JPH05127368A - Photosensitive planographic printing plate requiring no dampening water - Google Patents

Abstract

PURPOSE:To improve the scratch resistance, plate wear and image reproducibility of a silicone rubber layer and to increase production efficiency as well as to obtain satisfactory dyeability. CONSTITUTION:This planographic printing plate requiring no dampening water has a primer layer, a photosensitive layer and a silicone rubber layer successively formed on the substrate and the primer layer contains resin obtd. by allowing polyester resin having hydroxyl groups to react with a diisocyanato compd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate that does not require fountain solution, and more specifically, it improves the adhesive force between a support and a primer layer and also scratches a silicone rubber layer. The present invention relates to a photosensitive lithographic printing plate that does not require fountain solution and has improved dyeing resistance, scratch resistance, printing durability and image reproducibility.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a photosensitive lithographic printing plate which does not require a fountain solution (hereinafter, referred to as a "plate material" if necessary), there is known one in which a photosensitive layer and an ink repellent layer are sequentially coated on a support. Has been. By exposing and developing this plate material, a fountain solution-free planographic printing plate (hereinafter referred to as "printing plate" if necessary) can be obtained.

Generally, in such a plate material, in order to improve the adhesion between the support and the photosensitive layer, a primer layer is provided between them. Various materials are used as the material of the primer layer.
Japanese Patent Laid-Open No. 54219 discloses an epoxy resin having excellent adhesiveness to a photosensitive layer and thus improved printing durability.

In general, a photosensitive lithographic printing plate is a so-called inspection for checking the end of development during development, for checking image quality after development, and for checking whether the plate has scratches or the like. It is necessary to have plate formability, which is why the plate is dyed.

In this respect, however, the plate of the above-mentioned publication has excellent printing durability, but this plate has a problem that it has poor dyeability and therefore has no plate inspection property.

Therefore, for the purpose of improving the dyeability, JP-A-63-133153 describes that a primer layer containing gelatin is used in place of the primer layer made of epoxy resin or the like. Kaihei 2-3
Japanese Patent No. 4857 discloses a photosensitive lithographic printing plate which does not require a fountain solution, in which the primer layer contains at least one selected from casein, soybean protein and albumin.

However, although the dyeability of each of these plate materials is improved, when the primer layer contains gelatin, it takes time to harden the film, resulting in poor work efficiency and the case where the primer layer contains casein. In those containing, the hardening time is not satisfactory.

Further, Japanese Patent Application Laid-Open No. 60-229031 describes that a lithographic printing plate which does not require fountain solution and has excellent printing durability can be obtained by using a photodimerizing type curable resin as a primer layer. However, it is difficult to obtain a good image reproducibility with this resin, and the scratch resistance of the silicone rubber layer is not sufficient.

The present inventors have conducted various studies in view of the above problems, and as a result, by incorporating a specific resin in the primer layer, the above problems can be solved, and the scratch resistance and image of the silicone rubber layer can be improved. It was found that a product having satisfactory reproducibility can be obtained, and the present invention has been completed here.

[0010]

Therefore, the object of the present invention is to have sufficient dyeability and good adhesion between the support and the primer layer, and therefore to prevent damage to the silicone rubber layer, printing durability and image reproduction. Another object of the present invention is to provide a photosensitive lithographic printing plate which is improved in productivity and has high production efficiency and does not require a fountain solution.

[0011]

The above object of the present invention is to provide a photosensitive lithographic printing plate which does not require fountain solution having a primer layer, a photosensitive layer and a silicone rubber layer on a substrate in this order, wherein the primer layer has a hydroxyl group-containing polyester resin and diisocyanate. This is achieved by a fountain solution-free photosensitive lithographic printing plate characterized by containing a resin obtained by reacting a compound.

The structure of the present invention will be described in more detail below. The present invention contains a resin obtained by reacting a polyester resin having a hydroxyl group with a diisocyanate compound in a primer layer of a photosensitive lithographic printing plate that does not require fountain solution, and thus has excellent dyeability, and a support and a primer layer. The adhesive strength between the two is improved, thereby improving the scratch resistance of the silicone rubber layer (scratch resistance), the printing durability and the image reproducibility, and further improving the production efficiency.

The photosensitive lithographic printing plate requiring no fountain solution used in the present invention is also used in a type in which only the silicone rubber layer in the image area is removed after development. It is a type in which the layer is removed and the primer layer in the image area is exposed, and exhibits a greater effect.

The carboxylic acid component of the polyester resin having a hydroxyl group used in the primer layer in the present invention includes terephthalic acid, isophthalic acid, orthophthalic acid,
Aromatic dicarboxylic acid such as phthalic anhydride and 1,5-naphthalic acid-p-oxybenzoic acid, p- (hydroxyethoxy)
Examples include aromatic oxycarboxylic acids such as benzoic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and other aliphatic dicarboxylic acids.

Further, tri- and tetracarboxylic acid components such as trimellitic acid, trimesic acid and pyromellitic acid may be used in combination. As the glycol component, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-bentanediol, 1,6-hexanediol, neopentyl are used. Glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, bisphenol A ethylene oxide adduct and propylene oxide adduct,

Ethylene oxide adducts and propylene oxide adducts of hydrogenated bisphenol A, 1,4-bis (β-hydroxyethoxy) benzene, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxypropylene glycol, ethylene oxide-propylene. There are oxide copolymers, tetrahydrofuran-ethylene oxide copolymers, tetrahydrofuran-propylene oxide copolymers and the like. Further, tri- and tetraols such as trimethylolethane, trimethylolpropane, glycerin and pentaerythritol may be used in combination with these components.

Various functional groups such as a carboxylic acid group, an amino group, an amide group, a (meth) acrylate group, and a metal sulfonate group can be introduced into the polyester resin having a hydroxyl group used in the present invention. , The one in which the metal sulfonate base is introduced is the adhesiveness to the support, the dyeing last name,
It is preferable because it has the effect of improving the solvent resistance.

Examples of the dicarboxylic acid component containing a metal sulfonate group include 5-sodium sulfoisophthalic acid,
There are 5-potassium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, etc., and the copolymerization amount of these dicarboxylic acid components containing a sulfonic acid metal base is 0. Three
˜7.0 mol%, preferably 1.0 to 5.0 mol%. When the copolymerization amount is in the range of 0.3 to 7.0 mol, sufficient performance can be obtained and sufficient solvent solubility can be obtained.

The diisocyanate compound used in the present invention includes toluene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate,
Diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, o
-Trizine diisocyanate, isophorone diisocyanate, diphenyl ether diisocyanate, hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylene diisocyanate, lysine diisocyanate, dimer of toluene diisocyanate and the like.

The polyethylene resin having a hydroxyl group and the diisocyanate compound used in the present invention may be preliminarily reacted and then applied, or they may be reacted by heating or leaving them to stand after use. Even when the reaction is performed in advance and then the coating is performed, the reaction may not be completely completed, and a method may be used in which an unreacted polyester resin or a diisocyanate compound is contained and the reaction is completed after the coating.

The diisocyanate compound does not necessarily have to completely react with the polyester resin if only the polyester resin remains as an unreacted component. Further, in order to quickly complete the reaction of the polyester resin and the diisocyanate compound, tertiary amines such as triethylenediamine and tetramethylbutanediamine, and metal catalysts such as dibutyltin dilaurate, tin octoate and cobalt naphthenate may be used. it can.

The glass transition temperature of the resin used in the present invention is preferably 50 ° C. or less in view of the conformability to the support and printing durability. The weight average molecular weight is 5,000.
100 to 100,000 (GPC method; styrene conversion) is preferable from the viewpoint of image reproducibility and developability. Further, the weight% of NCO groups in the resin raw material is preferably 3 to 20%, more preferably 5 to 15%. When the content of the NCO group is low, the adhesiveness is insufficient and the printing durability is lowered, and when the content is high, the image reproducibility is lowered.

In the present invention, it is possible to use other organic solvent-soluble polymer compounds having film-forming ability, if necessary. Specific examples thereof include methacrylic acid copolymer, acrylic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, aqueous cellulose derivative, polyvinylpyrrolidone, polyethylene oxide, alcohol-soluble nylon, polyester, unsaturated polyester. ,

Polystyrene, epoxy resin, phenoxy resin, polyvinyl butyral, polyvinyl formal,
Polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, partially acetalized polyvinyl alcohol, water-soluble nylon, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyamide resin , Polyurethane resin, polycarbonate resin, etc., and photopolymerizable or photocrosslinkable to the side chain,

Further, those having an olefinic unsaturated double bond group include allyl (meth) acrylates as described in JP-A-59-53836 / and optionally other addition-polymerizable vinyls. Monomer copolymer,
And its alkali metal salts or amine salts; Japanese Patent Publication No. 59-
Hydroxyethyl (meth) acrylate / (meth) acrylic acid / alkyl (meth) acrylate copolymer as described in Japanese Patent No. 45979 and its alkali metal salt or amine salt are reacted with (meth) acrylic acid chloride. Things;

JP-A-59-71048 JP-A-59-71
No. 048, wherein maleic anhydride copolymer is added with pentaerythritol triacrylate by half-esterification and its alkali metal salt or amine salt; styrene / maleic anhydride copolymer monohydroxy Alkyl (meth) acrylate, polyethylene glycol mono (meth) acrylate or polypropylene glycol mono (meth) acrylate added by half-esterification and its alkali metal salt or amine salt;

A part of carboxylic acid of (meth) acrylic acid copolymer or crotonic acid copolymer reacted with glycidyl (meth) acrylate and its alkali metal salt or amine salt; hydroxyalkyl (meth) acrylate Polymers, polyvinyl formal, polyvinyl butyral, maleic anhydride or itaconic anhydride, and their alkali metal salts or amine salts; hydroxyalkyl (meth) acrylate / (meth) acrylic acid copolymers, 2,4- Toluene diisocyanate / hydroxyalkyl (meth) acrylate = 1/1 reaction product and its alkali metal salt or amine salt;

A part of (meth) acrylic acid copolymer as described in JP-A-59-53836 is reacted with allyl glycidyl ether and its alkali metal salt or amine salt; (meth) Vinyl acrylate / (meth) acrylic acid copolymer and its alkali metal salts or amine salts; allyl (meth) acrylate / sodium styrenesulfonate copolymer, vinyl (meth) acrylate / sodium styrenesulfonate copolymer, Allyl (meta)
Acrylate / acrylamide-1,1-dimethylethylene sulfonate sodium copolymer,

Vinyl (meth) acrylate / acrylamide-1,1-dimethylethylene sodium sulfonate copolymer, 2-allyloxyethyl methacrylate / methacrylic acid copolymer, 2-allyloxyethyl methacrylate / 2-methacryloxyethyl Examples thereof include hydrogen succinate copolymers.

The primer layer used in the present invention may be cured by heat such as curing by thermal polymerization or curing by thermal crosslinking, or by curing by photopolymerization, curing by photocrosslinking, curing by photodimerization, etc. It may be cured by any method such as a method of curing with a photosensitive resin composition or the like, or may be used in combination, but a method of curing with light is preferable, and a method of curing with photopolymerization is more preferable. Preferably.

Pigments and dyes can be added to the primer layer used in the present invention for the purpose of preventing halation and coloring. For example, as the pigment, insoluble azo pigment, azo lake pigment, condensed azo pigment, azo pigment such as metal complex salt azo pigment, copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, phthalocyanine pigment such as copper phthalocyanine lake, acidic dye lake, base Dyeing lakes such as organic dye lakes, anthracene pigments, thioindigo pigments, perinone pigments, perylene pigments, quinacridone pigments,

Fused polycyclic pigments such as dioxazine pigments, isoindolinone pigments, quinophthalone pigments, isoindoline pigments, fluorbin pigments and pyrocholine pigments, nitroso pigments, alizarin lakes, metal complex salt azomethine pigments, aniline black, alkali blue, Mica-like iron oxide, lead white, red lead, yellow lead, silver vermilion, ultramarine, navy blue, strontium chromate, titanium dioxide coated mica (pearl luster pigment), titanium yellow, titanium black, zinc chromate, iron black, molybdenum red, molybdenum white , Inorganic pigments such as litharge, lithobon, cobalt blue, titanium oxide, zinc oxide,

Examples include metal oxides such as aluminum oxide and fine powders of inorganic substances such as barium sulfate, calcium carbonate, magnesium carbonate, colloidal silica, silica gel and anhydrous silica. As the dye, azo disperse dyes, anthraquinone disperse dyes, quinophthalone disperse dyes, nitrodiphenylamine disperse dyes, styryl disperse dyes and other disperse dyes, conjugated cationic azo dyes, non-conjugated cationic azo dyes, methine cationic dyes, Cationic dyes such as anthraquinone-based cationic dyes,

Vinyl sulfone-based reactive dyes, triazine-based reactive dyes, pyrimidine-based reactive dyes, dichloroquinosaline-based reactive dyes, phosphonic acid-based reactive dyes, bromacrylamide-based reactive dyes, complex-type reactive dyes, bifunctional reactive dyes, etc. Examples include reactive dyes. When heat treatment is carried out at the time of producing the support or producing the primer layer on the support, a pigment / dye which is stable under the heat treatment conditions is selected.

Further, the pH value is set for the purpose of imparting print-out property.
It is also possible to add an indicator, a photoacid generator, and a leuco dye. Further, if necessary, an oil sensitizer, a surfactant,
It is also possible to add a stabilizer, a plasticizer, a thermal polymerization inhibitor, a photopolymerization initiator, a photosensitizer, a silane coupling agent, a titanium coupling and the like.

The coating solution obtained by dissolving in the solvent used in the present invention may contain either a positive photosensitive composition or a negative photosensitive composition.
As the positive photosensitive composition, a polymer compound containing an orthoquinonediazide group is mainly used. Here, the polymer compound containing an orthoquinonediazide group is a reaction between a compound containing an orthoquinonediazide group and an alkali-soluble resin. It is used to mean either or both of a product and a mixture of a compound containing an orthoquinonediazide group and an alkali-soluble resin.

Typical ones will be described below. Examples of the polymer compound containing an orthoquinone diazide group include ester compounds of o-naphthoquinone diazide sulfonic acid and a polycondensation resin of phenols and aldehydes or ketones.

Examples of the above-mentioned phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol, thymol, catechol, resorcin, hydroquinone and the like. Examples thereof include trihydric phenols such as dihydric phenol, pyrogallol, and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, furfural and the like. Preferred of these aldehydes are formaldehyde and benzaldehyde.

Further, examples of the above-mentioned ketone include acetone and methyl ethyl ketone. Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m-, o- mixed cresol / formaldehyde resin, resorcin / benzaldehyde resin, pyrogallol / acetone resin and the like.

The condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol of the o-naphthoquinonediazide compound (reaction rate with respect to one OH group) is 15 to 8
0% is preferable, and 20 to 45% is more preferable.
Further, as the o-quinonediazide compound used in the present invention, the compounds described in JP-A-58-43451 can also be used.

Of the above o-quinonediazide compounds, 1,2
-Benzoquinonediazide sulfonyl chloride or 1, 2
Most preferred is an o-quinonediazide ester compound obtained by reacting naphthoquinonediazidesulfonyl chloride with a pyrogallol-acetone condensation resin or 2,3,4-trihydroxybenzophenone.

As the o-quinonediazide compound used in the present invention, each of the above compounds may be used alone,
You may use combining 2 or more types of compounds. The polymer compound containing o-quinonediazide used in the present invention is
In consideration of coatability, those having a molecular weight of 1500 or more are preferable, and those having a molecular weight of 2000 or more are more preferable.

The above o-quinonediazide compound is preferably used as a mixture with an alkali-soluble resin. Examples of the alkali-soluble resin include novolac resins, vinyl polymers having a phenolic hydroxyl group, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841, and the like. Examples of the novolac resin include phenol / formaldehyde resin, cresol / formaldehyde resin, JP-A-55-5784.
Phenol / cresol / formaldehyde copolycondensation resin as described in JP-A-55-12.
Examples thereof include a copolycondensation resin of p-substituted phenol and phenol or cresol and formaldehyde as described in Japanese Patent No. 7553.

The vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having a phenolic hydroxyl group in its molecular structure, and is represented by the following formulas 1 to 5:
Polymers containing at least one structural unit of are preferred.

[0045]

[Formula 1]

[Formula 2]

[Formula 3]

[0046]

[Formula 4]

[Formula 5]

[In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R ₃ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ is a hydrogen atom, an alkyl group,
It represents an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an alkylene group which may have a substituent which connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B may have a substituent. It represents a good phenylene group or a naphthylene group which may have a substituent. ]

As the polymer used in the photosensitive composition of the present invention, a polymer having a copolymer type structure is preferable, and a monomer which can be used in combination with the structural unit represented by each of the above formulas 1 to 5 is used. Examples of the unit include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, for example, styrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene, such as acrylic acid and methacryl. Acrylic acids such as acids, for example, itaconic acid, maleic acid, unsaturated aliphatic dicarboxylic acids such as maleic anhydride, such as methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, acrylic Acid-2-chloroethyl,

Phenyl acrylate, α-chloromethyl acrylate, methyl methacrylate, ethyl methacrylate,
Esters of α-methylene aliphatic monocarboxylic acids such as ethyl ethacrylic acid, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, such as acrylanilide, p-chloroacrylamide, m-nitroacrylanilide, m -Anilides such as methoxyacrylanilide, for example vinyl acetate, vinyl propionate, vinyl benzoate,

Vinyl esters such as vinyl butyrate, eg, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, eg 1-methyl-1-
Methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene,
Ethylene derivatives such as 1-methyl-1-nitroethylene, such as N-vinylpyrrole, N-vinylcarbazole,
There are N-vinyl type monomers such as N-vinylindole, N-vinylpyrrolidene and N-vinylpyrrolidone. These vinyl-based monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved.

Of the above-mentioned monomers, aliphatic monocarboxylic acid esters and nitriles are preferable because they exhibit excellent performance for the purpose of the present invention. These alkali-soluble resins preferably have a molecular weight of 1500 or more, more preferably 2000 or more, in consideration of coatability.

In addition to the above-mentioned materials, these photosensitive compositions may optionally contain dyes such as dyes and pigments, dyes, sensitizers, plasticizers, surfactants, organic acids, acid anhydrides, and by exposure. A compound capable of generating an acid can be added. There are various negative photosensitive materials used in the present invention,
A typical one will be described as described below.

(1) Photosensitive Composition Containing Diazo Resin The diazo resin represented by the condensate of p-diazodiphenylamine and formaldehyde may be water-soluble or water-insoluble, but is preferably Japanese Patent Publication No. 47/47. -116
Water-insoluble and ordinary organic solvent-soluble substances such as those described in JP-A No. 7 and 57-43890 are used. A diazo resin represented by the following formula 6 is particularly preferable.

[0054]

[Formula 6]

[In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents a hydrogen atom, an alkyl group or a phenyl group. X represents a PF ₆ or BF _4, Y is -NH -, - shows S- or -O-. The diazo resin is preferably used as a mixture with a film-forming resin, particularly a lipophilic polymer compound having a hydroxyl group. As such a lipophilic polymer compound, in addition to those listed above, a monomer having an aliphatic hydroxyl group in its side chain, for example, 2-hydroxyethyl acrylate or 2-
Examples thereof include copolymers of hydroxyethyl methacrylate and other copolymerizable monomers. In addition to these, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, if necessary,
Natural resins and the like may be added.

As the binder used in combination with the diazonium salt, various polymer compounds can be used, but preferably a monomer having an aromatic hydroxyl group as described in JP-A-54-98613. , N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, or p-, for example.
Copolymers of hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate with other monomers,

Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as main repeating units as described in US Pat. No. 4,123,276, natural resins such as shellac and rosin, polyvinyl alcohol, US Patent No. 3,7
51,257 polyamide resin, US Pat. No. 3,660,097 linear polyurethane resin, polyvinyl alcohol phthalated resin, bisphenol A and epichlorohydrin condensed Contains celluloses such as epoxy resin, cellulose acetate, and cellulose acetate phthalate.

Examples of the alkali-soluble resin include novolac resins, vinyl polymers having phenolic hydroxyl groups, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. .. Examples of the novolak resin include phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde copolycondensation resin as described in JP-A-55-57841, and JP-A-55-127553. P-substituted phenol and phenol as described, or
Examples thereof include copolymer resins of cresol and formaldehyde.

In addition to the above-mentioned materials, these photosensitive compositions may further contain, if necessary, dyes such as dyes and pigments, sensitizers, plasticizers, surfactants, organic acids, acid anhydrides and exposures. A compound capable of generating an acid can be added. These binders are contained in the solid content of the photosensitive composition in an amount of 40 to 99% by weight, preferably 50 to 95% by weight. The diazo resin is contained in an amount of 1 to 60% by weight, preferably 3 to 30% by weight. These photosensitive compositions include other dyes,
Dyes such as pigments, oil sensitizers, plasticizers, surfactants and the like can be added.

(2) --CH.dbd.C on the main chain or side chain of the polymer.
Photosensitive Composition Containing Polymer Compound Having H—CO— Group As such a polymer compound, polyesters containing —CH═CH—CO— as a photosensitive group in the main chain or side chain of the polymer, Those containing a photosensitive polymer such as polyamides and polycarbonates as a main component (for example, described in US Pat. Nos. 3,030,208, 3,707,373 and 3,453,237). Such compounds); those based on (2-properidene) malonic acid compounds such as cinnamylidene malonic acid and photosensitive polyesters derived from bifunctional glycols as a main component (for example, US Pat. No. 2,956,878). No. and No. 3,17
A photosensitive polymer as described in 3,787);

Cinnamic acid esters of hydroxyl group-containing polymers such as polyvinyl alcohol, starch, cellulose and the like (eg, US Pat. No. 2,690,966,
Polymers such as those described in No. 2,752,372, No. 2,732,301 and the like can be mentioned. These photosensitive compositions may contain other sensitizers, stabilizers, plasticizers, pigments, dyes and the like.

(3) Photopolymerizable Composition Comprising Addition-Polymerizable Unsaturated Compound This composition preferably comprises (a) a monomer having at least two terminal vinyl groups, and (b) a photopolymerization initiator. And (c) a polymer compound as a binder.

As the vinyl monomer of this component (a),
Japanese Patent Publication Nos. 35-5093, 35-14719, 4
It is described in each publication of 4-28727. Acrylic acid or methacrylic acid ester of polyol, that is, diethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, or methylenebis (meth) acrylamide, Bis (meth) acrylamides such as ethylene bis (meth) acrylamide, or unsaturated monomers containing a urethane group,

For example, a diol mono (meth) acrylate such as di- (2'-methacryloxyethyl) -2,4-tolylenediurethane or di- (2-acryloxyethyl) trimethylenediurethane and a diisocyanate. Examples include reaction products. As the photopolymerization initiator of the component (b), the compound represented by the above formula 1 can be used, but other types can also be used.

For example, the above-mentioned J. Examples include carbonism compounds, organic sulfur compounds, persulfides, halogen compounds, and photoreducible dyes as described in Chapter 5 of "Light Sensitive Systems" by Kosar. More specifically, it is disclosed in British Patent No. 1,459,563.

The following may be used as the photopolymerization initiator. Benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy-
Benzoin derivatives such as α-phenylacetophenone, benzophenone, 2,4-diclobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, benzophenone such as 4,4'-bis (dieramino) benzophenone Derivative,

Thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone, anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone, acridone derivatives such as N-methylacridone and N-butylacridone, α and α -Diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, halogen compounds and the like.

Further, as the binder of the component (c),
Various known polymers can be used. Specific binder details are described in US Pat. No. 4,072,527.
No. In addition, the binder used when used in combination with the above-mentioned diazonium salt is used. These photopolymerizable compositions may contain a thermal polymerization inhibitor, a plasticizer, a dye, a pigment and the like.

(4) Photosensitive Composition Containing Azido Group As the photosensitive azide compound, an aromatic azido compound having an azido group bonded to an aromatic ring directly or through a carbonyl group or a sulfonyl group is preferably used. ..

For example, polyazidostyrene, polyvinyl-p-azidobenzoate, polyvinyl-p- as described in US Pat. No. 3,096,311.
Azidobenzal, a reaction product of an azidoarylsulfonyl chloride with an unsaturated hydrocarbon polymer described in JP-B-45-9613, and JP-B-43-2101.
No.7, No.44-229, No.44-22954, No.4
Examples thereof include polymers having a sulfonyl azide or a carbonyl azide as described in JP-A Nos. 5-24915.

An oil sensitizer added to the photosensitive composition,
Additives such as surfactants, sensitizers, stabilizers, thermal polymerization inhibitors, plasticizers, and dyes such as dyes and pigments are generally contained in the photosensitive coating liquid, although the addition amount varies depending on the type. 0.01 to 20% by weight, preferably 0.05 to 10% by weight, is suitable for the photosensitive composition.

The dyes preferably used in the present invention include basic dyes and oil-soluble dyes. In particular,
Victoria Pure Blue BOH, Victoria Blue BH, Methyl Violet, Eisen Malachite Green (above, Hodogaya Chemical Co., Ltd.), Patent
Basic dyes such as Pure Blue VX, Rhodamine B, Methylene Blue (above, Sumitomo Chemical Co., Ltd.), Sudan Blue II, Victoria Blue F4R
(Above, BASF) Oil Blue # 60
3, oil blue BOS, oil blue IIN
(Above, manufactured by Orient Chemical Industry) and the like oil-soluble dyes. In the present invention, of these photosensitive compositions, a photocrosslinking type (diazophotosensitive resin) resin is preferably used.

In the present invention, a silicone rubber layer is coated on the photosensitive layer. The silicone rubber used in the present invention is preferably a cotton-like or partially crosslinked polyorganosiloxane. The polyorganosiloxane has a molecular weight of usually 1,000 to several hundreds of thousands, and is appropriately crosslinked in the form of a liquid or wax or rice cake at room temperature. The polyorganosiloxane is classified into a condensation type and an addition type depending on the method of crosslinking.

In the condensation type, since crosslinking is carried out by a condensation reaction, water, alcohol, organic acid and the like are released by the reaction. As a particularly useful condensation type silicone rubber,
Examples thereof include a mixture of a linear polyorganosiloxane having a hydroxyl group or an acetoxy group at both ends or a part of the main chain and a silicone cross-linking agent, or a mixture of a hydroxyl group and a silicone cross-linking agent, both of which are added with a condensation catalyst. It is more advantageous in terms of crosslinking speed.

Particularly preferred are those obtained by condensation-crosslinking linear dimethylorganopolysiloxanes having hydroxyl groups at both ends. The main chain of the polyorganosiloxane has the following repeating units.

[0076]

[Formula 7]

In the formula, R ₁ and R ₂ are each an alkyl group which may have a substituent, an aryl group, an alkenyl group or a combination thereof, and a methyl group, a phenyl group, a vinyl group and a trifluoropropyl group are preferable. A methyl group is particularly preferable.

As the above silicone crosslinking agent, --OCO
CH ₃ , -ONR (R '), -ON = CR (R'),-
So-called deacetic acid type, deoxime type, dealcohol type, deamination having a functional group represented by OR, —NR (R ′) or —OH (wherein R and R ′ are alkyl groups). Examples include condensation type and crosslinking type condensation type silicone crosslinking agents.

Examples of such a cross-linking agent are tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diethylacetoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane. , Dimethyldimethoxysilane, vinyltrimethoxysilane, methyltris (acetoneoxime) silane, methyltri (N-methyl-N-acetylamino) silane, vinyltri (methylethylketoxime) silane, methyltri (methylethylketoxime) silane,
Or the oligomer etc. can be mentioned.

The amount of each of these crosslinking agents is preferably in the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of polyorganosiloxane. Examples of the condensation catalyst include organic carboxylic acids, titanic acid esters, acetylacetone metal complexes, chloroplatinic acid, and naphthenic acid.

The addition type means that an unsaturated group in the main body, for example, a vinyl group (—CH═CH ₂ ) is added with an aqueous group in the crosslinking agent to crosslink. Specific examples include vinyl group-containing organopolysiloxanes, hydrogenated organopolysiloxanes, and the like mixed with a platinum catalyst (for example, chloroplatinic acid).

The polyorganosiloxane has a repeating unit similar to the above condensation type in the main chain. For the silicone rubber layer used in the present invention, either or both of condensation type and addition type silicone rubbers can be used. It is also possible to use a condensation and addition type one having a hydroxyl group and an unsaturated group in one polyorganosiloxane.

In the present invention, an adhesive layer made of acrylic acid resin or the like may be provided between the photosensitive layer and the silicone rubber layer, and various reactive crosslinking agents, silane coupling agents, etc. may be provided in the adhesive layer. It can include, also 0.1mg / dm ² ~5mg / dm ² is preferred as the thickness of the adhesive layer.

As the substrate used in the present invention, any substrate can be used as long as it has flexibility such that it can be set in an ordinary lithographic printing machine and can withstand the load applied during printing. There is no particular limitation. Examples thereof include papers such as coated papers, metal plates such as aluminum plates (JIS standards H-16, H-18, etc.), and plastic films such as polyethylene terephthalate.

Particularly, an aluminum plate or an aluminum foil and another composite material is preferable, and an aluminum plate is particularly preferable from the viewpoint of printing durability. Further, from the viewpoint of storability, a substrate, particularly an aluminum plate, or an aluminum foil and another composite material may be surface-treated by a known method before use.

Examples of such surface treatment include a method of treating the surface of an aluminum plate with a silicate (US Pat. No. 2,714,066) and a method of treating with an organic acid salt (US Pat. No. 2,714, US Pat. No. 066), a method of treating with phosphonic acid and their derivatives (US Pat. No. 3,220,220,
832), a method of treating with potassium hexafluorozirconate (US Pat. No. 2,946,683), a method of anodizing and a method of treating with an aqueous solution of an alkali metal silicate after anodizing (US Pat. 181,461
No.) etc.

In order to obtain sufficient adhesiveness between the photosensitive layer and the support, such a support is provided with a primer layer, and the photosensitive layer is provided thereon. The thickness of each layer constituting the plate material of the present invention is as follows. That is, the support is 50 to 400
μm, preferably 100 to 300 μm, and the photosensitive layer is 0.05 to
The thickness is 10 μm, preferably 0.1 to 1.0 μm, and the silicone rubber layer is 0.5 to 100 μm, preferably 1 to 4 μm.
The primer layer is 0.1 to 30 μm, preferably 0.3 to 20
μm.

In the present invention, a protective layer may be optionally provided on the upper surface of the silicone rubber layer. As the material of this protective layer, it is preferable to use a water-soluble film such as polyvinyl alcohol or a biodegradable film such as polyhydroxyalkanoate or polyesteramide.
The plate material of the present invention that does not require dampening water is manufactured, for example, as follows.

An ordinary coater such as a reverse roll coater, an air knife coater, a Mayer bar coater, or a spin coater such as a whaler is used to coat and dry the composition solution for forming the primer layer on the support, followed by crosslinking and curing. Let Next, the composition solution for forming the photosensitive layer is applied and dried.

A silicone rubber solution is applied on the above-mentioned photosensitive layer in the same manner and heat-treated at a temperature of usually 100 to 120 ° C. for several minutes to be sufficiently cured to form a silicone rubber layer. If necessary, a protective film can be provided on the silicone rubber layer by using a laminator.

Next, a method for producing a printing plate that does not require dampening water using the plate material that does not require dampening water according to the present invention will be described. A positive film, which is an original, is brought into vacuum contact with the surface of a positive plate material and exposed. As the light source for this exposure, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, or the like, which generates abundant ultraviolet rays, is used.

Then, the positive film is peeled off, and development is performed using a developing solution. As the developing solution, a known developing solution for a plate material which does not require dampening water can be used, but an aqueous developing solution is preferably used. The water-based developer is a developer containing water as a main component and is described in, for example, JP-A-61-257559, and contains 30% by weight or more of water.
A developer containing 50% by weight to 98% by weight, an organic solvent and a surfactant can be preferably used, and more preferably an alkaline agent is contained.

As the organic solvent contained in the developer containing water as a main component, for example, aliphatic hydrocarbons (hexane, heptane, "Isopar E, H, G (commercial products of aliphatic hydrocarbons manufactured by Esso Chemical Co., Ltd. Name or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene etc.), halogenated hydrocarbons (triclene etc.), alcohols (methanol, ethanol, 1-butoxy-2-propanol, 3-methyl-) 3-methoxybutanol, β-anilinoethanol, benzyl alcohol, etc.),

Ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol dibutyl ether, propylene glycol, Dipropylene glycol butyl ether, tripropylene glycol methyl ether, polypropylene glycol methyl ether, etc.),

Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, 4
-Methyl-1,3-dioxolan-2-one etc.), esters (ethyl acetate, propyl acetate, hexyl acetate, methyl acetate, propyl acetate, diethyl succinate, dibutyl oxalate, diethyl maleate, benzyl benzoate, methyl cellosolve) Acetate, cellosolve acetate, carbitol acetate, etc.) and the like.

Anionic surfactants, nonionic surfactants, cationic surfactants and zwitterionic surfactants are used as the surfactants added to the developer used in the present invention. Further, a dye such as crystal violet or astrazonelet may be added to the developing solution to dye the image area simultaneously with the development.

Development can be carried out by, for example, rubbing with a developing pad containing the above-mentioned developing solution or pouring the developing solution onto the plate surface and then rubbing it with a developing brush. By the above development, a printing plate from which the photosensitive layer and silicone rubber in the unexposed area have been removed or a silicone rubber layer has been removed to expose the photosensitive layer and a printing plate in which the silicone rubber layer remains in the exposed area can be obtained.

[0098]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. [Synthesis of -1 of diazo resin] 14.5 g (50 mmol) of p-diazodiphenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under ice cooling. 1.35 g (45 mmol) in this reaction solution
Paraformaldehyde was gradually added so that the reaction temperature did not exceed 10 ° C.

The reaction mixture was added dropwise to 500 ml of ethanol under ice cooling, and the resulting precipitate was filtered.
After washing with ethanol, the precipitate was dissolved in 100 ml of pure water, and a cold concentrated aqueous solution containing 6.8 g of zinc chloride was added to the solution. The generated precipitate was filtered, washed with ethanol, and dissolved in 150 ml of pure water. To this solution was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and dried to obtain diazo resin-1.

[Production Example-1 of Polyester Resin] The following compounds (1) to (8) were placed in a reaction vessel equipped with a thermometer, a stirrer and a partial reflux type cooler, and 140 to 220
The transesterification reaction was carried out at 3 ° C for 3 hours. Then, after adding the compound (9) and reacting at 210 to 250 ° C. for 1 hour, the reaction system was depressurized to 1 to 5 mmHg over 60 minutes,
Further, the polycondensation reaction was carried out at 250 ° C. under a reduced pressure of 0.1 to 0.5 mmHg for 60 minutes.

[Polyester resin (A) material] (1) Dimethyl terephthalate 175 parts by weight (2) Dimethyl isophthalate 78 parts by weight (3) Ethylene glycol 161 parts by weight (4) Neopentyl glycol 145 parts by weight

(5) Dimethyl 5-sodium sulfoisophthalate 14.8 parts by weight (6) Zinc acetate 0.17 parts by weight (7) Sodium acetate 0.02 parts by weight (8) Antimony trioxide 0.16 parts by weight (9) Sebacic acid 131 parts by weight

The composition of the obtained polyester resin (A) was as follows from NMR analysis and the like. Terephthalic acid 22.5 mol% Isophthalic acid 10 mol% Sebacic acid 16.25 mol% 5-sodium sulfoisophthalic acid 1.25 mol% Ethylene glycol 25 mol% Neopentyl glycol 25 mol% Polyester resin (B) shown in Table 1 by the same production method ~ (F) was obtained.

[Production Example-2 of Polyester Resin] The following compounds (1) to (9) were placed in a reaction vessel equipped with a thermometer, a stirrer and a partial reflux type cooler, and 140 to 220 were used.
A transesterification reaction was performed at 3 ° C for 3 hours. Then, the compounds (10) and (11) were added and reacted at 210 to 250 ° C. for 1 hour, then the reaction system was depressurized to 1 to 5 mmHg over 60 minutes, and further at 250 ° C. to 0.1 to 0.5 mmHg. The polycondensation reaction was performed under reduced pressure for 60 minutes.

[Polyester resin (G) material] (1) dimethyl terephthalate 155 parts by weight (2) dimethyl isophthalate 155 parts by weight (3) ethylene glycol 150 parts by weight (4) neopentyl glycol 166 parts by weight (5) polyethylene glycol (Mw = 2000) 50 parts by weight

(6) Dimethyl 5-sodium sulfoisophthalate 17.5 parts by weight (7) Zinc acetate 0.15 parts by weight (8) Antimony trioxide 0.30 parts by weight (9) Sodium acetate 0.01 parts by weight (10) Adipic acid 49 parts by weight ( 11) 0.38 parts by weight of triphenylphosphite

The composition of the obtained polyester resin (G) was as follows from NMR analysis and the like. Terephthalic acid 20 mol% Isophthalic acid 20 mol% Adipic acid 8.5 mol% 5-Sodium sulfoisophthalic acid 1.5 mol% Ethylene glycol 22 mol% Neopentyl glycol 27 mol% Polyethylene glycol 1 mol%

Example 1 On a smooth degreased aluminum plate having a thickness of 0.3 mm, primer layer compositions (1) to (6) having the following compositions were mixed in a ball mill for about 70 hours, filtered, and degreased. After foaming, add the rest of the primer layer composition and apply.
50 minutes as a coating with a thickness of 5μ after drying in hot air at ℃ for 3 minutes
A front surface exposure of 0 mJ / cm ² was performed to cure and form a primer layer.

[Primer layer composition] (1) Polyester resin (A) 80 parts by weight (2) Diphenylmethane diisocyanate 20 parts by weight (3) Methyl ethyl ketone 160 parts by weight (4) Toluene 80 parts by weight (5) Methyl isobutyl ketone 30 parts by weight Department

(6) n-butyl alcohol 40 parts by weight (7) pentaerythritol triacrylate 50 parts by weight (8) 2,4-diethylthioxanthone 3 parts by weight (9) p-dimethylaminobenzoic acid ethyl ester 3 parts by weight ( 10) Yellow titanium oxide (Taipeque Yellow TY-100; manufactured by Ishihara Sangyo Co., Ltd.) 40 parts by weight

(11) Methyl ethyl ketone 400 parts by weight (12) Propylene glycol monomethyl ether 400 parts by weight Next, a photosensitive composition having the following composition was applied onto the cured primer layer and dried in hot air at 80 ° C. for 2 minutes. Then, a photosensitive layer having a thickness of 0.4 μm was formed.

[Photosensitive Composition] (1) 50 parts by weight of diazo resin-1 (2) 50 parts by weight of copolymer resin of 2-hydroxyethyl methacrylate / N- (4-hydroxyphenyl) methacrylamide with a molar ratio of 30/70 Part (3) Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd .; dye) 1 part by weight (4) Methyl Cellosolve 1500 parts by weight

Next, a silicone rubber layer composition having the following composition was coated on the photosensitive layer so that the dry weight was 1.8 g / m ^2, and dried in hot air at 90 ° C. for 5 minutes. It was a silicone rubber layer.

[Silicone rubber composition] (1) 100 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight of about 52,000) (2) 10 parts by weight of triacetoxymethylsilane (3) 0.8 parts by weight of dibutyltin laurate (4) Isobar E (manufactured by Exxon Chemical Co., Ltd .; solvent) 1000 parts by weight

Further, a thickness of 5 is formed on the silicone rubber layer.
A single-sided matt polypropylene film of μ was laminated to obtain a photosensitive lithographic printing plate which did not require fountain solution. After a positive film was brought into vacuum contact with the upper surface of the above plate material, it was exposed at 230 mJ / cm ² using a metal halide lamp as a light source.

Next, after immersing in the following developing solution at 27 ° C. for 1 minute, development is carried out by rubbing the surface of the plate material with a pad impregnated with the developing solution to develop the silicone rubber layer and the photosensitive layer in the unexposed area. Were removed, and a printing plate in which halftone dots were reproduced well was obtained. The image area of the printing plate was able to be dyed vividly by applying a dyeing solution having the following composition to a cloth, lightly rubbing the plate surface and then washing with water.

[Developer] (1) β-anilinoethanol 0.5 part by weight (2) Propylene glycol 1.0 part by weight (3) p-tert benzoic acid 1.0 part by weight (4) Potassium hydroxide 1 0.0 parts by weight

(5) Polyoxyethylene lauryl ether 0.1 parts by weight (6) Potassium sulfite 2.0 parts by weight (7) Potassium metasilicate 3.0 parts by weight (8) Water 91 parts by weight

[Staining Solution] (1) Solfit (Chrysoprene Chemical Co., Ltd .; Solvent) 20 parts by weight (2) Rheodor TW-O120 (Kao Co., Ltd .; Surfactant) 0.5 parts by weight ( 3) Benzyl alcohol 5.0 parts by weight (4) Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd .; dye 1.0 parts by weight (5) Water 100 parts by weight

As a result of printing using the obtained printing plate, it was possible to print about 30,000 sheets with almost no ink inking defect in the non-image area.

Examples 2 to 9 Printing plates were obtained and printing was carried out in the same manner as in Example 1 except that the types and blending amounts of the polyester resin and isocyanate compound of Example 1 were changed as shown in Table 2. The above results are shown in Table 3.

Example 10 Wetting was carried out in the same manner as in Example 1 except that the kinds and blending amounts of the polyester resin and the isocyanate compound of Example 1 were changed as shown in Table 2 and the composition of the photosensitive layer was changed as follows. Water-free photosensitive lithographic printing plate is obtained, and the image exposure amount is 220
When the developing solution was changed to mJ / cm 2 and the developing solution was changed as follows, the silicone rubber layer and the photosensitive layer in the unexposed area were removed, and a printing plate in which halftone dots were well reproduced was obtained. The above printing plate was also dyed and printed in the same manner as in Example 1.
The above results are summarized in Table 3.

[Photosensitive composition] (1) Photosensitive unsaturated polyester obtained by polycondensation of p-phenylenediacrylic acid ester and 1,4-dihydroxyethyloxycyclohexane in a molar ratio of 1: 1 10 parts by weight (2) 1-methyl-2-benzoylmethylene-β-naphthothiazoline 0.6 part by weight (3) N- (β-aminoethyl) aminomethylphenethyltrimethoxysilane 0.4 part by weight

(4) Dibutyltin dioctanoate 0.8 parts by weight (5) Sumitone cyanine blue VH514 (Phthalocyanine blue pigment manufactured by Sumitomo Chemical Co., Ltd.) 2 parts by weight (6) Methyl cellosolve acetate 80 parts by weight (7) Methyl glycol 40 parts by weight (8) Toluene 60 parts by weight

[Developer] (1) Isopar H (manufactured by Exxon Chemical Co., Ltd .; solvent) 90 parts by weight (2) Diethylene glycol monobutyl ether 7 parts by weight (3) Diethylene glycol monoethyl ether 3 parts by weight (4) Diethyl succinate 5 parts by weight

Example 11 A wet film was prepared in the same manner as in Example 10 except that the photosensitive layer composition of Example 10 was changed as follows to form a photosensitive layer and the laminated film was a single-sided matte film having a thickness of 3 μm. Water-free photosensitive lithographic printing plate is obtained, the image exposure amount is 250 mJ / cm
Then, the developing solution was changed as follows, and the development was carried out. As a result, the silicone rubber layer in the unexposed area was removed, and a printing plate in which halftone dots were well reproduced was obtained. The above printing plate was also dyed and printed in the same manner as in Example 1. The above results are summarized in Table 3.

[Photosensitive Layer Composition] (1) Copolymer with ethyl acrylate, methyl methacrylate and acrylic acid (molar ratio 70: 26: 4) 50 parts by weight (2) Addition of glycidyl methacrylate and xylylenediamine Reactant (molar ratio 4: 1) 46 parts by weight (3) Missiler's ketone 4 parts by weight (4) Methyl cellosolve 700 parts by weight

[Developer] (1) n-Heptane 99 parts by weight (2) Ethanol 1 part by weight

Example 12 1 part by weight of dibutyltin dilaurylate was added to the primer layer composition of Example 11 and the mixture was applied by a ball mill without mixing and reaction, and the drying conditions were 150 ° C. and 5 minutes, respectively. A printing plate was obtained and printed in the same manner as in 11. The above results are summarized in Table-3.

Example 13 The kind and blending amount of the polyester resin and isocyanate compound of Example 11 were changed as shown in Table 2, and the primer layer composition containing 1 part by weight of dibutyltin dilaurate was mixed and reacted by a ball mill. Without applying, a printing plate was obtained and printed in the same manner as in Example 11 except that the drying conditions were 150 ° C. and 5 minutes. The above results are summarized in Table 3.

Example 14 The kind and blending amount of the polyester resin and isocyanate compound of Example 11 were changed as shown in Table 2, and the primer layer composition containing 1 part by weight of dibutyltin dilaurate was mixed and reacted by a ball mill. Without applying, a printing plate was obtained in the same manner as in Example 11 except that the drying conditions were 150 ° C. and 5 minutes. The above results are summarized in Table 2.

Example 15 The primer layer composition of Example 1 was modified as follows,
A printing plate was obtained and printed in the same manner as in Example 1 except that coating was performed without mixing and reaction with a ball mill. The above results are summarized in Table 3.

[Primer layer composition] (1) Polyester polyurethane (Vylon UR-8300; manufactured by Toyobo Co., Ltd .; 30 wt% solution) 300 parts by weight (2) Pentaerythritol triacrylate 50 parts by weight (3) 2,4 -Diethylthioxanthone 3 parts by weight

(4) 2-Ethylanthraquinone 3 parts by weight (5) Ultrafine particle titanium oxide (Taipek TTO55; manufactured by Ishihara Sangyo Co., Ltd.) 40 parts by weight (6) Metal ethyl ketone 400 parts by weight (7) Propylene glycol monomethyl ether 400 parts by weight

Example 16 The primer layer composition of Example 1 was modified as follows,
A printing plate was obtained and printed in the same manner as in Example 1 except that coating was performed without mixing and reacting with a ball mill. The above results are summarized in Table 3.

[Primer layer composition] (1) Polyester polyurethane (Vylon UR-8700; manufactured by Toyobo Co., Ltd .; 30 wt% solution) 300 parts by weight (2) Pentaerythritol triacrylate 50 parts by weight (3) 2,4 -Diethylthioxanthone 3 parts by weight

(4) 2-Ethylanthraquinone 3 parts by weight (5) Ultrafine Titanium Oxide (Taipek TTO-55; manufactured by Ishihara Sangyo Co., Ltd.) 40 parts by weight (6) Metal ethyl ketone 400 parts by weight (7) Propylene glycol 400 parts by weight of monomethyl ether

Comparative Example 1 The primer layer composition of Example 1 was modified as follows,
After drying, a photosensitive lithographic printing plate unnecessary for fountain solution was obtained in the same manner as in Example 1 except that the heat treatment was carried out at 240 ° C. for 3 minutes without exposing the whole surface, and the same exposure, dyeing and printing were carried out. The above results are summarized in Table 3.

[Primer layer composition] (1) Epoxy / phenol / urea resin (KP Color 8482, manufactured by Kansai Paint Co., Ltd.) 100 parts by weight (2) Block type isocyanate (Takenate B-630, Takeda Pharmaceutical Co., Ltd.) 100 parts by weight (3) Titanium oxide 10 parts by weight (4) Ethyl cellosolve 1100 parts by weight (5) Dimethylformamide 200 parts by weight

Comparative Example 2 The primer layer composition of Example 1 was modified as follows,
A fountain solution-free photosensitive lithographic printing plate was obtained in the same manner as in Example 1 except that the total exposure amount was 500 mJ / cm.
It was developed, dyed and printed. Table 3 is a summary of the above results.
Shown in. [Primer layer composition] (1) 100 parts by weight of photosensitive unsaturated polyester obtained by polycondensation of p-phenylenediacrylic acid ester and 1,4-dihydroxyethyloxycyclohexane at a molar ratio of 1: 1.

(2) 1-Methyl-2-benzoylmethylene-β-naphthothiazoline 6 parts by weight (3) N- (β-aminoethyl) aminomethylphenethyl trimethoxysilane 5 parts by weight (4) FINEX-25 (oxidation Zinc) (Sakai Chemical Industry Co., Ltd .; white pigment) 80 parts by weight (5) Methyl cellosolve 600 parts by weight (6) Methyl cellosolve acetate 600 parts by weight (7) Toluene 600 parts by weight

[0142]

[Table 1]

[0143]

[Table 2]

[0144]

[Table 3]

[0145]

INDUSTRIAL APPLICABILITY The present invention provides a primer layer containing a resin obtained by reacting a polyester resin having a hydroxyl group with a diisocyanate compound, whereby sufficient dyeing properties can be obtained and scratch resistance of the silicone rubber layer,
It is possible to obtain a photosensitive lithographic printing plate which has improved printing durability and image reproducibility and is efficiently produced without the need for dampening water.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Nobumasa Inventor Nobumasa Satoshi No. 1 Sakuramachi, Hino City, Tokyo Konica Stock Company (72) Inventor Hiroshi Tomiyasu No. 1000 Kamoshidacho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd. Inside the laboratory (72) Inventor Akio Kasakura 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.

Claims (1)

[Claims] 1. A photosensitive lithographic printing plate which does not require fountain solution and has a primer layer, a photosensitive layer and a silicone rubber layer on a substrate in this order, wherein the primer layer is obtained by reacting a polyester resin having a hydroxyl group with a diisocyanate compound. A photosensitive lithographic printing plate that does not require a fountain solution, characterized by containing a resin.