JPH09183960A - Actinic-radiation-sensitive acid generator, actinic-radiation-sensitive acid generator composition and curing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an actinic-radiation-sensitive acid generator which is useful as a photopolymerization initiator for an acid-curable compound and scarcely forms a volatile component as a by-product when decomposed by selecting an iodonium borate complex prepared from a specified cationic moiety and a specified anionic moiety. SOLUTION: An iodonium borate complex composed of a cationic moiety being an iodonium cation represented by the formula and an anionic moiety being a borate ion represented by the formula: [BYm Zn ]<-> is selected. In the formulas, X is O or S; R is F, Cl, Br, OH, COOH, SH, CN, NO2 , azido; a 1-18C linear, branched or cyclic alkyl; a 2-18 C linear, branched or cyclic alkenyl or the like; (k) is 0-3; Y is F or Cl; Z is a phenyl substituted by at least two electron-attracting groups selected from among F, CN, NO2 and trifluoromethyl; (m) is 0-3; (n) is 1-4: and m+n=4. This complex is exemplified by di(2-furyl) iodonium tetrakis(pentafluorophenyl)borate.

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, for generating an acid by irradiation of energy rays, particularly light, for coloring a material capable of coloring with an acid, and further for polymerizing an acid-curable compound in a short time, for example, molding resin, casting Resin, stereolithography resin, sealant, dental polymerization resin, printing ink, paint, photosensitive resin for printing plate, color proof for printing, color filter resist, printed circuit board resist, semiconductor photoresist, microelectronics Energy-sensitive acid generator, energy-sensitive acid generator composition for obtaining a cured product having good physical properties in the fields of resists for holograms, hologram materials, overcoat materials, adhesives, pressure-sensitive adhesives, release agents, etc. And a curable composition.

[0002]

2. Description of the Related Art Conventionally, there have been many reports that various iodonium salts function as photopolymerization initiators for acid-curable compounds such as epoxy compounds.・ Application and Market of EB Curing Technology, p. 79 (1989, CMC)
And JV Crivello, "Advances in Polymer Science
, Volume 62, Initiators-Poly-Reactions-Optical Act
ivity, (1984, Springer-Verlag).

Further, US Pat. No. 4,250,311 discloses diphenyliodonium hexafluorophosphate and the like, and JP-A 1-311103 discloses diaryl iodonium salts by Ao Yamaoka and Hiroshi Morita, "Photosensitive Resin", Kyoritsu Shuppan (1988), page 20, describes diaryliodonium salts.

The iodonium salts reported in these documents and patents are all decomposed by irradiation of light to generate a cationic species or an acid, which initiates cationic polymerization of an acid-curable compound such as an epoxy compound. Although it is considered that, both its anion, BF ₄ ^-, PF
^{_{6 -, AsF 6 -, SbF}} 6 -, ClO 4 -, CF 3 S
It is composed of anions such as O ₃ ⁻ , FSO ₃ ⁻ , and F ₂ PO ₂ ⁻ .

By the way, in recent years, it has been clarified by Japanese Patent Laid-Open No. 6-184170 and International Patent No. 95/03338 that an iodonium compound having a certain type of organic boron anion exhibits good properties as a photopolymerization initiator. It was These specifications and the report of C. Priou et al. (RadTech '94 North America Proc. Vol. 1,
187 (1994) and Polymeric Materials Science and Engineering (Polym.
Mater.Sci.Eng.), 72, 417 (1995).
)), Diphenyliodonium tetrakis (pentafluorophenyl) borate is reported to have higher polymerization properties for epoxysilicon polymerization than conventional diphenyliodonium hexafluoroantimonate.

On the other hand, certain organic boron anions 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. JP-A-3-124706, JP-A-4-124706
No. 253711, JP-A-4-249503,
Japanese Patent Publication No. 5-505838, International Patent No. 95/10
551, Journal of American Chemical Society (J. Am. Chem. Soc.),
113, p. 8570 (1991), and that tetrakis (pentafluorophenyl) borates show high activity as catalysts for Diels-Alder reaction, Journal of American Chemical Society (J. .Am.Chem.Soc.), No. 111.
Volume, page 6070 (1989), but these patent specifications and references do not consider at all as a photopolymerization initiator.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to generate an acid upon irradiation with energy rays, particularly light, to develop a material capable of forming a color by the acid, and further to prepare an acid-curable compound for a short time. Another object of the present invention is to propose a highly sensitive curable composition that can be polymerized. For example, industrially providing practical oligomers and polymers in the fields of inks, paints, photosensitive printing plates, proof materials, photoresists, hologram materials, sealants, overcoat materials, stereolithography resins, adhesives, etc. To obtain a cured product with good physical properties,
An object is to provide an energy ray-sensitive acid generator, an energy ray-sensitive acid generator composition, and a curable composition.

The problems of the curable composition disclosed in the prior art in the field of industrial application aimed at by the present invention are listed below.

First, diphenyliodonium hexafluorophosphate described in US Pat. No. 4,250,311 and the like, diaryliodonium salts described in JP-A 1-311103, Ao Yamaoka, Hiroshi Morita, "Photosensitive Resin," p. 20, In all of the diaryliodonium salts described by Kyoritsu Shuppan (1988), the anion part is B
_{^{F 4 -, PF 6 -,}} AsF 6 -, SbF 6 -, ClO 4
_{^{-, CF 3 SO 3 -,}} FSO 3 -, F 2 PO 2 - and the like, Examples of the photopolymerization initiator that require high sensitivity, the sensitivity to inadequate.

Further, in Japanese Patent Laid-Open No. 6-184170 and International Patent No. 95/03338, diphenyliodonium tetrakis (pentafluorophenyl) is disclosed.
Diaryl iodonium tetrakis (pentafluorophenyl) borates such as borates are described. However, there is a concern that these may produce undesired volatile components such as benzene by decomposition. It is believed that the phenyl radical generated when the diphenyliodonium cation decomposes by irradiation with light abstracts hydrogen from a nearby compound to generate benzene, but the cation is changed from diphenyliodonium to diaryliodonium. However, there remains a problem that other aromatic volatile components are by-produced. Therefore, it has been desired to develop a photopolymerization initiator and a curable composition that can solve these problems.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems in consideration of the above problems, and as a result, have reached the present invention. That is, the present invention

It is characterized in that it is an iodonium borate complex composed of an iodonium cation whose cation portion is represented by the following general formula (1) and a borate anion whose anion portion is represented by the following general formula (2). Energy sensitive acid generator (A). General formula (1)

[0013]

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(However, X represents oxygen or sulfur, and R independently represents fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, azido group, or the following organic residue. And a substituent R adjacent to each other may form a ring structure by a covalent bond with each other, and k represents an integer of 0 to 3. Here, the organic residue means fluorine, chlorine, bromine, hydroxyl, carboxyl group, a mercapto group, a cyano group, a nitro group, may be substituted with an azido group C ₁ -C ₁₈ linear, branched, cyclic alkyl group, C ₂ -C ₁₈ Straight chain,
Branched, cyclic alkenyl group, monocyclic C ₆ -C ₁₈ condensed polycyclic aryl group, a monocyclic, fused polycyclic arylalkyl group _{C 7 ~C 18, C 1 ~C} 18 straight-chain, branched chain, cyclic alkoxyl group, monocyclic, fused polycyclic aryl group having _{C 6 ~C 18, C 1 ~C} 18 straight-chain, monocyclic branched, cyclic aliphatic or C ₇ -C _19, Fused polycyclic aromatic acyl group, C ₂
To C ₁₉ linear, branched or cyclic alkoxycarbonyl group, C _{7 to} C ₁₉ monocyclic or condensed polycyclic aryloxycarbonyl group. ) 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 comprising 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),
A fourth invention comprises an energy-sensitive acid generator (A) or an energy-sensitive acid generator composition, an acid-curable compound (C), a radically polymerizable compound (D) and a radical generator (E). It is a curable composition characterized by the above.

[0016]

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

As a C ₁ -C ₁₈ straight chain, branched chain or cyclic alkyl group which may be substituted with fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group or azido group. Is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, cyclopentyl group. , Cyclohexyl group, 4-decylcyclohexyl group, fluoromethyl group, chloromethyl group, bromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, hydroxymethyl group, carboxymethyl group, mercaptomethyl group, cyanomethyl group, Examples thereof include nitromethyl group and azidomethyl group.

As a C ₂ -C ₁₈ straight chain, branched chain, or cyclic alkenyl group which may be substituted with fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, or azido group. Is a vinyl group, 1-propenyl group, 2-propenyl group, 1-octenyl group, 1-octadecenyl group, isopropenyl group, 1-cyclohexenyl group, trifluoroethenyl group, 1-chloroethenyl group, 2,2-dibromo. Ethenyl group, 4-hydroxy-1
-Butenyl group, 1-carboxyethenyl group, 5-mercapto-1-hexenyl group, 1-cyanoethenyl group, 3-
Examples thereof include a nitro-1-propenyl group and a 4-azido-2-butenyl group.

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 Groups and the like.

As the C ₇ -C ₁₈ monocyclic or condensed 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.

As a C ₁ -C ₁₈ straight chain, branched chain, or cyclic alkoxyl group which may be substituted with fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, or azido group. Is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an octyloxy group,
Octadecaneoxy group, isopropoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy group, fluoromethoxy group, 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-naphthacenyl 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-fluoro Phenoxy group, m-chlorophenoxy group, p-bromophenoxy group, p-hydroxyphenoxy group, m-carboxyphenoxy group, o-mercaptophenoxy group, p-cyanophenoxy group, m-nitrophenoxy group, m-azidophenoxy group Etc.

Fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, C ₁ -C ₁₈ linear, branched or cyclic aliphatic which may be substituted with an azido group, or Examples of the C _{7 to} C ₁₉ monocyclic or condensed polycyclic aromatic acyl group include formyl group, acetyl group, hexanoyl group, lauroyl group, palmitoyl group, stearoyl group, isobutyryl group, isovaleryl group, pivaloyl group, cyclopentylcarbonyl group, Cyclohexylcarbonyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthroyl group, 5-naphthaceroyl group, cinnamoyl group, α-fluoroacetyl group, α-chloroacetyl group, α-bromoacetyl group, α- Hydroxyacetyl group, α-carboxyacetyl group, α-mercaptoacetyl group, α-cyano Cetyl group, alpha-nitro acetyl group, etc. alpha-azidoacetyl group.

Fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, C ₂ -C ₁₉ linear, branched or cyclic alkoxycarbonyl group which may be substituted. As, a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, octadecaneoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, Fluoromethoxycarbonyl group, chloromethoxycarbonyl group, bromomethoxycarbonyl group, trifluoromethoxycarbonyl group, trichloromethoxycarbonyl group, tribromomethoxycarbonyl group, hydroxymethoxycarbo group Group, carboxymethoxy group, mercapto methoxycarbonyl group, a cyano methoxycarbonyl group, a nitro methoxycarbonyl group, etc. azido methoxycarbonyl group.

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-cumenyloxycarbonyl group, p-cyclohexylphenoxycarbonyl group, 4-phenylphenoxycarbonyl group, o-fluorophenoxycarbonyl group Group, m-chlorophenoxycarbonyl group, p-bromophenoxycarbonyl group, p-hydroxyphenoxycarbonyl group, m-
Examples thereof include carboxyphenoxycarbonyl group, o-mercaptophenoxycarbonyl group, p-cyanophenoxycarbonyl group, m-nitrophenoxycarbonyl group, m-azidophenoxycarbonyl group and the like.

Further, these adjacent substituents R may form a ring structure by a covalent bond with each other, and as such, for example, alkylene such as methylene group, ethylene group, tetramethylene group, hexamethylene group and the like. Base,
Examples thereof include ether groups such as an ethylenedioxy group and a diethylenedioxy group, and thioether groups such as an ethylenedithio group and a diethylenedithio group, but the present invention is not limited to these.

Therefore, as the structure of the iodonium cation of the energy ray sensitive acid generator (A) of the present invention, specifically, bis (4,5-dimethyl-2-furyl) iodonium and bis (5-chloro-2) are used. -Thienyl) iodonium, bis (5-cyano-2-furyl) iodonium, bis (5-nitro-2-thienyl) iodonium, bis (5-acetyl-2-furyl) iodonium, bis (5
-Carboxy-2-thienyl) iodonium, bis (5
-Methoxycarbonyl-2-furyl) iodonium, bis (5-phenyl-2-furyl) iodonium, bis (5- (p-methoxyphenyl) -2-thienyl) iodonium, bis (5-vinyl-2-furyl) iodonium , Bis (5-ethynyl-2-thienyl) iodonium, bis (5-cyclohexyl-2-furyl) iodonium, bis (5-hydroxy-2-thienyl) iodonium, bis (5-phenoxy-2-furyl) iodonium, bis (5-Mercapto-2-thienyl) iodonium, bis (5-butylthio-2-thienyl) iodonium, bis (5-phenylthio-2-thienyl) iodonium, bis (5- (2-thienyl) -2-thienyl) iodonium Each iodonium cation of
The present invention is not limited to these.

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.

As the structure of the borate anion of the energy ray sensitive acid generator (A) of the present invention, tetrakis (pentafluorophenyl) borate and tetrakis [3,5-bis (trifluoromethyl) phenyl] borate are preferable. is there.

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

Di (2-furyl) iodonium pentafluorophenyl trifluoroborate, di (2-furyl)
Iodonium-3,5-bis (trifluoromethyl) phenyl trifluoroborate, di (2-furyl) iodonium bis (pentafluorophenyl) difluoroborate, di (2-furyl) iodonium bis [3,5-bis (trifluoro) Methyl) phenyl] difluoroborate, di (2-furyl) iodonium tris (pentafluorophenyl) fluoroborate, di (2-furyl) iodonium tris [3,5-bis (trifluoromethyl) phenyl] fluoroborate,

Di (2-thienyl) iodonium pentafluorophenyl trifluoroborate, di (2-thienyl) iodonium-3,5-bis (trifluoromethyl) phenyl trifluoroborate, di (2-thienyl) iodonium bis (penta Fluorophenyl) difluoroborate, di (2-thienyl) iodonium bis [3,5-bis (trifluoromethyl) phenyl] difluoroborate, di (2-thienyl) iodonium tris (pentafluorophenyl) fluoroborate, di (2- Thienyl) iodonium tris [3,5-bis (trifluoromethyl) phenyl] fluoroborate,

Bis (5-fluoro-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-chloro-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5
-Bromo-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-hydroxy-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-carboxy-2-furyl) iodonium tetrakis (pentafluoro) Phenyl) borate, bis (5-mercapto-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-cyano-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-nitro-2-) Furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-azido-2-furyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-methyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate,
Bis (5-butyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octadecyl-2-furyl) iodonium tetrakis (Pentafluorophenyl) borate, bis (5-t-butyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-cyclohexyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (3 -Chloromethyl-2-furyl)
Iodonium tetrakis (pentafluorophenyl) borate, bis (5-trifluoromethyl-2-furyl)
Iodonium tetrakis (pentafluorophenyl) borate, bis (5-trichloromethyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-tribromomethyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, Bis (5-hydroxymethyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-carboxymethyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (4-mercaptomethyl-2-furyl ) Iodonium tetrakis (pentafluorophenyl) borate, bis (5-nitromethyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-cyanomethyl-) - furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5
-Azidomethyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-vinyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate,
Bis (5- (2-propenyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate,
Bis (3- (1-octenyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate,
Bis (4- (1-octadecenyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-isopropenyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate,
Bis (5-1-cyclohexenyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (1-chloroethenyl) -2-furyl)
Iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-phenyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (2-naphthyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- ( 9-anthryl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (5-naphthacenyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p-tolyl) 2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (3- (2,3-xylyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (4- (dodecylphenyl) -2- Frills)
Iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p-cyclohexylphenyl)-
2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p-cyanophenyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-benzyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (3- (p-tolylmethyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (4- ( 9-anthrylmethyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (4- (9-anthryl) butyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis ( 5- (o-nitrobenzyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-methoxy-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-butoxy-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octadecaneoxy-2-) Furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-t-butoxy-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-
Chloromethoxy-2-furyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-phenoxy-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (1naphthyloxy) -2-furyl)
Iodonium tetrakis (pentafluorophenyl) borate, bis (5- (9-anthryloxy) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (5-naphthacenyl) -2-
Furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (o-tolyloxy) -2
-Furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p-decylphenoxy) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p-cyclohexylphenoxy) -2-furyl ) Iodonium tetrakis (pentafluorophenyl) borate, bis (5-
(P-cyanophenoxy) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-formyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-acetyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-stearoyl-2-furyl) ) Iodonium tetrakis (pentafluorophenyl) borate, bis (5-
Isobutyryl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-cyclopentylcarbonyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5
-Benzoyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (9
-Anthroyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-α
-Cyanoacetyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-cinnamoyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-methoxycarbonyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octyloxycarbonyl-)
2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octadecaneoxycarbonyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-t-butoxycarbonyl-2-furyl) iodonium tetrakis ( Pentafluorophenyl) borate, bis (5-cyclohexyloxycarbonyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-chloromethoxycarbonyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-phenoxycarbonyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (1naphthyloxycarbonyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis ( 5- (5-naphthacenyloxycarbonyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p-tolyloxycarbonyl) -2-furyl)
Iodonium tetrakis (pentafluorophenyl) borate, bis (5- (m-nitrophenoxycarbonyl) -2-furyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-fluoro-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-chloro-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-bromo-2-thienyl) ) Iodonium tetrakis (pentafluorophenyl) borate, bis (5-hydroxy-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-carboxy-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis ( 5-mercapto-2-
Thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-cyano-2-thienyl)
Iodonium tetrakis (pentafluorophenyl) borate, bis (5-nitro-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-azido-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-methyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-butyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octyl-2-thienyl) ) Iodonium tetrakis (pentafluorophenyl) borate, bis (5-octadecyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-t-
Butyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-cyclohexyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (3-chloromethyl-2-thienyl) iodonium tetrakis (pentafluoro) Phenyl) borate, bis (5-trifluoromethyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-trichloromethyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-tri) Bromomethyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-hydroxymethyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) Rate, bis (5-carboxymethyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (4-mercaptomethyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-nitromethyl -
2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-cyanomethyl-2-
Thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-azidomethyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-vinyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (2-propenyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (3- ( 1-octenyl) -2-thienyl)
Iodonium tetrakis (pentafluorophenyl) borate, bis (4- (1-octadecenyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-isopropenyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) Borate, bis (5-1-cyclohexenyl-2-
Thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (1-chloroethenyl)
-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-phenyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (2-naphthyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- ( 9-anthryl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (5-naphthacenyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p-tolyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (3- (2,3-xylyl) -2-
Thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (4- (dodecylphenyl)-
2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p-cyclohexylphenyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p
-Cyanophenyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-benzyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (3- (p-tolylmethyl) -2-thienyl)
Iodonium tetrakis (pentafluorophenyl) borate, bis (4- (9-anthrylmethyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (4- (9-anthryl))
Butyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (o-nitrobenzyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-methoxy-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-butoxy-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octadecaneoxy-2-) Thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-t-butoxy-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-chloromethoxy-2-thienyl) iodonium tetrakis (pentafluorophenyl) Borate,

Bis (5-phenoxy-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (1naphthyloxy) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (9 -Anthryloxy)-
2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (5-naphthacenyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (o-tolyloxy) -2-thienyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p-decylphenoxy) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-
(P-cyclohexylphenoxy) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p-cyanophenoxy) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-formyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-acetyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-stearoyl-2-thienyl) ) Iodonium tetrakis (pentafluorophenyl) borate, bis (5
-Isobutyryl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-cyclopentylcarbonyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-benzoyl-2-thienyl) iodonium tetrakis (penta Fluorophenyl) borate, bis (5-
(9-anthroyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-α-cyanoacetyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-cinnamoyl-2-thienyl) ) Iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-methoxycarbonyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octyloxycarbonyl-)
2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octadecaneoxycarbonyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-t-)
Butoxycarbonyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5
-Cyclohexyloxycarbonyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-chloromethoxycarbonyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-phenoxycarbonyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (1naphthyloxycarbonyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis ( 5- (5-naphthacenyloxycarbonyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (p-tolyloxycarbonyl) -2-
Thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5- (m-nitrophenoxycarbonyl) -2-thienyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-fluoro-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-chloro-2-furyl) iodonium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, bis (5-bromo-
2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5
-Hydroxy-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-carboxy-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate , Bis (5-mercapto-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-cyano-
2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5
-Nitro-2-furyl) iodonium tetrakis [3,
5-bis (trifluoromethyl) phenyl] borate,
Bis (5-azido-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-methyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl)]
Phenyl] borate, bis (5-butyl-2-furyl)
Iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-octyl-2)
-Furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-octadecyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5 -T-butyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-cyclohexyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl ] Borate, bis (3-chloromethyl-2-furyl) iodonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, bis (5-trifluoromethyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-trichloromethyl-2-
Furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-tribromomethyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis ( 5-hydroxymethyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-carboxymethyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) Phenyl] borate, bis (4
-Mercaptomethyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, bis (5-nitromethyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-cyanomethyl-2)
-Furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-azidomethyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-vinyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl)]
Phenyl] borate, bis (5- (2-propenyl)-
2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (3
-(1-octenyl) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (4- (1-octadecenyl) -2
-Furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-isopropenyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis ( 5-1-Cyclohexenyl-2-furyl)
Iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (1-chloroethenyl) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-phenyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (2-naphthyl)
2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5
-(9-anthryl) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (5-naphthacenyl) -2-
Furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (p
-Tolyl) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (3- (2,3-xylyl) -2-furyl)
Iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (4- (dodecylphenyl) -2-furyl) iodonium tetrakis [3,3
5-bis (trifluoromethyl) phenyl] borate,
Bis (5- (p-cyclohexylphenyl) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (p-cyanophenyl) -2-furyl) iodonium tetrakis [ 3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-benzyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (3- (p-tolylmethyl) -2-furyl) iodonium tetrakis [3,5] −
Bis (trifluoromethyl) phenyl] borate, bis (4- (9-anthrylmethyl) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (4- (9-anthryl) butyl) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (o-nitrobenzyl) -2-furyl) iodonium tetrakis [3,5 -Bis (trifluoromethyl) phenyl] borate,

Bis (5-methoxy-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-butoxy-2-furyl) iodonium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, bis (5-octadecaneoxy-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-t-butoxy-2-furyl) iodonium tetrakis [ 3,5-bis (trifluoromethyl)
Phenyl] borate, bis (5-chloromethoxy-2-
Furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-phenoxy-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (1naphthyloxy) -2-furyl) iodonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, bis (5- (9-anthryloxy) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (5 -Naphthacenyl) -2-furyl) iodonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, bis (5- (o-tolyloxy) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (p-decylphenoxy) ) -2-Furyl) iodonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, bis (5- (p-cyclohexylphenoxy) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (p-cyano) Phenoxy) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-formyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-acetyl-2-furyl) iodonium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, bis (5-stearoyl-2-furyl) iodonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, bis (5-isobutyryl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-cyclopentylcarbonyl-
2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5
-Benzoyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (9-anthroyl) -2-furyl)
Iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-α-cyanoacetyl-2-furyl) iodonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, bis (5-cinnamoyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-methoxycarbonyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-octyloxycarbonyl-2-furyl) iodonium tetrakis [3,5-] Bis (trifluoromethyl) phenyl] borate, bis (5-octadecaneoxycarbonyl-2
-Furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-t
-Butoxycarbonyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-cyclohexyloxycarbonyl-2-furyl) iodonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, bis (5-chloromethoxycarbonyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-phenoxycarbonyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (1naphthyloxycarbonyl) -2-furyl) iodonium tetrakis [ 3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (5-naphthacenyloxycarbonyl) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (p-tolyloxycarbonyl) -2
-Furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-
(M-nitrophenoxycarbonyl) -2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-fluoro-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-chloro-2-thienyl) iodonium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, bis (5-bromo-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-hydroxy-2-thienyl) iodonium tetrakis [3,5 -Bis (trifluoromethyl) phenyl]
Borate, bis (5-carboxy-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-mercapto-2-
Thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-cyano-2-thienyl) iodonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, bis (5-nitro-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-azido-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-methyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-butyl-2-thienyl) iodonium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, bis (5-octyl-2-thienyl) iodonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, bis (5-octadecyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-t-butyl-2-thienyl)
Iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-cyclohexyl-2-thienyl) iodonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, bis (3-chloromethyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-trifluoromethyl-2-thienyl) Iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-trichloromethyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-tri Bromomethyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-hydroxymethyl-2-thienyl) iodonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, bis (5-carboxymethyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (4-mercaptomethyl-2-thienyl) iodonium Tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-nitromethyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-cyanomethyl-2) -Thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-azidomethyl-2)
-Thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-vinyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (2-propenyl) -2-thienyl) iodonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, bis (3- (1-octenyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl)
Phenyl] borate, bis (4- (1-octadecenyl) -2-thienyl) iodonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, bis (5-isopropenyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-1-cyclohexenyl-2)
-Thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5
-(1-chloroethenyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-phenyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (2-naphthyl))
-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (9-anthryl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl ] Borate, bis (5- (5-naphthacenyl)-
2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5
-(P-Tolyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, bis (3- (2,3-xylyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (4- (dodecylphenyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (p-cyclohexylphenyl)-
2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5
-(P-cyanophenyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-benzyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (3- (p-tolylmethyl) -2-thienyl) iodonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, bis (4- (9-anthrylmethyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (4 -(9-anthryl) butyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (o-nitrobenzyl) -2
-Thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-methoxy-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-butoxy-2-thienyl) iodonium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, bis (5-octadecaneoxy-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-t-butoxy-2-thienyl) iodonium tetrakis [ 3,5-bis (trifluoromethyl) phenyl] borate, bis (5-chloromethoxy-
2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-phenoxy-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (1naphthyloxy) -2-thienyl) iodonium tetrakis [3,5- Bis (trifluoromethyl) phenyl] borate, bis (5- (9-anthryloxy) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (5-
Naphthalcenyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (o-tolyloxy) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) ) Phenyl] borate, bis (5- (p-decylphenoxybis (5-benzyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (3- (p-tolylmethyl)) -2-thienyl) iodonium tetrakis [3,
5-bis (trifluoromethyl) phenyl] borate,
Bis (4- (9-anthrylmethyl) -2-thienyl)
Iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (4- (9-
Anthryl) butyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (o-nitrobenzyl) -2
-Thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-methoxy-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-butoxy-2-thienyl) iodonium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, bis (5-octadecaneoxy-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-t-butoxy-2-thienyl) iodonium tetrakis [ 3,5-bis (trifluoromethyl) phenyl] borate, bis (5-chloromethoxy-
2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-phenoxy-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (1naphthyloxy) -2-thienyl) iodonium tetrakis [3,5- Bis (trifluoromethyl) phenyl] borate, bis (5- (9-anthryloxy) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (5-
Naphthalcenyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (o-tolyloxy) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) ) Phenyl] borate, bis (5- (p-decylphenoxy) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl]
Borate, bis (5- (p-cyclohexylphenoxy) -2-thienyl) iodonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, bis (5- (p-cyanophenoxy) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-formyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-acetyl-2-thienyl) iodonium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, bis (5-stearoyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-isobutyryl-2-thienyl) iodonium tetrakis [3,5 -Bis (trifluoromethyl) phenyl] borate, bis (5-cyclopentylcarbonyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-benzoyl-2-thienyl) iodonium Tetrakis [3,5-bi (Trifluoromethyl)
Phenyl] borate, bis (5- (9-anthroyl)
-2-Thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-α-cyanoacetyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] Borate, bis (5-cinnamoyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-methoxycarbonyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-octyloxycarbonyl-2-thienyl) iodonium tetrakis [3,5- Bis (trifluoromethyl) phenyl] borate, bis (5-octadecaneoxycarbonyl-2-thienyl) iodonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, bis (5-t-butoxycarbonyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-cyclohexyloxycarbonyl-2- Thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-chloromethoxycarbonyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-phenoxycarbonyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (1
Naphthyloxycarbonyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5- (5-naphthacenyloxycarbonyl) -2-thienyl) iodonium tetrakis [3. 5-bis (trifluoromethyl) phenyl] borate, bis (5- (p-tolyloxycarbonyl) -2-thienyl) iodonium tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate, bis (5- (m-nitrophenoxycarbonyl) -2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

[0076]

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The present invention is not limited to these examples. Furthermore, as a preferable structure as the energy ray sensitive acid generator (A) of the present invention, the cation moiety is an iodonium cation represented by the general formula (3) and the anion moiety is tetrakis (pentafluorophenyl) borate or tetrakis [3,3]. An iodonium borate complex composed of any of the borate anions of 5-bis (trifluoromethyl) phenyl] borate can be given. General formula (3)

[0078]

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(Wherein X represents oxygen or sulfur, R'is independently hydrogen, a C ₁ -C ₁₈ linear or branched alkyl group, a C ₁ -C ₁₈ linear or Represents a group selected from branched chain alkoxyl groups.)

Here, in the substituent R ′ in the iodonium cation represented by the general formula (3), C _{1 to} C
_As the linear or branched alkyl group of ₁₈ , a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-
Butyl group, t-butyl and the like, and C _{1 to} C ₁₈ linear or branched alkoxyl groups include methoxy group, ethoxy group, propoxy group, butoxy group, octyloxy group, octadecaneoxy group and iso Propoxy group,
Examples thereof include t-butoxy group.

Therefore, the preferable structure of the iodonium borate complex of the energy ray sensitive acid generator (A) of the present invention is:

Di (2-furyl) iodonium tetrakis (pentafluorophenyl) borate, di (2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, di (2-furyl) iodonium tetrakis [3,5-bis (trifluoro) Methyl) phenyl] borate, di (2-thienyl) iodonium [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-methyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate,
Bis (5-butyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octadecyl-2-furyl) iodonium tetrakis (Pentafluorophenyl) borate, bis (5-t-butyl-2-furyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-methoxy-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-butoxy-2-furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octadecaneoxy-2-) Furyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-t-butoxy-2-furyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-methyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-butyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octyl-2-thienyl) ) Iodonium tetrakis (pentafluorophenyl) borate, bis (5-octadecyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-t-
Butyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-methoxy-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-butoxy-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-octadecaneoxy-2-) Thienyl) iodonium tetrakis (pentafluorophenyl) borate, bis (5-t-butoxy-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate,

Bis (5-methyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl)]
Phenyl] borate, bis (5-butyl-2-furyl)
Iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-octyl-2)
-Furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-octadecyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5 -T-butyl-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-methoxy-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-butoxy-2-furyl) iodonium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, bis (5-octadecaneoxy-2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-t-butoxy-2-furyl) iodonium tetrakis [ 3,5-bis (trifluoromethyl)
Phenyl] borate,

Bis (5-methyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-butyl-2-thienyl) iodonium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, bis (5-octyl-2-thienyl) iodonium tetrakis [3,5-
Bis (trifluoromethyl) phenyl] borate, bis (5-octadecyl-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-t-butyl-2-thienyl)
Iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,

Bis (5-methoxy-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-butoxy-2-thienyl) iodonium tetrakis [3,5-bis (tri) Fluoromethyl) phenyl] borate, bis (5-octadecaneoxy-2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, bis (5-t-butoxy-2-thienyl) iodonium tetrakis [ 3,5-bis (trifluoromethyl) phenyl] borate.

By the way, the energy-sensitive acid generator (A)
Is required to be easily decomposed by the action of energy rays (irradiation, etc.) to generate a strong acid, and to be accompanied by a reduction in by-products, particularly a reduction in volatile components.

The energy rays used in the present specification refer to light such as ultraviolet light, visible light, and near infrared light, as well as electron beams and X-rays.

The first characteristic of the energy ray sensitive acid generator (A) of the present invention is to introduce a furan ring or thiophene ring derivative represented by the general formula (1) as a substituent of an iodonium ion. Therefore, it is more susceptible to decomposition by irradiation with energy rays than conventional diaryliodonium salts. For example, the Journal of American Chemical Society (J. Am.
Chem. Soc. ), 80, 4279 (195
8 years), the first half-wave potentials of the diphenyliodonium cation and the 2,2′-dithienyliodonium cation measured by polarography are −0.193 and −0.11, respectively, and 2,2 '-
It can be seen that the dithienyl iodonium cation is more susceptible to reduction than the diphenyl iodonium cation. This is because when an electron transfer reaction occurs due to irradiation with energy rays and electrons are given to these iodonium cations (that is, iodonium cations are reduced), the 2,2′-dithienyliodonium cation is more diphenyliodonium cation. It is more likely to be reduced and therefore more susceptible to decomposition than cations.

The second feature of the energy ray sensitive acid generator (A) of the present invention is that the amount of volatile components by-produced is small. For example, it has long been well known that compounds such as furan and thiophene are polymerized in the presence of an acid, and therefore, as a substituent bonded to the iodine atom of an iodonium cation, a conventionally known phenyl group or the like is used. By introducing a furan ring or thiophene ring derivative represented by the general formula (1) of the present invention instead of a representative aryl group, a by-product produced by irradiation with energy rays is a furan or thiophene derivative. Therefore, these furan or thiophene derivatives are characterized in that they are polymerized by the generated acid or copolymerized with the coexisting acid-curable compound (C) to reduce the volatile component.

The energy-sensitive ray acid generator (A) of the present invention
The third feature is the previously known BF_Four ^-, PF
₆ ^-, AsF₆ ^-, SbF₆ ^-, ClO_Four ^-, CF_ThreeS
O_Three ^-, FSO_Three ^-, F_TwoPO_Two ^-Such an anion
Acid, which is much stronger than the iodonium salt
And Generated by irradiation of energy rays, especially light
Acid strength varies greatly with the type of anion
Is a borate anion represented by the general formula (4) of the present invention.
Is the previously known PF₆, AsF₆, SbF ₆To
Compared to iodonium salts with different anions
It can generate strong acids and, as a result, hardenable
The sensitivity of the product can be improved.

Since most 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 sensitizers (B) are condensed polycyclic aromatic derivatives such as naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, naphthacene derivatives, perylene derivatives, pentacene derivatives and acridine derivatives, and benzo. Examples thereof include thiazole derivatives, and particularly preferable examples thereof include anthracene derivatives, acridine derivatives, and benzothiazole derivatives.

Specific examples of these are 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 (4) as a compound having a methylol group as a formaldehyde precursor or a substituted methylol group. In the general formula _{(4) (ROCH 2) n} -A- (CH 2 OR ') m ( above general formula (4), A is a group represented by B or B-Z-B, B is a substituted or It means an unsubstituted mononuclear or condensed polynuclear aromatic hydrocarbon group, or an oxygen-, sulfur-, or nitrogen-containing heterocyclic group, 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 a phenol resin.) R and R'independently of each other are hydrogen and C1-4.
Means an alkyl group, a cycloalkyl group, an aryl group which may have a substituent, an arylalkyl group, or an acyl group. n is an integer of 1 to 3 and m is an integer of 0 to 3.

Here, the substituted or unsubstituted mononuclear or condensed polynuclear aromatic hydrocarbon group represented by B to Z in the general formula (4) is an o-phenylene group, an m-phenylene group or 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,

Examples of the heterocyclic group containing oxygen, sulfur and nitrogen include 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.

As the alkyl group having 1 to 4 carbon atoms represented by R and R'in the general formula (4), a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, sec- A butyl group, a tert-butyl group, etc., a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc., and an aryl group which may have a substituent, a phenyl group, a p-tolyl group, a xylyl group, a 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, p-dimethylaminophenyl group, p-phenylthiophenyl group and the like, arylalkyl group, benzyl group, 2-naphthylmethyl group, 9-anthrylmethyl group, phenethyl group, Examples of the styryl group, cinnamyl group and the like, 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.

Specific examples of such an acid-curable compound (C) include various aminoblasts or phenoblasts, that is, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, glycoluril-formaldehyde resins and their resins. 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 methylol- or alkoxydimethyl-ized 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, Japanese Patent Application Laid-Open No. 2 (1998)
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.

As the alicyclic epoxy compound, 4-vinylcyclohexene monoepoxide, norbornene monoepoxide, limonene monoepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 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 and p-chloromethylstyrene. 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, alkynyl vinyl ethers such as ethynyl vinyl ether, 1-methyl-2-propenyl vinyl ether, 4-vinyl ether styrene, hydroquinone divinyl ether, phenyl Aryl vinyl ethers such as vinyl ether, p-methoxyphenyl vinyl ether, bisphenol A divinyl ether, tetrabromobisphenol A divinyl ether, bisphenol F divinyl ether, phenoxyethylene vinyl ether, p-bromophenoxyethylene vinyl ether, and 1,4-benzenedimethanol divinyl ether , Nm-chlorophenyldiethanol alcohol Nji ether, m- phenylene bis (ethylene glycol) aralkyl divinyl et one ether such as divinyl ether, urethane polyvinyl ether (e.g., ALLIED-SIGNAL Inc., V
ECtomer 2010).

The spiro orthoesters include
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-
Dioxolan and the like. 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.

Furthermore, the curable composition according to claim (4) of the present invention may further 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 ethylenic 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 in the present invention
Means Japanese Patent Laid-Open No. 5-213861 and Japanese Patent Laid-Open No. 5-2
55347 sulfonium complex and oxosulfonium complex, JP-B-59-1281, JP-B-61-96
21 and the triazine derivatives described in JP-A-60-60104, JP-A-59-1504 and JP-A-6-
Organic peroxides described in No. 1-243807, Japanese Examined Patent Publication No. 43-
No. 23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-
1604 and diazonium compounds described in USP 3567453, USP 2848328, USP
No. 2852379 and organic azide compounds described in USP No. 2,940,853, JP-B-36-22062,
Ortho-quinone diazides described in JP-B-37-13109, JP-B-38-18015 and JP-B-45-9610, JP-B-55-39162 and JP-A-59-
140203 and "Macromoculous
lecules) ”, vol. 10, p. 1307 (1977), various onium compounds including iodonium compounds, azo compounds described in JP-A-59-142205,
JP-A-1-54440, European Patent No. 10985
1, European Patent No. 126712, "Journal of Imaging Science (J.Imag.Sci.)",
Volume 30, page 174 (1986), metal allene complexes, JP 61-151197, titanocenes, "Coordination Chemistry Review (C
Orordination Chemistry Review) ", Vol. 84, No. 85
Pp. 277 (1988) and JP-A-2-182
701, a transition metal complex containing a transition metal such as ruthenium, an aluminate complex described in JP-A-3-209477, a borate compound described in JP-A-2-157760, JP-A-55-127550 and Kaisho 60-
2,4,5-Triarylimidazole dimer described in 202437, carbon tetrabromide and JP-A-59-107344.
Organohalogen Compounds, No. 16, Aka Yamaoka, Hiroshi Morita, "Photosensitive Resin," p. 26, Kyoritsu Shuppan (1988)
And the radical generator (E) is a radically polymerizable compound (D).
It is preferably contained in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight.

Energy-sensitive ray acid generator (A) of the present invention
Is used in an amount of 0.01 to 30 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 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 iodonium 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. The iodonium salts used as raw materials are
Of the American Chemical Society (JA
m. Chem. Soc. ), 80, 4279 (1
958), and borate compounds are described in Journal of Organic Chemistry (J.O.
rg. Chem. ), 57, 5545 (1992)
Alternatively, it can be synthesized with reference to the methods described in JP-A-6-184170 and International Patent Publication No. 95/03338. The energy-sensitive acid generator (A) thus obtained can determine the composition of the constituent elements by the elemental analysis value, and can also be determined by FD-MS (Field Desorption Mass Spectrometry).
Can determine the structure of the iodonium cation,
It can be identified by this.

[0133]

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 believed that hardening occurs.

Although the detailed reaction mechanism is not clear, only the energy ray sensitive acid generator (A) is irradiated with energy rays, and the energy ray sensitive acid generator (A) and the sensitizer (B). It is considered that the reaction mechanism differs between the case where the energy ray-sensitive acid generator composition containing the above is irradiated with energy rays, and the reaction mechanism also differs between energy transfer and electron transfer.

First, regarding the reaction mechanism in the case where only the energy ray sensitive acid generator (A) is irradiated with energy rays to cause a reaction by intramolecular electron transfer, Ao Yamaoka, Hiroshi Morita, “Photosensitive Resin”, 21 pages, Kyoritsu Publishing (1988
As described in (Year), it is considered to proceed by the following (Equation 1) to (Equation 4). ^{Ar-I + -Ar 'Q -} ----------> [Ar-I + -Ar' Q -] * ( Equation ^{1) [Ar-I + -Ar} 'Q -] * - ^{--------> Ar-I + · +} Ar '+ Q - ( equation ^{2) Ar-I + · +} MH ----------> Ar-I + -H + M (Formula 3) Ar-I ⁺ -H ---------------> Ar-I + H ⁺ (Formula 4) Here, Ar-I-Ar 'is represented by the general formula ( The iodonium cation represented by 1), Q ⁻ represents a borate anion represented by the general formula (2), and MH represents a hydrogen donor. First, the energy ray sensitive acid generator (A) absorbs an energy ray to be in an excited state (Equation 1). Then, the substituent of the iodonium cation of the excited energy ray sensitive acid generator (A) (in this case, Ar or A
From r ′), an intramolecular electron transfer reaction occurs to iodine of the iodonium cation, and the iodonium cation decomposes (Formula 2). Further, the cation radical (Ar-I ^+. ) Generated during this decomposition abstracts hydrogen from the hydrogen donor (MH) (equation 3), and this generates a proton (acid) (equation 4).

Further, regarding the reaction mechanism in the case where only the energy ray sensitive acid generator (A) is irradiated with energy rays to cause a reaction by energy transfer, the reaction mechanism as described above from the substituent Ar or Ar 'of the iodonium cation to iodonium It is considered that energy transfer occurs to iodine, which is a cation, and the iodonium cation is decomposed to generate a proton (acid).

Next, regarding the reaction mechanism when the energy ray-sensitive acid generator composition containing the energy ray-sensitive acid generator (A) and the sensitizer (B) is irradiated with energy rays, see Ao Yamaoka, As described in Hiroshi Morita, "Photosensitive Resin," p. 23, Kyoritsu Shuppan (1988), first, the sensitizer (B) absorbs an energy ray to be in an excited state, and this excited Energy transfer or electron transfer from the sensitizer (B) to the energy-sensitive acid generator (A) by forming an exciplex between the sensitizer (B) and the energy-sensitive acid generator (A). It is considered that a reaction occurs and, as a result, the energy ray sensitive acid generator (A) decomposes to generate a proton (acid).

As described above, when the acid-curable compound (C) is present when the proton (acid) is generated, the generated proton (acid) causes the polymerization or curing reaction of the acid-curable compound (C), resulting in As, a polymer or a cured product is given.

Further, by devising a substituent on the iodonium cation represented by the general formula (1), crystallinity, stability and solubility in various organic solvents can be improved, and further, conventional iodonium cations can be obtained. It gives better results in improving the sensitivity of the curable composition containing the acid-curable compound (C) than the compound.

[0140]

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, S = 32, I = 127, B = 1
1 shows the fragment when calculated with F = 19.

(Synthesis Example 1) Synthesis of di (2-furyl) iodonium tetrakis (pentafluorophenyl) borate 2.16 parts of di (2-furyl) iodonium chloride was dispersed in dichloromethane, and then lithium tetrakis (pentafluorophenyl) borate was added. 5.00 parts was added, and the mixture was stirred at 25 ° C for 2 hours. Then, the reaction product was filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 4.28 parts of white crystals of di (2-furyl) iodonium tetrakis (pentafluorophenyl) borate. FD-MS m / z 261 ((M-B (C
₆ F ₅ ) ₄ ) ⁺ ) Elemental analysis C ₃₂ H ₆ O ₂ BF ₂₀ I Theoretical value C; 40.89%, H; 0.64% Measured value C; 40.92%, H; 0.67%

(Synthesis Example 2) Synthesis of di (2-thienyl) iodonium tetrakis (pentafluorophenyl) borate 2.40 parts of di (2-thienyl) iodonium chloride was dispersed in dichloromethane and then lithium tetrakis (pentafluorophenyl) borate. 5.00 parts was added, and the mixture was stirred at 25 ° C for 2 hours. Then, this reaction product was filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 5.23 parts of white crystals of di (2-thienyl) iodonium tetrakis (pentafluorophenyl) borate. FD-MS m / z 293 ((M-B (C
₆ F ₅ ) ₄ ) ⁺ ) Elemental analysis C ₃₂ H ₆ S ₂ BF ₂₀ I Theoretical value C; 39.53%, H; 0.62%, S; 6.
60% measured value C; 39.58%, H; 0.64%, S; 6.
58%

(Synthesis Example 3) Synthesis of bis (5-methyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate 2.60 parts of bis (5-methyl-2-thienyl) iodonium chloride was dispersed in ethyl acetate, Then, 5.00 parts of lithium tetrakis (pentafluorophenyl) borate was added, and the mixture was stirred at 25 ° C. for 2 hours. Then, the reaction product was filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 5.38 parts of white bis (5-methyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate crystal. FD-MS m / z 321 ((M-B (C
₆ F ₅ ) ₄ ) ⁺ ) Elemental analysis C ₃₄ H ₁₀ S ₂ BF ₂₀ I Theoretical value C; 40.83%, H; 1.01%, S; 6.
41% measured value C; 39.58%, H; 0.64%, S; 6.
34%

Synthesis Example 4 Synthesis of Bis (5-acetyl-2-thienyl) iodonium tetrakis (pentafluorophenyl) borate 3.33 parts of bis (5-acetyl-2-thienyl) iodonium bromide was dissolved in 200 parts of water. Then, an aqueous solution of 5.00 parts of lithium tetrakis (pentafluorophenyl) borate dissolved in 200 parts of water was added over 30 minutes at 25 ° C. Shortly thereafter
The reaction slurry was filtered, and the obtained white crystals were washed with distilled water to obtain bis (5-acetyl-2-thienyl).
6.12 parts of crystals of iodonium tetrakis (pentafluorophenyl) borate were obtained. FD-MS m / z 377 ((M-B (C
₆ F ₅ ) ₄ ) ⁺ ) Elemental analysis C ₃₆ H ₁₀ O ₂ S ₂ BF ₂₀ I Theoretical value C; 40.94%, H; 0.95%, S; 6.
07% measured value C; 40.74%, H; 0.86%, S;
19%

Synthesis Example 5 Synthesis of di (2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2.16 parts of di (2-furyl) iodonium chloride was dispersed in dichloromethane, and then, Lithium tetrakis [3,5-bis (trifluoromethyl) phenyl]
5.10 parts of borate was added, and the mixture was stirred at 25 ° C for 1 hour. Thereafter, this reaction product was filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 2.28 parts of crystals of white di (2-furyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate. Got FD chromatography MS m / z 261 ((M -B (C 6 H 3 (C
F ₃ ) ₂ ))) ⁺ ) Elemental analysis C ₄₀ H ₁₈ O ₂ BF ₂₄ I Theoretical value C; 42.73%, H; 1.61% Measured value C; 42.54%, H; 1.84%

Synthesis Example 6 Di (2-thienyl) iodonium tetrakis [3,5-
Synthesis of bis (trifluoromethyl) phenyl] borate 2.16 parts of di (2-thienyl) iodonium chloride are dispersed in dichloromethane and then lithium tetrakis [3,5-bis (trifluoromethyl) phenyl].
5.10 parts of borate was added, and the mixture was stirred at 25 ° C for 1 hour. Then, the reaction product was filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 2.28 parts of crystals of white di (2-thienyl) iodonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate. Got FD chromatography MS m / z 293 ((M -B (C 6 H 3 (C
F ₃ ) ₂ )) ⁺ ) Elemental analysis C ₄₀ H ₁₈ S ₂ BF ₂₄ I Theoretical value C; 41.55%, H; 1.59% Measured value C; 41.34%, H; 1.72%

Other energy-sensitive ray acid generators (A) described in the specification were synthesized by the same method.

Example 1 As the acid-curable compound (C), 3,4-epoxycyclohexylmethyl-3,4-
Epoxy cyclohexane carboxylate (manufactured by Union Carbide Co., product name ERL-4221) 100 parts, as energy-sensitive ray acid generator (A), di (2-furyl)
An acid-curable composition consisting of 1 part of iodonium tetrakis (pentafluorophenyl) borate 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.).
When irradiated from a distance of cm for 5 minutes, a cured product was observed at the bottom of the aluminum cup.

(Examples 2 to 26) Energy Sensitive Rays As the acid generator (A), instead of 1 part of di (2-furyl) iodonium tetrakis (pentafluorophenyl) borate, the energy sensitive values shown in Table 1 were used. Linear acid generator (A)
An acid-curable composition consisting of 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

[0151]

[Table 1]

Examples 27 to 46 As the acid-curable compound (C), instead of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, the acid-curable compounds shown in Table 2 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 2

[0154]

[Table 2]

Example 47 As acid-curable compound (C), 3,4-epoxycyclohexylmethyl-3,4-
Epoxy cyclohexane carboxylate (manufactured by Union Carbide Co., product name ERL-4221) 100 parts, as energy-sensitive ray acid generator (A), di (2-furyl)
1 part of iodonium tetrakis (pentafluorophenyl) borate, 0.5% of anthracene as a sensitizer (B)
Part of the acid-curable composition was placed in an aluminum cup and irradiated with a 500 mW high-pressure mercury lamp through a heat ray cut filter for 3 minutes from a distance of 10 cm. As a result, a cured product was observed at the bottom of the aluminum cup.

(Examples 48 to 55) Sensitizer (B)
As an alternative, an acid-curable composition containing the sensitizer (B) shown in Table 3 was prepared in place of anthracene, and the same experiment as in Example 47 was carried out. In each case,
A cured product was observed at the bottom of the aluminum cup.

Table 3

[0158]

[Table 3]

Example 56 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 di (2-furyl) iodonium tetrakis (pentafluorophenyl) borate as the energy-sensitive ray acid generator (A). About 1.5 with a spin coater
Apply on a glass plate to a thickness of μm, 60 ° C in an oven,
It was dried for 10 minutes to obtain a photosensitive plate. Place a 21 / √2 step tablet (Dainippon Screen grayscale film) on this photosensitive plate, and use a 500 W high pressure mercury lamp light (Ushio Denki KK) to pass through a heat ray cut filter from a distance of 15 cm to 1 After exposing for a minute,
21 /
√ The sensitivity was defined as the maximum number of fully cured plates that correspond to a 2-step tablet.

(Example 57) As the energy ray sensitive acid generator (A), instead of 1 part of di (2-furyl) iodonium tetrakis (pentafluorophenyl) borate, di (2-thienyl) iodonium tetrakis (pentafluoro) was used. An acid-curable composition was prepared using phenyl) borate, and the same experiment as in Example 56 was conducted to determine the sensitivity.

Comparative Examples 1 to 5 As comparative examples, instead of the di (2-furyl) iodonium tetrakis (pentafluorophenyl) borate of the present invention, known diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyl Using iodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, and diphenyliodonium tetrafluoroborate, the same experiment as in Example 56 was performed to determine the sensitivity.

As described above, Table 4 shows the experimental results of Examples 56 and 57, and Table 5 shows the experimental results of Comparative Examples 1 to 5. As is clear from the results of Tables 4 and 5, when the energy ray-sensitive acid generator (A) of the present invention is used, the sensitivity is improved as compared with the known iodonium salts. Recognize.

Table 4

[0164]

[Table 4]

Table 5

[0166]

[Table 5]

(Examples 58 and 59) 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 6 (A) 1.2 × 10 ^-4 mol Was added to make a photosensitive solution. The photosensitive solution was applied on a glass plate with a spin coater to a thickness of about 1.5 μm and placed in an oven.
It was dried at 0 ° C. for 10 minutes to obtain a photosensitive plate. A 21 / √2 step tablet (Grayscale film manufactured by Dainippon Screen Co., Ltd.) is placed on this photosensitive plate, and 500 W of xenon lamp light (manufactured by USHIO INC.) Is passed through a heat ray cut filter for 1 minute from a distance of 15 cm. After exposure, impregnate in toluene for 30 seconds to develop,
The maximum number of completely cured plates corresponding to a 21 / √2 step tablet was defined as the sensitivity.

(Comparative Examples 6 to 10) As comparative examples,
Instead of the di (2-furyl) iodonium tetrakis (pentafluorophenyl) borate of the present invention, known diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexa Using fluorophosphate and diphenyliodonium tetrafluoroborate, the same experiment as in Example 58 was conducted to determine the sensitivity.

The experimental results in Examples 58 and 59 are shown in Table 6, and the experimental results in 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 ray-sensitive acid generator (A) of the present invention is used, the sensitivity is improved as compared with the known iodonium salts. Recognize.

Table 6

[0171]

[Table 6]

Table 7

[0173]

[Table 7]

Example 60 As the acid-curable compound (C), 3,4-epoxycyclohexylmethyl-3,4-
Epoxy cyclohexane carboxylate (manufactured by Union Carbide Co., product name ERL-4221) 100 parts, as energy-sensitive ray acid generator (A), di (2-furyl)
An acid-curable composition comprising 1 part of iodonium tetrakis (pentafluorophenyl) borate, 100 parts of pentaerythritol triacrylate as a radical polymerizable compound (D), and 1 part of benzyl dimethyl ketal as a radical generator (E) Put it in a 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.

The cation moiety of the present invention is an iodonium borate complex composed of an iodonium cation represented by the general formula (1) and an anion portion composed of a borate anion represented by the general formula (2). The characteristic energy ray-sensitive acid generator (A) is effective as a photopolymerization initiator for the acid-curable compound (C), and the curable composition containing these is polymerized and cured by application of energy rays. Is possible.

Therefore, the curable composition of the present invention comprises 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, an excimer lamp,
Excimer laser, nitrogen laser, argon ion laser,
By using light represented by various light sources such as helium-cadmium laser, helium-neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light-emitting diode, CRT light source, and plasma light source, and electron beam energy beam by EB generator, It is possible to obtain a polymer or a cured product.

Therefore, it is applied on a substrate together with a binder and the like, and is used as a core material of a photosensitive plate such as a printing plate material, photoresist, electrophotography, direct printing plate material, hologram material, microcapsules and the like, and various recording media and adhesives. It can be applied to.

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Claims (5)

[Claims] 1. An iodonium borate complex having a cation part composed of an iodonium cation represented by the following general formula (1) and an anion part comprising a borate anion represented by the following general formula (2). The energy ray-sensitive acid generator (A). General formula (1) (However, X represents oxygen or sulfur, and R is independently selected from fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group, cyano group, nitro group, azido group, or the following organic residue. Or a substituent R adjacent to each other may form a ring structure by a covalent bond with each other, and k represents an integer of 0 to 3. Here, the organic residue means fluorine, chlorine or bromine. , A hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group or an azido group, which may be substituted with a C _{1 to} C ₁₈ straight-chain, branched or cyclic alkyl group, or a C _{2 to} C ₁₈ straight chain. Chain, branched chain,
Cyclic alkenyl group, monocyclic, fused polycyclic aryl group C ₆ -C _18, monocyclic, fused polycyclic arylalkyl group _{C 7 ~C 18, C 1 ~C} 18 straight-chain, branched, cyclic alkoxyl group, monocyclic, fused polycyclic aryl group having C ₆ -C _18, C
_{1 to} C ₁₈ straight chain, branched chain, cycloaliphatic or C ₇
To C ₁₉ monocyclic and condensed polycyclic aromatic acyl groups, C _{2 to} C ₁₉ linear, branched and cyclic alkoxycarbonyl groups, C ₇
To C ₁₉ each represent a monocyclic or condensed polycyclic aryloxycarbonyl group. ) 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. An iodonium cation whose cation portion is represented by the general formula (3), and an anion portion which is either tetrakis (pentafluorophenyl) borate or tetrakis [3,5-bis (trifluoromethyl) phenyl] borate. An energy ray-sensitive acid generator (A), which is an iodonium borate complex composed of the borate anion. General formula (3) (However, X represents oxygen or sulfur, R ′ is independently hydrogen, a C _{1 to} C ₁₈ linear or branched alkyl group, or a C _{1 to} C ₁₈ linear or branched chain. Represents a group selected from alkoxy groups.) 3. An energy-sensitive acid generator composition containing the energy-sensitive acid generator (A) and the sensitizer (B) according to any one of claims (1) and (2). 4. The energy-sensitive acid generator (A) according to claim (1) or (2), or claim (3).
A curable composition comprising the energy ray sensitive acid generator composition described above and an acid curable compound (C). 5. The radically polymerizable compound (D) and the radical generator (E) in the curable fat composition according to claim 4.
A curable composition comprising: