JPH1010719A - Photopolymerizable composition for photosensitive planographic printing plate and photosensitive planographic printing plate using that - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable compsn. having excellent adhesion property with a base body, sensitivity and developing property and to provide a photosensitive planographic printing plate which uses this compsn. SOLUTION: This photopolymerizable compsn. contains monomers A having ethylene-type unsatd. bonds which enable addition polymn., a photopolymn. initiator B, and a polymer binder C having carboxyl groups in the molecule. The monomers A contain a specified monomer of a phosphate compd. having at least one (meth)acryloyl group and/or a compd. expressed by formula. The binder C is a compd. prepared by the reaction of at least a part of carboxyl groups with an alicyclic unsatd. compd. containing epoxy groups. In formula, R<1> is a hydrogen atom or methyl group, X is an alkylene group having 1 to 6C which may have halogens as substituents, and m is an integer >2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photopolymerizable composition for a photosensitive lithographic printing plate and a photosensitive lithographic printing plate using the same. More specifically, a photopolymerizable composition for a photosensitive lithographic printing plate, which has extremely high sensitivity to light rays in the visible light region, and has excellent developability and adhesion to a support, and a photosensitive lithographic plate using the same. Regarding the printing plate.

[0002]

2. Description of the Related Art Recently, high-sensitivity photosensitive materials using a photopolymerizable photosensitive material have been studied in various fields of application. Among these, there is a laser direct plate making as a system which is expected to be practically used.
Development of a high-sensitivity photopolymer system corresponding to exposure with 2 nm light has been desired and various proposals have been made.

However, these photopolymers have poor adhesion to an aluminum support, causing problems such as peeling of an image during development and extremely low printing durability in printing. Various attempts have been made from the side of the support and the photosensitive layer to improve the poor adhesion.

[0004] As a method of increasing the adhesive strength on the support side,
For example, there is a method of phosphoric acid anodizing an aluminum support described in JP-B-46-26521. However, in this method, since the pore diameter of the oxide film (anodized) on the support is large and the pore density is high, problems such as abrasion resistance of the support and wear of the non-image area during printing occur. I do. Also, Japanese Patent Application Laid-Open No. 49-842
No. 8, JP-A-46-12903, JP-A-50-138
No. 903 and JP-A-49-93101 disclose a technique for improving the adhesiveness of a photosensitive layer by anodizing a sulfuric acid and then performing an etching treatment using phosphoric acid, polyphosphoric acid or an alkali solution. Sufficient adhesive strength cannot be obtained because the pore diameter of anodized is not sufficient.

As an attempt to improve the adhesion from the photosensitive layer side, Japanese Patent Application Laid-Open No. 50-100120 discloses an addition-polymerizable unsaturated bond-containing phosphate ester such as 2-methacryloyloxyethylhydrodiene phosphate. For example, it describes that it adheres well to aluminum, iron, antimony and the like. However, the phosphoric acid ester monomer alone has a relatively low cured film density, so that it is easily susceptible to alkaline water or the like, and is not suitable for a photosensitive material premised on aqueous development.

JP-A-1-289820 discloses an active energy ray-curable resin composition containing a polymer obtained by reacting a part of a carboxyl group of a polymer binder with an alicyclic epoxy group-containing unsaturated compound. Is described. This type of resin has the advantage that the density of the cured film is relatively high and the adhesion to a support such as aluminum is increased, but the composition described in the publication is a photopolymerizable composition for a photosensitive lithographic printing plate. When used as such, both developability and printing durability are not sufficient.

[0007] Also, Japanese Patent Application Laid-Open No. H5-25232 discloses that
A photopolymerization composition using a phosphate compound of a hydroxyalkyl (meth) acrylate and a compound obtained by reacting a part of the carboxyl group of a polymer binder with glycidyl methacrylate is described. However, the printing durability and developability for lithographic printing plates are not yet satisfactory.

[0008]

SUMMARY OF THE INVENTION The present invention provides a photopolymerizable composition for a photosensitive lithographic printing plate, which is excellent in all of adhesiveness, sensitivity and developability to an aluminum support, and
It is an object of the present invention to provide a photosensitive lithographic printing plate having excellent printing suitability using this.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, a phosphate compound having at least one (meth) acryloyl group and / or a compound represented by the following general formula: By using a compound represented by (I) in combination with a polymer binder obtained by reacting a part of carboxyl groups with an alicyclic epoxy group-containing unsaturated compound, an aluminum support, particularly a sulfated oxide film is obtained. The present inventors have found that the adhesion to the aluminum support and the removability of the non-image area are greatly improved, and the present invention has been accomplished.

That is, the gist of the present invention is to provide (A) an ethylenically unsaturated bond-containing monomer capable of addition polymerization, (B) a photopolymerization initiation system, and (C) a polymer bond having a carboxyl group in the molecule. The photopolymerizable composition containing the material, wherein the addition-polymerizable ethylenically unsaturated bond-containing monomer (A) is
A phosphate compound (A-1) having at least one (meth) acryloyl group and / or the following general formula (I)
The polymer binder (C) containing a specific monomer which is the compound (A-2) represented by the formula (1) and having a carboxyl group in the molecule is partially unsaturated with an alicyclic epoxy group-containing unsaturated carboxyl group. A photopolymerizable composition for a photosensitive lithographic printing plate characterized by being a compound reacted with a compound.

[0011]

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(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, X represents an alkylene group which may be substituted by halogen and may have 1 to 6 carbon atoms and may be branched. Represents an integer of 2 or more.) Another gist of the present invention is that in a photosensitive lithographic printing plate having a photosensitive resin layer on an aluminum substrate, the photosensitive resin layer is formed of the above-described photopolymerizable polymer for a photosensitive lithographic printing plate. The present invention relates to a photosensitive lithographic printing plate characterized by comprising a composition.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The addition-polymerizable ethylenically unsaturated bond-containing monomer (A) (hereinafter abbreviated as “ethylenic monomer”) contained as a first essential component in the photopolymerizable composition of the present invention is a photopolymerizable composition. It is a monomer having an ethylenically unsaturated bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system, which is the second essential component, when the active composition is irradiated with actinic rays. In the present invention, the meaning of the monomer is a concept corresponding to a so-called polymer, and therefore includes not only a monomer in a narrow sense but also a dimer, a trimer, and an oligomer. It is.

In particular, the ethylenic monomer used in the present invention is represented by a phosphoric ester compound (A-1) having at least one (meth) acryloyl group and / or the following general formula (I): It is characterized by containing the compound (A-2).

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(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group; X represents an optionally branched alkylene group having 1 to 6 carbon atoms which may be substituted by halogen; Represents an integer of 2 or more.) In the present specification, the compound (A-1) and / or (A-2) is hereinafter referred to as a specific monomer.

The phosphoric acid ester compound (A-1) having at least one (meth) acryloyl group among the specific monomers used in the present invention includes an esterified product of phosphoric acid and a (meth) acryloyl group-containing compound. Is not particularly limited as long as it is, specifically, for example, a compound represented by the following general formula (II) is exemplified.

[0017]

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(In the general formula (II), R ² represents a hydrogen atom or a methyl group, n represents an integer of 1 to 25, and r represents 1 or 2.) Represented by the general formula (II) Among the compounds, n is preferably 1 to 10, and particularly preferably 1 to 4. Specific examples of particularly preferred compounds include methacryloxyethyl phosphate, bis (methacryloxyethyl) phosphate, and the like.

The compound (A-2) represented by the general formula (I), which is another specific monomer used in the present invention.
In the above, X is preferably an optionally branched alkylene group having 2 to 4 carbon atoms, and when the alkylene group is substituted with halogen, the substituent is preferably a chlorine atom.

In the compound (A-2), X is an unsubstituted and optionally branched alkylene group having 2 or 3 carbon atoms, such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Certain compounds are particularly preferred. Further, there is no problem if m in the general formula (I) is an integer of 2 or more, but m is 5 or more and 5 or more.
Those having a value of 0 or less are most balanced in terms of adhesion to a support, sensitivity, and developability.

The content of the specific monomer in the present invention is not particularly limited.
0% by weight, preferably 2 to 50% by weight, more preferably 3 to 40% by weight. If less than 1% by weight,
Adhesion to the support and developability are inferior, and if it exceeds 60% by weight, sensitivity tends to deteriorate. Further, within the above range, the sensitivity and the printing durability are improved, and the developability is particularly improved. The compound (I) and the phosphate compound having at least one (meth) acryloyl group contained in the composition of the present invention may be used alone or as a mixture of a plurality of compounds.

The composition of the present invention may contain, as the ethylenic monomer, a compound having one ethylenically unsaturated bond other than the specific monomer. Specific examples include (meth) acrylic acid, an alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, and a monoester of a carboxylic acid having one ethylenically unsaturated bond and a poly (mono) hydric alcohol.

In the present invention, together with the specific monomer, 1
It is desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in the molecule. Examples of such polyfunctional ethylenic compounds include, for example, esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds. Esters obtained by an esterification reaction of a polyhydroxy compound such as a compound with an unsaturated carboxylic acid and a polycarboxylic acid are exemplified.

The ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid is not limited, but ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and acrylates of these exemplified compounds as methacrylates Methacrylic acid ester replaced with itacone also replaced with itaconate Esters, maleic acid esters, and the like was replaced with crotonic acid ester or maleate was replaced Kuroneto.

Examples of the ester of an aromatic polyhydroxy compound with an unsaturated carboxylic acid include acrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. And methacrylic acid esters.

The ester obtained by the esterification reaction of the unsaturated carboxylic acid, polycarboxylic acid and polyhydroxy compound is not necessarily a single substance, but typical examples include acrylic acid, phthalic acid and There are condensates of ethylene glycol, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol, and glycerin.

Other examples of the polyfunctional ethylenic monomer used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) acrylate. Urethane (meth) acrylates obtained by reaction; epoxy acrylates such as addition products of diepoxy compounds with hydroxyethyl acrylate; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; divinyl Vinyl group-containing compounds such as phthalate are useful.

Of these polyfunctional ethylenic monomers, a polyisocyanate compound and a urethane (meth) acrylate compound obtained by reacting a hydroxyl group-containing (meth) acrylate ester and / or bisphenol A are modified and derived. (Meth) acrylic acid esters, particularly (meth) acrylic acid ester compounds represented by the following general formula (III), which are alkylene oxide adducts of bisphenol A, are preferred.

[0029]

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(In the formula (III), A represents an acryloyl group or a methacryloyl group, R ³ and R ⁴ each represent an optionally branched alkylene group, and R ⁵ and R ⁶ represent a hydrogen atom and a substituent, respectively. An alkyl group optionally having
A cycloalkyl group which may have a substituent, a phenyl group which may have a substituent, Ph represents a phenylene group, and p and q each represent a positive integer satisfying p + q = 2 to 30 . Among the compounds represented by the general formula (III), more preferred are those in which both R ⁵ and R ⁶ are methyl groups, and p + q = 2.
4, specifically 2,2-bis [4-
(Acryloxydiethoxy) phenyl] propane (A-
BPE-4: trade name of Shin-Nakamura Chemical Co., Ltd., 2,2-bis [4- (methacryloxyethoxy) phenyl] propane (BPE-100; trade name of Shin-Nakamura Chemical Co., Ltd.), 2,2
-Bis [4- (methacryloxydiethoxy) phenyl]
Propane (BPE-200; trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
And the like.

As the polyisocyanate compound used for synthesizing the urethane (meth) acrylate compound, various polyisocyanate compounds known as raw materials for polyurethane can be used, and aromatic diisocyanate and alicyclic diisocyanate can be used. And aliphatic diisocyanate compounds and derivatives thereof such as trimers. More preferred are diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, and isocyanurate compounds.

The hydroxyl group-containing (meth) acrylate to be reacted with the polyisocyanate compound is preferably a compound having a plurality of acryloyl groups or methacryloyl groups and having one hydroxy group. Specifically, a reaction product of glycidyl (meth) acrylate and (meth) acrylic acid, pentaerythritol tri (meth)
Acrylate and the like.

Next, the photopolymerization initiation system (B), which is the second essential component of the photopolymerizable composition of the present invention, will be described. As the photopolymerization initiation system, any system capable of initiating the polymerization of the ethylenic monomer can be used. In particular, any of them can be suitably used as long as they have activity with respect to light in the visible region. Among them, examples of the activator that generates an active radical by interacting with the photo-excited sensitizer, such as titanocenes, hexaarylbiimidazoles, halogenated hydrocarbon derivatives,
Examples include diaryliodonium salts and organic peroxides. Among them, a composition using titanocenes or hexaarylbiimidazoles is preferable because of good sensitivity, storage stability, adhesion of a coating film to a substrate, and the like.

As the titanocenes, various ones having a titanocene structure can be used. For example, various titanocenes described in JP-A-59-152396 and JP-A-61-151197 can be used. You can use it selectively. More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-Pentafluorophenyl-1-yl, di-cyclopentadienyl-
Ti-bis-2,3,5,6-tetrafluorophenyl
1-yl, di-cyclopentadienyl-Ti-bis-
2,4,6-trifluorophenyl-1-yl, dicyclopentadienyl-Ti-2,6-di-fluorophenyl
1-yl, di-cyclopentadienyl-Ti-bis-
2,4-di-fluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6
-Pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclocyclopentadienyl-Ti
-Bis-2,6-difluoro-3- (pyr-1-yl)
-Phenyl-1-yl and the like.

As the hexaarylbiimidazoles, various compounds having a hexaarylbiimidazole structure can be used. For example, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5 '-Tetra (p-fluorophenyl) biimidazole, 2,2'-
Bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) biimidazole, 2,2'
-Bis (o-chlorophenyl) -4,4 ', 5,5'-
Tetra (p-chloronaphthyl) biimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-tetra (p-chlorophenyl) biimidazole,
2,2'-bis (o-bromophenyl) -4,4 ',
5,5'-tetra (p-chloro-p-methoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) bi Imidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p
-Dibromophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole,
2'-bis (o, p-dichlorophenyl) -4,4 ',
Hexaarylbiimidazoles having a halogen substituent on the benzene ring such as 5,5'-tetra (o, p-dichlorophenyl) biimidazole are preferred.

These hexaarylbiimidazoles can be used in combination with various kinds of biimidazoles, if necessary. Biimidazoles are, for example, Bul
l. Chem. Soc. Japan. 33,565 (1
960) and J.M. Org. Chem. 36 [16] 22
62 (1971). Next, the sensitizer in the photopolymerization initiation system will be described. The sensitizer in the present invention means a compound capable of effectively generating an active radical upon irradiation with visible light when coexisting with the above-mentioned activator.

Examples of typical sensitizers include, for example, triphenylmethane leuco dyes such as leuco crystal violet and leucomalachite green disclosed in US Pat. No. 3,479,185, and erythrosine. Photoreducing dyes such as Eosin Y and US Pat. No. 3,549,367; US Pat.
Aminophenyl ketones such as Michler's ketone and aminostyryl ketone disclosed in US Pat.
The β-type disclosed in U.S. Pat. No. 3,844,790 is disclosed.
Diketones, indanones described in U.S. Pat. No. 4,162,162, ketocoumarins described in JP-A-52-112681, and JP-A-59-56403.
No. 4,594,3, disclosed in US Pat. No. 4,594,311.
No. 10, aminophenyl heterocycles described in U.S. Pat. No. 4,966,830, and pyrromethene dyes described in JP-A-5-241338.

Further, the photopolymerization initiation system used in the present invention may contain 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, N By adding a hydrogen-donating compound such as -phenylglycine or an alkyl N, N-dialkylbenzoate, the photopolymerization initiation ability can be further enhanced. Of these, particularly preferred are 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4
-A compound having a mercapto group such as triazole,
N, N-dialkyl benzoic acid alkyl ester.

Next, a polymer binder (C) having a carboxyl group in the molecule, which is the third essential component of the present invention, and having a part of the carboxyl group reacted with an alicyclic epoxy group-containing unsaturated compound. ) (Hereinafter abbreviated as “ethylenic polymer binder”). In the production of the ethylenic polymer binder, an inert organic solvent solution of a polymer binder having a carboxyl group in a molecule (for example, alcohol, ester, aromatic hydrocarbon, aliphatic hydrocarbon, etc.) ) And an unsaturated compound having an alicyclic epoxy group.
The reaction can be carried out under a reaction condition of 0 to 120 ° C. for about 1 to 50 hours. The ratio of the carboxyl group to be reacted with the alicyclic epoxy group-containing unsaturated compound is not particularly limited as long as the effects of the present invention can be achieved.
It is preferable to react 5 to 90 mol% with respect to all carboxyl groups, more preferably 20 to 80 mol%, and still more preferably 30 to 70 mol%. The developability in the above range is good and the adhesiveness is good.

Specific examples of the polymer binder having a carboxyl group in the molecule used for the production of the ethylenic polymer binder include (meth) acrylic acid, (meth) acrylate, (meth) acrylamide, Maleic acid,
Homo- or copolymers such as (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride and maleimide;
Other examples include polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetylcellulose, and polyvinyl butyral. Among them, a copolymer containing (meth) acrylic acid ester and at least one (meth) acrylic acid as a copolymer component is preferable. The preferred acid value of the polymer binder having a carboxyl group in the molecule is 10 to 250, and the preferred weight average molecular weight (hereinafter abbreviated as Mw) is 5,000 to 20.
It is ten thousand.

The alicyclic epoxy group-containing unsaturated compound used for producing the ethylenic polymer binder used in the present invention comprises at least one addition-polymerizable unsaturated bond in one molecule and an alicyclic epoxy group. And a compound having: Here, the alicyclic epoxy group is a group having a structure in which a non-aromatic ring and an oxirane skeleton are fused, and among these, a group having a structure in which a cyclalkane skeleton and an oxirane skeleton are fused is preferable. Preferred specific examples of the alicyclic epoxy group-containing unsaturated compound used in the present invention include, for example, compounds represented by the following general formulas (IV) to (XVII).

[0042]

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[0043]

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(In each formula, R ⁷ represents a hydrogen atom or a methyl group; R ⁸ represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms; and R ⁹ represents a C 1 to 10 carbon atom. Represents a divalent hydrocarbon group, and t represents an integer of 0 to 10.) In the general formula of the alicyclic epoxy group-containing unsaturated compound, R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is methylene. Group, ethylene group, propylene group, tetramethylene group,
An ethylethylene group, a pentamethylene group, or a hexamethylene group, wherein R ⁹ is a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, or a phenylene group; preferable. Among them, compounds of the formula (IV), (VI) or (VII), wherein R ⁷ is a hydrogen atom or a methyl group and R ⁸ is an alkylene group having 1 to 4 carbon atoms, are particularly preferred. Specific examples of particularly preferable compounds of the alicyclic epoxy group-containing unsaturated compound include 3,4-epoxycyclohexylmethyl acrylate and 2,3-epoxycyclopentylmethyl acrylate.

The following compounds may be used in combination with the above-mentioned ethylenic polymer binder as another polymer binder. For example, homo- or copolymers of (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride, maleimide, etc., polyethylene oxide, Examples include polyvinylpyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetylcellulose, and polyvinyl butyral. Among them, a copolymer of (meth) acrylate is preferred. Also,
The preferred Mw of these copolymers is from 5,000 to 200,000.

The main constituents of the photopolymerizable composition for a photosensitive lithographic printing plate according to the present invention have been described in detail above.
The photosensitizer-based internal sensitizer is preferably 0.01 to 20 parts by weight, particularly preferably 0.05 to 1 part by weight, based on 0 parts by weight.
0 parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.5 to 60 parts by weight of the activator, and preferably 10 to 400 parts by weight, particularly preferably 2 to 400 parts by weight of the polymer binder.
It is in the range of 0 to 200 parts by weight.

The photopolymerizable composition for a photosensitive lithographic printing plate of the present invention may further contain other substances depending on the purpose in addition to the above essential components. For example, thermal polymerization inhibitors such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol; coloring agents composed of organic or inorganic dyes and pigments; dioctyl phthalate, didodecyl phthalate, tricresyl Plasticizers such as phosphates,
An additive such as a sensitizing agent such as a tertiary amine or a thiol, and other additives such as a dye precursor can also be added.

The preferred amounts of the additives are 2 parts by weight or less of a thermal polymerization inhibitor, 20 parts by weight or less of a colorant, 40 parts by weight or less of a plasticizer, and 30 parts by weight of a dye precursor per 100 parts by weight of the ethylenic compound. The range is as follows. The photopolymerizable composition for a photosensitive lithographic printing plate described above is diluted with an appropriate solvent, coated on a support and dried to form a photosensitive layer.
When used as a photosensitive lithographic printing plate, an aluminum plate is usually used as a support. In particular, an aluminum support which has been roughened and then anodized may be suitably used. As a method of roughening, generally known brush polishing method, ball polishing method, electrolytic etching, chemical etching,
Examples thereof include methods such as liquid honing and sandblasting, and combinations thereof, and preferably include brush polishing, ball polishing, electrolytic etching, chemical etching, and liquid honing. Further, the surface-roughened aluminum plate is desmutted with an acid or alkali aqueous solution as required. The aluminum plate thus obtained is usually subjected to anodizing treatment, and particularly preferably,
There is a method of treating with an electrolytic solution containing sulfuric acid. The method of anodizing with an electrolytic solution containing sulfuric acid is performed according to a conventionally known method, for example, a method described in JP-A-58-21894. Specifically, for example, sulfuric acid 5 to 50% by weight, preferably 15 to 30% is used, and the temperature is 5 to 5%.
0 ° C., preferably 15-35 ° C.
で 60 A / dm ² for about 5 seconds to 60 seconds.
Further, if necessary, a treatment with an alkali silicate such as sodium silicate treatment or hot water, or a hydrophilic treatment such as immersion in an aqueous solution containing an aqueous polymer compound such as a resin having a cationic quaternary ammonium group or polyvinylphosphonic acid. A conversion process can also be performed.

The photosensitive composition can be applied by a known method such as dip coating, coating rod, spinner coating, spray coating, roll coating and the like. Further, an oxygen blocking layer can be provided on the above-mentioned photosensitive layer in order to prevent a polymerization inhibition effect by oxygen. Specific examples thereof include water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, and cellulose. Among them, those containing polyvinyl alcohol having particularly high oxygen gas barrier properties are preferable.

The exposure light source applicable to the composition of the present invention is not particularly limited. Examples thereof include a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a helium cadmium laser, and an argon ion. Laser, Y
AG laser, helium neon laser and the like can be particularly preferably used.

The photopolymerizable composition of the present invention can form an image on a support by performing image exposure with such a light source and developing with an aqueous solution containing a surfactant and an alkali. . The aqueous solution may further contain an organic solvent, a buffer, a dye or a pigment. Suitable alkali agents include inorganic alkalis such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. And organic amine compounds such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, and triethanolamine. These can be used alone or in combination. As a surfactant,
For example, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; alkylbenzene sulfonates;
Anionic surfactants such as alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate salts and the like; amphoteric surfactants such as alkyl betaines and amino acids can be used. Also,
As the organic solvent, for example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like can be contained as necessary.

[0052]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Synthesis of binder (1) Methyl methacrylate / isobutyl methacrylate / isobutyl acrylate / methacrylic acid = 35/20 /
10/35 mol% (charge ratio) copolymer, Mw = 7
200 parts by weight (hereinafter abbreviated as “binder-1”), 75 parts by weight of the following alicyclic epoxy-containing unsaturated compound,

[0053]

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2.5 parts by weight of p-methoxyphenol, 8 parts by weight of tetrabutylammonium chloride and 800 parts by weight of propylene glycol monomethyl ether acetate were added to the reaction vessel, and the mixture was stirred at 110 ° C. for 24 hours in the air for ethylenic reaction. A solution of a polymer binder (acid value 60, 60% of the entire methacrylic acid component of the binder-1 was reacted with an unsaturated group, hereinafter abbreviated as “binder-2”) was obtained.

Synthesis of Binder (2) Copolymer of α-methylstyrene / acrylic acid (trade name “SCX-690” manufactured by Johnson, acid number 240,
Mw = 15,000) (hereinafter abbreviated as “binder-3”) to 8
55 parts by weight of the following alicyclic epoxy-containing unsaturated compound 49
0 parts by weight,

[0056]

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1.3 parts by weight of p-methoxyphenol, 4.3 parts by weight of tetraethylammonium chloride, 180 parts by weight of propylene glycol monomethyl ether acetate
0 parts by weight was added to the reaction vessel, and the mixture was stirred and reacted in air at 120 ° C. for 15 hours to form an ethylenic polymer binder (acid value of about 1
70, 50% of the total methacrylic acid component of binder-2 reacted with unsaturated groups. Hereinafter, it is abbreviated as “binding material-4”. ) A solution was obtained.

Synthesis of binder (3) 196 parts by weight of binder-1, 52 parts by weight of glycidyl methacrylate, 2.4 parts by weight of p-methoxyphenol, 8 parts by weight of tetraethylammonium chloride, 490 parts by weight of propylene glycol monomethyl ether acetate Was added to the reaction vessel, and the mixture was stirred and reacted in air at 120 ° C. for 15 hours. As a result, the glycidyl methacrylate reacted with about 60% of the total methacrylic acid component of the binder -1 at an acid value of about 60. A solution was obtained.

Synthesis of binder (4) 428 parts by weight of binder-1, 137 parts by weight of glycidyl methacrylate, 6.5 parts by weight of p-methoxyphenol,
2.2 parts by weight of tetraethylammonium chloride, propylene glycol monomethyl ether acetate 90
0 parts by weight was added to the reaction vessel, and the mixture was stirred and reacted in air at 120 ° C. for 15 hours. The acid value was 170, and glycidyl methacrylate reacted to 50% of the entire methacrylic acid component of the binder-1. 6 "solution was obtained.

Production of Aluminum Support (1) An aluminum plate was degreased with 3% sodium hydroxide, and this was washed in a 11.5 g / l hydrochloric acid bath at 25 ° C. and 80 A / dm ^2.
Electrolytic etching at a current density of 11 seconds, washing with water, anodizing at 30 ° C. in a 30% sulfuric acid bath at 11.5 A / dm ² for 15 seconds, washing with water, drying, and drying the aluminum plate for lithographic printing plate ( Hereinafter, abbreviated as “support-1”).

Production of Aluminum Support (2) Support-1 was further hydrophilized at 85 ° C. for 30 seconds using a 1% aqueous sodium orthosilicate solution, washed with water and dried to obtain an aluminum plate for a lithographic printing plate (hereinafter referred to as “support”). Abbreviated as "body-2").

Examples 1 to 3 and Comparative Examples 1 to 4 The following photopolymerizable composition coating solution-1 was coated on the support-1.
Was applied and dried using a bar coater to a dry film thickness of 2 g / m ² . Further, a photosensitive lithographic printing plate was prepared by applying and drying an aqueous solution of polyvinyl alcohol using a bar coater to a dry film thickness of 3 g / m ² . The following items were evaluated for the obtained photosensitive lithographic printing plate. The results are shown in Table 1.

[Photopolymerizable Composition Coating Solution-1] Ethylene monomer shown in Table 1 Total 55 parts by weight Polymer binder shown in Table 1 45 parts by weight Compound 2 having the following structure (S-1) 0.0 parts by weight Titanocene compound having the following structure (T-1) 10 parts by weight 2-mercaptobenzothiazole 5.0 parts by weight N, N-dimethylbenzoic acid ethyl ester 10 parts by weight Copper phthalocyanine pigment 3.0 parts by weight Cyclohexanone 1090 Parts by weight

[0064]

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Evaluation items <Sensitivity> After exposing the photosensitive lithographic printing plate using a diffraction spectral irradiation apparatus (RM-23, manufactured by Narumi), 0.8% by weight of anhydrous sodium carbonate and Perex NBL (Kao (Kao) stock)
After immersion in an aqueous solution containing 3% by weight at 25 ° C. for 30 seconds, development was performed by rubbing with a sponge seven times, and based on the height of the obtained cured image, the amount of light energy required for photocuring with 532 nm light rays I asked.

<Developability> The photosensitive lithographic printing plate is developed without exposure as in the case of the evaluation of sensitivity. One drop of methyl cellosolve is dropped on the obtained sample and dried, and finally, ink is filled with a developing ink (trade name “SPO-1” manufactured by Konica Corporation). At this time, the level at which the ink was not applied at all was represented by ○, the level at which fringe was generated at the methylcellosolve drop mark was represented by Δ, and the level at which the ink was entirely deposited was represented by ×.

<Printing durability> The photosensitive lithographic printing plate was scanned and exposed with an air-cooled argon laser (trade name "PI-R" manufactured by Dainippon Screen Co., Ltd.) at an exposure of 100 μj / cm ² to evaluate the sensitivity. Development is performed in the same manner. The obtained printing plate is referred to as “DAIYA-1F-2 type” (manufactured by Mitsubishi Heavy Industries, Ltd.).
, And the number of printed sheets until the image area (120 lines, 4% small point) jumps is shown as the printing durability.

Examples 4 and 6, Comparative Examples 5 and 6 The following photopolymerizable composition coating solution-2 was coated on the support-2.
Was applied and dried using a bar coater to a dry film thickness of 2 g / m ² . Further, a photosensitive lithographic printing plate was prepared by applying and drying an aqueous solution of polyvinyl alcohol using a bar coater to a dry film thickness of 3 g / m ² . The above-mentioned items were evaluated for the obtained photosensitive lithographic printing plate. The results are shown in Table 2.

[Photopolymerizable Composition Coating Solution-2] Ethylene monomer shown in Table 2 55 parts by weight Polymer binder shown in Table 2 45 parts by weight Compound 2 of the above-mentioned structure (S-1) 0.0 parts by weight Titanocene compound of the structure (T-1) 10 parts by weight 2-mercaptobenzothiazole 5.0 parts by weight N, N-dimethylbenzoic acid ethyl ester 10 parts by weight Copper phthalocyanine pigment 3.0 parts by weight Cyclohexanone 1090 Parts by weight

Examples 7 to 10 and Comparative Examples 7 to 9 The same operation as in the above Examples 1 to 3 and Comparative Examples 1 to 4 except that the following coating solution-3 was used on the above-mentioned support-2. And evaluated. The results are shown in Table 3.

[Photopolymerizable Composition Coating Solution-3] Ethylene monomer shown in Table 3 Total 55 parts by weight Polymer binder shown in Table 3 45 parts by weight Compound 2 having the following structure (S-2) 0.0 parts by weight Compound of the following structure (T-2) 10 parts by weight 2-mercaptobenzothiazole 5.0 parts by weight N, N-dimethylbenzoic acid ethyl ester 10 parts by weight Copper phthalocyanine pigment 3.0 parts by weight Cyclohexanone 1090 parts by weight Department

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[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

In Tables 1 to 3, the abbreviations (compound-1 to compound-6) in the column of the ethylenic monomer represent the following compounds, respectively.

Compound-1

[0078]

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Compound-2

[0080]

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Compound-3

[0082]

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Compound-4

[0084]

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Compound-5

[0086]

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Compound-6

[0088]

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[0089]

Industrial Applicability According to the present invention, a photopolymerizable composition for a photosensitive lithographic printing plate excellent in all of adhesiveness, sensitivity and developability to an aluminum support, and photosensitive lithographic printing using the same. Version can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C09D 4/02 PDR C09D 4/02 PDR PDS PDS G03F 7/00 503 G03F 7/00 503 7/032 501 7/032 501 7/035 7/035

Claims (16)

[Claims] 1. A light comprising (A) an ethylenically unsaturated bond-containing monomer capable of addition polymerization, (B) a photopolymerization initiation system, and (C) a polymer binder having a carboxyl group in the molecule. In the polymerizable composition, the addition-polymerizable ethylenically unsaturated bond-containing monomer (A) is a phosphate compound having at least one (meth) acryloyl group (A-
1) and / or a polymer binder (C) containing a specific monomer which is a compound (A-2) represented by the following general formula (I) and having a carboxyl group in the molecule, A photopolymerizable composition for a photosensitive lithographic printing plate, characterized in that the compound is obtained by reacting at least a part of the compound with an alicyclic epoxy group-containing unsaturated compound. Embedded image (In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, and X represents a carbon number of 1 to 6 which may be substituted with halogen.
And m represents an integer of 2 or more. ) 2. The phosphoric ester compound (A-1) wherein the specific monomer has at least one (meth) acryloyl group and the compound (A-) represented by the general formula (I)
2. The photosensitive lithographic printing plate according to claim 1, which is 2) and accounts for 1 to 60% by weight of the monomer (A) containing all ethylenically unsaturated bonds capable of addition polymerization. Photopolymerizable composition. 3. The monomeric compound according to claim 1, wherein the specific monomer is a phosphate compound (A-1) having at least one (meth) acryloyl group, and the addition-polymerizable ethylenically unsaturated bond-containing monomer. The photopolymerizable composition for a photosensitive lithographic printing plate according to claim 1, wherein the photopolymerizable composition accounts for 1 to 60% by weight of the body (A). 4. The specific monomer is a compound (A-2) represented by the general formula (I), and a monomer (A) containing an addition-polymerizable ethylenically unsaturated bond. The photopolymerizable composition for a photosensitive lithographic printing plate according to claim 1, wherein the photopolymerizable composition accounts for 1 to 60% by weight of the composition. 5. The method according to claim 1, wherein the phosphate compound (A-1) having at least one (meth) acryloyl group is a compound represented by the following general formula (II). A photopolymerizable composition for a photosensitive lithographic printing plate. Embedded image (In the general formula (II), R ² represents a hydrogen atom or a methyl group, n represents an integer of 1 to 25, and r represents 1 or 2.) 6. The polymer binder (C) having a carboxyl group in the molecule is a compound obtained by reacting 5 to 90 mol% of a carboxyl group with an alicyclic epoxy group-containing unsaturated compound. The photopolymerizable composition for a photosensitive lithographic printing plate according to claim 1. 7. The composition further comprises a compound represented by the following general formula (III):
A compound represented by the formula (1) to (6).
3. The photopolymerizable composition for a photosensitive lithographic printing plate according to item 1. Embedded image(In the general formula (III), A represents an acryloyl group or a methacryloyl group.
Represents an yl group;^Three, R ^FourMay be branched
Represents an alkylene group;^Five, R⁶Are hydrogen sources
A substituent, an alkyl group which may have a substituent,
Optionally having a cycloalkyl group, a substituent
Represents a good phenyl group, Ph represents a phenylene group,
p and q are positive integers satisfying p + q = 2 to 30
You. ) 8. The photopolymerizable composition for a photosensitive lithographic printing plate according to claim 1, further comprising a urethane (meth) acrylate compound in the composition. 9. The photopolymerization for a photosensitive lithographic printing plate according to claim 1, wherein the alicyclic epoxy group-containing unsaturated compound has a structure in which a cycloalkane skeleton and an oxirane skeleton are condensed. Composition. 10. The alicyclic epoxy group-containing unsaturated compound is at least one of compounds represented by the following general formulas (IV), (V) or (VI). 10. The photopolymerizable composition for a photosensitive lithographic printing plate according to item 9. Embedded image (In each formula, R ⁷ represents a hydrogen atom or a methyl group;
⁸ represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms. ) 11. The photopolymerization initiation system according to claim 1, further comprising a sensitizer having absorption in a visible light region.
0. The photopolymerizable composition for a photosensitive lithographic printing plate according to 0. 12. The photopolymerizable composition for a photosensitive lithographic printing plate according to claim 1, wherein the photopolymerization initiation system contains titanocenes. 13. The photopolymerization initiation system according to claim 1, wherein the photopolymerization initiation system contains hexaarylbiimidazoles.
3. The photopolymerizable composition for a photosensitive lithographic printing plate according to item 1. 14. A photosensitive lithographic printing plate having a photosensitive resin layer formed on an aluminum support, wherein the photosensitive resin layer is made of the photopolymerizable composition according to claim 1. A photosensitive lithographic printing plate characterized by the following. 15. In a photosensitive lithographic printing plate having a photosensitive resin layer formed on an aluminum support having been subjected to surface roughening and anodizing, the anodizing is performed in an electrolytic solution containing sulfuric acid. The photosensitive lithographic printing plate according to claim 14, which is a lithographic printing plate. 16. A photosensitive lithographic printing plate comprising a photosensitive resin layer formed on an aluminum support which has been subjected to a surface roughening treatment and an anodic oxidation treatment and further subjected to a hydrophilic treatment.
The photosensitive lithographic printing plate according to claim 14, wherein the anodizing treatment is performed in an electrolytic solution containing sulfuric acid.