JPH10251317A - Polymerization initiator, polymerizable composition and cured product of the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerization initiator, which is a pyridinium borate complex with a cation section and anion section respectively consisting of specific pyridinium cation(s) and borate anion(s), and can generate radicals when irradiated with light to polymerize a polymerizable compound in a short time. SOLUTION: This polymerizable composition is obtained by including (A) a polymerization initiator, which is a pyridinium borate complex composed of (i) a cation section consisting of pyridinium cation(s) shown by the formula [R<1> is a (substituted) alkoxyl or (substituted) aryloxy; R is a 1-18C alkyl or the like which may be substituted with F, Cl, Br, OH or the like; and (k) is 0 to 5] and (ii) an anion section consisting of borate anion(s) shown by the formula [BAr3 R<2> ]<-> (R<2> is a 1-18C alkyl or the like which may be substituted with F, Cl, Br, OH or the like), (B) a radical polymerizable compound, and (C) a sensitizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polymerization initiator and a polymerizable composition. More specifically, a radical is generated by irradiation of energy rays, particularly light, and the polymerizable compound is polymerized in a short time. For example, a molding resin, a casting resin,
Stereolithography resin, sealant, dental polymer resin, printing ink,
Paint, photosensitive resin for printing plate, color proof for printing, resist for color filter, resist for printed circuit board,
Curing with good physical properties in the fields of photoresists for semiconductors, resists for microelectronics, hologram materials, overcoat materials, adhesives, adhesives, release agents, coating materials for paper, wood, metal, plastic, and optical fibers. The present invention relates to a polymerization initiator, a polymerizable composition and a cured product thereof for obtaining a product.

[0002]

2. Description of the Related Art Hitherto, many examples have been reported in which various onium compounds such as iodonium compounds and sulfonium compounds are used as an initiator for cationic polymerization.
Application and Market of Curing Technology ", p. 79 (1989, CMC); V. Crivello, "Adva
nces in Polymer Science ",
Vol. 62, Initiators-Poly-Reac
tions-Optical Activity, (1
984, Springer-Verlag).

In recent years, examples have been reported in which these onium compounds are used as initiators for radical polymerization. For example, Japanese Patent Publication No. Sho 63-2081 discloses triphenylsulfonium hexafluorophosphate and JP-A-59-14.
No. 0203 discloses triaryl and diarylsulfonium compounds, JP-A-63-243102 discloses various sulfonium and oxosulfonium compounds, and polymer bulletin (Polym. Bull.), Vol.
Page 89 (1994) discloses N-ethoxypyridinium hexafluorophosphate compounds.

Further, as an example of using a complex having an organic boron anion as an initiator for radical polymerization, a metal borate complex described in JP-A-2-4804 and JP-A-2-3460 is used. As the ammonium borate complex, the pyridinium borate complex described in JP-A-7-70068 is used.
The cationic dye-borate anion complex described in JP-A-3044 / 1990 is disclosed in JP-A-2-157760 and JP-A-2-166645.
No. 1 and JP-A-3-704 disclose diaryliodonium borates and the like. In each case, it is considered that the carbon-boron bonding portion of the borate anion is decomposed by the action of heat or light to generate radicals.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to propose a highly sensitive polymerizable composition which generates radicals upon irradiation with energy rays, particularly light, and can polymerize a polymerizable compound in a short time. is there. 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,
It is to provide a polymerization initiator and a polymerizable composition.

However, conventional onium compounds have anions whose BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , Sb
Since it is an anion such as F ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , and p-toluenesulfonate, a strong acid (Bronstead acid) is produced as a by-product at the time of decomposition, and it is difficult to leave the acid. In the field of coating materials, there were concerns such as deterioration of electrical characteristics and generation of rust.

Further, conventional onium compounds generally have poor solubility in organic solvents and poor compatibility with resins. Therefore, when using these compounds as radical polymerization initiators for radically polymerizable compounds, onium compounds must be used. , Its poor solubility was a major obstacle.

On the other hand, complexes having an organoboron anion functioning as a polymerization initiator for radically polymerizable compounds have the disadvantage that they have low sensitivity to light or lack storage stability. Also, Japanese Patent Application Laid-Open No. Sho 62-143044
Compounds having a borate anion having absorption in the visible region, such as the cationic dye-borate complex described in No. 2, are also known, but the cured products containing these remain in a color derived from the cationic dye. Had such a problem.

From the above viewpoint, it is necessary to find a polymerization initiator which has good solubility in an organic solvent and compatibility with a resin, has high sensitivity to low-energy light, and does not leave color in a cured product.

[0010]

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

A polymerization initiator (A), which is a pyridinium borate complex in which the cation portion is composed of a pyridinium cation represented by the general formula (1) and the anion portion is a borate anion represented by the general formula (2). General formula (1)

[0012]

Embedded image

(However, R¹Is an alkoxyl group, substituted
Alkoxyl group, aryloxy group, substituted
Represents a group selected from aryloxy groups, wherein R is
Independently, fluorine, chlorine, bromine, hydroxyl, carboxyl
Group, mercapto group, cyano group, and the following organic residues
Represents a group selected from the group consisting of
Is R ¹And R form a ring structure by a covalent bond with each other
And k represents an integer of 0 to 5. Here organic
Residues are fluorine, chlorine, bromine, hydroxyl, carboxyl
Which may be substituted with a group, a mercapto group or a cyano group
₁~ C₁₈Linear, branched or cyclic alkyl group of C_Two~
C₁₈Linear, branched, cyclic alkenyl group, C₆~ C
₁₈A monocyclic, fused polycyclic aryl group, C₇~ C₁₈Single ring, condensed
Polycyclic arylalkyl group, C₁~ C₁₈Linear, branched
Chain, cyclic alkoxyl group, C₆~ C₁₈Single ring, fused poly
Ring aryloxy group, C₁~ C₁₈Linear, branched,
Cycloaliphatic or C₇~ C₁₉Monocyclic and condensed polycyclic aromatic
Acyl group, C_Two~ C₁₉Linear, branched, and cyclic alcohols
Xycarbonyl group, C₇~ C₁₉Monocyclic and condensed polycyclic aryl
Represents any one of a luoxycarbonyl group. ) General formula (2) [BAr_ThreeR^Two]^- (R^TwoStands for fluorine, chlorine, bromine, hydroxyl, carboxyl
Which may be substituted with a group, a mercapto group or a cyano group
₁~ C₁₈Represents a linear, branched or cyclic alkyl group.
Ar is fluorine, chlorine, bromine, hydroxyl, carboxyl
Which may be substituted with a group, a mercapto group or a cyano group
₆~ C₁₈Represents a monocyclic or condensed polycyclic aryl group. )

The second invention of the present invention is a polymerizable composition comprising a polymerization initiator (A) and a radically polymerizable compound (B).
It is a polymerizable composition comprising a polymerization initiator (A), a radical polymerizable compound (B) and a sensitizer (C). The fourth invention of the present invention is a cured product of the polymerizable composition.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the polymerization initiator of the present invention
(A) will be described. The polymerization initiator (A) of the present invention
Pyridinium cation represented by general formula (1)
The above substituent R ¹At

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

The substituted alkoxyl group in the substituent R ¹ is a C ₁ -C ₁₈ substituted with a group selected from fluorine, chlorine, bromine, cyano group, nitro group, trifluoromethyl group and hydroxyl group. Linear and branched alkoxyl groups include, for example, fluoromethoxy, 2-chloroethoxy, 3-bromopropoxy, 4-cyanobutoxy, 18-trifluoromethyloctadecaneoxy, 2-hydroxyiso And a propoxy group and a trichloromethoxy group.

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

The substituted aryloxy group in the substituent R ¹ is the same as the substituted aryloxy group selected from fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro and azide. _{6- C18} monocyclic or condensed polycyclic aryloxy groups such as o-fluorophenoxy, m-chlorophenoxy, p-bromophenoxy, p-hydroxyphenoxy, m-carboxyphenoxy, -Mercaptophenoxy group, p-
Examples include a cyanophenoxy group, a 2-chloro-1-naphthyloxy group, and a 10-cyano-9-anthryloxy group.

Further, in the substituent R in the pyridinium cation represented by the general formula (1) constituting the polymerization initiator (A) of the present invention,

The C ₁ -C ₁₈ linear, branched or cyclic alkyl group which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto or cyano is methyl, ethyl or the like. 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 and the like. can give.

The C ₂ -C ₁₈ linear, branched, or cyclic alkenyl group which may be substituted with fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto or cyano includes vinyl, 1 -Propenyl group, 2-propenyl group, 1-octenyl group, 1-octadecenyl group, isopropenyl group, 1-cyclohexenyl group, trifluoroethenyl group, 1-chloroethenyl group, 2,2-dibromoethenyl group, 4- A hydroxy-1-butenyl group, a 1-carboxyethenyl group, a 5-mercapto-1-hexenyl group, a 1-cyanoethenyl group and the like.

The C ₆ -C ₁₈ monocyclic and condensed polycyclic aryl groups which may be substituted with fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto or cyano are phenyl, 1-naphthyl and the like. , 2-naphthyl, 9-anthryl, 9-phenanthryl, 1-pyrenyl, 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-
Examples include a mercaptophenyl group and a p-cyanophenyl group.

The C ₇ -C ₁₈ monocyclic and condensed polycyclic arylalkyl groups which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto or cyano are benzyl, 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 and the like.

The C ₁ -C ₁₈ linear, branched or cyclic alkoxyl group which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto or cyano is methoxy, ethoxy or the like. Group, propoxy group, butoxy group, octyloxy group, octadecaneoxy group, isopropoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy group, fluoromethoxy group,
Chloromethoxy, bromomethoxy, trifluoromethoxy, trichloromethoxy, tribromomethoxy, hydroxymethoxy, carboxymethoxy, mercaptomethoxy, cyanomethoxy and the like.

The C ₆ -C ₁₈ monocyclic and condensed polycyclic aryloxy groups which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto or cyano are phenoxy, naphthyloxy and the like. , 2-naphthyloxy, 9-anthryloxy, 9-phenanthryloxy, 1-pyrenyloxy, 5-naphthacenyloxy, 1-indenyloxy, 2-azulenyloxy, 1-acetyl Naphthyloxy group, 9-fluorenyloxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, 2,3-xylyloxy group,
2,5-xylyloxy group, mesityloxy group, p-cumenyloxy group, p-decylphenoxy group, p-cyclohexylphenoxy group, 4-biphenoxy group, o-fluorophenoxy group, m-chlorophenoxy group, p-bromophenoxy group, p-hydroxyphenoxy group, m-carboxyphenoxy group, o-mercaptophenoxy group,
p-cyanophenoxy group and the like.

C ₁ -C ₁₈ linear, branched, cycloaliphatic or C ₁ -C ₁₈ which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto or cyano.
Monocyclic ₇ -C _19, as the condensed polycyclic aromatic acyl group, a formyl group, an acetyl group, hexanoyl group, lauroyl group, a palmitoyl group, a stearoyl group, an isobutyryl group, an isovaleryl group, a pivaloyl group, cyclopentyl group, cyclohexyl Carbonyl 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-cyanoacetyl group and the like.

The C ₂ -C ₁₉ linear, branched or cyclic alkoxycarbonyl group which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto or cyano is methoxycarbonyl. , Ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, octadecaneoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, fluoromethoxycarbonyl group, chloro Methoxycarbonyl group, bromomethoxycarbonyl group, trifluoromethoxycarbonyl group, trichloromethoxycarbonyl group, tribromomethoxycarbonyl group, hydroxymethoxycarbonyl group, Alkoxycarbonyl group, mercapto methoxycarbonyl group, a cyano methoxycarbonyl group.

The C ₇ -C ₁₉ monocyclic or condensed polycyclic aryloxycarbonyl group which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto or cyano is phenoxycarbonyl, Naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group,
9-anthryloxycarbonyl group, 9-phenanthryloxycarbonyl group, 1-pyrenyloxycarbonyl group, 5-naphthacenyloxycarbonyl 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, m-chlorophenoxycarbonyl group, p-bromophenoxycarbonyl group, p-hydroxyphenoxycarbonyl group, m-carboxyphenoxycarbonyl group, o-mercaptophenoxycarbonyl group, p-cyano Phenoxycarbonyl group and the like.

Further, these adjacent substituents R may form a ring structure by a covalent bond with each other, and examples thereof include alkylene such as methylene, ethylene, tetramethylene and hexamethylene. Group,
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, the structure of the pyridinium cation represented by the general formula (1) of the polymerization initiator (A) of the present invention includes the following pyridinium cations.

Examples of N-alkoxypyridinium: N-methoxypyridinium, N-ethoxypyridinium, N-
Propoxypyridinium, N-butoxypyridinium,
N-octyloxypyridinium, N-octadecyloxypyridinium, N-isopropoxypyridinium,
N- (t-butoxy) pyridinium, N-cyclopentyloxypyridinium, N-cyclohexyloxypyridinium and the like.

Examples of N-substituted alkoxypyridinium: N
-(Fluoromethoxy) pyridinium, N- (2-chloroethoxy) pyridinium, N- (3-bromopropoxy) pyridinium, N- (4-cyanobutoxy) pyridinium, N- (18-trifluoromethyloctadecyloxy) pyridinium, N- (2-hydroxyisopropoxy) pyridinium and the like.

Example of N-aryloxypyridinium: N
-Phenoxypyridinium, N- (1-naphthyloxy) pyridinium, N- (2-naphthyloxy) pyridinium, N- (9-anthryloxy) pyridinium,
N- (9-phenanthryloxy) pyridinium, N-
(1-pyrenyloxy) pyridinium, N- (5-naphthenyloxy) pyridinium, N- (1-indenyloxy) pyridinium, N- (2-azulenyloxy)
Pyridinium, N- (1-acenaphthyloxy) pyridinium, N- (9-fluorenyloxy) pyridinium, N- (o-tolyloxy) pyridinium, N- (m
-Tolyloxy) pyridinium, N- (p-tolyloxy) pyridinium, N- (2,3-xylyloxy) pyridinium, N- (2,5-xylyloxy) pyridinium, N- (mesityloxy) pyridinium, N- (p
-Cumenyloxy) pyridinium, N- (p-decylphenoxy) pyridinium, N- (p-cyclohexylphenoxy) pyridinium, N- (4-phenylphenoxy) pyridinium and the like.

Examples of N-substituted aryloxypyridinium: N- (o-fluorophenoxy) pyridinium, N
-(M-chlorophenoxy) pyridinium, N- (p-
Bromophenoxy) pyridinium, N- (p-hydroxyphenoxy) pyridinium, N- (m-carboxyphenoxy) pyridinium, N- (o-mercaptophenoxy) pyridinium, N- (p-cyanophenoxy) pyridinium, N- (2- Chloro-1-naphthyloxy)
Pyridinium, N- (10-cyano-9-anthryloxy) pyridinium and the like.

Examples of 2-substituted-1-ethoxypyridinium: 2-fluoro-1-ethoxypyridinium, 2-chloro-1-ethoxypyridinium, 2-bromo-1-ethoxypyridinium, 2-hydroxy-1-ethoxypyridinium, 2-carboxy-1-ethoxypyridinium, 2-mercapto-1-ethoxypyridinium, 2-
Cyano-1-ethoxypyridinium and the like.

Examples of 2- (substituted) alkyl-1-ethoxypyridinium: 2-methyl-1-ethoxypyridinium, 2-ethyl-1-ethoxypyridinium, 2-propyl-1-ethoxypyridinium, 2-butyl-1- Ethoxypyridinium, 2-pentyl-1-ethoxypyridinium, 2-hexyl-1-ethoxypyridinium,
2-octyl-1-ethoxypyridinium, 2-decyl-1-ethoxypyridinium, 2-dodecyl-1-ethoxypyridinium, 2-octadecyl-1-ethoxypyridinium, 2-isopropyl-1-ethoxypyridinium, 2-isobutyl-1 -Ethoxypyridinium, 2
-Sec-butyl-1-ethoxypyridinium, 2-t
-Butyl-1-ethoxypyridinium, 2-cyclopentyl-1-ethoxypyridinium, 2-cyclohexyl-1-ethoxypyridinium, 2- (4-decylcyclohexyl) -1-ethoxypyridinium, 2-fluoromethyl-1-ethoxypyridinium, 2-chloromethyl-1-ethoxypyridinium, 2-bromomethyl-1-
Ethoxypyridinium, 2-trifluoromethyl-1-
Ethoxypyridinium, 2-trichloromethyl-1-ethoxypyridinium, 2-tribromomethyl-1-ethoxypyridinium, 2-hydroxymethyl-1-ethoxypyridinium, 2-carboxymethyl-1-ethoxypyridinium, 2-mercaptomethyl-1 -Ethoxypyridinium, 2-cyanomethyl-1-ethoxypyridinium and the like.

Examples of 2- (substituted) alkenyl-1-ethoxypyridinium: 2-vinyl-1-ethoxypyridinium, 2- (1-propenyl) -1-ethoxypyridinium, 2- (2-propenyl) -1-ethoxy Pyridinium, 2- (1-octenyl) -1-ethoxypyridinium, 2- (1-octadecenyl) -1-ethoxypyridinium, 2- (isopropenyl) -1-ethoxypyridinium, 2- (1-cyclohexenyl) -1 -Ethoxypyridinium, 2- (trifluoroethenyl) -1-ethoxypyridinium, 2- (1-chloroethenyl) -1
-Ethoxypyridinium, 2- (2,2-dibromoethenyl) -1-ethoxypyridinium, 2- (4-hydroxy-1-butenyl) -1-ethoxypyridinium,
-(1-carboxyethenyl) -1-ethoxypyridinium, 2- (5-mercapto-1-hexenyl) -1-
Ethoxypyridinium, 2- (1-cyanoethenyl)-
1-ethoxypyridinium and the like.

Examples of 2- (substituted) aryl-1-ethoxypyridinium: 2-phenyl-1-ethoxypyridinium, 2- (1-naphthyl) -1-ethoxypyridinium, 2- (2-naphthyl) -1-ethoxy Pyridinium, 2- (9-anthryl) -1-ethoxypyridinium, 2- (9-phenanthryl) -1-ethoxypyridinium, 2- (1-pyrenyl) -1-ethoxypyridinium, 2- (5-naphthacenyl) -1 -Ethoxypyridinium, 2- (1-indenyl) -1-ethoxypyridinium, 2- (2-azulenyl) -1-ethoxypyridinium, 2- (1-acenaphthyl) -1-ethoxypyridinium, 2- (9-fluorenyl) -1-ethoxypyridinium, 2- (o-tolyl) -1-ethoxypyridinium, 2- (m-to Le) -1-ethoxy pyridinium, 2-(p-tolyl) -1-ethoxy pyridinium,
2- (2,3-xylyl) -1-ethoxypyridinium, 2- (2,5-xylyl) -1-ethoxypyridinium, 2- (mesityl) -1-ethoxypyridinium,
2- (p-cumenyl) -1-ethoxypyridinium, 2
-(P-dodecylphenyl) -1-ethoxypyridinium, 2- (p-cyclohexylphenyl) -1-ethoxypyridinium, 2- (4-biphenyl) -1-ethoxypyridinium, 2- (o-fluorophenyl) -1 −
Ethoxypyridinium, 2- (m-chlorophenyl)-
1-ethoxypyridinium, 2- (p-bromophenyl) -1-ethoxypyridinium, 2- (p-hydroxyphenyl) -1-ethoxypyridinium, 2- (m-
Carboxyphenyl) -1-ethoxypyridinium, 2
-(O-mercaptophenyl) -1-ethoxypyridinium, 2- (p-cyanophenyl) -1-ethoxypyridinium and the like.

Examples of 2- (substituted) alkoxy-1-ethoxypyridinium: 2-methoxy-1-ethoxypyridinium, 2-ethoxy-1-ethoxypyridinium, 2-
Propoxy-1-ethoxypyridinium, 2-butoxy-1-ethoxypyridinium, 2-octyloxy-1
-Ethoxypyridinium, 2-octadecyloxy-1
-Ethoxypyridinium, 2-isopropoxy-1-ethoxypyridinium, 2- (t-butoxy) -1-ethoxypyridinium, 2-cyclopentyloxy-1-ethoxypyridinium, 2-cyclohexyloxy-1-
Ethoxypyridinium, 2- (fluoromethoxy-1-
Ethoxypyridinium, 2-chloromethoxy-1-ethoxypyridinium, 2-bromomethoxy-1-ethoxypyridinium, 2-trifluoromethoxy-1-ethoxypyridinium, 2-trichloromethoxy-1-ethoxypyridinium, 2-tribromomethoxy- 1-ethoxypyridinium, 2-hydroxymethoxy-1-ethoxypyridinium, 2-carboxymethoxy-1-ethoxypyridinium, 2-mercaptomethoxy-1-ethoxypyridinium, 2-cyanomethoxy-1-ethoxypyridinium and the like.

Examples of 2- (substituted) aryloxy-1-ethoxypyridinium: 2-phenoxy-1-ethoxypyridinium, 2- (1-naphthyloxy) -1-ethoxypyridinium, 2- (2-naphthyloxy) -1- Ethoxypyridinium, 2- (9-anthryloxy)-
1-ethoxypyridinium, 2- (9-phenanthryloxy) -1-ethoxypyridinium, 2- (1-pyrenyloxy) -1-ethoxypyridinium, 2- (5-
Naphthacenyloxy) -1-ethoxypyridinium, 2
-(1-indenyloxy) -1-ethoxypyridinium, 2- (2-azulenyloxy) -1-ethoxypyridinium, 2- (1-acenaphthyloxy) -1-ethoxypyridinium, 2- (9-fluorenyl) Oxy)-
1-ethoxypyridinium, 2- (o-tolyloxy)
-1-ethoxypyridinium, 2- (m-tolyloxy) -1-ethoxypyridinium, 2- (p-tolyloxy) -1-ethoxypyridinium, 2- (2,3-xylyloxy) -1-ethoxypyridinium, 2-
(2,5-xylyloxy) -1-ethoxypyridinium, 2-mesityloxy-1-ethoxypyridinium,
2- (p-cumenyloxy) -1-ethoxypyridinium, 2- (p-decylphenoxy) -1-ethoxypyridinium, 2- (p-cyclohexylphenoxy) -1
-Ethoxypyridinium, 2- (4-biphenoxy)-
1-ethoxypyridinium, 2- (o-fluorophenoxy) -1-ethoxypyridinium, 2- (m-chlorophenoxy) -1-ethoxypyridinium, 2- (p-
Bromophenoxy) -1-ethoxypyridinium, 2-
(P-hydroxyphenoxy) -1-ethoxypyridinium, 2- (m-carboxyphenoxy) -1-ethoxypyridinium, 2- (o-mercaptophenoxy)-
1-ethoxypyridinium, 2- (p-cyanophenoxy) -1-ethoxypyridinium and the like.

Examples of 2- (substituted) acyl-1-ethoxypyridinium: 2-formyl-1-ethoxypyridinium, 2-acetyl-1-ethoxypyridinium, 2-hexanoyl-1-ethoxypyridinium, 2-lauroyl-1- Ethoxypyridinium, 2-palmitoyl-1
-Ethoxypyridinium, 2-stearoyl-1-ethoxypyridinium, 2-isobutyryl-1-ethoxypyridinium, 2-isovaleryl-1-ethoxypyridinium, 2-pivaloyl-1-ethoxypyridinium, 2
-Cyclopentylcarbonyl-1-ethoxypyridinium, 2-cyclohexylcarbonyl-1-ethoxypyridinium, 2-benzoyl-1-ethoxypyridinium, 2- (1-naphthoyl) -1-ethoxypyridinium, 2- (2-naphthoyl) -1 -Ethoxypyridinium, 2- (9-anthroyl) -1-ethoxypyridinium, 2- (5-naphthateloyl) -1-ethoxypyridinium, 2- (cinnamoyl) -1-ethoxypyridinium, 2- (α-fluoroacetyl)- 1-ethoxypyridinium, 2- (α-chloroacetyl) -1-ethoxypyridinium, 2- (α-bromoacetyl) -1-
Ethoxypyridinium, 2- (α-hydroxyacetyl) -1-ethoxypyridinium, 2- (α-carboxyacetyl) -1-ethoxypyridinium, 2- (α-
Mercaptoacetyl) -1-ethoxypyridinium, 2
-(Α-cyanoacetyl) -1-ethoxypyridinium and the like.

2- (substituted) alkoxycarbonyl-1-
Example of ethoxypyridinium: 2-methoxycarbonyl-
1-ethoxypyridinium, 2-ethoxycarbonyl-
1-ethoxypyridinium, 2-propoxycarbonyl-1-ethoxypyridinium, 2-butoxycarbonyl-1-ethoxypyridinium, 2-octyloxycarbonyl-1-ethoxypyridinium, 2-octadecyloxycarbonyl-1-ethoxypyridinium, 2-iso Propoxycarbonyl-1-ethoxypyridinium,
2- (t-butoxycarbonyl) -1-ethoxypyridinium, 2-cyclopentyloxycarbonyl-1-ethoxypyridinium, 2-cyclohexyloxycarbonyl-1-ethoxypyridinium, 2-fluoromethoxycarbonyl-1-ethoxypyridinium, 2-chloro Methoxycarbonyl-1-ethoxypyridinium, 2-
Bromomethoxycarbonyl-1-ethoxypyridinium, 2-trifluoromethoxycarbonyl-1-ethoxypyridinium, 2-trichloromethoxycarbonyl-
1-ethoxypyridinium, 2-tribromomethoxycarbonyl-1-ethoxypyridinium, 2- (hydroxymethoxycarbonyl-1-ethoxypyridinium,
-Carboxymethoxycarbonyl-1-ethoxypyridinium, 2-mercaptomethoxycarbonyl-1-ethoxypyridinium, 2-cyanomethoxycarbonyl-1
-Ethoxypyridinium and the like.

2- (substituted) aryloxycarbonyl-
Examples of 1-ethoxypyridinium: 2-phenoxycarbonyl-1-ethoxypyridinium, 2- (1-naphthyloxycarbonyl) -1-ethoxypyridinium, 2-
(2-naphthyloxycarbonyl) -1-ethoxypyridinium, 2- (9-anthryloxycarbonyl)-
1-ethoxypyridinium, 2- (9-phenanthryloxycarbonyl) -1-ethoxypyridinium, 2-
(1-pyrenyloxycarbonyl) -1-ethoxypyridinium, 2- (5-naphthacenyloxycarbonyl)
-1-ethoxypyridinium, 2- (1-indenyloxycarbonyl) -1-ethoxypyridinium, 2-
(2-azulenyloxycarbonyl) -1-ethoxypyridinium, 2- (1-acenaphthyloxycarbonyl) -1-ethoxypyridinium, 2- (9-fluorenyloxycarbonyl) -1-ethoxypyridinium,
2- (o-tolyloxycarbonyl) -1-ethoxypyridinium, 2- (m-tolyloxycarbonyl) -1
-Ethoxypyridinium, 2- (p-tolyloxycarbonyl) -1-ethoxypyridinium, 2- (2,3-
Xylyloxycarbonyl) -1-ethoxypyridinium, 2- (2,5-xylyloxycarbonyl) -1-
Ethoxypyridinium, 2-mesityloxycarbonyl-1-ethoxypyridinium, 2- (p-cumenyloxycarbonyl) -1-ethoxypyridinium, 2- (p
-Cyclohexylphenoxycarbonyl) -1-ethoxypyridinium, 2- (4-phenylphenoxycarbonyl) -1-ethoxypyridinium, 2- (o-fluorophenoxycarbonyl) -1-ethoxypyridinium, 2- (m-chlorophenoxycarbonyl) -1-ethoxypyridinium, 2- (p-bromophenoxycarbonyl) -1-ethoxypyridinium, 2- (p-hydroxyphenoxycarbonyl) -1-ethoxypyridinium, 2- (m-carboxyphenoxycarbonyl)-
1-ethoxypyridinium, 2- (o-mercaptophenoxycarbonyl) -1-ethoxypyridinium, 2-
(P-cyanophenoxycarbonyl) -1-ethoxypyridinium and the like.

Examples of 3-substituted-1-ethoxypyridinium: 3-fluoro-1-ethoxypyridinium, 3-chloro-1-ethoxypyridinium, 3-bromo-1-ethoxypyridinium, 3-hydroxy-1-ethoxypyridinium, 3-carboxy-1-ethoxypyridinium, 3-mercapto-1-ethoxypyridinium, 3-
Cyano-1-ethoxypyridinium and the like.

Examples of 4-substituted-1-ethoxypyridinium: 4-fluoro-1-ethoxypyridinium, 4-chloro-1-ethoxypyridinium, 4-bromo-1-ethoxypyridinium, 4-hydroxy-1-ethoxypyridinium, 4-carboxy-1-ethoxypyridinium, 4-mercapto-1-ethoxypyridinium, 4-
Cyano-1-ethoxypyridinium and the like.

Examples of polysubstituted-1-ethoxypyridinium:
2,3-difluoro-1-ethoxypyridinium, 2,
4-dichloro-1-ethoxypyridinium, 2,5-dibromo-1-ethoxypyridinium, 2,6-dihydroxy-1-ethoxypyridinium, 3,4-dicarboxy-1-ethoxypyridinium, 3,5-dimercapto-1 -Ethoxypyridinium, 2,4,6-trimethyl-1-ethoxypyridinium, 2,3,5,6-tetramethyl-1-ethoxypyridinium, 2,3,4,5
6-pentamethyl-1-ethoxypyridinium and the like.

Examples of cyclic pyridinium: 2,3-tetramethylene-1-ethoxypyridinium, 1,2-ethylenedioxypyridinium, 2,6-diethylenedioxy-
1-methoxypyridinium, 2,3-ethylenedithio-
1-butoxypyridinium, 2,6-diethylenedithio-1-phenoxypyridinium and the like.

On the other hand, the polymerization initiator (A) of the present invention
Borate represented by the general formula (2) that constitutes a lithium complex
In the substituent Ar in the anion, fluorine, chlorine,
Bromine, hydroxyl, carboxyl, mercapto, cyano
Optionally substituted with a group ₆~ C₁₈Monocyclic and fused polycyclic
Aryl groups include phenyl, 1-naphthyl, 2
-Naphthyl group, 9-anthryl group, 9-phenanthryl
Group, 1-pyrenyl group, 5-naphthacenyl group, 1-indene
Nyl group, 2-azulenyl group, 1-acenaphthyl group, 9-
Fluorenyl group, o-tolyl group, m-tolyl group, p-tol
A lyl group, a 2,3-xylyl group, a 2,5-xylyl group,
Cytyl group, p-cumenyl group, p-dodecylphenyl group,
p-cyclohexylphenyl group, 4-biphenyl group, o
-Fluorophenyl group, m-chlorophenyl group, p-butyl
Lomophenyl group, p-hydroxyphenyl group, m-cal
Boxyphenyl group, o-mercaptophenyl group, p-cy
And an anophenyl group.

The substituent R ² in the borate anion represented by the general formula (2) constituting the pyridinium complex of the present invention is substituted with fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, or cyano. The C ₁ -C ₁₈ linear, branched or cyclic alkyl group which may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a 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, Examples thereof include a trichloromethyl group, a tribromomethyl group, a hydroxymethyl group, a carboxymethyl group, a mercaptomethyl group, and a cyanomethyl group.

Accordingly, specific examples of the structure of the borate anion represented by the general formula (2) constituting the pyridinium complex of the present invention include the following.

Triphenylmethyl borate, triphenylethyl borate, triphenylpropyl borate, triphenylbutyl borate, triphenylhexyl borate, triphenyl octyl borate, triphenyl octadecyl borate, triphenyl isopropyl borate, triphenyl isobutyl borate, triphenyl −
sec-butyl borate, triphenyl-t-butyl borate, triphenyl neopentyl borate,

Triphenylcyclopentyl borate, triphenylcyclohexyl borate, triphenyl (4
-Decylcyclohexyl) borate, triphenyl (fluoromethyl) borate, triphenyl (chloromethyl) borate, triphenyl (bromomethyl) borate, triphenyl (trifluoromethyl) borate, triphenyl (trichloromethyl) borate, triphenyl (hydroxy Methyl) borate, triphenyl (carboxymethyl) borate, triphenyl (cyanomethyl) borate,

Tris (1-naphthyl) butyl borate,
Tris (2-naphthyl) butyl borate, tris (o-
Tolyl) butyl borate, tris (m-tolyl) butyl borate, tris (p-tolyl) butyl borate, tris (2,3-xylyl) butyl borate, tris (2
5-xylyl) butyl borate and the like.

Of these, as the structure of the borate anion represented by the general formula (2) constituting the pyridinium complex of the present invention, triphenylbutyl borate is preferred, because the thermal stability is poor. It is an anion that is high in balance and good in solubility in a solvent, and is a well-balanced anion.

Accordingly, preferred specific examples of the pyridinium complex which is the polymerization initiator (A) of the present invention include the following, but the present invention is not limited thereto.

Examples of N-alkoxypyridinium triphenylbutyl borate: N-methoxypyridinium triphenylbutyl borate, N-ethoxypyridinium triphenylbutyl borate, N-propoxypyridinium triphenylbutyl borate, N-butoxypyridinium triphenylbutyl borate, N-octyloxypyridinium triphenylbutyl borate, N-octadecyloxypyridinium triphenylbutyl borate,
N-isopropoxypyridinium triphenylbutyl borate, N- (t-butoxy) pyridinium triphenylbutyl borate, N-cyclopentyloxypyridinium triphenylbutyl borate, N-cyclohexyloxypyridinium triphenylbutyl borate and the like.

Examples of N-substituted alkoxypyridinium triphenylbutyl borates: N- (fluoromethoxy) pyridinium triphenylbutyl borate, N- (2-chloroethoxy) pyridinium triphenylbutyl borate, N- (3-bromopropoxy) pyridinium Triphenylbutyl borate, N- (4-cyanobutoxy) pyridinium triphenylbutyl borate, N- (18-
Trifluoromethyloctadecyloxy) pyridinium triphenylbutyl borate, N- (2-hydroxyisopropoxy) pyridinium triphenylbutyl borate and the like.

Examples of N-aryloxypyridinium triphenylbutyl borate: N-phenoxypyridinium triphenylbutyl borate, N- (1-naphthyloxy) pyridinium triphenylbutyl borate, N-
(2-Naphthyloxy) pyridinium triphenylbutyl borate, N- (9-anthryloxy) pyridinium triphenylbutyl borate, N- (9-phenanthryloxy) pyridinium triphenylbutyl borate, N- (1-pyrenyloxy) Pyridinium triphenylbutyl borate, N- (5-naphthacenyloxy)
Pyridinium triphenylbutyl borate, N- (1-
Indenyloxy) pyridinium triphenylbutyl borate, N- (2-azulenyloxy) pyridinium triphenylbutyl borate, N- (1-acenaphthyloxy) pyridinium triphenylbutyl borate, N-
(9-fluorenyloxy) pyridinium triphenylbutyl borate, N- (o-tolyloxy) pyridinium triphenylbutyl borate, N- (m-tolyloxy) pyridinium triphenylbutyl borate, N-
(P-tolyloxy) pyridinium triphenylbutyl borate, N- (2,3-xylyloxy) pyridinium triphenylbutyl borate, N- (2,5-xylyloxy) pyridinium triphenylbutyl borate,
N- (mesityloxy) pyridinium triphenylbutyl borate, N- (p-cumenyloxy) pyridinium triphenylbutyl borate, N- (p-decylphenoxy) pyridinium triphenylbutyl borate, N-
(P-cyclohexylphenoxy) pyridinium triphenylbutyl borate, N- (4-phenylphenoxy) pyridinium triphenylbutyl borate and the like.

Examples of N-substituted aryloxypyridinium triphenylbutyl borates: N- (o-fluorophenoxy) pyridinium triphenylbutyl borate, N
-(M-chlorophenoxy) pyridinium triphenylbutyl borate, N- (p-bromophenoxy) pyridinium triphenylbutyl borate, N- (p-hydroxyphenoxy) pyridinium triphenylbutyl borate, N- (m-carboxyphenoxy) pyridinium Triphenylbutyl borate, N- (o-mercaptophenoxy) pyridinium triphenylbutyl borate,
N- (p-cyanophenoxy) pyridinium triphenylbutyl borate, N- (2-chloro-1-naphthyloxy) pyridinium triphenylbutyl borate, N-
(10-cyano-9-anthryloxy) pyridinium triphenylbutyl borate and the like.

Examples of 2-substituted-1-ethoxypyridinium triphenylbutyl borate: 2-fluoro-1-ethoxypyridinium triphenylbutyl borate, 2-chloro-1-ethoxypyridinium triphenylbutyl borate, 2-bromo-1- Ethoxypyridinium triphenylbutyl borate, 2-hydroxy-1-ethoxypyridinium triphenylbutyl borate, 2-carboxy-1-ethoxypyridinium triphenylbutyl borate, 2-mercapto-1-ethoxypyridinium triphenylbutyl borate, 2-cyano- 1-ethoxypyridinium triphenylbutyl borate and the like.

Examples of 2- (substituted) alkyl-1-ethoxypyridinium triphenylbutyl borate: 2-methyl-1-ethoxypyridinium triphenylbutyl borate, 2-ethyl-1-ethoxypyridinium triphenylbutyl borate, 2-propyl -1-ethoxypyridinium triphenylbutyl borate, 2-butyl-1-
Ethoxypyridinium triphenylbutyl borate, 2
-Pentyl-1-ethoxypyridinium triphenylbutyl borate, 2-hexyl-1-ethoxypyridinium triphenylbutyl borate, 2-octyl-1-ethoxypyridinium triphenylbutyl borate, 2-
Decyl-1-ethoxypyridinium triphenylbutyl borate, 2-dodecyl-1-ethoxypyridinium triphenylbutyl borate, 2-octadecyl-1-ethoxypyridinium triphenylbutyl borate, 2-
Isopropyl-1-ethoxypyridinium triphenylbutyl borate, 2-isobutyl-1-ethoxypyridinium triphenylbutyl borate, 2-sec-butyl-1-ethoxypyridinium triphenylbutyl borate, 2-t-butyl-1-ethoxypyridinium triborate Phenylbutyl borate, 2-cyclopentyl-1-ethoxypyridinium triphenylbutyl borate, 2-
Cyclohexyl-1-ethoxypyridinium triphenylbutyl borate, 2- (4-decylcyclohexyl)
-1-ethoxypyridinium triphenylbutyl borate, 2-fluoromethyl-1-ethoxypyridinium triphenylbutyl borate, 2-chloromethyl-1-ethoxypyridinium triphenylbutyl borate, 2-
Bromomethyl-1-ethoxypyridinium triphenylbutyl borate, 2-trifluoromethyl-1-ethoxypyridinium triphenylbutyl borate, 2-trichloromethyl-1-ethoxypyridinium triphenylbutyl borate, 2-tribromomethyl-1-ethoxypyridinium Triphenylbutyl borate, 2-hydroxymethyl-1-ethoxypyridinium triphenylbutyl borate, 2-carboxymethyl-1-ethoxypyridinium triphenylbutyl borate, 2-mercaptomethyl-1-ethoxypyridinium triphenylbutyl borate, 2-cyanomethyl -1-ethoxypyridinium triphenylbutyl borate and the like.

Examples of 2- (substituted) alkenyl-1-ethoxypyridinium triphenylbutyl borate: 2-vinyl-1-ethoxypyridinium triphenylbutyl borate, 2- (1-propenyl) -1-ethoxypyridinium triphenylbutyl borate 2- (2-propenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-octenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-octadecenyl) -1-ethoxypyridinium triphenylbutyl Borate, 2- (isopropenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-
Cyclohexenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (trifluoroethenyl)
-1-ethoxypyridinium triphenylbutyl borate, 2- (1-chloroethenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (2,2-dibromoethenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (4-hydroxy-1-butenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-carboxyethenyl) -1-ethoxypyridinium triphenylbutyl borate, 2-
(5-mercapto-1-hexenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-cyanoethenyl) -1-ethoxypyridinium triphenylbutyl borate and the like.

Examples of 2- (substituted) aryl-1-ethoxypyridinium triphenylbutyl borates: 2-phenyl-1-ethoxypyridinium triphenylbutyl borate, 2- (1-naphthyl) -1-ethoxypyridinium triphenylbutyl borate , 2- (2-naphthyl)
-1-ethoxypyridinium triphenylbutyl borate, 2- (9-anthryl) -1-ethoxypyridinium triphenylbutyl borate, 2- (9-phenanthryl) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-pyrenyl ) -1-ethoxypyridinium triphenylbutyl borate, 2- (5-naphthacenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-indenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (2- Azulenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-acenaphthyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (9
-Fluorenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (o-tolyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (m
-Tolyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (p-tolyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (2,3-
(Xylyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (2,5-xylyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (mesityl) -1-ethoxypyridinium triphenylbutyl borate, 2- (p -Cumenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (p-dodecylphenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (p-cyclohexylphenyl) -1-ethoxypyridinium triphenylbutyl borate, 2 -(4-biphenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (o-fluorophenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (m-chlorophenyl) -1-ethoxypyridinium Li phenylbutyl borate, 2-
(P-bromophenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (p-hydroxyphenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (m-carboxyphenyl) -1-ethoxypyridinium triphenylbutyl Borate, 2-
(O-mercaptophenyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (p-cyanophenyl) -1-ethoxypyridinium triphenylbutyl borate and the like.

Examples of 2- (substituted) alkoxy-1-ethoxypyridinium triphenylbutyl borate: 2-methoxy-1-ethoxypyridinium triphenylbutyl borate, 2-ethoxy-1-ethoxypyridinium triphenylbutyl borate, 2-propoxy -1-ethoxypyridinium triphenylbutyl borate, 2-butoxy-1-ethoxypyridinium triphenylbutyl borate, 2-octyloxy-1-ethoxypyridinium triphenylbutyl borate, 2-octadecyloxy-1-ethoxypyridinium triphenylbutyl borate , 2-isopropoxy-1-ethoxypyridinium triphenylbutyl borate, 2- (t-butoxy)-
1-ethoxypyridinium triphenylbutyl borate, 2-cyclopentyloxy-1-ethoxypyridinium triphenylbutyl borate, 2-cyclohexyloxy-1-ethoxypyridinium triphenylbutyl borate, 2- (fluoromethoxy-1-ethoxypyridinium triphenylbutyl Borate, 2-chloromethoxy-1-ethoxypyridinium triphenylbutyl borate, 2-bromomethoxy-1-ethoxypyridinium triphenylbutyl borate, 2-trifluoromethoxy-1-ethoxypyridinium triphenylbutyl borate, 2-trichloromethoxy- 1-ethoxypyridinium triphenylbutyl borate, 2-tribromomethoxy-1-ethoxypyridinium triphenylbutyl borate, 2-hydrido Xymethoxy-1-ethoxypyridinium triphenylbutyl borate, 2-carboxymethoxy-1-ethoxypyridinium triphenylbutyl borate, 2-mercaptomethoxy-1-ethoxypyridinium triphenylbutyl borate, 2-cyanomethoxy-1-ethoxypyridinium triphenyl Butyl borate and the like.

Example of 2- (substituted) aryloxy-1-ethoxypyridinium triphenylbutyl borate: 2-
Phenoxy-1-ethoxypyridinium triphenylbutyl borate, 2- (1-naphthyloxy) -1-ethoxypyridinium triphenylbutyl borate, 2-
(2-naphthyloxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (9-anthryloxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (9-phenanthryloxy) -1-ethoxypyridinium Triphenylbutyl borate, 2-
(1-pyrenyloxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (5-naphthenyloxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-indenyloxy) -1-ethoxypyridinium triborate Phenylbutyl borate, 2- (2
-Azulenyloxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-acenaphthyloxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (9-fluorenyloxy) -1-ethoxypyridinium triphenylbutyl Borate, 2- (o
-Tolyloxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (m-tolyloxy) -1-
Ethoxypyridinium triphenylbutyl borate, 2
-(P-tolyloxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (2,3-xylyloxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (2,5-xylyloxy) -1-ethoxypyridinium triborate Phenylbutyl borate, 2-mesityloxy-1-ethoxypyridinium triphenylbutyl borate, 2- (p-cumenyloxy) -1-ethoxypyridinium triphenylbutyl borate, 2-
(P-decylphenoxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (p-cyclohexylphenoxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (4-biphenoxy) -1-ethoxypyridinium triphenylbutyl borate , 2-
(O-fluorophenoxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (m-chlorophenoxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (p-bromophenoxy) -1-ethoxypyridinium triphenylbutyl Borate, 2-
(P-hydroxyphenoxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (m-carboxyphenoxy) -1-ethoxypyridinium triphenylbutyl borate, 2- (o-mercaptophenoxy)
-1-ethoxypyridinium triphenylbutyl borate, 2- (p-cyanophenoxy) -1-ethoxypyridinium triphenylbutyl borate and the like.

Examples of 2- (substituted) acyl-1-ethoxypyridinium triphenylbutyl borate: 2-formyl-1-ethoxypyridinium triphenylbutyl borate, 2-acetyl-1-ethoxypyridinium triphenylbutyl borate, 2-hexanoyl -1-ethoxypyridinium triphenylbutyl borate, 2-lauroyl-1-ethoxypyridinium triphenylbutyl borate, 2-palmitoyl-1-ethoxypyridinium triphenylbutyl borate, 2-stearoyl-1-
Ethoxypyridinium triphenylbutyl borate, 2
-Isobutyryl-1-ethoxypyridinium triphenylbutyl borate, 2-isovaleryl-1-ethoxypyridinium triphenylbutyl borate, 2-pivaloyl-1-ethoxypyridinium triphenylbutyl borate, 2-cyclopentylcarbonyl-1-ethoxypyridinium triphenylbutyl Borate, 2-cyclohexylcarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-benzoyl-1-ethoxypyridinium triphenylbutyl borate, 2- (1-naphthoyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (2 -Naphthoyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (9-
Anthroyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (5-naphthaceroyl) -1-
Ethoxypyridinium triphenylbutyl borate, 2
-(Cinnamoyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (α-fluoroacetyl)
-1-ethoxypyridinium triphenylbutyl borate, 2- (α-chloroacetyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (α-bromoacetyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (α -Hydroxyacetyl) -1-
Ethoxypyridinium triphenylbutyl borate, 2
-(Α-carboxyacetyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (α-mercaptoacetyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (α-cyanoacetyl) -1-ethoxypyridinium triphenyl Butyl borate and the like.

2- (substituted) alkoxycarbonyl-1-
Examples of ethoxypyridinium triphenylbutyl borate: 2-methoxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-ethoxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-propoxycarbonyl-1-ethoxypyridinium triphenylbutyl borate 2-butoxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-octyloxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-octadecyloxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-isopropoxycarbonyl -1-ethoxypyridinium triphenylbutyl borate, 2- (t-butoxycarbonyl) -1-ethoxypyridinium Phenylbutyl borate, 2-cyclopentyloxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-cyclohexyloxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-fluoromethoxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2 -Chloromethoxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-bromomethoxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-trifluoromethoxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-trichloromethoxycarbonyl -1-ethoxypyridinium triphenylbutyl borate, 2-tribromomethoxycarbonyl-1-ethoxy Sipi lysine bromide triphenyl butyl borate, 2- (hydroxy-methoxycarbonyl-1-ethoxy pyridinium triphenyl butyl borate, 2-carboxy-methoxycarbonyl -
1-ethoxypyridinium triphenylbutyl borate, 2-mercaptomethoxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-cyanomethoxycarbonyl-1-ethoxypyridinium triphenylbutyl borate and the like.

2- (substituted) aryloxycarbonyl-
Examples of 1-ethoxypyridinium triphenylbutyl borate: 2-phenoxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2- (1-naphthyloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (2-naphthyl) (Oxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (9-anthryloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (9-phenanthryloxycarbonyl)
-1-ethoxypyridinium triphenylbutyl borate, 2- (1-pyrenyloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2-
(5-naphthacenyloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-
(Indenyloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (2-azulenyloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (1-acenaphthyloxycarbonyl) -1-ethoxypyridinium Triphenylbutyl borate, 2- (9-fluorenyloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (o-tolyloxycarbonyl) -1
-Ethoxypyridinium triphenylbutyl borate,
2- (m-tolyloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (p-tolyloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (2,3-xylyloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (2,5-xylyloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2-mesityloxycarbonyl-1-ethoxypyridinium triphenylbutyl borate, 2-
(P-cumenyloxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (p-cyclohexylphenoxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (4-phenylphenoxycarbonyl) -1-ethoxy Pyridinium triphenylbutyl borate, 2- (o-fluorophenoxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (m-chlorophenoxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (p-bromo Phenoxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2- (p-hydroxyphenoxycarbonyl)
-1-ethoxypyridinium triphenylbutyl borate, 2- (m-carboxyphenoxycarbonyl) -1
-Ethoxypyridinium triphenylbutyl borate,
2- (o-mercaptophenoxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate, 2-
(P-cyanophenoxycarbonyl) -1-ethoxypyridinium triphenylbutyl borate and the like.

Examples of 3-substituted-1-ethoxypyridinium triphenylbutyl borate: 3-fluoro-1-ethoxypyridinium triphenylbutyl borate, 3-chloro-1-ethoxypyridinium triphenylbutyl borate, 3-bromo-1- Ethoxypyridinium triphenylbutyl borate, 3-hydroxy-1-ethoxypyridinium triphenylbutyl borate, 3-carboxy-1-ethoxypyridinium triphenylbutyl borate, 3-mercapto-1-ethoxypyridinium triphenylbutyl borate, 3-cyano- 1-ethoxypyridinium triphenylbutyl borate and the like.

Examples of 4-substituted-1-ethoxypyridinium triphenylbutyl borate: 4-fluoro-1-ethoxypyridinium triphenylbutyl borate, 4-chloro-1-ethoxypyridinium triphenylbutyl borate, 4-bromo-1- Ethoxypyridinium triphenylbutyl borate, 4-hydroxy-1-ethoxypyridinium triphenylbutyl borate, 4-carboxy-1-ethoxypyridinium triphenylbutyl borate, 4-mercapto-1-ethoxypyridinium triphenylbutyl borate, 4-cyano- 1-ethoxypyridinium triphenylbutyl borate and the like.

Example of polysubstituted-1-ethoxypyridinium triphenylbutyl borate: 2,3-difluoro-1-
Ethoxypyridinium triphenylbutyl borate,
2,4-dichloro-1-ethoxypyridinium triphenylbutyl borate, 2,5-dibromo-1-ethoxypyridinium triphenylbutyl borate, 2,6-dihydroxy-1-ethoxypyridinium triphenylbutyl borate, 3,4-di Carboxy-1-ethoxypyridinium triphenylbutyl borate, 3,5-dimercapto-1-ethoxypyridinium triphenylbutyl borate, 2,4,6-trimethyl-1-ethoxypyridinium triphenylbutyl borate, 2,3,5
6-tetramethyl-1-ethoxypyridinium triphenylbutyl borate, 2,3,4,5,6-pentamethyl-1-ethoxypyridinium triphenylbutyl borate and the like.

Examples of cyclic pyridinium triphenylbutyl borate: 2,3-tetramethylene-1-ethoxypyridinium triphenylbutyl borate, 1,2-ethylenedioxypyridinium triphenylbutyl borate,
2,6-diethylenedioxy-1-methoxypyridinium triphenylbutyl borate, 2,3-ethylenedithio-1-butoxypyridinium triphenylbutyl borate, 2,6-diethylenedithio-1-phenoxypyridinium triphenylbutyl borate and the like.

As a feature of the polymerization initiator (A) of the present invention,
Conventionally known BF_Four ^-, PF₆ ^-, AsF₆ ^-, S
bF₆ ^-, ClO_Four ^-, CF_ThreeSO_Three ^-, P-toluene
Onium compounds with anions such as sulfonates
Generates strong acids (Bronsted acids) that can be seen
That is not to be. Therefore, the acid
In areas where it is difficult to survive, such as coatings for resists and metals
It can be suitably used in the field of materials.

Further, as the characteristics of the polymerization initiator (A) of the present invention, conventionally known BF ₄ ⁻ , PF ₆ ⁻ , AsF
^{_{6 -, SbF 6 -, ClO}} 4 - , such than an onium compound having an anionic, compatibility with organic solvents and various radical polymerizable compound, the solubility is very high. This is one of the important properties when used as a polymerizable composition.

Many of the polymerization initiators (A) of the present invention usually do not absorb at wavelengths longer than the ultraviolet region, and thus have poor activity from near-ultraviolet to near-infrared light. By introducing into the substituent R in (1) a substituent having a condensed polycyclic aromatic ring such as a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a naphthacene ring, a perylene ring, and a pentacene ring, and other suitable chromophores It is also possible to have an absorption band up to the visible region to enhance the activity with respect to light having a wavelength longer than visible light.

Next, the radical polymerizable compound (B) will be described. The radically polymerizable compound (B) in the present specification means a compound having at least one or more radically polymerizable ethylenically unsaturated bonds in a molecule. Further, each of them has a chemical form of a monomer, oligomer or polymer which is liquid or solid at normal temperature and normal pressure.

Examples of such a radical polymerizable compound (B) include acrylic acid, methacrylic acid, itaconic acid,
Unsaturated carboxylic acids such as crotonic acid, isocrotonic acid, and maleic acid, and salts, esters, urethanes, acid amides and acid anhydrides thereof, and acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated poly Examples thereof include ethers, unsaturated polyamides, and unsaturated polyurethanes, but the present invention is not limited to these.

Hereinafter, specific examples of the radical polymerizable compound (B) in the present invention will be described. Examples of acrylates: Examples of monofunctional alkyl acrylates: methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate , Isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, benzyl acrylate.

Examples of monofunctional hydroxyacrylates:
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogen-containing acrylates:
2,2,2-trifluoroethyl acrylate, 2,
2,3,3-tetrafluoropropyl acrylate, 1
H-hexafluoroisopropyl acrylate, 1H,
1H, 5H-octafluoropentyl acrylate, 1
H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4,6-tribromophenol 3EO
Addition acrylate.

Examples of monofunctional acrylates containing ether groups:
2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 acrylate, methoxydipropylene glycol acrylate, methoxytripropylene glycol acrylate,
Methoxy polypropylene glycol acrylate, ethoxydiethylene glycol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyethylene glycol acrylate, p-nonylphenoxyethyl acrylate, p-nonyl Phenoxy polyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional carboxyl-containing acrylates: β-carboxyethyl acrylate, monoacryloyloxyethyl succinate, ω-carboxypolycaprolactone monoacrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate.

Examples of other monofunctional acrylates: N,
N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinoethyl acrylate, trimethylsiloxyethyl acrylate,
Diphenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, caprolactone-modified 2-acryloyloxyethyl acid phosphate.

Examples of bifunctional acrylates: 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate , Polyethylene glycol # 300 diacrylate, polyethylene glycol # 4
00 diacrylate, polyethylene glycol # 600
Diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, neopentyl glycol diacrylate, neopentyl glycol PO modified diacrylate, hydroxy Neopentyl glycol pivalate diacrylate, caprolactone adduct of hydroxypivalate neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3-acryloyloxypropyl)
Ether, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate,
Hydrogenated bisphenol A diacrylate, EO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol A Diacrylate, tricyclodecane dimethylol diacrylate, isocyanuric acid EO-modified diacrylate.

Examples of trifunctional acrylates: glycerin P
O-modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane PO-modified triacrylate, isocyanuric acid EO-modified triacrylate,
Isocyanuric acid EO-modified ε-caprolactone-modified triacrylate, 1,3,5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Examples of acrylates having four or more functional groups: pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylol methane tetraacrylate, oligoester tetraacrylate, tris (acryloyloxy) phosphate .

Examples of methacrylates: Examples of monofunctional alkyl methacrylates: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate , Stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate.

Examples of monofunctional hydroxy methacrylates include: 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3
-Allyloxypropyl methacrylate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate.

Examples of monofunctional halogen-containing methacrylates:
2,2,2-trifluoroethyl methacrylate, 2,
2,3,3-tetrafluoropropyl methacrylate,
1H-hexafluoroisopropyl methacrylate, 1
H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylphenyl methacrylate, 2,4,6-tribromophenoxyethyl methacrylate, 2 , 4,6-tribromophenol 3EO addition methacrylate.

Examples of monofunctional ether-containing methacrylates: 2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol # 400 methacrylate, methoxydipropylene glycol Methacrylate, methoxytripropylene glycol methacrylate, methoxy polypropylene glycol methacrylate, ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate Cresyl polyethylene glycol methacrylate, p- nonyl phenoxyethyl methacrylate, p- nonylphenoxy polyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl-containing methacrylates: β-carboxyethyl methacrylate, monomethacryloyloxyethyl succinate, ω-carboxypolycaprolactone monomethacrylate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxypropyl hydrogen phthalate,
2-methacryloyloxypropyl hexahydrohydrogen phthalate, 2-methacryloyloxypropyl tetrahydrohydrogen phthalate.

Examples of other monofunctional methacrylates:
N, N-dimethylaminoethyl methacrylate, N, N
-Dimethylaminopropyl methacrylate, morpholinoethyl methacrylate, trimethylsiloxyethyl methacrylate, diphenyl-2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl acid phosphate, caprolactone-modified 2-methacryloyloxyethyl acid phosphate.

Examples of bifunctional methacrylates: 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300 dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate Methacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neopentyl glycol dimethacrylate,
Neopentyl glycol PO-modified dimethacrylate, hydroxypivalate neopentyl glycol ester dimethacrylate, hydroxypivalate neopentyl glycol ester caprolactone adduct dimethacrylate, 1,6-hexanediol bis (2-hydroxy-3-methacryloyloxypropyl) Ether, 1,
9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, bisphenol A dimethacrylate, EO-modified bisphenol A dimethacrylate, PO-modified bisphenol A dimethacrylate,
Hydrogenated bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A dimethacrylate, bisphenol F dimethacrylate, EO modified bisphenol F dimethacrylate, PO modified bisphenol F dimethacrylate, EO modified tetrabromobisphenol A Dimethacrylate, tricyclodecane dimethylol dimethacrylate, isocyanuric acid EO-modified dimethacrylate.

Examples of trifunctional methacrylates: glycerin PO modified trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isocyanuric acid EO modified trimethacrylate, isocyanuric acid EO modified ε -Caprolactone-modified trimethacrylate, 1,3,5-trimethacryloylhexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates: pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate,
Dipentaerythritol hexamethacrylate, tetramethylolmethanetetramethacrylate, oligoestertetramethacrylate, tris (methacryloyloxy) phosphate.

Examples of allylates: allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate.

Examples of acid amides: acrylamide, N-methylol acrylamide, diacetone acrylamide,
N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylol methacrylamide, diacetone methacrylamide,
N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine.

Examples of styrenes: styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, p-
t-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene,
2,4-diphenyl-4-methyl-1-pentene.

Examples of other vinyl compounds: vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate,
Vinyl butyrate, vinyl laurate, divinyl adipate,
Vinyl methacrylate, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone and the like.

The above-mentioned radical polymerizable compound (B) can be easily obtained as a commercial product of the following manufacturer. Commercial products of such manufacturers include, for example, "Light Acrylate", "Light Ester", "Epoxy Ester", manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.
"Urethane acrylate" and "Highly functional oligomer" series, "NK Ester" and "NK Oligo" series manufactured by Shin-Nakamura Chemical Co., Ltd., "Fancryl" series manufactured by Hitachi Chemical Co., Ltd., Toagosei "Aronix M" series manufactured by Chemical Co., Ltd., "Functional monomer" series manufactured by Daihachi Chemical Industry Co., Ltd., "Special acrylic monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., Mitsubishi Rayon ( "Acryester" and "Diabeam Oligomer" series manufactured by Nippon Kayaku Co., Ltd. "Kayarad" and "Kayamer" series manufactured by Nippon Kayaku Co., Ltd. "Acrylic acid / methacrylic acid ester" manufactured by Nippon Shokubai Co., Ltd. Monomer series, Nippon Synthetic Chemical Industry Co., Ltd.
"NICHIGO-UV purple urethane acrylate oligomer" series manufactured by Shin-Etsu Vinyl Acetate Co., Ltd.
"Functional monomers" series manufactured by Kojin Co., Ltd. and the like.

The following cyclic compounds are also exemplified as the radical polymerizable compound (B). Examples of three-membered ring compounds: Journal of Polymer Science Polymer Chemistry Edition (J.
Polym. Sci. Polym. Chem. E
d. ), Vol. 17, p. 3169 (1979).
Rapid Communication (Makromol. C)
hem. Rapid Commun. ), Vol. 5, 63
1-phenyl-2-vinylcyclopropane, Journal of Polymer Science Polymer Chemistry Edition (J. Po.)
lym. Sci. Polym. Chem. Ed. 23, 1931 (1985) and Journal
Of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Le
tt. Ed. ), Volume 21, p. 4331 (1983)
Described 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 1564 (1985)
2,3-divinyloxiranes described in (Year).

Examples of cyclic ketene acetals: Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Poly)
m. Chem. Ed. ), Volume 20, p. 3021 (19
1982) and the Journal of Polymer Science Polymer Letter Edition (J. Poly)
m. Sci. Polym. Lett. Ed. ), 21st
Vol., P. 373 (1983).
3-dioxepane, polymer pre-preprint (Po
lym. Preprints), Vol. 34, p. 152 (1985), dioxolanes, Journal of Polymer Science, Polymer Letter Edition (J. Polym. Sci. Polym. Let).
t. Ed. 20, 361 (1982), Macromolecular Chemie (Makromol. Che).
m. 183, 1913 (1982) and Macromolecular Chemie (Makromol. Ch.).
em. 186, p. 1543 (1985), 2-methylene-4-phenyl-1,3-dioxepane, Macromolecules.
s), Vol. 15, p. 1711 (1982), 4,
7-dimethyl-2-methylene-1,3-dioxepane,
Polymer Prepreprint (Polym. Prepr)
5,6-benzo-2-methylene-1,3-diosepan described in Vol. 34, pp. 154 (1985).

Further, the radical polymerizable compound (B) is
Examples described in the following documents can also be given. Such documents include, for example, Shinzo Yamashita et al., “Handbook of Crosslinking Agents”, (1981, Taisei Corporation) and Kiyomi Kato, “Handbook of UV / EB Curing (Raw Materials)”, (1)
985, Polymer Publishing Association), edited by Radtech Research Group, “U
Application and Market of VEB Curing Technology ", p. 79, (1989
(CMC), edited by Kiyoshi Akamatsu, "New Technology for Photosensitive Resins", (1987, CMC), Tsuyoshi Endo,
"Refinement of Thermosetting Polymer" (1986, CMC), Eiichiro Takiyama, "Polyester Resin Handbook" (1988, Nikkan Kogyo Shimbun).

As the radical polymerizable compound (B), only one kind may be used, or two or more kinds may be used in an arbitrary ratio in order to improve desired properties. Further, the polymerization initiator (A) of the present invention is preferably used in a range of 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the radical polymerizable compound (B).
More preferably, it is used in the range of parts by weight.

Next, the polymerization initiator (A) in the present invention
By combining with a sensitizer (C) shown below, it becomes possible to further increase the activity with respect to energy rays or to lengthen the photosensitive wavelength region thereof. The sensitizer (C) as used herein is one that transfers energy or electrons to and from the polymerization initiator (A) by the action of an energy ray to promote the decomposition of the polymerization initiator (A). It is.

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

Among these sensitizers (C), particularly preferred are anthracene derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, styryl derivatives, cyanine derivatives, and acridine derivatives. , Porphyrin derivatives, pyrylium derivatives and thiopyrylium derivatives.

Further, the polymerizable composition of the present invention may be mixed with a binder such as an organic high molecular polymer and applied to a glass plate, an aluminum plate, another metal plate, or a polymer film such as polyethylene terephthalate. It is possible.

Examples of the binder that can be used by mixing with the polymerizable 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.

Further, the polymerizable composition of the present invention can be used in combination with other general-purpose polymerization initiators for the purpose of further improving the sensitivity.

Other general-purpose polymerization initiators which can be used in combination by mixing with the polymerizable composition of the present invention include JP-B-59-128.
No. 1, JP-B-61-9621 and JP-A-60-6
0104, triazine derivatives described in JP-A-59-15
No. 04 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6.
No. 413, JP-B-47-1604 and USP No. 3
No. 567453, diazonium compound, USP No. 2
No. 848328, US Pat. No. 2,852,379 and U
Organic azide compounds described in SP No. 290853, JP-B-36-22062, JP-B-37-13109, JP-B-38-18015 and JP-B-45-9610.
Ortho-quinonediazides described in JP-B-55-39
No. 162, JP-A-59-140203 and "Macromolecules", Vol. 10, No. 13
Various onium compounds including an iodonium compound described on page 07 (1977), JP-A-59-14220.
No. 5, azo compounds described in JP-A-1-54440, European Patent No. 109851, European Patent No. 126
No. 712, "Journal of Imaging Science (J. Imag. Sci.)", Vol. 30, p. 174 (198
6) described in JP-A-61-15119.
The titanocenes described in No. 7, “Coordination Chemistry Review”
84, pages 85-277 (1988) and a transition metal complex containing a transition metal such as ruthenium described in JP-A-2-182701, JP-A-3-2094.
No. 77, an aluminate complex described in JP-A-2-15776
No. 0, JP-A-55-127550
And 2,4 described in JP-A-60-202037.
5-triarylimidazole dimer, carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, and the like are used. 0.01 to 10
It is preferably contained in the range of parts by weight.

The polymerizable composition of the present invention can contain a thermal polymerization inhibitor for the purpose of preventing polymerization during storage. Specific examples of the thermal polymerization inhibitor that can be added to the polymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol,
Tert-butyl catechol, phenothiazine and the like can be mentioned. These thermal polymerization inhibitors are used in an amount of 0.001 to 5 based on 100 parts by weight of the radical polymerizable compound (B).
It is preferably added in the range of parts by weight.

The polymerizable composition of the present invention may further contain a polymerization accelerator represented by an amine, thiol, disulfide or the like, or a chain transfer catalyst, for the purpose of accelerating the polymerization.

Specific examples of polymerization accelerators and chain transfer catalysts that can be added to the polymerizable composition of the present invention include amines such as N-phenylglycine, triethanolamine, N, N-diethylaniline, USP Thiols described in JP-A-4414312 and JP-A-64-13144, disulfides described in JP-A-2-291561, U.S. Pat.
And thiones described in Japanese Patent Application Laid-Open No. Sho 64-17048, O-acylthiohydroxamate and N-alkoxypyridinethiones described in JP-A-2-291560.

The polymerizable composition of the present invention may further contain, depending on the purpose, dyes, organic and inorganic pigments, oxygen removing agents such as phosphines, phosphonates, phosphites and the like, reducing agents, antifoggants, antifading agents, antihalation agents. , Optical brightener,
Surfactants, coloring agents, plasticizers, flame retardants, antioxidants, ultraviolet absorbers, antifungal agents, antistatic agents, magnetic substances, fillers, and mixtures with solvents for the purpose of dilution may be used. .

It should be noted that ultraviolet rays, near ultraviolet rays,
Definitions of visible light, near infrared light, infrared light, etc. are based on "Iwanami Physical and Chemical Dictionary 4th Edition" (Iwanami, 1987) edited by Ryogo Kubo et al.
Therefore, the polymerizable composition of the present invention comprises a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon ion laser, a helium cadmium laser, and a helium laser. Neon laser, krypton ion laser, various semiconductor lasers, YAG laser,
Light energy from various light sources such as light emitting diodes, CRT light sources, plasma light sources, etc., electron beams and X-rays from an electron beam source using an electron beam irradiation device, etc. Alternatively, a cured product having good characteristics can be obtained.

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. .

The polymerization initiator (A) of the present invention is synthesized by reacting a corresponding pyridinium 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. Is possible. The pyridinium salts used as these raw materials are Chemiché Berichte (Chem.
Ber.), Vol. 99, p. 1969 (1966), Journal of Polymer Science Part A, Polymer Chemistry (J. Polym. Sci., A, Polym. Chem.), Vol. 30, 1987. Page (1992), German Patent (D
E) The method described in No. 4103906 (BASF) and the like, and the borate compound is described in Journal of Organic Chemistry (J. Org. Chem.), Vol.
The compound can be synthesized with reference to the method described on page 1971 (1964).

[0120]

The polymerization initiator (A) of the present invention acts very effectively as a polymerization initiator for the radically polymerizable compound (B),
Gives good sensitivity characteristics.

The reason for this is that the anion portion of the pyridinium complex of the present invention has an excellent electron donating property, and causes an efficient intramolecular electron transfer reaction from a borate anion to a pyridinium cation by light or thermal energy, and the As a result, radicals are easily generated.

When the sensitizer (C) is further added, energy or electron transfer occurs between the sensitizer (C) and the polymerization initiator (A) by irradiation with actinic rays, The polymerization initiator (A) decomposes more effectively to generate radicals. The radicals thus generated are considered to cause polymerization or crosslinking reaction of the radical polymerizable compound (B).

[0123]

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, synthetic examples of the polymerization initiator (A) of the present invention will be described. In addition, the measured value of FD-MS shows a reference peak. In addition, in the parentheses attached thereto, the atomic weight of each element is represented by C = 12, H = 1,
A fragment when O = 16, B = 11, and N = 14 is shown.

Synthesis Example 1 Synthesis of 1-ethoxy-2-methylpyridinium triphenylbutyl borate Journal of Polymer Science, Part A
Polymer Chemistry (J. Polym. Sci., A, Polym.Che
m.), Vol. 30, p. 1987 (1992), 1 part of 1-ethoxy-2-methylpyridinium hexafluorophosphate is dispersed in a mixed solvent consisting of 50 parts of distilled water and 50 parts of acetone. With agitation and stirring, Journal of Organic Chemistry (J. Org. Chem.), Vol. 29, p. 1971 (1964)
50 parts of an aqueous solution containing 1.00 part of lithium triphenylbutyl borate synthesized by the method described in 1) was added dropwise at 25 ° C. over 10 minutes. Thereafter, the solution was extracted with 50 parts of dichloromethane, and the extract was concentrated to obtain 0.972 parts of 1-ethoxy-2-methylpyridinium triphenylbutyl borate. FD-MS m / z 138 ((M- [B (C ₆ H ₅ )
₃ C ₄ H ₉ ]) ⁺ ) Elemental analysis C ₃₀ H ₃₆ ONB Theoretical C; 82.37%, H; 3.30%, N; 3.20% Measured C: 82.42%, H; .41%, N; 3.18%

In a similar manner, another polymerization initiator (A) described in the specification was synthesized.

Example 1 A polymerizable composition comprising 3 parts of 1-ethoxy-2-methylpyridinium triphenylbutyl borate as a polymerization initiator (A) and 100 parts of pentaerythritol triacrylate as a radical polymerizable compound (B) was prepared. , Using a bar coater to apply a thickness of about 10 μm on an aluminum plate,
UV irradiator (Metal halide lamp 3 manufactured by Toshiba Corporation)
When irradiated with a KW2 lamp at 120 W / cm ² and an irradiation distance of 180 mm) at a conveyor speed of 20 m / min, the polymerizable composition was cured, and a tack-free cured film was obtained.

Example 2 To the polymerizable composition in Example 1, 0.5 part of 4,4'-diethylaminobenzophenone was added as a sensitizer (C).
Further, the polymerizable composition obtained by the addition was applied on an aluminum plate to a thickness of about 10 μm using a bar coater, and an ultraviolet irradiation device (metal halide lamp 3KW, manufactured by Toshiba Corporation) was used.
2 lamps, 120 W / cm ² , irradiation distance 180 mm) 2
When irradiated at a conveyor speed of 5 m / min, the polymerizable composition was cured, and a tack-free cured film was obtained.

Examples 3 to 74 In place of 3 parts of 1-ethoxy-2-methylpyridinium triphenylbutyl borate in Example 1, 3 parts of the polymerization initiator (A) shown in Table 1 was used. Example 1
Experiments were carried out in exactly the same manner as in the above, and in each case, a tack-free cured film was obtained.

Table 1 Example Polymerization Initiator (A) ──────────────────────────────── 3 N-Methoxy-diphenyl triphenyl butyl phosphate Phthyl phosphate 5 N-fluorooxyphenyl cis triphenyl butyl phosphate 6 N-Phoxy dimethyl phenyl triphenyl butyl phosphate 7 N-octyl oxy dimethyl phenyl triphenyl butyl phosphate 8 N-octate oxy siloxy Trisium triphenylbutyl phosphate 9 N-Isopropyloxyphenyl triphenylbutyl phosphate 10 N- (t-ethoxy) trisulfonyl triphenyl Ruthyl phosphate 11 N-Cyclohexyloxyperidinium triphenylbutyl phosphate 12 N- (Fluoromethoxy) trithinium triphenylbutyl phosphate 13 N- (2-Chloroethoxy) trithinium triphenylbutyl phosphate 14 N -(2-Hydroxyisopropoxy) hydroxytriphenylbutyl phosphate 15 N-phenoxyhypercinium triphenylbutyl phosphate 16 N- (1-Naphthyloxy) hydroxytriphenylbutyl phosphate 17 N- (2-naphthyloxy) trisium triphenylbutyl phosphate 18 N- (9-anthryloxy) trisium triphenylbutyl phosphate 19 N- (p-tolyloxy) trisium triphenylbutyl phosphate 20 N -(p-Peromofenoki S) Hydroxytriphenylbutylphosphate 21 N- (p-cyanophenoxy) hyperniumtriphenylbutylphosphate 22 2-Fluoro-1-ethoxyhyperidiniumtriphenylbutylphosphate 23 2-Chloro- 1-Ethoxypolycintriyl triphenylbutyl phosphate 24 2-Fluoro-1-ethoxyphenylcinnyltriphenylbutyl phosphate 25 2-Human ethoxy-1-ethoxyphenyl ethysium triphenylbutyl phosphate 26 2-Carboxoxy-1 -Ethoxydiphenyltriphenylbutylphosphate 27 2-Cyano-1-ethoxydiphenyltriphenylbutylphosphate 28 2-Ethyl-1-ethoxypyridinium triphenylbutylphosphate 29 2-Octyl-1-ethoxypyridinium Triphenyl dimethyl pho Rate 30 2-Octatedecyl-1-ethoxyperidinium triphenylbutyl phosphate 31 2-Isopropyl-1-ethoxyperidinium triphenylbutyl phosphate 32 32-sec-butyl-1-ethoxyperidinium triphenylbutyl phosphate Perylate 33 2-Chloromethyl-1-ethoxyperidinium triphenylbutyl phosphate 34 2-Phenyl-1-ethoxyperidinium triphenylbutyl phosphate 35 2- (1-Phrophenyl) -1-ethoxypropyl Lithium triphenylbutyl phosphate 36 2- (Isopropylphenyl) -1-ethoxy perisium triphenylbutyl phosphate 37 2- (1-Cyclohexenyl) -1-ethoxy perthinium triphenylbutyl phosphate Rate 38 2- (trifluoroethenyl) -1-ethoxyperidinium Liphenylbutyl phosphate 39 2-Phenyl-1-ethoxyperidinium triphenylbutyl phosphate 40 2- (2-Naphthyl) -1-ethoxyperidinium triphenylbutyl phosphate 41 2- (2, (3-xylyl) -1-ethoxyperidinium triphenylbutyl phosphate 42 2-Methoxy-1-ethoxyperidinium triphenylbutyl phosphate 43 2-Isopropyloxy-1-ethoxyperidinium triphenylbutyl phosphate 44 2-human peroxymethoxy-1-ethoxyperidinium triphenylbutyl phosphate 45 2-phenoxy-1-ethoxyperidinium triphenylbutyl phosphate 46 2- (p-cyclohexylphenoxy) -1-ethoxy peroxyl Triphenylbutyl phosphate 47 2- (o-Fluorophenoxy) -1-ethoxy Peroxytriphenylbutyl phosphate 48 2-Acetyl-1-ethoxyperidinium triphenylbutyl phosphate 49 2-Isobutylyl-1-ethoxyperidinium triphenylbutyl phosphate 50 2-Cyclohexylcarboxyl- 1-Ethoxypolycidinium triphenylbutyl phosphate 51 2-Benzoyl-1-ethoxytricinium triphenylbutyl phosphate 52 2- (α-Chloroacetyl) -1-ethoxydicyclonium triphenylbutyl phosphate 53 2- Methoxycarbonyl-1-ethoxyperoxynium triphenylbutyl phosphate 54 2-Ethoxycarbonyl-1-ethoxytricinium triphenylbutyl phosphate 55 2- (t-Pethoxycarbonyl) -1-ethoxyhydroxytriphenylphenyl Fluorophosphate 56 2-Cyclohexyloxycarbonyl-1-ethoxyperoxynium triphenylbutyl carbonate 57 2-Fluoromethoxycarbonyl-1-ethoxyperoxynium triphenylbutyl carbonate 58 2-Phenoxycarboxyl-1-ethoxyhydrinium Triphenylbutyl phosphate 59 3-Fluoro-1-ethoxyperidinium triphenylbutyl phosphate 60 3-Carpoxy-1-ethoxyperidinium triphenylbutyl phosphate 61 3-Ethoxy-1-ethoxycarboxylhydroxy Triphenylbutyl phosphate 62 3-Cyano-1-ethoxyperidinium 63-Triphenylbutyl phosphate 63 4-Methyl-1-ethoxyperidinium triphenylbutyl phosphate 64 4-Carboxy-1-ethoxypropyl Cinium triphenylbutyl phosphate 65 4-Ethoxy-1-ethoxycarbonyldihydroxytriphenylbutylphosphate 66 4-Cyano-1-ethoxypolyciniumtriphenylbutylphosphate 67 2,3-Difluoro-1 -Ethoxy-dihydroxytriphenylbutyl phosphate 68 3,4-Dioxy-ethoxy-1-ethoxy-diphenyltriphenylbutyl phosphate 69 2,4,6-Trimethyl-1-ethoxy-dihydroxytriphenylbutyl phosphate 70 2, 3-tetramethylene-1-ethoxyperoxynium triphenylbutylphosphate 71 1,2-ethylenedioxyperoxynium triphenylbutylphosphate 72 2,6-diethylenedioxyoxy-1-methoxyperidiniumtriphenylbutylphosphate Rate 73 2,3-Ethylene O-1-Phoxytrisulfinium triphenylbutyl phosphate 74 2,6-diethylenedithio-1-phenoxyphosphorinium triphenylbutyl phosphate ─────────────────

Examples 75 to 87 Instead of 0.5 part of 4,4'-diethylaminobenzophenone in Example 2, sensitizers (C) shown in Table 2 were used.
Of the polymerizable composition obtained by adding 0.5 part of each of them, and the same operation as in Example 2 was performed. In each case, the tackiness was as high as in Example 2 at a conveyor speed of 25 m / min. A free cured film was obtained.

[0131]

Comparative Example 1 The procedure of Example 1 was repeated, except that N-phenacylpyridinium triphenylbutyl borate, which is a known polymerization initiator, was used in place of 1-ethoxy-2-methylpyridinium triphenylbutyl borate. After performing the same operation as in Example 1, the conveyor speed was 15 m / min.
A cured film was obtained, but a tack-free cured product was not obtained at 20 m / min.

Comparative Example 2 The procedure of Example 2 was repeated, except that N-phenacylpyridinium triphenylbutyl borate, which is a known polymerization initiator, was used in place of 1-ethoxy-2-methylpyridinium triphenylbutyl borate. When the same operation as in Example 1 was performed, the conveyor speed was 20 m / min.
A cured film was obtained, but a tack-free cured product was not obtained at 25 m / min.

Examples 88 to 103 Except that 100 parts of pentaerythritol triacrylate in Example 1 was replaced with the radical polymerizable compound (B) shown in Table 3, the same procedure as in Example 1 was carried out. Experiments were performed by operation, and in each case, a tack-free cured film was obtained.

[0135]

Example 104 A polymerizable composition comprising 3 parts of 1-ethoxy-2-methylpyridinium triphenylbutyl borate as the polymerization initiator (A) and 100 parts of pentaerythritol triacrylate as the radical polymerizable compound (B) was prepared. , Using a bar coater to apply a thickness of about 10 μm on an aluminum plate,
20m / m at an electron beam irradiation device (MIN-EB) manufactured by AIT, electron beam acceleration 60keV, irradiation distance 100mm
When irradiated at an in conveyor speed, the polymerizable composition was cured, and a tack-free cured film was obtained.

Example 105 A polymerizable composition comprising 50 parts by weight of pentaerythritol triacrylate as the radical polymerizable compound (B) and 1 part by weight of 1-ethoxy-2-methylpyridinium triphenylbutyl borate as the polymerization initiator (A) The product was applied on a glass plate to a thickness of about 5 μm, and a polyethylene film having a thickness of about 25 μm was further adhered on this to prepare a sample. The sample did not cure when the sample was kept in an oven at 40 ° C. for one week. From this, it became clear that the present polymerizable composition was excellent in storage stability.

The polymerization initiator (A) of the present invention is effective as a polymerization initiator for a radically polymerizable compound (B), and a polymerizable composition containing these is polymerized and cured by application of energy rays. It is possible. Therefore, the polymerizable composition of the present invention is a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an excimer lamp, an excimer laser, and a nitrogen laser argon. Light represented by various light sources such as ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, plasma light source, and EB
The target polymer or cured product can be obtained by the energy beam of the electron beam from the generator. Therefore, it is applied on a substrate together with a binder and the like, and is used as a core material for photosensitive plates and microcapsules such as plate materials, photoresists, electrophotographs, direct plate materials, and hologram materials, and is applied to various recording media and adhesives. It is possible.

Claims (4)

[Claims] (1) a cation moiety represented by the general formula (1):
The iridium cation and the anion moiety are represented by the general formula (2)
Pyridinium composed of a borate anion represented
A polymerization initiator (A) which is a mborate complex. General formula (1)(However, R¹Is an alkoxyl group, a substituted alcohol
Xyl group, aryloxy group, substituted aryloxy
R represents a group selected from the group consisting of
Element, chlorine, bromine, hydroxyl group, carboxyl group, mercapto
Group, a cyano group, and a group selected from the following organic residues:
And further adjacent, R or R ¹And R
A ring structure may be formed by a covalent bond with each other,
k represents an integer of 0 to 5. Here, the organic residue is
Element, chlorine, bromine, hydroxyl group, carboxyl group, mercapto
C which may be substituted with a group or a cyano group₁~ C₁₈Straight chain
, Branched, cyclic alkyl, C_Two~ C₁₈Linear,
Branched, cyclic alkenyl group, C₆~ C₁₈Monocyclic, fused
Polycyclic aryl group, C₇~ C₁₈Monocyclic and fused polycyclic aryl
Alkyl group, C₁~ C₁₈Linear, branched, and cyclic al
Coxyl group, C₆~ C₁₈Monocyclic and condensed polycyclic aryloxy
Si group, C₁~ C₁₈Linear, branched or cycloaliphatic if
Kuha C₇~ C₁₉A monocyclic, condensed polycyclic aromatic acyl group,_Two
~ C₁₉Linear, branched, and cyclic alkoxycarbonyl
Group, C₇~ C₁₉Monocyclic and condensed polycyclic aryloxycarbo
A nyl group. ) General formula (2) [BAr_ThreeR^Two]^- (R^TwoStands for fluorine, chlorine, bromine, hydroxyl, carboxyl
Which may be substituted with a group, a mercapto group or a cyano group
₁~ C₁₈Represents a linear, branched or cyclic alkyl group.
Ar is fluorine, chlorine, bromine, hydroxyl, carboxyl
Which may be substituted with a group, a mercapto group or a cyano group
₆~ C₁₈Represents a monocyclic or condensed polycyclic aryl group. ) 2. A polymerizable composition comprising the polymerization initiator (A) according to claim 1 and a radically polymerizable compound (B). 3. The method according to claim 2, further comprising a sensitizer (C).
The polymerizable composition according to the above. 4. A cured product of the polymerizable composition according to claim 2 or 3.