JPH10158039A - Optical fiber coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve energy beam sensitivity and to attain hardening in a short time by irradiation with energy beams by incorporating a polymn. initiator made of an onium borate complex consisting of an onium cation and a specified borate anion and an acid curable compd. SOLUTION: A polymn. initiator is made of an onium borate complex consisting of an onium cation such as iodonium, sulfonium, sulfoxonium, selenonium, phosphonium, ammonium or metallic arene and a borate anion represented by the formula [BYm Zn ] [where Y is F or Cl, Z is phenyl substd. by two or more electron withdrawing groups selected from among F, cyano, nitro and trifluoromethyl, (m) is 0-3, (n) is 1-4 and m+n=4] and 0.1-10wt.% of the polymn. initiator is mixed with an acid curable compd. convertible into a high molecular material by polymn. or crosslinking reaction under energy beams, e.g. an epoxy compd. or vinyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an optical fiber coating material and an optical fiber obtained by using the material. More specifically, the present invention relates to an optical fiber coating material for curing the optical fiber coating material in an extremely short time by irradiation with an energy ray to obtain a coating film having good physical properties, and an optical fiber obtained using the material.

[0002]

2. Description of the Related Art Conventionally, photocurable resin compositions have been used as coating materials for optical fibers. This photocurable resin composition is applied to bare optical fiber immediately after spinning, and by irradiating light such as ultraviolet light, the polymerization initiator is decomposed, the resin composition is polymerized and cured, and the coating film and Become. These are disclosed, for example, in JP-A-5-9242.

[0003]

A photocurable resin composition used as a conventional optical fiber coating material is:
Insufficient curability to light (ie, low sensitivity) requires the use of a light source that generates extremely high output energy, or the application and curing of the composition at low speeds, There was a problem of poor sex. However, using a light source that generates an extremely high output energy requires a large-scale light source and ancillary devices (cooling device and light protection device), which not only raises the introduction cost and running cost, but also increases the cost. In particular, when the light source is a large ultraviolet light source, there is a concern that the light source may affect the human body, and sufficient care in handling is required. Therefore, there has been a need to develop a photocurable resin composition having a high sensitivity so as to be sufficiently cured with light of lower energy.

[0004]

[Means for Solving the Problems]

[0005] In order to solve the above problems, the present inventor has proposed:
As a result of intensive research, we have developed an optical fiber coating material with high sensitivity that cures sufficiently with lower energy rays. That is, the present invention provides an energy ray-curable optical fiber coating material comprising an polymerization initiator, which is an onium borate complex comprising an onium cation and a borate anion of the general formula (1), and an acid-curable compound, and an optical fiber obtained using the same. It is. Formula _{(1) [BY m Z n} ] - ( however, Y is fluorine or chlorine, Z is fluorine, a cyano group, a nitro group, at least two or more electron-withdrawing group selected from trifluoromethyl group A substituted phenyl group, m represents an integer of 0 to 3, n represents an integer of 1 to 4,
+ N = 4. )

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the polymerization initiator of the present invention will be described. The onium cation constituting the polymerization initiator of the present invention includes iodonium, sulfonium, sulfoxonium, selenonium, phosphonium, ammonium, metal arene cations, pyridinium, quinolinium, isoquinolinium, benzoxazolium, benzothiazolium and the like. And the heterocyclic cation of

[0007] Of these, as a preferred structure of the onium cation as the polymerization initiator of the present invention, an onium cation selected from the general formulas (2) to (13) can be mentioned. General formula (2)

[0008]

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General formula (3)

[0010]

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General formula (4)

[0012]

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General formula (5)

[0014]

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General formula (6)

[0016]

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General formula (7)

[0018]

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General formula (8)

[0020]

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General formula (9)

[0022]

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Formula (10)

[0024]

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General formula (11)

[0026]

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General formula (12)

[0028]

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General formula (13)

[0030]

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

Among them, a more preferred structure of the onium cation is that the central element of the onium cation of the polymerization initiator includes a benzyl group, a substituted benzyl group, a phenacyl group, a substituted phenacyl group, an allyl group, and a substituted allyl group. Group, alkoxyl group, substituted alkoxyl group,
A group selected from an aryloxy group and a substituted aryloxy group has a direct chemical bond. Specifically, general formulas (2), (3), (5) and (5) An onium cation selected from the formula (7).

Further, other more preferred structures of the onium cation include the onium cations represented by the general formulas (9) to (13).

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

The substituent in the onium cation constituting the polymerization initiator of the present invention will be described below. First, the substituent R ¹ in the onium cation represented by the general formulas (2) to (8) constituting the polymerization initiator of the present invention.
At

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Further, the substituent R ² in the onium cation represented by the general formulas (2) to (4) and the substitution in the onium cation represented by the general formula (8) constituting the polymerization initiator of the present invention. A group R ³ , a substituent R ⁴ in the onium cation represented by the general formula (9), a general formula (5) to
In the substituent R in the onium cation represented by the general formula (8),

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

The substituent R ² in the onium cation represented by the general formulas (2) to (4) constituting the polymerization initiator of the present invention, and the substituents R ² represented by the general formulas (5) to (8). The substituent R in the onium cation represented by the general formula (1
0) to the substituent Ar in the onium cation represented by the general formula (13):

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

Further, in the substituent R ³ in the onium cation represented by the general formula (8) constituting the polymerization initiator of the present invention,

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

The substituent R in the onium cation represented by the general formula (9) constituting the polymerization initiator of the present invention is
^{4. In} the substituent R in the onium cation represented by the general formulas (5) to (8),

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

Further, in the substituent R in the onium cation represented by the general formulas (5) to (8) constituting the polymerization initiator of the present invention,

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

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

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

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

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

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

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

Hereinafter, specific examples of the structure of the onium cation represented by the general formulas (2) to (13) of the polymerization initiator of the present invention will be given.

An onium cation (sulfonium cation) corresponding to the general formula (2):

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

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

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

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

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

Onium cations corresponding to the general formula (3) (sulfoxonium cations):

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Onium cation (quinolinium cation) corresponding to general formula (6):

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

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

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

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

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

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

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

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

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

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

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

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

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

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

An onium cation (furyl or thienyl iodonium cation) corresponding to the general formula (9):

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

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

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

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

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

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

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

On the other hand, the substituent Z in the borate anion represented by the general formula (1) constituting the polymerization initiator of the present invention is
As a 3,5-difluorophenyl group, 2,4,6
-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-dinitro Phenyl group, 2,4,6-trifluoro-3,5-dinitrophenyl group, 2,4-dicyanophenyl group, 4-cyano-3,5-dinitrophenyl group, 4-cyano-2,6-bis ( Examples thereof include a trifluoromethyl) phenyl group, but the present invention is not limited thereto.

Accordingly, specific examples of the structure of the borate anion of the polymerization initiator of the present invention include pentafluorophenyltrifluoroborate, 3,5-bis (trifluoromethyl) phenyltrifluoroborate, and bis (pentafluorophenyl). ) Difluoroborate, bis [3,5-bis (trifluoromethyl) phenyl] difluoroborate, tris (pentafluorophenyl) fluoroborate, tris [3,5-bis (trifluoromethyl) phenyl] fluoroborate, tetrakis (penta Fluorophenyl) borate, tetrakis [3,5
-Bis (trifluoromethyl) phenyl] borate and the like. Of these, tetrakis (pentafluorophenyl) borate is particularly preferred as the structure of the borate anion of the polymerization initiator of the present invention.

Accordingly, specific examples of preferred onium borate complexes that constitute the polymerization initiator of the present invention include the following, but the present invention is not limited thereto.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0155]

Embedded image

[0156]

Embedded image

The polymerization initiator of the present invention is characterized in that it is easily decomposed by irradiation with energy rays, particularly light, to generate a strong acid. The acids generated here are BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻
Is considered to be a stronger acid than an onium salt having such an anion. In addition, it is characterized in that no acid remains by heating after being decomposed to generate an acid.

The onium borate complex, which is a polymerization initiator of the present invention, has a high electron accepting property and is easily susceptible to decomposition by irradiation with energy rays, so that it gives a high sensitivity when used as a polymerizable composition. The electron-accepting properties of these onium borate complexes can be explained by a reduction potential determined by an electrochemical measurement method such as polarography or cyclic voltammetry. Note that the reduction potential of the onium borate complex described in this specification is determined by the journal
Of Polymer Science Part A Polymer Chemistry (J. Polym. Sci., A, Poly)
m. Chem. 28, p. 3137 (1990).
), Journal of the American Chemical Society (J. Am. Chem. Soc.), No. 10
6, 4121 (1984).

Further, the polymerization initiator of the present invention can be prepared by using BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻
Than the onium salt having an anion as described above, the compatibility and solubility in various organic solvents, polymers and oligomers are extremely high.

[0160]

Further, the optical fiber coating material of the present invention comprises:
Unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthenes Derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, polymethine dyes such as cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives , Porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinopo Philazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxaliloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran derivative, spirooxazine derivative, thiospiropyran Derivatives, metal arene complexes,
By including a sensitizer such as an organic ruthenium complex, sensitivity to light in the visible region can be particularly improved.

Among these sensitizers, particularly preferred are anthracene derivatives, benzophenone derivatives,
Xanthene derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, pyrylium derivatives, thiopyrylium derivatives, styryl derivatives. Specific examples of these sensitizers include the following, but the present invention is not limited thereto.

(Specific Examples of Anthracene Derivatives) Anthracene, 1-anthracenecarboxylic acid, 2-anthracenecarboxylic acid, 9-anthracenecarboxylic acid, 9-anthralaldehyde, 9,10-bis (chloromethyl) anthracene, 9,10- Bis (phenylethynyl) anthracene, 9-bromoanthracene, 1-chloro-9,10
-Bis (phenylethynyl) anthracene, 9-chloromethylanthracene, 9-cyanoanthracene, 9.1
0-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-hydroxy Methylanthracene, 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, 9-vinylanthracene,
9-anthracenemethanol, trimethylsiloxy ether of 9-anthracenemethanol, and the like.

(Specific Examples of Benzophenone Derivatives) Benzophenone, 4,4′-dimethylbenzophenone,
4'-di-tert-butyl-benzophenone, 4,
4'-dimethoxybenzophenone, 4,4'-dibutoxybenzophenone, 4,4'-bis (methylthio) benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, -Butylbenzophenone, KAYACURE BMS manufactured by Nippon Kayaku Co., Ltd.

(Specific examples of xanthene derivatives and thioxanthone derivatives) Xanthene, 3,6-dimethoxyxanthone, 3,6-dimethoxyxanthan, rose bengal, eosin Y, rhodamine B, rhodamine 6G, erythrosine, fluorescein, uranine, 2,4 , 5,7
-Tetraiodo-3-hydroxy-6-fluorone, 3
-Butoxy-5,7-diiodo-6-fluorone, 9-
Cyano-3-butoxy-5,7-diiodo-6-fluorone, 2-octanoyl-4,5,7-triiodo-6
-Fluorone, 9-cyano-2-octanoyl-4,
5,7-triiodo-3-hydroxy-6-fluorone, 2-octyl-4,5,7-triiodo-3-hydroxy-6-fluorone, 9-cyano-2-octyl-
4,5,7-triiodo-3-hydroxy-6-fluorone, thioxanthone, KAYACURE BMS manufactured by Nippon Kayaku Co., Ltd., Kayacure CPT
X, Kaya Cure ITX, Kaya Cure DETX-S,
Kaya cure and the like.

(Specific Examples of Coumarin Derivatives and Ketocoumarin Derivatives) Coumarin, 7-methylcoumarin, 7-methoxycoumarin, 7-dimethylaminocoumarin, 7-diethylaminocoumarin, 5,7-dimethoxycoumarin,
6,7-dimethoxycoumarin, 7-diethylamino-4
-Methylcoumarin, 7-diethylamino-4-cyanocoumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-diethylamino-3-acetylcoumarin, 7-diethylamino-3-benzoylcoumarin, 7
-Diethylamino-3-ethoxycarbonylcoumarin,
7-diethylamino-3- (2-benzothiazolyl) coumarin, 7-diethylamino-3- (2-benzoxazolyl) coumarin, 7-diethylamino-3- (2-benzimidazolyl) coumarin, 7-diethylamino-3
-(2-benzothiazolyl) coumarin, 3,3'-carbonylbis (coumarin), 3,3'-carbonylbis (7-methylcoumarin), 3,3'-carbonylbis (7-butylcoumarin), 3,3 '-Carbonylbis (7-tert-butylcoumarin), 3,3'-carbonylbis (7-methoxycoumarin), 3,3'-carbonylbis (7-butoxycoumarin), 3,3'-carbonylbis (7 -Tert-butoxycoumarin), 3,
3′-carbonylbis (7-dimethylaminocoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3,3′-carbonylbis (7-dibutylaminocoumarin), 10,10′-carbonylbis [ 1,1,7,7-Tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one], furthermore Japan NKX-131 manufactured by Photosensitive Dye Laboratories, Inc.
7, NKX-1318, NKX-1767, NKX-1
768, NKX-1320, NKX-1769, NKX
-1770, NKX-1771 and the like.

(Specific examples of pyrylium derivatives) 2,4,6
-Triphenylpyrylium tetrafluoroborate,
2,4,6-tri (p-tris) pyrylium tetrafluoroborate, 2,4,6-tris (4-butylphenyl) pyrylium tetrafluoroborate, 2,4,6-
Tris (4-tert-butylphenyl) pyrylium tetrafluoroborate, 2,4,6-tris (4-methoxyphenyl) pyrylium tetrafluoroborate,
2,4,6-tris (4-butoxyphenyl) pyrylium tetrafluoroborate, 2,4,6-tris (4-
tert-butoxyphenyl) pyrylium tetrafluoroborate, 2,4,6-tris (4-dimethylaminophenyl) pyrylium tetrafluoroborate, 2,
4,6-tris (4-diethylaminophenyl) pyrylium tetrafluoroborate, 4- (4-butylphenyl) -2,6-diphenylpyrylium tetrafluoroborate, 4- (4-tert-butylphenyl-) 2
6-diphenylpyrylium tetrafluoroborate, 4
-(4-methoxyphenyl) -2,6-diphenylpyrylium tetrafluoroborate, 4- (4-butoxyphenyl) -2,6-diphenylpyrylium tetrafluoroborate, 4- (4-tert-butoxyphenyl)
-2,6-diphenylpyrylium tetrafluoroborate, 4- (4-dimethylaminophenyl) -2,6-diphenylpyrylium tetrafluoroborate, 4- (4
-Diethylaminophenyl) -2,6-diphenylpyrylium tetrafluoroborate, 4- (4-butoxyphenyl) -2,6-bis (methoxyphenyl) pyrylium tetrafluoroborate, 4- (4-diethylaminophenyl) -2 , 6-Bis (methoxyphenyl) pyrylium tetrafluoroborate, 2- (4-methoxyphenyl) -4,6-diphenylpyrylium tetrafluoroborate, 2- (4-diethylaminophenyl) -4,
6-diphenylpyrylium tetrafluoroborate,
2,4,6-triphenylpyrylium perchlorate,
2,4,6-triphenylpyrylium hexafluorophosphate, 2,4,6-triphenylpyryliumtetraphenylborate, 2,4,6-triphenylpyryliumtriphenylbutylborate and the like.

(Specific examples of thiopyrylium derivatives)
4,6-triphenylthiopyrylium tetrafluoroborate, 2,4,6-tri (p-tris) thiopyrylium tetrafluoroborate, 2,4,6-tris (4-
Butylphenyl) thiopyrylium tetrafluoroborate, 2,4,6-tris (4-tert-butylphenyl) thiopyrylium tetrafluoroborate, 2,4
6-tris (4-methoxyphenyl) thiopyrylium tetrafluoroborate, 2,4,6-tris (4-butoxyphenyl) thiopyrylium tetrafluoroborate, 2,4,6-tris (4-tert-butoxyphenyl) ) Thiopyrylium tetrafluoroborate, 2,
4,6-tris (4-dimethylaminophenyl) thiopyrylium tetrafluoroborate, 2,4,6-tris (4-diethylaminophenyl) thiopyrylium tetrafluoroborate, 4- (4-butylphenyl) -2,
6-diphenylthiopyrylium tetrafluoroborate, 4- (4-tert-butylphenyl-) 2,6-
Diphenylthiopyrylium tetrafluoroborate, 4
-(4-methoxyphenyl) -2,6-diphenylthiopyrylium tetrafluoroborate, 4- (4-butoxyphenyl) -2,6-diphenylthiopyrylium tetrafluoroborate, 4- (4-tert-butoxyphenyl) ) -2,6-Diphenylthiopyrylium tetrafluoroborate, 4- (4-dimethylaminophenyl)
-2,6-diphenylthiopyrylium tetrafluoroborate, 4- (4-diethylaminophenyl) -2,6
-Diphenylthiopyrylium tetrafluoroborate,
4- (4-butoxyphenyl) -2,6-bis (methoxyphenyl) thiopyrylium tetrafluoroborate,
4- (4-diethylaminophenyl) -2,6-bis (methoxyphenyl) thiopyrylium tetrafluoroborate, 2- (4-methoxyphenyl) -4,6-diphenylthiopyrylium tetrafluoroborate, 2-
(4-diethylaminophenyl) -4,6-diphenylthiopyrylium tetrafluoroborate, 2,4,6-
Triphenylthiopyrylium perchlorate, 2,4
6-triphenylthiopyrylium hexafluorophosphate, 2,4,6-triphenylthiopyrylium tetraphenylborate, 2,4,6-triphenylthiopyrylium triphenylbutyl borate and the like.

(Specific Examples of Styryl Derivatives) 2- [2-
(4-Dimethylamino) phenyl] ethynyl] benzoxazole, 2- [2- (4-dimethylamino) phenyl] ethynyl] benzothiazole, 2- [2- (4-dimethylamino) phenyl] ethynyl] -3,3 -Dimethyl-3H-indole, 2- [2- (4-dimethylamino) phenyl] ethynyl] quinoline, 4- [2- (4-
Dimethylamino) phenyl] ethynyl] quinoline, 2-
[2- (4-Dimethylamino) phenyl] ethynyl] naphtho [1,2-d] thiazole, and NK-528, NK-97, NK-
91, NK-342, NK-1055, NK-557,
NK-92, NK-96, NK-375, NK-37
6, NK-383, NK-526, NK-3578, N
K-3576, NK-3798, NKX-1595, N
K-1473 and the like.

Next, the acid-curable compound used in the optical fiber coating material of the present invention will be described. here,
The acid-curable compound means a compound which can be converted into a high molecular weight substance by polymerization or cross-linking reaction by the action of energy rays in the presence of a polymerization initiator in the present specification, for example, an epoxy compound, styrenes, Vinyl compounds, vinyl ethers, spiroorthoesters, bicycloorthoesters, spiroorthocarbonates,
Examples include cyclic ethers, lactones, oxazolines, aziridines, cyclosiloxanes, ketals, cyclic acid anhydrides, lactams and aryl dialdehydes.

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

Examples of the alicyclic epoxy compound include 4-vinylcyclohexene monoepoxide, norbornene monoepoxide, limonene monoepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis- (3,4 -Epoxycyclohexylmethyl) adipate, 2- (3,4-
Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, 2-
(3,4-epoxycyclohexyl-5,5-spiro-
3,4-epoxy) cyclohexane-meta-dioxane, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane, and the like.

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

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

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

The spiro orthoesters include 1,1
4,6-trioxaspiro (4,4) nonane, 2-methyl-1,4,6-trioxaspiro (4,4) nonane,
1,4,6-trioxaspiro (4,5) decane and the like, as bicycloorthoesters, 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, 3,9-dibenzyl-1,5,7,11-tetraoxaspiro (5,5) undecane Is raised.

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

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

Further, the radical polymerizable compound used in the optical fiber coating material of the present invention will be described. By incorporating these radically polymerizable compounds, it becomes possible to construct an optical fiber coating material with even higher sensitivity.

In the present invention, the radical polymerizable compound refers to a compound having at least one radically polymerizable ethylenically unsaturated bond in a molecule, and has a chemical form such as a monomer, oligomer, or polymer. For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, unsaturated carboxylic acids such as maleic acid and salts thereof, esters, urethanes, amides and anhydrides, acrylonitrile, styrene, and various other unsaturated polyesters, Radical polymerizable compounds such as unsaturated polyethers, unsaturated polyamides, and unsaturated polyurethanes are exemplified.

As the radical polymerizable compound in the present invention, specifically, 2-ethylhexyl acrylate,
-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, tetramethylol methane tetraacrylate, oligoester acrylate, N
-Acrylic acid derivatives such as methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl 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-methacryloxypolyethoxyphenyl)
Examples include methacrylic acid derivatives such as propane, and derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate. More specifically, “Handbook of Crosslinking Agents”, edited by Shinzo Yamashita et al., ( 1981, Taiseisha) and edited by Kato Kiyomi, "UV
EB Curing Handbook (Raw Materials Edition) ", (1985, Polymer Publishing Association), edited by Radotech Kenkyukai," Applications and Markets of UV / EB Curing Technology ", 79 pages, (1989, CMC), edited by Kiyoshi Akamatsu , "Practical technology of new photosensitive resin",
(1987, CMC), edited by Tsuyoshi Endo, "Refinement of thermosetting polymer", (1986, CMC), Eiichiro Takiyama, "Polyester Resin Handbook", (1)
988, Nikkan Kogyo Shimbun) or radically polymerizable or crosslinkable monomers, oligomers and polymers known in the art.

Urethane acrylates are particularly preferred as the radically polymerizable compound used in the present invention. Specific examples of the urethane acrylates include, for example, Aronix M-1100, M-1200, and M-121 manufactured by Toa Gosei Chemical Industry Co., Ltd.
0, M-1310, M-1600, Kyoeisha Yushi Kagaku Kogyo Co., Ltd. urethane acrylate AH-600,
AI-600, AT-600, UA-101H,
UA-101I, UA-101T, UA-306
H, UA-306I and UA-306T are preferably used.

The amount of the polymerization initiator used in the present invention is:
It is preferably in the range of 0.1% to 10% by weight of the optical fiber coating material, particularly preferably 1% to 5% by weight of the optical fiber coating material.

Incidentally, the energy ray referred to in this specification is
In addition to light such as ultraviolet light, near ultraviolet light, visible light, near infrared light, and infrared light, electron beams can be used. The definition of each of these energy rays is described in Ryogo Kubo et al., "Iwanami Physical and Chemical Dictionary 4th Edition"
(1987, Iwanami). 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 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 lasers, light emitting diodes, C
By irradiating light from various light sources such as an RT light source and a plasma light source and, if necessary, heating after irradiating light, the optical fiber coating material of the present invention can obtain a coating film having good characteristics.

[0185]

The polymerization initiator of the present invention is considered to generate an acid and a radical by decomposing extremely efficiently by causing energy transfer or electron transfer reaction in the molecule by irradiation with energy rays. In the case of an energy-sensitive acid generator composition containing a polymerization initiator and a sensitizer, energy or electron transfer from the sensitizer to the polymerization initiator occurs by irradiation with energy rays, It is considered that the polymerization initiator is decomposed to generate an acid and a radical. As described above, in the process in which the polymerization initiator is decomposed to generate an acid and a radical, when either the acid-curable compound or the radical-polymerizable compound coexists, the generated acid and the radical cause the acid-curable compound or the radical polymerization. It is considered that polymerization or curing of the acidic compound occurs.

Therefore, the optical fiber coating material containing the polymerization initiator of the present invention is cured in a short time by irradiation with energy rays, and gives a coating film having good characteristics.

[0187]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the examples, “parts” means “parts by weight” unless otherwise specified.

Example 1 As a polymerization initiator, 3 parts of diphenyl (9-anthrylmethyl) sulfoniumtetrakis (pentafluorophenyl) borate was used. As a radical polymerizable compound, ARONIX M- manufactured by Toa Gosei Chemical Industry Co., Ltd. was used. 1100
Was mixed with 20 parts of urethane acrylate UA-306H manufactured by Kyoeisha Yushi Kagaku Kogyo KK and 10 parts of tetrahydrofurfuryl acrylate to obtain an optical fiber coating material of the present invention. Subsequently, a core material (quartz rod, diameter 1 mmφ) was impregnated into the optical fiber coating material, and a 500 W high-pressure mercury lamp was irradiated at a speed of 50 cm / sec while pulling up the core material from the end of the core material. The optical fiber coating thus obtained was completely cured without distortion.

Example 2 As a polymerization initiator, diphenyliodonium sulfonium tetrakis (pentafluorophenyl) borate was used in an amount of 3
Part, 0.5 part of 3,3′-carbonylbis (7-diethylaminocoumarin) as a sensitizer, 70 parts of dipentaerythritol hexaacrylate as a radical polymerizable compound, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd. 20 parts of urethane acrylate UA-306H and 10 parts of isobornyl acrylate were mixed to obtain an optical fiber coating material of the present invention. Next, a core material (quartz rod, diameter 1 mmφ) is impregnated into this optical fiber coating material,
A 500 W xenon lamp was irradiated at a speed of 50 cm per second while pulling up the core from the end of the core. The optical fiber coating thus obtained was completely cured without distortion.

Example 3 As a polymerization initiator, 3 parts of diphenyl (9-anthrylmethyl) sulfoniumtetrakis (pentafluorophenyl) borate was used, and as an acid-curable compound, ERL-
1002 parts of 4221 (manufactured by Union Carbide Co., Ltd.) were mixed to obtain an optical fiber coating material of the present invention. Then
In this optical fiber coating material, a core material (quartz rod,
A diameter of 1 mmφ) was impregnated and irradiated with a 500 W metal halide lamp at a speed of 50 cm / sec while pulling up the core from the end of the core. The optical fiber coating thus obtained was completely cured without distortion.

Example 4 As a polymerization initiator, 3 parts of dimethylphenacylsulfonium tetrakis (pentafluorophenyl) borate was used.
0.5 parts of 9,10-bis (phenylethynyl) anthracene as a sensitizer and ERL as an acid-curable compound
1004 parts of -4221 (manufactured by Union Carbide Co., Ltd.) were mixed to obtain an optical fiber coating material of the present invention. Next, a core material (quartz rod, diameter of 1 mmφ) was impregnated into the optical fiber coating material, and a 500 W metal halide lamp was irradiated at a rate of 30 cm / sec while lifting the core material from the end of the core material. The optical fiber coating thus obtained was completely cured without distortion.

Example 5 3 parts of diphenyl (9-anthrylmethyl) sulfoniumtetrakis (pentafluorophenyl) borate as a polymerization initiator, 10 parts of pentaerythritol triacrylate as a radical polymerizable compound, Kyoeisha Yushi Kagaku Kogyo Co., Ltd. Urethane acrylate UA-3
06H and 30 parts of tetrahydrofurfuryl acrylate, as an acid-curable compound, ERL-4221
40 parts (manufactured by Union Carbide Co., Ltd.) were mixed to obtain an optical fiber coating material of the present invention. Next, a core material (quartz rod, 1 mm in diameter) was placed in this optical fiber coating material.
φ) was impregnated and irradiated with a 500 W Deep UV lamp at a speed of 50 cm / sec while pulling up the core from the end of the core. The optical fiber coating thus obtained was completely cured without distortion.

Example 6 Dimethylphenacylsulfonium tetrakis (pentafluorophenyl) borate (3 parts) was used as a polymerization initiator, and 1-methoxy-9,10-bis (phenylethynyl) anthracene was used as a sensitizer (0.3 parts and 3 parts). 0.2 parts of 3,3'-carbonylbis (7-diethylaminocoumarin),
As a radical polymerizable compound, 30 parts of tetramethylolpropane triacrylate, Kyoeisha Yushi Kagaku Kogyo Co., Ltd.
20 parts of urethane acrylate UA-306H and 10 parts of tetrahydrofurfuryl acrylate, 100 parts of ERL-4221 (manufactured by Union Carbide) as an acid-curable compound, and 0.05 parts of p-methoxyphenol as a thermal polymerization inhibitor. The parts were mixed to obtain an optical fiber coating material of the present invention. Next, a core material (a quartz rod, a diameter of 1 mmφ) was impregnated into the optical fiber coating material, and a 500 W metal halide lamp was irradiated while pulling up the core material from an end of the core material at a speed of 100 cm per second. The optical fiber coating thus obtained was completely cured without distortion.

[0194]

【The invention's effect】

Since the optical fiber coating material of the present invention has a very high curing speed, the melt spinning speed of the optical fiber can be increased, and the productivity of the optical fiber can be improved.

Claims (3)

[Claims] 1. An energy ray-curable optical fiber coating material comprising a polymerization initiator which is an onium borate complex comprising an onium cation and a borate anion of the general formula (1), and an acid-curable compound. Formula _{(1) [BY m Z n} ] - ( however, Y is fluorine or chlorine, Z is fluorine, a cyano group, a nitro group, at least two or more electron-withdrawing group selected from trifluoromethyl group A substituted phenyl group, m represents an integer of 0 to 3, n represents an integer of 1 to 4,
+ N = 4. ) 2. The optical fiber coating material according to claim 1, wherein the acid-curable compound is an epoxy compound or a vinyl ether. 3. An optical fiber obtained by using the optical fiber coating material according to claim 1.