JPH107709A - Energy ray-sensitive active composition, and responsive compositions and image-forming composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition composed of energy ray-sensitive active agents which has an excellent characteristics in sensitivity to an active ray as well as a curable and responsive composition, a positive type responsive compound and further a color image-forming composition which are produced using the above energy ray- sensitive composition. SOLUTION: This energy ray-sensitive composition comprises an energy ray-sensitive, acid-generating agent which generates an acid when irradiated with an active ray and which is an onium borate complex consisting of an onium cation and a borate anion represented by the formula: [BYm Zn ]<-> wherein Y represents a fluorine atom or a chlorine atom, Z represents a phenyl group substituted with two or more electron- withdrawing groups selected from among a fluorine atom, a cyano group, a nitro group and a trifluoromethyl group, m represents an integer of 0 to 3 and n represents an integer of 1 to 4 with a proviso that m+n=4, and an energy ray-sensitive, base- generating agent, and further a sensitizer. This curable, responsive composition, this positive type responsive compound and this color image-forming composition are produced by using the energy ray-sensitive composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an energy-sensitive radiation activator composition, a sensitive composition using the composition, and the composition. More specifically, an energy-sensitive activator composition comprising an acid generator that generates an acid under irradiation with energy rays and a base generator that generates a base under irradiation with energy rays, and the activator composition was used. The present invention relates to a curable sensitive composition, a positive-working sensitive composition, and an image forming composition. These compositions include molding resin, casting resin, sealant, dental polymerization resin, stereolithography resin, resist for printed circuit board, resist for color filter, resist for microelectronics, photosensitive resin for printing plate, photosensitive resin Ink jet, printing (offset, gravure, silk screen)
Inks, color proofs for print proofing, paints, surface coating agents, adhesives, adhesives, release agents, hologram recording materials, and the like.

[0002]

2. Description of the Related Art As compounds which generate an acid upon irradiation with energy rays, onium salts represented by aromatic diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenonium salts and the like and metal arene complexes are already known. When the onium salt or the metal arene complex is used in a mixture with a cationically polymerizable substance, the Lewis acid generated by light irradiation induces polymerization, as described in U.S. Patent Nos. 4069054 and 44503.
No. 60, No. 4576999, No. 4640967
No. 1,274,646 and European Patent 203,829;
dvances in Polymer Science
e 62, Initiators-Poly R
actions-Optical Active
ty, pp. 1-48, Springer-Verlag
(1984), latest UV curing technology, edited by Technical Information Association,
Detailed reports are made on page 29 (1991) and the like. In particular, triarylsulfonium salts or iron arene complexes are marketed as industrially useful acid generators, and onium salts whose anion is composed of hexafluoroantimonate are considered to be particularly suitable as those which give particularly high sensitivity characteristics. I have.

[0003] In recent years, it has been reported that iodonium compounds having a certain kind of organoboron anion exhibit good properties as initiators for cationic photopolymerization.
C. Priou et al. [(RadTech '94 North America Proceedings (RadTech '94
North America Proc. ,) Volume 1,
187 (1994) and Polymeric Materials Science and Engineering (Pol
ym. Mater. Sci. Eng. ,), Vol. 72,
417, (1995)] that diphenyliodonium tetrakis (pentafluorophenyl) borate is more effective at polymerizing epoxysilicon than conventional diphenyliodonium hexafluoroantimonate.
It has been reported to have higher polymerization properties and less toxicity. Further, JP-A-6-184170 and WO95 / 03338 propose novel onium organoborates and metal arene organoborates (eg, iodonium, sulfonium, selenonium, phosphonium, ammonium, iron arenes). Have been.

By the way, in order to improve image forming characteristics of various sensitive materials using an acid as an active species, in particular, a positive photoresist, image formation is controlled by combining a photoacid generator with a photobase generator. The proposal is disclosed in JP-A-4-162.
No. 040. According to the known technique, a positive image having excellent image characteristics can be obtained by neutralizing an acid present in a non-image portion of a photoresist film with a photobase generator.

[0005]

As described above, various onium salts have been studied as a source of an acid. There is a need for an imaging composition.

As described above, various onium salts have been studied. However, they exhibit higher sensitivity, have higher solubility in various organic materials and resins, and have a by-product Lewis acid remaining in the reaction system forever. There is a need for an energy-sensitive linear acid generator that does not.

Among the onium salts described in the prior art, a triarylsulfonium salt or an iron arene complex has been proposed as being particularly industrially useful. Among these, hexaanion is given as an anion which gives high sensitivity characteristics. Fluorantimonates are said to be suitable. But,
Onium salts containing hexafluoroantimonate have a danger of toxicity, and other anions, for example, hexafluorophosphate, have the drawback of poor sensitivity characteristics. In addition, among the above-mentioned onium salts, tetrafluoroborate, hexafluorophosphate, and hexafluoroantimonate salts generally have a solubility in various organic materials and resins that is not always at a satisfactory level. The development of anionic species that can improve the concentration was also one of the issues. Further, all of these onium salts have a fundamental problem that a Lewis acid by-produced by decomposition thereof remains in the reaction system forever and causes corrosion of metals and the like.

Therefore, as described above, various onium salts have been studied. However, they exhibit higher sensitivity, have high solubility in various organic materials and resins, and have a Lewis acid by-produced in the reaction system. There has been a demand for a photoacid generator that does not remain forever.

On the other hand, C.I. Although diphenyliodonium tetrakis (pentafluorophenyl) borate reported by Priou et al. Is reported to have higher polymerization properties for the polymerization of epoxysilicon than conventional diphenyliodonium hexafluoroantimonate. No consideration has been given to a combination system with a base generator.

In JP-A-4-162040, the photoacid generator used is exemplified by only alkyl esters of organic sulfonic acids. However, these alkyl esters of organic sulfonic acids are generally used in the presence of solvents or reactive compounds. However, there is a drawback that the range of use is limited, for example, the solubility in a reactive monomer or the like is low, and a compound capable of being cured and polymerized is limited due to its acid strength.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems in consideration of the above problems, and as a result, have reached the present invention. That is, the first invention in the present invention is:
Energy-sensitive actinic acid composition which is an energy-sensitive acid generator (A), which is an onium borate complex composed of an onium cation and a borate anion of the general formula (1), and an energy-sensitive base generator (B) , and the general formula _{(1) [bY m Z n} ] - ( however, Y is fluorine or chlorine, Z is fluorine, a cyano group, a nitro group, at least two electron-withdrawing group selected from trifluoromethyl group A substituted phenyl group; m represents an integer of 0 to 3; n represents an integer of 1 to 4;
n = 4. The second invention is an energy-sensitive activator composition obtained by adding a sensitizer (C) to the energy-sensitive activator composition, and the third invention is an energy-sensitive activator composition And a curable composition comprising an acid-curable compound (D) and a base-curable compound (E). The fourth invention is directed to a reaction using an energy-sensitive activator composition and an acid as a catalyst. A positive-sensitive composition comprising a compound (F) having a property of changing affinity or solubility with respect to a developer, wherein a fifth invention provides the energy-sensitive activator composition;
An image forming composition comprising a dye precursor (G) having a property of developing color by reaction with an acid.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the energy-sensitive linear acid generator (A) of the present invention will be described. The onium cations constituting the energy-sensitive acid generator (A) of the present invention include iodonium, sulfonium, sulfoxonium, selenonium, phosphonium, ammonium, metal arene cations, pyridinium, quinolinium, isoquinolinium, benzoxazolium And heterocyclic cations such as benzothiazolium.

Among these, as the structure of the onium cation which is preferable as the energy-sensitive acid generator (A) of the present invention, there can be mentioned onium cations selected from the general formulas (2) to (13). General formula (2)

[0014]

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General formula (3)

[0016]

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General formula (4)

[0018]

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General formula (5)

[0020]

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General formula (6)

[0022]

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General formula (7)

[0024]

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General formula (8)

[0026]

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General formula (9)

[0028]

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General formula (10)

[0030]

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General formula (11)

[0032]

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General formula (12)

[0034]

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General formula (13)

[0036]

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(Where R ¹ is a benzyl group, a substituted benzyl group, a phenacyl group, a substituted phenacyl group, an allyl group, or a substituted benzyl group, which is common to the general formulas (2) to (8)) R ² represents a group selected from an allyl group, an alkoxyl group, a substituted alkoxyl group, an aryloxy group, and a substituted aryloxy group, wherein R ² is a group represented by general formulas (2) to (4), Independently, fluorine, chlorine, bromine, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, a C ₁ -C ₁₈ linear, branched or cyclic alkyl group which may be substituted with an azide group or represents fluorine, chlorine, bromine, hydroxyl, carboxyl group, a mercapto group, a cyano group, a nitro group, a monocyclic good C ₆ -C ₁₈ optionally substituted with an azido group, one of the fused polycyclic aryl group. R ³ They are each independently hydrogen, a mercapto group or a fluorine, chlorine, bromine, hydroxyl, carboxyl group, a mercapto group, a cyano group, a nitro group, may be substituted with an azido group C ₁ -C ₁₈ linear, C which may be substituted with a branched or cyclic alkyl group or a fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide group
Represents a group selected from ₁ to _C18 linear, branched, and cyclic alkylthio groups. R ⁴ is each independently fluorine,
Chlorine, bromine, hydroxyl, carboxyl, mercapto,
A C ₁ -C ₁₈ linear, branched, or cyclic alkyl group which may be substituted with a cyano group, a nitro group or an azide group, or a fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto or cyano group represents a nitro group, it may be substituted with an azido group C ₁ -C ₁₈ linear, branched, either cyclic alkoxyl group. R is, independently of fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro and carbamoyl groups, common to the general formulas (5) to (8), Represents a group selected from organic residues. Here, the organic residue means a linear or branched C _{1 to} C ₁₈ which may be substituted with fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide. , Cyclic alkyl group,
A C ₂ -C ₁₈ linear, branched, cyclic alkenyl group,
Monocyclic ₆ -C ₁₈ condensed polycyclic aryl group, a monocyclic, fused polycyclic arylalkyl group _{C 7 ~C 18, C 1 ~C} 18 straight-chain, branched-chain, cyclic alkoxyl group, C ₆ monocyclic -C _18, condensed polycyclic aryloxy group, C ₁ -C ₁₈ linear,
Branched, monocyclic aliphatic or C7～C19, condensed polycyclic aromatic acyl groups, C of ₂ -C ₁₉ linear, branched, cyclic alkoxycarbonyl group, a monocyclic C ₇ -C ₁₉ ,
A condensed polycyclic aryloxycarbonyl group. Ar is independently substituted with fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro, and azide in common with the general formulas (10) to (13). Represents a C _{6 to} C ₁₈ monocyclic or fused polycyclic aryl group. Cp represents a cyclopentadienyl group. X represents an oxygen or sulfur atom. i is 0
Represents an integer of from 5 to 5. j is a general formula (6) to a general formula (8)
Represents an integer of 0 to 4 in common. k is the general formula (6)
-Represents an integer of 0 to 3 in common with the general formula (7). Further, adjacent, R to each other, R ² to each other, Ar each other or,, R ¹ and R ^2, R ¹ and R ³ may form a ring structure by a covalent bond to each other. )

Of these, the more preferred structure of the onium cation is such that the central element of the onium cation of the energy-sensitive acid generator (A) is benzyl, substituted benzyl, phenacyl, substituted phenacyl, allyl. Group, a group selected from a substituted allyl group, an alkoxyl group, a substituted alkoxyl group, an aryloxy group, and a substituted aryloxy group are those which are chemically bonded directly. (2), general formula (3),
An onium cation selected from the general formulas (5) and (7).

Other preferred structures of the onium cation include the onium cations of the general formulas (9) to (13).

The reason for this is that the onium cation described above generally has a high reduction potential, that is, a high electron accepting property. Therefore, it is decomposed by irradiation of energy rays, especially light, and easily generates an acid. It is seen as a remarkable result, especially when combined with sensitizer (C).

The substituents in the onium cation constituting the energy-sensitive linear acid generator (A) of the present invention will be described below. First, in the substituent R ¹ in the onium cation represented by the general formulas (2) to (8) constituting the energy-sensitive acid generator (A) of the present invention,

The substituted benzyl group includes fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, hydroxyl, mercapto, methylsulfinyl, methylsulfonyl, acetyl, benzoyl, C _1-
C ₁₈ linear, branched or cyclic alkyl group, C ₁ -C ₁₈
Linear, branched or cyclic alkoxyl group of C ₂ -C ₁₈
And a benzyl group substituted with a group selected from the group consisting of linear, branched and cyclic alkoxycarbonyl groups. Further, the benzene ring in the benzyl group may be a C ₁₀ -C ₂₂ Examples of the structure include a structure that may form a condensed polycyclic aromatic ring.

Specific examples of these substituted benzyl groups include o-fluorobenzyl, m-fluorobenzyl, p-fluorobenzyl, o-chlorobenzyl,
m-chlorobenzyl group, p-chlorobenzyl group, o-bromobenzyl group, m-bromobenzyl group, p-bromobenzyl group, o-cyanobenzyl group, m-cyanobenzyl group, p-cyanobenzyl group, o- Nitrobenzyl group, m
-Nitrobenzyl group, p-nitrobenzyl group, 2,4-
Difluorophenylmethyl group, 2,6-dichlorophenylmethyl group, 2,4,6-tribromophenylmethyl group, pentafluorophenylmethyl group, p- (trifluoromethyl) benzyl group, 3,5-bis (trifluoromethyl ) Phenylmethyl group, o-hydroxybenzyl group, m-hydroxybenzyl group, p-hydroxybenzyl group, o-mercaptobenzyl group, m-mercaptobenzyl group, p-mercaptobenzyl group, o-methylsulfinylbenzyl group, m- Methylsulfinylbenzyl group, p-methylsulfinylbenzyl group, o-methylsulfonylbenzyl group, m-methylsulfonylbenzyl group, p-methylsulfonylbenzyl group, o-acetylbenzyl group, m-acetylbenzyl group, p-acetylbenzyl group , O-benzoylbe Jill group, m- benzoyl benzyl, p- benzoyl benzyl, o- methylbenzyl group, m- methylbenzyl group, p- methylbenzyl group, p- ethylbenzyl group, p- propyl benzyl group,
p-isopropylbenzyl group, pt-butylbenzyl group, p-octadecylbenzyl group, p-cyclohexylbenzyl group, o-methoxybenzyl group, m-methoxybenzyl group, p-methoxybenzyl group, p-ethoxybenzyl group, p-propoxybenzyl group, p-isopropoxybenzyl group, pt-butoxybenzyl group, p-octadecyloxybenzyl group, p-cyclohexaneoxybenzyl group, o-methoxycarbonylbenzyl group, m-
Methoxycarbonylbenzyl group, p-methoxycarbonylbenzyl group, p-ethoxycarbonylbenzyl group, p
-Propoxycarbonylbenzyl group, p-isopropoxycarbonylbenzyl group, pt-butoxycarbonylbenzyl group, p-octadecyloxycarbonylbenzyl group, p-cyclohexaneoxycarbonylbenzyl group, 1-naphthylmethyl group, 2-naphthylmethyl group , 9
-Anthrylmethyl group, 1-pyrenylmethyl group, 5-naphthacenylmethyl group, 6-pentacenylmethyl group and the like.

The substituted phenacyl group in the substituent R ¹ includes fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, hydroxyl, mercapto, methylsulfinyl, methylsulfonyl, and acetyl. , benzoyl group, C ₁ -C ₁₈ linear, branched, cyclic alkyl group, C ₁ -C ₁₈ linear, branched, cyclic alkoxyl group, C ₂ -C ₁₈ linear, A phenacyl group substituted by a group selected from a branched or cyclic alkoxycarbonyl group; and further, a benzene ring in the phenacyl group is a C _{10 to} C ₂₂ condensed polycyclic aromatic group formed by an unsaturated hydrocarbon group. There may be mentioned a structure which may form a ring.

Specific examples of these substituted phenacyl groups include o-fluorophenacyl, m-fluorophenacyl, p-fluorophenacyl, o-chlorophenacyl, m-chlorophenacyl, p-chlorophenacyl group, o-bromophenacyl group, m-bromophenacyl group, p-bromophenacyl group, o-cyanophenacyl group, m-cyanophenacyl group, p-cyanophenacyl group, o-nitrophenacyl group, m-nitrophenacyl group , P-nitrophenacyl group, 2,4-difluorophenylcarbonylmethyl group, 2,6-dichlorophenylcarbonylmethyl group, 2,4,6-tribromophenylcarbonylmethyl group, pentafluorophenylcarbonylmethyl group, p- ( Trifluoromethyl) phenacyl group,
3,5-bis (trifluoromethyl) phenylcarbonylmethyl group, o-hydroxyphenacyl group, m-hydroxyphenacyl group, p-hydroxyphenacyl group, o-
Mercaptophenacyl group, m-mercaptophenacyl group, p-mercaptophenacyl group, o-methylsulfinylphenacyl group, m-methylsulfinylphenacyl group, p-methylsulfinylphenacyl group, o-methylsulfonylphenacyl group M-methylsulfonylphenacyl group, p-methylsulfonylphenacyl group, o-acetylphenacyl group, m-acetylphenacyl group, p-acetylphenacyl group, o-benzoylphenacyl group, m
-Benzoylphenacyl group, p-benzoylphenacyl group, o-methylphenacyl group, m-methylphenacyl group, p-methylphenacyl group, p-ethylphenacyl group, p-propylphenacyl group, p- Isopropylphenacyl group, pt-butylphenacyl group, p-octadecylphenacyl group, p-cyclohexylphenacyl group,
o-methoxyphenacyl group, m-methoxyphenacyl group, p-methoxyphenacyl group, p-ethoxyphenacyl group, p-propoxyphenacyl group, p-isopropoxyphenacyl group, pt-butoxyphenacyl Group, p-
Octadecyloxyphenacyl group, p-cyclohexaneoxyphenacyl group, o-methoxycarbonylphenacyl group, m-methoxycarbonylphenacyl group, p-methoxycarbonylphenacyl group, p-ethoxycarbonylphenacyl group, p-propoxycarbonyl Phenacyl group, p-isopropoxycarbonylphenacyl group, p-
t-butoxycarbonylphenacyl group, p-octadecyloxycarbonylphenacyl group, p-cyclohexaneoxycarbonylphenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 9-anthroylmethyl group, 1-pyre And a carbonylcarbonylmethyl group, a 5-naphthacenylcarbonylmethyl group and a 6-pentacenylcarbonylmethyl group.

The substituted allyl group in the substituent R ¹ includes fluorine, nitro, trifluoromethyl,
Selected from a cyano group, an acetyl group, a benzoyl group, a C ₁ -C ₁₈ linear, branched, cyclic alkyl group, a C ₂ -C ₁₈ linear, branched, cyclic alkoxycarbonyl group, and a phenyl group Allyl group substituted with a group represented by

Specific examples of these substituted allyl groups include a 2,3,3-trifluoro-2-propenyl group,
3,3-dinitro-2-propenyl group, 3,3-bis (trifluoromethyl) -2-propenyl group, 3,3-
Dicyano-2-propenyl group, 2-methyl-3,3-dicyano-2-propenyl group, 2-hexyl-3,3-dicyano-2-propenyl group, 2-octadecyl-3,3
-Dicyano-2-propenyl group, 2-isopropyl-
3,3-dicyano-2-propenyl group, 2-t-butyl-3,3-dicyano-2-propenyl group, 2-cyclohexyl-3,3-dicyano-2-propenyl group, 2-acetyl-3,3 -Dicyano-2-propenyl group, 2-benzoyl-3,3-dicyano-2-propenyl group, 2-
A phenyl-3,3-dicyano-2-propenyl group, 3,
3-bis (methoxycarbonyl) -2-propenyl group,
2-methyl-3,3-bis (methoxycarbonyl) -2
-Propenyl group, 2-hexyl-3,3-bis (methoxycarbonyl) -2-propenyl group, 2-octadecyl-3,3-bis (methoxycarbonyl) -2-propenyl group, 2-isopropyl-3,3- Bis (methoxycarbonyl) -2-propenyl group, 2-t-butyl-3,3
-Bis (methoxycarbonyl) -2-propenyl group, 2
-Cyclohexyl-3,3-bis (methoxycarbonyl) -2-propenyl group, 2-acetyl-3,3-bis (methoxycarbonyl) -2-propenyl group, 2-benzoyl-3,3-bis (methoxycarbonyl) group -2-propenyl group, 2-phenyl-3,3-bis (methoxycarbonyl) -2-propenyl group, 2-phenyl-3,3
-Bis (hexyloxycarbonyl) -2-propenyl group, 2-phenyl-3,3-bis (octadecyloxycarbonyl) -2-propenyl group, 2-phenyl-3,
Examples thereof include a 3-bis (t-butoxycarbonyl) -2-propenyl group and a 2-phenyl-3,3-bis (cyclohexyloxycarbonyl) -2-propenyl group.

Examples of the alkoxyl group in the substituent R ¹ include C ₁ -C ₁₈ linear, branched and cyclic alkoxyl groups, and include methoxy, ethoxy, propoxy, butoxy and octyloxy. Group, octadecaneoxy group, isopropoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy group and the like.

The substituted alkoxyl group in the substituent R ¹ is a C ₁ -C ₁₈ substituted with a group selected from fluorine, chlorine, bromine, cyano group, nitro group, trifluoromethyl group and hydroxyl group. Linear and branched alkoxyl groups, such as fluoromethoxy, 2-chloroethoxy, 3-bromopropoxy, 4-cyanobutoxy, 8-nitrooctyloxy, and 18-trifluoromethyloctadecaneoxy; , 2-hydroxyisopropoxy group, trichloromethoxy group and the like.

The aryloxy group in the substituent R ¹ is a C ₆ -C ₁₈ monocyclic or condensed polycyclic aryloxy group, such as a phenoxy group, a naphthyloxy group, a 2-naphthyloxy group, a 9-anthyl group. Thrilloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azulenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy Group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, 2,3-xylyloxy group, 2,5-xylyloxy group, mesityloxy group, p
-Cumenyloxy group, p-decylphenoxy group, p-cyclohexylphenoxy group, 4-phenylphenoxy group and the like.

The substituted aryloxy group in the substituent R ¹ is the same as the substituted aryloxy group selected from the group consisting of fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro and azide. _{6- C18} monocyclic, condensed polycyclic aryloxy group, o-fluorophenoxy group, m-chlorophenoxy group, p-bromophenoxy group, p-hydroxyphenoxy group, m-carboxyphenoxy group, o-mercapto Phenoxy group, p-cyanophenoxy group, m-nitrophenoxy group, m-azidophenoxy group, 2-chloro-1-naphthyloxy group, 10-
Cyano-9-anthryloxy group, 11-nitro-5-
And a naphthacenyloxy group.

The substituent R described above¹Preferred in
Fluorine, cyano group, nitro group, triflu
Oromethyl group, C₁~ C_FourLinear or branched acyl
Group, C _Two~ C_FiveLinear or branched alkoxy carbonyl
Group, benzoyl group, methylsulfinyl group, methyls
Substitution with an electron-withdrawing group such as a rufonyl group or p-tosyl group
Benzyl, phenacyl and allyl groups
You. Examples of such are

O-cyanobenzyl group, p-cyanobenzyl group, o-nitrobenzyl group, p-nitrobenzyl group,
Pentafluorophenylmethyl group, 3,5-bis (trifluoromethyl) phenylmethyl group, o-acetylbenzyl group, p-acetylbenzyl group, o-methoxycarbonylbenzyl group, p-methoxycarbonylbenzyl group,
o-t-butoxycarbonylbenzyl group, p-t-butoxycarbonylbenzyl group, o-benzoylbenzyl group, p-benzoylbenzyl group, o-methylsulfinylbenzyl group, p-methylsulfinylbenzyl group, o
-Methylsulfonylbenzyl group, p-methylsulfonylbenzyl group, o- (p-tosyl) benzyl group,

O-cyanophenacyl group, p-cyanophenacyl group, o-nitrophenacyl group, p-nitrophenacyl group, pentafluorobenzoylmethyl group, 3,5-
Bis (trifluoromethyl) benzoylmethyl group, o-
Acetylphenacyl group, p-acetylphenacyl group, o
-Methoxycarbonylphenacyl group, p-methoxycarbonylphenacyl group, ot-butoxycarbonylphenacyl group, pt-butoxycarbonylphenacyl group,
o-benzoylphenacyl group, p-benzoylphenacyl group, o-methylsulfinylphenacyl group, p-methylsulfinylphenacyl group, o-methylsulfonylphenacyl group, p-methylsulfonylphenacyl group, o-
A (p-tosyl) phenacyl group, a p- (p-tosyl) phenacyl group,

3,3-dicyano-2-propenyl group, 1
-Methyl-3,3-dicyano-2-propenyl group, 2-
A phenyl-3,3-dicyano-2-propenyl group, 3,
3-bis (methoxycarbonyl) -2-propenyl group,
2-phenyl-3,3-bis (methoxycarbonyl)-
Examples thereof include a 2-propenyl group, a cyanomethoxy group, an acetylmethoxy group, a benzoylmethoxy group, a p-cyanophenoxy group, and a pentafluorophenylmethoxy group.

The reason is that among these benzyl group, phenacyl group, allyl group, alkoxyl group and aryloxy group, cyano group, nitro group, fluoro group, trifluoromethyl group, acetyl group, methoxycarbonyl group, t-
By introducing an electron-withdrawing group such as a butoxycarbonyl group, a benzoyl group, a methylsulfinyl group, a methylsulfonyl group, and a p-tosyl group, an irreversible reaction occurs when an onium cation receives an electron by the action of an energy ray. It is considered that the substituent R ¹ is easily eliminated during the reduction and decomposition by, and the reduction potential of the onium cation is increased, that is, the electron accepting property is enhanced.

Further, the substituent R ² in the onium cation represented by the general formulas (2) to (4) constituting the energy sensitive acid generator (A) of the present invention, the general formula (8)
And the substituent R ³ on the onium cation represented by the general formula (9).
^{4. In} the substituent R in the onium cation represented by the general formulas (5) to (8),

C ₁ -C ₁₈ linear or branched, which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide;
As the cyclic alkyl group, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl Group, cyclopentyl, cyclohexyl, 4-decylcyclohexyl, fluoromethyl, chloromethyl, bromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, hydroxymethyl, carboxymethyl, mercaptomethyl , A cyanomethyl group, a nitromethyl group, an azidomethyl group and the like.

The substituent R ² in the onium cation represented by the general formulas (2) to (4) constituting the energy-sensitive linear acid generator (A) of the present invention, the general formula (5)
To the substituent R in the onium cation represented by the general formula (8), the substituent Ar in the onium cation represented by the general formula (10) to the general formula (13),

As a C ₆ -C ₁₈ monocyclic or condensed polycyclic aryl group which may be substituted with fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide, phenyl Group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group,
1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphthyl group, 9-fluorenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl Group, 2,5-xylyl group, mesityl group, p-cumenyl group, p-dodecylphenyl group, p-
Cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group and the like.

Further, in the substituent R ³ in the onium cation represented by the general formula (8) constituting the energy-sensitive linear acid generator (A) of the present invention,

C ₁ -C ₁₈ linear or branched, which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide;
As the cyclic alkylthio group, methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio,
Dodecylthio, octadecylthio, isopropylthio, isobutylthio, sec-butylthio, t-
Butylthio, cyclopentylthio, cyclohexylthio, 4-decylcyclohexylthio, fluoromethylthio, chloromethylthio, bromomethylthio, trifluoromethylthio, trichloromethylthio, tribromomethylthio, hydroxymethylthio, carboxymethylthio Group, mercaptomethylthio group, cyanomethylthio group, nitromethylthio group, azidomethylthio group and the like.

The substituent R ⁴ in the onium cation represented by the general formula (9) constituting the energy-sensitive linear acid generator (A) of the present invention, and the general formulas (5) to (8)
In the substituent R in the onium cation represented by

C ₁ -C ₁₈ linear or branched, which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide;
Examples of the cyclic alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an octyloxy group, an octadecaneoxy group, an isopropoxy group, a t-butoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a fluoromethoxy group, and a chloromethoxy group. , Bromomethoxy group, trifluoromethoxy group, trichloromethoxy group, tribromomethoxy group, hydroxymethoxy group,
Examples include a carboxymethoxy group, a mercaptomethoxy group, a cyanomethoxy group, a nitromethoxy group, an azidomethoxy group, and the like.

Further, in the substituent R in the onium cation represented by the general formulas (5) to (8) constituting the energy-sensitive linear acid generator (A) of the present invention,

C ₂ -C ₁₈ linear or branched, which may be substituted with fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide;
Examples of the cyclic alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-octenyl group, a 1-octadecenyl group, an isopropenyl group, a 1-cyclohexenyl group, a trifluoroethenyl group, a 1-chloroethenyl group,
2,2-dibromoethenyl group, 4-hydroxy-1-butenyl group, 1-carboxyethenyl group, 5-mercapto-1-hexenyl group, 1-cyanoethenyl group, 3-nitro-1-propenyl group, 4- An azido-2-butenyl group and the like.

C ₇ -C ₁₈ monocyclic and condensed polycyclic arylalkyl groups which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide include: Benzyl group, p-tolylmethyl group, 2-naphthylmethyl group, 9-anthrylmethyl group, 4- (9-anthryl) butyl group, o-fluorobenzyl group, m-chlorobenzyl group, p-bromobenzyl group, p -Hydroxybenzyl group, m-carboxybenzyl group, o-mercaptobenzyl group, p-cyanobenzyl group, m-nitrobenzyl group, m-azidobenzyl group and the like.

C ₆ -C ₁₈ monocyclic and condensed polycyclic aryloxy groups which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide include: Phenoxy, 1-naphthyloxy, 2-naphthyloxy, 9-anthryloxy, 9-phenanthryloxy, 1-pyrenyloxy, 5-naphthacenyloxy, 1-indenyloxy, 2- Azulenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, o-tolyloxy group,
m-tolyloxy group, p-tolyloxy group, 2,3-xylyloxy group, 2,5-xylyloxy group, mesityloxy group, p-cumenyloxy group, p-decylphenoxy group, p-cyclohexylphenoxy group, 4-biphenoxy group, o -Fluorophenoxy group, m-chlorophenoxy group, p-bromophenoxy group, p-hydroxyphenoxy group, m-carboxyphenoxy group, o-mercaptophenoxy group, p-cyanophenoxy group, m-nitrophenoxy group, m-azide Phenoxy groups and the like.

C ₁ -C ₁₈ linear or branched, which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide;
Examples of the cycloaliphatic or C _{7 to} C ₁₉ monocyclic or condensed polycyclic aromatic acyl groups include formyl, acetyl, hexanoyl, lauroyl, palmitoyl, stearoyl, isobutyryl, isovaleryl, pivaloyl,
Cyclopentylcarbonyl group, cyclohexylcarbonyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthroyl group, 5-naphthaseroyl group, cinnamoyl group, α-fluoroacetyl group, α-chloroacetyl group, α-bromoacetyl Groups, α-hydroxyacetyl groups, α-carboxyacetyl groups, α-mercaptoacetyl groups, α-cyanoacetyl groups, α-nitroacetyl groups, α-azidoacetyl groups, and the like.

C ₂ -C ₁₉ linear or branched, which may be substituted with fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide;
Examples of the cyclic alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, an octadecaneoxycarbonyl group, an isopropoxycarbonyl group, a t-butoxycarbonyl group, a cyclopentyloxycarbonyl group, and cyclohexyl. Oxycarbonyl group, fluoromethoxycarbonyl group, chloromethoxycarbonyl group, bromomethoxycarbonyl group, trifluoromethoxycarbonyl group, trichloromethoxycarbonyl group, tribromomethoxycarbonyl group, hydroxymethoxycarbonyl group, carboxymethoxycarbonyl group, mercaptomethoxycarbonyl group , Cyanomethoxycarbonyl, nitromethoxycarbonyl, azidomethoxycarbonyl Group, and the like.

Examples of the C ₇ -C ₁₉ monocyclic or condensed polycyclic aryloxycarbonyl group which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide include: Phenoxycarbonyl group, 1 naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 9-anthryloxycarbonyl group, 9-phenanthryloxycarbonyl group, 1-pyrenyloxycarbonyl group, 5-naphthacenyloxy Carbonyl group, 1-indenyloxycarbonyl group, 2-azulenyloxycarbonyl group, 1-acenaphthyloxycarbonyl group, 9-fluorenyloxycarbonyl group,
o-tolyloxycarbonyl group, m-tolyloxycarbonyl group, p-tolyloxycarbonyl group, 2,3-xylyloxycarbonyl group, 2,5-xylyloxycarbonyl group, mesityloxycarbonyl group, p-c Enyloxycarbonyl group, p-cyclohexylphenoxycarbonyl group, 4-phenylphenoxycarbonyl group,
o-fluorophenoxycarbonyl group, m-chlorophenoxycarbonyl group, p-bromophenoxycarbonyl group, p-hydroxyphenoxycarbonyl group, m-carboxyphenoxycarbonyl group, o-mercaptophenoxycarbonyl group, p-cyanophenoxycarbonyl group, m -Nitrophenoxycarbonyl group, m-azidophenoxycarbonyl group and the like.

Further, adjacent R, R ² , Ar
Each other, or R ¹ and R ² , R ¹ and R, R ¹ and R
³ may form a ring structure by a covalent bond with each other, such as an alkylene group such as a methylene group, an ethylene group, a tetramethylene group, a hexamethylene group, an ethylenedioxy group, a diethylenedioxy group. Examples include ether groups such as a group, and thioether groups such as an ethylenedithio group and a diethylenedithio group, but the present invention is not limited thereto.

The specific examples of the structures of the onium cations represented by the general formulas (2) to (13) of the energy-sensitive acid generator (A) of the present invention are shown below.

Onium cations corresponding to the general formula (2) (sulfonium cations):

Examples of benzylsulfonium cations: dimethyl (benzyl) sulfonium, dimethyl (o-fluorobenzyl) sulfonium, dimethyl (m-chlorobenzyl) sulfonium, dimethyl (p-bromobenzyl)
Sulfonium, dimethyl (p-cyanobenzyl) sulfonium, dimethyl (m-nitrobenzyl) sulfonium, dimethyl (2,4,6-tribromophenylmethyl) sulfonium, dimethyl (pentafluorophenylmethyl) sulfonium, dimethyl (p- (tri- Fluoromethyl) benzyl) sulfonium, dimethyl (p-hydroxybenzyl) sulfonium, dimethyl (p-mercaptobenzyl) sulfonium, dimethyl (p-methylsulfinylbenzyl) sulfonium, dimethyl (p-methylsulfonylbenzyl) sulfonium, dimethyl (o)
-Acetylbenzyl) sulfonium, dimethyl (o-benzoylbenzyl) sulfonium, dimethyl (p-methylbenzyl) sulfonium, dimethyl (p-isopropylbenzyl) sulfonium, dimethyl (p-octadecylbenzyl) sulfonium, dimethyl (p-cyclohexylbenzyl) sulfonium Dimethyl (p-methoxybenzyl) sulfonium, dimethyl (o-methoxycarbonylbenzyl) sulfonium, dimethyl (p-isopropoxycarbonylbenzyl) sulfonium, dimethyl (2-naphthylmethyl) sulfonium, dimethyl (9-
Anthrylmethyl) sulfonium, diethyl (benzyl) sulfonium, methylethyl (benzyl) sulfonium, methylphenyl (benzyl) sulfonium, diphenyl (benzyl) sulfonium, diisopropyl (benzyl) sulfonium and the like.

Examples of phenacylsulfonium cations: dimethyl (phenacyl) sulfonium, dimethyl (o-fluorophenacyl) sulfonium, dimethyl (m-chlorophenacyl) sulfonium, dimethyl (p-bromophenacyl) sulfonium, dimethyl (p-cyanophenacyl) Sulfonium, dimethyl (m-nitrophenacyl) sulfonium, dimethyl (2,4,6-tribromophenylmethyl) sulfonium, dimethyl (p- (trifluoromethyl) phenacyl) sulfonium, dimethyl (p-hydroxyphenacyl) sulfonium, Dimethyl (p-mercaptophenacyl) sulfonium, dimethyl (p-methylsulfinylphenacyl) sulfonium,
Dimethyl (p-methylsulfonylphenacyl) sulfonium, dimethyl (o-acetylphenacyl) sulfonium, dimethyl (o-benzoylphenacyl) sulfonium, dimethyl (p-methylphenacyl) sulfonium,
Dimethyl (p-isopropylphenacyl) sulfonium, dimethyl (p-octadecylphenacyl) sulfonium, dimethyl (p-cyclohexylphenacyl) sulfonium, dimethyl (p-methoxyphenacyl) sulfonium, dimethyl (o-methoxycarbonylphenacyl) sulfonium Dimethyl (p-isopropoxycarbonylphenacyl) sulfonium, dimethyl (2-naphthoylmethyl) sulfonium, dimethyl (9-anthroylmethyl) sulfonium, diethyl (phenacyl) sulfonium, methylethyl (phenacyl) sulfonium, methylphenyl (phenacyl) ) Sulfonium, diphenyl (phenacyl) sulfonium, diisopropyl (phenacyl) sulfonium, tetramethylene (phenacyl) sulfonium, pen Methylene (phenacyl) sulfonium, hexamethylene (phenacyl) sulfonium, ethylenedioxy (phenacyl) sulfonium, diethylene dioxy (phenacyl) sulfonium, ethylene dithio (phenacyl) sulfonium.

Examples of allylsulfonium cations: dimethyl (allyl) sulfonium, dimethyl (2,3,3-trifluoro-2-propenyl) sulfonium, dimethyl (3,3-dicyano-2-propenyl) sulfonium,
Dimethyl (2-methyl-3,3-dicyano-2-propenyl) sulfonium, dimethyl (2-acetyl-3,3
-Dicyano-2-propenyl) sulfonium, dimethyl (2-benzoyl-3,3-dicyano-2-propenyl) sulfonium, dimethyl (2-phenyl-3,3-
Dicyano-2-propenyl) sulfonium, dimethyl (3,3-bis (methoxycarbonyl) -2-propenyl) sulfonium and the like.

Examples of alkoxysulfonium cations: dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecaneoxy) sulfonium, dimethyl (iso) Propoxy) sulfonium, dimethyl (t-butoxy) sulfonium,
Dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl ( 8-nitrooctyloxy) sulfonium, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium, dimethyl (2-
(Hydroxyisopropoxy) sulfonium, dimethyl (tris (trichloromethyl) methyl) sulfonium and the like.

Examples of aryloxysulfonium cations: dimethyl (phenoxy) sulfonium, dimethyl (1-naphthyloxy) sulfonium, dimethyl (2-
Naphthyloxy) sulfonium, dimethyl (9-anthryloxy) sulfonium, dimethyl (9-phenanthryloxy) sulfonium, dimethyl (p-tolyloxy) sulfonium, dimethyl (2,3-xylyloxy) sulfonium, dimethyl (o-fluorophenoxy) ) Sulfonium, dimethyl (m-chlorophenoxy)
Sulfonium, dimethyl (p-bromophenoxy) sulfonium, dimethyl (p-hydroxyphenoxy) sulfonium, dimethyl (m-carboxyphenoxy) sulfonium, dimethyl (o-mercaptophenoxy) sulfonium, dimethyl (p-cyanophenoxy) sulfonium, dimethyl (m -Nitrophenoxy) sulfonium, dimethyl (m-azidophenoxy) sulfonium,
Dimethyl (2-chloro-1-naphthyloxy) sulfonium, dimethyl (11-nitro-5-naphthacenyl) sulfonium and the like.

Onium cation (sulfoxonium cation) corresponding to general formula (3):

Examples of benzylsulfoxonium cations:
Dimethyl (benzyl) sulfoxonium, dimethyl (p
-Bromobenzyl) sulfoxonium, dimethyl (p-
Cyanobenzyl) sulfoxonium, dimethyl (m-nitrobenzyl) sulfoxonium, dimethyl (pentafluorophenylmethyl) sulfoxonium, dimethyl (p-hydroxybenzyl) sulfoxonium, dimethyl (o-acetylbenzyl) sulfoxonium Dimethyl (o-benzoylbenzyl) sulfoxonium, dimethyl (p-isopropylbenzyl) sulfoxonium,
Dimethyl (p-methoxybenzyl) sulfoxonium,
Dimethyl (o-methoxycarbonylbenzyl) sulfoxonium, dimethyl (2-naphthylmethyl) sulfoxonium, dimethyl (9-anthrylmethyl) sulfoxonium, diethyl (benzyl) sulfoxonium, methylethyl (benzyl) sulfoxo , Methylphenyl (benzyl) sulfoxonium, diphenyl (benzyl) sulfoxonium, diisopropyl (benzyl) sulfoxonium and the like.

Examples of phenacylsulfoxonium cations: dimethyl (phenacyl) sulfoxonium, dimethyl (p-bromophenacyl) sulfoxonium, dimethyl (p-cyanophenacyl) sulfoxonium, dimethyl (m-nitrophenacyl) sulfoxonium , Dimethyl (2,4,6-tribromophenylmethyl) sulfoxonium, dimethyl (p-hydroxyphenacyl) sulfoxonium, dimethyl (p-mercaptophenacyl)
Sulfoxonium, dimethyl (o-benzoylphenacyl) sulfoxonium, dimethyl (p-methylphenacyl) sulfoxonium, dimethyl (p-methoxyphenacyl) sulfoxonium, dimethyl (o-methoxycarbonylphenacyl) sulfo Xonium, dimethyl (2-
Naphthylmethyl) sulfoxonium, dimethyl (9-anthrylmethyl) sulfoxonium, diethyl (phenacyl) sulfoxonium, methylethyl (phenacyl)
Sulfoxonium, methylphenyl (phenacyl) sulfoxonium, diphenyl (phenacyl) sulfoxonium, diisopropyl (phenacyl) sulfoxonium, tetramethylene (phenacyl) sulfoxonium and the like.

Examples of allylsulfoxonium cations: dimethyl (allyl) sulfoxonium, dimethyl (3,3
-Dicyano-2-propenyl) sulfoxonium, dimethyl (2-benzoyl-3,3-dicyano-2-propenyl) sulfoxonium, dimethyl (2-phenyl-
3,3-dicyano-2-propenyl) sulfoxonium, dimethyl (3,3-bis (methoxycarbonyl)-
2-propenyl) sulfoxonium and the like.

Examples of alkoxysulfoxonium cations: dimethyl (ethoxy) sulfoxonium, dimethyl (propoxy) sulfoxonium, dimethyl (octyloxy) sulfoxonium, dimethyl (isopropoxy) sulfoxonium, dimethyl (cyclohexyloxy) Sulfoxonium, dimethyl (2-chloroethoxy) sulfoxonium and the like.

Examples of aryloxysulfoxonium cations: dimethyl (phenoxy) sulfoxonium, dimethyl (2-naphthyloxy) sulfoxonium, dimethyl (9-anthryloxy) sulfoxonium, dimethyl (p-tolyloxy) sulfonium Xonium, dimethyl (m-chlorophenoxy) sulfoxonium, dimethyl (m-carboxyphenoxy) sulfoxonium, dimethyl (p-cyanophenoxy) sulfoxonium and the like.

Onium cation (phosphonium cation) corresponding to general formula (4):

Examples of benzylphosphonium cations: trimethylbenzylphosphonium, triethylbenzylphosphonium, triphenylbenzylphosphonium, triphenyl (p-fluorobenzyl) phosphonium, triphenyl (o-chlorobenzyl) phosphonium, triphenyl (m-bromobenzyl) Phosphonium, triphenyl (p-cyanobenzyl) phosphonium, triphenyl (m-nitrobenzyl) phosphonium, triphenyl (o-hydroxybenzyl) phosphonium, triphenyl (o-acetylbenzyl) phosphonium, triphenyl (m-benzoylbenzyl) Phosphonium, triphenyl (p-methylbenzyl) phosphonium, triphenyl (p-isopropoxybenzyl) phosphonium, triphenyl (o-meth Aryloxycarbonyl benzyl) phosphonium, triphenyl (1-naphthylmethyl) phosphonium, triphenyl (9-anthrylmethyl) phosphonium like.

Examples of phenacylphosphonium cations: trimethylphenacylphosphonium, triethylphenacylphosphonium, triphenylphenacylphosphonium, triphenyl (p-fluorophenacyl) phosphonium, triphenyl (o-chlorophenacyl) phosphonium, triphenyl (M-bromophenacyl) phosphonium, triphenyl (p-cyanophenacyl) phosphonium, triphenyl (m-nitrophenacyl) phosphonium, triphenyl (o-hydroxyphenacyl) phosphonium, triphenyl (o-acetylphenacyl) phosphonium, triphenyl Phenyl (m-benzoylphenacyl) phosphonium, triphenyl (p-methylphenacyl) phosphonium, triphenyl (p-isopropoxyphenacyl) phosphonium Arm, triphenyl (o-methoxycarbonyl phenacyl) phosphonium, triphenyl (1- naphthoquinone Ciro yl methyl) phosphonium, triphenyl (9 anthrocyclins yl methyl) phosphonium like.

Examples of allylphosphonium cations: triphenylallylphosphonium, triphenyl (3,3-dicyano-2-propenyl) phosphonium, triphenyl (2-hexyl-3,3-dicyano-2-propenyl)
Phosphonium, triphenyl (2-acetyl-3,3-
Dicyano-2-propenyl) phosphonium, triphenyl (2-phenyl-3,3-dicyano-2-propenyl) phosphonium and the like.

Examples of alkoxyphosphonium cations: triphenylmethoxyphosphonium, triphenylbutoxyphosphonium, triphenyloctadecyloxyphosphonium, triphenylisopropoxyphosphonium,
Triphenyl (2-chloroethoxy) phosphonium, triphenyl (4-cyanobutoxy) phosphonium and the like.

Examples of aryloxyphosphonium cations: triphenylphenoxyphosphonium, triphenyl (1-naphthyloxy) phosphonium, triphenyl (2-naphthyloxy) phosphonium, triphenyl (9-anthryloxy) phosphonium, triphenyl (p -Tolyloxy) phosphonium, triphenyl (2,3-xylyloxy) phosphonium, triphenyl (p-hydroxyphenoxy) phosphonium, triphenyl (m-carboxyphenoxy) phosphonium and the like.

Onium cation (pyridinium cation) corresponding to general formula (5):

Examples of benzylpyridinium cations: N-
Benzylpyridinium, N- (o-chlorobenzyl) pyridinium, N- (m-chlorobenzyl) pyridinium, N- (p-cyanobenzyl) pyridinium, N-
(O-nitrobenzyl) pyridinium, N- (p-acetylbenzyl) pyridinium, N- (p-isopropylbenzyl) pyridinium, N- (p-octadecyloxybenzyl) pyridinium, N- (p-methoxycarbonylbenzyl) pyridinium, N- (9-anthrylmethyl) pyridinium, 2-chloro-1-benzylpyridinium, 2-cyano-1-benzylpyridinium, 2-
Methyl-1-benzylpyridinium, 2-vinyl-1-
Benzylpyridinium, 2-phenyl-1-benzylpyridinium, 1,2-dibenzylpyridinium, 2-methoxy-1-benzylpyridinium, 2-phenoxy-
1-benzylpyridinium, 2-acetyl-1-benzylpyridinium, 2-methoxycarbonyl-1-benzylpyridinium, 3-fluoro-1-benzylpyridinium, 4-methyl-1-benzylpyridinium and the like.

Examples of phenacylpyridinium cations: N
-Phenacylpyridinium, N- (o-chlorophenacyl) pyridinium, N- (m-chlorophenacyl) pyridinium, N- (p-cyanophenacyl) pyridinium, N- (o-nitrophenacyl) pyridinium, N-
(P-acetylphenacyl) pyridinium, N- (p-
Isopropylphenacyl) pyridinium, N- (p-octadecyloxyphenacyl) pyridinium, N- (p
-Methoxycarbonylphenacyl) pyridinium, N-
(9-anthroylmethyl) pyridinium, 2-chloro-1-phenacylpyridinium, 2-cyano-1-phenacylpyridinium, 2-methyl-1-phenacylpyridinium, 2-vinyl-1-phenacylpyridinium,
2-phenyl-1-phenacylpyridinium, 1,2-
Diphenacylpyridinium, 2-methoxy-1-phenacylpyridinium, 2-phenoxy-1-phenacylpyridinium, 2-acetyl-1-phenacylpyridinium, 2-methoxycarbonyl-1-phenacylpyridinium, 3-fluoro- 1-phenacylpyridinium, 4
-Methyl-1-phenacylpyridinium and the like.

Examples of allylpyridinium cations: N-allylpyridinium, N- (2-methyl-3,3-dicyano-2-propenyl) pyridinium, N- (2-isopropyl-3,3-dicyano-2-propenyl) Pyridinium, N- (2-benzoyl-3,3-dicyano-2-
Propenyl) pyridinium, N- (2-hexyl-3,
3-bis (methoxycarbonyl) -2-propenyl) pyridinium and the like.

Examples of N-alkoxypyridinium cations: N-methoxypyridinium, N-octyloxypyridinium, N-octadecyloxypyridinium,
-Isopropoxypyridinium, N-cyclohexyloxypyridinium, 1-ethoxy-2-methylpyridinium, N- (2-chloroethoxy) pyridinium and the like.

Examples of N-aryloxypyridinium cations: N-phenoxypyridinium, N- (2-naphthyloxy) pyridinium, N- (9-anthryloxy) pyridinium, N- (p-tolyloxy) pyridinium, N- ( 2,3-xylyloxy) pyridinium,
N- (p-bromophenoxy) pyridinium, N- (p
-Hydroxyphenoxy) pyridinium and the like.

Onium cations corresponding to the general formula (6) (quinolinium cations):

Examples of benzylquinolinium cations: N-
Benzylquinolinium, N- (o-chlorobenzyl) quinolinium, N- (m-chlorobenzyl) quinolinium, N- (p-cyanobenzyl) quinolinium, N-
(O-nitrobenzyl) quinolinium, N- (p-acetylbenzyl) quinolinium, N- (p-isopropylbenzyl) quinolinium, N- (p-octadecyloxybenzyl) quinolinium, N- (p-methoxycarbonylbenzyl) quinolinium, N- (9-anthrylmethyl) quinolinium, 2-chloro-1-benzylquinolinium, 2-cyano-1-benzylquinolinium, 2-
Methyl-1-benzylquinolinium, 2-vinyl-1-
Benzylquinolinium, 2-phenyl-1-benzylquinolinium, 1,2-dibenzylquinolinium, 2-methoxy-1-benzylquinolinium, 2-phenoxy-
1-benzylquinolinium, 2-acetyl-1-benzylquinolinium, 2-methoxycarbonyl-1-benzylquinolinium, 3-fluoro-1-benzylquinolinium, 4-methyl-1-benzylquinolinium Etc.

Examples of phenacylquinolinium cations: N
-Phenacylquinolinium, N- (o-chlorophenacyl) quinolinium, N- (m-chlorophenacyl) quinolinium, N- (p-cyanophenacyl) quinolinium, N- (o-nitrophenacyl) quinolinium, N-
(P-acetylphenacyl) quinolinium, N- (p-
Isopropylphenacyl) quinolinium, N- (p-octadecyloxyphenacyl) quinolinium, N- (p
-Methoxycarbonylphenacyl) quinolinium, N-
(9-Anthroylmethyl) quinolinium, 2-chloro-1-phenacylquinolinium, 2-cyano-1-phenacylquinolinium, 2-methyl-1-phenacylquinolinium, 2-vinyl-1-phenacylki Norinium,
2-phenyl-1-phenacylquinolinium, 1,2-
Diphenacylquinolinium, 2-methoxy-1-phenacylquinolinium, 2-phenoxy-1-phenacylquinolinium, 2-acetyl-1-phenacylquinolinium, 2-methoxycarbonyl-1-phenacylquinolinium , 3-fluoro-1-phenacylquinolinium, 4
-Methyl-1-phenacylquinolinium and the like.

Examples of allylquinolinium cations: N-allylquinolinium, N- (2-methyl-3,3-dicyano-2-propenyl) quinolinium, N- (2-isopropyl-3,3-dicyano-) 2-propenyl) quinolinium, N- (2-benzoyl-3,3-dicyano-2-
Propenyl) quinolinium, N- (2-hexyl-3,
3-bis (methoxycarbonyl) -2-propenyl) quinolinium and the like.

Examples of N-alkoxyquinolinium cations: N-methoxyquinolinium, N-octyloxyquinolinium, N-octadecyloxyquinolinium, N
-Isopropoxyquinolinium, N-cyclohexyloxyquinolinium, 1-ethoxy-2-methylquinolinium, N- (2-chloroethoxy) quinolinium and the like.

Examples of N-aryloxyquinolinium cations: N-phenoxyquinolinium, N- (2-naphthyloxy) quinolinium, N- (9-anthryloxy) quinolinium, N- (p-tolyloxy) quinolinium , N- (2,3-xylyloxy) quinolinium,
N- (p-bromophenoxy) quinolinium, N- (p
-Hydroxyphenoxy) quinolinium and the like.

Onium cations (isoquinolinium cations) corresponding to the general formula (7):

Examples of benzylisoquinolinium cations:
N-benzylisoquinolinium, N- (o-chlorobenzyl) isoquinolinium, N- (m-chlorobenzyl)
Isoquinolinium, N- (p-cyanobenzyl) isoquinolinium, N- (o-nitrobenzyl) isoquinolinium, N- (p-acetylbenzyl) isoquinolinium, N- (p-isopropylbenzyl) isoquinolinium, N- (p-octadecyloxybenzyl) ) Isoquinolinium, N- (p-methoxycarbonylbenzyl) isoquinolinium, N- (9-anthrylmethyl) isoquinolinium, 1,2-dibenzylisoquinolinium and the like.

Examples of phenacylisoquinolinium cations: N-phenacylisoquinolinium, N- (o-chlorophenacyl) isoquinolinium, N- (m-chlorophenacyl) isoquinolinium, N- (p-cyanophenacyl ) Isoquinolinium, N- (o-nitrophenacyl) isoquinolinium, N- (p-acetylphenacyl) isoquinolinium, N- (p-isopropylphenacyl) isoquinolinium, N- (p-octadecyloxyphenacyl) isoquinolinium, N- (P-methoxycarbonylphenacyl) isoquinolinium, N- (9-
Anthroylmethyl) isoquinolinium and the like.

Examples of allylisoquinolinium cations: N
-Allylisoquinolinium, N- (2-methyl-3,3
-Dicyano-2-propenyl) isoquinolinium, N-
(2-isopropyl-3,3-dicyano-2-propenyl) isoquinolinium, N- (2-benzoyl-3,3
-Dicyano-2-propenyl) isoquinolinium, N-
(2-hexyl-3,3-bis (methoxycarbonyl)
-2-propenyl) isoquinolinium and the like.

Examples of N-alkoxyisoquinolinium cations: N-methoxyisoquinolinium, N-octyloxyisoquinolinium, N-octadecyloxyisoquinolinium, N-isopropoxyisoquinolinium, N
-Cyclohexyloxyisoquinolinium and the like.

Examples of N-aryloxyisoquinolinium cations: N-phenoxyisoquinolinium, N- (2
-Naphthyloxy) isoquinolinium, N- (9-anthryloxy) isoquinolinium, N- (p-tolyloxy) isoquinolinium, N- (2,3-xylyloxy) isoquinolinium, N- (p-bromophenoxy)
Isoquinolinium, N- (p-hydroxyphenoxy)
Isoquinolinium and the like.

Onium cations corresponding to the general formula (8) (benzoxazolium cations, benzothiazolium cations):

Examples of benzoxazolium cations: N-
Benzylbenzoxazolium, N- (p-fluorobenzyl) benzoxazolium, N- (p-chlorobenzyl) benzoxazolium, N- (p-cyanobenzyl) benzoxazolium, N- (o- (Methoxycarbonylbenzyl) benzoxazolium, N-phenacylbenzoxazolium, N- (o-fluorophenacyl) benzoxazolium, N- (p-cyanophenacyl) benzoxazolium, N- (m-nitro Phenacyl) benzoxazolium, N- (p-isopropoxycarbonylphenacyl) benzoxazolium, N-allylbenzoxazolium, N- (2-methyl-3,3
-Dicyano-2-propenyl) benzoxazolium,
N- (2-benzoyl-3,3-dicyano-2-propenyl) benzoxazolium, N- (3,3-bis (methoxycarbonyl) -2-propenyl) benzoxazolium, N-methoxybenzoxazol Lium, N- (t
-Butoxy) benzoxazolium, N- (3-bromopropoxy) benzoxazolium, N-phenoxybenzoxazolium, N- (1-naphthyloxy) benzoxazolium, N- (m-carboxyphenoxy)
Benzoxazolium, 2-mercapto-3-benzylbenzoxazolium, 2-methyl-3-benzylbenzoxazolium, 2-methylthio-3-benzylbenzoxazolium, 6-hydroxy-3-benzylbenzoxalium Zolium, 7-mercapto-3-benzylbenzoxazolium, 4,5-difluoro-3-benzylbenzoxazolium and the like.

Examples of benzothiazolium cations: N-benzylbenzothiazolium, N- (p-fluorobenzyl) benzothiazolium, N- (p-chlorobenzyl)
Benzothiazolium, N- (p-cyanobenzyl) benzothiazolium, N- (o-methoxycarbonylbenzyl) benzothiazolium, N-phenacylbenzothiazolium, N- (o-fluorophenacyl) Benzothiazolium, N- (p-cyanophenacyl) benzothiazolium, N- (m-nitrophenacyl) benzothiazolium, N- (p-isopropoxycarbonylphenacyl)
Benzothiazolium, N-allylbenzothiazolium,
N- (2-methyl-3,3-dicyano-2-propenyl) benzothiazolium, N- (2-benzoyl-3,
3-dicyano-2-propenyl) benzothiazolium,
N- (3,3-bis (methoxycarbonyl) -2-propenyl) benzothiazolium, N-methoxybenzothiazolium, N- (t-butoxy) benzothiazolium,
N- (3-bromopropoxy) benzothiazolium, N
-Phenoxybenzothiazolium, N- (1-naphthyloxy) benzothiazolium, N- (m-carboxyphenoxy) benzothiazolium, 2-mercapto-3-
Benzylbenzothiazolium, 2-methyl-3-benzylbenzothiazolium, 2-methylthio-3-benzylbenzothiazolium, 6-hydroxy-3-benzylbenzothiazolium, 7-mercapto-3-benzylbenzo Thiazolium, 4,5-difluoro-3-benzylbenzothiazolium and the like.

Onium cations corresponding to the general formula (9) (furyl or thienyl iodonium cations):

Difuryl iodonium, dithienyl iodonium, bis (4,5-dimethyl-2-furyl) iodonium, bis (5-chloro-2-thienyl) iodonium, bis (5-cyano-2-furyl) iodonium, bis (5-nitro-2-thienyl) iodonium, bis (5-acetyl-2-furyl) iodonium, bis (5
-Carboxy-2-thienyl) iodonium, bis (5
-Methoxycarbonyl-2-furyl) iodonium, bis (5-phenyl-2-furyl) iodonium, bis (5- (p-methoxyphenyl) -2-thienyl) iodonium, bis (5-vinyl-2-furyl) iodonium , Bis (5-ethynyl-2-thienyl) iodonium, bis (5-cyclohexyl-2-furyl) iodonium, bis (5-hydroxy-2-thienyl) iodonium, bis (5-phenoxy-2-furyl) iodonium, bis (5-mercapto-2-thienyl) iodonium, bis (5-butylthio-2-thienyl) iodonium, bis (5-phenylthio-2-thienyl) iodonium and the like.

Onium cations corresponding to the general formula (10) (diaryliodonium cations):

Diphenyliodonium, bis (p-tolyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) Iodonium, phenyl (p-octadecyloxyphenyl) iodonium and the like.

Onium cations corresponding to the general formula (11) (triarylsulfonium cations):

Triphenylsulfonium, tris (p-
Tolyl) sulfonium, tris (phenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-cyanophenyl) sulfonium, tris (p-chlorophenyl) sulfonium and the like.

Onium cations (triarylsulfoxonium cations) corresponding to the general formula (12):

Triphenylsulfoxonium, tris (p-tolyl) sulfoxonium, tris (phenyl)
Sulfoxonium, tris (2,6-dimethylphenyl) sulfoxonium, tris (p-cyanophenyl)
Sulfoxonium, tris (p-chlorophenyl) sulfoxonium and the like.

On the other hand, as the substituent Z in the borate anion represented by the general formula (1) constituting the energy-sensitive acid generator (A) of the present invention, 3,5-difluorophenyl group, 2,4,4 6-trifluorophenyl group, 2,
3,4,6-tetrafluorophenyl group, pentafluorophenyl group, 2,4-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-trifluoro -3,5-bis (trifluoromethyl) phenyl group, 3,5-dinitrophenyl group, 2,4,6-trifluoro-3,5-dinitrophenyl group, 2,4-dicyanophenyl group, 4-cyano −
Examples thereof include a 3,5-dinitrophenyl group and a 4-cyano-2,6-bis (trifluoromethyl) phenyl group, but the present invention is not limited thereto.

Therefore, specific examples of the structure of the borate anion of the energy-sensitive linear acid generator (A) of the present invention include pentafluorophenyltrifluoroborate,
3,5-bis (trifluoromethyl) phenyltrifluoroborate, bis (pentafluorophenyl) difluoroborate, bis [3,5-bis (trifluoromethyl) phenyl] difluoroborate, tris (pentafluorophenyl) fluoroborate, Tris [3,5-
Bis (trifluoromethyl) phenyl] fluoroborate, tetrakis (pentafluorophenyl) borate,
And tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

Of these, preferred structures of the borate anion of the energy-sensitive acid generator (A) of the present invention include tetrakis (pentafluorophenyl) borate and tetrakis [3,5-bis (trifluoromethyl) borate.
[Phenyl] borate.

Accordingly, specific examples of preferred onium borate complexes constituting the energy-sensitive linear acid generator (A) of the present invention include the following, but the present invention is not limited thereto. Not something.

Examples of tetrakis (pentafluorophenyl) borate:

Examples of benzylsulfonium tetrakis (pentafluorophenyl) borate: dimethyl (benzyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (p-bromobenzyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (p-cyanobenzyl) ) Sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (m-nitrobenzyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (pentafluorophenylmethyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (p- (trifluoromethyl) ) Benzyl) sulfoniumtetrakis (pentafluorophenyl) borate, dimethyl (p-methylsulfonylbenzyl) Sulfo tetrakis (pentafluorophenyl) borate, dimethyl (o-acetyl-benzyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (o-benzoyl benzyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (p- isopropylbenzyl)
Sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (p-methoxybenzyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-naphthylmethyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (9-
(Anthrylmethyl) sulfoniumtetrakis (pentafluorophenyl) borate, diethyl (benzyl) sulfoniumtetrakis (pentafluorophenyl) borate, methylethyl (benzyl) sulfoniumtetrakis (pentafluorophenyl) borate, methylphenyl (benzyl) sulfoniumtetrakis (pentafluoro) Phenyl) borate, diphenyl (benzyl) sulfoniumtetrakis (pentafluorophenyl) borate and the like.

Examples of phenacylsulfonium tetrakis (pentafluorophenyl) borate: dimethyl (phenacyl) sulfoniumtetrakis (pentafluorophenyl) borate, dimethyl (p-cyanophenacyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (m-nitrophena) Sil) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (p- (trifluoromethyl) phenacyl) sulfonium tetrakis (pentafluorophenyl) borate,
Dimethyl (p-methylsulfonylphenacyl) sulfonium tetrakis (pentafluorophenyl) borate,
Dimethyl (o-acetylphenacyl) sulfoniumtetrakis (pentafluorophenyl) borate, dimethyl (o-benzoylphenacyl) sulfoniumtetrakis (pentafluorophenyl) borate, dimethyl (p-
Isopropylphenacyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (p-isopropoxycarbonylphenacyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-naphthoylmethyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (9-Anthroylmethyl) sulfoniumtetrakis (pentafluorophenyl) borate, diethyl (phenacyl) sulfoniumtetrakis (pentafluorophenyl) borate, methylethyl (phenacyl) sulfoniumtetrakis (pentafluorophenyl) borate, methylphenyl (phenacyl) sulfoniumtetrakis (Pentafluorophenyl) borate, diphenyl (phenacyl) sulfoniumtetraki (Pentafluorophenyl) borate, tetramethylene (phenacyl) sulfonium tetrakis (pentafluorophenyl) borate and the like.

Examples of allylsulfonium tetrakis (pentafluorophenyl) borate: dimethyl (allyl) sulfoniumtetrakis (pentafluorophenyl) borate, dimethyl (3,3-dicyano-2-propenyl)
Sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-methyl-3,3-dicyano-2)
-Propenyl) sulfoniumtetrakis (pentafluorophenyl) borate, dimethyl (2-benzoyl-
3,3-dicyano-2-propenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (3,3-bis (methoxycarbonyl) -2-propenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like.

Examples of alkoxysulfonium tetrakis (pentafluorophenyl) borate: dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (butoxy) sulfonium tetrakis (pentafluoro) Phenyl) borate, dimethyl (isopropoxy) sulfoniumtetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobutoxy) sulfoniumtetrakis (pentafluorophenyl) borate and the like.

Examples of aryloxysulfonium tetrakis (pentafluorophenyl) borate: dimethyl (phenoxy) sulfoniumtetrakis (pentafluorophenyl) borate, dimethyl (1-naphthyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-naphthyloxy) Sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (9-anthryloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (p-tolyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (p-bromophenoxy) sulfonium tetrakis (Pentafluorophenyl) borate and the like.

Examples of benzylsulfoxonium tetrakis (pentafluorophenyl) borate: dimethyl (benzyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (p-bromobenzyl) sulfoxonium tetrakis (pentafluorophenyl)
Borate, dimethyl (p-cyanobenzyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (m-nitrobenzyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (pentafluorophenylmethyl) sulfoxonium tetrakis ( Pentafluorophenyl) borate, dimethyl (p- (trifluoromethyl) benzyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (p-methylsulfonylbenzyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (o) -Acetylbenzyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (o-benzoylbenzyl) sulfoxonium tetrakis (pen Fluorophenyl) borate,
Dimethyl (p-isopropylbenzyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (p-methoxybenzyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (2-naphthylmethyl) sulfoxonium tetrakis (pentafluoro Phenyl) borate, dimethyl (9-
(Anthrylmethyl) sulfoxonium tetrakis (pentafluorophenyl) borate, diethyl (benzyl)
Sulfoxonium tetrakis (pentafluorophenyl) borate, methylethyl (benzyl) sulfoxonium tetrakis (pentafluorophenyl) borate,
Methylphenyl (benzyl) sulfoxonium tetrakis (pentafluorophenyl) borate, diphenyl (benzyl) sulfoxonium tetrakis (pentafluorophenyl) borate and the like.

Examples of phenacylsulfoxonium tetrakis (pentafluorophenyl) borate: dimethyl (phenacyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (p-cyanophenacyl) sulfoxonium tetrakis (pentafluorophenyl) borate, Dimethyl (m-nitrophenacyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (p- (trifluoromethyl) phenacyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (p-methylsulfonylphenacyl) Sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (o-acetylphenacyl) sulfoxonium tetrakis (pentafluorophenyl) borate Dimethyl (o-benzoylphenacyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (p-isopropylphenacyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (p-isopropoxycarbonylphenacyl) sulfo Xonium tetrakis (pentafluorophenyl) borate, dimethyl (2
-Naphthoylmethyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (9-anthroylmethyl) sulfoxonium tetrakis (pentafluorophenyl) borate, diethyl (phenacyl)
Sulfoxonium tetrakis (pentafluorophenyl) borate, methylethyl (phenacyl) sulfoxonium tetrakis (pentafluorophenyl) borate, methylphenyl (phenacyl) sulfoxonium tetrakis (pentafluorophenyl) borate, diphenyl (phenacyl) sulfoxonium Tetrakis (pentafluorophenyl) borate, tetramethylene (phenacyl) sulfoxonium tetrakis (pentafluorophenyl) borate and the like.

Examples of allylsulfoxonium tetrakis (pentafluorophenyl) borate: dimethyl (allyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (3,3-dicyano-2-propenyl) sulfoxonium tetrakis (pentane) Fluorophenyl) borate, dimethyl (2-methyl-3,3)
-Dicyano-2-propenyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (2-benzoyl-3,3-dicyano-2-propenyl) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (3,3 -Bis (methoxycarbonyl) -2-propenyl) sulfoxonium tetrakis (pentafluorophenyl) borate and the like.

Examples of alkoxysulfoxonium tetrakis (pentafluorophenyl) borate: dimethyl (methoxy) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (butoxy) ) Sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobutoxy) sulfoxonium tetrakis (pentafluorophenyl) borate and the like.

Examples of aryloxysulfoxonium tetrakis (pentafluorophenyl) borate: dimethyl (phenoxy) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (1-naphthyloxy) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (2-naphthyloxy) sulfoxonium tetrakis (pentafluorophenyl)
Borate, dimethyl (9-anthryloxy) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (p-tolyloxy) sulfoxonium tetrakis (pentafluorophenyl) borate, dimethyl (p-bromophenoxy) sulfoxonium tetrakis ( (Pentafluorophenyl) borate and the like.

Examples of benzylphosphonium tetrakis (pentafluorophenyl) borate: trimethylbenzylphosphonium tetrakis (pentafluorophenyl) borate, triethylbenzylphosphoniumtetrakis (pentafluorophenyl) borate, triphenylbenzylphosphonium tetrakis (pentafluorophenyl) borate, triphenyl Phenyl (p-cyanobenzyl) phosphonium tetrakis (pentafluorophenyl) borate, triphenyl (m-nitrobenzyl) phosphonium tetrakis (pentafluorophenyl) borate, triphenyl (1-naphthylmethyl) phosphonium tetrakis (pentafluorophenyl) borate, Triphenyl (9-anthrylmethyl) phosphonium tetrakis (pentafluorophen Le) borate, such as.

Examples of phenacylphosphonium tetrakis (pentafluorophenyl) borate: triethylphenacylphosphoniumtetrakis (pentafluorophenyl) borate, triphenylphenacylphosphoniumtetrakis (pentafluorophenyl) borate, triphenyl (p-cyanophenacyl) phosphonium tetrakis (Pentafluorophenyl) borate, triphenyl (m-nitrophenacyl) phosphonium tetrakis (pentafluorophenyl) borate, triphenyl (1-
Naphthaloylmethyl) phosphonium tetrakis (pentafluorophenyl) borate, triphenyl (9-anthroylmethyl) phosphonium tetrakis (pentafluorophenyl) borate and the like.

Examples of allylphosphonium tetrakis (pentafluorophenyl) borate: triphenylallylphosphoniumtetrakis (pentafluorophenyl) borate, triphenyl (3,3-dicyano-2-propenyl) phosphonium tetrakis (pentafluorophenyl) borate, triphenyl Phenyl (2-phenyl-3,3-
Dicyano-2-propenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like.

Examples of alkoxyphosphonium tetrakis (pentafluorophenyl) borate: triphenylmethoxyphosphonium tetrakis (pentafluorophenyl) borate, triphenylisopropoxyphosphonium tetrakis (pentafluorophenyl) borate, triphenyl (2-chloroethoxy) phosphonium tetrakis (Pentafluorophenyl) borate and the like.

Examples of aryloxyphosphonium tetrakis (pentafluorophenyl) borate: triphenylphenoxyphosphonium tetrakis (pentafluorophenyl) borate, triphenyl (9-anthryloxy) phosphonium tetrakis (pentafluorophenyl) borate, triphenyl (p -Tolyloxy) phosphonium tetrakis (pentafluorophenyl) borate, triphenyl (p-hydroxyphenoxy) phosphonium tetrakis (pentafluorophenyl) borate and the like.

Examples of benzylpyridinium tetrakis (pentafluorophenyl) borate: N-benzylpyridinium tetrakis (pentafluorophenyl) borate, N- (p-cyanobenzyl) pyridinium tetrakis (pentafluorophenyl) borate, N- (o-nitro) Benzyl) pyridinium tetrakis (pentafluorophenyl) borate, N- (p-acetylbenzyl)
Pyridinium tetrakis (pentafluorophenyl) borate, N- (9-anthrylmethyl) pyridinium tetrakis (pentafluorophenyl) borate, 4-cyano-1-benzylpyridinium tetrakis (pentafluorophenyl) borate and the like.

Examples of phenacylpyridinium tetrakis (pentafluorophenyl) borate: N-phenacylpyridiniumtetrakis (pentafluorophenyl) borate, N- (p-cyanophenacyl) pyridinium tetrakis (pentafluorophenyl) borate, N- (o
-Nitrophenacyl) pyridinium tetrakis (pentafluorophenyl) borate, N- (p-acetylphenacyl) pyridinium tetrakis (pentafluorophenyl) borate, N- (9-anthroylmethyl) pyridinium tetrakis (pentafluorophenyl) borate, 2-cyano-1-phenacylpyridinium tetrakis (pentafluorophenyl) borate and the like.

Examples of allylpyridinium tetrakis (pentafluorophenyl) borate: N-allylpyridinium tetrakis (pentafluorophenyl) borate, N
-(2-isopropyl-3,3-dicyano-2-propenyl) pyridinium tetrakis (pentafluorophenyl) borate, N- (2-benzoyl-3,3-dicyano-2-propenyl) pyridinium tetrakis (pentafluorophenyl) borate Such.

Example of N-alkoxypyridinium tetrakis (pentafluorophenyl) borate: N-methoxypyridinium tetrakis (pentafluorophenyl)
Borate, 1-ethoxy-2-methylpyridinium tetrakis (pentafluorophenyl) borate, N- (2
-Chloroethoxy) pyridinium tetrakis (pentafluorophenyl) borate and the like.

Examples of N-aryloxypyridinium tetrakis (pentafluorophenyl) borate: N-phenoxypyridiniumtetrakis (pentafluorophenyl) borate, N- (9-anthryloxy) pyridinium tetrakis (pentafluorophenyl) borate,
N- (p-tolyloxy) pyridinium tetrakis (pentafluorophenyl) borate and the like.

Examples of benzylquinolinium tetrakis (pentafluorophenyl) borate: N-benzylquinolinium tetrakis (pentafluorophenyl) borate, N- (p-cyanobenzyl) quinolinium tetrakis (pentafluorophenyl) borate, N- (o-nitrobenzyl) quinolinium tetrakis (pentafluorophenyl) borate, N- (p-acetylbenzyl)
Quinolinium tetrakis (pentafluorophenyl) borate, N- (9-anthrylmethyl) quinolinium tetrakis (pentafluorophenyl) borate, 2-cyano-1-benzylquinolinium tetrakis (pentafluorophenyl) borate and the like.

Examples of phenacylquinolinium tetrakis (pentafluorophenyl) borate: N-phenacylquinolinium tetrakis (pentafluorophenyl) borate, N- (p-cyanophenacyl) quinolinium tetrakis (pentafluorophenyl) borate, N − (O
-Nitrophenacyl) quinolinium tetrakis (pentafluorophenyl) borate, N- (p-isopropylphenacyl) quinolinium tetrakis (pentafluorophenyl) borate, N- (p-methoxycarbonylphenacyl) quinolinium tetrakis (Pentafluorophenyl) borate, N- (9-anthroylmethyl) quinolinium tetrakis (pentafluorophenyl) borate, 2-cyano-1-phenacylquinolinium tetrakis (pentafluorophenyl) borate and the like.

Examples of allylquinolinium tetrakis (pentafluorophenyl) borate: N-allylquinolinium tetrakis (pentafluorophenyl) borate, N
-(2-benzoyl-3,3-dicyano-2-propenyl) quinolinium tetrakis (pentafluorophenyl) borate, N- (2-hexyl-3,3-bis (methoxycarbonyl) -2-propenyl) quinoli And tetrakis (pentafluorophenyl) borate.

Examples of N-alkoxyquinolinium tetrakis (pentafluorophenyl) borate: N-methoxyquinolinium tetrakis (pentafluorophenyl)
Borate, N-isopropoxyquinolinium tetrakis (pentafluorophenyl) borate, 1-ethoxy-
2-methylquinolinium tetrakis (pentafluorophenyl) borate, N- (2-chloroethoxy) quinolinium tetrakis (pentafluorophenyl) borate and the like.

Examples of N-aryloxyquinolinium tetrakis (pentafluorophenyl) borate: N-phenoxyquinolinium tetrakis (pentafluorophenyl) borate, N- (2-naphthyloxy) quinolinium tetrakis (pentafluorophenyl) ) Borate, N
-(9-anthryloxy) quinolinium tetrakis (pentafluorophenyl) borate, N- (p-tolyloxy) quinolinium tetrakis (pentafluorophenyl) borate, N- (p-bromophenoxy) quinolinium tetrakis ( (Pentafluorophenyl) borate and the like.

Examples of benzylisoquinolinium tetrakis (pentafluorophenyl) borate: N-benzylisoquinolinium tetrakis (pentafluorophenyl)
Borate, N- (p-cyanobenzyl) isoquinolinium tetrakis (pentafluorophenyl) borate, N
-(O-nitrobenzyl) isoquinolinium tetrakis (pentafluorophenyl) borate, N- (9-anthrylmethyl) isoquinolinium tetrakis (pentafluorophenyl) borate, 1,2-dibenzylisoquinolinium Tetrakis (pentafluorophenyl) borate and the like.

Examples of phenacylisoquinolinium tetrakis (pentafluorophenyl) borate: N-phenacylisoquinolinium tetrakis (pentafluorophenyl) borate, N- (p-cyanophenacyl) isoquinolinium tetrakis (pentafluoro) Phenyl) borate, N- (p-acetylphenacyl) isoquinolinium tetrakis (pentafluorophenyl) borate, N
-(P-methoxycarbonylphenacyl) isoquinolinium tetrakis (pentafluorophenyl) borate,
N- (9-anthroylmethyl) isoquinolinium tetrakis (pentafluorophenyl) borate and the like.

Examples of allylisoquinolinium tetrakis (pentafluorophenyl) borate: N-allylisoquinolinium tetrakis (pentafluorophenyl) borate, N- (2-isopropyl-3,3-dicyano-2)
-Propenyl) isoquinolinium tetrakis (pentafluorophenyl) borate, N- (2-benzoyl-
3,3-dicyano-2-propenyl) isoquinolinium tetrakis (pentafluorophenyl) borate and the like.

Examples of N-alkoxyisoquinolinium tetrakis (pentafluorophenyl) borate: N-methoxyisoquinolinium tetrakis (pentafluorophenyl) borate, N-octadecyloxyisoquinolinium tetrakis (pentafluorophenyl) borate ,
N-isopropoxyisoquinolinium tetrakis (pentafluorophenyl) borate and the like.

Examples of N-aryloxyisoquinolinium tetrakis (pentafluorophenyl) borate:
Phenoxyisoquinolinium tetrakis (pentafluorophenyl) borate, N- (9-anthryloxy)
Isoquinolinium tetrakis (pentafluorophenyl) borate, N- (p-tolyloxy) isoquinolinium tetrakis (pentafluorophenyl) borate,
N- (p-hydroxyphenoxy) isoquinolinium tetrakis (pentafluorophenyl) borate and the like.

Examples of benzoxazolium tetrakis (pentafluorophenyl) borate: N-benzylbenzoxazolium tetrakis (pentafluorophenyl)
Borate, N- (p-cyanobenzyl) benzoxazolium tetrakis (pentafluorophenyl) borate, N-phenacylbenzoxazolium tetrakis (pentafluorophenyl) borate, N- (p-cyanophenacyl) benzoxazolium tetrakis (Pentafluorophenyl) borate, N-allylbenzoxazolium tetrakis (pentafluorophenyl) borate, N- (2-methyl-3,3-dicyano-2-propenyl) benzoxazolium tetrakis (pentafluorophenyl) borate N-methoxybenzoxazolium tetrakis (pentafluorophenyl) borate, N- (3-bromopropoxy) benzoxazolium tetrakis (pentafluorophenyl) borate, N
-Phenoxybenzoxazolium tetrakis (pentafluorophenyl) borate, N- (1-naphthyloxy) benzoxazolium tetrakis (pentafluorophenyl) borate, 2-mercapto-3-benzylbenzoxazolium tetrakis (pentafluorophenyl) ) Borates, 2-methylthio-3-benzylbenzoxazolium tetrakis (pentafluorophenyl) borate, and the like.

Examples of benzothiazolium tetrakis (pentafluorophenyl) borate: N-benzylbenzothiazolium tetrakis (pentafluorophenyl) borate, N- (p-cyanobenzyl) benzothiazolium tetrakis (pentafluorophenyl) Borate, N-
Phenacylbenzothiazolium tetrakis (pentafluorophenyl) borate, N- (p-cyanophenacyl) benzothiazolium tetrakis (pentafluorophenyl) borate, N-allylbenzothiazolium tetrakis (pentafluorophenyl) borate, N- (2
-Methyl-3,3-dicyano-2-propenyl) benzothiazolium tetrakis (pentafluorophenyl) borate, N-methoxybenzothiazolium tetrakis (pentafluorophenyl) borate, N- (3-bromopropoxy) benzothia Zolium tetrakis (pentafluorophenyl) borate, N-phenoxybenzothiazolium tetrakis (pentafluorophenyl) borate, N- (1-naphthyloxy) benzothiazolium tetrakis (pentafluorophenyl) borate, 2-
Mercapto-3-benzylbenzothiazolium tetrakis (pentafluorophenyl) borate, 2-methylthio-3-benzylbenzothiazolium tetrakis (pentafluorophenyl) borate and the like.

Examples of furyl or thienyliodonium tetrakis (pentafluorophenyl) borate: difuryliodonium tetrakis (pentafluorophenyl) borate, dithienyliodonium tetrakis (pentafluorophenyl) borate, bis (4,5-dimethyl-2-furyl) ) Iodonium tetrakis (pentafluorophenyl) borate, bis (5-chloro-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bioidonium tetrakis (pentafluorophenyl) borate, bis (5-acetyl-2-)
Furyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (5- (p-methoxyphenyl)
-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate and the like.

Examples of diaryliodonium tetrakis (pentafluorophenyl) borate: diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) iodonium Tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate and the like.

Examples of triarylsulfonium tetrakis (pentafluorophenyl) borate: triphenylsulfoniumtetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (2,6
-Dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like.

Examples of triarylsulfoxonium tetrakis (pentafluorophenyl) borate: triphenylsulfoxonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfoxonium tetrakis (pentafluorophenyl) borate, tris ( 2,6-dimethylphenyl) sulfoxonium tetrakis (pentafluorophenyl) borate, tris (p-cyanophenyl) sulfoxonium tetrakis (pentafluorophenyl) borate and the like.

Tetrakis [3,5-bis (trifluoromethyl) phenyl] borate

Benzylsulfonium tetrakis [3,5
Examples of -bis (trifluoromethyl) phenyl] borate: dimethyl (benzyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-bromobenzyl) sulfonium tetrakis [3,5-bis ( Trifluoromethyl) phenyl] borate, dimethyl (p-cyanobenzyl) sulfoniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (m-nitrobenzyl) sulfoniumtetrakis [3,5-bis (trifluoro Methyl) phenyl] borate, dimethyl (pentafluorophenylmethyl) sulfonium tetrakis [3
5-bis (trifluoromethyl) phenyl] borate,
Dimethyl (p- (trifluoromethyl) benzyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-methylsulfonylbenzyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl ] Borate, dimethyl (o-acetylbenzyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (o-benzoylbenzyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate Dimethyl (p-isopropylbenzyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-methoxybenzyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) Phenyl] borate, dimethyl (2-naphthylmethyl) sulfonium tetrakis [3,
5-bis (trifluoromethyl) phenyl] borate,
Dimethyl (9-anthrylmethyl) sulfoniumtetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, diethyl (benzyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, methylethyl (benzyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, methylphenyl (benzyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, diphenyl (benzyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Phenacylsulfonium tetrakis [3,
Examples of 5-bis (trifluoromethyl) phenyl] borate: dimethyl (phenacyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-cyanophenacyl) sulfonium tetrakis [3,5-bis ( Trifluoromethyl) phenyl] borate, dimethyl (m-nitrophenacyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p- (trifluoromethyl) phenacyl) sulfonium tetrakis [3,5 -Bis (trifluoromethyl) phenyl] borate, dimethyl (p-methylsulfonylphenacyl) sulfoniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (o-acetylphenacyl) sulfonium Tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (o
-Benzoylphenacyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-isopropylphenacyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p -Isopropoxycarbonylphenacyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (2-naphthoylmethyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (9-Anthroylmethyl)
Sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, diethyl (phenacyl)
Sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, methylethyl (phenacyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, methylphenyl (phenacyl) sulfonium tetrakis [3,5 -Bis (trifluoromethyl) phenyl] borate, diphenyl (phenacyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, tetramethylene (phenacyl) sulfonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate and the like.

Allylsulfonium tetrakis [3,5-
Examples of bis (trifluoromethyl) phenyl] borate:
Dimethyl (allyl) sulfonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, dimethyl (3,3-dicyano-2-propenyl) sulfoniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (2-methyl-3,3-dicyano -2-propenyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (2-benzoyl-3,3-dicyano-
2-propenyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (3,3-bis (methoxycarbonyl) -2-propenyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) Phenyl] borate and the like.

Alkoxysulfonium tetrakis [3,
Examples of 5-bis (trifluoromethyl) phenyl] borate: dimethyl (methoxy) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (ethoxy) sulfonium tetrakis [3,5-bis (trifluoro) Methyl) phenyl] borate, dimethyl (butoxy) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (isopropoxy) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, dimethyl (4-cyanobutoxy) sulfoniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Example of aryloxysulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: dimethyl (phenoxy) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, dimethyl (1-naphthyloxy) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (2-naphthyloxy) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl ( 9-anthryloxy) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-
Tolyloxy) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-bromophenoxy) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Examples of benzylsulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: dimethyl (benzyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl ( p-bromobenzyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-cyanobenzyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, Dimethyl (m
-Nitrobenzyl) sulfoxonium tetrakis [3,
5-bis (trifluoromethyl) phenyl] borate,
Dimethyl (pentafluorophenylmethyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p- (trifluoromethyl) benzyl) sulfoxonium tetrakis [3,5-bis (trifluoro Methyl) phenyl] borate, dimethyl (p-methylsulfonylbenzyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (o-acetylbenzyl) sulfoxonium tetrakis [3,5-bis (Trifluoromethyl) phenyl] borate, dimethyl (o-benzoylbenzyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-isopropylbenzyl) sulfoxonium tetrakis [ , 5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-methoxybenzyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (2-naphthylmethyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (9-anthrylmethyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl)
Phenyl] borate, diethyl (benzyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, methylethyl (benzyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate And methylphenyl (benzyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and diphenyl (benzyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

Examples of phenacylsulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: dimethyl (phenacyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (P-cyanophenacyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (m-nitrophenacyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate Dimethyl (p- (trifluoromethyl) phenacyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-methylsulfonylphenacyl) sulfoxonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, dimethyl (o-acetylphenacyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (o-benzoylphenacyl)
Sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-isopropylphenacyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p- Isopropoxycarbonylphenacyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (2
-Naphthoylmethyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (9-anthroylmethyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate , Diethyl (phenacyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, methylethyl (phenacyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, methylphenyl (Phenacyl) sulfoxonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, diphenyl (phenacyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, tetramethylene (phenacyl) sulfoxonium tetrakis [3,5-bis (tri Fluoromethyl) phenyl] borate and the like.

Allylsulfoxonium tetrakis [3,
Examples of 5-bis (trifluoromethyl) phenyl] borate: dimethyl (allyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (3,3-dicyano-2-propenyl)
Sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (2-methyl-3,3-dicyano-2-propenyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl)
Phenyl] borate, dimethyl (2-benzoyl-3,
3-dicyano-2-propenyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (3,3-bis (methoxycarbonyl) -2-propenyl) sulfoxonium tetrakis [3 5-bis (trifluoromethyl) phenyl] borate and the like.

Examples of alkoxysulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: dimethyl (methoxy) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl ( Ethoxy) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (butoxy) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (isopropoxy) sulfo Oxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (4-cyanobutoxy) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Examples of aryloxysulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: dimethyl (phenoxy) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (1 naphthyloxy) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (2-naphthyloxy) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (9-anthryloxy) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dimethyl (p-tolyloxy) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate The Chill (p- bromophenoxy) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Benzylphosphonium tetrakis [3,5
Examples of -bis (trifluoromethyl) phenyl] borate: trimethylbenzylphosphonium tetrakis [3,
5-bis (trifluoromethyl) phenyl] borate,
Triethylbenzylphosphonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, triphenylbenzylphosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenyl (p-cyanobenzyl) phosphonium tetrakis [3,5-bis (trifluoromethyl ) Phenyl] borate, triphenyl (m-nitrobenzyl) phosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenyl (1-naphthylmethyl) phosphonium tetrakis [3,5-bis (trifluoromethyl) ) Phenyl] borate, triphenyl (9-
Anthrylmethyl) phosphonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate and the like.

Phenacylphosphonium tetrakis [3,
Examples of 5-bis (trifluoromethyl) phenyl] borate: triethylphenacylphosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenylphenacylphosphonium tetrakis [3,5-bis (trifluoromethyl) ) Phenyl] borate, triphenyl (p-cyanophenacyl) phosphoniumtetrakis [3,5-bis (trifluoromethyl)
Phenyl] borate, triphenyl (m-nitrophenacyl) phosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenyl (1
-Naphthaloylmethyl) phosphonium tetrakis [3,
5-bis (trifluoromethyl) phenyl] borate,
Triphenyl (9-anthroylmethyl) phosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Allylphosphonium tetrakis [3,5-
Examples of bis (trifluoromethyl) phenyl] borate:
Triphenylallylphosphonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, triphenyl (3,3-dicyano-2-propenyl) phosphoniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenyl (2-phenyl-3,3 -Dicyano-2-propenyl) phosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

The alkoxyphosphonium tetrakis [3,
Examples of 5-bis (trifluoromethyl) phenyl] borate: triphenylmethoxyphosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenylisopropoxyphosphonium tetrakis [3,5-bis (trifluoromethyl) ) Phenyl]
Borate, triphenyl (2-chloroethoxy) phosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Examples of aryloxyphosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: triphenylphenoxyphosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, triphenyl (9-anthryloxy) phosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenyl (p-tolyloxy) phosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] Borate, triphenyl (p
-Hydroxyphenoxy) phosphonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Benzylpyridinium tetrakis [3,5
Examples of -bis (trifluoromethyl) phenyl] borate: N-benzylpyridiniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N-
(P-cyanobenzyl) pyridinium tetrakis [3,
5-bis (trifluoromethyl) phenyl] borate,
N- (o-nitrobenzyl) pyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-acetylbenzyl) pyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (9-anthrylmethyl) pyridinium tetrakis [3,5-bis (trifluoromethyl)
Phenyl] borate, 4-cyano-1-benzylpyridiniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Phenacylpyridinium tetrakis [3,
Example of 5-bis (trifluoromethyl) phenyl] borate: N-phenacylpyridinium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, N-
(P-cyanophenacyl) pyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (o-nitrophenacyl) pyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (P-acetylphenacyl) pyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (9-anthroylmethyl) pyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2-cyano-1-phenacylpyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Allylpyridinium tetrakis [3,5-
Examples of bis (trifluoromethyl) phenyl] borate:
N-allylpyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (2-isopropyl-3,3-dicyano-2-propenyl) pyridinium tetrakis [3,5-bis (trifluoromethyl) Phenyl] borate, N- (2-benzoyl-3,
3-dicyano-2-propenyl) pyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Examples of N-alkoxypyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: N-methoxypyridinium tetrakis [3
5-bis (trifluoromethyl) phenyl] borate,
1-ethoxy-2-methylpyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (2-chloroethoxy) pyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate and so on.

Examples of N-aryloxypyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: N-phenoxypyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (9 -Anthryloxy) pyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-tolyloxy) pyridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Benzylquinolinium tetrakis [3,5
Examples of -bis (trifluoromethyl) phenyl] borate: N-benzylquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N-
(P-cyanobenzyl) quinolinium tetrakis [3,
5-bis (trifluoromethyl) phenyl] borate,
N- (o-nitrobenzyl) quinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-acetylbenzyl) quinolinium tetrakis [3,5-bis (trifluoromethyl) Phenyl] borate, N- (9-anthrylmethyl) quinolinium tetrakis [3,5-bis (trifluoromethyl)
Phenyl] borate, 2-cyano-1-benzylquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Phenacylquinolinium tetrakis [3,
Example of 5-bis (trifluoromethyl) phenyl] borate: N-phenacylquinolinium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, N-
(P-cyanophenacyl) quinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (o-nitrophenacyl) quinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] Borate, N- (p-isopropylphenacyl) quinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-methoxycarbonylphenacyl) quinolinium tetrakis [3,5-bis (Trifluoromethyl) phenyl] borate, N-
(9-Anthroylmethyl) quinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2-cyano-1-phenacylquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate and so on.

Allylquinolinium tetrakis [3,5-
Examples of bis (trifluoromethyl) phenyl] borate:
N-allylquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (2-benzoyl-3,3-dicyano-2-propenyl) quinolinium tetrakis [3,5-bis ( Trifluoromethyl) phenyl] borate, N- (2-hexyl-3,3
-Bis (methoxycarbonyl) -2-propenyl) quinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Example of N-alkoxyquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: N-methoxyquinolinium tetrakis [3
5-bis (trifluoromethyl) phenyl] borate,
N-isopropoxyquinolinium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, 1-
Ethoxy-2-methylquinolinium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, N
-(2-chloroethoxy) quinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Examples of N-aryloxyquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: N-phenoxyquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate; N- (2-naphthyloxy) quinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, N- (9-anthryloxy) quinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-tolyloxy) quinolinium tetrakis [3,5-bis (trifluoro Methyl) phenyl] borate, N- (p-bromophenoxy) quinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Examples of benzylisoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: N-benzylisoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N -(P-cyanobenzyl) isoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (o-nitrobenzyl) isoquinolinium tetrakis [3,5-bis (trifluoromethyl ) Phenyl] borate, N- (9-anthrylmethyl) isoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 1,2-dibenzylisoquinolinium tetrakis [3,5- Bis (trifluoromethyl) phenyl] borate and the like.

Examples of phenacylisoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: N-phenacylisoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate N- (p-cyanophenacyl) isoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-acetylphenacyl) isoquinolinium tetrakis [3,5-bis (tri Fluoromethyl) phenyl] borate, N- (p-methoxycarbonylphenacyl) isoquinolinium tetrakis [3,
5-bis (trifluoromethyl) phenyl] borate,
N- (9-anthroylmethyl) isoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Allylisoquinolinium tetrakis [3,
Example of 5-bis (trifluoromethyl) phenyl] borate: N-allylisoquinolinium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, N-
(2-isopropyl-3,3-dicyano-2-propenyl) isoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (2-benzoyl-3,3-dicyano-2- And propenyl) isoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

Examples of N-alkoxyisoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: N-methoxyisoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate , N-octadecyloxyisoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, N-isopropoxyisoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate and so on.

Example of N-aryloxyisoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: N-phenoxyisoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] Borate, N- (9-anthryloxy) isoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-tolyloxy) isoquinolinium tetrakis [3,5-bis ( Trifluoromethyl) phenyl] borate, N- (p-hydroxyphenoxy) isoquinolinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Benzoxazolium tetrakis [3,5
Examples of -bis (trifluoromethyl) phenyl] borate: N-benzylbenzoxazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-cyanobenzyl) benzoxazolium tetrakis [ 3,5-bis (trifluoromethyl) phenyl] borate, N-phenacylbenzoxazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-cyanophenacyl) benzoxazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N-allylbenzoxazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (2-methyl-3,
3-dicyano-2-propenyl) benzoxazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N-methoxybenzoxazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate , N- (3-bromopropoxy) benzoxazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N-phenoxybenzoxazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] Borate, N- (1-naphthyloxy) benzoxazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2-mercapto-3-benzylbenzoxazolium tetrakis [3,5-bis (tri Fluoromethyl) phenyl] borate, 2-methylthio Benzyl-benzoxazolium tetrakis [3,5-bis (trifluoromethyl)
Phenyl] borate and the like.

Benzothiazolium tetrakis [3,5-
Examples of bis (trifluoromethyl) phenyl] borate:
N-benzylbenzothiazolium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, N-
(P-cyanobenzyl) benzothiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N-phenacylbenzothiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-cyanophenacyl) benzothiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N-allylbenzothiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (2-methyl-3,3-dicyano-
2-propenyl) benzothiazolium tetrakis [3,
5-bis (trifluoromethyl) phenyl] borate,
N-methoxybenzothiazolium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, N-
(3-bromopropoxy) benzothiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N-phenoxybenzothiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N -(1-Naphthyloxy) benzothiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2-mercapto-3-benzylbenzothiazolium tetrakis [3,5-bis (trifluoromethyl) Phenyl] borate, 2-methylthio-3-benzylbenzothiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Examples of furyl or thienyl iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: difuryl iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, dithienyl iodonium tetrakis [3 , 5-Bis (trifluoromethyl) phenyl] borate, bis (4,5-dimethyl-2-furyl) iodoniumtetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, bis (5-chloro-2-thienyl) iodoniumtetrakis [3,5-bis (trifluoromethyl)
Phenyl] borate, biodonium tetrakis [3,
5-bis (trifluoromethyl) phenyl] borate,
Bis (5-acetyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, bis (5- (p-methoxyphenyl) -2-
Thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Diaryliodonium tetrakis [3,
Examples of 5-bis (trifluoromethyl) phenyl] borate: diphenyliodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (p
-Octadecylphenyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (p-octadecyloxyphenyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, phenyl (p- Octadecyloxyphenyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Examples of triarylsulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: triphenylsulfonium tetrakis [3,3
5-bis (trifluoromethyl) phenyl] borate,
Tris (p-tolyl) sulfonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, tris (2,6-dimethylphenyl) sulfoniumtetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, tris (p-cyanophenyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Examples of triarylsulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate: triphenylsulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, tris (p -Tolyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, tris (2,6-dimethylphenyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, Tris (p-cyanophenyl) sulfoxonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

Further, onium borate complexes represented by the following chemical formulas are also preferred examples.

[0200]

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[0201]

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The energy-sensitive acid generator (A) of the present invention
Is characterized by being easily decomposed by irradiation with energy rays, particularly light, to generate a strong acid. The acids generated here are BF ₄ ⁻ , PF ₆ ⁻ , A
It is considered to be a stronger acid than onium salts having anions such as sF ₆ ⁻ and SbF ₆ ⁻ . In addition, it is characterized in that no acid remains by heating after being decomposed to generate an acid.

Further, the onium borate complex which is the energy-sensitive acid generator (A) of the present invention has a high electron-accepting property and is easily decomposed by irradiation with energy rays. To give high sensitivity. The electron-accepting properties of these onium borate complexes can be explained by a reduction potential determined by an electrochemical measurement method such as polarography or cyclic voltammetry. Note that the reduction potential of the onium borate complex described in this specification is determined by Journal of Polymer Science, Inc.
Part A Polymer Chemistry (J. Polym.
Sci. , A, Polym. Chem. ), Volume 28,
3137 (1990) and the Journal of American Chemical Society (J. Am. Che
m. Soc. 106, 4121 (1984).
Year), it can be easily measured.

Further, the energy-sensitive linear acid generator of the present invention
(A) shows a conventionally known BF_Four ^-, PF₆ ^-, As
F₆ ^-, SbF₆ ^-Onium salts with anions such as
Rather than various organic solvents, polymers and oligomers
Extremely high compatibility and solubility.

Next, the energy-sensitive base generator (B) used in the present invention will be described. The suitable energy-sensitive base generator (B) that can be used in the present invention includes:
A compound that generates an amine upon irradiation with energy rays, and examples thereof include compounds represented by the following general formulas (14) to (22).

Formula (14): Benzyl carbamates(Where R^AIs a hydrogen atom or a substitution having 1 to 18 carbon atoms
An alkyl group which may be^BHas 1 to 1 carbon atoms
18 optionally substituted alkyl groups or aromatic rings
Represents an optionally substituted aryl group having 6 to 20 carbon atoms
Then R^CAnd R ^DEach independently has 1 to 18 carbon atoms
An optionally substituted alkyl group or an aromatic ring carbon
Represents an aryl group which may be substituted, represented by Formulas 6 to 20,
Ar ′ may be substituted with 6 to 20 aromatic ring carbon atoms.
Indicates an aryl group. )

Formula (15): Carbamates (Wherein, R ^A represents a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, and R ^B represents
An optionally substituted alkyl group having 18 or an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms, wherein R ^C is an optionally substituted alkyl group having 1 to 18 carbon atoms, or The following is an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms. )

General formula (16): Benzoin carbamates (Wherein, R ^A represents a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, and R ^B represents
18 represents an optionally substituted alkyl group or an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms, and Ar ′ represents an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms. , Ar ″ represents an optionally substituted arylene group having 6 to 20 aromatic ring carbon atoms.)

Formula (17): o-carbamoylhydro
Xyamines(Where R^AIs a hydrogen atom or a substitution having 1 to 18 carbon atoms
An alkyl group which may be^BHas 1 to 1 carbon atoms
18 optionally substituted alkyl groups or aromatic rings
Represents an optionally substituted aryl group having 6 to 20 carbon atoms
Then R^CAnd R ^DEach independently has 1 to 18 carbon atoms
An optionally substituted alkyl group or an aromatic ring carbon
Represents an optionally substituted aryl group represented by Formulas 6 to 20:
You. )

Formula (18): o-carbamoyl oximes (Wherein, R ^A represents a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, and R ^B represents
An optionally substituted alkyl group of 18 or an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms, wherein R ^C and R ^D each independently represent 1 to 18 carbon atoms;
Or an optionally substituted alkyl group or an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms. )

Formula (19): Aromatic sulfonamides (Wherein, R ^A represents a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, and R ^B represents
18 represents an optionally substituted alkyl group or an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms, and Ar ′ represents an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms. Is shown. )

Formula (20): Alpha-lactones (Wherein, R ^B represents an aryl group which may be substituted having 6 to 20 of the optionally substituted alkyl group or an aromatic ring carbon atoms, having 1 to 18 carbon atoms, R ^C is 1 to carbon atoms 18
Or an optionally substituted alkyl group or an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms. )

Formula (21): N- (2-arylethenyl) amides (Wherein, R ^C and R ^D are each independently a group having 1 to 1 carbon atoms.
18 represents an optionally substituted alkyl group, an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms,
r ′ represents an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms. )

Formula (22): Amides (In the formula, Ar ′ represents an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms.)

Here, the general formulas (14) to (2)
Each substituent shown in 2) will be described. First, the alkyl group which may be substituted having 1 to 18 carbon atoms includes fluorine, chlorine, bromine, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, and a carbon number which may be substituted with an azide group. Examples thereof include linear, branched, and cyclic alkyl groups of 1 to 18, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl groups. Octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, cyclopentyl, cyclohexyl, 4-decylcyclohexyl, fluoromethyl, chloromethyl, bromomethyl, trifluoromethyl, trichloromethyl Group, tribromomethyl group, hydroxymethyl group, carboxymethyl group, mercaptomethyl group, cyanomethyl Group, nitromethyl group, azidomethyl group, and the like.

Examples of the optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms include fluorine, chlorine, bromine,
A hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, a monocyclic or condensed polycyclic aryl group having 6 to 20 aromatic ring carbon atoms which may be substituted with an azide group, and specifically, phenyl Group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2
-Azulenyl group, 1-acenaphthyl group, 9-fluorenyl group, o-tolyl group, m-tolyl group, p-tolyl group,
2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group and the like.

The optionally substituted arylene group having 6 to 20 aromatic ring carbon atoms may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide. And a monocyclic or condensed polycyclic arylene group having 6 to 20 carbon atoms of an aromatic ring which may be mentioned. Specific examples include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group. 1,4-naphthylene group, 2,6-naphthylene group, 9,10-anthrylene group, 1,2-acenaphthylene group, 4,4′-biphenylene group, 3-fluoro-1,2-phenylene group, 2- Bromo-1,4-phenylene group and the like.

These energy-sensitive base generators (B)
The amine evolved from is desirably of a structure sufficient to prevent substantial loss of the amine by evaporation during the heating step, and has a boiling point at normal pressure of 60 ° C or higher, preferably 80 ° C.
It is desirable that the temperature is not less than ° C. As such a method,
It is preferable to adopt a method such as an amine compound having 4 or more carbon atoms or a high molecular weight amine.

Preferred examples of the energy-sensitive base generator (B) include compounds having the following structures.

[0220]

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As exemplified below, the energy-sensitive base generator (B) used in the present invention may be a polymer compound.

[0222]

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Further, as exemplified below, dendrimers, which are starburst oligomers produced by a Michael addition reaction of a diamine and an acrylate ester, can also be used as the energy-sensitive base generator (B).

[0224]

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The above-mentioned energy-sensitive base generator (B)
Is, for example, J.I. F. Cameron et al. M. J.
Frechet, J.A. Photochem. Photo
biol. , A: Chem. 59, 105 (1
991); F. Cameron et al. Am. C
hem. Soc. 113, p. 4303 (1991).
Year), J.M. F. Cameron et al. Org. Che
m. 55, 5919 (1990); E. FIG.
Beecher et al., Polym. Mat. Sci. En
g. 64, 71 (1991); M. J.
Frechet et al., Polym. Bull. Thirtieth
Volume, p. 369 (1993), C.I. Kutal et al.
Electrochem. Soc. , Vol. 134, 22
It can be obtained by referring to a method described in a known document such as page 80 (1987). Furthermore, Yoshida et al., 4th Polymer Material Forum, p. 105 (199)
5 years) can also be used as the energy-sensitive base generator (B).

Next, the energy-sensitive acid generator (A) of the present invention can be further combined with a sensitizer (C) shown below to further enhance the activity against energy rays or to increase the photosensitive wavelength region to longer wavelengths. It becomes possible to make it. The sensitizer (C) mentioned here exchanges energy or electrons with the energy-sensitive acid generator (A) by the action of energy rays, and the energy-sensitive acid generator (A) It promotes decomposition.

Specific examples of these sensitizers (C) include condensed polycyclic aromatic derivatives such as naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, naphthacene derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, benzothiazoles Derivatives, chalcone derivatives, unsaturated ketones represented by dibenzalacetone, etc .; 1,2 represented by benzyl, camphorquinone, etc.
-Polymethine dyes such as diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and acridine derivatives , Azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative,
Tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative,
Tetraazaporphyrazine derivative, tetraquinoxaliloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative,
Examples include spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, and the like. More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al. "Functional Dye Chemistry" (CMC, 1981), edited by Chusaburo Ikemori et al., "Special Functional Materials" (19
1986, CMC), but are not limited thereto.
Dyes and sensitizers that absorb light in the ultraviolet to near-infrared region may be mentioned, and if necessary, two or more of them may be used in any ratio.

Of these sensitizers (C), particularly preferred are anthracene derivatives, benzophenone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, styryl derivatives, and cyanine derivatives. , Acridine derivatives, porphyrin derivatives, pyrylium derivatives, thiopyrylium derivatives.

As specific examples of these, anthracene,
1-anthracenecarboxylic acid, 2-anthracenecarboxylic acid, 9-anthracenecarboxylic acid, 9-anthracealdehyde, 9,10-bis (chloromethyl) anthracene, 9,10-bis (phenylethynyl) anthracene, 9-bromoanthracene, 1-chloro-9,10-
Bis (phenylethynyl) anthracene, 9-chloromethylanthracene, 9-cyanoanthracene, 9,10
-Dibromoanthracene, 9,10-dichloroanthracene, 9,10-dicyanoanthracene, 9,10-dimethylanthracene, 9,10-dibutylanthracene, 9,10-diphenylanthracene, 9,10-di-p-tolylanthracene, 9,10-bis (p-methoxyphenyl) anthracene, 2-hydroxymethylanthracene, 9-hydroxymethylanthracene, 9-
Methyl anthracene, 9-phenylanthracene, 9,
10-dimethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenoxyanthracene,
Sodium 9,10-dimethoxyanthracene-2-sulfonate, 1,4,9,10-tetrahydroxyanthracene, 2,2,2-trifluoro-1- (9-anthryl) ethanol, 1,8,9-trihydroxy Anthracene, 1,8-dimethoxy-9,10-bis (phenylethynyl) anthracene, and
No. 7106, 9-vinylanthracene, 9-anthracenemethanol, anthracene derivatives such as trimethylsiloxyether of 9-anthracenemethanol,
Examples include acridine derivatives such as acridine orange, benzoflavin, acridine yellow, and phosphine R, and benzothiazole derivatives such as setoflavin T.

Next, the acid-curable compound (D) used in the present invention will be described. Here, the acid-curable compound (D) is a compound which can be converted into a high molecular weight substance by polymerization or cross-linking reaction by the action of actinic rays in the presence of the active ray-sensitive acid generator composition in the present specification. Which includes the following compounds or mixtures thereof.

First, a compound which has a high molecular weight by a crosslinking reaction or a polymerization reaction in the presence of an acid catalyst or in combination with heating is mentioned as the acid-curable compound (D). A typical example is a compound having a structure represented by the following general formula (23) as a compound having a methylol group as a formaldehyde precursor or a substituted methylol group. General formula (23) (QOCH ₂ ) _r -A- (CH ₂ OQ ′) _s [In the above general formula (23), A is a group represented by G or GH-G, and G is substituted or It means an unsubstituted mononuclear or condensed polynuclear aromatic hydrocarbon group, or an oxygen, sulfur or nitrogen-containing heterocyclic group. H is a single bond or an alkylene group which may have a substituent group having 1 to 4 carbon atoms, arylene group which may have a substituent, arylalkylene group or -O, -, - S -, - SO 2 - , -CO-, -CO
O-, -OCOO-, -CONH-, and an alkylene group which may have a substituent partially having these bonds are meant. Z ′ may be a polymer such as a phenolic resin.] Q and Q ′ are, independently of each other, hydrogen, carbon number 1-4.
Means an alkyl group, a cycloalkyl group, an aryl group which may have a substituent, an arylalkyl group, or an acyl group. r is an integer of 1 to 3, and s is an integer of 0 to 3.

Here, G or H in the general formula (23) is used.
Substituted or unsubstituted mononuclear or fused polynuclear
Examples of the aromatic hydrocarbon group include an o-phenylene group and an m-phenyl group.
Nylene group, p-phenylene group, 4-methyl-1,2-phenyl
Phenylene group, 4-chloro-1,2-phenylene group, 4-
Hydroxy-1,2-phenylene group, 2-methyl-1,
4-phenylene group, p, p'-biphenylylene group, 1,
2-naphthylene group, 9,10-anthrylene group, 2,7
-When phenanthrylene groups and the like contain oxygen, sulfur, and nitrogen
Examples of the cyclic group include a 2,5-furylene group and a 2,5-thienyl group.
Ene group, 2,4-oxazolylene group, 2,4-thiazolyl
Len group, 2,5-benzofurylene group, 2,5-benzothiene
Enylene group, 2,6-pyridylene group, 5,8-quinolylene
Wherein the alkyl group may have a substituent having 1 to 4 carbon atoms
Methylene, ethylene, and trimethylene
Group, tetramethylene group, propylene group, ethylmethyl
Group, chloromethylene group, dimethylmethylene group, bis
(Trifluoromethyl) methylene group etc. has a substituent
The arylene group which may be used includes an o-phenylene group, m
-Phenylene group, p-phenylene group, 4-methyl-1,
2-phenylene group, 4-chloro-1,2-phenylene
Group, 4-hydroxy-1,2-phenylene group, 2-methyl
1,4-phenylene group, p, p'-biphenylylene
Group, 1,2-naphthylene group, 9,10-anthrylene
Group, 2,7-phenanthrylene group, etc.
As the len group, a benzylidene group, p-tolylmethylene
Group, 2-naphthylmethylene group, etc.
O-, -S-, -SO_Two-, -CO-, -COO-,-
An arrangement having a part of an OCOO- or -CONH- bond
As the alkylene group which may have a substituent, methylenedi
Oxy group, ethylenedioxy group, propylenedioxy
Group, diethylenedioxy group, triethylenedioxy group,
Methylenedithio, ethylenedithio, propylenedithio
O, diethylenedithio, triethylenedithio,
Tylene disulfonyl group, ethylene disulfonyl group, malo
Nil group, succinyl group, glutaryl group, adipoyl group,
-OOC-CH_Two-COO- group, -OOC- (CH_Two)
_Two-COO- group, -CH_Two-OCOO-CH _Two-Group,-
CH_Two-(OCOO-CH_Two)_Two-Groups and the like.

The alkyl group having 1 to 4 carbon atoms represented by Q and Q ′ in the general formula (23) is a methyl group,
An ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and an aryl which may have a substituent; Examples of the group include a phenyl group, p-tolyl group, xylyl group, mesityl group, cumenyl group, p-methoxyphenyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, p-cyanophenyl group, p-nitrophenyl group ,
3,5-bis (trifluoromethyl) phenyl group, p-
Examples of a fluorophenyl group, a p-chlorophenyl group, a p-dimethylaminophenyl group, a p-phenylthiophenyl group, and the like include, as an arylalkyl group, a benzyl group, a 2-naphthylmethyl group, a 9-anthrylmethyl group, a phenylyl group, Examples of a styryl group, a cinnamyl group, and an acyl group include an acetyl group, a hexanoyl group, a benzoyl group, a cyclohexanoyl group, a methoxalyl group, and a salicyloyl group.

Specific examples of such an acid-curable compound (D) include various aminoplasts or phenoplasts, that is, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, glycoluril-formaldehyde resins, and the like. There are monomers or oligomers. Many of these are commercially available for applications such as vehicles for paints. For example, Cymel manufactured by American Cyanamid
(Registered trademark) 300, 301, 303, 350, 37
0, 380, 1116, 1130, 1123, 112
5, 1170, etc., or Nikarac (registered trademark) Mw30, Mw 30M, Mw30HM, manufactured by Sanwa Chemical Co., Ltd.
Series such as Mx45 and Bx4000 can be mentioned as typical examples. These may be used alone or in combination of two or more.

Further, a specific example of another acid-curable compound (D) is a phenol derivative which is methylolated or alkoxydimethylated so as to be a formaldehyde precursor. These may be used as a monomer or may be used as a resin such as a resole resin or a benzyl ether resin.

Further, as another system of the acid-curable compound (D), a compound having a silanol group, for example,
And compounds disclosed in JP-A-154266 and JP-A-2-173647.

Also, a mixture of a polyene and a polythiol,
For example, as polyene, diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl carbonate, triallyl isocyanurate, urethane-based polyene produced from polyisocyanate and allyl alcohol (for example, obtained by polycondensation reaction of hexamethylene diisocyanate and allyl alcohol) A mixture of a compound selected from, for example, a urethane compound) and a compound selected from, for example, trimethylolpropanetrithiol glycolate, pentaerythritol-tetra-3-mercaptopropionate as a polythiol, and an acid-curable compound. (D).

Also, the following alkoxysilanes can be mentioned as the acid-curable compound (D). Specific examples include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyl Trimethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, γ-
Compounds having an alkoxysilyl group such as methacryloxypropylmethyldimethoxysilane, more specifically, a product catalog of Dow Corning Toray, page 59 or
"Silane coupling agent" described in Shin-Etsu silicone silane coupling agent product catalog (issued in September 1987)
Alternatively, Toray Dow Corning's product catalog, page 61 or Toshiba Silicone's general catalog, page 27 (1
Compounds having an alkoxysilyl group known in the industry as “silane compounds” described in “April 986)” can be mentioned as alkoxysilanes.

Further, as the acid-curable compound (D), a cationically polymerizable compound or a mixture thereof can be mentioned. The compound capable of cationic polymerization referred to herein includes, for example, epoxy compounds, styrenes, vinyl compounds, vinyl ethers, spiroorthoesters, bicycloorthoesters, spiroorthocarbonates,
Examples include cyclic ethers, lactones, oxazolines, aziridines, cyclosiloxanes, ketals, cyclic acid anhydrides, lactams and aryl dialdehydes.

First, examples of the epoxy compound include conventionally known aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, epoxide monomers and episulfite monomers. Examples of the aromatic epoxy compound include a monofunctional epoxy compound such as phenylglycidyl ether and a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, such as bisphenol A. Glycidyl ethers produced by reacting a bisphenol compound such as tetrabromobisphenol A, bisphenol F, bisphenol S or an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of a bisphenol compound with epichlorohydrin;
Novolak type epoxy resins (for example, phenol novolak type epoxy resin, cresol novolak type epoxy resin, brominated phenol novolak type epoxy resin, etc.), trisphenol methane triglycidyl ether and the like.

Examples of the alicyclic epoxy compound include 4-vinylcyclohexene monoepoxide, norbornene monoepoxide, limonene monoepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis- (3,4 -Epoxycyclohexylmethyl) adipate, 2- (3,4-
Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, 2-
(3,4-epoxycyclohexyl-5,5-spiro-
3,4-epoxy) cyclohexane-meta-dioxane, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane, BHP
E-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin (softening point: 71 ° C.)) and the like.

As the aliphatic epoxy compound, for example, 1,4-butanediol dicricidyl ether, 1,6
-Hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, propylene glycol monoglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether , Neopentyl glycol monoglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether,
Examples include trimethylolpropane monoglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and the like.

Examples of the styrenes include styrene, α-methylstyrene, p-methylstyrene, p-chloromethylstyrene and the like. Examples of the vinyl compound include N-vinylcarbazole, N-vinylpyrrolidone, and the like.

As the vinyl ethers, for example, n-
(Or iso-, t-) butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 1,4 butanediol divinyl ether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, propylene Glycol divinyl ether, propylene glycol monovinyl ether, neopentyl glycol divinyl glycol, neopentyl glycol monovinyl glycol, glycerol divinyl ether, glycerol trivinyl ether, trimethylol propane monovinyl ether, trimethylol propane divinyl ether, trimethylol propane trivinyl ether, diglycerol Li ether, sorbitol tetravinyl ether, cyclohexanedimethanol divinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether 2,2-bis (4-cyclohexanol) propane divinyl ether, 2,2-bis (4
-Cyclohexanol) alkyl vinyl ethers such as trifluoropropane divinyl ether, alkenyl vinyl ethers such as allyl vinyl ether, alkynyl vinyl ethers such as ethynyl vinyl ether, 1-methyl-2-propenyl vinyl ether, 4-vinyl ether styrene, hydroquinone divinyl ether, phenyl Aryl vinyl ethers such as vinyl ether, p-methoxyphenyl vinyl ether, bisphenol A divinyl ether, tetrabromobisphenol A divinyl ether, bisphenol F divinyl ether, phenoxyethylene vinyl ether, p-bromophenoxyethylene vinyl ether, and 1,4-benzenedimethanol divinyl ether , Nm-chlorophenyldiethanol alcohol Nji ether, m- phenylene bis (ethylene glycol) aralkyl divinyl et one ether such as divinyl ether, urethane polyvinyl ether (e.g., ALLIED-SIGNAL Inc., V
ECtomer 2010).

The spiro orthoesters include 1,1
4,6-trioxaspiro (4,4) nonane, 2-methyl-1,4,6-trioxaspiro (4,4) nonane,
1,4,6-Trioxaspiro (4,5) decane and the like, and bicycloorthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo (2,5
2,2) octane, 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo (2,2,2) octane and the like include spiroorthocarbonates,
Cyclic ethers such as 1,5,7,11-tetraoxaspiro (5,5) undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro (5,5) undecane Is raised.

Examples of the cyclic ethers include oxetanes such as oxetane and phenyloxetane; tetrahydrofurans such as tetrahydrofuran and 2-methyltetrahydrofuran; tetrahydropyrans such as tetrahydropyran and 3-propyltetrahydropyran; trimethylene oxide; and s-trioxane. And so on. Lactones include β-propiolactone, γ-
Butyl lactone, δ-caprolactone, δ-valerolactone and the like can be mentioned. Examples of the oxazolines include oxazoline, 2-phenyloxazoline, 2-decyloxazoline and the like.

As the aziridine, aziridine, N-
Ethyl aziridine and the like. Examples of cyclosiloxanes include hexamethyltrisiloxane, octamethylcyclotetrasiloxane, triphenyltrimethylcyclotrisiloxane, and the like. Ketals include 1,3-dioxolan, 1,3-dioxane,
2,2-dimethyl-1,3-dioxane, 2-phenyl-1,3-dioxane, 2,2-dioctyl-1,3-
Dioxolan and the like. The cyclic acid anhydrides include phthalic anhydride, maleic anhydride, succinic anhydride and the like, and the lactams include β-propiolactam, γ-butyrolactam, δ-caprolactam and the like.
Examples of the aryl dialdehydes include 1,2-benzenedicarboxaldehyde, 1,2-naphthalenedialdehyde, and the like.

Next, the base-curable compound (E) used in the present invention will be described. Examples of the base-curable compound (E) in the present invention include compounds that undergo a curing or cross-linking reaction upon reaction with an amine generated from the energy-sensitive base generator (B) used in the present invention.

Accordingly, as the base-curable compound (E), the epoxy compounds exemplified above as the acid-curable compound (D) can be mentioned. ) Can be suitably used. In particular, in the present invention, the amine generated from the energy-sensitive base generator (B) further increases the polymerization rate, that is, the gelation rate of the crosslinked or polymerized epoxy compound by the energy-sensitive acid generator (A). Becomes possible. That is, after the polymerization or cross-linking reaction of the epoxy compound is caused by the acid generated from the energy-sensitive acid generator (A) used in the present invention, the amine is then generated from the energy-sensitive base generator (B), Further, the polymerization or crosslinking reaction can be caused more strongly. At this time, the energy-sensitive acid generator (A) used in the present invention
Has the property that the function as an acid generator is deactivated by heating, so that the heating of the energy-sensitive base generator (B) before the irradiation with energy rays does not inhibit the reaction of the basic compound. This can be achieved only by using the energy-sensitive linear acid generator (A) of the present invention.

Other base-curable compounds (E) include isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, water-added xylylene diisocyanate, hexamethylene diisocyanate, diisocyanomethylnorbornene, paraphenylene diisocyanate, and tetramethyl xylylene diisocyanate. Isocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, 2-
Chloro-1,4-phenyldiisocyanate, 1,5-
Naphthalene diisocyanate, diphenylmethane diisocyanate, 3,3-dimethyl-4,4-biphenylene diisocyanate, 3,3-dimethyl-4,4-diphenylmethane diisocyanate, 3,3-dimethoxy-4,
4-biphenylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethyl Aliphatic, alicyclic, or aromatic isocyanate compounds such as hexanemethylene diisocyanate, blocked polyisocyanate, and
It is possible to use a terminal isocyanate oligomer or polymer obtained from a polyol, a polyether polyol or a polyester polyol and a polyisocyanate compound.

Further, compounds which cross-link with amines, such as chloroprene rubber, epichlorohydrin rubber, polyvinyl chloride, polyvinylidene chloride, poly (vinylidene chloride) described in Shinzo Yamashita et al., Handbook of Crosslinking Agents, p34 (Taiseisha) / Acrylonitrile) copolymer, chlorine-based polymer such as poly (vinyl chloride / β-chloroethyl vinyl ether) copolymer, vinylidene fluoride / perfluoropropylene copolymer, Lumiflon (manufactured by Asahi Glass Co., Ltd.), Cefral Coat (Central Glass Co., Ltd.) Polymer), chlorosulfonated polyethylene, carboxyl group-containing polymers such as (meth) acrylic acid and copolymers thereof with (meth) acrylate, and acid anhydrides such as styrene / maleic anhydride copolymer Cross-linking with amines such as polymers Can be mentioned the resulting can compound the present invention is not limited thereto.

When the curable sensitive composition of the present invention is in a liquid state at room temperature, it can be applied to a substrate by a coater or the like, dropped by a dispenser or an injector, or sprayed by an ink jet nozzle or the like. It can be used for any purpose. Furthermore, it is also possible to use a binder such as a high molecular weight polymer together. If the polymer is in a solid state, it is mixed in a solvent and mixed with various substrates such as a glass plate, an aluminum plate, a copper plate, a metal plate such as a steel plate, a polymer film such as polyethylene terephthalate, polycarbonate and polyolefin, or a plastic plate. It is also possible to apply it on a material and use it.

Examples of the binder that can be used by mixing with the curable composition of the present invention include polyacrylates and poly-α.
-Alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes, polymers such as polyvinyl esters, copolymers, and more specifically, polymethacrylate, polymethacrylate Methyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral,
Polyvinyl acetate, novolak resin, phenolic resin, epoxy resin, alkyd resin, siloxane polymer, etc.
(CMC, 1987) and "Chemical Products of 10188", pp. 657-767 (Kagaku Kogyo Nippo, 1988).
Year) described in the art.

In the curable sensitive composition as described above,
In order to effectively polymerize or crosslink both the acid-curable compound (D) and the base-curable compound (E), the following method is preferably employed. For example, in the following scheme, after the acid-curable compound (D) is polymerized or cross-linked with an acid previously generated from the energy-sensitive acid generator (A) by energy ray irradiation (step (a)), The energy ray acid generator (A) is deactivated by a thermal reaction (step (b)), and then an amine is generated from the energy sensitive ray base generator (B) by irradiation with an energy ray, whereby a base curable compound is obtained. (E) may be polymerized or crosslinked (step (c)).

At this time, the energy level of the energy ray used to generate an acid from the energy-sensitive acid generator (A) and the energy level used to generate an amine from the energy-sensitive base generator (B) When the energy level of the light is different, especially when the former is lower than the latter, for example, in light energy, the former (light 1) uses light having a longer wavelength than the latter (light 2) to first selectively generate only acid. And then generate the base,
It is possible to cause a desired polymerization or crosslinking reaction. Furthermore, it should be particularly noted that the energy-sensitive acid generator (A) used in the present invention can deactivate the acid generating function by heating, so that the polymerization or crosslinking reaction of the base-curable compound (E) can be prevented. It has the feature of not inhibiting. This is an effect which can be achieved for the first time by using the energy-sensitive acid generator (A) of the present invention.
Although the polymerization or the crosslinking reaction of the curable sensitive composition of the present invention can be extremely effectively promoted by the above method, the present invention is not limited to this curing method.

[0256]

The curable photosensitive composition of the present invention may further contain a dye, an organic or inorganic pigment, an antifoggant, a discoloration inhibitor, an antihalation agent, a fluorescent brightener, a surfactant, a plasticizer, It may be used by mixing with a flame retardant, an antioxidant, an ultraviolet absorber, a foaming agent, a fungicide, an antibacterial agent, an antistatic agent, a magnetic substance, or an organic solvent for the purpose of dilution.

As described above, as a method for polymerizing or crosslinking the curable sensitive composition of the present invention, it is possible to polymerize by irradiating with energy rays. Alternatively, it is also possible to obtain a desired polymer or cured product by post-baking by applying heat energy by heating or a thermal head or the like after irradiation with energy rays.

Examples of the energy ray source include low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, excimer laser, nitrogen laser, and argon ion laser. , Helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light source such as light emitting diode, CRT light source, plasma light source, etc., and electron beam source by EB generator. Can be

Therefore, according to the purpose, the curable sensitive composition of the present invention comprises a molding resin, a casting resin, a sealant, a dental polymerization resin, an optical molding resin, a resist for a printed board, a resist for a color filter, Various curability of microelectronics resist, photosensitive resin for printing plate, photosensitive ink jet, printing ink, color proof for print proofing, paint, surface coating agent, adhesive, adhesive, release agent, hologram recording material, etc. It is possible to apply to the energy ray sensitive material.

Next, the compound (F) used in the present invention, which has a property of increasing affinity or solubility in a developer by a reaction using an acid as a catalyst, will be described. As used herein, the compound (F) having a property of increasing affinity or solubility in a developer by a reaction using an acid as a catalyst includes, for example, carboxylic acid esters, carbonic acid esters, and alkoxysilanes. In any of these, the ester bond or siloxy bond is changed into a carboxyl group, a hydroxyl group, or a silanol group by a reaction catalyzed by an acid, and the affinity or dissolution of the ester bond or the siloxy group to a developing solution such as an alkaline solution is increased. Refers to compounds that increase the sex.
Also, those known in the art as “chemically amplified resists” are included in this.

Accordingly, as a specific example of the compound (F) having a property of increasing affinity or solubility in a developer by a reaction using an acid as a catalyst, poly (pt-ptoxycarbonyloxystyrene [Polym. En
g. Sci. 23, p. 1012 (1983).
Years)], poly (p-vinylbenzoate), polymethacrylate [Proc. of SPIE,
Vol. 771, p. 24 (1987), Macromol
ecules, vol. 21, p. 1475 (1988
Year)], α, α′-dimethylbenzyl methacrylate and α
-Methylstyrene copolymer [ACS, p. 57 (198
9 years)], t-butoxycarbonylmaleimide-styrene copolymer, t-butoxycarbonylphenylmaleimide-styrene copolymer [Proc. SPIE, No. 631
Vol. 68, 1981], a polymer compound obtained by protecting an alkali-soluble phenol resin such as poly (P-hydroxystyrene) with a trialkylsilyl group, a tetrahydropyranyl group, a furanyl group or the like [Polym. Eng. Sc
i. 29, 856 (1989), ACS D
vision PMSE, vol. 61, p. 417 (19
1989)], poly (α-acetoxystyrene) [J. P
photopolym. Sci. Technol. , Third
Volume, p. 335 (1990)], poly (4-methylene-
4H-1,3-benzodioxy-2-one) [Macr
Omolecules, Vol. 23, p. 2885 (199
0)), polyphthalaldehyde [A
CS, p. 11 (1984)], poly (4-chlorophthalaldehyde) [J. Electrochem. So
c. 136, 241 (1989)], polycarbonate [ACS, 100, 1989], poly (4-trimethylsilylphthalaldehyde) [J. El
electrochem. Soc. 136, p. 245 (1988)].

These polymer compounds can be used alone, but can also be used as a mixture with another alkali-soluble resin, for example, a phenolic novolak resin. In this case, the exemplified polymer compounds act as an inhibitor for dissolving the alkali-soluble resin in alkali. Further, in the present invention, t-butyl esters, t-butyl carbonates and t-butyl ethers of aromatic compounds [Proc. SPIE, 920, p60 (1988
Year), Polym. Eng. Sci. , Vol. 29, 84
6 (1989)], polyhydroxy compounds protected with a tetrahydropyranyl group [JP-A-1-67500.
No.] and other acetal compounds [Polym. En
g. Sci. , Vol. 29, p. 874 (1989)].

There is no particular limitation on such a high molecular compound, but if the molecular weight of the compound is lower than 50, the film-forming property is deteriorated. Therefore, as the range of molecular weight,
2,000 to 2 in weight average molecular weight (in terms of gel permeation chromatography in terms of polystyrene)
Polymeric compounds in the range of 000,000 are preferably used. The polymer compound is used in an amount of 5 to 98% by weight, preferably 10 to 95% by weight, based on the weight of the entire sensitive composition (not including the coating solvent). The effects of the present invention become more remarkable when these exemplified compounds are used in combination with an alkali-soluble resin. As the alkali-soluble resin that can be used in the present invention, novolak resin,
Examples include acetone-pyrogallol resin, polyhydroxystyrene, and derivatives thereof. Among these,
Particularly preferred is a novolak resin, which is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

As the predetermined monomer, cresols such as phenol, m-cresol, p-cresol, o-cresol, 2,5-xylenol, 3,5
Xylenols such as -xylenol, 3,4-xylenol, 2,3-xylenol, m-ethylphenol,
p-ethylphenol, o-ethylphenol, pt
Alkylphenols such as -butylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-
Alkoxyphenols such as dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol and m-butoxyphenol, and bisalkylphenols such as 2-methyl-4-isopropylphenol Kind,
Hydroxyaromatic compounds such as m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or as a mixture of two or more. However, the present invention is not limited to this. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde,
β-phenylpropyl aldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-
Hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-
Methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde and acetal thereof, such as chloroacetaldehyde diethyl acetal, can be used. Among them, it is preferable to use formaldehyde. These aldehydes are used alone or in combination of two or more.
As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used. The weight average molecular weight of the novolak resin thus obtained is from 2,000 to 30,000.
Is preferably within the range. If it is less than 2,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed becomes low. Particularly preferred is 6,
The range is from 000 to 20,000. The content of these alkali-soluble resins is suitably from 0 to 80% by weight, preferably from 20 to 60% by weight, based on the total weight of the sensitive composition (not including the coating solvent).

Such a positive-type sensitive composition may further contain a dye or the like, if necessary, for the purpose of coloring or the like. Suitable dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 6
03, oil plaque BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.), crystal violet (CI-4255)
5), methyl violet (CI-42535), rhodamine B (CI-45170B), malachite green (CI-42000), methylene blue (CI-520)
15) and the like.

The curable and positive-type sensitive composition of the present invention as described above can be used by dissolving it in a solvent capable of dissolving the above-mentioned components and applying it on a support. As the solvent used here, 1,1,2,2-tetrachloroethane, ethylene dichloride, cyclohexanone, cyclopentanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate , Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, toluene, ethyl acetate, methyl lactate, ethyl lactate, N, N
Mono-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and the like are preferable, and these solvents are used alone or in combination.

Therefore, in forming an image using the curable or positive-type sensitive composition as described above, a substrate (eg, silicon / silicon dioxide coating) used in the manufacture of precision integrated circuit elements is used. ), Substrates used for printed circuits (eg, copper-clad laminates), glass plates (or plastic plates) used for color filters, or substrates used for lithographic printing plates (eg, After coating on an anodized Al plate) by an appropriate coating method such as a spinner or a coater, pre-baking is performed under controlled conditions, and light (or an electron beam) is irradiated through a predetermined mask, or After direct writing with a laser (or electron beam), the irradiation area is developed and selectively removed under controlled conditions, It is possible to form a turn images.

Further, the developer referred to in the present specification includes a solution of an inorganic or organic base shown below.
The compound (F) having the property of increasing the affinity or solubility in a developer by the reaction using an acid as described above is converted into a carboxyl group, a hydroxyl group, a silanol group, or the like by the reaction using an acid as a catalyst. The changes are used to dissolve.

Therefore, as a developer suitable for it, specifically, sodium hydroxide, potassium hydroxide,
Inorganic alkalis such as sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; triethylamine and methyldiethylamine Tertiary amines such as
Use aqueous solutions of alkali amines such as alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and piperidine. Is desirable. Furthermore, alcohols,
Surfactants can also be used after being added in an appropriate amount.

Next, the dye precursor (G) used in the present invention and having the property of developing a color by reaction with a generated acid will be described. Examples of such compounds include known dye precursors such as triphenylmethane dyes, trimethanephthalide dyes, phenothiazine dyes, phenoxazine dyes, fluoran dyes, indolylphthalide dyes, azaphthalide dyes, and diphenylmethane dyes. Dyes, chromenopyrazole dyes, leuco auramine dyes, rhodamine lactam dyes, azomethine dyes, leuco xanthene dyes and the like can be mentioned.

Specific examples of these dye precursors (G) include:
JP-A-59-190891, JP-A-60-20215
No. 5, JP-A-62-167086, JP-A-61-51
No. 381, JP-A-60-184878 and JP-A-50-
195173, JP-A-62-27171, JP-A-6-27171
2-106964, JP-A-62-4752, JP-A-61-230981, JP-A-61-101556,
JP-A-62-84157, JP-A-56-52759
JP-A-60-196177, JP-A-58-745
3, JP-A-58-76458 and JP-A-59-135.
No. 254, JP-A-55-265, JP-A-52-822
No. 43, JP-A-57-195155, JP-A-62-7
No. 4961, JP-A-63-236679, JP-A-sho,
JP-A-58-209589, JP-A-62-17998
No. 3, JP-A-63-317558, JP-A-49-10
3710, JP-A-63-251278, JP-A-63-251278
JP-A-251279, JP-A-63-251280, JP-A-51-8012, JP-A-58-192887, JP-A-58-192885, JP-A-62-77132
JP-A-54-126114, JP-A-64-251
No. 148, JP-A-47-460110, JP-A-61-460
195164, JP-A-61-230981, JP-A-63-270662, JP-A-53-90255, JP-A-63-199268, JP-A-51-121035
JP-A-55-115448, JP-A-58-157
779, JP-A-61-87758, JP-A-62-2
43652, JP-A-61-113589, JP-A-61-1
2-176881, JP-A-60-230890, JP-A-48-95420, JP-A-59-162886
JP-A-62-198495 and JP-A-59-199.
No. 757, JP-A-64-51978, JP-A-62-1
No. 27353, JP-A-62-292959, JP-A-5
0-124930, JP-A-54-111528, JP-A-49-59127, JP-A-52-92618,
JP-A-50-137549, JP-A-54-61637
JP-A-59-25393, JP-A-53-9751
No. 2, JP-A-62-94841, JP-A-62-198
No. 494, JP-A-64-3176, JP-B-46-1605.
No. 2, JP-B-51-92207, JP-B-48-432
No. 96, Japanese Patent Publication No. 51-23204, Japanese Patent Publication No. 52-10
No. 871, No. 58-40991, No. 51-1
No. 5445, Japanese Patent Publication No. 60-27692, Japanese Patent Publication No. 54-
No. 26929, No. 55-49086, No. 56
162690, JP-B-46-4614, JP-B-Showa, 47-20479 JP-B-47-42364, JP-B-60-1341, JP-B-59-30748, JP-B-47-1179, and JP-B-45 No. 4698, JP-B-46-16053, JP-B-49-3047, JP-B-45-8557, JP-B-61-12952, JP-B-56-12515, JP-B-64-2589, and JP-B-46-22649 No., JP-B-54-25445, JP-B-47-19799, JP-B-51-23202, JP-B-55-7473, JP-B-56-11596, JP-B-57-24233, and JP-B-60-25275 ,
JP-B-60-23991, JP-B-51-92207
No., JP-B-48-18725, JP-B-61-2574
No. 5, JP-B-51-16807, JP-B-63-433
98, JP-B-42-25654, JP-B-59-32
No. 79, Japanese Patent Publication No. 60-6794, Japanese Patent Publication No. 50-145
No. 32, JP-B-37-4041, JP-B-46-122
No. 48, JP-A-4-224990, JP-A-4-225
No. 982, JP-A-4-18060, JP-A-2-267
No. 89, JP-A-3-143680, JP-A-3-294
No. 280, JP-A-2-58574, JP-A-3-127
794, JP-A-1-190484, JP-A-2-26
No. 783, JP-A-4-223467, JP-A-1-21
3636, JP-A-1-160979, JP-A1-2
No. 64889, JP-A-2-135264, JP-A-2-
39987, JP-A-2-26782, JP-B-4-6
No. 0035, US Pat. No. 4,444,591, US Pat. No. 4,515,971, US Pat. No. 4,341,403, US Pat. No. 3,560,229, US Pat. No. 4,436,920.
No. 4,390,616; U.S. Pat.
No. 656, U.S. Pat. No. 3,514,310, U.S. Pat.
No. 417897, U.S. Pat. No. 2,548,366, U.S. Pat. No. 2,505,472, U.S. Pat.
U.S. Pat. No. 4,057,562, U.S. Pat.
6, U.S. Pat. No. 4,505,093, U.S. Pat.
No. 2,449, U.S. Pat. No. 3,873,573, U.S. Pat. No. 4,119,777, U.S. Pat. No. 4,795,736, U.S. Pat.
No. 4,820,841 and U.S. Pat.
No. 150, US Pat. No. 4,446,321, British Patent No. 1
Materials disclosed in known documents such as 339316, British Patent No. 1160940, and European Patent No. 433024 can be used. Specific compounds are shown below.

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[0279]

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[0280]

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[0281]

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[0282]

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It is desirable that the above-mentioned image forming composition is further mixed with a polymer binder. Such a polymer binder is not particularly limited, but the energy-sensitive acid generator (A), the energy-sensitive base generator (B), the dye precursor (G), or the sensitizer used in the present invention. There is no particular problem as long as it is compatible with (C) and can be dissolved and coated with an appropriate solvent, and is preferably a thermoplastic polymer compound. It is more preferable that a polymer compound having no carboxyl group, sulfonic acid group, phenolic hydroxyl group, silanol group or the like capable of inducing color development is available. It is desired to appropriately select the minimum content of these functional groups.

Specific examples of the polymer binder include:
Polystyrene, styrene / acrylate copolymer, styrene / methacrylate copolymer, polyacrylates such as polymethyl acrylate and polyethyl acrylate, and polymethacryls such as polymethyl methacrylate and polyethyl methacrylate Acid esters, polyvinyl acetate, ethylene / vinyl acetate copolymer, polyurethane, bisphenol A (or tetrabromobisphenol A, bisphenol F, bisphenol S, etc.) type epoxy resin, novolak type epoxy resin, cellulose acetate, cellulose acetate sac Nitrate, methyl cellulose, cellulose derivatives such as ethyl cellulose, polyvinyl butyral, polyvinyl formal, polyamide resin, polyester resin, alkyd resin and the like. It can be. In the image forming composition of the present invention, it is also possible to use a mixture of the above-mentioned compounds curable by the generated acid and basic compound.

As described above, the compounding ratio of the composition for image formation used in the present invention is not particularly limited.
The content of the energy-sensitive acid generator (A) is 0.1 to 40.
% By weight, the content of the energy-sensitive base generator (B) is in the range of 0.1 to 40% by weight, the content of the dye precursor (G) is in the range of 0.1 to 40% by weight, Sensitizer (C)
Is in the range of 0.1 to 40% by weight, and the content of the polymer binder is in the range of 10 to 95% by weight. When the acid-curable compound (D) or the base-curable compound (E) is further mixed, the compounding ratio of the compound is 1/10 to 5 times the weight of the polymer binder. Can be blended. In particular, the content of the dye precursor (G) is such that the maximum color density is the optical density (optical density).
It is desirable that the density is adjusted to be at least 1.0 or more, more preferably at least 1.5.

When the image forming composition having the above-mentioned compounding ratio is used as an image forming medium having a film formed on a sheet-like substrate, the image forming composition is dissolved in a solvent and An application method can be adopted. The solvent used here is not particularly limited, but for example, MEK, MIB
K, ketone solvents such as cyclohexanone, cyclopentanone, ethyl acetate, amyl acetate (or isoamyl), acetate solvents such as butyl acetate, lactate esters such as methyl lactate and ethyl lactate, 1, 1, 2, and
Halogen solvents such as 2-tetrachloroethane and ethylene dichloride, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl Preferred are glycol derivative solvents such as ether, aromatic solvents such as toluene and xylene, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and the like. These solvents may be used alone or in combination. I do. In addition, a method in which an image forming medium once formed on a base material is transferred to another base material by a thermal transfer method or the like to form an image forming medium can be selected.

Further, additives such as a surfactant, an antihalation agent, an antistatic agent, a leveling agent and an antifoaming agent may be appropriately mixed with the above-mentioned solvent and used.

The solution containing the composition for image formation of the present invention thus prepared is applied to a sheet-like substrate using a roll coater, spin coater, gravure coater, bar coater or the like, and dried. By doing so, a film can be formed. The sheet-like substrate is not limited to those used in the present invention, but includes paper, non-woven fabric, fabric, porous substrate such as porous glass sheet, or synthetic paper, coated paper, polymer film, metal foil, etc. And the like. These substrates may be used alone or in the form of a laminated composite substrate.
Further, for the purpose of protecting the film of the image forming medium thus formed, a protective film such as a polymer film can be further provided.

In order to form an image using the image forming medium of the present invention prepared as described above, the following four methods are preferably used. First, as a first method, the entire surface of the medium is irradiated with energy rays to sufficiently develop the color of the dye precursor (G), and then selectively heating the area corresponding to the negative image area to completely decolor the colored area. This is a method for forming a desired image pattern. This is a method that can be achieved because the energy-sensitive acid generator (A) used in the present invention has a property of deactivating an acid by heating.

As a second method, the portion corresponding to the negative image area is first selectively heated to thermally decompose the energy-sensitive acid generator (A), and then the entire surface of the medium is irradiated with an energy beam to obtain a desired part. This is a method for forming an image pattern. It has already been confirmed by the present inventors that these first and second methods can form an image even without the presence of the energy-sensitive base generator (B). Is a method which can be realized only by the combined use of the energy-sensitive base generator (B), and has led to the present invention.

That is, as a third method, after irradiating the entire surface of the medium with an energy beam to sufficiently develop the color of the dye precursor (G), a portion corresponding to the negative image area is passed through a mask film or directly by a laser beam. To selectively generate a base and neutralize the acid-developed dye to neutralize it to form a desired image pattern.

A fourth method is to selectively generate a basic compound by irradiating a portion corresponding to a negative image portion through a mask film or directly by irradiating a laser beam, and then apply an energy-sensitive acid generator ( A) (or sensitizer)
This is a method of irradiating an energy ray absorbed by the compound to generate an acid in an amount equal to or more than the generated base, thereby forming a color of the dye precursor. In these third and fourth methods, if there is a difference between the energy levels of the energy rays on which the energy-sensitive acid generator (A) and the energy-sensitive base generator (B) act, only one of them is selectively used. It is preferable because it becomes possible to react with In particular, in the present invention, it is preferable that the energy-sensitive base generator (B) acts at a higher level of energy rays than the energy-sensitive acid generator (A) (or the sensitizer).

[0293]

In the energy-sensitive activator composition of the present invention, the energy-sensitive acid generator (A) generates an acid by causing an energy transfer or an electron transfer reaction within the molecule upon irradiation with actinic radiation and decomposing. I do. Further, the acid generated here is decomposed by heating and disappears.

When the sensitizer (C) is further added, energy or electron transfer between the sensitizer (C) and the energy-sensitive acid generator (A) is caused by irradiation with actinic radiation. Occurs, and the energy-sensitive acid generator (A)
It is possible to decompose more effectively to generate an acid.

On the other hand, an energy-sensitive base generator (B)
The compound generates a base (amine) by causing an energy transfer or an electron transfer reaction in the molecule and decomposing by irradiation with an actinic ray.

Therefore, by using an energy-sensitive activator composition obtained by combining the energy-sensitive acid generator (A) and the energy-sensitive base generator (B), the function as an acid generator can be improved. The respective effects can be exhibited without each function of the base generator being suppressed from neutralizing each other.

Therefore, by using the energy-sensitive activator composition of the present invention, a curable sensitive composition of an acid-curable compound (D) or a base-curable compound (E), which can be sensitive to low-energy actinic radiation. -Sensitive composition containing a compound (E) having a property of increasing affinity or solubility in a developing solution by a reaction using a product or an acid as a catalyst, and a property of forming a color by reaction with the generated acid It is possible to provide an image forming composition using the dye precursor (F) having the following formula:

[0298]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited only to the following examples. In the example,
Parts are parts by weight.

Example 1 As an acid-curable compound (D) and a base-curable compound (E), 3,4-epoxycyclohexylmethyl-3,4
-100 parts of epoxy cyclohexane carboxylate (manufactured by Union Carbide, product name: ERL-4221),
Dimethylphenacylsulfonium tetrakis (pentafluorophenyl) as an energy-sensitive acid generator (A)
A curable composition comprising 3 parts of borate and 3 parts of PBG-1 as an energy-sensitive base generator (B) was applied on an aluminum plate to a thickness of about 10 μm using a bar coater. ) UV irradiation device (metal halide lamp 3KW2 lamps, 120W / cm, irradiation distance 180m)
m, using a long wavelength light of 340 nm or more with a cut filter) at a conveyor speed of 15 m / min. As a result, a cured product was obtained although there was tack. Next, the cured product was heated at 120 ° C. for 2 minutes, and the above-described ultraviolet irradiation device (metal halide lamp 3KW, manufactured by Toshiba Corporation) was used.
When irradiation was performed at a conveyor speed of 5 m / min without using a cut filter at two lights, 120 W / cm, irradiation distance of 180 mm), a tack-free cured product was obtained.

Comparative Example 1 The same operation as in Example 1 was carried out except that PBG-1 was not used, and no tack-free cured product was obtained.

Comparative Example 2 Example 1 was repeated except that dimethylphenacylsulfonium tetrakis (pentafluorophenyl) borate in Example 1 was replaced with 3 parts of dimethylphenacylsulfonium hexafluorophosphate, a known photoacid generator. As a result, no tack-free cured product was obtained.

Example 2 A curable composition obtained by further adding 3 parts of 9,10-dimethylanthracene as a sensitizer (C) to the curable composition of Example 1 was obtained using a bar coater. About 1
It is applied on an aluminum plate to a thickness of 0 μm, and an ultraviolet irradiation device manufactured by Toshiba Corporation (metal halide lamp 3KW2, 120
W / cm, irradiation distance 180mm, cut filter 3
25 m / min at 80 nm or longer wavelength)
Irradiation at a conveyor speed of 2. The cured product was obtained although there was tack. Then, the cured product was heated at 120 ° C. for 2 minutes, and 5 m / mi without a cut filter using the above-mentioned ultraviolet irradiation device (metal halide lamp 3 KW2, 120 W / cm, irradiation distance 180 mm) manufactured by Toshiba Corporation.
Irradiation at a conveyor speed of n gave a tack-free cured product.

Examples 3 to 56 The same procedure as in Example 1 was repeated, except that 3 parts of dimethylphenacylsulfonium tetrakis (pentafluorophenyl) borate was replaced with the energy-sensitive linear acid generator (A) shown in Table 1. In each case, an experiment was performed in exactly the same manner as in Example 1, and in each case, a tack-free cured film was obtained.

Table 1 Example Energy-sensitive linear acid generator (A 3) tetramethylenephenacylsulfonium tetrakis (pentafluorophenyl) borate 4 Methylhexylsulfonium tetrakis (pentafluorophenyl) borate 5 diphenylphenylsulfonium tetrakis (pentafluorophenyl) borate 6 methyl (p-cyanohexyl) sulfonium tetrakis (pentafluorophenyl) borate Phenylphenacylsulfonium tetrakis (pentafluorophenyl) borate 8dimethyl (p-cyanophenacyl) sulfonium Lakis (pentafluorophenyl) borate 9-methylmethylsulfonium tetrakis (pentafluorophenyl) borate 10-phenylphenylsulfonium tetrakis (pentafluorophenyl) borate 11-phenylphenylphenoxysulfonium tetrakis (pentafluorophenyl) borate 12 dimethylbenzenesulfoxonium tetrakis (pentafluorophenyl) borate 13 diphenylbenzenesulfoxonium tetrakis (pentafluorophenyl) borate 14 methylphenylbenzenesulfoxonium tetrakis (pentafluorophenyl) Borate 15 dimethyl (p-cyanobenzene) sulfoxonium tetrakis (pentafluorophenyl) borate 16 diphenyl Enacilsulfoxonium tetrakis (pentafluorophenyl) borate 17 dimethyl (p-cyanophenacyl) sulfoxonium tetrakis (pentafluorophenyl) borate 18 triphenylphenoxyphosphonium tetrakis (pentafluorophenyl) borate 19 Trimethylphensilphosphonium tetrakis (pentafluorophenyl) borate 20 Methyldiphenylphenylphosphonium tetrakis (pentafluorophenyl) phosphate 21 Triphenyl (p-cyanohexyl) phosphonium tetrakis (pentafluorophenyl) phosphate 22 Trimethylphena Silphosphonium tetrakis (pentafluorophenyl) borate 23 Triphenyl (p-cyanophenacyl) phosphonium tetrakis (pentane) Fluorophenyl) borate 24 N-pentachloroperidinium tetrakis (pentafluorophenyl) borate 25 N- (p-cyanopentaphenyl) pyridinium tetrakis (pentafluorophenyl) borate 26 4-cyano-1- Phenacylpolycinium tetrakis (pentafluorophenyl) borate 27 2-Methyl-1-ethoxyperidinium tetrakis (pentafluorophenyl) borate 28 N-benzoylquinolinium tetrakis (pentafluorophenyl) borate 29 N- (p-cyanohexyl) quinolinium tetrakis (pentafluorophenyl) borate 30 4-cyano-1-phenacylquinolinium tetrakis (pentafluorophenyl) borate 31 2-methyl-1-ethoxyquinolinium tetrakis ( Pentafluorofe Nyl) borate 32 N-phenylisoquinolinium tetrakis (pentafluorophenyl) borate 33 N- (p-cyanophenyl) isoquinolinium tetrakis (pentafluorophenyl) borate 346-Chloro-1-phenacylyl Soquinolinium tetrakis (pentafluorophenyl) borate 35 2-Methyl-1-ethoxyisoquinolinium tetrakis (pentafluorophenyl) borate 36 N-pentachlorothiazolium tetrakis (pentafluorophenyl) borate 37 N- (p-cyanohexyl) thiazolium tetrakis (pentafluorophenyl) borate 38 2-Mercaphth-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 39 6-Hetoxy-3-fe Nasirthia sodium tetrakis (Pentaful (Orophenyl) borate 40 N-benzoyloxasorium tetrakis (pentafluorophenyl) borate 41 N- (p-cyanohexyl) oxasorium tetrakis (pentafluorophenyl) borate 42 2-Chloro-3-phenyl Human peryloxazolium tetrakis (pentafluorophenyl) borate 43 6-Humanoxy-3-phenacyloxazolium tetrakis (pentafluorophenyl) borate 44 bis (2-furyl) iodinium tetrakis (pentane) Fluorophenyl) borate 45 di (2-thienyl) iodium tetrakis (pentafluorophenyl) borate 46 bis (2- (3-methyl) furyl) iodium tetrakis (pentafluorophenyl) borate 47 hydrogen Di (2- (3-methyl) thienyl) iodopenmium Trakis (pentafluorophenyl) borate 48 diphenyliodinotetrakis (pentafluorophenyl) borate 49 Bis (pt-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate 50 Triphenylsulfonium Tetrakis (pentafluorophenyl) borate 51 Triphenylsulfoxonium tetrakis (pentafluorophenyl) borate 52-methylphenylsulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 53-methylmethylphenylsulfoxo N-Tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 54 2-Methyl-1-ethoxydicaridinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 55 borate (2 -H Nyl) iodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 56 (η5-2,4-cyclopentadienyl-1-yl) [(1,2,3,4, 5,6-η)-(1-Methylethyl) benzene] iron tetrakis [3,5-bis (trifluoromethyl) phenyl] borate ───────────────────

Examples 57 to 65 9,10-dimethylanthracene in Example 2
Instead of 5 parts, sensitizer (C) shown in Table 2 was added to 0.5 part
In the same manner as in Example 2, a tack-free cured film was obtained as in Example 2.

Table 2 Example sensitizer (C) ──────────── 57 Anthracene 58 9,10-Bis (phenylethynyl) anthracene 59 9-Phlomoanthracene 60 9,10-Diethylanthracene 61 9,10-Diphenylanthracene 62 1,8-Dimethoxy-9,10-bis (phenylethynyl) anthracene 63 Acrylic acid 64 Phenol sodium 65 Setofuran T ─────

Examples 66 to 68 PBG-1 in Example 1 was replaced by PBG instead of 3 parts.
Experiments were performed in exactly the same manner as in Example 1 except that each of -2, PBG-3, and PBG-3 was changed to 3 parts, respectively. In each case, a tack-free cured film was obtained. Was.

Example 69 As a compound (F) having a property of changing the affinity or solubility with respect to a developer by a reaction using an acid as a catalyst,
3 parts of poly (p-tert-butoxycarbonyloxystyrene) (weight average molecular weight: 30,000), and 0.3 parts of dimethylphenacylsulfonium tetrakis (pentafluorophenyl) borate as an energy-sensitive acid generator (A). Parts, 0.3 parts of PBG-1 as an energy-sensitive base generator (B) and 9, 9 parts as a sensitizer (C).
10-bis (phenylethynyl) anthracene to 0.3
Part of the positive-type sensitive composition comprising cyclohexanone 2
The photosensitive solution obtained by dissolving in 7 parts was applied on anodized aluminum plate to a thickness of 2.0 μm using a spinner, and then prebaked in an oven at 60 ° C. for 10 minutes to obtain a photosensitive plate. It was created. First, the photosensitive plate was entirely exposed to 315 nm of an ultra-high pressure mercury lamp (500 W, manufactured by Ushio Inc.). Then, an 435 nm ultra-high pressure mercury lamp (500 W, manufactured by Ushio Inc.) was exposed through a positive mask (L / S = 30 μm), and post-baked at 100 ° C. for 3 minutes. Then, development with a 1.2% aqueous sodium carbonate solution (25 ° C.)
/ 1 minute), washed with water and dried to obtain a good rectangular pattern (L / S = 30 μm). The amount of exposure energy required for pattern formation was 35 mJ / cm ² (remaining film ratio: 99%).

Example 70 3 parts of polyvinyl butyral was used as a polymer binder.
0.3 parts of dimethylphenacylsulfonium tetrakis (pentafluorophenyl) borate as the energy-sensitive linear acid generator (A) and 0.3 parts of PBG-1 as the energy-sensitive linear base generator (B). An image forming composition comprising 0.2 parts of 9,10-dimethylanthracene as the agent (C) and 0.5 parts of crystal violet lactone (CVL) as the dye precursor (G),
Cyclohexanone is dissolved in 27 parts, and the solution is applied to a polyester film (50 μm thick) using a roll coater.
After pre-baking in an oven at 60 ° C. for 10 minutes, an image forming medium having a recording layer thickness of 3 μm was prepared. The entire surface of the medium was exposed to light of 405 nm from an ultra-high pressure mercury lamp (500 W, manufactured by Ushio Inc.), and CVL was colored (blue) (color density OD = 1.3). Then, exposure was performed through a positive mask film using 315 nm light from an ultra-high pressure mercury lamp (500 W, manufactured by Ushio Inc.), whereby only the negative portion (non-image portion) could be decolorized (OD = 0.05). ).

[0310]

As described above, an energy-sensitive activator composition comprising an energy-sensitive acid generator (A) and an energy-sensitive base generator (B) is provided. The composition is provided with a curable sensitive composition of an acid-curable compound (D) and a base-curable compound (E), or the developer is prepared by reacting the energy-sensitive activator composition with an acid as a catalyst. By mixing the compound (F) having a property of increasing affinity or solubility for the compound, a positive-type sensitive composition is provided.
An image forming composition is provided by mixing the energy-sensitive activator composition with a dye precursor (G) having a property of developing a color with an acid. Therefore, the composition of the present invention comprises a molding resin, a casting resin, a sealant, a dental polymerization resin, an optical molding resin, a resist for a printed circuit board, a resist for a color filter, a resist for microelectronics, and a photosensitive resin for a printing plate. , Photosensitive ink jet, printing (offset, gravure, silk screen) ink, print proof color proof, paint, surface coating agent,
It is suitably used for various materials such as adhesives, pressure-sensitive adhesives, release agents, and hologram recording materials.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08G 65/00 NQE C08G 65/00 NQE 69/20 NRT 69/20 NRT 73/00 NTB 73/00 NTB 75/00 NTV 75/00 NTV 77/08 NUD 77/08 NUD 85/00 NUX 85/00 NUX G03F 7/004 503 G03F 7/004 503 7/029 7/029

Claims (5)

[Claims] An energy-sensitive acid generator (A), which is an onium borate complex composed of an onium cation and a borate anion of the general formula (1), and an energy-sensitive base generator (B). Energy ray activator composition. Formula _{(1) [BY m Z n} ] - ( however, Y is fluorine or chlorine, Z is fluorine, cyano group, nitro group, substituted with at least two electron-withdrawing group selected from trifluoromethyl group M represents an integer of 0 to 3; n represents an integer of 1 to 4;
n = 4. ) 2. The energy-sensitive activator composition according to claim 1, further comprising a sensitizer (C). 3. A curable sensitive composition obtained by adding an acid-curable compound (D) and a base-curable compound (E) to the energy-sensitive activator composition according to claim 1 or 2. 4. A compound (F) having a property of changing the affinity or solubility in a developer by a reaction using an acid as a catalyst, to the energy-sensitive activator composition according to claim 1 or 2. A positive-type sensitive composition characterized by comprising: 5. An image-forming composition comprising the energy-sensitive activator composition according to claim 1 and a dye precursor (G) having a property of developing a color by reaction with an acid.