JP2002038040A - Sensitizing dye, photopolymerizable composition containing the same, and photopolymerizable image forming material - Google Patents

Abstract

[PROBLEMS] To provide a high-performance sensitizing dye and a photopolymerizable composition and a photopolymerizable image-forming material using the same, which exhibit extremely high sensitivity to light in the visible region. Offer. SOLUTION: A photopolymerizable composition comprising a sensitizing dye represented by the general formula [1], an ethylenically unsaturated compound, and a photopolymerization initiator. [In the formula, the pyrrole ring may be substituted, and the two substituents at the β-position may be linked to each other to form a fused bicyclo ring. R ¹ represents H, a substitutable C1-10 alkyl group, a substitutable C6-10 aryl group, or a substitutable C4-10 heterocyclic group. Me is a metal that can form a complex with porphyrin. X ¹ and X ² are a bond extending from N of the two pyrrole rings of the α, α-bipyrromethene moiety similar to the bond to the halogen or metal Me. ]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sensitizing dye and a photopolymerizable composition and a photopolymerizable image-forming material which use the sensitizing dye and exhibit extremely high sensitivity to light in the visible region.

[0002]

2. Description of the Related Art Conventionally, the following methods have been known as methods for forming an image by exposing a photopolymerizable composition. For example, an ethylenically unsaturated compound and a photopolymerization initiator,
Alternatively, a layer of a photopolymerizable composition further containing a polymer binder is formed on the surface of the support, and imagewise exposed to polymerize and cure the ethylenically unsaturated compound in the exposed portion, and then to the unexposed portion. There is known a method of forming a cured relief image by dissolving and removing the compound. As another method, a method is also known in which an image is formed by exfoliating the support after exposing the photopolymerizable composition layer to a change in the adhesive strength to the support. As still another method, an image forming method utilizing a change in toner adhesion due to exposure of a photopolymerizable composition layer is also known. As the photopolymerization initiator used in these methods, benzoin,
Those that can respond to short-wavelength light mainly in the ultraviolet region of 400 nm or less, such as benzoin alkyl ether, benzyl ketal, benzophenone, anthraquinone, benzyl ketone, and Michler's ketone, have been used.

On the other hand, in recent years, with the development of image forming technology,
There is a strong demand for a photosensitive material exhibiting high sensitivity to light in the visible region. For example, 48 of argon ion laser
In response to the laser plate making method using an oscillating beam of 8 nm or YAG laser of 532 nm, the aforementioned photopolymerization initiator, organic peroxide, hexaarylbiimidazole compound, trihalomethyl-s-triazine compound, trihalomethyl- Many photopolymerizable compositions have been proposed in which a sensitizing dye or the like is used in combination with a polymerization initiator such as a 1,3,4-oxadiazole compound or a titanocene compound to extend the sensitivity range to about 500 nm. The applicant also has α, α-
A photopolymerizable composition in which a sensitizing dye comprising a boron complex of bipyrromethene is used in combination with a photopolymerization initiator such as a titanocene compound has been proposed (for example, JP-A-5-241338).
JP-A-7-5885 and JP-A-7-225474
No., JP-A-8-76377, etc.).

Here, sensitizing dyes decompose these materials by excitation energy or electron transfer from a dye that has become excited by absorbing light to a radical generator, an acid generator, a silver salt, or the like. Is a dye having a function of generating active radicals, acids, silver and the like. As a use, a silver salt photograph utilizing active silver precipitation is known. Further, various types of negative or positive resists described in Japanese Patent Application No. 11-176337, etc., utilizing the color formation or fading of leuco dyes using the generated acid as a catalyst, and cationic polymerization using this acid. Materials, various resist materials using photopolymerization by generated radicals, and the like can also be mentioned as the uses.

[0005]

However, usually,
When the wavelength of light used for exposure is 500 nm or more,
It is known that, as the photoexcitation energy decreases, the ability of the photopolymerization initiator to generate active radicals sharply decreases, so that the sensitivity as a photopolymerizable composition also decreases. For this reason, at present, in order to obtain a photopolymerizable composition having sufficient sensitivity to light in the visible region, a combination of a photopolymerization initiator and a high-performance sensitizing dye is indispensable, Development of a new sensitizing dye that provides such a photopolymerizable composition is awaited.

[0006] The present invention has been made in view of such prior art. Accordingly, an object of the present invention is to provide a high-performance sensitizing dye, and a photopolymerizable composition and a photopolymerizable image-forming material which exhibit extremely high sensitivity to light in the visible region using the same. .

[0007]

The sensitizing dye according to the present invention comprises a metal capable of forming a complex with porphyrin,
It is represented by the following general formula [2], comprising a metal complex with α, α-bipyrromethene represented by [1].

Embedded image [In the general formula [1], the pyrrole ring may have a substituent, and the two β-position substituents may be linked to each other to form a condensed bicyclo ring. R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent,
Or a heterocyclic group having 4 to 10 carbon atoms which may have a substituent. ]

Embedded image [In the general formula [2], the α, α-bipyrromethene moiety is a general formula
Same as [1]. Me is a metal that can form a complex with porphyrin. X ¹ and X ² each independently represent a halogen atom or a bond extending from the nitrogen atom of two pyrrole rings of the α, α-bipyrromethene moiety similar to the general formula [1] Hand. However, in this α, α-bipyrromethene moiety, the substituents of R ¹ and the pyrrole ring may be the same as or different from those of the other α, α-bipyrromethene moiety sandwiching the metal Me. ]

The photopolymerizable composition according to the present invention is characterized by containing the following components (A), (B) and (C). (A) an ethylenically unsaturated compound (B) a sensitizing dye represented by the general formula [2] (C) a photopolymerization initiator

Further, the photopolymerizable image forming material according to the present invention is characterized in that a layer of the photopolymerizable composition is formed on the surface of a support.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The sensitizing dye according to the present invention is represented by the following general formula [2] consisting of a metal complex of a metal capable of forming a complex with porphyrin and α, α-bipyrromethene. is there.

Embedded image In the general formula [2], R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent, or And represents a heterocyclic group having 4 to 10 carbon atoms which may have a substituent.
R ¹ is preferably an alkyl group having 1 to 5 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a pyrrole group which may have a substituent. Either. As the substituent of R ¹ , a hydroxyl group, a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acyl group and the like are preferable.

Further, the pyrrole ring may have a substituent. The substituent can be bonded to the α-position or β-position in the pyrrole ring.
It may be bonded to any of the positions. A plurality of these substituents may be present, and when a plurality of these substituents are present, they may be different from each other. Examples of the substituent include an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group,
Examples include an arylalkyl group, an alkylthio group, a hydroxyl group, and a halogen atom. Among these, carbon number 1-5
And a phenyl group are preferred.

Further, two substituents at the β-position of the pyrrole ring may be linked to each other to form a condensed bicyclo ring. As the condensed bicyclo ring, 2 constituting a pyrrole ring
The two carbon atoms forming the fused bicyclo ring are bonded to the two carbon atoms at the β-positions, and one of the three bridges shares the two carbon atoms constituting the pyrrole ring and the other two carbon atoms form the pyrrole ring. One bridge is formed by a divalent group such as an ethylene group, a vinylene group, a 1,2-phenylene group, a 2,3-naphthylene group, and a 1,8-naphthylene group. These condensed bicyclo rings may further have a substituent such as an alkoxy group, an acyl group, an acyloxy group, a phenylthio group, a hydroxyl group, and a halogen atom.

Preferred as these condensed bicyclo rings are bicyclo [2.2.2] octane in which both divalent groups forming the other two bridges are ethylene groups, or other bicyclo [2.2.2] octane.
Bicyclo wherein two divalent groups are an ethylene group and a vinylene group
[2.2.2] octene.

Me is a metal capable of forming a complex with porphyrin, and is preferably a transition metal, 3-6A of group 3-4A.
It is an element having a period of 4 to 6 periods of Group 5A, an element of 3 to 7 periods of Group 2A, or zinc of Group 2B. Among them, transition metals, aluminum, indium, silicon, tin, lead, arsenic, and zinc are more preferable, and silicon,
Aluminum, tin, lead, indium, zinc, copper, nickel, platinum, iron, ruthenium, titanium, most preferably zinc.

X ¹ and X ² each independently represent a halogen atom. The halogen atom may be any of fluorine, chlorine, bromine and iodine, and among them, chlorine, bromine and fluorine atoms are preferred.

X ¹ and X ² may be a bond extending from the nitrogen atom of the two pyrrole rings of the α, α-bipyrromethene moiety. That is, the sensitizing dye according to the present invention represented by the general formula [2] may have a structure in which metal Me is sandwiched between two α, α-bipyrromethene moieties. However, R ^{1 of the} two α, α-bipyrromethene portions and the substituents of the pyrrole ring may be the same or different.

The sensitizing dye of the general formula [2] according to the present invention is described in, for example, US Pat. No. 4,774,339 and JH Boger et al, Heteroatom Chemistry, Vol.
o, 5,389 (1990), etc., can be synthesized by reacting α, α-bipyrromethene of the general formula [1] with dichlorozinc. During the reaction, α,
By changing the ratio of the charged amount of dichlorozinc to α-bipyrromethene, a compound having a desired structure can be synthesized.

The photopolymerizable composition according to the present invention is basically composed of the following components (A) to (C). (A) Ethylenically unsaturated compound (B) Sensitizing dye according to the present invention represented by the general formula [2] (C) Photopolymerization initiator Among these, the content of the component (A) depends on the amount of light excluding the solvent. It is preferably from 20 to 80% by weight, particularly preferably from 30 to 70% by weight, based on the entire polymerizable composition. or,
Component (B) and component (C) are 0.1 to 100 parts by weight of component (A) in a total amount of component (B) and component (C) of 0.1 to 100 parts by weight.
It is preferably 30 parts by weight, particularly preferably 0.5 to 20 parts by weight. The ratio of the component (B) to the component (C) is (B) :( C) in a weight ratio of 1:20 to 10: 1.
And particularly preferably in the range of 1: 8 to 4: 1.

The ethylenically unsaturated compound of the component (A)
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 (C). These ethylenically unsaturated compounds form radically polymerizable ethylenically unsaturated double bonds from the viewpoints of polymerizability, crosslinkability, and the accompanying difference in developer solubility between exposed and unexposed areas. Compounds having two or more in the molecule are preferred. Further, the radically polymerizable ethylenically unsaturated double bond is preferably derived from a (meth) acryloyloxy group. In this specification, “(meth) acryl” means acryl and / or
Alternatively, methacryl, "(meth) acrylate" means acrylate and / or methacrylate, and "(meth) acryloyl" means acryloyl and / or methacryloyl.

Preferred (meth) for use in the present invention
As the acrylate compound, poly (meth) acrylates of (meth) acrylic acid and a polyhydroxy compound,
Epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate with a polyepoxy compound, urethane (meth) acrylates of hydroxy (meth) acrylate with a polyisocyanate compound,
And (meth) acryloyloxy group-containing phosphates.

Examples of the poly (meth) acrylates include (meth) acrylic acid, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol, trimethylene glycol, tetramethylene glycol, Esters with pentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylolethane, tetramethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol and the like. Esters of these polyols with ethylene oxide adducts, propylene oxide adducts and the like are also used. Specifically, for example, ethylene glycol di (meth) acrylate, 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, trimethylolpropaneethylene oxide adduct tri (meth) acrylate, Glycerol di (meth) acrylate, glycerol tri (meth) acrylate, tri (meth) acrylate of glycerol propylene oxide adduct, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth)
Acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate and the like can be mentioned.

Also, a reaction product of (meth) acrylic acid and an aromatic polyhydroxy compound such as hydroquinone, resorcin, and pyrogallol, for example, hydroquinone di (meth)
Acrylate, resorcinol di (meth) acrylate, pyrogallol tri (meth) acrylate and the like are also used.
Further, a reaction product of (meth) acrylic acid and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, tri (meth) acrylate, (Meth) acrylate and the like are also used.

Examples of epoxy (meth) acrylates include (meth) acrylic acid, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, and pentaerythritol tri (meth) acrylate. ) Acrylate,
Hydroxy (meth) acrylate compounds such as tetramethylolethanetri (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 ) Aliphatic polyepoxy compounds such as sorbitol polyglycidyl ether, phenol novolak polyepoxy compound, brominated phenol novolak polyepoxy compound, (o-, m-, p-) cresol novolak polyepoxy compound, bisphenol A polyepoxy compound, bisphenol Aromatic polyepoxy compounds such as F polyepoxy compounds, sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris 2-hydroxyethyl) a reaction product of a polyepoxy compound heterocyclic polyepoxy compounds such as isocyanurate.

The urethane (meth) acrylates include, for example, a hydroxy (meth) acrylate compound as described above, hexamethylene diisocyanate,
4,4-trimethylhexamethylene diisocyanate,
Lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,11-undecatriisocyanate,
1,3,6-hexamethylene triisocyanate, 1,
Aliphatic polyisocyanates such as 8-diisocyanate-4-isocyanatemethyloctane; cycloaliphatic polyisocyanates such as cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate and bicycloheptane triisocyanate; -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 (isocyanatephenylmethane), tris (isocyanatephenyl)
Reaction products with a polyisocyanate compound such as an aromatic polyisocyanate such as thiophosphate and a heterocyclic polyisocyanate such as isocyanurate are exemplified.

The (meth) acryloyloxy group-containing phosphates include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) acryloyloxyethylene glycol phosphate and the like. .

The photopolymerization initiator of the component (C) constituting the photopolymerizable composition according to the present invention, when irradiated with light in the presence of the component (B) and the sensitizing dye, generates an active radical. It is a radical generator that is generated. As the photopolymerization initiator,
Examples thereof include a titanocene compound, a halogenated hydrocarbon derivative, a hexaarylbiimidazole compound, an organic boron complex, a carbonyl compound, and an organic peroxide. In the present invention, a titanocene compound is preferable.

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 (2,4-difluorophenyl), 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 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 2,2-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,
2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.

As the hexaarylbiimidazole compound, for example, 2,2'-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, p-dichlorophenyl) -4,4 ', 5,5'-tetra (o, p-
Dichlorophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole,
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-chlorophenyl) -4
4 ', 5,5'-tetra (p-chloronaphthyl) biimidazole and the like.

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, an organic boron transition metal coordination complex and the like. Are, for example, benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, etc., as organic peroxides, for example, ketone peroxide, diacyl peroxide, hydroperoxide, dialkyl peroxide, peroxyketal, alkyl perester, peroxy Carbonate and the like are each mentioned.

In addition to the components (A) to (C), the photopolymerizable composition according to the present invention has improved mechanical strength and the like as a coating film and improved developability such as compatibility with a developer. For the purpose, etc., it is preferable that a polymer binder is contained as the component (D). The content is preferably in the range of 50 to 400 parts by weight, particularly preferably 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). As the polymer binder, usually an alkali-soluble resin, for example, a carboxyl group-containing vinyl resin,
A phenolic hydroxyl group-containing resin or the like is used. Among them, a carboxyl group-containing vinyl resin is preferable in terms of sensitivity.

Examples of the carboxyl group-containing vinyl resin include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid,
Unsaturated carboxylic acids such as citraconic acid, styrene, α-
Methyl styrene, hydroxy styrene, 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) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Copolymers with vinyl compounds such as N, N-dimethylaminoethyl (meth) acrylamide and vinyl acetate are exemplified. The acid value of these carboxyl group-containing vinyl resins is 30 to 250 KOH.
Mg / g, weight average molecular weight in terms of polystyrene is 1,
It is preferably from 000 to 300,000.

Preferred among the carboxyl group-containing vinyl resins are those having an ethylenically unsaturated bond in the side chain. As such a material, for example, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) ) Unsaturated compounds containing aliphatic epoxy groups such as acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate, and monoalkyl monoglycidyl maleate , Or 3,4-
A reaction product obtained by reacting an alicyclic epoxy group-containing unsaturated compound such as epoxycyclohexylmethyl (meth) acrylate is exemplified. Also, allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, N, N-diallyl (meth) acrylamide, vinyl (Meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth)
Acrylate, 1-propenyl (meth) acrylate,
A compound having two or more kinds of unsaturated groups such as vinyl crotonate and vinyl (meth) acrylamide and an unsaturated carboxylic acid such as (meth) acrylic acid and its ester are combined with the former compound having an unsaturated group. 10 to 10
A reaction product obtained by copolymerization so as to be 90 mol%, preferably about 30 to 80 mol%, is also included.

Examples of the phenolic hydroxyl group-containing resin include 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-
At least one kind of phenols such as naphthol, 4,4′-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, phloroglucinol, etc., is added under an acidic catalyst, for example. Novolak resins, acid catalysts, polycondensed with aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, benzaldehyde, furfural, or ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone A resole resin polycondensed in the same manner except that an alkaline catalyst is used instead, and, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene , Trihydroxystyrene,
Tetrahydroxystyrene, pentahydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2-
Polyvinylphenol resin obtained by polymerizing hydroxystyrenes such as (m-hydroxyphenyl) propylene and 2- (p-hydroxyphenyl) propylene alone or in combination of two or more thereof in the presence of a radical polymerization initiator or a cationic polymerization initiator. Is mentioned. These phenolic hydroxyl group-containing resins have a weight average molecular weight of 1,500 to 50,000.
It is preferred that

The photopolymerizable composition according to the present invention may further comprise, in addition to the above components,
As the component (E), a polymerization accelerator is used.
0.5 to 50 parts by weight, especially 1 to 5 parts by weight
It is preferable to contain it in the range of 30 parts by weight. In general, a hydrogen-donating compound is used as a polymerization accelerator. For example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol Mercapto group-containing compounds such as dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, N, N-dialkylaminobenzoate, N-phenylglycine, and ammonium and sodium salts thereof And derivatives thereof such as salts of the above, esters and the like, phenylalanine or salts thereof such as ammonium and sodium salts, and amino acids having an aromatic ring such as derivatives of the above esters and the like, and derivatives thereof.

Incidentally, the photopolymerizable composition according to the present invention may further contain various conventional additives, if necessary. For example, per 100 parts by weight of the photopolymerizable composition excluding the solvent, hydroquinone, p-methoxyphenol, 2,6-
2 parts by weight or less of a thermal polymerization inhibitor such as di-t-butyl-p-cresol, 50 parts by weight or less of a coloring agent composed of an organic or inorganic dye or pigment, dioctyl phthalate, didodecyl phthalate, tricresyl phosphate, dioctyl 40 parts by weight or less of a plasticizer such as adipate or triethylene glycol dicaprylate, 5 parts by weight or less of a sensitivity improving agent such as a tertiary amine or thiol, a triarylmethane, a bisarylmethane, a xanthene compound, a fluoran compound or a 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 its partial skeleton can be contained in an amount of 10 parts by weight or less.

The image forming material using the photopolymerizable composition according to the present invention can be produced by a usual method. In general, the solution may be applied to the surface of a support without solvent or diluted with an appropriate solvent, and dried. If desired, a protective layer for blocking oxygen may be provided thereon. Further, an image forming material can also be manufactured by enclosing in a microcapsule and applying it on a support. Preferably, an image forming material is produced by applying the photopolymerizable composition as a solution in a suitable solvent to the surface of the support, followed by heating and drying. Such an image forming material is suitable for use as, for example, a lithographic printing plate.

The solvent is not particularly limited as long as it has sufficient solubility in the photopolymerizable composition according to the present invention and gives good coating properties. Examples of the solvent include methyl cellosolve, ethyl cellosolve, and the like. Cellosolve solvents such as methyl cellosolve acetate and 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, dipropylene Propylene glycol solvents such as glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, Ethyl, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate,
Ethyl lactate, ester solvents such as methyl 3-methoxypropionate, methanol, ethanol, propanol,
Alcoholic solvents such as butanol, heptanol, hexanol, diacetone alcohol, and furfuryl alcohol; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; and high solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone. Examples thereof include a polar solvent, a mixed solvent thereof, and a solvent obtained by adding an aromatic hydrocarbon thereto. The use ratio of the solvent is usually in the range of about 1 to 20 times by weight based on the weight of the photopolymerizable composition.

As the support, aluminum, zinc,
Copper, steel or other metal plate, aluminum, zinc, copper, iron, chromium, nickel or the like plated or vapor-deposited metal plate, paper, resin-coated paper, aluminum or other metal-foiled paper,
Examples include a plastic film, a plastic film subjected to a hydrophilic treatment, and a glass plate. Among them, an aluminum plate is preferable, and surface treatment such as graining treatment by electrolytic etching or brush polishing in a hydrochloric acid or nitric acid solution, anodizing treatment in a sulfuric acid solution, and, if necessary, sealing treatment is performed. A coated aluminum plate is more preferred.
The surface roughness of the support is 0.3 to 1.0 μm, particularly 0.4 to 1.0 μm in average roughness Ra specified in JIS B0601.
It is preferably about 0.8 μm.

As a method for coating the surface of the support, a conventionally known method is used. 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 is usually in the range of 0.5 to 100 μm as a dry film thickness. As an example, in the case of a lithographic printing plate, preferably 0.5 to 5 μm
m, more preferably 1-3 μm. The drying temperature of the applied photopolymerizable composition is, for example, 30 to 15
A temperature range of about 0 ° C., preferably about 40 to 110 ° C. is used, and a drying time is, for example, about 5 seconds to 60 minutes, preferably about 10 seconds to 30 minutes.

On the photopolymerizable composition layer thus formed, it is preferable to provide a protective layer of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, cellulose or the like in order to prevent the polymerization inhibition effect by oxygen.

As a light source used for image exposure of the photopolymerizable image forming material according to the present invention, a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, etc., and a HeNe laser, Argon ion laser, YA
A laser light source such as a G laser, a HeCd laser, a semiconductor laser, and a ruby laser may be used. These light sources are generally used for scanning exposure and then developing with a developer to form an image.

Examples of the developing solution include sodium silicate, potassium silicate, lithium silicate, ammonium silicate,
Sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, dibasic sodium phosphate, tertiary sodium phosphate, dibasic ammonium phosphate, tertiary ammonium phosphate, Sodium borate, potassium borate,
Inorganic alkali salts such as ammonium borate, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine 0.1 of organic amine compounds such as
An alkali developer consisting of an aqueous solution of about 5% by weight is used. Among them, aqueous solutions of alkali metal silicates such as sodium silicate and potassium silicate as inorganic alkali salts are preferable.

The development is preferably carried out 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.

[0045]

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 The photopolymerizable lithographic printing plate used in the experiment was prepared by dissolving a photopolymerizable composition in a solvent, coating the following coating solution on a support, drying the coating solution, and then coating the solution. Manufactured by providing a protective layer. (A) Trimethylolpropane triacrylate: 10
0 parts by weight (B) Sensitizing dye of the following formula: 2 parts by weight (C) dicyclopentadienyltitanium bis [2,6
-Difluoro-3- (1-pyrrolyl) phenyl]: 10
Parts by weight (D) Methyl methacrylate / methacrylic acid copolymer (molar ratio 85/15, weight average molecular weight 45,000): 10
0 parts by weight (E) Ethyl p-dimethylaminobenzoate: 20 parts by weight The above components were charged into 1800 parts by weight of methyl ethyl ketone, and the mixture was stirred for 10 minutes at room temperature.
After applying the above coating solution to the surface of an aluminum plate (thickness 0.24 mm) subjected to graining treatment and anodizing treatment using a wire bar, the coating solution was dried at 80 ° C. for 2 minutes.
A photopolymerizable composition layer having a thickness of 2 μm was formed. Next, an aqueous solution of polyvinyl alcohol was applied onto the photopolymerizable composition layer and dried at 80 ° C. for 2 minutes to form a protective layer having a thickness of 3 μm.

[0047]

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The photopolymerizable lithographic printing plate obtained above was exposed using a spectral sensitivity measuring device (manufactured by Narumi). Xenon lamp (Ushio Electric Co., Ltd. “UI-501”) as a light source
C)), and irradiation was performed for 10 seconds while setting the exposure wavelength to change linearly in the horizontal axis direction and the exposure intensity to change logarithmically in the vertical axis direction. Thereafter, 30% at 25 ° C. was added to a 1% by weight aqueous solution of sodium silicate containing 1% by weight of butyl cellosolve.
Development was performed by immersion for 2 seconds. The sensitivity of the photopolymerizable composition was evaluated based on the thus obtained resist image corresponding to the sensitivity at each exposure wavelength. As a result, the minimum exposure required for image formation at a wavelength of 532 nm in the spectral sensitivity curve was 300 μJ / cm ² .

Comparative Example 1 A photopolymerizable lithographic printing plate was prepared and exposed and developed in the same manner as in Example 1, except that "Eosin Yellowish" was used as the sensitizing dye of the component (B). No image formation itself was carried out.

Comparative Example 2 A photopolymerizable lithographic printing plate was prepared, exposed and developed in the same manner as in Example 1 except that a sensitizing dye represented by the following formula was used as the component (B). Did not form itself.

[0051]

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Comparative Example 3 A photopolymerizable lithographic printing plate was prepared, exposed and developed in the same manner as in Example 1 except that a sensitizing dye represented by the following formula was used as the component (B), and an image was formed at 532 nm. Was found to be 600 μJ / cm ² .

[0053]

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[0054]

According to the present invention, there are provided a high-performance sensitizing dye, and a photopolymerizable composition and a photopolymerizable image-forming material which use the sensitizing dye and exhibit extremely high sensitivity to light in the visible region. Can do things.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 57/10 C09B 57/10 G03F 7/004 501 G03F 7/004 501 503 503Z 7/027 502 7/027 502 7/029 7/029 F-term (reference) 2H025 AA01 AB03 AB15 AC01 AD01 BC13 BC31 CA27 CA39 CA41 CB43 CC20 4H056 CA01 CC02 CC08 CE03 DD03 FA05 4J011 PA43 PA47 PA49 PA69 PA85 PB25 PB40 PC02 QA03 QA12 QA13 QA12 QA13 QA12 QA13 QA13 QA12 QA13 QA12 QA13 QA12 QA12 SA86 SA88 UA02 UA06 VA01 WA01 4J026 AA43 AA44 AA57 AB01 AC23 BA28 DA02 DA08 DB06 DB17 DB36 FA05 GA06

Claims (8)

[Claims] 1. A sensitizing dye represented by the general formula [2], comprising a metal complex of a metal capable of forming a complex with porphyrin and α, α-bipyrromethene represented by the general formula [1]. Embedded image [In the general formula [1], the pyrrole ring may have a substituent, and the two β-position substituents may be linked to each other to form a condensed bicyclo ring. R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent,
Or a heterocyclic group having 4 to 10 carbon atoms which may have a substituent. ] [In the general formula [2], the α, α-bipyrromethene moiety is a general formula
Same as [1]. Me is a metal that can form a complex with porphyrin. X ¹ and X ² each independently represent a halogen atom or a bond extending from the nitrogen atom of two pyrrole rings of the α, α-bipyrromethene moiety similar to the general formula [1] Hand. However, in this α, α-bipyrromethene moiety, the substituents of R ¹ and the pyrrole ring may be the same as or different from those of the other α, α-bipyrromethene moiety sandwiching the metal Me. ] 2. A sensitizing dye represented by the general formula [3], comprising a metal complex of a metal capable of forming a complex with porphyrin and α, α-bipyrromethene represented by the general formula [1]. Embedded image [In the general formula [1], the pyrrole ring may have a substituent, and the two β-position substituents may be linked to each other to form a condensed bicyclo ring. R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent,
Or a heterocyclic group having 4 to 10 carbon atoms which may have a substituent. ] [In the general formula [3], Me is a metal capable of forming a complex with porphyrin. The two α, α-bipyrromethene moieties sandwiching Me are the same as in general formula [1], but R ¹
And the substituents of the pyrrole ring may be different from each other in the two α, α-bipyrromethene moieties. ] 3. The sensitizing dye according to claim 1, wherein the metal capable of forming a complex with porphyrin is zinc. 4. A photopolymerizable composition comprising the following components (A), (B) and (C). (A) an ethylenically unsaturated compound (B) a sensitizing dye according to any one of claims 1 to 3 (C) a photopolymerization initiator 5. The photopolymerizable composition according to claim 4, wherein the photopolymerization initiator of the component (C) is a titanocene compound. 6. The photopolymerizable composition according to claim 4, comprising a polymer binder. 7. The photopolymerizable composition according to claim 4, further comprising a polymerization accelerator. 8. A photopolymerizable image forming material comprising a support and a layer of the photopolymerizable composition according to claim 4 formed on a surface of the support.