WO2022054554A1

WO2022054554A1 - Actinic-ray-sensitive acid generator

Info

Publication number: WO2022054554A1
Application number: PCT/JP2021/030762
Authority: WO
Inventors: 淳舩山; 篤志白石; 秀基木村
Original assignee: サンアプロ株式会社
Priority date: 2020-09-09
Filing date: 2021-08-23
Publication date: 2022-03-17
Also published as: TW202210457A; JPWO2022054554A1

Abstract

Provided is a highly active actinic-ray-sensitive acid generator which, upon irradiation with actinic rays, comes to have cationic-polymerization performance or crosslinking reaction performance and which enables curable compositions containing the acid generator to have satisfactory storage stability. This actinic-ray-sensitive acid generator comprises sulfonium salt (A), which is represented by general formula (1), and sulfonium salt (B), which is represented by general formula (2), and has a content of the sulfonium salt (B) of 0.01-2 mol% with respect to the total number of moles of the sulfonium salt (A) and the sulfonium salt (B).

Description

Sensitive energy linear acid generator

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

Conventionally, an onium salt such as a sulfonium salt is known as a cationic polymerization initiator that cures a cationically polymerizable compound by irradiation with an active energy ray such as light or an electron beam. Photoacid generators that generate acid are known (Patent Documents 1 to 3). Further, these onium salts are also called acid generators because they generate an acid by irradiation with active energy rays, and are also used in resists and photosensitive materials (Patent Documents 4 to 6).

By the way, known methods for producing active energy linear acid generators, particularly sulfonium salts, described in these specifications are used (Patent Documents 1 and 3). However, the sulfonium salt produced by these methods has a problem in reactivity with active energy rays (that is, the amount of acid generated), and the bissulfonium salt produced as a by-product and decomposition over time make it an active energy ray-curable composition. When formulated as, there is a problem with long-term storage stability. In order to solve these problems, improvements in the manufacturing method that suppresses the by-product of bissulfonium salt, which has been the cause of deterioration of storage stability, have been reported, but even this does not mean that long-term storage stability is sufficient. (Patent Document 7).

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 WO2005 / 00801 Gazette

In the above background, the first object of the present invention is to have cation polymerization performance and cross-linking reaction performance by irradiation with active energy rays, and a curable composition using this is highly active with good storage stability. It is to provide a sensitive energy linear acid generator. A second object of the present invention is to provide an active energy ray-curable composition, a chemically amplified positive photoresist composition, and a chemically amplified negative photoresist composition using the above acid generator.

The present inventor has found an active energy linear acid generator suitable for the above purpose. That is, the present invention contains a sulfonium salt (A) represented by the following general formula (1) and a sulfonium salt (B) represented by the following general formula (2), and the sulfonium salt (A) and the sulfonium salt (B). It is a sensitive energy linear acid generator (hereinafter referred to as a photoacid generator or an acid generator) in which the content of the sulfonium salt (B) is 0.01 to 2 mol% with respect to the total number of moles.

[In the formula (1), R ¹ to R ⁴ are organic groups bonded to the benzene ring, the number of R ² is 0 to 4, the number of R ¹ , R ³ and R ⁴ is 0 to 5. , 0 means that hydrogen atoms are bonded, and when multiple ^R1 to ^R4 are bonded, they may be the same or different from each other, and ^R1 to ^R4 may be directly or -O-, respectively. A ring structure may be formed via -S-, -SO-, -SO _2- , -NH-, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group, and X ^- is an element. It is a monovalent anion having a group 13 or group 15 element in the periodic table and having a halogen.]

[In the formula (2), R ¹ to R ⁴ are organic groups bonded to the benzene ring, and the number of R ² is 0 to 4, the number of R ¹ , R ³ and R ⁴ is 0 to 5. , 0 means that hydrogen atoms are bonded, and when multiple ^R1 to ^R4 are bonded, they may be the same or different from each other, and ^R1 to ^R4 may be directly or -O-, respectively. A ring structure may be formed via -S-, -SO-, -SO _2- , -NH-, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group, and Y ^- is a halogen. It is a monovalent anion selected from the group consisting of anions that do not have.]

The present invention is also characterized in that an active energy ray-curable composition containing the acid generator and a cationically polymerizable compound; obtained by curing the active energy ray-curable composition. A cured product; a chemically amplified positive photoresist composition comprising the above-mentioned acid generator and a component (B) which is a resin whose solubility in an alkali is increased by the action of the acid; the above-mentioned acid generation. A chemically amplified negative photoresist composition comprising an agent, a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a cross-linking agent component (G); the above-mentioned chemically amplified negative. It is a cured product characterized by being obtained by curing a type photoresist composition.

The acid generator of the present invention has high activity with respect to active energy rays, and also has cationic polymerization performance and cross-linking reaction performance, and a composition using this has good storage stability.

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

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

In the above, examples of the aryl group having 6 to 30 carbon atoms include a monocyclic aryl group such as a phenyl group and a biphenylyl group, and naphthyl, anthrasenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthalsenyl, benzanthrasenyl, anthracinyl, naphthoquinyl, fluorenyl and the like. A fused polycyclic aryl group can be mentioned.

Examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic compounds containing 1 to 3 heterocyclic atoms such as oxygen, nitrogen, and sulfur, which may be the same or different, and are specific examples. Examples include monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, etc. Examples thereof include fused polycyclic heterocyclic groups such as quinazolinyl, carbazolyl, acridinyl, phenothiazine, phenazinyl, xanthenyl, thiantranyl, phenoxadinyl, phenoxatyynyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl and dibenzofuranyl. The

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. Branched Alkyl Group, Cycloalkyl Group such as Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, etc.
Examples of the alkenyl group having 2 to 30 carbon atoms include linear or branched alkenyl groups such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl and 1-methyl-1-propenyl. Can be mentioned.
Further, examples of the alkynyl group having 2 to 30 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl and 1-methyl-2-propynyl. Such as linear or branched ones can be mentioned.

The above-mentioned aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms is at least 1 It may have a substituent of the species, and examples of the substituent include a linear alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl and octadecyl; isopropyl, isobutyl, sec-butyl and tert-butyl. Branched alkyl groups with 1 to 18 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and other cycloalkyl groups with 3 to 18 carbon atoms; hydroxy groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, etc. Linear or branched alkoxy group having 1 to 18 carbon atoms such as tert-butoxy and dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyle, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl and the like. 2-18 linear or branched alkylcarbonyl groups; arylcarbonyl groups with 7-11 carbon atoms such as benzoyl, naphthoyl; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxy Linear or branched alkoxycarbonyl group with 2 to 19 carbon atoms such as carbonyl, tert-butoxycarbonyl; aryloxycarbonyl group with 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; carbon such as phenylthiocarbonyl and naphthoxythiocarbonyl An arylthiocarbonyl group having a number of 7 to 11; a linear or linear group having 2 to 19 carbon atoms such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, and octadecylcarbonylokishi. Branched asyloxy groups; phenylthio, biphenylylthio, methylphenylthio, chlorophenylthio, bromophenylthio, fluorophenylthio, hydroxyphenylthio, methoxyphenylthio, naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (Phenylthio) phenoxy] phenylthio, 4- [4- (phenylthio) phenyl] phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl- Chlorophenylthio, 4-benzoyl-methylthiophenylthio, 4- (methylthiobenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio, etc. Arylthio groups having 6 to 20 carbon atoms; methylthio, ethylthio, propylthio, tert-butylthio , Neopentylthio, dodecylthio, etc., linear or branched alkylthio groups with 1 to 18 carbon atoms; phenyl, tolyl, dimethylphenyl, naphthyl, etc., 6 to 10 carbon atoms aryl groups; thienyl, furanyl, pyranyl, xanthenyl, chromanyl, Heterocyclic groups having 4 to 20 carbon atoms such as isochromanyl, xanthonyl, thioxanthonyl and dibenzofuranyl; aryloxy groups having 6 to 10 carbon atoms such as phenoxy and naphthyloxy; methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl and octyl Linear or branched alkylsulfinyl groups with 1-18 carbon atoms such as sulfinyl; arylsulfinyl groups with 6-10 carbon atoms such as phenylsulfinyl, trillsulfinyl, naphthylsulfinyl; methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl , Octylsulfonyl, etc., linear or branched alkylsulfonyl group with 1-18 carbon atoms; phenylsulfonyl, tolylsulfonyl (tosyl group), naphthylsulfonyl, etc. with 6-10 carbon atoms, arylsulfonyl group; alkyleneoxy group; cyano group; Nitro group; halogens such as fluorine, chlorine, bromine and iodine can be mentioned.

When multiple ^R1 to ^R4 are bonded, they are directly or -O-, -S-, -SO-, _-SO2- , -NH-, -CO-, -COO-, -CONH-, alkylene group. Alternatively, a ring structure may be formed via a phenylene group. For example, when R ¹ is 2 or more, two R ^1s are directly or -O-, -S-, -SO-, -SO _2- , -NH-, -CO-, -COO-,-. It means forming a ring structure via a CONH-, an alkylene group or a phenylene group.

Of these organic groups, preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and a carbon element number. An arylthio group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a chlorine atom and a fluorine atom, more preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms and 1 to 1 carbon atoms. It is an alkoxy group of 6.

The number of substituents ^R1 to ^R4 in the formula (1) or (2) is 0 to 5, and in the case of 0, a hydrogen atom is bonded. The number of R ¹ to R ⁴ is preferably 0 to 3, and more preferably 0 or 1. When the number of R ¹ to R ⁴ is in these preferable ranges, the photosensitivity and solubility of the sulfonium salt become good.

Among the sulfonium salts represented by the formula (1) or (2), specific examples of preferable cation portions are shown below.

In formula (1), X ^- is an acid generated by irradiating an atom (group) that can be a monovalent anion, that is, a sulfonium salt, with active energy rays (visible light, ultraviolet rays, electron beams, X-rays, etc.). It is an anion corresponding to (HX). X ^- is not limited except that it is a monovalent polyatomic anion having Group 13 or Group 15 elements and having a halogen in the Periodic Table of the Elements, but MZ _a- ^, (Rf) _b PF. Anions represented by 6 ^- _b- ^, R ⁸ _c BZ _4-c- ^, R ⁸ _c GaZ _4-c ^- or (R ⁹ SO ₂ ) ₂ N- are preferable from the viewpoint of photosensitivity.

M represents a phosphorus atom, a boron atom or an antimony atom.
Z 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 a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroaryl group having 6 to 20 carbon atoms, and the perfluoroalkyl group may be linear, branched or cyclic.

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 MZ _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 BZ _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 preferred.

The anions represented by R ⁸ _c GaZ _4-c- ^are (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.

Of these X- ^, MZ _a- ^, (Rf) _b PF _6-b- ^, R ⁸ _c BZ _4-c- ^, R ⁸ _c GaZ _4-c- ^, R ⁹ SO _3- ^, or (R ⁹ SO). ₂ ) Anions represented by ₂ N- are 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 ^- and (CF ₃ SO ₂ ) ₂ N ^- are more preferable in that the resist resolution and pattern shape are improved, and (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- ^and ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B- ^, (CF ₃ SO ₂ ) ₃ C ^- is particularly preferable because it has good compatibility with the resist composition.

In formula (2), Y ^- is a monovalent anion selected from the group consisting of halogen ^- free anions, and the atoms (groups) that can be monovalent anions are HSO _4- ^, HNO _3- , H ₂ PO _4- ^, methanesulphonate anion, halogen-free carboxylic acid anion, and anion represented by the following general formula (3) are preferably selected from the group.

[In the formula (3), R ⁵ and R ⁶ are hydrogen atoms or organic groups, the number of R ⁵ and R ⁶ is 0 to 5, and in the case of 0, hydrogen atoms are bonded and R ⁵ and R 6 are bonded. When multiple R ^6s are bonded, they may be the same or different from each other, and R ⁵ and R ⁶ may be directly attached to each other or -O-, -S-, -SO-, -SO _2- , -NH-. , -CO-, -COO-, -CONH-, an alkylene group or a phenylene group may form a ring structure, and m and n are 0 or 1, respectively, and m + n = 1. ]

Carboxylic acids that do not have halogen include formic acid, glycolic acid, acetic acid, propionic acid, butyric acid, valeric acid, octyl acid, 2-ethylhexanoic acid, cyanoacetic acid, trimethylacetic acid, methoxyacetic acid, cyclopentanecarboxylic acid, and mercaptoacetic acid. , Lactic acid, pyruvate, levulinic acid, acrylic acid, crotonic acid, vinyl acetic acid, methacrylic acid, anisic acid, benzoic acid, silicate acetic acid, naphthoic acid, phenylacetic acid, phenoxyacetic acid, mandelic acid and the like.

R ⁵ and R ⁶ of the formula (3) represent an organic group bonded to a benzene ring, and may be the same or different. Examples of R ⁵ and R ⁶ include an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms. Represents the alkynyl group of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl. , Alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro and at least one selected from the group consisting of halogen.

The aryl group having 6 to 30 carbon atoms is the same as the specific example of the aryl group having 6 to 30 carbon atoms mentioned as R ¹ to R ⁴ above.

The heterocyclic group having 4 to 30 carbon atoms is the same as the specific example of the heterocyclic group having 4 to 30 carbon atoms mentioned as R ¹ to R ⁴ above.

The alkyl group having 1 to 30 carbon atoms is the same as the specific example of the alkyl group having 1 to 30 carbon atoms mentioned as R ¹ to R ⁴ above.
The alkenyl group having 2 to 30 carbon atoms is the same as the specific example of the alkenyl group having 2 to 30 carbon atoms listed as R ¹ to R ⁴ above.
Further, the alkynyl group having 2 to 30 carbon atoms is the same as the specific example of the alkynyl group having 2 to 30 carbon atoms mentioned as R ¹ to R ⁴ above.

The above-mentioned aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms is at least 1 It may have a substituent of the species, and examples of the substituent include a linear alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl and octadecyl; isopropyl, isobutyl, sec-butyl and tert-butyl. Branched alkyl groups with 1 to 18 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and other cycloalkyl groups with 3 to 18 carbon atoms; hydroxy groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, etc. Linear or branched alkoxy group having 1 to 18 carbon atoms such as tert-butoxy and dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyle, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl and the like. 2-18 linear or branched alkylcarbonyl groups; arylcarbonyl groups with 7-11 carbon atoms such as benzoyl, naphthoyl; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxy Linear or branched alkoxycarbonyl group with 2 to 19 carbon atoms such as carbonyl, tert-butoxycarbonyl; aryloxycarbonyl group with 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; carbon such as phenylthiocarbonyl and naphthoxythiocarbonyl An arylthiocarbonyl group having a number of 7 to 11; a linear or linear group having 2 to 19 carbon atoms such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, and octadecylcarbonylokishi. Branched asyloxy groups; phenylthio, biphenylylthio, methylphenylthio, chlorophenylthio, bromophenylthio, fluorophenylthio, hydroxyphenylthio, methoxyphenylthio, naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (Phenylthio) phenoxy] phenylthio, 4- [4- (phenylthio) phenyl] phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl -Chlorophenylthio, 4-benzoyl-methylthiophenylthio, 4- (methylthiobenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio, etc. Arylthio groups having 6 to 20 carbon atoms; methylthio, ethylthio, propylthio, tert- Linear or branched alkylthio groups with 1-18 carbon atoms such as butylthio, neopentylthio, dodecylthio; aryl groups with 6-10 carbon atoms such as phenyl, trill, dimethylphenyl, naphthyl; thienyl, furanyl, pyranyl, xanthenyl, chromanyl , Isochromanyl, xanthonyl, thioxanthonyl, dibenzofuranyl and other heterocyclic groups having 4 to 20 carbon atoms; phenoxy, naphthyloxy and other aryloxy groups having 6 to 10 carbon atoms; methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, Linear or branched alkylsulfinyl groups with 1-18 carbon atoms such as octylsulfinyl; arylsulfinyl groups with 6-10 carbon atoms such as phenylsulfinyl, trillsulfinyl, naphthylsulfinyl; methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butyl A linear or branched alkylsulfonyl group having 1 to 18 carbon atoms such as sulfonyl and octylsulfonyl; an arylsulfonyl group having 6 to 10 carbon atoms such as phenylsulfonyl, tolylsulfonyl (tosyl group) and naphthylsulfonyl; an alkyleneoxy group; a cyano group. ; Nitro group and the like can be mentioned.

R ⁵ and R ⁶ are directly with each other or via -O-, -S-, -SO-, -SO _2- , -NH-, -CO-, -COO-, -CONH-, alkylene group or phenylene group. A ring structure may be formed.

Of these organic groups, preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and a carbon element number. It is an arylthio group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a chlorine atom and a fluorine atom, more preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms and 1 to 1 carbon atoms. It is an alkoxy group of 6.

M and n in the equation (3) are 0 or 1, respectively, and m + n = 1.

Of these Y- ^, the compounds represented by HSO _4- ^and the general formula (3) are preferable from the viewpoint of storage stability.

As R5 or R6 of the ^formula ( ³ ), an arylthio group and an arylsulfinyl group are preferable from the viewpoint of storage stability.

From the viewpoint of solubility in the resist, a more preferable structure as the formula (3) is the following structure.

The content of the sulfonium salt (B) is 0.01 to 2 mol with respect to the total number of moles of the sulfonium salt (A) represented by the general formula (1) and the sulfonium salt (B) represented by the general formula (2). %, If it is 0.01 mol% or more, the storage stability is good, and if it exceeds 2 mol%, the curability of cationic polymerization and the sensitivity of the resist are deteriorated. Further, from the viewpoint of storage stability, 0.1 to 2 mol% is preferable.

The sulfonium salt (A) represented by the general formula (1) and the sulfonium salt (B) represented by the general formula (2) can be produced by a known production method. For example, there are a method of reacting diaryl sulfide with chlorine, a method of reacting diaryl sulfide with aromatic hydrocarbons such as chlorine and benzene, and a method of reacting diaryl sulfide with diaryl sulfoxide in the presence of a dehydrating agent.

The dehydrating agent is not particularly limited as long as it is used as a dehydrating agent in an organic chemical reaction, and examples thereof include concentrated sulfuric acid, phosphoric acid anhydride, methanesulfonic acid, acetic acid anhydride, trifluoromethanesulfonic acid or an anhydride thereof. These may be mixed and used in two or more kinds. Moreover, you may use a solvent as appropriate.

When diaryl sulfoxide and diaryl 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 50 ° C., preferably −5 ° C. to 30 ° C., and most preferably 0 ° C. to 10 ° C. By reacting under these conditions, the sulfonium salt of the present invention can be produced with high purity.

After the reaction, the sulfonium salt can be efficiently produced by exchanging the anion with the acid (HX) and the salt (AXn) having the anion represented by X in the formula (1). 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.

Similarly, a sulfonium salt can be efficiently produced by exchanging anions with an acid (HY) and a salt (AYn) having an anion represented by Y in the general formula (2).

The acid generator of the present invention can be produced by mixing the sulfonium salts of the general formulas (1) and (2), and is represented by the sulfonium salt (A) represented by the general formula (1) and the general formula (2). The content of the sulfonium salt (B) is 0.01 to 2 mol% with respect to the total number of moles of the sulfonium salt (B).

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

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

Other acid 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 acid 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 acid generator of the present invention. The solvent used may be used alone or in combination of two or more.

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

Examples of the cationically polymerizable compound that is a component of the active energy ray-curable composition include cyclic ethers (epoxide and oxetane, etc.), ethylenically unsaturated compounds (vinyl ether, styrene, etc.), bicycloorthoesters, spirolotocarbonates, and spirololt. Examples thereof include: {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 , JP-A-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, "UV / EB Curing Materials" (1992, CMC), Technical Information Association, "Causes of Curing Poorness / Inhibition in UV Curing and Countermeasures" (2003, Technical Information) Association), Coloring Materials, 68, (5), 286-293 (1995), Fine Chemicals, 29, (19), 5-14 (2000), etc.}.

As the epoxide, known 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 novolak and compounds having alkylene oxide adducts 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.).

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 and cyclohexyl vinyl ether.

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

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

Examples of styrene include styrene, α-methylstyrene, p-methoxystyrene, 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, a polyorganosiloxane having at least one cationically polymerizable group in one molecule can be used (Japanese Patent Laid-Open No. 2001-348482, JP-A-2000-281965, JP-A-7-242828, JP. JP-A-2008-19593, Journal of Polymer.Sci., Part A, Polymer. Chem., Vol. 28, 497 (1990), etc. These polyorganosiloxanes are linear, branched chains. It may be in the form of a ring or a ring, and 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 acid generator of the present invention in the active energy ray-curable 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. Is. 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 and irradiation amount of the active energy ray, the temperature, the curing time, the humidity, and the thickness of the coating film, and is within the above range. Not limited.

The active energy ray-curable composition of the present invention contains, if necessary, known additives (sensitizers, pigments, fillers, antistatic agents, flame retardants, defoamers, flow modifiers, light stabilizers). , Antioxidant, Adhesion-imparting agent, Ion-supplementing agent, Anticoloring agent, Solvent, Non-reactive resin, Radical polymerizable compound, etc.) can be contained.

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-methoxynaphthrene, 1,4-dihydroxynaphthrene, 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 acid 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 acid 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 acid generator.

As the antistatic agent, known antistatic agents and the like can be used, and examples thereof include nonionic 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 20000 parts by weight, more preferably 0.6 to 5000 parts by weight, based on 100 parts by weight of the acid 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, decabromobiphenyl ether, 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 acid 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, known anti-coloring agents can be used, and in general, antioxidants are effective, and phenol-based antioxidants (monophenol-based, bisphenol-based, high-molecular-weight 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 coloring inhibitor is contained, the content of each is 0 with respect to 100 parts of the acid generator. It is preferably 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 a cationically polymerizable compound or adjusting the viscosity of an active energy ray-curable composition, and the above-mentioned solvent for an acid 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 acid 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 acid generator.

When a non-reactive resin is contained, it is desirable to dissolve the non-reactive resin in a solvent in advance in order to 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 acid generator.

When a radically polymerizable compound is contained, it is preferable to use a radical polymerization initiator that initiates polymerization by heat or light in order to increase the 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 active energy ray-curable composition of the present invention uniformly comprises a cationically polymerizable compound, an acid 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 prepared by mixing and dissolving in, or by kneading with three rolls or the like.

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

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

Specific applications of the active energy ray-curable composition of the present invention include paints, coating agents, various coating materials (hard coats, stain-resistant coating materials, anti-fog coating materials, anti-fog coating materials, anti-contact coating materials, optical fibers, etc.), adhesives, etc. Tape 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, Positive resists (connection terminals for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, wiring pattern formation, etc.), resist films, liquid resists, negative resists (surface protective films for semiconductor elements, interlayer insulating films, flattening, etc.) Permanent film materials such as films), resists for MEMS, positive photosensitive materials, negative photosensitive materials, various adhesives (temporary fixing agents for various electronic parts, adhesives for HDDs, adhesives for pickup lenses, adhesives for FPDs, etc.) Adhesives for functional films (deflectors, antireflection films, etc.), holographic resins, FPD materials (color filters, black matrices, partition materials, photospacers, ribs, alignment films for liquid crystals, sealants for FPDs, etc.) , Optical members, molding materials (for building materials, optical parts, lenses), casting materials, putties, glass fiber impregnants, sealing materials, sealing materials, encapsulants, opto-semiconductor (LED) encapsulants, optical waveguides Examples thereof include materials, nano-imprint materials, materials for optical molding, and materials for micro-optical modeling. In particular, the obtained cured product is less colored and has excellent transparency, so that 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.

The chemically amplified positive photoresist composition of the present invention has increased solubility in alkali due to the action of the component (A) containing the photoacid generator of the present invention, which is a compound that generates an acid by light irradiation, and the acid. It is characterized by containing the resin component (B).

In the chemically amplified positive photoresist composition of the present invention, the component (A) may be used in combination with other conventionally known 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 of 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 (A) is preferably 0.05 to 5% by weight based on the solid content of the chemically amplified positive photoresist composition.

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

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

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

Further, as the acid dissociative dissolution inhibitor group represented by R ^1b , a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and a cyclic group having 3 to 6 carbon atoms are used. Alkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, or trialkylsilyl group is preferable.

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

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

In the above general formula (b4), R ^8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^9b represents an acid dissociative dissolution inhibitory group, and n represents the number of repeating units of the structure in parentheses. show.

The above-mentioned alkyl group having 1 to 6 carbon atoms is a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. And so on.

As the acid dissociative dissolution inhibitory group represented by R ^9b , the same acid dissociative dissolution inhibitory group as exemplified in R ^1b can be used.

Further, the polyhydroxystyrene resin (B2) can contain another polymerizable compound as a constituent unit for the purpose of appropriately controlling the physical and chemical properties. Examples of such a polymerizable compound include known radically polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; methacrylic acid derivatives having a carboxyl group and ester bond such as 2-methacryloyloxyethyl succinic acid; methyl (meth) acrylate and the like. (Meta) acrylic acid alkyl esters; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate; vinyl group-containing fragrances such as styrene and vinyl toluene. Group compounds; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugate diolefins such as butadiene and isoprene; Nitrile group-containing polymerizable compounds such as acrylonitrile; Chlorine-containing polymerizable compounds such as vinyl chloride; Examples thereof include amide bond-containing polymerizable compounds.

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

In the above general formulas (b5) to (b7), R ^10b to R ^17b are independently hydrogen atoms, linear alkyl groups having 1 to 6 carbon atoms, and branched alkyl groups having 3 to 6 carbon atoms, respectively. A group, a fluorine atom, or a linear fluorinated alkyl group having 1 to 6 carbon atoms or a branched chain fluorinated alkyl group having 3 to 6 carbon atoms, in which X ^b is represented by the carbon atom to which the group is bonded. A hydrocarbon ring having 5 to 20 carbon atoms is formed, Y ^b represents an aliphatic cyclic group or an alkyl group which may have a substituent, and n represents the number of repeating units of the structure in parentheses. p is an integer from 0 to 4, and q is 0 or 1.

In the general formula (b8), the general formula (b9) and the general formula (b10), R ^18b , R ^20b and R ^21b represent hydrogen atoms or methyl groups independently of each other, and in the general formula (b8), respectively. R ^19b is a hydrogen atom, a hydroxyl group, a cyano group or a COOR ^23b group (provided that R ^23b is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a branch having 3 to 4 carbon atoms. Represents a chain alkyl group or a cycloalkyl group having 3 to 20 carbon atoms), and in the general formula (b10), each R ^22b is a monovalent alicyclic group having 4 to 20 carbon atoms independently of each other. A hydrogen group or a derivative thereof, a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, and at least one of R ^22b is the alicyclic hydrogen group or the alicyclic hydrogen group. A divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, which is a derivative thereof, or in which any two R ^22bs are bonded to each other and has a common carbon atom to which each is bonded. The remaining R ^22b is a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. Or it represents a derivative thereof.

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

The polystyrene-equivalent weight average molecular weight of the component (B) is preferably 10,000 to 600,000, more preferably 50,000 to 600,000, and further preferably 230,000 to 550,000. be. By setting such a weight average molecular weight, the resin physical properties of the resist become excellent.

Further, the component (B) is preferably a resin having a dispersity of 1.05 or more. Here, the "dispersity" is a value obtained by dividing the weight average molecular weight by the number average molecular weight. With such a degree of dispersion, the plating resistance of the resist and the physical characteristics of the resin are excellent.

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

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

The content of the component (C) is preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, based on 100 parts by weight of the component (B). When the amount is 5 parts by weight or more, the resin physical properties of the resist can be improved, and when the amount is 95 parts by weight or less, the film loss during development tends to be prevented.

<Acid diffusion control agent (D)>
In the chemically amplified positive photoresist composition for thick films of the present invention, in order to improve the shape of the resist pattern, the retention stability, etc., the acid diffusion control agent (D) (in the present specification, the component ( D) ”) is preferably contained. As the component (D), a nitrogen-containing compound is preferable, and if necessary, an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof can be contained.

Further, the chemically amplified positive photoresist composition of the present invention may further contain an adhesive aid in order to improve the adhesiveness with the substrate. As the adhesive aid used, a functional silane coupling agent is preferable.

Further, the chemically amplified positive photoresist composition of the present invention may further contain a surfactant in order to improve coatability, defoaming property, leveling property and the like.

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

Further, the chemically amplified positive photoresist composition of the present invention basically does not require a sensitizer, but may contain a sensitizer as necessary to supplement the sensitivity. As such a sensitizer, conventionally known ones can be used, and specific examples thereof include the above-mentioned ones.

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

Further, an organic solvent can be appropriately added to the chemically amplified positive photoresist composition of the present invention in order to adjust the viscosity. Specific examples of the organic solvent include those mentioned above.

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

To prepare the chemically amplified positive photoresist composition for thick films of the present invention, for example, it is only necessary to mix and stir each of the above components by a usual method, and if necessary, a dissolver, a homogenizer, a three-roll mill, or the like. It may be dispersed and mixed using a disperser. Further, after mixing, the mixture may be further filtered using a mesh, a membrane filter or the like.

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

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

The photoresist laminate can be manufactured, for example, as follows. That is, a solution of the chemically amplified positive photoresist composition prepared as described above is applied onto the support, and the solvent is removed by heating to form a desired coating film. As a coating method on the support, a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like can be adopted. The prebaking conditions for the coating film of the composition of the present invention vary depending on the type of each component in the composition, the mixing ratio, the coating film thickness, etc., but are usually 70 to 150 ° C., preferably 80 to 140 ° C., 2 to It may be about 60 minutes.

The film thickness of the photoresist layer may be usually in the range of 5 to 150 μm, preferably 10 to 120 μm, and more preferably 10 to 100 μm.

In order to form a resist pattern using the photoresist laminate thus obtained, light or radiation, for example, a wavelength of 300 to 500 nm, is formed on the obtained photoresist layer through a mask of a predetermined pattern. Ultraviolet rays or visible light may be irradiated (exposed) in a site-selective manner.

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. As the radiation source of light or radiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, an LED lamp, or the like can be used. The amount of radiation irradiation varies depending on the type of each component in the composition, the blending amount, the film thickness of the coating film, and the like, but is 50 to 10,000 mJ / cm ² when, for example, an ultrahigh pressure mercury lamp is used.

Then, after the exposure, the oxidation is promoted by heating using a known method to change the alkali solubility of the photoresist layer in the exposed portion. Then, for example, a predetermined alkaline aqueous solution is used as a developing solution to dissolve and remove unnecessary portions to obtain a predetermined resist pattern.

The developing time varies depending on the type of each component of the composition, the mixing ratio, and the dry film thickness of the composition, but is usually 1 to 30 minutes, and the developing method is a liquid filling method, a dipping method, a paddle method, or a spray developing method. And so on. After development, wash with running water for 30 to 90 seconds, and dry using an air gun or an oven.

By embedding a conductor such as metal in the non-resist portion (the portion removed by the alkaline developer) of the resist pattern thus obtained, for example, by plating or the like, a connection terminal such as a metal post or a bump is formed. Can be done. The plating treatment method is not particularly limited, and various conventionally known methods can be adopted. As the plating solution, solder plating, copper plating, gold plating, and nickel plating solution are particularly preferably used. Finally, the remaining resist pattern is removed using a stripping solution or the like according to a conventional method.

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

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

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

On the photoresist layer thus obtained on the support, a resist pattern can be formed in the same manner as described above for the photoresist layer formed by directly applying the resist layer on the support. ..

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.

The content of the above 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
Examples of the "alkali-soluble resin having a phenolic hydroxyl group" (hereinafter referred to as "phenolic resin (F)") in the present invention include 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 shock 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.
Examples of the radiation used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-ray steppers, h-ray steppers, i-line steppers, gh-line steppers, and ghi-line steppers, electron beams, and laser beams. .. The exposure amount is appropriately selected depending on the light source used, the resin film thickness, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the resin film thickness 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.

Production Example 1 (Production of PAG-1)
36 g of potassium hexafluorophosphate, 100 mL of acetonitrile, 40 g of diphenyl sulfoxide, 60 g of acetic anhydride, and 30 g of concentrated sulfuric acid were charged and mixed uniformly. 36 g of diphenyl sulfide was added dropwise thereto so as not to exceed 40 ° C. After stirring at 40 ° C. for 1 hour, 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 90 mL of 20% caustic soda and 100 mL of water, and then acetonitrile and ethyl acetate were distilled off under reduced pressure to obtain 90 g of a pale yellow solid (yield 94%).
The product obtained as a result of analysis by 1 H-NMR, C-NMR, F-NMR, IR, IC, and HPLC (using a high performance liquid chromatograph device L-7000, manufactured by Hitachi, Ltd., trade name, the same applies hereinafter). Contained 99.0% of hexafluorophosphate having a cation of (C-1) and 1.0% of an anion having a cation of (C-1) and having a structure of (Y-1). ..

Production Example 2 (Production of PAG-2)
96 g (yield 85%) of a white solid was obtained in the same manner as in Production Example 1 except that 43 g of potassium hexafluorophosphate was changed to 55 g of potassium hexafluoroantimonate.
As a result of the same analysis as in Production Example 1, 99.1% of the hexafluoroantimonate having a cation of (C-1) and an anion having a cation of (C-1) and having a structure of (Y-1). It contained 0.9% salt.

Production Example 3 (Production of PAG-3)
121 g (yield 85%) of a white solid was obtained in the same manner as in Production Example 1 except that 43 g of potassium hexafluorophosphate was changed to 160 g of lithium tetrakispentafluorophenylborate.
As a result of the same analysis as in Production Example 1, the cation is (C-1) and the tetrakispentafluorophenylborate salt is 99.1%, and the cation is (C-1) and has the structure of (Y-1). It contained 0.9% of anionic salt.

Production Example 4 (Production of PAG-4)
43 g of potassium hexafluorophosphate, 100 mL of acetonitrile, 40 g of diphenyl sulfoxide, 60 g of acetic anhydride, and 23 g of concentrated sulfuric acid were charged and mixed uniformly. 36 g of diphenyl sulfide was added dropwise thereto at 40 ° C. for 1 hour, cooled to room temperature, 200 mL of water was added, and the mixture was stirred for 10 minutes. The oil 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 once with 90 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. Washing with methanol gave 90 g (yield 94%) of a white solid.
As a result of the same analysis as in Production Example 1, the obtained product was 99.6% hexafluorophosphate having a cation (C-1) and a sulfate having a cation (C-1). It contained 0.4%.

Production Example 5 (Production of PAG-5)
43 g of potassium hexafluorophosphate, 100 ml of acetonitrile, 40 g of diphenyl sulfoxide, 60 g of acetic anhydride, and 20 g of methanesulfonic acid were charged and mixed uniformly. 36 g of diphenyl sulfide was added dropwise thereto so as not to exceed 40 ° C. After stirring at 40 ° C. for 1 hour, 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 once with 90 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. Washing with methanol gave 88 g (yield 92%) of a white solid. As a result of the same analysis as in Production Example 1, the obtained product was 99.7% hexafluorophosphate having a cation (C-1) and methanesulfonic acid having a cation (C-1). It contained 0.3% salt.

Production Example 6 (Production of PAG-6)
130 g (yield 63%) of a white solid was obtained in the same manner as in Production Example 5, except that 43 g of potassium hexafluorophosphate was changed to 177 g of sodium tetrakispentafluorophenyl gallate. As a result of the same analysis as in Production Example 1, the obtained product contained 99.8% of the tetrakispentafluorophenyl gallate salt having a cation of (C-1) and methanesulfone having a cation of (C-1). It contained 0.2% acid salt.

Production Example 7 (Production of PAG-7)
106 g (yield 70%) of a white solid was obtained in the same manner as in Production Example 5, except that 43 g of potassium hexafluorophosphate was changed to 101 g of potassium trispentafluoroethyltrifluorophosphate. As a result of the same analysis as in Production Example 1, the obtained product was 99.7% trispentafluoroethyltrifluorophosphate having a cation of (C-1) and having a cation of (C-1). It contained 0.3% methanesulfonate.

Production Example 8 (Production of PAG-8)
43 g of potassium hexafluorophosphate, 100 mL of acetonitrile, 55 g of 4-[(phenyl) sulfinyl] biphenyl, 60 g of acetic anhydride, and 20 g of methanesulfonic acid were charged and mixed uniformly. 51 g of 4- (phenylthio) biphenyl was added dropwise thereto so as not to exceed 40 ° C. After stirring at 40 ° C. for 1 hour, 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 once with 90 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. Washing with methanol gave 100 g (yield 94%) of a white solid.
As a result of the same analysis as in Production Example 1, the obtained product was 99.5% hexafluorophosphate having a cation (C-2) and methanesulfonic acid having a cation (C-2). It contained 0.5% salt.

Production Example 9 (Production of PAG-9)
55 g of potassium hexafluoroantimonate, 100 mL of acetonitrile, 55 g of 4-[(phenyl) sulfinyl] biphenyl, 60 g of acetic anhydride, and 23 g of concentrated sulfuric acid were charged and mixed uniformly. 51 g of 4- (phenylthio) biphenyl was added dropwise thereto so as not to exceed 40 ° C. After stirring at 40 ° C. for 1 hour, 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 once with 90 mL of 20% caustic soda and 200 mL of water, and then acetonitrile and ethyl acetate were distilled off under reduced pressure to obtain a pale yellow solid substance. Washing with methanol gave 100 g (yield 83%) of a white solid.
As a result of the same analysis as in Production Example 1, the obtained product was 99.5% hexafluoroantimontate having a cation of (C-2) and (Y-) having a cation of (C-2). It contained 0.5% of anion salt having the structure of 2).

Production Example 10 (Production of PAG-10)
145 g (yield 76%) of a pale yellow solid was obtained in the same manner as in Production Example 9, except that 55 g of potassium hexafluoroantimonate was changed to 160 g of lithium tetrakispentafluorophenylborate. As a result of the same analysis as in Production Example 1, the obtained product was 99.6% tetrakispentafluorophenylborate salt having a cation of (C-2) and (Y) having a cation of (C-2). It contained 0.4% of anion salt having the structure of -2).

Production Example 11 (Production of PAG-11)
152 g (yield 76%) of a pale yellow solid was obtained in the same manner as in Production Example 9, except that 55 g of potassium hexafluoroantimonate was changed to 177 g of lithium tetrakispentafluorophenyl gallate. As a result of the same analysis as in Production Example 1, the obtained product was 99.5% tetrakispentafluorophenyl gallate salt having a cation of (C-2) and (Y) having a cation of (C-2). It contained 0.5% of anion salt having the structure of -2).

Production Example 12 (Production of PAG-12)
105 g (yield 69%) of a pale yellow solid was obtained in the same manner as in Production Example 9, except that 55 g of potassium hexafluoroantimonate was changed to 101 g of potassium trispentafluoroethyltrifluorophosphate. As a result of the same analysis as in Production Example 1, the resulting product was 99.6% trispentafluoroethyltrifluorophosphate having a cation of (C-2) and a cation of (C-2). It contained 0.4% of the salt of the anion having the structure of (Y-2).

Production Example 13 (Production of PAG-13)
43 g of potassium hexafluorophosphate, 100 mL of acetonitrile, 55 g of 2- (phenylsulfinyl) thioxanthone, 60 g of acetic anhydride, and 46 g of concentrated sulfuric acid were charged and mixed uniformly. 51 g of 2- (phenylthio) thioxanthone was added dropwise thereto. The temperature rose due to heat generation on the way, but it was cooled so as not to exceed 40 ° C. After stirring at 40 ° C. for 1 hour, 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 once with 90 mL of 20% caustic soda and 200 mL of water, and then acetonitrile and ethyl acetate were distilled off under reduced pressure to obtain a pale yellow solid substance. Washing with methanol gave 132 g of a yellow solid (yield 91%).
As a result of the same analysis as in Production Example 1, the obtained product was 99.6% hexafluorophosphate having a cation of (C-3) and (Y-) having a cation of (C-3). It contained 0.4% of anion salt having the structure of 3).

Production Example 14 (Production of PAG-14)
126 g (yield 78%) of a yellow solid was obtained in the same manner as in Production Example 13, except that 43 g of potassium hexafluorophosphate was changed to 55 g of potassium hexafluoroantimonate. As a result of the same analysis as in Production Example 1, the obtained product was 99.6% hexafluoroantimontate having a cation of (C-3) and (Y-) having a cation of (C-3). It contained 0.4% of anion salt having the structure of 3).

Production Example 15 (Production of PAG-15)
151 g of a pale yellow solid in the same manner as in Production Example 4 except that 40 g of diphenyl sulfoxide was changed to 47 g of 4,4'-difluorodiphenylsulfoxide and 43 g of potassium hexafluorophosphate was changed to 177 g of sodium tetrakispentafluorophenyl gallate in Production Example 4. Yield 71%) was obtained. As a result of the same analysis as in Production Example 1, the obtained product contained 99.5% of the tetrakispentafluorophenyl gallate salt having a cation of (C-4) and a sulfate having a cation of (C-4). Was contained at 0.5%.

Production Example 16 (Production of PAG-16)
87 g (yield 73%) of a pale yellow solid was obtained in the same manner as in Production Example 15 except that 177 g of sodium tetrakispentafluorophenyl gallate was changed to 55 g of potassium hexafluoroantimonate in Production Example 15. As a result of the same analysis as in Production Example 1, the obtained product was 99.5% hexafluoroantimontate having a cation of (C-4) and a sulfate having a cation of (C-4). It contained 0.5%.

Production Example 17 (Production of PAG-17)
In Production Example 1, 101 g (70% yield) of a yellow solid was obtained in the same manner as in Production Example 1, 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. rice field. As a result of the same analysis as in Production Example 1, the obtained product was 98.8% hexafluorophosphate having a cation of (C-5) and (Y-) having a cation of (C-5). It contained 1.2% of anion salt having the structure of 5).

Production Example 18 (Production of PAG-18)
47 g of yellow solid (yield 32%) in the same manner as in Production Example 1 except 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-phenylthiothiantolen. Got As a result of the same analysis as in Production Example 1, the obtained product was 98.4% hexafluorophosphate having a cation of (C-6) and (Y-) having a cation of (C-6). It contained 1.6% of anion salt having the structure of 6).

Comparative Production Examples 1 to 6 (Production of PAG-H1 to H6)
(Manufacturing of PAG-H1)
The pale yellow solid obtained in Production Example 1 was repeatedly recrystallized from dichloromethane / methanol to obtain a white solid. As a result of the same analysis as in Production Example 1, it was confirmed that the obtained product contained substantially 100% of the cation hexafluorophosphate having the structure of (C-1).
(Manufacturing of PAG-H2-H6)
Similar to PAG-H1, the solids obtained in Production Examples 8, 13, 16, 17, and 18 for PAG-H2 to H6 were recrystallized to produce them. The composition is as shown in Table 2.

Comparative Production Examples 7 to 15 (Production of PAG-H7 to H15)
(Manufacturing of PAG-H7)
The crystallization filtrate obtained by the recrystallization operation in Comparative Production Example 1 was collected, concentrated, and the obtained oil was washed with methanol and hexane to obtain a pale yellow solid. The same analysis as in Production Example 1 was performed, and the obtained solid contained 95.2% of cation hexafluorophosphate having the structure of (C-1), and the anion having the structure of (Y-1) thereof. It contained 4.8% salt.
(Manufacturing of PAG-H8 to H15)
Similarly, for PAG-H8 to H15, the same operation was performed using the solids obtained in Production Examples 4, 5, 8, 9, 13, 16, 17, and 18, respectively, to obtain pale yellow to yellow solids. The composition of the obtained solid is as shown in Table 2.

Production Examples 19 to 27 (Production of PAG-19 to 27)
PAG-1, 4, 5, 8, 9, 13, 16, 17, 18 were mixed with PAG-H7 to H15 obtained in Comparative Production Examples 7 to 15 in an appropriate amount, and a solid photoacid generator PAG-19 was mixed. -27 was obtained. The composition of the obtained solid is as shown in Table 1.

<Preparation of photocurable composition and its evaluation>
The above photoacid generator was previously dissolved in propylene carbonate (solvent-1) in an amount of 50% by weight, and the mixture was added to an epoxy resin (listed below) as a cationically polymerizable compound in the amounts shown in Tables 3 and 4. Uniformly mixed to prepare photocurable compositions (Examples 1 to 51 and Comparative Examples 1 to 27). The composition was placed in a light-shielding bottle, stored at a predetermined temperature and for a period (the storage conditions below), and the storage stability and light (UV) curability (cationic polymerization performance) were evaluated by the following methods. .. The results are shown in Tables 3 and 4.
<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

<Storage conditions>
Storage conditions: 40 ° C x 3 months <Storage stability>
A part of the above composition was taken out from the light-shielding bottle, and the change in viscosity of the composition and the presence or absence of precipitation were evaluated.
(Evaluation criteria)
◯: The change in viscosity of the composition before and after storage is less than 1.5 times.
X: The change in viscosity of the composition before and after storage is 1.5 times or more.
<Evaluation of photocurability (cationic polymerization performance)>
The composition obtained above 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 coating film hardness 40 minutes after irradiation was measured by pencil hardness (JIS K5600-5-4: 1999), and the results evaluated according to the following criteria are shown in Tables 3 and 4. 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 Co., Ltd.)
-Lamp: 1.5kW high-pressure mercury lamp-Filter: IRCF02 filter (manufactured by Eye Graphics Co., Ltd.)
-Illuminance (measured with a 365 nm head illuminance meter): 150 mW / cm ²
-Integrated light intensity (measured with a 365 nm head illuminance meter): 200 mJ / cm ²

As shown in Tables 3 and 4, from Examples 1 to 51 and Comparative Examples 1 to 27, the composition containing the photoacid generator of the present invention has excellent UV curability and an excellent balance with storage stability. I understand. From Comparative Examples 1 to 6, it was found that a very high-purity photoacid generator has excellent UV curability but is inferior in storage stability, and a photoacid generator containing a small amount of anion Y is used as in the examples. It can be seen that this improves storage stability. Further, comparing Examples 20 to 27 and Comparative Examples 7 to 15, it can be seen that if the molar ratio of anion Y is too large, the UV curability is affected, so that the molar ratio of anion Y is 2 mol% or less. .. Further, from Examples 28 to 51 and Comparative Examples 16 to 27, it can be seen that the tendency does not depend on the type of the cationically polymerizable epoxy resin to be blended.

<Evaluation of positive photoresist composition>
(Preparation of sample for evaluation)
1 part of the photoresist generator, 40 parts of the resin represented by the following chemical formula (Resin-1) as the resin component (B), and m-cresol and p-cresol as the resin component (C) of formaldehyde and acid catalyst. 60 parts of the novolak resin obtained by addition condensation in the presence was uniformly dissolved in 150 parts of 2-methoxy-1-methylethyl acetate (solvent-2), filtered through a membrane filter having a pore size of 1 μm, and had a solid content concentration of 40. By weight% positive photoresist compositions (Examples 52-78) were prepared. Comparative Examples were also carried out in the same manner as in the above Examples to prepare positive photoresist compositions (Comparative Examples 28 to 42).
These compositions were stored at a predetermined temperature and for a period of time, and the positive photoresist composition was evaluated by the following method and compared with that immediately after compounding. The results are shown in Table 5.

<Storage conditions>
Storage conditions: 20 ° C x 3 months

<Sensitivity evaluation>
The positive resist composition was spin-coated on a silicon wafer substrate and then dried to obtain a photoresist layer having a film thickness of about 20 μm. This resist layer was prebaked on a hot plate at 130 ° C. for 6 minutes. After pre-baking, pattern exposure (i-line) was performed using TME-150RSC (manufactured by Topcon), and post-exposure heating (PEB) was performed at 75 ° C. for 5 minutes using a hot plate. Then, it was developed by a dipping method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 5 minutes, washed with running water, and blown with nitrogen to obtain a 10 μm line and space (L & S) pattern. Further, below that, the minimum exposure amount at which the residue of this pattern is not recognized, that is, the minimum essential exposure amount (corresponding to the sensitivity) required to form the resist pattern was measured.

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

As shown in Table 5, the chemically amplified positive photoresist composition containing the photoacid generator of the present invention from Examples 52 to 78 and Comparative Examples 28 to 42 has excellent resist sensitivity and storage stability. Recognize. From Comparative Examples 28 to 33, it was found that the resist sensitivity is excellent in the very high-purity photoacid generator, but it affects the storage stability, and the photoacid generator containing a small amount of anion Y is used as in the examples. It can be seen that this improves storage stability. Further, comparing Examples 70 to 78 and Comparative Examples 34 to 42, if the molar ratio of anion Y is too large, the resist sensitivity and the pattern shape are affected. Therefore, the molar ratio of anion Y is preferably 2 mol% or less. I understand.

<Preparation of negative photoresist composition and its evaluation>
(Preparation of sample for evaluation)
1 part of photoresist generator, 100 parts of copolymer (Mw = 10,000) composed of p-hydroxystyrene / styrene = 80/20 (molar ratio) as a component (F) which is a phenol resin, with a cross-linking agent 20 parts of hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd., trade name "Nicarac MW-390") as a certain component (G), and butadiene / acrylonitrile / hydroxybutylmethacrylate / methacrylic as a component (H) which is a crosslinked fine particle. 10 parts of a copolymer (average particle size = 65 nm, Tg = −38 ° C.) composed of acid / divinylbenzene = 64/20/8/6/2 (% by weight) as a component (J) as an adhesion aid. , Gamma-glycidoxypropyltrimethoxysilane (manufactured by Chisso, trade name "S510") is uniformly dissolved in 145 parts of ethyl lactate (solvent-2) to form the negative photoresist composition of the present invention (the negative photoresist composition of the present invention). Examples 79 to 105 and Comparative Examples 43 to 57) were prepared.
These compositions were stored at a predetermined temperature and for a period of time, and the negative photoresist composition was evaluated by the following method and compared with that immediately after compounding. The results are shown in Table 6.

<Storage conditions>
Storage conditions: 20 ° C x 3 months <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.
◯: 0.85 ≦ Lb / La ≦ 1
X: Lb / La <0.85

As shown in Table 6, from Examples 79 to 105 and Comparative Examples 43 to 57, the chemically amplified negative photoresist composition containing the photoacid generator of the present invention is excellent in resist sensitivity and storage stability. Recognize. From Comparative Examples 43 to 48, it was found that the resist sensitivity was excellent in the very high-purity photoacid generator, but it affected the storage stability, and the photoacid generator containing a small amount of anion Y was used as in the examples. It can be seen that this improves storage stability. Further, comparing Examples 97 to 105 and Comparative Examples 49 to 57, if the molar ratio of anion Y is too large, the resist sensitivity and the pattern shape are affected. Therefore, the molar ratio of anion Y is preferably 2 mol% or less. I understand.

The active energy ray-curable composition using the active energy ray-curable acid 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.), resist for MEMS, negative type photosensitive material, various adhesives (Temporary fixing agents for various electronic parts, adhesives for HDDs, adhesives for pickup lenses, adhesives for functional films for FPDs (deflectors, antireflection films, etc.), etc.), resins for holographic, FPD materials (color filters, Black matrix, partition material, photo spacer, rib, liquid crystal alignment film, FPD sealant, etc.), optical member, molding material (building material, optical component, lens), casting material, putty, glass fiber impregnating agent, It is suitably used as a sealing material, a sealing material, a sealing material, an optical semiconductor (LED) sealing material, an optical waveguide material, a nanoimprint material, an optical molding material, a micro optical molding material, and the like.

Claims

It contains a sulfonium salt (A) represented by the following general formula (1) and a sulfonium salt (B) represented by the following general formula (2), and the total number of moles of the sulfonium salt (A) and the sulfonium salt (B) is increased. On the other hand, a sensitive energy linear acid generator having a sulfonium salt (B) content of 0.01 to 2 mol%.

[In the formula (1), R 1 to R 4 are organic groups bonded to the benzene ring, the number of R 2 is 0 to 4, the number of R 1 , R 3 and R 4 is 0 to 5. , 0 means that hydrogen atoms are bonded, and when multiple R1 to R4 are bonded, they may be the same or different from each other, and R1 to R4 may be directly or -O-, respectively. A ring structure may be formed via -S-, -SO-, -SO 2- , -NH-, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group, and X - is an element. It is a monovalent anion having a group 13 or group 15 element in the periodic table and having a halogen.]

[In the formula (2), R 1 to R 4 are organic groups bonded to the benzene ring, and the number of R 2 is 0 to 4, the number of R 1 , R 3 and R 4 is 0 to 5. , 0 means that hydrogen atoms are bonded, and when multiple R1 to R4 are bonded, they may be the same or different from each other, and R1 to R4 may be directly or -O-, respectively. A ring structure may be formed via -S-, -SO-, -SO 2- , -NH-, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group, and Y - is a halogen. It is a monovalent anion selected from the group consisting of anions that do not have.]
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 - , Trifluoromethanesulphonic acid anion, nonafluorobutanesulphonic acid anion, selected from the group consisting of the anions represented by (CF 3 SO 2 ) 3 C- , and (CF 3 SO 2 ) 2 N- , claimed. Item 2. The sensitive energy linear acid generator according to Item 1.
Y - is selected from the group consisting of HSO 4- , HNO 3- , H 2 PO 4- , methanesulfonic acid anion, halogen-free organic carboxylic acid anion, and anion represented by the following general formula (3). The active energy linear acid generator according to claim 1 or 2.

[In the formula (3), R 5 and R 6 are hydrogen atoms or organic groups, the number of R 5 and R 6 is 0 to 5, and in the case of 0, hydrogen atoms are bonded and R 5 and R 6 are bonded. When a plurality of R 6s are bonded, they may be the same or different from each other, and R 5 and R 6 may be directly attached to each other or -O-, -S-, -SO-, -SO 2- , -NH. -, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group may form a ring structure, and m and n are 0 or 1, respectively, and m + n = 1. ]
An active energy ray-curable composition comprising the sensitive energy ray-induced acid generator according to any one of claims 1 to 3 and a cationically polymerizable compound.
A cured product obtained by curing the active energy ray-curable composition according to claim 4.
It comprises a component (A) containing the active energy linear acid generator according to any one of claims 1 to 3, and a component (B) which is a resin whose solubility in an alkali is increased by the action of an acid. , Chemically amplified positive photoresist composition.
The sixth aspect of claim 6, wherein the component (B) contains at least one resin selected from the group consisting of a novolak resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3). Chemically amplified positive photoresist composition.
The chemically amplified positive photoresist composition according to claim 6 or 7, further comprising an alkali-soluble resin (C) and an acid diffusion control agent (D).
A component (E) containing the active energy linear acid generator according to any one of claims 1 to 3, a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a cross-linking agent component (G). A chemically amplified negative photoresist composition comprising.
The chemically amplified negative photoresist composition according to claim 9, further comprising a crosslinked fine particle component (H).
A cured product obtained by curing the chemically amplified negative photoresist composition according to claim 9 or 10.