JP2002069110A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition having both high sensitivity and excellent shelf stability in a photoradical-polymerizing composition having the highest sensitivity on which a hopeful view is taken in image forming technique, and is suitable for the use of a lithographic printing plate material which can directly make a printing plate from digital data stored in a computer, etc., particularly by recording using a solid-state laser and a semiconductor laser which emit ultraviolet light, visible light or infrared light. SOLUTION: The photopolymerizable composition contains a photopolymerization initiator having at least one specific structure, and a polymerizable compound having an unsaturated double bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to three-dimensional stereolithography, holography, lithographic printing plate materials, color proofs, image forming materials such as photoresists and color filters, and photocurable resin materials such as inks, paints and adhesives. The present invention relates to a photopolymerizable material that can be used for: In particular, the present invention relates to a photopolymerizable composition which can be directly made from digital signals from a computer or the like by using various lasers, that is, which is suitably used as a so-called direct plate making lithographic printing plate.

[0002]

2. Description of the Related Art Solid-state lasers, semiconductor lasers, and gas lasers that emit ultraviolet light, visible light, and infrared light having a wavelength of 300 nm to 1200 nm can be easily obtained with high output and small size. Is very useful as a recording light source when making a plate directly from digital data of a computer or the like. Various studies have been made on recording materials sensitive to these various laser beams. As a typical example, first, as a material recordable with an infrared laser having a photosensitive wavelength of 760 nm or more, US Pat. No. 4,708,892.
There is a positive recording material described in No. 5, an acid-catalyzed cross-linkable negative recording material described in JP-A-8-276558, and the like. Second, as a recording material compatible with an ultraviolet or visible light laser of 300 nm to 700 nm, US Pat.
There are many radical polymerization type negative recording materials described in JP-A-445 and JP-B-44-20189.

On the other hand, short-wavelength light of 300 nm or less and electron beams are particularly important as a photoresist material. In recent years, integrated circuits have been increasing their integration degree,
In the manufacture of semiconductor substrates such as I, processing of ultra-fine patterns with a line width of less than half a micron is required.
In order to meet the need, the wavelength used in an exposure apparatus used for photolithography has been increasingly shortened, and far ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) have been studied. Has been considered. In particular, electron beams are promising as light sources for next-generation pattern formation technology.

A problem common to all of these image forming materials is how to expand ON-OFF of the image in the above-mentioned various energy irradiated portions and unirradiated portions, that is, high sensitivity and preservation of the image forming materials. It is a balance of stability. Usually, the photoradical polymerization system has high sensitivity, but the sensitivity is greatly reduced due to polymerization inhibition by oxygen in the air. Therefore, means for providing an oxygen barrier layer on the image forming layer has been adopted. However, if an oxygen-barrier layer is provided, fogging due to dark polymerization or the like occurs, and storage stability deteriorates. Therefore, it is a difficult task to achieve both high sensitivity and storage stability, and a sufficiently satisfactory result has not been obtained with the conventional technology, and a new technology that has not been used in the past has been required.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photo-radical polymerization composition, which is considered to be the most sensitive and promising among image forming techniques, to achieve high sensitivity and excellent storage stability. An object of the present invention is to provide a compatible photopolymerizable composition. In particular, a photopolymerizable composition suitable as a lithographic printing plate material capable of directly making a plate from digital data of a computer or the like by recording using a solid-state laser and a semiconductor laser light emitting ultraviolet light, visible light and infrared light. To provide.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by using a photopolymerization initiator having a specific polymerizable group in a photopolymerizable composition. . That is, the present invention has the following configuration. At least one structure represented by the following general formula (I)
A photopolymerizable composition comprising a photopolymerization initiator having one or more polymerizable compounds having an unsaturated double bond.

[0007]

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(In the general formula (I), X ¹ and X ² each independently represent ^a heteroatom or a halogen atom. R ^a and R ^b each independently represent ^a hydrogen atom, a halogen atom, a cyano group or Represents an organic residue, and X ¹ and X ² , R ^a and R ^b , or X ¹ and R ^a or R ^b may combine with each other to form a cyclic structure.

Conventionally, the most common radically polymerizable compounds include monomers, oligomers, and polymers having a high polymerizability having an acrylate group, an acrylamide group, a methacrylate group, a methacrylamide group, or the like. However, these compounds suffer from polymerization inhibition by oxygen, so that when used in a photopolymerizable composition, the problem of achieving both sensitivity and storage stability cannot be achieved.

On the other hand, compounds (monomers) having an α-hetero-substituted methyl acryl group or an α-halogen-substituted methyl acryl group as a polymer having a polymerizability comparable to that of an acrylic compound are known. These compounds are different from low-polymerizable itaconic acid groups and α-alkylacrylic groups having a substituent at the same α-position, unlike the electronic and steric effects of heteroatoms or halogen atoms substituted at the α-position. Is said to improve the polymerizability as a component of the polymer.

The present inventors have proposed that a conventional radical polymerizable compound can be obtained by using a photopolymerization initiator having a structure having a polymerizable group in which a hetero atom or a halogen atom is substituted at the α-position in the photopolymerizable composition. It has been found that the problem, that is, the effect of the above-described inhibition of the polymerization of oxygen can be significantly reduced, and that both the high sensitivity and the excellent storage stability, which are problems specific to the photopolymerizable composition, can be solved. Although the mechanism for reducing the effect of the polymerization inhibition of oxygen is not clear, the compound having the structure represented by the general formula (I) in the present invention has the α
Due to the substituent effect at the -position, the polymerization growth rate constant is not very high compared to conventional acrylic or methacrylic systems,
It is considered that since the stopping rate constant is extremely small, it hardly reacts with oxygen during chain growth, and as a result, it is hardly affected by oxygen polymerization inhibition. Furthermore, by linking the structure having the specific polymerizable group to the photopolymerization initiator, the generated radicals could be efficiently reacted with the polymerizable group, and a more sensitive system could be achieved. . The present invention can be suitably used for a photosensitive lithographic printing plate in which the photopolymerizable composition of the present invention is coated on a support.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION <Photopolymerization initiator having a structure represented by general formula (I) in the present invention> A photopolymerization initiator characterized in the present invention has at least a structure represented by general formula (I). It is a photopolymerization initiator having one. General formula (I)
Is a monovalent or divalent or higher valent substituent, and at least one of R ^a , R ^b , X ¹ , and X ^{2 in} the general formula (I) has one or more bonds. Have. Further, X ¹ and X ² may be a linking group having n linkable sites, and at least one photopolymerization initiator may be linked to the group represented by the general formula (I) at its terminal. (N is 2
(An integer greater than or equal to) (multimer).

In the general formula (I), X ¹ and X ² represent a hetero atom or a halogen atom, which may be a terminal group, or a linking group, and other substituents (here, As described above, the substituent may be linked to the structure of general formula (I) and the photopolymerization initiator. The hetero atom is preferably a nonmetallic atom, and specific examples include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Further, these hetero atoms may have a charge. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. When the structure represented by the general formula (I) is bonded to the photopolymerization initiator in X ^1, X ^2, as a hetero atom represented by X ^1, X ^2, heteroatoms also serves as a part of a photopolymerization initiator Is also good. X ¹ is preferably a halogen atom or X ¹ is a linking group,
As a group to which another substituent is linked, a photopolymerization initiator having at least one bond or a hydroxyl group, a substituted oxy group, a mercapto group, a substituted thio group,
Amino group, substituted amino group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, phosphonate group, substituted phosphonate group, nitro group, heterocyclic group (however, Yes)
Represents X ² is preferably a halogen atom or a group in which X ² is a linking group to which another substituent is linked, such as a photopolymerization initiator having at least one bond, a hydroxyl group, or a substituted oxy group. , A mercapto group, a substituted thio group, an amino group, a substituted amino group, and a heterocyclic group (however, linked by a hetero atom).

In the case where X ¹ or X ² is a linking group and another substituent is linked to the group, excluding n hydrogens from those groups, n linkable sites are changed to And the terminal may be connected with n groups of the general formula (I) (n is an integer of 2 or more). X ¹ ,
X ² may combine with each other to form a cyclic structure.

R ^a and R ^b are each independently more preferably a hydrogen atom, a halogen atom, a cyano group, or an organic residue, which may have a substituent and contain an unsaturated bond. which may hydrocarbon group, a substituted oxy group, a substituted thio group, substituted amino group, substituted carbonyl group, a carboxylate group and R ^a and R ^b may be bonded to form a cyclic structure.

Next, X ¹ , X ² , R in the general formula (I)
Examples of the above-mentioned substituents in ^a and ^Rb are shown below. As the hydrocarbon group which may have a substituent and may contain an unsaturated bond, an alkyl group, a substituted alkyl group,
Examples include an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group and a substituted alkynyl group.

The alkyl group has 1 to 2 carbon atoms.
Examples thereof include a linear, branched, or cyclic alkyl group up to 0, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group,
Isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-norbornyl be able to. Among these, straight-chains having 1 to 12 carbon atoms, 3 to 12 carbon atoms.
And a cyclic alkyl group having 5 to 10 carbon atoms is more preferred.

The substituted alkyl group is constituted by a bond between a substituent and an alkylene group. As the substituent, a monovalent nonmetallic atomic group other than hydrogen is used. Preferred examples thereof include a halogen atom (-F, -Br, -Cl, -I), hydroxyl, alkoxy, aryloxy, mercapto, alkylthio, arylthio, alkyldithio, aryldithio, amino, N-alkylamino, N, N-dialkyl Amino group, N-arylamino group, N, N-diarylamino group, N-alkyl-
N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N An arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group,
Acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group,
N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido Group, N-arylureido group, N'-alkyl-N-alkylureido group,
N'-alkyl-N-arylureido group, N ', N'
-Dialkyl-N-alkylureido group, N ', N'-
Dialkyl-N-arylureido, N'-aryl-N-alkylureido, N'-aryl-N-arylureido, N ', N'-diaryl-N-alkylureido, N', N'- Diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-
N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-
N-alkoxycarbonylamino group, N-alkyl-N
-Aryloxycarbonylamino group, N-aryl-N
-Alkoxycarbonylamino group, N-aryl-N-
Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugate base group (hereinafter referred to as carboxylate), alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N- Dialkylcarbamoyl group, N
- arylcarbamoyl group, N, N- di arylcarbamoyl group, N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugate Base group (hereinafter, referred to as sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N , N-diarylsulfinamoyl, N-alkyl-N-arylsulfinamoyl, sulfamoyl, N-alkylsulfamoyl, N, N-dialkylsulfamoyl, N-arylsulfamoyl, N, N-diarylsulfamoyl , N- alkyl -N- arylsulfamoyl group, N- acylsulfamoyl group and a conjugate base group, N- alkylsulfonylsulfamoyl group _{(-SO 2 NHSO 2 (alkyl)} ) and its conjugated base group, N-arylsulfonylsulfamoyl group (-S
O ₂ NHSO ₂ (allyl)) and its conjugate base group, N
-Alkylsulfonylcarbamoyl group (-CONHSO
₂ (alkyl)) and its conjugated base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (all)
yl)) and its conjugate base group, alkoxysilyl group (-
Si (Oalkyl) ₃ ), an aryloxysilyl group (-
Si (Oallyl) ₃ ), hydroxysilyl group (-S
i (OH) ₃ ) and its conjugate base group, phosphono group (-P
O ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group), dialkylphosphono group (—PO ₃ (alky)
l) ₂ ), a diarylphosphono group (—PO ₃ (aryl)
₂ ), an alkylarylphosphono group (—PO ₃ (alky
l) (aryl)), monoalkylphosphono group (-PO
₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group) ), A phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as a phosphonatoxy group), a dialkylphosphonooxy group (—
OPO ₃ (alkyl) ₂ , diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) (ary)
1)), a monoalkylphosphonooxy group (—OPO ₃ H
(Alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter, the aryl phosphite Hona preparative group ), A cyano group, a nitro group, an aryl group, an alkenyl group, and an alkynyl group.

In these substituents, specific examples of the alkyl group include the aforementioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and mesityl groups. , Cumenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylca Ba carbamoylphenyl group, a phenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group,
And a phosphonatophenyl group. Examples of the alkenyl group include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-
Examples thereof include a 1-ethenyl group and the like, and examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, and a phenylethynyl group.

The above-mentioned acyl group (R4CO-) includes
R4 is a hydrogen atom and the above-mentioned alkyl, aryl, alkenyl and alkynyl groups. On the other hand, the alkylene group in the substituted alkyl group can be a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms, and is preferably a divalent organic residue. May be a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, or a cyclic alkylene group having 5 to 10 carbon atoms. Specific examples of preferred substituted alkyl groups include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, Luthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group,
Benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Carbonylethyl group, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonylmethyl group,
Butoxycarbonylmethyl group, allyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl Group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group,

[0021]

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Phosphonobutyl, phosphonatohexyl, diethylphosphonobutyl, diphenylphosphonopropyl, methylphosphonobutyl, methylphosphonatobutyl, tolylphosphonohexyl, tolylphosphonatohexyl, phosphonooxy Propyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p
-Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be given.

Examples of the aryl group include a group in which one to three benzene rings form a condensed ring and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group,
And a phenyl group and a naphthyl group are more preferable.

The substituted aryl group is a group in which a substituent is bonded to an aryl group, and those having a monovalent nonmetallic atomic group excluding hydrogen as a substituent on a ring-forming carbon atom of the above-mentioned aryl group are used. Can be Preferred examples of the substituent include the aforementioned alkyl group, substituted alkyl group, and those described above as the substituent for the substituted alkyl group. Preferred specific examples of these substituted aryl groups include a biphenyl group, a tolyl group, a xylyl group,
Mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group,
Methylthiophenyl group, tolylthiophenyl group, phenylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxy Phenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group,
Allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-
Methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfa Moylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, Phosphonophenyl, phosphonatophenyl, diethylphosphonophenyl, diphenylphosphonophenyl, methylphosphonophenyl, methylphosphonatophenyl, tolylphosphonophenyl, tolylphosphonatophenyl, allyl, 1 -Propenylmethyl group, 2 Butenyl, 2-methyl-allyl phenyl group, 2-methyl propenyl phenyl group, 2-propynyl phenyl group, 2-butynyl phenyl group, 3-butynyl phenyl group, etc. may be mentioned.

Examples of the alkenyl group include those described above. A substituted alkenyl group is a compound in which a substituent is replaced by a hydrogen atom of an alkenyl group and bonded to the alkenyl group. As the substituent, the substituent in the above-mentioned substituted alkyl group is used, while the alkenyl group is the above-mentioned alkenyl group. Can be. Examples of preferred substituted alkenyl groups include

[0026]

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And the like. Examples of the alkynyl group include those described above. A substituted alkynyl group is a substituent in which a substituent is replaced by a hydrogen atom of an alkynyl group and bonded to the alkynyl group, and the substituent is the substituent in the above-mentioned substituted alkyl group, while the alkynyl group uses the alkynyl group described above. be able to.

A heterocyclic group is a monovalent group obtained by removing one hydrogen on a heterocyclic ring, and further removing one hydrogen from the monovalent group, and a substituent in the above-mentioned substituted alkyl group is bonded. The resulting monovalent group (substituted heterocyclic group). Examples of preferred heterocycles include

[0029]

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[0030]

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And the like.

As the substituted oxy group (R5O-), those wherein R5 is a monovalent nonmetallic atomic group except for hydrogen can be used. Preferred substituted oxy groups include an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N, N-dialkylcarbamoyloxy group, and an N, N-diarylcarbamoyloxy group. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group. Further, an acyl group (R
Examples of 6CO-) include those wherein R6 is the aforementioned alkyl group, substituted alkyl group, aryl group and substituted aryl group. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferred. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy,
Benzyloxy group, allyloxy group, phenethyloxy group, carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, Morpholinopropyloxy, allyloxyethoxyethoxy, phenoxy, tolyloxy, xylyloxy, mesityloxy, cumenyloxy, methoxyphenyloxy, ethoxyphenyloxy, chlorophenyloxy, bromophenyloxy, acetyloxy, benzoyl Examples include an oxy group, a naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, and a phosphonatoxy group.

As the substituted thio group (R7S-), those wherein R7 is a monovalent nonmetallic atomic group except for hydrogen can be used. Preferred examples of the substituted thio group include an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, and an acylthio group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group, and R6 of the acyl group (R6CO-) in the acylthio group is as described above. It is. Among these, an alkylthio group and an arylthio group are more preferred. Specific examples of preferred substituted thio groups include a methylthio group, an ethylthio group, a phenylthio group, an ethoxyethylthio group, a carboxyethylthio group, and a methoxycarbonylthio group.

A substituted amino group (R8NH-, (R9) (R1
0) As N-), those in which R8, R9, and R10 are monovalent nonmetallic atomic groups other than hydrogen can be used. Preferred examples of the substituted amino group include N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acylamino group, N-alkylacylamino group, N
An arylacylamino group, a ureido group, an N′-alkylureido group, an N ′, N′-dialkylureido group,
N'-arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido Group, N'-
Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-
Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N ' -Aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl —N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, and N-aryl-N-aryloxycarbonylamino group. As the alkyl group and the aryl group in these, the above-mentioned alkyl group,
Examples of the substituted alkyl group, the aryl group, and the substituted aryl group include those described above. R6 of the acyl group (R6CO-) in the acylamino group, the N-alkylacylamino group, and the N-arylacylamino group is as described above. It is. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include a methylamino group, an ethylamino group, a diethylamino group, a morpholino group, a piperidino group, a pyrrolidino group, a phenylamino group, a benzoylamino group, an acetylamino group, and the like.

As the substituted carbonyl group (R11-CO-), those wherein R11 is a monovalent nonmetallic atomic group can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group and N-alkyl-N-arylcarbamoyl group are exemplified. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Among them, more preferred substituted carbonyl groups include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-aryl And more preferably, a formyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl, acetyl, benzoyl, carboxyl, methoxycarbonyl, allyloxycarbonyl, N-methylcarbamoyl, N-phenylcarbamoyl,
N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like can be mentioned.

As the substituted sulfinyl group (R12-SO-), those in which R12 is a monovalent nonmetallic atomic group can be used. Preferred examples include an alkylsulfinyl group, an arylsulfinyl group, a sulfinamoyl group, an N-alkylsulfinamoyl group, an N, N-dialkylsulfinamoyl group, an N-arylsulfinamoyl group, and an N, N-diarylsulfinamoyl. And N-alkyl-N-arylsulfinamoyl groups. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group,
Examples include a benzylsulfinyl group and a tolylsulfinyl group.

The substituted sulfonyl group (R13-SO ₂ -) as the, R13 can be used a monovalent nonmetallic radical.
More preferred examples include an alkylsulfonyl group and an arylsulfonyl group. As the alkyl group and the aryl group in these, the above-mentioned alkyl group,
Examples of the substituted alkyl group, the aryl group, and the substituted aryl group can be given. like this,
Specific examples of the substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

The sulfonato group (-SO ₃ ^-) are as described above, means a conjugate base anion group of a sulfo group (-SO ₃ H), it is usually used preferably in combination with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , C ⁺
a ²⁺ , Zn ^2+, etc.).

As described above, the carboxylate group (—CO ₂ ⁻ ) means a conjugate base anion group of the carboxyl group (CO ₂ H), and is usually preferably used together with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (N
a ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted by another organic oxo group. Preferred examples include the above-mentioned dialkylphosphono group, diarylphosphono group, Examples include an alkylarylphosphono group, a monoalkylphosphono group, and a monoarylphosphono group. Among these, a dialkylphosphono group and a diarylphosphono group are more preferred. Specific examples include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group, and the like.

[0041] phosphonate group ^{_{(-PO 3 2-, -PO 3 H}} -)
As I mentioned above the means phosphono group (-PO ₃ H _2), first dissociation or acid, a conjugated base anion group derived from the second dissociation acid. Usually it is preferred to use it with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums: aziniums, etc.), and metal ions (Na
⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

The substituted phosphonate group is a conjugate base anion group obtained by substituting one hydroxyl group with an organic oxo group among the above-mentioned substituted phosphono groups, and specific examples thereof include a monoalkylphosphono group (-PO ₃ H (alkyl)) and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)). Usually it is preferred to use it with a counter cation. As such counter cations, those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums,
Iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

Next, X ¹ and X ² , R ^a and R ^b , or X ¹ and R ^a
Alternatively, an example of a cyclic structure formed by combining ^Rb with each other is shown. X ¹ and X ² , R ^a and R ^b , or X ¹ and R ^a or R
^Examples of the aliphatic ring formed by combining ^b with each other include a 5-membered ring, a 6-membered ring, a 7-membered ring and an 8-membered ring, and more preferably a 5-membered ring or a 6-membered ring And a cyclic aliphatic ring. These may further have a substituent on the carbon atom constituting them (examples of the substituent include the substituents on the above-mentioned substituted alkyl group). May be substituted with a hetero atom (an oxygen atom, a sulfur atom, a nitrogen atom, or the like). Further, a part of the aliphatic ring may form a part of an aromatic ring.

Most preferably, the photopolymerization initiator in the present invention has a structure represented by the general formula (I) in the molecule.
Polyfunctional type (bifunctional or higher and high-molecular type) having at least two or more radically polymerizable groups having the structure represented by the general formula (I) in the molecule and the contribution of polyfunctionality in substantial photopolymerization It is what you do.

In the photopolymerization initiator having the structure represented by the above general formula (I), the photopolymerization initiator as a skeleton thereof includes (a) an aromatic ketone, (b) an aromatic onium salt compound, c) an organic peroxide, (d) a thio compound,
(E) a hexaarylbiimidazole compound, (f) a ketoxime ester compound, (g) a borate compound,
(H) an azinium compound, (i) a metallocene compound,
(J) an active ester compound; and (k) a compound having a carbon-halogen bond. The structure represented by the general formula (I) is preferably bonded to the photopolymerization initiator as a skeleton at the X ¹ or X ² portion of the general formula (I). On the other hand, the photopolymerization initiator, which is the skeleton, may be bonded to the structure represented by the general formula (I) at any position as long as the effects of the present invention are exhibited.

A linking group may be present between the structure represented by the general formula (I) and the photopolymerization initiator as the skeleton. Examples of such a linking group include an oxygen atom, a nitrogen atom, and a carbon atom which may contain a sulfur atom.
And an alkylene group or a single bond.

Next, the photopolymerization initiator which is the skeleton of the photopolymerization initiator having the structure represented by the general formula (I) will be described. Preferred photopolymerization initiators, as described above,
(A) aromatic ketones, (b) aromatic onium salt compound, (c) organic peroxide, (d) thio compound, (e) hexaarylbiimidazole compound, (f) ketoxime ester compound, (g A) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, and (k) compounds having a carbon-halogen bond. (A) Preferable examples of aromatic ketones include “RADIATION CURING IN POLYMER SCIENCE AND
TECHNOLOGY '' JPFOUASSIER JFRABEK (1993), p77 ~
Compounds having a benzophenone skeleton or thioxanthone skeleton according to 117, for example,

[0048]

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[0049]

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[0050]

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And the like. More preferred examples of (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416 and JP-B-47-3981.
The benzoin ether compound described, for example,

[0052]

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Α-Substituted benzoin compounds described in JP-B-47-22326, for example,

[0054]

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Benzoin derivatives described in JP-B-47-23664, aroylphosphonic esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, for example,

[0056]

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JP-B-60-26403, JP-A-62-8
Benzoin ethers described in 1345, for example,

[0058]

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Japanese Patent Publication No. 1-34242, U.S. Pat.
18,791 and α-aminobenzophenones described in EP 0284561 A1, for example,

[0060]

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P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-21452, for example,

[0062]

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Thio-substituted aromatic ketones described in JP-A-61-194062, for example,

[0064]

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The acylphosphine sulfide described in JP-B-2-9597, for example,

[0066]

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Acylphosphines described in JP-B-2-9596, for example,

[0068]

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The thioxanthones described in JP-B-63-61950 and the coumarins described in JP-B-59-42864 can be exemplified. Further, another example of (b) an aromatic onium salt is an element belonging to Groups V, VI and VII of the periodic table, specifically N, P, As, Sb, Bi, O,
Includes aromatic onium salts of S, Se, Te, or I. Examples of such aromatic onium salts include the compounds disclosed in JP-B-52-14277, JP-B-52-14278, and JP-B-52-14279. In particular,

[0070]

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[0071]

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[0072]

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[0073]

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The following can be mentioned. Further, the following diazonium salts can be mentioned.

[0075]

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[0076]

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Another example of the photopolymerization initiator (c) “organic peroxide” used in the present invention is an organic peroxide in the molecule.
Almost all organic compounds having one or more oxygen bonds are included, and examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide,
3,5-trimethylcyclohexanone peroxide,
Methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (Tertiary butyl peroxide) butane, tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane hydroperoxide, 2,5-dimethylhexane-2,5
-Dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, bis (tertiary butylperoxyisopropyl) benzene, 2,5
-Dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-xanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide , Diisopropyl peroxydicarbonate, di-
2-ethylhexyl peroxydicarbonate, di-2
Ethoxyethyl peroxydicarbonate, dimethoxyisopropylperoxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate,
Tertiary butyl peroxy acetate, tertiary butyl peroxy pivalate, tertiary butyl peroxy neodecanoate, tertiary butyl peroxy octanoate, tertiary butyl peroxy-
3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, tertiary carbonate, 3,3'4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4 4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4 '
-Tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4 '
-Tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

Of these, 3,3'4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4
Peroxide esters such as 4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate Systems are preferred.

The thio compound (d) as a photopolymerization initiator used in the present invention is represented by the following general formula [II].

[0080]

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(Where R ²⁰ represents an alkyl group, an aryl group or a substituted aryl group, R ²¹ represents a hydrogen atom or an alkyl group. R ²⁰ and R ²¹ are bonded to each other to form oxygen, sulfur and The group of nonmetallic atoms necessary for forming a 5- to 7-membered ring which may include a hetero atom selected from nitrogen atoms is shown below.) The alkyl group in the general formula [II] has 1 to 4 carbon atoms. Are preferred. The aryl group is preferably a group having 6 to 10 carbon atoms such as phenyl and naphthyl. The substituted aryl group is preferably a halogen atom such as a chlorine atom and an alkyl group such as a methyl group. And those substituted with an alkoxy group such as a methoxy group or an ethoxy group. R ²¹ is preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the thio compound represented by the general formula [II] include the following compounds.

[0082]

[Table 1]

Other examples of the photopolymerization initiator used in the present invention, (e) hexaarylbiimidazole include:
Lophin dimers described in JP-B-45-37377 and JP-B-44-86516, for example, 2,2'-bis (o
-Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2 '-Bis (o, p-dichlorophenyl)
-4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (o-nitrophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-methylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-
And tetraphenylbiimidazole.

(F) Ketoxime esters which are other examples of the photopolymerization initiator used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, -Propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-
ON, 2-acetoxyimino-1-phenylpropane-
1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like Is mentioned. Examples of the borate salt (g), which is another example of the photopolymerization initiator in the present invention, include a compound represented by the following general formula [III].

[0085]

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(Wherein R ²² , R ²³ , R ²⁴ and R ²⁵ may be the same or different from each other and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic ^{group, R 22, R 23, R} 24 and R ²⁵ are a ring structure formed by combining two or more groups of You can, however,
At least one of R ²² , R ²³ , R ²⁴ and R ²⁵ is a substituted or unsubstituted alkyl group. Z ⁺ represents an alkali metal cation or a quaternary ammonium cation). The alkyl group of R ^{22 to} R ²⁵ includes linear, branched and cyclic alkyl groups, and preferably has 1 to 18 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Further, as the substituted alkyl group, a halogen atom (for example, -C
l, -Br etc.), a cyano group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group,

[0087]

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(Wherein R ²⁶ and R ²⁷ are independently a hydrogen atom,
It represents an alkyl group having 1 to 14 carbon atoms or an aryl group. ), -COOR ²⁸ (where R ²⁸ represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group),-
OCOR ²⁹ or -OR ³⁰ (where R ²⁹ and R ^{30 each} have 1 carbon atom)
And 14 to 14 alkyl groups or aryl groups. ) As a substituent. Examples of the aryl group of R ^{22 to} R ²⁵ include a phenyl group and a naphthyl group.
A cyclic aryl group is included, and examples of the substituted aryl group include those having a substituent of the above-described substituted alkyl group or an alkyl group having 1 to 14 carbon atoms in the above-described aryl group. The alkenyl group represented by R ^{22 to} R ²⁵ includes a straight-chain, branched, or cyclic one having 2 to 18 carbon atoms. Examples of the substituent of the substituted alkenyl group include those described above as the substituent of the substituted alkyl group. Examples of the alkynyl group of R ^{22 to} R ²⁵ include straight-chain or branched ones having 2 to 28 carbon atoms. Examples of the substituent of the substituted alkynyl group include those described above as the substituent of the substituted alkyl group. included. The heterocyclic group of the R ²² ~R ²⁵ N, 5-membered ring or more, including at least one of S and O, preferably include heterocyclic groups 5- to 7-membered ring, this heterocyclic group May contain a fused ring. Further, it may have the substituents described above as the substituents of the substituted aryl group. Specific examples of the compound represented by the general formula [III] include US Pat. Nos. 3,567,453 and 4,343,8.
No. 91, European Patent Nos. 109,772 and 109,772.
No. 773 and the compounds shown below.

[0089]

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Examples of (h) azinium salt compounds which are other examples of the photopolymerization initiator of the present invention are described in
No. 138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143535, and JP-B-46-42363.

Another example of the photopolymerization initiator (i) as a metallocene compound is described in JP-A-59-152396.
JP-A-61-151197, JP-A-63-414
No. 84, JP-A-2-249, JP-A-2-4705 and the titanocene compounds described in JP-A-1-30445.
No. 3 and JP-A-1-152109.

Specific examples of the titanocene compound include:
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-
Cyclopentadienyl-Ti-bis-2,3,4,5
6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-T
i-bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-T
i-bis-2,4-difluorophenyl-1-yl, di-
Methylcyclopentadienyl-Ti-bis-2,3,
4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,
6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3 -(Pyri-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamide)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylbiaroyl-
Amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methylacetylamino) phenyl] titanium, bis (cyclopentadi Enil)
Bis [2,6-difluoro-3- (N-ethylpropionylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (2,2-dimethylbuta Noyl) amino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (N-butyl- (2,2-dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-
Pentyl- (2,2-dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl)-(2,
2-dimethylbutanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-methylbutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-methylpentanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-ethylcyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylisobutyrylamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3-
(N-ethylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (2,2,5,5-tetramethyl-1,2,5-azadisirolidin-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (octylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-tolylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2 6-difluoro-3- (4-dodecylphenylsulfonylamido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (4- (1-pentylheptyl)
Phenylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (ethylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-((4-bromophenyl) -sulfonylamide)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-naphthylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( Hexadecylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methyl- (4-dodecylphenyl) sulfonylamido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-methyl-4- (1-pentylheptyl) phenyl) sulfonylamido)] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-tolyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3- (pyrrolidine-
2,5-dion-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (3,4-dimethyl-3-pyrrolidin-2,5-dion-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phthalimido) phenyl] titanium , Bis (cyclopentadienyl) bis [2,6-difluoro-3-isobutoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (ethoxycarbonylamino) phenyl ] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-((2
-Chloroethoxy) -carbonylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (phenoxycarbonylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylthioureido) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (3-butylthioureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylureido) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (3-butylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N, N-diacetylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,3-dimethylureido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (acetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (butyrylamino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (decanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (octadecanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (isobutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 6-difluoro-
3- (2-ethylhexanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-methylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) Screw [2
6-difluoro-3- (pivaloylamino) phenyl]
Titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethyl-2)
-Methylheptanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (cyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-chloropropanoylamino) phenyl] titanium, bis (cyclopentane Dienyl) bis [2,6-difluoro-3- (3-phenylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(2-chloromethyl-2-methyl-3-chloropropanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (3,4-xyloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-ethylbenzoylamino) phenyl] titanium, bis (cyclo Pentadienyl) bis [2,6-difluoro-3- (2,4,6-mesitylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(Benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-(3-phenylpropyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (3-ethylheptyl)-
2,2-dimethylpentanoylamino] phenyltitanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadiene) Enil)
Bis [2,6-difluoro-3- (N-isobutylbenzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-cyclohexylmethylpivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxolan-2-ylmethyl) benzoylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (3-ethylheptyl)-
2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl- (4-toluyl) amino) phenyl] titanium, Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-
(Oxolani-2-ylmethyl)-(4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-toluylmethyl) benzoylamino) phenyl] Titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N- (4-toluylmethyl)-
(4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-butylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) ) Screw [2
6-difluoro-3- (N-hexyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2,
4-dimethylpentyl) -2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,4-dimethylpentyl) -2,2-dimethyl Pentanoylamino)
Phenyl) titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3-((4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethylpentanoylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (2,2-
Dimethyl-3-ethoxypropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (2,2-dimethyl-3-allyloxypropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-allylacetylamino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl) Methylbenzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-cyclohexylmethyl-
(4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N- (2-ethylhexyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) Bis [2,6-difluoro-3- (N- (3-
Phenylpropyl) -2,2-dimethylpentanoyl)
Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-cyclohexylmethyl-2,2-dimethylpentanoyl)
Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylbenzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N- (2-ethylhexyl)-
2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N- (3-phenylpropyl) pivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-butyl-2,2-dimethylpentanoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl) benzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-benzylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-benzyl- (4
-Toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-(2-methoxyethyl)-(4-toluyl) amino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-methylphenylmethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadi Enyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-cyclohexylmethyl-
(2-ethyl-2-methylheptanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (2-ethyl- 2-methylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-cyclohexyl-2,2-dimethylpentanoyl) amino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (N- (oxolan-2-ylmethyl) -2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-cyclohexyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-cyclohexyl- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (3,3-dimethyl-
2-azetidinoni-1-yl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3-isocyanatophenyl) titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-hexyl- (4
-Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-butyl- (4-tolylsulfonyl) amino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4-
Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-butyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N- (3-phenylpropanoyl) -2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3- (N-cyclohexylmethyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- ( 2,2-dimethyl-3-chloropropanoyl) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-butyl- (2-
Chloromethyl-2-methyl-3-chloropropanoyl)
Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (butylthiocarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (Phenylthiocarbonylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3-isocyanatophenyl) titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-hexyl- (4
-Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-butyl- (4-tolylsulfonyl) amino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4-
Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-butyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-(3-phenylpropanoyl) -2,2-dimethyl-
3-chloropropanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-cyclohexylmethyl-
(2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-isobutyl-
(2,2-dimethyl-3-chloropropanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-butyl- (2-chloromethyl-2-methyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (Butylthiocarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenylthiocarbonylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6 -Difluoro-3-
(N-hexyl-2,2-dimethylbutanoyl) amino) phenyl] titanium,

Bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-2,2-
Dimethylpentanoylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2
6-difluoro-3- (N-ethylpropionylamino) phenyl] titanium, bis (trimethylsilylpentadienyl) bis [2,6-difluoro-3- (N-butyl-2,2-dimethylpropanoylamino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (N- (2-methoxyethyl) -trimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-Butylhexyldimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (1,1,2, -trimethylpropyl) dimethylsilylamino) phenyl] Titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (3-ethoxymethyl-3-methyl-2-azethiodinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-allyloxy) Methyl-3-methyl-
2-azetidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (3-chloromethyl-3-methyl-2-azetidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2- Dimethylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (5,5-dimethyl-2-pyrrolidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (6,
6-diphenyl-2-piperidinoni-1-yl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N- (2,3-dihydro-1,
2-Benzisothiazolo-3-one (1,1-dioxide) -2-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-chlorobenzoyl) ) Amino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (N-hexyl- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl- (4-chlorobenzoyl) amino] ) Phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (4-methylphenylmethyl)-(4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- ( 4-methylphenylmethyl)-
(2-chlorobenzoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2-dimethyl) Pentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (2-ethylhexyl)-
4-tolyl-sulfonyl) amino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (trifluoromethylsulfonyl) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (trifluoroacetylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,
6-dioxadecyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,7-
Dimethyl-7-methoxyoctyl) benzoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylbenzoylamino) phenyl] titanium, and the like.

Examples of the (j) active ester compound which is another example of the photopolymerization initiator include imide sulfonate compounds described in JP-B-62-6223 and JP-B-63-14340.
And active sulfonates described in JP-A-59-174831.

Preferred examples of the compound (k) having a carbon-halogen bond, which is an example of a photopolymerization initiator, include those represented by the following general formulas [IV] to [X].

[0119]

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(Wherein X ² represents a halogen atom; Y ^{2
_{-C (X 2) 3, -NH}} 2, -NHR 3 2, -NR 32, the -
Represent OR ^32. Here, ^R32 represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Also R ³¹
Represents -C (X ²⁾ _3, alkyl group, substituted alkyl group, an aryl group, a substituted aryl group, a substituted alkenyl group, an. ).

[0121]

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(Where R ³³ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group; ^Three
Is a halogen atom, and n is an integer of 1 to 3. ).

[0123]

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(Where R ³⁴ is an aryl group or a substituted aryl group, and R ³⁵ is

[0125]

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Or Z ² is —C (＝ O)
—, —C (＝ S) — or —SO ₂ —, and R ³⁶ , R ³⁷
Is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group;
³⁸ is the same as R ³² in the general formula [IV], X ³ is a halogen atom, and m is 1 or 2. ).

[0127]

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In the formula, R ³⁹ is an optionally substituted aryl group or a heterocyclic group, and R ⁴⁰ is carbon atom 1
A trihaloalkyl or trihaloalkenyl group having up to 3; and p is 1, 2 or 3.

[0129]

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(Where L is a hydrogen atom or a compound of the formula: CO—
(R ⁴¹ ) q (C (X ⁴ ) ₃ ) r is a substituent, and Q represents a sulfur, selenium or oxygen atom, a dialkylmethylene group, an alkene-1,2-ylene group, a 1,2-phenylene group or an N group.
-R group, M is a substituted or unsubstituted alkylene group or alkenylene group, or a 1,2-arylene group, R ⁴² is an alkyl group, an aralkyl group or an alkoxyalkyl group, and R ⁴¹ is X ⁴ is a carbocyclic or heterocyclic divalent aromatic group, X ⁴ is a chlorine, bromine or iodine atom, and q = 0 and r = 1, or q = 1 and r =
1 or 2. A) a carbonylmethylene heterocyclic compound having a trihalogenomethyl group;

[0131]

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(Where X ⁵ is a halogen atom, t
Is an integer of 1 to 3, s is an integer of 1 to 4, R ⁴³
A hydrogen atom or a CH _3-t X _5t group, R ⁴⁴ is represented by a is) s-valent optionally substituted unsaturated organic group, 4- halogeno-5- (halogenomethyl-phenyl) -
-Oxazole derivatives.

[0133]

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(Where X ⁶ is a halogen atom;
Is an integer of 1 to 3, u is an integer of 1 to 4, R ⁴⁵
Is a hydrogen atom or a CH _3-v X _6v group, R ⁴⁶ is an unsaturated organic group which may be substituted for u-valent. ), A 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative.

Specific examples of such a compound having a carbon-halogen bond include, for example, Wakabayashi et al., Bull. Ch.
em. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis ( Trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S -Triazine, 2- (2 ', 4'-dichlorophenyl) -4,6
-Bis (trichloromethyl) -S-triazine, 2,
4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl)-
S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-
Trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine and the like. Other compounds described in GB 1388492, for example, 2
-Styryl-4,6-bis (trichloromethyl) -S-
Triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-
(Methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl)
Compounds described in JP-A-53-133428, such as -4-amino-6-trichloromethyl-S-triazine, for example, 2- (4-methoxy-naphth-1-yl) -4,6
-Bis-trichloromethyl-S-triazine, 2- (4
-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl -S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphth-5-
Yl) -4,6-bis-trichloromethyl-S-triazine, such as the compounds described in DE 3337024, for example,

[0136]

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[0137]

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And the like. Also, FC Sc
Haefer et al., J. Org. Chem. 29, 1527 (196
The compounds described in 4), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-
Tris (tribromomethyl) -S-triazine, 2,
4,6-tris (dibromomethyl) -S-triazine,
2-amino-4-methyl-6-tribromomethyl-S-
Triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like can be mentioned. Further, compounds described in JP-A-62-58241, for example,

[0139]

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[0140]

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And the like. Further, Japanese Patent Laid-Open No. 5-
No. 281,728, for example,

[0142]

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And the like. Or even more
Jou by MP Hutt, EF Elslager and LM Herbel
rnalof Heterocyclic chemistry ", Vol. 7 (No.
3) The following compound groups that can be easily synthesized by those skilled in the art according to the synthesis methods described on pages 511 et seq. (1970).

[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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Alternatively, compounds such as those described in German Patent No. 2641100, such as 4- (4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3,4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone or the compounds described in DE 33 33 450, for example,

[0151]

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In the formula, R ⁴¹ represents a benzene ring, and R ⁴² represents an alkyl group, an aralkyl group or an alkoxyalkyl group.

[0153]

[Table 2]

Alternatively, a compound group described in German Patent No. 3021590,

[0155]

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[0156]

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Alternatively, the compounds described in German Patent No. 3021599, for example,

[0158]

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The following can be mentioned. As a more preferred example of the photopolymerization initiator having a structure represented by the general formula (I) in the present invention, a photopolymerization initiator that generates a radical by the action of laser light having a wavelength of 300 nm to 1200 nm is preferable. Still more preferred examples of the photopolymerization initiator in the present invention include, as a skeleton, the above-mentioned (a) aromatic ketones, (b) aromatic onium salt, (c) organic peroxide, and (e) hexaarylbiimidazole. , (I) a metallocene compound, and (k) a compound having a carbon-halogen bond.
Examples include an aromatic iodonium salt, an aromatic diazonium salt, a titanocene compound, and a trihalomethyl-S-triazine compound represented by the general formula [IV]. Next, specific examples of the photopolymerization initiator having the structure represented by the general formula (I) will be shown.

[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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[0179]

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[0180]

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[0181]

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[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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[0192]

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[0193]

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[0194]

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[0195]

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[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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[0213]

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[0214]

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[0215]

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[0216]

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[0219]

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[0218]

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[0219]

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[0220]

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[0221]

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[0222]

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The photopolymerization initiator in the present invention is suitably used alone or in combination of two or more. The photopolymerization initiator having the structure represented by the general formula (I) can be easily synthesized generally by the method shown in the following scheme. However, it is not limited to these.

[0224]

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That is, mainly -CO ₂ H group, -OH group, -S
H group, -N (R) ₂ group (R is an alkyl group, an aryl group)
(A similar synthesis method is described in the patents of the respective photopolymerization initiators described above), and a compound precursor (Br) corresponding to the structure represented by the general formula (I) OH-form, CO ₂ H-form, COCl-form, etc.).

The amount of the photopolymerization initiator to be used in the composition of the present invention is from 0.01 to 0.01 based on the weight of all components of the photopolymerizable composition.
It is 60% by weight, more preferably 0.05 to 30% by weight. When a sensitizing dye is used, the molar ratio of the photopolymerization initiator in the photopolymerizable composition and the sensitizing dye described below is 10 in the present invention.
0: 0 to 1:99, more preferably 90:10
10:90, most preferably 80:20 to 20:
80. When a co-sensitizer described below is used, it is appropriate to use 0.01 to 50 parts by weight, more preferably 0.02 to 20 parts by weight, and most preferably 1 part by weight of the photopolymerization initiator. 0.05 to 10 parts by weight.

The photopolymerizable composition of the present invention contains a polymerizable compound having an unsaturated double bond. As such a polymerizable compound having an unsaturated double bond, it is possible to use a conventionally known compound having an addition-polymerizable ethylenically unsaturated bond alone and a mixture of two or more thereof as described below. it can. Examples of conventionally known compounds having an addition-polymerizable ethylenically unsaturated bond include, for example, unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid,
Esters of aliphatic polyhydric alcohol compounds with itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc., and amides of the above unsaturated carboxylic acids with aliphatic polyhydric amine compounds.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate Acrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetra Acrylate, SO Bi penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylic acid ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3 -Methacryloxy-2-h Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (acryloxy ethoxy)
Phenyl] dimethylmethane. Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diitaconate. And sorbitol tetritaconate.

Examples of crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned. Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, and 1,6-hexane. Examples include methylenebis-methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylamide.

As another example, see JP-B-48-417.
JP-A-08-208, in which a hydroxyl-containing vinyl monomer represented by the following general formula (A) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule. Vinyl urethane compounds containing the above polymerizable vinyl groups are exemplified. CH ₂ ＣC (R) COOCH ₂ CH (R ′) OH (A) (where R and R ′ represent H or CH ₃ ). Further, as described in JP-A-51-37193. Urethane acrylates, JP-A-48-64183
No., JP-B-49-43191, JP-B-52-3049
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in Japanese Patent Publication No. 0 are mentioned. Furthermore, the Journal of the Adhesion Society of Japan vol.20, No. 7, pages 300 to 308 (19
(1984) as photocurable monomers and oligomers can also be used. In the present invention, these monomers may be used in a chemical form such as a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

The amount of all the polymerizable group-containing compounds used is usually 1 to 99.99 based on the weight of all components of the photopolymerizable composition.
%, Preferably 5 to 90.0%, more preferably 10 to 70%
% Amounts are used. (The percentages here are weight percentages).

The sensitizing dye which can be one component of the photopolymerizable composition of the present invention includes a spectral sensitizing dye, and a dye or pigment which absorbs light from a light source and interacts with a photopolymerization initiator. Can be Preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene) and xanthenes (eg, fluorescein, eosin,
Erythrosine, Rhodamine B, Rose Bengal) Cyanines (eg, thiacarbocyanine, oxacarbocyanine) Merocyanines (eg, merocyanine, carbomerocyanine) Thiazines (eg, thionin, methylene blue, toluidine blue) Acridines (eg, acridine orange) , Chloroflavin, acriflavin) Phthalocyanines (eg, phthalocyanine, metal phthalocyanine) Porphyrins (eg, tetraphenylporphyrin, porphyrin substituted with central metal) Chlorophylls (eg, chlorophyll, chlorophyllin, chlorophyll with central metal substitution) Metal complexes, anthraquinones For example, (anthraquinone) squariums, for example, (squarium) and the like.

Examples of more preferred spectral sensitizing dyes or dyes include styryl dyes described in JP-B-37-13034, cationic dyes described in JP-A-62-143044,
Quinoxalinium salts described in JP-B-59-24147;
New methylene blue compounds described in JP-A-64-33104, anthraquinones described in JP-A-64-56767, and benzoxanthene dyes described in JP-A-2-1714. JP-A-2-226148 and JP-A-2-2261
No. 49, pyrrolium salts described in JP-B-40-28499, cyanines described in JP-B-46-43363, benzofuran dyes described in JP-A-2-63053, JP-A-2-85858, JP-A-2-85. -216
No. 154, conjugated ketone dyes described in JP-A-57-10605. Azocinnamylidene derivatives described in JP-B-2-30321, cyanine dyes described in JP-A-1-287105, JP-A-62-31844, and JP-A-62-18744.
No. 31848, Xanthene dyes described in JP-A-62-143043, aminostyryl ketones described in JP-B-59-28325, merocyanine dyes described in JP-B-61-9621, and dyes described in JP-A-2-179463. Merocyanine dyes described in JP-A-2-244050; merocyanine dyes described in JP-B-59-28326; merocyanine dyes described in JP-A-59-89303;
No. 2,690,047, merocyanine dyes, Japanese Patent Application No. Hei 7-
And benzopyran-based dyes described in US Pat.

In addition, the following infrared absorbers (dyes or pigments) are particularly preferably used as sensitizing dyes. Preferred examples of the dye include, for example, JP-A-58-12524.
No. 6, JP-A-59-84356, JP-A-59-202
No. 829, JP-A-60-78787 and the like, and cyanine dyes described in British Patent No. 434,875.

The near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and further, the substituted sensitizer described in US Pat. No. 3,881,924 is used. Arylbenzo (thio) pyrylium salts described in JP-A-57-142645 (U.S. Pat. No. 4,327,169).
No. 5) Trimethine thiapyrylium salts described in JP-A-58-181051, JP-A-58-220143, and JP-A-58-220143.
Nos. 9-41363, 59-84248 and 59-8
No. 4249, No. 59-146063, No. 59-146
No. 061, JP-A-5961
Cyanine dyes described in JP-A-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and Japanese Patent Publication Nos.
Pyrylium compounds described in 19702 are also preferably used.

Also preferred are near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 and phthalocyanine dyes described in EP 916513 A2. It can be mentioned as.

Further, the anionic infrared absorber described in Japanese Patent Application No. 10-79912 can also be suitably used. The anionic infrared absorbing agent refers to a dye that substantially has no anionic structure in the mother nucleus of a dye that absorbs infrared light and has an anionic structure. For example, (c1) an anionic metal complex, (c2) anionic carbon black,
(C3) Anionic phthalocyanine, and (c4) a compound represented by the following general formula 6 and the like. The counter cation of these anionic infrared absorbers is a monovalent cation containing a proton or a polyvalent cation.

[0239]

Embedded image

Here, the (c1) anionic metal complex refers to an anion in which the central metal and the ligand in the complex part which substantially absorbs light become anions.

(C2) The anionic carbon black is
Examples of the substituent include carbon black to which an anionic group such as a sulfonic acid, a carboxylic acid, and a phosphonic acid group is bonded. To introduce these groups into carbon black,
Carbon Black Handbook Third Edition (edited by The Carbon Black Association, April 5, 1995)
As described on page 12, means such as oxidation of carbon black with a predetermined acid may be employed.

(C3) Anionic phthalocyanine refers to an anionic phthalocyanine in which the anion group described in (c2) above is bonded as a substituent to the phthalocyanine skeleton to form an anion as a whole.

Next, the compound (c4) represented by the general formula 6 will be described in detail. Wherein in formula 6, G _a ^-
Represents an anionic substituent, G _b represents a neutral substituent. X ^{m +} represents a cation having 1 to m valence including a proton, and m represents an integer of 1 to 6. M represents a conjugated chain,
This conjugated chain M may have a substituent or a ring structure. The conjugated chain M can be represented by the following formula.

[0244]

Embedded image

In the above formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group,
It represents an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group, and these may be linked to each other to form a ring structure. n represents an integer of 1 to 8.

Further, cationic infrared absorbers and nonionic infrared absorbers can also be preferably used.

Other dyes include commercially available dyes and, for example, “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, published in 1970).
And the like can be used. Specifically, dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, diimmonium dyes, aminium dyes, squalilium dyes, and metal thiolate complexes Is mentioned.

As other sensitizing dyes, commercially available pigments and Color Index (CI) Handbook, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association, 1977)
Annual Publication), “Latest Pigment Application Technology” (CMC Publishing, 1986)
Pigments described in "Printing Ink Technology", CMC Publishing, 1984). For example, the types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bound dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments And quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like. Preferred among these pigments is carbon black.

These pigments may be used without being subjected to a surface treatment, or may be used after being subjected to a surface treatment. Examples of the surface treatment include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface. Can be considered. The surface treatment method is described in "Properties and Applications of Metallic Soaps" (Koshobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably from 0.01 μm to 10 μm, more preferably from 0.05 μm to 1 μm, particularly preferably from 0.1 μm to 1 μm. When the particle size of the pigment is less than 0.01 μm, the dispersion is not preferred in terms of stability in the coating solution for the image recording layer, and when it exceeds 10 μm, the uniformity of the image recording layer is not preferred.

As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 1
986).

More preferred examples of the sensitizing dye in the present invention include the merocyanine dye described in JP-B-61-9621, the merocyanine dye described in JP-A-2-179463, and the merocyanine described in JP-A-2-244050. Dyes, merocyanine dyes described in JP-B-59-28326, merocyanine dyes described in JP-A-59-89303, merocyanine dyes described in Japanese Patent Application No. 6-269047, and benzopyran-based dyes described in Japanese Patent Application No. 7-164585 are disclosed. Can be mentioned. And the above-mentioned JP-A-11-2
The infrared absorber described in No. 09001 can be mentioned. The sensitizing dye in the present invention is also preferably used alone or in combination of two or more. Further, a known compound having an action of further improving sensitivity or suppressing polymerization inhibition by oxygen may be added to the photopolymerizable composition of the present invention as a cosensitizer.

Examples of such co-sensitizers include amines such as those described in MR Sander et al., Journal of Polymer Soc.
Society, Vol. 10, p. 3173 (1972);
No. 20189, JP-A-51-82102, JP-A-52
-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 3382
No. 5 and the like, and specific examples include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

Other examples of the co-sensitizer include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, and JP-A-5-142772; No. 75643, specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, and the like. Is raised.

Another example is an amino acid compound (eg, N-phenylglycine, etc.), Japanese Patent Publication No. 48-429.
No. 65, organometallic compounds (eg, tributyltin acetate, etc.), hydrogen donors described in JP-B-55-34414, and sulfur compounds described in JP-A-5-91089 (eg,
Trithiane, etc.), phosphorus compounds described in Japanese Patent Application No. 5-32147 (diethyl phosphite, etc.), and Japanese Patent Application No. 6-1916.
No. 05, Si-H and Ge-H compounds.

The photopolymerizable composition of the present invention preferably contains a linear organic high molecular polymer as a binder. Such a “linear organic high molecular polymer” includes
Any linear organic high molecular polymer having compatibility with the photopolymerizable ethylenically unsaturated compound may be used. Preferably, a water- or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic high molecular polymer is appropriately selected and used depending on whether water, weakly alkaline water or an organic solvent is used as a developer as well as a film forming agent of the composition. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such a linear organic high molecular polymer include an addition polymer having a carboxylic acid group in a side chain, for example, Japanese Unexamined Patent Publication No.
-44615, JP-B-54-34327, JP-B-5
Nos. 8-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048, that is, methacrylic acid copolymers, There are acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer and the like. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate /
(Meth) acrylic acid / if necessary, other addition-polymerizable vinyl monomers] copolymer is preferable. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble polyamide or 2,2
Polyethers of -bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.

Any of these linear organic high molecular weight polymers can be incorporated into the entire composition. However, if the amount exceeds 90% by weight based on the weight of all components of the composition, no favorable result is obtained in terms of the strength of the formed image and the like. Preferably it is 30 to 85% by weight. The weight ratio of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer is preferably in the range of 1/9 to 7/3. A more preferred range is 3/7 to 5/5.

Polymerization Inhibitor In the present invention, unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond which can be polymerized during the production or storage of the photopolymerizable composition in addition to the above basic components is prevented. For this purpose, it is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p
-Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4- Methyl-
6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, and the like. The amount of the thermal polymerization inhibitor added is about 0.01 to the weight of the whole composition.
% By weight to about 5% by weight is preferred. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. Good. The amount of the higher fatty acid derivative to be added is about 0.5% by weight of the total composition.
About 10% by weight is preferred.

Colorant, etc. Further, a dye or pigment may be added for the purpose of coloring the photosensitive layer. This makes it possible to improve the so-called plate inspection, such as the visibility of the printing plate after plate making and the suitability for an image density measuring device. As many colorants, pigments are particularly preferable because many dyes lower the sensitivity of the photopolymerizable photosensitive layer. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of the dye or pigment added is preferably about 0.5% to about 5% by weight of the total composition.

Other additives In order to improve the physical properties of the cured film, known additives such as inorganic fillers, other plasticizers, and oil-sensitizing agents capable of improving the ink adhesion on the surface of the photosensitive layer are added. May be added.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. A binder was used. In this case, it can be added in an amount of 10% by weight or less based on the total weight of the compound having an ethylenically unsaturated double bond and the binder.

Further, a UV initiator, a thermal crosslinking agent and the like can be added to enhance the effect of heating and exposure after development for the purpose of improving the film strength (printing durability) described later.

In addition, additives for improving the adhesion between the photosensitive layer and the support, and improving the development removability of the unexposed photosensitive layer,
It is possible to provide an intermediate layer. For example, by adding or undercoating a compound having a relatively strong interaction with the substrate, such as a compound having a diazonium structure or a phosphone compound, the adhesion can be improved and the printing durability can be increased. Addition of an acid or a hydrophilic polymer such as polysulfonic acid or undercoating improves the developability of the non-image area and improves the stainability.

When coating the photopolymerizable composition of the present invention on a support, it is used after dissolving it in various organic solvents.
As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxy Ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N N- dimethylformamide, dimethyl sulfoxide, .gamma.-butyrolactone, methyl lactate and ethyl lactate. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 2 to 50% by weight.

The amount of the photosensitive layer coated on the support mainly affects the sensitivity and developability of the photosensitive layer, and the strength and printing durability of the exposed film, and it is desirable to appropriately select the amount according to the application. If the coating amount is too small, the printing durability will be insufficient. On the other hand, if the amount is too large, the sensitivity is lowered, the exposure takes time, and the developing process requires a longer time, which is not preferable. As is the principal object lithographic printing plate for scan exposure of the present invention, the coating amount in the range of about 0.1 g / m ² ~ about 10 g / m ² in weight after drying is suitable. More preferably 0.5 to
It is 5 g / m ² .

[Support] In order to obtain a lithographic printing plate, which is one of the main objects of the present invention, it is desirable to provide the photosensitive layer on a support having a hydrophilic surface. As the hydrophilic support, a conventionally known hydrophilic support used for a lithographic printing plate can be used without limitation. The support used is preferably a dimensionally stable plate-like material, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc) , Copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.),
Such metals include paper or plastic films or the like on which the metal is laminated or vapor-deposited, and imparting hydrophilicity to these surfaces, if necessary, and improving the strength thereof, by using known physical or chemical materials suitable for the purpose. May be applied.

Particularly preferred examples of the support include paper, polyester film and aluminum plate. Among them, the dimensional stability is good, the cost is relatively low, and the hydrophilicity and strength are excellent by the surface treatment as required. Aluminum plates that can provide a surface are particularly preferred. Further, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Aluminum which is particularly preferred in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.2 mm to 0.4 mm.
mm to 0.3 mm.

In the case of a support having a metal surface, particularly an aluminum surface, a roughening (graining) treatment, an immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodic oxidation Preferably, a surface treatment such as a treatment is performed.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically roughening the surface. Is selectively dissolved. As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, a buffing method and a polishing method can be used. In addition, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in an electrolytic solution such as hydrochloric acid or nitric acid. Further, a method combining both of them can be used as disclosed in JP-A-54-63902. Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove the rolling oil on the surface.

Further, an aluminum plate which has been roughened and then immersed in an aqueous solution of sodium silicate can be preferably used. As described in JP-B-47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is performed, for example, in an electrolytic solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or an aqueous solution or a non-aqueous solution of a salt thereof alone or in combination of two or more. This is performed by flowing a current using an aluminum plate as an anode.

Also, silicate electrodeposition as described in US Pat. No. 3,658,662 is effective.

Further, a support provided with electrolytic grains as disclosed in JP-B-46-27481, JP-A-52-58602, and JP-A-52-30503, the anodizing treatment and sodium silicate Surface treatments that combine treatments are also useful.

Further, those obtained by sequentially performing mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.

After these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, and water-soluble metal salts (eg, zinc borate) ) Or those undercoated with a yellow dye, an amine salt or the like are also suitable.

Further, a sol-gel processed substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in Japanese Patent Application No. 5-304358 is also preferably used.

As another preferred example, there can be mentioned a support in which a water-resistant hydrophilic layer is provided as a surface layer on an arbitrary support. As such a surface layer, for example, US3
No. 055295, a layer composed of an inorganic pigment and a binder described in JP-A-56-13168, a hydrophilic swelling layer described in JP-A-9-80744, a titanium oxide and a polyvinyl oxide described in JP-A-8-507727. A sol-gel film made of alcohol or silicic acid can be used.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon and to adhere the photosensitive layer. This is performed for the purpose of improving the performance.

[Protective Layer] In the present invention, in the lithographic printing plate for scanning exposure, a protective layer can be further provided on the layer of the photopolymerizable composition since the exposure is usually performed in the air. The protective layer prevents low-molecular compounds such as basic substances present in the atmosphere, which inhibit an image forming reaction caused by exposure in the photosensitive layer, from being mixed into the photosensitive layer, and enables exposure in the atmosphere. Therefore, the property desired for such a protective layer is that the low molecular compound has low permeability, and further, does not substantially inhibit the transmission of light used for exposure, has excellent adhesion to the photosensitive layer, and Desirably, it can be easily removed in the developing step after exposure. Such a device for the protective layer has been conventionally devised, and is disclosed in US Pat. No. 3,458,31.
No. 1 and JP-A-55-49729. As a material that can be used for the protective layer, for example,
It is preferable to use a water-soluble polymer compound having excellent crystallinity, and specifically, water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, acidic celluloses, gelatin, gum arabic, and polyacrylic acid are known. However, among these, use of polyvinyl alcohol as a main component gives the best results in terms of basic characteristics such as oxygen barrier property and development removal property. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, or an acetal as long as it contains an unsubstituted vinyl alcohol unit for obtaining necessary oxygen barrier properties and water solubility. Similarly, a part thereof may have another copolymer component. As a specific example of polyvinyl alcohol, 71 to 100 mol% is hydrolyzed,
Those having a weight average molecular weight in the range of 300 to 2400 can be mentioned. Specifically, Kuraray's PVA-105, PVA-110, and PVA-11
7, PVA-117H, PVA-120, PVA-12
4, PVA-124H, PVA-CS, PVA-CS
T, PVA-HC, PVA-203, PVA-204,
PVA-205, PVA-210, PVA-217, P
VA-220, PVA-224, PVA-217EE,
PVA-217E, PVA-220E, PVA-224
E, PVA-405, PVA-420, PVA-61
3, L-8 and the like.

The components of the protective layer (selection of PVA, use of additives), coating amount, etc. are selected in consideration of fogging properties, adhesion and scratch resistance in addition to low-molecular substance blocking properties and development removability. .
Generally, the higher the hydrolysis rate of the PVA used (the higher the content of unsubstituted vinyl alcohol units in the protective layer) and the thicker the film thickness, the higher the barrier properties of low molecular substances, which is advantageous in terms of sensitivity. . However, if the low-molecular substance blocking property is extremely increased, an unnecessary polymerization reaction occurs during production or raw storage,
Further, at the time of image exposure, there is a problem that unnecessary fogging and thickening of image lines occur. Further, the adhesion to the image area and the scratch resistance are also extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on a lipophilic polymer layer, film peeling due to insufficient adhesive strength tends to occur. On the other hand, various proposals have been made to improve the adhesiveness between these two layers. For example, U.S. Pat. No. 2,925,501 and U.S. Pat. No. 4,456,397 disclose an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer mixed in a hydrophilic polymer mainly composed of polyvinyl alcohol at 20 to 60% by weight. It is described that sufficient adhesiveness can be obtained by laminating on a polymer layer. Any of these known techniques can be applied to the protective layer in the present invention. Regarding the method of applying such a protective layer, for example, US Pat.
458, 311 and JP-A-55-49729.

Further, other functions can be imparted to the protective layer. For example, when a laser beam is used as a light source, the photosensitive composition may have excellent photosensitivity at the wavelength of the light source, but may not want to be exposed at other wavelengths. For example, if the light source is in the infrared region of 750 nm or more, the light source can be used substantially in a bright room, but in practice, it may be exposed to short-wave light such as light from a fluorescent lamp. In this case, it is preferable to add a colorant (a water-soluble dye or the like) which is excellent in light transmittance of the light source and can efficiently absorb light having a wavelength of less than 700 nm. As another example, the light source is 45
If it is in the ultraviolet region of 0 nm or less, it can be used substantially under safelight. But in fact, 50
It may be exposed to visible light of 0 nm or more. In this case, the addition of a colorant (such as a water-soluble dye), which is excellent in light transmittance of the light source and can efficiently absorb light of 500 nm or more, further enhances safe light suitability without lowering sensitivity. be able to.

When a photosensitive material using the photopolymerizable composition of the present invention is used as an image forming material, usually, after image exposure, an unexposed portion of the photosensitive layer is removed with a developing solution to obtain an image. . Preferred developers when these photopolymerizable compositions are used for preparing a lithographic printing plate are JP-B-57-74.
No. 27, such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate and tertiary phosphorus. Ammonium acid,
Aqueous solutions of inorganic alkali agents such as ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia and organic alkali agents such as monoethanolamine or diethanolamine are suitable. The alkaline solution is added so that the concentration of the alkaline solution is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Further, such an alkaline aqueous solution includes:
If necessary, a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol can be contained. For example, those described in U.S. Pat. Nos. 3,375,171 and 3,615,480 can be mentioned.

Further, JP-A-50-26601, 5
8-54341, JP-B-56-39464, 56
The developing solutions described in JP-A-42860 are also excellent.

In addition, as a plate-making process of a lithographic printing plate precursor, which is a preferable use of the photopolymerizable composition of the present invention, if necessary, before or during exposure, or between exposure and development,
The entire surface may be heated. By such heating, the image forming reaction in the photosensitive layer is promoted, and the sensitivity and printing durability are improved,
Advantages such as stabilization of sensitivity may result. Furthermore, for the purpose of improving image strength and printing durability,
It is also effective to perform post-surface heating or overall surface exposure. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. If the temperature is too high, there arises a problem that a non-image portion is covered. Very strong conditions are used for heating after development. Usually, it is in the range of 200 to 500 ° C. If the temperature is too low, a sufficient image strengthening effect cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area occur. Known methods can be used for the exposure method of the scanning exposure planographic printing plate according to the present invention without any limitation. A laser is preferable as the light source.
As the available laser light source having a wavelength of 450 nm, the following can be used.

As a gas laser, an Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), a Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), He-
Cd laser (441nm, 325nm, 1mW ~ 100m
W), a combination of Nd: YAG (YVO ₄ ) and SHG crystal × 2 times (355 nm, 5 mW to 1
W), Cr: Combination of LiSAF and SHG crystal (4
30nm, 10mW), KNbO as a semiconductor laser system
_3. Ring resonator (430 nm, 30 mW), combination of waveguide type wavelength conversion element and AlGaAs or InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), combination of waveguide type wavelength conversion element and AlGaInP, AlGaAs semiconductor (300 nm to 350nm, 5mW ~ 100mW),
AlGaInN (350 nm to 450 nm, 5 mW to 30 mW) In addition, an N ₂ laser (337 n
m, pulse 0.1 to 10 mJ), XeF (351 nm, pulse 10 to 250 mJ)

In particular, among these, an AlGaInN semiconductor laser (commercially available InGaN semiconductor laser 400 to 410 n
m, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost.

Other available light sources of 450 nm to 700 nm include Ar + laser- (488 nm), YAG
-SHG laser (532 nm), He-Ne laser (633 nm), He-Cd laser, red semiconductor laser (650-690 nm), and 700 nm-120
A semiconductor laser (800
850 nm), Nd-YAG laser (1064 nm)
Can be suitably used.

In addition, ultra-high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, ultraviolet laser lamps (ArF excimer laser, KrF excimer laser, etc.), and radiation as electron X-rays, X-rays, ion beams, far-infrared rays and the like can be used, but the above-mentioned laser light source having a wavelength of 350 nm or more (preferably 1200 nm or less) is particularly preferable because of its low cost.

The exposure mechanism may be any of an internal drum type, an external drum type, a flat bed type and the like. The photosensitive layer component of the present invention can be made soluble in neutral water or weakly alkaline water by using a highly water-soluble one.However, a lithographic printing plate having such a configuration can be used on a printing press. After loading, a system such as exposure-development can be performed on the machine.

The application of the photopolymerizable composition according to the present invention is not limited to a lithographic printing plate for scanning exposure, and is widely applicable to a photocurable resin. For example, when applied to a liquid photopolymerizable composition used in combination with a cationic polymerizable compound as needed, a highly sensitive stereolithographic material can be obtained. In addition, a hologram material can be formed by utilizing a change in refractive index due to photopolymerization. It can be applied to various transfer materials (peeling-sensitive material, toner-developing material, etc.) by utilizing the change in surface tackiness accompanying photopolymerization. It can also be applied to light curing of microcapsules. It can also be applied to the manufacture of electronic materials such as photoresists, and photocurable resin materials such as inks, paints, and adhesives.

[0292]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.

<Synthesis of Photopolymerization Initiator Having Structure of General Formula (I)><Synthesis Example 1: Compound A-2> Methyl 2- (bromomethyl) acrylate (Aldrich Co., Ltd.) (0.
1 mol), A-2a (0.1 mol) having the following structure, acetone (100 ml), triethylamine (0.1 mol) were added, and the mixture was reacted at room temperature for 3 hours.
Crystals precipitate when poured into 0 ml. After filtration and washing of the crude crystals with methanol, compound A-2 was obtained in a yield of 85%. The structure of the compound was confirmed by NMR, MASS, and IR.

<Synthesis Example 2: Compound A-9> Methyl 2- (bromomethyl) acrylate (Aldrich) (0.1 mol) was placed in a flask, and A-9a (0.1
mol) and acetone (100 ml), then triethylamine (0.1 mol), and reacted at room temperature for 3 hours. After filtration and washing of the crude crystals with methanol, compound A-9 was obtained at a yield of 80%.
Was obtained. The structure of the compound was confirmed by NMR, MASS, and IR.

<Synthesis Example 3: Compound A-18> Methyl 2- (bromomethyl) acrylate (manufactured by Aldrich) (0.1 mol) in a flask, A-18a having the following structure
(0.1 mol), acetone (100 ml), and then triethylamine (0.1 mol).
After the reaction for a period of time, the crystals are precipitated when poured into 200 ml of water. After filtration and washing of the crude crystals with methanol, compound A-18 was obtained in a yield of 60%. The structure of the compound is NMR, MA
Confirmed by SS and IR.

<Synthesis Example 4: Compound B-32> Compound B-32b (0.1 mol) having the following structure, acetone (100 ml), pyridine (0.1 mol), DM
AP (4-dimethylaminopyridine) (0.01 mol
Insert l). Next, 2- (acetoxymethyl) acrylic acid chloride (0.1 mol) is added dropwise over 30 minutes under ice-cooling, and the mixture is returned to room temperature and stirred for 3 hours. After the reaction, 200 ml of water
Crystallized when put in. After filtration and washing of the crude crystals with methanol, compound B-32 was obtained in a yield of 65%. The structure of the compound was confirmed by NMR, MASS, and IR.

<Synthesis Example 5: Compound C-34> Dicyclohexylcarbodiimide (0.1 mol: D
CC), C-34c (0.1 mol) having the following structure, and chloroform (100 ml), and then ethyl 2- (hydroxymethyl) acrylate (Aldrich) (0.
1 mol), reacted at room temperature for 5 hours, filtered through a silica gel column, and the filtrate was concentrated under reduced pressure.
Crystals precipitate when poured into a mixture of 200 ml of water and 200 ml of water. Filtration and washing of the crude crystals with methanol gave Compound C-34.
Was obtained with a yield of 70%. The structure of the compound is NMR, M
Confirmed by ASS and IR.

<Synthesis Example 6: Compound F-37> Methyl 2- (bromomethyl) acrylate (manufactured by Aldrich) (0.1 mol) in a flask, F-37f having the following structure
(0.1 mol), acetone (100 ml), and then triethylamine (0.1 mol).
After the reaction for a period of time, the crystals are precipitated when poured into 200 ml of water. After filtration and washing of the crude crystals with methanol, compound F-37 was obtained in a yield of 70%. The structure of the compound is NMR, MA
Confirmed by SS and IR.

[0299]

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As described above, all the compounds shown in the specific examples can be synthesized.

<Example 1 of photopolymerizable composition> (Preparation of support) An aluminum plate having a thickness of 0.3 mm was
After etching by immersion in 60% by weight of sodium hydroxide at 60 ° C for 25 seconds, it was washed with running water, neutralized and washed with 20% by weight nitric acid, and then washed with water. This was subjected to electrolytic surface roughening treatment in a 1% by weight nitric acid aqueous solution using a sinusoidal alternating waveform current at an anode electricity of 300 coulomb / dm ² . Followed by 1
After immersion in a 30% by weight aqueous solution of sulfuric acid at 40 ° C. for 5 seconds, immersion in a 30% by weight aqueous solution of sulfuric acid and desmutting at 60 ° C. for 40 seconds, a current density of 2 A / dm ² in a 20% by weight aqueous solution of sulfuric acid 1. The thickness of the anodic oxide film is 2.
Anodizing treatment was performed for 2 minutes so as to obtain 7 g / m ² . The surface roughness was measured to be 0.3 μm (JIS B06
Ra display of 01).

The following sol-gel reaction solution was applied to the back surface of the substrate thus treated with a bar coater,
The support was then provided with a back coat layer having an applied amount of 70 mg / m ² after drying.

Sol-gel reaction liquid Tetraethyl silicate 50 parts by weight Water 20 parts by weight Methanol 15 parts by weight Phosphoric acid 0.05 parts by weight

When the above components were mixed and stirred, heat generation started in about 5 minutes. After reacting for 60 minutes, the following solution was added to prepare a back coat coating solution.

Pyrogallol formaldehyde condensation resin (molecular weight: 2000) 4 parts by weight Dimethyl phthalate 5 parts by weight Fluorinated surfactant (N-butyl perfluorooctane 0.7 parts by weight) Sulfonamidoethyl acrylate / polyoxyethylene acrylate copolymer: molecular weight 2 10,000) Methanol silica sol (manufactured by Nissan Chemical Industries, Ltd., methanol 30% by weight) 50 parts by weight Methanol 800 parts by weight

(Preparation of photosensitive layer) A photopolymerizable composition having the following composition was applied on the aluminum plate treated in this manner so that the dry coating amount was 1.5 g / m ² ,
After drying for a minute, a photosensitive layer was formed. (Sensitive layer forming solution) 0.2 g of the present invention or comparative photoinitiator [X] in Table A below 0.2 g of sensitizing dye [Y] in Table A below 2.0 g of polymer binder [Z] in Table A below 2.0 g of the polymerizable compound [R] in the following table A 0.4 g of the additive [S] in the following table A 0.03 g of a fluorinated surfactant (Mechanical Fac F-177: manufactured by Dainippon Ink and Chemicals, Inc.) Thermal polymerization inhibitor N-nitrosophenylhydroxylamine aluminum salt 0.01 g Pigment dispersion 2.0 g Composition of pigment dispersion Composition: Pigment Blue 15: 6 15 parts by weight Allyl methacrylate / methacrylic acid copolymer 10 parts by weight (copolymerization) Molar ratio 83/17) cyclohexanone 15 parts by weight methoxypropyl acetate 20 parts by weight propylene glycol monomethyl ether 40 parts by weight methyl ethyl ketone 20 g propylene glycol mono Chirueteru 20g

(Adjustment of Protective Layer) A part of the above-mentioned photosensitive layer (shown in Table A below) had 3% by weight of polyvinyl alcohol (98 mol% saponification degree, polymerization degree 550) on the photosensitive layer.
Was applied so that the dry coating weight was 2 g / m ^2, and dried at 100 ° C. for 2 minutes.

(Evaluation of Sensitivity) The sensitivity of the thus obtained photosensitive material was evaluated using different light sources depending on the exposure wavelength. For example, as a wavelength, a semiconductor laser of 400 nm, an FD-YAG laser of 532 nm,
Exposure was performed in the air using an 830 nm semiconductor laser. Immersed in a developer having the following composition at 25 ° C. for 10 seconds,
After the development, the sensitivity under each exposure condition was calculated in mJ / cm ² from the minimum exposure amount at which an image could be formed. The smaller the value, the higher the sensitivity. However, if the wavelength of the light source is different, the amount of energy per photon is different. Therefore, even if it is simply considered, the shorter the wavelength is, the more sensitive it is to be able to sensitize even if the above exposure amount is smaller, and the shorter wavelength is more sensitive. Becomes Therefore, Table-B is meaningless for comparing the sensitivity under different exposure conditions, and is merely to see the difference between the example and the comparative example under the same exposure condition. The results are shown in Table-B below.
Shown in (Composition of developer) DP-4 (Fuji Photo Film Co., Ltd.) 65.0 g Water 880.0 g Lipomin LA (20% aqueous solution, manufactured by Lion Corporation) 50.0 g

(Evaluation of Storage Stability) The above-mentioned photosensitive material before laser exposure was left under high-temperature conditions (60 ° C.) for 3 days, and then the photosensitive material after storage was subjected to laser exposure in the same manner as described above to perform recording. The energy amount was calculated, and the energy ratio before and after high-temperature storage (energy after high-temperature storage / energy before high-temperature storage) was determined. It is preferable in terms of production that the energy ratio is 1.1 or less, and it can be said that storage stability is also good. This evaluation result is also shown in Table-B below.

[0310]

[Table 3]

[0311]

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[0312]

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[0313]

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[0314]

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[0315]

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[0316]

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[0317]

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[0318]

[Table 4]

According to Table-B, the light-sensitive material of the present invention has high sensitivity and good storage stability.

[0320]

According to the present invention, a photo-polymerizable composition which can achieve both high sensitivity and excellent storage stability in a photo-radical polymerization composition which is considered to be the most sensitive and promising among image forming techniques. It is to provide things. Especially ultraviolet light,
It is possible to provide a photopolymerizable composition suitable as a plate material for a lithographic printing plate capable of making a plate directly from digital data of a computer or the like by recording using a solid-state laser and a semiconductor laser beam emitting visible light and infrared light. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 230/02 C08F 230/02 236/20 236/20 G03F 7/004 503 G03F 7/004 503Z 7/031 7/031 F term (reference) 2H025 AA01 AA02 AA11 AA12 AB03 AB14 AC01 AC06 AC08 AD01 BC13 BC42 BC83 CA00 CA41 FA10 2H114 AA04 AA23 BA01 BA10 DA03 DA21 DA32 DA34 DA39 DA41 DA52 DA53 EA01 EA08 EA10 FA18 QA03 QA03 QA03 QA03 QA03 QA17 QA18 QA19 QA20 QA22 QA23 QA24 QA25 QA26 QA32. AN04P AN05P AN13P AN14P AP01P AP02P BA02P BA02Q BA03P BA03Q BA05P BA11P BA12P BA15P BA27P BA28P BA31P BA32P BA34P BA46P BA51P BA53P BA54P BA55P BA56P BA58P BA62P BA63P BA87P BA95P BB01P BB03P BB05P BB07P BC04Q BC42P BC43P BC43Q BC45Q BC49P BC53P BC65P BC69P BC73P BC75P BC75Q BC79P CA04 FA03 JA38

Claims (1)

[Claims] 1. A photopolymerizable composition comprising a photopolymerization initiator having at least one structure represented by the following general formula (I) and a polymerizable compound having an unsaturated double bond. Embedded image (In the general formula (I), X ¹ and X ² each independently represent ^a heteroatom or a halogen atom. R ^a and R ^b each independently represent
Represents a hydrogen atom, a halogen atom, a cyano group or an organic residue. Further, X ¹ and X ² , R ^a and R ^b , or X ¹ and R ^a or R ^b may be bonded to each other to form a cyclic structure. )