WO2022030139A1 - Photoacid generator - Google Patents

Abstract

The present invention provides a useful photoacid generator which is used for a photocurable composition or a chemically amplified negative photoresist composition, and which is useful for yellowing resistance of these compositions. The present invention provides a photoacid generator which is characterized by containing a sulfonium salt (CA) represented by general formula (1) and a compound (S) represented by general formula (2), and which is also characterized in that if the total content of the sulfonium salt (CA) and the compound (S) is determined by high-speed liquid chromatography (HPLC) and the total area of the sulfonium salt (CA) and the compound (S) is taken as 100, the area ratio of the compound (S) is from 0.02 to 3.0.

Description

Photoacid generator

The present invention relates to a photoacid generator useful as a photocurable composition and a chemically amplified negative photoresist composition, and is a photoacid generator useful for yellowing resistance of these compositions.

Onium salts such as sulfonium salts are used as photocationic polymerization initiators that cure cationically polymerizable compounds such as epoxy compounds by irradiation with active energy rays (hereinafter referred to as light) such as light and electron beams (Patent Documents 1 to 3). Alternatively, it is known as a photoacid generator because it generates acid by light irradiation, and is widely used in photoresists, photosensitive materials, and the like (Patent Documents 4 to 6).

By the way, known methods are known as methods for producing the photoacid generators described in these specifications, particularly sulfonium salts (Patent Documents 1 and 3). However, the sulfonium salt produced by such a method produces a bissulfonium salt having two sulfonio groups in one molecule in addition to the monosulfonium salt having one sulfonio group in one molecule. In general, the bissulfonium salt has a higher photopolymerization initiation ability than the monosulfonium salt, but has low solubility in a cationically polymerizable monomer and a diluting solvent used as needed. After addition and dissolution, the problem that the bissulfonium salt precipitates and precipitates from the sulfonium salt solution over time may occur. Further, the cationically polymerizable compound containing a bissulfonium salt has a problem that it tends to thicken over time and cannot be stored for a long period of time. Therefore, the applicant discloses a production method for efficiently obtaining a high-purity monosulfonium salt in order to solve the above problems (Patent Document 7). However, in the photocurable composition and the resist composition, the change in hue of the cured product over time (a phenomenon in which the cured product is colored yellow to brown over time; hereinafter referred to as yellowing) is balanced with the curability. There was a request for further improvement in.

Japanese Unexamined Patent Publication No. 55-125105 Japanese Unexamined Patent Publication No. 61-190524 Japanese Unexamined Patent Publication No. 62-1254 JP-A-2002-193925 Japanese Unexamined Patent Publication No. 2001-354669 Japanese Unexamined Patent Publication No. 2001-294570 Japanese Patent No. 4602252

In the above background, an object of the present invention is a useful photoacid generator for a photocurable composition or a chemically amplified negative photoresist composition, which is useful for yellowing resistance of these compositions. It is a provision of a photoacid generator.

The present inventor has found a photoacid generator suitable for the above purpose.
That is, the present invention contains a sulfonium salt (CA) represented by the following general formula (1) and a compound (S) represented by the general formula (2), and is the sum of the sulfonium salt (CA) and the compound (S). When the content is measured by high-speed liquid chromatography (HPLC) and the total area of the sulfonium salt (CA) and the compound (S) is 100, the area ratio of the compound (S) is 0.02 or more and 3.0 or less. It is a photoacid generator characterized by being present.

[In the formulas (1) to (2), R ¹ to R ³ are organic groups bonded to the benzene ring, p, q, and r represent the number of R ¹ to R ³ , respectively, and p is 0 to. It is an integer of 4, q and r are integers of 0 to 5, and when it is 0, hydrogen atoms are bonded, and when p, q and r are 2 or more, they are different even if they are the same. Also good, R ¹ to R ³ are direct to each other or -O-, -S-, -SO-, -SO _2- , -NH-, -CO-, -COO-, -CONH-, alkylene group or phenylene. A ring structure may be formed via a group, X is an atom (group) that can be a monovalent anion, and Ar ¹ to Ar ³ may have the same or different carbon atoms from each other. Or a heteroaryl group having 4 to 18 carbon atoms, and the aryl group or heteroaryl group of Ar ¹ may be further substituted with a group represented by the formula (3), and R in the formula (3). ² , R ³ , r, q and X are the same as in equation (1), and n in equation (2) is an integer of 1 or 2. ]

Further, the present invention is a photocurable composition comprising the photoresist generator and a cationically polymerizable compound; a curing characterized by being obtained by curing the photoresistable composition. Body; A chemically amplified negative photoresist composition comprising the above-mentioned photoacid generator, a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a cross-linking agent component (G). A cured product obtained by curing the chemically amplified negative photoresist composition.

The photoacid generator of the present invention has high activity against light, has cationic polymerization performance and cross-linking reaction performance, and is useful for yellowing resistance by using the photoacid generator of the present invention. Useful compositions can be obtained.

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

R ¹ to R ³ in the formulas (1) to (3) represent an organic group bonded to a benzene ring, and may be the same or different. Examples of the organic group of R ¹ to R ³ include an aryl group having 6 to 30 carbon atoms, a heteroaryl 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 an alkenyl group having 2 to 30 carbon atoms. 2 to 30 alkynyl group, hydroxy group, 1 to 18 carbon number alkoxy group, 6 to 10 carbon number aryloxy group, 2 to 19 carbon number alkylcarbonyl group, 7 to 11 carbon number arylcarbonyl group, carbon An alkoxycarbonyl group having 2 to 19, an aryloxycarbonyl group having 7 to 11 carbon atoms, an arylthiocarbonyl group having 7 to 11 carbon atoms, an acyloxy group having 2 to 19 carbon atoms, an arylthio group having 6 to 20 carbon atoms, and carbon. An alkylthio group having 1 to 18 carbon atoms, an alkylsulfinyl group having 1 to 18 carbon atoms, an arylsulfinyl group having 6 to 10 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms, an arylsulfonyl group having 6 to 10 carbon atoms, and an alkylene group. Examples include oxy, amino, cyano, nitro and halogen groups.

In the above, the aryl group having 6 to 30 carbon atoms includes a monocyclic aryl group such as a phenyl group and a biphenylyl group, and naphthyl, anthrasenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthalsenyl, benzanthrasenyl, anthraquinolyl, fluorenyl, naphthoquinone and anthraquinone. Examples thereof include fused polycyclic aryl groups such as.

Examples of the heteroaryl group having 4 to 30 carbon atoms include cyclic compounds containing 1 to 3 complex atoms such as oxygen, nitrogen, and sulfur, which may be the same or different, and as a specific example. Are monocyclic heteroaryl groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl. , Carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantranyl, phenoxadinyl, phenoxatyynyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl and the like.

Alkyl groups having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl and octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and isohexyl. Examples thereof include branched alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

Examples of the alkenyl group having 2 to 30 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl and the like.

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, 1-methyl-2-propynyl and the like. Can be mentioned.

Examples of the alkoxy group having 1 to 18 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and dodecyloxy.

Examples of the aryloxy group having 6 to 10 carbon atoms include phenoxy and naphthyloxy.

Examples of the alkylcarbonyl group having 2 to 19 carbon atoms include acetyl, trifluoroacetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyle, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl and the like.

Examples of the arylcarbonyl group having 7 to 11 carbon atoms include benzoyl, 4-tert-butylbenzoyl, and naphthoyl.

Examples of the alkoxycarbonyl group having 2 to 19 carbon atoms include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl and the like.

Examples of the aryloxycarbonyl group having 7 to 11 carbon atoms include phenoxycarbonyl and naphthoxycarbonyl.

Examples of the arylthiocarbonyl group having 7 to 11 carbon atoms include phenylthiocarbonyl and naphthoxythiocarbonyl.

Examples of the asyloxy group having 2 to 19 carbon atoms include acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octadecylcarbonyloxy and the like.

Examples of the arylthio group having 6 to 20 carbon atoms include 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- Examples thereof include benzoyl-methylthiophenylthio, 4- (methylthiobenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio and the like.

Examples of the alkylthio group having 1 to 18 carbon atoms include methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, dodecylthio and the like.

Examples of the alkylsulfinyl group having 1 to 18 carbon atoms include methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, octylsulfinyl and the like.

Examples of the arylsulfinyl group having 6 to 10 carbon atoms include phenylsulfinyl, trillsulfinyl, and naphthylsulfinyl.

Examples of the alkylsulfonyl group having 1 to 18 carbon atoms include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and octylsulfonyl.

Examples of the arylsulfonyl group having 6 to 10 carbon atoms include phenylsulfonyl, tolylsulfonyl, and naphthylsulfonyl.

Examples of the halogen group include fluoro, chloro, bromo and iodine.

Among these organic groups, 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 alkylcarbonyl group having 2 to 6 carbon atoms, and a carbon number of carbon atoms are preferable. It is an arylcarbonyl group having 7 to 11, an alkylthio group having 1 to 6 carbon atoms, an arylthio group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a chloro group and a fluorogroup, and more preferably 1 carbon group. Alkyl group of 6 to 6, aryl group of 6 to 14 carbon atoms, heteroaryl group of 4 to 14 carbon atoms, alkoxy group of 1 to 6 carbon atoms, alkylcarbonyl group of 2 to 6 carbon atoms, benzoyl group, 6 carbon atoms It is an aryloxy group to 10 and a fluoro group.

In equations (1) to (3), p, q, and r represent the number of R ¹ to R ³ , respectively, p is an integer of 0 to 4, q, and r are integers of 0 to 5, and 0. In the case of, hydrogen atoms are bonded, and when p, q, and r are 2 or more, they may be the same or different from each other, and R ¹ to R ³ 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. For example, when p is 2 or more, ^two R1s thereof are directly or -O-, -S-, -SO-, -SO _2- , -NH-, -CO-, -COO-, -CONH. -, Means to form a ring structure via an alkylene group or a phenylene group.

In the formula ( ¹ ) or (2), Ar ¹ to Ar ³ are aryl groups having 6 to 18 carbon atoms or heteroaryl groups having 4 to 18 carbon atoms, which may be the same or different from each other, respectively. The aryl group or heteroaryl group may be further substituted with the group represented by the formula (3). Examples of the aryl group having 6 to 18 carbon atoms include the aryl group having 6 to 18 carbon atoms among the aryl groups having 6 to ³⁰ carbon atoms in ^R1 to R3 in the above formula (1), and preferably. It is an aryl group having 6 to 14 carbon atoms. Examples of the heteroaryl group having 4 to 18 carbon atoms include heteroaryl groups having 4 to 18 carbon atoms among the heteroaryl groups having 4 to ³⁰ carbon atoms in ^R1 to R3 in the above formula (1). , Preferably a heteroaryl group having 4 to 14 carbon atoms. These aryl groups and heteroaryl groups may have a substituent, and the substituents include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Examples thereof include an alkylcarbonyl group having 2 to 6 carbon atoms, an arylcarbonyl group having 7 to 11 carbon atoms, an arylthio group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a chloro group and a fluoro group.

In equation (2), n represents an integer of 1 or 2. When n is in this range, the effect of suppressing coloring (yellowing) is exhibited without affecting the photoresponsiveness of the sulfonium salt. When n = 0, there is no effect on yellowing resistance, and it is complicated to obtain a compound having n of 3 or more, which is industrially disadvantageous.

Among the sulfonium salts represented by the formula (1), specific examples of the preferable cation portion (C) are shown below.

Among the compounds (S) represented by the formula (2), preferable specific examples are shown below.

Among the sulfonium salts (CA) represented by the formula (1), specific examples of the cation portion (C), which is more preferable from the viewpoint of sensitivity and solubility, are shown below.

Among the compounds (S) represented by the formula (2), more preferable specific examples from the viewpoint of solubility are shown below.

In the formulas (1) and (3), X is an atom (group) that can be a monovalent anion, that is, X ⁻ irradiates a sulfonium salt with light (visible light, ultraviolet light, electron beam, X-ray, etc.). It is an anion corresponding to the acid (HX) generated by the above. 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 Anions represented by _-c- ^, R ⁹ SO _3- ^, (R ⁹ SO ₂ ) ₃ C- ^or (R ⁹ SO ₂ ⁾ ₂ N- are preferred.

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

Rf represents an alkyl group in which 80 mol% or more of a hydrogen atom is substituted with a fluorine atom (an alkyl group having 1 to 8 carbon atoms is preferable). Alkyl groups to be Rf by fluorine substitution include linear alkyl groups (methyl, ethyl, propyl, butyl, pentyl, octyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, etc.) and Cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and the like can be mentioned. The ratio of hydrogen atoms of these alkyl groups substituted with fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90, based on the number of moles of hydrogen atoms possessed by the original alkyl group. % Or more, particularly preferably 100%. When the substitution ratio by the fluorine atom is in these preferable ranges, the photosensitivity of the sulfonium salt is further improved. Particularly preferred Rf are 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 Rfs are independent of each other and therefore may be the same 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 a hydrogen atom is substituted with at least one element or an electron-withdrawing group. Examples of such one element include a halogen atom and include a fluorine atom, a chlorine atom, a bromine atom and the like. Examples of the electron-withdrawing group include a trifluoromethyl group, a nitro group and a cyano group. Of these, a phenyl group in which one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable. The c ^R8s are independent of each other and therefore 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, an aryl group having 6 to 20 carbon atoms or a fluorine atom, and the alkyl group and the perfluoroalkyl group are linear and fractionated. It may be branched or cyclic, and the aryl group may be unsubstituted or has 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, and more preferably 4.

Examples of the anion represented by MY _a ⁻ include anions represented by SbF ₆ ⁻ , PF ₆ ⁻ and BF ₄ ⁻ .

The anions 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- Examples thereof include anions to be formed. Of these, (CF ₃ CF ₂ ) ₃ PF _3- ^, (CF ₃ CF ₂ CF ₂ ) ₃ PF _3- ^, ((CF ₃ ) ₂ CF) ₃ PF _3- ^, ((CF ₃ ) ₂ CF) ₂ 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 anions represented by R ⁸ _c BY _4-c- ^are (C ₆ F ₅ ) ₄ B- ^, ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B- ^, (CF ₃ C ₆ H ₄ ) ₄ Examples thereof include 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-. Of these, anions represented by (C ₆ F ₅ ) ₄ B- ^and ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- are preferable.

The anions represented by R ⁸ _c GaY _4-c- ^include (C ₆ F ₅ ) ₄ Ga- ^, ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga- ^, (CF ₃ C ₆ H ₄ ) ₄ Examples thereof include anions represented by Ga ⁻ , (C ₆ F ₅ ) ₂ GaF ₂ ⁻ , C ₆ F ₅ GaF ₃ ⁻ and (C ₆ H ₃ F ₂ ) ₄ Ga ⁻ . Of these, anions represented by (C ₆ F ₅ ) ₄ Ga ⁻ and ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ are preferred.

Examples of the ^anion represented by R ⁹ SO _3- include trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutane sulfonic acid anion, pentafluorophenylsulfonic acid anion, and fluorosulfonic acid. Examples thereof include anion, p-toluene sulfonic acid anion, benzene sulfonic acid anion, camphor sulfonic acid anion, methane sulfonic acid anion, ethane sulfonic acid anion, propane sulfonic acid anion, butane sulfonic acid anion and octane sulfonic acid anion. Of these, trifluoromethanesulfonic acid anion, nonafluorobutane sulfonic acid anion, methanesulfonic acid anion, butane sulfonic acid anion, camphor sulfonic acid anion, benzenesulfonic acid anion and p-toluene sulfonic acid anion are preferable.

The anions represented by (R ⁹ SO ₂ ⁾ ₃ C- include (FSO ₂ ) ₃ C- ^, (CF ₃ SO ₂ ) ₃ C- ^, (C ₂ F ₅ SO ₂ ) ₃ C- ^, and (C ₃ ). Examples thereof include anions represented by F ₇ SO ₂ ) ₃ C- ^and (C ₄ F ₉ SO ₂ ⁾ ₃ C-.

The anions represented by (R ⁹ SO ₂ ⁾ ₂ N- include (FSO ₂ ) ₂ N- ^, (CF ₃ SO ₂ ) ₂ N- ^, (C ₂ F ₅ SO ₂ ) ₂ N- ^, and (C ₃ ). Examples thereof include anions represented by F ₇ SO ₂ ) ₂ N ⁻ and (C ₄ F ₉ SO ₂ ) ₂ N ⁻ .

The monovalent polyatomic anions include 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 ) In addition to the anion represented by ₃ C- ^or (R ⁹ SO ₂ ) ₂ N-, ^{perhalochloride} ion (ClO _4- ^, BrO _4- ^, etc.), halogenated sulfonate ion (FSO _3- ^, ClSO) ₃ ^- etc.), Sulfate ion (CH ₃ SO _4- ^, CF ₃ SO _4- ^, HSO _4- ^, etc.), Carbonate ion (HCO _3- ^, CH ₃ CO _3- ^, etc.), Aluminate ion (AlCl _4- ^, AlF) _4- ^, Al (OC ₄ F ₉ ) _4- ^, etc.), Hexafluorobismuth acid ion (BiF _6- ⁾ , Carboxylic acid ion (CH ₃ COO- ^, CF ₃ COO- ^, C ₆ H ₅ COO- ^, CH ₃ C ₆ H ₄ COO- ^, C ₆ F ₅ COO- ^, CF ₃ C ₆ H ₄ COO- ^, etc.), aryl borate ion (B (C ₆ H ₅ ) _4- ^, CH ₃ CH ₂ CH ₂ CH ₂ B (C ₆ ) H ₅ ) ₃ ^- etc.), ^Thiosyanate ion (SCN-), nitrate ion (NO _3- ⁾ and the like can be used.

Of these X- ^, 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 the ^anion represented by (R ⁹ SO ₂ ) ₂ N- is preferred, 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- ^, trifluoromethanesulphonic acid anion, nonafluorobutane sulphonic acid anion, methanesulphonic acid anion, butane sulphonic acid anion, camphor sulphonic acid anion, benzenesulphonic acid anion, p. -Toluene sulfonic acid anion, (FSO ₂ ) ₃ C- ^, (CF ₃ SO ₂ ) ₃ C- ^, (FSO ₂ ) ₂ N- ^and (CF ₃ SO ₂ ) ₂ N- improve the resolution ^and pattern shape of the resist. More preferably, (CF ₃ CF ₂ ) ₃ PF _3- ^, ((CF ₃ ) ₂ CF) ₃ PF _3- ^, (CF ₃ CF ₂ CF ₂ ) ₃ PF _3- ^, nonafluorobutane sulfonate anion, ( C ₆ F ₅ ) ₄ B- ^and ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B- ^, (CF ₃ SO ₂ ) ₃ C ^- are particularly preferable because they have good compatibility with the resist composition.

The sulfonium salt represented by the formula (1) can be produced by a known production method. For example, a method of reacting diaryl sulfide with chlorine, a method of reacting diaryl sulfide with aromatic hydrocarbons such as chlorine and benzene, a method of reacting diaryl sulfide with a copper-catalyzed diaryl iodonium salt, and a method of reacting diaryl sulfide and diaryl sulfoxide with a dehydrating agent. There is a way to react in the presence.

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, anhydrous phosphoric acid, methanesulfonic acid, trifluoromethanesulfonic acid or an anhydride thereof. Two or more of these may be mixed and used. Moreover, you may use a solvent as appropriate.

When the diallyl sulfoxide and the diallyl sulfide are reacted in the presence of a dehydrating agent, the molar ratio of sulfoxide: sulfide = 10: 1 to 1: 1, more preferably 7: 1 to 2: 1, and most preferably 5: 1 to 2. It is 5: 1. The reaction temperature is −10 ° C. to 70 ° C., preferably 0 ° C. to 50 ° C., and most preferably 10 ° C. to 30 ° C.

After the reaction, a sulfonium salt can be efficiently produced by exchanging anions with an acid (HX) and a salt (AXn) having an anion represented by X in the formulas (1) and (3). Here, A is a counter cation of anion X ⁻ , and n represents the number of anions X with respect to the valence of cation A. A represents an alkali metal such as Na, K, Li, an alkaline earth metal such as Mg, Ca, or an ammonium cation. Alkali metals are more preferable because of the availability of raw materials and the ease of purification of the sulfonium salt to be produced.

High performance liquid chromatography is used as a method for analyzing the content of a photoacid generator containing a sulfonium salt (CA) represented by the general formula (1) and a compound (S) represented by the general formula (2) of the present invention. (HPLC) is used. In order to determine the content, the ratio of the peak area of the compound (S) when the peak areas of the sulfonium salt (CA) and the compound (S) obtained by the HPLC method are totaled and set to 100 may be obtained.
The following are the measurement conditions for HPLC.
Equipment: Model name (L-2130), Manufacturer (Hitachi), Column: (Ph-3) Manufacturer (GL Sciences Inc), Moving layer: Methanol: Water: Sodium perchlorate monohydrate = 600: 68: 20 : Solution, detector: UV (210 nm), injection volume 10 μl, column temperature 40 ° C.

The contents of the sulfonium salt (CA) represented by the general formula (1) and the compound (S) represented by the general formula (2) are those of the sulfonium salt (CA) and the compound (S) according to the above-mentioned content measurement method. The area ratio of the compound (S) when the total area is 100 is 0.02 or more and 3.0 or less. Conjugate acid generated by containing a certain amount of the compound (S) represented by the general formula (2) with the sulfonium salt (CA) represented by the general formula (1) can be trapped, or oxygen in the system can be removed. It is considered that the trapping suppresses coloring due to protonation, oxidation, and the like.

The photoacid generator of the present invention may contain other conventionally known photoacid generators in addition to the sulfonium salts listed above, if necessary. In the following, the photoacid generator of the present invention contains a sulfonium salt (CA) represented by the general formula (1) and a compound (S) represented by the general formula (2), and other photoacid generators are generated. It means that the agent is not included.

When another photoacid generator is contained, the content (mol%) of the other photoacid generator is based on the number of moles of the sulfonium salt (CA) represented by the general formula (1) of the present invention. It is preferably 0.1 to 100, more preferably 0.5 to 50.

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

The photoacid generator of the present invention may be previously dissolved in a solvent that does not inhibit polymerization, cross-linking, deprotection reaction, etc. in order to facilitate dissolution in a cationically polymerizable compound or a chemically amplified resist composition.

Examples of the solvent 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, methylisoamyl ketone and 2-heptanone; ethylene glycol and ethylene glycol. Polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate. And its derivatives; cyclic ethers such as dioxane; ethyl acetate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate , Methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl Examples include esters such as acetate and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene.

When a solvent is used, the ratio of the solvent used is preferably 15 to 1000 parts by weight, more preferably 30 to 500 parts by weight, based on 100 parts by weight of the photoacid generator of the present invention. The solvent used may be used alone or in combination of two or more.

The photocurable composition of the present invention comprises the above photoacid generator and a cationically polymerizable compound.

Examples of the cationically polymerizable compound that is a constituent of the photocurable composition include cyclic ethers (epoxides and oxetane, etc.), ethylenically unsaturated compounds (vinyl ethers, styrene, etc.), bicycloorthoesters, spiroletocarbonates, spiroletoesters, and the like. {Japanese Patent Laid-Open No. 11-060996, JP-A-09-302269, JP-A-2003-026993, JP-A-2002-206017, JP-A-11-349895, JP-A-10-212343, JP-A-2000- 119306, JP-A-10-67812, JP-A-2000-186071, JP-A-08-85775, JP-A-08-134405, JP-A-2008-20838, JP-A-2008-20389, JP-A-2008-20841, Kai 2008-26660, JP-A-2008-266444, JP-A-2007-277327, Photopolymer Social gathering edition "Photopolymer Handbook" (1989, Industrial Research Council), Comprehensive Technology Center edition "UV / EB curing technology" (1982) , Comprehensive Technology Center), Radtech Study Group ed. "UV / EB Curing Material" (1992, CMC), Technical Information Association ed. , Coloring Materials, 68, (5), 286-293 (1995), Fine Chemicals, 29, (19), 5-14 (2000), etc.}.

As the epoxide, known epoxides and the like 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 (phenols, bisphenol A, phenol novolacs and compounds obtained by adding alkylene oxides thereof) having at least one aromatic ring.

The alicyclic epoxide is 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.). Can be mentioned.

Examples of the aliphatic epoxide include an aliphatic polyhydric alcohol or a polyglycidyl ether (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.) of this alkylene oxide adduct, and an aliphatic polybasic acid. Examples thereof include polyglycidyl esters (diglycidyl tetrahydrophthalate, etc.) and epoxidized long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

As the oxetane, known ones and the like 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, oxetanyl sill sesquioxetane, phenol novolac oxetane, etc. Can be mentioned.

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

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

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, p-tert-butoxystyrene and the like.

Examples of the cationically 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 can be mentioned.

Examples of the spiro orthocarbonate include 1,5,7,11-tetraoxaspiro [5.5] undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5.5] undecane. Be done.

Spiro-ortho esters include 1,4,6-trioxaspiro [4.4] nonane, 2-methyl-1,4,6-trioxaspiro [4.4] nonane and 1,4,6-trioxas. Pyro [4.5] decane and the like can be mentioned.

Further, polyorganosiloxane having at least one cationically polymerizable group in one molecule can be used (Japanese Patent Laid-Open Nos. 2001-348482, 2000-281965, 7-242828, JP. JP-A-2008-19593, Journal of Polymer. Sci., Part A, Polymer. Chem., Vol. 28,497 (1990), etc.).
These polyorganosiloxanes may be linear, branched, or cyclic, or may be a mixture thereof.

Of these cationically polymerizable compounds, epoxides, oxetane and vinyl ethers are preferable, and epoxides and oxetanees are more preferable, and alicyclic epoxides and oxetanees are particularly preferable. Further, these cationically polymerizable compounds may be used alone or in combination of two or more.

The content of the photoacid generator of the present invention in the photocurable composition is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. be. Within this range, the polymerization of the cationically polymerizable compound becomes more sufficient, and the physical properties of the cured product become even better. This content is determined by considering various factors such as the properties of the cationically polymerizable compound, the type of light (light source, wavelength, etc.), irradiation amount, temperature, curing time, humidity, and coating thickness. , Not limited to the above range.

The photocurable composition of the present invention may contain known additives (sensitizers, pigments, fillers, antistatic agents, flame retardants, defoamers, flow modifiers, light stabilizers, oxidations, if necessary. It can contain an inhibitor, an adhesion-imparting agent, an ion-supplementing agent, an anti-coloring agent, a solvent, a non-reactive resin, a radically polymerizable compound, etc.).

As the sensitizer, known sensitizers (Japanese Patent Laid-Open Nos. 11-279212 and Japanese Patent Laid-Open No. 09-183960, etc.) can be used, and anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, etc. can be used. , 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronen; thioxanthone {thioxanthone, 2 -Methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.}; Naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, and 4-methoxy-1-naphthol, etc.}; Ketone {dimethoxyacetophenone, diethoxyacetophenone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone and 4-benzoyl-4'-methyldiphenylsulfide, etc.}; Carbazole {N-phenylcarbazole, etc.} , N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole, etc.}; Clycene {1,4-dimethoxycrisen and 1,4-di-α-methylbenzyloxyclycene, etc.}; Phenanthrene {9-hydroxyphenanthrene, etc. , 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.} and the like.

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, based on 100 parts by weight of the photoacid generator.

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

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, based on 100 parts by weight of the photoacid generator.

As the filler, known fillers and the like can be used, and molten silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate, lithium aluminum silicate and the like can be used. 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, based on 100 parts by weight of the photoacid generator.

As the antistatic agent, known antistatic agents and the like can be used, and examples thereof include non-ionic antistatic agents, anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents and polymer antistatic agents. ..

When the antistatic agent is contained, the content of the antistatic agent is preferably 0.1 to 20,000 parts by weight, more preferably 0.6 to 5,000 parts by weight, based on 100 parts by weight of the photoacid generator.

As the flame retardant, a known flame retardant or the like can be used, and an inorganic flame retardant {antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide , Magnesium hydroxide and calcium aluminate}; brominated flame retardants {tetrabromophthalic anhydride, hexabromobenzene and decabromobiphenyl ethers, etc.}; and phosphoric acid ester flame retardants {tris (tribromophenyl) phosphate, etc.} Be done.

When the flame retardant is contained, the content of the flame retardant is preferably 0.5 to 40,000 parts by weight, more preferably 5 to 10,000 parts by weight, based on 100 parts by weight of the photoacid generator.

As the defoaming agent, a known defoaming agent or the like can be used, and an alcohol defoaming agent, a metal soap defoaming agent, a phosphoric acid ester defoaming agent, a fatty acid ester defoaming agent, a polyether defoaming agent, a silicone defoaming agent. And mineral oil defoaming agents and the like.

As the flow conditioner, known fluidity adjusters and the like can be used, and examples thereof include hydrogenated castor oil, polyethylene oxide, organic bentonite, colloidal silica, amidowax, metal soap and acrylic acid ester polymers.
As the light stabilizer, known light stabilizers and the like can be used, and ultraviolet absorption type stabilizers {benzotriazole, benzophenone, salicylate, cyanoacrylate and derivatives thereof, etc.}; radical supplement type stabilizers {hindered amine, etc.}; and quenching. Examples thereof include type stabilizers {nickel complexes, etc.}.
As the antioxidant, known antioxidants and the like can be used, and examples thereof include phenol-based antioxidants (monophenol-based, bisphenol-based and high molecular weight phenol-based, etc.), sulfur-based antioxidants, phosphorus-based antioxidants, and the like. Be done.
As the adhesion-imparting agent, a known adhesion-imparting agent or the like can be used, and examples thereof include a coupling agent, a silane coupling agent, and a titanium coupling agent.
As the ion catching agent, known ion catching agents and the like can be used, and examples thereof include organoaluminum (alkoxyaluminum, phenoxyaluminum and the like).
As the anti-coloring agent, a known anti-coloring agent can be used, and in general, an antioxidant is effective, and a phenol-based antioxidant (monophenol-based, bisphenol-based, polymer phenol-based, etc.), sulfur-based oxidation Examples thereof include antioxidants and phosphorus-based antioxidants, but they have little effect in preventing coloration during heat resistance tests at high temperatures.

When a defoaming agent, a flow regulator, a light stabilizer, an antioxidant, an adhesion-imparting agent, an ion-supplementing agent, or a color-preventing agent is contained, the content of each is based on 100 parts of the photoacid generator. It is preferably 0.1 to 20000 parts by weight, more preferably 0.5 to 5000 parts by weight.

The solvent is not limited as long as it can be used for dissolving the cationically polymerizable compound and adjusting the viscosity of the photocurable composition, and the solvent mentioned above as the solvent for the photoacid generator can be used.

When the solvent is contained, the content of the solvent is preferably 50 to 2000000 parts by weight, more preferably 200 to 500,000 parts by weight, based on 100 parts by weight of the photoacid generator.

Non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, styrene butadiene block copolymer hydrogenated materials, and (meth) acrylic acid esters. Examples include coalescence and polyurethane. The number average molecular weight of these resins is preferably 1000 to 500,000, more preferably 5000 to 100,000 (the number average molecular weight is a value measured by a general method such as GPC).

When the non-reactive resin is contained, the content of the non-reactive resin is preferably 5 to 400,000 parts by weight, more preferably 50 to 150,000 parts by weight, based on 100 parts by weight of the photoacid generator.

When a non-reactive resin is contained, it is desirable to dissolve the non-reactive resin in a solvent in advance in order to easily dissolve the non-reactive resin with a cationically polymerizable compound or the like.

Known radically polymerizable compounds include {Photopolymer Handbook edited by Photopolymer Council (1989, Industrial Research Council), UV / EB Curing Technology edited by Comprehensive Technology Center (1982, Comprehensive Technology Center), Radtech Research. "UV / EB Curing Materials" (1992, CMC) edited by the Society, "Causes of Curing Poorness / Inhibition in UV Curing and Countermeasures" (2003, Technical Information Association)}, etc. It can be used and includes monofunctional monomers, bifunctional monomers, polyfunctional monomers, epoxy (meth) acrylates, polyester (meth) acrylates and urethane (meth) acrylates.

When the radically polymerizable compound is contained, the content of the radically polymerizable compound is preferably 5 to 400,000 parts by weight, more preferably 50 to 150,000 parts by weight, based on 100 parts by weight of the photoacid 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 polymer by radical polymerization.

As the radical polymerization initiator, a known radical polymerization initiator or the like can be used, and a thermal radical polymerization initiator (organic peroxide, azo compound, etc.) and a photoradical polymerization initiator (acetophenone-based initiator, benzophenone-based initiator, etc.) can be used. Michler ketone-based initiators, benzoin-based initiators, thioxanthone-based initiators, acylphosphine-based initiators, etc.) are included.

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

The photocurable composition of the present invention uniformly comprises a cationically polymerizable compound, a photoacid generator and, if necessary, an additive at room temperature (about 20 to 30 ° C.) or, if necessary, heating (about 40 to 90 ° C.). It can be mixed and dissolved, or further kneaded with three rolls or the like to prepare.

The photocurable composition of the present invention can be cured by irradiating with light to obtain a cured product. The light used here may be any light as long as it has the energy to induce the decomposition of the photoacid generator of the present invention, but low-pressure, medium-pressure, high-pressure or ultra-high-pressure mercury lamps, metal halide lamps, LED lamps, excimer lamps, etc. Light in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from carbon arc lamp, fluorescent lamp, semiconductor solid-state laser, argon laser, He _- Cd laser, KrF excimer laser, ArF excimer laser, F2 laser, etc. Is preferable. As the light, radiation having high energy such as electron beam or X-ray can also be used.

The irradiation time of light is affected by the intensity of the light source and the transparency of light to the photocurable composition, but at room temperature (about 20 to 30 ° C.), about 0.1 to 10 seconds is sufficient. However, when the light transmission is low or the film thickness of the photocurable composition is thick, it may be preferable to take a longer time. Most of the photocurable compositions are cured by cation polymerization 0.1 seconds to several minutes after light irradiation, but if necessary, after light irradiation, at room temperature (about 20 to 30 ° C.) to 200 ° C. for several seconds to It is also possible to heat for several hours and aftercure.

Specific applications of the photocurable composition of the present invention include paints, coating agents, various coating materials (hard coats, stain-resistant coating materials, anti-fog coating materials, touch-resistant coating materials, optical fibers, etc.), and adhesive tapes. Back treatment agent, release coating material for adhesive label release sheet (release paper, release plastic film, release metal foil, etc.), printing board, dental material (dental compound, dental composite) ink, inkjet ink, resist film , Liquid resist, negative type resist (surface protective film for semiconductor elements, interlayer insulating film, permanent film material such as flattening film, etc.), resist for MEMS, negative type photosensitive material, various adhesives (temporary for various electronic parts) Fixing agent, HDD adhesive, pickup lens adhesive, FPD functional film (deflection plate, antireflection film, etc.) adhesive, holographic resin, FPD material (color filter, black matrix, partition material, etc.) Photospacer, rib, alignment film for liquid crystal, sealant for FPD, etc.), optical member, molding material (for building material, optical component, lens), casting material, putty, glass fiber impregnating agent, sealing material, sealing material , Encapsulant, optical semiconductor (LED) encapsulant, optical waveguide material, nanoimprint material, optical molding material, micro optical modeling material, etc., and in particular, the obtained cured product is less colored and has excellent transparency. Therefore, it is most suitable for optical applications.

Since the photoacid generator of the present invention generates a strong acid by light irradiation, it is a chemically amplified type known (Japanese Patent Laid-Open No. 2003-267768, JP-A-2003-261259, JP-A-2002-193925, etc.). It can also be used as a photoacid generator for resist materials.

The chemically amplified resist material includes (1) a two-component chemically amplified positive resist containing a resin that becomes soluble in an alkaline developer due to the action of an acid and a photoacid generator as essential components, and (2) an alkaline developer. Suitable for 3-component chemically amplified positive resists containing a soluble resin, a dissolution inhibitor that becomes soluble in an alkaline developer due to the action of an acid, and a photoacid generator as essential components, and (3) an alkaline developer. Includes a soluble resin, a cross-linking agent that cross-links the resin by heat treatment in the presence of an acid to make it insoluble in an alkaline developer, and a chemically amplified negative resist containing a photoacid generator as an essential component. From the viewpoint of yellowing resistance, the photoacid generator of the present invention is preferably used for a chemically amplified negative resist that is used as a protective film or the like even after pattern formation.

The chemically amplified negative photoresist composition of the present invention comprises a component (E) containing the photoacid generator of the present invention, which is a compound that generates an acid by light or irradiation, and an alkali-soluble having a phenolic hydroxyl group. It is characterized by containing a resin (F) and a cross-linking agent (G).

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

As the other conventionally known photoacid generator, preferably one or more selected from the group of onium compound, sulfoneimide compound, diazomethane compound and oxime sulfonate compound is preferable.

When such other conventionally known photoacid generators are used in combination, the proportion thereof may be arbitrary, but usually, the other photoacid generators are used with respect to 100 parts by weight of the total weight of the photoacid generators of the present invention. Is 10 to 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 based on the solid content of the chemically amplified negative photoresist composition.

Alkali-soluble resin (F) having a phenolic hydroxyl group
The "alkali-soluble resin having a phenolic hydroxyl group" (hereinafter referred to as "phenolic resin (F)") in the present invention includes, for example, novolak resin, polyhydroxystyrene, a copolymer of polyhydroxystyrene, hydroxystyrene and styrene. , Hydroxystyrene, styrene and (meth) acrylic acid derivative copolymers, phenol-xylylene glycol condensed resin, cresol-xylylene glycol condensed resin, phenol-dicyclopentadiene condensed resin and the like are used. Among these, novolak resin, polyhydroxystyrene, polyhydroxystyrene copolymer, hydroxystyrene and styrene copolymer, hydroxystyrene, styrene and (meth) acrylic acid derivative copolymer, phenol-xylylene glycol. Condensed resin is preferred. In addition, these phenol resins (F) may be used individually by 1 type, and may be used by mixing 2 or more types.

Further, the phenol resin (F) may contain a phenolic small molecule compound as a part of the component.
Examples of the phenolic small molecule compound include 4,4'-dihydroxydiphenylmethane and 4,4'-dihydroxydiphenyl ether.

Crosslinking 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 cross-linking agent (G) include a compound having at least two or more alkyl etherified amino groups in the molecule, and a compound having at least two or more alkyl etherified benzenes in the molecule as a skeleton. Examples thereof include an oxylan ring-containing compound, a thiirane ring-containing compound, an oxetanyl group-containing compound, and an isocyanate group-containing compound (including blocked compounds).

Among these cross-linking agents (G), a compound having at least two or more alkyl etherified amino groups in the molecule and an oxylan ring-containing compound are preferable. Furthermore, it is more preferable to use a compound having at least two or more alkyl etherified amino groups in the molecule and an oxylan ring-containing compound in combination.

The blending amount of the cross-linking agent (G) in the present invention is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the phenol resin (F). When the amount of the cross-linking agent (G) is 1 to 100 parts by weight, the curing reaction proceeds sufficiently, and the obtained cured product has a high resolution and a good pattern shape, and has heat resistance and electrical insulation. It is preferable because it has excellent properties.
Further, when the compound having an alkyl etherified amino group and the oxylan ring-containing compound are used in combination, the content ratio of the oxylan ring-containing compound is 100, which is the total of the compound having an alkyl etherified amino group and the oxylan ring-containing compound. In terms of% by 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 has excellent chemical resistance without impairing high resolution.

Crosslinked 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 impact resistance of the obtained cured product. Can be made to.

The average particle size of the crosslinked fine particles (H) is usually 30 to 500 nm, preferably 40 to 200 nm, and 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 emulsifier used to control the particle size. You can control it.
The average particle size of the crosslinked fine particles (H) is a value measured by diluting the dispersion liquid of the crosslinked fine particles according to a conventional method using a light scattering flow distribution measuring device or the like.

The blending amount of the crosslinked fine particles (H) is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the phenol resin (F). When the blending 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 obtained 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 aid 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 blending amount of the adhesion aid is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the phenol resin (F). When the blending amount of this adhesion aid is 0.2 to 10 parts by weight, it 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 can contain a solvent in order to improve the handleability of the resin composition and to adjust the viscosity and storage stability.
The solvent is not particularly limited, and specific examples thereof include those described above.

Other Additives Further, the chemically amplified negative photoresist composition of the present invention may contain, if necessary, other additives to the extent that the characteristics of the present invention are not impaired. Examples of such other additives include inorganic fillers, sensitizers, quenchers, leveling agents, surfactants and the like.

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 inside and completely plugged on a wave rotor.

The cured product in the present invention is characterized in that the chemically amplified negative photoresist composition is cured.
The chemically amplified negative photoresist composition according to the present invention described above has a high residual film ratio and is excellent in resolution, and the cured product is excellent in electrical insulation, thermal shock resistance and the like. The cured product can be suitably used as a surface protective film, a flattening film, an interlayer insulating film material, or the like for electronic components such as semiconductor devices 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 (copper foil with resin, copper-clad laminate, silicon wafer with metal sputter film, or the like. Alumina substrate, etc.) is coated and dried to volatilize the solvent, etc. to form a coating film. Then, it is exposed through a desired mask pattern and heat-treated (hereinafter, this heat treatment is referred to as "PEB") to promote the reaction between the phenol resin (F) and the cross-linking agent (G). Then, the desired pattern can be obtained by developing with an alkaline developer to dissolve and remove the unexposed portion. Further, a cured film can be obtained by performing a heat treatment in order to exhibit the 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. Further, 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.
Here, "light" is synonymous with active energy rays, and may be any light that activates a photoacid generator in order to generate an acid, and includes ultraviolet rays, visible rays, and far ultraviolet rays, and also "radiation". "" Means X-rays, electron beams, ion rays and the like. Examples of the source of light or radiation include ultraviolet rays, electron beams, laser beams and the like of low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-ray steppers, h-ray steppers, i-line steppers, gh-line steppers, ghi-line steppers and the like. Be done. 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 of 1 to 50 μm is about 100 to 50,000 J / m ² .

After the exposure, the above PEB treatment is performed in order to accelerate the curing reaction between the phenol resin (F) and the cross-linking agent (G) by the generated acid. The PEB conditions vary depending on the blending amount of the resin composition, the film thickness used, and the like, but are usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes. Then, it is developed with an alkaline developer to dissolve and remove the unexposed portion to form a desired pattern. Examples of the developing method in this case include a shower developing method, a spray developing method, a dipping developing method, a paddle developing method, and the like. The developing conditions are usually about 1 to 10 minutes at 20 to 40 ° C.

Further, in order to sufficiently exhibit the characteristics as an insulating film after development, it can be sufficiently cured by performing a 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 intended use of the cured product. In addition, it can be heated in two steps in order to sufficiently proceed with curing and prevent deformation of the obtained pattern shape. For example, in the first step, the temperature is 50 to 120 ° C. for 5 minutes to 2 minutes. It can be cured by heating for about an hour and then heating at a temperature of 80 to 250 ° C. for about 10 minutes to 10 hours. Under such curing conditions, a general oven, an infrared oven, or the like can be used as the heating equipment.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the part in each example shows the weight part.

[Production Example 1] Synthesis of photoacid generator (PAG-1) 43 g of potassium hexafluorophosphate, 100 mL of acetonitrile, 36 g of diphenyl sulfide, 60 g of acetic anhydride, and 23 g of concentrated sulfuric acid were charged and mixed uniformly. A solution of 40 g of diphenyl sulfoxide in 50 mL of acetonitrile was added dropwise thereto at 40 ° C. or lower. After stirring at 40 ° C. for 3 hours, the mixture was cooled to room temperature, 200 mL of water was added, and the mixture was stirred for 10 minutes, and the oily substance was separated. 200 mL of ethyl acetate was added thereto to dissolve the oil, and the organic layer was separated. The organic layer was washed 3 times with 100 mL of 20% caustic soda and 100 mL of water, and then acetonitrile and ethyl acetate were distilled off under reduced pressure to obtain a pale yellow solid substance. Crystallization with dichloromethane / hexane was performed to obtain 85 g of a white solid (yield 88%). By analysis by 1 H-NMR, C-NMR, and HPLC, this white solid is a mixture of hexafluorophosphate (CA-1) having a cationic structure of (C-1) and compound (S1-1). It was confirmed that the ratio was 99.25: 0.75.

[Production Example 2] Synthesis of photoacid generator (PAG-2) 98 g of white solid in the same manner as in Production Example 1 except that 43 g of potassium hexafluorophosphate was changed to 55 g of potassium hexafluoroantimonate in Production Example 1. (Yield 87%) was obtained. Analysis by 1 H-NMR, C-NMR, and HPLC revealed that this white solid is a mixture of hexafluoroantimontate (CA-2) having a cationic structure of (C-1) and compound (S1-1). It was confirmed that the ratio was 99.81: 0.19.

[Production Example 3] Synthesis of photoacid generator (PAG-3) A white solid in the same manner as in Production Example 1 except that 43 g of potassium hexafluorophosphate was changed to 160 g of lithium tetrakispentafluorophenylborate in Production Example 1. 115 g (yield 59%) was obtained. By analysis by 1 H-NMR, C-NMR, and HPLC, this white solid is a mixture of a tetrakispentafluorophenylborate salt (CA-3) having a cationic structure of (C-1) and a compound (S1-1). It was confirmed that the ratio was 99.45: 0.55.

[Production Example 4] Synthesis of photoacid generator (PAG-4) In the same manner as in Production Example 1, 43 g of potassium hexafluorophosphate was changed to 101 g of potassium trispentafluoroethyltrifluorophosphate in Production Example 1. 106 g (yield 70%) of a white solid was obtained. By analysis by 1 H-NMR, C-NMR, and HPLC, this white solid is a mixture of trispentafluoroethyltrifluorophosphate (CA-4) having a cationic structure of (C-1) and compound (S1-1). Yes, it was confirmed that the ratio was 99.64: 0.36.

[Production Example 5] Synthesis of photoacid generator (PAG-5) A white solid in the same manner as in Production Example 1 except that 43 g of potassium hexafluorophosphate was changed to 177 g of sodium tetrakispentafluorophenyl gallate in Production Example 1. 130 g (yield 63%) was obtained. By analysis by 1 H-NMR, C-NMR, and HPLC, this white solid is a mixture of a tetrakispentafluorophenyl gallate salt (CA-5) having a cationic structure of (C-1) and a compound (S1-1). It was confirmed that the ratio was 99.01: 0.99.

[Production Example 6] Synthesis of photoacid generator (PAG-6) A pale yellow solid in the same manner as in Production Example 1 except that 40 g of diphenyl sulfoxide was changed to 47 g of 4,4'-difluorodiphenylsulfoxide in Production Example 1. 86 g (yield 84%) was obtained. By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a mixture of hexafluorophosphate (CA-6) having a cationic structure of (C-2) and compound (S2-1). It was confirmed that the ratio was 99.14: 0.86.

[Production Example 7] Synthesis of photoacid generator (PAG-7) In Production Example 1, 40 g of diphenyl sulfoxide is 4,4'-difluorodiphenylsulfoxide 47 g, and 43 g of potassium hexafluorophosphate is potassium trispentafluoroethyltrifluorophosphate. 109 g (yield 69%) of a pale yellow solid was obtained in the same manner as in Production Example 1 except that the content was changed to 101 g. Analysis by 1 H-NMR, C-NMR, and HPLC revealed that this pale yellow solid is a mixture of trispentafluoroethyltrifluorophosphate (CA-7) having a cationic structure of (C-2) and compound (S2-1). It was confirmed that the ratio was 99.04: 0.96.

[Production Example 8] Synthesis of photoacid generator (PAG-8) In Production Example 1, 40 g of diphenyl sulfoxide was added to 47 g of 4,4'-difluorodiphenylsulfoxide, and 43 g of potassium hexafluorophosphate was added to 177 g of sodium tetrakispentafluorophenyl gallate. 151 g (yield 71%) of a pale yellow solid was obtained in the same manner as in Production Example 1 except that it was changed. By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a mixture of tetrakispentafluorophenyl gallate salt (CA-8) having a cationic structure of (C-2) and compound (S2-1). , The ratio was confirmed to be 99.11: 0.89.

[Production Example 9] Synthesis of photoacid generator (PAG-9) Production example except that 40 g of diphenyl sulfoxide was changed to 67 g of 2-phenylsulphenylthioxanthone and 36 g of diphenylsulfide was changed to 62 g of 2-phenylthiothioxanthone. 117 g (yield 80%) of yellow solid was obtained in the same manner as in 1. By analysis by 1 H-NMR, C-NMR, and HPLC, this yellow solid is a hexafluorophosphate (CA-9) having a cationic structure of (C-8), a compound (S8-1), and a compound (S8-2). ), And its ratio was confirmed to be 99.22: 0.75: 0.03.

[Production Example 10] Synthesis of photoacid generator (PAG-10) In Production Example 1, 40 g of diphenyl sulfoxide was added to 67 g of 2-phenylsulphenylthioxanthone, 36 g of diphenylsulfide was added to 62 g of 2-phenylthiothioxanthone, and 43 g of potassium hexafluorophosphate was added. 182 g (yield 74%) of a yellow solid was obtained in the same manner as in Production Example 1 except that the lithium tetrakispentafluorophenylborate was changed to 160 g. By analysis by 1 H-NMR, C-NMR, and HPLC, this yellow solid is a tetrakispentafluorophenylborate salt (CA-10) having a cationic structure of (C-8), a compound (S8-1), and a compound (S8-). It was confirmed that it was a mixture of 2) and its ratio was 99.22: 0.75: 0.03.

[Production Example 11] Synthesis of photoacid generator (PAG-11) In Production Example 1, 40 g of diphenyl sulfoxide was added to 67 g of 2-phenylsulphenylthioxanthone, 36 g of diphenylsulfide was added to 62 g of 2-phenylthiothioxanthone, and 43 g of potassium hexafluorophosphate was added. 149 g (yield 74%) of a yellow solid was obtained in the same manner as in Production Example 1 except that the content was changed to 101 g of potassium trispentafluoroethyl trifluorophosphate. Analysis by 1 H-NMR, C-NMR, and HPLC revealed that this yellow solid has a cationic structure of (C-8), trispentafluoroethyltrifluorophosphate (CA-11), compound (S8-1), and compound (S8-1). It was confirmed that it was a mixture of S8-2) and its ratio was 99.32: 0.65: 0.03.

[Production Example 12] Synthesis of photoacid generator (PAG-12) Production example except that 40 g of diphenyl sulfoxide was changed to 66 g of 2-phenylsulphenylanthraquinone and 36 g of diphenyl sulfide was changed to 61 g of 2-phenylthioanthraquinone. In the same manner as in No. 1, 101 g of a yellow solid (yield 70%) was obtained. By analysis by 1 H-NMR, C-NMR, and HPLC, this yellow solid is a hexafluorophosphate (CA-12) having a cationic structure of (C-9), a compound (S9-1), and a compound (S9-2). ), And its ratio was confirmed to be 99.71: 0.27: 0.02.

[Production Example 13] Synthesis of photoacid generator (PAG-13) In Production Example 1, 40 g of diphenyl sulfoxide is 61 g of 2-phenylthioanthraquinone, 36 g of diphenyl sulfide is 66 g of 2-phenylsulphenyl anthraquinone, and 43 g of potassium hexafluorophosphate. 168 g (yield 66%) of a yellow solid was obtained in the same manner as in Production Example 1 except that the amount was changed to 160 g of lithium tetrakispentafluorophenylborate. By analysis by 1 H-NMR, C-NMR, and HPLC, this yellow solid is a tetrakispentafluorophenylborate salt (CA-13) having a cationic structure of (C-9), compound (S9-1), and compound (S9-). It was confirmed that it was a mixture of 2) and its ratio was 99.44: 0.54: 0.02.

[Production Example 14] Synthesis of photoacid generator (PAG-14) In Production Example 1, 40 g of diphenyl sulfoxide is 61 g of 2-phenylthioanthraquinone, 36 g of diphenyl sulfide is 66 g of 2-phenylsulphenyl anthraquinone, and 43 g of potassium hexafluorophosphate. 191 g (yield 75%) of a yellow solid was obtained in the same manner as in Production Example 1 except that the sodium tetrakispentafluorophenyl gallate was changed to 177 g. Analysis by 1 H-NMR, C-NMR, and HPLC revealed that this yellow solid is a tetrakispentafluorophenyl gallate salt (CA-14) having a cationic structure of (C-9), compound (S9-1), and compound (S9-). It was confirmed that it was a mixture of 2) and its ratio was 99.32: 0.65: 0.03.

[Production Example 15] Synthesis of photoacid generator (PAG-15) Except for the fact that 40 g of diphenyl sulfoxide was changed to 67 g of 2-phenylsulphenylthiantorene and 36 g of diphenylsulfide was changed to 62 g of 2-phenylthiothiantolene in Production Example 1. 47 g (yield 32%) of a yellow solid was obtained in the same manner as in Production Example 1. By analysis by 1 H-NMR, C-NMR, and HPLC, this yellow solid is a hexafluorophosphate (CA-15) having a cationic structure of (C-10), a compound (S10-1), and a compound (S10-2). ), And its ratio was confirmed to be 99.23: 0.75: 0.02.

[Production Example 16] Synthesis of photoacid generator (PAG-16) In Production Example 1, 40 g of diphenyl sulfoxide is 67 g of 2-phenylsulphenylthiantorene, 36 g of diphenylsulfide is 62 g of 2-phenylthiothiantolen, and potassium hexafluorophosphate. 99 g (yield 40%) of a yellow solid was obtained in the same manner as in Production Example 1 except that 43 g was changed to 160 g of lithium tetrakispentafluorophenylborate. By analysis by 1 H-NMR, C-NMR, and HPLC, this yellow solid is a tetrakispentafluorophenylborate salt (CA-16) having a cationic structure of (C-10), compound (S10-1), and compound (S10-). It was confirmed that it was a mixture of 2) and its ratio was 99.12: 0.85: 0.03.

[Production Example 17] Synthesis of photoacid generator (PAG-17) In Production Example 1, 40 g of diphenyl sulfoxide is 67 g of 2-phenylsulphenylthiantorene, 36 g of diphenylsulfide is 62 g of 2-phenylthiothiantolen, and potassium hexafluorophosphate. 93 g (yield 36%) of a yellow solid was obtained in the same manner as in Production Example 1 except that 43 g was changed to 177 g of sodium tetrakispentafluorophenyl gallate. Analysis by 1 H-NMR, C-NMR, and HPLC revealed that this yellow solid is a tetrakispentafluorophenyl gallate salt (CA-17) having a cationic structure of (C-10), compound (S10-1), and compound (S10-). It was confirmed that it was a mixture of 2) and its ratio was 99.27: 0.71: 0.02.

[Production Example 18] Synthesis of photoacid generator (PAG-18) Dissolved in 7.9 g of diphenyl sulfoxide, 16 g of methanesulfonic acid, and 22 g of acetic anhydride. A solution prepared by dissolving 8.9 g of 4- (phenylthio) acetophenone in 30 mL of acetonitrile was added dropwise thereto so as not to exceed 40 ° C., and the mixture was further reacted at 65 ° C. for 3 hours. The reaction solution was cooled to room temperature, poured into 100 mL of ion-exchanged water, extracted with 100 g of dichloromethane, and washed with water until the pH of the aqueous layer became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a brown solid. This was washed with ethyl acetate and hexane, and the organic solvent was concentrated to obtain a methanesulfonate (intermediate-1) having a cationic structure of (C-3). The structure was confirmed by 1 H-NMR.
(Intermediate-1) 5.1 g is dissolved in 60 mL of dichloromethane, 50 g of an equimolar sodium hexafluorophosphate aqueous solution is mixed at room temperature, stirred as it is for 3 hours, and the dichloromethane layer is separated 5 times with water. After washing, the mixture was transferred to a rotary evaporator and the solvent was distilled off to obtain a yellow solid. Further, crystallization was carried out with dichloromethane / hexane to obtain 4.3 g of a pale yellow solid (yield 75%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a mixture of hexafluorophosphate (CA-18) having a cationic structure of (C-3) and compound (S3-1). It was confirmed that the ratio was 99.17: 0.83.

[Production Example 19] Synthesis of photoacid generator (PAG-19) In Production Example 18, the same procedure as in Production Example 18 except that 50 g of the sodium hexafluorophosphate aqueous solution was changed to 100 g of the lithium tetrakispentafluorophenylborate aqueous solution. 8.2 g of a pale yellow solid was obtained (yield 74%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a mixture of a tetrakispentafluorophenylborate salt (CA-19) having a cationic structure of (C-3) and a compound (S3-1). , The ratio was confirmed to be 99.07: 0.93.

[Production Example 20] Synthesis of photoacid generator (PAG-20) In Production Example 18, the yield is the same as in Production Example 18 except that 50 g of the sodium hexafluorophosphate aqueous solution is changed to 50 g of the potassium trifluoromethanesulfonate aqueous solution. 4.7 g of a yellow solid was obtained (yield 81%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a mixture of trifluoromethanesulfonate (CA-20) having a cationic structure of (C-3) and compound (S3-1). It was confirmed that the ratio was 99.23: 0.77.

[Production Example 21] Synthesis of photoacid generator (PAG-21) Similar to Production Example 18 except that 50 g of a sodium hexafluorophosphate aqueous solution was changed to 50 g of a potassium trispentafluoroethyl trifluorophosphate aqueous solution. To obtain 7.4 g of a pale yellow solid (yield 84%). Analysis by 1 H-NMR, C-NMR, and HPLC revealed that this pale yellow solid is a mixture of trispentafluoroethyltrifluorophosphate (CA-21) having a cationic structure of (C-3) and compound (S3-1). It was confirmed that the ratio was 99.23: 0.77.

[Production Example 22] Synthesis of photoacid generator (PAG-22) In Production Example 18, 7.9 g of diphenyl sulfoxide was added to 12 g of (3-benzoylphenyl) phenyl sulfoxide, and 8.9 g of 4- (phenylthio) acetophenone was added to (3-). 6.2 g of a pale yellow solid was obtained in the same manner as in Production Example 18 except that the benzoylphenyl) phenylsulfide was changed to 11 g (yield 85%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a mixture of hexafluorophosphate (CA-22) having a cationic structure of (C-4) and compound (S4-1). It was confirmed that the ratio was 98.85: 1.15.

[Production Example 23] Synthesis of photoacid generator (PAG-23) In Production Example 18, 7.9 g of diphenyl sulfoxide was added to 12 g of (3-benzoylphenyl) phenyl sulfoxide, and 8.9 g of 4- (phenylthio) acetophenone was added to (3-). 7.4 g of a pale yellow solid was obtained in the same manner as in Production Example 18 except that 11 g of benzoylphenyl) phenylsulfide and 50 g of sodium hexafluorophosphate aqueous solution were changed to 50 g of trispentafluoroethyltrifluorophosphate potassium aqueous solution (yield). 72%). Analysis by 1 H-NMR, C-NMR, and HPLC revealed that this pale yellow solid is a mixture of trispentafluoroethyltrifluorophosphate (CA-23) having a cationic structure of (C-4) and compound (S4-1). It was confirmed that the ratio was 98.86: 1.14.

[Production Example 24] Synthesis of photoacid generator (PAG-24) In Production Example 18, 7.9 g of diphenyl sulfoxide was added to 12 g of (3-benzoylphenyl) phenyl sulfoxide, and 8.9 g of 4- (phenylthio) acetophenone was added to (3-). Benzoylphenyl) 5.1 g of a pale yellow solid was obtained in the same manner as in Production Example 18 except that 11 g of phenyl sulfide and 50 g of an aqueous sodium hexafluorophosphate solution were changed to 50 g of an aqueous solution of potassium trifluoromethanesulfonate (yield 70%). .. By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a mixture of trifluoromethanesulfonate (CA-24) having a cationic structure of (C-4) and compound (S4-1). It was confirmed that the ratio was 98.92: 1.08.

[Production Example 25] Synthesis of photoacid generator (PAG-25) In Production Example 18, 7.9 g of diphenylsulfoxide is 4-[(phenyl) sulfinyl] biphenyl 11 g, and 4- (phenylthio) acetophenone 8.9 g is 4-. (Phenylthio) 5.3 g of a pale yellow solid was obtained in the same manner as in Production Example 18 except that it was changed to 10 g of (phenylthio) biphenyl (yield 79%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a hexafluorophosphate (CA-25) having a cationic structure of (C-5) and the compounds (S5-1) and (S5-2). ), And its ratio was confirmed to be 99.44: 0.55: 0.01.

[Production Example 26] Synthesis of photoacid generator (PAG-26) In Production Example 18, 7.9 g of diphenylsulfoxide is 4-[(phenyl) sulfinyl] biphenyl 11 g, and 4- (phenylthio) acetophenone 8.9 g is 4-. 7.5 g of a pale yellow solid was obtained in the same manner as in Production Example 18 except that 10 g of (phenylthio) biphenyl and 50 g of an aqueous sodium hexafluorophosphate solution were changed to 50 g of an aqueous solution of potassium trispentafluoroethyltrifluorophosphate (yield 77). %). By analysis by 1 H-NMR, C-NMR, HPLC, this pale yellow solid has a cation structure of (C-5), trispentafluoroethyltrifluorophosphate (CA-26) and compound (S5-1) and ( It was confirmed that it was a mixture of S5-2) and its ratio was 99.51: 0.47: 0.02.

[Production Example 27] Synthesis of photoacid generator (PAG-27) In Production Example 18, 7.9 g of diphenylsulfoxide was added to 4- [(phenyl) sulfinyl] biphenyl (11 g), and 4- (phenylthio) acetophenone was added to 8.9 g. 5.5 g of a pale yellow solid was obtained in the same manner as in Production Example 18 except that 10 g of (phenylthio) biphenyl and 50 g of an aqueous sodium hexafluorophosphate solution were changed to 50 g of an aqueous solution of potassium trifluoromethanesulfonate (yield 82%). By analysis by 1 H-NMR, C-NMR, HPLC, this pale yellow solid is a trifluoromethanesulfonate (CA-27) having a cationic structure of (C-5) and compounds (S5-1) and (S5-2). ), And its ratio was confirmed to be 99.24: 0.75: 0.01.

[Production Example 28] Synthesis of photoacid generator (PAG-28) In Production Example 18, 7.9 g of diphenyl sulfoxide is 3-[(phenyl) sulfinyl] biphenyl 11 g, and 4- (phenylthio) acetophenone 8.9 g is 3-. (Phenylthio) 5.4 g of a pale yellow solid was obtained in the same manner as in Production Example 18 except that it was changed to 10 g of (phenylthio) biphenyl (yield 80%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a hexafluorophosphate (CA-28) having a cationic structure of (C-6) and the compounds (S6-1) and (S6-2). ), And its ratio was confirmed to be 98.89: 1.07: 0.04.

[Production Example 29] Synthesis of photoacid generator (PAG-29) In Production Example 18, 7.9 g of diphenylsulfoxide is 3-[(phenyl) sulfinyl] biphenyl 11 g, and 4- (phenylthio) acetophenone 8.9 g is 3-. 7.1 g of a pale yellow solid was obtained in the same manner as in Production Example 18 except that 12 g of (phenylthio) biphenyl and 50 g of an aqueous sodium hexafluorophosphate solution were changed to 50 g of an aqueous solution of potassium trispentafluoroethyltrifluorophosphate (yield 73). %). By analysis by 1 H-NMR, C-NMR, HPLC, this pale yellow solid has a cation structure of (C-6), hetrispentafluoroethyltrifluorophosphate (CA-29) and compound (S6-1) and It was confirmed that it was a mixture of (S6-2) and its ratio was 98.88: 1.07: 0.05.

[Production Example 30] Synthesis of photoacid generator (PAG-30) In Production Example 18, 7.9 g of diphenylsulfoxide was added to 3-[(phenyl) sulfinyl] biphenyl to 11 g, and 4- (phenylthio) acetophenone was added to 8.9 g. 5.3 g of a pale yellow solid was obtained in the same manner as in Production Example 18 except that 12 g of (phenylthio) biphenyl and 50 g of an aqueous sodium hexafluorophosphate solution were changed to 50 g of an aqueous solution of potassium trifluoromethanesulfonate (yield 79%). By analysis by 1 H-NMR, C-NMR, HPLC, this pale yellow solid is a trifluoromethanesulfonate (CA-30) having a cationic structure of (C-6) and compounds (S6-1) and (S6-2). ), And its ratio was confirmed to be 98.97: 0.99: 0.04.

[Production Example 31] Synthesis of photoacid generator (PAG-31) In Production Example 18, 7.9 g of diphenyl sulfoxide was added to 4- [(2-methoxyphenyl) sulfinyl] biphenyl 12 g, 4- (phenylthio) acetophenone 8.9 g. Was changed to 11 g of 4- (2-methoxyphenylthio) biphenyl, and 6.0 g of a pale yellow solid was obtained in the same manner as in Production Example 18 (yield 82%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a hexafluorophosphate (CA-31) having a cationic structure of (C-7) and the compounds (S7-1) and (S7-2). ), And its ratio was confirmed to be 99.25: 0.52: 0.23.

[Production Example 32] Synthesis of photoacid generator (PAG-32) In Production Example 18, 7.9 g of diphenyl sulfoxide was added to 4- [(2-methoxyphenyl) sulfinyl] biphenyl 12 g, 4- (phenylthio) acetophenone 8.9 g. In the same manner as in Production Example 18, 6.0 g of a pale yellow solid was obtained, except that 11 g of 4- (2-methoxyphenylthio) biphenyl and 50 g of an aqueous sodium hexafluorophosphate solution were changed to 50 g of an aqueous solution of potassium trifluoromethanesulfonate. (Yield 82%). By analysis by 1 H-NMR, C-NMR, HPLC, this pale yellow solid is a trifluoromethanesulfonate (CA-32) having a cationic structure of (C-7) and compounds (S7-1) and (S7-2). ), And its ratio was confirmed to be 99.21: 0.56: 0.23.

[Production Example 33] Synthesis of photoacid generator (PAG-33) In Production Example 18, 7.9 g of diphenylsulfoxide was added to 4-[(2-methoxyphenyl) sulfinyl] biphenyl 12 g, 4- (phenylthio) acetophenone 8.9 g. To obtain 8.3 g of a pale yellow solid in the same manner as in Production Example 18, except that 11 g of 4- (2-methoxyphenylthio) biphenyl and 50 g of an aqueous sodium hexafluorophosphate solution were changed to 100 g of an aqueous solution of lithium tetrakispentafluorophenylborate. (Yield 66%). By analysis by 1 H-NMR, C-NMR, HPLC, this pale yellow solid is a tetrakispentafluorophenylborate salt (CA-33) having a cationic structure of (C-7) and the compounds (S7-1) and (S7-). It was confirmed that it was a mixture of 2) and its ratio was 99.33: 0.34: 0.33.

[Production Example 34] Synthesis of photoacid generator (PAG-34) In Production Example 18, 7.9 g of diphenyl sulfoxide, 12 g of (4-phenyloxyphenyl) phenyl sulfoxide, and 8.9 g of 4- (phenylthio) acetophenone were added (4-). Phenoxyphenyl) 5.9 g of a pale yellow solid was obtained in the same manner as in Production Example 18 except that the phenyl sulfide was changed to 11 g (yield 84%). By analysis by 1 H-NMR, C-NMR, HPLC, this pale yellow solid is a tohexafluorophosphate (CA-34) having a cationic structure of (C-11) and a compound (S11-1) and (S11-). It was confirmed that it was a mixture of 2) and its ratio was 99.62: 0.34: 0.04.

[Production Example 35] Synthesis of photoacid generator (PAG-35) In Production Example 18, 7.9 g of diphenyl sulfoxide was added to 12 g of (4-phenyloxyphenyl) phenyl sulfoxide, and 8.9 g of 4- (phenylthio) acetophenone was added to (4-). In the same manner as in Production Example 18, 6.0 g of a pale yellow solid was obtained (yield 85%), except that 11 g of phenyl sulfide and 50 g of an aqueous sodium hexafluorophosphate solution were changed to 50 g of an aqueous solution of potassium trifluoromethanesulfonate. .. By analysis by 1 H-NMR, C-NMR, HPLC, this pale yellow solid is a trifluoromethanesulfonate (CA-35) having a cationic structure of (C-11) and compounds (S11-1) and (S11-2). ), And its ratio was confirmed to be 99.67: 0.27: 0.06.

[Production Example 36] Synthesis of photoacid generator (PAG-36) In Production Example 18, 7.9 g of diphenyl sulfoxide was added to 12 g of (4-phenyloxyphenyl) phenyl sulfoxide, and 8.9 g of 4- (phenylthio) acetophenone was added to (4-). A pale yellow solid of 8.2 g was obtained in the same manner as in Production Example 18 except that 11 g of phenylsulfide (phenoxyphenyl) and 50 g of an aqueous sodium hexafluorophosphate solution were changed to 100 g of an aqueous solution of lithium tetrakispentafluorophenylborate (yield 66%). ). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a tetrakispentafluorophenylborate salt (CA-36) having a cationic structure of (C-11) and the compounds (S11-1) and (S11-). It was confirmed that it was a mixture of 2) and its ratio was 99.68: 0.25: 0.07.

[Production Example 37] Synthesis of photoacid generator (PAG-37) 60.6 g of diphenyl sulfoxide was dissolved in 200 g of sulfuric acid and cooled to 0 ° C. in an ice bath. A solution of 18.6 g of diphenyl sulfide in 30 mL of acetonitrile was added dropwise thereto at 10 ° C. or lower. The reaction solution was put into 300 g of ice water, and 41 g of potassium hexafluorophosphate was put into it. After stirring for 3 hours, the mixture was extracted with 600 parts of dichloromethane and washed with water until the pH of the aqueous layer became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a pale yellow solid product. This was repeatedly crystallized twice with 100 parts of methanol to obtain 57.6 g (yield 68%) of a white solid. Analysis by 1 H-NMR, C-NMR, and HPLC revealed that this white solid is a mixture of hexafluorophosphate (CA-37) having a cationic structure of (C-12) and compound (S12-1). It was confirmed that the ratio was 99.54: 0.46.

[Production Example 38] Synthesis of photoacid generator (PAG-38) A white solid in the same manner as in Production Example 37, except that 41 g of potassium hexafluorophosphate was changed to 151 g of lithium tetrakispentafluorophenylborate in Production Example 37. 105 g was obtained (yield 55%). By analysis by 1 H-NMR, C-NMR, and HPLC, this white solid is a mixture of a tetrakispentafluorophenylborate salt (CA-38) having a cationic structure of (C-12) and a compound (S12-1). It was confirmed that the ratio was 99.65: 0.35.

[Production Example 39] Synthesis of photoacid generator (PAG-39) A white solid in the same manner as in Production Example 37, except that 41 g of potassium hexafluorophosphate was changed to 167 g of sodium tetrakispentafluorophenyl gallate in Production Example 37. 83 g was obtained (yield 57%). By analysis by 1 H-NMR, C-NMR, and HPLC, this white solid is a mixture of tetrakistetrakispentafluorophenyl gallate salt (CA-39) having a cationic structure of (C-12) and compound (S12-1). , The ratio was confirmed to be 99.22: 0.78.

[Production Example 40] Synthesis of photoacid generator (PAG-40) In Production Example 37, the same procedure as in Production Example 37 except that 60.6 g of diphenyl sulfoxide was changed to 78.7 g of di (4-methoxyphenyl) sulfoxide. Obtained 56 g of a pale yellow solid (yield 55%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a hexafluorophosphate (CA-40) having a cationic structure of (C-13) and a compound (S13-1) and (S13-2). ), And its ratio was confirmed to be 98.9: 0.95: 0.06.

[Production Example 41] Synthesis of photoacid generator (PAG-41) In Production Example 37, 60.6 g of diphenyl sulfoxide is 78.7 g of di (4-methoxyphenyl) sulfoxide, and 41 g of potassium hexafluorophosphate is lithium tetrakispentafluoro. 122 g of a pale yellow solid was obtained in the same manner as in Production Example 37 except that the phenylborate was changed to 151 g (yield 60%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a tetrakispentafluorophenylborate salt (CA-41) having a cationic structure of (C-13) and the compounds (S13-1) and (S13-). It was confirmed that it was a mixture of 2) and its ratio was 98.98: 0.95: 0.07.

[Production Example 42] Synthesis of photoacid generator (PAG-42) In Production Example 37, 60.6 g of diphenyl sulfoxide is 78.7 g of di (4-methoxyphenyl) sulfoxide, and 41 g of potassium hexafluorophosphate is trispentafluoroethyl. 92 g of a pale yellow solid was obtained in the same manner as in Production Example 37, except that the content was changed to 107 g of potassium trifluorophosphate (yield 59%). By analysis by 1 H-NMR, C-NMR, HPLC, this pale yellow solid has a cation structure of (C-13), trispentafluoroethyltrifluorophosphate (CA-42) and compound (S13-1) and ( It was confirmed that it was a mixture of S13-2) and its ratio was 98.95: 0.99: 0.06.

[Production Example 43] Synthesis of photoacid generator (PAG-43) In Production Example 37, 60.6 g of diphenyl sulfoxide was 4-[(phenyl) sulfinyl] biphenyl 83.5, and 18.6 g of diphenyl sulfide was 4- (phenylthio). ) 67 g of a pale yellow solid was obtained in the same manner as in Production Example 37 except that it was changed to 26.2 g of biphenyl (yield 62%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid contains hexafluorophosphate (CA-43) having a cationic structure of (C-14) and compounds (S14-1) to (S14-3). ), And its ratio was confirmed to be 99.01: 0.95: 0.03: 0.01.

[Production Example 44] Synthesis of photoacid generator (PAG-44) In Production Example 37, 60.6 g of diphenyl sulfoxide was 4-[(phenyl) sulfinyl] biphenyl 83.5, and 18.6 g of diphenyl sulfide was 4- (phenylthio). ) Biphenyl 26.2 g and potassium hexafluorophosphate 41 g were changed to 38 g of sodium trifluoromethanesulfonate, and 64 g of a pale yellow solid was obtained in the same manner as in Production Example 37 (yield 59%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid contains trifluoromethanesulfonate (CA-44) having a cationic structure of (C-14) and compounds (S14-1) to (S14-3). ), And its ratio was confirmed to be 99.03: 0.95: 0.01: 0.01.

[Production Example 45] Synthesis of photoacid generator (PAG-45) In Production Example 37, 60.6 g of diphenyl sulfoxide was 4-[(phenyl) sulfinyl] biphenyl 83.5, and 18.6 g of diphenyl sulfide was 4- (phenylthio). ) 102 g of a pale yellow solid was obtained in the same manner as in Production Example 37, except that 26.2 g of biphenyl and 41 g of potassium hexafluorophosphate were changed to 107 g of potassium trispentafluoroethyltrifluorophosphate (yield 61%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid contains trispentafluoroethyltrifluorophosphate (CA-45) having a cationic structure of (C-14) and compounds (S14-1) to (S14-1). It was confirmed that it was a mixture of S14-3) and its ratio was 99.11: 0.86: 0.02: 0.01.

[Production Example 46] Synthesis of photoacid generator (PAG-46) In Production Example 37, 60.6 g of diphenyl sulfoxide was added to (4-phenoxyphenyl) phenyl sulfoxide 88.3, and 18.6 g of diphenyl sulfide was added to (4-phenoxyphenyl). ) A pale yellow solid (61 g) was obtained in the same manner as in Production Example 37 except that the phenyl sulfide was changed to 27.8 g (yield 54%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid contains hexafluorophosphate (CA-46) having a cationic structure of (C-15) and compounds (S15-1) to (S15-3). ), And its ratio was confirmed to be 99.29: 0.67: 0.02: 0.02.

[Production Example 47] Synthesis of photoacid generator (PAG-47) In Production Example 37, 60.6 g of diphenyl sulfoxide was added to (4-phenoxyphenyl) phenyl sulfoxide 88.3, and 18.6 g of diphenyl sulfide was added to (4-phenoxyphenyl). ) A pale yellow solid 130 g was obtained in the same manner as in Production Example 37 (yield 59%) except that 27.8 g of phenyl sulfide and 41 g of potassium hexafluorophosphate were changed to 151 g of lithium tetrakispentafluorophenyl borate. By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid is a tetrakispentafluorophenylborate salt (CA-47) having a cationic structure of (C-15) and compounds (S15-1) to (S15-). It was confirmed that it was a mixture of 3) and its ratio was 99.18: 0.76: 0.04: 0.02.

[Production Example 48] Synthesis of photoacid generator (PAG-48) In Production Example 37, 60.6 g of diphenyl sulfoxide was added to (4-phenoxyphenyl) phenyl sulfoxide 88.3, and 18.6 g of diphenyl sulfide was added to (4-phenoxyphenyl). ) 119 g of a pale yellow solid was obtained in the same manner as in Production Example 37, except that 27.8 g of phenylsulfide and 41 g of potassium hexafluorophosphate were changed to 107 g of potassium trispentafluoroethyltrifluorophosphate (yield 69%). By analysis by 1 H-NMR, C-NMR, and HPLC, this pale yellow solid contains trispentafluoroethyltrifluorophosphate (CA-48) having a cationic structure of (C-15) and compounds (S15-1) to (S15-1). It was confirmed that it was a mixture of S15-3) and its ratio was 99.16: 0.80: 0.03: 0.01.

[Reference Manufacturing Example 1] (PAG H-1 to H-15)
The white solid obtained in Production Example 1 was repeatedly recrystallized from dichloromethane / methanol to obtain a hexafluorophosphate (PAG H-1) consisting substantially only of cation C-1 (compound (S-1). ) Is below the detection limit by HPLC (0.005% or less)). Similarly, the solids obtained in Production Examples 6, 9, 12, 15, 18, 22, 25, 28, 31, 34, 40, 43, and 46 for PAG H-2 to H-15, respectively, are purified by recrystallization. Was done. The composition is as shown in Table 1 for PAG H-1 to H-8 and in Table 3 for PAG H-9 to H15.

[Reference Manufacturing Example 2] (PAG-49, PAG H-16)
In Production Example 1, a crystallization filtrate with dichloromethane / hexane was collected, concentrated with an evaporator, and the obtained oil was washed with methanol and hexane to obtain a pale yellow solid. It was found by 1 H-NMR and HPLC that this solid was a compound (S1-1) represented by the formula (2). Using this, PAG-49 and PAG H-16 were obtained by adding an appropriate amount to PAG H-1 obtained in Reference Production Example 1. The composition of each was analyzed by HPLC. The composition is as shown in Table 1.

[Reference Manufacturing Example 3] (PAG-50 to 56, PAG H-17 to H23)
Reference In the same manner as in Production Example 2, the solids or oils recovered from the crystallization filtrate in Production Examples 6, 9, 12, 15, 37, 40 and 46 for PAG-50 to 56 and PAG H-17 to 23, respectively. The compounds represented by the formula (S2, S8, S9, S10, S12, S13, S15) obtained by purifying the above were used as PAG H-2 to H obtained in the corresponding Reference Production Example 1. By adding an appropriate amount to -8, PAG-42 to 47 and PAG H-14 to 18 were obtained. The composition of each was analyzed by HPLC. The composition is as shown in Table 1.

[Reference Manufacturing Example 4] (PAG-57 to 63, PAG H-24 to H30)
Reference In the same manner as in Production Example 2, the solids or oils recovered from the crystallization filtrate in Production Examples 18, 22, 25, 28, 31, 34, and 43 for PAG-57 to 63 and PAG H-24 to 30, respectively. The compounds represented by the formula (S3, S4, S5, S6, S7, S11, S14) obtained by purifying the above were used as PAG H-9 to H obtained in the corresponding Reference Production Example 1. By adding an appropriate amount to -15, PAG-57 to 63 and PAG H-24 to 30 were obtained. The composition of each was analyzed by HPLC. The composition is as shown in Table 3.

[Reference Manufacturing Example 5] (PAG H-31 to H36)
For comparison, diphenyl sulfide was added as compound (S'-1) instead of compound (S) represented by the formula (2) to PAG H-1 obtained in Reference Production Example 1 in an appropriate amount, and PAG H- 31-H-33 were obtained. The composition of each was analyzed by HPLC, and the composition is shown in Table 1. Similarly, an appropriate amount of 3-phenylthiobiphenyl as a compound (S'-2) was added to PAG H-6 obtained in Reference Production Example 1 to obtain PAG H-34 to H-36. The composition of each was analyzed by HPLC, and the composition is shown in Table 3.

<Preparation of photocurable composition and its evaluation>
The above photoacid generator is previously dissolved in propylene carbonate (solvent-1) in an amount of 50% by weight, and uniformly mixed with an epoxy resin (listed below), which is a cationically polymerizable compound, in the blending amount shown in Table 1. Then, a photocurable composition (Examples 1 to 50 and Comparative Examples 1 to 19) was prepared. The obtained curable composition was evaluated according to the following evaluation method. The results are shown in Table 2.
<Epoxy resin>
EP-1: 2,2-bis (4-glycidyloxyphenyl) propane EP-2: 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate EP-3:3-ethyl-3-{ [(3-Ethyloxetane-3-yl) methoxy] Methyl} oxetane

<Evaluation of photocurability (cationic polymerization performance)>
The above composition was applied on a polyethylene terephthalate (PET) film with an applicator to a film thickness of 25 μm. The PET film after the coating was irradiated with light having a wavelength limited by a filter using an ultraviolet irradiation device. As the filter, an IRCF02 filter (manufactured by Eye Graphics Co., Ltd., a filter that cuts light of less than 340 nm) was used. The hardness of the coating film 40 minutes after the irradiation was measured by the pencil hardness (JIS K5600-5-4: 1999), and the evaluation results according to the following criteria are shown in Table 2. The higher the pencil hardness, the better the sensitivity (cationic polymerization curability) of the photocurable composition.

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

(Light irradiation conditions)
・ Ultraviolet irradiation device: Belt conveyor type UV irradiation device (manufactured by Eye Graphics)
・ Lamp: 1.5kW high pressure mercury lamp ・ Filter: IRCF02 filter (manufactured by Eye Graphics)
-Illuminance (measured with a 365 nm head illuminance meter): 150 mW / cm ²
-Integrated light intensity (measured with a 365 nm head illuminance meter): 300 mJ / cm ²

<Yellow degeneration resistance evaluation-1>
A Teflon (registered trademark) spacer having a length of 20 mm, a width of 20 mm, and a thickness of 0.1 mm was prepared and sandwiched with slide glass (trade name "S2111", manufactured by Matsunami Glass Co., Ltd.). The curable composition was cast into the gaps, irradiated with light in the same manner as described above, and left at room temperature for 60 minutes after light irradiation to obtain a cured product. The yellowness (YI) of the obtained cured product was measured using a spectrophotometer (“U-3900”, manufactured by Hitachi High-Tech). Let this be YI ₀ . Further, the obtained cured product was heated at 180 ° C. for 30 minutes, and after heating, YI ₁ of the cured product was measured. Based on the following formula, the degree of discoloration ΔYI value was obtained and compared. The results are shown in Table 2. The degree of yellowness (YI) is obtained by reading the value of the two-degree field of view in the D65 light source, and the larger the value, the larger the degree of yellowness.
ΔYI = (YI ₁ )-(YI ₀ )

<Yellow degeneration resistance evaluation-2>
The thermosetting product before heating obtained in the yellowing resistance evaluation-1 was irradiated with light under the conditions described below, and a light resistance test was carried out. The light yellowing resistance was evaluated by measuring the yellowness YI ₂ by the same method as described above. Based on the following formula, the degree of discoloration ΔYI value was obtained and compared. The results are shown in Table 2.
ΔYI = (YI ₂ )-(YI ₀ )
(Light irradiation conditions)
Irradiation device: "LC-8" (manufactured by Hamamatsu Photonics)
Illuminance (measured with a 365 nm head illuminance meter): 100 mW / cm ²
Integrated irradiation dose (measured with a 365 nm head illuminance meter): 10 J / cm ²

As shown in Table 2, it can be seen from Examples 1 to 50 and Comparative Examples 1 to 19 that the photocurable composition containing the photoacid generator composition of the present invention is excellent in UV curability and yellowing resistance. Further, from Comparative Examples 1 to 8, it can be seen that the structure of the formula (1) alone has excellent UV curability, but the yellowing resistance is reduced. Further, as can be seen from Examples 27 to 34 and Comparative Examples 9 to 16, if the compound (S) represented by the formula (2) is contained in a certain ratio or more, the UV curability is deteriorated. It can be seen that the content needs to be 3.0 or less. On the other hand, when a compound (S'-1) similar to the compound (S) and not represented by the formula (2) is contained, it does not contribute to yellowing resistance and has UV curability as shown in Comparative Examples 17 to 19. It turns out that it affects. Further, as shown in Examples 1 to 26 and Examples 35 to 50, the UV curability and resistance of the photocurable composition containing the photoacid generator composition of the present invention are not limited to the anion structure and the type of epoxy resin. It can be seen that the yellowing is excellent.

<Preparation of negative photoresist composition and its evaluation>
(Preparation of sample for evaluation)
As shown in Table 3, a copolymer (Mw = 10,000) composed of 1 part of a photoresist generator and p-hydroxystyrene / styrene = 80/20 (molar ratio) as a component (F) which is a phenol resin. 100 parts, 20 parts of hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd., trade name "Nicarac MW-390") as a component (G) which is a cross-linking agent, and butadiene / as a component (H) which is a cross-linked fine particle. 10 parts of a copolymer (average particle size = 65 nm, Tg = -38 ° C.) composed of acrylonitrile / hydroxybutylmethacrylate / methacrylic acid / divinylbenzene = 64/20/8/6/2 (% by weight), adhesion aid As the component (J), 5 parts of γ-glycidoxypropyltrimethoxysilane (manufactured by Chisso, trade name “S510”) is uniformly dissolved in 145 parts of ethyl lactate (solvent-2) to form the present invention. Negative photoresist compositions (Examples 51-79, Comparative Examples 20-36) were prepared. In addition, the negative photoresist composition was evaluated by the following method. The results are shown in Table 4.

<Sensitivity evaluation>
Each composition was spin-coated on a silicon wafer substrate and then heated and dried at 110 ° C. for 3 minutes using a hot plate to obtain a resin coating film having a film thickness of about 20 μm. Then, pattern exposure (i-line) was performed using TME-150RSC (manufactured by Topcon), and post-exposure heating (PEB) was performed at 110 ° C. for 3 minutes using a hot plate. Then, it was developed by a dipping method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 2 minutes, washed with running water, and blown with nitrogen to obtain a line-and-space pattern of 10 μm. Further, the minimum essential exposure amount (corresponding to the sensitivity) required to form a pattern having a residual film ratio of 95% or more, which indicates the ratio of the residual 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 shape 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.
⊚: 0.90 ≦ La / Lb ≦ 1
◯: 0.85 ≦ La / Lb <0.90
X: La / Lb <0.85

<Yellow Degeneration Resistance Evaluation-3>
After each composition was spin-coated on a glass substrate, it was heated and dried at 110 ° C. for 3 minutes using a hot plate to obtain a resin coating film having a film thickness of about 20 μm. Then, full exposure (i-line) was performed using TME-150RSC (manufactured by Topcon), and post-exposure heating (PEB) was performed at 110 ° C. for 3 minutes using a hot plate. Then, it was developed by a dipping method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 2 minutes, washed with running water, and blown with nitrogen to obtain a cured film. The yellowness (YI) of the obtained cured product was measured using a spectrophotometer (“U-3900”, manufactured by Hitachi High-Tech). Let this be YI ₀ . Further, the obtained cured product was heated at 180 ° C. for 30 minutes, and after heating, YI ₃ of the cured product was measured. From these differences, the degree of discoloration ΔYI value was obtained and compared.

As shown in Table 4, it can be seen from Examples 51 to 79 and Comparative Examples 20 to 36 that the chemically amplified negative photoresist composition containing the photoacid generator of the present invention is excellent in yellowing resistance. From Comparative Examples 20 to 26, it can be seen that although the resist performance is excellent only with the structure of the formula (1), the yellowing resistance is lowered. Further, as can be seen from Examples 73 to 79 and Comparative Examples 27 to 33, if the compound (S) represented by the formula (2) is contained in a certain ratio or more, the resist performance is deteriorated, and therefore the compound (S) is contained. It can be seen that the amount needs to be 3.0 or less. On the other hand, when a compound (S'-2) similar to the compound (S) and not represented by the formula (2) is contained, it does not contribute to yellowing resistance as shown in Comparative Examples 34 to 36, and the resist performance is improved. It turns out that it affects. Further, as shown in Examples 51 to 72, it can be seen that the composition containing the photoacid generator of the present invention is excellent in yellowing resistance regardless of the anionic structure.

The sensitive energy ray-curable composition using the photoacid generator of the present invention is a paint, a coating agent, various coating materials (hard coat, stain-resistant coating material, anti-fog coating material, touch-resistant coating material, optical fiber, etc.). , Adhesive tape back treatment agent, adhesive label release sheet (release paper, release plastic film, release metal foil, etc.) release coating material, printing board, dental material (dental compound, dental composite) ink, inkjet Ink, resist film, liquid resist, negative type resist (surface protective film for semiconductor elements, interlayer insulating film, permanent film material such as flattening film, etc.), MEMS resist, negative type photosensitive material, various adhesives (various types) Temporary fixing agent for electronic parts, adhesive for HDD, adhesive for pickup lens, adhesive for functional film for FPD (deflection plate, antireflection film, etc.), resin for holographic, FPD material (color filter, black matrix, etc.) , Bulkhead material, Photo spacer, Rib, Alignment film for liquid crystal, Sealing agent for FPD, etc.), Optical member, Molding material (For building material, Optical component, Lens), Casting material, Putty, Glass fiber impregnating agent, Sealing It is suitably used for materials, sealing materials, encapsulants, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, optical production materials, micro optical modeling materials and the like.

Claims (7)

It contains a sulfonium salt (CA) represented by the following general formula (1) and a compound (S) represented by the general formula (2), and the total content of the sulfonium salt (CA) and the compound (S) is a high-speed liquid. The feature is that the area ratio of the compound (S) is 0.02 or more and 3.0 or less when the total area of the sulfonium salt (CA) and the compound (S) as measured by chromatography (HPLC) is 100. Photoacid generator.

[In the formulas (1) to (2), R ¹ to R ³ are organic groups bonded to the benzene ring, p, q, and r represent the number of R ¹ to R ³ , respectively, and p is 0 to. It is an integer of 4, q and r are integers of 0 to 5, and when it is 0, hydrogen atoms are bonded, and when p, q and r are 2 or more, they are different even if they are the same. Also good, R ¹ to R ³ are direct to each other or -O-, -S-, -SO-, -SO _2- , -NH-, -CO-, -COO-, -CONH-, alkylene group or phenylene. A ring structure may be formed via a group, X is an atom (group) that can be a monovalent anion, and Ar ¹ to Ar ³ may have the same or different carbon atoms from each other. Or a heteroaryl group having 4 to 18 carbon atoms, and the aryl group or heteroaryl group of Ar ¹ may be further substituted with a group represented by the formula (3), and R in the formula (3). ² , R ³ , r, q and X are the same as in equation (1), and n in equation (2) is an integer of 1 or 2. ]

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 ^- , Trifluoromethanesulfonic acid anion, nonafluorobutane sulfonic acid anion, methanesulfonic acid anion, butane sulfonic acid anion, camphor sulfonic acid anion, benzenesulfonic acid anion, p-toluene sulfonic acid anion, (CF ₃ SO ₂ ) _3C The photoacid generator according to claim 1, which is selected from the group consisting of anions represented by ^{- and} (CF ₃ SO ₂ ) ₂ N-. A photocurable composition comprising the photoacid generator according to claim 1 or 2 and a cationically polymerizable compound. A cured product obtained by curing the photocurable composition according to claim 3. A chemistry comprising the component (E) containing the photoresist generator according to claim 1 or 2, the component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and the cross-linking agent component (G). Amplified negative photoresist composition. The chemically amplified negative photoresist composition according to claim 5, further comprising a crosslinked fine particle component (H). A cured product obtained by curing the chemically amplified negative photoresist composition according to claim 5 or 6.