JPH09241614A - Energy ray-sensitive acid-generating agent, energy ray-sensitive acid-generating agent composition, curable composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject acid-generating agent comprising an onium borate complex produced from a specific onium cation and a specific borate anion, generating an acid by the irradiation of energy rays, especially light, and capable of polymerizing an acid-curable compound in a short time. SOLUTION: This acid-generating agent comprises a complex produced from (A) an onium cation of the formula [X is S, O, preferably S; R is independently F, Cl, Br, OH, carboxyl, etc.; (k) is an integer of 0-2; R<1> is benzyl, phenacyl, allyl, etc.; R<2> is H, an alkyl which may be substituted by a mercapto, F, Cl, Br, etc.,] as a cation portion, and (B) a borate anion of the formula: [BYm Zn ]<-> (Y is F, Cl; Z is phenyl substituted by an electron-attracting group; (m) is an integer of 0-3; (n) is an integer of 1-4; (m)+(n)=4) as an anion portion. This acid-generating agent composition comprises the acid-generating agent and a sensitizer, and this curable composition comprises the acid-generating agent, an acid-curable compound, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an energy sensitive acid generator, an energy sensitive acid generator composition and a curable composition. More specifically, an acid ray is generated by irradiation of energy rays, particularly light, and an acid-curable compound is polymerized in a short time, for example, molding resin, casting resin, resin for stereolithography,
Sealant, Dental polymerization resin, Printing ink, Paint, Photosensitive resin for printing plate, Color proof for printing, Color filter resist, Printed board resist, Semiconductor photoresist, Microelectronic resist, Hologram material, Overcoat An energy-sensitive acid generator, an energy-sensitive acid generator composition, a curable composition, and a curable composition for obtaining a cured product having good physical properties in the fields of coating materials, adhesives, pressure-sensitive adhesives, release agents, etc. Regarding the cured product.

[0002]

2. Description of the Related Art Heretofore, it has been reported that various onium salts function as heat- and photo-latent acid catalysts of acid-curable compounds such as epoxy compounds. Volume, Issue 5, page 5 (19
1993, CMC).

By the way, as an example of using a thiazolium salt, an oxazolium salt or an imidazolium salt as an initiator for polymerization of light or electron beam, it has not been known until now.
Further, as an example of using a pyrrolinium salt as a thermal polymerization initiator, the pyrrolinium salts described in JP-A-6-321897 are known, but examples of using it as a polymerization initiator for light or electron beam have been heretofore known. Not known to.

By the way, in recent years, tetrakis (pentafluor)
O with a borate anion such as (rophenyl) borate.
PFs that have been known as₆ ^-And Sb
F₆ ^-Light weight than onium salts with anions such as
It is disclosed in Japanese Patent Application Laid-Open No. 6-1
84170 and International Patent No. 95/03338
Revealed by news. These specifications and C.Pr
Report of iou et al. (Radtech '94, North America
・ Proceedings (RadTech '94 North America Pr
oc.) Volume 1, p. 187 (1994) and Polymeri.
Cook Materials Science and Engineer
Ring (Polym. Mater. Sci. Eng.), Vol. 72, p. 417
(1995)), diphenyliodonium te
Trakis (pentafluorophenyl) borate is traditionally
Diphenyliodonium hexafluoroantimony
Higher weight for epoxy silicone polymerisation than
It is reported to have a composite property. However, this
The onium borates reported in these references are thiaborates.
There is no description of zolium compounds.

On the other hand, these borate compounds such as tetrakis (pentafluorophenyl) borate show high activity as a thermal polymerization catalyst for vinyl compounds such as styrene and olefins such as ethylene and propylene. -124706, JP-A-4-253711
Japanese Patent Laid-Open No. 4-249503, Japanese Patent Laid-Open No. 5-5
No. 05838, International Patent No. 95/10551, Journal of American Chemical Society (J. Am. Chem. Soc.), No. 113.
Vol., 8570 (1991), that tetrakis (pentafluorophenyl) borates show high activity as catalysts for Diels-Alder reaction.
Journal of American Chemical Society (J. Am. Chem. Soc.), Vol. 111, 6
Although it is specified on page 070 (1989), no investigation as a photopolymerization initiator has been made in these patent specifications and documents.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to propose a highly sensitive curable composition capable of generating an acid upon irradiation with energy rays, particularly light, and polymerizing an acid curable compound in a short time. It is in. For example, ink, paint, photosensitive printing plate, proof material, photoresist, hologram material,
Energy-sensitive ray acid generation to industrially provide practical oligomers and polymers in the fields of sealants, overcoat materials, stereolithography resins, adhesives, etc., and to obtain cured products with good physical properties To provide an agent, an energy-sensitive acid generator composition, and a curable composition.

The problems of the curable composition disclosed in the prior art in the industrial fields of application of the present invention are listed below.

First, the pyrrolinium salt described in JP-A-6-321897 was developed as a thermal polymerization initiator, and the anion part thereof is
It is composed of anions such as F ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , and SbF ₆ ⁻ , and is not sufficiently sensitive as a photopolymerization initiator for acid-curable compounds such as epoxy compounds requiring high sensitivity. Is.

Further, diphenyliodonium tetrakis (pentafluorophenyl) described in JP-A-6-184170 and International Patent Publication No. 95/03338.
Although borate is reported to have higher polymerization properties for the polymerization of epoxysilicon than conventional diphenyliodonium hexafluoroantimonate,
It has an unfavorable property of producing a harmful substance such as benzene as a by-product during decomposition. In addition, triphenylsulfonium tetrakis (pentafluorophenyl) borate is also reported to have higher polymerization characteristics than conventional triphenylsulfonium hexafluoroantimonate, but it does not react with malodorous substances such as diphenyl sulfide upon decomposition. It has an unfavorable property of producing a substance as a by-product. Further, when photopolymerization or photocuring is generally performed, heat from a light source is actually added, but since sulfonium complexes and iodonium complexes are stable against heat, heat energy applied at the same time as light irradiation is applied to the curable composition. It has the drawback that it cannot be effectively used for the curing reaction of an object. Therefore, development of a polymerization initiator and a curable composition that can solve these problems has been desired.

[0010]

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 energy characterized by being an onium borate complex whose cation portion is composed of an onium cation represented by the general formula (1) and an anion portion composed of a borate anion represented by the general formula (2). A linear acid generator (A). General formula (1)

Embedded image (Wherein, X is, -S -, - O -, - N (R 2) -, - C
It represents a group selected from (R ² ) _2- . Each R independently represents a group selected from the following organic residues in addition to fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group and carbamoyl group, and k is 0 to 2
Represents an integer. Here, the organic residue means a linear or branched C _{1 to} C ₁₈ which may be substituted with fluorine, chlorine, bromine, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, or an azide group. , Cyclic alkyl group, C ₂
-C ₁₈ linear, branched, cyclic alkenyl group, C ₆ ~
A C ₁₈ monocyclic ring, a condensed polycyclic aryl group, a C ₇ -C ₁₈ monocyclic ring,
Fused polycyclic arylalkyl group, C _{1 to} C ₁₈ straight chain, branched chain, cyclic alkoxyl group, C _{6 to} C ₁₈ monocycle, fused polycyclic aryloxy group, C _{1 to} C ₁₈ straight chain , Branched, cycloaliphatic or C _{7 to} C ₁₉ monocyclic, condensed polycyclic aromatic acyl group, C _{2 to} C ₁₉ straight chain, branched chain, cyclic alkoxycarbonyl group, C _{7 to} C ₁₉ Represents a monocyclic ring or a condensed polycyclic aryloxycarbonyl group. R
¹ is a benzyl group, a substituted benzyl group, a phenacyl group, a substituted phenacyl group, an allyl group, a substituted allyl group, an alkoxyl group, a substituted alkoxyl group,
It represents a group selected from an aryloxy group and a substituted aryloxy group. R ² is hydrogen, a mercapto group, and
Fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, C ₁ -C ₁₈ linear, branched or cyclic alkyl group which may be substituted with azido group, fluorine, chlorine , A bromine group, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, and a C _{1 to} C ₁₈ linear, branched, or cyclic alkylthio group which may be substituted with an azido group. Further, adjacent Rs, R and R ¹ , R and R ² , and R ¹ and R ² may form a ring structure by a covalent bond. ) General formula (2) [BY _m Z _n ] ^- (wherein Y is fluorine or chlorine, Z is at least two or more fluorine, a cyano group, a nitro group, an electron-withdrawing group selected from a trifluoromethyl group. A phenyl group substituted with, m is an integer of 0 to 3, n is an integer of 1 to 4, and m is
+ N = 4. )

The second invention is an energy-sensitive acid generator composition containing an energy-sensitive acid generator (A) and a sensitizer (B), and the third invention is an energy-sensitive acid generator. A curable composition comprising an acid generator (A) or an energy ray sensitive acid generator composition and an acid curable compound (C),
The fourth invention comprises an energy-sensitive acid generator (A) or an energy-sensitive acid generator composition, an acid-curable compound (C), a radical polymerizable compound (D) and a radical generator (E). The fifth invention is a cured product obtained from these curable compositions.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION First, the energy ray sensitive acid generator (A) of the present invention will be described. In the substituent R ¹ in the onium cation represented by the general formula (1) that constitutes the energy ray sensitive acid generator (A) of the present invention,

The substituted benzyl group means fluorine, chlorine, bromine, cyano group, nitro group, trifluoromethyl group, hydroxyl group, mercapto group, methylsulfinyl group, methylsulfonyl group, acetyl group, benzoyl group, 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 group, m-fluorobenzyl group, p-fluorobenzyl group, o-chlorobenzyl group,
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.

Further, the substituted phenacyl group in the substituent R ¹ is fluorine, chlorine, bromine, cyano group, nitro group, trifluoromethyl group, hydroxyl group, mercapto group, methylsulfinyl group, methylsulfonyl group, acetyl group. , benzoyl group, C ₁ -C _{1 8} linear, branched,
Phenacyl group substituted with a group selected from a cyclic alkyl group, a C _{1 to} C ₁₈ linear, branched, or cyclic alkoxyl group, a C _{2 to} C ₁₈ linear, branched, or cyclic alkoxycarbonyl group. And a structure in which the benzene ring in the phenacyl group may form a C _{10 to} C ₂₂ fused polycyclic aromatic ring by an unsaturated hydrocarbon group.

Specific examples of these substituted phenacyl groups include o-fluorophenacyl group, m-fluorophenacyl group, p-fluorophenacyl group, o-chlorophenacyl group, m-chlorophenacyl group, 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.

Further, the substituted allyl group in the substituent R ¹ means fluorine, nitro group, trifluoromethyl group,
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 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 or cyclic alkoxyl groups, such as methoxy group, ethoxy group, propoxy group, butoxy group, octyloxy group. 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. Examples include linear and branched alkoxyl groups, fluoromethoxy group, 2-chloroethoxy group, 3-bromopropoxy group, 4-cyanobutoxy group, 8-nitrooctyloxy group, 18-trifluoromethyloctadecaneoxy group. , 2-hydroxyisopropoxy group, trichloromethoxy group and the like.

Further, the aryloxy group in the substituent R ¹ is a C ₆ -C ₁₈ monocyclic or condensed polycyclic aryloxy group, and includes a phenoxy group, a naphthyloxy group, a 2-naphthyloxy group and a 9-ane. Thryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azulenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group 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 C substituted with a group selected from fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group and azido group. _{6- C18} monocyclic or condensed polycyclic aryloxy group, which is an o-fluorophenoxy group, m-chlorophenoxy group, p-bromophenoxy group, p-hydroxyphenoxy group, m-carboxyphenoxy group, o-mercapto group. 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. One such example is:

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-
(P-tosyl) phenacyl group, 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 for this 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, the thiazolium cation receives an electron by the action of an energy ray as described later. It is considered that the substituent R ¹ is easily released during reduction and decomposition by an irreversible reaction, and the reduction potential of the onium cation is increased, that is, the electron accepting property is increased.

Other preferable examples of the substituent R ¹ include C ₁ -C ₁₈ straight chain, branched chain, and cyclic alkyl groups or C ₁ -C ₁₈ straight chain, branched chain, and cyclic groups. Examples thereof include a benzyl group substituted with an alkoxyl group, a phenacyl group, and an allyl group. Specific examples thereof include o-methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group, pt-butylbenzyl group, pt-butoxybenzyl group, o-methylphenacyl group, m -Methylphenacyl group, p-methylphenacyl group, pt-butylphenacyl group, pt-butoxyphenacyl group,
These substituents are expected to improve the compatibility of the acid-curable compound (C) with the acid-curable compound (C) when it is used as a curable composition.

Further, as another preferable substituent R ¹ , a benzyl group having a C _{11 to} C ₁₉ condensed polycyclic aromatic ring,
Examples thereof include a phenacyl group, an allyl group and a C _{10 to} C ₁₈ condensed polycyclic aryloxy group. Specific examples thereof include 1-naphthylmethyl group, 2-naphthylmethyl group, 9
-Anthrylmethyl group, 1-naphthoylmethyl group, 2-
Naphthoylmethyl group, 9-anthroylmethyl group, 3-
(2-naphthyl) -2-propenyl group, 3- (2-naphthoyl) -2-propenyl group, 1-naphthyloxy group,
Examples thereof include a 2-naphthyloxy group and a 9-anthryloxy group, and these are expected to improve the absorption of ultraviolet rays.

Furthermore, in the substituent R in the onium cation represented by the general formula (1) which constitutes the energy ray sensitive acid generator (A) of the present invention,

Fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, C ₁ -C ₁₈ linear or branched chain which may be substituted with azido group,
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.

C ₂ -C ₁₈ straight or branched chain which may be substituted with fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group or azido group,
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.

The C ₆ -C ₁₈ monocyclic or condensed polycyclic aryl group which may be substituted with fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group or azido group is 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.

As the C ₇ -C ₁₈ monocyclic or fused polycyclic arylalkyl group which may be substituted with fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group or azido group, 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 can be mentioned.

C ₁ -C ₁₈ straight or branched chain which may be substituted with fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group or azido group,
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.

As the C ₆ -C ₁₈ monocyclic or condensed polycyclic aryloxy group which may be substituted with fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group or azido group, Phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy 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-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.

Fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, C ₁ -C ₁₈ straight or branched chain which may be substituted,
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 straight or branched chain which may be substituted with fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group or azido group,
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.

As the C ₇ -C ₁₉ monocyclic or condensed polycyclic aryloxycarbonyl group which may be substituted with fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group or azido group, , 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, in the substituent R ² in the onium cation represented by the general formula (1) which constitutes the energy-sensitive ray acid generator (A) of the present invention,

Fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, C ₁ -C ₁₈ straight or branched chain which may be substituted,
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.

As a C ₁ -C ₁₈ linear, branched or cyclic alkylthio group which may be substituted with fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group or azido group. Is a methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group, isopropylthio group, isobutylthio group, sec-butylthio group,
t-butylthio group, cyclopentylthio group, cyclohexylthio group, 4-decylcyclohexylthio group, fluoromethylthio group, chloromethylthio group, bromomethylthio group, trifluoromethylthio group, trichloromethylthio group, tribromomethylthio group, hydroxymethylthio group, Examples thereof include a carboxymethylthio group, a mercaptomethylthio group, a cyanomethylthio group, a nitromethylthio group, and an azidomethylthio group.

Further adjacent Rs, R and R ¹ , R and R
² , R ¹ and R ² may form a ring structure by a covalent bond with each other, and examples thereof include alkylene groups such as methylene group, ethylene group, tetramethylene group, hexamethylene group, and ethylenedi Examples include ether groups such as oxy group and diethylenedioxy group, thioether groups such as ethylenedithio group and diethylenedithio group.
The present invention is not limited to these.

Specific examples of the structure of the onium cation represented by the general formula (1) of the energy ray sensitive acid generator (A) of the present invention will be given below.

Examples of thiazolium Examples of N- (substituted) benzylthiazolium N-benzylthiazolium, N- (o-fluorobenzyl) thiazolium, N- (m-fluorobenzyl) thiazolium, N- (p-fluoro) Benzyl) thiazolium, N- (p-chlorobenzyl) thiazolium, N-
(P-bromobenzyl) thiazolium, N- (p-cyanobenzyl) thiazolium, N- (m-nitrobenzyl) thiazolium, N- (2,6-dichlorophenylmethyl) thiazolium, N- (pentafluorophenylmethyl) thiazolium, N- (p- (trifluoromethyl) benzyl) thiazolium, N- (p-hydroxybenzyl) thiazolium, N- (p-mercaptobenzyl) thiazolium, N- (p-methylsulfinylbenzyl) thiazolium, N- (p- Methylsulfonylbenzyl) thiazolium, N- (p-acetylbenzyl) thiazolium, N- (p-benzoylbenzyl) thiazolium, N- (p-methylbenzyl) thiazolium, N-
(P-ethylbenzyl) thiazolium, N- (p-isopropylbenzyl) thiazolium, N- (p-t-butylbenzyl) thiazolium, N- (p-octadecylbenzyl) thiazolium, N- (p-cyclohexylbenzyl) thiazolium, N- (p-methoxybenzyl) thiazolium, N- (p-ethoxybenzyl) thiazolium, N- (p-isopropoxybenzyl) thiazolium, N- (pt-butoxybenzyl) thiazolium,
N- (p-octadecyloxybenzyl) thiazolium, N- (p-cyclohexaneoxybenzyl) thiazolium, N- (o-methoxycarbonylbenzyl) thiazolium, N- (p-ethoxycarbonylbenzyl) thiazolium, N- (p-iso Propoxycarbonylbenzyl) thiazolium, N- (pt-butoxycarbonylbenzyl) thiazolium, N- (p-octadecyloxycarbonylbenzyl) thiazolium, N- (p-cyclohexaneoxycarbonylbenzyl) thiazolium, N- (1-naphthylmethyl ) Thiazolium, N-
(2-naphthylmethyl) thiazolium, N- (9-anthrylmethyl) thiazolium, N- (1-pyrenylmethyl) thiazolium, N- (5-naphthacenylmethyl) thiazolium, N- (6-pentacenylmethyl) Thiazolium.

Examples of N- (substituted) phenacylthiazolium N-phenacylthiazolium, N- (o-fluorophenacyl) thiazolium, N- (m-fluorophenacyl) thiazolium, N- (p- Fluorophenacyl) thiazolium, N- (p-chlorophenacyl) thiazolium, N- (p-bromophenacyl) thiazolium, N-
(P-Cyanophenacyl) thiazolium, N- (m-nitrophenacyl) thiazolium, N- (2,4-difluorophenylcarbonylmethyl) thiazolium, N-
(Pentafluorophenylcarbonylmethyl) thiazolium, N- (p- (trifluoromethyl) phenacyl)
Thiazolium, N- (o-hydroxyphenacyl) thiazolium, N- (p-mercaptophenacyl) thiazolium, N- (p-methylsulfinylphenacyl) thiazolium, N- (p-methylsulfonylphenacyl) thiazolium, N- (O-Acetylphenacyl) thiazolium, N- (p-benzoylphenacyl) thiazolium, N- (o-methylphenacyl) thiazolium, N-
(P-Ethylphenacyl) thiazolium, N- (p-isopropylphenacyl) thiazolium, N- (pt-
Butylphenacyl) thiazolium, N- (p-octadecylphenacyl) thiazolium, N- (p-cyclohexylphenacyl) thiazolium, N- (p-methoxyphenacyl) thiazolium, N- (p-ethoxyphenacyl) thiazolium, N- (P-Isopropoxyphenacyl) thiazolium, N- (pt-butoxyphenacyl) thiazolium, N- (p-octadecyloxyphenacyl) thiazolium, N- (p-cyclohexaneoxyphenacyl) thiazolium, N- ( p-methoxycarbonylphenacyl) thiazolium, N- (p-isopropoxycarbonylphenacyl) thiazolium, N- (p
-T-butoxycarbonylphenacyl) thiazolium,
N- (p-octadecyloxycarbonylphenacyl)
Thiazolium, N- (p-cyclohexaneoxycarbonylphenacyl) thiazolium, N- (1-naphthoylmethyl) thiazolium, N- (2-naphthoylmethyl)
Thiazolium, N- (9-anthroylmethyl) thiazolium, N- (1-pyrenylcarbonylmethyl) thiazolium, N- (5-naphthacenylcarbonylmethyl) thiazolium, N- (6-pentacenylcarbonylmethyl) thiazolium .

Examples of N- (substituted) allyl thiazolium N-allyl thiazolium, N- (2,3,3-trifluoro-2-propenyl) thiazolium, N- (3,3-)
Dinitro-2-propenyl) thiazolium, N- (3,
3-dicyano-2-propenyl) thiazolium, N-
(2-Methyl-3,3-dicyano-2-propenyl) thiazolium, N- (2-octadecyl-3,3-dicyano-2-propenyl) thiazolium, N- (2-isopropyl-3,3-dicyano-2) -Propenyl) thiazolium, N- (2-cyclohexyl-3,3-dicyano-
2-propenyl) thiazolium, N- (2-acetyl-
3,3-dicyano-2-propenyl) thiazolium, N
-(2-benzoyl-3,3-dicyano-2-propenyl) thiazolium, N- (2-phenyl-3,3-dicyano-2-propenyl) thiazolium, N- (3,3-
Bis (methoxycarbonyl) -2-propenyl) thiazolium, N- (2-methyl-3,3-bis (methoxycarbonyl) -2-propenyl) thiazolium, N- (2
-Isopropyl-3,3-bis (methoxycarbonyl)
2-propenyl) thiazolium, N- (2-cyclohexyl-3,3-bis (methoxycarbonyl) -2-propenyl) thiazolium, N- (2-phenyl-3,3
-Bis (methoxycarbonyl) -2-propenyl) thiazolium, N- (2-phenyl-3,3-bis (hexyloxycarbonyl) -2-propenyl) thiazolium, N- (2-phenyl-3,3-bis ( Cyclohexyloxycarbonyl) -2-propenyl) thiazolium.

Examples of N-alkoxythiazolium N-methoxythiazolium, N-ethoxythiazolium, N-propoxythiazolium, N-butoxythiazolium, N-octyloxythiazolium, N-octadecyl Oxythiazolium, N-isopropoxythiazolium, N- (t-butoxy) thiazolium, N-cyclopentyloxythiazolium, N-cyclohexyloxythiazolium, 3-ethoxy-2-methylthiazolium.

Examples of N-substituted alkoxythiazolium N- (fluoromethoxy) thiazolium, N- (2-chloroethoxy) thiazolium, N- (3-bromopropoxy) thiazolium, N- (4-cyanobutoxy) thiazolium, N- (8-nitrooctyloxy) thiazolium, N- (18-trifluoromethyloctadecyloxy) thiazolium, N- (2-hydroxyisopropoxy) thiazolium.

Examples of N-aryloxythiazolium N-phenoxythiazolium, N- (1-naphthyloxy) thiazolium, N- (2-naphthyloxy) thiazolium, N- (9-anthryloxy) thiazolium,
N- (9-phenanthryloxy) thiazolium, N-
(1-Pyrenyloxy) thiazolium, N- (5-naphthacenyloxy) thiazolium, N- (1-indenyloxy) thiazolium, N- (2-azurenyloxy)
Thiazolium, N- (1-acenaphthyloxy) thiazolium, N- (9-fluorenyloxy) thiazolium, N- (o-tolyloxy) thiazolium, N- (m
-Tolyloxy) thiazolium, N- (p-tolyloxy) thiazolium, N- (2,3-xylyloxy) thiazolium, N- (2,5-xylyloxy) thiazolium, N- (mesityloxy) thiazolium, N- (p
-Cumenyloxy) thiazolium, N- (p-decylphenoxy) thiazolium, N- (p-cyclohexylphenoxy) thiazolium, N- (4-phenylphenoxy) thiazolium.

Examples of N-Substituted Aryloxythiazolium N- (o-fluorophenoxy) thiazolium, N-
(M-Chlorophenoxy) thiazolium, N- (p-bromophenoxy) thiazolium, N- (p-hydroxyphenoxy) thiazolium, N- (m-carboxyphenoxy) thiazolium, N- (o-mercaptophenoxy) thiazolium, N- (P-Cyanophenoxy) thiazolium, N- (m-nitrophenoxy) thiazolium, N- (m-azidophenoxy) thiazolium, N-
(2-chloro-1-naphthyloxy) thiazolium, N
-(10-Cyano-9-anthryloxy) thiazolium, N- (11-nitro-5-naphthacenyloxy) thiazolium.

Examples of 2-substituted-3- (substituted) benzylthiazolium 2-fluoro-3-benzylthiazolium, 2-chloro-3-benzylthiazolium, 2-bromo-3-benzylthiazolium , 2-hydroxy-3-benzylthiazolium, 2-carboxy-3-benzylthiazolium,
2-mercapto-3-benzylthiazolium, 2-cyano-3-benzylthiazolium, 2-nitro-3-benzylthiazolium, 2-carbamoyl-3-benzylthiazolium.

Examples of 2- (substituted) alkyl-3- (substituted) benzylthiazolium 2-methyl-3-benzylthiazolium, 2-ethyl-
3-benzylthiazolium, 2-butyl-3-benzylthiazolium, 2-octyl-3-benzylthiazolium, 2-decyl-3-benzylthiazolium, 2-octadecyl-3-benzylthiazolium , 2-isopropyl-3-benzylthiazolium, 2-cyclohexyl-
3-benzylthiazolium, 2- (4-decylcyclohexyl) -3-benzylthiazolium, 2-fluoromethyl-3-benzylthiazolium, 2-chloromethyl-
3-benzylthiazolium, 2-bromomethyl-3-benzylthiazolium, 2-trifluoromethyl-3-benzylthiazolium, 2-trichloromethyl-3-benzylthiazolium, 2-hydroxymethyl-3- Benzylthiazolium, 2-carboxymethyl-3-benzylthiazolium, 2-mercaptomethyl-3-benzylthiazolium, 2-cyanomethyl-3-benzylthiazolium, 2-nitromethyl-3-benzylthiazolium ,
2-Azidomethyl-3-benzylthiazolium.

Examples of 2- (substituted) alkenyl-3- (substituted) benzylthiazolium 2-vinyl-3-benzylthiazolium, 2- (1-propenyl) -3-benzylthiazolium, 2- ( 2-propenyl) -3-benzylthiazolium, 2- (1-octadecenyl) -3-benzylthiazolium, 2- (isopropenyl) -3-benzylthiazolium, 2- (1
-Cyclohexenyl) -3-benzylthiazolium, 2
-(Trifluoroethenyl) -3-benzylthiazolium, 2- (1-chloroethenyl) -3-benzylthiazolium, 2- (2,2-dibromoethenyl) -3-benzylthiazolium, 2- (4-Hydroxy-1-butenyl) -3-benzylthiazolium, 2- (1-carboxyethenyl) -3-benzylthiazolium, 2- (5-
Mercapto-1-hexenyl) -3-benzylthiazolium, 2- (1-cyanoethenyl) -3-benzylthiazolium, 2- (3-nitro-1-propenyl) -3-
Benzylthiazolium, 2- (4-azido-2-butenyl) -3-benzylthiazolium.

Examples of 2- (substituted) aryl-3- (substituted) benzylthiazolium 2-phenyl-3-benzylthiazolium, 2- (1-
Naphthyl) -3-benzylthiazolium, 2- (2-naphthyl) -3-benzylthiazolium, 2- (9-anthryl) -3-benzylthiazolium, 2- (1-pyrenyl) -3- Benzylthiazolium, 2- (5-naphthacenyl) -3-benzylthiazolium, 2- (1-indenyl) -3-benzylthiazolium, 2- (2-azulenyl) -3-benzylthiazolium, 2- (p-tolyl) -3-benzylthiazolium, 2- (2,3-xylyl) -3-benzylthiazolium, 2- (p-cumenyl) -3-benzylthiazolium, 2- ( p-dodecylphenyl) -3-benzylthiazolium, 2- (p-cyclohexylphenyl) -3-benzylthiazolium,
2- (4-biphenyl) -3-benzylthiazolium,
2- (o-fluorophenyl) -3-benzylthiazolium, 2- (m-chlorophenyl) -3-benzylthiazolium, 2- (p-bromophenyl) -3-benzylthiazolium, 2- ( p-hydroxyphenyl) -3-
Benzylthiazolium, 2- (m-carboxyphenyl) -3-benzylthiazolium, 2- (o-mercaptophenyl) -3-benzylthiazolium, 2- (p-
Cyanophenyl) -3-benzylthiazolium, 2-
(M-nitrophenyl) -3-benzylthiazolium,
2- (m-azidophenyl) -3-benzylthiazolium.

Examples of 2- (substituted) aralkyl-3- (substituted) benzylthiazolium 2- (p-tolylmethyl) -3-benzylthiazolium, 2- (2-naphthylmethyl) -3-benzylthiazol Lithium, 2- (9-anthrylmethyl) -3-benzylthiazolium, 2- (4- (9-anthryl) butyl)
-3-benzylthiazolium, 2- (o-fluorobenzyl) -3-benzylthiazolium, 2- (m-chlorobenzyl) -3-benzylthiazolium, 2- (p-bromobenzyl) -3 -Benzylthiazolium, 2- (p
-Hydroxybenzyl) -3-benzylthiazolium,
2- (m-carboxybenzyl) -3-benzylthiazolium, 2- (o-mercaptobenzyl) -3-benzylthiazolium, 2- (p-cyanobenzyl) -3-benzylthiazolium, 2- (M-nitrobenzyl) -3
-Benzylthiazolium, 2- (m-azidobenzyl)
-3-benzylthiazolium.

Examples of 2- (substituted) alkoxy-3- (substituted) benzylthiazolium 2-methoxy-3-benzylthiazolium, 2-butoxy-3-benzylthiazolium, 2-octyloxy-
3-benzylthiazolium, 2-octadecyloxy-
3-benzylthiazolium, 2-isopropoxy-3-
Benzyl thiazolium, 2-cyclopentyloxy-3
-Benzylthiazolium, 2-fluoromethoxy-3-
Benzylthiazolium, 2-chloromethoxy-3-benzylthiazolium, 2-bromomethoxy-3-benzylthiazolium, 2-trifluoromethoxy-3-benzylthiazolium, 2-trichloromethoxy-3-benzyl Thiazolium, 2-hydroxymethoxy-3-benzylthiazolium, 2-carboxymethoxy-3-benzylthiazolium, 2-mercaptomethoxy-3-benzylthiazolium, 2-cyanomethoxy-3-benzylthiazol Lithium, 2- (nitromethoxy-3-benzylthiazolium, 2-azidomethoxy-3-benzylthiazolium.

Examples of 2- (substituted) aryloxy-3- (substituted) benzylthiazolium 2-phenoxy-3-benzylthiazolium, 2- (1
Naphthyloxy) -3-benzylthiazolium, 2-
(2-naphthyloxy) -3-benzylthiazolium,
2- (9-anthryloxy) -3-benzylthiazolium, 2- (9-phenanthryloxy) -3-benzylthiazolium, 2- (1-pyrenyloxy) -3-benzylthiazolium, 2- (5-naphthacenyloxy)
-3-benzylthiazolium, 2- (1-acenaphthyloxy) -3-benzylthiazolium, 2- (9-fluorenyloxy) -3-benzylthiazolium, 2-
(P-Tolyloxy) -3-benzylthiazolium, 2
-(2,3-Xylyloxy) -3-benzylthiazolium, 2- (p-decylphenoxy) -3-benzylthiazolium, 2- (p-cyclohexylphenoxy)-
3-benzylthiazolium, 2- (o-fluorophenoxy) -3-benzylthiazolium, 2- (m-chlorophenoxy) -3-benzylthiazolium, 2- (p-
Bromophenoxy) -3-benzylthiazolium, 2-
(P-Hydroxyphenoxy) -3-benzylthiazolium, 2- (m-carboxyphenoxy) -3-benzylthiazolium, 2- (o-mercaptophenoxy)-
3-benzylthiazolium, 2- (p-cyanophenoxy) -3-benzylthiazolium, 2- (m-nitrophenoxy) -3-benzylthiazolium, 2- (m-azidophenoxy) -3- Benzyl thiazolium.

Examples of 2- (substituted) acyl-3- (substituted) benzylthiazolium 2-formyl-3-benzylthiazolium, 2-acetyl-3-benzylthiazolium, 2-hexanoyl-3
-Benzylthiazolium, 2-lauroyl-3-benzylthiazolium, 2-stearoyl-3-benzylthiazolium, 2-isobutyryl-3-benzylthiazolium, 2-pivaloyl-3-benzylthiazolium, 2-
Cyclohexylcarbonyl-3-benzylthiazolium, 2-benzoyl-3-benzylthiazolium, 2-
(1-naphthoyl) -3-benzylthiazolium, 2-
(2-naphthoyl) -3-benzylthiazolium, 2-
(9-anthroyl) -3-benzylthiazolium, 2
-(5-naphthaceroyl) -3-benzylthiazolium, 2- (cinnamoyl) -3-benzylthiazolium, 2- (α-fluoroacetyl) -3-benzylthiazolium, 2- (α-chloroacetyl ) -3-Benzylthiazolium, 2- (α-bromoacetyl) -3-benzylthiazolium, 2- (α-hydroxyacetyl)-
3-benzylthiazolium, 2- (α-carboxyacetyl) -3-benzylthiazolium, 2- (α-mercaptoacetyl) -3-benzylthiazolium, 2- (α
-Cyanoacetyl) -3-benzylthiazolium, 2-
(Α-nitroacetyl) -3-benzylthiazolium,
2- (α-azidoacetyl) -3-benzylthiazolium.

2- (substituted) alkoxycarbonyl-3-
Examples of (substituted) benzylthiazolium 2-methoxycarbonyl-3-benzylthiazolium,
2-ethoxycarbonyl-3-benzylthiazolium,
2-octyloxycarbonyl-3-benzylthiazolium, 2-octadecyloxycarbonyl-3-benzylthiazolium, 2- (t-butoxycarbonyl) -3
-Benzylthiazolium, 2-cyclohexyloxycarbonyl-3-benzylthiazolium, 2-fluoromethoxycarbonyl-3-benzylthiazolium, 2-chloromethoxycarbonyl-3-benzylthiazolium,
2-Bromomethoxycarbonyl-3-benzylthiazolium, 2-trifluoromethoxycarbonyl-3-benzylthiazolium, 2-trichloromethoxycarbonyl-3-benzylthiazolium, 2-tribromomethoxycarbonyl-3-benzyl Thiazolium, 2- (hydroxymethoxycarbonyl-3-benzylthiazolium,
2-carboxymethoxycarbonyl-3-benzylthiazolium, 2-mercaptomethoxycarbonyl-3-benzylthiazolium, 2-cyanomethoxycarbonyl-
3-benzylthiazolium, 2-nitromethoxycarbonyl-3-benzylthiazolium, 2-azidomethoxycarbonyl-3-benzylthiazolium.

2- (substituted) aryloxycarbonyl-
Examples of 3- (substituted) benzylthiazolium 2-phenoxycarbonyl-3-benzylthiazolium, 2- (1 naphthyloxycarbonyl) -3-benzylthiazolium, 2- (9-anthryloxycarbonyl) -3-benzylthiazolium, 2- (1-pyrenyloxycarbonyl) -3-benzylthiazolium, 2
-(5-naphthacenyloxycarbonyl) -3-benzylthiazolium, 2- (2-azulenyloxycarbonyl) -3-benzylthiazolium, 2- (p-tolyloxycarbonyl) -3-benzylthiah Zolium, 2-
(2,5-Xylyloxycarbonyl) -3-benzylthiazolium, 2- (p-cyclohexylphenoxycarbonyl) -3-benzylthiazolium, 2- (4-phenylphenoxycarbonyl) -3-benzylthiazol Lithium, 2- (o-fluorophenoxycarbonyl) -3
-Benzylthiazolium, 2- (m-chlorophenoxycarbonyl) -3-benzylthiazolium, 2- (p-
Bromophenoxycarbonyl) -3-benzylthiazolium, 2- (p-hydroxyphenoxycarbonyl)-
3-benzylthiazolium, 2- (m-carboxyphenoxycarbonyl) -3-benzylthiazolium, 2-
(O-Mercaptophenoxycarbonyl) -3-benzylthiazolium, 2- (p-cyanophenoxycarbonyl) -3-benzylthiazolium, 2- (m-nitrophenoxycarbonyl) -3-benzylthiazolium, 2
-(M-Azidophenoxycarbonyl) -3-benzylthiazolium.

Examples of 4-substituted-3- (substituted) benzylthiazolium 4-fluoro-3-benzylthiazolium, 4-chloro-3-benzylthiazolium, 4-bromo-3-benzylthiazolium 4-hydroxy-3-benzylthiazolium, 4-carboxy-3-benzylthiazolium,
4-Mercapto-3-benzylthiazolium, 4-cyano-3-benzylthiazolium, 4-nitro-3-benzylthiazolium, 4-carbamoyl-3-benzylthiazolium, 4-methyl-3- Benzyl thiazolium,
4-octyl-3-benzylthiazolium, 4-decyl-3-benzylthiazolium, 4-octadecyl-3-
Benzylthiazolium, 4-isopropyl-3-benzylthiazolium, 4-cyclohexyl-3-benzylthiazolium, 4-fluoromethyl-3-benzylthiazolium, 4-vinyl-3-benzylthiazolium, 4-
Phenyl-3-benzylthiazolium, 4- (p-tolylmethyl) -3-benzylthiazolium, 4-methoxy-3-benzylthiazolium, 4-phenoxy-3-benzylthiazolium, 4-acetyl- 3-benzylthiazolium, 4-methoxycarbonyl-3-benzylthiazolium, 4-phenoxycarbonyl-3-benzylthiazolium.

Examples of 5-substituted-3- (substituted) benzylthiazolium 5-fluoro-3-benzylthiazolium, 5-chloro-3-benzylthiazolium, 5-bromo-3-benzylthiazolium , 5-hydroxy-3-benzylthiazolium, 5-carboxy-3-benzylthiazolium,
5-Mercapto-3-benzylthiazolium, 5-cyano-3-benzylthiazolium, 5-nitro-3-benzylthiazolium, 5-carbamoyl-3-benzylthiazolium, 5-methyl-3- Benzyl thiazolium,
5-octyl-3-benzylthiazolium, 5-decyl-3-benzylthiazolium, 5-octadecyl-3-
Benzylthiazolium, 5-isopropyl-3-benzylthiazolium, 5-cyclohexyl-3-benzylthiazolium, 5-fluoromethyl-3-benzylthiazolium, 5-vinyl-3-benzylthiazolium, 5-
Phenyl-3-benzylthiazolium, 5- (p-tolylmethyl) -3-benzylthiazolium, 5-methoxy-3-benzylthiazolium, 5-phenoxy-3-benzylthiazolium, 5-acetyl- 3-benzylthiazolium, 5-methoxycarbonyl-3-benzylthiazolium, 5-phenoxycarbonyl-3-benzylthiazolium.

Examples of polysubstituted-3- (substituted) benzylthiazolium 4,5-difluoro-3-benzylthiazolium, 4,
5-dichloro-3-benzylthiazolium, 4,5-dibromo-3-benzylthiazolium, 2,4-dihydroxy-3-benzylthiazolium, 2-mercapto-4
-Methyl-3-benzylthiazolium, 2,4,5-trimethyl-3-benzylthiazolium.

Examples of fused ring substituted-3- (substituted) benzylthiazolium 4,5-tetramethylene-3-benzylthiazolium,
4,5-ethylenedioxy-3-benzylthiazolium, 4,5-diethylenedioxy-3-benzylthiazolium, 4,5-ethylenedithio-3-benzylthiazolium, 4,5-diethylenedithio -3-benzylthiazolium, 2-methyl-4,5-tetramethylene-3-
Benzyl thiazolium.

Examples of Oxazolium N-benzyloxazolium, N- (p-fluorobenzyl) oxazolium, N- (p-hydroxybenzyl) oxazolium, N- (p-mercaptobenzyl)
Oxazolium, (p-methylbenzyl) oxazolium, N- (p-ethylbenzyl) oxazolium, N-
(P-Methoxybenzyl) oxazolium, N-phenacyloxazolium, N- (o-fluorophenacyl)
Oxazolium, N- (m-fluorophenacyl) oxazolium, N- (p-ethylphenacyl) oxazolium, N-allyloxazolium, N- (2-methyl-
3,3-dicyano-2-propenyl) oxazolium,
N- (2-benzoyl-3,3-dicyano-2-propenyl) oxazolium, N-methoxyoxazolium,
N- (fluoromethoxy) oxazolium, N-phenoxyoxazolium, N- (o-fluorophenoxy)
Oxazolium, 2-mercapto-3-benzyloxazolium, 2-methyl-3-benzyloxazolium,
2-vinyl-3-benzyloxazolium, 2-phenyl-3-benzyloxazolium, 2- (p-tolylmethyl) -3-benzyloxazolium, 2-butoxy-
3-benzyloxazolium, 2- (1 naphthyloxy) -3-benzyloxazolium, 2-acetyl-3
-Benzyloxazolium, 2-methoxycarbonyl-
3-benzyloxazolium, 2-phenoxycarbonyl-3-benzyloxazolium, 4-chloro-3-benzyloxazolium, 5-isopropyl-3-benzyloxazolium, 5-cyclohexyl-3-benzyloxazo Lithium, 5-vinyl-3-benzyloxazolium, 2-mercapto-4-methyl-3-benzyloxazolium, 4,5-tetramethylene-3-benzyloxazolium.

Examples of imidazolium N-benzylimidazolium, N- (p-fluorobenzyl) imidazolium, N- (p-hydroxybenzyl) imidazolium, N- (p-mercaptobenzyl)
Imidazolium, (p-methylbenzyl) imidazolium, N- (p-ethylbenzyl) imidazolium, N-
(P-Methoxybenzyl) imidazolium, N-phenacylimidazolium, N- (o-fluorophenacyl)
Imidazolium, N- (m-fluorophenacyl) imidazolium, N- (p-ethylphenacyl) imidazolium, N-allylimidazolium, N- (2-methyl-)
3,3-dicyano-2-propenyl) imidazolium,
N- (2-benzoyl-3,3-dicyano-2-propenyl) imidazolium, N-methoxyimidazolium,
N- (fluoromethoxy) imidazolium, N-phenoxyimidazolium, N- (o-fluorophenoxy)
Imidazolium, 2-mercapto-1-benzylimidazolium, 2-methyl-1-benzylimidazolium,
2-Vinyl-1-benzylimidazolium, 2-phenyl-1-benzylimidazolium, 2- (p-tolylmethyl) -1-benzylimidazolium, 2-butoxy-
1-Benzylimidazolium, 2- (1naphthyloxy) -1-benzylimidazolium, 2-acetyl-1
-Benzylimidazolium, 2-methoxycarbonyl-
1-Benzylimidazolium, 2-phenoxycarbonyl-1-benzylimidazolium, 4-chloro-1-benzylimidazolium, 5-isopropyl-1-benzylimidazolium, 5-cyclohexyl-1-benzylimidazolium, 5-vinyl -1-Benzylimidazolium, 2-mercapto-4-methyl-1-benzylimidazolium, 4,5-tetramethylene-1-benzylimidazolium.

Examples of pyrrolium N-benzylpyrrolium, N- (p-fluorobenzyl) pyrorium, N- (p-hydroxybenzyl) pyrorium, N- (p-mercaptobenzyl) pyrorium, (p-methylbenzyl) pyrorium, N- (p
-Ethylbenzyl) pyrorium, N- (p-methoxybenzyl) pyrorium, N-phenacylpyrorium, N- (o-fluorophenacyl) pyrorium, N
-(M-fluorophenacyl) pyrorium, N- (p
-Ethylphenacyl) pyrrolium, N-allylpyrrolium, N- (2-methyl-3,3-dicyano-2-propenyl) pyrrolium, N- (2-benzoyl-3,
3-dicyano-2-propenyl) pyrorium, N-methoxypyrrolium, N- (fluoromethoxy) pyrorium, N-phenoxypyrorium, N- (o-fluorophenoxy) pyrorium, 2-mercapto-1-
Benzylpyrrolium, 2-methyl-1-benzylpyrrolium, 2-vinyl-1-benzylpyrrolium, 2
-Phenyl-1-benzylpyrorium, 2- (p-tolylmethyl) -1-benzylpyrrolium, 2-butoxy-1-benzylpyrorium, 2- (1naphthyloxy) -1-benzylpyrorium, 2-acetyl- 1
-Benzylpyrrolium, 2-methoxycarbonyl-1
-Benzylpyrrolium, 2-phenoxycarbonyl-
1-benzylpyrrolium, 4-chloro-1-benzylpyrrolium, 5-isopropyl-1-benzylpyrrolium, 5-cyclohexyl-1-benzylpyrrolium, 5-vinyl-1-benzylpyrrolium, 2-mercapto- 4-methyl-1-benzylpyrrolium, 4,
5-tetramethylene-1-benzylpyrrolium.

On the other hand, as the substituent Z in the borate anion represented by the general formula (2) which constitutes the energy ray sensitive acid generator (A) of the present invention, the substituent Z is 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, as the structure of the borate anion of the energy ray sensitive acid generator (A) of the present invention, specifically, pentafluorophenyl trifluoroborate,
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, tetrakis (pentafluorophenyl) borate is preferred as the structure of the borate anion of the energy ray sensitive acid generator (A) of the present invention.
It is tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

Therefore, specific examples of the onium borate complex constituting the energy ray sensitive acid generator (A) of the present invention include:

N- (o-cyanobenzyl) thiazolium 3,5-bis (trifluoromethyl) phenyl trifluoroborate, N- (o-nitrobenzyl) oxazolium bis (pentafluorophenyl) difluoroborate, N- ( p-Bromobenzyl) imidazolium bis [3,5-bis (trifluoromethyl) phenyl] difluoroborate, N- (o-hydroxybenzyl) pyrrolium tris (pentafluorophenyl) fluoroborate, N- (p-cyanobenzyl) ) Thiazolium tris [3,5-bis (trifluoromethyl) phenyl] fluoroborate,

N-phenacyl thiazolium pentafluorophenyl trifluoroborate, N- (o-cyanophenacyl) oxazolium 3,5-bis (trifluoromethyl) phenyl trifluoroborate, N- (m-chlorophenacyl) imidazo Lithium bis (pentafluorophenyl) difluoroborate, N- (o-hydroxyphenacyl) pyrrolium bis [3,5-bis (trifluoromethyl) phenyl] difluoroborate, N-
(P-Methoxyphenacyl) thiazolium tris (pentafluorophenyl) fluoroborate, N- (p-benzoylphenacyl) oxazolium tris [3,5-
Examples thereof include bis (trifluoromethyl) phenyl] fluoroborate and dioctadecyl (phenacyl) imidazolium tetrakis (pentafluorophenyl) borate, but the present invention is not limited to these examples.

Further, as a preferable structure of the onium borate complex of the energy ray sensitive acid generator (A) of the present invention, a thiazolium cation in which X is —S— in the general formula (1) and an anion are preferred. A thiazolium borate complex whose part is composed of a borate anion of either tetrakis (pentafluorophenyl) borate or tetrakis [3,5-bis (trifluoromethyl) phenyl] borate. The specifics are given below.

Examples of thiazolium tetrakis (pentafluorophenyl) borate N- (substituted) benzyl thiazolium tetrakis (pentafluorophenyl) borate Examples N-benzylthiazolium tetrakis (pentafluorophenyl) borate, N- ( o-Fluorobenzyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (p-bromobenzyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (p-
Cyanobenzyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (m-nitrobenzyl)
Thiazolium tetrakis (pentafluorophenyl) borate, N- (2,6-dichlorophenylmethyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (pentafluorophenylmethyl) thiazolium tetrakis (pentafluorophenyl) borate , N
-(P- (trifluoromethyl) benzyl) thiazolium tetrakis (pentafluorophenyl) borate, N
-(P-Hydroxybenzyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (p-mercaptobenzyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (p-methylsulfinylbenzyl) thiazolium tetrakis (Pentafluorophenyl) borate, N- (p-methylsulfonylbenzyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (p-acetylbenzyl) thiazolium tetrakis (pentafluorophenyl) borate,
N- (p-benzoylbenzyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (p-methylbenzyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (o-methoxycarbonylbenzyl) thiazolium Tetrakis (pentafluorophenyl) borate, N- (1-naphthylmethyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (2-naphthylmethyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (9 -Anthrylmethyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (1-pyrenylmethyl)
Thiazolium tetrakis (pentafluorophenyl) borate.

Examples of N- (substituted) phenacyl thiazolium tetrakis (pentafluorophenyl) borate N-phenacyl thiazolium tetrakis (pentafluorophenyl) borate, N- (o-fluorophenacyl) thiazolium tetrakis (Pentafluorophenyl) borate, N- (p-chlorophenacyl) thiazolium tetrakis (pentafluorophenyl) borate,
N- (p-bromophenacyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (p-cyanophenacyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (m-nitrophenacyl)
Thiazolium tetrakis (pentafluorophenyl) borate, N- (2,4-difluorophenylcarbonylmethyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (p- (trifluoromethyl) phenacyl) thiazolium tetrakis (Pentafluorophenyl) borate, N- (o-acetylphenacyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (p-benzoylphenacyl) thiazolium tetrakis (pentafluorophenyl) borate, N-
(O-Methylphenacyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (p-methoxycarbonylphenacyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (1-naphthoylmethyl) thiazo Lithium tetrakis (pentafluorophenyl) borate, N- (2-naphthoylmethyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (9-anthroylmethyl) thiazolium tetrakis (pentafluorophenyl) borate.

Examples of N- (substituted) allyl thiazolium tetrakis (pentafluorophenyl) borate N-allyl thiazolium tetrakis (pentafluorophenyl) borate, N- (3,3-dicyano-2-propenyl) thiazo Lithium tetrakis (pentafluorophenyl) borate, N- (2-methyl-3,3-dicyano-2-propenyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (2-benzoyl-
3,3-Dicyano-2-propenyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (2
-Phenyl-3,3-dicyano-2-propenyl) thiazolium tetrakis (pentafluorophenyl) borate, N- (3,3-bis (methoxycarbonyl) -2-
Propenyl) thiazolium tetrakis (pentafluorophenyl) borate.

Examples of N-alkoxythiazolium tetrakis (pentafluorophenyl) borate N-methoxythiazolium tetrakis (pentafluorophenyl) borate, N-isopropoxythiazolium tetrakis (pentafluorophenyl) borate, N-
(T-butoxy) thiazolium tetrakis (pentafluorophenyl) borate, N-cyclopentyloxythiazolium tetrakis (pentafluorophenyl) borate, N-cyclohexyloxythiazolium tetrakis (pentafluorophenyl) borate.

Examples of N-substituted alkoxy thiazolium tetrakis (pentafluorophenyl) borate N- (fluoromethoxy) thiazolium tetrakis (pentafluorophenyl) borate, N- (2-chloroethoxy) thiazolium tetrakis (penta) Fluorophenyl) borate, N- (3-bromopropoxy) thiazolium tetrakis (pentafluorophenyl) borate, N- (4-cyanobutoxy) thiazolium tetrakis (pentafluorophenyl) borate, N- (8-nitrooctyl Oxy) thiazolium tetrakis (pentafluorophenyl) borate.

Examples of N-aryloxythiazolium tetrakis (pentafluorophenyl) borate N-phenoxythiazolium tetrakis (pentafluorophenyl) borate, N- (1-naphthyloxy) thiazolium tetrakis (pentafluorophenyl) Borate, N- (2-naphthyloxy) thiazolium tetrakis (pentafluorophenyl) borate, N- (9-
Anthryloxy) thiazolium tetrakis (pentafluorophenyl) borate, N- (9-phenanthryloxy) thiazolium tetrakis (pentafluorophenyl) borate.

Examples of N-substituted aryloxythiazolium tetrakis (pentafluorophenyl) borate N- (o-fluorophenoxy) thiazolium tetrakis (pentafluorophenyl) borate, N- (m-chlorophenoxy) thiazolium Tetrakis (pentafluorophenyl) borate, N- (p-bromophenoxy) thiazolium tetrakis (pentafluorophenyl) borate, N- (p-hydroxyphenoxy) thiazolium tetrakis (pentafluorophenyl) borate.

Examples of 2-substituted-3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 2-fluoro-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-chloro-3
-Benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-bromo-3-benzylthiazolium tetrakis (pentafluorophenyl) borate.

Examples of 2- (substituted) alkyl-3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 2-methyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-isopropyl-
3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-cyclohexyl-3-benzylthiazolium tetrakis (pentafluorophenyl)
Borate.

Examples of 2- (substituted) alkenyl-3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 2-vinyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- (trifluoro) Loethenyl) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- (1-cyanoethenyl) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate.

Examples of 2- (substituted) aryl-3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 2-phenyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- (1 -Naphthyl) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- (p-tolyl) -3
-Benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- (p-bromophenyl) -3-
Benzyl thiazolium tetrakis (pentafluorophenyl) borate.

Examples of 2- (substituted) aralkyl-3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 2- (p-tolylmethyl) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-
(2-naphthylmethyl) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-
(P-Cyanobenzyl) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate.

Examples of 2- (substituted) alkoxy-3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 2-methoxy-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-isopropoxy -3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-cyclopentyloxy-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-trifluoromethoxy-3
-Benzylthiazolium tetrakis (pentafluorophenyl) borate.

Examples of 2- (substituted) aryloxy-3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 2-phenoxy-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- ( 1-naphthyloxy) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- (2,3-
Xylyloxy) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- (m-carboxyphenoxy) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate.

2- (Substituted) acyl-3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl)
Examples of borates 2-acetyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- (9-anthroyl) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- (cinnamoyl) -3 -Benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- (α-carboxyacetyl) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate.

2- (substituted) alkoxycarbonyl-3-
Examples of (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 2-ethoxycarbonyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-
(T-Butoxycarbonyl) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2
-Cyclohexyloxycarbonyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-fluoromethoxycarbonyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate.

2- (substituted) aryloxycarbonyl-
Examples of 3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 2-phenoxycarbonyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-
(P-Tolyloxycarbonyl) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2- (p-bromophenoxycarbonyl) -3-benzylthiazolium tetrakis (pentafluorophenyl) borate.

Examples of 4-substituted-3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 4-chloro-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 4-isopropyl-
3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 4-cyclohexyl-3-benzylthiazolium tetrakis (pentafluorophenyl)
Borate, 4-fluoromethyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate,
4-phenoxy-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 4-methoxycarbonyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate.

Examples of 5-substituted-3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 5-hydroxy-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 5-octyl-
3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 5-phenyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 5-acetyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate.

Examples of polysubstituted-3- (substituted) benzylthiazolium tetrakis (pentafluorophenyl) borate 4,5-difluoro-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 4,5-dichloro- 3-Benzylthiazolium tetrakis (pentafluorophenyl) borate, 4,5-dibromo-3-
Benzylthiazolium tetrakis (pentafluorophenyl) borate, 2,4-dihydroxy-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 2-mercapto-4-methyl-3-benzylthiazolium tetrakis (pentafluoro) Phenyl) borate, 2,4,5-trimethyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate.

Examples of fused ring substituted-3- (substituted) benzyl thiazolium tetrakis (pentafluorophenyl) borate 4,5-tetramethylene-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 4,5
-Ethylenedioxy-3-benzylthiazolium tetrakis (pentafluorophenyl) borate, 4,5-ethylenedithio-3-benzylthiazolium tetrakis (pentafluorophenyl) borate.

Examples of thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate N- (substituted) benzyl thiazolium tetrakis [3,5]
Examples of -bis (trifluoromethyl) phenyl] borate N-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (o
-Fluorobenzyl) thiazolium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, N
-(P-Bromobenzyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-cyanobenzyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl ]
Borate, N- (m-nitrobenzyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (2,6-dichlorophenylmethyl) thiazolium tetrakis [3,5-bis ( Trifluoromethyl) phenyl] borate, N- (pentafluorophenylmethyl) thiazolium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, N-
(P- (trifluoromethyl) benzyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-hydroxybenzyl) thiazolium tetrakis [3,5-bis (trifluoro) Methyl) phenyl] borate, N- (p-mercaptobenzyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-methylsulfinylbenzyl) thiazolium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, N
-(P-Methylsulfonylbenzyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-acetylbenzyl) thiazolium tetrakis [3,5-bis (trifluoromethyl)
Phenyl] borate, N- (p-benzoylbenzyl)
Thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-methylbenzyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (o -Methoxycarbonylbenzyl) thiazolium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, N
-(1-naphthylmethyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (2-naphthylmethyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl ]
Borate, N- (9-anthrylmethyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (1-pyrenylmethyl) thiazolium tetrakis [3,5-bis (trifluoro) Methyl)
Phenyl] borate.

Examples of N- (substituted) phenacyl thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate N-phenacyl thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] ] Borate, N- (o
-Fluorophenacyl) thiazolium tetrakis [3
5-bis (trifluoromethyl) phenyl] borate,
N- (p-chlorophenacyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-bromophenacyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) Phenyl] borate, N- (p-cyanophenacyl) thiazolium tetrakis [3,5-bis (trifluoromethyl)]
Phenyl] borate, N- (m-nitrophenacyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (2,4-difluorophenylcarbonylmethyl) thiazolium tetrakis [3 , 5-Bis (trifluoromethyl) phenyl] borate, N- (p- (trifluoromethyl) phenacyl)
Thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (o-acetylphenacyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- ( p-benzoylphenacyl) thiazolium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, N-
(O-Methylphenacyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-methoxycarbonylphenacyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) ) Phenyl] borate, N- (1-naphthoylmethyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (2-naphthoylmethyl) thiazolium tetrakis [3,5] -Bis (trifluoromethyl) phenyl] borate, N- (9-anthroylmethyl) thiazolium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate.

Examples of N- (substituted) allyl thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate N-allyl thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate , N- (3,3
-Dicyano-2-propenyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (2-methyl-3,3-dicyano-2-propenyl) thiazolium tetrakis [3,3 5-bis (trifluoromethyl) phenyl] borate, N- (2-benzoyl-3,3-dicyano-2-propenyl) thiazolium tetrakis [3,5-bis (trifluoromethyl)]
Phenyl] borate, N- (2-phenyl-3,3-dicyano-2-propenyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (3,3-bis (methoxy) Carbonyl) -2
-Propenyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

Examples of N-alkoxythiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate N-methoxythiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- Isopropoxy thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (t-butoxy) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N-cyclopentyl Oxythiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N-cyclohexyloxythiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

Examples of N-Substituted Alkoxythiazolium Tetrakis [3,5-bis (trifluoromethyl) phenyl] borate N- (Fluoromethoxy) thiazolium Tetrakis [3,5-bis (trifluoromethyl) phenyl] Borate, N- (2-chloroethoxy) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, N- (3-bromopropoxy) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (4-cyanobutoxy) thiazolium tetrakis [3,5-bis (trifluoro) Methyl)
Phenyl] borate, N- (8-nitrooctyloxy) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

Examples of N-aryloxythiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate N-phenoxythiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N -(1
-Naphthyloxy) thiazolium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, N-
(2-naphthyloxy) thiazolium tetrakis [3
5-bis (trifluoromethyl) phenyl] borate,
N- (9-anthryloxy) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (9-phenanthryloxy) thiazolium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate.

Examples of N-substituted aryloxythiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate N- (o-fluorophenoxy) thiazolium tetrakis [3,5-bis (trifluoromethyl) ) Phenyl] borate, N- (m-chlorophenoxy) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N- (p-bromophenoxy) thiazolium tetrakis [3,5-bis (Trifluoromethyl)
Phenyl] borate, N- (p-hydroxyphenoxy) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

2-Substituted-3- (substituted) benzylthiazolium tetrakis [3,5-bis (trifluoromethyl)]
Examples of phenyl] borate 2-fluoro-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2-chloro-3-benzylthiazolium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, 2-bromo-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate.

Examples of 2- (substituted) alkyl-3- (substituted) benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2-methyl-3-benzylthiazolium tetrakis [3,3] 5-bis (trifluoromethyl) phenyl] borate, 2-isopropyl-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2-cyclohexyl-3-benzylthiazolium tetrakis [ 3,5-bis (trifluoromethyl) phenyl] borate.

Examples of 2- (substituted) alkenyl-3- (substituted) benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2-vinyl-3-benzylthiazolium tetrakis [3,3] 5-bis (trifluoromethyl) phenyl] borate, 2- (trifluoroethenyl) -3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2- (1-cyanoethenyl)- 3-benzylthiazolium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate.

Examples of 2- (substituted) aryl-3- (substituted) benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2-phenyl-3-benzylthiazolium tetrakis [3,3] 5-bis (trifluoromethyl) phenyl] borate, 2- (1-naphthyl) -3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2- (p-tolyl)- 3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2- (p-bromophenyl) -3-benzylthiazolium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate.

Examples of 2- (substituted) aralkyl-3- (substituted) benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2- (p-tolylmethyl) -3-benzylthiazolium Tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2- (2-naphthylmethyl) -3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2- ( p-Cyanobenzyl) -3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

Examples of 2- (substituted) alkoxy-3- (substituted) benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2-methoxy-3-benzylthiazolium tetrakis [3,3] 5-bis (trifluoromethyl) phenyl] borate, 2-isopropoxy-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2-cyclopentyloxy-3-benzylthiazolium Tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2-trifluoromethoxy-3-benzylthiazolium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate.

Examples of 2- (substituted) aryloxy-3- (substituted) benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2-phenoxy-3-benzylthiazolium tetrakis [3] , 5-Bis (trifluoromethyl) phenyl] borate, 2- (1naphthyloxy) -3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2- (2,3-xylyloxy ) -3-Benzylthiazolium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, 2-
(M-carboxyphenoxy) -3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl)
Phenyl] borate.

Examples of 2- (substituted) acyl-3- (substituted) benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2-acetyl-3-benzylthiazolium tetrakis [3,3] 5-bis (trifluoromethyl) phenyl] borate, 2- (9-anthroyl) -3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2- (cinnamoyl) -3-
Benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2- (α-carboxyacetyl) -3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate .

2- (Substituted) alkoxycarbonyl-3-
Examples of (substituted) benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2-ethoxycarbonyl-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate , 2- (t-butoxycarbonyl) -3-
Benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2-cyclohexyloxycarbonyl-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2- Fluoromethoxycarbonyl-3-
Benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

2- (substituted) aryloxycarbonyl-
3- (Substituted) benzylthiazolium tetrakis [3,5
Examples of -bis (trifluoromethyl) phenyl] borate 2-phenoxycarbonyl-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2- (p-tolyloxycarbonyl)
-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2- (p
-Bromophenoxycarbonyl) -3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

4-Substituted-3- (substituted) benzyl thiazolium tetrakis [3,5-bis (trifluoromethyl)
Examples of phenyl] borate 4-chloro-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 4-isopropyl-3-benzylthiazolium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, 4-cyclohexyl-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 4-fluoromethyl-3-benzylthiazolium tetrakis [3,5- Bis (trifluoromethyl) phenyl] borate, 4-phenoxy-
3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 4-methoxycarbonyl-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

5-Substituted-3- (substituted) benzyl thiazolium tetrakis [3,5-bis (trifluoromethyl)
Examples of phenyl] borate 5-hydroxy-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 5-octyl-3-benzylthiazolium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl]
Borate, 5-phenyl-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 5-acetyl-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) Phenyl] borate.

Examples of polysubstituted-3- (substituted) benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 4,5-difluoro-3-benzylthiazolium tetrakis [3,5-] Bis (trifluoromethyl) phenyl]
Borate, 4,5-Dichloro-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 4,5-Dibromo-3-benzylthiazolium tetrakis [3,5-bis ( Trifluoromethyl) phenyl] borate, 2,4-dihydroxy-3
-Benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 2-mercapto-4-methyl-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate , 2,4,5-Trimethyl-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl)]
Phenyl] borate.

Examples of fused ring substituted-3- (substituted) benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 4,5-tetramethylene-3-benzylthiazolium tetrakis [3] 5-bis (trifluoromethyl) phenyl] borate, 4,5-ethylenedioxy-3-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, 4,5-ethylenedithio-3 -Benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

Further, each onium borate complex represented by the following chemical formula is also preferred.

[0120]

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[0121]

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[0122]

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[0123]

[Chemical 6]

[0124]

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The onium borate complex which is the energy ray sensitive acid generator (A) of the present invention is easily decomposed by irradiation with energy rays, particularly light, to generate a strong acid. The reason for this is the high electron-accepting property of the onium borate complex. That is, the reduction potential of the onium borate complex is mainly determined by the structure of the onium cation portion, and the higher the reduction potential, the higher the electron accepting property, and the more easily it is susceptible to decomposition by the electron transfer reaction by irradiation with energy rays. is there.

The first characteristic of the energy ray sensitive acid generator (A) of the present invention is that the substituent R ¹ in the general formula (1) is
In addition, when the onium cation is reduced by receiving an electron, a substituent which introduces an irreversible reaction and is likely to be eliminated and which increases the reduction potential of the onium cation is introduced. Further, by introducing an electron-withdrawing group such as a cyano group, a nitro group or an alkoxycarbonyl group into the substituent on the onium ring, that is, the substituent R or R ² in the general formula (1), a higher reduction can be achieved. It is expected that the potential, that is, the electron accepting property is improved.

The reduction potential of these onium borate complexes can be easily determined by polarography or an electrochemical measurement method such as cyclic voltammetry. The onium borate complex described in this specification is a compound of Journal of Polymer Science Part A Polymer Chemistry (J. Pol.
ym. Sci. , A, Polym. Chem. ), The second
Volume 8, page 3137 (1990) and Journal of American Chemical Society (J. Am. C.
hem. Soc. ), 106, 4121 (198)
4 years), it can be easily measured.

The reduction potential of the onium borate complex which is the energy-sensitive ray acid generator (A) of the present invention is preferably -1.3 V or more, more preferably -1.0 V with respect to the saturated calomel electrode (SCE). As described above, the value is more preferably −0.8 V or more.

The second feature of the energy ray-sensitive acid generator (A) of the present invention is that it has been known that BF ₄ ⁻ and PF are known.
_This is to generate an extremely stronger acid than an onium salt having anions such as ₆ ⁻ , AsF ₆ ⁻ , and SbF ₆ ⁻ . Energy beam, in particular the strength of the acid generated by irradiation of light, varies greatly depending on the type of anion, a borate anion represented by the general formula (2) of the present invention, BF ₄ previously known ^-, PF ₆ ^-, AsF ₆ ^-, SbF
₆ ^- like compared with an onium salt having an anion can be generated even more stronger acids, as a result, it is possible to improve the sensitivity of the curable composition.

The third characteristic of the energy ray sensitive acid generator (A) of the present invention is that it has been known that BF ₄ ⁻ and PF are known.
_It is extremely compatible and soluble in organic solvents and various epoxy compounds than onium salts having anions such as ₆ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ . This is one of the important properties when used as a curable composition.

The fourth characteristic of the energy ray-sensitive acid generator (A) of the present invention is that it does not generate an undesired decomposition product unlike the conventionally known publicly known iodonium salts and sulfonium salts. For example, the known diphenyliodonium hexafluorophosphate produces highly toxic benzene, and the known triphenylphosphonium hexafluorophosphate produces malodorous diphenyl sulfide. Does not generate such undesirable decomposition products.

Many of the energy ray-sensitive acid generators (A) of the present invention usually do not absorb at wavelengths longer than the ultraviolet region.
Although it is poorly active in the near-ultraviolet to near-infrared light, a naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, naphthacene ring,
By introducing a substituent having a condensed polycyclic aromatic ring such as a perylene ring or a pentacene ring and other appropriate chromophores, an absorption band can be provided even in the visible region and an activity can be provided even in the wavelength region longer than the visible region. It is also possible.

Energy-sensitive ray acid generator (A) of the present invention
Can also be combined with a sensitizer (B) shown below to enhance the activity against energy rays and to provide an energy ray-sensitive acid generator composition with extremely high sensitivity. The sensitizer (B) as used herein means that energy or electrons are transferred between the energy-sensitive acid generator (A) and the energy-sensitive acid generator (A) by the action of energy rays. It promotes decomposition.

Specific examples of the sensitizer (B) include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, and 1,2-diketone derivatives represented by benzyl and camphorquinone. , Benzoin derivative,
Fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives,
Polymethine dyes such as xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives,
Acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives,
Azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalilloporphyrazine derivative, naphthalocyanine Derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes,
Examples include organic ruthenium complexes, and more specifically, "Dye Handbook" (1986) edited by Nobu Okawara et al.
, Kodansha), Nobu Okawara et al., "Chemistry of functional dyes"
(1981, CMC), Tadashiro Ikemori et al., "Special Functional Materials" (1986, CMC), but not limited to these dyes and sensitizers. Examples thereof include dyes and sensitizers that absorb light in the range from to the near infrared region, and two or more kinds of these may be used in an optional ratio as needed.

Preferred examples of these sensitizers (B) include condensed polycyclic aromatic derivatives such as naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, naphthacene derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, and benzo. Examples thereof include thiazole derivatives, and particularly preferable examples thereof include anthracene derivatives, acridine derivatives, and benzothiazole 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 thereof include acridine orange, benzoflavin, acridine yellow, acridine derivatives such as phosphine R, and benzothiazole derivatives such as cetoflavin T.

Next, the acid-curable compound (C) used in the present invention will be described. Here, the acid-curable compound (C) refers to polymerization or crosslinking by the action of energy rays in the presence of the energy ray-sensitive acid generator (A) or the energy ray-sensitive acid generator composition in the present specification. It means a compound that can be converted into a high molecular weight substance by a reaction, and includes the compounds shown below or a mixture thereof.

First, a compound that reduces the solubility of the novolak resin in alkali by a crosslinking or polymerization reaction under an acid catalyst or in combination with heating is an acid-curable compound (C). A typical example is a compound having a structure represented by the following general formula (3) as a compound having a methylol group as a formaldehyde precursor or a substituted methylol group. In the general formula _{(3) (ROCH 2) n} -A- (CH 2 OR ') m ( above formula (3), A is a group represented by B or B-Z-B, B is a substituted or An unsubstituted mononuclear or condensed polynuclear aromatic hydrocarbon group, or a heterocyclic group containing oxygen, sulfur, or nitrogen, Z is a single bond or alkylene which may have a substituent having 1 to 4 carbon atoms. Group, an arylene group which may have a substituent, an arylalkylene group, or —O—, —S—, —SO ₂ —, —CO—, —COO
-, -OCOO-, -CONH-, and an alkylene group which may have a substituent having a part of these bonds. Further, Z may be a polymer such as phenol resin. R and R ′ are independently of each other hydrogen, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group which may have a substituent, an arylalkyl group,
Or, it means an acyl group. n is an integer of 1 to 3, m is 0
-3. )

The substituted or unsubstituted mononuclear or condensed polynuclear aromatic hydrocarbon group represented by B to Z in the general formula (3) is an o-phenylene group, an m-phenylene group, a p-phenylene group. 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,

As the heterocyclic group containing oxygen, sulfur and nitrogen, 2,5-furylene group, 2,5-thienylene group, 2,
4-oxazolylene group, 2,4-thiazolylene group, 2,
5-benzofurylene group, 2,5-benzothienylene group,
Examples of the alkylene group such as 2,6-pyridylene group and 5,8-quinolylene group which may have a substituent having 1 to 4 carbon atoms include methylene group, ethylene group, trimethylene group, tetramethylene group and propylene group. , Ethylmethylene group, chloromethylene group, dimethylmethylene group, bis (trifluoromethyl) methylene group, and the like, arylene groups which may have a substituent include o-phenylene group, m-phenylene group, p-phenylene group. 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,

Examples of the arylalkylene group include a benzylidene group, a p-tolylmethylene group, a 2-naphthylmethylene group and the like, and further -O-, -S-, -SO _2- , -CO.
Examples of the alkylene group which may have a substituent having a part of —, —COO—, —OCOO—, and —CONH— bonds include a methylenedioxy group, an ethylenedioxy group, a propylenedioxy group, and diethylene. Dioxy group, triethylenedioxy group, methylenedithio group, ethylenedithio group, propylenedithio group, diethylenedithio group, triethylenedithio group, methylenedisulfonyl group, ethylenedisulfonyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, -OOC-CH ₂ -COO- group, -
OOC- (CH _{2) 2} -COO- groups, -CH ₂ --OCO
O-CH ₂ - _{group, -CH 2 - (OCOO-CH} 2) 2 -
Groups and the like.

Further, R and R ′ in the general formula (3) are
As the alkyl group having 1 to 4 carbon atoms represented by, 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 a cycloalkyl group, Cyclopentyl group, cyclohexyl group and the like, aryl groups which may have a substituent include 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-fluorophenyl group, p-chlorophenyl group,
A p-dimethylaminophenyl group, a p-phenylthiophenyl group and the like are arylalkyl groups such as a benzyl group, a 2-naphthylmethyl group, a 9-anthrylmethyl group,
Examples thereof include a phenylyl group, a styryl group and a cinnamyl group, and examples of the acyl group include an acetyl group, a hexanoyl group, a benzoyl group, a cyclohexanoyl group, a methoxallyl group and a salicyloyl group.

As specific examples of such an acid-curable compound (C), various aminoblasts or phenoblasts, that is, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, glycoluril-formaldehyde resins and their resins can be used. 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, as another specific example of the acid-curable compound (C), there is a methylolated or alkoxydimethylated phenol derivative which can serve as 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 (C), a compound having a silanol group, for example, JP-A No. 2-9
Examples thereof include compounds disclosed in JP-A-154266 and JP-A-2-173647.

Also, a mixture of polyene and 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 urethane compounds and the like, and a compound selected from trimethylolpropanetrithiol glycolate and pentaerythritol-tetra-3-mercaptopropionate as a polythiol, for example, are also acid-curable compounds. (C) can be exemplified.

The alkoxysilanes shown below can also be mentioned as the acid-curable compound (C). 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 (C), a compound capable of cationic polymerization 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, as the epoxy compound, conventionally known aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and further epoxide monomers and episulfite monomers can be mentioned. 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.

Examples of the aliphatic epoxy compound include 1,4-butanediol diglycidyl ether and 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 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.

Examples of vinyl ethers include 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, ethynyl vinyl ether, alkynyl vinyl ethers such as 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, 1,4-benzenedimethanol divinyl ether , M-phenylene bis (ethylene glycol ) Aralkyl divinyl et one ether such as divinyl ether, urethane polyvinyl ether (e.g., ALLIED-SIGNAL Inc., vect
omer2010) and the like.

The spiro orthoesters include
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.

Examples of aziridines include aziridine and 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-dioxolane and the like can be mentioned. Examples of cyclic acid anhydrides include phthalic anhydride, maleic anhydride, succinic anhydride, and examples of lactams include β-propiolactam, γ-butyrolactam, and δ-caprolactam.
In addition, examples of the aryl dialdehydes include 1,2-benzenedicarboxaldehyde, 1,2-naphthalenedialdehyde, and the like.

Further, the curable composition according to claim (4) of the present invention may contain a radically polymerizable compound (D) and a radical generator (E), if necessary, to further enhance the sensitivity. The curable composition possessed can be constructed.

The radically polymerizable compound (D) referred to in the present invention means a compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule,
It has a chemical form such as a monomer, an oligomer or a polymer.

Examples of such radically polymerizable compound (D) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and salts thereof, esters, urethanes,
Examples thereof include radically polymerizable compounds such as amides, anhydrides, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides and unsaturated polyurethanes. Specifically, 2-ethylhexyl acrylate, 2- Hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate,
Cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, tetramethylolmethanateto Acrylate, oligoester acrylate, acrylic acid derivatives such as N-methylol acrylamide, diacetone acrylamide, and epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylamino. Methyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacrylo Shi polyethoxy phenyl) methacrylic acid derivatives, such as propane, other, allyl glycidyl ether, diallyl phthalate,
Examples thereof include derivatives of allyl compounds such as triallyl trimellitate, and more specifically, Shinzo Yamashita et al., “Crosslinking Agent Handbook” (1981, Taiseisha) and Kiyomi Kato, “UV / EB. Curing handbook (raw materials) ", (1
1985, Kobunshi Kogyokai, edited by Radtech Research Group, "U
Application and Market of V / EB Curing Technology ", p. 79, (1989
Year, CMC), Kiyoshi Akamatsu, "Practical Technology of New Photosensitive Resins", (1987, CMC), Takeshi Endo,
Commercially available products described in "Refining Thermosetting Polymers" (1986, CMC), Eiichiro Takiyama, "Polyester Resin Handbook" (1988, Nikkan Kogyo Shimbun) or radical polymerization known in the industry. Examples of the monomer include a polymerizable or crosslinkable monomer, oligomer and polymer.

Further, the radical generator (E) referred to herein is the one disclosed in JP-A-5-213861 and JP-A-5-25.
5347 sulfonium complex and oxosulfonium complex, such as dimethylphenacylsulfonium triphenylbutyl borate, dimethylphenacylsulfoxonium triphenylbutyl borate, dimethylbenzylsulfonium triphenylbutyl borate, diphenylphenacylsulfonium triphenylbutyl borate, Triazine derivatives having a trichloromethyl group and a chromophore described in JP-B-59-1281, JP-B-61-9621 and JP-A-60-60104, for example,
2,6-bis (trichloromethyl) -4- (4-methoxynaphthyl) -1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (p-methoxystyryl)
-1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (3,4,5-trimethoxystyryl)
-1,3,5-triazine and the like, JP-A-59-1504
And the organic peroxides described in JP-A-61-243807, such as 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and 4-phenoxydichloroacetophenone (acetophenone initiator ( Sandoz, Sandoray 1000), 4-
t-Butyl-dichloroacetophenone (AKZO, Tr
Igonal-P2), 4-t-butyl-trichloroacetophenone (AKZO, Trigonal-P1),
Diethoxyacetophenone (Upjohn, DEA
P), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck, Darocur 1173), 1
-(4-Isopropylphenyl) -2-hydroxy-2
-Methylpropan-1-one (Merck, Darocur 1
116), 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one (Merck, Darocur 953), 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl). ) Ketone (Merck, Darocur 2959), 1-hydroxycyclohexyl phenyl ketone (Ciba Geigy, Irgacure 184), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 (Ciba Geigy, Irgacure 907) ), A benzoin-based initiator such as benzoin (Nippon Soda, Nisso Cure BO),
Benzoin Methyl Ether (Nippon Soda, Nisso Cure MBO), Benzoin Ethyl Ether (Nippon Soda, Nisso Cure EBO), Benzoin Isopropyl Ether (Nippon Soda, Nisso Cure IBPO), Benzoin Isobutyl Ether (Kurokane Kasei, Solvathlon BIB)
E), benzyl dimethyl ketal (Ciba Geigy, Irgacure 651) and the like, α-acyloxime ester which is a ketone type initiator, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone. , 2-ethylanthraquinone, 4 ′, 4 ″ -diethylisophthalophenone and the like. As other initiators, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1, which is an imidazole-based initiator,
2'-imidazole (Esprit, BCIM), carbazole initiator A-Cure (Asahi Denka Kogyo),
Acylphosphine oxide-based initiator 2,4,6
-Trimethylbenzoyldiphenylphosphine oxide, etc., JP-B-43-23684, JP-B-44-64
No. 13, Japanese Patent Publication No. 47-1604 and USP No. 35
67453, a diazonium compound such as benzenediazonium tetrafluoroborate, an organic azide compound described in USP No. 2848328, USP No. 2852379 and USP No. 2940853, JP-B-36-22062, JP-B-37-13109,
Japanese Patent Publication No. 38-18015 and Japanese Patent Publication No. 45-961
Ortho-quinonediazides described in No. 0, JP-B-55-3
9162, JP-A-59-140203, and "Macromolecules".
s) ”, Vol. 10, pp. 1307 (1977), various onium compounds such as iodonium compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, and European Patent 109851.
No., EP 126712, "Journal
Of Imaging Science (J.Imag.Sc
i. ) ”, Vol. 30, p. 174 (1986), for example, metal allene complexes described in Ciba Geigy, Inc., Irgacure 261; and titanocenes described in JP-A No. 61-151197, such as CGI 784, Ciba Geigy.・ Review (Coordi
Nation Chemistry Review
w) ", Vol. 84, pp. 85-277 (1988).
And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701, JP-A-3-209
Aluminate complex described in JP-A No. 2-1577.
No. 60 borate compound, JP-A-55-12755
No. 0 and 2, described in JP-A-60-202437.
4,5-Triarylimidazole dimer, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344, Ao Yamaoka, Hiroshi Morita, "Photosensitive Resin," 26
And sulfonic acid esters described in Kyoritsu Shuppan (1988). These radical generators are contained in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the radically polymerizable compound. Is preferred.

Energy-sensitive ray acid generator (A) of the present invention
Is used in an amount of 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and most preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the acid-curable compound (C). .

The curable composition of the present invention is mixed with a binder such as an organic high molecular polymer to prepare a glass plate, an aluminum plate,
It can be used by coating it on other metal plates or polymer films such as polyethylene terephthalate.

Binders usable 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, etc., supervised by Kiyoshi Akamatsu, "Practical technology of new photosensitive resin", (CMC,
1987) and "10188 Chemical Products", 657-7
An organic polymer known in the art described on page 67 (Kagaku Kogyo Nippo, 1988) can be used.

The curable composition of the present invention further comprises, according to purposes, dyes, organic and inorganic pigments, antifoggants, antifading agents, antihalation agents, optical brighteners, surfactants, and
Plasticizer, flame retardant, antioxidant, UV absorber, foaming agent,
It may be used by mixing with an antifungal agent, an antibacterial agent, an antistatic agent, a magnetic substance, or an organic solvent for the purpose of dilution.

As the method for polymerizing the curable composition of the present invention, it is possible to polymerize by irradiation with energy rays. In addition to this, at the same time as irradiation with these energy rays or after irradiation with energy rays, By adding heat energy such as heating or a thermal head,
It is also possible to obtain a desired polymer or cured product.

As an energy source for polymerizing the curable composition of the present invention, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, Light energy sources such as excimer lamps, excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers, various semiconductor lasers, YAG lasers, light emitting diodes, CRT light sources, and plasma light sources. Alternatively, an electron beam source using an EB generator may be used, and heat energy from a heating head or a thermal head may be used in combination.

Therefore, various inks, various printing plate materials, photoresists,
It can be applied to various recording media such as photosensitive materials such as electrophotography, direct printing plate materials, hologram materials and microcapsules, as well as adhesives, adhesives, adhesives, sealants and various paints. .

Energy-sensitive ray acid generator (A) of the present invention
Can be synthesized by reacting the corresponding onium salt with a borate compound as a raw material in a predetermined organic solvent or water or a mixed solvent of water and an organic solvent.
These onium salts, which are raw materials, are obtained by addition reaction of a thiazole derivative, an oxazole derivative, an imidazole derivative and a pyrrole derivative with an alkyl halide.
It can be easily synthesized by a known method. For example, N-phenacyl thiazolium bromide can be easily obtained by heating thiazole and phenacyl bromide in an organic solvent such as ethyl acetate.

On the other hand, the borate compound is a compound of Journal of Organic Chemistry (J. Org. Che).
m. ), 57, 5545 (1992), JP-A-6-184170, International Patent No. 95/03338.
It can be synthesized with reference to the method described in the publication. The energy-sensitive acid generator (A) thus obtained can determine the composition of the constituent elements by the elemental analysis value, and by FD-MS (Field Desorption Mass Spectrometry) The structure of the onium cation moiety can be determined and can be identified by this.

[0170]

The energy-sensitive acid generator (A) of the present invention is considered to generate an acid when it undergoes an energy transfer or electron transfer reaction in the molecule and is decomposed by irradiation with energy rays. . Further, when the energy ray sensitive acid generator composition containing the energy ray sensitive acid generator (A) and the sensitizer (B) is used, the energy ray sensitive energy is irradiated from the sensitizer (B) by irradiation with energy rays. Transfer of energy or electrons to the linear acid generator (A) occurs,
It is considered that the energy ray sensitive acid generator (A) decomposes to generate an acid. As described above, when the acid-curable compound (C) coexists in the process of decomposing the energy ray-sensitive acid generator (A) and generating an acid, the generated acid causes polymerization of the acid-curable compound (C) or It is considered that a crosslinking reaction occurs to give a cured product.

By improving the substituents on the onium cation represented by the general formula (1), the crystallinity, stability and solubility in various organic solvents can be improved.
Further, it gives better results in improving the sensitivity of the curable composition containing the acid-curable compound (C) than the conventional onium salt.

[0172]

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. First, prior to the examples, synthesis examples of the energy ray-sensitive acid generator (A) of the present invention will be shown. Note that F
The measured value of D-MS shows a standard peak. In addition, the number in parentheses attached to this indicates the atomic weight of each element as C = 1.
2, H = 1, O = 16, N = 14, S = 32, B = 1
1 shows the fragment when calculated with F = 19.

Synthesis Example 1 Synthesis of N-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 0.239 parts of N-benzylthiazolium chloride
50 parts of an aqueous solution containing 1.00 parts of sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate was dissolved in 50 parts of distilled water and stirred to give 1 part.
It was added dropwise at 25 ° C. over 0 minutes. The produced crystal was filtered, washed with distilled water, and dried under reduced pressure to obtain 0.815 part of N-benzylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate. FD chromatography MS m / z 176 ((M -B (C 6 H 3 (C
^{_{F 3) 2) 4) +}} ) Elemental analysis C ₄₂ H ₂₂ NSBF ₂₄ theoretical C; 48.53%, H; 2.13 %, N; 1.35%, S; 3.08%. Measurements C; 48.75%, H; 2.35%, N; 1.51%, S; 3.19%.

Synthesis Example 2 Synthesis of 1-phenacyl-2-methylthiazolium tetrakis (pentafluorophenyl) borate 0.435 parts of 1-phenacyl-2-methylthiazolium bromide was dissolved in 50 parts of distilled water. Lithium tetrakis (pentafluorophenyl) while stirring and stirring
50 parts of an aqueous solution containing 1.00 parts of borate was added dropwise at 25 ° C. over 10 minutes. The formed crystals are filtered, washed with distilled water, dried under reduced pressure, and 1-phenacyl-2-methylthiazolium tetrakis (pentafluorophenyl)
Obtained was 0.918 part of borate. FD-MS m / z 218 ((M-B (C
₆ F ₅ ) ₄ ) ⁺ ) Elemental analysis C ₃₆ H ₁₂ ONSBF ₂₀ Theoretical value C; 48.19%, H; 1.35%, N; 1.56%, S; 3.57%. Measurements C; 48.42%, H; 1.52%, N; 1.64%, S; 3.71%.

Synthesis Example 3 Synthesis of 1-phenacyl-2-methyloxazolium tetrakis (pentafluorophenyl) borate 0.411 parts of 1-phenacyl-2-methyloxazolium bromide was dissolved in 50 parts of distilled water. Lithium tetrakis (pentafluorophenyl) while stirring and stirring
50 parts of an aqueous solution containing 1.00 parts of borate was added dropwise at 25 ° C. over 10 minutes. The produced crystal was filtered, washed with distilled water, and dried under reduced pressure to obtain 0.721 part of 1-phenacyl-2-methyloxazolium tetrakis (pentafluorophenyl) borate. FD-MS m / z 202 ((M-B (C
₆ F ₅ ) ₄ ) ⁺ ) Elemental analysis C ₃₆ H ₁₂ O ₂ NBF ₂₀ Theoretical value C; 49.06%, H; 1.37%, N; 1.59%. Measurements C; 49.27%, H; 1.51%, N; 1.71%.

Synthesis Example 4 Synthesis of 3-phenacyl-1,2-dimethylimidazolium tetrakis (pentafluorophenyl) borate 0.430 parts of 3-phenacyl-1,2-dimethylimidazolium bromide and 50 parts of distilled water 50 parts of an aqueous solution containing 1.00 parts of lithium tetrakis (pentafluorophenyl) borate while stirring and
It was added dropwise at 25 ° C. over 0 minutes. The crystals formed are filtered, washed with distilled water, dried under reduced pressure, and then treated with 3-phenacyl-
0.718 parts of 1,2-dimethylimidazolium tetrakis (pentafluorophenyl) borate was obtained. FD-MS m / z 215 ((M-B (C
₆ F ₅ ) ₄ ) ⁺ ) Elemental analysis C ₃₇ H ₁₅ ON ₂ BF ₂₀ Theoretical value C; 49.69%, H; 1.69%, N; 3.13%. Measurements C; 49.91%, H; 1.82%, N; 3.21%.

(Synthesis Example 5) Synthesis of 1-phenacyl-2,3,3-trimethylpyrrolium tetrakis (pentafluorophenyl) borate 0.449 parts of 1-phenacyl-2,3,3-trimethylpyrrolium bromide 50 parts of an aqueous solution containing 1.00 parts of lithium tetrakis (pentafluorophenyl) borate was dissolved in 50 parts of distilled water and stirred at 25 ° C. over 10 minutes. The produced crystal was filtered, washed with distilled water, and dried under reduced pressure to obtain 0.814 part of 1-phenacyl-2,3,3-trimethylpyrrolium tetrakis (pentafluorophenyl) borate. FD-MS m / z 228 ((M-B (C
₆ F ₅ ) ₄ ) ⁺ ) Elemental analysis C ₃₉ H ₁₈ ONBF ₂₀ Theoretical value C; 51.63%, H; 2.00%, N; 1.54%. Measurements C; 51.84%, H; 2.15%, N; 1.64%.

In the same manner, another energy-sensitive acid generator (A) described in the specification was synthesized.

Example 1 As the acid-curable compound (C), 3,4-epoxycyclohexylmethyl-3,4-
Epoxycyclohexanecarboxylate (manufactured by Union Carbide Co., product name ERL-4221) 100 parts, and an energy curable acid-curable acid generator (A) consisting of 1 part of N-benzyl thiazolium tetrakis (pentafluorophenyl) borate. The composition was placed in an aluminum cup and passed through a heat ray cut filter using a 500 mW high-pressure mercury lamp (manufactured by Ushio Inc.) to obtain 10c.
When irradiated for 5 minutes from a distance of m, a cured product was observed at the bottom of the aluminum cup.

(Examples 2 to 94) As energy-sensitive acid generator (A), instead of 1 part of N-benzylthiazolium tetrakis (pentafluorophenyl) borate, Tables 1 to 3 show. An acid-curable composition comprising the energy ray-sensitive acid generator (A) shown below was prepared, and the same experiment as in Example 1 was carried out. In each case, a cured product was observed at the bottom of the aluminum cup. .

Table 1 ────────────────────────────────── Example Energy ray sensitive acid generator (A ) ────────────────────────────────── 1 N-Benzylthiasolium tetrakis (pentafluorophenyl) borate 2 N- (p-cyanobenzyl) thiazolium tetrakis (pentafluorophenyl) borate 3 N- (m-nitrobenzene) thiasolium tetrakis (pentafluorophenyl) borate 4 N- (pentafluorophenylmethyl) thiaso Lithium tetrakis (pentafluorophenyl) borate 5 N- (o- (t-butyl) benzyl) thiazolium tetrakis (pentafluorophenyl) borate 6 N- (p-acetylhexenyl) thiazolium tetra Sus (pentafluorophenyl) borate 7 N- (p-methoxycarbenylbenzyl) thiazolium tetrakis (pentafluorophenyl) borate 8 N- (p-octadecylbenzyl) thiasolium tetrakis (pentafluorophenyl) borate 9 N- (2-naphthylmethyl) thiazolium tetrakis (pentafluorophenyl) borate 10 N- (9-anthrylmethyl) thiazolium tetrakis (pentafluorophenyl) borate 11 2-Fluoro-3- (α-methylhexyl Benzyl) thiazolium tetrakis (pentafluorophenyl) borate 12 4-chloro-3-benzhydrylthiazolyl tetrakis (pentafluorophenyl) borate 13 5-chloro-3-benzylthiazolium tetrakis (pentafluorophenyl) Brate 14 6-Human Ethoxy-3-benzilthiazolium Tetrakis (pentafluorophenyl) borate 15 7-Carboxy-3-Benzylthiazolium Tetrakis (pentafluorophenyl) borate 16 2-Mercapto-3-hexa Benzyl thiatrium tetrakis (pentafluorophenyl) borate 17 4-Cyano-3-pentylthiazolium tetrakis (pentafluorophenyl) borate 18 5-Nitro-3-benzylthiasolium tetrakis (pentafluorophenyl) borate 19 2 -Carbamoyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate 20 2-Methyl-3-pentylthiazolium tetrakis (pentafluorophenyl) borate 21 2-Isopropoyl-3-hexenylthiazolium tet Kiss (pentafluorophenyl) borate 22 4-Cyclohexyl-3-pentylthiazolium tetrakis (pentafluorophenyl) borate 23 2-Fluoromethyl-3-pentylthiazolium tetrakis (pentafluorophenyl) borate 24 2-Phenyl-3 -Benzylthiazolium tetrakis (pentafluorophenyl) borate 25 2- (m-chlorophenyl) -3-benzylthiasolium tetrakis (pentafluorophenyl) borate 26 2-Acetyl-3-hexylthiazolium tetrakis (Pentafluorophenyl) borate 27 2-Benzoyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate 28 2- (α-mercaptoacetyl) -3-pentylthiasolium tetrakis (pentafluorophene) Nyl) borate 29 2-Ethoxycarbenyl-3-pentylthiazolium tetrakis (pentafluorophenyl) borate 30 2- (t-Butoxycarbonyl) -3-pentylthiasolium tetrakis (pentafluorophenyl) borate 31 2-Cyclopentyloxycarbenyl-3-benzylthiazolium tetrakis (pentafluorophenyl) borate 32 2-Chloromethoxycarbonyl-3-pentylthiazolium tetrakis (pentafluorophenyl) borate 33 4,5-Dichloro-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 34 2,4,5-Trimethyl-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate ───────── ───────────────────── ─────

Table 2 ────────────────────────────────── Example Energy ray sensitive acid generator (A ) ────────────────────────────────── 35 N-phenacyl thiasolium tetrakis (pentafluorophenyl) borate 36 N -(p-Cyanophenacyl) thiazolium tetrakis (pentafluorophenyl) borate 37 N- (m-nitrophenacyl) thiazolium tetrakis (pentafluorophenyl) borate 38 N- (o-cyanophenacyl) thiazolium tetrakis (penta) Fluorophenyl) borate 39 N- (o- (t-butyl) phenacyl) thiazolium tetrakis (pentafluorophenyl) borate 40 N- (p-acetylphenacyl) thiasolium tetrakis (pentafluorophenyl) Nyl) borate 41 N- (p-methoxycarbenylphenylphenacyl) thiazolium tetrakis (pentafluorophenyl) borate 42 N- (p-octadecylphenacyl) thiazolium tetrakis (pentafluorophenyl) borate 43 N- (2-naphtho) Ilmethyl) thiazolium tetrakis (pentafluorophenyl) borate 44 N- (9-anthroylmethyl) thiazolium tetrakis (pentafluorophenyl) borate 45 2-fluoro-3-phenacylthiazolium tetrakis (pentafluorophenyl) ) Borate 46 2-Chloro-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 47 4-Bromo-3-phenacylthiasolium tetrakis (pentafluorophenyl) borate 48 5-Human peroxy-3-phenacylthiazolium Tet Lakis (pentafluorophenyl) borate 49 2-Carboxy-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 50 2-Mercapto-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 51 2-Cyano- 3-Phenacyl thiazolium tetrakis (pentafluorophenyl) borate 52 4-Nitro-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 53 5-Carboxamoyl-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 54 2 -Methyl-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 55 2-Isoprophyl-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 56 4-Cyclohexyl-3-phenyl Enacyl thiazolium tetrakis (pentafluorophenyl) borate 57 5-Fluoromethyl-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 58 2-Phenyl-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 59 2- (m-Chlorophenyl) -3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 60 2-Acetyl-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 61 4-Benzoyl-3-phenacylthiasodium tetrakis (penta) Fluorophenyl) borate 62 4- (α-mercaptoacetyl) -3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 63 4-Ethoxycarbenyl-3-phenacylthiazolium tetrakis (Pentafluorophenyl) borate 64 4- (t-butoxycarbonyl) -3-phenacyl thiasol tetrakis (pentafluorophenyl) borate 65 4-cyclopentyloxycarbenyl-3-phenacyl thiasolium Tetrakis (pentafluorophenyl) borate 66 5-Chloromethoxycarbenyl-3-phenacyloxazolium tetrakis (pentafluorophenyl) borate 67 4,5-Dichloro-3-phenacylimidazo-tetrakis (pentafluoro) Phenyl) borate 68 2,4,5-Trimethyl-1-phenacyl laurium tetrakis (pentafluorophenyl) borate ───────────────────────── ─────────

Table 3 ────────────────────────────────── Example Energy ray sensitive acid generator (A ) ────────────────────────────────── 69 N-allyl thiazolium tetrakis (pentafluorophenyl) borate 70 N -(2-Phenyl-3,3-dicyano-2-fluorophenyl) thiazolium tetrakis (pentafluorophenyl) borate 71 N- (t-butoxy) thiazolium tetrakis (pentafluorophenyl) borate 72 N -(Chloromethoxy) thiazolium tetrakis (pentafluorophenyl) borate 73 N- (phenoxy) thiazolium tetrakis (pentafluorophenyl) borate 74 N- (p-cyanophenoxy) thiazolium tetrakis (pentafluorophenyl) 2-methyl-3-ethoxythiazolium tetrakis (pentafluorophenyl) borate 76 4,6-bis (ethoxycarbenyl) -3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 77 N-benzyl thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 78 N- (p-cyanobenzyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] phenyl Blate 80 N-phenacylthiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 80 N- (p-cyanophenacyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] Borate 81 N-allyl thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 82 N- (2-phenyl- 3,3-Dicyano-2-fluorophenyl) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 83 N- (t-butoxy) thiazolium tetrakis [3,5-bis] (Trifluoromethyl) phenyl] borate 84 N-Benzyloxythiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 85 N-Phenoxythiazolium tetrakis [3,5-bis ( Trifluoromethyl) phenyl] borate 86 N- (p-cyanophenoxy) thiazolium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 87 N-phenacylthiasonium pentafluorophenyl trifluoroborate Rate 88 N- (o-cyanophenacyl) thiazolium 3,5-bis (trifluoromethyl) phenyl trifluoroborate 89 N- (m-chlorophenacyl) Azolium bis (pentafluorophenyl) difluoroborate 90 N- (o-human oxyphenacyl) thiazolium bis [3,5-bis (trifluoromethyl) phenyl] difluoroborate 91 N- (p-methoxy) Phenacyl) oxazolium tris (pentafluorophenyl) fluoroborate 92 N- (p-benzenyl) oxazolium tris [3,5-bis (trifluoromethyl) phenyl] fluoroborate 93 1-methyl- 3-phenacyl imidazole tetrakis (pentafluorophenyl) borate 94 2,3,4-trimethyl-1-phenacyl fluorium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate ───── ─────────────────────────────

Examples 95 to 114 As acid-curable compounds (C), instead of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, acid-curable compounds shown in Table 4 were used. An acid-curable composition comprising (C) was prepared and the same experiment as in Example 1 was carried out. In each case, a cured product was observed at the bottom of the aluminum cup.

Table 4 ────────────────────────────────── Example Acid-curable compound (C) ───────────────────────────────── 95 Cymel300 (manufactured by American Cyanamid Co., Ltd.) 97) Mixture of diallyl phthalate and trimethylolpropane trithioglycolate 98 Tetramethoxysilane 99 γ-chloropropyltrimethoxysilane 100 Limonene monoepoxysite 101 BHPE-3150 (manufactured by Daicel Chemical Industries) 102 1, 4-Butanedioxyl ether 103 Styrene 104 N-vinyl carbazole 105 Isobutylyl vinyl ether 106 Ethylene glycol divinyl ether 107 1,4,6-Trioxaspiro (4,4) Nan 108 2-Methyl-1,4,6-trioxaspiro (4,4) nonane 109 1,4,6-Trioxaspiro (4,5) decane 110 1-Phenyl-4-ethyl-2, 6,7-Trioxabicyclo (2,2,2) octane 111 1,5,7,11-Tetraoxaspiro (5,5) undecane 112 Phenyloxetane 113 Tetrahiturofuran 114 γ-Butyl lactone ───── ─────────────────────────────

Example 115 As the acid-curable compound (C), 3,4-epoxycyclohexylmethyl-3,4
-100 parts of epoxy cyclohexane carboxylate (manufactured by Union Carbide, product name: ERL-4221),
An acid-curable composition comprising 1 part of N-benzylthiazolium tetrakis (pentafluorophenyl) borate as an energy ray-sensitive acid generator (A) and 0.5 part of anthracene as a sensitizer (B) was used in an aluminum cup. put in,
Irradiation from a distance of 10 cm for 3 minutes through a heat ray cut filter using a 500 mW high-pressure mercury lamp revealed a cured product at the bottom of the aluminum cup.

(Examples 116 to 123) Instead of anthracene as the sensitizer (B), an acid-curable composition containing the sensitizer (B) shown in Table 5 was prepared, and Example 115 was used. When the same experiment was carried out, a cured product was found at the bottom of the aluminum cup in each case.

Table 5 ──────────────────────── Example Sensitizer (B) ───────────── ──────────── 115 Anthracene 116 9,10-Vise (phenylethynyl) anthracene 117 9-Bromoanthracene 118 9,10-Dimethylanthracene 119 9,10-Diphenylanthracene 120 1,8-Dimethoxy-9,10-bis (phenylethynyl) anthracene 121 Acrigen orange 122 Benzoflavin 123 Setoflavin T ──────────────────── ─────

Example 124 1200 parts of methyl ethyl ketone as a diluting solvent, 100 parts of polymethyl methacrylate as a binder, and an acid-curable compound (C),
Photosensitive liquid comprising 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 1 part of N-phenacyl thiazolium tetrakis (pentafluorophenyl) borate as an energy ray sensitive acid generator (A). About 1.5μ with a spin coater
It is applied on a glass plate to a thickness of m, and it is placed in an oven at 60 ° C for 1
It was dried in 0 minutes to obtain a photosensitive plate. A 21 / √2 step tablet (Grayscale film manufactured by Dainippon Screen Co., Ltd.) was placed on this photosensitive plate, and 500 W high pressure mercury lamp light (manufactured by USHIO INC.) Was passed through a heat ray cut filter from a distance of 15 cm to 1 After exposure for 2 minutes, it is impregnated with toluene for 30 seconds and developed to obtain 21 / √
The maximum number of completely cured plates corresponding to a 2-step tablet was defined as the sensitivity.

(Example 125) Instead of 1 part of N-phenacylthiazolium tetrakis (pentafluorophenyl) borate as the energy ray sensitive acid generator (A),
An acid-curable composition was prepared using 4-cyano-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate, and an experiment similar to that in Example 124 was performed to determine the sensitivity.

Comparative Examples 1 to 5 As a comparative example, a known 4-cyano-3-phenacylthiazolium was used instead of the N-phenacylthiazolium tetrakis (pentafluorophenyl) borate of the present invention. Hexafluoroantimonate, N-phenacylthiazolium hexafluoroantimonate, N-phenacylthiazolium hexafluoroarsenate, N-phenacylthiazolium hexafluorophosphate, N-phenacylthiazolium tetrafluoro The same experiment as in Example 69 was performed using borate to determine the sensitivity.

The experimental results of Examples 124 and 125 are shown in Table 6, and the experimental results of Comparative Examples 1 to 5 are shown in Table 7. As is clear from the results shown in Tables 6 and 7, when the energy-sensitive acid generator (A) of the present invention is used, the sensitivity is improved as compared with the known thiazolium salt. Recognize.

Table 6 ────────────────────────────────── Example Energy-sensitive acid generator (A ) Sensitivity ────────────────────────────────── 124 N-phenacylthiasolium tetrakis (pentafluorophenyl) borate 9 125 4-Cyano-3-phenacylthiazolium tetrakis (pentafluorophenyl) borate 10 ──────────────────────────────── ──

Table 7 ────────────────────────────────── Comparative Example Thiazonium salt Sensitivity ─── ─────────────────────────────── 1-Cyano-3-phenacylthiasonium hexafluoroantimonate 8 2 N-phenacylthiaso "Hexafluoroantimonate 7 3 N-phenacylthiaso" "Hexafluoroarsenate" 5 4 N-phenacylthiaso "Hexafluorofluorophosphate" 4 5 N-phenacylthiazoylium tetrafluoroborate 1 ────────────────────────

(Examples 126 and 127) 1200 parts of methyl ethyl ketone as a diluting solvent, 100 parts of polymethyl methacrylate as a binder, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane as an acid-curable compound (C). Carboxylate 1
00 parts of a sensitizer (B), 9,10-dimethyl anthracene and 0.1 parts of a solution 26 g, the energy-sensitive Sensan generating agent shown in Table 8 (A) 1.2 × 10 ^-4 mol Was added to each to make a photosensitive solution. The photosensitive solution was applied on a glass plate with a thickness of about 1.5 μm by a spin coater and dried in an oven at 60 ° C. for 10 minutes to obtain a photosensitive plate. Place a 21 / √2 step tablet (Grayscale film made by Dainippon Screen Co., Ltd.) on this photosensitive plate, and use a 500 W xenon lamp light (made by Ushio Inc.).
Then, after passing through a heat ray cut filter at a distance of 15 cm for 1 minute, it was impregnated with toluene for 30 seconds and developed, and the maximum number of completely cured stages corresponding to a 21 / √2 step tablet was taken as the sensitivity.

(Comparative Examples 6 to 10) As comparative examples,
Instead of the N-phenacyl thiazolium tetrakis (pentafluorophenyl) borate of the present invention, the known 4-
Cyano-3-phenacyl thiazolium hexafluoroantimonate, N-phenacyl thiazolium hexafluoroantimonate, N-phenacyl thiazolium hexafluoroarsenate, N-phenacyl thiazolium hexafluorophosphate, Using N-phenacyl thiazolium tetrafluoroborate, the same experiment as in Example 126 was carried out to determine the sensitivity.

The experimental results of Examples 126 and 127 are shown in Table 8 above, and the experimental results of Comparative Examples 1 to 5 are shown in Table 9. As is clear from the results shown in Tables 8 and 9, when the energy ray-sensitive acid generator (A) of the present invention is used, the sensitivity is improved as compared with the known thiazolium salt. Recognize.

Table 8 ────────────────────────────────── Example Energy ray sensitive acid generator (A ) Sensitivity ────────────────────────────────── 126 N-phenacyl thiasolium tetrakis (pentafluorophenyl) borate 9 127 4-Cyano-3-phenacyl thiazolium tetrakis (pentafluorophenyl) borate 10 ───────────────────────────────── ──

Table 9 ────────────────────────────────── Comparative Examples Thiazonium salt Sensitivity ─── ─────────────────────────────── 6 4-Cyano-3-phenacylthiasoium Hexafluoroantimonate 8 7 N-phenacylthiaso "Hexafluoroantimonate 7 8 N-phenacyl thiaso" "Hexafluoroarsenate" 5 9 N-phenacyl thiaso "Hexafluorophosphate" 4 10 N-phenacyl thiazolium tetrafluoroborate 1 ────────────────────────

Example 128 As acid-curable compound (C), 3,4-epoxycyclohexylmethyl-3,4
-100 parts of epoxy cyclohexane carboxylate (manufactured by Union Carbide, product name: ERL-4221),
1 part of N-phenacyl thiazolium tetrakis (pentafluorophenyl) borate as the energy ray sensitive acid generator (A), 100 parts of pentaerythritol triacrylate as the radical polymerizable compound (D), radical generator (E) As an acid-curable composition consisting of 1 part of benzyl dimethyl ketal, placed in an aluminum cup,
When a 500 mW high-pressure mercury lamp (manufactured by Ushio Inc.) was used to irradiate through a heat ray cut filter from a distance of 10 cm for 1 minute, a cured product was observed at the bottom of the aluminum cup. (Example 129) As the acid-curable compound (C), 3,4
-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Union Carbide, product name ERL-4221) 100 parts, N-phenacylthiazolium tetrakis (pentafluoro) as an energy ray sensitive acid generator (A) 1 part phenyl) borate,
An acid consisting of 0.5 parts of 9,10-dimethylanthracene as a special number (B), 100 parts of pentaerythritol triacrylate as a radical polymerizable compound (D), and 1 part of benzyl dimethyl ketal as a radical generator (E). Put the curable composition in an aluminum cup and
When a high-pressure mercury lamp of 00 mW (manufactured by USHIO INC.) Was used to irradiate through a heat ray cut filter for 30 seconds from a distance of 10 cm, a cured product was observed at the bottom of the aluminum cup.

[0201]

EFFECT OF THE INVENTION Energy-sensitive ray acid generator (A) of the present invention
Is effective as a photopolymerization initiator for the acid-curable compound (C), and a curable composition containing these can be polymerized and cured by application of energy rays. Therefore, the curable composition of the present invention, 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 Argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, light source represented by various light sources such as plasma light source, and electron beam by EB generator The intended polymer or cured product can be obtained by the energy ray of

Therefore, it is coated on a substrate together with a binder and the like and used as a core material for a photosensitive plate or microcapsule such as a printing plate material, photoresist, electrophotography, direct printing plate material, hologram material, etc. It can be applied to agents.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 63/84 NLY C08G 63/84 NLY 65/10 NQE 65/10 NQE 69/20 NRT 69/20 NRT 73 / 00 NTM 73/00 NTM 77/08 NUD 77/08 NUD // C07F 5/02 C07F 5/02 D

Claims (6)

[Claims] 1. An onium borate complex, wherein the cation moiety is composed of an onium cation represented by the general formula (1) and the anion portion is composed of a borate anion represented by the general formula (2). Energy sensitive acid generator (A). General formula (1) (Wherein, X is, -S -, - O -, - N (R 2) -, - C
It represents a group selected from (R ² ) _2- . Each R independently represents a group selected from the following organic residues in addition to fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group and carbamoyl group, and k is 0 to 2
Represents an integer. Here, the organic residue means a linear or branched C _{1 to} C ₁₈ which may be substituted with fluorine, chlorine, bromine, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, or an azide group. , Cyclic alkyl group, C ₂
-C ₁₈ linear, branched, cyclic alkenyl group, C ₆ ~
A C ₁₈ monocyclic ring, a condensed polycyclic aryl group, a C ₇ -C ₁₈ monocyclic ring,
Fused polycyclic arylalkyl group, C _{1 to} C ₁₈ straight chain, branched chain, cyclic alkoxyl group, C _{6 to} C ₁₈ monocycle, fused polycyclic aryloxy group, C _{1 to} C ₁₈ straight chain , Branched, cycloaliphatic or C _{7 to} C ₁₉ monocyclic, condensed polycyclic aromatic acyl group, C _{2 to} C ₁₉ straight chain, branched chain, cyclic alkoxycarbonyl group, C _{7 to} C ₁₉ Represents a monocyclic ring or a condensed polycyclic aryloxycarbonyl group. R
¹ is a benzyl group, a substituted benzyl group, a phenacyl group, a substituted phenacyl group, an allyl group, a substituted allyl group, an alkoxyl group, a substituted alkoxyl group,
It represents a group selected from an aryloxy group and a substituted aryloxy group. R ² is hydrogen, a mercapto group, and
Fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, C ₁ -C ₁₈ linear, branched or cyclic alkyl group which may be substituted with azido group, fluorine, chlorine , A bromine group, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, and a C _{1 to} C ₁₈ linear, branched, or cyclic alkylthio group which may be substituted with an azido group. Further, adjacent Rs, R and R ¹ , R and R ² , and R ¹ and R ² may form a ring structure by a covalent bond. ) General formula (2) [BY _m Z _n ] ^- (wherein Y is fluorine or chlorine, Z is at least two or more fluorine, a cyano group, a nitro group, an electron-withdrawing group selected from a trifluoromethyl group. A phenyl group substituted with, m is an integer of 0 to 3, n is an integer of 1 to 4, and m is
+ N = 4. ) 2. In the general formula (1) according to claim 1, X
Is a -S- thiazolium cation and the anion part is tetrakis (pentafluorophenyl) borate or tetrakis [3,5-bis (trifluoromethyl)
An energy ray-sensitive acid generator (A), which is a thiazolium borate complex composed of any of the borate anions of phenyl] borate. 3. An energy-sensitive acid generator composition comprising the energy-sensitive acid generator (A) according to claim 1 or claim 2 and a sensitizer (B). 4. An energy-sensitive acid generator (A) according to claim 1 or 2, or an energy-sensitive acid generator composition according to claim 3, and a curing agent containing an acid-curable compound (C). Sex composition. 5. The energy ray-sensitive acid generator (A) according to claim 1 or 2, or the energy ray-sensitive acid generator composition according to claim 3, an acid-curable compound (C), and radical polymerization. The curable composition according to claim 4, which contains a polymerizable compound (D) and a radical generator (E). 6. A cured product of the curable composition according to claim 4 or 5.