JP2640573B2 - Method for developing photosensitive material containing diazo resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing a photosensitive material containing a diazo resin.

[0002]

2. Description of the Related Art In general, a photosensitive printing plate is prepared by applying a photosensitive composition onto a support such as an aluminum plate, irradiating the active composition such as ultraviolet rays through a negative image or the like, and polymerizing or irradiating the irradiated portion. Crosslinking and insolubilization in the developing solution, the non-irradiated portion of the light is eluted in the developing solution, and the respective portions are repelled by water to receive the oil-based ink, and by the non-light-receiving portion repelled by the oil-based ink. It is obtained by forming an image part.

In this case, the photosensitive composition includes:
Diazo resins such as condensates of p-diazodiphenylamine and formaldehyde have been widely used.

On the other hand, when developing a photosensitive lithographic printing plate using these diazo resins after exposure, examples of aqueous alkaline developer compositions used include, for example, JP-A-51-774.
No. 01, a developer composition comprising benzyl alcohol, an anionic surfactant, an alkali agent and water, benzyl alcohol, an anionic surfactant described in JP-A-53-44202, A developer composition comprising an aqueous solution containing a water-soluble sulfite;
155355, a developer composition containing an organic solvent having an solubility in water of 10% by weight or less at room temperature, an alkali agent and water, and the like.

All of these contain an organic substance such as an organic solvent and a surfactant in the developer composition. However, organic solvents are generally toxic and odorous, have a risk of fire, and have many disadvantages such as being subject to BOD regulations in waste liquids, and are expensive.

However, simply removing the organic solvent,
The desired development is not achieved. That is, if the development is carried out only by using a developing solution containing no organic solvent, a portion to be removed by the development remains, and this becomes a stain when used for printing. Such stains are unacceptable and cannot be put to practical use, especially when used as a photosensitive material for printing.

Further, while removing the organic solvent, the pH is adjusted to 12
It is conceivable to increase the development to increase the progress of development, but there is a problem of safety due to strong alkali and disposal of waste liquid.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems and to use a developing solution which does not contain an organic solvent, so that the problems associated with the use of an organic solvent can be solved. An object of the present invention is to provide a method for developing a diazo resin-containing light-sensitive material in which desired development is achieved and no stain or the like occurs even when used for printing.

It is a further object of the present invention to provide a work-related toxicity,
Aqueous alkaline developer containing virtually no organic solvent, free from odors and other hygiene problems, fire and gas explosion and other safety problems, foaming and other workability problems, and wastewater pollution. An object of the present invention is to provide a method capable of developing.

[0010]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that these objects can be achieved by using a novel photosensitive composition. Reached.

That is, according to the present invention, 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 an oxygen acid group of phosphorus is provided on a support. A photosensitive lithographic printing plate having a photosensitive layer
This is achieved by developing with an aqueous alkaline developer having a pH of 8 to less than 12 and substantially no organic solvent.

An aromatic compound having at least one of the carboxyl group, phenolic hydroxyl group, sulfonic acid group, sulfinic acid group and oxyacid group of phosphorus used in the present invention (hereinafter, these groups are also referred to as "acid group"). Examples of group diazonium compounds include (I), (II) and (II) shown below.
Examples shown in I) are given.

(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 an oxygen acid group of phosphorus, and an aromatic diazonium compound represented by the following general formula (A): Diazo resin containing as a structural unit:

[0014]

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In the formula, R ¹ represents a hydrogen atom, an optionally substituted alkyl group, a hydroxyl group, a carboxyester group or a carboxyl group, preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms. Or a hydroxyl group. R ² 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, and preferably represents a hydrogen atom. X ^- represents an anion, and Y-
NH-, -O- or -S- is shown.

The aromatic ring of the aromatic compound preferably includes a phenyl group or a naphthyl group. The carboxyl group, phenolic hydroxyl group,
The sulfonic acid group, sulfinic acid group and oxygen acid group of phosphorus may be directly bonded to the aromatic ring or may be bonded via a linking group. Examples of such a linking group include groups having 1 or more carbon atoms including an ether bond.

Specific examples of the aromatic compound having a carboxyl group in the molecule include benzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, phthalic acid, terephthalic acid, diphenylacetic acid, and phenoxy acid. Acetic 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
-Dimethoxy benzoic acid, 2,4-dimethylbenzoic acid, p-
Phenoxybenzoic acid, p-methoxyphenylacetic acid, 4-
Anilinobenzoic acid, 4- (m-methoxyanilino) benzoic 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, phloroglucin carboxylic acid, 2,
4,5-trihydroxybenzoic acid, m-galloyl gallic acid, tannic acid, m-benzoyl gallic acid, m- (p-
Toluyl) gallic acid, protocatechu oil-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,
-(2,4-dihydroxybenzoyl) benzoic acid, 4-
(P-hydroxyphenoxy) benzoic acid, 4- (p-hydroxyanilino) benzoic acid, bis (3-carboxy-
4-hydroxyphenyl) amine, 4- (p-hydroxysulfonyl) benzoic acid, 4- (p-hydroxyphenylthio) benzoic acid and the like.

Specific examples of the aromatic compound having a phenolic hydroxyl group include phenol, (o, m, p) -cresol, xylenol, resorcin, 2-methylresorcin, (o, m, p) -methoxyphenol, m-phenol -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 a sulfinic acid group include benzenesulfonic acid, p-toluenesulfonic acid, benzenesulfinic acid, p-toluenesulfinic acid, aniline-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-
Examples include naphthalenedisulfonic acid, 2-amino-1,5-naphthalenedisulfonic acid, and 2-sulfobenzoic acid.

These may be free sulfonic acids or sulfinic acids, metal salts such as sodium, potassium, cesium, calcium, barium, magnesium, aluminum and zinc, or unsubstituted or substituted ammonium salts. Is also good.

Specific examples of the aromatic compound having an oxygen acid group of phosphorus in the molecule include phenylphosphoric acid, phenylphosphorous acid, phenylphosphonic acid, phenylphosphonic acid, phenylphosphinic acid, phenylphosphinic acid, -Hydroxyphenylphosphoric acid, 4-hydroxyphenylphosphorous acid, 4-hydroxyphenylphosphonic acid, 4-hydroxyphenylphosphonic acid, 4-hydroxyphenylphosphinic acid, 4-hydroxyphenylphosphinic acid,
4-methylphenylphosphoric acid, 4-methylphenylphosphorous acid, 4-methylphenylphosphonic acid, 4-methylphenylphosphorous acid, 4-methylphenylphosphinic acid,
-Methylphenylphosphinous acid, 4-t-butylphenylphosphoric acid, 4-t-butylphenylphosphite, 4-t
-Butylphenylphosphonic acid, 4-t-butylphenylphosphonic acid, 4-t-butylphenylphosphinic acid,
4-t-butylphenylphosphinous acid, 4-aminophenylphosphoric acid, 4-aminophenylphosphorous acid, 4-aminophenylphosphonic acid, 4-aminophenylphosphonous acid, 4-aminophenylphosphinic acid, 4-amino Phenylphosphinous acid, 4-methoxyphenylphosphoric acid, 4
-Methoxyphenylphosphorous acid, 4-methoxyphenylphosphonic acid, 4-methoxyphenylphosphonic acid, 4-methoxyphenylphosphinic acid, 4-methoxyphenylphosphinous acid, 4-ethoxyphenylphosphoric acid, 4-ethoxyphenylphosphorous acid Acid, 4-ethoxyphenylphosphonic acid, 4-ethoxyphenylphosphonous acid, 4-ethoxyphenylphosphinic acid, 4-ethoxyphenylphosphinous acid, 4-ethylphenylphosphoric acid, 4-ethylphenylphosphorous acid, 4-ethyl Phenylphosphonic acid, 4-ethylphenylphosphonic acid, 4-ethylphenylphosphinic acid, 4-ethylphenylphosphinous acid, 2-aminophenylphosphoric acid, 2-aminophenylphosphoric acid, 2-aminophenylphosphonic acid, 2 -Aminophenylphosphonous acid, 2-amino Phenylphosphinic acid, 2-aminophenylphosphinous acid, 2,4-dimethylphenylphosphoric acid, 2,4-dimethylphenylphosphorous acid, 2,4-dimethylphenylphosphonic acid, 2,4-dimethylphenylphosphonic acid, 2,4-dimethylphenylphosphinic acid,
2,4-dimethylphenylphosphinous acid, 2,6-diaminophenylphosphoric acid, 2,6-diaminophenylphosphorous acid, 2,6-diaminophenylphosphonic acid, 2,6-
Diaminophenylphosphonous acid, 2,6-diaminophenylphosphinic acid, 2,6-diaminophenylphosphinous acid, 2,5-dihydroxyphenylphosphoric 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-hydroxyphenylphosphite, 2-amino-4
-Hydroxyphenylphosphonic acid, 2-amino-4-hydroxyphenylphosphonous acid, 2-amino-4-hydroxyphenylphosphinic acid, 2-amino-4-hydroxyphenylphosphinous acid, mesityl phosphoric acid, mesityl phosphorous acid, Tylphosphonic acid, mesityl phosphonous acid, mesityl phosphinic acid, mesityl phosphinous acid,
2,4-dihydroxy-6-methylphenyl phosphate,
2,4-dihydroxy-6-methylphenyl phosphite,
2,4-dihydroxy-6-methylphenylphosphonic acid, 2,4-dihydroxy-6-methylphenylphosphonic acid, 2,4-dihydroxy-6-methylphenylphosphinic acid, 2,4-dihydroxy-6-methylphenyl Phosphinous acid, benzylphosphoric acid, benzylphosphorous acid, benzylphosphonic acid, benzylphosphonous acid, benzylphosphinic acid, benzylphosphinous acid, 4-methoxybenzylphosphoric acid, 4-methoxybenzylphosphoric acid,
4-methoxybenzylphosphonic acid, 4-methoxybenzylphosphorous acid, 4-methoxybenzylphosphinic acid,
4-methoxybenzylphosphinous acid, 4-hydroxybenzylphosphoric acid, 4-hydroxybenzylphosphite, 4
-Hydroxybenzylphosphonic acid, 4-hydroxybenzylphosphonous acid, 4-hydroxybenzylphosphinic acid, 4-hydroxybenzylphosphinous acid, 4- (2
-Hydroxyethyl) phenylphosphoric acid, 4- (2-hydroxyethyl) phenylphosphorous acid, 4- (2-hydroxyethyl) phenylphosphonic acid, 4- (2-hydroxyethyl) phenylphosphonic acid, 4- (2 -Hydroxyethyl) phenylphosphinic acid, 4- (2-hydroxyethyl) phenylphosphinous acid, 2-phenylethylphosphoric acid, 2-phenylethylphosphorous acid, 2-phenylethylphosphonic acid, 2-phenylethylphosphonic acid , 2
-Phenylethyl phosphinic acid, 2-phenylethyl phosphinic acid, 1-naphthyl phosphoric acid, 1-naphthyl phosphite, 1-naphthyl phosphonic acid, 1-naphthyl phosphite, 1-naphthyl phosphinic acid, 1-naphthyl phosphine Acid, 2-naphthyl phosphoric acid, 2-naphthyl phosphite, 2-naphthyl phosphonic acid, 2-naphthyl phosphinous acid, 2-naphthyl phosphinic acid, 2-naphthyl phosphinous acid, 2-amino-1-naphthyl phosphoric acid, -Amino-1-naphthyl phosphite, 2-amino-1-naphthyl phosphonic acid, 2-amino-1-naphthyl phosphonous acid, 2
-Amino-1-naphthylphosphinic acid, 2-amino-1
-Naphthyl phosphinous acid, 4-amino-1-naphthyl phosphoric acid, 4-amino-1-naphthyl phosphite, 4-amino-1-naphthyl phosphonic acid, 4-amino-1-naphthyl phosphonous acid, 4-amino -1-naphthylphosphinic acid, 4-amino-1-naphthylphosphinous acid, 5-amino-2-naphthylphosphoric acid, 5-amino-2-naphthylphosphite, 5-amino-2-naphthylphosphonic acid, 5-
Amino-2-naphthylphosphonous acid, 5-amino-2-
Naphthylphosphinic acid, 5-amino-2-naphthylphosphinous acid, 4-amino-3-hydroxy-1-naphthylphosphoric acid, 4-amino-3-hydroxy-1-naphthylphosphonic acid, 4-amino-5-hydroxy- 1-naphthylphosphoric acid, 4-amino-5-hydroxy-1-naphthylphosphonic acid, 7-amino-3-hydroxy-2-naphthylphosphoric acid, 7-amino-3-hydroxy-2-naphthylphosphonic acid, 5-dimethylamino -2-naphthyl phosphate, 5-dimethylamino-2-naphthylphosphonic acid, 5
-Hydroxy-1-naphthyl phosphate, 5-hydroxy-
1-naphthylphosphonic acid, 5-methoxy-2-naphthylphosphoric acid, 5-methoxy-2-naphthylphosphonic acid, 4-
Phenoxyphenylphosphoric acid, 4-phenoxyphenylphosphonic acid, 4- (4-methoxyphenoxy) phenylphosphoric acid, 4- (4-methoxyphenoxy) phenylphosphonic acid, 4-diphenylaminophosphoric acid, 4-diphenylaminophosphoric acid, 4-diphenylaminophosphonic acid, 4-
Diphenylaminophosphonous acid, 4-diphenylaminophosphinic acid, 4-diphenylaminophosphinous acid,
4'-methoxy-4-diphenylaminophosphoric acid, 4'-
Methoxy-4-diphenylaminophosphoric acid, 4'-methoxy-4-diphenylaminophosphonic acid, 2-phenoxyethylphosphoric acid, 2-phenoxyethylphosphorous acid, 2-
Phenoxyethyl phosphonic acid, 2-phenoxyethyl phosphonous acid, 2-phenoxyethyl phosphinic acid,
Phenoxyethyl phosphinous acid, benzyl (2-dihydroxyphosphenyloxy) acetate, benzyl (2-dihydroxyphosphenyl) acetate, 4-methoxybenzyl, 2-dihydroxyphosphinyloxy acetate, 4-methoxybenzyl, 2-dihydroxyphos Phenyl acetate, phenyl 3-dihydroxyphosphinyloxypropionate, phenyl 3-dihydroxyphosphinylpropionate, 3-dihydroxyphosphinyloxypropionate (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-phosphoric acid, 2,
6-naphthalene-bis-phosphonic acid, 7-amino-1,
3-naphthalene-bis-phosphoric acid, 7-amino-1,3-
Naphthalene-bis-phosphonic acid, 3-methoxy-2,7
-Naphthalene-bis-phosphoric acid, 3-methoxy-2,7-
And naphthalene-bis-phosphonic acid.

Of these, particularly preferred are 4-methoxybenzoic acid, 3-chlorobenzoic acid, 2,4-dimethoxybenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, phenoxyacetic acid, phenylacetic acid, -Hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, benzenesulfonic acid, p-toluenesulfinic acid, 1-naphthalenesulfonic acid, phenylphosphoric acid and phenoxymethylphosphonic acid.

In the present invention, a condensation type resin (hereinafter referred to as a diazo co-condensation resin) of an active carbonyl compound containing at least one aromatic compound having an acid group and an aromatic diazonium compound as constituent units can be prepared by a known method. For example, Photographic Science and Engineering (Photo, Sci., Eng.), Vol. 17, p. 33 (1973), U.S. Pat. Nos. 2,063,631 and 2,679,4.
No. 98, JP-B-49-48001, diazonium salts, aromatic compounds having at least one acid group and aldehydes such as formaldehyde, acetaldehyde in sulfuric acid, phosphoric acid or hydrochloric acid.
It can be obtained by polycondensing propionaldehyde, butyraldehyde, iso-butyraldehyde, benzaldehyde or a ketone, for example, an active carbonyl compound such as acetone, methyl ethyl ketone or acetophenone, or an acetal thereof.

The aromatic compound having an acid group in the molecule, the aromatic diazonium compound and the active carbonyl compound or the acetal thereof can be freely combined with each other. It is possible. Further, a cocondensable aromatic compound having no acid group can be added for cocondensation. Here, examples of the aromatic compound that can be co-condensed include the aromatic compounds described in JP-B-49-48001.

In place of the active carbonyl compound or the acetal thereof, a methylol derivative described in JP-B-49-45322 and JP-B-49-45323, or JP-A-58-187925 is used. Olefinically unsaturated compounds as described can also be used.

By changing the molar ratio of these co-condensation components, the acid group content of the resulting diazo resin can be adjusted.

At this time, the molar ratio of the charged aromatic compound to the aromatic diazonium compound is 1: 0.1 to 0.1.
1: 1; preferably 1: 0.2 to 0.2: 1, more preferably 1: 0.5 to 0.2: 1. Further, in this case, the molar ratio of the total of the aromatic compound having an acid group and the aromatic diazonium compound to the active carbonyl compound is usually 1: 0.6 to 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, to obtain a diazo co-condensation resin.

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

[0029]

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In the formula, R ⁴ is a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, an oxygen acid group of phosphorus, or a group having at least one of them and having 15 or less carbon atoms. R ¹ , R ² , R ³ , X ^- and Y are the same as the groups represented by formula (A).

As a method for synthesizing the diazo resin (II) used in the present invention, for example, a 4-diazodiphenylamine skeleton,
A diazo monomer having a 4-diazodiphenylether skeleton or a 4-diazodiphenylsulfide skeleton and an aldehyde or an acetal thereof having one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group and an oxygen acid group of phosphorus; In a molar ratio of preferably 1:10 to 1: 0.05, more preferably 1: 2 to 1:
A method of condensing in an acidic medium at a ratio of 0.2 is exemplified. When performing 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 resulting diazo resin. Compounds or their acetal can be used in combination as a condensing agent. The above active carbonyl compound is most preferably formaldehyde, and its charging ratio is preferably from 0 to 5, more preferably from 0.1 to 1 in molar ratio to the diazo monomer.
In addition, when an aldehyde having one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group and an oxygen acid group of phosphorus and an active carbonyl compound not having the same are used, first, a diazo monomer is used. The above-mentioned aldehyde having an acid group is condensed in an acidic medium,
When post-condensation is performed using a more reactive, for example, active carbonyl compound such as formaldehyde or an acetal thereof, a higher molecular weight diazo resin can be obtained.

Further, in place of the above active carbonyl compounds or their acetal, JP-B-49-45322 is used.
And the olefinically unsaturated compounds described in JP-A-58-187925 can also be used.

The aldehyde having one of the carboxyl group, phenolic hydroxyl group, sulfonic acid group, sulfinic acid group and oxygen acid group of phosphorus or an acetal thereof preferably has a structure represented by the following general formula (C). Aldehydes or acetal thereof. Z-R ⁵ -CHO (C)

[Wherein, R ⁵ is a single bond or a divalent organic group having 0 to 14 carbon atoms which may have a substituent (for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group) Group). Examples of the group that can be substituted for R ⁵ include an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
Examples include a halogen atom, a hydroxy group, a substituted or unsubstituted amino group, a carboxyester group or a carboxyl group. Z is a carboxyl group, a phenolic hydroxyl group,
One of a sulfonic acid group, a sulfinic acid group and an oxygen acid group of phosphorus is shown. ]

Specific examples of the aldehyde having a carboxyl group or an acetal thereof include glyoxylic acid, malonaldehyde acid, succinaldehyde acid,
Methylsuccinaldehyde acid, 2-methoxysuccinaldehyde acid, 2-hydroxysuccinaldehyde acid, 2
-Chlorosuccinaldehyde acid, 2-aminosuccinaldehyde acid, glutaraldehyde acid, 2-methylglutaraldehyde acid, 2-methoxyglutaraldehyde acid,
2-hydroxyglutaraldehyde acid, 2-chloroglutaraldehyde acid, adipaldehyde acid, pimelinaldehyde acid, suberaldehyde acid, azelaic aldehyde acid, sebacic aldehyde acid, 2-formylmethylsuccinic acid, 2-formylethylsuccinic acid, formyl Methylmalonic 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, malealdehyde acid, fumaric acid, dibromomalealdehyde acid, glucuronic acid, galacturonic acid, mannuronic acid, idronic acid, guluronic acid,
Phthalaldehyde acid, 3,4-dimethoxyphthalaldehyde acid, isophthalaldehyde acid, terephthalaldehyde acid, 3-formyl-4-methoxybenzoic acid, 4-formylphthalic acid, 5-formylisophthalic acid, 4-formylmethylphthalic acid, 4-formylethylphthalic acid, 4-
Formylethoxyphthalic acid, 5-formylethoxyisophthalic acid, 4-carboxymethylphthalic acid, 3-formyl-1-naphthoic acid, 6-formyl-1-naphthoic acid,
Or, those acetals and the like can be mentioned.

Specific examples of the aldehyde having a phenolic hydroxyl group, a sulfonic acid group or a sulfinic acid group, or an acetal thereof include, for example, 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-hexanesulfonic 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-benzenedisulfonic acid, 2-formyl-1,3-benzenedisulfonic acid, 2-formyl-1
-Naphthalenesulfonic acid, 4-formyl-1-naphthalenesulfonic acid, 4-formyl-1-naphthalenesulfinic acid, 5-formyl-2-naphthalenesulfonic acid, 7-
Formyl-1,4-naphthalenedisulfonic acid, 5-amino-7-formyl-2-naphthalenesulfonic acid, 5-formyl-2-furansulfonic acid, 3-formyl-2-furansulfonic acid, 5-formyl-3- Furansulfonic 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, 2-sulfonylethyl p-formylbenzoate, 3-sulfonylpropyl p-formylbenzoate, 4-sulfonylbutyl m-formylbenzoate, p-sulfonylbenzoate-
2-formylethyl, 3-formylpropyl p-sulfonylbenzoate, m-sulfonylphenyl 3-formylpropionate, N- (2-sulfonylethyl) -3-
Formylpropionamide, 2-sulfonylethyl 3-formylpropionate, N- (3-sulfonylphenyl) glyoxylate, N- (2-sulfonylethyl) glyoxylate, 2-sulfonylethyl glyoxylate, or a mixture thereof Acetal is an example.

Of course, these may be free sulfonic acids or sulfinic acids, metal salts of sodium, potassium, lithium, cesium, calcium, barium, magnesium, aluminum, zinc or unsubstituted or substituted ammonium. It may be a salt.

Specific examples of the aldehyde having an oxygen acid group of phosphorus or an acetal thereof include, for example, 2-oxo-
1-ethylphosphoric acid, 2-oxo-1-ethylphosphorous acid,
2-oxo-1-ethylphosphonic acid, 2-oxo-1-
Ethyl phosphonous acid, 2-oxo-1-ethylphosphinic acid, 2-oxo-1-ethylphosphinic acid, 3-oxo-1-propylphosphoric acid, 3-oxo-1-propylphosphoric acid, 3-oxo -1-propylphosphonic acid, 3-
Oxo-1-propylphosphonous acid, 3-oxo-1-
Propylphosphinic acid, 3-oxo-1-propylphosphinous acid, 4-oxo-1-butylphosphoric acid, 4-oxo-1-butylphosphorous acid, 4-oxo-1-butylphosphonic acid, 4-oxo-1 -Butylphosphonous acid, 4-oxo-1-butylphosphinic acid, 4-oxo-1-butylphosphinous acid, 5-oxo-1-pentylphosphoric acid,
5-oxo-1-pentyl phosphite, 5-oxo-1-
Pentylphosphonic acid, 5-oxo-1-pentylphosphonous acid, 5-oxo-1-pentylphosphinic acid, 5-
Oxo-1-pentylphosphinic acid, 5-oxo-1-
Pentylphosphinous acid, 6-oxo-1-hexylphosphoric acid, 6-oxo-1-hexylphosphoric acid, 6-oxo-1-hexylphosphonic acid, 6-oxo-1-hexylphosphonic acid, 6-oxo- 1-hexylphosphinic acid, 6-oxo-1-hexylphosphinous acid, 2-formylphenylphosphoric acid, 2-formylphenylphosphite, 2-formylphenylphosphonic acid, 2-formylphenylphosphonous acid, 2-formyl Phenylphosphinic acid, 2-formylphenylphosphinous acid, 3-formylphenylphosphoric acid, 3-formylphenylphosphite, 3
-Formylphenylphosphonic acid, 3-formylphenylphosphonic acid, 3-formylphenylphosphinic acid, 3
-Formylphenyl phosphinous acid, 4-formylphenyl phosphoric acid, 4-formylphenyl phosphite, 4-formylphenylphosphonic acid, 4-formylphenyl phosphonous acid, 4-formylphenylphosphinic acid, 4-formylphenyl phosphine Acid, 2,2-dimethyl-3-
Oxo-1-propyl phosphoric acid, 2,2-dimethyl-3-
Oxo-1-propylphosphite, 2,2-dimethyl-3
-Oxo-1-propylphosphonic acid, 2,2-dimethyl-3-oxo-1-propylphosphonous acid, 2,2-dimethyl-3-oxo-1-propylphosphinic acid, 2,
2-dimethyl-3-oxo-1-propylphosphinous acid, 2,3-dimethyl-4-oxo-1-butylphosphoric acid, 2,3-dimethyl-4-oxo-1-butylphosphonic acid, 2-methyl- 6-oxo-1-hexyl phosphoric acid,
2-methyl-6-oxo-1-hexylphosphonic acid, 2
-Formyl-4-methoxyphenylphosphoric acid, 2-formyl-4-methoxyphenylphosphonic acid, 4-amino-3
-Formylphenylphosphoric acid, 4-amino-3-formylphenylphosphonic acid, 4- (2-oxoethyl) phenylphosphonic acid, 4- (2-oxoethyl) phenylphosphonic acid, 3- (3-oxopropyl) phenylphosphoric 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-naphthyl phosphoric acid, 2-formyl-1-naphthylphosphonic acid, 4-formyl-1-naphthyl phosphoric acid, 4-formyl-1-naphthylphosphonic acid, 5-formyl-2-naphthyl phosphoric acid, 5-formyl-2 -Naphthylphosphonic acid, 1,4-bis- (dihydroxyphosphinyloxy) -7-naphthylaldehyde, 1,4-bis- (dihydroxyphosphinyl) -7-naphthylaldehyde, 5-amino-7-formyl- 2-naphthyl phosphoric acid, 5-amino-7-formyl-2-naphthylphosphonic acid, 5-formyl-2-furyl phosphoric acid, 5-formyl-
2-furylphosphonic acid, 3-formyl-2-furylphosphoric acid, 3-formyl-2-furylphosphonic acid, 5-formyl-3-furylphosphoric acid, 5-formyl-3-furylphosphonic acid, 1-oxo-1- Methyl phosphate, 1-oxo-
1-methylphosphonic acid, 3- (4-formylphenoxy) -1-propylphosphoric acid, 3- (4-formylphenoxy) -1-propylphosphonic acid, 4- (4-formylphenoxy) -1-butylphosphoric acid, -(4-formylphenoxy) -1-butylphosphonic acid, 3- (3-formylphenoxy) -1-butylphosphoric 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- (4-dihydroxyphosphinyloxybutyl) benzoic acid, or Acetals and the like are mentioned.

(III) Formula (D) having at least one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group and an oxygen acid group of phosphorus;
A diazo resin obtained by a condensation reaction of an aromatic diazonium compound represented by (E) or (F) with an aldehyde or ketone or an equivalent of an active carbonyl compound thereof:

[0040]

Embedded image

In the formula, R ⁴ is a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group or an acid group of phosphorus, and R ¹ , R ² , R ³ , X ^- and Y are those of the above-mentioned general formula ( It is the same as the group shown in A).

Specific examples of the compound represented by 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, '-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-bis-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-diazodiphenylether-4'-sulfone Acid, 4-diazodiphenyl sulfide-4'-sulfonic acid, 4-diazodiphenyl ether-2-sulfonic acid, 4-diazodiphenyl ether-3-sulfonic acid, 4-diazodiphenyl sulfide-2-sulfonic acid, 4-diazodiphenyl sulfide -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'-sulfonylmethoxydiphenyl ether, 4-diazo-4'-(2-sulfonylethoxy) diphenyl sulfide, -Diazo-2- (2-sulfonylethyl) diphenyl ether, 4-diazo-3
-Sulfonylmethyldiphenyl 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'-dihydroxyphosphini 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'-
Ethyl diphenylamine, 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-
Dihydroxyphosphinyloxyethoxy) diphenylamine, 4-diazo-4 '-(2-dihydroxyphosphinyloxyethoxy) diphenylamine, 4-diazo-4'-(3-dihydroxyphosphinylpropoxy)
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,
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- (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- (dihydroxyphosphinylpropoxy) diphenylamine, 4-diazo-2,5-bis- (3-dihydroxyphosphinyloxypropoxy) diphenylamine , 4-diazo-4 '
-Dihydroxyphosphinyl diphenyl ether, 4-
Diazo-4'-dihydroxyphosphinyloxydiphenylether, 4-diazo-4'-dihydroxyphosphinyldiphenylsulfide, 4-diazo-4'-dihydroxyphosphinyloxydiphenylsulfide,
-Diazo-2-dihydroxyphosphinyl diphenyl ether, 4-diazo-2-dihydroxyphosphinyloxy diphenyl ether, 4-diazo-3-dihydroxyphosphinyl diphenyl ether, 4-diazo-3-
Dihydroxyoxydiphenyl ether, 4-diazo-
3-dihydroxyphosphinyl diphenyl 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'-dihydroxyphosphinylmethyldiphenylsulfide, 4-diazo-4'-dihydroxyphosphinyloxymethyldiphenylsulfide, 4-diazo-4 '-(2-dihydroxyphosphinylethyl) diphenyl Sulfide, 4-diazo-4 '-(2-dihydroxyphosphinyloxyethyl) diphenyl sulfide, 4-diazo-4'-dihydroxyphosphinylmethoxydiphenyl ether, 4
-Diazo-4'-dihydroxyphosphinyloxymethoxydiphenyl ether, 4-diazo-4 '-(2-dihydroxyphosphinylethoxy) diphenyl sulfide, 4-diazo-4'-(2-dihydroxyphosphinyloxyethoxy) Diphenyl sulfide, 4-diazo-2- (2-dihydroxyphosphinylethyl) diphenyl ether, 4-diazo-2- (2-dihydroxyphosphinyloxyethyl) diphenyl sulfide,
Diazo-3-dihydroxyphosphinylmethyldiphenylether, 4-diazo-3-dihydroxyphosphinyloxymethyldiphenylsulfide, 4-diazo-
4'-dihydroxyphosphinooxydiphenylamine, 4-diazo-4'-dihydroxyphosphinodiphenylamine, 4-diazo-4'-dihydroxyphosphinodiphenylamine, 4-diazo-4'-hydroxyphosphinyldiphenylamine, 4-diazo- 3-dihydroxyphosphinooxydiphenylamine, 4-diazo-3-dihydroxyphosphinodiphenylamine, 4-
Diazo-2-dihydroxyphosphinooxydiphenylamine, 4-diazo-2-dihydroxyphosphinodiphenylamine, 4-diazo-2'-hydroxyphosphinodiphenylamine, 4-diazo-2'-hydroxyphosphinyldiphenylamine, 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-2-dihydroxyphosphinomethoxydiphenylamine, 4-diazo-
2 '-(2-hydroxyphosphinoethyl) diphenylamine, 4-diazo-3'-(2-hydroxyphosphinylethoxy) diphenylamine and the like.

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

Diazo resins (I) and (II) used in the present invention
Alternatively, specific examples of the acidic medium used when synthesizing (III) include, for example, strong acids such as hydrochloric acid, phosphoric acid, methanesulfonic acid, and sulfuric acid.

These media are used in a concentration of at least 30% by weight, preferably 70 to 100% by weight. Generally, the balance is water, but it may be partially or completely composed 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.

[0046] Next diazo resin (I), the counter anion X in (II) The (III) ^- is described.

The counter anion is an anion that forms a stable salt with the diazo resin and makes the resin soluble in an organic solvent. Examples of such anions include halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid; perhalogenated acids such as ClO ₄ and IO _4; and organic carboxylic acids such as decanoic acid and benzoic acid and benzoic acid. Acid, organic phosphoric acid such as phenylphosphoric acid and sulfonic acid.

Preferred examples include hexafluorophosphoric acid, tetrafluoroboric acid and the following aliphatic or aromatic sulfonic acids.

Fluoroalkanesulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, camphorsulfonic acid, tolyloxy-3-propanesulfonic acid, and 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-chlorobenzenesulfonic 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-bromo Benzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, butoxybenzenesulfonic acid, dodecyloxybenzene Sulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, butoxynaphthalenesulfonic acid, dodecyloxynaphthalenesulfonic acid, dibutyl Naphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, 1,8-dinitro-naphthalene -3,6-disulfonic acid, 4,4'-diazido-stilbene-3,3'-disulfonic acid, 1,2-naphthoquinone-2-diazide-4
-Sulfonic acid, 1,2-naphthoquinone-2-diazide-
Includes the anion of 5-sulfonic acid and 1,2-naphthoquinone-1-diazido-4-sulfonic acid, or a mixture of these anions. Particularly preferred among these anions are anions of alkyl-substituted naphthalenesulfonic acids such as butylnaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, and tributylnaphthalenesulfonic acid.

The molecular weight of the diazo resin used in the present invention can be arbitrarily determined by varying the molar ratio of each monomer and the condensation conditions, but it is effective for the intended use of the present invention. Molecular weight of about 400
From 100,000 to 100,000, preferably from about 800 to 5,000.

The photosensitive diazo resin described above is preferably used in combination with an alkali-soluble or swellable lipophilic polymer compound as a binder resin.

As such a lipophilic polymer compound,
Copolymers having a molecular weight of usually from 100,000 to 200,000 using the monomers shown in the following (1) to (15) as structural units are exemplified.

(1) Acrylamides, methacrylamides, acrylates, methacrylates and hydroxystyrenes having an aromatic hydroxyl group, for example, N- (4-
(Hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m-, p
-Hydroxystyrene, o-, m-, p-hydroxyphenyl-acrylate or methacrylate; (2) acrylates and methacrylates having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate (3) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and itaconic acid; (4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, Octyl acrylate, acrylic acid-
(Substituted) alkyl acrylates such as 2-chloroethyl, glycidyl acrylate, 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-hexylmethacryl Acrylamide or methacrylamides such as amide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, (7) ethyl vinyl ether, 2-chloroethyl Vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, Vinyl ethers such as phenyl vinyl ether; (8) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate; (9) styrenes such as styrene, α-methylstyrene, and chloromethylstyrene; ) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, (11) olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, (12) N-vinylpyrrolidone, N-vinylcarbazole , 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like, (13) maleimide, N-acryloylacrylamide,
Unsaturated imides such as N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide, (14) N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonyl) Methacrylamides such as phenyl) methacrylamide, N- (p-amino) sulfonylphenylmethacrylamide, N- (1- (3-aminosulfonyl) naphthyl) methacrylamide, N- (2-aminosulfonylethyl) methacrylamide; And acrylamides having the same substituents as above, and o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p
-Aminosulfonylphenyl methacrylate, 1- (3
(15) N- [2- (methacryloyloxy) -ethyl], unsaturated sulphonamides such as methacrylates such as -aminosulfonylnaphthyl) methacrylate and acrylates having the same substituents as described above;
-Unsaturated monomers having a crosslinkable group in the side chain, such as -2,3-dimethylmaleimide and vinyl cinnamate.

Further, a monomer copolymerizable with the above monomer may be copolymerized. In addition, a copolymer obtained by copolymerization of the above-mentioned monomers, for example, modified with glycidyl methacrylate, glycidyl acrylate, or the like is also included, but is not limited thereto.

More specifically, a copolymer having a hydroxyl group or a sulfonamide group, containing the monomers listed in the above (1), (2) and (14), is preferred, and an aromatic hydroxyl group or a sulfonamide group is preferred. Copolymers having groups are more preferred.

The copolymer preferably contains the unsaturated carboxylic acid listed in (3), and the carboxylic acid value of the copolymer is preferably 0 to 3 meq / g, more preferably 0.5 meq / g. ~ 2.5 meq / g. The preferred molecular weight of the copolymer is from 150,000 to 150,000.

If necessary, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, an epoxy resin, a novolak resin, a natural resin, etc. may be added to the above copolymer.

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 generally contained in an amount of 1 to 60% by weight, preferably 3 to 40% by weight.

Dyes can be further used in the photosensitive composition of the present invention. The dye is used for the purpose of obtaining a visible image by exposure (exposure visible image) and a visible image after development.

As the dye, those which change color tone by reacting with free radicals or acids can be preferably used.
Here, the term “color tone changes” includes both a change from colorless to a color tone and a change from color to colorless or a different color tone. Preferred dyes are those that form a salt with an acid to change the color tone.

For example, Victoria Pure Blue BOH
[Hodogaya Chemical Co., Ltd.], Oil Blue 03 (Orient Chemical Co., Ltd.), Patent Pure Blue [Sumitomo Mikuni Chemical Co., Ltd.], Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Basic Fuchsin , Malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, cyano-p-diethylaminophenylacetanilide, etc., triphenylmethane, diphenylmethane, oxazine, xanthene Examples of the color-changing agent in which a system, iminonaphthoquinone-based, azomethine-based or anthraquinone-based dyes change from color to colorless or different color tone.

On the other hand, examples of the color changing agent that changes 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, Primary or secondary arylamine dyes represented by p ', p "-triaminotriphenylmethane are exemplified.

Particularly preferred are triphenylmethane-based and diphenylmethane-based dyes, and more preferred are triphenylmethane-based dyes, particularly Victoria Pure Blue BOH.

The above dye is usually used in the photosensitive composition in an amount of about 0.5.
The content is preferably about 10% by weight, more preferably about 1 to 5% by weight.

Various additives can be further added to the photosensitive composition of the present invention.

For example, alkyl ethers (eg, ethylcellulose, methylcellulose) for improving coating properties, fluorine-based surfactants, nonionic surfactants (particularly fluorine-based surfactants are preferable), and flexibility of the coating film Plasticizers (eg, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate,
Oligomers and polymers of tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid, of which tricresyl phosphate is particularly preferred), and a sensitizing agent for improving the lipophilicity of the image area ( For example, a half-esterified product of a styrene-maleic anhydride copolymer with an alcohol described in JP-A-55-527, a novolak resin such as PP-3121, a 50% fatty acid ester of p-hydroxystyrene, etc.), a stabilizer [ For example, 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.) It used Mashiku. The amount of these additives varies depending on the purpose of use, but is generally 0.01 to 30% by weight based on the total solid content.

When such a photosensitive composition is applied to the production of a photosensitive lithographic printing plate, it is coated on a suitable support.

The support used in the photosensitive lithographic printing plate includes paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, aluminum (including aluminum alloy), zinc,
A metal plate such as silk, a plastic film such as cellulose diacetate, cellulose triacetate, cellulose propionate, polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyvinyl acetal, etc., or a metal as described above was laminated or vapor-deposited. Examples thereof include paper or a plastic film, aluminum or a chromium-plated steel plate, and among them, aluminum and an aluminum-coated composite support are particularly preferable.

The surface of the aluminum material is desirably subjected to a surface roughening treatment for the purpose of increasing water retention and improving adhesion to 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, sand blast and the like, and combinations thereof.
Examples include electrolytic etching, chemical etching, and liquid honing, of which a surface roughening method including the use of electrolytic etching is particularly preferable. Further, as an electrolytic bath used in the electrolytic etching, an aqueous solution containing an acid, an alkali or a salt thereof or an aqueous solution containing an organic solvent is used, and among these, an electrolytic solution containing hydrochloric acid, nitric acid or a salt thereof is used. Liquids are preferred. Further, the roughened aluminum plate is desmutted with an acid or alkali aqueous solution as required. The aluminum plate thus obtained is desirably subjected to anodic oxidation treatment, and particularly preferably a method of treating the aluminum plate with a bath containing sulfuric acid or phosphoric acid. Further, if necessary, surface treatment such as sealing treatment with alkali silicate or hot water, or immersion in a water-soluble polymer compound or an aqueous solution of potassium fluorozirconate can be performed.

To provide the above-described photosensitive composition on a support, a predetermined amount of a photosensitive diazo co-condensation resin, a lipophilic polymer compound, and, if necessary, various additives are added to a suitable solvent (methyl cellosolve). , Ethyl cellosolve, dimethoxyethane, diethylene glycol monomethyl ether, diethylene glycol-dimethyl ether, 1-methoxy-
2-propanol, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethylformamide, dimethylacetamide, cyclohexanone,
Dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, ethylene dichloride, dimethyl sulfoxide,
Water or a mixture thereof) to prepare a coating solution of the photosensitive composition, apply the solution on a support, and dry the solution. The solid content concentration of the photosensitive composition at the time of application is 1 to 50.
It is desirable to be in the range of weight%. In this case, the application amount of the photosensitive composition may be about 0.2 to 10 g / m ² (dry weight).

It is preferable to apply a mat layer comprising a fine pattern of discontinuous projections on the applied photosensitive composition to improve the vacuum adhesion to the film at the time of contact exposure. Japanese Patent Application Laid-Open No.
No. 12,974, a method of thermally fusing powdered solid powder, or a method of spraying and drying polymer-containing water described in JP-A-58-182636, and any method may be used. It is desirable that the mat layer itself be dissolved in an aqueous alkaline developer containing substantially no organic solvent or be removable by this.

The photosensitive material according to the present invention can be exposed and developed by a conventional method. That is, for example, by exposing through a transparent original having a line image, a halftone dot image and the like, and then developing with an aqueous developer, a negative relief image can be obtained for the original. Light sources suitable for exposure include a carbon arc lamp, a mercury lamp, a xenon lamp, a metal halide lamp, and a strobe.

In the present invention, the photosensitive material according to the present invention has a pH at 25 ° C. of 8 or more and less than 12 and contains substantially no organic solvent (hereinafter referred to as “developer according to the present invention” as appropriate). ).

Incidentally, “substantially contains no organic solvent” means
It means that no organic solvent is contained to such an extent that it causes inconvenience in view of the above-mentioned environmental hygiene, safety, workability, etc. In the present invention, the proportion of the substance in the composition is 2% by weight or less. And preferably 1% by weight or less.

Hereinafter, the developer according to the present invention will be described. The developer according to the present invention has a pH of 8 or more at 25 ° C.
Less than 2 alkaline aqueous solutions. In the developer according to the present invention, the pH can be adjusted to the above range by containing an alkali agent. As the alkali agent to be contained, potassium silicate, lithium silicate, sodium silicate, and tertiary salt are preferably used. Examples thereof include sodium phosphate, dibasic sodium phosphate, tribasic potassium phosphate, dibasic potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, monoethanolamine, diethanolamine, and triethanolamine.

The pH of the developer according to the present invention at 25 ° C. is from 8 to less than 12, preferably from 9.5 to 11.8.

Further, water-soluble sulfites such as sodium sulfite, potassium sulfite, lithium sulfite and magnesium sulfite can be added to the developer.
The preferred content of the sulfite in the developer composition is
It is 0.05 to 4% by weight, more preferably 0.1 to 1% by weight.

Further, in the developer according to the present invention, anionic surfactants and amphoteric surfactants described in JP-A-50-51324, and JP-A-59-7
Nos. 5255, 60-11246 and 6
By incorporating at least one kind of nonionic surfactants as described in JP-A-213,943 or the like, or JP-A-55-95946, JP-A-5-95946.
By containing a polymer electrolyte as described in JP-A-6-142528, the wettability to the photosensitive composition and the gradation can be further increased, and it is preferably used. The amount of the surfactant is not particularly limited, but is preferably 0.003 to 3% by weight, and more preferably 0.006 to 1% by weight.

Further, the developer according to the present invention may contain an antifoaming agent. Suitable antifoaming agents include organosilane compounds.

The photosensitive material according to the present invention can be exposed to the developer according to the present invention after imagewise exposure, or rubbed with the developer.
After 10 to 60 seconds, the unexposed portion of the photosensitive composition is completely removed without adversely affecting the exposed portion of the photosensitive composition layer. In this case, the developing ability is high,
Also, no stains or the like occur. In addition, pollution and occupational health problems are solved because substantially no organic solvents are used.

The present invention can be used particularly advantageously when a photosensitive lithographic printing plate is used as the photosensitive material to be developed and is processed with the developing solution according to the present invention.

In this case, a method for developing a photosensitive lithographic printing plate (hereinafter sometimes referred to as “PS plate”) which has been subjected to image exposure with the developer according to the present invention is optional. Can be used. Specifically, a method of immersing a PS plate exposed to image in a developer, a method of ejecting a developer from a number of nozzles to a photosensitive layer of the PS plate, and a method of sensitizing a PS plate with a sponge wetted with a developer. Various methods such as a method of wiping the layer and a method of applying a developer to the surface of the photosensitive layer of the PS plate with a roller can be used. After the developer is applied to the photosensitive layer of the PS plate in this manner, the surface of the photosensitive layer can be lightly rubbed with a brush or the like.

The development conditions can be appropriately selected according to the development method. As an example, for example, in a developing method by immersion, about 10 to 80 ° C.
A method of dipping for seconds can be used.

The developer in the present invention can be used as a developer for a positive type lithographic printing plate. At this time, a positive type lithographic printing plate generally includes a sulfonic acid ester-substituted product at the 4-position and / or 5-position of o-naphthoquinonediazide and a photosensitive layer containing a binder soluble in alkaline water having a pH of 8 or more and less than 12. What you have is used. Preferable binders include phenol-formalin resins. Thus, the present invention is also characterized in that the negative and the positive can be developed with the same developer.

Further, in the development process of this type of photosensitive lithographic printing plate, the alkaline aqueous solution is consumed depending on the processing amount to decrease the alkaline concentration, or the alkaline concentration is reduced by air by operating the automatic developing solution for a long time. The processing capacity is reduced due to the decrease, but in that case,
As described in No. 4, the processing capacity may be restored by using a replenisher.

If necessary, after the development processing, washing with water and desensitization treatment, or as it is, desensitization treatment, treatment with an aqueous solution containing an acid, or desensitization treatment after treatment with an aqueous solution containing an acid May be applied.

[0088]

According to the invention, when a photosensitive lithographic printing plate using a conventional diazo resin is developed using a developer composition having a pH of from 8 to less than 12 at 25 ° C. and containing substantially no organic solvent, Since the resin has essentially no solubility in alkaline water and has low developability, it cannot be developed without forming a residual film, and is stained by printing. Use of an aromatic diazonium compound having a group that is soluble in alkaline water, such as a sulfinic acid group and an oxygen acid group of phosphorus, increases the pH.
However, even if the development is carried out with an aqueous alkali developing solution containing substantially no organic solvent, the development can be carried out without forming a residual film. Therefore, when used for a lithographic printing plate, there is no print stain.

Further, since the developing method of the present invention uses an aqueous alkali developing solution which is not strong alkali and substantially contains no organic solvent, problems such as toxicity and odor during operation, fire, gas explosion, etc. It can be implemented at low cost without the problem of safety and the problem of pollution caused by waste liquid.

Further, in the present invention, a negative type lithographic printing plate can be developed using an aqueous alkali developing solution known as a developing solution for a positive type lithographic printing plate. For this reason, when processing both a positive type lithographic printing plate and a negative type lithographic printing plate, a developer composition is prepared so as to be compatible with each, a developer composition is replaced, and two kinds of developer are used in advance. It is possible to save labor such as preparing the composition and the development processing apparatus, and the working efficiency, equipment cost, arrangement space, and the like are significantly improved.

Next, typical examples of the synthesis of the diazo resin according to the present invention will be described.

[0092]

[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 were dissolved in 90 g of concentrated sulfuric acid under cooling with water. After this reaction, 2.7 g of paraformaldehyde (0.09 mol) was slowly added. At this time, the reaction was added so that the reaction temperature did not exceed 10 ° C. Thereafter, stirring was continued under ice cooling for 2 hours. The reaction mixture was poured into 1 l 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 10.5 was added to the solution.
g of zinc chloride dissolved in a cold concentrated aqueous solution. The precipitate formed was filtered and washed with ethanol.
In pure water. To this solution was added a cold concentrated aqueous solution in which 28.7 g of sodium dibutylnaphthalenesulfonate was dissolved. The resulting precipitate was separated by filtration, washed with water, and dried at 30 ° C. for 24 hours to obtain diazo resin-1.

The molecular weight of this diazo resin-1 was measured by GPC (gel permeation chromatography) and found to be about 1600 in weight average molecular weight.

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 in the synthesis of diazo resin-1. Was. The molecular weight was measured by GPC and found to be 1650 in weight average molecular weight.

Synthesis of diazo resin-3 6.1 g (0.040 mol) of phenoxyacetic acid and 11.3 g (0.040 mol) of 4-diazodiphenylamine sulfate were dissolved in 90 g of concentrated sulfuric acid under cooling with water. Add 3.0
g of paraformaldehyde (0.10 mol) was added slowly. At this time, the reaction was added so that the reaction temperature did not exceed 10 ° C. Thereafter, stirring was continued under ice cooling for 2 hours. The reaction mixture was poured into 1 l of ethanol under ice cooling, and the resulting precipitate was filtered. After washing with ethanol, the 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. A cold concentrated aqueous solution in which 41 g of sodium dibutylnaphthalenesulfonate was dissolved was added to this solution. The resulting precipitate was separated by filtration, washed with water, and dried at 30 ° C. for 24 hours to obtain diazo resin-3. This diazo co-condensation resin-3 is G
The molecular weight was measured by PC and found to be about 2300 in weight average molecular weight.

Synthesis of diazo resin-4 2-diazodiphenylamine hydrogen sulfate 24.9 g (0.0
850 mol) and 2.61 g (0.0150 g) of phenylphosphoric acid
mol) was dissolved in 70 ml of 96% sulfuric acid. To this, 3.16 g (0.100 mol) of paraformaldehyde (95%) was added, and the mixture was stirred at 5 ° C for 2 hours. Then, the reaction solution is cooled with ice water.
The mixture was poured into 1.5 l with stirring, and 220 g of a 50% aqueous solution of zinc chloride was further added to precipitate a yellow precipitate. The yellow precipitate was separated by filtration to obtain a zinc chloride double salt of a condensate of 4-diazodiphenylamine / phenylphosphoric acid and formaldehyde.

The above condensate was dissolved in 800 ml of water, and 34.2 g of sodium dibutylnaphthalenesulfonate (0.
(100 mol) in 600 ml of water was added with vigorous stirring. The resulting yellow precipitate was collected by filtration and dried to obtain dibutylnaphthalene sulfonate (diazo resin-4) of a condensate of 4-diazodiphenylamine / phenylphosphoric acid and formaldehyde. It was 2320 when the weight average molecular weight was measured using GPC.

Synthesis of diazo resin-5 29.3 g of 4-diazodiphenylamine hydrogen sulfate (0.1
00 mol) was dissolved in 70 ml of 85% phosphoric acid. Glyoxylic acid monohydrate (97%) 4.74 g (0.0500 g)
mol) was added and stirred at 40 ° C. for 20 hours. The reaction mixture was then added to 1.5% paraformaldehyde (95%).
8 g (0.0500 mol) are added and at 40 ° C., a further 20
Stirred for hours. Thereafter, the reaction solution was poured into 800 ml of isopropyl alcohol with stirring to precipitate a yellow precipitate. The yellow precipitate was separated by filtration and washed with isopropyl alcohol to obtain dihydrogen phosphate of 4-diazodiphenylamine-glyoxylic acid / formaldehyde condensate.

The above condensate was dissolved in 400 ml of water, and 41.8 g of sodium dibutylnaphthalenesulfonate (0.
A solution of 120 mol) in 600 ml of water was added with stirring.
The resulting yellow precipitate was collected by filtration and dried to obtain 44 g of dibutylnaphthalenesulfonic acid salt of 4-diazodiphenylamine-glyoxylic acid / formaldehyde condensate.

The carboxylic acid value of the obtained diazo resin-5 was 0.98 meq / g. The weight average molecular weight of the obtained diazo resin-5 measured by GPC was 1950.

Synthesis of Diazo Resin-6 32.3 g (0.100 mol) of 4-diazo-4'-methoxydiphenylamine hydrogen sulfate was dissolved in 75 ml of 96% sulfuric acid. To this, 4.14 g (0.0300 mol) of 3-dihydroxyphosphinylpropanal was added, and the mixture was stirred at 5 ° C for 2 hours. Next, 2.21 g (0.0700 mol) of paraformaldehyde (95%) was added to the reaction mixture, and the mixture was further stirred at 5 ° C. for 2 hours. Thereafter, the reaction solution was poured into 1.5 liters of ice water with stirring, and further a 180% aqueous solution of zinc oxide 180
g was added to precipitate a yellow precipitate. The yellow precipitate was separated by filtration to obtain a zinc chloride double salt of a condensate of 4-diazo-4'-methoxydiphenylamine and 3-dihydroxyphosphinylpropanal-formaldehyde.

The above condensate was mixed with 200 ml of water and 500 ml of MEK.
And a solution of 29.2 g (0.0840 mol) of sodium dodecylbenzenesulfonate in 600 ml of water was added thereto with vigorous stirring. After stirring for a while, the mixture was allowed to stand and separated into two layers. The upper layer was poured into 2 l of water while stirring, and the resulting yellow precipitate was collected by filtration and dried to give dodecyl condensate of 4-diazo-4'-methoxydiphenylamine and 3-dihydroxyphosphinylpropanal-formaldehyde. 36 g of benzenesulfonate were obtained.

The obtained diazo resin-6 was converted to 1-phenyl-
After coupling with 3-methyl-5-pyrazolone, the weight average molecular weight was measured using GPC.
090.

Synthesis of diazo resin-7 7.79 g (0.0200 mol) of 4-diazo-4'-dihydroxyphosphinyloxydiphenylamine hydrogen sulfate and 23.5 g of 4-diazodiphenylamine hydrogen sulfate (0.
0800 mol) was dissolved in 70 ml of 96% sulfuric acid. to this,
3.16 g of paraformaldehyde (95%) (0.100mo
l) was added and the mixture was stirred at 5 ° C for 2 hours. Thereafter, the reaction solution was poured into 1.5 liters of ice water with stirring, and further, zinc chloride 5
260 g of a 0% aqueous solution was added to precipitate a yellow precipitate. The yellow precipitate was separated by filtration to obtain a zinc chloride double salt of a condensate of 4-diazo-4'-dihydroxyphosphinyloxydiphenylamine / 4-diazodiphenylamine and formaldehyde.

The above condensate was dissolved in 800 ml of water, and a solution of 41 g of sodium dibutylnaphthalenesulfonate in 600 ml of water was added thereto with stirring. The resulting yellow precipitate was collected by filtration and dried to obtain 33 g of dibutylnaphthalenesulfonic acid salt of 4-diazo-4'-dihydroxyphosphinyloxydiphenylamine / condensate of 4-diazodiphenylamine and formaldehyde. It was 1950 when the weight average molecular weight was measured using GPC.

Next, as a comparative synthesis example, the following diazo resin
8 was synthesized.

Synthesis of diazo resin-8 14.5 g (50 mmol) of p-diazodiphenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under ice cooling. To this reaction solution, 1.5 g (50 mmol) of paraformaldehyde was slowly added dropwise. At this time, the reaction was added so that the reaction temperature did not exceed 10 ° C. Thereafter, stirring was continued under ice cooling for 2 hours.

The reaction mixture was added dropwise to 500 ml of ethanol under ice cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 100 ml of pure water, and a cold concentrated aqueous solution in which 6.8 g of zinc chloride was dissolved was added to this solution.
The precipitate formed was filtered and washed with ethanol.
It was dissolved in 50 ml of pure water. To this solution was added a cold concentrated aqueous solution in which 16.8 g of sodium dibutylnaphthalenesulfonate was dissolved. The resulting precipitate was collected by filtration, washed with water,
It was dried for one day to obtain diazo resin-8.

When the molecular weight of this diazo resin-8 was measured by GPC, it was found that about 50 mol% of pentamers or more was contained.

Next, a synthesis example of the lipophilic polymer compound will be described.

Synthesis of Lipophilic Polymer Compound-1 N- (4-hydroxyphenyl) methacrylamide 53
g, acrylonitrile 16 g, 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 a 1: 1 mixed solvent of acetone-ethanol, and the mixture was purged with nitrogen and heated at 60 ° C. for 8 hours. After completion of the reaction, the reaction solution was diluted with 5 l of water.
The mixture was poured under stirring and the resulting white precipitate was collected by filtration and dried to obtain 90 g of polymer compound-1.

When the molecular weight of this lipophilic polymer compound-1 was measured by GPC, the weight average molecular weight was 29,000.

Synthesis of Lipophilic Polymer Compound-2 2-Hydroxyethyl methacrylate 5.0 g, N- (4
A mixture of 20 g of -hydroxyphenyl) acrylamide, 60 g of methyl methacrylate, 8.0 g of methacrylic acid and 1.2 g of benzoyl peroxide was added dropwise to 300 g of ethylene glycol monomethyl ether heated to 100 ° C over 2 hours. After completion of the dropwise addition, 300 g of ethylene glycol monomethyl ether and 0.3 g of benzoyl peroxide were added, and the mixture was allowed to react for 4 hours. After completion of the reaction, the reaction mixture was diluted with methanol, poured into 5 l of water with stirring, and the resulting white precipitate was collected by filtration and dried to obtain 86 g of lipophilic polymer compound-2.

When the molecular weight of this lipophilic polymer compound-2 was measured by GPC, the weight average molecular weight was 82,000.

Synthesis of Lipophilic Polymer Compound-3 4.57 g (0.0192 mol) of N- (p-aminosulfonylphenyl) methacrylamide, 2.55 of acrylonitrile
g (0.0480 mol), methacrylic acid 1.66 g (0.019 g)
2 mol), 18.40 g (0.1136 g) of benzyl acrylate
mol), 0.41 g of α, α'-azobisisobutyronitrile
And 25 g of N, N-dimethylformamide,
Put into a 100 ml three-necked flask equipped with a cooling tube,
While stirring for 5 hours. The reaction mixture is mixed with 2 l of water.
After stirring for 30 minutes, the mixture was filtered and dried to obtain 19 g of a polymer compound-3. GPC
As a result, the weight average molecular weight (polystyrene standard) of this polymer compound-3 was measured to be 18,000.

Example 1 An aluminum plate was degreased with a 3% aqueous sodium hydroxide solution, electrolytically etched in a 2% hydrochloric acid bath at 25 ° C. and a current density of 3 A / dm ² , washed with water, and then washed with a 15% sulfuric acid bath. 30 in
Anodizing was performed for 2 minutes at 1.5 ° C. and 1.5 A / dm ² . Next, a 1% aqueous sodium metasilicate solution was sealed at 85 ° C. for 30 seconds, washed with water and dried to obtain an aluminum plate for a lithographic printing plate. The aluminum plate photosensitive solution -1 following composition film weight after drying was coated to a 1.8 g / m ^2.

Photosensitive solution-1 Lipophilic polymer compound-1 5.0 g Diazo resin-1 0.6 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.1 g Julimer AC-10L (Nippon Pure Chemical Co., Ltd.) 0.3 g methylcellosolve 100 ml

A part of the photosensitive lithographic printing plate thus obtained was stored at 45 ° C. and a relative humidity of 65% for 5 days due to forced deterioration for accelerating aging.

A negative transparent original was brought into close contact with the obtained sample,
After exposing for 30 seconds from a distance of 60 cm with a 2 KW metal halide lamp, the film was immersed in a developer 1 having the following composition at 27 ° C. for 20 seconds, and developed by gently rubbing with absorbent cotton.

Developer-1 No. 3 sodium silicate 100 g Water 600 g (pH at 25 ° C. is 11.6)

The developed samples were printed on high quality paper using a commercially available ink on a Heidelberg SOR printing machine.

Example 2 A sample was prepared in the same manner as above except that the diazo resin-1 and the lipophilic polymer compound-1 of the photosensitive solution-1 were changed to those shown in Table 1, and the same evaluation as described above was carried out. Was done. Table 1 shows the obtained results.

As can be seen from Table 1, the developing method of the present invention was excellent in that the printed matter was free from or less stained even in the developer 1 which was not a strong alkali and contained substantially no organic solvent.

[0124]

[Table 1]

Claims (1)

(57) [Claims] 1. 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 an oxygen acid group of phosphorus is formed on a support made of aluminum. A binder comprising a copolymer having a structural unit of at least one unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, and itaconic acid; After imagewise exposing a photosensitive lithographic printing plate provided with a photosensitive layer containing 40 to 99% by weight as a resin, the plate is developed with an aqueous alkaline developer having a pH of 8 or more and less than 12 at 25 ° C and containing substantially no organic solvent. A method for developing a photosensitive material containing a diazo resin, comprising: