JP2001318462A - Photopolymerizable composition and photopolymerizable image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition having high sensitivity to laser beam in the range from the visible region to infrared region and excellent in solubility in a coating solvent and to provide a photopolymerizable image forming material. SOLUTION: The photopolymerizable composition contains (A) an ethylenically unsaturated compound, (B) a sub-phthalocyanine dye containing boron as the central element represented by formula (1) [where R is alkyl which may have a substituent, phenyl which may have a substituent or halogen, rings U, V and W are each a condensed aromatic ring or a condensed aromatic heterocycle formed in the two β-positions of each pyrrole ring and each of the aromatic ring and the condensed aromatic heterocycle may have a substituent] and (C) a photopolymerization initiator. The photopolymerizable image forming material is obtained by forming a layer of the photopolymerizable composition on the surface of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lithographic printing plate, a printed circuit board, a large scale integrated circuit (LSI), a thin transistor (TFT), a liquid crystal display (LCD), a plasma display (PDP), and a semiconductor package (TAB).
Photopolymerizable composition and light that are used for fine processing such as holography, etc., and have high sensitivity to laser light in the visible region to the infrared region, and are particularly suitable for direct drawing by a semiconductor laser, a YAG laser, or the like. The present invention relates to a polymerizable image forming material.

[0002]

2. Description of the Related Art Conventionally, as a method for forming an image by exposing a photopolymerizable composition, for example, a photopolymerizable composition comprising an ethylenically unsaturated compound and a photopolymerization initiator, or further comprising a polymer binder is used. A method for forming a cured relief image by forming a layer on the support surface, polymerizing and curing the ethylenically unsaturated compound in the exposed portion by image exposure, and then dissolving and removing the non-exposed portion is widely used. However, in recent years, with the remarkable advancement of laser light, it has become easy to use laser light in the visible region to the infrared region, and image forming methods using such laser light as an exposure light source, especially computer digital information Attention has been paid to direct drawing, which directly obtains an image from a computer.

[0003] Various photopolymerization initiator systems having sensitivity to laser light in the visible region to the infrared region have been proposed. For example, a photopolymerizable composition comprising a combination of a cationic dye and an organic boron complex has been proposed. (For example, see Japanese Patent Application Laid-Open No. 5-2
No. 16227, JP-A-5-247110, JP-A-5-247110
JP-A-265204, JP-A-6-59450, JP-A-6-59450
See each publication such as 332175. ), A photopolymerizable composition comprising a combination of a photothermal conversion element, an onium salt and a radical generator (for example, JP-A-9-34110, JP-A-9-13)
See each publication such as 4009. ).

[0004] However, these photopolymerizable compositions proposed to be sensitive to laser light are not always sufficient in sensitivity, and even when high sensitivity can be obtained, the sensitizing dye is not soluble in a solvent. There were also problems such as poor solubility and restrictions on the conditions for applying the composition solution to the support surface.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and accordingly, the present invention has high sensitivity to laser light in the visible region to the infrared region, and Another object of the present invention is to provide a photopolymerizable composition and a photopolymerizable image-forming material having excellent solubility in a coating solvent.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a photopolymerizable compound containing an ethylenically unsaturated compound, a specific subphthalocyanine dye and a photopolymerization initiator is contained. The present invention has been accomplished by finding that the composition can achieve the above object, that is, the present invention provides a photopolymerization comprising the following components (A), (B), and (C): The present invention provides a photopolymerizable image forming material comprising a photopolymerizable composition and a layer of the photopolymerizable composition formed on the surface of a support.

(A) Ethylenically unsaturated compounds (B) Subphthalocyanine dyes containing boron as a central element and represented by the following general formula (I)

[0008]

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[In the formula (I), R represents an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a halogen atom. Each ring W independently represents a condensed aromatic ring or a condensed aromatic heterocyclic ring formed at the two β-positions of the pyrrole ring, and the aromatic ring or the aromatic heterocyclic ring has a substituent. You may. ]

(C) Photopolymerization initiator

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The ethylenically unsaturated compound (A) constituting the photopolymerizable composition of the present invention will be described later (C) when the photopolymerizable composition is irradiated with actinic rays. )
It is a compound having a radically polymerizable ethylenically unsaturated double bond, which undergoes addition polymerization by the action of the photopolymerization initiator of the component and optionally crosslinks and cures, and is polymerizable and crosslinkable.
It is preferable to use a compound having two or more such double bonds in the molecule, in view of the fact that the difference in solubility between the exposed part and the unexposed part in the developing solution can be enlarged. Acrylate compounds in which the bond is derived from a (meth) acryloyloxy group are preferred. Here, "(meta)
“Acrylic” shall mean acryl and methacryl.

As the acrylate compound, typically, ester (meth) acrylates of (meth) acrylic acid and polyhydroxy compound, and (meth) acrylic acid or hydroxy (meth) acrylate compound and polyepoxy compound Epoxy (meth) acrylates, urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound, and
(Meth) acryloyloxy group-containing phosphates and the like.

Specific examples of the ester (meth) acrylates include (meth) acrylic acid, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol and trimethylene glycol. , Tetramethylene glycol, neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylolethane, tetramethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene oxide A reaction product with an aliphatic polyhydroxy compound such as an adduct, specifically, for example, ethylene glycol di (meth) acrylate Over DOO, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Hexamethylene glycol di (meth) acrylate, nonamethylene glycol di (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolethanetri (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropanetri ( (Meth) acrylate, trimethylolpropane ethylene oxide added tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide added tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acryle , Dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate Acrylate,
Sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate and the like can be mentioned.

Further, as the ester (meth) acrylates, a reaction product of (meth) acrylic acid with an aromatic polyhydroxy compound such as hydroquinone, resorcinol, pyrogallol, etc., for example, hydroquinone di (meth) acrylate ) Acrylate, resorcinol di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like, and a reaction product of (meth) acrylic acid with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically Examples thereof include di (meth) acrylate and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate.

As the epoxy (meth) acrylates, specifically, for example, (meth) acrylic acid,
Or hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth)
Hydroxy (meth) acrylate compounds such as acrylate and tetramethylolethane tri (meth) acrylate, (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) ) Pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol Aliphatic polyepoxy compounds such as polyglycidyl ether, phenol novolak polyepoxy compounds, brominated phenol novolak Riepokishi compound, (o-, m-,
p-) Aromatic polyepoxy compounds such as cresol novolak polyepoxy compound, bisphenol A polyepoxy compound, bisphenol F polyepoxy compound, sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, etc. And a reaction product thereof with a polyepoxy compound such as a heterocyclic polyepoxy compound.

Examples of the urethane (meth) acrylates include, for example, hydroxy (meth) acrylate compounds as described above, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl Aliphatic polyisocyanates such as ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane Isocyanate, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicyclohepta Alicyclic polyisocyanates such as triisocyanate, p-phenylene diisocyanate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, tris (isocyanate phenyl methane) Reaction products with a polyisocyanate compound such as an aromatic polyisocyanate such as tris (isocyanatephenyl) thiophosphate and a heterocyclic polyisocyanate such as isocyanurate.

Examples of the (meth) acryloyloxy group-containing phosphates include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate,
(Meth) acryloyloxyethylene glycol phosphate and the like.

(B) Constituting the Photopolymerizable Composition of the Invention
The component subphthalocyanine dye is particularly preferably 450 to 13
It efficiently absorbs light having a wavelength from the visible region to the infrared region of 00 nm, transmits the photoexcitation energy to the photopolymerization initiator of the component (C) described below, decomposes the photopolymerization initiator, and (A)
It is a compound having a sensitizing function of generating an active radical that induces polymerization of the ethylenically unsaturated compound as a component.

In the present invention, it is essential that the subphthalocyanine dye has boron as a central element represented by the following general formula (I).

[0020]

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[In the formula (I), R represents an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a halogen atom. Each ring W independently represents a condensed aromatic ring or a condensed aromatic heterocycle formed at the two β-positions of the pyrrole ring, and these aromatic rings and aromatic heterocycles have a substituent. You may. ]

Here, when R is an alkyl group, the number of carbon atoms is usually 1 to 15, preferably 1 to 10, and
Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Among them, in the present invention, a methyl group, an ethyl group, a phenyl group, chlorine and bromine are preferred.

The ring U, ring V and ring W of the condensed aromatic ring formed at the two β-positions of the pyrrole ring include, for example, a benzene ring and a naphthene ring. Examples of the ring include a pyridine ring, a piperazine ring, a thiophene ring and the like, and examples of the substituent thereof include an alkyl group, an alkoxy group, an acyl group, a phenoxy group, an alkylsilyl group, an alkylthio group, a phenylthio group, Examples include an anilino group, an acylamino group, an allyl group, an alkynyl group, an alkenyl group, a halogen atom, and the like, which may further have a substituent. Ring U, ring V, and ring W are preferably any of a benzene ring, a pyridine ring, and a piperazine ring, and rings U, V, and W may be different from each other, but are preferably the same. Also, ring U,
When V and W have a substituent, a C ₁ -C ₁₀ alkyl group;
A phenylthio group and a halogen atom are preferred.

In the present invention, examples of the condensed aromatic ring which may have a substituent include, for example,
Benzene, 3-t-butylbenzene, 4-t-butylbenzene, trimethylsilylbenzene, phenyl-dimethylsilylbenzene, 3,4,5,6-tetrakisphenylthiobenzene, 3,5,6-trifluoro-4-difluoro Methylthiobenzene, 3,5,6-trifluoro-4-methoxyanilinobenzene, 3,5,6-trifluoro-4-dimethoxyanilinobenzene, 3,6-difluoro-4-methoxyanilino-5-methoxy Benzene, naphthalene, pentyloxymethylnaphthalene, pentylnaphthalene, 1,4-dihexylnaphthalene,
1,4-dimethyl-5,8-dihexylnaphthalene, phenylethoxynaphthalene, butoxynaphthalene, octyloxynaphthalene, 6-dodecyloxynaphthalene, phenylpropionylnaphthalene, phenoxynaphthalene, pentylthionaphthalene, phenylthionaphthalene, 6-lauroylaminonaphthalene And the like. Examples of the heteroaromatic ring which may have a substituent include a pyridine ring and a piperazine ring.

As described above, among the subphthalocyanine dyes represented by the general formula (I), those having an absorption maximum (λ _max ) in the wavelength range of 450 to 1300 nm are particularly preferable in the present invention.

These subphthalocyanine dyes are described, for example, in JP-A-60-23451 and JP-A-61-215.
662, JP-A-61-215663 and JP-A-63-163.
270765, JP-A-64-60660, JP-A-1
JP-A-100171, JP-A-1-108264, JP-A-1-108265, JP-A-1-287175, JP-A-2-43269, JP-A-2-138382, JP-A-2-296885, JP-A-3-3 JP-A-31247, JP-A-3-43461, JP-A-3-77840, JP-A-3-1000066, JP-A-3-265664, JP-A-3-265665, JP-A-4-15263, JP-A-4-15264 JP-A-4-15265, JP-A-4-15266, JP-A-4-348168, JP-A-8-120186, JP-A-8-225751, JP-A-8-325468, JP-A-9-202860 JP-A-10-120927, JP-A-10-182959
No., etc., phthalocyanine-based, and used in the synthesis of naphthalocyanine-based compounds, dicyanobenzene having various substituents, or dicyanonaphthalene having various substituents, and trihalogen boron or trialkyl Nagao Kobayashi, Journal of P
orphyrins and Phthalocyanines, 3, 453-467 (1999).

(C) Constituting the Photopolymerizable Composition of the Invention
The photopolymerization initiator of the component is a radical generator that generates an active radical when irradiated with light in the co-presence of the component (B) and the subphthalonine-based dye, and includes, for example, an organic boron complex, Examples thereof include halogenated hydrocarbon derivatives, hexaarylbiimidazole compounds, titanocene compounds, carbonyl compounds, and organic peroxides. In the present invention, organic boron complexes, hexaarylbiimidazole compounds, titanocene compounds, and halogenated Hydrocarbon derivatives are preferred.

Here, specific examples of the halogenated hydrocarbon derivative include, for example, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,
6-bis (trichloromethyl) -s-triazine, 2-
n-propyl-4,6-bis (trichloromethyl) -s
-Triazine, 2- (α, α, β-trichloroethyl)
-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl)
-S-triazine, 2- (p-methoxyphenyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- [1- (p-methoxyphenyl)-
2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4, 6-bis (trichloromethyl)
-S-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4, 6
-Bis (trichloromethyl) -s-triazine, 2,
4,6-tris (dibromomethyl) -s-triazine,
2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl)
-S-triazine compounds having di or tristrihalomethyl such as -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, and preferably s-triazine having a trihalomethyl group Triazine compounds, particularly preferably 4,6-bis (trichloromethyl) -s-triazine compounds having a C _1-15 organic residue at the 2-position.

The hexaarylbiimidazole compound is a dimer of an imidazole compound having three aryl groups and is a compound that generates a radical by exposure to light directly or by interaction with a coexisting sensitizer. As the hexaarylbiimidazole-based compound, for example, hexaarylbiimidazoles described in JP-B-45-37377, JP-A-47-2528, JP-A-54-15529 and the like can be used. And specifically, for example, 2,2′-bis (o
-Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-methoxyphenyl) Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-methylphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ', 5,5'-Tetra (p-ethoxycarbonylphenyl) biimidazole, 2,2'-
Bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-fluorophenyl) biimidazole, 2,
2'-bis (o-bromophenyl) -4,4 ', 5
5′-tetra (p-iodophenyl) biimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′,
5,5′-tetra (p-chloronaphthyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (p-chlorophenyl) biimidazole, 2,2'-bis (o-bromophenyl)-
4,4 ′, 5,5′-tetra (p-chloro-p-methoxyphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o , P
-Dichlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dibromophenyl) biimidazole,
2'-bis (o-bromophenyl) -4,4 ', 5
5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl)-
4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole and the like can be mentioned, and among them, a hexaphenylbiimidazole compound is preferable, and particularly, a 2,2'-position on the imidazole ring is preferable. Preferably, the o-position of the benzene ring is substituted with a halogen. Further, the benzene ring at the 4,4 ′, 5,5 ′ position on the imidazole ring is unsubstituted or substituted with an electron-withdrawing halogen or alkoxycarbonyl. Is preferred.

These hexaarylbiimidazoles can be used in combination with various kinds of biimidazoles, if necessary. Biimidazoles are, for example, Bul
l. Chem. Soc. Japan. 33,565 (1
960) and J.M. Org. Chem. 36 [16] 22
62 (1971).

Specific examples of the titanocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,
4-difluorophenyl), dicyclopentadienyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2 , 3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2,3,4,
5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,4,6-trifluorophenyl), Di (methylcyclopentadienyl) titanium bis (2,
3,5,6-tetrafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,
5,6-pentafluorophenyl), dicyclopentadienyl titanium bis [2,6-difluoro-3- (1
-Pyrrolyl) phenyl] and other titanium-based compounds having a dicyclopentadienyl structure and a biphenyl structure, and a halogen atom is preferably substituted at the o-position of the biphenyl ring. Examples of the carbonyl compound include benzophenone derivatives, acetophenone derivatives, and thioxanthone derivatives. Examples of the organic peroxide include ketone peroxide, diacyl peroxide, hydroperoxide, dialkyl peroxide, and peralkyl peroxide. Oxyketals, alkyl peresters, peroxycarbonates and the like are each mentioned.

Examples of the organic boron complex include an organic boron ammonium complex, an organic boron sulfonium complex or an organic boron oxosulfonium complex, an organic boron iodonium complex, an organic boron phosphonium complex, and an organic boron transition metal coordination complex. However, in the present invention, an organic boron complex represented by the following general formula (II) is particularly preferable.

[0033]

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[In the formula (II), R ¹ , R ² , R ³ and R ⁴
Are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, A good aryl group, an alicyclic group which may have a substituent,
Or substituted indicates also heterocyclic group, they may be linked to each other to form a cyclic structure, X ⁺
Represents a counter cation. ]

Here, the alkyl group and alicyclic group of R ¹ , R ² , R ³ and R ⁴ have 1 to 10 carbon atoms, and the alkenyl group and the alkynyl group have carbon atoms. Those having a number of 1 to 15 are preferable, and those having 6 to 20 carbon atoms are preferable as the aryl group, and a phenyl group is particularly preferable as the aryl group. Examples of the substituent include an alkyl group, an alkoxy group, a carboxy group, an acyloxy group, an alkoxycarbonyl group, a hydroxyl group, an amino group, an alkylamino group, a halogenated alkyl group, and a halogen atom. preferable.

In the formula, ^{three of} R ¹ , R ² , R ³ and R ⁴ are an aryl group which may have a substituent, and one is an alkyl group which may have a substituent. Certain triarylalkyl boron complexes are preferred.

Specific examples of preferred anions in these organoboron complexes include, for example, n-butyl-triphenylboron, n-butyl-tris (p-methylphenyl) boron, n-butyl-tris (2,
4,6-trimethylphenyl) boron anion, n-butyl-tris (p-methoxyphenyl) boron anion, n
-Butyl-tris (m-chlorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron anion, n-butyl-tris (m-fluorophenyl)
Boron anion, n-butyl-tris (p-fluorophenyl) boron, n-butyl-tris (2,6-difluorophenyl) boron, n-butyl-tris (2,4,6-trifluorophenyl) boron Anions,
n-butyl-tris (2,3,4,5,6-pentafluorophenyl) boron anion, n-butyl-tris (m
-Trifluoromethylphenyl) boron anion, n-butyl-tris (3,5-di-trifluoromethylphenyl) boron anion, n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) -boron anion , N-
Hexyl-tris (m-fluorophenyl) boron anion and the like.

Examples of the counter cation include onium compounds such as ammonium cation, phosphonium cation, arsonium cation, stibonium cation, oxonium cation, sulfonium cation, selenonium cation, stannonium cation, and iodonium cation. And a transition metal coordination cation. Among them, an ammonium cation is preferable, and a tetraalkyl (C1 to C10) ammonium cation is particularly preferable.

Among these, particularly preferred organic boron complexes include, for example, compounds having the following structures. In the following examples, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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The photopolymerizable composition of the present invention comprises, as essential components, the ethylenically unsaturated compound as the component (A), the subphthalocyanine dye as the component (B), and the photopolymerization initiator as the component (C). The components (B) and (C) are contained in an amount of 2 to 30 parts by weight of the component (B) and 5 to 40 parts by weight of the component (C) based on 100 parts by weight of the component (A). It is preferable that the amount of the component (B) is 5 to 2 parts by weight.
More preferably, it is 5 parts by weight and 5 to 30 parts by weight of the component (C). When the content ratio of each of the component (B) and the component (C) is less than the above range, the sensitivity tends to be insufficient as the photopolymerizable composition of the present invention. In this case, problems such as loss of uniformity as a composition layer tend to occur.

The photopolymerizable composition of the present invention may further comprise, in addition to the above components, an alkali-soluble resin as a polymer binder (D) component for the purpose of improving coating properties and developability. It is preferably contained in the range of 50 to 400 parts by weight, particularly in the range of 70 to 200 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound as the component (A). Examples include a carboxyl group-containing vinyl resin and a phenolic hydroxyl group-containing resin. Among them, a carboxyl group-containing vinyl resin is preferable in terms of sensitivity.

Specific examples of the carboxyl group-containing vinyl resin include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid and citraconic acid. And styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) Acrylate, N- (meth) acryloyl morpholine, (meth) acrylonitrile,
(Meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, copolymers with vinyl compounds such as vinyl acetate, and the like. The carboxyl group-containing vinyl resin preferably has an acid value of 30 to 250 KOH.mg/g and a weight average molecular weight in terms of polystyrene of 1,000 to 300,000.

Further, as the carboxyl group-containing vinyl resin, those having an ethylenically unsaturated bond in the side chain are preferable. Specifically, for example, allyl glycidyl ether, glycidyl ( (Meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate, monoalkyl monoglycidyl maleate And the like. An aliphatic epoxy group-containing unsaturated compound such as an epoxy compound or an alicyclic epoxy group-containing unsaturated compound such as 3,4-epoxycyclohexylmethyl (meth) acrylate 90 mol%, preferably 30 to 70
Mole% of the reaction product obtained, and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) ) Acrylates, compounds having two or more unsaturated groups such as N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate , A compound having two or more unsaturated groups such as 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) acrylamide, and an unsaturated carboxylic acid such as (meth) acrylic acid or further unsaturated carboxylic acid Ester and the former compound having an unsaturated group 10 to 90 mol%, preferably and the like reaction product obtained by copolymerizing such that about 30 to 80 mol%.

Examples of the phenolic hydroxyl group-containing resin include, for example, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethyl Phenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, 4,
At least one of phenols such as 4'-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, phloroglucinol, etc. is added under an acidic catalyst to formaldehyde, Novolak resin polycondensed with at least one of aldehydes such as formaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, benzaldehyde, and furfural, or ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; polycondensation of the novolak resin In the above, a resol resin polycondensed in the same manner except that an alkaline catalyst is used in place of the acidic catalyst, and, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxys Tylene, dihydroxystyrene,
Trihydroxystyrene, tetrahydroxystyrene,
A radical polymerization initiator comprising one or more hydroxystyrenes such as pentahydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, and 2- (p-hydroxyphenyl) propylene Or a polyvinyl phenol resin polymerized in the presence of a cationic polymerization initiator, and the like, and the phenolic hydroxyl group-containing resin preferably has a weight average molecular weight of 1,500 to 50,000.

The photopolymerizable composition of the present invention may further comprise, in addition to the above components, a hydrogen-donating compound as a polymerization accelerator (E) for the purpose of improving photopolymerization initiation ability.
0.5 to 50 parts by weight per 100 parts by weight of the component,
In particular, it may be contained in the range of 1 to 30 parts by weight, and as the hydrogen donating compound, specifically, for example, 2
-Mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3
-Mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate Group-containing compounds such as N, N-dialkylaminobenzoic acid ester, N-phenylglycine or salts thereof such as ammonium and sodium salts, derivatives such as the above esters, phenylalanine, and salts such as ammonium and sodium salts thereof And amino acids having an aromatic ring, such as derivatives of the above esters, and derivatives thereof.

The photopolymerizable composition of the present invention further comprises:
If necessary, various additives such as hydroquinone, p
-Methoxyphenol, 2,6-di-t-butyl-p-
2 parts by weight or less of a thermal polymerization inhibitor such as cresol, 50 parts by weight or less of a colorant comprising an organic or inorganic dye or pigment, dioctyl phthalate, didodecyl phthalate, tricresyl phosphate, dioctyl adipate, triethylene glycol dicaprylate Etc. plasticizer is 40 parts by weight or less,
5 parts by weight or less of a sensitivity improver such as a tertiary amine or thiol
Triarylmethane, bisarylmethane, xanthene compound, fluoran compound, thiazine compound, and
A dye precursor such as a dye leuco body such as a compound having a lactone, lactam, sultone, or spiropyran structure as a partial skeleton may be added in an amount of 10 parts by weight or less.

The use form of the photopolymerizable composition of the present invention as an image forming material is, for example, applied to a support surface without solvent or after dilution with an appropriate solvent, followed by drying. Or a further layer provided with a protective layer for blocking oxygen, a mode in which droplets are dispersed in a heterogeneous medium and a plurality of types are coated in a multi-layer, a mode in which they are encapsulated in microcapsules and coated on a support The photopolymerizable composition of the present invention is applied to a support surface as a solution in which the composition is dissolved in an appropriate solvent, and then heated and dried to form the photopolymerizable composition on the support surface. A use form such as a planographic printing plate having a layer of the photopolymerizable composition of the invention formed thereon is suitable.

Here, the solvent is not particularly limited as long as it has sufficient solubility for the components used and gives good coating properties. Examples thereof include methyl cellosolve,
Cellosolve solvents such as ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate , Propylene glycol solvents such as dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, Ester solvents such as methyl 3-methoxypropionate, methanol, Ethanol, propanol, butanol, heptanol, hexanol, diacetone alcohol, alcohol solvents such as furfuryl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ketone solvents such as methyl amyl ketone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N
-Highly polar solvents such as -methylpyrrolidone, or a mixed solvent thereof, and further, a mixture of these with an aromatic hydrocarbon. The usage ratio of the solvent is usually in the range of about 1 to 20 times by weight based on the total amount of the photopolymerizable composition.

As the support, aluminum,
Metal plate such as zinc, copper, steel, aluminum, zinc, copper,
Metal plates plated or evaporated with iron, chromium, nickel, etc.
Examples include paper, paper coated with resin, paper to which metal foil such as aluminum is adhered, plastic film, plastic film subjected to hydrophilic treatment, and glass plate. Inside,
Preferable is an aluminum plate, which has been subjected to surface treatment such as electrolytic etching in a hydrochloric acid or nitric acid solution or graining similar to brush polishing, anodizing treatment in a sulfuric acid solution, and if necessary, sealing treatment. Aluminum plate is more preferred. The surface roughness of the support is JIS B0
Average roughness R _a as defined in 601, typically 0.3
The thickness is 1.0 μm, preferably about 0.4 to 0.8 μm.

As the coating method, conventionally known methods, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating and the like can be used. The coating amount varies depending on the application, but as a dry film thickness, usually 0.5 to 10
In the case of a lithographic printing plate, the thickness is 0.5 to 5 μm, and more preferably 1 to 3 μm.
In addition, as a drying temperature at that time, for example, 30 to 150
The drying time is, for example, about 5 seconds to 60 minutes, preferably about 10 seconds to 30 minutes.

Incidentally, a protective layer of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, cellulose or the like is usually provided on the photopolymerizable composition layer in order to prevent a polymerization inhibition effect by oxygen.

The light source for imagewise exposing the photopolymerizable composition layer of the photopolymerizable image forming material of the present invention includes a carbon arc, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp and the like. In addition, laser light sources such as HeNe laser, argon ion laser, YAG laser, HeCd laser, semiconductor laser, ruby laser, and the like,
Preferably, a light source that generates a laser beam in a visible region from 450 to 1300 nm to an infrared region is preferable.
Solid lasers, such as a ruby laser, a YAG laser, and a semiconductor laser, can be mentioned, and a small-sized and long-life semiconductor laser or a YAG laser is particularly preferable. Usually, after scanning and exposure with these light sources, an image is formed by developing with a developer.

Examples of the developer used for developing the photosensitive material obtained by imagewise exposing the photopolymerizable image forming material include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, and sodium hydroxide. Inorganic such as potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium diphosphate, sodium tertiary phosphate, ammonium diphosphate, ammonium tertiary phosphate, sodium borate, potassium borate, ammonium borate Alkali salts, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine Emissions, monoisopropanolamine, alkaline developing solution comprising an aqueous solution of about 0.1 to 5% by weight of an organic amine compound such as diisopropanolamine is used. Among them, alkali metal silicates such as sodium silicate and potassium silicate which are inorganic alkali salts are preferable.

The development is preferably performed by immersion development, spray development, brush development, ultrasonic development, or the like.
The temperature is about 10 ° C. and the time is about 10 to 80 seconds.

[0060]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention.

Example 1 An aluminum plate (size: 500 mm × 500 mm, thickness: 0.24 mm) subjected to graining treatment and anodizing treatment
Using as a support, on the aluminum plate support surface,
The following component (A), component (B), component (C), and component (D) were mixed with 1800 parts by weight of cyclohexanone at room temperature under stirring to prepare a coating solution, which was applied using a wire bar. At 2 ° C. for 2 minutes to form a photopolymerizable composition layer having a thickness of 1 μm, on which a 10% by weight aqueous solution of a polyvinyl alcohol / vinyl acetate copolymer (copolymer molar ratio: 7/3) was further coated with a wire bar. And dried to form a protective layer having a thickness of 1 μm to prepare a lithographic printing plate having a clear brown photopolymerizable composition layer. In this case, the solubility of the component (B) in the solvent was good.

(A) Urethane acrylates which are reaction products of hexamethylene diisocyanate and pentaerythritol triacrylate (“UA-30” manufactured by Kyoeisha Co., Ltd.)
6H "); 100 parts by weight (B) a subphthalocyanine dye represented by the following formula: 5 parts by weight

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(C) 5 parts by weight of the organoboron complex of the specific example B-15; (D) 3,4-epoxycyclohexylmethyl added to a styrene / acrylic acid copolymer (weight average molecular weight 5,000, acid value 200) Reaction product obtained by reacting acrylate (oxidation 80, 5 of carboxyl group of acrylic acid component)
0 mol% is reacted); 100 parts by weight

Using a spectral sensitivity measuring device (manufactured by Narumi), the obtained photopolymerizable lithographic printing plate was subjected to spectroscopy using a xenon lamp (“US-501C” manufactured by Ushio Inc.) as a light source, and the abscissa was used. Exposure is performed by irradiating for 10 seconds with exposure wavelength set linearly in the direction and logarithmically changing the exposure intensity in the vertical direction, and then immersed in a 1% by weight aqueous sodium carbonate solution at 25 ° C. for 30 seconds. Then, a resist image corresponding to the sensitivity at each exposure wavelength was obtained as a spectral sensitivity curve, and the minimum exposure amount required for image formation at a wavelength of 630 nm in the spectral sensitivity curve was determined to be 4 mJ / cm ²
Met.

Example 2 A photopolymerizable lithographic printing plate was prepared, exposed and developed in the same manner as in Example 1, except that the amount of the subphthalocyanine dye (B) was changed to 2 parts by weight. The minimum exposure required for image formation was determined to be 3 mJ / cm ² .

Comparative Example 1 A photopolymerizable planographic printing plate was prepared in the same manner as in Example 1 except that a phthalocyanine dye represented by the following formula was used as the component (B). It did not dissolve, and a coating solution could not be prepared.

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Comparative Example 2 A photopolymerizable lithographic printing plate was prepared in the same manner as in Example 1 except that a dithiol-based metal complex (“MIR-101” manufactured by Midori Kagaku) was used as the component (B). Exposure and development, but no image formation itself was made.

Comparative Example 3 A photopolymerizable lithographic printing plate was prepared in the same manner as in Example 1 except that octabutoxyphthalocyanine having no central metal (manufactured by Aldrich) was used as the component (B). After exposure and development, no image was formed.

Comparative Example 4 A photopolymerizable planographic printing plate was prepared in the same manner as in Example 1 except that octabutoxyphthalocyanine containing nickel as a central metal (manufactured by Aldrich) was used as the component (B). After exposure and development, no image was formed.

Examples 3 to 11 In Example 1, the component (D) was replaced with a methacrylic acid: acrylic acid (90:10 molar ratio) copolymer (polymerization average molecular weight 5
0000), and the components (B) and / or (C) are changed to those shown in Table 1.
A lithographic printing plate having a photopolymerizable layer was prepared in the same manner except that the additives described in Table 1 in parts by weight were added, and the sensitivity at 600 nm was evaluated in the same manner. In addition, as a developer, a developer for negative planographic printing plate manufactured by Konica Corporation, SDN-2
A 10-fold dilution of 1 was used.

[0073]

[Table 1]

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[0075]

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[0078]

According to the present invention, a photopolymerizable composition and a photopolymerizable image-forming material having high sensitivity to laser light in the visible region to the infrared region and having excellent solubility in a coating solvent are provided. Can be provided.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C09B 47/08 C09B 47/08 F term (reference) 2H025 AA00 AA01 AB03 AB15 AB16 AB17 AC01 AC08 AD01 BC14 BC42 BC45 BC74 CA01 CA14 CA28 CA39 CA42 CA50 FA03 FA17 4J011 PA48 PC02 SA78 SA85 SA86 SA88 UA02 WA01

Claims (5)

[Claims] 1. A photopolymerizable composition comprising the following components (A), (B) and (C). (A) an ethylenically unsaturated compound (B) a subphthalocyanine dye represented by the following general formula (I) and containing boron as a central element: [In the formula (I), R represents an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a halogen atom, and a ring U, a ring V, and a ring W are Each independently,
A condensed aromatic ring or a condensed aromatic heterocyclic ring formed at two β-positions of a pyrrole ring, and these aromatic ring and aromatic heterocyclic ring may have a substituent; (C) Photopolymerization initiator 2. The subphthalocyanine dye as the component (B) is preferably a compound wherein the ring U, ring V, and ring W formed on the pyrrole ring in the general formula (I) are any of a benzene ring, a pyridine ring, and a piperazine ring. The photopolymerizable composition according to claim 1, wherein 3. The photopolymerizable compound according to claim 1, wherein the photopolymerization initiator of the component (C) is a trihalomethyl-s-triazine compound, a hexaarylbiimidazole compound, a titanocene compound, or an organic boron complex. Composition. 4. The photopolymerizable composition according to claim 3, wherein the organic boron complex is represented by the following general formula (II). Embedded image [In the formula (II), R ¹ , R ² , R ³ , and R ⁴ are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, An alkynyl group which may have a group, an aryl group which may have a substituent, an alicyclic group which may have a substituent, or a heterocyclic group which may have a substituent And these may be linked to each other to form a cyclic structure, and X ⁺ represents a counter cation. ] 5. A photopolymerizable image forming material comprising a support and a layer of the photopolymerizable composition according to claim 1 formed on a surface of the support.