar ratio of compound (p) to compound (q) is Were 70 mol% and 30 mol%, respectively].
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethyl sulfoxide; δ (ppm) 7.6 to 8.0 (m), 7.3 to 7.6 (m), 3.6 to 3.75 (m). IR (KBr tablet method): BC bond characteristic absorption; near 980 cm ⁻¹ . LC-MS: molecular ion peak of compound (p); 710, molecular ion peak of compound (q); 531}. The ratio (mol%) of the mixture was calculated from the peak area ratio by HPLC analysis.

Example 15
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tris (trifluoromethanesulfonyl) methide [compound (u)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl ] Sulphonio] phenylthio} benzene Preparation of a mixture of bis [tris (trifluoromethanesulfonyl) methide] [compound (v)] "52.7 parts of 10% aqueous tris (pentafluoroethyl) potassium trifluorophosphate" was replaced with "10% Tris In the same manner as in Example 3, except for changing to “(trifluoromethanesulfonyl) methide lithium aqueous solution 45.5 parts”, phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium tris (trifluoromethanesulfone) ) Methide [compound (u)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] phenylthio} benzene bis [tris (trifluoromethanesulfonyl) methide] [compound (v)] 7.2 parts of a mixture (molar ratios of the compound (u) and the compound (v) were 70 mol% and 30 mol%, respectively) were obtained.
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethyl sulfoxide; δ (ppm) 7.6 to 8.0 (m), 7.3 to 7.6 (m). IR (KBr tablet method: CF bond characteristic absorption; around 1200 cm ^−1. LC-MS: molecular ion peak of compound (a); 588, molecular ion peak of compound (b); 441). The ratio (mol%) of the mixture was calculated from the peak area ratio by HPLC analysis.

Example 16
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium bis (trifluoromethanesulfonyl) imide [compound (w)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl ] Sulphonio] phenylthio} benzene Preparation of a mixture of bis [bis (trifluoromethanesulfonyl) imide] [compound (x)] “52.7 parts of a 10% aqueous solution of potassium tris (pentafluoroethyl) trifluorophosphate” (Triphenylmethane) phenylsulfonium bis (trifluoromethane) in the same manner as in Example 3 except that it was changed to “31.2 parts of (trifluoromethanesulfonyl) imidolithium aqueous solution”. Sulfonyl) [Compound (w)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] phenylthio} benzene bis [bis (trifluoromethanesulfonyl) imide] [compound (x)] 5.9 parts of compound (w) and compound (x) were 70 mol% and 30 mol%, respectively.
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethyl sulfoxide; δ (ppm) 7.6 to 8.0 (m), 7.3 to 7.6 (m). IR (KBr tablet method: CF bond characteristic absorption; around 1200 cm ^−1. LC-MS: molecular ion peak of compound (a); 588, molecular ion peak of compound (b); 441). The ratio (mol%) of the mixture was calculated from the peak area ratio by HPLC analysis.

Example 17
Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium nonafluorobutanesulfonate [compound (y)] and 1,4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] Preparation of a mixture of phenylthio} benzene bis (nonafluorobutanesulfonate) [compound (z)] Mixture prepared in Preparation Example 3 [42% of [4- (phenylthio) phenyl] phenyl sulfide and [4- (phenylthio) phenyl] A mixture containing 58% of phenyl sulfoxide] 4.9 parts, 2.8 parts of acetic anhydride and 16.5 parts of acetonitrile were added and mixed uniformly, and 3.3 parts of nonafluorobutanesulfonic acid was added dropwise at room temperature. Subsequent operations were carried out in the same manner as in Example 1. Phenyl [4- (4-phenylthio) phenylthio] phenyl (4-phenylthio) phenylsulfonium nonaflate (nonaflate = nonafluorobutanesulfonate anion) [compound (y)] and 1 , 4-bis {4-[[4- (phenylthio) phenylphenyl] sulfonio] phenylthio} benzene mixture of bis (nonaflate) [compound (z)] [molar ratio of compound (y) and compound (z) is 6.3 parts were obtained.
The product was identified by ¹ H-NMR, infrared absorption spectroscopy (IR), and LC-MS. { ¹ H-NMR: d6-dimethyl sulfoxide; δ (ppm) 7.6 to 8.0 (m), 7.3 to 7.6 (m). IR (KBr tablet method: CF bond characteristic absorption; around 1200 cm ^−1. LC-MS: molecular ion peak of compound (a); 588, molecular ion peak of compound (b); 441). The ratio (mol%) of the mixture was calculated from the peak area ratio by HPLC analysis.

[Comparative Example 1]
CPI-110P [4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, manufactured by San Apro Co., Ltd.] was used as a comparative sulfonium salt.

[Comparative Example 2]
CPI-110A [4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, manufactured by San Apro Co., Ltd.] was used as a comparative sulfonium salt.

[Comparative Example 3]
Synthesis of 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate (compound (r))

While stirring 12.1 parts of diphenyl sulfoxide, 9.3 parts of diphenyl sulfide and 43.0 parts of methanesulfonic acid, 7.9 parts of acetic anhydride was added dropwise thereto and reacted at 40 to 50 ° C. for 5 hours. After cooling to room temperature (about 25 ° C.), the reaction solution was put into 121 parts of 20% aqueous potassium tris (pentafluoroethyl) trifluorophosphate and stirred at room temperature (about 25 ° C.) for 1 hour. A viscous oil precipitated. This oily substance was extracted with ethyl acetate, the organic layer was washed several times with water, the solvent was distilled off from the organic layer, and toluene was added to the resulting residue to dissolve it. The mixture was stirred well for 1 hour and allowed to stand. After 1 hour, since the solution was separated into two layers, the upper layer was removed by liquid separation. When hexane was added to the remaining lower layer and mixed well at room temperature (about 25 ° C.), pale yellow crystals were precipitated. This was filtered off and dried under reduced pressure to obtain 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate in a yield of 60%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.72-7.87 (12H, m), 7.54-7.63 (5H, m), 7.42. (2H, d)}. In addition, absorption of C—F bond was confirmed in the vicinity of 1200 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

[Comparative Example 4]
Synthesis of 4- (phenylthio) phenyldiphenylsulfonium tetrakis (pentafluorophenyl) borate (compound (s))

4 except that “20% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 121 parts” was changed to “10% lithium tetrakis (pentafluorophenyl) lithium borate 342.9 parts”. -(Phenylthio) phenyldiphenylsulfonium tetrakis (pentafluorophenyl) borate was obtained in a yield of 60%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.72-7.87 (12H, m), 7.54-7.63 (5H, m), 7.42. (2H, d)}. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

[Comparative Example 5]
Synthesis of diphenyl-2-thioxanthonylsulfonium tris (pentafluoroethyl) trifluorophosphate (compound (t))

15.0 parts of 2- (phenylthio) thioxanthone synthesized in Production Example 7, 41.9 parts of diphenyliodonium hexafluorophosphate, 0.4 part of copper (II) benzoate and 300 parts of chlorobenzene were uniformly mixed at 120 to 125 ° C. Then, the reaction solution was cooled to room temperature (about 25 ° C.) and poured into 300 parts of distilled water to precipitate the product. This was filtered, the residue was washed with water until the pH of the filtrate became neutral, the residue was dried under reduced pressure, 100 parts of diethyl ether was added, and the mixture was dispersed in diethyl ether with an ultrasonic cleaner and allowed to stand for about 15 minutes. Then, the operation of removing the supernatant was repeated 3 times to wash the produced solid. The solid was then transferred to a rotary evaporator and the solvent was distilled off to obtain a yellow solid. This yellow solid was dissolved in 770 parts of dichloromethane and charged into 342 parts of a 10% aqueous solution of potassium tris (pentafluoroethyl) trifluorophosphate, followed by stirring at room temperature (about 25 ° C.) for 2 hours and the organic layer several times with water. By washing and drying under reduced pressure, diphenyl-2-thioxanthonylsulfonium tris (pentafluoroethyl) trifluorophosphate was obtained with a yield of 98% and a purity of 85%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.72 (1H, s), 8.47 (1H, d), 8.30 (1H, d), 8. 13 (2H, d), 7.78-7.98 (11 H, m), 7.70 (1 H, t)}. Purity was quantified by HPLC. Further, absorption of C—F bond was confirmed in the vicinity of 1200 cm ⁻¹ by infrared absorption analysis (KBr tablet method).

<Evaluation of energy beam curable composition>
1. Preparation of curable composition Evaluation sample {sulfonium salt of Examples 1 to 15 and Comparative Examples 1 to 5} and epoxide (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Dow Chemical Co., Ltd. , UVR-6110) at 60 ° C. in the blending amounts (parts by weight) shown in Table 1, and uniformly mixed to prepare a composition for a photocuring test.

The sulfonium salt obtained in Example 10 and Comparative Example 1 is hexafluorophosphate, and tris (pentafluoroethyl) trifluorophosphoric acid obtained in Examples 1 to 9, 11 to 15 and Comparative Examples 2 to 5 was used. Incorporation of sulfonium salt due to weaker acid strength and lower activity against cationic polymerization than acid salt, hexafluoroantimonate, tetrakis (pentafluorophenyl) borate and tris (trifluoromethanesulfonyl) methide salt Increased the amount.

2. Photocurability evaluation The curable composition obtained above was applied to a polyethylene terephthalate (PET) film with an applicator (40 μm). The PET film was irradiated with ultraviolet light having a wavelength limited by a filter using an ultraviolet irradiation device. The filter used was a 365 filter (manufactured by Eye Graphics Co., Ltd., a filter that cuts light of less than 365 nm) and L-34 (manufactured by Kenko Optical Co., Ltd., a filter that cuts light of less than 340 nm). After irradiation, the film hardness after 40 minutes was measured by pencil hardness (JIS K5600-5-4: 1999) and evaluated according to the following criteria (coating thickness after curing was about 40 μm). It was shown in 2. The higher the pencil hardness, the better the photocurability of the energy ray-curable composition, that is, the better the polymerization initiation ability of the sulfonium salt with respect to the cationically polymerizable compound (the photosensitivity of the sulfonium salt).

(Evaluation criteria)
◎: Pencil hardness is 2H or more ○: Pencil hardness is H to B
Δ: Pencil hardness is 2B-4B
×: There is liquid to tack, and pencil hardness cannot be measured

(Ultraviolet light irradiation conditions)
・ Ultraviolet irradiation device: Belt conveyor type UV irradiation device (manufactured by Eye Graphics Co., Ltd.)
・ Lamp: 1.5kW high pressure mercury lamp ・ Filter: 365 filter (manufactured by Eye Graphics Co., Ltd.)
L-34 (manufactured by Kenko Optical Co., Ltd.)
Illuminance (measured with a 365 nm head illuminometer): 145 mW / cm ²

-Integrated light quantity (measured with 365nm head illuminometer):
Condition-1: 200 mJ / cm ²
Condition-2: 400 mJ / cm ²
Condition-3: 600 mJ / cm ²

3. Storage stability evaluation (sample preparation)
3 parts of an evaluation sample {sulfonium salt of Examples 1 to 15 and Comparative Examples 1 to 5} and epoxide (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Dow Chemical Co., Ltd., UVR-6110 ) 100 parts of each were blended, mixed at 60 ° C., and then mixed uniformly to prepare a storage stability test sample.
This blended sample was heated at 80 ° C. under light shielding and stored for 1 month, and then the viscosity of the blended sample before and after heating was measured and evaluated according to the following criteria. The storage stability is better as the viscosity does not increase.
(Evaluation criteria)
X: Viscosity change after heating is 1.5 times or more.
○: Viscosity change after heating is less than 1.5 times.
These results are shown in Table 2.

As can be seen from the results in Table 2, it was found that the sulfonium salt of the present invention was superior in curing performance (photosensitivity) of the cationically polymerizable compound under ultraviolet light of 365 nm or more as compared with the comparative sulfonium salt. . Moreover, it turned out that storage stability worsens, when the ratio of the sulfonium salt shown by Formula (2) increases.

The sulfonium salt of the present invention comprises a coating material, a coating agent, various coating materials (hard coat, antifouling coating material, antifogging coating material, touchproof coating material, optical fiber, etc.), a back surface treatment agent for adhesive tape, and a release sheet for an adhesive label. Release coating materials (release paper, release plastic film, release metal foil, etc.), printing plates, dental materials (dental compounds, dental composites, etc.), inks, inkjet inks, positive resists (circuit boards, CSP, Used for connecting terminals and wiring patterns for manufacturing electronic components such as MEMS elements), resist films, liquid resists, negative resists (formation of permanent films such as surface protective films for semiconductor elements, interlayer insulating films, planarization films, etc.) ), MEMS resist, positive photosensitive material, negative photosensitive material, various adhesives (temporary fixing agent for various electronic parts, adhesion for HDD) , Pickup lens adhesive, FPD functional film (deflection plate, antireflection film, etc.), holographic resin, FPD material (color filter, black matrix, partition material, photospacer, rib, liquid crystal Used for forming alignment films and sealing agents for FPDs, etc.), optical members, molding materials (for building materials, optical components, lenses, etc.), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, It is suitably used as a photoacid generator for use in encapsulants, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, photofabrication, and micro stereolithography materials.

Claims

A photoacid generator comprising a sulfonium salt represented by the following formula (1) and a sulfonium salt represented by (2).

[In the formulas (1) and (2), R 1 to R 9 are independently of each other an alkyl group, a hydroxyl group, an alkoxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl. Ruthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group , Represents an optionally substituted amino group, cyano group, nitro group or halogen atom, m 1 to m 9 represent the number of R 1 to R 9 , and m 4 , m 6 , m 7 and m 9 represent an integer of 0 to 5, an integer of m 1, m 2, m 3 , m 5 and m 8 0-4 And, A 1 is S or SO, X - represents an monovalent polyatomic anion. ]
For R 1 to R 9 , the alkyl group is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms, and the alkoxyl group Is a straight-chain alkoxyl group having 1 to 18 carbon atoms or a branched-chain alkoxyl group having 3 to 18 carbon atoms, and the alkylcarbonyl group is a straight-chain alkylcarbonyl group having 2 to 18 carbon atoms or a group having 4 to 18 carbon atoms. A branched alkylcarbonyl group, the arylcarbonyl group is an arylcarbonyl group having 7 to 11 carbon atoms, and the alkoxycarbonyl group is a linear alkoxycarbonyl group having 2 to 19 carbon atoms or a branched chain having 4 to 19 carbon atoms. A chain alkoxycarbonyl group, the aryloxycarbonyl group is an aryloxycarbonyl group having 7 to 11 carbon atoms, and the arylthiocarbonyl group is a carbon atom. An arylthiocarbonyl group having 7 to 11 carbon atoms, wherein the acyloxy group is a linear acyloxy group having 2 to 19 carbon atoms or a branched chain acyloxy group having 4 to 19 carbon atoms, and the arylthio group has 6 to 20 carbon atoms The alkylthio group is a linear alkylthio group having 1 to 18 carbon atoms or a branched alkylthio group having 3 to 18 carbon atoms, and the aryl group is an aryl group having 6 to 10 carbon atoms, The heterocyclic hydrocarbon group is a heterocyclic hydrocarbon group having 4 to 20 carbon atoms, the aryloxy group is an aryloxy group having 6 to 10 carbon atoms, and the alkylsulfinyl group is 1 to 18 carbon atoms. A straight-chain alkylsulfinyl group or a branched alkylsulfinyl group having 3 to 18 carbon atoms, and the arylsulfinyl group is an arylsulfinyl group having 6 to 10 carbon atoms, The alkylsulfonyl group is a straight-chain alkylsulfonyl group having 1 to 18 carbon atoms or a branched alkylsulfonyl group having 3 to 18 carbon atoms, and the arylsulfonyl group is an arylsulfonyl group having 6 to 10 carbon atoms; The (poly) alkyleneoxy group has the formula (3),

[AO represents an ethyleneoxy group and / or propyleneoxy group, and q represents an integer of 1 to 5. And the optionally substituted amino group may include an amino group (—NH 2 ) or a saturated hydrocarbon group or aromatic group having 1 to 15 carbon atoms. The photoacid generator according to claim 1, which is a substituted amino group substituted with a hydrocarbon group, and the halogen atom group is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The photoacid generator according to claim 1 or 2, wherein R 1 to R 9 independently represent one selected from the group consisting of a methyl group, a methoxy group, and an acetyl group.
4. The photoacid generator according to claim 1, wherein m 1 to m 9 are all 0.
X − represents MY a − , (Rf) b PF 6-b − , R 10 c BY 4-c − , R 10 c GaY 4-c − , R 11 SO 3 − , (R 11 SO 2 ) 3 C An anion represented by — or (R 11 SO 2 ) 2 N — , wherein M is a phosphorus atom, boron atom, arsenic atom or antimony atom, Y is a halogen atom, Rf is 80 mol% or more of hydrogen atoms is fluorine An alkyl group substituted with an atom, P is a phosphorus atom, F is a fluorine atom, R 10 is a phenyl group in which at least one hydrogen atom is substituted with a halogen atom, a trifluoromethyl group, a nitro group or a cyano group, B Is a boron atom, Ga is a gallium atom, R 11 is an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, a is an integer of 4 to 6, b Is 1-5 , C is an integer of 1-4. The photoacid generator according to any one of claims 1 to 4, wherein
X − represents PF 6 − , SbF 6 − , (CF 3 CF 2 ) 3 PF 3 − , (C 6 F 5 ) 4 B − , ((CF 3 ) 2 C 6 H 3 ) 4 B − , (C 6. The anion represented by 6 F 5 ) 4 Ga − , ((CF 3 ) 2 C 6 H 3 ) 4 Ga − or (CF 3 SO 2 ) 3 C —. Photoacid generator.
Of the total amount of the sulfonium salt represented by formula (1) and the sulfonium salt represented by (2) contained in the photoacid generator, the proportion of the sulfonium salt represented by formula (1) is at least 50 mol%. The photoacid generator according to any one of claims 1 to 6, wherein
An energy ray-curable composition comprising the photoacid generator according to claim 1 and a cationically polymerizable compound.
A cured product obtained by curing the energy beam curable composition according to claim 8.