JPH04314054A - Production of planographic printing plate - Google Patents

Abstract

PURPOSE:To improve a printing ink deposition property. CONSTITUTION:The photosensitive planographic printing plate having photosensitive layers contg. an arom. diazonium compd. having at least one kind selected from a group consisting of a carboxyl group, phenolic hydroxyl group, sulfonic acid group, sulfinic acid group, and oxygen acid group of phosphorus on a base is subjected to image exposing then to developing with an aq. alkaline developer having >=12pH at 25 deg.C and contg. substantially no org. solvent. The planographic printing plate is thereafter subjected to desensitization processing by using a finisher contg. a hydrophilic org. high-polymer compd. and having 0 to 5wt.% gum arabic content.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing lithographic printing plates.

0002

[Prior Art] Photosensitive printing plates are generally produced by coating a photosensitive composition on a support such as an aluminum plate, irradiating active light such as ultraviolet rays through a negative image, and polymerizing or polymerizing the irradiated areas. It is cross-linked and insolubilized 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 accepts 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.

[0003] The photosensitive composition in this case is
Diazo resins such as condensates of p-diazodiphenylamine and formaldehyde have been widely used. On the other hand, when developing a photosensitive planographic printing plate using these diazo resins after exposure, examples of the aqueous alkaline developer composition used include benzyl alcohol, as disclosed in JP-A-51-77401, Developing solution composition consisting of anionic surfactant, alkaline agent and water, JP-A-53-442
A developer composition consisting of an aqueous solution containing benzyl alcohol, an anionic surfactant, and a water-soluble sulfite is described in No. 10% by weight in
Examples include the following developer compositions containing an organic solvent, an alkaline agent, and water.

[0004] All of these developer compositions contain organic substances such as organic solvents and surfactants. However, organic solvents have many drawbacks, such as being generally toxic and odorous, and pose a risk of fire, and are subject to BOD regulations even in waste liquid, and are also expensive. Attempts to develop photosensitive lithographic printing plates using diazo resins with developer compositions that do not substantially contain these organic solvents are described in JP-A-57-192952 and JP-A-58-27141. ing.

However, these developer compositions are used when developing positive-working photosensitive lithographic printing plates containing an o-naphthoquinone diazide compound as a photosensitive compound, and these developer compositions are substantially free of organic solvents. When a photosensitive lithographic printing plate using the above-mentioned diazo resin is developed using the liquid composition, the diazo resin is essentially not soluble in alkaline water, so it can be developed without leaving a residual film. Furthermore, there was a problem that proper developability could not be obtained, such as yellowing of unexposed areas.

On the other hand, JP-A-2-189544 discloses that a diazo resin can be obtained by using a co-condensed diazo resin containing an aromatic compound having a group selected from a carboxyl group, a hydroxyl group, a sulfonic acid group, and a sulfinic acid group. It is described that by imparting alkaline water solubility, it is possible to develop with a developer substantially free of organic solvents. However, when a photosensitive lithographic printing plate made of these diazo resins is actually developed using a developer that does not substantially contain an organic solvent, the surface of the photosensitive layer lacks oil sensitivity because the diazo resin is hydrophilic. Put it away. After development, the lithographic printing plate is usually subjected to a desensitization process using a finisher to protect non-image areas.

The purpose of the desensitization treatment is to remove the alkaline developer component adhering to the developed planographic printing plate, change the non-image areas of the planographic printing plate to be more compatible with water, and further prevent scratches and Its purpose is to form a film that prevents dirt. However, if the surface of the photosensitive layer has low oil sensitivity, the desensitization will extend to the image area, so when such a lithographic printing plate is run on a printing press, there is a problem that ink is difficult to adhere to the image area.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to develop a photosensitive lithographic printing plate having a photosensitive layer containing a diazo resin with an aqueous alkaline developer containing substantially no organic solvent to obtain a lithographic plate. An object of the present invention is to provide a method for producing a lithographic printing plate that has good developability during development and good inkling during printing.

[0009]

[Means for Solving the Problem] As a result of intensive studies to achieve the above object, the present inventors have developed a photosensitive lithographic printing plate having a photosensitive layer using a highly hydrophilic diazo resin at a pH of 12.
It was discovered that the ink adhesion does not deteriorate by desensitization treatment with a finisher containing gum arabic of 0 to 5% by weight even when developed with a developer that does not substantially contain an organic solvent and has arrived at the present invention. did.

That is, the present invention contains an aromatic diazonium compound having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, and a phosphorus oxygen acid group on a support. After image exposure of a photosensitive lithographic printing plate having a photosensitive layer, the temperature is 25°C.
A lithographic printing plate characterized in that it is developed with an aqueous alkaline developer having a pH of 12 or higher and substantially free of organic solvents, and then subjected to a desensitization treatment using a finisher containing gum arabic from 0 to 5% by weight. This is a manufacturing method.

The present invention will be explained below. Examples of aromatic diazonium compounds having at least one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, and a phosphorus oxygen acid group, which are used in the present invention, are shown below. (I) An aromatic compound having at least 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 aromatic diazonium compound represented by the following general formula (A) as a structural unit Co-condensed diazo resin including:

0012

[Chemical formula 1]

In the formula, R1 represents a hydrogen atom, an alkyl group which may have a substituent, a hydroxyl group, a carboxyester group, or a carboxyl group, preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or Indicates a hydroxyl group. R2 represents a hydrogen atom, an alkyl group or an alkoxy group, preferably a hydrogen atom or a methoxy group. R
3 represents a hydrogen atom, an alkyl group or an alkoxy group, preferably a hydrogen atom.

[0014] X- represents an anion, preferably an aliphatic or aromatic sulfonic acid anion, and Y represents -NH-, -
Indicates O- or -S-. Preferable examples of the aromatic ring of the aromatic compound include a phenyl group and a naphthyl group. Further, the carboxyl group, phenolic hydroxyl group, sulfonic acid group, sulfinic acid group, and phosphorus oxygen acid group may be bonded directly to the aromatic ring or may be bonded via a linking group. Examples of the freezing group include a group having 1 or more carbon atoms and containing an ether bond.

Specific examples of aromatic compounds having a carboxyl group in the molecule utilized in the present invention include benzoic acid,
-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, phthalic acid, terephthalic acid, diphenylacetic acid, phenoxyacetic acid, p-methoxyphenylacetic acid, 3-phenoxypropionic acid, 2-phenoxypropionic acid, 2-
Phenoxybutanoic acid, 4-(4-methoxyphenoxy)
Butanoic acid, 3-(2,4-dimethylphenoxy)butanoic acid, 6-phenoxyhexanoic acid, phenylacetic acid, 4-methoxyphenylacetic acid, 4-methylphenylacetic acid, phenylpropionic acid, phenylbutanoic acid, p-methoxybenzoic acid , 2,4-dimethoxybenzoic acid, 2,4-dimethylbenzoic acid, p-phenoxybenzoic acid, p-methoxyphenylacetic acid, 4-anilinobenzoic acid, 4-(m-methoxyanilinobenzoic acid, 4-(p -Methoxybenzoyl)benzoic acid, 4-(p-methylanilino)benzoic acid, 4-phenylsulfonylbenzoic acid, 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-hydroxybenzoic 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, 2,6-dihydroxybenzoic acid, 2,
6-dihydroxy-4-methylbenzoic acid, 4-chloro-
2,6-dihydroxybenzoic acid, 4-methoxy-2,6
-dioxybenzoic 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 and the like.

Specific examples of the aromatic compound having a phenolic hydroxyl group used in the present invention include phenol, (o
, m, p) Cresol, xylenol, resorcinol, 2
-Methylresorcin, (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'-dihydroxydiphenyl sulfide, cumylphenol, (o,m,p)-chlorophenol, (o
, m, p)-bromophenol, and the like.

Specific examples of the aromatic compound having a sulfonic acid group and/or sulfinic acid group used in the present invention include benzenesulfonic acid, p-toluenesulfonic acid, benzenesulfinic acid, p-toluenesulfinic acid, and aniline-sulfonic acid. 2-sulfonic acid, 4-amino-m-toluenesulfonic acid, 2,5-diaminobenzenesulfonic 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 and the like.

These may be free sulfonic acids or sulfinic acids, and may include sodium, potassium, lithium, cesium, calcium, barium, magnesium,
It may be a metal salt such as aluminum or zinc, or an unsubstituted or substituted ammonium salt. Specific examples of aromatic compounds having a phosphorus oxygen acid group in the molecule used in the present invention include phenylphosphoric acid, phenylphosphorous acid, phenylphosphonic acid, phenylphosphonic acid, phenylphosphinic acid, and phenylphosphinic acid. , 4-hydroxyphenyl phosphoric acid, 4-hydroxyphenyl phosphorous acid, 4-
Hydroxyphenylphosphonic acid, 4-hydroxyphenylphosphonic acid, 4-hydroxyphenylphosphinic acid, 4-hydroxyphenylphosphinic acid, 4-methylphenylphosphonic acid, 4-methylphenylphosphonic acid, 4-methylphenylphosphonic acid, 4-Methylphenylphosphonic acid, 4-methylphenylphosphinic acid, 4-methylphenylphosphinic acid, 4-t-butylphenylphosphonic acid, 4-t-butylphenylphosphonic acid, 4-t-butylphenylphosphonic acid , 4-t-butylphenylphosphonic acid, 4-t-butylphenylphosphinic acid, 4-t-butylphenylphosphinic acid, 4-aminophenylphosphonic acid, 4-aminophenylphosphorous acid, 4-aminophenylphosphonic acid acid, 4-aminophenylphosphonic acid, 4-aminophenylphosphinic acid, 4-aminophenylphosphinic acid, 4-methoxyphenylphosphonic acid, 4-methoxyphenylphosphonic acid, 4-methoxyphenylphosphonic acid,
4-Methoxyphenylphosphonic acid, 4-methoxyphenylphosphinic acid, 4-methoxyphenylphosphinic acid, 4-ethoxyphenylphosphonic acid, 4-ethoxyphenylphosphonic acid, 4-ethoxyphenylphosphonic acid, 4-ethoxyphenylphosphonic acid Phosphonic acid, 4-ethoxyphenylphosphinic acid, 4-ethoxyphenylphosphinic acid, 4
-Ethylphenylphosphonic acid, 4-ethylphenylphosphorous acid, 4-ethylphenylphosphonic acid, 4-ethylphenylphosphonic acid, 4-ethylphenylphosphinic acid, 4-
Ethylphenylphosphinic acid, 2-aminophenylphosphonic acid, 2-aminophenylphosphonic acid, 2-aminophenylphosphonic acid, 2-aminophenylphosphonic acid, 2-
Aminophenylphosphinic acid, 2-aminophenylphosphinic acid, 2,4-dimethylphenylphosphoric acid, 2,4
-dimethylphenylphosphonic acid, 2,4-dimethylphenylphosphonic acid, 2,4-dimethylphenylphosphonic acid, 2,4-dimethylphenylphosphinic acid, 2,4-dimethylphenylphosphinic acid, 2,6-diamino Phenyl phosphoric acid, 2,6-diaminophenyl phosphorous acid, 2,
6-diaminophenylphosphonic acid, 2,6-diaminophenylphosphonic acid, 2,6-diaminophenylphosphinic acid, 2,6-diaminophenylphosphinic acid, 2
, 5-dihydroxyphenylphosphonic acid, 2,5-dihydroxyphenylphosphorous acid, 2,5-dihydroxyphenylphosphonic acid, 2,5-dihydroxyphenylphosphonic acid, 2,5-dihydroxyphenylphosphinic acid, 2,
5-dihydroxyphenylphosphinic acid, 2-amino-4-hydroxyphenylphosphoric acid, 2-amino-4-hydroxyphenylphosphonic acid, 2-amino-4-hydroxyphenylphosphonic acid, 2-amino-4-hydroxyphenyl Phosphonous acid, 2-amino-4-hydroxyphenylphosphinic acid, 2-amino-4-hydroxyphenylphosphinic acid, mesityl phosphonic acid, mesityl phosphorous acid, mesityl phosphonic acid, mesityl phosphonous acid, mesitylphosphinic acid, Mesitylphosphinic acid, 2,4-dihydroxy-6-methylphenylphosphoric acid, 2,4-dihydroxy-6-methylphenylphosphonic acid, 2,4-dihydroxy-6-methylphenylphosphonic acid, 2,4-dihydroxy -6-methylphenylphosphonic acid, 2,4
-dihydroxy-6-methylphenylphosphinic acid, 2
, 4-dihydroxy-6-methylphenylphosphinic acid, benzyl phosphoric acid, benzyl phosphorous acid, benzyl phosphonic acid, benzyl phosphonic acid, benzyl phosphinic acid, benzyl phosphinic acid, 4-methoxybenzyl phosphoric acid, 4-methoxy Benzyl phosphorous acid, 4-methoxybenzyl phosphonic acid, 4-methoxybenzyl phosphonic acid,
4-methoxybenzylphosphinic acid, 4-methoxybenzylphosphinic acid, 4-hydroxybenzylphosphoric acid,
4-hydroxybenzyl phosphonic acid, 4-hydroxybenzyl phosphonic acid, 4-hydroxybenzyl phosphonic acid, 4-hydroxybenzyl phosphinic acid, 4-hydroxybenzyl phosphinic acid, 4-(2-hydroxyethyl) phenyl phosphonic acid, 4-(2-hydroxyethyl)phenylphosphonic acid, 4-(2-hydroxyethyl)phenylphosphonic acid, 4-(2-hydroxyethyl)phenylphosphonic acid, 4-(2-hydroxyethyl)phenylphosphinic acid, 4-(2-hydroxyethyl)phenylphosphinic acid, 2-phenylethyl phosphoric acid, 2-phenylethyl phosphorous acid, 2-phenylethylphosphonic acid,
2-phenylethyl phosphonic acid, 2-phenylethyl phosphinic acid, 2-phenylethyl phosphinic acid, 1
-Naphthyl phosphoric acid, 1-naphthyl phosphorous acid, 1-naphthylphosphonic acid, 1-naphthyl phosphonic acid, 1-naphthyl phosphinic acid, 1-naphthyl phosphinic acid, 2-naphthyl phosphorous acid, 2-naphthyl phosphorous acid, 2 -Naphthylphosphonic acid, 2-naphthylphosphonic acid, 2-naphthylphosphinic acid, 2-naphthylphosphinic acid, 2-amino-1-naphthylphosphonic acid, 2-amino-1-naphthylphosphorous acid, 2-amino-1 -Naphthylphosphonic acid, 2-amino-1-naphthylphosphonic acid, 2-amino-1-naphthylphosphinic acid, 2-amino-1-naphthylphosphinic acid, 4-amino-1-naphthylphosphonic acid, 4-amino- 1-naphthylphosphonic acid, 4-amino-1-naphthylphosphonic acid, 4-amino-1-naphthylphosphonic acid, 4
-amino-1-naphthylphosphinic acid, 4-amino-1
-Naphthylphosphinic acid, 5-amino-2-naphthylphosphonic acid, 5-amino-2-naphthylphosphonic acid, 5-amino-2-naphthylphosphonic acid, 5-amino-2-naphthylphosphonic acid, 5-amino -2-naphthylphosphinic acid, 5-amino-2-naphthylphosphinic acid, 4-amino-3-hydroxy-1-naphthylphosphonic acid, 4-amino-3-hydroxy-1-naphthylphosphonic acid, 4-amino-5 -Hydroxy-1-naphthylphosphonic acid, 4-amino-5-hydroxy-1-naphthylphosphonic acid, 7-amino-3-hydroxy-2-naphthylphosphonic acid, 7-amino-3-hydroxy-2-naphthylphosphonic acid, 5 -dimethylamino-2-naphthylphosphonic acid, 5-dimethylamino-2-naphthylphosphonic acid, 5-hydroxy-1-naphthylphosphonic acid, 5-hydroxy-1-naphthylphosphonic acid, 5-methoxy-2-naphthylphosphonic acid, 5- Methoxy-2-naphthylphosphonic acid, 4-phenoxyphenylphosphonic acid, 4-phenoxyphenylphosphonic acid, 4-(4-
Methoxyphenoxy)phenylphosphonic acid, 4-(4-methoxyphenoxy)phenylphosphonic acid, 4-diphenylaminophosphonic acid, 4-diphenylaminophosphorous acid, 4-diphenylaminophosphonic acid, 4-diphenylaminophosphonic acid, 4- Diphenylaminophosphinic acid, 4-diphenylaminophosphinic acid, 4'-methoxy-4-
Diphenylaminophosphoric acid, 4'-methoxy-4-diphenylaminophosphorous acid, 4'-methoxy-4-diphenylaminophosphonic acid, 2-phenoxyethyl phosphoric acid, 2-
Phenoxyethyl phosphorous acid, 2-phenoxyethylphosphonic acid, 2-phenoxyethylphosphonic acid, 2-phenoxyethylphosphinic acid, 2-phenoxyethylphosphinic acid, benzyl (2-dihydroxyphosphinyloxy) acetate, benzyl ( 2-dihydroxyphosphinyl) acetate, 4-methoxybenzyl 2-
Dihydroxyphosphinyloxyacetate, 4-methoxybenzyl 2-dihydroxyphosphinyl acetate, phenyl 3-dihydroxyphosphinyloxypropionate, phenyl 3-dihydroxyphosphinylpropionate, 3-dihydroxyphosphinyloxypropionic acid ( 3-methoxyphenyl), 4-dihydroxyphosphinylbutyric acid (3-methoxyphenyl), 4-dihydroxyphosphinyloxybutyric acid (4-hydroxyphenyl), 3-dihydroxyphosphinylpropionic acid (4-
hydroxyphenyl), 2,4,6-trimethyl-1,
3-benzene-bis-phosphoric acid, 2,4,6-trimethyl-1,3-benzene-bis-phosphonic acid, 2,5-dihydroxy-1,4-benzene-bis-phosphoric acid, 2,5-
dihydroxy-1,4-benzene-bis-phosphonic acid,
2,5-dihydroxy-1,3-benzene-bis-phosphoric acid, 2,5-dihydroxy-1,3-benzene-bis-
Phosphonic acid, 1,5-naphthalene-bis-phosphoric acid, 1,
5-Naphthalene-bis-phosphonic acid, 2,6-naphthalene-bis-phosphonic acid, 2,6-naphthalene-bis-phosphonic acid, 7-amino-1,3-naphthalene-bis-phosphonic acid, 7-amino- 1,3-naphthalene-bis-phosphonic acid, 3-methoxy-2,7-naphthalene-bis-phosphoric acid,
Examples include 3-methoxy-2,7-naphthalene-bis-phosphonic acid.

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 phenoxymethylphosphonic acid.

[0020] The compound used in the present invention contains an aromatic compound having an acid group and an aromatic diazo compound as a constituent unit.
A condensation type resin with an active carbonyl compound (hereinafter referred to as a diazo cocondensation resin) can be prepared by a known method, for example, by the Photographic Science and Engineering (Ph.D.
oto, Sci. , Eng. ) Vol. 17, p. 33 (1973), U.S. Patent No. 2,063,631, U.S. Pat. Diazonium salts, aromatic compounds with acid groups and aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, is
It is obtained by polycondensation of o-butyraldehyde, benzaldehyde or ketones, such as active carbonyl compounds such as acetone, methyl ethyl ketone, acetophenone, or their acetals.

[0021] Further, these aromatic compounds having acid groups in their molecules, aromatic diazo compounds and active carbonyl compounds or their acetals can be freely combined with each other,
Furthermore, it is also possible to co-condense a mixture of two or more of each. Furthermore, co-condensation can be carried out by adding a co-condensable aromatic compound which does not have an acid group. Here, as the aromatic compound that can be co-condensed, for example,
Examples include aromatic compounds described in Japanese Patent No. 48001.

[0022] Instead of the active carbonyl compounds or their acetals, methylol derivatives as described in Japanese Patent Publication Nos. 49-45322 and 49-45323, or as described in Japanese Patent Application Laid-Open No. 187925-1980, may be used. It is also possible to use olefinically unsaturated compounds as described. The acid group content of the resulting diazo resin can be adjusted by changing the molar ratio of these cocondensation components.

At this time, the molar ratio of the aromatic compound having an acid group to the aromatic diazo compound is 1:0.1 to 0.1.
:1; preferably 1:0.2 to 0.2:1, more preferably 1:0.5 to 0.2:1. In this case, the molar ratio of the sum of the aromatic compound having an acid group and the aromatic diazo compound to the active carbonyl compound is usually 1:0.6 to 1:0.6.
A diazo cocondensation resin can be obtained by charging the mixture at a ratio of 1.5, preferably 1:0.7 to 1.2, and reacting at a low temperature for a short time, for example, about 1 to 20 hours.

(II) A diazo resin having at least one repeating unit represented by the following general formula (B)

[
0025

[Case 2]

In the formula, R4 is one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, and a phosphorus oxyacid group, or a group having 15 or less carbon atoms and having at least one of these. It is. R1
, R2, R3, X- and Y represent the above general formula (A)
This is the same as the group shown in . As a method for synthesizing the diazo resin (II) used in the present invention, for example, a diazo monomer having a 4-diazodiphenylamine skeleton, a 4-diazodiphenyl ether skeleton, or a 4-diazodiphenyl sulfide skeleton and a carboxyl group, a phenolic hydroxyl group, a sulfone 1 of acid groups, sulfinic acid groups, and phosphorus oxygen acid groups
or an acetal thereof in an acidic medium in a molar ratio of preferably 1:10 to 1:0.05, more preferably 1:2 to 1:0.2. . When carrying out the condensation reaction, an active carbonyl such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, iso-butyraldehyde, benzaldehyde, acetone, methyl ethyl ketone or acetophenone is used to adjust the acid value and molecular weight of the diazo resin produced. Compounds or their acetals can be used in combination as condensing agents. Formaldehyde is most preferable as the active carbonyl compound, and its molar ratio to the diazo monomer is preferably 0 to 5, more preferably 0.1 to 1. 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 aldehydes having alkali-soluble groups in an acidic medium followed by post-condensation with more reactive active carbonyl compounds such as formaldehyde or their acetals yields higher molecular weight diazo Resin can be obtained.

[0027] In place of the above active carbonyl compounds or their acetals, Japanese Patent Publication No. 49-45322
and methylol derivatives as described in JP-A No. 49-45323, or JP-A-58-187925.
It is also possible to use olefinically unsaturated compounds such as those described in the specification. The above-mentioned aldehyde or acetal thereof having one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, and a phosphorus oxygen acid group is preferably an aldehyde having a structure represented by the following general formula (C). or their acetals.

Z-R5-CHO
(C) In the formula, R5 is a single bond or a divalent organic group having 0 to 14 carbon atoms which may have a substituent (e.g., an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, etc.) shows. Groups that can be substituted for R5 include, for example, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, hydroxy groups, substituted or unsubstituted amino groups, carboxyester groups, and carboxyl groups. Z represents one group among a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, and a phosphorus oxygen acid group.

Specific examples of aldehydes or acetals thereof having a carboxyl group include glyoxylic acid, malonaldehydic acid, succinaldehydic acid, 2-methylsuccinaldehydic acid, 2-methoxysuccinaldehydic acid, 2-hydroxysuccinic acid, and 2-hydroxysuccinic acid. Cinaldehyde acid, 2-
Chlorosuccinic aldehydic acid, 2-aminosuccinic aldehydic acid, glutaraldehydic acid, 2-methylglutaraldehydic acid, 2-methoxyglutaraldehydic acid, 2
-Hydroxyglutaraldehydic acid, 2-chloroglutaraldehydic acid, adipinaldehydic acid, pimelinaldehydic acid, suberaldehydic acid, azelaic aldehydic acid, sebacic aldehydic acid, 2-formylmethylsuccinic acid, 2-formylethylsuccinic acid, formylmethyl Malonic 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-formyl Ethyl phthalic acid, 4-formylethoxyphthalic acid, 5-formylethoxyisophthalic acid, 4-carboxymethylphthalic acid, 3-formyl-1-naphthoic acid, 6-formyl-1-naphthoic acid, or their acetals, etc. Can be mentioned.

Specific examples of aldehydes or acetals thereof having a phenolic hydroxyl group, sulfonic acid group or sulfinic acid group include p-hydroxybenzaldehyde, 2-oxo-1-ethanesulfonic acid, 3-oxo-1-propane. Sulfonic acid, 4-oxo-1-butanesulfonic acid, 5-oxo-1-pentanesulfonic acid, 6-
Oxo-1-hexane sulfonic acid, 2-formylbenzenesulfonic acid, 3-formylbenzenesulfonic acid, 4-
Formylbenzenesulfonic acid, 4-formylbenzenesulfinic acid, 2,2-dimethyl-3-oxo-1-propanesulfonic acid, 2,3-dimethyl-4-oxo-1-
Butanesulfonic acid, 2-methyl-6-oxo-1-hexanesulfonic acid, 2-formyl-4-methoxybenzenesulfonic acid, 4-amino-3-formylbenzenesulfonic acid, 4-(2-oxoethyl)benzenesulfonic acid ,
3-(3-oxopropyl)benzenesulfonic acid, 4-
Formyl-1,3-benzenesulfonic acid, 2-formyl-1,3-benzenesulfonic acid, 2-formyl-1-naphthalenesulfonic acid, 4-formyl-1-naphthalenesulfonic acid, 4-formyl-1-naphthalenesulfine acid, 5-formyl-2-naphthalenesulfonic acid, 7-formyl-1,4-naphthalenedisulfonic acid, 5-amino-
7-formyl-2-naphthalenesulfonic acid, 5-formyl-2-francesulfonic acid, 3-formyl-2-francesulfonic acid, 5-formyl-3-francesulfonic acid, 1
-Oxo-1-methanesulfonic acid, 4-formylphenoxy-3-propanesulfonic acid, 4-formylphenoxy-4-butanesulfonic acid, 3-formylphenoxy-
3-Butanesulfonic acid, p-formyl-N-(2-sulfonylethyl)benzamide, m-formyl-N-(3
-sulfonylpropyl)benzamide, p-formylbenzoic acid-2-sulfonylethyl, p-formylbenzoic acid-3-sulfonylpropyl, m-formylbenzoic acid-4
-Sulfonylbutyl, p-sulfonylbenzoate-2-formylethyl, p-sulfonylbenzoate-3-formylpropyl, 3-formylpropionate-m-sulfonylphenyl, N-(2-sulfonylethyl)-3-formylpropion Amide, 3-formylpropionic acid-2-
Examples thereof include sulfonylethyl, N-(3-sulfonylphenyl)glyoxylate amide, N-(2-sulfonylethyl)glyoxylate amide, 2-sulfonylethyl glyoxylate, and acetals thereof.

Of course, these may be free sulfonic acids or sulfinic acids, or metal salts such as sodium, potassium, lithium, cesium, calcium, barium, magnesium, aluminum, zinc, or unsubstituted or substituted ammonium salts. It may be. Specific examples of aldehydes or acetals thereof having a phosphorus oxygen acid group include 2-oxo-1-ethyl phosphoric acid, 2-oxo-1-ethyl phosphoric acid, 2-oxo-1-ethyl phosphoric acid,
-oxo-1-ethylphosphonic acid, 2-oxo-1-ethylphosphonic acid, 2-oxo-1-ethylphosphonic acid,
2-oxo-1-ethylphosphinic acid, 2-oxo-1
-Ethylphosphinic acid, 3-oxo-1-propylphosphonic acid, 3-oxo-1-propylphosphonic acid, 3-oxo-1-propylphosphonic acid, 3-oxo-1-propylphosphonic acid, 3- Oxo-1-propylphosphinic acid, 3-oxo-1-propylphosphinic acid, 4-oxo-1-butyl phosphoric acid, 4-oxo-1-butyl phosphorous acid, 4-oxo-1-butylphosphonic acid, 4 -Oxo-
1-Butylphosphonic acid, 4-oxo-1-butylphosphinic acid, 4-oxo-1-butylphosphinic acid, 5
-Oxo-1-pentyl phosphoric acid, 5-oxo-1-pentyl phosphorous acid, 5-oxo-1-pentylphosphonic acid,
5-oxo-1-pentylphosphonic acid, 5-oxo-
1-pentylphosphinic acid, 5-oxo-1-pentylphosphinic acid, 5-oxo-1-pentylphosphinic acid, 6-oxo-1-hexylphosphoric acid, 6-oxo-1
-Hexylphosphonic acid, 6-oxo-1-hexylphosphonic acid, 6-oxo-1-hexylphosphonic acid, 6-oxo-1-hexylphosphinic acid, 6-oxo-1-hexylphosphinic acid, 2- formyl phenyl phosphate,
2-formylphenylphosphonic acid, 2-formylphenylphosphonic acid, 2-formylphenylphosphonic acid, 2-
Formylphenylphosphinic acid, 2-formylphenylphosphinic acid, 3-formylphenylphosphoric acid, 3-formylphenylphosphorous acid, 3-formylphenylphosphonic acid, 3-formylphenylphosphonic acid, 3-formylphenylphosphinic acid, 3-formylphenyl phosphinic acid, 4-formylphenyl phosphorous acid, 4-formylphenyl phosphorous acid, 4-formylphenylphosphonic acid,
4-Formylphenylphosphonic acid, 4-formylphenylphosphinic acid, 4-formylphenylphosphinic acid, 2,2-dimethyl-3-oxo-1-propyl phosphoric acid, 2,2-dimethyl-3-oxo-1 -Propyl phosphorous acid, 2,2-dimethyl-3-oxo-1-propylphosphonic acid, 2,2-dimethyl-3-oxo-1-propylphosphonic acid, 2,2-dimethyl-3-oxo-1 −
Propylphosphinic acid, 2,2-dimethyl-3-oxo-1-propylphosphinic acid, 2,3-dimethyl-4
-oxo-1-butyl phosphate, 2,3-dimethyl-4-
Oxo-1-butylphosphonic acid, 2-methyl-6-oxo-1-hexylphosphonic acid, 2-methyl-6-oxo-1
-hexylphosphonic acid, 2-formyl-4-methoxyphenylphosphonic acid, 2-formyl-4-methoxyphenylphosphonic acid, 4-amino-3-formylphenylphosphonic acid,
4-amino-3-formylphenylphosphonic acid, 4-(
2-oxoethyl)phenylphosphonic acid, 4-(2-oxoethyl)phenylphosphonic acid, 3-(3-oxopropyl)phenylphosphonic acid, 3-(3-oxopropyl)phenylphosphonic acid, 2,4-bis-( dihydroxyphosphinyloxy)benzaldehyde, 2,4-bis-(dihydroxyphosphinyl)benzaldehyde, 2,6-
Bis-(dihydroxyphosphinyloxy)benzaldehyde, 2,6-bis-(dihydroxyphosphinyl)
Benzaldehyde, 2-formyl-1-naphthylphosphonic acid, 2-formyl-1-naphthylphosphonic acid, 4-formyl-1-naphthylphosphonic acid, 4-formyl-1-naphthylphosphonic acid, 5-formyl-2-naphthylphosphonic acid, 5 −
Formyl-2-naphthylphosphonic acid, 1,4-bis-(
dihydroxyphosphinyloxy)-7-naphthylaldehyde, 1,4-(bis-(dihydroxyphosphinyl)-7-naphthylaldehyde, 5-amino-7-formyl-2-naphthylphosphate, 5-amino-7- Formyl-
2-naphthylphosphonic acid, 5-formyl-2-furylphosphonic acid, 5-formyl-2-furylphosphonic acid, 3-formyl-2-furylphosphonic acid, 3-formyl-2-furylphosphonic acid, 5-formyl-3- Furylphosphonic acid, 5-formyl-3-furylphosphonic acid, 1-oxo-1-methylphosphonic acid, 1-oxo-1-methylphosphonic acid, 3-(4
-formylphenoxy)-1-propyl phosphate, 3-(
4-formylphenoxy)-1-propylphosphonic acid,
4-(4-formylphenoxy)-1-butyl phosphoric acid,
4-(4-formylphenoxy)-1-butylphosphonic acid, 3-(3-formylphenoxy)-1-butylphosphonic acid, 3-(3-formylphenoxy)-1-butylphosphonic acid, 4-formyl-2- (2-dihydroxyphosphinyloxyethyl)benzoic acid, 4-formyl-3-(
2-dihydroxyphosphinylethyl)benzoic acid, 4-
Formyl-3-(3-dihydroxyphosphinyloxypropyl)benzoic acid, 4-formyl-2-(3-dihydroxyphosphinyl)benzoic acid, 4-formyl-4-(
Examples include 4-dihydroxyphosphinyloxybutyl)benzoic acid and acetals thereof.

(III) At least one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group and a phosphorus oxygen acid group is represented by the general formula (D), (E
) or (F), and a diazo resin obtained by the condensation reaction of an aromatic diazonium compound with an aldehyde or ketone or an equivalent of an active carbonyl compound thereof

[0033]

[Chemical formula 3]

In the formula, at least one of R6 and R7 is a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, or a phosphorus oxygen acid group, and when it is not an acid group, it is a hydrogen atom. . R1, R2
, R3, X- and Y are the same as in the general formula (A). Specifically, the compounds represented by the general formula (D), (E) or (F) include, for example, 4-diazodiphenylamine-4'-carboxylic acid, 4-diazodiphenylamine-2
-carboxylic acid, 4-diazodiphenylamine-3-carboxylic acid, 4-diazodiphenylamine-2'-carboxylic acid, 4'-methoxy-4-diazodiphenylamine-2
'-Carboxylic acid, 4'-methoxy-4-diazodiphenylamine-2-carboxylic acid, 4'-methoxy-4-diazodiphenylamine-3-carboxylic acid, 4'-hydroxy-4-diazodiphenylamine, 4-diazodiphenylamine- 4'-sulfonic acid, 4-diazodiphenylamine-2-sulfonic acid, 4-diazodiphenylamine-
3-sulfonic acid, 4-diazodiphenylamine-2'-
Sulfonic acid, 4'-methoxy-4-diazodiphenylamine-2'-sulfonic acid, 4'-methoxy-4-diazodiphenylamine-2-sulfonic acid, 4'-methoxy-
4-diazodiphenylamine-3-sulfonic acid, 4'-
Ethoxy-4-diazodiphenylamine-2'-sulfonic acid, 4'-ethoxy-4-diazodiphenylamine-
2-sulfonic acid, 4'-ethoxy-4-diazodiphenylamine-3-sulfonic acid, 4'-methyl-4-diazodiphenylamine-2'-sulfonic acid, 4'-methyl-
4-diazodiphenylamine-2-sulfonic acid, 4'-
Methyl-4-diazodiphenylamine-3-sulfonic acid, 4'-ethyl-4-diazodiphenylamine-2'-
Sulfonic acid, 4'-ethyl-4-diazodiphenylamine-2-sulfonic acid, 4'-ethyl-4-diazodiphenylamine-3-sulfonic acid, 4-diazo-4'-(2
-sulfonylethyl)diphenylamine, 4-diazo-
4'-Sulfonylmethyldiphenylamine, 4-diazo-4'-sulfonylmethoxydiphenylamine, 4-diazo-4'-(2-sulfonylethoxy)diphenylamine, 4-diazo-4'-(3-sulfonylpropoxy)diphenylamine, 4- Diazo-4'-(3-sulfonylpropyl)diphenylamine, 4-diazo-2,5
-disulfonylmethyldiphenylamine, 4-diazo-
2,5-bis-(2-sulfonylethyl)diphenylamine, 4-diazo-2,5-bis-(3-sulfonylpropyl)diphenylamine, 4-diazo-2-(3-sulfonylpropyl)diphenylamine, 4-diazo- 3
-sulfonylmethyldiphenylamine, 4-diazo-3
-(2-sulfonylethyl)diphenylamine, 4-diazo-2,5-disulfonylmethoxydiphenylamine, 4-diazo-3-sulfonylmethoxydiphenylamine, 4-diazo-2-(3-sulfonylpropoxy)diphenylamine, 4-diazo- 2,5-bis-(2-sulfonylethoxy)diphenylamine, 4-diazo-2
, 5-bis-(3-sulfonylpropoxy)diphenylamine, 4-diazodiphenyl ether-4'-sulfonic acid, 4-diazodiphenyl sulfide-4'-sulfonic acid, 4-diazodiphenyl ether-2-sulfonic acid, 4-diazodiphenyl ether -3-sulfonic acid, 4
-diazodiphenylsulfide-2-sulfonic acid, 4-
Diazodiphenylsulfide-3-sulfonic acid, 4-diazo-4'-sulfonylmethyldiphenyl ether, 4
-Diazo-4'-(2-sulfonylethyl)diphenyl ether, 4-diazo-4'-sulfonylmethyldiphenyl sulfide, 4-diazo-4'-(2-sulfonylethyl)diphenyl sulfide, 4-diazo-4'-sulfonyl Methoxydiphenyl ether, 4-diazo-4
'-(2-sulfonylethoxy) diphenyl sulfide, 4-diazo-2-(2-sulfonylethyl) diphenyl ether, 4-diazo-3-sulfonylmethyl diphenyl ether, 4-diazo-2-(2-sulfonylethyl) diphenyl sulfide, 4-Diazo-3-sulfonylmethyldiphenyl sulfide, 4-diazodiphenylamine-4'-sulfinic acid, 4-diazodiphenylamine-2-sulfinic acid, 4-diazodiphenylamine-3-sulfinic acid, 4-diazodiphenylamine-2
'-Sulfinic acid, 4-diazo-4'-dihydroxyphosphinyldiphenylamine, 4-diazo-4'-dihydroxyphosphinyloxydiphenylamine, 4-diazo-2-dihydroxyphosphinyldiphenylamine, 4-diazo-2- Dihydroxyphosphinyloxydiphenylamine, 4-diazo-3-dihydroxyphosphinyldiphenylamine, 4-diazo-3-dihydroxyphosphinyloxydiphenylamine, 4-diazo-
2'-dihydroxyphosphinyldiphenylamine, 4
-Diazo-2'-dihydroxyphosphinyloxydiphenylamine, 4-diazo-2'-dihydroxyphosphinyl-4'-methoxydiphenylamine, 4-diazo-2'-dihydroxyphosphinyloxy-4'-methoxydiphenylamine, 4-Diazo-3-dihydroxyphosphinyl-4'-methoxydiphenylamine, 4-
Diazo-3-dihydroxyphosphinyloxy-4'-
Methoxydiphenylamine, 4-diazo-2-dihydroxyphosphinyl-4'-ethoxydiphenylamine,
4-Diazo-2-dihydroxyphosphinyloxy-4
'-Ethoxydiphenylamine, 4-diazo-2'-dihydroxyphosphinyl-4'-ethoxydiphenylamine, 4-diazo-2'-dihydroxyphosphinyloxy-4'-ethoxydiphenylamine, 4-diazo-
3-dihydroxyphosphinyl-4'-ethoxydiphenylamine, 4-diazo-3-dihydroxyphosphinyloxy-4'-ethoxydiphenylamine, 4-diazo-2'-dihydroxyphosphinyl-4'-methyldiphenylamine, 4 -diazo-2'-dihydroxyphosphinyloxy-4'-methyldiphenylamine, 4-
Diazo-2-dihydroxyphosphinyl-4'-methyldiphenylamine, 4-diazo-2-dihydroxyphosphinyloxy-4'-methyldiphenylamine, 4-
Diazo-3-dihydroxyphosphinyl-4'-methyldiphenylamine, 4-diazo-3-dihydroxyphosphinyloxy-4'-methyldiphenylamine, 4-
Diazo-2-dihydroxyphosphinyl-4'-ethyldiphenylamine, 4-diazo-2-dihydroxyphosphinyloxy-4'-ethyldiphenylamine, 4-
Diazo-2'-dihydroxyphosphinyl-4'-ethyldiphenylamine, 4-diazo-2'-dihydroxyphosphinyloxy-4'-ethyldiphenylamine,
4-Diazo-3-dihydroxyphosphinyl-4'-ethyldiphenylamine, 4-diazo-3'-dihydroxyphosphinyl-4'-ethyldiphenylamine, 4-
Diazo-4'-(2-dihydroxyphosphinylethyl)diphenylamine, 4-diazo-4'-(2-dihydroxyphosphinyloxyethyl)diphenylamine,
4-Diazo-4'-dihydroxyphosphinylmethyldiphenylamine, 4-diazo-4'-dihydroxyphosphinyloxymethyldiphenylamine, 4-diazo-
4'-(2-dihydroxyphosphonyloxyethoxy)
Diphenylamine, 4-diazo-4'-(2-dihydroxyphosphonyloxyethoxy)diphenylamine, 4
-Diazo-4'-(3-dihydroxyphosphonylpropoxy)diphenylamine, 4-diazo-4'-(3-dihydroxyphosphinyloxypropoxy)diphenylamine, 4-diazo-4'-(3-dihydroxyphosphinylpropyl) ) diphenylamine, 4-diazo-4'
-(3-dihydroxyphosphinyloxypropyl)diphenylamine, 4-diazo-2,5-bis-(dihydroxyphosphinylmethyl)diphenylamine, 4-diazo-2,5-bis-(dihydroxyphosphinyloxymethyl) Diphenylamine, 4-diazo-2,5-bis-(2-dihydroxyphosphinylethyl)diphenylamine, 4-diazo-2,5-bis-(2-dihydroxyphosphinyloxyethyl)diphenylamine, 4
-Diazo-2,5-bis-(3-dihydroxyphosphinylpropyl)diphenylamine, 4-diazo-2,5
-bis-(3-dihydroxyphosphinyloxypropyl)diphenylamine, 4-diazo-2-(3-dihydroxyphosphinylpropyl)diphenylamine, 4-
Diazo-2-(3-dihydroxyphosphinyloxypropyl)diphenylamine, 4-diazo-3-dihydroxyphosphinylmethyldiphenylamine, 4-diazo-3-dihydroxyphosphinylmethyldiphenylamine, 4-diazo-3-( 2-dihydroxyphosphinylethyl) diphenylamine, 4-diazo-3-(
2-dihydroxyphosphinyloxyethyl) diphenylamine, 4-diazo-2,5-bis-(dihydroxyphosphinylmethoxy) diphenylamine, 4-diazo-2,5-bis-(dihydroxyphosphinyloxymethoxy) diphenylamine, 4-Diazo-2,5-bis-(3-dihydroxyphosphinylpropoxy)diphenylamine, 4-diazo-2,5-bis-(3-dihydroxyphosphinyloxypropoxy)diphenylamine, 4-diazo-4'- Dihydroxyphosphinyl diphenyl ether, 4-diazo-4'-dihydroxyphosphinyloxyphenyl ether, 4-diazo-4'-
Dihydroxyphosphinyl diphenyl sulfide, 4-
Diazo-4'-dihydroxyphosphinyloxydiphenyl sulfide, 4-diazo-2-dihydroxyphosphinyldiphenyl ether, 4-diazo-2-dihydroxyphosphinyloxydiphenyl ether, 4-diazo-3-dihydroxyphosphinyldiphenyl ether, 4-Diazo-3-dihydroxyoxydiphenyl ether, 4-diazo-3-dihydroxyphosphinyldiphenyl sulfide, 4-diazo-3-dihydroxyphosphinyloxydiphenyl sulfide, 4-diazo-
4'-dihydroxyphosphinylmethyldiphenyl ether, 4-diazo-4'-dihydroxyphosphinyloxymethyldiphenyl ether, 4-diazo-4'-(
2-dihydroxyphosphinylethyl)diphenyl ether, 4-diazo-4'-(2-dihydroxyphosphinyloxyethyl)diphenyl ether, 4-diazo-
4'-dihydroxyphosphinylmethyldiphenyl sulfide, 4-diazo-4'-dihydroxyphosphinyloxymethyldiphenyl sulfide, 4-diazo-4'
-(2-dihydroxyphosphinylethyl) diphenyl sulfide, 4-diazo-4'-(2-dihydroxyphosphinyloxyethyl) diphenyl sulfide, 4-
Diazo-4'-dihydroxyphosphinyl methoxydiphenyl ether, 4-diazo-4'-dihydroxyphosphinyloxymethoxydiphenyl ether, 4-diazo-4'-(2-dihydroxyphosphinyl ethoxy)
diphenyl sulfide, 4-diazo-4'-(2-dihydroxyphosphinyloxyethoxy) diphenyl sulfide, 4-diazo-2-(2-dihydroxyphosphinylethyl) diphenyl ether, 4-diazo-2-(
2-dihydroxyphosphinyloxyethyl) diphenyl sulfide, 4-diazo-3-dihydroxyphosphinylmethyl diphenyl ether, 4-diazo-3-dihydroxyphosphinyloxymethyl diphenyl sulfide, 4-diazo-4'-dihydroxyphosphino Oxydiphenylamine, 4-diazo-4'-dihydroxyphosphinodiphenylamine, 4-diazo-4'-hydroxyphosphinodiphenylamine, 4-diazo-4'-
Dihydroxyphosphinyldiphenylamine, 4-diazo-3-dihydroxyphosphinooxydiphenylamine, 4-diazo-3-dihydroxyphosphinodiphenylamine, 4-diazo-2-dihydroxyphosphinooxydiphenylamine, 4-diazo-2-dihydroxyphosphino Diphenylamine, 4-diazo-2'-hydroxyphosphinodiphenylamine, 4-diazo-2'
-dihydroxyphosphinyldiphenylamine, 4-diazo-4'-dihydroxyphosphinooxymethyldiphenylamine, 4-diazo-4'-dihydroxyphosphinomethyldiphenylamine, 4-diazo-4'-dihydroxyphosphinooxymethoxydiphenylamine,
4-Diazo-4'-dihydroxyphosphinomethoxydiphenylamine, 4-diazo-4'-(2-dihydroxyphosphinooxyethoxy)diphenylamine, 4-
Diazo-4'-(2-dihydroxyphosphinoethoxy)diphenylamine, 4-diazo-3-dihydroxyphosphinooxymethyldiphenylamine, 4-diazo-
Examples include 2-dihydroxyphosphinomethoxydiphenylamine, 4-diazo-2'-(2-hydroxyphosphinoethyl)diphenylamine, and 4-diazo-3'-(2-hydroxyphosphinylethoxy)diphenylamine.

The method for synthesizing the diazo resin of formula (III) used in the present invention includes, for example, a diazonium resin having one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, and a phosphorus oxygen acid group. The molar ratio of the compound to an active carbonyl compound having no acid group or an acetal thereof such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, iso-butyraldehyde, benzaldehyde, acetone, methyl ethyl ketone or acetophenone is preferably 1. :100 to 1:0.2, more preferably 1:10 to 1:0.5, in an acidic medium. When carrying out the condensation reaction, in order to adjust the acid group content of the diazo resin produced,
A diazonium compound having no acid group and/or an aromatic compound having neither an acid group nor a diazonium group can be used in combination.

Diazo resins (I) and (II) used in the present invention
Specific examples of the acidic medium used when synthesizing ) or (III) include strong acids such as hydrochloric acid, phosphoric acid, methanesulfonic acid, or sulfuric acid. These media are used in concentrations of at least 30% by weight, preferably from 70 to 100% by weight. Generally the balance is water, but may also consist partially or completely of organic solvents such as methanol, acetic acid, N-methylpyrrolidone, and the like. Good results are achieved, for example, with 85-93% phosphoric acid, 80-98% sulfuric acid or 90% methanesulfonic acid or mixtures of these acids.

The temperature during the condensation is about 0 to 70°C, preferably about 0 to 50°C. Next, diazo resin (I), (I
The counteranion X- of I) or (III) will be explained. X- represents an aliphatic or aromatic sulfonic acid anion, and preferred examples thereof include methanesulfonic acid, fluoroalkanesulfonic acids such as trifluoromethanesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, and camphor. Sulfonic acid, tolyloxy-3-propanesulfonic acid, nonylphenoxy-3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutylphenoxy-3-propanesulfonic acid, diamylphenoxy-
3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid, dibutylphenoxy-4-butanesulfonic acid, dinonylphenoxy-4-butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, p-chlorobenzene Sulfonic acid, 2,5
-dichlorobenzenesulfonic acid, sulfosalicylic acid, 2
, 5-dimethylbenzenesulfonic acid, p-acetylbenzenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5- Nitrobenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, butoxybenzenesulfonic acid, dodecyloxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid, Isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, butoxynaphthalenesulfonic acid, dodecyloxynaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid acid, 1-naphthol-5-sulfonic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, 1,8-dinitro-naphthalene-3,6-disulfonic acid, 4,4'-diazide-stilbene-3 , 3'-disulfonic acid, 1,2-naphthoquinone-2-diazido-4-sulfonic acid, 1,2-naphthoquinone-2-diazido-5-sulfonic acid and 1,2-naphthoquinone-1-diazido-4-sulfone Included are acid anions or mixtures of these anions. Particularly preferred among these anions are anions of alkyl-substituted naphthalene sulfonic acids such as butylnaphthalene sulfonic acid, dibutylnaphthalene sulfonic acid, dioctylnaphthalene sulfonic acid, and tributylnaphthalene sulfonic acid.

The diazo resin used in the present invention can have any molecular weight by varying the molar ratio of each monomer and the condensation conditions; The molecular weight must be about 400 in order to be used for
A number between about 800 and 5,000 is suitable, although numbers between about 100,000 and about 800 may be used. The photosensitive diazo resin described above is desirably used in combination with an alkali-soluble or swellable lipophilic polymer compound as a binder resin.

As this lipophilic polymer compound, the following (
1) Copolymers having the monomers shown in (15) as structural units and usually having a molecular weight of 10,000 to 200,000 are exemplified. (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) Acrylic acid, methacrylic acid, maleic anhydride,
Unsaturated carboxylic acids such as itaconic acid, (4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, (Substituted) alkyl acrylate such as N-dimethylaminoethyl acrylate, (5
) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 4-
(Substituted) alkyl methacrylates such as hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide , N-cyclohexyl acrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, and other acrylamides or methacrylamides, (7) Ethyl vinyl ether, 2-chloroethyl vinyl ether , vinyl ethers such as hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (8) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, (9) styrene, methyl Styrenes such as styrene and chloromethylstyrene, (10)
Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone; (11) olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene; (12)
N-vinylpyrrolidone, N-vinylcarbazole,
4-vinylpyridine, acrylonitrile, methacrylonitrile, etc., (13) maleimide, N-acryloyl acrylamide, N-acetylmethacrylamide, N-
Unsaturated imides such as propionyl methacrylamide and N-(p-chlorobenzoyl) methacrylamide, (14)
N-(o-aminosulfonylphenyl)methacrylamide, N-(m-aminosulfonylphenyl)methacrylamide, N-(p-amino)sulfonylphenylmethacrylamide, N-(1-(3-aminosulfonyl)
methacrylic acid amides such as naphthyl) methacrylamide, N-(2-aminosulfonylethyl)methacrylamide, acrylamides having the same substituents as above, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate ,p-
Aminosulfonylphenyl methacrylate, 1-(3-
unsaturated sulfonamides such as methacrylic esters such as aminosulfonylnaphthyl methacrylate, and acrylic esters having the same substituents as above. (1
5) Unsaturated monomers having a photocrosslinkable group in their side chains, such as N-[2-(methacryloyloxy)-ethyl]-2,3-dimethylmaleimide and vinyl cinnamate.

Furthermore, a monomer that can be copolymerized with the above monomer may be copolymerized. Copolymers obtained by copolymerizing the above monomers may also be modified with glycidyl methacrylate, glycidyl acrylate, etc., but are not limited thereto. More specifically, a copolymer having a hydroxyl group or a sulfonamide group containing the monomers listed in (1), (2), and (14) above is preferable, and a copolymer having an aromatic hydroxyl group or a sulfonamide group is preferable. Copolymers are more preferred.

The above copolymer preferably contains an unsaturated carboxylic acid listed in (3), and the preferred carboxylic acid value of the copolymer is 0 to 3 meq/g, more preferably 0.5. ~2.5 meq/g. The preferred molecular weight of the above copolymer is 10,000 to 150,000. In addition, the above copolymer may include polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin,
Novolak resin, natural resin, etc. may be added.

The lipophilic polymer compound used in the present invention is usually contained in the solid content of the photosensitive composition in an amount of 40 to 99% by weight, preferably 50 to 95% by weight. Further, the photosensitive diazo resin used in the present invention is usually contained in an amount of 1 to 60% by weight, preferably 3 to 40% by weight. A dye can further be used in the photosensitive composition of the present invention. The dye is
It is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development.

[0043] As the dye, one that "changes in 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 [manufactured by Hodogaya Chemical Co., Ltd.], Oil Blue #603 [manufactured by Orient Chemical Industry Co., Ltd.], Patent Pure Blue [manufactured by 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-diethylaminophenyl iminaphthoquinone,
Discoloration in which triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based pigments, such as cyano-p-diethylaminophenylacetanilide, change from colored to colorless or a different colored tone. Examples of agents include:

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 preferably, triphenylmethane and diphenylmethane dyes are effectively used, more preferably triphenylmethane dyes, and especially Victoria Pure Blue BOH. The above-mentioned dye is usually contained preferably in an amount of about 0.5 to about 10% by weight, more preferably in an amount of about 1 to 5% by weight in the photosensitive composition.

Various additives can be further added to the photosensitive composition of the present invention. For example, alkyl ethers (e.g. ethyl cellulose,
methyl cellulose), fluorine-based surfactants, nonionic surfactants (fluorine-based surfactants are particularly preferred),
Plasticizers to impart flexibility and abrasion resistance to coatings (e.g., butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate) , trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid (among them, tricresyl phosphate is particularly preferred), a liposensitizing agent for improving the liposensitivity of the image area (for example, Half esterified product of styrene-maleic anhydride copolymer with alcohol described in Japanese Patent Publication No. 55-527, novolak resin such as pt-butylphenol-formaldehyde resin, fluorine surfactant, 50% of p-hydroxystyrene fatty acid esters, etc.), stabilizers [e.g., phosphoric acid, phosphorous acid, organic acids (citric acid, oxalic acid, dipicolinic acid, benzenesulfonic acid, naphthalenesulfonic acid, sulfosalicylic acid,
4-methoxy-2-hydroxybenzophenone-5-sulfonic acid, tartaric acid, etc.)], development accelerators (eg, higher alcohols, acid anhydrides, etc.), and the like are preferably used. The amount of these additives added varies depending on the target and purpose of use, but is generally 0.01 to 30% by weight based on the total solid content.
It is.

When such a photosensitive composition is applied to the production of a photosensitive lithographic printing plate, it is coated on a suitable support. Supports used in the photosensitive lithographic printing plates include paper, plastics (e.g., polyethylene, polypropylene, polstyrene, etc.), laminated paper, aluminum (including aluminum alloys), metal plates such as zinc, copper, etc. , cellulose diacetate, cellulose triacetate,
Cellulose propionate, polyethylene terephthalate, polyethylene, polypropylene, polycarbonate,
Examples include plastic films such as polyvinyl acetal, paper or plastic films laminated or vapor-deposited with metals such as those mentioned above, and steel plates plated with aluminum or chrome. Composite supports are preferred. In addition, as aluminum materials, iron is about 0.3%, silicon is about 0.1%, and copper is about 0.00%.
IS material containing 5 to 0.03% titanium and 0.005 to 0.04% titanium is preferred.

[0048] Furthermore, the surface of the aluminum material is desirably treated for the purpose of increasing water retention and adhesion with the photosensitive layer. Examples of the surface roughening method include generally known methods such as brush polishing, ball polishing, electrolytic etching, chemical etching, liquid honing, and sandblasting, and combinations thereof. Preferably, brush polishing, electrolytic etching, and chemical Mention may be made of etching and liquid honing, among which surface roughening methods are particularly preferred which involve the use of electrolytic etching.

Furthermore, it is also preferable to perform electrolytic etching after polishing with a brush, as described in JP-A No. 54-63902. In addition, the electrolytic bath used in electrolytic etching is an aqueous solution containing an acid, an alkali, or a salt thereof, or an aqueous solution containing an organic solvent. Liquid is preferred. Further, the roughened aluminum plate is desmutted with an acid or alkali aqueous solution, if necessary. It is desirable that the aluminum plate thus obtained is subjected to anodizing treatment, and particularly preferred is a method of treatment in a bath containing sulfuric acid or phosphoric acid. Further, if necessary, surface treatment such as pore sealing treatment with an alkali silicate or hot water, or immersion in a water-soluble polymer compound or potassium fluorozirconate aqueous solution can be performed.

More specifically, the supports suitable for use in the present invention include 0.3% iron, 0.1% silicon, 0.01% copper, and 0.03% titanium.
The IS aluminum plate containing an alkali, preferably 1 to
Etching is performed by immersing the substrate in a 30% aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, etc. at a temperature of 20 to 80° C. for 5 seconds to 250 seconds. Approximately 1/5 of aluminum may be added to the etching bath.

[0051] Next, it is immersed in a 10 to 30% nitric acid or sulfuric acid aqueous solution at a temperature of 20 to 70°C for 5 to 250 seconds.
Neutralize and remove smut after alkali etching. After surface cleaning of this aluminum alloy plate, the following roughening treatment is performed. As the surface roughening treatment, brush polishing and/or electrolytic etching treatment is suitable.

[0052] For brush polishing, it is preferable to use a pumice stone-water suspension and a nylon brush, and the average surface roughness is preferably 0.25 to 0.9μ. The electrolytic solution used in the electrolytic etching process is an aqueous solution of hydrochloric acid or nitric acid, and the concentration is preferably in the range of 0.01 to 3% by weight, more preferably 0.05 to 2.5% by weight. preferable. In addition, corrosion inhibitors (or stabilizers) such as nitrates, chlorides, monoamines, diamines, aldehydes, phosphoric acid, chromic acid, boric acid, oxalic acid, and ammonium salts are added to this electrolyte as necessary. , grain leveling agent, etc. can be added. In addition, an appropriate amount (1 to 10 g/l) is added to the electrolyte.
) may contain aluminum ions.

[0053] The temperature of the electrolytic solution is usually 10 to 60°C. The alternating current used at this time can be any rectangular wave, trapezoidal wave, or sine wave as long as the positive and negative polarities are alternately exchanged. Alternating current can be used. Also, the current density is
It is desirable to process at 5 to 100 A/dm2 for 10 to 300 seconds.

[0054] The surface roughness of the aluminum alloy support in the present invention is adjusted by the amount of electricity, and is 0.2 to 0.8μ.
Let it be m. It is preferable that smut adhering to the surface of the thus grained aluminum alloy be removed using 10 to 50% hot sulfuric acid (40 to 60° C.) or dilute alkali (sodium hydroxide, etc.). If removed with alkali, it is subsequently neutralized by immersion in acid (nitric acid or sulfuric acid) for cleaning.

After removing the smut from the surface, an anodic oxide film is provided. Although conventionally well-known methods can be used for the anodic oxidation method, sulfuric acid is used as the most useful electrolyte. Subsequently, phosphoric acid is also a useful electrolyte. Furthermore, JP-A-55-28400
Also useful are the mixed acids of sulfuric acid and phosphoric acid disclosed in the US Pat.

[0056] In the sulfuric acid method, treatment is usually carried out using direct current, but alternating current can also be used. The concentration of sulfuric acid is 5~
Used at 30%, 5-25 in the temperature range of 20-60℃
Electrolytic treatment is performed for 0 seconds to form an oxide film of 1 to 10 g/m2 on the surface. It is preferable that this electrolytic solution contains aluminum ions. Further, the current density at this time is preferably 1 to 20 A/dm2. In the case of the phosphoric acid method, at a concentration of 5-50% and a temperature of 30-60°C,
The treatment is carried out for 10-300 seconds at a current density of 1-15 A/dm2.

It is desirable that the thus treated aluminum support is further subjected to a surface treatment with silicates as described in US Pat. No. 2,714,066. To provide the above photosensitive composition on a support, predetermined amounts of a photosensitive diazo resin, a lipophilic polymer compound, and various additives as necessary are mixed with a suitable solvent (methyl cellosolve, ethyl cellosolve, dimethoxy Ethane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl acetamide, cyclohexanone, dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, ethylene dichloride, dimethyl sulfoxide , water, a mixture thereof, etc.) to prepare a coating solution of the photosensitive composition, and this may be coated on a support and dried. It is desirable that the solid content concentration of the photosensitive composition at the time of coating is in the range of 1 to 50% by weight. In this case, the coating amount of the photosensitive composition may be approximately 0.2 to 10 g/m2 (dry weight).

[0058] It is preferable to provide a matte layer constituted by projections provided independently of each other on the photosensitive layer. The purpose of the matte layer is to improve the vacuum adhesion between the negative image film and the photosensitive lithographic printing plate during contact exposure, thereby shortening the vacuum evacuation time and further preventing the collapse of minute halftone dots during exposure due to poor adhesion. That's true.

[0059] As a method for applying the matte layer, there is
-12974, a method of heat-sealing powdered solid powder, and a method of spraying and drying polymer-containing water described in JP-A-58-182636, any method may be used. However, it is desirable that the matte layer itself be soluble in or removable in an aqueous alkaline developer substantially free of organic solvents.

[0060] The solid powder used in the method of heat-sealing a powdered solid powder is preferably one in which the first transition point and the second transition point of the substance or composition are higher than 40°C, and the substance or composition is preferably Alternatively, the first-order transition point or second-order transition point of the composition is lower than the first-order transition point of the photosensitive layer. Specific examples include polyvinyl acetate, polyvinylidene chloride, polyethylene oxide, polyethylene glycol, polyacrylic acid, polyacrylamide,
Examples include polyacrylic esters, polystyrene and polystyrene derivatives, copolymers of these monomers, polyvinyl methyl ether, epoxy resins, phenol resins, polyamides, polyvinyl butyral, and the like.

The diameter of the solid powder particles is suitably in the range of about 0.5-40μ, preferably in the range of 1-17μ, particularly preferably in the range of 1-8μ. Powdering can be carried out using known methods, for example J. J. Sokol, R. C. Hendrickson, Plastics Engineering
Handbook, P. 426, P. 431 (1976)
(J. J. Sokol and R. C. He
ndrickson Plastic Eng. Ha
ndbook (1976))
In addition to electrostatic spray, electrostatic fluidized bed, etc., methods using air spray, brush, buff, etc. may be used.

The amount of solid powder fixed on the surface of the photosensitive planographic printing plate is 1 solid powder per 1 mm2 of the photosensitive planographic printing plate.
~1,000 pieces is appropriate, and 5~500 pieces is preferable. The solid powder powdered and deposited on the surface of a photosensitive lithographic printing plate is generally randomly distributed. In order to fix the solid powder to the surface of the photosensitive planographic printing plate, the solid powder that has been powdered and adhered to the surface of the photosensitive planographic printing plate is fixed to the surface by heat.

That is, the surface of the solid powder is exposed to light by blowing heated air onto the powdered surface, or by passing the powdered photosensitive lithographic printing plate through a heated air chamber or between heated rolls to melt the surface of the solid powder. It adheres to the surface of the lithographic printing plate. In the present invention, an aqueous alkaline developer that does not substantially contain an organic solvent means that it does not contain an excessive amount of an organic solvent from the viewpoint of hygiene and safety, and generally the developer composition does not contain an excessive amount of organic solvent. There is no problem if the content is 2% by weight or less. The preferred organic solvent content is 1% by weight or less, and more preferably, it does not contain at all. Preferred alkaline agents used in the developer of the present invention include potassium silicate, lithium silicate, sodium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, Examples include potassium triphosphate, dibasic potassium phosphate, sodium carbonate, potassium carbonate, and the like. Among these, a developer containing an alkali silicate such as potassium silicate, lithium silicate, or sodium silicate is most preferable because it has good development gradation, and the composition of the alkali silicate is [S
iO2]/[M]=0.2~1.5 (here [SiO2
] and [M] represent the molar concentration of SiO2 and the molar concentration of total alkali metals, respectively. ), and SiO2 is 0.
A developer containing 4 to 8% by weight is preferably used. The pH (25° C.) of the developer according to the present invention is 12 or more, preferably 12.5 to 14.

[0064] Also, in the developer, JP-A-50-5132
Anionic surfactants and amphoteric surfactants as described in Japanese Patent Application Laid-Open No. 59-75255 and Japanese Patent Application Laid-open No. 60-111246. By containing at least one of the agents, or by containing a polymer electrolyte as described in JP-A-55-95946 and JP-A-56-142528, photosensitive compositions can be improved. It is possible to improve wettability and further enhance gradation. There is no particular limit to the amount of surfactant added, but
0.003 to 3% by weight is preferred, especially 0.006 to 1% by weight.
Concentrations in weight percent are preferred. Furthermore, it is preferable that the alkali silicate contains 20 mol% or more of potassium as the alkali metal in all the alkali metals, since the generation of insoluble matter in the developer is small, and more preferably 90 mol% or more of potassium. , most preferably when the potassium content is 100 mol%.

[0065] Further, additives such as an antifoaming agent and a water softener can also be included, if necessary. Examples of water softeners include phosphoric acid chelating agents such as polyphosphoric acid and its sodium salts, potassium salts and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylenediaminetriacetic acid, nitrilotriacetic acid, 1 , 2-diaminocyclohexanetetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) ), diethylenetriaminepenta(methylenephosphonic acid), triethylenetetraminehexa(methylenephosphonic acid), hydroxyethylethylenediaminetri(methylenephosphonic acid), 1-hydroxyethane-
Examples include phosphonic acid-based chelating agents such as 1,1-diphosphonic acid and phosphonotricarboxylic acid, and their sodium salts, potassium salts, and ammonium salts. The optimum amount of such water softeners varies depending on the hardness of the hard water used and the amount used, but the general amount used is 0.01 to 5% by weight in the developer when used. ,
More preferably, it is contained in a range of 0.01 to 0.5% by weight.

As such an aqueous alkaline developer containing substantially no organic solvent, for example, Japanese Patent Application Laid-Open No. 59-8424
1 and JP-A No. 57-192952, etc., developer compositions used when developing a positive planographic printing plate after image exposure can be mentioned. Furthermore, various methods can be considered as development process systems for this type of photosensitive lithographic printing plate. The analogy is Japanese Patent Application Publication No. 54-6
As described in No. 2004, the processing capacity is restored by using a replenisher whose processing capacity has decreased due to the alkaline aqueous solution being consumed depending on the processing amount or the alkali concentration being reduced by air due to long-term operation of the automatic developer. , Japanese Patent Publication No. 1983
A method of automatically controlling the replenishment amount of replenisher as described in Japanese Patent Application Laid-open No. 1-303440, a method such as providing a floating lid above the developing bath, and a method of automatically controlling the amount of replenishment solution as described in There is a method using a dip-type developing bath as described in Japanese Patent No. 3065. These techniques are summarized as the automatic processor Stavron series manufactured by Fuji Photo Film Co., Ltd., and therefore it is particularly preferable to use an automatic processor of the Stavron series in the present invention.

[0067] It is desirable that the developed lithographic printing plate be washed with water to remove the developing solution adhering to the plate before being desensitized. In particular, the pH of the washing water is JP-A-63-17226.
It is preferable that the temperature be controlled by the method described in No. 9. Next, in the present invention, desensitization treatment is performed using a finisher containing 0 to 5% by weight of gum arabic. If a lithographic printing plate having a photosensitive layer containing a diazonium compound with an alkali-soluble group as used in the present invention is desensitized with a finisher containing more than 5% by weight of gum arabic, poor inking may occur during printing. occurs. The content of gum arabic should be 0-5% by weight, more preferably 0-2% by weight.

[0068] Conventionally, known types of finishers include a uniform solution type, a solubilized type in which a lipophilic component is solubilized, and an emulsion type in which a lipophilic component is emulsified and dispersed, and any of these types may be used. Various compounds can be used as components in the finisher other than gum arabic, but the finisher contains a water-soluble organic polymer compound as an essential component. Examples of water-soluble organic polymer compounds include the following.

Roasted starches such as white dextrin, yellow dextrin and British gum, enzyme-modified dextrins such as enzymatically decomposed tegistrin and Schardinger's dextrin, acid decomposed starches as shown in solubilized starch, oxidized starches as shown in dialdehyde starch,
Pregelatinized starches such as modified pregelatinized starch and undenatured pregelatinized starch, esterified starches such as phosphate starch, fatty starch, sulfate starch, nitrate starch, xanthate starch and carbamate starch, carboxyalkyl starch, hydroxyalkyl starch, Etherified starches such as sulfoalkyl starch, cyanoethyl starch, allyl starch, benzyl starch, carbamylethyl starch and dialkylaminoalkyl starch, crosslinking such as methylol crosslinked starch, hydroxyalkyl crosslinked starch, phosphoric acid crosslinked starch and dicarboxylic acid crosslinked starch starch,
Starch polyacrylamide copolymer, starch polyacrylic acid copolymer, starch polyvinyl acetate copolymer,
Starch graft copolymers such as starch polyacrylonitrile copolymers, cationic starch polyacrylic acid ester copolymers, cationic acid starch vinyl polymer copolymers, starch polystyrene maleic acid copolymers, and starch polyethylene oxide copolymers; Starches such as starch, potato starch, tapioca starch, wheat starch and corn starch, and their derivatives, carrageenan, laminaran, sea buckthorn mannan,
Those obtained from algae such as funori, Irish moss, agar and sodium alginate, vegetable mucilage such as succulent mallow, mannan, quince seed, and pectin, homopolysaccharides such as dextran, glucan and levan, and succinoglucan and xanthan gum. Microbial mucilages such as heteropolysaccharides, water-soluble cellulose ethers such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose, polyvinyl alcohol and its derivatives, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, vinyl Copolymers of methyl ether and maleic anhydride, etc.

These can be used alone or in combination of two or more. Among these, particularly preferred are modified starch, dextrin, and carboxymethyl cellulose. These water-soluble organic polymer compounds are preferably contained in the finisher in an amount of 1 to 30% by weight. Various compounds shown below can be used as components other than the water-soluble organic polymer compound.

For example, the following surfactants are also preferably used. For example, fatty acid salts, alkyl sulfate ester salts, alkyl sulfonate salts, alkylbenzene sulfonate salts, alkylnaphthalene sulfonate salts, dialkyl sulfosuccinate ester salts, alkyl phosphate ester salts, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester Anionic surfactants such as salts, polyoxyethylene alkylphenol ether sulfates, and alkyl phosphates are particularly preferred, among which dialkyl sulfosuccinates and polyoxyethylene alkylphenol ether sulfates are particularly preferred.

Further, as nonionic surfactants, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, glycerin fatty acid ester, phosphoric acid of oxyethylene oxypropylene block polymer alkanols, etc. Examples include esters. The preferred HLB value expressing the balance between hydrophilicity and lipophilicity of a nonionic surfactant is 12 or more in the case of a solution type finisher and 14 or less in the case of an emulsion type finisher.

Further examples include cationic surfactants such as alkylamine salts, quaternary ammonium salts, and polyoxyethylene alkylamine salts, and amphoteric surfactants typified by betaine surfactants such as alkylbetaine. can do. Two or more of these surfactants may be used in combination.

The above surfactants can be used in an amount of about 0.001 to about 5% by weight, more preferably 0.005 to 3% by weight, based on the total weight of the finisher liquid. Furthermore, monohydric alcohols such as propanol, butanol, pentanol, hexanol, octanol, and benzyl alcohol may be added. Polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerin, sorbitol, and polyethylene glycol are preferably used as wetting agents. It is preferable to add the wetting agent in an amount of 0.01 to 1% by weight.

Further, phosphorus-containing acids and their salts such as phosphoric acid, polyphosphoric acid, organic phosphonic acid, phytic acid, hexametaphosphoric acid, oxalic acid, succinic acid, citric acid, tartaric acid, lactic acid, acetic acid dehydroacetic acid, benzoic acid, p - Organic acids and their salts such as toluenesulfonic acid and salicylic acid, and inorganic acids and their salts such as hydrochloric acid, nitric acid, sulfuric acid, boric acid and molybdic acid may be added. As the salt, an alkali metal salt or an ammonium salt is preferred.

These acids may be used alone or in combination of two or more. Among these, phosphoric acid and succinic acid are particularly preferred since they have the effect of desensitizing the non-image areas of the lithographic printing plate. The amount of acid used depends on the pH of the finisher.
The amount is such that the amount of carbon is at an appropriate value, and is usually 0.05 to 5% by weight. Furthermore, it is also preferable to add a chelating agent such as EDTA, a silicone resin, an antifoaming agent such as a lower alcohol, and a preservative. Examples of preservatives include benzoic acid and its derivatives, phenol-formalin, sodium dehydroacetate, and isothiazolone compounds, etc.
It is preferable to add it in a range of 2.0% by weight.

Furthermore, a so-called emulsion type finisher in which a lipophilic component is added and emulsified and dispersed is also preferably used. An organic solvent and a surfactant are essential in the oil phase of an emulsion type finisher. The organic solvents used are water-insoluble, such as hydrocarbons such as turpentine, xylene, toluene, n-heptane, solvent naphtha, kerosene, mineral spirits, petroleum fractions with a boiling point of about 120° to about 250°C. such as dibutyl phthalate,
Diheptyl phthalate, di-n-octyl phthalate,
Phthalic acid diesters such as di(2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butylbenzyl phthalate,
Aliphatic dibasic acid esters such as dioctyl adipate, butyl glycol adipate, dioctyl azelate, dibutyl sebacate, di(2-ethylhexyl) sebacate, dioctyl sebacate, epoxidized triglycerides such as epoxidized soybean oil, e.g. Phosphate esters such as tricresyl phosphate, trioctyl phosphate, and trichloroethyl phosphate, and benzoate esters such as benzyl benzoate, have a freezing point of 15°C or lower and a boiling point of 300°C at 1 atmosphere. The above plasticizers are included.

Other lipophilic substances contained in the lipophilic phase include:
Melamine resins, alkyd resins, polyester resins, epoxy resins, rosins such as hydrogenated rosins, modified rosins such as rosin esters, petroleum resins such as gilsonite, such as oleic acid, lauric acid, valeric acid, nonyl acid,
Included are organic carboxylic acids having 5 to 25 carbon atoms, such as capric acid, mystilic acid, palmitic acid, and castor oil. These lipophilic substances can be used alone or in combination of two or more, and are 0.01 to 1% by weight, more preferably 0.05 to 1% by weight, based on the total weight of the finisher liquid.
It can be used in a range of 0.5% by weight.

Contains each of the above components and has a pH of 2.5 to 7.
If you use a finisher controlled to 5, it will be fleshed out,
Particularly good results are obtained on dirt. Treatment methods with desensitizing agents include dipping, roller application,
Various methods are possible, such as spraying the desensitizing agent from multiple nozzles onto the PS plate or roller, but it is necessary to use the desensitizing agent repeatedly, or to use a small amount of unused desensitizing agent each time. This makes it possible to greatly reduce the amount of desensitizing agent used per PS plate subjected to plate-making processing.

It is desirable that the lithographic printing plate treated with the desensitizing agent be squeegeeed so that the coating amount and coating thickness of the desensitizing agent are as uniform as possible and in an appropriate amount. The desired coating amount is 0.01 g/m2 or more, which increases the ability to prevent fingerprints from adhering to the plate surface in a dry state, and allows the desensitizing agent to be easily removed with a small amount of water before printing. 1 g/m2 or less. A more preferable coating amount is 0.05 g/m2 or more, which provides the ability to prevent scratches on the plate surface.
The amount is 0.5 g/m2 or less, which reduces coating unevenness including the edge portions (commonly called selvage portions) of the lithographic printing plate. Examples of methods for squeezing the surface of a lithographic printing plate include a method in which the lithographic printing plate is passed between a pair of elastic rollers whose surfaces are coated with an elastic material such as rubber, and the liquid on the plate surface is removed by the nip pressure. Roller materials include butyl rubber, nitrile butadiene rubber, ethylene propylene rubber, acrylic rubber, silicone rubber, fluorine rubber,
Polysulfide rubber and the like are preferred.

[0081] The lithographic printing plate treated with the desensitizing agent is preferably dried to prevent dust from adhering thereto or to facilitate handling. The preferred drying temperature is 20°C to 120°C. The lithographic printing plate thus obtained can be subjected to steps such as development ink application, addition, erasure-washing, erasure-washing-desensitization treatment, etc., as necessary before printing.

[0082]

Effects of the Invention In the present invention, as a result of using a finisher with a gum arabic content of 0 to 5% by weight, hydrophilic groups such as carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, sulfinic acid groups, and phosphorus oxygen acid groups Even if the lithographic printing plate is obtained by developing a photosensitive lithographic printing plate having a photosensitive layer containing a diazo compound having a highly reactive group with a developer containing no organic solvent and having a pH of 12 or more, The meat quality never deteriorates.

[0083] Since the present invention uses an aqueous alkaline developer that does not substantially contain an organic solvent during development processing, there are no hygiene problems such as toxicity and odor during work, and safety problems such as fire and gas explosion. Furthermore, there is no problem of pollution caused by waste liquid, and it can be implemented at low cost. Further, in the present invention, a negative-working planographic printing plate can be developed using an aqueous alkaline developer that is known as a developer for positive-working planographic printing plates. For this reason, when processing both positive-working planographic printing plates and negative-working planographic printing plates, it is necessary to prepare developer compositions suitable for each, or to change the developer compositions.
It becomes possible to save time and effort such as preparing two types of developer compositions and development processing equipment in advance, and work efficiency, equipment costs, installation space, etc. are significantly improved.

Next, a typical structural example of the diazo resin according to the present invention will be shown.

[0085]

[Synthesis Example] Synthesis of Diazo Resin-1 3.5 g (0.025 mol) of p-hydroxybenzoic acid and 7.1 g (0.025 mol) of 4-diazodiphenylamine sulfate.
025 mol) was dissolved in 90 g of concentrated sulfuric acid under water cooling. After this reaction, 2.7 g of paraformaldehyde (0.09
mol) was added slowly. At this time, the reaction temperature was 10℃
It was added so as not to exceed. 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 dissolved in 300 ml of pure water. Add 28.7 ml of sodium dibutylnaphthalene sulfonate to this solution.
A cold concentrated aqueous solution of g was added. The resulting precipitate was filtered, washed with water, and then dried at 30°C for 1 day to obtain diazo resin-1.
I got it.

The molecular weight of this diazo resin-1 was measured by GPC (gel permeation chromatography), and the weight average molecular weight was about 1,600. Synthesis of Diazo Resin-2 Diazo Resin-2 was obtained in the same manner as in the synthesis of Diazo Resin-1, except that p-hydroxybenzoic acid was replaced with 4.5 g of sodium benzenesulfonate.

[0087] The molecular weight was measured by GPC, and the weight average molecular weight was 1,650. Synthesis of diazo resin-3 6.1 g (0.040 mol) of phenoxyacetic acid and 4-
Diazodiphenylamine sulfate 11.3g (0.040
mol) was dissolved in 90 g of concentrated sulfuric acid under water cooling. After this reaction 3.0 g of paraformaldehyde (0.10 mol)
was added slowly. 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 41 g of sodium dibutylnaphthalene sulfonate was dissolved. The resulting precipitate was filtered, washed with water, and then dried at 30°C for one day and night to obtain diazo resin 3. This diazo cocondensation resin
When the molecular weight of No. 3 was measured by GPC, the weight average molecular weight was about 2,300. Synthesis of Diazo Resin-4 14.5 g (50 mmol) of p-diazodiphenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under ice cooling. 1.5 g (50 mmol) of paraformaldehyde was slowly added dropwise to this reaction solution. At this time, the reaction temperature was 10℃
It was added so as not to exceed. Thereafter, stirring was continued under ice cooling for 2 hours.

[0088] This reaction mixture was diluted with 500 ml under ice cooling.
was added dropwise to ethanol, and the resulting precipitate was filtered. 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. To this liquid was added a cold concentrated aqueous solution in which 16.8 g of sodium dibutylnaphthalene sulfonate was dissolved. After filtering the resulting precipitate and washing with water,
Diazo resin-4 was obtained by drying at 30°C for one day and night.

When the molecular weight of this diazo resin-4 was measured by GPC, it was found that it contained about 50 mol% of pentamers or more. The molecular weight was 1,970. Next, an example of synthesis of a lipophilic polymer compound will be shown. Synthesis of lipophilic polymer compound-1 N-(4-hydroxyphenyl) methacrylamide 53
g, acrylonitrile 16g, methyl methacrylate 30
g, 8 g of ethyl acrylate, 2 g of methacrylic acid, and 3.3 g of azobisisobutyronitrile were dissolved in 220 ml of an acetone-ethanol 1:1 mixed solution, and the mixture was purged with nitrogen and then heated at 60° C. for 8 hours.

After the reaction was completed, the reaction solution was poured into 5 liters of water with stirring, and the resulting white precipitate was filtered and dried to obtain 90 g of polymer compound-1. This lipophilic polymer compound-1 is
When the molecular weight was measured by PC, the weight average molecular weight was 29,000. Synthesis of lipophilic polymer compound-2 N-(p-aminosulfonylphenyl)methacrylamide 4.57 g (0.0192 mol), acrylonitrile 2.55 (0.0480 mol), methacrylic acid 1.66 g (0.0192 mol), Benzyl acrylate 18.40g (0.1136mol), α, α'
-Azobisisobutyronitrile 0.41g and N,N-
25 g of dimethylformamide was placed in a 100 ml three-necked flask equipped with a stirrer and a cooling tube, and stirred for 5 hours while warming to 64°C. This reaction mixture was poured into 2 liters of water with stirring, stirred for 30 minutes, filtered and dried to obtain 19 g of polymer compound-2. The weight average molecular weight (polystyrene standard) of this polymer compound-2 was measured by GPC and found to be 18,000. Example 1 0.02% copper, 0.01% titanium, 0.30% iron
A JISA1050 aluminum plate containing 0.1 silicon was etched in a 5% aqueous sodium hydroxide solution at 50°C for 10 seconds, then neutralized in a 30% nitric acid bath at 25°C for 30 seconds, and then etched in a 2% hydrochloric acid bath. Inside 25℃, 20A/d
Electrolytically etched at a current density of m2, then at 1
% sodium hydroxide aqueous solution for 30 seconds, washed with water, and anodized in a 15% sulfuric acid bath at 30° C. and 1.5 A/dm 2 for 2 minutes. Next, the pores were sealed in a 1% aqueous sodium metasilicate solution at 85° C. for 30 seconds, washed with water, and dried to obtain an aluminum plate for lithographic printing. Photosensitive liquid 1 having the following composition was coated on this aluminum plate using a whiler coater so that the film weight after drying was 2.4 g/m<2>.

[0091] Drying in this case was carried out at 100°C for 1 minute. Photosensitive liquid-1 Lipophilic polymer compound-1
5.0g
Diazo resin-1
0.
6g Victoria Pure Blue BOH
0.1g
(Manufactured by Hodogaya Chemical Co., Ltd.) Julimar AC-10L
0.3g
(manufactured by Nippon Pure Chemical Industries, Ltd.) Methyl cellosolve
50
ml methanol

30ml methyl ethyl ketone

20 ml On top of this photosensitive layer, a solid powder consisting of the resin shown below, which had been ground with a ball mill and classified with a classifier (albime zigzag classifier), was powdered with a spray gun, and the mixture was placed in an air bath at 150°C for 5 minutes. It was exposed for a second to allow it to solidify. The amount of powder per 1 mm2 was 55 pieces. Solid powder resin: Styrene/methyl acrylate/acrylic acid (2:1:1) copolymer powder particle size 0.5-10 (μ
) The obtained photosensitive lithographic printing plate was brought into close contact with a negative transparent original image and a step wedge (optical density increased in steps of 0.150) and exposed for 30 seconds from a distance of 1 m using a 5 KW metal halide lamp.

Further, development processing was carried out under the following conditions. Namely, the automatic processor Stablen 9 manufactured by Fuji Photo Film Co., Ltd.
The following developer-1 was added to the first bath of 00D, water was added to the second bath, and the following finisher-1 was added to the third bath, and processing was carried out at a developer temperature of 30° C. to obtain a lithographic printing plate. Composition of developer-1 1K potassium silicate
60
g potassium hydroxide

12g boron surfactant

0.1g (Emalbon T-20) Chelating agent

0.1g (EDTA) Silicone antifoaming agent

0.1g (Toshiba Silicon TSA-731
) cobalt acetate

0.3g water

The pH of 600 g developer solution-1 was 13.1. Composition of finisher-1 Gum arabic

10g hydroxypropylating enzyme
150g
Modified dextrin Urea-phosphorylated starch
20g
Sodium alkyl sulfosuccinate
3g (Rapizole B-80 manufactured by NOF Corporation) Anionic surfactant
10g (Eleminol MON2 manufactured by Sanyo Chemical Co., Ltd.) Ethylene glycol
20g ammonium phosphate
2g sodium hydroxide
1g sodium dehydroacetate
1g silicone antifoaming agent
0.3g
EDTA

5g water

The pH of 777.7g Finisher-1 was 6.3.

The lithographic printing plate thus obtained was used to print on high-quality paper using a commercially available ink using a Heidelberg SOR printing machine. Table 1 shows the number of sheets on which ink was sufficiently applied to the paper from the start of printing, that is, the number of sheets on which ink was applied. Example 2 The same procedure as in Example 1 was carried out except that diazo resin-1 in photosensitive liquid-1 in Example 1 was replaced with diazo resin-2. Example 3 0.01% copper, 0.03% titanium, 0.3% iron,
After graining the surface of a 0.24 mm thick IS aluminum plate containing 0.1% silicon using a nylon brush and an aqueous suspension of 400 mesh pumice stone,
Washed thoroughly with water. This was etched by immersing it in a 10% sodium hydroxide aqueous solution at 70°C for 60 seconds, then washed with running water, and neutralized with 20% nitric acid. VA = 12.7V.
, using sinusoidal alternating waveform current of VC = 9.1V, 1%
Electrolytic surface roughening treatment was carried out in a nitric acid aqueous solution with an anodic electricity amount of 160 coulombs/dm2. Subsequently, it was immersed in a 30% aqueous sulfuric acid solution and desmutted at 55°C for 2 minutes.
% sulfuric acid aqueous solution, the coating amount of aluminum oxide is 2.0g.
/m2. then 70
The sample was immersed in a 3% aqueous solution of sodium silicate at ℃ for 1 minute, washed with water and dried. Applying photosensitive liquid 3 shown below to the aluminum plate obtained as above using a wheeler,
It was dried at 80°C for 2 minutes. The dry weight was 1.8 g/m2. Photosensitive liquid-3 Lipophilic polymer compound-1
5.0g Diazo resin-3
1.1g Victoria Pure Blue BOH
0.2g (manufactured by Hodogaya Chemical Co., Ltd.) Fluorine surfactant F-177
0.02g (
Manufactured by Dainippon Ink Co., Ltd.) Tricresyl phosphate

0.1g malic acid

0.05g of styrene-maleic anhydride copolymer
g Harvest with n-hexyl alcohol
Fester 2-methoxypropanol
50g methanol
20g methyl lactate

10g of this photosensitive printing plate was coated with a 20% by weight aqueous solution of a copolymer having the composition shown below by electrostatic spraying, and dried by exposing it to an atmosphere at a temperature of 60°C for 5 seconds to form a surface of the photosensitive planographic printing plate. became matte.

Copolymer composition Methyl methacrylate-ethyl acrylate-2-acrylamide-2-methylpropanesulfonic acid sodium (5:3:2) Coating amount of copolymer: 0.1 g/m2, 50-100 pieces/
The number of droplets is mm2, and the height of the resin layer after drying is 2
~6μ, and the width was 20μ to 150μ.

The obtained photosensitive lithographic printing plate was exposed, developed and printed in the same manner as in Example 1. The results are shown in Table 1. Example 4 The same procedure as in Example 3 was carried out except that in the photosensitive liquid-3 in Example 3, lipophilic polymer compound-1 was replaced with lipophilic polymer compound-2. Example 5 The same procedure as Example 3 was carried out except that Finisher-1 in Example 3 was replaced with Finisher-2 having the following composition.

Composition of Finisher-2 Gum Arabic

15g octenyl succinate starch
70g
dextrin cream
100g
glycerin
20
g phosphoric acid (85%)

3g ammonium monophosphate

2g dibutyl sebacate

3g Nonionic surfactant (Nonion OP-80R manufactured by NOF Corporation)
) 3g Nonionic surfactant (Emulgen 903 manufactured by Kao Atlas Co., Ltd.
) 3g Sodium alkyl sulfosuccinate
20g (Rapizole B-80 manufactured by NOF Corporation) Polymerized rosin ester

3g water

763g This finisher was prepared by emulsifying and dispersing a lipophilic component in an aqueous solution. The pH of Finisher-2 was 3.2. Example 6 The automatic processing machine Stablen 900D in Example 1 was manufactured by Konica (
Example 1 was carried out in the same manner as in Example 1, except that PSU-820 (manufactured by Konica Corporation) was used and developer-1 was replaced with SDP-12 (manufactured by Konica Corporation). Note that the pH of SDP-12 was 13.0. Example 7 The same procedure as Example 1 was carried out except that the finisher in Example 1 was replaced with Finisher-3 having the following composition.

Composition of Finisher-3 Gum Arabic

45g Hydroxypropylating enzyme
80g
Modified dextrin carboxymethylcellulose
75g
Phosphoric acid (85%)
3.4g
calcium phosphate

0.6g Sodium hexametaphosphate
5
g Sodium alkyl sulfonate
7g
(Takemoto Yushi Co., Ltd. type Pionin A-32B)
Silicone antifoaming agent
0.
3g water

783.7g Finisher-3 pH
was 3.6. Example 8 The same procedure as in Example 1 was carried out except that Finisher 4 was used in which 10 g of gum arabic among the components of Finisher 1 in Example 1 was replaced with 10 g of carboxymethyl cellulose. Comparative Example 1 Example except that Finisher 5 was used, in which among the components of Finisher-1 in Example-1, 10 g of gum arabic was changed to 80 g, 150 g of hydroxypropylated enzyme-modified dextrin was changed to 100 g, and 20 g of urea phosphorylated starch was changed to 10 g. Same as 1. Comparative Example 2 The same procedure as in Example 5 was carried out except that Finisher 6 was used in which the components of Finisher 2 in Example 5 were changed from 15 g of gum arabic to 100 g and 15 g of dextrin cream. Comparative Example 3 The same procedure as in Example 7 was carried out, except that Finisher-7 was used in which the components of Finisher 3 in Example 7 were changed from 45 g of gum arabic to 75 g and 45 g of carboxymethyl cellulose. Comparative Example 4 The same procedure as Example 1 was carried out except that Diazo Resin-1 in Photosensitive Solution-1 in Example 1 was replaced with Diazo Resin-4. However, when the lithographic printing plate thus obtained was run on a printing press, stains occurred.

[0098]
Table 1────────────
────────────────────────Example Printing result of alkali-soluble group of diazo compound in finisher Gum arabic
Number of inlays Dirty
Content rate (%)
──────────────────────────
──────────── 1 carboxyl group and 1
10 None
Phenolic hydroxyl group 2 Sulfonic acid group 1
12 None 3
carboxyl group
1 12 None 4 Carboxyl group
1 12
None 5 Carboxyl group
1.5
8 None 6 Carboxyl group and 1
25 Slightly dirty
Phenolic hydroxyl group 7 carboxyl group and 4.5
40 None
Phenolic hydroxyl group 8 carboxyl group and 0
8 Slightly dirty
Phenolic hydroxyl group────────────
────────────────────────Comparative Example 1 Carboxyl group and
8 120 None Phenolic hydroxyl group
2 carboxyl group 1
0 90 None 3 Carboxyl group and
7.5 200 pieces
None Phenolic hydroxyl group
No fleshing 4 None
1
10 Stained From Table 1, in the method for producing a lithographic printing plate of the present invention, a finisher with a gum arabic content of 5% or less is used, so the photosensitive layer containing the above-mentioned highly hydrophilic diazo resin is heated to a pH of 12 or higher. It can be seen that even when developed with alkali, no defective ink adhesion occurs and no stains are generated, making it an extremely excellent product.

Claims (1)

[Claims] 1. A photosensitive layer containing, on a support, an aromatic diazonium compound having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, and a phosphorus oxygen acid group. After imagewise exposure of a photosensitive lithographic printing plate having
After developing with an aqueous alkaline developer having a pH of 12 or more and containing substantially no organic solvent, an insensitive resin is developed using a finisher containing a hydrophilic organic polymer compound and having a gum arabic content of 0 to 5% by weight. 1. A method for producing a lithographic printing plate, characterized by carrying out a chemical treatment.