JPH10168341A - Resin composition for coating metal can - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for coating metal cans, comprising a specific polymerization initiator and an acid-curable compound, excellent in a curing rate, and capable of giving cured coating films and good in physical properties such as hardness, adhesion to substrates, retort resistance and mechanical processability. SOLUTION: This resin composition for coating metal cans comprises a polymerization initiator and an onium borate complex comprising an onium cation such as iodonium and a borate anion of the formula [Y is fluorine, chlorine; Z is phenyl substituted by two or more electron-attracting groups selected from fluoro, cyano, nitro, and trifluoromethyl; (m) is 0-3; (n) is 1-4; (m)+(n)=4], such as tetrakis(pentafluorophenyl) borate, and an acid-curable compound such as an epoxy compound or a vinyl ether compound. The composition preferably further contains a free radical-polymerizable compound such as a (meth)acrylic acid derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for coating a metal can. More specifically, the resin composition for coating a metal can is used to cure the resin composition for coating a metal can in a short time by irradiating an energy ray such as light or an electron beam to obtain a metal can having good properties. About.

[0002]

2. Description of the Related Art In recent years, radiation curable resin compositions have been studied in the can making industry for the purpose of environmental preservation, improvement of working environment, and improvement of productivity and quality. However, resin compositions (paints) which have been studied so far for coating metal cans are insufficient in terms of curing speed. Therefore, to improve these curing speeds,
Attempts to modify the resin itself and the mixing ratio of the resin in these resin compositions (paints) have been made, for example, in JP-A-2-28.
As can be seen in Japanese Patent Application Publication No. 9661 and the like, even with such a method, a sufficient curing speed has not yet been achieved.

[0003]

SUMMARY OF THE INVENTION Resin compositions (paints) that have been studied for the purpose of coating metal cans are described below.
Since the curing speed for light is insufficient, it is necessary to use a light source that generates extremely high output energy or to develop a highly sensitive resin composition for metal can coating that cures sufficiently with lower energy light. was there.

However, if a light source that generates an extremely high output energy is used, a large-scale light source and ancillary devices (cooling device and light protection device) are required, so that the introduction cost and the running cost are only increased. 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 must be taken in handling.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies and as a result, have developed a resin composition for coating metal cans having a high sensitivity which can be sufficiently cured with lower energy light. It has been developed. That is, a first invention according to the present invention comprises a polymerization initiator and an acid-curable compound, which is an onium borate complex comprising an onium cation and a borate anion of the general formula (1), and is used for coating a metal can. A second invention according to the present invention, which is a resin composition, includes a polymerization initiator, an acid-curable compound, and a radical-polymerizable compound, which is an onium borate complex including an onium cation and a borate anion of the general formula (1). A resin composition for coating a metal can, characterized in that:
The third invention in the present invention is a metal can produced using the resin composition for coating a metal can.

Formula (1) [BY _m Z _n ] ^- (where Y is fluorine or chlorine, and Z is at least two or more electron-withdrawing atoms selected from fluorine, cyano group, nitro group and trifluoromethyl group) A phenyl group substituted with a functional group, m represents an integer of 0 to 3, n represents an integer of 1 to 4,
+ N = 4. )

[0007]

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

[0008] 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)

[0009]

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General formula (3)

[0011]

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General formula (4)

[0013]

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General formula (5)

[0015]

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General formula (6)

[0017]

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General formula (7)

[0019]

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General formula (8)

[0021]

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Formula (9)

[0023]

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General formula (10)

[0025]

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General formula (11)

[0027]

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General formula (12)

[0029]

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General formula (13)

[0031]

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

Of these, 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).

As other more preferred structures of onium cations, there can be mentioned the onium cations of 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
C ₁₈ linear, branched or cyclic alkyl group, C ₁ -C ₁₈
Linear, branched or cyclic alkoxyl group of C ₂ -C ₁₈
And a benzyl group substituted with a group selected from the group consisting of linear, branched and cyclic alkoxycarbonyl groups. Further, the benzene ring in the benzyl group may be a C ₁₀ -C ₂₂ Examples of the structure include a structure that may form a condensed polycyclic aromatic ring.

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

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

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

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

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

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

The substituted alkoxyl group in the substituent R ¹ is a C ₁ -C ₁₈ substituted with a group selected from fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl and hydroxyl. 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 the group consisting of fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro and azide. _{6- C18} monocyclic, condensed polycyclic aryloxy group, o-fluorophenoxy group, m-chlorophenoxy group, p-bromophenoxy group, p-hydroxyphenoxy group, m-carboxyphenoxy group, o-mercapto Phenoxy group, p-cyanophenoxy group, m-nitrophenoxy group, m-azidophenoxy group, 2-chloro-1-naphthyloxy group, 10-
Cyano-9-anthryloxy group, 11-nitro-5-
And a naphthacenyloxy group.

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

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

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

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

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

Further, the substituent R ² in the onium cation represented by the general formulas (2) to (4) 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 by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide;
As the cyclic alkyl group, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl Group, cyclopentyl, cyclohexyl, 4-decylcyclohexyl, fluoromethyl, chloromethyl, bromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, hydroxymethyl, carboxymethyl, mercaptomethyl , A cyanomethyl group, a nitromethyl group, an azidomethyl group and the like.

The substituent R ² in the onium cation represented by the general formulas (2) to (4) constituting the 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 with fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide, phenyl Group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group,
1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphthyl group, 9-fluorenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl Group, 2,5-xylyl group, mesityl group, p-cumenyl group, p-dodecylphenyl group, p-
Cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group and the like.

Further, in the substituent R ³ in the onium cation represented by the general formula (8) constituting the 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 with fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide include: Benzyl group, p-tolylmethyl group, 2-naphthylmethyl group, 9-anthrylmethyl group, 4- (9-anthryl) butyl group, o-fluorobenzyl group, m-chlorobenzyl group, p-bromobenzyl group, p -Hydroxybenzyl group, m-carboxybenzyl group, o-mercaptobenzyl group, p-cyanobenzyl group, m-nitrobenzyl group, m-azidobenzyl group and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

An onium cation (pyridinium cation) corresponding to the general formula (5):

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

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

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

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

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

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

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

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

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

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

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

An 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):

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

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

Diphenyliodonium, bis (p-tolyl) iodonium, bis (p-isopropylphenyl)
Iodonium, bis (pt-butylphenyl) iodonium, bis (p-octylphenyl) iodonium,
Bis (p-octadecylphenyl) iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, p
-Tolyl (p-isopropylphenyl) iodonium,
Phenyl (p-octadecyloxyphenyl) iodonium and the like.

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

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, triethylbenzylphosphonium tetrakis (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: triphenylallylphosphonium tetrakis (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-phenoxypyridiniumtetrakis (pentafluorophenyl) borate, N- (9-anthryloxy) pyridinium tetrakis (pentafluorophenyl) borate,
N- (p-tolyloxy) pyridinium tetrakis (pentafluorophenyl) borate and the like.

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

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

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

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 (pentafluorophenyl) Phenyl) borate, N- (p-acetylphenacyl) isoquinolinium tetrakis (pentafluorophenyl) borate, N
-(P-methoxycarbonylphenacyl) isoquinolinium tetrakis (pentafluorophenyl) borate,
N- (9-anthroylmethyl) isoquinolinium tetrakis (pentafluorophenyl) borate and the like.

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

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

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

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

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

[0156]

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[0157]

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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, since it is characterized by the fact that the acid does not remain by heating after being decomposed and generating an acid, it can be suitably used for the purpose of coating a metal, which is concerned about corrosion by the acid. .

The onium borate complex, which is the 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).

Furthermore, 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.

The resin composition for coating metal cans of the present invention includes 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, thioxanthene derivatives,
Polymethine dyes such as xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives,
Acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives,
Azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalilloporphyrazine derivative, naphthalocyanine Derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes,
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.

Further, the resin composition for coating a metal can of the present invention may be used in combination with the following radical generator for the purpose of further improving the sensitivity. Preferred radical generators include methyl o-benzoylbenzoate,
Benzoyl-4′-methyldiphenyl sulfide, benzoylethyl ether, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,2-diethoxyacetophenone, p-dimethylbenzoic acid Isoamyl, dimethylethanolamine and the like. Further, as a particularly preferably used radical generator, there is Irgacure 184 manufactured by Ciba-Geigy. These radical generators have the effect of increasing the decomposition efficiency of the polymerization initiator used in the present invention and efficiently generating acids and radicals from the polymerization initiator.

Next, the acid-curable compound used in the resin composition for coating a metal can 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 crosslinking reaction by the action of light in the presence of a polymerization initiator in the present specification, for example, an epoxy compound, styrene , Vinyl compounds, vinyl ether compounds, spiroorthoesters, bicycloorthoesters, spiroorthocarbonates, cyclic ethers, lactones, oxazolines, aziridines, cyclosiloxanes, ketals, cyclic acid anhydrides, Lactams and aryl dialdehydes are exemplified.

Of these, particularly preferred acid curable compounds include epoxy compounds and vinyl ether compounds. Epoxy compounds increase the toughness of metal cans and contribute to improvements in properties such as abrasion resistance, flex resistance, and heat resistance.On the other hand, vinyl ether compounds increase the sensitivity of the composition, that is, rapid curing during curing. It contributes to the improvement of performance. These may be used alone, or may be used by mixing at an arbitrary ratio.

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, limonene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate,
Bis- (3,4-epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,
5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane -Meta-dioxane, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane 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.

Examples of the vinyl ether compound include, for example, n
-(Or iso-, t-) butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 1,4 butanediol divinyl ether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, Propylene glycol divinyl ether, propylene glycol monovinyl ether, neopentyl glycol divinyl glycol, neopentyl glycol monovinyl glycol, glycerol divinyl ether, glycerol trivinyl ether, trimethylol propane monovinyl ether, trimethylol propane divinyl ether, trimethylol propane trivinyl ether, diglycerol Trivinyl 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 ether compounds such as trifluoropropane divinyl ether, alkenyl vinyl ether compounds such as allyl vinyl ether, alkynyl vinyl ether compounds such as ethynyl vinyl ether, 1-methyl-2-propenyl vinyl ether, 4-vinyl ether styrene, hydroquinone divinyl ether, phenyl Aryl vinyl ether compounds 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 ,
Aralkyl divinyl ethers such as Nm-chlorophenyldiethanolamine divinyl ether, m-phenylenebis (ethylene glycol) divinyl ether, and urethane polyvinyl ether (for example, ALLIED-S
IGNAL, VECtomer 2010).

Examples of the spiro ortho esters 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 resin composition for coating a metal can of the present invention will be described. By including the radical polymerizable compound shown below in the resin composition for coating a metal can of the present invention, it is possible to construct a resin composition for coating a metal can with 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, an oligomer, or a 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.

Accordingly, as the radical polymerizable compound referred to in the present invention, specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate , Bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate,
Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate,
Acrylic acid derivatives such as trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, N-methylolacrylamide, diacetoneacrylamide, 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,
Methacrylic acid derivatives such as triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and others 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, Taisei Corporation) and Kato Kiyomi,
"UV / EB Curing Handbook (Raw Materials)", (198
5th year, Polymer Publishing Association), edited by Radtech Research Group, “UV ・
Application and Market of EB Curing Technology ", p. 79, (1989,
(CMC), edited by Kiyoshi Akamatsu, "Practical technology of new photosensitive resin", (1987, CMC), edited by Tsuyoshi Endo, "Precision of thermosetting polymer", (1986, CMC), Commercial products described in Eiichiro Takiyama, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun), or radical polymerizable or crosslinkable monomers, oligomers and polymers known in the industry.

Further, the resin composition for coating a metal can of the present invention may contain a wax, a silicone resin, an alcohol compound, and a solvent, if necessary.

The amount of the polymerization initiator used in the present invention is:
It is preferably in the range of 0.1% by weight to 10% by weight of the resin composition for coating a metal can, and particularly preferably 1% to 5% by weight of the resin composition for coating a metal can.

Light sources for curing the resin composition for coating metal cans of the present invention include a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a Deep UV lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a gallium lamp, and a fluorescent lamp. Lamps and tungsten lamps. In addition to the light source, an electron beam source is also suitable as an energy source for curing.

The resin composition for coating a metal can of the present invention is not particularly limited, but can be suitably used for coating the inner and outer surfaces of a beverage can. The resin composition for coating a metal can is applied to a substrate by a suitable coating device. The type of the base material is not particularly limited, and examples thereof include a metal and a resin film.
In the case of a beverage can, iron and aluminum are used as the metal, and polyester (PET) is used as the resin film.

[0188]

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 resin composition for coating a metal can containing the polymerization initiator of the present invention is cured in a short time by irradiation with energy rays, and as a result, a high curing speed (sensitivity) is obtained and good film properties are obtained. Is provided.

[0190]

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 following, unless otherwise specified, "parts" means "parts by weight" in the examples.

Example 1 The following formulation was blended to obtain a metal can coating resin composition of the present invention. Component name Amount (parts) Polymerization initiator Dimethylphenacylsulfonium 3 Tetrakis (pentafluorophenyl) borate Acid curable compound 3,4-epoxycyclohexylmethyl-3,4-37 epoxycyclohexanecarboxylate Propylene glycol diglycidyl ether 20 1 , 6-hexanediol diglycidyl ether 20 limonenedioxide 10 cyclohexene oxide 10

(Examples 2 to 17) Instead of dimethylphenacylsulfonium tetrakis (pentafluorophenyl) borate in Example 1, the polymerization initiators shown in Table 1 were added. A composition was obtained.

Table 1 Example Polymerization Initiator (A) ────────────────────────────────2 Dimethyl (p-cyanobenzene) sulfonium tetrakis (pentafluorophenyl) ) Borate 3 Methylphenyl (phenacyl) sulfonium tetrakis (pentafluorophenyl) borate 4 perphenyl (phenacyl) sulfonium tetrakis (pentafluorophenyl) borate 5 perphenylphenyliodinium tetrakis (pentafluorophenyl) borate 6 carbon p-tolyl (p-isopropylphenyl) iodiumtetrakis (pentafluorophenyl) borate 7 bis (pt-butylphenyl) iodiumtetrakis (Pentafluorophenyl) borate 8 bis (p-octatecylphenyl) iodiumtetrakis (pentafluorophenyl) borate 9 bis (p-octatedecyloxyphenyl) iodiumtetrakis (pentafluorophenyl) borate 10 phenyl (p- Octadecyloxyphenyl) iodium tetrakis (pentafluorophenyl) borate 11 Triphenylsulfonium tetrakis (pentafluorophenyl) borate 12 Tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate 13 Triphenylsulfo Xonium tetrakis (pentafluorophenyl) borate 14 (η ⁵ -2,4-cyclopentanenyl-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl ) Hentsen] Iron Tetrakis (Hentaffluo) L-phenyl) borate 15 diphenyliodinotetrakis [3,5-bis (trifluoromethyl) phenyl] borate 16 triphenylsulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 17 tris (p-cyanophenyl) sulfonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate ────────

(Examples 18 to 25) The sensitizers shown in Table 2 were further added to the resin composition for coating a metal can of Example 1 to obtain a resin composition for coating a metal can. .

Table 2 Example sensitizers ───────── 18,4,4'-Methoxyphensophenone 19 4,4'-Methylthiobenzenesophenone 20 2-Chlorothioxanthone 21 2,4-Diethylthioxanthone 22 Anthracene 23 9,10-Dimethylanthracene 24 1,8-Dimethoxy-9,10-bis (phenylethynyl) anthracene 25 Acceleration Orange

(Examples 26 to 31) In place of 1,6-hexanediol diglycidyl ether in Example 1, an acid-curable compound shown in Table 3 was added. I got something.

Table 3 Example Acid-Curable Compounds ────────────── 26 1,4-Phenyldiol cyclisyl ether 27 Isobutyl phenyl ether 28 Ethylene glycol phenyl ether 29 1,4,6-Trioxasulfite B (4,4) nonane 30 2-methyl-1,4,6-trioxasperro (4,4) nonane 31 phenyloxetane ──────────────────── ───────

(Examples 32 to 40) In place of 1,6-hexanediol diglycidyl ether in Example 1, radical polymerizable compounds shown in Table 4 were added. I got something.

Table 4 Example: Radical polymerizable compound ────────── 32 Trimethylol cellulose triacrylate 33 1,6-Hexanediol acrylate 34 Ethylene glycol acrylate 35 38 Polyethylene glycol methacrylate 39 Trimethylol phenol trimethacrylate 40 Serial phthalate

Comparative Examples 1 to 6 Known photoacid generators shown in Table 5 were added in place of dimethylphenacylsulfonium tetrakis (pentafluorophenyl) borate in Example 1, and each was photocured. A resin composition was obtained.

Table 5 Comparative Example Photoacid Generator ──────────── ────────────── 1 dimethyl (phenacyl) sulfonium hexafluorophosphate 2 diphenyl (phenacyl) sulfonium hexafluorophosphate 3 diphenyl iodinium hexafluorophosphate 4 triphenylsulfonium Hexafluorophosphate 5 (η ⁵ -2,4-cyclopentenyl-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] iron hexafluoro Phosphate 6 methyl (phenacyl) sulfonium hexafluoroantimonate

Table 6 shows the results of the following three kinds of test evaluations of the resin composition for coating metal cans obtained as described above. As a comparative example, Table 7 shows the results of the same evaluation of the photocurable resin composition.

(1) Low irradiation dose test The resin composition was treated with a polyester coater using a bar coater # 4.
Paint on the film laminate, and immediately after the conveyor
120 W / cm at a speed of 120 m / min ^TwoIrradiation
Conveyor type UV with energy ultra-high pressure mercury lamp
Irradiates light using an irradiation device, eliminating tack (stickiness)
Measure the time until it becomes
A brush hardness test and an adhesion test were performed by the following methods. Pencil hardness test: According to JIS K 5400, paragraph 6.14
I went there. Harder pencils show better results
You. Adhesion test: Cross cut with a cutter knife (x mark)
Cut) and peel off with cellophane tape
The peeled area was visually measured. The peeled area is
Smaller ones show better results.

(2) High Irradiation Amount Test The resin composition was coated on a polyester film laminated plate using a bar coater # 4, and immediately thereafter, at an irradiation speed of 240 W / cm ² at a conveyor speed of 40 m / min. Light irradiation was performed using a conveyor-type ultraviolet irradiation device equipped with a metal halide lamp. One minute after irradiation, a pencil hardness test, an adhesion test, and a scratch resistance test were performed. The pencil hardness test and the adhesion test were performed in the same manner as the low irradiation dose test.
In addition, in the scratch test, the test piece was rubbed with a nail to observe whether or not it was scratched (：: no scratch, x: scratch).

(3) Heat treatment test A test piece obtained by irradiating light under the same conditions as in the low irradiation dose test was heat-treated at 200 ° C./100 seconds in a hot air oven.
After the test piece was cooled to room temperature, a pencil hardness test, an adhesion test, a retort resistance test, and a workability test were performed. The pencil hardness test and the adhesion test were performed in the same manner as the low irradiation dose test. Further, the retort resistance test and the workability test were performed by the following methods. Retort resistance test: The test piece was tested using a steam sterilizer.
After retorting at 130 ° C. for 30 minutes, the presence or absence of whitening was visually observed, and the test piece was further subjected to an adhesion test.

Workability test: A test piece was molded to a height of 14 cm by Erichsen extrusion and then retorted in the same manner as described above. Thereafter, the edge portion of the test piece was peeled off with a cellophane tape, and the degree of the peeling was visually observed. The evaluation criteria were evaluated according to the following five levels (larger numbers indicate better results). 5: No peeling is observed at all. 4: A small number of spot-like peelings are observed. 3: Many spot-like peelings are observed. 2: Continuous planar peeling is observed. 1: Complete peeling is observed.

Table 6

[0208]

Table 6 (continued)

[0210]

Table 7

[0212]

As is clear from Tables 6 and 7,
According to the test evaluation results (Table 6) when the resin composition for coating a metal can of the present invention in Examples 1 to 40 is used (Table 6),
In each case, the test evaluation results of Comparative Examples 1 to 6 (No. 7)
It can be seen that it is superior to Table).

The resin composition for coating metal cans of the present invention is excellent in curing speed (sensitivity), and therefore has physical properties after curing such as hardness, adhesion to a substrate, retort resistance and machinability. Can efficiently produce a metal can having a good cured film.

Claims (4)

[Claims] 1. A resin composition for coating metal cans, 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 resin composition for coating a metal can according to claim 1, wherein the acid-curable compound is an epoxy compound or a vinyl ether compound. 3. The resin composition for coating a metal can according to claim 1, further comprising a radical polymerizable compound. 4. The resin composition for coating a metal can according to claim 3, wherein the radical polymerizable compound is one of an acrylic acid derivative and a methacrylic acid derivative.