Active energy ray-sensitive acid generator

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

[Technical Field]

[0001] The present invention relates first to an actinic ray-sensitive acid generator, more particularly to a sulfonium salt-based actinic ray-sensitive acid generator, and second to an actinic ray-curable composition, a chemically amplified positive-working photoresist composition, and a chemically amplified negative-working photoresist composition, each containing the acid generator. [Background technology]

[0002] Onium salts such as sulfonium salts have been known as cationic polymerization initiators that cure cationic polymerizable compounds upon irradiation with active energy rays such as light or electron beams. Photoacid generators that generate acid are also known (Patent Documents 1 to 3). These onium salts are also called acid generators because they generate acid upon irradiation with active energy rays, and are used in resists and photosensitive materials (Patent Documents 4 to 6).

[0003] The actinic ray-sensitive acid generators described in these specifications, particularly the sulfonium salts, are produced using known methods (Patent Documents 1 and 3). However, the sulfonium salts produced by these methods have problems with their reactivity to actinic rays (i.e., the amount of acid generated), and when incorporated into actinic ray-curable compositions, they have problems with long-term storage stability due to the by-product bissulfonium salts and decomposition over time. To solve these problems, improvements to the production method have been reported that suppress the by-production of bissulfonium salts, which were the cause of the deterioration of storage stability, but even this improvement did not achieve sufficient long-term storage stability (Patent Document 7). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 55-125105 [Patent Document 2] Japanese Unexamined Patent Publication No. 61-190524 [Patent Document 3] Japanese Patent Application Publication No. 61-212554 [Patent Document 4] Japanese Patent Application Laid-Open No. 2002-193925 [Patent Document 5] Japanese Patent Application Publication No. 2001-354669 [Patent Document 6] Japanese Patent Application Publication No. 2001-294570 [Patent Document 7] WO2005 / 000801 publication Summary of the Invention [Problem to be solved by the invention]

[0005] In light of the above background, a first object of the present invention is to provide a highly active actinic ray-sensitive acid generator that exhibits cationic polymerization and crosslinking properties upon irradiation with actinic ray, and in which curable compositions using the acid generator have good storage stability. A second object of the present invention is to provide an actinic ray-curable composition, a chemically amplified positive photoresist composition, and a chemically amplified negative photoresist composition that utilize the acid generator.

[0006] The present inventors have discovered an actinic ray-sensitive acid generator suitable for the above-mentioned purpose. Specifically, the present invention relates to an actinic ray-sensitive acid generator (hereinafter referred to as a photoacid generator or an acid generator) that contains a sulfonium salt (A) represented by the following general formula (1) and a sulfonium salt (B) represented by the following general formula (2), in which the content of the sulfonium salt (B) is 0.01 to 2 mol % relative to the total number of moles of the sulfonium salt (A) and the sulfonium salt (B).

[0007] [ka]

[0008] [In formula (1), R 1 ~R 4 is an organic group attached to the benzene ring, and R 2 The number of is 0 to 4, R 1 , R 3 , R4 The number of is 0 to 5. When it is 0, a hydrogen atom is bonded, and when it is R 1 ~R 4 When a plurality of R are bonded, they may be the same or different. 1 ~R 4 may form a ring structure either directly or via —O—, —S—, —SO—, —SO2—, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group, and X - is a monovalent anion containing an element from group 13 or 15 of the periodic table and a halogen.

[0009] [ka]

[0010] [In formula (2), R 1 ~R 4 is an organic group attached to the benzene ring, and R 2 The number of is 0 to 4, R 1 , R 3 , R 4 The number of is 0 to 5. When it is 0, a hydrogen atom is bonded, and when it is R 1 ~R 4 When a plurality of R are bonded, they may be the same or different. 1 ~R 4 may form a ring structure either directly or via —O—, —S—, —SO—, —SO2—, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group; Y - is a monovalent anion selected from the group consisting of anions containing no halogens.

[0011] The present invention also provides an active energy ray-curable composition containing the above-mentioned acid generator and a cationically polymerizable compound; a cured product obtained by curing the above-mentioned active energy ray-curable composition; a chemically amplified positive photoresist composition containing the above-mentioned acid generator and component (B) which is a resin whose solubility in alkali increases under the action of acid; a chemically amplified negative photoresist composition containing the above-mentioned acid generator, component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinker component (G); and a cured product obtained by curing the above-mentioned chemically amplified negative photoresist composition. [Effects of the Invention]

[0012] The acid generator of the present invention has high activity to actinic rays, cationic polymerization properties and crosslinking reaction properties, and further, a composition using this has good storage stability. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described in detail.

[0014] R in formula (1) or (2) 1 ~R 4 R represents an organic group bonded to a benzene ring, and may be the same or different. 1 ~R 4 represents 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 alkynyl group having 2 to 30 carbon atoms, which may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogens.

[0015] Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl and biphenylyl groups, and condensed polycyclic aryl groups such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinonyl, naphthoquinonyl, and fluorenyl.

[0016] Examples of heterocyclic groups having 4 to 30 carbon atoms include rings containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, which may be the same or different. Specific examples include monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, and pyrazinyl, and fused polycyclic heterocyclic groups such as indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl.

[0017] Examples of the alkyl group having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, and octadecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkenyl group having 2 to 30 carbon atoms include straight-chain or branched ones such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl. Furthermore, examples of the alkynyl group having 2 to 30 carbon atoms include straight-chain or branched ones such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, and 1-methyl-2-propynyl.

[0018] The above-mentioned aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, or alkynyl group having 2 to 30 carbon atoms may have at least one substituent, and examples of the substituent include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, and octadecyl; isopropyl, isobutyl branched alkyl groups having 1 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; hydroxy groups; linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and dodecyloxy; linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms such as acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, and octanoyl; arylcarbonyl groups having 7 to 11 carbon atoms such as benzoyl and naphthoyl; linear or branched alkoxycarbonyl groups having 2 to 19 carbon atoms, such as ethoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, and tert-butoxycarbonyl; aryloxycarbonyl groups having 7 to 11 carbon atoms, such as phenoxycarbonyl and naphthoxycarbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; linear or branched acyloxy groups having 2 to 19 carbon atoms, such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, and octadecylcarbonyloxy;Arylthio groups having 6 to 20 carbon atoms, such as 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, and 4-(p-tert-butylbenzoyl)phenylthio; methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, dodecylthio, etc. Straight-chain or branched alkylthio groups having 1 to 18 carbon atoms, such as ruthio; aryl groups having 6 to 10 carbon atoms, such as phenyl, tolyl, dimethylphenyl, and naphthyl; heterocyclic groups having 4 to 20 carbon atoms, such as thienyl, furanyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthonyl, thioxanthonyl, and dibenzofuranyl; aryloxy groups having 6 to 10 carbon atoms, such as phenoxy and naphthyloxy; straight-chain alkylthio groups having 1 to 18 carbon atoms, such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, and octylsulfinyl. or branched alkylsulfinyl groups; arylsulfinyl groups having 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and octylsulfonyl; arylsulfonyl groups having 6 to 10 carbon atoms such as phenylsulfonyl, tolylsulfonyl (tosyl), and naphthylsulfonyl; alkyleneoxy groups; cyano groups; nitro groups; and halogens such as fluorine, chlorine, bromine, and iodine.

[0019] R 1 ~R 4When a plurality of R are bonded to each other, they may form a ring structure directly or via -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group. For example, R 1 If is 2 or more, two of them R 1 form a ring structure either directly or via -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group.

[0020] Of these organic groups, preferred are alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 14 carbon atoms, hydroxy groups, alkoxy groups having 1 to 6 carbon atoms, alkylthio groups having 1 to 6 carbon atoms, arylthio groups having 6 to 14 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, chlorine atoms, and fluorine atoms, and more preferred are alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 14 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms.

[0021] The substituent R in formula (1) or (2) 1 ~R 4 The number of R is 0 to 5, and if it is 0, a hydrogen atom is bonded. 1 ~R 4 The number of R is preferably 0 to 3, and more preferably 0 or 1. 1 ~R 4 When the number of is within these preferred ranges, the photosensitivity and solubility of the sulfonium salt are good.

[0022] Among the sulfonium salts represented by formula (1) or (2), specific examples of preferred cation moieties are shown below.

[0023] [ka]

[0024] [ka]

[0025] In formula (1), X - is an atom (group) that can become a monovalent anion, i.e., an anion corresponding to the acid (HX) generated by irradiating a sulfonium salt with active energy rays (visible light, ultraviolet light, electron beam, X-ray, etc.). X - is not limited to being a monovalent polyatomic anion having an element from group 13 or 15 of the periodic table and a halogen, but MZ a - , (Rf) b PF 6-b - , R 8 c BZ 4-c - , R 8 c GaZ 4-c - or (R 9 SO2)2N - Anions represented by the following formula are preferred from the viewpoint of photosensitivity.

[0026] M represents a phosphorus atom, a boron atom, or an antimony atom. Z represents a halogen atom (preferably a fluorine atom).

[0027] Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) in which 80 mol % or more of the hydrogen atoms have been substituted with fluorine atoms. Examples of alkyl groups that become Rf through 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.). The proportion of hydrogen atoms in these alkyl groups substituted with fluorine atoms in Rf is preferably 80 mol % or more, more preferably 90 mol % or more, and particularly preferably 100%, based on the number of moles of hydrogen atoms in the original alkyl group. When the substitution ratio with fluorine atoms is within these preferred ranges, the photosensitivity of the sulfonium salt is further improved. Particularly preferred Rf include CF3-, CF3CF2-, (CF3)2CF-, CF3CF2CF2-, CF3CF2CF2CF2-, (CF3)2CFCF2-, CF3CF2(CF3)CF- and (CF3)3C-. The b Rfs are independent of each other and may therefore be the same or different.

[0028] P represents a phosphorus atom, and F represents a fluorine atom.

[0029] R 8 represents a phenyl group in which a portion of the hydrogen atoms has been substituted with at least one element or electron-withdrawing group. Examples of such an element include a halogen atom, such as a fluorine atom, a chlorine atom, and a bromine atom. Examples of electron-withdrawing groups include a trifluoromethyl group, a nitro group, and a cyano group. Of these, a phenyl group in which one hydrogen atom has been substituted with a fluorine atom or a trifluoromethyl group is preferred. c R 8 are mutually independent and therefore may be the same or different from each other.

[0030] B represents a boron atom, and Ga represents a gallium atom.

[0031] R 9represents 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.

[0032] 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.

[0033] MZ a - The anion represented by is SbF6 - , PF6 - and BF4 - Examples include anions represented by the following formula:

[0034] (Rf) b PF 6-b - The anion represented by (CF3CF2)2PF4 - , (CF3CF2)3PF3 - , ((CF3)2CF)2PF4 - , ((CF3)2CF)3PF3 - , (CF3CF2CF2)2PF4 - , (CF3CF2CF2)3PF3 - , ((CF3)2CFCF2)2PF4 - , ((CF3)2CFCF2)3PF3 - , (CF3CF2CF2CF2)2PF4 - and (CF3CF2CF2CF2)3PF3 - Among these, anions represented by (CF3CF2)3PF3 - , (CF3CF2CF2)3PF3 - , ((CF3)2CF)3PF3 - , ((CF3)2CF)2PF4 - , ((CF3)2CFCF2)3PF3 - and ((CF3)2CFCF2)2PF4 - Anions represented by the following formula are preferred.

[0035] R 8 c BZ 4-c - As an anion represented by (C6F5)4B - , ((CF3)2C6H3)4B - , (CF3C6H4)4B - , (C6F5)2BF2 - , C6F5BF3 - and (C6H3F2)4B - Among these, anions represented by (C6F5)4B - and ((CF3)2C6H3)4B - Anions represented by the following formula are preferred.

[0036] R 8 c GaZ 4-c - The anion represented by the formula is (C6F5)4Ga - , ((CF3)2C6H3)4Ga - , (CF3C6H4)4Ga - , (C6F5)2GaF2 - , C6F5GaF3 - and (C6H3F2)4Ga - Among these, (C6F5)4Ga - and ((CF3)2C6H3)4Ga - Anions represented by the following formula are preferred.

[0037] These X - Among them, MZ a - , (Rf) b PF 6-b - , R 8 c BZ 4-c - , R 8 c GaZ 4-c - , R 9 SO3 - , or (R 9 SO2)2N -The anion represented by the formula: SbF6 is preferred. - , PF6 - , (CF3CF2)3PF3 - , ((CF3)2CF)3PF3 - , (CF3CF2CF2)3PF3 - , (C6F5)4B - , ((CF3)2C6H3)4B - , (C6F5)4Ga - , ((CF3)2C6H3)4Ga - , and (CF3SO2)2N - is more preferable in terms of improving the resist resolution and pattern shape, and (CF3CF2)3PF3 - , ((CF3)2CF)3PF3 - , (CF3CF2CF2)3PF3 - , (C6F5)4B - and ((CF3)2C6H3)4B - , (CF3SO2)3C - is particularly preferred because it has good compatibility with the resist composition.

[0038] In equation (2), Y - is a monovalent anion selected from the group consisting of anions that do not contain halogens, and the atom (group) that can be a monovalent anion is HSO4 - , HNO3 - , H2PO4 - It is preferable that the anion is selected from the group consisting of methanesulfonate anion, halogen-free carboxylate anion, and an anion represented by the following general formula (3).

[0039] [ka]

[0040] [In formula (3), R 5 , R 6 is a hydrogen atom or an organic group, and R 5 , R 6 The number of is 0 to 5. When it is 0, a hydrogen atom is bonded, and when it is R 5 , R 6When multiple R are bonded, they may be the same or different. 5 , R 6 may form a ring structure either directly or via —O—, —S—, —SO—, —SO2—, —NH—, —CO—, —COO—, —CONH—, an alkylene group, or a phenylene group, and m and n are each 0 or 1, so that m+n=1.]

[0041] Examples of halogen-free carboxylic acids include formic acid, glycolic acid, acetic acid, propionic acid, butyric acid, valeric acid, octylic acid, 2-ethylhexanoic acid, cyanoacetic acid, trimethylacetic acid, methoxyacetic acid, cyclopentanecarboxylic acid, mercaptoacetic acid, lactic acid, pyruvic acid, levulinic acid, acrylic acid, crotonic acid, vinylacetic acid, methacrylic acid, anisic acid, benzoic acid, cinnamic acid, naphthoic acid, phenylacetic acid, phenoxyacetic acid, and mandelic acid.

[0042] R in Equation (3) 5 and R 6 R represents an organic group bonded to a benzene ring, and may be the same or different. 5 and R 6 represents 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 alkynyl group having 2 to 30 carbon atoms, which may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, and halogen.

[0043] The aryl group having 6 to 30 carbon atoms includes the above-mentioned R 1 ~R 4 These are the same as the specific examples of the aryl group having 6 to 30 carbon atoms given above.

[0044] The heterocyclic group having 4 to 30 carbon atoms includes the above-mentioned R 1 ~R 4 These are the same as the specific examples of the heterocyclic group having 4 to 30 carbon atoms given above.

[0045] The alkyl group having 1 to 30 carbon atoms includes the above-mentioned R 1 ~R 4 These are the same as the specific examples of alkyl groups having 1 to 30 carbon atoms given above. In addition, the alkenyl group having 2 to 30 carbon atoms includes the above-mentioned R 1 ~R 4 These are the same as the specific examples of the alkenyl group having 2 to 30 carbon atoms given above. Furthermore, the alkynyl group having 2 to 30 carbon atoms includes the above-mentioned R 1 ~R 4 These are the same as the specific examples of the alkynyl group having 2 to 30 carbon atoms given above.

[0046] The above-mentioned aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, or alkynyl group having 2 to 30 carbon atoms may have at least one substituent, and examples of the substituent include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, and octadecyl; isopropyl, isobutyl branched alkyl groups having 1 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; hydroxy groups; linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and dodecyloxy; linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms such as acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, and octanoyl; arylcarbonyl groups having 7 to 11 carbon atoms such as benzoyl and naphthoyl; linear or branched alkoxycarbonyl groups having 2 to 19 carbon atoms, such as ethoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, and tert-butoxycarbonyl; aryloxycarbonyl groups having 7 to 11 carbon atoms, such as phenoxycarbonyl and naphthoxycarbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; linear or branched acyloxy groups having 2 to 19 carbon atoms, such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, and octadecylcarbonyloxy;Arylthio groups having 6 to 20 carbon atoms, such as 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, and 4-(p-tert-butylbenzoyl)phenylthio; methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, dodecylthio, etc. Straight-chain or branched alkylthio groups having 1 to 18 carbon atoms, such as ruthio; aryl groups having 6 to 10 carbon atoms, such as phenyl, tolyl, dimethylphenyl, and naphthyl; heterocyclic groups having 4 to 20 carbon atoms, such as thienyl, furanyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthonyl, thioxanthonyl, and dibenzofuranyl; aryloxy groups having 6 to 10 carbon atoms, such as phenoxy and naphthyloxy; straight-chain or branched alkylthio groups having 1 to 18 carbon atoms, such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, and octylsulfinyl. Examples of such groups include linear or branched alkylsulfinyl groups; arylsulfinyl groups having 6 to 10 carbon atoms, such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and octylsulfonyl; arylsulfonyl groups having 6 to 10 carbon atoms, such as phenylsulfonyl, tolylsulfonyl (tosyl), and naphthylsulfonyl; alkyleneoxy groups; cyano groups; and nitro groups.

[0047] R 5 , R 6 may form a ring structure either directly or via —O—, —S—, —SO—, —SO 2 —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group.

[0048] Of these organic groups, preferred are alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 14 carbon atoms, hydroxy groups, alkoxy groups having 1 to 6 carbon atoms, alkylthio groups having 1 to 6 carbon atoms, arylthio groups having 6 to 14 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, chlorine atoms, and fluorine atoms, and more preferred are alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 14 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms.

[0049] In formula (3), m and n are each 0 or 1, and m+n=1.

[0050] These Y - Among these, HSO4 is preferred from the viewpoint of storage stability. - and a compound represented by general formula (3):

[0051] R in Equation (3) 5 or R 6 As the alkyl group, from the viewpoint of storage stability, an arylthio group or an arylsulfinyl group is preferred.

[0052] From the viewpoint of solubility in the resist, the following structure is more preferable as the formula (3).

[0053] [ka]

[0054] The content of sulfonium salt (B) is 0.01 to 2 mol% relative to the total number of moles of sulfonium salt (A) represented by general formula (1) and sulfonium salt (B) represented by general formula (2). If it is 0.01 mol% or more, storage stability is improved, but if it exceeds 2 mol%, the curability of cationic polymerization and the sensitivity of the resist deteriorate. From the viewpoint of storage stability, 0.1 to 2 mol% is also preferable.

[0055] The sulfonium salt (A) represented by general formula (1) and the sulfonium salt (B) represented by general formula (2) can be produced by known production methods, such as reacting a diaryl sulfide with chlorine, reacting a diaryl sulfide with chlorine and an aromatic hydrocarbon such as benzene, or reacting a diaryl sulfide with a diaryl sulfoxide in the presence of a dehydrating agent.

[0056] The dehydrating agent is not particularly limited, and any agent that is used as a dehydrating agent in organic chemical reactions may be used, such as concentrated sulfuric acid, phosphoric anhydride, methanesulfonic acid, acetic anhydride, trifluoromethanesulfonic acid, or anhydrides thereof, and two or more of these may be mixed and used. A solvent may also be used as appropriate.

[0057] When diaryl sulfoxide and diaryl sulfide are reacted in the presence of a dehydrating agent, the molar ratio of sulfoxide to sulfide is 10:1 to 1:1, more preferably 7:1 to 2:1, and most preferably 5:1 to 2.5:1. The reaction temperature is -10°C to 50°C, preferably -5°C to 30°C, and most preferably 0°C to 10°C. By carrying out the reaction under these conditions, the sulfonium salt of the present invention can be produced with high purity.

[0058] After the reaction, the sulfonium salt can be efficiently produced by exchanging the anion with an acid (HX) and salt (AXn) having the anion represented by X in formula (1). Here, A is the counter cation of the anion X-, and n represents the number of anions X relative to the valence of the cation A. A represents an alkali metal such as Na, K, or Li, an alkaline earth metal such as Mg or Ca, or an ammonium cation. Alkali metals are more preferred due to the ease of obtaining raw materials and the ease of purifying the sulfonium salt produced.

[0059] Similarly, sulfonium salts can be produced efficiently by exchanging anions with an acid (HY) and a salt (AYn) having an anion represented by Y in general formula (2).

[0060] The acid generator of the present invention can be produced by mixing the sulfonium salts of general formulas (1) and (2), and the content of the sulfonium salt (B) is 0.01 to 2 mol % relative to the total number of moles of the sulfonium salt (A) represented by general formula (1) and the sulfonium salt (B) represented by general formula (2).

[0061] 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 is defined as consisting of the sulfonium salts represented by formulas (1) and (2), and does not include other acid generators.

[0062] When other acid generators are contained, the content of the other acid generators is preferably 0.1 to 100 mol, more preferably 0.5 to 50 mol, relative to the total number of moles of the sulfonium salts represented by formulas (1) and (2) of the present invention.

[0063] Other acid generators include conventionally known salts such as onium salts (sulfonium, iodonium, selenium, ammonium, and phosphonium), and salts of transition metal complex ions and anions.

[0064] In order to facilitate dissolution of the acid generator of the present invention in the cationically polymerizable compound or chemically amplified resist composition, the acid generator may be dissolved in advance in a solvent that does not inhibit the polymerization, crosslinking, deprotection reaction, etc.

[0065] 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, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols and derivatives thereof such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and the monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether of dipropylene glycol monoacetate; and cyclic ethers such as dioxane. Examples of the ester include ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; and aromatic hydrocarbons such as toluene and xylene.

[0066] When a solvent is used, the proportion of the solvent used is preferably 15 to 1000 parts by weight, more preferably 30 to 500 parts by weight, relative to 100 parts by weight of the acid generator of the present invention. The solvents used may be used alone or in combination of two or more kinds.

[0067] The active energy ray-curable composition of the present invention comprises the 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 coloration of the cured product.

[0068] Examples of the cationically polymerizable compound that is a component of the active energy ray-curable composition include cyclic ethers (epoxides, oxetanes, etc.), ethylenically unsaturated compounds (vinyl ethers, styrenes, etc.), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters (see JP-A Nos. 11-060996, 09-302269, 2003-026993, 2002-206017, 11-349895, 10-212343, 2000-119306, 10-67812, 2000-186071, 08-85775, 08-134405, JP-A No. 2008-20838, JP 2008-20839, JP 2008-20841, JP 2008-26660, JP 2008-26644, JP 2007-277327, "Photopolymer Handbook" edited by the Photopolymer Forum (1989, Industrial Research Institute), "UV / EB Curing Technology" edited by the General Technology Center (1982, General Technology Center), "UV / EB Curing Materials" edited by the RadTech Research Group (1992, CMC), "Causes of Curing Defects and Inhibitions in UV Curing and Countermeasures" edited by the Technical Information Association (2003, Technical Information Association), Color Materials, 68, (5), 286-293 (1995), Fine Chemicals, 29, (19), 5-14 (2000), etc.

[0069] As the epoxide, known epoxides can be used, including aromatic epoxides, alicyclic epoxides and aliphatic epoxides.

[0070] Examples of aromatic epoxides include glycidyl ethers of mono- or polyhydric phenols having at least one aromatic ring (phenol, bisphenol A, phenol novolak, and alkylene oxide adducts thereof).

[0071] Alicyclic epoxides include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (e.g., 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate).

[0072] The aliphatic epoxides include aliphatic polyhydric alcohols and their alkylene oxide adducts. Examples of suitable glycidyl ethers include polyglycidyl ethers of the above-mentioned compounds (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), polyglycidyl esters of aliphatic polybasic acids (diglycidyl tetrahydrophthalate, etc.), and epoxidized long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

[0073] As the oxetane, known oxetanes can be used, and examples thereof include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanylsilsesquioxetane, and phenol novolac oxetane.

[0074] As the ethylenically unsaturated compound, known cationically polymerizable monomers can be used, including aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene, and cationically polymerizable nitrogen-containing monomers.

[0075] Examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

[0076] Examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

[0077] Examples of polyfunctional vinyl ethers include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

[0078] Examples of the styrene include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

[0079] Examples of the cationically polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.

[0080] Examples of bicyclo orthoesters 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.

[0081] Examples of spiro orthocarbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0082] Examples of spiro orthoesters include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane.

[0083] Furthermore, polyorganosiloxanes having at least one cationically polymerizable group per molecule can be used (such as those described in JP 2001-348482 A, JP 2000-281965 A, JP 7-242828 A, JP 2008-195931 A, Journal of Polym. Sci., Part A, Polym. Chem., Vol. 28, 497 (1990) and the like). These polyorganosiloxanes may be linear, branched, or cyclic, or may be a mixture of these.

[0084] Among these cationically polymerizable compounds, epoxides, oxetanes, and vinyl ethers are preferred, epoxides and oxetanes are more preferred, and alicyclic epoxides and oxetanes are particularly preferred. These cationically polymerizable compounds may be used alone or in combination of two or more.

[0085] 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, per 100 parts by weight of the cationically polymerizable compound. Within this range, polymerization of the cationically polymerizable compound becomes more sufficient, resulting in better physical properties of the cured product. Note that this content is determined by taking into consideration various factors such as the properties of the cationically polymerizable compound, the type and dose of active energy rays, temperature, curing time, humidity, and coating thickness, and is not limited to the above range.

[0086] The active energy ray-curable composition of the present invention may contain known additives (sensitizers, pigments, fillers, antistatic agents, flame retardants, antifoaming agents, flow control agents, light stabilizers, antioxidants, adhesion imparting agents, ion scavengers, coloration inhibitors, solvents, non-reactive resins, radically polymerizable compounds, etc.) as needed.

[0087] As the sensitizer, known sensitizers (such as those disclosed in JP-A-11-279212 and JP-A-09-183960) can be used, and examples thereof include anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthone {thioxanthone, 2 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.}; phenothiazines {phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N-phenylphenothiazine, etc.}; xanthone; naphthalenes {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol, etc.}; ketones {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 4-benzoyl-4'-methyldiphenyl sulfide, etc.} carbazole {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole, etc.}; chrysene {1,4-dimethoxychrysene, 1,4-di-α-methylbenzyloxychrysene, etc.}; phenanthrene {9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.} and the like.

[0088] When a sensitizer is contained, the content of the sensitizer is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, per 100 parts of the acid generator.

[0089] As the pigment, known pigments can be used, including inorganic pigments (titanium oxide, iron oxide, carbon black, etc.) and organic pigments (azo pigments, cyanine pigments, phthalocyanine pigments, quinacridone pigments, etc.).

[0090] When a pigment is contained, the content of the pigment is preferably 0.5 to 400,000 parts by weight, and more preferably 10 to 150,000 parts by weight, relative to 100 parts of the acid generator.

[0091] As the filler, known fillers can be used, such as fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate, and lithium aluminum silicate.

[0092] When a filler is contained, the content of the filler is preferably 50 to 600,000 parts by weight, and more preferably 300 to 200,000 parts by weight, relative to 100 parts of the acid generator.

[0093] As the antistatic agent, known antistatic agents can be used, such as nonionic antistatic agents, anionic antistatic agents, and the like. Examples of antistatic agents include cationic antistatic agents, amphoteric antistatic agents, and polymeric antistatic agents. It can be obtained.

[0094] When an antistatic agent is contained, the content of the antistatic agent is preferably 0.1 to 20,000 parts by weight, and more preferably 0.6 to 5,000 parts by weight, relative to 100 parts of the acid generator.

[0095] As the flame retardant, known flame retardants can be used, and examples thereof include inorganic flame retardants {antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, calcium aluminate, etc.}; bromine flame retardants {tetrabromophthalic anhydride, hexabromobenzene, decabromobiphenyl ether, etc.}; and phosphate ester flame retardants {tris(tribromophenyl)phosphate, etc.}.

[0096] When a flame retardant is contained, the content of the flame retardant is preferably 0.5 to 40,000 parts by weight, and more preferably 5 to 10,000 parts by weight, per 100 parts of the acid generator.

[0097] As the flame retardant, known flame retardants can be used, and examples thereof include inorganic flame retardants {antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, calcium aluminate, etc.}; bromine flame retardants {tetrabromophthalic anhydride, hexabromobenzene, decabromobiphenyl ether, etc.}; and phosphate ester flame retardants {tris(tribromophenyl)phosphate, etc.}.

[0098] When a flame retardant is contained, the content of the flame retardant is preferably 0.5 to 40,000 parts by weight, and more preferably 5 to 10,000 parts by weight, per 100 parts of the acid generator.

[0099] As the defoaming agent, known defoaming agents can be used, and examples thereof include alcohol defoaming agents, metal soap defoaming agents, phosphate ester defoaming agents, fatty acid ester defoaming agents, polyether defoaming agents, silicone defoaming agents, and mineral oil defoaming agents.

[0100] As the flow modifier, known flow modifiers can be used, and examples thereof include hydrogenated castor oil, oxidized polyethylene, organic bentonite, colloidal silica, amide wax, metal soap, and acrylic ester polymer. As the light stabilizer, known light stabilizers can be used, and examples thereof include ultraviolet absorbing stabilizers (benzotriazole, benzophenone, salicylate, cyanoacrylate, and derivatives thereof, etc.); radical scavenging stabilizers (hindered amines, etc.); and quenching stabilizers (nickel complexes, etc.). As the antioxidant, known antioxidants can be used, and examples thereof include phenol-based antioxidants (monophenol-based, bisphenol-based, polymeric phenol-based, etc.), sulfur-based antioxidants, and phosphorus-based antioxidants. As the adhesion promoter, known adhesion promoters can be used, and examples thereof include coupling agents, silane coupling agents, and titanium coupling agents. As the ion scavenger, known ion scavenger can be used, and examples thereof include organic aluminum (alkoxy aluminum, phenoxy aluminum, etc.). As the coloring inhibitor, known coloring inhibitors can be used, and generally, antioxidants are effective, and examples thereof include phenol-based antioxidants (monophenol-based, bisphenol-based, polymeric phenol-based, etc.), sulfur-based antioxidants, and phosphorus-based antioxidants, but they are almost ineffective in preventing coloring during heat resistance tests at high temperatures.

[0101] When an antifoaming agent, a flow control agent, a light stabilizer, an antioxidant, an adhesion imparting agent, an ion scavenger, or a coloring inhibitor is contained, the content of each is preferably 0.1 to 20,000 parts by weight, and more preferably 0.5 to 5,000 parts by weight, relative to 100 parts of the acid generator.

[0102] There are no limitations on the solvent as long as it can be used to dissolve the cationically polymerizable compound and adjust the viscosity of the active energy ray-curable composition, and the solvents exemplified above as solvents for the acid generator can be used.

[0103] When a solvent is contained, the content of the solvent is preferably 50 to 2,000,000 parts by weight, and more preferably 200 to 500,000 parts by weight, relative to 100 parts of the acid generator.

[0104] Examples of non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, hydrogenated styrene-butadiene block copolymer, (meth)acrylic acid ester copolymer, polyurethane, etc. The number average molecular weight of these resins is preferably 1,000 to 500,000, more preferably 5,000 to 100,000 (the number average molecular weight is a value measured by a general method such as GPC).

[0105] When a non-reactive resin is contained, the content of the non-reactive resin is preferably 5 to 400,000 parts by weight, and more preferably 50 to 150,000 parts by weight, relative to 100 parts of the acid generator.

[0106] When a non-reactive resin is contained, the non-reactive resin is dissolved in a cationic polymerizable compound, etc. To facilitate the use, it is desirable to dissolve the compound in a solvent beforehand.

[0107] Examples of radical polymerizable compounds that can be used include known radical polymerizable compounds such as those described in "Photopolymer Handbook" edited by the Photopolymer Forum (1989, Industrial Research Institute), "UV / EB Curing Technology" edited by the General Technology Center (1982, General Technology Center), "UV / EB Curing Materials" edited by the RadTech Research Group (1992, CMC), and "Causes of Curing Failure and Inhibition in UV Curing and Countermeasures Therefor" edited by the Technical Information Association (2003, Technical Information Association), and include monofunctional monomers, bifunctional monomers, polyfunctional monomers, epoxy (meth)acrylates, polyester (meth)acrylates, and urethane (meth)acrylates.

[0108] When a radical polymerizable compound is contained, the content of the radical polymerizable compound is preferably 5 to 400,000 parts by weight, and more preferably 50 to 150,000 parts by weight, relative to 100 parts of the acid generator.

[0109] When a radically polymerizable compound is contained, it is preferable to use a radical polymerization initiator that initiates polymerization by heat or light in order to increase the molecular weight of the compound by radical polymerization.

[0110] As the radical polymerization initiator, known radical polymerization initiators can be used, including thermal radical polymerization initiators (organic peroxides, azo compounds, etc.) and photoradical polymerization initiators (acetophenone-based initiators, benzophenone-based initiators, Michler's ketone-based initiators, benzoin-based initiators, thioxanthone-based initiators, acylphosphine-based initiators, etc.).

[0111] When a radical polymerization initiator is contained, the content of the radical polymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts of the radical polymerizable compound.

[0112] The active energy ray-curable composition of the present invention can be prepared by uniformly mixing and dissolving the cationically polymerizable compound, the acid generator, and, if necessary, the additives at room temperature (about 20 to 30°C) or, if necessary, under heating (about 40 to 90°C), or further by kneading them using a three-roll mill or the like.

[0113] The active energy ray-curable composition of the present invention can be cured by irradiation with active energy rays to give a cured product. The active energy rays may be any rays as long as they have energy sufficient to induce decomposition of the acid generator of the present invention, but are preferably active energy rays in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from low-pressure, medium-pressure, high-pressure, or ultra-high-pressure mercury lamps, metal halide lamps, LED lamps, xenon lamps, carbon arc lamps, fluorescent lamps, semiconductor solid-state lasers, argon lasers, He—Cd lasers, KrF excimer lasers, ArF excimer lasers, F2 lasers, etc. High-energy radiation such as electron beams or X-rays can also be used as the active energy rays.

[0114] The irradiation time of the active energy rays is affected by the intensity of the active energy rays and the permeability of the active energy rays to the active energy ray-curable composition, but about 0.1 to 10 seconds at room temperature (about 20 to 30°C) is sufficient. However, if the permeability of the active energy rays is low or the film thickness of the active energy ray-curable composition is thick, it may be preferable to apply a longer time. Most active energy ray-curable compositions cure by cationic polymerization within 0.1 seconds to several minutes after irradiation with the active energy rays, but if necessary, after irradiation with the active energy rays, they can be post-cured by heating at room temperature (about 20 to 30°C) to 200°C for several seconds to several hours.

[0115] Specific applications of the active energy ray-curable composition of the present invention include paints, coating agents, various coating materials (hard coats, stain-resistant coatings, anti-fogging coatings, contact-resistant coatings, optical fibers, etc.), backside treatment agents for adhesive tapes, release coating materials for release sheets for adhesive labels (release paper, release plastic films, release metal foils, etc.), printing plates, dental materials (dental compounds, dental composites), inkjet inks, positive resists (connection terminals and wiring pattern formation in the manufacture of electronic parts such as circuit boards, CSPs, MEMS elements, etc.), resist films, liquid resists, negative resists (permanent film materials such as surface protective films for semiconductor elements, interlayer insulating films, planarizing films, etc.), resists for MEMS, positive photosensitive resins, and the like. Examples of applications of this material include photosensitive materials, negative photosensitive materials, various adhesives (temporary fixing agents for various electronic components, adhesives for HDDs, adhesives for pickup lenses, adhesives for functional films for FPDs (deflectors, anti-reflection films, etc.)), holographic resins, FPD materials (color filters, black matrices, partition materials, photospacers, ribs, alignment films for liquid crystal displays, sealants for FPDs, etc.), optical components, molding materials (for construction materials, optical components, lenses), casting materials, putty, glass fiber impregnation agents, fillers, sealants, encapsulants, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, materials for stereolithography and microstereolithography, and the resulting cured products have little coloring and excellent transparency, making them ideal for optical applications.

[0116] Since the photoacid generator of the present invention generates a strong acid upon irradiation with light, it can also be used as a photoacid generator for known chemically amplified resist materials (e.g., JP-A Nos. 2003-267968, 2003-261529, and 2002-193925).

[0117] Chemically amplified resist materials include (1) two-component chemically amplified positive resists whose essential components are a resin that becomes soluble in alkaline developer by the action of acid and a photoacid generator; (2) three-component chemically amplified positive resists whose essential components are a resin that is soluble in alkaline developer, a dissolution inhibitor that becomes soluble in alkaline developer by the action of acid, and a photoacid generator; and (3) chemically amplified negative resists whose essential components are a resin that is soluble in alkaline developer, a crosslinker that crosslinks the resin by heat treatment in the presence of acid to make it insoluble in alkaline developer, and a photoacid generator.

[0118] The chemically amplified positive photoresist composition of the present invention is characterized by containing a component (A) containing the photoacid generator of the present invention, which is a compound that generates acid upon irradiation with light, and a resin component (B) whose solubility in alkali increases under the action of acid.

[0119] In the chemically amplified positive photoresist composition of the present invention, component (A) may be used in combination with other conventionally known photoacid generators, such as onium salt compounds, sulfone compounds, sulfonate ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, and nitrobenzyl compounds, as well as organic halides and disulfones.

[0120] As other conventionally known photoacid generators, preferably, at least one member selected from the group consisting of onium compounds, sulfonimide compounds, diazomethane compounds and oxime sulfonate compounds is preferred.

[0121] When such other conventionally known photoacid generators are used in combination, the proportions thereof may be arbitrary, but typically the proportion of the other photoacid generators is 10 to 900 parts by weight, preferably 25 to 400 parts by weight, per 100 parts by weight of the total weight of the photoacid generators of the present invention.

[0122] 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.

[0123] <Resin component (B) whose solubility in alkali increases under the action of an acid> The "resin (B) whose alkali solubility increases under the action of an acid" (referred to herein as "component (B)") used in the thick-film chemically amplified positive photoresist composition of the present invention is at least one resin selected from the group consisting of novolak resins (B1), polyhydroxystyrene resins (B2), and acrylic resins (B3), or a mixed resin or copolymer thereof.

[0124] [Novolac resin (B1)] As the novolak resin (B1), a resin represented by the following general formula (b1) can be used.

[0125] [ka]

[0126] In the above general formula (b1), R 1b represents an acid-dissociable dissolution-inhibiting group, and R 2b , R 3b each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents the number of repeating units of the structure in the parentheses.

[0127] Furthermore, the above R 1b The acid dissociable, dissolution inhibiting group represented by the formula (I) is preferably a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cyclic alkyl group having 3 to 6 carbon atoms, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

[0128] Here, the above R 1bSpecific examples of acid-dissociable, dissolution-inhibiting groups represented by the formula (I) include a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, an isobutoxyethyl group, a tert-butoxyethyl group, a cyclohexyloxyethyl group, a methoxypropyl group, an ethoxypropyl group, a 1-methoxy-1-methylethyl group, a 1-ethoxy-1-methylethyl group, a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl group, and a tri-tert-butyldimethylsilyl group.

[0129] [Polyhydroxystyrene resin (B2)] As the polyhydroxystyrene resin (B2), a resin represented by the following general formula (b4) can be used.

[0130] [ka]

[0131] In the above general formula (b4), R 8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 9b represents an acid dissociable, dissolution inhibiting group, and n represents the number of repeating units of the structure in parentheses.

[0132] The alkyl group having 1 to 6 carbon atoms is a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, such as 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, or a neopentyl group, and examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

[0133] Above R 9b The acid dissociable dissolution inhibiting group represented by the formula (I) is the same as the above R 1b Acid-dissociable, dissolution-inhibiting groups similar to those exemplified in can be used.

[0134] Furthermore, the polyhydroxystyrene resin (B2) may contain other polymerizable compounds as structural units in order to appropriately control the physical and chemical properties. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically polymerizable compounds. Examples include monocarboxylic acids such as acrylic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond, such as 2-methacryloyloxyethyl succinic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate; vinyl group-containing aromatic compounds such as styrene and vinyltoluene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride; and amide bond-containing polymerizable compounds such as acrylamide.

[0135] [Acrylic resin (B3)] As the acrylic resin (B3), resins represented by the following general formulas (b5) to (b10) can be used.

[0136] [ka]

[0137] [ka]

[0138] In the above general formulas (b5) to (b7), R 10b ~R 17b each independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a fluorine atom, a linear fluorinated alkyl group having 1 to 6 carbon atoms, or a branched fluorinated alkyl group having 3 to 6 carbon atoms; X bforms a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is attached, and Y b represents an aliphatic cyclic group or alkyl group which may have a substituent; n represents the number of repeating units of the structure in the parentheses; p is an integer of 0 to 4; and q is 0 or 1.

[0139] In the general formula (b8), the general formula (b9) and the general formula (b10), R 18b , R 20b and R 21b are each independently a hydrogen atom or a methyl group, and in general formula (b8), each R 19b are each independently a hydrogen atom, a hydroxyl group, a cyano group or a COOR 23b group (where R 23b represents a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. 22b are each independently a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms 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 R 22b At least one of R is the alicyclic hydrocarbon group or a derivative thereof, or any two of R 22b are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the common carbon atom to which each is bonded, and the remaining R 22b represents 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 a derivative thereof.

[0140] Among the above components (B), it is preferable to use the acrylic resin (B3).

[0141] Furthermore, the polystyrene-equivalent weight average molecular weight of component (B) is preferably 10,000 to 600,000, more preferably 50,000 to 600,000, and even more preferably 230,000 to 550,000. By adjusting the weight average molecular weight within this range, the physical properties of the resist resin will be excellent.

[0142] Furthermore, component (B) is preferably a resin with a polydispersity of 1.05 or more. Here, "polydispersity" refers to the value obtained by dividing the weight-average molecular weight by the number-average molecular weight. By achieving such a polydispersity, the resist has excellent plating resistance and resin physical properties.

[0143] The content of the component (B) is preferably 5 to 60% by weight based on the solid content of the chemically amplified positive photoresist composition.

[0144] <Alkali-soluble resin (C)> In order to improve the resin properties of the resist, the chemically amplified positive photoresist composition of the present invention preferably further contains an alkali-soluble resin (herein referred to as "component (C)"). Component (C) is preferably at least one resin selected from the group consisting of novolak resins, polyhydroxystyrene resins, acrylic resins, and polyvinyl resins.

[0145] The content of the component (C) is preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, per 100 parts by weight of the component (B). By using an amount of 5 parts by weight or more, the resin properties of the resist can be improved, and by using an amount of 95 parts by weight or less, film loss during development tends to be prevented.

[0146] <Acid diffusion controller (D)> The thick-film chemically amplified positive photoresist composition of the present invention preferably further contains an acid diffusion controller (D) (herein referred to as "component (D)") in order to improve the resist pattern shape, deposition stability, etc. Component (D) is preferably a nitrogen-containing compound, and may further contain an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof, as necessary.

[0147] The chemically amplified positive photoresist composition of the present invention may further contain an adhesion promoter to improve adhesion to a substrate. The adhesion promoter used is preferably a functional silane coupling agent.

[0148] The chemically amplified positive photoresist composition of the present invention may further contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, and the like.

[0149] The chemically amplified positive photoresist composition of the present invention may further contain an acid, an acid anhydride, or a high-boiling solvent in order to finely adjust the solubility in an alkaline developer.

[0150] Furthermore, the chemically amplified positive photoresist composition of the present invention does not basically require a sensitizer, but may contain a sensitizer to enhance sensitivity, if necessary. As such a sensitizer, any of the conventionally known sensitizers can be used, and specific examples thereof include those listed above.

[0151] The amount of these sensitizers used is 5 to 500 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight of the total weight of the photoacid generator of the present invention.

[0152] The chemically amplified positive photoresist composition of the present invention may contain an organic solvent to adjust the viscosity. Specific examples of the organic solvent include those listed above.

[0153] The amount of these organic solvents used is preferably in the range of 30% by weight or more solids concentration so that the thickness of the photoresist layer obtained using the chemically amplified positive photoresist composition of the present invention (e.g., by spin coating) is 5 μm or more.

[0154] The thick-film chemically amplified positive photoresist composition of the present invention can be prepared, for example, by simply mixing and stirring the above-mentioned components by a conventional method, or, if necessary, by using a dispersing machine such as a dissolver, homogenizer, or triple-roll mill to disperse and mix the components. After mixing, the components may be further filtered using a mesh, membrane filter, or the like.

[0155] The chemically amplified positive photoresist composition of the present invention is suitable for forming a photoresist layer having a thickness of typically 5 to 150 μm, more preferably 10 to 120 μm, and even more preferably 10 to 100 μm, on a support. This photoresist laminate comprises a photoresist layer comprising the chemically amplified positive photoresist composition of the present invention laminated on a support.

[0156] The substrate is not particularly limited and can be a conventionally known substrate, such as a substrate for electronic components or a substrate having a predetermined wiring pattern formed thereon. Examples of the substrate include substrates made of metals 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 form a good resist pattern even on a copper substrate. Examples of materials for the wiring pattern include copper, solder, chromium, aluminum, nickel, and gold.

[0157] The photoresist laminate can be produced, for example, as follows. That is, a solution of the chemically amplified positive photoresist composition prepared as described above is applied to a substrate, and the solvent is removed by heating to form a desired coating film. Methods that can be used to apply the composition to a substrate include spin coating, slit coating, roll coating, screen printing, and applicator methods. The pre-baking conditions for the coating film of the composition of the present invention vary depending on the type and blending ratio of each component in the composition, the coating film thickness, etc., but are typically 70 to 150°C, preferably 80 to 140°C, for about 2 to 60 minutes.

[0158] The thickness of the photoresist layer is usually in the range of 5 to 150 μm, preferably 10 to 120 μm, and more preferably 10 to 100 μm.

[0159] To form a resist pattern using the photoresist laminate obtained in this manner, the obtained photoresist layer may be selectively irradiated (exposed) to light or radiation, for example, ultraviolet light or visible light having a wavelength of 300 to 500 nm, through a mask having a predetermined pattern.

[0160] Here, "light" is synonymous with active energy rays and may be any light that activates a photoacid generator to generate an acid, including ultraviolet light, visible light, and far ultraviolet light, while "radiation" refers to X-rays, electron beams, ion beams, etc. Examples of light or radiation sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, and LED lamps. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc., but for example, when an ultra-high-pressure mercury lamp is used, it is 50 to 10,000 mJ / cm. 2 is.

[0161] After exposure, the photoresist layer is heated by a known method to promote diffusion of the acid and change the alkali solubility of the exposed portions of the photoresist layer. The unwanted portions are then dissolved and removed using, for example, a specific alkaline aqueous solution as a developer, to obtain the desired resist pattern.

[0162] The development time varies depending on the type and blending ratio of each component of the composition and the dry film thickness of the composition, but is usually 1 to 30 minutes, and the development method may be any of the puddle method, dipping method, puddle method, spray development method, etc. After development, the film is washed with running water for 30 to 90 seconds and dried using an air gun, oven, etc.

[0163] By embedding a conductor such as a metal by plating or the like in the non-resist portions (portions removed with the alkaline developer) of the resist pattern thus obtained, it is possible to form connection terminals such as metal posts or bumps. The plating method is not particularly limited, and various conventionally known methods can be used. Suitable plating solutions include solder plating, copper plating, gold plating, and nickel plating. Finally, the remaining resist pattern is removed using a stripper or the like according to a standard method.

[0164] The chemically amplified positive photoresist composition of the present invention can also be used as a dry film. This dry film has a protective film formed on both sides of a layer of the chemically amplified positive photoresist composition of the present invention. The thickness of the layer of the chemically amplified positive photoresist composition is typically 10 to 150 μm, preferably 20 to 120 μm, and more preferably 20 to 80 μm. The protective film is not particularly limited, and any resin film conventionally used in dry films can be used. For example, one film can be a polyethylene terephthalate film, and the other film can be one selected from the group consisting of polyethylene terephthalate film, polypropylene film, and polyethylene film.

[0165] The above-described chemically amplified positive dry film can be produced, for example, as follows. A solution of the chemically amplified positive photoresist composition prepared as described above is applied to one of the protective films, and the solvent is removed by heating to form the desired coating film. Drying conditions vary depending on the type and proportion of each component in the composition, the coating film thickness, etc., but typically require drying at 60 to 100°C for about 5 to 20 minutes.

[0166] To form a resist pattern using the chemically amplified dry film obtained in this manner, one protective film of the chemically amplified positive dry film is peeled off, and the exposed surface is laminated onto a support with the support facing the above-mentioned support to obtain a photoresist layer, and then the resist is pre-baked to dry, and the other protective film is peeled off.

[0167] A resist pattern can be formed on the photoresist layer thus obtained on the support in the same manner as described above for the photoresist layer formed by directly coating on the support.

[0168] The chemically amplified negative photoresist composition of the present invention is characterized by containing a component (E) containing the photoacid generator of the present invention, which is a compound that generates an acid upon exposure to light or radiation, an alkali-soluble resin (F) having a phenolic hydroxyl group, and a crosslinking agent (G).

[0169] In the chemically amplified negative photoresist composition of the present invention, component (E) may be used in combination with other conventionally known photoacid generators, such as onium salt compounds, sulfone compounds, sulfonate ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, and nitrobenzyl compounds, as well as organic halides and disulfones.

[0170] As other conventionally known photoacid generators, one or more compounds selected from the group consisting of onium compounds, sulfonimide compounds, diazomethane compounds and oxime sulfonate compounds are preferred.

[0171] When such other conventionally known photoacid generators are used in combination, the proportions thereof may be arbitrary, but typically the proportion of the other photoacid generators is 10 to 900 parts by weight, preferably 25 to 400 parts by weight, per 100 parts by weight of the total weight of the photoacid generators of the present invention.

[0172] The content of the component (E) is preferably 0.01 to 10% by weight of the solid content of the chemically amplified negative photoresist composition.

[0173] Alkali-soluble resin containing phenolic hydroxyl groups (F) Examples of the "alkali-soluble resin having a phenolic hydroxyl group" (hereinafter referred to as "phenolic resin (F)") used in the present invention include novolak resins, polyhydroxystyrenes, copolymers of polyhydroxystyrenes, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and a (meth)acrylic acid derivative, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, and phenol-dicyclopentadiene condensation resins. Among these, novolak resins, polyhydroxystyrenes, copolymers of polyhydroxystyrenes, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and a (meth)acrylic acid derivative, and phenol-xylylene glycol condensation resins are preferred. These phenolic resins (F) may be used alone or in combination of two or more.

[0174] The phenolic resin (F) may contain a low molecular weight phenolic compound as part of its components. Examples of the phenolic low molecular weight compound include 4,4'-dihydroxydiphenylmethane and 4,4'-dihydroxydiphenyl ether.

[0175] Crosslinker (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 phenolic resin (F). Examples of the crosslinking agent (G) include compounds having at least two or more alkyl-etherified amino groups in the molecule, compounds having at least two or more alkyl-etherified benzene groups in the molecule as a skeleton, oxirane ring-containing compounds, thiirane ring-containing compounds, oxetanyl group-containing compounds, and isocyanate group-containing compounds (including blocked compounds).

[0176] Among these crosslinking agents (G), compounds having at least two alkyl-etherified amino groups in the molecule and oxirane ring-containing compounds are preferred, and it is more preferred to use a compound having at least two alkyl-etherified amino groups in the molecule and an oxirane ring-containing compound in combination.

[0177] The amount of the crosslinking agent (G) in the present invention is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, relative to 100 parts by weight of the phenolic resin (F). When the amount of the crosslinking agent (G) is 1 to 100 parts by weight, the curing reaction proceeds sufficiently, and the resulting cured product has a high resolution and a good pattern shape, and is excellent in heat resistance and electrical insulation, which is preferable. Furthermore, when a compound having an alkyl-etherified amino group and an oxirane ring-containing compound are used in combination, the content of the oxirane ring-containing compound is preferably 50% by weight or less, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight, when the total of the compound having an alkyl-etherified amino group and the oxirane ring-containing compound is taken as 100% by weight. In this case, the resulting cured film is preferable because it has excellent chemical resistance without impairing high resolution.

[0178] Crosslinked fine particles (H) The chemically amplified negative photoresist composition of the present invention may further contain crosslinked fine particles (hereinafter also referred to as "crosslinked fine particles (H)") in order to improve the durability and thermal shock resistance of the resulting cured product.

[0179] 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 microparticles (H) is not particularly limited. For example, when synthesizing crosslinked microparticles by emulsion polymerization, the particle size can be controlled by controlling the number of micelles during emulsion polymerization through the amount of emulsifier used. The average particle size of the crosslinked fine particles (H) is a value measured by diluting a dispersion of the crosslinked fine particles in a conventional manner using a light scattering flow distribution measuring device or the like.

[0180] The amount of crosslinked fine particles (H) blended is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, per 100 parts by weight of the phenolic resin (F). When the amount of crosslinked fine particles (H) blended is 0.5 to 50 parts by weight, excellent compatibility or dispersibility with other components can be achieved, and the thermal shock resistance and heat resistance of the resulting cured film can be improved.

[0181] Adhesion aid The chemically amplified negative photoresist composition of the present invention may also contain an adhesion aid in order to improve adhesion to a substrate. Examples of the adhesion aid include functional silane coupling agents having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group.

[0182] The amount of the adhesion aid is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, relative to 100 parts by weight of the phenolic resin (F). When the amount of the adhesion aid is 0.2 to 10 parts by weight, excellent storage stability and good adhesion can be obtained, which is preferable.

[0183] solvent The chemically amplified negative photoresist composition of the present invention may 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, but specific examples include those described above.

[0184] Other additives The chemically amplified negative photoresist composition of the present invention may contain other additives, if necessary, to the extent that the properties of the present invention are not impaired. Examples of such additives include inorganic fillers, sensitizers, quenchers, leveling agents, surfactants, etc.

[0185] The method for preparing the chemically amplified negative photoresist composition of the present invention is not particularly limited, and it can be prepared by any known method. It can also be prepared by stirring a sample bottle containing each component and a completely stoppered sample bottle on a wave rotor.

[0186] The cured product of the present invention is characterized by being obtained by curing the chemically amplified negative photoresist composition. The chemically amplified negative photoresist composition according to the present invention has a high film retention rate and excellent resolution, and the cured product thereof has excellent electrical insulation properties, thermal shock resistance, etc., and therefore the cured product thereof can be suitably used as a surface protection film, a planarizing film, an interlayer insulating film material, etc. for electronic components such as semiconductor elements and semiconductor packages.

[0187] To form the cured product of the present invention, the aforementioned chemically amplified negative photoresist composition of the present invention is first applied to a support (such as a resin-coated copper foil, a copper-clad laminate, or a silicon wafer or alumina substrate with a metal sputtered film), and then dried to volatilize the solvent, forming a coating film. The resulting coating is then exposed to light through a desired mask pattern and heat-treated (hereinafter, this heat treatment is referred to as "PEB") to promote the reaction between the phenolic resin (F) and the crosslinking agent (G). The resulting coating is then developed with an alkaline developer to dissolve and remove the unexposed areas, yielding the desired pattern. A heat treatment is then performed to develop insulating film properties, yielding a cured film.

[0188] The resin composition can be applied to a support by a coating method such as dipping, spraying, bar coating, roll coating, spin coating, etc. The thickness of the coating film can be appropriately controlled by adjusting the coating means and the solids concentration and viscosity of the composition solution. Examples of radiation used for exposure include ultraviolet rays from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, h-line steppers, i-line steppers, gh-line steppers, ghi-line steppers, etc., electron beams, laser beams, etc. The exposure dose is appropriately selected depending on the light source used, the resin film thickness, etc. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the exposure dose is 100 to 50,000 J / m for a resin film thickness of 1 to 50 μm. 2 That's about it.

[0189] After exposure, the PEB treatment is carried out to promote the curing reaction between the phenolic resin (F) and the crosslinking agent (G) due to the generated acid. The PEB conditions vary depending on the amount of resin composition used, the film thickness used, and other factors, but are typically performed at 70 to 150°C, preferably 80 to 120°C, for approximately 1 to 60 minutes. The film is then developed with an alkaline developer to dissolve and remove the unexposed areas, forming the desired pattern. Examples of development methods include shower development, spray development, immersion development, and puddle development. Development conditions typically involve a temperature of 20 to 40°C for approximately 1 to 10 minutes.

[0190] Furthermore, after development, the composition can be sufficiently cured by a heat treatment to fully develop its insulating film properties. The curing conditions are not particularly limited, but depending on the intended use of the cured product, the composition can be cured by heating at a temperature of 50 to 250°C for approximately 30 minutes to 10 hours. Alternatively, to fully promote curing or prevent deformation of the resulting pattern, the composition can be heated in two stages. For example, in the first stage, the composition can be heated at a temperature of 50 to 120°C for approximately 5 minutes to 2 hours, and then further heated at a temperature of 80 to 250°C for approximately 10 minutes to 10 hours to achieve curing. Under these curing conditions, a typical oven, infrared furnace, or the like can be used as heating equipment. [Example]

[0191] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0192] 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 to the mixture, ensuring the temperature did not 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, resulting in the separation of an oily substance. 200 mL of ethyl acetate was added to dissolve the oily substance, and the organic layer was separated. This organic layer was washed with 90 mL of 20% caustic soda and then three times with 100 mL of water. The acetonitrile and ethyl acetate were then distilled off under reduced pressure to obtain 90 g of a pale yellow solid (94% yield). Analysis by H-NMR, C-NMR, F-NMR, IR, IC, and HPLC (using a high-performance liquid chromatograph L-7000, manufactured by Hitachi, Ltd., trade name; the same applies hereinafter) revealed that the obtained product contained 99.0% hexafluorophosphate salt of cation (C-1) and 1.0% salt of an anion having the structure (Y-1) and the cation (C-1).

[0193] [ka]

[0194] [ka]

[0195] Production Example 2 (Production of PAG-2) 96 g of a white solid was obtained (yield 85%) in the same manner as in Production Example 1, except that 43 g of potassium hexafluorophosphate was changed to 55 g of potassium hexafluoroantimonate. Analysis similar to that in Production Example 1 revealed that the product contained 99.1% hexafluoroantimony salt with cation (C-1) and 0.9% salt with anion (C-1) and anion (Y-1) structure.

[0196] Production Example 3 (Production of PAG-3) The same procedures as in Production Example 1 were carried out except that 43 g of potassium hexafluorophosphate was changed to 160 g of lithium tetrakispentafluorophenylborate, and 121 g of a white solid was obtained (yield 85%). Analysis similar to that in Production Example 1 revealed that the product contained 99.1% tetrakispentafluorophenylborate salt with the cation (C-1) and 0.9% salt of an anion having the structure (Y-1) with the cation (C-1).

[0197] 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 mixed uniformly. 36 g of diphenyl sulfide was added dropwise to the mixture, ensuring the temperature did not exceed 40°C. After stirring at 40°C for 1 hour, the mixture was cooled to room temperature, and 200 mL of water was added. After stirring for 10 minutes, an oily substance separated. 200 mL of ethyl acetate was added to dissolve the oily substance, and the organic layer was separated. This organic layer was washed with 90 mL of 20% caustic soda and then once with 100 mL of water. The acetonitrile and ethyl acetate were then distilled off under reduced pressure to yield a pale yellow solid. Washing with methanol yielded 90 g of a white solid (94% yield). The same analysis as in Production Example 1 revealed that the obtained product contained 99.6% hexafluorophosphate having a cation (C-1) and 0.4% sulfate having a cation (C-1).

[0198] 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 mixed uniformly. 36 g of diphenyl sulfide was added dropwise to the mixture, ensuring the temperature did not exceed 40°C. After stirring at 40°C for 1 hour, the mixture was cooled to room temperature, and 200 mL of water was added. After stirring for 10 minutes, an oily substance separated. 200 mL of ethyl acetate was added to dissolve the oily substance, and the organic layer was separated. This organic layer was washed with 90 mL of 20% caustic soda and then once with 100 mL of water. The acetonitrile and ethyl acetate were then distilled off under reduced pressure to obtain a pale yellow solid. After washing with methanol, 88 g of a white solid (92% yield) was obtained. Analysis performed as in Preparation 1 revealed that the product contained 99.7% hexafluorophosphate salt with the cation (C-1) and 0.3% methanesulfonate salt with the cation (C-1).

[0199] Production Example 6 (Production of PAG-6) Except for changing 43 g of potassium hexafluorophosphate to 177 g of sodium tetrakispentafluorophenyl gallate, 130 g of a white solid was obtained (yield 63%) in the same manner as in Production Example 5. As a result of carrying out the same analysis as in Production Example 1, the obtained product contained 99.8% of tetrakispentafluorophenyl gallate salt having a cation (C-1) and 0.2% of methanesulfonate salt having a cation (C-1).

[0200] Production Example 7 (Production of PAG-7) Except for changing 43 g of potassium hexafluorophosphate to 101 g of potassium trispentafluoroethyl trifluorophosphate, 106 g of a white solid was obtained (70% yield) in the same manner as in Production Example 5. As a result of carrying out the same analysis as in Production Example 1, the obtained product contained 99.7% trispentafluoroethyl trifluorophosphate salt having a cation (C-1) and 0.3% methanesulfonate salt having a cation (C-1).

[0201] 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 to the mixture, ensuring the temperature did not exceed 40°C. After stirring at 40°C for 1 hour, the mixture was cooled to room temperature, and 200 mL of water was added. The mixture was stirred for 10 minutes, resulting in the separation of an oily substance. 200 mL of ethyl acetate was added to dissolve the oily substance, and the organic layer was separated. This organic layer was washed with 90 mL of 20% caustic soda and then once with 100 mL of water. The acetonitrile and ethyl acetate were then distilled off under reduced pressure to yield a pale yellow solid. After washing with methanol, 100 g of a white solid was obtained (yield: 94%). Analysis similar to that in Production Example 1 revealed that the product contained 99.5% hexafluorophosphate salts having a cation of (C-2) and 0.5% methanesulfonate salts having a cation of (C-2).

[0202] [ka]

[0203] 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 mixed uniformly. 51 g of 4-(phenylthio)biphenyl was added dropwise to the mixture, ensuring the temperature did not 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, resulting in the separation of an oily substance. 200 mL of ethyl acetate was added to dissolve the oily substance, and the organic layer was separated. This organic layer was washed with 90 mL of 20% caustic soda and then once with 200 mL of water. The acetonitrile and ethyl acetate were then distilled off under reduced pressure to yield a pale yellow solid. After washing with methanol, 100 g of a white solid was obtained (83% yield). Analysis similar to that in Production Example 1 revealed that the obtained product contained 99.5% hexafluoroantimonate having the cation (C-2) and 0.5% salt of an anion having the cation (C-2) and the structure (Y-2).

[0204] [ka]

[0205] Production Example 10 (Production of PAG-10) Except for changing 55 g of potassium hexafluoroantimonate to 160 g of lithium tetrakispentafluorophenylborate, 145 g of a pale yellow solid was obtained (76% yield) in the same manner as in Production Example 9. As a result of carrying out the same analysis as in Production Example 1, the obtained product contained 99.6% of tetrakispentafluorophenylborate salt in which the cation was (C-2) and 0.4% of a salt in which the cation was (C-2) and the anion had the structure (Y-2).

[0206] Production Example 11 (Production of PAG-11) Except for changing 55 g of potassium hexafluoroantimonate to 177 g of lithium tetrakispentafluorophenyl gallate, 152 g of a pale yellow solid was obtained (76% yield) in the same manner as in Production Example 9. As a result of carrying out the same analysis as in Production Example 1, the obtained product contained 99.5% of tetrakispentafluorophenyl gallate salt in which the cation was (C-2) and 0.5% of a salt in which the cation was (C-2) and the anion had the structure (Y-2).

[0207] Production Example 12 (Production of PAG-12) Except for changing 55 g of potassium hexafluoroantimonate to 101 g of potassium trispentafluoroethyl trifluorophosphate, 105 g of a pale yellow solid was obtained (yield 69%) in the same manner as in Production Example 9. As a result of carrying out the same analysis as in Production Example 1, the obtained product contained 99.6% trispentafluoroethyl trifluorophosphate in which the cation was (C-2) and 0.4% of a salt in which the cation was (C-2) and the anion had the structure (Y-2).

[0208] 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 mixed uniformly. 51 g of 2-(phenylthio)thioxanthone was added dropwise. The temperature rose due to heat generation, but was cooled to below 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, resulting in the separation of an oily substance. 200 mL of ethyl acetate was added to dissolve the oily substance, and the organic layer was separated. This organic layer was washed with 90 mL of 20% caustic soda and then 200 mL of water once. The acetonitrile and ethyl acetate were then distilled off under reduced pressure to obtain a pale yellow solid. Washing with methanol yielded 132 g of a yellow solid (91% yield). Analysis similar to that in Production Example 1 revealed that the product contained 99.6% hexafluorophosphate salt having a cation of (C-3) and 0.4% salt of an anion having a cation of (C-3) and a structure of (Y-3).

[0209] [ka]

[0210] Production Example 14 (Production of PAG-14) Except for changing 43 g of potassium hexafluorophosphate to 55 g of potassium hexafluoroantimonate, 126 g of a yellow solid was obtained (78% yield) in the same manner as in Production Example 13. As a result of carrying out the same analysis as in Production Example 1, the obtained product contained 99.6% hexafluoroantimonate salt having the cation (C-3) and 0.4% salt of an anion having the structure (Y-3) and the cation (C-3).

[0211] Production Example 15 (Production of PAG-15) A pale yellow solid (151 g, yield 71%) was obtained in the same manner as in Production Example 4, except that 40 g of diphenyl sulfoxide was replaced with 47 g of 4,4'-difluorodiphenyl sulfoxide and 43 g of potassium hexafluorophosphate was replaced with 177 g of sodium tetrakispentafluorophenyl gallate. Analysis similar to that in Production Example 1 showed that the obtained product contained 99.5% tetrakispentafluorophenyl gallate salt having a cation of (C-4) and 0.5% sulfate salt having a cation of (C-4).

[0212] [ka]

[0213] Production Example 16 (Production of PAG-16) A pale yellow solid (87 g, yield 73%) 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. As a result of analysis similar to that in Production Example 1, the obtained product contained 99.5% hexafluoroantimonate having a cation of (C-4) and 0.5% sulfate having a cation of (C-4).

[0214] Production Example 17 (Production of PAG-17) Except for changing the amount of diphenyl sulfoxide (40 g) to 66 g of 2-phenylsulfenyl anthraquinone and the amount of diphenyl sulfide (36 g) to 61 g of 2-phenylthioanthraquinone in Production Example 1, 101 g of a yellow solid was obtained (70% yield) in the same manner as in Production Example 1. As a result of carrying out the same analysis as in Production Example 1, the obtained product contained 98.8% hexafluorophosphate salt in which the cation was (C-5) and 1.2% salt in which the cation was (C-5) and the anion had the structure (Y-5).

[0215] [ka]

[0216] Manufacturing Example 18 (Manufacturing of PAG-18) Except for changing 40 g of diphenyl sulfoxide to 67 g of 2-phenylsulfenylthianthrene and 36 g of diphenyl sulfide to 62 g of 2-phenylthiothianthrene in Production Example 1, 47 g of a yellow solid was obtained (yield 32%) in the same manner as in Production Example 1. As a result of carrying out the same analysis as in Production Example 1, the obtained product contained 98.4% hexafluorophosphate salt in which the cation was (C-6) and 1.6% salt in which the cation was (C-6) and the anion had the structure (Y-6).

[0217] [ka]

[0218] Comparative Production Examples 1 to 6 (Production of PAG-H1 to H6) (PAG-H1 manufacturing) The pale yellow solid obtained in Production Example 1 was repeatedly recrystallized from dichloromethane / methanol to obtain a white solid. As a result of carrying out the same analysis as in Production Example 1, it was confirmed that the obtained product contained substantially 100% of the hexafluorophosphate salt of a cation having the structure (C-1). (PAG-H2 to H6 manufacturing) As with PAG-H1, PAG-H2 to PAG-H6 were purified by recrystallization of the solids obtained in Production Examples 8, 13, 16, 17, and 18, respectively.

[0219] Comparative Manufacturing Examples 7 to 15 (Manufacturing of PAG-H7 to H15) (PAG-H7 manufacturing) The crystallization filtrate obtained by the recrystallization procedure in Comparative Production Example 1 was collected and concentrated, and the resulting oil was washed with methanol and hexane to obtain a pale yellow solid. Analysis similar to that in Production Example 1 revealed that the resulting solid contained 95.2% of the hexafluorophosphate salt of a cation having the structure (C-1) and 4.8% of the salt of the anion having the structure (Y-1). (PAG-H8~H15 production) Similarly, the same procedure was carried out for PAG-H8 to H15 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 compositions of the obtained solids are shown in Table 2.

[0220] Manufacturing Examples 19 to 27 (Manufacturing of PAG-19 to 27) Appropriate amounts of PAG-H7 to PAG-H15 obtained in Comparative Production Examples 7 to 15 were mixed with PAG-1, 4, 5, 8, 9, 13, 16, 17, and 18 to obtain solid photoacid generators PAG-19 to 27. The compositions of the obtained solids are shown in Table 1.

[0221] [Table 1]

[0222] [Table 2]

[0223] <Preparation and Evaluation of Photocurable Compositions> The above photoacid generators were dissolved in propylene carbonate (solvent-1) to a concentration of 50% by weight, and then uniformly mixed with an epoxy resin (described below), a cationically polymerizable compound, in the amounts shown in Tables 3 and 4 to prepare photocurable compositions (Examples 1 to 51 and Comparative Examples 1 to 27). The compositions were placed in light-shielding bottles and stored at the specified temperature for the specified period (storage conditions described below), and their storage stability and photo (UV) curability (cationic polymerization performance) were evaluated using 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-ethyloxetan-3-yl)methoxy]methyl}oxetane

[0224] <Storage conditions> Storage conditions: 40°C x 3 months <Storage stability> A portion of the composition was taken out of the light-shielding bottle and evaluated for changes in viscosity and the presence or absence of precipitation. (Evaluation criteria) ○: The change in viscosity of the composition before and after storage is less than 1.5 times. ×: The viscosity of the composition changed by 1.5 times or more before and after storage. <Photocuring (cationic polymerization performance) evaluation> The composition obtained above was applied to a polyethylene terephthalate (PET) film with an applicator to a thickness of 25 μm. The coated PET film was irradiated with light of a wavelength limited by a filter using an ultraviolet irradiation device. The filter used was an IRCF02 filter (manufactured by iGraphics Co., Ltd., a filter that cuts off light of less than 340 nm). The hardness of the coating film 40 minutes after irradiation was measured using pencil hardness (JIS K5600-5-4:1999), and the results were evaluated according to the following criteria. Tables 3 and 4 show the results. A higher pencil hardness indicates better sensitivity (cationic polymerization curability) of the photocurable composition.

[0225] (Evaluation criteria) ◎: Pencil hardness is 2H or more ○: Pencil hardness is H to B △: Pencil hardness is 2B to 4B ×: Liquid to tacky, pencil hardness cannot be measured

[0226] (Light irradiation conditions) Ultraviolet irradiation device: Belt conveyor type UV irradiation device (manufactured by iGraphics Co., Ltd.) Lamp: 1.5kW high-pressure mercury lamp Filter: IRCF02 filter (manufactured by iGraphics Co., Ltd.) Illuminance (measured with a 365nm head illuminometer): 150mW / cm 2 Accumulated light output (measured with a 365nm head illuminometer): 200mJ / cm 2

[0227] [Table 3]

[0228] [Table 4]

[0229] As shown in Tables 3 and 4, Examples 1 to 51 and Comparative Examples 1 to 27 demonstrate that compositions containing the photoacid generators of the present invention exhibit excellent UV curability and a good balance with storage stability. Comparative Examples 1 to 6 demonstrate that highly pure photoacid generators exhibit excellent UV curability but poor storage stability, and that storage stability can be improved by using a photoacid generator containing a small amount of anion Y, as in the Examples. Furthermore, a comparison of Examples 20 to 27 and Comparative Examples 7 to 15 demonstrates that an excessively high molar ratio of anion Y affects UV curability, and therefore a molar ratio of 2 mol% or less is preferable. Furthermore, Examples 28 to 51 and Comparative Examples 16 to 27 demonstrate that this tendency is independent of the type of cationically polymerizable epoxy resin used.

[0230] <Evaluation of Positive Photoresist Compositions> (Preparation of evaluation samples) One part photoacid generator, 40 parts of a resin represented by the following chemical formula (Resin-1) as resin component (B), and 60 parts of a novolak resin obtained by addition condensation of m-cresol and p-cresol in the presence of formaldehyde and an acid catalyst as resin component (C) were uniformly dissolved in 150 parts of 2-methoxy-1-methylethyl acetate (solvent-2) and filtered through a membrane filter with a pore size of 1 μm to prepare positive photoresist compositions with a solids concentration of 40 wt% (Examples 52 to 78). Positive photoresist compositions (Comparative Examples 28 to 42) were also prepared for the comparative examples in the same manner as in the above examples. These compositions were stored at a predetermined temperature for a predetermined period of time, and the positive photoresist compositions were evaluated using the following method and compared with those immediately after blending. The results are shown in Table 5.

[0231] <Storage conditions> Storage conditions: 20°C x 3 months

[0232] <Sensitivity evaluation> The positive resist composition was spin-coated onto a silicon wafer substrate and then dried to obtain a photoresist layer with a thickness of approximately 20 μm. This resist layer was pre-baked on a hot plate at 130°C for 6 minutes. After pre-baking, a pattern exposure (i-line) was performed using a TME-150RSC (manufactured by Topcon Corporation), followed by post-exposure baking (PEB) on a hot plate at 75°C for 5 minutes. The resist layer was then developed for 5 minutes by immersion using a 2.38 wt% aqueous tetramethylammonium hydroxide solution, rinsed with running water, and blown with nitrogen to obtain a 10 μm line-and-space (L&S) pattern. Furthermore, the minimum exposure dose below which no residue was observed in this pattern, i.e., the minimum required exposure dose (corresponding to sensitivity) required to form a resist pattern, was measured.

[0233] <Pattern shape evaluation> The dimension La of the lower side and the dimension Lb of the upper side of the cross section of the 10 μm L&S pattern formed on the silicon wafer substrate by the above operation were measured using a scanning electron microscope, and the pattern shape was judged according to the following criteria. ○: 0.85≦Lb / La≦1 ×: Lb / La<0.85

[0234] [Table 5]

[0235] [ka]

[0236] As shown in Table 5, Examples 52 to 78 and Comparative Examples 28 to 42 demonstrate that chemically amplified positive photoresist compositions containing a photoacid generator of the present invention exhibit excellent resist sensitivity and excellent storage stability. Comparative Examples 28 to 33 demonstrate that a highly pure photoacid generator provides excellent resist sensitivity but affects storage stability, and that storage stability can be improved by using a photoacid generator containing a small amount of anion Y, as in the Examples. Furthermore, a comparison of Examples 70 to 78 and Comparative Examples 34 to 42 demonstrates that a molar ratio of anion Y of 2 mol % or less is preferable, since a too high content of anion Y affects resist sensitivity and pattern shape.

[0237] <Preparation and Evaluation of Negative Photoresist Composition> (Preparation of evaluation samples) Negative photoresist compositions (Examples 79 to 105, Comparative Examples 43 to 57) of the present invention were prepared by uniformly dissolving 1 part photoacid generator, 100 parts of a copolymer (Mw=10,000) consisting of p-hydroxystyrene / styrene = 80 / 20 (molar ratio) as component (F) which is a phenolic resin, 20 parts of hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd., trade name "Nikarac MW-390") as component (G) which is a crosslinking agent, 10 parts of a copolymer (average particle size=65 nm, Tg=-38°C) consisting of butadiene / acrylonitrile / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 64 / 20 / 8 / 6 / 2 (wt%) as component (H) which is a crosslinked fine particle, and 5 parts of γ-glycidoxypropyltrimethoxysilane (manufactured by Chisso Corporation, trade name "S510") as component (J) which is an adhesion aid, in 145 parts of ethyl lactate (solvent-2). These compositions were stored at a predetermined temperature for a predetermined period of time, and the negative photoresist compositions were evaluated using the following method and compared with those immediately after blending. The results are shown in Table 6.

[0238] <Storage conditions> Storage conditions: 20°C x 3 months <Sensitivity evaluation> Each composition was spin-coated onto 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 with a thickness of approximately 20 μm. Subsequently, pattern exposure (i-line) was performed using a TME-150RSC (manufactured by Topcon Corporation), followed by post-exposure baking (PEB) at 110°C for 3 minutes using a hot plate. Subsequently, development was performed for 2 minutes using an immersion method using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, followed by rinsing with running water and blowing with nitrogen to obtain a 10 μm line-and-space pattern. Furthermore, the minimum required exposure dose (corresponding to sensitivity) required to form a pattern with a residual film ratio of 95% or more, which indicates the ratio of the residual film before and after development, was measured.

[0239] <Pattern shape evaluation> The dimension La of the lower side and the dimension Lb of the upper side of the cross section of the 20 μm L&S pattern formed on the silicon wafer substrate by the above operation were measured using a scanning electron microscope, and the pattern shape was judged according to the following criteria. ○: 0.85≦Lb / La≦1 ×: Lb / La<0.85

[0240] [Table 6]

[0241] As shown in Table 6, Examples 79 to 105 and Comparative Examples 43 to 57 demonstrate that chemically amplified negative photoresist compositions containing a photoacid generator of the present invention exhibit excellent resist sensitivity and excellent storage stability. Comparative Examples 43 to 48 demonstrate that a highly pure photoacid generator provides excellent resist sensitivity but affects storage stability, and that storage stability can be improved by using a photoacid generator containing a small amount of anion Y, as in the Examples. Furthermore, a comparison of Examples 97 to 105 and Comparative Examples 49 to 57 demonstrates that a molar ratio of anion Y of 2 mol % or less is preferable, since a high molar ratio affects resist sensitivity and pattern shape. [Industrial Applicability]

[0242] The active energy ray-curable composition using the active energy ray-sensitive acid generator of the present invention can be used in paints, coating agents, various coating materials (hard coats, stain-resistant coatings, anti-fogging coatings, contact-resistant coatings, optical fibers, etc.), backside treatment agents for adhesive tapes, release coating materials for release sheets for adhesive labels (release paper, release plastic films, release metal foils, etc.), printing plates, dental materials (dental compounds, dental composites), inkjet inks, resist films, liquid resists, negative resists (surface protective films for semiconductor elements, etc., interlayer insulating films, permanent film materials such as planarizing films, etc.), resists for MEMS, negative resists, They are suitable for use in mold photosensitive materials, various adhesives (temporary fixing agents for various electronic components, adhesives for HDDs, adhesives for pickup lenses, adhesives for functional films for FPDs (deflectors, anti-reflection films, etc.)), holographic resins, FPD materials (color filters, black matrices, partition materials, photospacers, ribs, alignment films for liquid crystals, sealants for FPDs, etc.), optical components, molding materials (for construction materials, optical components, lenses), casting materials, putty, glass fiber impregnation agents, sealing materials, encapsulants, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, materials for stereolithography, and materials for micro stereolithography.

Claims

1. An actinic ray-sensitive acid generator comprising a sulfonium salt (A) represented by the following general formula (1) and a sulfonium salt (B) represented by the following general formula (2), wherein the content of the sulfonium salt (B) is 0.01 to 2 mol % relative to the total number of moles of the sulfonium salt (A) and the sulfonium salt (B): 【Chemistry 1】 [In formula (1), R １ ~R ４ is an organic group bonded to the benzene ring, and R ２ The number of is 0 to 4, R １ , R ３ , R ４ The number of is 0 to 5, and when it is 0, a hydrogen atom is bonded, and R １ ~R ４ When a plurality of R are bonded, they may be the same or different. １ ~R ４ are directly connected to each other or -O-, -S-, -SO-, -SO ２ A ring structure may be formed via -, -NH-, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group, and X － is a monovalent anion having an element from group 13 or 15 of the periodic table and a halogen. 【Chemistry 2】 [In formula (2), R １ ~R ４ is an organic group bonded to the benzene ring, and R ２ The number of is 0 to 4, R １ , R ３ , R ４ The number of is 0 to 5, and when it is 0, a hydrogen atom is bonded, and R １ ~R ４ When a plurality of R are bonded, they may be the same or different. １ ~R ４ are directly connected to each other or -O-, -S-, -SO-, -SO ２ A ring structure may be formed via -, -NH-, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group; Y － is a monovalent anion selected from the group consisting of HSO 4 − and anions represented by the following general formula (3): 【Transformation 3】 [In 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 when R 5 and R 6 are 0, a hydrogen atom is bonded, and when a plurality of R 5 and R 6 are bonded, they may be the same or different, and R 5 and R 6 may form a ring structure either directly or via —O—, —S—, —SO—, —SO 2 —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group, and m and n are each 0 or 1, and m+n=1.]

2. X － is SbF ６ － , P.F. ６ － , B.F. ４ － , (CF ３ CF ２ ) ３ PF ３ － , ((CF ３ ) ２ CF) ３ PF ３ － , (CF ３ CF ２ CF ２ ) ３ PF ３ － , (C ６ F ５ ) ４ B － , ((CF ３ ) ２ C ６ H ３ ) ４ B － , (C ６ F ５ ) ４ Ga － , ((CF ３ ) ２ C ６ H ３ ) ４ Ga － , trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, (CF ３ SO ２ ) ３ C － , and (CF ３ SO ２ ) ２ N － 2. The active energy ray-sensitive acid generator according to claim 1, wherein the anion is selected from the group consisting of anions represented by the formula:

3. 3. An active energy ray-curable composition comprising the active energy ray-sensitive acid generator according to claim 1 or 2 and a cationically polymerizable compound.

4. A cured product obtained by curing the active energy ray-curable composition according to claim 3.

5. A chemically amplified positive photoresist composition comprising: a component (A) containing the active energy ray-sensitive acid generator according to any one of claims 1 to 4; and a component (B) which is a resin whose solubility in alkali increases under the action of an acid.

6. 6. The chemically amplified positive photoresist composition according to claim 5, wherein the component (B) comprises at least one resin selected from the group consisting of a novolak resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3).

7. 7. The chemically amplified positive photoresist composition according to claim 5, further comprising an alkali-soluble resin (C) and an acid diffusion controller (D).

8. 3. A chemically amplified negative photoresist composition comprising: a component (E) containing the actinic ray-sensitive acid generator according to claim 1; a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group; and a crosslinker component (G).

9. 9. The chemically amplified negative photoresist composition according to claim 8, further comprising a crosslinked fine particle component (H).

10. A cured product obtained by curing the chemically amplified negative photoresist composition according to claim 8 or 9.

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