JP2002182391A - Photopolymerizable composition and photopolymerizable planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition and a photopolymerizable planographic printing plate having high sensitivity as well as superior printing resistance. SOLUTION: The photopolymerizable composition contains (A) a polymer binder containing a constitutional unit of formula ( I) [where R31 is methyl or H; R32 is alkyl or H; and V is the residue of an epoxy-containing ethylenically unsaturated compound] and a constitutional unit derived from (meth)acrylonitrile, (B) an ethylenically unsaturated compound and (C) a photopolymerization initiator. The photopolymerizable planographic printing plate is obtained by forming a layer of the photopolymerizable composition on the surface of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable composition and a photopolymerizable lithographic printing plate, and more particularly, to a photopolymerizable composition and a photopolymerizable lithographic printing plate having excellent printing durability and high sensitivity. About.

[0002]

2. Description of the Related Art Conventionally, as a method of forming an image by exposing a photopolymerizable composition, a photopolymerizable composition comprising a polymer binder, an ethylenically unsaturated compound, a photopolymerization initiator, or a sensitizing dye or the like has been used. A method of forming a cured relief image by forming a layer of the product on the surface of the support, exposing the image, polymerizing and curing the ethylenically unsaturated compound in the exposed portion, and then dissolving and removing the unexposed portion is commonly used. For the purpose of improving the sensitivity of the photopolymerizable composition, various proposals have been made for various types of ethylenically unsaturated compounds, or photopolymerization initiators, or sensitizing dyes. However, it is not satisfactory in terms of printing durability.On the other hand, for the purpose of improving the printing durability, a part of the carboxyl groups of the carboxyl group-containing polymer is reacted with the epoxy group-containing ethylenically unsaturated compound. ~ side A photopolymerizable composition using a polymer having an ethylenically unsaturated bond introduced therein as a polymer binder has also been proposed (see, for example, Japanese Patent Application Laid-Open No. 10-10719), but still has satisfactory resistance. I could not reach the printing power.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art. Therefore, the present invention provides a photopolymerizable composition having excellent printing durability and high sensitivity. An object is to provide a photopolymerizable lithographic printing plate.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a photopolymerizable composition containing a polymer binder containing a specific structural unit has achieved the above-mentioned object. The present invention has been accomplished by finding out what can be achieved, that is, the present invention provides a photopolymerizable composition containing the following components (A), (B) and (C), and a support surface. And photopolymerizable lithographic printing in which a layer of the photopolymerizable composition is formed.

(A) A polymer binder containing a structural unit represented by the following general formula (I) and a structural unit derived from (meth) acrylonitrile

[0006]

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[In the formula (I), R ³¹ represents a methyl group or a hydrogen atom; R ³² represents an alkyl group or a hydrogen atom;
Represents a residue of an epoxy group-containing ethylenically unsaturated compound. ]

(B) Ethylenically unsaturated compound (C) Photopolymerization initiator

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer binder of the component (A) constituting the photopolymerizable composition of the present invention includes an ethylenically unsaturated compound of the component (B) and a photopolymerization of the component (C) described later. It has a function as a binder for an initiator and the like. In the present invention, as the polymer binder, the structural unit represented by the general formula (I) and (meth) acrylonitrile [here, "( "Meth) acryl" means acryl or methacryl, and the same applies hereinafter. The present invention achieves the object of the present invention when it does not include any of the structural unit represented by the general formula (I) or the structural unit derived from (meth) acrylonitrile. Can not do.

[0010] Here, in the general formula (I), the carbon number of the alkyl group for R ³² is generally 1 to 10, is preferably 1-4.

The residue of the epoxy group-containing ethylenically unsaturated compound represented by V is derived from a method for producing a polymer binder containing a structural unit represented by the general formula (I) described below. The structural unit represented by the following general formula (II) is preferable as the structural unit represented by the general formula (I).

[0012]

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[In the formula (II), R ³¹ and R ³² represent the above-mentioned general formula
Are the same as in (I), R ³³ represents an alkyl group or a hydrogen atom, if R ³³ there are a plurality, each of R ³³
May be different, also may form a cyclic structure linked R ³² and R ³³ each other, m is an integer of 0. ]

Here, in the general formula (II), R³³of
The carbon number of the alkyl group is usually 1 to 10, and 1 to 4
Preferably, m is from 0 to 5.
Also, R ³²And R³³Are connected to each other to form a cyclic group having 4 to 7 carbon atoms
Preferably, it forms a structure.

Further, as the structural unit of the general formula (II), a structural unit represented by the following general formula (III) is preferable.

[0016]

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[In the formula (III), R ³¹ and R ³³ are the same as those in the general formula (II). ]

The structural unit of the above-mentioned general formula (I) of the polymer binder of the component (A) in the present invention is a copolymer of a carboxyl group-containing monomer and (meth) acrylonitrile [hereinafter referred to as a precursor] , "Carboxyl group-containing copolymer". And the epoxy group of the epoxy group-containing ethylenically unsaturated compound.

Here, as the carboxyl group-containing copolymer as a precursor, specifically, for example, (meth) acrylic acid [here, “(meth) acryl” means acryl or methacryl; The same shall apply hereinafter. ], Crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, carboxyl group-containing monomers such as unsaturated carboxylic acids such as cinnamic acid,
Binary copolymers with (meth) acrylonitrile, and these carboxyl group-containing monomers, (meth) acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate,
Benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-
(Meth) acrylic acid derivatives such as dimethyl (meth) acrylamide; vinyl heterocyclic compounds such as N-vinylpyrrolidone; vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; vinyl acetate; vinyl chloride And terpolymers with other comonomers such as vinyl compounds.

These carboxyl group-containing monomers, (meth) acrylonitrile and comonomer may be used in combination of two or more kinds. Among them, (meth) acrylic acid is preferable as the carboxyl group-containing monomer,
As the comonomer, (meth) acrylates such as methyl (meth) acrylate and butyl (meth) acrylate are preferable.

The carboxyl group-containing copolymer as the precursor preferably has a carboxyl group-containing monomer content of 3 to 50 mol%, particularly preferably 5 to 30 mol%. , (Meth) acrylonitrile preferably accounts for 1 to 60 mol%,
It is particularly preferred that the content is ４０40 mol%.

Examples of the epoxy group-containing ethylenically unsaturated compound to be reacted with the carboxyl group-containing copolymer as a precursor include aliphatic epoxy group-containing ethylenically unsaturated compounds and alicyclic epoxy group. Containing ethylenically unsaturated compounds.

Examples of the aliphatic epoxy group-containing ethylenically unsaturated compounds include allyl glycidyl ether, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, and crotonyl. Examples include glycidyl ether, isocrotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate, and monoalkyl monoglycidyl maleate.

In the case of the alicyclic epoxy group-containing ethylenically unsaturated compounds, examples of the alicyclic epoxy group include a 2,3-epoxycyclopentyl group,
A 4-epoxycyclohexyl group, a 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] group, and the like. Examples of the ethylenically unsaturated bond include (meth)
It is preferably derived from an acryloyl group, and suitable alicyclic epoxy group-containing ethylenically unsaturated compounds include, for example, the following compounds. still,
In the following compounds, R ³⁵ is a hydrogen atom or a methyl group,
R ³⁶ represents an alkylene group having 1 to 10 carbon atoms.

[0025]

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In the present invention, among the above-mentioned epoxy group-containing ethylenically unsaturated compounds, alicyclic epoxy group-containing ethylenically unsaturated compounds are preferable, and in particular, 3,4-epoxycyclohexylmethyl (meth) acrylate Is particularly preferred.

In the present invention, the epoxy group-containing ethylenically unsaturated compound is reacted with the carboxyl group-containing copolymer as a precursor, and an ethylenically unsaturated bond is introduced into a side chain of the carboxyl group-containing copolymer. to do so,
For example, tertiary amines such as triethylamine and benzylmethylamine; quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride and tetraethylammonium chloride; A known method of reacting at a temperature of 50 to 150 ° C. for about 1 to 50 hours is employed.

The polymer binder of the component (A) in the present invention includes a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester,
A structural unit represented by (I), (II), or (III); and
It is preferably composed of a structural unit derived from (meth) acrylonitrile.

The polymer binder of the component (A) in the present invention includes a structural unit represented by the general formula (I), (II) or (III), and a polymer derived from (meth) acrylonitrile. It is preferable that each of the structural units contains 1 to 30 mol%, and it is particularly preferable that each of the structural units contain 2 to 20 mol%. When the content of the general formula and the structural unit derived from (meth) acrylonitrile is less than the above range, the printing durability as a photopolymerizable composition tends to be inferior. On the other hand, when the content is more than the above range, the photopolymerizable composition Tends to deteriorate image forming properties. The polymer binder of the present invention may contain a polymer binder other than the component (A) in addition to the polymer binder of the component (A).

(B) Constituting the Photopolymerizable Composition of the Invention
The component ethylenically unsaturated compound undergoes addition polymerization by the action of a photopolymerization initiation system including a photopolymerization initiator of component (C) described below when the photopolymerizable composition is irradiated with actinic rays. It is a compound having at least one radically polymerizable ethylenically unsaturated bond in a molecule which is crosslinked and cured by the following method.

As the ethylenically unsaturated compound in the present invention, a compound having one ethylenically unsaturated bond in a molecule, specifically, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, Unsaturated carboxylic acids such as itaconic acid and citraconic acid, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene and the like may be used. It is preferable that the compound has two or more ethylenically unsaturated bonds in the molecule, for example, from the viewpoint that the difference in developer solubility between the exposed portions can be enlarged.
Further, an acrylate compound whose unsaturated bond is derived from a (meth) acryloyloxy group is particularly preferred.

The compound having two or more ethylenically unsaturated bonds in a molecule is typically an ester of an unsaturated carboxylic acid with a polyhydroxy compound, or a compound of a hydroxy (meth) acrylate compound with a polyisocyanate compound. Examples include urethane (meth) acrylates, epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound, and (meth) acryloyloxy group-containing phosphates.

Examples of the esters include, for example, unsaturated carboxylic acids as described above, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol, trimethylene glycol and tetramethylene glycol. Methylene glycol, neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylolethane, tetramethylolethane,
Trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, reactants with aliphatic polyhydroxy compounds such as triethanolamine, 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, trimethylolethane tri (meth) acrylate, tetramethylolethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol Propane ethylene oxide added tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycer Lumpur propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth)
Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth)
Acrylates and the like, and similar crotonates, isocrotonates, maleates, itaconates, citraconates and the like can be mentioned.

Further, as the esters, a reaction product of the unsaturated carboxylic acid as described above with an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, specifically, for example, hydroquinone Di (meth) acrylate, resorcinol di (meth) acrylate, pyrogallol tri (meth)
Acrylates and the like, and an unsaturated carboxylic acid as described above,
Reaction product with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically, for example, di (meth) acrylate, tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate A reaction product of an unsaturated carboxylic acid, a polycarboxylic acid and a polyhydroxy compound, specifically, for example, a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, (meth) acrylic acid And condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, and condensates of (meth) acrylic acid, adipic acid, butanediol and glycerin.

Examples of the urethane (meth) acrylates include, 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 polyisocyanate compounds such as aromatic polyisocyanates such as tris (isocyanatephenyl) thiophosphate and heterocyclic polyisocyanates such as isocyanurate.

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

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

Other ethylenically unsaturated compounds other than those described above include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, and vinyl groups containing divinyl phthalate and the like. And the like. The above ethylenically unsaturated compounds may be used alone or in combination of two or more.

In the present invention, as the above-mentioned ethylenically unsaturated compound as the component (B), (meth) acryloyloxy group-containing phosphates, urethane (meth) acrylates or ester (meth) acrylates are preferable. The proportion of the (meth) acryloyloxy group-containing phosphate in the whole ethylenically unsaturated compound as the component (B) is preferably 1 to 60% by weight, and the urethane (meth) acrylates Is preferably 10 to 60% by weight, and ester (meth) acrylates are preferably 10 to 60% by weight.

(C) Constituting the Photopolymerizable Composition of the Invention
The component photopolymerization initiator is a radical generator that generates an active radical when irradiated with light in the presence of a component (D) described below, such as a sensitizing dye, and is typically a halomethylated compound. s-Triazine derivatives, halomethylated 1,3,4
-Oxadiazole derivatives, hexaarylbiimidazole compounds, titanocene compounds, organic borates and the like. In the present invention, halomethylated s
-Triazine derivatives, titanocene compounds and organic borates are preferred.

Here, as the halomethylated s-triazine derivatives, 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- (Α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4- Epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-
Chlorophenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6
-Bis (trichloromethyl) -s-triazine, 2-
(P-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (p-ethoxynaphthyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (p-ethoxycarbonylnaphthyl) -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 halomethylated 1,3,4-oxadiazole derivatives, specifically, for example, 2
-(P-methoxyphenyl) -5-trichloromethyl-
1,3,4-oxadiazole, 2- (p-methoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 2- (o-benzofuryl) -5-trichloromethyl-1,3 , 4-oxadiazole, 2- [β-
(O-benzofuryl) vinyl] -5-trichloromethyl-1,3,4-oxadiazole and the like.

Specific examples of the hexaarylbiimidazole derivatives include, for example, 2,2′-bis (o-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2'-bis (p-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'- Tetraphenylbiimidazole, 2,2′-bis (o-fluorophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5′-tetra (m, m-dimethoxyphenyl) biimidazole, 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, 2,2'-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 titanocene derivatives include, for example, dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis (2,4-difluorophenyl). ), Dicyclopentadienyltitanium 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), dicyclopentadienyltitanium bis [2,6-difluoro-3- (1 -Pyrrolyl)
Phenyl] and the like.

As the organic borates, in particular,
Those represented by the following general formula (IV) are preferred.

[0046]

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[In the formula (IV), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸
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 or a heterocyclic group is shown, which may be linked to each other to form a cyclic structure, and at least one of them is an alkyl group which may have a substituent. X _b ⁺ is a counter cation. ]

Here, when R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ in the formula (IV) are alkyl groups, the number of carbon atoms is usually from 1 to 1.
5, preferably 1 to 5, the number of carbon atoms when it is an alkenyl group or an alkynyl group is usually 2 to 15, preferably 2 to 5,
When it is an aryl group, it usually has 6 to 20, preferably 6 to 15, and when it is a heterocyclic group, it usually has 4 to 4 carbon atoms.
20, preferably 4 to 15, and examples of the substituent therefor include a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group, and a trimethylsilyl group.

As the organic boron anion of the organic borate represented by the formula (IV), specifically, for example, n-
Butyl-methyl-diphenyl boron anion, n-butyl-triphenyl boron anion, n-butyl-tris (2,4,6-trimethylphenyl) boron anion, n
-Butyl-tris (p-methoxyphenyl) boron anion, n-butyl-tris (p-fluorophenyl) boron anion, n-butyl-tris (m-fluorophenyl) boron anion, n-butyl-tris (3-fluoro -4-methylphenyl) boron anion, n-butyl-tris (2,6-difluorophenyl) boron anion, n
-Butyl-tris (2,4,6-trifluorophenyl) boron anion, n-butyl-tris (2,3,4,
5,6-pentafluorophenyl) boron anion, n-
Butyl-tris (p-chlorophenyl) boron anion,
n-butyl-tris (trifluoromethyl) boron anion; n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) -boron anion;

As the counter cation X _b ⁺ , for example,
Onium compounds such as alkali metal cations, ammonium cations, phosphonium cations, sulfonium cations, iodonium cations, and pyriumium cations, thiapyrylium cations, indolium cations, and the like, and organic ammonium cations such as tetraalkylammonium Is preferred. In the present invention, as a method for allowing an organic borate as a photopolymerization initiator of the component (C) to be present in the photopolymerizable composition, an organic boron anion of the organic borate and a counter cation appropriately selected are used. In addition to the usual method of compounding a salt of (a), a method of compounding a salt formed by an organic boron anion of the above-mentioned organic borate and a dye cation of a sensitizing dye of the component (D) described later can also be employed.

The photopolymerizable composition of the present invention comprises the polymer binder of component (A), the ethylenically unsaturated compound of component (B), and the photopolymerization initiator of component (C). It is an essential component, but preferably further contains a sensitizing dye (D) component.

In the present invention, the sensitizing dye has a wavelength range of 30.
In addition to efficiently absorbing light in the near-infrared region from the ultraviolet region of 0 to 1200 nm, the photoexcitation energy is transmitted to the photopolymerization initiator of the component (C) to decompose the photopolymerization initiator, The sensitizing function for generating an active radical that induces the polymerization of the ethylenically unsaturated compound is enhanced.

In the present invention, the sensitizing dye includes:
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, and typically, the hetero atom forms a heterocyclic ring and is linked via a polymethine chain. So-called cyanine-based dyes having a structure in which a heterocyclic ring is bonded as a basic structure, specifically, for example, quinoline-based (so-called cyanine-based), indole-based (so-called indocyanine-based), benzothiazole-based ( So-called thiocyanine-based), pyrylium-based, thiopyrylium-based, squarylium-based, croconium-based, azurenium-based, and the like, and
So-called polymethine dyes and the like having a basic structure having a structure in which an acyclic heteroatom is bonded via a polymethine chain, and the like,
Among them, quinoline-based, indole-based, benzothiazole-based, pyrylium-based, thiopyrylium-based cyanine-based dyes, and polymethine-based dyes are preferable.

In the present invention, among the cyanine-based dyes, quinoline-based dyes are preferably represented by the following general formula (Va):
, (Vb) or (Vc) is preferred.

[0055]

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In the formulas (Va), (Vb) and (Vc), R ¹ and R
² each independently has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a group which has a substituent. L ¹ represents a tri, penta, hepta, nona, or undecamethine group which may have a substituent, and two substituents on the penta, hepta, nona, or undecamethine group Are linked to each other to have 5 to 7 carbon atoms
May form a cycloalkene ring, and the condensed benzene ring may have a substituent. In this case, two adjacent substituents may be connected to each other to form a condensed benzene ring. . X _a ^- represents a counter anion. ]

Here, R in formulas (Va), (Vb) and (Vc)¹
And R^TwoIs an alkyl group, the number of carbon atoms is usually 1 to
15, preferably 1 to 10, alkenyl group, alkynyl
When it is a group, it usually has 2 to 15, preferably 2 carbon atoms.
-10, and those substituents including a phenyl group
In general, the number of carbon atoms is usually 1 to 15, preferably 1 to 10.
Lucoxy, phenoxy, hydroxy, or phenyl
And the like. ¹In benzene and fused benzene rings
Examples of the substituent include an alkyl group having the same number of carbon atoms as described above.
You.

As the indole and benzothiazole dyes, those represented by the following general formula (VI) are particularly preferred.

[0059]

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[In the formula (VI), Y ¹ and Y ² each independently represent a dialkylmethylene group or a sulfur atom, and R ³ and R ⁴ each independently may have a substituent. An alkyl group, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a phenyl group which may have a substituent, and L ² has a substituent Represents a tri, penta, hepta, nona, or undecamethine group which may be substituted, and two substituents on the penta, hepta, nona, or undecamethine group are linked to each other to have 5 carbon atoms.
To 7 may form a cycloalkene ring, and the condensed benzene ring may have a substituent. In this case, two adjacent substituents are connected to each other to form a condensed benzene ring. Is also good. X _a ^- represents a counter anion. ]

Here, when R ³ and R ⁴ in the formula (VI) are an alkyl group, the number of carbon atoms is usually 1 to 15, preferably 1 to 10, and the carbon number when an alkenyl group or an alkynyl group is used. Is usually 2 to 15, preferably 2 to 10, and as a substituent thereof including a phenyl group, an alkoxy group having a carbon number of usually 1 to 15, preferably 1 to 10, a phenoxy group, a hydroxy group, Or a phenyl group. Examples of the substituent in L ² and the fused benzene ring include:
Alkyl groups having the same number of carbon atoms as mentioned above.

Further, as the pyrylium-based and thiopyrylium-based dyes, the following general formulas (VIIa), (VIIb), or
Those represented by (VIIc) are preferred.

[0063]

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[In the formulas (VIIa), (VIIb) and (VIIc), Z ¹
And Z ² each independently represent an oxygen atom or a sulfur atom; R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom or an alkyl group, or R ⁵ and R ⁷ , and R ⁶ and R
⁸ may be linked to each other to form a cycloalkene ring having 5 or 6 carbon atoms, and L ³ represents a mono, tri, penta, or heptamethine group which may have a substituent; Two substituents on the penta or heptamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms, and the pyrylium ring and the thiapyrylium ring may have a substituent, In this case, two adjacent substituents may be connected to each other to form a fused benzene ring. X _a ^- represents a counter anion. ]

In the formulas (VIIa), (VIIb) and (VIIc)
R^Five, R⁶, R⁷, And R⁸Is an alkyl group
Has usually 1 to 15, preferably 1 to 10
L ^ThreeIn the above, the substituent is
A pyrylium ring and a thiapyrylium ring
As the substituent, an aryl group such as a phenyl group
Is mentioned.

As the polymethine dye, those represented by the following general formula (VIII) are particularly preferable.

[0067]

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[In the formula (VIII), R ⁹ , R ¹⁰ , R ¹¹ and R
¹² each independently represents an alkyl group; R ¹³ and R ¹⁴ each independently represent an aryl group which may have a substituent;
L ⁴ represents a mono-, tri-, penta- or heptamethine group which may have a substituent, and two substituents on the tri-, penta- or heptamethine group are linked to each other; To form a cycloalkene ring having 5 to 7 carbon atoms, and the quinone ring and the benzene ring may have a substituent. X _a ^- represents a counter anion. ]

Here, R ⁹ , R ¹⁰ , R ¹¹ in formula (VIII)
And the carbon number of the alkyl group of R ¹² is usually 1 to 15, preferably 1 to 10, and the carbon number when R ¹³ and R ¹⁴ are an aryl group is usually 6 to 20, preferably 6 to 15. , R ¹³ and R ¹⁴ are specifically a phenyl group, 1-
A naphthyl group, a 2-naphthyl group, a 2-furyl group, a 3-furyl group, a 2-thienyl group, a 3-thienyl group, and the like,
Examples of such a substituent include an alkyl group having the same number of carbon atoms as described above, an alkoxy group having the same number of carbon atoms as described above, a dialkylamino group, a hydroxy group, and a halogen atom. As the substituents on L ⁴ , and a quinone ring and a benzene ring, Is
Alkyl groups having the same number of carbon atoms as mentioned above.

The compounds represented by the above general formulas (Va-c), (VI) and (VIIa-
c), and the counter anion X _a in (VIII) ^- as, specifically, for ^{example, Cl -, Br -, I} -, Cl
O ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , and B
Inorganic acid anions such as inorganic boric acid such as F ₄ ⁻ , BCl ₄ ^{− and the} like, and benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, acetic acid, and methyl, ethyl, propyl, butyl, phenyl, methoxyphenyl,
Organic acid anions such as organic boric acid having an organic group such as naphthyl, fluorophenyl, difluorophenyl, pentafluorophenyl, thienyl and pyrrolyl can be mentioned.

The quinoline compounds represented by the above formulas (V ac), the indole compounds or benzothiazole compounds represented by the above formula (VI), and the quinoline compounds represented by the above formulas (VII ac) Cyanine dyes such as pyrylium or thiopyrylium,
Among the polymethine dyes represented by the general formula (VIII), the indole or benzothiazole dyes represented by the general formula (VI) are particularly preferred in the present invention.

Preferred examples of the cyanine dye or the polymethine dye which are preferable as the sensitizing dye of the component (D) in the present invention are shown below.

[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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In the above specific examples, the counter anion X _a
^{-, specifically,} Cl ^-, Br ^-, I -, Cl
O ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , p-toluenesulfonic acid, or 1-naphthalenesulfonic acid.

Further, the compounds represented by the above general formulas (Va-c), (VI), (VIIa-
c), and having a barbiturate anion group or a thiobarbiturate anion group represented by the following general formula (IX) on the polymethine chain of L ¹ , L ² , L ³ , and L ⁴ in (VIII). Or L ¹ , L ² , L ³ ,
And in the polymethine chain of L ^4, squaric acid anion group or a thio Square anion groups represented by the following general formula (X), or croconic acid anion group or Chiokurokon anion represented by the following general formula (XI) Those which form an inner salt by forming a group are also preferable.

[0084]

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[In the formulas (IX), (X) and (XI), Z ³ ,
Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , and Z ⁸ each independently represent an oxygen atom or a sulfur atom, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent. A good alkyl group,
It represents an alkenyl group which may have a substituent, an alkoxy group which may have a substituent, or a phenyl group which may have a substituent. ]

Here, when R ¹⁹ and R ²⁰ in the formula (IX) are an alkyl group or an alkoxy group, the number of carbon atoms is usually from 1 to 1
5, preferably 1 to 5, the number of carbon atoms when it is an alkenyl group is usually 2 to 15, preferably 2 to 5, and is preferably an alkyl group, and as the alkyl group, specifically, a methyl group , An ethyl group, a propyl group, or a butyl group.

The sensitizing dye of the present invention also includes a so-called phthalocyanine dye having a basic structure in which a heterocyclic ring is bonded via an azapolymethine chain. Those represented by the formula (XII) are preferred.

[0088]

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[In the formula (XII), R ²¹ and R ²² each independently represent an alkoxy group, a thioalkoxy group, an aryloxy group, a thioaryloxy group, an alkylamino group, an arylamino group, a halogen atom, or Represents a hydrogen atom, M
Represents Zn, Cu, Ni, SnCl ₂ , AlCl, or a hydrogen atom, and two adjacent substituents on the benzene ring may be connected to each other to form a condensed ring. ]

Here, when R ²¹ and R ²² in the formula (XII) are an alkoxy group, a thioalkoxy group or an alkylamino group, the number of carbon atoms is usually 1 to 10, preferably 1 to 4
And the aryloxy group, thioaryloxy group, or arylamino group includes a phenoxy group, a thiophenoxy group, or a phenylamino group.
Is preferably Zn or SnCl ₂ .

The sensitizing dye of the present invention also includes a dialkylaminobenzene dye, and among them, a dialkylaminobenzophenone dye represented by the following formula (XV) is preferable.

[0092]

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[In the formula (XIII), R ²³ , R ²⁴ , R ²⁵ and R
²⁶ each independently represents an alkyl group; R ²⁷ , R ²⁸ , R
²⁹ and R ³⁰ each independently represent an alkyl group or a hydrogen atom, and R ²³ and R ²⁴ , R ²⁵ and R ²⁶ , or R ²³ and R ²⁷ , R ²⁴ and R ²⁸ , R ²⁵ and R ²⁹ , or R ²⁶ and R ³⁰ may be independently linked to each other to form a condensed ring. ]

Here, R ²³ , R ²⁴ , R ²⁵ in formula (XIII)
The alkyl group of R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , and R ³⁰ preferably has 1 to 6 carbon atoms. Suitable dialkylaminobenzophenone dyes represented by the formula (XVI) include: For example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like can be mentioned.

Further, as the sensitizing dye in the present invention,
For example, triphenylmethane leuco dyes such as leuco crystal violet and leucomalachite green disclosed in U.S. Pat. No. 3,479,185, photoreducing dyes such as erythrosin and eosin Y, U.S. Pat.
Nos. 5,493,67 and 3,652,275, aminophenyl ketones such as Michler's ketone and aminostyryl ketone, β-diketones disclosed in U.S. Pat. No. 3,844,790, U.S. Pat.
No. 162, the indanones disclosed in JP-A-6-162.
No. 301208, JP-A-8-129258, JP-A-8-129
Coumarin-based pigments disclosed in JP-A-129259, JP-A-8-146605 and JP-A-8-21605, ketocoumarin-based pigments disclosed in JP-A-52-112681, No. 56403, aminostyrene derivatives and aminophenylbutadiene derivatives, US Pat. No. 4,594,310, aminophenyl heterocycles, US Pat.
Jurolidine heterocycles disclosed in US Pat.
Examples include compounds such as pyrromethene dyes disclosed in JP-A-5-241338, JP-A-7-5885, and JP-A-10-144242.

The photopolymerizable composition of the present invention comprises the polymer binder of component (A), the ethylenically unsaturated compound of component (B), and the photopolymerization initiator of component (C) as essential components. The content of the polymer binder of the component (A) is determined according to the content of the ethylenically unsaturated compound 10 of the component (B).
The amount is preferably from 10 to 400 parts by weight, particularly preferably from 20 to 200 parts by weight, based on 0 parts by weight. or,
The content of the photopolymerization initiator (C) is 0.0 to 100 parts by weight of the ethylenically unsaturated compound (B).
It is preferably from 1 to 30 parts by weight, particularly preferably from 0.05 to 20 parts by weight.

The content of the sensitizing dye of component (D) is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the ethylenically unsaturated compound of component (B). It is particularly preferably 0.5 to 20 parts by weight.

The photopolymerizable composition of the present invention preferably further contains a hydrogen-donating compound (E) for the purpose of improving photopolymerization initiation ability, in addition to the above components. Examples of the hydrogen donating compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, and 2-mercapto-
4 (3H) -quinazoline, β-mercaptonaphthalene,
Mercapto group-containing compounds such as ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate, etc. Polyfunctional thiol compounds, N, N-dialkylaminobenzoic acid ester,
N-phenylglycine or a salt such as ammonium or sodium salt thereof, a derivative such as an ester thereof, phenylalanine, or a salt such as ammonium or sodium salt thereof,
Amino acids having an aromatic ring, such as derivatives of the above esters, and derivatives thereof.

Further, if necessary, various additives such as hydroquinone, p-methoxyphenol and 2,6-di-tert-butyl-p-cresol may be added to the photopolymerizable composition of the present invention. Polymerization inhibitors, plasticizers such as dioctyl phthalate, didodecyl phthalate, tricresyl phosphate, dioctyl adipate, and triethylene glycol dicaprylate; adhesion improvers such as silane coupling agents; coating improvers; and developability improvers Various commonly used additives such as a sensitivity improver and a sensitizer may be further contained.

The use form of the photopolymerizable composition of the present invention as a light-sensitive material may be, for example, without a solvent or after being diluted with an appropriate solvent, applied to the surface of a support and dried. A form, or a form in which an overcoat layer for blocking oxygen is further provided thereon, a form 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 in which microcapsules are included Although the form and the like coated on the top can be adopted, the photopolymerizable composition of the present invention is applied to the support surface as a solution in which the composition is dissolved in an appropriate solvent,
It is suitable for use as a photopolymerizable lithographic printing plate in which a layer of the photopolymerizable composition of the present invention is formed on the surface of a support by heating and drying.

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

As the coating method, conventionally known methods, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating and the like can be used. The coating amount varies depending on the application, but is usually 0.3 to 7 μm as a dry film thickness.
m, preferably 0.5-5 μm, particularly preferably 1-3
μm range. The drying temperature at that time is, for example, about 60 to 170 ° C, preferably 70 to 150 ° C.
The drying time is about 5 seconds to 10 minutes, preferably about 10 seconds to 5 minutes.

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

The support is made of aluminum,
Metal plate such as zinc, copper, steel, aluminum, zinc, copper,
Metal plates plated or evaporated with iron, chromium, nickel, etc.
Examples include paper, paper coated with resin, paper to which metal foil such as aluminum is adhered, plastic film, plastic film subjected to hydrophilic treatment, and glass plate. Inside,
Preferable is an aluminum plate, which has been subjected to surface treatment such as 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. Aluminum plates are more preferred. The surface roughness of the support is JIS B0
Average roughness R _a as defined in 601, typically 0.3
The thickness is 1.0 μm, preferably about 0.4 to 0.8 μm.

The light source for imagewise exposing the photopolymerizable composition layer of the photopolymerizable lithographic printing plate of the present invention includes carbon arc,
High-pressure mercury lamp, xenon lamp, metal halide lamp,
Fluorescent lamp, tungsten lamp, halogen lamp, HeNe laser, argon ion laser, YA
G laser, HeCd laser, semiconductor laser, near infrared semiconductor laser, ruby laser, laser light source such as violet laser, etc.
A light source that generates a light ray in the near infrared region from the ultraviolet region of 200 nm can be used.

The developer used for developing the photoreceptor obtained by imagewise exposing the photopolymerizable lithographic printing plate of the present invention includes, for example,
Sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate,
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
Inorganic alkali salts such as sodium carbonate, sodium bicarbonate, potassium carbonate, dibasic sodium phosphate, tertiary sodium phosphate, dibasic ammonium phosphate, tertiary ammonium phosphate, sodium borate, potassium borate, ammonium borate, monomethylamine, dimethylamine, Trimethylamine,
Monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine,
Use is made of an alkali developer consisting of an aqueous solution of an organic amine compound such as monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and the like in a concentration of about 0.1 to 5% by weight. Of these, alkali metal silicates such as sodium silicate and potassium silicate which are inorganic alkali salts are preferable.

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.

[0108]

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.

Production Example of Polymer Binder of Component (A) As a precursor, methyl methacrylate (60 mol%) /
Methacrylic acid (20 mol%) / acrylonitrile (20
Mole%) copolymer (weight average molecular weight 70,000) 200 g,
3,4-epoxycyclohexylmethyl acrylate 9
g, 2.5 mg of p-methoxyphenol, 8 mg of tetrabutylammonium chloride and 800 g of propylene glycol monomethyl ether acetate were charged into a reaction vessel and reacted at 110 ° C. with stirring for 24 hours to obtain 50 moles of the carboxyl group of the methacrylic acid component. % With an epoxy group, and methyl methacrylate (60 mol%) / methacrylic acid (10 mol%) / the formula (II)
Structural unit of I) (10 mol%) / acrylonitrile (2
0 mol%).

Example 1 An aluminum plate (0.24 mm thick) subjected to graining and anodizing was used as a support, and the following components (A) to (E) were applied to the surface of the aluminum plate support. A coating solution prepared by stirring at room temperature to 1090 parts by weight of cyclohexanone was applied using a bar coater, and dried to form a photopolymerizable composition layer having a thickness of 2 μm. Apply and dry to a film thickness of 3
A photopolymerizable lithographic printing plate was prepared by forming an overcoat layer having a thickness of μm.

(A) Component: 45 parts by weight of the copolymer obtained in the above Production Example (B-1) Component: 10 parts by weight of bis (methacryloyloxyethyl) phosphate of the following B-1 (B-2) Component: 22.5 parts by weight of 2,2-bis (4′-acryloyloxydiethylene glycol phenyl) propane of the following B-2 Component (B-3) Component: hexamethylene bis [tris (acryloyloxymethyl) of the following B-3 ) Ethyl urethane] 22.5 parts by weight Component (C-1): dicyclopentadienyltitanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl] 5 parts by weight Component (D-1): D-1 Pyromethene-based sensitizing dye 2 parts by weight (D-2) component: copper phthalocyanine coloring dye 3 parts by weight (E-1) component: 2-mercaptobenzothiazole 5 parts by weight ( -2) Component: N, N-dimethylaminoethyl benzoate 5 parts by weight

[0112]

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The resulting photopolymerizable lithographic printing plate was exposed using a diffraction spectroscopy irradiator (“RM-23” manufactured by Narumi), and then 0.8% by weight of anhydrous sodium carbonate and an anionic surfactant (Kao) ("Perex NBL", manufactured by Co., Ltd.) Dipped in a 3% by weight aqueous solution at 25 ° C. for 30 seconds, and developed by rubbing with a sponge seven times. When the energy amount was determined as the sensitivity, it was 60 μJ / cm ² .

Further, the photopolymerizable lithographic printing plate was converted to an air-cooled argon laser lithographic exposure apparatus (“PI-
R ") at a light exposure of 100 μJ / cm ² , followed by development in the same manner as described above, and the resulting lithographic printing plate (" DAIYA 1F "manufactured by Mitsubishi Heavy Industries, Ltd.).
-2 ") and printing ink (" HYEC "manufactured by Toyo Ink Co., Ltd.)
OO Beni ") and a fountain solution (Nichiken Kagaku's Astro No. 1
Mark II ”(1% aqueous solution), every time 10,000 sheets are printed, the printing plate is washed with an ultraplate cleaner (manufactured by OpenShaw) while the printing plate is washed, and the image area (175) is printed.
When the number of printed sheets until the line (small dot of 5%) jumped was evaluated as the printing durability, it was 80,000.

Example 2 In place of the component (C-1) in Example 1, the component (C-2) was replaced by 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine 5 Parts by weight and 1.5 parts by weight of the following cyanine sensitizing dye of D-3 as the component (D-3) instead of the component (D-1), and the components (E-1) and ( Except that the component E-2) was not used, a photopolymerizable lithographic printing plate was prepared in the same manner as in Example 1, and the obtained lithographic printing plate was subjected to a 830 nm near-infrared laser plate-making exposure apparatus (TrendSetter “3442T”). ), And 175 lines of halftone image exposure were performed at an exposure amount of 100 mJ / cm ² , developed and printed in the same manner as in Example 1, and the printing durability was evaluated. It was a sheet.

[0116]

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Example 3 Instead of the component (C-1) in Example 1, the component (C-3) was replaced by 2,2′-bis (o-chlorophenyl)-
4,4 ′, 5,5′-tetraphenylbiimidazole,
And as a component (D-4) instead of the component (D-1),
4,4'-bis (diethylamino) benzophenone, and N as a component (E-3) instead of the component (E-2)
A lithographic printing plate was prepared in the same manner as in Example 1 except that phenylglycine benzyl ester was used.
20 μJ / cm using a W violet laser plate-form exposure apparatus (“Covalt 8” manufactured by Eschergraft)
After performing 175-line halftone image exposure at an exposure amount of ² , the same development and printing were performed as in Example 1, and the printing durability was evaluated to be 80,000.

Comparative Example 1 In place of the component (A) in Example 1, the precursor was
Manufactured by reacting 3,4-epoxycyclohexylmethyl acrylate in the same manner as in Example 1 using a methyl methacrylate (80 mol%) / methacrylic acid (20 mol%) copolymer (weight average molecular weight: 50,000). Example 1 except that a copolymer of methyl methacrylate (80 mol%) / methacrylic acid (10 mol%) / the structural unit of the general formula (III) (10 mol%) was used.
A photopolymerizable lithographic printing plate was prepared in the same manner as described above, and the resulting lithographic printing plate was measured and evaluated in the same manner as in Example 1 to have a sensitivity of 60 μJ / cm ² and a printing durability of 60,000. It was a sheet.

[0119]

According to the present invention, it is possible to provide a photopolymerizable composition and a photopolymerizable lithographic printing plate having excellent printing durability and high sensitivity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/027 G03F 7/027 7/028 7/028 F term (Reference) 2H025 AA01 AA12 AB03 AC01 AC08 AD01 BC14 BC32. QA39 QA42 QB03 QB16 QB20 QB22 QB24 SA78 SA85 SA86 SA87 SA88 TA01 TA07 UA01 UA02 VA01 WA01 4J027 AA02 AC03 AC04 AC06 AE02 AE03 AE07 BA04 BA05 BA06 BA13 BA14 BA16 BA17 BA19 BA20 BA21 BA23 BA10 BA28 BA27 BA10

Claims (7)

[Claims] 1. A photopolymerizable composition comprising the following components (A), (B) and (C). (A) A polymer binder containing a structural unit represented by the following general formula (I) and a structural unit derived from (meth) acrylonitrile: [In the formula (I), R ³¹ represents a methyl group or a hydrogen atom;
³² represents an alkyl group or a hydrogen atom, and V represents a residue of an epoxy group-containing ethylenically unsaturated compound. (B) Ethylenically unsaturated compound (C) Photopolymerization initiator 2. The photopolymerizable composition according to claim 1, wherein the structural unit of the general formula (I) in the component (A) is represented by the following general formula (II). Embedded image In [Formula (II), R ³¹ and R ³² are the same as in the general formula (I), R ³³ represents an alkyl group or a hydrogen atom, if R ³³ there are a plurality, each of R ³³ may be different, also may form a cyclic structure linked R ³² and R ³³ each other, m is an integer of 0. ] 3. The photopolymerizable composition according to claim 2, wherein the constituent unit of the general formula (II) in the component (A) is represented by the following general formula (III). Embedded image [In the formula (III), R ³¹ and R ³³ are the same as those in the general formula (II). ] 4. The polymer binder as the component (A) is (meth)
Structural unit derived from acrylic acid, structural unit derived from (meth) acrylic acid ester, the general formula (I), (II), or (III)
The photopolymerizable composition according to any one of claims 1 to 3, comprising a structural unit represented by: and a structural unit derived from (meth) acrylonitrile. 5. The polymer binder as the component (A) is a structural unit represented by the general formula (I), (II) or (III), and
Structural units derived from (meth) acrylonitrile are each 1 to
The photopolymerizable composition according to any one of claims 1 to 4, which contains 30 mol%. 6. The photopolymerizable composition according to claim 1, further comprising a sensitizing dye (D). 7. A photopolymerizable lithographic printing plate comprising a support and a layer of the photopolymerizable composition according to claim 1 formed on a surface of the support.