JPH10282658A - Photosensitive composition and photosensitive litho-graphic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the negative photosensitive composition and the negative photosensitive lithographic printing plate good in adhesion to a metallic support and superior in developability and printing resistance by incorporating a binder resin, a diazo resin, a monomer or oligomer having polymerizable ethylenically unsaturated double bonds, and a photopolymerization initiator. SOLUTION: This photosensitive composition contains the binder resin having urethane bonds on the side chains, the diazo resin, the monomer or oligomer having at least 2 polymerizable ethylenically unsaturated double bonds, and the photopolymerization initiator. The binder resin having urethane bonds on the side chains is embodied by vinyl polymer resins like polyacrylates, polycondensation resins like novolak type resins, and addition polymerization resins. The diazo resin is embodied by the ones typified by the salts of the condensation products of diazodiarylamine and an active carbonyl compound, preferably, the one soluble in organic solvents. The above-mentioned monomer or oligomer can be embodied by monofunctional (meth)acrylate, such as polyethylene glycol (meth)acrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable photosensitive composition useful for producing a plate surface of a photosensitive lithographic printing plate and, more particularly, to a photosensitive composition excellent in developability and printing durability. This is related to a lithographic printing plate.

[0002]

2. Description of the Related Art Hitherto, many image forming methods using a combination of a photopolymerizable photosensitive composition and a diazo resin have been known. For example, a composition comprising a polymer as a binder, a diazo resin, an addition-polymerizable ethylenically unsaturated compound, and a photopolymerization initiator as described in JP-A-59-53836 is known. However, the polymers described have the drawbacks that gelation tends to occur during the synthesis and that the photosensitive compositions are not excellent in aqueous alkaline developability.

As a method for introducing an ethylenically unsaturated bond into a polymer compound, for example, a method of reacting acrylic acid or methacrylic acid with a polymer compound having an epoxy group in a side chain, or a method having a carboxyl group in a side chain. A method of reacting glycidyl methacrylate with a polymer compound,
Further, a method of reacting a polymer compound having a carboxyl group in a side chain with allyl bromide or the like as described in JP-A-59-53836 is also known. However,
In these methods, since the epoxy group and the carboxyl group and the bromo group and the carboxyl group are relatively difficult to react with each other, it is necessary to use a large amount of an amine catalyst or to add a large amount of the compound to be reacted. There was a drawback that it was difficult to remove these unreacted substances.

Japanese Patent Application Laid-Open No. 61-200536 describes an image forming method utilizing photopolymerization, in which methacryloyloxyethyl isocyanate is reacted with hydroxyl groups in a resin to introduce an ethylenically unsaturated bond. A composition comprising a polymer as a binder and a photopolymerization initiator is known, but has a disadvantage that adhesion to a metal support is poor and when used as a lithographic printing plate, printing durability is not excellent. I was

[0005]

An object of the present invention is to use a combination of a photopolymerizable photosensitive composition and a diazo resin to provide good adhesion to a metal support, developability and printing durability. An object of the present invention is to provide an excellent negative photosensitive composition, and a negative photosensitive lithographic printing plate.

[0006]

Means for Solving the Problems The present inventors synthesized various polymers as a binder having an atomic group of a specific structure, prepared a photosensitive composition, and evaluated the physical properties.
The photosensitive composition having the following constitution was found to be excellent in developability and printing durability as compared with a conventional polymer as a binder having an atomic group, and completed the present invention.

That is, the present invention relates to (A) a binder resin having a urethane bond in a side chain, (B) a diazo resin, and (C)
A photosensitive composition comprising a monomer or oligomer having at least two polymerizable ethylenically unsaturated double bonds, and (D) a photopolymerization initiator, and a photosensitive layer comprising the composition A photosensitive lithographic printing plate having the formula:

The present invention also relates to a negative photosensitive composition wherein the binder resin having a urethane bond in the side chain has an ethylenically unsaturated bond.

The present invention also relates to a negative photosensitive composition in which the binder resin having a urethane bond in the side chain has an alkali-soluble group.

The present invention also relates to a negative photosensitive composition wherein the binder resin is an adduct of an acrylic resin having a hydroxyl group in a side chain and an isocyanate compound having an unsaturated group.

The present invention also relates to a negative photosensitive composition wherein the binder resin contains an acrylic resin having at least a structural unit of the general formula (I).

[0012]

Embedded image —R ¹ —O—CO—NH—R ² —X—CR ³ ＣＨCH ₂ General formula (I) (wherein R ¹ and R ² are alkyl which may have a substituent,
Aryl or single bond, R ³ is hydrogen, alkyl which may have a substituent, aryl, X is -CO-, -CO-O
-, -NH-CO- or a group selected from a single bond. )

[0013] The present invention also relates to the present invention, wherein the binder resin comprises at least one polymerizable monomer selected from the group consisting of a polymerizable monomer having a nitrile group and a polymerizable monomer having an amide group. The present invention relates to a negative photosensitive composition containing an acrylic resin obtained by copolymerizing a polymerizable monomer having a structural unit of the general formula (I).

Further, the present invention relates to a negative photosensitive lithographic printing plate comprising the above-mentioned photosensitive composition provided on a metal support.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a photosensitive composition having a urethane bond in a side chain and other components used in the photosensitive composition of the present invention and a method for producing the same,
The method for preparing the negative photosensitive composition used in the present invention and the method for producing the negative planographic printing plate of the present invention will be described in detail.

The resin (A) having a urethane bond in the side chain used in the present invention includes, for example, polyacrylates,
Any of vinyl polymer-based resins such as polystyrenes, polyvinyl ethers and polyacrylonitriles, condensation-polymerized resins such as novolaks, polyesters and polyamides, and polyaddition resins may be used in the present invention. Can be.

The photosensitive compounds used in the negative photosensitive composition of the present invention include the following (B) to (D). (B) diazo resin (C) monomer or oligomer having at least two polymerizable ethylenically unsaturated double bonds (D) photopolymerization initiator

The diazo resin (B) includes, for example, a diazo resin typified by a salt of a condensate of a diazodiarylamine and an active carbonyl compound, and is preferably photosensitive, water-insoluble and soluble in an organic solvent.

Particularly preferred diazo resins are, for example, 4-diazodiphenylamine, 4-diazo-3-methyldiphenylamine, 4-diazo-4'-methyldiphenylamine, 4-diazo-3'-methyldiphenylamine,
Diazo-4'-methoxydiphenylamine, 4-diazo-3-methyl-4'-ethoxydiphenylamine, 4-
Condensation of at least one compound selected from diazo-3-methoxydiphenylamine and at least one compound selected from formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, 4,4'-bis-methoxymethyldiphenyl ether and the like Organic or inorganic acid salts.

Examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, mesitylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, propylnaphthalenesulfonic acid, and 1-naphthol-5-. Sulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,4-dihydroxybenzophenone, benzenephosphinic acid, and the like.Examples of inorganic acids include hexafluorophosphoric acid, Examples include tetrafluoroboric acid and thiocyanic acid.

Further, diazo resins having a polyester-based main chain as described in JP-A-54-30121 are disclosed.
No. 1-273538, a diazo resin obtained by reacting a polymer having a carboxylic anhydride residue with a diazo compound having a hydroxyl group, and a diazo resin obtained by reacting a polyisocyanate compound with a diazo compound having a hydroxyl group. And a diazo resin having a carboxyl group and a diazo resin having a phenolic hydroxyl group.

The amount of the diazo resin used is preferably in the range of 1 to 40% by weight based on the solid content of the composition. If necessary, two or more diazo resins may be used in combination.

Compound (C) having an ethylenically unsaturated group
A monomer or oligomer having a boiling point of 100 ° C. or higher at normal pressure and having at least one, preferably two or more addition-polymerizable ethylenically unsaturated groups per molecule. Examples of such a monomer or oligomer include, for example, polyethylene glycol mono (meth) acrylate [hereinafter, methacrylate and acrylate are collectively referred to as
It is called (meth) acrylate. Monofunctional (meth) acrylates such as polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate,
Polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Hexanediol di (meth) acrylate, tri (acryloyloxyethyl) isocyanurate, (meth) acrylate of a polyhydric alcohol / alxylene oxide adduct, (meth) acrylate of a polyhydric phenol / alkylene oxide adduct, No. 41708, Special Publication No. 50-6
Urethane acrylates described in JP-A-34-34 and JP-B-51-37193;
No. 3, JP-B-49-43191, JP-B 52-304
No. 90, polyfunctional (meth) acrylates such as polyester acrylates and epoxy acrylates obtained by adding an epoxy resin and (meth) acrylic acid.

As the photopolymerization initiator (D), for example, α-α described in US Pat. No. 2,367,661 is used.
Carbonyl compounds, acyloin ethers described in U.S. Pat. No. 2,448,828, U.S. Pat.
No. 22512, α-hydrocarbon-substituted aromatic acyloin compounds, US Pat. No. 30,461
No. 27, the combination of triarylbiimidazole / p-aminophenyl ketone described in U.S. Pat. No. 3,549,367, and the compound described in U.S. Pat. No. 4,239,850. Trihalomethyl-s-triazine compounds, oxadiazole compounds described in U.S. Pat. No. 4,221,970, acridine and phenazine compounds described in U.S. Pat. No. 3,751,259, JP-B-51-48516. The benzothiazole-based compound described in JP-A No. 5-2350, for example, is used, and the amount of the benzothiazole-based compound is preferably in the range of 0.5 to 20% by weight based on the solid content of the composition.

Resin having urethane bond in side chain (A)
Preferably has an ethylenically unsaturated bond at the terminal and increases the crosslink density by photocrosslinking with a monomer or oligomer (C) having at least two polymerizable ethylenically unsaturated double bonds. , Abrasion resistance and printing durability are improved.

When the photosensitive composition of the present invention is developed with an aqueous alkaline developer, the resin (A) having a urethane bond in the side chain is a vinyl-polymerizable or condensation-polymerizable alkali-soluble resin. Is preferred.

Accordingly, in the resin (A) having a urethane bond in the side chain, since the urethane bond itself does not act as an alkali-soluble group, for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group It is preferable that an alkali-soluble group such as an active imide group is separately provided in the resin skeleton. In order to further improve the developing characteristics, it is more preferable to use a phenolic hydroxyl group. However, in the case where the sensitivity of the photosensitive composition is to be enhanced, or in the case where development is possible even with a developer having a significantly reduced activity, a carboxyl group or a sulfonamide group may be contained in the resin skeleton.

The resin (A) having a urethane bond in the side chain used in the present invention is obtained, for example, by adding an isocyanate compound to a polymer of a compound having one vinyl group and one or more hydroxyl groups in one molecule. Things.

Examples of the compound having one vinyl group and one or more hydroxyl groups in one molecule include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; An acrylamide derivative such as N-methylolacrylamide and the like can be mentioned. These compounds are used alone or in combination of two or more.

One specific example of a resin that can be particularly preferably used in the present invention is that a methacryloyloxyethyl isocyanate is added to a copolymer of 2-hydroxyethyl methacrylate in an amount of 5 to 100 mol%. . These resins can be used alone or in combination with the above-mentioned known compound having an ethylenically unsaturated group as a compound having an ethylenically unsaturated group.

The resin preferably used in the present invention contains 5-80 parts by weight of the structural unit represented by the general formula (I) per 100 parts by weight of the resin. Solvent resistance, abrasion resistance,
Excellent performance in developing characteristics.

The alkali-soluble resin having a urethane bond in the side chain preferably used in the present invention is a homopolymer of a polymerizable monomer having a polymerizable unsaturated bond and a urethane bond, or a copolymer of two or more kinds. Although it may be a polymer, it is preferable that a resin having a urethane bond in a side chain and one or more compounds containing one or more polymerizable unsaturated bonds and not containing a urethane bond are used. It is a polymer.

Specifically, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2, Acrylic acid esters such as 2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, and tetrahydroacrylate;

Aryl acrylates such as phenyl acrylate and furfuryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate Methacrylates such as, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate; Alkenyl methacrylate, cresyl methacrylate, such as aryl methacrylates of naphthyl methacrylate,

Acrylamide or a derivative thereof includes N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, Nt-butylacrylamide, N-heptylacrylamide, N-octylacrylamide, N-cyclohexylacrylamide. , N-alkylacrylamides such as N-benzylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N-nitrophenylacrylamide, N-naphthylacrylamide, N-alkyl such as N-hydroxyphenylacrylamide
-Aryl acrylamides,

N, N-dimethylacrylamide, N, N
N, N-dialkylacrylamides such as diethylacrylamide, N, N-dibutylacrylamide, N, N-dibutylacrylamide, N, N-diisobutylacrylamide, N, N-diethylhexylacrylamide, N, N-dicyclohexylacrylamide, N −
N, N such as methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide
-Arylacrylamides, methacrylamide or derivatives thereof include N-methylmethacrylamide, N
N-alkyl methacryls such as -ethyl methacrylamide, N-propyl methacrylamide, N-butyl methacrylamide, Nt-butyl methacrylamide, N-ethylhexyl methacrylamide, N-hydroxyethyl methacrylamide, N-cyclohexyl methacrylamide Amides, N-arylmethacrylamides such as N-phenylmethacrylamide, N-naphthylmethacrylamide, N, N-diethylmethacrylamide, N, N
N, N-dialkyl methacrylamides, such as -dipropyl methacrylamide, N, N-dibutyl methacrylamide, N, N, such as N, N-diphenyl methacrylamide;
N-diaryl methacrylamides, N-hydroxyethyl-N-methyl methacrylamide, N-methyl-N-
Methacrylamide derivatives such as phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide,

Allyl compounds such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, allyloxyethanol, hexyl vinyl ether, octyl Vinyl ether, dodecyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether,
1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether Vinyl ethers such as vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether;

Vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl aceto acetate, vinyl lactate , Vinyl-β-
Vinyl esters such as phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate;

Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene,
Isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, dodecylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3
-Methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, 2-bromo-4-trifluoromethylstyrene,
Styrenes such as 4-fluoro-3-trifluoromethylstyrene,

Butyl crotonate, hexyl crotonate,
Crotonic acid, crotonic esters such as glycerin monocrotonate, dimethyl itaconate, diethyl itaconate, dialkyl itaconates such as dibutyl itaconate, dimethyl malate, dialkyls of maleic acid or fumaric acid such as dibutyl fumarate, Maleimides such as maleimide, N-phenylmaleimide, N-2-methylphenylmaleimide, N-2,6-diethylphenylmaleimide, N-2-chlorophenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-hydroxyphenylmaleimide And N-vinylpyrrolidone, N-vinylpyridine, acrylonitrile, methacrylonitrile and the like.

Among these compounds having a polymerizable unsaturated bond, preferably used are, for example, (meth) acrylic esters, (meth) acrylamides, maleimides, and (meth) acrylonitriles.

As the alkali-soluble acrylic resin binder, a copolymer of a monomer mixture containing (meth) acrylonitrile in an amount of from 20 mol% to 80 mol% is excellent in solvent resistance and abrasion resistance. A) A copolymer of a monomer mixture containing 5 mol% or more of acrylamide is excellent in developability.

It is also possible to use (meth) acrylic acids in combination with these suitably used compounds.

In the present invention, the term "(meth) acrylate" or "(meth) acrylic acid" includes not only acrylate but also methacrylate, and includes not only acrylic acid but also methacrylic acid. (Meth) acrylonitrile includes acrylonitrile and methacrylonitrile, and (meth) acrylamide includes acrylamide and methacrylamide.

One or more of these compounds having a polymerizable unsaturated bond and one or more copolymers of a compound having a urethane bond and having a polymerizable unsaturated bond may be a block, a random, a graft or a copolymer. Any structure such as a body can be used.

The molecular weight of the copolymer thus obtained is preferably 2,000 or more in weight average molecular weight and 1,000 or more in number average molecular weight. More preferably, the weight average molecular weight ranges from 3,000 to 500,000, and the number average molecular weight ranges from 2,000 to 400,000.

As a solvent used in synthesizing such a resin, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol,
Ethanol, ethylene glycol monomethyl ether,
Ethylene glycol monoethyl glycol, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methoxy-
2-propyl acetate, 1-ethoxy-2-propyl acetate, N, N-dimethylformamide, N, N-
Examples include dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, toluene, ethyl acetate, methyl lactate, and ethyl lactate. These solvents are used alone or in combination of two or more.

The photosensitive composition of the present invention can be used as a negative type lithographic printing plate by coating it on an aluminum support.

In the case of a negative type lithographic printing plate, an organic polymer binder can be used in addition to the negative type photosensitive compound and the alkali-soluble resin having a urethane bond. As such an organic polymer binder, for example, acrylic resin,
Polyamide resin, polyurethane resin, phenoxy resin,
Epoxy resins, polyacetal resins, polystyrene resins, novolak resins and the like can be mentioned. Further, known additives such as a thermal polymerization inhibitor, a dye, a surfactant, a plasticizer, and a stability improver can be added to improve the performance.

As the surfactant, JP-A-62-366
No. 57, JP-A-62-226143, and the like. Examples of the plasticizer include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate, tri (2-chloroethyl) phosphate, and tributyl citrate.

As the colorant for the image, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow #
101, oil yellow # 130, oil pink # 31
2. Oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, crystal violet (CI42555), methyl Violet (CI42535), Rhodamine B (CI4517)
OB), malachite green (CI42000), methylene blue (CI52015) and the like.

Known stability improvers include, for example, phosphoric acid, phosphorous acid, oxalic acid, tartaric acid, malic acid, citric acid,
Dipicolinic acid, polyacrylic acid, benzenesulfonic acid,
Toluenesulfonic acid and the like can be mentioned.

The amount of these various additives varies depending on the purpose, but generally, the amount of the solid content of the photosensitive composition is from 0 to 0%.
A range of 30% by weight is preferred.

The above-mentioned photosensitive composition can be dissolved in various solvents as necessary and applied on a support. As the solvent, for example, methylene chloride, chloroform, dichloroethane, trichloroethane, trichloroethylene, monochlorobenzene, dichlorobenzene, a halogenated solvent such as carbon tetrachloride, hexane, heptane, cyclohesan,
Benzene, toluene, aliphatic or alicyclic or aromatic hydrocarbon solvents such as xylene, tetrahydrofuran,
Ether solvents such as dioxane and diethyl ether,
Ester solvents such as methyl acetate, butyl acetate, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, methanol, ethanol, butanol,
Alcoholic solvents such as benzyl alcohol, diacetone alcohol, methyl cellosolve, ethyl cellosolve, cyclohexanol, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-
Examples thereof include a nitrogen-containing solvent such as methylpyrrolidone, and dimethyl sulfoxide. The above solvents can be used alone or in combination of two or more. In some cases, a mixed solvent with water can also be used.

The photosensitive composition thus produced can be used, for example, by dip coating, curtain coating, roll coating,
It is applied to the support by a well-known application method such as spray application, wheeler application, spinner application, air knife application, doctor knife application and the like.

As the support, for example, aluminum,
Metal plate of zinc, copper, stainless steel, iron, etc., plastic film of polyethylene terephthalate, polycarbonate, polyvinyl acetal, polyethylene, etc., paper on which synthetic resin is melt-coated or synthetic resin solution is applied, metal layer is vacuum-deposited and laminated on plastic film And various materials used as a support for a printing plate.

In the case of a support having a metal surface, particularly an aluminum surface, it is preferable that a surface treatment such as graining treatment, anodic oxidation treatment, and hydrophilization treatment is performed. The coating amount of the photosensitive composition is usually about 0.5 to 5 g / m ² by dry weight.

After coating, the resultant is dried by a known method to obtain a photosensitive lithographic printing plate having a photosensitive layer provided on a support.

The photosensitive lithographic printing plate thus obtained can be used by a known method. For example, a negative type film is brought into close contact with this photosensitive lithographic printing plate, exposed with an ultra-high pressure mercury lamp, a metal halide lamp, etc., and developed with an alkaline aqueous solution such as an organic amine, sodium metasilicate, potassium metasilicate, sodium phosphate, and caustic soda. And used as a printing plate.

[0060]

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

(Preparation of Polymer-1) A 200 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer was placed
Add 18.75 g of N, N-dimethylacetamide and add 8
Heat to 0 ° C. While blowing in nitrogen gas, 2-hydroxyethyl methacrylate 9.0 g methyl methacrylate 7.0 g methacrylic acid 4.0 g 2,2 ′
-Azobis (2,4-dimethylvaleronitrile)
A monomer solution in which 5 g was dissolved in 18.75 g of N, N-dimethylacetamide was added dropwise over 1 hour. The reaction solution was maintained at 80 ° C., and one hour after the completion of the dropwise addition, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and stirring was continued for another hour. After the completion of the polymerization reaction, the introduction of nitrogen was stopped, and the introduction of air was changed. Then, 0.2 g of hydroquinone monomethyl ether was added, and the mixture was cooled to 50 ° C. At 50 ° C., 10.7 g of methacryloyloxyethyl isocyanate was added, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst, and the reaction was allowed to proceed for 3 hours. The polymer was precipitated, filtered, washed and dried to obtain polymer-1 having a weight average molecular weight of 32,000 in terms of polystyrene.
7 g were obtained.

(Preparation of Polymer-2) In a 200 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer,
Add 18.75 g of N, N-dimethylacetamide and add 8
Heat to 0 ° C. While blowing in nitrogen gas, 2-hydroxyethyl methacrylate 9.0 g acrylonitrile 3.5 g methyl methacrylate 3.5 g methacrylic acid 4.0 g 2,2′-azobis (2,4-dimethylvaleronitrile) A monomer solution in which 5 g was dissolved in 18.75 g of N, N-dimethylacetamide was added dropwise over 1 hour. The reaction solution was maintained at 80 ° C., and one hour after the completion of the dropwise addition, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and stirring was continued for another hour. After the completion of the polymerization reaction, the introduction of nitrogen was stopped, and the introduction of air was replaced with the introduction of hydroquinone monomethyl ether 0.2.
g was added and cooled to 50 ° C. At 50 ° C., 10.7 g of methacryloyloxyethyl isocyanate was added, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst, and the reaction was carried out for 3 hours. Precipitate the polymer, filter, wash and dry.Polystyrene equivalent weight average molecular weight
21.8 g of 29,000 polymer-2 was obtained.

(Preparation of Polymer-3) A 200 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer and a stirrer was placed
Add 18.75 g of N, N-dimethylacetamide and add 8
Heat to 0 ° C. While blowing in nitrogen gas, 2-hydroxyethyl methacrylate 9.0 g methacrylamide 3.5 g methyl methacrylate 3.5 g methacrylic acid 4.0 g 2,2′-azobis (2,4-dimethylvaleronitrile) 0 A monomer solution in which 0.5 g was dissolved in 18.75 g of N, N-dimethylacetamide was added dropwise over 1 hour. The reaction solution was maintained at 80 ° C., and one hour after the completion of the dropwise addition, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and stirring was continued for another hour. After the completion of the polymerization reaction, the introduction of nitrogen was stopped, and the introduction of air was replaced with the introduction of hydroquinone monomethyl ether 0.2.
g was added and cooled to 50 ° C. At 50 ° C., 10.7 g of methacryloyloxyethyl isocyanate was added, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst, and the reaction was carried out for 3 hours. Precipitate the polymer, filter, wash and dry.Polystyrene equivalent weight average molecular weight
22.6 g of 24,000 polymer-3 was obtained.

(Preparation of Polymer-4) In a 200 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer,
Add 18.75 g of N, N-dimethylacetamide and add 8
Heat to 0 ° C. While blowing in nitrogen gas, 2-hydroxyethyl methacrylate 9.0 g acrylonitrile 3.5 g methacrylamide 3.5 g methacrylic acid 4.0 g 2,2′-azobis (2,4-dimethylvaleronitrile) 0.5 g with N And a monomer solution dissolved in 18.75 g of N-dimethylacetamide was added dropwise over 1 hour. The reaction solution was maintained at 80 ° C., and one hour after the completion of the dropwise addition, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and stirring was continued for another hour. After the completion of the polymerization reaction, the introduction of nitrogen was stopped, and the introduction of air was changed. Then, 0.2 g of hydroquinone monomethyl ether was added, and the mixture was cooled to 50 ° C. At 50 ° C., 10.7 g of methacryloyloxyethyl isocyanate was added, and 0.1 g of dibutyltin dilaurate was added as a reaction catalyst.
After completion of the reaction, the reaction solution was cooled to room temperature, and the reaction solution was dropped into 2 liters of water to precipitate a polymer, which was filtered, washed and dried, and the weight average molecular weight was 2.0 in terms of polystyrene.
20.4 g of Polymer-4 was obtained.

(Preparation of Polymer-5) 1.68 l of 1,2-dichloroethane as a reaction solvent was placed in a 3 liter four-necked flask equipped with a stirrer, a stirring blade, a reflux condenser, a dropping funnel and a thermometer. Put nitrogen while replacing 7
Heated to 0 ° C. Allyl methacrylate 10 in dropping funnel
0.8 g, 7.6 g of methacrylic acid, and 1.68 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were placed in 0.44 liter of a 1,2-dichloroethane solution. The mixed solution was dropped into the flask over a period of time with stirring. After completion of the dropwise addition, the mixture was further stirred at a reaction temperature of 70 ° C. for 5 hours to complete the reaction. After completion of the heating, 0.04 g of hydroquinone monomethyl ether was added as a polymerization inhibitor, and the reaction solution was concentrated to 500 ml.
The concentrated solution was added to 4 liters of hexane to precipitate and was dried under vacuum to obtain 75.2 g of polymer-5.

(Examples 1 to 4, Comparative Example 1) Thickness 0.30
mm aluminum plate was degreased with an aqueous sodium hydroxide solution and subjected to electrolytic polishing in a 2% hydrochloric acid bath to obtain a grained plate having a center line average roughness (Ra) of 0.6 μm. Then
Anodizing at a current density of 2 A / dm ² in a 20% sulfuric acid bath to form an oxide film of 2.7 g / m ² , and then in a 3% aqueous solution of No. 3 sodium silicate at 60 ° C. for 1 minute It was sealed, washed with water and dried to obtain a support.

The following photosensitive solution was applied to this support by a roll coater and dried at 100 ° C. for 3 minutes to obtain a photosensitive lithographic printing plate. At this time, the weight of the dried coating film was 2.0 g / m ² .

[Photosensitive Liquid (Photosensitive Composition) Examples 1 to 4, Comparative Example 1] Polymer-1 to 5 9.0 g diazo resin * 1) 1.0 g DPHA 1.5 g Triazine B 0.2 g malic acid 0.1 g "Victoria Pure Blue BOH" * 2) 0.2 g Ethylene glycol monomethyl ether 200 g

However, the diazo resin * 1) is a 4-dodecylbenzenesulfonate of a condensate of 4-diazodiphenylamine and paraformaldehyde, and * 2) Victoria Pure Blue BOH is Hodogaya Chemical stock)
Is a basic oil-soluble dye.

A solid and halftone dot negative image film and a step 0.15 step wedge were brought into close contact with the obtained photosensitive lithographic printing plate, and an output of 2 k was provided at a position 1 m away from this.
Exposure was performed using a W metal halide lamp for an exposure time at which the light sensitivity became four-step solid. Thereafter, the film was developed at 30 ° C. for 19 seconds using a developing solution ND-1 (4-fold dilution) manufactured by Polychrome Japan Co., Ltd. sold by Dainippon Ink and Chemicals, and washed with water. Company-made "NF-
2) A two-fold dilution was applied as a gum solution to obtain a lithographic printing plate.

The prepared lithographic printing plate was mounted on a Roland Fabolit printing machine, and the printing ink “CAPS-G Beni” was used.
(Manufactured by Dainippon Ink and Chemicals, Inc.), fountain solution “DH-7”
8 "(manufactured by Dainippon Ink and Chemicals, Inc.) using a 400-fold dilution.

For the purpose of comparison, the following tests were carried out in the same manner as in Examples 1 to 4 by adjusting the composition of the following photosensitive solution using Polymer-1.

[Photosensitive Liquid (Photosensitive Composition) Comparative Example 2] Polymer-1 10.0 g DPHA 1.5 g Triazine B 0.2 g Malic acid 0.1 g "Victoria Pure Blue BOH" 0.2 g Ethylene glycol monomethyl ether 200g

The evaluation results are summarized in Table 1.

[0075]

[Table 1]

As can be seen from Table 1, lithographic printing plates Examples 1 to 4 using the photosensitive solution composition of the present invention have excellent developability as compared with Comparative Example 1, and can be understood as compared with Comparative Example 2. It has good adhesion to the support and very good printing durability.

[0077]

EFFECT OF THE INVENTION The photosensitive resin composition of the present invention is a negative photosensitive composition having good adhesion to a metal support, excellent developability and excellent printing durability, and further a negative photosensitive lithographic printing plate. Can be provided.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/038 G03F 7/038 (72) Inventor Eiji Hayakawa 15-1 Sumiyoshicho, Utsunomiya City, Tochigi Prefecture (72) Inventor Koji Koe 5-90 Higashima, Kitamoto-shi, Saitama Sun apartment 2-505 Kitamoto

Claims (7)

[Claims] 1. A binder resin (A) having a urethane bond in a side chain, a diazo resin (B), a monomer or oligomer having at least two polymerizable ethylenically unsaturated double bonds (C), and photopolymerization initiation A negative photosensitive composition comprising the agent (D). 2. The negative photosensitive composition according to claim 1, wherein the binder resin (A) having a urethane bond in a side chain has an ethylenically unsaturated bond. 3. The negative photosensitive composition according to claim 1, wherein the binder resin (A) having a urethane bond in a side chain has an alkali-soluble group. 4. The negative photosensitive material according to claim 1, wherein the binder resin (A) having a urethane bond in a side chain is an adduct of an acrylic resin having a hydroxyl group in a side chain and an isocyanate compound having an unsaturated group. Composition. 5. The negative photosensitive composition according to claim 1, wherein the binder resin (A) having a urethane bond in a side chain contains an acrylic resin having a structural unit of the general formula (I). Embedded image —R ¹ —O—CO—NH—R ² —X—CR ³ ＣＨCH ₂ General formula (I) (wherein R ¹ and R ² are alkyl which may have a substituent.
Aryl or single bond, R ³ is hydrogen, alkyl which may have a substituent, aryl, X is —CO—, —CO—O
Represents a group selected from-, -NH-CO- or a single bond. ) 6. The binder resin (A) having a urethane bond in a side chain thereof is at least one polymerizable monomer selected from the group consisting of a polymerizable monomer having a nitrile group and a polymerizable monomer having an amide group. The negative photosensitive composition according to claim 1, comprising an acrylic resin obtained by copolymerizing a monomer and a polymerizable monomer having a structural unit represented by the general formula (I). 7. A negative photosensitive lithographic printing plate comprising the photosensitive composition according to claim 1 provided on a metal support.