JP2013227368A - Active energy ray-sensitive acid-generating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly active acid-generating agent exhibiting cation polymerization activity and crosslinking activity by the irradiation with active energy rays, and providing a cured product obtained by using the agent, and capable of maintaining good transparency after a heat resistance test.SOLUTION: There is provided an active energy ray-sensitive acid-generating agent containing a sulfonium salt represented by general formula (1) [wherein, Rto Rare each an organic group bonded to a benzene ring; the numbers of Rto Rare each 0-5; the numbers of Rto Rare each 0-4; with the proviso that when the number is 0, a hydrogen atom is bonded].

Description

The present invention firstly relates to an active energy-sensitive linear acid generator, and more particularly to a sulfonium salt-based active energy linear acid generator.
Secondly, the present invention relates to an active energy ray-curable composition, a chemically amplified positive photoresist composition and a chemically amplified negative photoresist composition containing the acid generator.

Conventionally, onium salts such as sulfonium salts are known as cationic polymerization initiators for curing cationic polymerizable compounds such as epoxy compounds by irradiation with active energy rays such as light and electron beams (Patent Documents 1 to 3).
These onium salts are also referred to as acid generators because they generate acid upon irradiation with active energy rays, and are also used in resists and photosensitive materials (Patent Documents 4 to 6).

By the way, as a method for producing an active energy linear acid generator, particularly a sulfonium salt described in these specifications, known methods are used (Patent Documents 1 and 3). However, the sulfonium salt produced by such a method has a problem in reactivity to active energy rays (that is, the amount of acid generated), and when formulated as an active energy ray curable composition, there is a problem in long-term storage stability. is there. Furthermore, for members that require optical properties such as displays, optical waveguides, and optical lenses, transparency of the cured product and transparency of the cured product after the heat resistance test and after the moisture resistance test are regarded as important. It was not something.

JP-A-55-125105 JP 61-190524 A Japanese Patent Laid-Open No. 61-212554 JP 2002-193925 A JP 2001-354669 A JP 2001-294570 A

In the above background, the first object of the present invention is to have a cationic polymerization performance and a crosslinking reaction performance by active energy ray irradiation, and a cured product using the same can maintain high transparency after a heat test. It is to provide an active acid generator.
The second object of the present invention is to provide an active energy ray-curable composition, a chemically amplified positive photoresist composition, and a chemically amplified negative photoresist composition using the acid generator.

The present inventor has found an acid generator suitable for the above purpose.
That is, the present invention is an active energy linear acid generator (hereinafter abbreviated as an acid generator) containing a sulfonium salt represented by the following general formula (1).

[In the formula (1), R ^{1 to} R ⁶ are organic groups bonded to a benzene ring, the number of R ^{1 to} R ⁴ is 0 to 5, and the number of R ^{5 to} R ⁶ is 0 to 4. In the case of 0, hydrogen atoms are bonded, and when a plurality of R ^{1 to} R ⁶ are bonded, they may be the same as or different from each other, and R ^{1 to} R ⁶ may be directly or —O—, A ring structure may be formed via —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group, and X is monovalent. It is an atom (group) that can be an anion. ]

The present invention also includes an energy ray curable composition comprising the acid generator and a cationic polymerizable compound; a cured product obtained by curing the energy ray curable composition A chemically amplified positive photoresist composition comprising the acid generator and a component (B) which is a resin whose solubility in alkali is increased by the action of an acid; and the acid generator; A chemically amplified negative photoresist composition comprising a component (F), which is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinking agent component (G); A cured product obtained by curing a resist composition.

The acid generator of the present invention has high activity with respect to active energy rays, and has cationic polymerization performance and crosslinking reaction performance. Further, a composition using the acid generator is cured by irradiation with active energy rays. The cured product can maintain good transparency after the heat test.

  Hereinafter, embodiments of the present invention will be described in detail.

R ^{1 to} R ⁶ in the formula (1) represent an organic group bonded to the benzene ring, and may be the same or different. R ^{1 to} R ⁶ include an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or 2 to 30 carbon atoms. Which represent alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl , Alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups and halogen may be substituted with at least one selected from the group consisting of halogen.

In the above, the aryl group having 6 to 30 carbon atoms includes monocyclic aryl groups such as phenyl group and biphenylyl group, and naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrycenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, anthraquinone And a condensed polycyclic aryl group such as

Examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 hetero atoms such as oxygen, nitrogen and sulfur, which may be the same or different. Are monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl A condensed polycyclic heterocyclic group such as carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl It is below.

Examples of the alkyl group having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, okdadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, etc. And a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkenyl group having 2 to 30 carbon atoms include linear, branched, etc. such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl. Can be mentioned. Further, examples of the alkynyl group having 2 to 30 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl and 1-methyl-2-propynyl. And straight chain or branched ones.

The aryl group having 6 to 30 carbon atoms, the heterocyclic group having 4 to 30 carbon atoms, the alkyl group having 1 to 30 carbon atoms, the alkenyl group having 2 to 30 carbon atoms, or the alkynyl group having 2 to 30 carbon atoms is at least 1 It may have a kind of substituent, and examples of the substituent include a linear alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, okdadecyl; isopropyl, isobutyl, sec-butyl, tert-butyl A branched alkyl group having 1 to 18 carbon atoms; a cycloalkyl group having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; a hydroxy group; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, straight-chain or branched alkoxy groups having 1 to 18 carbon atoms such as tert-butoxy and dodecyloxy; C2-C18 linear or branched alkylcarbonyl groups such as pionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl; benzoyl, naphthoyl, etc. Arylcarbonyl group; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, etc., a straight or branched alkoxycarbonyl group having 2 to 19 carbon atoms; phenoxy Aryloxycarbonyl groups having 7 to 11 carbon atoms such as carbonyl and naphthoxycarbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms such as phenylthiocarbonyl and naphthoxythiocarbonyl; A linear or branched acyloxy group having 2 to 19 carbon atoms such as xyl, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octadecylcarbonyloxy; phenylthio, biphenylylthio, Methylphenylthio, chlorophenylthio, bromophenylthio, fluorophenylthio, hydroxyphenylthio, methoxyphenylthio, naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4 -[4- (phenylthio) phenyl] phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-chlorophenylthio, 4-benzoyl-methyl Thiophenylthio, 4- (methylthiobenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio, etc. arylthio groups having 6 to 20 carbon atoms; methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, dodecylthio, etc. Straight chain or branched alkylthio group having 1 to 18 carbon atoms; aryl group having 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl, naphthyl, and the like; A heterocyclic group having 4 to 20 carbon atoms such as nyl; an aryloxy group having 6 to 10 carbon atoms such as phenoxy and naphthyloxy; methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, octylsulfur A linear or branched alkylsulfinyl group having 1 to 18 carbon atoms such as nyl; an arylsulfinyl group having 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl; methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl A linear or branched alkylsulfonyl group having 1 to 18 carbon atoms such as octylsulfonyl; an arylsulfonyl group having 6 to 10 carbon atoms such as phenylsulfonyl, tolylsulfonyl (tosyl group) and naphthylsulfonyl; an alkyleneoxy group; a cyano group; Nitro group; halogen such as fluorine, chlorine, bromine and iodine.

R ^{1 to} R ⁶ are each directly or via —O—, —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group. A ring structure may be formed.

  Among these organic groups, preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and 6 carbon atoms. -14 arylthio group, aryloxy group having 6 to 10 carbon atoms, chlorine atom and fluorine atom, more preferably alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 14 carbon atoms, and 1 to 6 carbon atoms. Of the alkoxy group.

The number of substituents R ^{1 to} R ^{4 in} the formula (1) is 0 to 5, and the number of R ^{5 to} R ⁶ is 0 to ^{4. In} the case of 0, a hydrogen atom is bonded. The number of R ^{1 to} R ⁴ is preferably 0 to 3, the number of R ^{5 to} R ⁶ is preferably 0 to 2, and the number of R ^{1 to} R ⁶ is more preferably 0 or 1. When the number of R ^{1 to} R ⁶ is within these preferable ranges, the photosensitivity and solubility of the sulfonium salt are improved. In addition, the sulfonio group (S ⁺ ) to be substituted in formula (1) may be substituted at any of the o-position, m-position and p-position with respect to the sulfur atom. From the viewpoint of safety, it is more preferable that two sulfonio groups (S ⁺ ) are both substituted at the p-position.
That is, a sulfonium salt represented by the following general formula (1 ′) is more preferable.

[In Formula (1 ′), R ^{1 to} R ⁶ are organic groups bonded to the benzene ring, R ^{1 to} R ⁴ are 0 to 5, and R ^{5 to} R ⁶ are 0 to 4. In the case of 0, a hydrogen atom is bonded, and when a plurality of R ^{1 to} R ⁶ are bonded, they may be the same or different, and R ^{1 to} R ⁶ may be directly or —O— , —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group may form a ring structure. An atom (group) that can be a valent anion. ]

Of the sulfonium salts represented by the formula (1 '), preferred specific examples are shown below.

In the formula (1) or (1 ′), X ⁻ irradiates an active energy ray (visible light, ultraviolet ray, electron beam, X-ray, etc.) to an atom (group) that can be a monovalent anion, that is, a sulfonium salt. It is an anion corresponding to the acid (HX) generated by this. X ⁻ is not limited except that it is a monovalent polyatomic anion, but MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ⁸ _c BY _4-c ⁻ , R ⁸ _c GaY _{4 ^{-c -, R 9 SO 3 -}} , (R 9 SO 2) 3 C - or _{^{(R 9 SO 2) 2 N}} - anion represented by are preferred.

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

Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms. Examples of the alkyl group to be converted into Rf by fluorine substitution include linear alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl and octyl), branched chain alkyl groups (such as isopropyl, isobutyl, sec-butyl and tert-butyl) and And cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and the like. The ratio of hydrogen atoms of these alkyl groups substituted by fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90, based on the number of moles of hydrogen atoms that the original alkyl group had. % Or more, particularly preferably 100%. When the substitution ratio by fluorine atoms is within these preferable ranges, the photosensitivity of the sulfonium salt is further improved. As particularly preferred Rf, 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 ⁸ represents a phenyl group in which a part of hydrogen atoms is substituted with at least one element or electron withdrawing group. Examples of such one element include a halogen atom, and include a fluorine atom, a chlorine atom and a bromine atom. Examples of the electron withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group. Of these, a phenyl group in which one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable. c number of R ⁸ is independently from each other, therefore, it may be the same or different from each other.

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

R ⁹ 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, it may be cyclic, and 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 anions represented by SbF ₆ ⁻ , PF ₆ ⁻ and 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 ⁻ , ((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 ⁻ and (CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ Anions and the like. Among 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 Anions represented by PF ₄ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^— and ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^— are preferred.

The anion represented ^{_{by, (C 6 F 5) 4}} B - - R 8 c BY 4-c, ((CF 3) 2 C 6 H 3) 4 B -, (CF 3 C 6 H 4) 4 Anions represented by B ⁻ , (C ₆ F ₅ ) ₂ BF ₂ ⁻ , C ₆ F ₅ BF ₃ ⁻ and (C ₆ H ₃ F ₂ ) ₄ B ⁻ are included. Of _{these, (C 6 F 5) 4} B - , and _{((CF 3) 2 C 6} H 3) 4 B - anion represented by are preferred.

The anion represented ^{_{by, (C 6 F 5) 4}} Ga - - R 8 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 - and _{(C 6 H 3 F 2)} 4 Ga - anion represented by like. Among these, anions represented by (C ₆ F ₅ ) ₄ Ga ⁻ and ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ are preferable.

Examples of the anion represented by R ⁹ SO ₃ ^— include trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutanesulfonic acid anion, pentafluorophenylsulfonic acid anion, p-toluene. Examples include a sulfonate anion, a benzenesulfonate anion, a camphorsulfonate anion, a methanesulfonate anion, an ethanesulfonate anion, a propanesulfonate anion, and a butanesulfonate anion. Of these, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion and p-toluenesulfonate anion are preferred.

Examples of the anion represented by (R ⁹ 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 ^−. and _{(C 4 F 9 SO 2)} 3 C - anion such as represented and the like.

The anion represented ^{_{by, (CF 3 SO 2) 2}} N - - (R 9 SO 2) 2 N, (C 2 F 5 SO 2) 2 N -, (C 3 F 7 SO 2) 2 N - and _{(C 4 F 9 SO 2)} 2 N - anion, and the like represented.

As monovalent polyatomic anions, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ⁸ _c BY _4-c ⁻ , R ⁸ _c GaY _4-c ⁻ , R ⁹ SO ₃ ⁻ , (R ⁹ SO _{2) 3} C ^- or ^{_{(R 9 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 ^- 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 CO ^{_{-, CF 3 C 6 H 4}} COO - , etc.), an aryl boronic acid ions ^{_{(B (C 6 H 5)}} 4 -, CH 3 CH 2 CH 2 CH 2 B (C 6 H 5) 3 - , etc.), thiocyanate ion (SCN ⁻ ), nitrate ion (NO ₃ ⁻ ) and the like can be used.

These X ^{- _{of, MY a -, (Rf)}} b PF 6-b -, R 8 c BY 4-c -, R 8 c GaY 4-c -, R 9 SO 3 -, (R 9 SO 2 ) ₃ C ^- or _{^{(R 9 SO 2) 2 N}} - anion is preferably represented _{^{by, SbF 6 -, PF 6 -}} , (CF 3 CF 2) 3 PF 3 -, ((CF 3) 2 CF) 3 PF _{^{3 -, (CF 3 CF 2}} 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 ⁻ , trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion , P-toluenesulfonic acid anion, (CF ₃ SO ₂ ) ₃ C ^— and (CF ₃ SO ₂ ) ₂ N ^— are more preferable in terms of improving the resolution and pattern shape of the resist, and (CF ₃ CF ₂ ) ₃ PF _{^{3 -, ((CF 3)}} 2 CF) 3 PF 3 -, (CF 3 CF 2 CF 2) 3 PF 3 -, nonafluorobutanesulfonic acid _{anion, (C 6 F 5) 4} B - , and ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ and (CF ₃ SO ₂ ) ₃ C ^— are particularly preferred because they are more compatible with the resist composition.

Of the sulfonium salts represented by the formula (1 ′), preferred specific examples include thiodi-p-phenylenebis (4-anisylphenylsulfonium) bis (hexafluorophosphate), thiodi-p-phenylenebis (diphenyl). Sulfonium) bis (hexafluoroantimonate), thiodi-p-phenylenebis (diphenylsulfonium) bis [tris (pentafluoroethyl) trifluorophosphate], thiodi-p-phenylenebis (diphenylsulfonium) bis [tris (heptafluoro) Propyl) trifluorophosphate], thiodi-p-phenylenebis (diphenylsulfonium) bis [tetrakis (pentafluorophenyl) borate], thiodi-p-phenylenebis (diphenylsulfonium) bis (nonafluorobut Sulfonate), thiodi-p-phenylenebis (diphenylsulfonium) bis (hexafluoropropane-1,3-disulfonimide), thiodi-p-phenylenebis (di-p-chlorophenylsulfonium) bis (hexafluorophosphate), thiodi -P-phenylenebis (di-p-chlorophenylsulfonium) bis (hexafluoroantimonate), thiodi-p-phenylenebis (di-p-chlorophenylsulfonium) bis [tris (pentafluoroethyl) trifluorophosphate], thiodi -P-phenylenebis (di-p-chlorophenylsulfonium) bis [tris (heptafluoropropyl) trifluorophosphate], thiodi-p-phenylenebis (di-p-chlorophenylsulfonium) bis [tetra (Pentafluorophenyl) borate], thiodi-p-phenylenebis (di-p-chlorophenylsulfonium) bis (nonafluorobutanesulfonate), thiodi-p-phenylenebis (di-p-chlorophenylsulfonium) bis (hexafluoro Propane-1,3-disulfonimide), thiodi-p-phenylenebis (di-tert-butylphenylphenylsulfonium) bis (hexafluorophosphate), thiodi-p-phenylenebis (di-tert-butylphenylphenylsulfonium) Bis (hexafluoroantimonate), thiodi-p-phenylenebis (di-tert-butylphenylphenylsulfonium) bis [tris (pentafluoroethyl) trifluorophosphate], thiodi-p-phenylenebis ( Di-tert-butylphenylphenylsulfonium) bis [tris (heptafluoropropyl) trifluorophosphate], thiodi-p-phenylenebis (di-tert-butylphenylphenylsulfonium) bis [tetrakis (pentafluorophenyl) borate], Thiodi-p-phenylenebis (di-tert-butylphenylphenylsulfonium) bis (nonafluorobutanesulfonate), thiodi-p-phenylenebis (di-tert-butylphenylphenylsulfonium) bis (hexafluoropropane-1,3) -Disulfonimide), thiodi-p-phenylenebis (4-biphenylylphenylsulfonium) bis (hexafluorophosphate), thiodi-p-phenylenebis (4-biphenylylphenylsulfoniu) ) Bis (hexafluoroantimonate), thiodi-p-phenylenebis (4-biphenylylphenylsulfonium) bis [tris (pentafluoroethyl) trifluorophosphate], thiodi-p-phenylenebis (4-biphenylylphenylsulfonium) ) Bis [tris (heptafluoropropyl) trifluorophosphate], thiodi-p-phenylenebis (4-biphenylylphenylsulfonium) bis [tetrakis (pentafluorophenyl) borate], thiodi-p-phenylenebis (4-biphenyl) Rylphenylsulfonium) bis (nonafluorobutanesulfonate), thiodi-p-phenylenebis (4-biphenylylsulfonium) bis (hexafluoropropane-1,3-disulfonimide), thiodi-p- Enylene bis (4-anisylphenylsulfonium) bis (hexafluorophosphate), thiodi-p-phenylenebis (4-anisylphenylsulfonium) bis (hexafluoroantimonate), thiodi-p-phenylenebis (4-anisyl) Phenylsulfonium) bis [tris (pentafluoroethyl) trifluorophosphate], thiodi-p-phenylenebis (4-anisylphenylsulfonium) bis [tris (heptafluoropropyl) trifluorophosphate], thiodi-p-phenylene Bis (4-anisylphenylsulfonium) bis [tetrakis (pentafluorophenyl) borate], thiodi-p-phenylenebis (4-anisylphenylsulfonium) bis (nonafluorobutanesulfonate), thiodi-p -Phenylenebis (4-anisylphenylsulfonium) bis (hexafluoropropane-1,3-disulfonimide) and the like.

The sulfonium salt represented by the formula (1) or (1 ′) can be produced by a known production method. For example, there are a method of reacting diaryl sulfide with chlorine, a method of reacting diaryl sulfide with chlorine and an aromatic hydrocarbon such as benzene, and a method of reacting diaryl sulfide and diaryl sulfoxide in the presence of a dehydrating agent.

The dehydrating agent is not particularly limited as long as it is used as a dehydrating agent in an organic chemical reaction, and examples thereof include concentrated sulfuric acid, phosphoric anhydride, methanesulfonic acid, trifluoromethanesulfonic acid, and anhydrides thereof. Two or more of these may be mixed and used. Moreover, you may use a solvent suitably.

When diaryl sulfoxide and diaryl sulfide are reacted in the presence of a dehydrating agent, the molar ratio is sulfoxide: sulfide = 10: 1 to 1: 1, more preferably 7: 1 to 2: 1, most preferably 5: 1 to 2. 5: 1. The reaction temperature is -10 ° C to 50 ° C, preferably -5 ° C to 30 ° C, and most preferably 0 ° C to 10 ° C. By reacting under these conditions, the sulfonium salt of the present invention can be produced with high purity.

After the reaction, the sulfonium salt can be efficiently produced by exchanging the anion with the acid (HX) having the anion represented by X and the salt (AXn) in the formula (1) or (1 ′). Here, A is a counter cation of the anion X ⁻ , and n represents the number of the anion X with respect to the valence of the cation A. A represents an alkali metal such as Na, K or Li, an alkaline earth metal such as Mg or Ca, or an ammonium cation. Alkali metals are more preferred because of the availability of raw materials and the ease of purification of the sulfonium salts to be produced.

  The acid generator of the present invention further contains a sulfonium salt represented by the general formula (2), and the content thereof is less than 1 mol% with respect to the total number of moles of (1) and (2). Preferably there is. By containing a certain amount of the sulfonium salt represented by the general formula (2), solubility and blending stability are improved. Here, the compounding stability means that problems such as precipitation do not occur when the acid generator is mixed with a solvent and a resin.

Wherein ^(2), R 1 ~R ⁴ is an organic group bonded to the benzene ^ring, the number of R 1 to R ² and the ^{R 4} is 0-5, the number of ^{R 3} is 0-4 In the case of 0, a hydrogen atom is bonded, and when a plurality of R ^{1 to} R ⁴ are bonded, they may be the same or different from each other, and R ^{1 to} R ⁴ may be directly or —O— , —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group may form a ring structure. An atom (group) that can be a valent anion. ]

  The organic group X in the formula (2) is the same as that in the formula (1).

  In addition to the sulfonium salts listed above, the acid generator of the present invention may contain other conventionally known acid generators if necessary. In addition, in the following, the acid generator of this invention consists of a sulfonium salt represented by Formula (1) and (2), and the meaning which does not contain another acid generator.

  When the other acid generator is contained, the content (mol%) of the other acid generator is 0 with respect to the total number of moles of the sulfonium salt represented by the formulas (1) and (2) of the present invention. 0.1 to 100 is preferable, and 0.5 to 50 is more preferable.

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

  The acid generator of the present invention may be dissolved in advance in a solvent that does not inhibit polymerization, crosslinking, deprotection reaction or the like in order to facilitate dissolution in a cationically polymerizable compound or a chemically amplified resist composition.

Solvents include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; ethylene glycol, ethylene glycol Polyhydric alcohols such as monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether And derivatives thereof; cyclic ethers such as dioxane Ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, 2- Such as methyl hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. Esters: aromatic hydrocarbons such as toluene and xylene.

  When a solvent is used, the use ratio of the solvent 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 acid generator of the present invention. The solvent to be used may be used independently or may use 2 or more types together.

The energy beam curable composition of the present invention comprises the acid generator and a cationically polymerizable compound.
The alkali metal content in the energy ray curable composition is preferably 1.5 ppm or less from the viewpoint of coloring of the cured product.

Examples of the cationic polymerizable compound that is a constituent of the energy ray-curable composition include cyclic ethers (epoxides and oxetanes), ethylenically unsaturated compounds (vinyl ether and styrene, etc.), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters. {JP-A-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-A-2000-186071, JP-A-08-85775, JP-A-08-134405, JP-A-2008-20838, JP-A-2008-20839, JP-A-2008-20841, JP2008-26 60, JP2008-26644, JP2007-277327, 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 Materials” (1992, CMC), Technical Information Association “UV Curing Failure / Inhibition Causes and Countermeasures” (2003, Technical Information Association), Coloring Materials 68, (5), 286-293 (1995), fine chemical, 29, (19), 5-14 (2000), etc.}.

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

  Examples of the aromatic epoxide include glycidyl ethers of monovalent or polyvalent phenols (phenol, bisphenol A, phenol novolac and compounds obtained by adducting these alkylene oxides) having at least one aromatic ring.

  As the alicyclic epoxide, a compound obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, etc.) Is mentioned.

  Aliphatic epoxides include aliphatic polyhydric alcohols or polyglycidyl ethers of this alkylene oxide adduct (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), aliphatic polybasic acids. Examples thereof include polyglycidyl esters (such as diglycidyl tetrahydrophthalate) and epoxidized products of long chain unsaturated compounds (such as epoxidized soybean oil and epoxidized polybutadiene).

As oxetane, known ones can be used. For example, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3- Oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, oxetanylsilsesquioxetane, phenol novolac oxetane, etc. Is mentioned.

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

  Examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

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

  Examples of the polyfunctional vinyl ether include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

  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.

Furthermore, polyorganosiloxane having at least one cationic polymerizable group in one molecule can be used (Japanese Patent Laid-Open No. 2001-348482, Japanese Patent Laid-Open No. 2000-281965, Japanese Patent Laid-Open No. 7-242828, JP-A-2008-195931, Journal of Polym. Sci., Part A, Polym. Chem., Vol. 28, 497 (1990)).
These polyorganosiloxanes may be linear, branched or cyclic, or a mixture thereof.

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. Moreover, these cationically polymerizable compounds may be used alone or in combination of two or more.

  The content of the acid generator of the present invention in the energy ray curable composition is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound. is there. Within this range, the polymerization of the cationically polymerizable compound is further sufficient, 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 cationically polymerizable compound, the type of energy beam and the irradiation amount, temperature, curing time, humidity, and coating thickness, and is limited to the above range. Not.

  In the energy beam curable composition of the present invention, if necessary, known additives (sensitizers, pigments, fillers, antistatic agents, flame retardants, antifoaming agents, flow regulators, light stabilizers, An antioxidant, an adhesion-imparting agent, an ion scavenger, a coloring inhibitor, a solvent, a non-reactive resin, a radically polymerizable compound, and the like).

  As the sensitizer, known sensitizers (JP-A-11-279212 and JP-A-09-183960) can be used, and anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene. , 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthone {thioxanthone, 2 -Methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.}; phenothiazine {phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N-phenylphenol Xanthone; naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol, etc.}; ketone {dimethoxyacetophenone, di Ethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 4-benzoyl-4′-methyldiphenyl sulfide, etc.}; carbazole {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole and N-glycidylcarbazole and the like}; chrysene {1,4-dimethoxychrysene and 1,4-di-α-methylbenzyloxychrysene and the like}; phenanthrene {9 -Hydroxyphenanthrene, 9-methoxyphenanthrene, 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 acid 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 acid generator.

  As the filler, known fillers can be used, 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 acid generator.

  As the antistatic agent, known antistatic agents can be used, and examples include nonionic antistatic agents, anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents, and polymeric antistatic agents. .

  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 acid generator.

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

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

As the antifoaming agent, known antifoaming agents can be used, such as alcohol defoaming agents, metal soap defoaming agents, phosphate ester defoaming agents, fatty acid ester defoaming agents, polyether defoaming agents, and silicone defoaming agents. And mineral oil defoaming agents.

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.
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 amines, etc.}; and quenching And a type stabilizer {nickel complex etc.}.
As the antioxidant, known antioxidants can be used, and examples include phenolic antioxidants (monophenolic, bisphenolic and polymeric phenolic), sulfur antioxidants and phosphorus antioxidants. It is done.
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.
As the ion scavenger, known ion scavengers can be used, and organic aluminum (alkoxyaluminum, phenoxyaluminum, etc.) and the like can be mentioned.
Known anti-coloring agents can be used as the anti-coloring agent. In general, antioxidants are effective. Phenol type antioxidants (monophenol type, bisphenol type and high molecular phenol type, etc.), sulfur type oxidation Inhibitors and phosphorus-based antioxidants may be mentioned, but they are hardly effective in preventing coloring during a heat resistance test at high temperatures.

  When an antifoaming agent, a flow control agent, a light stabilizer, an antioxidant, an adhesion promoter, an ion scavenger, or a coloring inhibitor is contained, each content is 0 with respect to 100 parts of the acid generator. 0.1 to 20000 parts by weight is preferable, and 0.5 to 5000 parts by weight is more preferable.

  The solvent is not limited as long as it can be used for dissolving the cationic polymerizable compound and adjusting the viscosity of the energy ray-curable composition, and those mentioned as the solvent for the acid generator can be used.

  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 acid 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, and 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, more preferably 50 to 150,000 parts by weight with respect to 100 parts of the acid generator.

  When a non-reactive resin is contained, it is desirable to dissolve the non-reactive resin in a solvent in advance in order to facilitate dissolution of the non-reactive resin with the cationic polymerizable compound.

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

  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 acid generator.

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

  As the radical polymerization initiator, known radical polymerization initiators can be used, thermal radical polymerization initiators (organic peroxides, azo compounds, etc.) and photo radical polymerization initiators (acetophenone initiators, benzophenone initiators, Michler ketone-based initiator, benzoin-based initiator, thioxanthone-based initiator, acylphosphine-based initiator, etc.).

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

  The energy ray curable composition of the present invention is prepared by uniformly mixing a cationically polymerizable compound, an acid generator and, if necessary, an additive at room temperature (about 20 to 30 ° C.) or as necessary under heating (about 40 to 90 ° C.). It can be prepared by mixing and dissolving, or further kneading with three rolls or the like.

The energy ray-curable composition of the present invention can be cured by irradiation with 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 acid generator 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 beams in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from fluorescent lamps, semiconductor solid lasers, argon lasers, He—Cd lasers, KrF excimer lasers, ArF excimer lasers, F ₂ lasers, etc. are preferable . In addition, the radiation which has high energy, such as an electron beam or an X-ray, can also be used for an energy beam.

  The irradiation time of the energy beam is affected by the energy beam intensity and the energy beam permeability to the energy beam curable composition, but about 0.1 to 10 seconds is sufficient at room temperature (about 20 to 30 ° C.). It is. However, it may be preferable to spend more time when energy beam permeability is low or when the energy beam curable composition is thick. Most energy ray-curable compositions are cured by cationic polymerization 0.1 seconds to several minutes after irradiation with energy rays, but if necessary, after irradiation with energy rays, room temperature (about 20 to 30 ° C.) to 200. It is also possible to heat and cure at a temperature of several seconds to several hours.

  Specific applications of the energy ray curable composition of the present invention include paints, coating agents, various coating materials (hard coat, anti-stain coating, anti-fogging coating, touch-resistant coating, optical fiber, etc.), adhesive tape Back coating agent, Release coating material for adhesive labels (release paper, release plastic film, release metal foil, etc.), printing plate, dental material (dental compound, dental composite) ink, inkjet ink, positive Type resist (connecting terminals and wiring pattern formation for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, etc.), resist films, liquid resists, negative resists (surface protective films for semiconductor elements, interlayer insulating films, planarization films) Permanent film materials, etc.), MEMS resist, positive photosensitive materials, negative photosensitive materials, various adhesives (temporary fixing agents for various electronic components, DD adhesive, pickup lens adhesive, FPD functional film (deflection plate, antireflection film, etc. adhesive), holographic resin, FPD material (color filter, black matrix, partition material, photospacer, Ribs, alignment films for liquid crystals, sealants for FPD, etc.), optical members, molding materials (for building materials, optical components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, sealing Materials, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, photofabrication materials, and micro stereolithography materials, etc. Ideal for use.

  Since the acid generator of the present invention generates a strong acid even when irradiated with light, the chemical amplification type known in the art (JP 2003-267968 A, JP 2003-261529 A, JP 2002-193925 A, etc.) is known. It can also be used as an acid generator for resist materials.

  As the chemically amplified resist material, (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 an acid generator, and (2) an alkali developer Soluble resin, three-component chemical amplification type positive resist containing, as essential components, a dissolution inhibitor that becomes soluble in an alkali developer by the action of an acid and an acid generator, and (3) soluble in an alkali developer A chemically amplified negative resist containing an acid generator and a crosslinking agent that crosslinks the resin by heat treatment in the presence of the resin and acid and makes the resin insoluble in an alkaline developer is included.

The chemically amplified positive photoresist composition of the present invention is soluble in alkali by the action of the component (A) containing the acid generator of the present invention, which is a compound that generates acid upon irradiation with light or radiation, and the acid. It contains an increasing resin component (B).

  In the chemically amplified positive photoresist composition of the present invention, the component (A) may be used in combination with other conventionally known acid generators. Examples of other acid generators include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, and nitrobenzyl compounds. In addition, organic halides, disulfone and the like can be mentioned.

  As other conventionally known acid generators, one or more of the group of onium compounds, sulfonimide compounds, diazomethane compounds and oxime sulfonate compounds are preferred.

  When such other conventionally known acid generators are used in combination, the ratio of use may be arbitrary, but usually the total weight of the sulfonium salt represented by the general formulas (1) and (2) is 100 parts by weight. On the other hand, the other acid generator is 10 to 900 parts by weight, preferably 25 to 400 parts by weight.

  The content of the component (A) is preferably 0.05 to 5% by weight in the solid content of the chemically amplified positive photoresist composition.

<Resin component (B) whose solubility in alkali is increased by the action of acid>
The above-mentioned “resin (B) whose solubility in alkali is increased by the action of an acid” used in the chemically amplified positive photoresist composition for thick film of the present invention (referred to herein as “component (B)”) .) Is at least one resin selected from the group consisting of novolak resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3), or a mixed resin or copolymer thereof.

[Novolac resin (B1)]
As the novolac resin (B1), a resin represented by the following general formula (b1) can be used.

In the general formula (b1), R ^1b represents an acid dissociable, dissolution inhibiting group, R ^2b and R ^3b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is in parentheses. Represents the number of repeating units in the structure.

Furthermore, ^examples of the acid dissociable, dissolution inhibiting group represented by R ^1b include a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and a cyclic group having 3 to 6 carbon atoms. Are preferably an alkyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

Here, specific examples of the acid dissociable, dissolution inhibiting group represented by R ^1b include methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, isobutoxyethyl. Group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group, tert-butoxycarbonyl group, tert-butoxy group Examples include carbonylmethyl group, trimethylsilyl group, and tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene resin (B2)]
As the polyhydroxystyrene resin (B2), a resin represented by the following general formula (b4) can be used.

In the general formula (b4), R ^8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^9b represents an acid dissociable, dissolution inhibiting group, and n represents the number of repeating units in the parenthesis. Represent.

  The alkyl group having 1 to 6 carbon atoms is a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The cyclic alkyl group includes a cyclopentyl group and a cyclohexyl group. Etc.

As the acid dissociable, dissolution inhibiting group represented by R ^9b , the same acid dissociable, dissolution inhibiting groups as those exemplified for R ^1b can be used.

  Furthermore, the polyhydroxystyrene resin (B2) can contain other polymerizable compounds as structural units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid; methyl (meth) acrylate, etc. (Meth) acrylic acid alkyl esters of (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate; vinyl group-containing fragrances such as styrene and vinyltoluene Aliphatic compounds; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride; And the like amide bond-containing polymerizable compounds such as.

[Acrylic resin (B3)]
As the acrylic resin (B3), resins represented by the following general formulas (b5) to (b10) can be used.

In the general formulas (b5) to (b7), R ^{10b to} R ^17b each independently represent a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms. Represents a group, a fluorine atom, a linear fluorinated alkyl group having 1 to 6 carbon atoms or a branched fluorinated alkyl group having 3 to 6 carbon atoms, and ^Xb together with the carbon atom to which it is bonded Forming a hydrocarbon ring having 5 to 20 carbon atoms, Y ^b represents an aliphatic cyclic group or an alkyl group which may have a substituent, n represents the number of repeating units of the structure in parentheses, p is an integer of 0 to 4, and q is 0 or 1.

In General Formula (b8), General Formula (b9), and General Formula (b10), R ^18b , R ^20b, and R ^21b each independently represent a hydrogen atom or a methyl group, and in General Formula (b8), R ^19b is independently of each other a hydrogen atom, a hydroxyl group, a cyano group or a COOR ^23b group (where R ^23b is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a branched group having 3 to 4 carbon atoms). Represents a chain alkyl group or a cycloalkyl group having 3 to 20 carbon atoms.) In the general formula (b10), each R ^22b is independently a monovalent alicyclic group having 4 to 20 carbon atoms. A hydrocarbon group or a derivative thereof, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, and at least one of R ^22b is the alicyclic hydrocarbon group or Either its derivatives or any two R ^22b of each other are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the common carbon atom to which each is bonded, and the remaining R ^22b is carbon A linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof is represented.

  Among the components (B), it is preferable to use an acrylic resin (B3).

  Moreover, the polystyrene conversion weight average molecular weight of a component (B) becomes like this. Preferably it is 10,000-600,000, More preferably, it is 50,000-600,000, More preferably, it is 230,000-550,000. is there. By setting it as such a weight average molecular weight, the resin physical property of a resist becomes excellent.

  Furthermore, the component (B) is preferably a resin having a dispersity of 1.05 or more. Here, the “dispersion degree” is a value obtained by dividing the weight average molecular weight by the number average molecular weight. By setting such a degree of dispersion, the resist plating resistance and resin physical properties are excellent.

  The content of the component (B) is preferably 5 to 60% by weight in the solid text of the chemically amplified positive photoresist composition.

<Alkali-soluble resin (C)>
The chemically amplified positive photoresist composition of the present invention preferably further contains an alkali-soluble resin (hereinafter referred to as “component (C)”) in order to improve the resin physical properties of the resist. . The component (C) is preferably at least one selected from the group consisting of novolak resins, polyhydroxystyrene resins, acrylic resins and polyvinyl resins.

  The content of the component (C) is preferably 5 to 95 parts by weight, and more preferably 10 to 90 parts by weight with respect to 100 parts by weight of the component (B). By setting the amount to 5 parts by weight or more, the resin physical properties of the resist can be improved.

<Acid diffusion control agent (D)>
In the chemically amplified positive photoresist composition for thick film of the present invention, an acid diffusion control agent (D) (in this specification, “component ( D) ").) Is preferably included. As the component (D), a nitrogen-containing compound is preferable, and an organic carboxylic acid, an oxo acid of phosphorus, or a derivative thereof can be further contained as necessary.

  In addition, the chemically amplified positive photoresist composition of the present invention may further contain an adhesion assistant in order to improve the adhesion to the substrate. As the adhesion assistant used, a functional silane coupling agent is preferable.

  The chemically amplified positive photoresist composition of the present invention may further contain a surfactant in order to improve coating properties, antifoaming properties, leveling properties and the like.

  In addition, the chemically amplified positive photoresist composition of the present invention may further contain an acid, an acid anhydride, or a high boiling point solvent in order to finely adjust the solubility in an alkali developer.

  In addition, the chemically amplified positive photoresist composition of the present invention basically does not require a sensitizer, but can contain a sensitizer as necessary to complement the sensitivity. As such a sensitizer, conventionally known ones can be used, and specific examples thereof include those described above.

  The amount of these sensitizers used is 5 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the total weight of the acid generator of the present invention.

  In addition, an organic solvent can be appropriately blended in the chemically amplified positive photoresist composition of the present invention for viscosity adjustment. Specific examples of the organic solvent include those described above.

  The amount of these organic solvents used is such that the solid layer concentration is such that the film thickness of the photoresist layer obtained by using the chemically amplified positive photoresist composition of the present invention (for example, spin coating method) is 5 μm or more. Is preferably 30% by weight or more.

  The chemical amplification type positive photoresist composition for thick film of the present invention can be prepared, for example, by mixing and stirring each of the above components by a usual method. If necessary, a dissolver, a homogenizer, a three roll mill, etc. You may disperse and mix using a disperser. Moreover, after mixing, you may further filter using a mesh, a membrane filter, etc.

  The chemically amplified positive photoresist composition of the present invention is suitable for forming a photoresist layer having a thickness of usually 5 to 150 μm, more preferably 10 to 120 μm, and still more preferably 10 to 100 μm on a support. ing. In this photoresist laminate, a photoresist layer made of the chemically amplified positive photoresist composition of the present invention is laminated on a support.

  The support is not particularly limited, and a conventionally known one can be used. Examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed. Examples of the substrate include a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, a glass substrate, and the like. In particular, the chemically amplified positive photoresist composition of the present invention can form a resist pattern satisfactorily even on a copper substrate. As a material for the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold, or the like is used.

  The said photoresist laminated body can be manufactured as follows, for example. That is, a desired coating film is formed by applying a solution of a chemically amplified positive photoresist composition prepared as described above onto a support and removing the solvent by heating. As a coating method on the support, methods such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, and an applicator method can be employed. The pre-baking conditions of the coating film of the composition of the present invention vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but are usually 70 to 150 ° C., preferably 80 to 140 ° C. What is necessary is just about 60 minutes.

  The film thickness of the photoresist layer is usually 5 to 150 μm, preferably 10 to 120 μm, more preferably 10 to 100 μm.

  In order to form a resist pattern using the thus-obtained photoresist laminate, light or radiation, for example, having a wavelength of 300 to 500 nm is applied to the obtained photoresist layer through a mask having a predetermined pattern. Irradiation (exposure) with ultraviolet rays or visible rays may be performed selectively.

Here, the “light” may be light that activates the acid generator to generate an acid, and includes ultraviolet rays, visible rays, and far ultraviolet rays, and “radiation” means X-rays, electron beams, It means an ion beam. As a light or radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon gas laser, an LED lamp, or the like can be used. Moreover, although the amount of radiation irradiation changes with kinds of each component in a composition, a compounding quantity, the film thickness of a coating film, etc., when using an ultrahigh pressure mercury lamp, it is 50-10,000 mJ / cm < ² >, for example.

  Then, after the exposure, the diffusion of the acid is promoted by heating using a known method to change the alkali solubility of the exposed photoresist layer. Next, for example, using a predetermined alkaline aqueous solution as a developer, unnecessary portions are dissolved and removed to obtain a predetermined resist pattern.

  The development time varies depending on the type of each component of the composition, the blending ratio, and the dry film thickness of the composition, but it is usually 1 to 30 minutes. Any of these may be used. After the development, washing with running water is performed for 30 to 90 seconds and dried using an air gun or an oven.

  Forming connection terminals such as metal posts and bumps by embedding a conductor such as metal in the non-resist portion (the portion removed with the alkali developer) of the resist pattern thus obtained, for example, by plating. Can do. The plating method is not particularly limited, and various conventionally known methods can be employed. As the plating solution, solder plating, copper plating, gold plating, or nickel plating solution is particularly preferably used. The remaining resist pattern is finally removed using a stripping solution or the like according to a conventional method.

  The chemically amplified positive photoresist composition of the present invention can also be used as a dry film. This dry film has a protective film formed on both sides of a layer made of the chemically amplified positive photoresist composition of the present invention. The thickness of the layer made of the chemically amplified positive photoresist composition is usually 10 to 150 μm, preferably 20 to 120 μm, more preferably 20 to 80 μm. Moreover, a protective film is not specifically limited, The resin film conventionally used for the dry film can be used. As an example, one may be a polyethylene terephthalate film and the other may be one selected from the group consisting of a polyethylene terephthalate film, a polypropylene film, and a polyethylene film.

  The chemical amplification type positive dry film as described above can be produced, for example, as follows. That is, a solution of a chemically amplified positive photoresist composition prepared as described above is applied onto one protective film, and the solvent is removed by heating to form a desired coating film. The drying conditions vary depending on the type of each component in the composition, the blending ratio, the coating film thickness and the like, but are usually 60 to 100 ° C. and about 5 to 20 minutes.

  In order to form a resist pattern using the thus obtained chemically amplified dry film, one protective film of the chemically amplified positive dry film is peeled off and the exposed surface is directed to the support side described above. Then, after laminating on the support to obtain a photoresist layer, after prebaking to dry the resist, the other protective film may be peeled off.

  In the photoresist layer thus obtained on the support, a resist pattern can be formed in the same manner as described above with respect to the photoresist layer formed by coating directly on the support. .

The chemically amplified negative photoresist composition of the present invention is an alkali-soluble resin having a component (E) comprising the acid generator of the present invention, which is a compound that generates an acid upon irradiation with light or radiation, and a phenolic hydroxyl group. (F) and a crosslinking agent (G) are contained.

  In the chemically amplified negative photoresist composition of the present invention, the component (E) may be used in combination with other conventionally known acid generators. Examples of other acid generators include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, and nitrobenzyl compounds. In addition, organic halides, disulfone and the like can be mentioned.

  As other conventionally known acid generators, one or more selected from the group of onium compounds, sulfonimide compounds, diazomethane compounds and oxime sulfonate compounds are preferable.

  When such other conventionally known acid generators are used in combination, the ratio of use may be arbitrary, but the other acid generators are usually 10 to 10 parts by weight based on the total weight of the acid generator of the present invention. 900 parts by weight, preferably 25 to 400 parts by weight.

  The content of the component (E) is preferably 0.01 to 10% by weight in the solid content of the chemically amplified negative photoresist composition.

Alkali-soluble resin (F) having phenolic hydroxyl group
Examples of the “alkali-soluble resin having a phenolic hydroxyl group” in the present invention (hereinafter referred to as “phenol resin (F)”) include, for example, novolak resin, polyhydroxystyrene, a copolymer of polyhydroxystyrene, hydroxystyrene and styrene. Copolymer of hydroxystyrene, styrene and (meth) acrylic acid derivative, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, and the like. Among these, novolac resin, polyhydroxystyrene, copolymer of polyhydroxystyrene, copolymer of hydroxystyrene and styrene, copolymer of hydroxystyrene, styrene and (meth) acrylic acid derivative, phenol-xylylene glycol Condensed resins are preferred. In addition, these phenol resin (F) may be used individually by 1 type, and may mix and use 2 or more types.

Moreover, the phenolic resin (F) may contain a phenolic low molecular weight compound as a part of the component.
Examples of the phenolic low molecular weight compound include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, and the like.

Cross-linking agent (G)
The “crosslinking agent” (hereinafter also referred to as “crosslinking agent (G)”) in the present invention is not particularly limited as long as it acts as a crosslinking component (curing component) that reacts with the phenol resin (F). Examples of the crosslinking agent (G) include a compound having at least two or more alkyl etherified amino groups in the molecule, a compound having at least two or more alkyl etherified benzenes in the molecule as a skeleton, An oxirane ring-containing compound, a thiirane ring-containing compound, an oxetanyl group-containing compound, an isocyanate group-containing compound (including a blocked one), and the like can be given.

Of these crosslinking agents (G), compounds having at least two alkyl etherified amino groups in the molecule and oxirane ring-containing compounds are preferred. Furthermore, it is more preferable to use a compound having at least two alkyl etherified amino groups in the molecule and an oxirane ring-containing compound in combination.

The blending amount of the crosslinking agent (G) in the present invention is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the phenol resin (F). When the amount of the crosslinking agent (G) is 1 to 100 parts by weight, the curing reaction proceeds sufficiently, and the resulting cured product has a good pattern shape with high resolution, heat resistance and electrical insulation. It is preferable because of its excellent properties.
When the compound having an alkyl etherified amino group and the oxirane ring-containing compound are used in combination, the content ratio of the oxirane ring-containing compound is the sum of the compound having an alkyl etherified amino group and the oxirane ring-containing compound being 100. In the case of weight%, it is preferably 50% by weight or less, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight.
In this case, the obtained cured film is preferable because it is excellent in chemical resistance without impairing high resolution.

Cross-linked fine particles (H)
The chemically amplified negative photoresist composition of the present invention further contains crosslinked fine particles (hereinafter also referred to as “crosslinked fine particles (H)”) in order to improve the durability and thermal shock resistance of the resulting cured product. Can be made.

The average particle size of the crosslinked fine particles (H) is usually 30 to 500 nm, preferably 40 to 200 nm, more preferably 50 to 120 nm.
The method for controlling the particle size of the crosslinked fine particles (H) is not particularly limited. For example, when the crosslinked fine particles are synthesized by emulsion polymerization, the number of micelles during emulsion polymerization is controlled by the amount of the emulsifier used, and the particle size is controlled. Can be controlled.
The average particle diameter of the crosslinked fine particles (H) is a value measured by diluting a dispersion of crosslinked fine particles according to a conventional method using a light scattering flow distribution measuring device or the like.

The amount of the crosslinked fine particles (H) is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the phenol resin (F). When the blended amount of the crosslinked fine particles (H) is 0.5 to 50 parts by weight, the compatibility or dispersibility with other components is excellent, and the thermal shock resistance and heat resistance of the resulting cured film are improved. be able to.

Adhesion aid In addition, the chemically amplified negative photoresist composition of the present invention may contain an adhesion aid in order to improve the adhesion to the substrate.
Examples of the adhesion assistant include a functional silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.

The compounding amount of the adhesion assistant is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of the phenol resin (F). A blending amount of the adhesion aid of 0.2 to 10 parts by weight is preferable because it is excellent in storage stability and good adhesion can be obtained.

Solvent Further, the chemically amplified negative photoresist composition of the present invention may contain a solvent for improving the handleability of the resin composition and adjusting the viscosity and storage stability.
The solvent is not particularly limited, but specific examples include those described above.

Other Additives In addition, the chemically amplified negative photoresist composition of the present invention can contain other additives as necessary so as not to impair the characteristics of the present invention. Examples of such other additives include inorganic fillers, sensitizers, quenchers, leveling agents and surfactants.

The method for preparing the chemically amplified negative photoresist composition of the present invention is not particularly limited, and can be prepared by a known method. It can also be prepared by stirring a sample bottle with each component in it and completely plugged on the wave rotor.

The cured product in the present invention is obtained by curing the chemically amplified negative photoresist composition.
The above-mentioned chemically amplified negative photoresist composition according to the present invention has a high residual film ratio and excellent resolution, and its cured product is excellent in electrical insulation, thermal shock, etc. The cured product can be suitably used as a surface protective film, planarizing film, interlayer insulating film material, etc. for electronic components such as semiconductor elements and semiconductor packages.

In order to form the cured product of the present invention, first, the chemically amplified negative photoresist composition according to the present invention is used as a support (a silicon wafer with a resin-coated copper foil, a copper-clad laminate, a metal sputtered film, Coating onto an alumina substrate and the like, and drying to volatilize the solvent and the like to form a coating film. Then, it exposes through a desired mask pattern, heat processing (henceforth this heat processing is called "PEB") is performed, and reaction with a phenol resin (F) and a crosslinking agent (G) is accelerated | stimulated. Subsequently, it develops with an alkaline developing solution, A desired pattern can be obtained by melt | dissolving and removing an unexposed part. Furthermore, a cured film can be obtained by performing a heat treatment in order to develop insulating film characteristics.

As a method of applying the resin composition to the support, for example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, or a spin coating method can be used. The thickness of the coating film can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of the composition solution.
Examples of radiation used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, h-line steppers, i-line steppers, gh-line steppers, and ghi-line steppers, electron beams, and laser beams. . The exposure amount is appropriately selected depending on the light source used, the resin film thickness, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the resin film thickness is about 100 to 50000 J / m ² when the resin film thickness is 1 to 50 μm.

After the exposure, the PEB treatment is performed to promote the curing reaction of the phenol resin (F) and the crosslinking agent (G) by the generated acid. The PEB condition varies depending on the blending amount of the resin composition, the used film thickness, etc., but is usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes. Thereafter, development is performed with an alkaline developer, and a desired pattern is formed by dissolving and removing unexposed portions. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The development conditions are usually 20 to 40 ° C. and about 1 to 10 minutes.

Furthermore, in order to sufficiently develop the characteristics as an insulating film after development, the film can be sufficiently cured by heat treatment. Such curing conditions are not particularly limited, but the composition can be cured by heating at a temperature of 50 to 250 ° C. for about 30 minutes to 10 hours depending on the use of the cured product. Moreover, in order to fully advance hardening and to prevent the deformation | transformation of the obtained pattern shape, it can also heat in two steps, for example, at the temperature of 50-120 degreeC in a 1st step, 5 minutes-2 It can also be cured by heating for about an hour and further heating for about 10 minutes to 10 hours at a temperature of 80 to 250 ° C. Under such curing conditions, a general oven, an infrared furnace, or the like can be used as a heating facility.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited by this. In addition, the part in each example shows a weight part.

[Production Example 1]
Synthesis of thiodi-p-phenylenebis (diphenylsulfonium) bis (hexafluorophosphate) (1-1) (the following structural formula) and diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate (2-1)

  101 parts of diphenyl sulfoxide was dissolved in 200 parts of sulfuric acid and cooled to 0 ° C. in an ice bath. Thereto, 18.6 parts of diphenyl sulfide was added dropwise so as not to exceed 10 ° C. The reaction solution was added to 300 parts of distilled water, and 40.5 parts of potassium hexafluorophosphate was added thereto. After stirring for 3 hours, the mixture was extracted with 600 parts of ethyl acetate and washed with water until the pH of the aqueous layer became neutral. The organic layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a light yellow solid product. This was washed twice with 100 parts of methanol and dried to obtain 38.1 g (yield 45%) of a white solid. According to 1 H-NMR, this white solid was converted into thiodi-p-phenylenebis (diphenylsulfonium) bis (hexafluorophosphate) (1-1) and diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate (2-1). It was confirmed that the molar ratio was 99.1: 0.9.

[Production Example 2]
Synthesis of thiodi-p-phenylenebis (diphenylsulfonium) bis (hexafluorophosphate) (1-1) 20.0 parts of the white solid obtained in Production Example 1 was dissolved in 100 parts of ethyl acetate. Recrystallization was performed with 600 parts of diethyl ether to obtain 18.0 g of a white solid (yield 90%). This white solid was confirmed to be thiodi-p-phenylenebis (diphenylsulfonium) bis (hexafluorophosphate) (1-1) by 1 H-NMR.

[Production Example 3]
Thiodi-p-phenylenebis (di-p-chlorophenylsulfonium) bis (hexafluorophosphate) (1-2) (the following structural formula) and di (p-chlorophenyl) (4-phenylthio) phenylsulfonium hexafluorophosphate ( Synthesis of 2-2)

In the same manner as in Production Example 1, except that 101 parts of diphenyl sulfoxide was changed to 135.6 parts of di-p-chlorophenyl sulfoxide in Production Example 1, 41.4 g (yield 42%) g of a white solid was obtained. According to 1 H-NMR, this white solid was converted to thiodi-p-phenylenebis (di-p-chlorophenylsulfonium) bis (hexafluorophosphate) (1-2) and di (p-chlorophenyl) [4- (phenylthio) phenyl] sulfonium. It was a mixture of hexafluorophosphate (2-2), and it was confirmed that the molar ratio was 99.2: 0.8.

[Production Example 4]
Synthesis of thiodi-p-phenylenebis (di-p-chlorophenylsulfonium) bis (hexafluorophosphate) (1-2) In Production Example 2, 20.0 parts of the white solid obtained in Production Example 1 was obtained in Production Example 3. The white solid was obtained in 17.1 g (yield 86%) in the same manner as in Production Example 2, except that the white solid was changed to 20.0 parts. This white solid was confirmed by 1 H-NMR to be thiodi-p-phenylenebis (di-p-chlorophenylsulfonium) bis (hexafluorophosphate) (1-2).

[Production Example 5]
Thiodi-p-phenylenebis (di-tert-butylphenylphenylsulfonium) bis (hexafluorophosphate) (1-3) (the following structural formula) and (p-tert-butylphenyl) (p-phenylthiophenyl) phenyl Synthesis of sulfonium hexafluorophosphate (2-3)

In the same manner as in Production Example 1, except that 101 parts of diphenyl sulfoxide was changed to 129.2 parts of p-tert-butyldiphenyl sulfoxide in Production Example 1, 43.8 g (yield 46%) of a white solid was obtained. According to 1 H-NMR, this white solid was converted into thiodi-p-phenylenebis (di-tert-butylphenylphenylsulfonium) bis (hexafluorophosphate) (1-3) and (p-tert-butylphenyl) (p-phenylthio). Phenyl) phenylsulfonium hexafluorophosphate (2-3) mixture, the molar ratio of which was 99.1: 0.9.

[Production Example 6]
Synthesis of thiodi-p-phenylenebis (di-tert-butylphenylphenylsulfonium) bis (hexafluorophosphate) (1-3) In Production Example 2, 20.0 parts of the white solid obtained in Production Example 1 was produced. The white solid was obtained in 18.1 g (yield 91%) in the same manner as in Production Example 2, except that the white solid obtained in 5 was changed to 20.0 parts. This white solid was confirmed by 1 H-NMR to be thiodi-p-phenylenebis (di-tert-butylphenylphenylsulfonium) bis (hexafluorophosphate) (1-3).

[Production Example 7]
Thiodi-p-phenylenebis (4-biphenylylphenylsulfonium) bis (hexafluorophosphate) (1-4) (the following structural formula) and (4-biphenylyl) (4-phenylthiophenyl) phenylsulfonium hexafluorophosphate Synthesis of (2-4)

In the same manner as in Production Example 1 except that 101 parts of diphenyl sulfoxide was changed to 139.2 parts of 4-biphenylylphenyl sulfoxide in Production Example 1, 43.9 g (yield 44%) of a yellowish white solid was obtained. According to 1 H-NMR, this solid was converted into thiodi-p-phenylenebis (4-biphenylylphenylsulfonium) bis (hexafluorophosphate) (1-4) and (4-biphenylyl) (4-phenylthiophenyl) phenylsulfonium hexafluoro. It was a mixture of phosphate (2-4), and it was confirmed that the molar ratio was 99.3: 0.7.

[Production Example 8]
Synthesis of thiodi-p-phenylenebis (4-biphenylylphenylsulfonium) bis (hexafluorophosphate) (1-4) In Production Example 2, 20.0 parts of the white solid obtained in Production Example 1 was obtained in Production Example 7. The product was obtained in 18.0 g (yield 90%) as a yellowish white solid in the same manner as in Production Example 2 except that the obtained yellowish white solid was changed to 20.0 parts. This yellowish white solid was confirmed by 1 H-NMR to be thiodi-p-phenylenebis (4-biphenylylphenylsulfonium) bis (hexafluorophosphate) (1-4).

[Production Example 9]
Thiodi-p-phenylenebis (4-methoxyphenylsulfonium) bis (hexafluorophosphate) (1-5) (the following structural formula) and di (4-methoxyphenyl) (4-phenylthiophenyl) sulfonium hexafluorophosphate Synthesis of (2-5)

In the same manner as in Production Example 1 except that 101 parts of diphenyl sulfoxide was changed to 131.2 parts of di (4-methoxyphenyl) sulfoxide in Production Example 1, 43.5 g of a yellowish white solid (45% yield) was obtained. . According to 1 H-NMR, this yellowish white solid was thiodi-p-phenylenebis (4-methoxyphenylsulfonium) bis (hexafluorophosphate) (1-5) and di (4-methoxyphenyl) (4-phenylthiophenyl) sulfonium. It was a mixture of hexafluorophosphate (2-5), and it was confirmed that the molar ratio was 99.2: 0.8.

[Production Example 10]
Synthesis of thiodi-p-phenylenebis (4-methoxyphenylsulfonium) bis (hexafluorophosphate) (1-5) In Production Example 2, 20.0 parts of the white solid obtained in Production Example 1 was obtained in Production Example 9. The product was obtained in 18.0 g (yield 90%) as a yellowish white solid in the same manner as in Production Example 2 except that the obtained yellowish white solid was changed to 20.0 parts. This yellowish white solid was confirmed by 1 H-NMR to be thiodi-p-phenylenebis (4-methoxyphenylsulfonium) bis (hexafluorophosphate) (1-5).

[Production Example 11]
Synthesis of thiodi-p-phenylenebis (diphenylsulfonium) bis (hexafluoroantimonate) (1-6) (the following structural formula) and diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (2-6)

51.5 g (yield 50%) of a white solid was obtained in the same manner as in Production Example 1 except that 40.5 parts of potassium hexafluorophosphate in Production Example 1 was changed to 60.5 parts of potassium hexafluoroantimonate. It was. According to H-NMR and F-NMR, this white solid was converted into thiodi-p-phenylenebis (diphenylsulfonium) bis (hexafluoroantimonate) (1-6) and diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate ( It was confirmed that the molar ratio was 99.1: 0.9.

[Production Example 12]
Thiodi-p-phenylenebis (diphenylsulfonium) bis [tris (heptafluoropropyl) trifluorophosphate] (1-7) (the following structural formula) and diphenyl [4- (phenylthio) phenyl] sulfonium tris (heptafluoropropyl) Synthesis of trifluorophosphate (2-7)

In the same manner as in Production Example 1 except that 40.5 parts of potassium hexafluorophosphate in Production Example 1 was changed to 136 parts of sodium tris (heptafluoropropyl) trifluorophosphate, 90.8 g of a white solid (52% yield) ) According to H-NMR and F-NMR, this white solid was converted into thiodi-p-phenylenebis (diphenylsulfonium) bis [tris (heptafluoropropyl) trifluorophosphate] (1-7) and diphenyl [4- (phenylthio) phenyl]. It was a mixture of sulfonium tris (heptafluoropropyl) trifluorophosphate (2-7), and it was confirmed that the molar ratio was 99.1: 0.9.

[Production Example 13]
Thiodi-p-phenylenebis (diphenylsulfonium) bis [tetrakis (pentafluorophenyl) borate] (1-8) (the following structural formula) and diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate (2 Synthesis of -8)

In the same manner as in Production Example 1, except that 40.5 parts of potassium hexafluorophosphate in Production Example 1 was changed to 1500 parts of a 10% aqueous solution of lithium tetrakis (pentafluorophenyl) borate, 78.6 g (yield) 41%). According to H-NMR and F-NMR, this white solid was converted into thiodi-p-phenylenebis (diphenylsulfonium) bis [tetrakis (pentafluorophenyl) borate] (1-8) and diphenyl [4- (phenylthio) phenyl] sulfoniumtetrakis ( Pentafluorophenyl) borate (2-8), and the molar ratio was 99.1: 0.9.

[Production Example 14]
Of thiodi-p-phenylenebis (diphenylsulfonium) bis (nonafluorobutanesulfonate) (1-9) (the following structural formula) and diphenyl [4- (phenylthio) phenyl] sulfonium nonafluorobutanesulfonate (2-9) Composition

54.5 g (47%) of a white solid was obtained in the same manner as in Production Example 1 except that 40.5 parts of potassium hexafluorophosphate in Production Example 1 was changed to 74.6 parts of potassium nonafluorobutanesulfonate. . According to H-NMR and F-NMR, this white solid was converted to thiodi-p-phenylenebis (diphenylsulfonium) bis (nonafluorobutanesulfonate) (1-9) and diphenyl [4- (phenylthio) phenyl] sulfonium nonafluorobutanesulfone. It was a mixture of natto (2-9) and the molar ratio was 99.1: 0.9.

<Preparation of active energy ray-curable composition and its evaluation>
The acid generator of the present invention is dissolved in solvent-1 (propylene carbonate) in the blending amounts shown in Table 1, and an epoxide (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxy) which is a cationic polymerizable compound. The active energy ray-curable compositions (Examples 1 to 13 and Comparative Examples 1 and 2) were prepared by uniformly mixing with the rate, Daicel Chemical Industries, Ltd., Celoxide 2021P) in the blending amounts shown in Table 1. . These compositions were subjected to UV curability (cationic polymerization performance) evaluation and heat resistance (yellowing) test by the following methods. The results are shown in Table 1.
In addition, as an acid generator of Comparative Example 1, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate (R-1) [trade name: CPI-110P, manufactured by San Apro Co., Ltd.] was used, and Comparative Example 2 was used. As the acid generator, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (R-2) [trade name: CPI-110A, manufactured by San Apro Co., Ltd.] was used.

<Evaluation of UV curability (cationic polymerization performance)>
The composition obtained above was applied to a polyethylene terephthalate (PET) film with a film thickness of 40 μm using an applicator. The PET film after the application was irradiated with ultraviolet light having a wavelength limited by a filter using an ultraviolet irradiation device. The filter used was an IRCF02 filter (manufactured by Eye Graphics Co., Ltd., a filter that cuts light of less than 340 nm). Table 1 shows the results of measuring the coating film hardness after 40 minutes after irradiation with pencil hardness (JIS K5600-5-4: 1999) and evaluating according to the following criteria. It shows that the sensitivity (cationic polymerization curability) of an energy beam curable composition is so favorable that pencil hardness is high.

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

(Ultraviolet light irradiation conditions)
・ Ultraviolet irradiation device: Belt conveyor type UV irradiation device (manufactured by Eye Graphics Co., Ltd.)
・ Lamp: 1.5kW high pressure mercury lamp ・ Filter: IRCF02 filter (manufactured by Eye Graphics Co., Ltd.)
Illuminance (measured with a 365 nm head illuminometer): 145 mW / cm ²

-Integrated light quantity (measured with 365nm head illuminometer):
Condition-1: 140 mJ / cm ²
Condition-2: 170 mJ / cm ²

<Heat resistance (yellowing) test>
The composition obtained above was applied with a film thickness of 40 μm onto a slide glass with an applicator. The slide glass after the application was irradiated with ultraviolet rays using an ultraviolet irradiation device.
(Ultraviolet light irradiation conditions)
・ Ultraviolet irradiation device: Belt conveyor type UV irradiation device (manufactured by Eye Graphics Co., Ltd.)
Lamp: 1.5 kW high-pressure mercury lamp Illuminance (measured with a 365 nm head illuminometer): 190 mW / cm ²
Integrated light quantity (measured with a 365 nm head illuminometer): 800 mJ / cm ²
After curing for 30 minutes at room temperature, after-curing at 120 ° C. for 30 minutes on a hot plate, a sample for a heat resistance test was prepared.
This sample was heated on a hot plate adjusted to 240 ° C. for 15 minutes, and the hue of the coating film was visually evaluated. The evaluation criteria are as follows.

(Evaluation criteria)
A: Colorless (no yellowing of the coating film)
○: Light yellow to yellow ×: Brown

  From Table 1, it can be seen that the acid generator of the present invention is superior in curability of the cationically polymerizable compound as compared with the comparative acid generator, and that the cured product after the heat test is highly transparent (not easily yellowed).

<Evaluation of positive photoresist composition>
(Preparation of sample for evaluation)
1 part by weight of component (A) as an acid generator, 40 parts by weight of resin represented by the following chemical formula (Resin-1) as resin component (B), and m-cresol and p-cresol as resin component (C) 60 parts by weight of a novolak resin obtained by addition condensation in the presence of formaldehyde and an acid catalyst is uniformly dissolved in solvent-2 (propylene glycol monomethyl ether acetate), and filtered through a membrane filter having a pore size of 1 μm to obtain a solid content. A positive photoresist composition (Examples 14 to 19) having a concentration of 40% by weight was prepared. Comparative examples were also carried out in the same manner as in the above examples, and positive photoresist compositions (Comparative Examples 3 to 5) were prepared. The positive photoresist composition was evaluated by the following method. The results are shown in Table 2.
In addition, (R-1) is used for the acid generator of Comparative Example 3, (R-2) is used for the acid generator of Comparative Example 4, and the acid generator of Comparative Example 5 is Triphenylsulfonium triflate (R-3) [manufactured by Wako Pure Chemical Industries] was used.

<Sensitivity evaluation>
The positive resist composition was spin coated on a silicon wafer substrate and dried to obtain a photoresist layer having a thickness of about 20 μm. This resist layer was pre-baked at 130 ° C. for 6 minutes using a hot plate. After pre-baking, pattern exposure (i-line) was performed using TME-150RSC (manufactured by Topcon Corporation), and post-exposure heating (PEB) was performed at 75 ° C. for 5 minutes using a hot plate. Thereafter, a development process for 5 minutes was performed by an immersion method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, washed with running water, and blown with nitrogen to obtain a 10 μm line and space (L & S) pattern. Further, below that, the minimum exposure amount at which no residue of this pattern was observed, that is, the minimum essential exposure amount (corresponding to the sensitivity) necessary for forming the resist pattern was measured.

<Pattern shape evaluation>
By the above operation, the lower side dimension La and the upper side dimension Lb of the cross section of the 10 μm L & S pattern formed on the silicon wafer substrate were measured using a scanning electron microscope, and the pattern shape was judged according to the following criteria.
A: 0.90 ≦ Lb / La ≦ 1
○: 0.85 ≦ Lb / La <0.90
X: Lb / La <0.85

* No pattern is formed and measurement is not possible.

  As shown in Table 2, the chemically amplified positive photoresist compositions of Examples 14 to 19 are more sensitive and have a pattern shape than the conventional acid generators as in Comparative Examples 3 to 5. It turns out that it is excellent.

<Preparation of negative photoresist composition and its evaluation>
(Preparation of sample for evaluation)
As a component (E) 1 part by weight as an acid generator and a component (F) as a phenol resin, a copolymer (Mw = 10,000) composed of p-hydroxystyrene / styrene = 80/20 (molar ratio) is used. 100 parts by weight, 20 parts by weight of hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MW-390”) as component (G) which is a crosslinking agent, and butadiene as component (H) which is crosslinked fine particles 10 parts by weight of a copolymer (average particle size = 65 nm, Tg = −38 ° C.) composed of / acrylonitrile / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 64/20/8/6/2 (wt%) As component (J) as an auxiliary agent, 5 parts by weight of γ-glycidoxypropyltrimethoxysilane (trade name “S510”, manufactured by Chisso Corporation) was added to solvent-3 (lactic acid ester). Le) was uniformly dissolved in 145 parts by weight, the negative photoresist composition of the present invention (Examples 20-25 and Comparative Examples 6-8) were prepared. Moreover, the negative photoresist composition was evaluated by the following method. The results are shown in Table 3.
In addition, (R-1) is used for the acid generator of Comparative Example 6, (R-2) is used for the acid generator of Comparative Example 7, and the acid generator of Comparative Example 8 is Triphenylsulfonium triflate (R-3) [manufactured by Wako Pure Chemical Industries] was used.

<Sensitivity evaluation>
Each composition was spin-coated on a silicon wafer substrate, and then heat-dried at 110 ° C. for 3 minutes using a hot plate to obtain a resin coating film having a thickness of about 20 μm. Then, pattern exposure (i line | wire) was performed using TME-150RSC (made by Topcon Corporation), and the post-exposure heating (PEB) for 3 minutes was performed at 110 degreeC with the hotplate. Thereafter, a development process for 2 minutes was performed by an immersion method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, washed with running water, and blown with nitrogen to obtain a 10 μm line and space pattern. Further, the minimum essential exposure amount (corresponding to the sensitivity) necessary for forming a pattern having a remaining film ratio of 95% or more indicating the ratio of the remaining film before and after development was measured.

<Pattern shape evaluation>
By the above operation, the lower side dimension La and the upper side dimension Lb of the cross section of the 20 μm L & S pattern formed on the silicon wafer substrate were measured using a scanning electron microscope, and the pattern shape was judged according to the following criteria.
A: 0.90 ≦ La / Lb ≦ 1
○: 0.85 ≦ La / Lb <0.90
X: La / Lb <0.85

<Heat resistance (yellowing) test>
The patterned silicon substrate obtained by the sensitivity evaluation was heated for 15 minutes on a hot plate adjusted to 200 ° C., and the hue of the pattern portion was visually evaluated. The evaluation criteria are as follows.
(Evaluation criteria)
A: Colorless (no yellowing of the coating film)
○: Light yellow to yellow ×: Brown

** No pattern is formed and measurement is not possible.

As shown in Table 3, the chemically amplified negative photoresist compositions of Examples 20 to 25 are more sensitive than those using conventional acid generators as in Comparative Examples 6 to 8, and have a pattern shape. It is understood that it is excellent. Moreover, since the transparency of the hardened | cured material after a heat test is high (it is hard to yellow), it turns out that it is useful as a member by which optical characteristics, such as a display, an optical waveguide, and an optical lens, are calculated | required.

The energy ray curable composition using the acid generator of the present invention is composed of paint, coating agent, various coating materials (hard coat, anti-stain coating, anti-fogging coating, touch-resistant coating, optical fiber, etc.), adhesive tape Back coating agent, Release coating material for adhesive labels (release paper, release plastic film, release metal foil, etc.), printing plate, dental material (dental compound, dental composite) ink, inkjet ink, positive Type resist (connecting terminals and wiring pattern formation for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, etc.), resist films, liquid resists, negative resists (surface protective films for semiconductor elements, interlayer insulating films, planarization films) Permanent film materials, etc.), MEMS resists, positive photosensitive materials, negative photosensitive materials, various adhesives (various adhesives for electronic components, H D adhesive, pickup lens adhesive, FPD functional film (deflection plate, antireflection film, etc. adhesive), holographic resin, FPD material (color filter, black matrix, partition material, photospacer, Ribs, alignment films for liquid crystals, sealants for FPD, etc.), optical members, molding materials (for building materials, optical components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, sealing It is suitably used for materials, optical semiconductor (LED) sealing materials, optical waveguide materials, nanoimprint materials, photofabrication materials, and micro stereolithography materials.

Claims (12)

An active energy linear acid generator containing a sulfonium salt represented by the following general formula (1).

[In the formula (1), R ^{1 to} R ⁶ are organic groups bonded to a benzene ring, the number of R ^{1 to} R ⁴ is 0 to 5, and the number of R ^{5 to} R ⁶ is 0 to 4. In the case of 0, hydrogen atoms are bonded, and when a plurality of R ^{1 to} R ⁶ are bonded, they may be the same as or different from each other, and R ^{1 to} R ⁶ may be directly or —O—, A ring structure may be formed via —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group, and X is monovalent. It is an atom (group) that can be an anion. ] The active energy linear acid generator according to claim 1, wherein the sulfonium salt is represented by the following general formula (1 ').

[In Formula (1 ′), R ^{1 to} R ⁶ are organic groups bonded to the benzene ring, R ^{1 to} R ⁴ are 0 to 5, and R ^{5 to} R ⁶ are 0 to 4. In the case of 0, a hydrogen atom is bonded, and when a plurality of R ^{1 to} R ⁶ are bonded, they may be the same or different, and R ^{1 to} R ⁶ may be directly or —O— , —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group may form a ring structure. An atom (group) that can be a valent anion. ] Furthermore, it contains a sulfonium salt represented by the following general formula (2), and the content thereof is less than 1 mol% with respect to the total number of moles of (1) and (2). Item 3. The active energy linear acid generator according to Item 1 or 2.

Wherein ^(2), R 1 ~R ⁴ is an organic group bonded to the benzene ^ring, the number of R 1 to R ² and the ^{R 4} is 0-5, the number of ^{R 3} is 0-4 In the case of 0, a hydrogen atom is bonded, and when a plurality of R ^{1 to} R ⁴ are bonded, they may be the same or different from each other, and R ^{1 to} R ⁴ may be directly or —O— , —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group may form a ring structure. An atom (group) that can be a valent anion. ] X ⁻ is SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ 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 ⁻ , Trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, (CF ₃ SO ₂ ) ₃ C ^-, and _{(CF 3 SO 2) 2 N} - are those selected from the group consisting of anions represented by the actinic energy according to claim 1 -Linear acid generator.   An active energy ray-curable composition comprising the active energy ray acid generator according to any one of claims 1 to 4 and a cationically polymerizable compound.   A cured product obtained by curing the active energy ray-curable composition according to claim 5.   A component (A) comprising the active energy linear acid generator according to any one of claims 1 to 4, and a component (B) which is a resin whose solubility in alkali is increased by the action of an acid. Chemically amplified positive photoresist composition.   The component (B) comprises at least one resin selected from the group consisting of a novolak resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3). Chemically amplified positive photoresist composition.   The chemically amplified positive photoresist composition according to claim 7 or 8, further comprising an alkali-soluble resin (C) and an acid diffusion controller (D).   A component (E) comprising the active energy linear acid generator according to any one of claims 1 to 4, a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinking agent component (G) A chemically amplified negative photoresist composition comprising:   The chemically amplified negative photoresist composition according to claim 10, further comprising a crosslinked fine particle component (H). A cured product obtained by curing the chemically amplified negative photoresist composition according to claim 10 or 11.