JP5576139B2 - Sulfonium salt, photoacid generator, photocurable composition, and cured product thereof - Google Patents

Description

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

  Conventionally, triarylsulfonium salts (Patent Document 1), naphthalene are used as photopolymerization initiators used for curing cationically polymerizable compounds such as epoxy compounds by the action of active energy rays such as light, electron beam or X-ray. A phenacylsulfonium salt having a skeleton (Patent Document 2), a dialkylbenzylsulfonium salt (Patent Document 3), a sulfonium salt having a thioxanthone skeleton introduced (Patent Document 4), and an oxime sulfonate compound (Patent Document 5) are known. Yes.

Japanese Patent Laid-Open No. 50-151997 JP-A-9-118663 JP-A-2-178303 JP-A-8-165290 JP 2000-66385 A

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, it is considered that the need for a photopolymerization initiator exhibiting high sensitivity to i-line will further increase in the future.
However, among existing photopolymerization initiators, 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. Further, the oxime sulfonate compound (Patent Document 5) is sensitive to i-line, but has poor storage stability.
An object of the present invention is to provide a new sulfonium salt having high photosensitivity to i-line.

  The present inventor has synthesized a sulfonium salt represented by the following formula (1) and found it suitable for the above purpose. That is, the sulfonium salt of the present invention has the formula (1)

[In the formula (1), R ^{1 to} R ⁶ are each an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an 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, amino which may be substituted Represents a group, a cyano group, a nitro group or a halogen atom, m ^{1 to} m ⁶ each represents the number of R ^{1 to} R ⁶ , m ¹ , m ⁴ and m ⁶ are integers from 0 to 5, m ² , m ³ and m ⁵ represent an integer of 0 to 4, and X ⁻ represents a monovalent polyatomic anion. ] Is shown.

  The present invention also provides a photoacid generator characterized by containing the sulfonium salt.

  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 is excellent in photosensitivity to active energy rays such as visible light, ultraviolet rays, electron beams and X-rays.
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 can be used for paints, coating agents, inks, inkjet inks, positive resists (formation of connection terminals and wiring patterns for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, etc.), resist films, liquid resists. , Negative resist (permanent film materials such as semiconductor device surface protection film, interlayer insulation film, planarization film, etc.), MEMS resist, photosensitive material, various adhesives, molding material, casting material, putty, glass As a photoacid generator used in fiber impregnating agents, sealing materials, sealing materials, sealing materials, optical semiconductor (LED) sealing materials, nanoimprint materials, optical waveguide materials, optical modeling materials, and micro-optical modeling materials , Is preferred. Moreover, the energy beam curable composition and the cured product of the present invention are suitable for the above applications.

In the formula (1), among R ^{1 to} R ⁶ , 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 1 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 ⁶ , the alkoxy group is a linear or branched alkoxy group having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyl). Oxy, decyloxy, dodecyloxy, octadecyloxy, etc.).

Among R ^{1 to} R ⁶ , the alkylcarbonyl group is a linear or branched alkylcarbonyl group having 2 to 18 carbon atoms (acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3 -Methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl and the like).

Among R ^{1 to} R ⁶ , examples of the arylcarbonyl group include arylcarbonyl groups having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

Among R ^{1 to} R ⁶ , the alkoxycarbonyl group is a straight or branched alkoxycarbonyl group having 2 to 18 carbon atoms (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxy). Carbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc.).

Among R ^{1 to} R ⁶ , examples of the aryloxycarbonyl group include aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

Among R ^{1 to} R ⁶ , examples of the arylthiocarbonyl group include arylthiocarbonyl groups having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

Among R ^{1 to} R ⁶ , the acyloxy group is a linear or branched acyloxy group having 2 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 ⁶ , 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] Enylthio, 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 ⁶ , the alkylthio group is a linear or branched alkylthio group having 1 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 ⁶ , 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 ⁶ , 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 ⁶ , examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

Among R ^{1 to} R ⁶ , the alkylsulfinyl group is a linear or branched sulfinyl group having 1 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butyl). Sulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, isooctadecylsulfinyl, etc.).

Among R ^{1 to} R ⁶ , 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 ⁶ , the alkylsulfonyl group is a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec- Butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, octadecylsulfonyl, etc.).

Among R ^{1 to} R ⁶ , 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 ⁶ , examples of the hydroxy (poly) alkyleneoxy group include a hydroxy (poly) alkyleneoxy group represented by the formula (2).

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

Among R ^{1 to} R ⁶ , an amino group includes an amino group (—NH ₂ ) and a substituted amino group having 1 to 15 carbon atoms (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 and the like).

Among R ^{1 to} R ⁶ , examples of the halogen atom group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ^{1 to} R ⁶ are independent of each other, and therefore may be the same as or different from each other.

Of R ^{1 to} R ⁶ , preferred are an alkyl group, an alkoxy group, an alkylcarbonyl group and a halogen atom, and particularly preferred are a methyl group, a methoxy group and an acetyl group.

m ^{1 to} m ⁶ each represent the number of R ^{1 to} R ⁶ , and m ¹ , m ⁴ and m ⁶ are integers of 0 to 5, preferably 0 to 3, more preferably 0 to 2, particularly preferably. Is 0 or 1. M ² , m ³ and m ⁵ are integers of 0 to 4, preferably 0 to 3, more preferably 0 to 2, particularly preferably 0 or 1. When m ^{1 to} m ⁶ are in these preferable ranges, the photosensitivity of the sulfonium salt is further improved.

  Of the sulfoniums represented by formula (1), the following are preferred.

  Of these sulfoniums, the following are particularly preferable from the viewpoint of photosensitivity.

In the formula (1), X ⁻ is an anion corresponding to an acid (HX) generated by irradiating the sulfonium salt of the present invention with an active energy ray (visible light, ultraviolet ray, electron beam, X-ray, etc.). X ⁻ is not limited except that it is a monovalent polyatomic anion, but MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ⁷ _c BY _4-c ⁻ , R ⁷ _c GaY _{4 ^{-c -, R 8 SO 3 -}} , (R 8 SO 2) 3 C - or _{^{(R 8 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 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 preferred 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 ⁷ 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. The c R ^{7 s} are independent of each other, and therefore may be the same as or different from each other.

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

R ⁸ 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, and 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 MY _a ⁻ include an anion represented by SbF ₆ ⁻ , PF ₆ ⁻ or BF ₄ ⁻ .

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 ⁻ , and ((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 ⁻ Anions and the like. 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 An anion represented by PF ₄ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ⁻ or ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ⁻ is preferred.

The anion represented _{by, (C 6 F 5) 4} B - - R 7 c BY 4-c, ((CF 3) 2 C 6 H 3) 4 B -, (CF 3 C 6 H 4) 4 Examples include an anion represented by B ⁻ , (C ₆ F ₅ ) ₂ BF ₂ ⁻ , C ₆ F ₅ BF ₃ ⁻ or (C ₆ H ₃ F ₂ ) ₄ B ⁻ . Of these, anions represented by (C ₆ F ₅ ) ₄ B ⁻ or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ are preferred.

The anion represented _{by, (C 6 F 5) 4} Ga - - R 7 c GaY 4-c, ((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 - an anion, and the like represented. Of _{these, (C 6 F 5) 4} Ga - or _{((CF 3) 2 C 6} H 3) 4 Ga - anion represented by are preferred.

Examples of the anion represented by R ⁸ SO ₃ ^— include trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nonafluorobutanesulfonate anion, pentafluorophenylsulfonate anion, p-toluene. Examples include sulfonate anion, benzenesulfonate anion, camphorsulfonate anion, methanesulfonate anion, ethanesulfonate anion, propanesulfonate anion and butanesulfonate anion. Of these, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, benzenesulfonate anion or p-toluenesulfonate anion is preferred.

Examples of the anion represented by (R ⁸ SO ₂ ) ₃ C ⁻ include (CF ₃ SO ₂ ) ₃ C ⁻ , (C ₂ F ₅ SO ₂ ) ₃ C ⁻ , and (C ₃ F ₇ SO ₂ ) ₃ C ^−. or _{(C 4 F 9 SO 2)} 3 C - anion such as represented and the like.

Examples of the anion represented by (R ⁸ SO ₂ ) ₂ N ⁻ include (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , and (C ₃ F ₇ SO ₂ ) ₂ N ^−. or _{(C 4 F 9 SO 2)} 2 N - anion, and the like represented.

The monovalent polyatomic ^{_{anion, MY a -, (Rf)}} b PF 6-b -, R 7 c BY 4-c -, R 7 c GaY 4-c -, R 8 SO 3 -, (R 8 In addition to anions represented by SO ₂ ) ₃ C ⁻ or (R ⁸ SO ₂ ) ₂ N ⁻ , perhalogenate ions (ClO ₄ ⁻ , BrO ₄ ⁻ etc.), halogenated sulfonate ions (FSO ₃ ⁻ , ClSO) ₃ ^- and the like), 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 - , etc.), an aryl boronic acid ions _{(B (C 6 H 5)} 4 -, CH 3 CH 2 CH 2 _{H 2 B (C 6 H 5} ) 3 - , etc.), thiocyanate ion (SCN ^-) and nitrate ion (NO ₃ ^-) and the like can be used.

Among these X ⁻ , in terms of cationic polymerization performance, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ⁷ _c BY _4-c ⁻ , R ⁷ _c GaY _4-c ⁻ and (R ⁸ SO ₂ ) An anion represented by ₃ C ⁻ is preferable, and 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 ⁻ and (CF ₃ SO ₂ ) ₃ C ⁻ are particularly preferred.

Preferred examples of the sulfonium salt represented by the formula (1) of the present invention include, but are not limited to, the following.
(A) R ³ and R ⁴ are methyl groups or methoxy groups, m ³ and m ⁴ are 1, and m ¹ , m ² , m ⁵ and m ⁶ are 0, and (b) m ¹ ~m ⁶ those both zero.

  Of the sulfonium salts represented by the formula (1) of the present invention, preferred examples include 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, 4 -(4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium hexafluoroantimonate, 4- (4-Biphenylylthio) phenyl] -4-biphenylylphenylsulfonium hexafluorophosphate, 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium trifluoromethanesulfonate, 4- (4-biphe Nylylthio) phenyl] -4-biphenylylphenylsulfonium nonafluorobutanesulfonate, 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium methanesulfonate, 4- (4-biphenylylthio) phenyl] -4 -Biphenylylphenylsulfonium butanesulfonate and 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium p-toluenesulfonate.

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

<Manufacturing method (1)>
Methods represented by the following reaction formulas (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- And the method described in JP-A No. 212286 or JP-A-10-7680).

In the above reaction formula, R ^{1 to} R ⁶ , S, O, X ⁻ , m ^{1 to} m ⁶ are the same as defined in the formula (1). 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, acetic anhydride, concentrated sulfuric acid, and the like.
The monovalent polyatomic anion (X ′ ⁻ ) can be exchanged for another anion (X ⁻ ) of the present invention by, for example, a metathesis reaction as described above.
DX represents an alkali metal (lithium, sodium, potassium, etc.) cation and another anion of the present invention (for example, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ⁷ _c BY _4-c ⁻ , R ⁷ _c An anion represented by GaY _4-c ⁻ , R ⁸ SO ₃ ⁻ , (R ⁸ SO ₂ ) ₃ C ⁻ , R ⁸ SO ₂ ) ₂ N ⁻ ).
DX ′ represents a salt of an alkali metal (lithium, sodium, potassium, etc.) cation and a monovalent polyatomic anion (methanesulfonic acid anion, perfluoromethanesulfonic acid anion, hydrogensulfate anion, etc.).

  In the above reaction formula, the first stage reaction may be carried out in the absence of a solvent, or may be carried out in an organic solvent (acetonitrile, tetrahydrofuran, dioxane, ethanol, acetone, etc.) if necessary. 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 intermediate (G3) is isolated (purified as necessary). The reaction intermediate (G3) and an aqueous solution of a salt (DX) of an alkali metal cation and a monovalent polyatomic anion are mixed and stirred to perform a metathesis reaction, and the precipitated solid is separated by filtration or separated. By extracting the obtained oily substance with an organic solvent and removing the organic solvent, the sulfonium salt of the present invention can be 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).

  The reaction intermediate (G4) of the raw materials (G1) and (G2) used in the above production method can be obtained by a known method. For example, the reaction formulas (1) and (2) shown below can be obtained. It can manufacture in this way.

<Reaction Formula (1)>
The reaction described in Bulletin of the Chemical Society of Japan, 53, 1385-1389 (1980), etc. can be applied to the reaction formula (1).

In the reaction formula, R ^{1 to} R ⁶ , S, and m ^{1 to} m ⁶ are the same as defined in the formula (1).
Y represents a halogen atom.
H represents a hydrogen atom.
The base represents a base (potassium hydroxide, t-sodium butoxide, etc.).
The catalyst represents a catalyst (copper iodide, tetrakistriphenylphosphine palladium, etc.).

  By reacting a biphenyl derivative and a thiophenol derivative in an organic solvent (ethanol, 1-butanol, dimethyl sulfoxide, dimethylformamide, etc.) in the presence of a base and a catalyst, a sulfide having a biphenyl skeleton (G1) and (G4) is obtained.

<Reaction Formula (2)>
For the reaction formula (2), the oxidation reaction described in the 4th edition, Experimental Chemistry Course Vol. 23 (1991, Maruzen), pages 276 to 277, etc. can be applied.

In the reaction formula, R ^{4 to} R ⁶ , S, O, m ^{4 to} m ⁶ are the same as defined in the formula (1).
H represents a hydrogen atom.
The oxidizing agent represents an oxidizing agent (hydrogen peroxide or the like).

  When the sulfide (G4) having a biphenyl skeleton, which is a reaction intermediate of (G2), is oxidized in the presence of an oxidizing agent, a sulfoxide (G2) having a biphenyl skeleton is obtained.

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 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.
The photoacid generator of the present invention may be used alone or in combination with another photoacid generator.

  When other photoacid generators are contained, the content (mol%) is preferably 1 to 100, more preferably 5 to 50, based on the total number of moles of the sulfonium salt of the present invention.

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

Examples of the ^{_{anionic, MY a -, (Rf)}} b PF 6-b -, R 7 c BY 4-c -, R 7 c GaY 4-c -, R 8 SO 3 -, (R 8 SO 2) 3 C ^- or _{^{(R 8 SO 2) 2 N}} - besides the anion represented by the perhalogenated acid ion (ClO ₄ ^-, BrO ₄ ^-, etc.), halogenated sulfonic acid ion (FSO ₃ ^-, ClSO ₃ ^-, etc.), Sulfate 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.), Hexafluorobismuth 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 ⁻ ), aryl borate ion (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 ion (NO ₃ ⁻ ) and the like can be used.

  Examples of the 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) E) 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-be Zoylphenylthio) 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. 4231951, U.S. Pat. No. 4,256,828, JP-A-7-61964, JP-A-7-10914, JP-A-7-25922, JP-A-8-27208, JP-A-8-27209, JP-A-8-165290. JP-A-8-301991, JP-A-9-1432 2, 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-8-245466, 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-8-325259, JP 8-160606, JP 2000-186071 (US Pat. No. 6,368,769), Special Table 2005-5. 1040 No., 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-anthracenylmethylphenacils Examples include Honium (JP-A-6-345726, JP-A-8-325225, JP-A-9-118663 (US Pat. No. 6093753), JP-A-2-196812, JP-A2-1470, 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, octadecylmethylphenacylsulfonium, and the like (JP-A-4-308563, JP-A-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, Open No. 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, diphenylbenzyl selenium, diphenylmethyl selenium, etc.), monoaryl selenium (phenylmethyl benzyl selenium, 4-hydroxyphenylmethy) Benzyl selenium, phenylmethyl phenacyl selenium, 4-hydroxyphenyl methyl phenacyl selenium, 4-methoxyphenyl methyl phenacyl selenium) and trialkyl selenium (dimethyl phenacyl selenium, phenacyl tetrahydroselenophenium, dimethyl benzyl selenium, benzyl) Tetrahydroselenophenium, 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, -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.), morpho Ni (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, N-phenacylpyridium, etc.), 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-isopropyliso Quinolium, Nn-butylisoquinolium, N-benzylisoquinolium, N-phenacylisoquinolium, etc.), thiazonium (benzylbenzothiazonium, phenacylbenzothiazonium, etc.), and alridinium (benzyl) (U.S. Patent No. 4069) No. 55, 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. 10-101718. JP-A-2-268173, JP-A-9-328507, JP-A-5-132461, JP-A-9-216552, 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, and JP-A-9-221651).

  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 Bromide, 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- naphthalate Emissions) 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-indenyl) (η6-cumene) Fe ⁺ , bis (η6-mesi Tylene) Fe2 ⁺ , bis (η6-xylene) Fe2 ⁺ , bis (η6-cumene) Fe2 ⁺ , bis (η6-toluene) Fe2 ⁺ , (η6-toluene) (η6-xylene) Fe2 ⁺ , (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), US Pat. No. 4,973,722 No. 4,992,572, No. 3,895,954, European Patent Publication No. 203829, No. 354181, No. 94914, No. 109851, No. 94915, and Japanese Patent Laid-Open No. 58-210904 (US Pat. No. 4,868,288). No.), 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 the cationic 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 Ether (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 Fine 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 energy beam curable composition of the present invention comprises the above-mentioned photoacid generator and a cationically polymerizable compound.

  Examples of the cationic polymerizable compound 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 2 07-277327, 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 chemical, 29, (19), 5-14 (2000), etc.).

  Known epoxides can be used and include aromatic epoxides, alicyclic epoxides and aliphatic epoxides.

  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 alicyclic epoxides, compounds 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, 4 Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanemetadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis (3,4 Epoxycyclohexane), dicyclopentadiene diepoxide, ethylene bis (3,4-epoxycyclohexanecarboxylate) and the like.

  Examples of the aliphatic epoxide include aliphatic polyhydric alcohol or polyglycidyl ether 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, etc.), 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-3 Oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ) 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, pen Bromophenyl (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, dipentaerythritoltetrakis (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-Naphoxy) 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 can be used, and examples thereof 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 the spiro ortho carbonate 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.

  Of these cationically polymerizable compounds, epoxide, oxetane and vinyl ether are preferable, epoxide and oxetane are more preferable, and alicyclic epoxide and oxetane 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, relative 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, An antioxidant, an adhesion-imparting agent, an ion scavenger, a coloring inhibitor, a solvent, a non-reactive resin, a radical polymerizable compound, and the like).

  The energy beam curable composition of the present invention basically does not require a sensitizer, but can contain a sensitizer as necessary to supplement the curability. As such a sensitizer, known sensitizers (JP-A-11-279212 and JP-A-09-183960) can be used, and anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10 -Dimethoxyanthracene, 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, 9,10-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-dibenzyloxy Anthracene, 2,3-dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10-methylanthracene, 9,10-di-α-methylbenzyloxyanthracene, 2-ethyl-9,10-di- α-methylbenzyloxyanthracene, 2-tert-9,1 -Di-α-methylbenzyloxyanthracene, 2,3-dimethyl-9,10-di-α-methylbenzyloxyanthracene, 9- (α-methylbenzyloxy) -10-methylanthracene, 9,10-diphenylanthracene , 9-methoxyanthracene, 9-ethoxyanthracene, 9-methylanthracene, 9-bromoanthracene, 9-methylthioanthracene, 9-ethylthioanthracene, etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; {Thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone}; Phenothiazine and its derivatives {phenothiazine, N Methylphenothiazine, N-ethylphenothiazine, N-phenylphenothiazine, etc.}; 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) and 4-methoxy -1-naphthol and the like}; ketone {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2 -Hydroxymethyl-2-methyl Propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, 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'-dichlorobenzoph Non- and 4-benzoyl-4′-methyldiphenyl sulfide, etc.]; carbazole {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole, etc.}; chrysene {1,4-dimethoxychrysene, 1,4-diethoxychrysene, 1,4-dipropoxychrysene, 1,4-dibenzyloxychrysene, 1,4-di-α-methylbenzyloxychrysene, etc.}; phenanthrene {9-hydroxyphenanthrene, 9-methoxy Phenanthrene, 9-ethoxyphenanthrene, 9-benzyloxyphenanthrene, 9,10-dimethoxyphenanthrene, 9,10-diethoxyphenanthrene, 9,10-dipropoxyphenanthrene, 9,10-dibenzyloxyphenanthrene, 9,1 0-di-α-methylbenzyloxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.}.

  When the 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.

  Known pigments can be used as the pigment, and examples include 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).

  When the 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 600,000 parts by weight, more preferably 300 to 200,000 parts by weight with respect to 100 parts of the photoacid generator.

  As the antistatic agent, a known antistatic agent can be used, and a nonionic antistatic agent {glycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl 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 Inhibitors {tetraalkylammonium salts and trialkylbenzylammonium salts, etc.}; amphoteric antistatic agents {alkylbetaines and alkylimidazolium betaines, etc.}; polymeric antistatic agents {quaternary ammo-containing styrene- (meta 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 40,000 parts by weight, more preferably 5 to 10,000 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.

  When the ion scavenger is contained, 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.

  Known anti-coloring agents can be used as anti-coloring agents. In general, antioxidants are effective, phenolic antioxidants (monophenolic, bisphenolic and high-molecular phenolic, etc.), sulfur-based oxidation Examples thereof include an inhibitor and a phosphorus-based antioxidant.

  When a coloring inhibitor is contained, the content thereof 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 cationic polymerizable compound or adjusting the viscosity of an energy ray curable composition, such as ether {anisole, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethyl-tert-butyl ether, etc. }; Aromatic hydrocarbons {toluene, xylene, cumene, ethylbenzene, mesitylene, etc.}; ketones {acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc.}; alcohols {methanol, ethanol, isopropyl alcohol, tert-butanol, etc.}; nitriles {acetonitrile Etc.}.

  When the solvent is contained, 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 5,000 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, and more preferably 50 to 150,000 parts by weight with respect to 100 parts of the photoacid generator.

  When a non-reactive resin is contained, 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 (meth) ) 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 alkylene oxide adducts thereof).

  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- Esterifying hydroxy-terminated polyesters obtained from hexanediol, trimethylolpropane, glycerin, pentaerythritol, bisphenol and their alkylene oxide adducts with (meth) acrylic acid More resulting polyester (meth) acrylate.

  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, pen An isocyanate-terminated prepolymer obtained from erythritol, bisphenol, hydrogenated bisphenol, polycaprolactone diol, polyester diol, polycarbonate diol, etc.} is converted into a hydroxy group-containing (meth) acrylate {2-hydroxyethyl (meth) acrylate, 2-hydroxy And urethane (meth) acrylate obtained by urethanization reaction of propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and pentaerythritol with tri (meth) acrylate, etc.}.

  When the radically polymerizable compound is contained, the content of the radically 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 radically polymerizable compounds are contained, a radical polymerization initiator that initiates polymerization by heat or light is preferably used 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.), hydroperoxide (such as tert-butylhydroperoxide and cumene hydroperoxide), dialkyl peroxide (such as di-tert-butylperoxide), diacyl peroxide (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'-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-methylpro Onato) and the like}.

  As photo radical polymerization initiators, 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 acylphosphine Such initiator {mono acyl phosphine oxides and bisacylphosphine oxides and the like} 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, based on 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 optionally an additive, uniformly 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, an F ₂ laser or the like 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. From 0.1 seconds to several minutes after irradiation with energy rays, most energy ray curable compositions are cured by cationic polymerization. If necessary, after irradiation with energy rays, room temperature (about 20 to 30 ° C.) to 150 It is also possible to heat and cure at a temperature of several seconds to several hours.

  Specific applications of the energy beam curable composition of the present invention include paints, coating agents, inks, inkjet inks, positive resists, resist films, liquid resists, negative resists, MEMS resists, photosensitive materials, and various types. Adhesive, molding material, casting material, putty, glass fiber impregnating agent, sealing material, sealing material, sealing material, optical semiconductor (LED) sealing material, nanoimprint material, photofabrication, micro stereolithography material, etc. Can be mentioned.

  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 (Japanese Patent Application Laid-Open Nos. 2003-267968, 2003-261529, 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. As the anion of the sulfonium salt of the present invention used as the photoacid generator of (1) and (2), the anion represented by the aforementioned “R ⁸ SO ₃ ⁻ ” is preferable.

  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) Synthesis of 4- (phenylthio) biphenyl 3.0 parts of 4-bromobiphenyl, 1.7 parts of thiophenol, 2.5 parts of sodium t-butoxide, 0.15 parts of tetrakistriphenylphosphine palladium and 1 -64.3 parts of butanol were mixed uniformly and reacted at 120 ° C for 2 hours. The reaction solution was cooled to room temperature (about 25 ° C.) and filtered. The filtrate was transferred to a rotary evaporator and the solvent was distilled off to obtain a reddish brown crystalline product. This was dissolved in 70 parts of dichloromethane, 50 parts of a saturated aqueous sodium hydrogen carbonate solution was added, washed three times by liquid separation, and the dichloromethane layer was washed with 70 parts of distilled water until the pH became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a brown crystalline product. Add 20 parts of hexane, disperse in hexane with an ultrasonic cleaner, let stand for about 15 minutes, and then repeat the operation of removing the supernatant three times to wash the resulting solid, and remove the solvent with a rotary evaporator. By leaving, brown crystalline 4- (phenylthio) biphenyl was obtained in a yield of 84%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.6 to 7.7 (4H, m), 7.3 to 7.5 (10 H, m)}.

(Production Example 2) Synthesis of a mixture containing 4-[(phenyl) sulfinyl] biphenyl and 4- (phenylthio) biphenyl 2.0 parts of 4- (phenylthio) biphenyl synthesized in Production Example 1, 8.0 parts of acetonitrile, sulfuric acid 0.037 parts and 0.43 parts of 30% aqueous hydrogen peroxide were mixed uniformly and reacted at 65 ° C. for 3 hours. After cooling the reaction solution to room temperature (about 25 ° C.), 30 parts of dichloromethane was added and washed with liquid separation operation with 40 parts of distilled water until the pH became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a mixture containing 55% of brown liquid 4-[(phenyl) sulfinyl] biphenyl and 45% of 4- (phenylthio) biphenyl. After isolation by column chromatography (eluent: ethyl acetate / hexane = 1/1: volume ratio), the product was identified by ¹ H-NMR. ¹ H-NMR data of 4-[(phenyl) sulfinyl] biphenyl: {d6-dimethylsulfoxide, δ (ppm) 7.7 to 7.9 (4H, m), 7.3 to 7.6 (10H, m )}. The content was calculated from the peak area ratio by HPLC analysis of the mixture.

Production Example 3 Synthesis of 4-[(2-methylphenyl) thio] biphenyl Same as Production Example 1 except that “1.7 parts of thiophenol” was changed to “1.8 parts of 2-methylthiophenol” As a result, brown crystalline 4-[(2-methylphenyl) thio] biphenyl was obtained in a yield of 89%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.6 to 7.7 (4H, m), 7.3 to 7.5 (9 H, m), 2.3. (3H, s)}.

(Production Example 4) Synthesis of a mixture containing 4-[(2-methylphenyl) sulfinyl] biphenyl and 4-[(2-methylphenyl) thio] biphenyl [Production of 2.0 parts of 4- (phenylthio) biphenyl] A brown liquid 4-[(2-methylphenyl) sulfinyl] was prepared in the same manner as in Production Example 2, except that the compound was changed to 2.1 parts of “4-[(2-methylphenyl) thio] biphenyl” synthesized in Example 3. A mixture containing 51% biphenyl and 49% 4-[(2-methylphenyl) thio] biphenyl was obtained. The product was identified by column chromatography (eluent: ethyl acetate / hexane = 1/1: volume ratio) and then identified by ¹ H-NMR. ¹ H-NMR data of 4-[(2-methylphenyl) sulfinyl] biphenyl: {d6-dimethylsulfoxide, δ (ppm) 7.6-8.0 (7H, m), 7.1-7.6 ( 6H, m), 2.3-2.4 (3H, s). The content was calculated from the peak area ratio by HPLC analysis of the mixture.

(Production Example 5) Synthesis of 4-[(2-methoxyphenyl) thio] biphenyl Production Example 1 except that “1.7 parts of thiophenol” was changed to “2.2 parts of 2-methoxythiophenol” Similarly, brown crystalline 4-[(2-methoxyphenyl) thio] biphenyl was obtained in a yield of 85%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.6 to 7.7 (4H, m), 7.3 to 7.5 (9H, m), 3.7. (3H, s)}.

(Production Example 6) Synthesis of a mixture containing 4-[(2-methoxyphenyl) sulfinyl] biphenyl and 4-[(2-methoxyphenyl) thio] biphenyl [Production of 2.0 parts of 4- (phenylthio) biphenyl] A brown liquid 4-[(2-methoxyphenyl) sulfinyl] was prepared in the same manner as in Production Example 2 except that the synthesis was changed to 2.2 parts of “4-[(2-methoxyphenyl) thio] biphenyl” synthesized in Example 5. A mixture containing 51% biphenyl and 49% 4-[(2-methoxyphenyl) thio] biphenyl was obtained. The product was identified by column chromatography (eluent: ethyl acetate / hexane = 1/1: volume ratio) and then identified by ¹ H-NMR. ¹ H-NMR data of 4-[(2-methoxyphenyl) sulfinyl] biphenyl: {d6-dimethylsulfoxide, δ (ppm) 7.6 to 8.0 (7H, m), 7.1 to 7.6 ( 6H, m), 3.6-3.7 (3H, s)}. The content 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]
Synthesis of [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate (3)

2.0 parts of a mixture containing 55% of 4-[(phenyl) sulfinyl] biphenyl synthesized in Production Example 2 and 45% of 4- (phenylthio) biphenyl, and 0.4% of 4- (phenylthio) biphenyl synthesized in Production Example 1. 24 parts, 1.2 parts of acetic anhydride, 0.72 parts of trifluoromethanesulfonic acid and 6.5 parts of acetonitrile were mixed uniformly and reacted at 60 ° C. for 2 hours. The reaction solution was cooled to room temperature (about 25 ° C.), poured into 30 parts of distilled water, extracted with 30 parts of dichloromethane, and washed with water until the pH of the aqueous layer became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a brown liquid product. After adding 10 parts of ethyl acetate and dissolving in a 60 ° C water bath, adding 30 parts of hexane, stirring, and allowing to stand for 30 minutes in a refrigerator (about 5 ° C), then removing the supernatant twice. And the product was washed. This was transferred to a rotary evaporator and the solvent was distilled off to obtain [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium triflate (triflate = trifluoromethanesulfonic acid anion).
(Double decomposition method)
Dissolve this triflate in 27 parts of dichloromethane, add it into 21 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate, and stir at room temperature (about 25 ° C) for 3 hours to separate the dichloromethane layer. After washing with water three times, the solution was transferred to a rotary evaporator and the solvent was distilled off to obtain [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluoro. The phosphate was obtained in 88% yield. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6. (8H, m)}. Further, absorption of a PF bond was confirmed in the vicinity of 840 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 2 Synthesis of [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium hexafluoroantimonate (4)

In the same manner as in Example 1, except that “21 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate” was changed to “24 parts of 5% potassium hexafluoroantimonate”, [4- (4-biphenyl Rilthio) phenyl] -4-biphenylylphenylsulfonium hexafluoroantimonate was obtained in 85% yield. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6. (8H, m)}. Further, absorption of Sb—F bond was confirmed in the vicinity of 650 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 3 Synthesis of [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate (5)

Except that “10% tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 21 parts” was changed to “10% lithium tetrakis (pentafluorophenyl) borate 30 parts”, in the same manner as in Example 1, [4- (4-Biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate was obtained in a yield of 90%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6. (8H, m)}. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 4 Synthesis of [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium hexafluorophosphate (6)

[4- (4-biphenyl) was prepared in the same manner as in Example 1, except that “21 parts of 10% potassium tris (pentafluoroethyl) trifluorophosphate” was changed to “16 parts of 5% potassium hexafluorophosphate”. Rilthio) phenyl] -4-biphenylylphenylsulfonium hexafluorophosphate was obtained in 89% yield. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6. (8H, m)}. Further, absorption of a PF bond was confirmed in the vicinity of 540 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 5 Synthesis of 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium nonafluorobutanesulfonate (7) “0.72 part of trifluoromethanesulfonic acid” was converted to “nonafluorobutanesulfonic acid 1 .42 parts "and [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium nonafluorobutanesulfonate was obtained in a yield of 87% in the same manner as in Example 1 without metathesis. It was. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6. (8H, m)}. In addition, absorption of C—F bond was confirmed in the vicinity of 1200 cm ⁻¹ by infrared absorption spectroscopy (KBr tablet method).

[Example 6] Synthesis of 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium bis (trifluoromethanesulfonyl) imide (8) [10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate 21 [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium in the same manner as in Example 1, except that “part” was changed to “14 parts of 10% bis (trifluoromethanesulfonyl) imide lithium”. Bis (trifluoromethanesulfonyl) imide was obtained with a yield of 85%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6. (8H, m)}. In addition, absorption of C—F bond was confirmed in the vicinity of 1200 cm ⁻¹ by infrared absorption spectroscopy (KBr tablet method).

Example 7 Synthesis of 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (trifluoromethanesulfonyl) methide (9) “10% Tris (pentafluoroethyl) potassium trifluorophosphate aqueous solution 21 [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris in the same manner as in Example 1, except that “part” was changed to “20 parts of 10% tris (trifluoromethanesulfonyl) methide lithium”. (Trifluoromethanesulfonyl) methide was obtained in 86% yield. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6. (8H, m)}. In addition, absorption of C—F bond was confirmed in the vicinity of 1200 cm ⁻¹ by infrared absorption spectroscopy (KBr tablet method).

Example 8 Synthesis of 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium methanesulfonate (10) “0.72 part of trifluoromethanesulfonic acid” was replaced with “2.28 parts of methanesulfonic acid” [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium methanesulfonate was obtained in a yield of 65% in the same manner as in Example 1 without metathesis. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6. (8H, m), 2.7 (3H, s)}.

Example 9 Synthesis of (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium tris (pentafluoroethyl) trifluorophosphate (11)

Synthesized in Preparation Example 3, 2.0 parts of a mixture containing 51% of 4-[(2-methylphenyl) sulfinyl] biphenyl synthesized in Preparation Example 4 and 49% of 4-[(2-methylphenyl) thio] biphenyl 0.08 parts of 4-[(2-methylphenyl) thio] biphenyl, 1.1 parts of acetic anhydride, 0.65 parts of trifluoromethanesulfonic acid and 7.7 parts of acetonitrile were mixed uniformly and reacted at 60 ° C. for 2 hours. It was. The reaction solution was cooled to room temperature (about 25 ° C.), poured into 30 parts of distilled water, extracted with 30 parts of dichloromethane, and washed with water until the pH of the aqueous layer became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a brown liquid product. After adding 10 parts of ethyl acetate and dissolving in a 60 ° C water bath, adding 30 parts of hexane, stirring, and allowing to stand for 30 minutes in a refrigerator (about 5 ° C), then removing the supernatant twice. And the product was washed. By transferring this to a rotary evaporator and distilling off the solvent, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium triflate (triflate = trifluoromethane) A sulfonic acid anion).
(Double decomposition method)
Dissolve this triflate in 25 parts of dichloromethane, add it into 21 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate, and stir at room temperature (about 25 ° C) for 3 hours to separate the dichloromethane layer. After washing with water three times, the mixture was transferred to a rotary evaporator and the solvent was distilled off to obtain (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium. Tris (pentafluoroethyl) trifluorophosphate was obtained in a yield of 92%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (15H, m), 7.3-7.6. (8H, m), 2.5 (6H, s)}. Further, absorption of a PF bond was confirmed in the vicinity of 840 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 10 Synthesis of (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium hexafluoroantimonate (12)

In the same manner as in Example 9, except that “21 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate” was changed to “22 parts of potassium 5% hexafluoroantimonate”, (2-methyl) phenyl [ 4- (4-Biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium hexafluoroantimonate was obtained in a yield of 85%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (15H, m), 7.3-7.6. (8H, m), 2.5 (6H, s)}. Further, absorption of Sb—F bond was confirmed in the vicinity of 650 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

  [Example 11] Synthesis of (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium tetrakis (pentafluorophenyl) borate (13)

In the same manner as in Example 9, except that “21 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate” was changed to “27 parts of 10% lithium tetrakis (pentafluorophenyl) borate” (2- Methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium tetrakis (pentafluorophenyl) borate was obtained in 92% yield. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (15H, m), 7.3-7.6. (8H, m), 2.5 (6H, s)}. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

[Example 12] Synthesis of (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium hexafluorophosphate (14)

In the same manner as in Example 9, except that “21 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate” was changed to “15 parts of 5% potassium hexafluorophosphate”, (2-methyl) phenyl [ 4- (4-Biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium hexafluorophosphate was obtained in a yield of 90%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (15H, m), 7.3-7.6. (8H, m), 2.5 (6H, s)}. Further, absorption of a PF bond was confirmed in the vicinity of 540 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 13 Synthesis of (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium tris (pentafluoroethyl) trifluorophosphate (15)

Synthesized in Preparation Example 5, 2.0 parts of a mixture containing 51% 4-[(2-methoxyphenyl) sulfinyl] biphenyl synthesized in Production Example 6 and 49% 4-[(2-methoxyphenyl) thio] biphenyl 0.08 part of 4-[(2-methoxyphenyl) thio] biphenyl, 1.0 part of acetic anhydride, 0.6 part of trifluoromethanesulfonic acid and 7.7 parts of acetonitrile were mixed uniformly and reacted at 60 ° C. for 2 hours. It was. The reaction solution was cooled to room temperature (about 25 ° C.), poured into 30 parts of distilled water, extracted with 30 parts of dichloromethane, and washed with water until the pH of the aqueous layer became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a brown liquid product. After adding 10 parts of ethyl acetate and dissolving in a 60 ° C water bath, adding 30 parts of hexane, stirring, and allowing to stand for 30 minutes in a refrigerator (about 5 ° C), then removing the supernatant twice. And the product was washed. This was transferred to a rotary evaporator and the solvent was distilled off to obtain (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium triflate (triflate = trifluoromethane). A sulfonic acid anion).
(Double decomposition method)
Dissolve this triflate in 25 parts of dichloromethane, add it into 19 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate, and stir at room temperature (about 25 ° C) for 3 hours to separate the dichloromethane layer. After washing with water three times, the mixture was transferred to a rotary evaporator and the solvent was distilled off to obtain (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium. Tris (pentafluoroethyl) trifluorophosphate was obtained with a yield of 90%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (15H, m), 7.3-7.6. (8H, m), 3.6-3.8 (6H, d)}. Further, absorption of a PF bond was confirmed in the vicinity of 840 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

[Comparative Example 1] Synthesis of 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate (16)

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)}. Further, absorption of a PF bond was confirmed in the vicinity of 840 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

[Comparative Example 2] Synthesis of diphenyl-2-thioxanthonylsulfonium tris (pentafluoroethyl) trifluorophosphate (17)

15.0 parts of 2- (phenylthio) thioxanthone synthesized in Production Example 3, 41.9 parts of diphenyliodonium hexafluorophosphate, 0.4 part of copper (II) benzoate and 300 parts of chlorobenzene were mixed uniformly, and the temperature was 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. By washing and drying under reduced pressure, diphenyl-2-thioxanthonylsulfonium tris (pentafluoroethyl) trifluorophosphate was obtained in a yield of 98%. 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)}. Further, absorption of PF bond was confirmed in the vicinity of 840 cm ⁻¹ by infrared absorption analysis (KBr tablet method).

[Comparative Example 3] Synthesis of 4- (phenylthio) phenyldiphenylsulfonium tetrakis (pentafluorophenyl) borate (18)

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

[Comparative Example 5]
CPI-110P {4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, manufactured by San Apro Co., Ltd.} was used as a comparative sulfonium salt.

(Preparation of energy ray-curable composition and evaluation thereof)
The photoacid generator of the present invention and the compound of the comparative example were dissolved in solvent-1 (propylene carbonate) in the blending amounts shown in Table 1, and then the epoxide (3,4-epoxycyclohexylmethyl-) which is a cationic polymerizable compound. 3,4-epoxycyclohexanecarboxylate (manufactured by Dow Chemical Co., Ltd., UVR-6110) at a blending amount (parts by weight) shown in Table 1 to prepare energy ray curable compositions (Examples C1 to C9). did.
Moreover, the comparative example was similarly performed by the compounding quantity shown in Table 1, and the energy-beam curable composition (comparative example C1-C5) was prepared.

  The sulfonium salt obtained in Examples 4 and 12 or Comparative Example 5 is a hexafluorophosphate, and the tris (pentafluoroethyl) of Examples 1 to 3, 9 to 11 and 13 or Comparative Examples 1 to 4 is used. Compared to trifluorophosphate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate, the amount of the generated sulfonium salt was increased because the strength of the acid generated was lower and the activity against cationic polymerization was lower. Along with this, the amount of solvent was increased.

<Photosensitivity (photocurability)>
The energy ray-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 coating hardness after 40 minutes was measured with pencil hardness (JIS K5600-5-4: 1999) and evaluated according to the following criteria (coating thickness after curing was about 40 μm). It is shown in Table 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
(Triangle | delta): Pencil hardness is 2B-4B
×: 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: 300 mJ / cm ²
Condition-3: 600 mJ / cm ²

<Storage stability>
The energy ray-curable composition obtained above 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.

  From the results of Table 2, the comparative sulfonium salt has a significantly low curing of the cationically polymerizable compound with ultraviolet light of 365 nm or more, whereas the sulfonium salt of the present invention has the properties of the cationically polymerizable compound due to this ultraviolet light. Curing has been found to occur well.

  The sulfonium salt of the present invention includes paints, coating agents, inks, inkjet inks, positive resists (formation of connection terminals and wiring patterns for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, etc.), resist films, liquid resists, negatives. Type resists (permanent film materials such as surface protection films for semiconductor elements, interlayer insulation films, planarization films, etc.), resists for MEMS, photosensitive materials, various adhesives, molding materials, casting materials, putty, glass fiber impregnation Suitable as a photoacid generator for use in adhesives, sealing materials, sealing materials, sealing materials, optical semiconductor (LED) sealing materials, nanoimprint materials, optical waveguide materials, stereolithography, microstereolithography materials, etc. Used.

Claims (10)

Formula (1),

Wherein ^(1), R 1 ~R ⁶ each represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkylcarbonyl group having 2 to 4 carbon ^{atoms, m} 1 ~ m ⁶ represents the number of R ^{1 to} R ⁶ , m ¹ , m ⁴ and m ⁶ are integers from 0 to 3 , m ² , m ³ and m ⁵ are integers from 0 to 3 , and X ⁻ is monovalent Represents a polyatomic anion. ] The sulfonium salt characterized by the above-mentioned. The sulfonium salt according to claim 1, wherein R ^{1 to} R ⁶ are independently selected from the group consisting of a methyl group, a methoxy group, and an acetyl group. The sulfonium salt according to claim 1 or 2, wherein R ³ and R ⁴ are a methyl group or a methoxy group, m ³ and m ⁴ are 1, and m ¹ , m ² , m ⁵ and m ⁶ are 0. . The sulfonium salt according to claim 1, wherein m ^{1 to} m ⁶ are all 0. Wherein X _{^{-, MY a -, (Rf)}} b PF 6-b -, R 7 c BY 4-c -, R 7 c GaY 4-c -, R 8 SO 3 -, (R 8 SO 2) 3 C ^- or _{^{(R 8 SO 2) 2 N}} - anion (here represented by, M is a phosphorus atom, a boron atom, an arsenic atom or an antimony atom, Y is a halogen atom, Rf is fluorine least 80 mol% of hydrogen atoms An alkyl group substituted with an atom, P is a phosphorus atom, F is a fluorine atom, R ⁷ 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 ⁸ 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 an integer of 1-5, c is 1-4 Represents an integer.) Sulfonium salt according to any one of claims 1 to 4 is. X ⁻ is SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (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 -, trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, butanoic acid anion, The sulfonium salt according to any one of claims 1 to 5, which is an anion represented by a benzenesulfonate anion or a p-toluenesulfonate anion.   4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tetrakis (pentafluoro Phenyl) borate, 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium hexafluoroantimonate, 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium hexafluorophosphate, 4 -(4-Biphenylylthio) phenyl] -4-biphenylylphenylsulfonium trifluoromethanesulfonate, 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium nonafluo Butanesulfonate, 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium methanesulfonate, 4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium butanesulfonate, and 4- (4 The sulfonium salt according to claim 1, which is a kind selected from the group consisting of -biphenylylthio) phenyl] -4-biphenylylphenylsulfonium p-toluenesulfonate.   A photoacid generator comprising the sulfonium salt according to any one of claims 1 to 7.   An energy ray-curable composition comprising the photoacid generator according to claim 8 and a cationically polymerizable compound. A cured product obtained by curing the energy beam curable composition according to claim 9.