JPH04212965A - Manufacture of planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain a planographic printing plate with excellent wear resisting plates (Druckwiderstandsfahigkeit) by developing a specific sensitive planographic printing plate with an alkali water solution having a pH of 8 or more below 12 and substantially not including an organic solvent after exposure of image. CONSTITUTION:A sensitizing planographic printing plate having a sensitive layer including a diazo compound, a lipophilic polymer compound and a nonionic surface active agent and/or a fluorine surface active agent is image-exposed. After that, an alkali water solution having a pH of 8 or more below 12 and substantially not including an organic solvent is used as developer.

Description

Description: FIELD OF INDUSTRIAL APPLICATION [0001] The present invention relates to a method for manufacturing a lithographic printing plate, and more particularly to a method for manufacturing a lithographic printing plate using a negative photosensitive lithographic printing plate. [0002] Planographic printing plates are generally produced by coating a photosensitive composition on a support such as an aluminum plate, irradiating it with active light such as ultraviolet rays through a negative image, and polymerizing the irradiated areas. Alternatively, it is cross-linked to make it insoluble in a developing solution, and the non-irradiated areas are eluted into the developing solution, and each area is divided into an image area that repels water and receives oil-based ink, and a non-image area that accepts water and repels oil-based ink. This can be obtained by making it an image part. In this case, a diazo resin such as a condensate of p-diazodiphenylamine and formaldehyde is used as the photosensitive composition, and an organic solvent or an alkaline aqueous solution containing an organic solvent has been widely used as the developer. . [0003] However, organic solvents generally have many disadvantages such as toxicity, odor, and fire danger, and waste liquids are subject to BOD regulations, as well as high costs. However, sufficient developability cannot be obtained simply by removing the organic solvent from the developer. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for producing a lithographic printing plate with excellent printing durability without using a developer containing an organic solvent. . [Means for Solving the Problems] As a result of intensive studies to solve these problems, the present inventors have developed a photosensitive lithographic printing method in which the photosensitive layer contains a specific component in addition to the diazo resin. The inventors have discovered that by using a printing plate and using an alkaline aqueous solution with a pH of 8 or more and less than 12 during development, a printing plate with good developability and printing characteristics can be obtained without using an organic solvent, and the present invention has been achieved. That is, the gist of the present invention is a photosensitive lithographic printing method having a photosensitive layer containing a diazo compound, a lipophilic polymer compound, and a nonionic surfactant and/or a fluorine surfactant on a support. The present invention relates to a method for producing a lithographic printing plate, which comprises developing the plate with an alkaline aqueous solution substantially free of organic solvents and having a pH of 8 or more and less than 12 after imagewise exposure. As the diazo compound contained in the photosensitive composition used in the present invention, conventionally known ones can be used as appropriate, but condensates of aromatic diazonium salts and, for example, active carbonyl-containing compounds, particularly formaldehyde, are representative examples. Among them, diazo resins soluble in organic solvents are preferred. Examples of the diazo resin include diazo resin inorganic salts which are organic solvent-soluble reaction products of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, and hexafluorophosphate or tetrafluoroborate. and sulfonic acids such as para-toluenesulfonic acid or its salts, phosphinic acids such as benzenephosphinic acid or its salts, hydroxyl group-containing compounds such as those described in U.S. Pat. No. 3,300,309, Examples include organic solvent-soluble diazo resin organic acid salts which are reaction products such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, or salts thereof. In the present invention, the diazo resin is contained in the photosensitive layer in an amount of 1 to 70% by weight, especially 3% by weight, including those mentioned below.
It is desirable that the content be 60% by weight. Other diazo resins that can be suitably used in the present invention include carboxyl groups, sulfonic acid groups,
It is a (co)condensate containing as a structural unit an aromatic compound having at least one organic group among a sulfinic acid group, a phosphorus oxygen acid group, and a hydroxyl group, and a diazonium compound, preferably an aromatic diazonium compound. [0011] The aromatic compound having at least one of the above-mentioned carboxyl group, sulfonic acid group, sulfinic acid group, phosphorus oxygen acid group, and hydroxyl group (hereinafter, these groups are referred to as "acid group") is The molecule contains an aromatic ring substituted with at least one acid group, and in this case, two or more of the acid groups may be substituted with the same aromatic ring. Preferred examples of the aromatic ring include phenyl and naphthyl groups. Further, the acid group may be bonded directly to the aromatic ring or may be bonded via a linking group. Examples of the linking group include a group having 1 or more carbon atoms and containing an ether bond. Specific examples of aromatic compounds containing at least one of the aforementioned carboxyl group, sulfonic acid group, sulfinic acid group, phosphorus oxygen acid group, and hydroxyl group include benzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, phthalic acid, terephthalic acid, diphenylacetic acid, phenoxyacetic acid, p-methoxyphenylacetic acid, p-methoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,4-dimethylbenzoic acid Acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, 4-(m-methoxyanilino)benzoic acid, 4-(p-methoxybenzoyl)
Benzoic acid, 4-(p-methylanilino)benzoic acid, 4-
Phenylsulfonylbenzoic acid, phenol, (o, m,
p)-Cresol, xylenol, resorcinol, 2-methylresorcinol, (o,m,p)-methoxyphenol, m-ethoxyphenol, catechol, phloroglucin, p-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone, p-hydroxybenzyl Alcohol, 4-chlororesorcin, biphenyl 4,4'
-diol, 1,2,4-benzenetriol, bisphenol A, 2,4-dihydroxybenzophenone, 2
, 3,4-trihydroxybenzophenone, p-hydroxyacetophenone, 4,4-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylamine,
4,4'-dihydroxydiphenylsulfide cumylphenol, (o,m,p)-chlorophenol, (o,
m,p)-bromophenol, salicylic acid, 4-methylsalicylic acid, 6-methylsalicylic acid, 4-ethylsalicylic acid, 6-propylsalicylic acid, 6-laurylsalicylic acid, 6-stearylsalicylic acid, 4,6-dimethylsalicylic acid, p-hydroxy Benzoic acid, 2-methyl-4-hydroxybenzoic acid, 6-methyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 2,
4-dihydroxybenzoic acid, 2,4-dihydroxy-6
-Methylbenzoic acid, 6-dihydroxybenzoic acid, 2
, 6-dihydroxy-4-benzoic acid, 4-chloro-2,
6-dihydroxybenzoic acid, 4-methoxy-2,6-dihydroxybenzoic acid, gallic acid, phloroglucincarboxylic acid, 2,4,5-trihydroxybenzoic acid, m-galloyl gallic acid, tannic acid, m-benzoyl gallic acid,
m-(p-tolyl) gallic acid, protocatechuoyl-
Gallic acid, 4,6-dihydroxyphthalic acid, (2,4-
dihydroxyphenyl)acetic acid, (2,6-dihydroxyphenyl)acetic acid, (3,4,5-trihydroxyphenyl)acetic acid, p-hydroxymethylbenzoic acid, p-hydroxyethylbenzoic acid, 4-(p-hydroxyphenyl)
Methylbenzoic acid, 4-(o-hydroxybenzoyl)benzoic acid, 4-(2,4-dihydroxybenzoyl)benzoic acid, 4-(p-hydroxyphenoxy)benzoic acid, 4
-(p-hydroxyanilino)benzoic acid, bis(3-carboxy-4-hydroxyphenyl)amine, 4-(p-
-hydroxyphenylsulfonyl)benzoic acid, 4-(p
-Hydroxyphenylthio)benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid, benzenesulfinic acid, p-toluenesulfinic acid, aniline-2-sulfonic acid, 4-amino-m-toluenesulfonic acid, 2,5-diamino Benzenesulfonic acid, 1-naphthalenesulfonic acid, 1-amino-2-naphthalenesulfonic acid, 5-amino-2-naphthalenesulfonic acid, 7-amino-1,3-naphthalenedisulfonic acid, 2-amino-1,5- naphthalenedisulfonic acid, 2-sulfobenzoic acid (these sulfonic acids or sulfinic acids may be free sulfonic acids or sulfinic acids, sodium, potassium, lithium, cesium, calcium, barium, magnesium,
metal salts such as aluminum and zinc, or unsubstituted or substituted ammonium salts), phenylphosphoric acid, phenylphosphorous acid, phenylphosphonic acid, phenylphosphonic acid, phenylphosphinic acid, phenylphosphinic acid, benzyl Phosphoric acid, benzyl phosphorous acid, benzyl phosphonic acid, benzyl phosphorous acid, benzyl phosphinic acid, benzyl phosphinic acid, 2-phenylethyl phosphoric acid, 2-phenylethyl phosphorous acid, 1-naphthyl phosphoric acid, 1-naphthyl phosphorous acid Phosphoric acid, 1-naphthylphosphonic acid,
1-naphthylphosphonic acid, 1-naphthylphosphinic acid, 1-naphthylphosphinic acid, 2-naphthylphosphonic acid,
etc. can be mentioned. Particularly preferred among these are 4-methoxybenzoic acid, 3-chlorobenzoic acid, 2,4-dimethoxybenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, phenoxyacetic acid, phenylacetic acid, and p-phenoxybenzoic acid. -hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, benzenesulfonic acid, p-toluenesulfinic acid, 1-naphthalenesulfonic acid, phenylphosphoric acid, and phenylphosphonic acid. [0014] The aromatic diazonium compounds constituting the constituent units of the above-mentioned co-condensed diazo resin include, for example, Japanese Patent Publication No. 49-4
Although diazonium salts such as those listed in 8001 can be used, diphenylamine-4-diazonium salts are particularly preferred. Diphenylamine-4-diazonium salts are derived from 4-amino-diphenylamines, and such 4-amino-diphenylamines include 4-amino-diphenylamine, 4-amino-3-methoxy-diphenylamine, , 4-amino-2-methoxy-diphenylamine, 4'-amino-2-methoxy-diphenylamine, 4'-amino-4-methoxy-diphenylamine, 4-amino-3-methyldiphenylamine, 4-amino-3-ethoxy- diphenylamine, 4-
Amino-3-β-hydroxyethoxydiphenylamine, 4-amino-diphenylamine-2-sulfonic acid, 4
Examples include -amino-diphenylamine-2-carboxylic acid, 4-amino-diphenylamine-2'-carboxylic acid, and particularly preferred are 3-methoxy-4-amino-diphenylamine and 4-amino-diphenylamine. [0016] The co-condensed diazo resin can be prepared by a known method, for example, by Photographic Science and Engineering (Photo. Sci., Eng.).
Volume 17, Page 33 (1973), U.S. Patent No. 2,06
According to the methods described in the specifications of No. 3,631 and No. 2,679,498, diazonium salts, aromatic compounds having acid groups, and aldehydes such as paraformaldehyde, acetaldehyde,
benzaldehyde or ketones such as acetone,
Obtained by polycondensation with acetophenone. The molar ratio of the aromatic compound having at least one acid group to the aromatic diazo compound is 1:0.1 to 0.
The ratio is 1:1, preferably 1:0.5 to 0.2:1, more preferably 1:1 to 0.2:1. In this case, the molar ratio of the sum of aromatic compounds and aromatic diazo compounds having at least one of the acid groups to aldehydes or ketones is usually 1:0.6 to 1.2, preferably 1:0.
A co-condensed diazo resin can be obtained by charging the mixture at a temperature of 7 to 1.5 and reacting at a low temperature for a short period of time, for example, about 3 hours. In addition, as a diazo resin other than the above-mentioned diazo resin co-condensed with an aromatic compound having an acid group, Japanese Patent Application No.
Diazo resins condensed with acid group-containing aldehydes or their acetal compounds described in Japanese Patent Application No. 130493, Japanese Patent Application No. 1-303705, and Japanese Patent Application No. 2-53101 can also be preferably used. Specific examples of aldehydes or acetals thereof containing acid groups include glyoxylic acid, malonaldehydic acid, succinaldehydic acid, 2-methylsuccinaldehydic acid, 2-methoxysuccinaldehydic acid, and 2-hydroxysuccinaldehydic acid. , 2-chlorosuccinic aldehydic acid, 2-aminosuccinic aldehydic acid, glutaraldehydic acid, 2-methylglutaraldehydic acid, 2-methoxyglutaraldehydic acid, 2-hydroxyglutaraldehydic acid, 2-chloroglutaraldehydic acid, adipine Aldehydic acid, pimelic aldehydic acid, suberaldehydic acid, azelaic aldehydic acid, sebacic aldehydic acid, 2-formylmethylsuccinic acid, 2-formylethylsuccinic acid, formylmethylmalonic acid, formylethylmalonic acid, N-(2-
formyl-2-hydroxyethyl)glycine, N-(2
-formyl-2-hydroxyvinyl)glycine, 4,6
-dioxo-hexanoic acid, 6-oxo-2,4-hexadienoic acid, 3-formylcyclohexanecarboxylic acid, 4
- formylphenylacetic acid, malealdehydic acid, fumaraldehydic acid, dibromomalaldehydic acid, glucuronic acid, galactronic acid, mannuronic acid, idronic acid, guluronic acid, phthalaldehydic acid, 3,4-dimethoxyphthalaldehydic acid, isophthalaldehydic acid, Terephthalaldehydic acid, 3-formyl-4-methoxybenzoic acid, 4
-Formylphthalic acid, 5-formylisophthalic acid, 4-
Formylmethylphthalic acid, 4-formylethyl phthalic acid, 4-formylethoxyphthalic acid, 5-formylethoxyisophthalic acid, 4-carboxymethylphthalic acid, 3-
Formyl-1-naphthoic acid, 6-formyl-1-naphthoic acid, p-hydroxybenzaldehyde, 2-oxo-
1-ethanesulfonic acid, 3-oxo-1-propanesulfonic acid, 4-oxo-1-butanesulfonic acid, 5-oxo-1-pentanesulfonic acid, 6-oxo-1-hexanesulfonic acid, 2-formylbenzene Sulfonic acid, 3-
Formylbenzenesulfonic acid, 4-formylbenzenesulfonic acid, 4-formylbenzenesulfinic acid, 4-formyl-1,3-benzenedisulfonic acid, 2-formyl-1,3-benzenedisulfonic acid, 2-formyl-1-
Naphthalenesulfonic acid, 4-formyl-1-naphthalenesulfonic acid, 4-formyl-1-naphthalenesulfinic acid, 5-formyl-2-naphthalenesulfonic acid, 2-oxo-1-ethyl phosphoric acid, 2-oxo-1-ethyl Phosphous acid, 2-oxo-1-ethylphosphonic acid, 2-oxo-1-ethylphosphonic acid, 2-oxo-1-ethylphosphinic acid, 2-oxo-1-ethylphosphinic acid,
Examples include 3-oxo-1-propyl phosphoric acid, 3-oxo-1-propyl phosphorous acid, 3-oxo-1-propylphosphonic acid, or acetals thereof. The method for synthesizing the diazo resin condensed with the above-mentioned aldehyde having an acid group or its acetal compound is as follows:
For example, a diazo monomer having a 4-diazodiphenylamine skeleton, a 4-diazodiphenyl ether skeleton, or a 4-diazodiphenyl sulfide skeleton and one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, and a phosphorus oxygen acid group. and an aldehyde or an acetal thereof in a molar ratio of preferably 1:10 to 1.
:0.05, more preferably 1:2 to 1:0.2, in an acidic medium. When carrying out the condensation reaction, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, iso-butyraldehyde, benzaldehyde,
Active carbonyl compounds such as acetone, methyl ethyl ketone or acetophenone or their acetals can be used in combination as condensing agents. The active carbonyl compound is most preferably formaldehyde;
The charging ratio is preferably 0 to 5, more preferably 0.1 to 1 in molar ratio to the diazo monomer. In addition, when using an aldehyde having one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, and a phosphorus oxygen acid group together with an active carbonyl compound that does not have one, first, the diazo monomer and the above-mentioned aldehyde are used together. condensation with an aldehyde having an alkali-soluble group in an acidic medium,
If a post-condensation is then carried out using a more reactive active carbonyl compound such as formaldehyde or an acetal thereof, a diazo resin with a higher molecular weight can be obtained. [0019] In place of the above-mentioned active carbonyl compounds or their acetals, Japanese Patent Publication No. 49-45322
It is also possible to use methylol derivatives such as those described in Japanese Patent Application Laid-open No. 1879-1988 and 49-45323, or olefinically unsaturated compounds such as those described in JP-A-58-187925. The counter anion of the diazo resin used in the present invention includes an anion that stably forms a salt with the diazo resin and makes the resin soluble in an organic solvent. These include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and sulfonic acids; typical examples include methanesulfonic acid, chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid. , toluenesulfonic acid, naphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, mesitylenesulfonic acid, and anthraquinonesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroxysulfonic acid, 4-acetylbenzenesulfonic acid, dimethyl- 5
- Aliphatic and aromatic sulfonic acids such as sulfoisophthalate, 2,2',4,4'-tetrahydroxybenzophenone, 1,2,3-trihydroxybenzophenone,
Aromatic compounds containing hydroxyl groups such as 2,2',4-trihydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, ClO4, IO
Examples include perhalogen acids such as No. 4, but are not limited thereto. Among these, particularly preferred are:
Dibutylnaphthalene sulfonic acid, hexafluorophosphoric acid, 2-hydroxy-4-methoxybenzophenone-5-
It is sulfonic acid. The above-mentioned co-condensed diazo resin can have an arbitrary molecular weight by varying the molar ratio of each monomer and the condensation conditions, but it can be effectively used for the purpose of the present invention. For this purpose, those having a molecular weight of about 400 to 10,000 can be used, but preferably,
Approximately 800 to 5,000 is suitable. The above-mentioned diazo compound is preferably used together with a water-insoluble, alkali-soluble (or swellable) lipophilic polymer compound as a binder. [0023] As this lipophilic polymer compound, the following (
Examples include copolymers having the monomers shown in 1) to (15) as structural units and usually having a molecular weight of 20,000 to 200,000. (1) Acrylamides, methacrylamides, acrylic esters, methacrylic esters and hydroxystyrenes having an aromatic hydroxyl group, such as N-(4
-hydroxyphenyl)acrylamide or N-(4-
hydroxyphenyl) methacrylamide, o-, m-,
p-hydroxystyrene, o-, m-, p-hydroxyphenyl-acrylate or methacrylate, (2)
Acrylic esters and methacrylic esters having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (3) α,β-unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride, etc. acid, (4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
(Substituted) alkyl acrylates such as hexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate,
(Substituted) alkyl methacrylates such as 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexyl Acrylamides or methacrylamides such as methacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, (7) Ethyl vinyl ether, 2-chloro Vinyl ethers such as ethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (8) vinyl acetate, vinyl chloroacetate,
Vinyl esters such as vinyl butyrate and vinyl benzoate; (9) Styrenes such as styrene, α-methylstyrene, and chloromethylstyrene; (10) Methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, etc. vinyl ketones, (11) olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, etc., (12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc., (13) maleimide. , N-acryloyl acrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N-(p-chlorobenzoyl)methacrylamide, etc., (14) N-(o-aminosulfonylphenyl)methacrylamide, N -(m-aminosulfonylphenyl)methacrylamide, N-(p-amino)sulfonylphenylmethacrylamide, N-(1-(3-aminosulfonyl)naphthyl)methacrylamide, N-(2-aminosulfonylethyl)methacrylamide and acrylamides having the same substituents as above, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate,
-aminosulfonylphenyl methacrylate, 1-(3
-aminosulfonylnaphthyl) methacrylate, and unsaturated sulfonamides such as acrylic esters having the same substituents as above, (
15) N-(2-(methacryloyloxy)-ethyl)
-Unsaturated monomers having crosslinkable groups in their side chains, such as 2,3-dimethylmaleimide and vinyl cinnamate. Furthermore, a monomer that can be copolymerized with the above monomer may be copolymerized. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with glycidyl methacrylate, glycidyl acrylate, and the like. More specifically, a copolymer having a hydroxyl group containing the monomers listed in (1) and (2) above is preferred, and a copolymer having an aromatic hydroxyl group is more preferred. [0027] The above copolymer contains α, β- listed in (3).
It is particularly preferred that the copolymer contains an unsaturated carboxylic acid, and the preferred acid value of the copolymer is 10-100. The preferred molecular weight of the lipophilic polymer compound is 40,000 to 150,000. The above lipophilic polymer compound may be used in combination with polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, or natural resin, if necessary. [0030] The above-mentioned lipophilic polymer compound is usually 40 to 99% by weight, preferably 50 to 99% by weight in the solid content of the photosensitive composition.
Contains 95% by weight. Particularly preferred as the lipophilic polymer compound as a binder is a polymer having methyl acrylate as a structural unit. In this case, more preferred are the following copolymers. That is, in the molecular structure, (a) 1 to 50 mol% of a structural unit having an alcoholic hydroxyl group and/or a structural unit having a phenolic hydroxyl group, (b) the following general formula I, -CH2 -CR1 ( CN) -

...5 to 40 mol% of the structural unit represented by I (in the formula, R1 represents a hydrogen atom or an alkyl group)
, (c) 5 units formed from methyl acrylate
~40 mol%, (d) General formula II below, -CH2-CR2(COOR3
)−
...II (in the formula, R1 represents a hydrogen atom, a methyl group, or an ethyl group, and R3 represents a carbon atom number of 2 to 12
represents an alkyl group or an alkyl-substituted aryl group. )
It is a copolymer containing 25 to 60 mol% of a structural unit represented by (e) and 2 to 30 mol% of a structural unit having a carboxyl group, and having a weight average molecular weight of 50,000 to 200,000. Specific examples of the monomer forming the structural unit having an alcoholic hydroxyl group include those described in Japanese Patent Publication No. 52-7
(Meth)acrylic acid esters (such as the compounds shown in the following general formula III as described in Publication No. 364)
Hereinafter, acrylic and methacrylic compounds will be collectively referred to as (meth)acrylic, etc. ) and acrylamides. CH2=CR4
[COO-(CH2CHR5-O)n-H]
...III In the formula, R4 represents a hydrogen atom or a methyl group, R5 represents a hydrogen atom, a methyl group, an ethyl group, or a chloromethyl group, and n represents an integer of 1 to 10. Examples of (meth)acrylic esters include 2-hydroxyethyl (meth)acrylate, 2-
Hydroxypropyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, etc., and examples of acrylamides include N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, etc. Preferably 2-hydroxyethyl (
meth)acrylate. Further, examples of monomers forming structural units having a phenolic hydroxyl group include N-(4-hydroxyphenyl)-(meth)acrylamide, N-(2-hydroxyphenyl)-(meth)acrylamide,
-Hydroxyphenyl)-(meth)acrylamide, N
Monomers of (meth)acrylamides such as -(4-hydroxynaphthyl)-(meth)acrylamide: o-, m
- or p-hydroxyphenyl (meth)acrylate monomers: o-, m- or p-hydroxystyrene monomers and the like. Preferably o-, m- or p-hydroxyphenyl (meth)acrylate monomers, N-
(4-hydroxyphenyl)-(meth)acrylamide monomer, more preferably N-(4-hydroxyphenyl)-(meth)acrylamide monomer. The structural unit having an alcoholic hydroxyl group and/or the structural unit having a phenolic hydroxyl group is preferably selected from the range of 1 to 50 mol%, more preferably 5 to 30 mol%, in the polymer compound. It will be done. Monomers having a cyano group in the side chain and forming the structural unit represented by the general formula I include acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, and 2-cyanoethyl. Examples include acrylate, o-, m-, p-cyanostyrene, and the like. Preferred are acrylonitrile and methacrylonitrile. The proportion of the structural unit having a cyano group in the side chain contained in the molecule of the polymer compound is selected from the range of 5 to 40 mol%, preferably 15 to 35 mol%. The unit formed from methyl acrylate accounts for 5 to 40 mol%, preferably 10% by mole in the polymer compound.
-30 mol%. Examples of monomers having a carboxy ester group in the side chain forming the structural unit represented by the general formula II include ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, and octyl acrylate. Examples include acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, and the like. The unit formed from the monomer is 25 to 60 mol% in the polymer compound,
Preferably, it is selected from the range of 35 to 60 mol%. [0040] Examples of the monomer forming the structural unit having a carboxyl group include methacrylic acid, acrylic acid, maleic anhydride, maleic acid, and the like. The monomer is selected from a range of 2 to 30 mol%, preferably 5 to 15 mol% in the polymer compound. [0041] The above structural units are not limited to units formed from the monomers listed as specific examples. The lipophilic polymer compound as a binder in the photosensitive composition is prepared using a generally known radical polymerization method or the like using an initiator such as azobisisobutyronitrile or benzoyl peroxide (0.1-4. 0 mol %) by a solution polymerization method. In the present invention, various known nonionic surfactants can be used as the nonionic surfactant contained in the photosensitive layer of the photosensitive lithographic printing plate together with the diazo compound and the lipophilic polymer compound. Examples include the following: ##STR1## ##STR2## Specific examples of the above-mentioned compounds include the following. That is, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether,
Polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate ,
Polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitate tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene These include glycol distearate, polyoxyethylene nonylphenyl ether formaldehyde condensate, oxyethylene oxypropylene block copolymer, tetraethylene glycol, polyethylene glycol, and the like. The proportion of the nonionic surfactant in the photosensitive composition is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight based on the total composition. To be elected. Further, in the present invention, the above-mentioned nonionic surfactants may be used alone or in combination of two or more. Further, the fluorine-based surfactants used in the present invention are those in which the hydrogen atoms bonded to the carbon atoms of the hydrophobic group of the surfactant are partially or completely replaced with fluorine atoms, and the following anion type, cation type,
Any of nonionic, amphoteric and polymeric surfactants can be used, but nonionic fluorosurfactants are preferred. 1) Anionic fluorosurfactant Hydrophilic groups include -COOM, -OSO3M, -SO3M, -
Contains OPO(OH)2, etc., such as RfCO
OM, RfSO2N(R1)CH2COOM, RfB
NR1 C2H4OSO3M, RfSO3M, RfCH
2OC m H2m SO3M, MO3S-HC(CO
OCH2Rf)-CH2 COOCH2Rf', RfB
Examples include N(R1)C m H2m OPO(OH)2. (In the formula, Rf and Rf' each represent a fluorinated carbon group (having 2 to 20 carbon atoms) in which some or all of the hydrogen atoms of an alkyl group are substituted with fluorine atoms, and B is C
O or SO2, R1 represents a hydrogen atom or a lower alkyl group, and M represents a hydrogen atom, an alkali metal or an alkaline earth metal. ) 2) Cationic fluorosurfactant [Chemical formula 3
3) Amphoteric fluorosurfactant such as R
fBNH(C2H4)H+ (R1)2Cm H2m
COO − RfBNHCm H2mN + (R1)
3Cl - RfB -N (C m H2m COO
− )(C n H2n N + )(R1)2RfB
NHCm H2m N + (R1)2Cn H2n
O − SO2OC n H2n+1 (wherein, Rf,
B and R1 have the same meanings as Rf, B and R1 in the anionic surfactant, respectively. )0054]4)
-OH as a nonionic fluorosurfactant hydrophilic group,
-SH, -O-, etc., such as RfOH
, RfSH, Rf-A-(C2H4O)mR3, and the like. (wherein A is -(CH2)l-S
O2NR4-,-(CH2)l-O-,-
(CH2) l -CONR5 -, -SO3 -
, -CO2 -, and -SO2N(R6)CH2CO
m is an integer of 0 to 20, l is an integer of 0 to 5, and R4, R5 and R6 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or -(CH2CH2O) x R7, and R4, R5 and R6 may each be the same or different. x represents an integer of 1 to 20, and R7 represents an alkyl group having 1 to 6 carbon atoms. )0056]5)
Polymer-type fluorine-based surfactant such as (CH2CH(
Examples include polymer compounds containing the structural unit COOCH2Rf)). Preferred specific examples of the nonionic fluorosurfactant are illustrated below. [Exemplary compounds] (1) CF3(CF2)7.(CH2CH2O)1
0H(2) CF3(CF2)7SO2N(C2H5
)(CH2CH2O)14H(3) CF3(CF2
)7SO2N(C2H5)CH2COO(CH2CH2
O)10H(4) CF3(CF2)7・(CF2)
3・CON(CH3)(CH2CH2O)10H(5)
CF3(CF2)7SO2N(C2H5)C2H4
(OC3H6)5OH The amount of the fluorine-based surfactant used in the present invention in the photosensitive composition is 0.
05 to 10% by weight is preferable, more preferably 0.1 to 10% by weight.
It is 5% by weight. Further, in the present invention, the above-mentioned fluorosurfactants may be used alone or in combination of two or more. Furthermore, in the present invention, both the above-mentioned nonionic surfactant and fluorine-based surfactant may be used, or only one of them may be used. When a nonionic surfactant and a fluorine surfactant are used together, the total amount of both surfactants in the photosensitive composition is 0.05 to 10.
It is preferably 0.1 to 5% by weight, more preferably 0.1 to 5% by weight. Further, there is no particular restriction on the ratio of both surfactants. A dye may further be used in the photosensitive layer of the photosensitive lithographic printing plate of the present invention. The dye is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development. [0064] As the dye, one that changes color tone by reacting with free radicals or acids can be preferably used. Here, "change in tone" includes both a change from colorless to a colored tone and a change from a colored to colorless or a different colored tone. Preferred dyes are those that change color tone by forming salts with acids. For example, Victoria Pure Blue BOH [
Hodogaya Chemical Co., Ltd.], Oil Blue #603 [Orient Chemical Co., Ltd.], Patent Pure Blue [Sumitomo Mikuni Chemical Co., Ltd.], Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Basic Fuchsin , malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenyl acetanilide, triphenylmethane type, diphenylmethane type, oxazine type, xanthene. Examples of color changing agents that change color from colored to colorless or to a different colored tone include dyes based on color, iminonaphthoquinone, azomethine, or anthraquinone. On the other hand, examples of color changing agents that change from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p '-bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p',
p″-tris-dimethylaminotriphenylmethane, p
, p'-bis-dimethylaminodiphenylmethylimine, p,p',p''-triamino-o-methyltriphenylmethane, p,p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, p,p Examples include primary or secondary arylamine dyes represented by ',p''-triaminotriphenylmethane. Particularly preferred are triphenylmethane and diphenylmethane pigments, more preferably triphenylmethane pigments, and especially Victoria Pure Blue BOH. The content of the above dye in the photosensitive composition is generally preferably about 0.5 to about 10% by weight, more preferably about 1 to 5% by weight. Various additives can be further added to the photosensitive layer of the photosensitive lithographic printing plate of the present invention. For example, alkyl ethers (e.g. ethyl cellulose, methyl cellulose) are used as coating properties improvers, butylphthalyl is used as a plasticizer to impart flexibility and abrasion resistance to the coating film.
Polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate,
Examples include dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers or polymers of acrylic acid or methacrylic acid, and are sensitizing agents for improving the oil sensitivity of image areas. For example, JP-A-55-527
Examples of stabilizers include alcohol-based half esters of styrene-maleic anhydride copolymers described in the above publication, and examples of stabilizers include polyacrylic acid, tartaric acid, phosphoric acid, phosphorous acid, and organic acids (acrylic acid, methacrylic acid). , citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5
-sulfonic acid, etc.). The amount of these additives added varies depending on the purpose of use, but is generally 0.01 to 30% by weight based on the total solid content. A photosensitive lithographic printing plate can be obtained by applying the above photosensitive composition onto the surface of a support and drying it. Examples of the coating solvent include cellosolves such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate, dimethyl formamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents may be used alone or in combination of two or more. As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used. The coating amount is 0.2 to 10 g/solid content.
m2 is preferred. It is preferable to apply a matte layer consisting of a fine pattern of discontinuous protrusions on top of the applied photosensitive composition in order to improve the vacuum adhesion to the film during contact exposure. [0074] As a method for applying the matte layer, Japanese Patent Application Laid-Open No. 1986-
12974, or the method of spraying and drying polymer-containing water as described in JP-A-58-182636, any method may be used. It is desirable that the matte layer itself be soluble or removable with an aqueous alkaline developer that does not substantially contain an organic solvent. It is preferable to use an aluminum plate as the support for the photosensitive lithographic printing plate of the present invention. Graining is carried out by electrolytic roughening in nitric acid or an electrolyte solution containing nitric acid as the main component, or hydrochloric acid or an electrolyte solution containing hydrochloric acid as the main component, preferably further anodized and sealed if necessary. Use one that has undergone surface treatment such as hole treatment. [0076] Electrolytic surface roughening is carried out at 0.1 to 0.5 mol/
An aluminum plate is immersed in a bath containing nitric acid or hydrochloric acid, preferably 0.2 to 0.4 mol/l.
Preferably, electrolytic etching is performed at a temperature of 0 to 50°C, preferably 25 to 40°C, and a current density of 20 to 200 A/dm2 for about 10 seconds to 3 minutes. After this graining treatment, if necessary, a desmut treatment is performed with an aqueous alkali or acid solution to neutralize the material, and the material is washed with water. The anodic oxidation treatment is carried out by electrolyzing using an aluminum plate as an anode using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolyte. The amount of anodic oxide film formed is 1~
50 mg/dm2 is appropriate, preferably 10-4
It is 0 mg/dm2. Here, the amount of anodized film can be determined by, for example, immersing an aluminum solution in a phosphochromic acid solution (produced by dissolving 35 ml of an 85% phosphoric acid aqueous solution and 20 g of chromium (VI) oxide in 1 liter of water). It can be determined by dissolving and measuring the change in weight of the plate before and after the film is dissolved. Pore sealing treatments include boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, and the like. In addition, the aluminum support can also be subjected to subbing treatment with an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconate. The photosensitive lithographic printing plate thus obtained can be used by a known method. Typically, a negative film is brought into close contact with a photosensitive printing plate, exposed to light using an ultra-high pressure mercury lamp, metal halide lamp, etc., and developed using various known developers to obtain a printing plate. The lithographic printing plate produced in this way can be used in sheet-fed and off-wheel printing presses. That is, by exposing a transparent original image having a line image, halftone image, etc. to light and then developing it with an aqueous developer, a negative relief image can be obtained with respect to the original image. Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, and the like. The developer used in the development of the photosensitive lithographic printing plate in the present invention is an alkaline aqueous solution containing substantially no organic solvent. [0082] "Substantially not containing" organic solvents means
This means that the organic solvent should not be contained in excess from the above-mentioned hygiene and safety viewpoints, and generally there is no problem as long as it is 1% by weight or less in the developer composition. In the present invention, the preferred organic solvent content is 0.5% by weight or less, and more preferably no organic solvent is contained at all. Preferred alkaline agents used in the developer used in the present invention include calcium silicate, lithium silicate, sodium silicate, tribasic sodium phosphate, dibasic sodium phosphate, tribasic potassium phosphate, and dibasic phosphate. Examples include acid potassium, sodium carbonate, potassium carbonate, lithium carbonate, monoethanolamine, diethanolamine, triethanolamine, and the like. [0084] pH of the developer used in the present invention (25°C
) is 8 or more and less than 12, preferably 10.0 to 11
．． It is 8. Furthermore, water-soluble sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite can be added to the developer. The preferred content of sulfite in the developer composition is 0.05 to 4% by weight, more preferably 0.1 to 1% by weight. [0085] Also, in the developer, JP-A-50-513
Anionic surfactants and amphoteric surfactants, such as those described in Japanese Patent Application Laid-Open No. 59-75255
JP-A-55-95946 and JP-A-56-142528 by containing at least one type of nonionic surfactant as described in JP-A-55-95946 and JP-A-56-142528. By containing a polymer electrolyte as described above, the wettability to the photosensitive composition can be improved and the gradation can be further improved. The amount of such surfactant added is not particularly limited, but is preferably 0.003 to 3% by weight, particularly 0.006 to 3% by weight.
A concentration of 1% by weight is preferred. Furthermore, the developer used in the present invention can contain an antifoaming agent. Suitable antifoaming agents include organosilane compounds. [0087] Various conventionally known methods can be used to develop the photosensitive lithographic printing plate imagewise exposed with the developer as described above. Specifically, there are methods in which an image-exposed photosensitive lithographic printing plate (PS plate) is immersed in a developer, a method in which a developer is ejected from a number of nozzles onto the photosensitive layer of the PS plate, and a method in which the developer is wetted with the photosensitive layer of the PS plate. Examples include a method of wiping the photosensitive layer of the PS plate with a sponge, and a method of applying a developer to the surface of the photosensitive layer of the PS plate with a roller. Further, after applying the developer to the photosensitive layer of the PS plate in this manner, the surface of the photosensitive layer can be lightly rubbed with a brush or the like. The developing conditions can be appropriately selected depending on the developing method. For example, in the development method by immersion, a method of immersing the material in a developer at about 10 to 40° C. for about 10 to 80 seconds is selected. The developer of the present invention can also be used as a developer for positive planographic printing plates. In this case, the positive lithographic printing plate generally has a photosensitive layer containing a sulfonic acid ester substituted product at the 4th and/or 5th position of o-naphthoquinone diazide and a binder soluble in alkaline water with a pH of 8 or more and less than 12. is used. A preferred binder is phenol-formalin resin. It is also a feature of the present invention that negative-type and positive-type lithographic printing plates can be developed with the same developer. [Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples unless the gist of the invention is exceeded. (Manufacture of aluminum plate-1) Thickness 0.2
A 4 mm aluminum plate was electrolytically polished in a 17 g/l hydrochloric acid bath at a bath temperature of 25° C. and 50 A/dm 2 for 25 seconds to obtain a grained plate with a maximum roughness of 4 μm. 4.
3.2 A/d in a 0 wt% sulfuric acid bath at a bath temperature of 35°C
Anodizing was performed at m2 for 20 seconds. Next, the anodized aluminum plate was immersed in a 1% by weight aqueous sodium metasilicate solution at 90° C. for 30 seconds to seal the holes. After that, the aluminum plate-1 was washed with water and dried.
And so. (Synthesis of Diazo Compound-1) 14.5 g (50 mmol) of p-diazodiphenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under ice cooling. 1 in this reaction solution
．． 5 g (50 mmol) of paraformaldehyde was slowly added dropwise. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C. Thereafter, stirring was continued under ice cooling for 2 hours. This reaction mixture was added dropwise to 500 ml of ethanol under ice cooling, and the resulting precipitate was filtered. After washing with ethanol, this 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 this solution. The resulting precipitate was filtered, washed with ethanol, and dissolved in 150 ml of pure water. 8g in this liquid
A cold concentrated aqueous solution of ammonium hexafluorophosphate was added. The resulting precipitate was collected by filtration and washed with water, and then
The mixture was dried at ℃ for 1 day and night to obtain diazo compound-1. When the molecular weight of this diazo compound-1 was measured by GPC (gel permeation chromatography), it was found that it contained about 50 mol% of pentamers or more. (Synthesis of Diazo Compound-2) 3.5 g (0.025 mol) of p-hydroxybenzoic acid and 2.20 g (0.025 mol) of 4-diazodiphenylamine sulfate were mixed with 90 g of concentrated sulfuric acid under ice cooling. dissolved in After this reaction, 2.7 g of paraformaldehyde (0.09 mol) was slowly added. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C. Thereafter, stirring was continued under ice cooling for 2 hours. This reaction mixture was poured into 1 liter of ethanol under ice cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 200 ml of pure water, and to this solution was added a cold concentrated aqueous solution in which 10.5 g of zinc chloride was dissolved. The resulting precipitate was filtered, washed with ethanol, and washed with 3
It was dissolved in 00ml of pure water. To this liquid was added a cold concentrated aqueous solution in which 13.7 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was filtered and washed with water, and then heated at 30°C.
After drying for one day and night, diazo compound-2 was obtained. [0095] The molecular weight of this diazo compound-2 was measured by GPC, and the weight average molecular weight was about 2,000. (Synthesis of lipophilic polymer compound-1) N-(
4-hydroxyphenyl) methacrylamide 10.0g
, acrylonitrile 25g, ethyl acrylate 60g
, methacrylic acid 5g and azobisisobutyronitrile 2
．． 0g to 120ml of acetone-methanol 1:1 mixed solution
After dissolving the solution in 1 ml of nitrogen and purging with nitrogen, the mixture was heated at 60°C for 8 hours. After the reaction was completed, the reaction solution was stirred and poured into 5 liters of water, and the resulting white precipitate was filtered and dried to obtain polymer compound-1.
90g of was obtained. When the molecular weight of this lipophilic polymer compound-1 was measured by GPC, the weight average molecular weight was 6.3.
It was 10,000. Examples 1 to 6, Comparative Examples 1 to 2 A photosensitive solution having the following composition was applied to the aluminum plate 1 obtained as described above using a whirler, and then dried at 85°C for 3 minutes. A photosensitive lithographic printing plate shown in Table 1 was obtained. (Photosensitive liquid composition) Lipophilic polymer compound-1
5.0g
diazo compound
Listed in Table-1
Julimar AC-10L
0.3g (Nippon Pure Pharmaceutical Co., Ltd.
(manufactured by) Victoria Pure Blue BOH
0.2g (Hodogaya Chemical Co., Ltd.)
(manufactured by) Surfactant
P listed in Table-1
P-3121*
0.05g methyl cellosolve
70ml *P
P-3121

##STR00004## After exposing the obtained photosensitive planographic printing plate to a 3 kW ultra-high pressure mercury lamp from a distance of 100 cm for 30 seconds,
Dilute developer-1 shown below 6 times with water and heat it at 25℃ for 45 minutes.
Development was carried out under conditions of 2 seconds. Note that the pH of developer solution-1 was 11.7. [0103] Among these, those developed at a dilution rate of 4 times were printed on high-quality paper using a GTO printing machine manufactured by Heidelberg Co., Ltd. using general ink (Toyo Ultra King Red), and a printing durability test was conducted. The above results are shown in Table-2. (Developer-1) JIS Sodium Silicate No. 3
2210g (manufactured by Asahi Denka Kogyo Co., Ltd.) Sodium sulfite
67g water

2500ml [0106] According to the above Examples 1 to 6 and Comparative Examples 1 to 2, the photosensitive lithographic printing plate according to the present invention has excellent developability when developed using the developer according to the present invention. It can be seen that a lithographic printing plate with excellent printing durability can be obtained. Effects of the Invention As explained above, the method for producing a lithographic printing plate of the present invention provides a lithographic printing plate with excellent developability and printing durability without using a developer containing an organic solvent. This effect is achieved. [Formula 1] [Formula 1] [Formula 2] [Formula 3] [Formula 4] [Formula 4] [Table 1] [Table 2]

Claims (1)

[Claims] Claim 1: A photosensitive lithographic printing plate having a photosensitive layer containing a diazo compound, a lipophilic polymer compound, and a nonionic surfactant and/or a fluorine surfactant on a support is subjected to imagewise exposure. A method for producing a lithographic printing plate, comprising: developing with an alkaline aqueous solution substantially free of organic solvents having a pH of 8 or more and less than 12 to produce a lithographic printing plate.