JP2002244290A - Photopolymerizable composition - Google Patents

Abstract

(57) [Summary] [Object] To provide a photopolymerizable composition which has high sensitivity to a laser beam in an infrared region and can be handled under a white lamp. A photopolymerizable composition comprising the following components (A), (B), (C), and (D). (A) an ethylenically unsaturated compound (B) a photopolymerization initiator (C) a sensitizing dye (D) an aromatic cyano compound having a basic structure represented by the following general formula (III): [In the formula (III), Z ¹ and Z ² represent a dicyanomethylidene group or an oxygen atom, and at least one of Z ¹ and Z ²
Is a dicyanomethylidene group, the quinoid ring has a substituent, and these substituents may be connected to each other to form a condensed ring, and the condensed ring further has a substituent. You may. ]

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).
It is used for microfabrication, etc., and has high sensitivity to light rays in the infrared region, especially infrared laser light, and is directly drawn by a semiconductor laser, YAG laser, etc., for a photopolymerizable composition that can be handled under white light. The present invention also relates to a photopolymerizable composition which is also suitable.

[0002]

2. Description of the Related Art Conventionally, planographic printing plates, printed circuit boards,
For microfabrication of LSI, TFT, LCD, PDP, TAB, etc., an image forming material in which a layer of a photosensitive composition is formed on the surface of a support is irradiated with ultraviolet light through a mask film to perform image exposure, and an exposed portion and a non-exposed portion are provided. The lithography method for forming an image by utilizing the difference in solubility in a developing solution has been widely used, but in recent years, remarkable progress of semiconductor lasers and the like has made it possible to easily use an infrared laser beam in a long wavelength region. As a result, the direct drawing method that uses a laser beam as the exposure light source and obtains an image directly from digital information of a computer without using a mask film has improved not only productivity but also resolution and positional accuracy. It is attracting attention because it can be planned.

[0003] On the other hand, as the photosensitive composition, from the viewpoint of sensitivity and the like, for example, a photopolymerizable composition comprising an ethylenically unsaturated compound and a photopolymerization initiator, or a sensitizing dye, an alkali-soluble resin, or the like is used. A method of forming a cured image by polymerizing and curing an ethylenically unsaturated compound in an exposed portion by exposure and then dissolving and removing the unexposed portion is widely used.

As a photopolymerizable composition used in the above-described direct drawing method using a laser beam, for example, Japanese Patent Application Laid-Open
JP-A-53319 discloses a resin and / or compound having a photosensitive functional group, and a photocurable resin composition comprising a photopolymerization initiator, and JP-A-5-289335 discloses
An addition-polymerizable compound having an ethylenically unsaturated bond,
A photopolymerizable composition comprising a titanocene compound and a coumarin compound is disclosed in JP-A-6-43642.
A visible light curable resin, a specific dye, a photopolymerizable composition comprising a leuco dye, and a radical generator are further disclosed in JP-A-10-142790, a photocurable resin, a coumarin-based dye having a specific structure, And a visible light laser curable resin composition comprising a titanocene compound and the like have been proposed.

[0005] However, these photopolymerizable compositions proposed to be sensitive to a laser beam are not always sufficiently sensitive to a laser beam in the infrared region, and they also become sensitive when handled under a white lamp. In addition, a high-output laser is required for exposure, and direct writing with a low-output semiconductor laser, a YAG laser, or the like has been difficult.

In order to solve these problems, Japanese Patent Application Laid-Open No. 2000-122274 discloses an ethylenically unsaturated double bond compound, a polymerization initiator, and a sensitizing dye of a specific pentacene compound. Although a photosensitive composition comprising the following has been proposed, the present inventors have found that this composition is not satisfactory in terms of sensitivity.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art. Therefore, the present invention has a high sensitivity to a laser beam in an infrared region and has a high sensitivity under a white light. An object of the present invention is to provide a photopolymerizable composition which can be handled.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by including a specific aromatic cyano compound in a photopolymerizable composition. Completed the present invention,
That is, the present invention provides the following component (A), component (B),
The gist is a photopolymerizable composition containing the component (C) and the component (D). (A) Ethylenically unsaturated compound (B) Photopolymerization initiator (C) Sensitizing dye (D) Aromatic cyano compound having a basic structure represented by the following general formula (III)

[0009]

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[In the formula (III), Z ¹ and Z ² represent a dicyanomethylidene group or an oxygen atom, at least one of Z ¹ and Z ² is a dicyanomethylidene group, and the quinoid ring is a substituent. And these substituents may be connected to each other to form a condensed ring, and the condensed ring may further have a substituent. ]

[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 (B) when the photopolymerizable composition is irradiated with actinic rays. )
Such as addition polymerization by the action of the photopolymerization initiator of the component and the sensitizing dye of the component (C), and optionally crosslinking and curing;
It is a compound having a radical polymerizable ethylenically unsaturated double bond. In view of the polymerizability, crosslinkability, and the accompanying difference in developer solubility between exposed and unexposed areas, such a compound is preferred. A compound having two or more heavy bonds in the molecule is preferable, and an acrylate compound in which the double bond is derived from a (meth) acryloyloxy group is preferable. Here, “(meth) acryl” means acryl and methacryl.

The acrylate compound is not particularly limited, but is typically an ester (meth) acrylate of (meth) acrylic acid and a polyhydroxy compound, (meth) acrylic acid or hydroxy (meth) acrylate. ) Epoxy (meth) acrylates of an acrylate compound and a polyepoxy compound, urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound, and (meth) acryloyloxy group-containing phosphates.

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 G, 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, “Celloxide 2000” and “20” manufactured by Daicel Chemical Industries, Ltd.
21 "," 2080 "," 3000 "," Epolide GT300 "," GT400 ", etc., alicyclic polyepoxy compounds, sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) Heterocyclic polyepoxy compound such as isocyanurate, phenol novolak polyepoxy compound, brominated phenol novolak polyepoxy compound, (o-, m-, p-) cresol novolak polyepoxy compound, bisphenol A polyepoxy compound, bisphenol F polyepoxy Reaction products with a polyepoxy compound such as an aromatic polyepoxy compound such as a compound are exemplified.

As the urethane (meth) acrylates, specifically, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate , A hydroxy (meth) acrylate compound such as tetramethylolethane tri (meth) acrylate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, , 6,11-Undecatriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane Aliphatic polyisocyanates, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, alicyclic polyisocyanates such as bicycloheptane 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) And a reaction product with a polyisocyanate compound such as an aromatic polyisocyanate such as tris (isocyanatephenyl) thiophosphate.

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

In the present invention, as the ethylenically unsaturated compound as the component (A), among the acrylate compounds, ester (meth) acrylates having at least three (meth) acryloyloxy groups in the molecule, or Urethane (meth) acrylates are particularly preferred.

(B) 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 presence of the sensitizing dye of the component (C) described later.
No. 3428, British Patent No. 1388492, Wakabayashi et al .; Bull.Chem. Soc. Japan; 42, 2924 (1969), FCSchaef
J. Org. Chem .; 29, 1527 (1964) and the like, halogenated hydrocarbon derivatives described in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484.
JP-A-2-249, JP-A-2-4705, JP-A-5-83588, etc., titanocene compounds, hexaarylbiimidazole compounds described in JP-B-6-29285 and the like, Examples include an organic boron complex, a carbonyl compound, and an organic peroxide.

The halogenated hydrocarbon derivatives include:
Specifically, 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-n-nonyl-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, -(P-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'
-Dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -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-methylstyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p- (Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4-amino-6-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- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [4-
(2-ethoxyethyl) naphthyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4,7-dimethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- Acenaphthyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s- Triazine, 2-methoxy-4-methyl-6-trichloromethyl-s-triazine, 2,4,6
-Tris (tribromomethyl) -s-triazine, 2-
Methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, 2-amino-4-methyl-6
And s-triazine compounds such as tribromomethyl-s-triazine.

Specific examples of the titanocene compound include, for example, dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium 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 the like.

Examples of the hexaarylbiimidazole compound include, for example, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chlorophenyl) 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 (p-fluorophenyl) biimidazole, 2,2′-
Bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dibromophenyl) biimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′,
5,5′-tetra (p-chloronaphthyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,
4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 '-Bis (o, p-dichlorophenyl)-
4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, , 2'-bis (o-bromophenyl) -4,
4 ', 5,5'-tetra (o, p-dichlorophenyl)
Biimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4 , 4 ', 5,5'-tetra (o-chloro-p
-Methoxyphenyl) biimidazole, 2,2'-bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole and the like.

Specific examples of the organoboron complex include, for example, Japanese Patent Application Laid-Open Nos.
06242, JP-A-9-188865, JP-A-9-188
188686, JP-A-9-188710, and Kunz, Martin "Rad Tech'98. Proceeding April 19-
22,1998, Chicago "and the like, JP-A-6-1576232 and JP-A-6-1755.
No. 61, JP-A-6-175564 and the like, and organic boron sulfonium complexes or organic boron oxosulfonium complexes described in JP-A-6-175553 and JP-A-6-17.
5554, the organic boron iodonium complex described in each of the publications, the organic boron phosphonium complex described in JP-A-9-188710, and the like, JP-A-6-34811, JP-A-7-128785, JP-A-7-140589, Organic boron transition metal coordination complexes described in JP-A-7-292014, JP-A-7-306527 and the like can be mentioned.

Specific examples of the carbonyl compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Benzophenone derivatives such as Michler's ketone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 1-hydroxy -1-methylethyl- (p
-Isopropylphenyl) ketone, 1-trichloromethyl- (p-butylphenyl) ketone, α-hydroxy-
2-methylphenylpropanone, 2-methyl- (4'-
Acetophenone derivatives such as (methylthio) phenyl) -2-morpholino-1-propanone, thioxanthone,
And thioxanthone derivatives such as 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

Specific examples of the organic peroxide include methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, and the like.
Ketone peroxides such as 3,3,5-trimethylcyclohexanone peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-
Diacyl peroxides such as dichlorobenzoyl peroxide, m-toluoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane- 2,5-dihydroperoxide,
Hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 1,3 (or 1,4) -Bis (t-butylperoxyisopropyl) benzene, 2,
Dialkyl peroxides such as 5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; Bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,
3,5-trimethylcyclohexane, 2,2-bis (t
-Butylperoxy) butane and other peroxyketals, t-butylperoxyacetate, t-butylperoxyoctoate, t-butylperoxypivalate, t-butylperoxyneodecanoate, t-butylperoxide Alkyl peresters such as oxy-3,5,5-trimethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate;
2-ethylhexylperoxydicarbonate, diisopropylperoxydicarbonate, dimethoxyisopropylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, bis (3-methyl-3
-Methoxybutyl) peroxydicarbonate, peroxycarbonates such as t-butylperoxyisopropyl carbonate, and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) 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, 3,3 ′, 4,4′-tetra (aminoperoxycarbonyl) benzophenone, carbonyl bis (t-butylperoxy dihydrogen 2-phthalate), carbonyl bis (t-hexyl peroxy dihydrogen 2-phthalate) and the like No.

In the present invention, as the photopolymerization initiator of the component (B), an organic boron complex is preferable among the above, and an organic boron complex represented by the following general formula (I) is particularly preferable.

[0027]

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[In the formula (I), 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. ]

The alkyl and alicyclic groups of R ¹ , R ² , R ³ and R ⁴ have 1 to 10 carbon atoms, and the alkenyl and alkynyl groups have 1 to 10 carbon atoms. Those having 1 to 15 are preferable, and those having 6 to 20 carbon atoms are preferable as the aryl group. 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 hydroxy group, an amino group, an alkylamino group, a halogenated alkyl group, and a halogen atom. Particularly preferred.

In the present invention, R ¹ , R ² , R
^A triarylalkyl boron complex in which three of R ³ and R ⁴ are an aryl group which may have a substituent and one of which is an alkyl group which may have a substituent is particularly preferable.

Specific examples of preferable anions in these organic boron complexes include, for example, n-butyl-triphenylboron anion, n-butyl-tris (p-methylphenyl) boron anion, 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 tetraalkylammonium cation having an alkyl group having 1 to 10 carbon atoms is particularly preferable.

Specific examples of the preferred organoboron complex include compounds having the following structures.
In the following examples, Et represents an ethyl group, and Bu represents a butyl group.

[0034]

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[0035]

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(C) Constituting the Photopolymerizable Composition of the Invention
The component sensitizing dye efficiently absorbs light in the infrared region when the photopolymerizable composition is irradiated with actinic light, and transmits the photoexcitation energy to the photopolymerization initiator of the component (B). It is a compound having a sensitizing function of decomposing the component (B) and generating an active radical that induces polymerization of the ethylenically unsaturated compound of the component (A).
As the sensitizing dye, for example, "chemical chemistry of functional dyes"
(Edited by Higaki, 1981, published by CMC Corporation),
"Specially-functional dyes" (edited by Ikemori and Pillar Valley, 1986,
Published by CMC Corporation), "Dye Handbook" (edited by Okawa, Hirashima, Matsuoka, Kitao, published by Kodansha), Excit
on Inc. Described in a laser dye catalog issued in 1989, a catalog issued by the Japan Photographic Dye Laboratories in 1995, etc., and a dye having an absorption in a wavelength region of 700 to 1200 nm, and JP-A-2-2074.
No. 2-2075, No. 2-2076, No. 3-26
No. 593, No. 3-63285, No. 3-97589,
Pigments having absorption in the infrared region described in JP-A-3-97590 and JP-A-3-97591 are preferred.

Specific examples of these sensitizing dyes include:
For example, phthalocyanine dye, cyanine dye, polymethine dye, anthraquinone dye, aminium dye, iminium dye, diimmonium dye, nickel-thio complex dye, naphthoquinone dye, anthraquinone dye, quinoid dye, merocyanine Dyes, naphtholactam dyes, oxyindolizine dyes, fulgide dyes, and the like. Among them, phthalocyanine dyes, cyanine dyes, and polymethine dyes are preferable, and phthalocyanine dyes are particularly preferable.

As the phthalocyanine dye, a phthalocyanine complex salt having a structure represented by the following general formula (II) is preferable.

[0039]

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[In the formula (II), M represents a metal atom, the aromatic ring may have a substituent, and the substituents may be connected to each other to form a condensed ring. The condensed ring may have a substituent. ]

Here, M represents Ia group or Ib of the periodic table.
Group, IIa, IIb, IIIa, IIIb, IVa, IVb
Group, Va group, Vb group, VIb group, VIIb group, VIII group, etc., and examples of the substituent of the aromatic ring and the condensed ring include an alkyl group, an alkoxy group, an alkoxyalkyl group, and a carboxyl group. An alkoxycarbonyl group, a vinyl group, an acryloyl group, a hydroxyl group, a phenyl group, a phenoxy group, an alkylthio group, a phenylthio group, an amino group, a nitro group, a cyano group, a silyl group, a halogen atom, and the like. They may be the same or different. Among them, M is preferably a complex salt of a metal atom of the group Ib such as copper, group IIb such as zinc, group IIIb such as aluminum and gallium, group IVb such as tin, and group Va such as vanadium.
Complex salts of Group IVb are preferred, especially those of zinc or tin.

Further, it is preferable that the solvent is soluble in a solvent exhibiting a solubility of 0.01% by weight or more as a solubility in a solvent at the time of forming a photopolymerizable composition layer described later. Compounds having a substituent are preferable, and as the substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, a phenoxy group, and a An alkylthio group, a phenylthio group, or a halogen atom, or a substituent linked to each other to form a naphthalocyanine structure, and an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms Having a substituent of any one of a group, an alkoxyalkyl group having 2 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 6 carbon atoms, a phenylthio group, and a halogen atom. Compounds are preferred.

Specific examples of these suitable phthalocyanine complex salts include compounds having the following structures. In the following examples, Ph represents a phenyl group.

[0044]

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[0045]

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[0046]

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The cyanine dyes and polymethine dyes have a structure in which a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom is bonded by a polymethine (—CH ＝) _n chain, which is a so-called broad definition. Has a structure in which a hetero atom forms a heterocyclic ring and the heterocyclic ring is bonded via a polymethine chain. Specifically, for example, a quinoline-based (so-called cyanine-based in a narrow sense) , Indole type (so-called indocyanine type), benzothiazole type (so-called,
Thiocyanine), pyrylium, thiapyrylium,
Squarylium-based, croconium-based, azurenium-based, and the like, and the polymethine dye has a structure in which an acyclic heteroatom is bonded via a polymethine chain,
Among them, quinoline-based, indole-based, benzothiazole-based and other cyanine dyes, and polymethine-based dyes are preferred.

Specific examples of the preferred cyanine dyes and polymethine dyes include compounds having the following structures. In the following examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and P represents a butyl group.
h represents a phenyl group, respectively.

Among the cyanine dyes, quinoline compounds include the following compounds.

[0050]

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The indole compounds include the following compounds.

[0052]

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[0053]

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The benzothiazole compounds include the following compounds.

[0055]

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The polymethine dyes include the following compounds.

[0057]

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(D) Constituting the Photopolymerizable Composition of the Invention
The aromatic cyano compound of the component has a basic structure represented by the following general formula (III).

[0059]

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[In the formula (III), Z ¹ and Z ² represent a dicyanomethylidene group or an oxygen atom, at least one of Z ¹ and Z ² is a dicyanomethylidene group, and the quinoid ring is a substituent. And these substituents may be connected to each other to form a condensed ring, and the condensed ring may further have a substituent. ]

The aromatic cyano compound in the present invention is preferably a condensed polycyclic compound having five or more rings condensed among the compounds having the basic structure represented by the above general formula (III). Since it is preferable that the compound is soluble in a solvent exhibiting a solubility of 0.01% by weight or more as a solubility in a solvent at the time of forming a photopolymerizable composition layer described below, one or more oxygen atoms or sulfur atoms in the molecule, Further, the compound preferably contains two or more, and particularly preferably a condensed polycyclic compound having a structure represented by the following general formula (IV).

[0062]

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[In the formula (IV), Z ¹ and Z ² are the same as those in the formula (III), and R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently have a substituent. Alkyl group which may be, an alkoxy group which may have a substituent, a halogen atom,
Or a hydrogen atom, and R ⁹ and R ¹⁰ each independently represent a halogen atom or a hydrogen atom. ]

Here, the alkyl group and the alkoxy group represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably those having 1 to 8 carbon atoms, and the substituents thereof are an alkyl group or And a halogen atom. Also, Z ¹ and Z
² together is what is preferable dicyanomethylidene group.

As these preferred fused polycyclic compounds,
Specifically, for example, a compound having the following structure is given. In the following examples, Me represents a methyl group and Et represents
Represents an ethyl group, and Pr represents a propyl group.

[0066]

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[0067]

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The photopolymerizable composition of the present invention comprises the component (A), an ethylenically unsaturated compound, the component (B), a photopolymerization initiator, the component (C), a sensitizing dye, and the component (D). )) It is essential that the component (A) contains an aromatic cyano compound, and the content ratio of each component is based on 100 parts by weight of the ethylenically unsaturated compound (A) and photopolymerization initiation of the component (B). The amount of the agent is preferably 1 to 30 parts by weight, the sensitizing dye of the component (C) is 1 to 20 parts by weight, and the aromatic cyano compound of the component (D) is preferably 1 to 30 parts by weight.

The photopolymerizable composition of the present invention may further comprise, in addition to the above components, an alkali-soluble resin (E) as a binder for the purpose of improving coating properties and developability. )
5 parts per 100 parts by weight of the component ethylenically unsaturated compound
The alkali-soluble resin is preferably contained in an amount of 0 to 500 parts by weight, and preferred examples of the alkali-soluble resin include a carboxyl group-containing vinyl resin, an epoxy acrylate resin, and a phenolic hydroxyl group-containing phenol resin.

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. These carboxyl group-containing vinyl resins preferably have 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%.

The epoxy acrylate resin is obtained by modifying an epoxy resin with (meth) acrylic acid and an acid anhydride. Specifically, for example, bisphenol A epoxy resin, bisphenol S epoxy resin, After adding (meth) acrylic acid to the epoxy group of epoxy resin such as phenol novolak epoxy resin, cresol novolak epoxy resin, and trisphenol epoxy resin, succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, Tetrahydrophthalic anhydride,
Methyltetrahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, hexahydrophthalic anhydride, those modified with acid anhydrides such as methylhexahydrophthalic anhydride, and those epoxy acrylate-based The resin is
It is preferable that the acid value is 20 to 150 KOH · mg / g and the weight average molecular weight in terms of polystyrene is 1,000 to 20,000.

Examples of the phenolic hydroxyl group-containing phenolic resin include, for example, phenol, o
-Cresol, m-cresol, p-cresol, 2,
5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t
-Butylphenol, 1-naphthol, 2-naphthol, 4,4'-biphenyldiol, bisphenol-
A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol,
At least one kind of phenols such as phloroglucinol is acid-catalyzed, for example, aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, benzaldehyde, and furfural, or acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like. A novolak resin polycondensed with at least one of the following ketones, a resol resin polycondensed in the same manner except that an alkali catalyst is used instead of the acid catalyst in the polycondensation of the novolak resin, and, for example, o- Hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, pentahydroxystyrene, 2- (o-hydroxyphenyl) propyl , 2- (m-hydroxyphenyl) propylene, 2- (p-hydroxyphenyl) propylene or other hydroxystyrenes, alone or in combination of two or more, in the presence of a radical polymerization initiator or a cationic polymerization initiator. Phenol resins and the like, which have a weight average molecular weight of 1,500 to 50,0
00 is preferred.

In the present invention, as the alkali-soluble resin of the component (E), a carboxyl group-containing vinyl resin and a novolak epoxy resin are exemplified by (meth)
Epoxy acrylate resins modified with acrylic acid and tetrahydrophthalic anhydride or hexahydrophthalic anhydride are preferred.

The photopolymerizable composition of the present invention may further comprise a hydrogen-donating compound (F) as a polymerization accelerator in addition to the component (A) for the purpose of improving photopolymerization initiation ability.
3 parts per 100 parts by weight of the ethylenically unsaturated compound
It is preferably contained in an amount of 0 parts by weight or less. 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, etc. And N, N-dialkylaminobenzoic acid esters (preferably, esters of an alkyl group which may have a substituent, such as methyl, ethyl, propyl, and benzyl). , N-phenylglycine, or a salt thereof such as ammonium or sodium salt,
Amino acids having an aromatic ring such as derivatives of the above-mentioned esters and the like, phenylalanine or salts thereof such as ammonium and sodium salts, and derivatives of the above-mentioned esters and the like, and derivatives thereof.

The photopolymerizable composition of the present invention may contain, if necessary, a coating improver such as a nonionic, anionic, cationic or fluorine-based surfactant, an antifoaming agent, a visible image. Additives such as a property imparting agent, a colorant, an adhesion improver, a developability improver, an ultraviolet absorber, and a polymerization stabilizer may be added.

Depending on the purpose of use, the photopolymerizable composition of the present invention may be used as a photosensitive material according to the purpose of use, for example, without a solvent or after being diluted with a suitable solvent, applied to the surface of a support, and dried. Or a further layer provided with a protective layer for blocking oxygen, a mode in which droplets are dispersed in a heterogeneous medium and applied in multiple layers as a plurality of types of photosensitive materials, and a support encapsulated in microcapsules. The photopolymerizable composition of the present invention may be applied to the surface of a support as a coating solution obtained by dissolving or dispersing the composition in an appropriate solvent, and then heated and dried. Thus, the use form as a photopolymerizable lithographic printing plate in which a layer of the photopolymerizable composition of the present invention is formed on the support surface is suitable.

In this case, as the support, aluminum,
Metal plate such as zinc, copper, steel, aluminum, zinc, copper,
Metal plates plated or evaporated with iron, chromium, nickel, etc.
Paper, paper coated with resin, paper bonded with metal foil such as aluminum, plastic film, plastic film subjected to hydrophilic treatment, epoxy resin, polyimide resin, copper-clad laminate such as glass cloth base epoxy resin, and glass Plates and the like can be mentioned. Among them, an aluminum plate is preferable.

The solvent for applying the photopolymerizable composition to the surface of the support is not particularly limited as long as it has sufficient solubility for the components used and gives good coating properties. There are no, for example, cellosolve solvents such as methyl cellosolve, 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 mono Propylene glycol solvents such as ethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyrate , Diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, ester solvents such as methyl 3-methoxypropionate, heptanol, hexanol, diacetone alcohol, furfuryl Alcohol solvents such as alcohols, ketone solvents such as cyclohexanone and methyl amyl ketone, highly polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, or mixed solvents thereof, and aromatic hydrocarbons added thereto And the like. In addition, the usage ratio of the solvent is usually in a range of about 1 to 20 times by weight based on the total amount of the photopolymerizable composition.

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. Although the amount of application varies depending on the application, the dry film thickness is preferably about 0.1 to 100 μm, and more preferably about 0.5 to 70 μm. The drying temperature at that time is, for example, about 30 to 150 ° C., preferably about 40 to 110 ° C., and the drying time is, for example, about 5 seconds to 60 minutes.
Preferably, about 10 seconds to 30 minutes are employed.

Light sources for imagewise exposing the photopolymerizable composition of the present invention include a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a HeNe laser, an argon ion laser, and a YAG laser. , HeCd laser, semiconductor laser, ruby laser, etc., and a laser light source is suitable for direct drawing, and among them, preferably 700 nm or more, more preferably 750 nm or more.
A light source that generates a near-infrared laser beam having a wavelength of about 1200 nm is preferable. For example, a solid-state laser such as a ruby laser, a YAG laser, or a semiconductor laser is preferable, and a small-sized and long-life YAG laser or semiconductor laser is particularly preferable. These laser light sources are focused on beams, scanned and exposed based on image data, and then developed with a developer to form an image.

The developing solution used in this case includes, for example, sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, Inorganic alkali salts such as sodium bicarbonate, potassium carbonate, dibasic sodium phosphate, tertiary sodium phosphate, dibasic ammonium phosphate, tertiary ammonium phosphate, sodium borate, potassium borate, ammonium borate, etc., monomethylamine, dimethylamine, trimethylamine, mono Ethylamine, diethylamine, triethylamine,
An alkaline developer comprising an aqueous solution of about 0.1 to 10% by weight of an organic amine compound such as monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and diisopropanolamine is used. Can be Incidentally, the developing solution is added with a surfactant such as a nonionic surfactant, an anionic surfactant, a cationic surfactant and an amphoteric surfactant, and an organic solvent such as alcohol, if necessary. You may.

The development is usually carried out by immersion development, spray development, brush development, ultrasonic development, or the like.
To about 60 ° C, more preferably about 15 to 45 ° C.

[0084]

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.

Examples 1 to 3 and Comparative Examples 1 to 2 An aluminum plate (0.24 mm thick) subjected to graining treatment and anodizing treatment was used as a support. 40 parts by weight of pentaerythritol triacrylate (manufactured by Kyoeisha Co., Ltd.) as the ethylenically unsaturated compound as the component, 10 parts by weight of the organic boron complex shown in the specific example (B-1) as the photopolymerization initiator of the component (B), As a sensitizing dye of the component (C), 5 parts by weight of the compound shown in the following Table 1, and as an aromatic cyano compound of the component (D),
A styrene / acrylic acid copolymer (weight average molecular weight: 5,000, acid value: 200 KOH · m) was used as an alkali-soluble resin of component (E) in an amount of 10 parts by weight of the compounds shown in Table 1 below.
g / g) with 3,4-epoxycyclohexylmethyl acrylate (80 K oxidation).
OH.mg/g, 5 of carboxyl group of acrylic acid component
A reaction solution prepared by stirring 60 parts by weight of propylene glycol monomethyl ether acetate at 1,200 parts by weight at room temperature using a wire bar is applied using a wire bar, and dried at 70 ° C. for 1 minute in a convection oven. As a result, a photopolymerizable composition layer having a thickness of 2 μm was formed, and 10% by weight of polyvinyl alcohol was further formed thereon.
An aqueous solution was applied and dried to form an overcoat layer having a thickness of 2 μm to prepare a photopolymerizable lithographic printing plate.

Each of the resulting photopolymerizable lithographic printing plates was adjusted to a diameter of 10
cm of the photopolymerizable composition layer is fixed to the outside of the drum, and a semiconductor laser having a wavelength of 830 nm and an output of 40 mW (“HL8325C” manufactured by Hitachi, Ltd.) is rotated while rotating the drum in the range of 5 to 800 rpm. ) To 70μ
The image was exposed by irradiating with a beam spot diameter of m, and then developed by immersing in an alkali developing solution composed of a 1% by weight aqueous solution of sodium carbonate at 25 ° C. for 1 minute. At that time, sensitivity and safelight property were evaluated by the following methods, and the results are shown in Table 1.

Sensitivity The minimum amount of exposure energy required for image formation was determined from the maximum number of rotations of the drum on which an image could be formed, and was defined as sensitivity.

Safelight Property Each of the photopolymerizable lithographic printing plates obtained above was used as a white fluorescent lamp (Mitsubishi Electric 36W white fluorescent lamp “Neorumi Super F”).
LR40S-W / M / 36 ”) after being left for 1 hour under irradiation with a light intensity of 400 lux, subjected to exposure and development in the same manner as described above, and the sensitivity to the lithographic printing plate before leaving and the unexposed area The dissolution times were compared, and the case where no difference was observed was regarded as good.

[0089]

[Table 1]

[0090]

According to the present invention, it is possible to provide a photopolymerizable composition which is highly sensitive to a laser beam in the infrared region and can be handled under a white lamp.

Continued on front page F term (reference) 2H025 AA00 AA01 AB03 AB15 AB16 AB17 AC08 AD01 BC14 BC32 BC42 CA01 CA14 CA18 CA28 CA39 CA41 CA50 CC20 FA03 FA17 4J011 CA01 CA03 CA05 PA35 PA44 PB25 PB30 PC02 QA03 QA04 QA13 QA24 QA23 QA24 QA42 QA45 QA46 QB14 QB16 QB19 QB22 QB24 SA04 SA06 SA07 SA22 SA24 SA26 SA27 SA61 SA64 SA76 SA78 SA86 SA88 UA01 UA02 VA01 WA01

Claims (6)

[Claims] 1. The following components (A), (B) and (C)
A photopolymerizable composition comprising a component and a component (D). (A) Ethylenically unsaturated compound (B) Photopolymerization initiator (C) Sensitizing dye (D) Aromatic cyano compound having a structure represented by the following general formula (III) as a basic structure [In the formula (III), Z ¹ and Z ^{2 each} represent a dicyanomethylidene group or an oxygen atom, and at least one of Z ¹ and Z ²
Is a dicyanomethylidene group, the quinoid ring has a substituent, and those substituents may be connected to each other to form a condensed ring, and the condensed ring further has a substituent. You may. ] 2. The photopolymerizable composition according to claim 1, wherein the aromatic cyano compound as the component (D) has a structure represented by the following general formula (IV). Embedded image [In formula (IV), Z ¹ and Z ² are the same as those in formula (III), and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently
An alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a hydrogen atom, wherein R ⁹ and R ¹⁰ are each independently a halogen atom,
Or a hydrogen atom. ] 3. The photopolymerizable composition according to claim 1, wherein the photopolymerization initiator (B) is an organic boron complex. 4. The photopolymerizable composition according to claim 3, wherein the organoboron complex (B) has a structure represented by the following general formula (I). Embedded image [In the formula (I), 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. The sensitizing dye of the component (C) has the following general formula (I)
A phthalocyanine complex having a structure represented by I).
5. The photopolymerizable composition according to any one of items 1 to 4. Embedded image [In the formula (II), M represents a metal atom, the aromatic ring may have a substituent, and those substituents may be connected to each other to form a condensed ring. May have a substituent. ] 6. The photopolymerizable composition according to claim 1, further comprising an alkali-soluble resin (E).