JPH02217859A - Method of developing diazo resin-containing photosensitive material - Google Patents

Abstract

PURPOSE:To solve problems arising from the use of an org. solvent and to improve developability and more particularly the developability in the case of preserving the photosensitive material over a long period of time as well as to prevent the generation of contamination by using a developing soln. which does not contain the org. solvent. CONSTITUTION:This photosensitive material has a photosensitive layer contg. a diazo resin and a high-polymer compd. having >=100 acid value on a base. The diazo resin is used as a photosensitive body and the high-polymer compd. can function as a binder at the time of constituting a photosensitive compsn. The photosensitive material is developed by the developing soln. which is an alkaline aq. soln. which has >=12.0 pH at 25 deg.C and contains substantially no org. solvent. The problems arising from the use of the org. solvent are solved by using the developing soln. which does not contain the org. solvent in this way; in addition, the desired development is attained with the good developability and the developability in the case of preserving the photosensitive material over a long period of time is good as well. The generation of the contamination, etc., is obviated even when the material is subjected to printing.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for developing a photosensitive material containing a diazo resin. This type of photosensitive material can be used, for example, as a photosensitive printing plate.

[Background of the invention]

Conventionally, diazo resin is contained and used as a photoreceptor,
Furthermore, binder resin etc. are mixed to form a photosensitive composition.
This is applied to a support such as a hydrophilic metal, paper, preferably aluminum (particularly grained aluminum), and the like to produce a photosensitive material. Such materials are widely used, for example, as photosensitive planographic printing plates, and are used in offset printing and the like.

Conventionally, diazo resin-containing photosensitive materials have been developed with a developer containing an organic solvent. When an organic solvent is contained in the developer, good development can be achieved without necessarily increasing the pH of the developer.

However, organic solvents are generally troublesome to maintain and manage. Furthermore, from the standpoint of occupational hygiene, it is desirable to avoid handling organic solvents or chemicals containing them. Furthermore, in view of recent pollution control problems, it is not preferable for the waste liquid to contain organic solvents. If an organic solvent is used, it will take time and money for waste liquid treatment.

[Problem that the invention seeks to solve]

As mentioned above, conventionally, development was performed using a developer containing an organic solvent, but the use of organic solvents has various problems, and a technology that does not use organic solvents is desired. be.

However, simply removing the organic solvent does not achieve the desired development. If development is simply carried out using a developer that does not contain an organic solvent, the developability is poor, and portions that should be removed by development remain, resulting in stains when used for printing.

In particular, when a photosensitive material is stored for a long period of time, the problem of developability is significant, and the above-mentioned stains are unacceptable, and especially when used as a photosensitive material for printing, it is impossible to put it to practical use. While removing the organic solvent, p
It may be possible to increase H to speed up the progress of development, but
After all, this alone does not solve the problem of dirt and the like mentioned above.

The present invention solves the above-mentioned problems by using a developer that does not contain an organic solvent, thus solving the problems associated with the use of organic solvents, achieving desired development with good developability, and achieving long-term storage. The developability is also good when
It is an object of the present invention to provide a method for developing a diazo resin-containing photosensitive material that does not cause stains even when used for printing.

[Means for solving problems]

As a result of various studies, the present inventors have found that a photosensitive material having a photosensitive layer containing a diazo resin and a polymer compound with an acid value of 100 or more on a support has a pH of 12.0 or more at 25°C and The inventors have discovered that the above-mentioned problems can be solved by a method for developing a diazo resin-containing photosensitive material, which involves developing with a developer that does not substantially contain an organic solvent, leading to the present invention.

That is, the present inventors have repeatedly conducted various experiments regarding both developer components and photosensitive materials to be developed, and as a result, have found that the above method meets the object of the present invention.

The present invention will be explained in more detail below.

First, a photosensitive material to be developed (hereinafter referred to as "photosensitive material according to the present invention" as appropriate) processed by the developing method of the present invention will be described.

The photosensitive material according to the present invention is a photosensitive material having a photosensitive layer containing a diazo resin and a polymer compound having an acid value of 100 or more on a support.

The above diazo resin is used as a photoreceptor.

Any diazo resin can be used in the present invention.

In the present invention, as the diazo resin, a co-condensed diazo resin containing an aromatic compound having one or more of at least one of a carboxyl group or a hydroxyl group and an aromatic diazonium compound as a constituent unit can be preferably used.

Such an aromatic compound having a carboxyl group and/or a hydroxyl group is one that contains an aromatic ring substituted with at least one carboxyl group and/or an aromatic ring substituted with at least one hydroxyl group in the molecule. In this case, the carboxyl group and the hydroxyl group may be substituted on the same aromatic ring, or may be substituted on different aromatic rings. This carboxyl group or hydroxyl group may be bonded directly to the aromatic ring or may be bonded via a bonding group.

Preferred examples of the aromatic group include aryl groups such as phenyl and naphthyl groups.

In the co-condensed diazo resin that can be used in the present invention, the number of carboxyl groups bonded to one aromatic ring is preferably 1 or 2, and the number of hydroxyl groups bonded to one aromatic ring is 1 to 3. is preferred. When a carboxyl group or a hydroxyl group is bonded to an aromatic ring via a bonding group, examples of the bonding group include an alkylene group having 1 to 4 carbon atoms.

Specific examples of the aromatic compound containing a carboxyl group and/or hydroxyl group as a constitutional unit of the co-condensed diazo resin include benzoic acid, 0-chlorobenzoic acid, m-chlorobenzoic acid, P-chlorobenzoic acid, phthalate. Acid, terephthalic acid, diphenylacetic acid, phenoxyacetic acid, p-methoxyphenylacetic acid, p-methoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,4-dimethylbenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid , 4-(m-methoxyanilino)benzoic acid, 4-(p-methylbenzoyl)benzoic acid, 4-(p-methylanilino)benzoic acid,
4-phenylsulfonylbenzoic acid, phenol, (o,
m, p) - cresol, xylenol, resorcinol,
2-Methylresorcin, (o,m,p)-methoxyphenol, m-ethoxyphenol, catechol, phloroglycin, p-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone, p-hydroxybenzyl alcohol, 4-chlororesorcin, biphenyl −
4,4°-diol, 1.2°4-benzenetriol, bisphenol A12°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, salicylic acid, 4-methylsalicylic acid, 6-methylsalicylic acid, 4-ethylsalicylic acid, 6-propylsalicylic acid, 6
-Laurylsalicylic acid, 6-styarylsalicylic 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
-dihydroxydi-6-methylbenzoic acid, 2゜6-dihydroxybenzoic acid, 2,6-cyhydroxy-4-benzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2,6-dioxybenzoic acid M , gallic acid, phloroglucincarboxylic acid, 2.4.5-1-dihydroxybenzoic 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-hydroxyphenyl)acetic acid, (3,4,5-1-
hydroxyphenyl)acetic acid, P-hydroxyethylbenzoic 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) )
Examples include benzoic acid, 4-(p-hydroxyphenylthio)benzoic acid, and the like. Particularly preferred among these are salicylic acid, p-hydroxybenzoic acid, P-methoxybenzoic acid, and metachlorobenzoic acid.

As the aromatic diazonium compound used as a constitutional unit of the co-condensed diazo resin, for example, diazonium salts such as those listed in Japanese Patent Publication No. 49-48001 can be used, but diphenylamine-4-diazonium salts are particularly preferred. Diphenylamine-4-diazonium salts are
Although derived from 4-amino-diphenylamines, such 4-amino-diphenylamines include 4-amino-diphenylamines.
-Amino-diphenylamine, 4-amino-3-methoxy-diphenylamine, 4-amino-2-methoxy-diphenylamine, 4'-amino-2-methoxy-diphenylamine, 4'-amino-4-methoxydiphenylamine, 4-amino- 3-methyldiphenylamine, 4
-amino-3-ethoxy-diphenylamine, 4-amino-3-β-hydroxy-ethoxydiphenylamine,
4-amino-diphenylamine-2-sulfonic acid, 4-
Examples include amino-diphenylamine-2-carboxylic acid v4-amino-diphenylamine-2'-carboxylic acid. Particularly preferably, 3-methoxy-4-amino-diphenylamine and 4-amino-cocondensed diazo resins that can be used in the present invention are represented by the following general formula [I]
The one represented by is preferable.

General Formula (I) In General Formula (1), A is a group derived from an aromatic compound having at least one of a carboxyl group and hydroxylation, and examples of such aromatic compounds include those exemplified above. can be mentioned.

In the formula, R1, R2 and R1 represent a hydrogen atom, an alkyl group or a phenyl group, R represents a hydrogen atom, an alkyl group or a phenyl group, and X represents a counter anion. n preferably represents a number from 1 to 200.

When a co-condensed diazo resin is used in the present invention, it is more preferable to use it in combination with a condensed diazo resin obtained by condensing an aromatic diazonium compound.

In this case, the co-condensed diazo resin is preferably used in an amount of 5% by weight or more in the diazo resin, and the condensed diazo resin is preferably used in an amount of 95% by weight or less in the diazo resin.

Furthermore, in this case, the weight % ratio of co-condensed diazo resin to condensed diazo resin is preferably 30 to 70: 70 to 30 in order to achieve both excellent sensitivity and developability.
It is.

The above-mentioned co-condensed diazo resins and condensed diazo resins used in combination with these or independently as diazo resins are:
Known methods such as Photographic Science and Engineering (Photo, Sci, E.
ng, Volume 17, Page 33 (1973), U.S. Patent No. 2,063,631, U.S. Patent No. 2,679,498. Salts are obtained by polycondensation of aromatic compounds containing carboxyl and hydroxyl groups and aldehydes such as paraformaldehyde, acetaldehyde, benzaldehyde or ketones such as acetone and acetophenone.

In addition, these aromatic compounds, aromatic diazo compounds, and aldehydes or ketones having carboxyl and/or hydroxyl groups in their molecules can be freely combined with each other, and two or more of each may be mixed and co-condensed. It is also possible.

The molar ratio of the aromatic compound having at least one of a carboxyl group and a hydroxyl group to the aromatic diazonium compound is preferably l:0.1 to o, i:t,
More preferably, the ratio is i:o, s to 0.2:1, and still more preferably l:1 to 0,2:1. In this case, the molar ratio of the sum of aromatic compounds and aromatic diazonium compounds having at least one of a carboxyl group and a hydroxyl group to aldehydes or ketones is usually preferably 1:0.6 to 1.2, more preferably 1:0.6 to 1.2. is 1:0.7~1.
A co-condensed diazo resin can be obtained by charging the mixture in step 5 and reacting at a low temperature for a short period of time, for example, about 3 hours.

The counter anion of the diazo resin includes an anion that stably forms a salt with the diazo resin and makes the resin soluble in an organic solvent. Those that form such anions include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and sulfonic acids; typical examples include methanesulfonic acid, Chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, and anthraquinonesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroxysulfonic acid, 4-acetylbenzenesulfonic acid, Aliphatic and aromatic sulfonic acids such as dimethyl-5-sulfoisophthalate, 2° 2° 4.4°-tetrahydroxybenzophenone, 1,2.3-trihydroxybenzophenone, 2.2°, 4-trihydroxybenzophenone hydroxyl group-containing aromatic compounds such as, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, ClO4
, 10, etc. can be mentioned. However, it is not limited to this. Among these, particularly preferred are hexafluorophosphoric acid, 2-hydroxy-
4-methoxybenzophenone-5-sulfonic acid.

The above-mentioned co-condensed diazo resin can have an arbitrary molecular weight by varying the molar ratio of each monomer and the condensation conditions. In the present invention, preferably, those having a molecular weight of about 400 to 10,000 can be effectively used, more preferably about 800 to 5,000.
is appropriate.

In addition, in the present invention, other than the above-mentioned co-condensed diazo resins, those that can be preferably used as diazo resins include, for example, the above-mentioned Photographic Science &
Engineering (Photo.

Scj, Eng.) Vol. 17, p. 33 (1973) and U.S. Pat.
No. 98, Specifications of No. 3,050,502, JP-A-59
A diazo resin obtained by condensing a diazo compound and an active carbonyl compound, such as formaldehyde, acetaldehyde or benzaldehyde, etc., in an acidic medium such as sulfuric acid, phosphoric acid, or hydrochloric acid, the manufacturing method of which is described in Publication No. 78340, etc. Examples include diazo compounds and diphenyl resins whose production methods are described in Japanese Patent Publication No. 49-4001.

Among the above, the diazo resin that can be preferably used in the present invention is represented by the following general formula (II) and contains 20 mol% or more of the resin in which n in each formula is 5 or more, more preferably 20 mol% or more. It contains ~60 mol%. During the ceremony,
R1-R3, R, X, and n have the same meanings as in the general formula (1). In the general formula CU), R,, R,
Examples of the alkyl group and alkoxy group of R3 include an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms; (II) Such a photosensitive diazo resin can be produced according to a known method, for example, the method described in the above-mentioned Photographic Science and Engineering and other US patent specifications cited above.

At that time, when polycondensing the diazonium salt and the aldehyde, the molar ratio of both is usually 1:0.6 to 1:
2. Preferably, the ratio is 1:0.7 to 1:1.5, and the mixture is heated at a low temperature for a short period of time, for example, at a temperature of 10° C. or less, 3 or less.

Examples of the counter anion of the diazo resin represented by formula (II) 1a include the same counter anions as those listed for the co-condensed diazo resin.

Next, in the photosensitive material according to the present invention, the polymer compound contained in the photosensitive layer together with the diazo resin will be explained. This polymer compound can function as a binder when forming a photosensitive composition.

In the present invention, the photosensitive layer contains a polymer compound having an acid value of 1 oo or more.

In the present invention, the acid value of a polymer compound is the number of potassium hydroxides required to neutralize 1 g of the polymer compound.

Acid value can be measured as follows. The sample is diluted 50 times with methyl cellosolve and titrated with O81 normal potassium hydroxide aqueous solution. At this time, the neutralization point is the inflection point of the pH curve determined using a pH meter. The acid value is calculated from the amount of potassium hydroxide aqueous solution required to reach this neutralization point.

In addition, in carrying out the present invention, in order to specify the molecular weight of the polymer compound used, the value of the molecular weight measured by GPC using a polystyrene standard can be used. That is, the weight average molecular weight can be measured by GPC (gel permeation chromatography), and the number average molecular weight Mn and weight average molecular weight MW can be calculated by Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka, "Nippon Kagaku. Journal” 800 pages ~
This can be done by leveling the peaks of the oligomer region (connecting the center lines of the peaks and valleys) by the method described on page 805 (1972).

The polymer compound that can be used in the present invention may be of any type as long as it has an acid value of 100 or more as described above, and for example, the following compounds can be used. That is, examples of polymer compounds that can be used include polyamide, polyether, polyester, polycarbonate,
Examples include polystyrene, polyurethane, polyvinyl chloride and its copolymers, polyvinyl butyral resin, polyvinyl formal resin, Sierran, epoxy resin, phenol resin, acrylic resin, and the like.

Preferably, the seven-mer copolymers shown in (1) to (12) below are preferred, and the copolymers have an acid value within the range of the present invention.

(1) N-(4
-hydroxyphenyl)acrylamide or N-(4
-hydroxyphenyl) methacrylamide, o-'1m
-1p-hydroxystyrene, Q'+m, p-hydroxyphenyl-acrylate or monomethacrylate.

(2) Monomers having aliphatic hydroxyl groups, such as 2- and hydroxyethyl acrylate or 2,2-hydroxyethyl methacrylate.

(3) α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride.

(4) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acinate, octyl acrylate, acrylic H-
(Substituted) alkyl acrylates such as 2-chloroethyl, 2-hydroxyethyl acrylate, glycidyl acrylate, and N-dimethylaminoethyl acrylate.

(5) Methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 2
-Hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-
(Substituted) alkyl methacrylates such as dimethylaminoethyl methacrylate.

(6) Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide,
Acrylamides or methacrylamides such as N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylamide, and N-ethyl-N-phenylacrylamide.

(7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.

(8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate.

(9) Styrenes such as styrene, α-methylstyrene, methylstyrene, 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-ruvinylcarbazole 4-vinylpyridine, acrylonitrile, methacrylatel, etc.

Furthermore, a monomer that can be copolymerized with the above monomer may be copolymerized. Further, the copolymerization pair obtained by copolymerization of the above monomers may be, for example, glycidyl methacrylate,
It also includes, but is not limited to, those modified with glycidyl acrylate and the like.

The polymer compound having an acid value of 100 or more used in the present invention preferably contains a heptad unit listed in (3) above.

For example, when containing methacrylic acid, the methacrylic acid in the polymer compound is 10 mol% or more, more preferably 15 mol% or more.
It is preferably selected from the range of 30 mol %.

More specifically, a hydroxyl group-containing copolymer containing the monomers listed in (1) and (2) above is preferred, and an aromatic hydroxyl group-containing copolymer is even more preferred.

Further, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, natural resin, etc. may be added to the above copolymer as necessary.

Particularly preferred as the polymer compound having an acid value of 100 or more used in the present invention are the following copolymers.

That is, in the molecular structure, (a) 10 mol% or more of structural units having a carboxyl group, preferably 15 to 30 mol%, (b) structural units having an alcoholic hydroxyl group and/or
or 1 to 50 structural units having a phenolic hydroxyl group.
Mol%, (C) Following - Formula IA - CH, -C-......! 5 to 40 mol% of the structural unit represented by AN (in the formula, R11 represents a hydrogen atom or an alkyl group), (d) the following general 2IIA -CH, -C-...・IIAC00I?
"(In the formula, pi represents a hydrogen atom, a methyl group, or an ethyl group, and R'' represents an alkyl group having 2 to 12 carbon atoms or an alkyl-substituted aryl group.) A polymer compound containing 60 mol% is preferred.

As a specific example of the above (bl) seven-termer forming a structural unit having an alcoholic hydroxyl group,
Examples include (meth)acrylic acid esters and acrylamides, such as the compounds shown in General 2mA below as described in No. 4.

C1h-C-・・・・・・・・・IIIACoobe-C
H, Cll0→1-11 IS In the formula, RI4 represents a hydrogen atom or a methyl group, RIS represents a hydrogen atom, a methyl group, an ethyl group, or a chloromethyl group, and n represents an integer of 1 to 10.

Examples of (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybentyl (meth)acrylate.
Examples of acrylamides include N-methylol(meth)acrylamide, N-meth)acrylate, etc.
-Hydroxyethyl (meth)acrylamide and the like.

Preferably it is 2-hydroxyethyl (meth)acrylate.

In addition, examples of monomers forming the structural unit having a phenolic hydroxyl group (b) above include N-(4-hydroxyphenyl)-(meth)acrylamide, N-(
2-hydroxyphenyl)-(meth)acrylamide,
C-meth)acrylamide monomers such as N-(4-hydroxynaphthyl)-(meth)acrylamide; O-,
m- or p-hydroxyphenyl (meth)acrylate mono? -;0-. Examples include m- or p-hydroxystyrene monomers. Preferably, 0-5m- or p-hydroxyphenyl (meth)acrylate monomer, N-(4-hydroxyphenyl)(meth)acrylamide monomer, more preferably N-(4-hydroxyphenyl)-(meth)acrylamide. It is a monomer.

The structural unit having an alcoholic hydroxyl group and/or the structural unit having a phenolic hydroxyl group is selected from the range of 1 to 50 mol%, preferably 5 to 30 mol%, in the polymer compound.

Examples of monomers having a cyano group in the side chain that form the structural unit represented by the general formula IA include acrylonitrile, methacrylonitrile, 2-pentenenitrile, and 2-pentenenitrile.
Examples include methyl-3-butenenitrile, 2-cyanoethyl acrylate, o-, m-p-cyanostyrene, and the like. Preferred are acrylonitrile and methacrylonitrile.

The proportion of the structural unit having a cyano group in the side chain contained in the molecule of the polymer compound is preferably selected from the range of 5 to 40 mol%, more preferably 15 to 35 mol%.

Examples of the seven polymers having a carboxy ester group in the side chain that form the structural unit represented by General IIIA include ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate, amyl methacrylate, and hexyl acrylate. ,
Examples include octyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, and glycidyl acrylate. The unit formed from the 7-mer is preferably 25 to 60 mol% in the polymer compound,
More preferably, it is selected from the range of 35 to 60 mol%.

In addition, each structural unit below is not limited to the unit formed from the heptadium mentioned as a specific example.

The polymer compound contained in the photosensitive material according to the present invention is
In the solid content of the photosensitive composition constituting the photosensitive layer, preferably 40 to 99% by weight, more preferably 50 to 95% by weight.
% by weight. Further, the photosensitive diazo resin contained in the photosensitive material according to the present invention is preferably
The content is 60% by weight, more preferably 3 to 30% by weight.

The photosensitive layer of the photosensitive material according to the present invention can contain an acid and/or an acid anhydride.

In this case, the acid contained in the photosensitive layer can be arbitrarily selected from any organic acid or inorganic acid. The organic acid is preferably a monocarboxylic acid or a polycarboxylic acid having at least one carboxyl group. Malic acid, tartaric acid, and polyacrylic acid (such as those commercially available under the trade name Jurimer) can be preferably used. As the inorganic acid, phosphoric acid or the like can be used.

When containing an acid anhydride, the type of acid anhydride is arbitrary, such as acetic anhydride, propionic anhydride, benzoic anhydride,
Examples include those derived from aliphatic/aromatic monocarboxylic acids, and those derived from aliphatic/aromatic dicarboxylic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride.

The photosensitive material composition for forming the photosensitive layer of the photosensitive material according to the present invention may contain a dye, particularly a dye that changes color from color to colorless or changes color upon processing.

Preferably, it contains a pigment that changes color from color to colorless.

In carrying out the present invention, the following can be mentioned as dyes that can be preferably used.

That is, for example, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue 6603 (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 B1 auramine, 4-p-dimethylaminophenyl imino naphthoquine, cyano - Triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes such as p-diethylaminophenylacetanilide are pigments that change color from colored to colorless or to a different color. This can be cited as an example.

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

The above-mentioned color changing agent is generally included in the photosensitive composition at about 0.5 to about IO
Preferably, it contains about 1% by weight, more preferably about 1% by weight.
Contain up to 5% by weight.

Various additives can be further added to the photosensitive composition forming the photosensitive layer of the photosensitive material according to the present invention.

In addition, alkyl ethers [(e.g. ethyl cellulose, methyl cellulose), fluorine surfactants, nonionic surfactants [e.g. Pluroninc L-64 (manufactured by Asahi Denka Corporation)] to improve coating properties, and Plasticizers for imparting flexibility and abrasion resistance (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), oil sensitivity of image area Sensitizers (for example, half esters of styrene-maleic anhydride M with alcohol as disclosed in JP-A-55-527), stabilizers [for example, phosphoric acid, phosphorous acid, etc.] , mfa (citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-
2-hydroxybenzophenone-5-sulfonic acid, tartaric acid, etc.). The amount of these additives to be added varies depending on the object and purpose of the product, but it is preferably 0.01 to 30% by weight based on the total solid content.

In order to place such a photosensitive composition on a support, predetermined amounts of the above-mentioned diazo resin and various additives as necessary are mixed with a suitable solvent (methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, acetone, A coating solution of the photosensitive composition may be prepared by dissolving the photosensitive composition in methyl ethyl ketone, methanol, dimethylformamide, dimethyl sulfoxide, water, or a mixture thereof, and this may be coated on a support and dried. The concentration of the photosensitive composition during coating is preferably in the range of 1 to 50%. In this case, the coating amount of the photosensitive composition is preferably approximately 0.
．． It may be about 2 to 10 g/rd.

In the photosensitive material according to the present invention, various types of supports can be used as the support on which the photosensitive composition is applied to form the photosensitive layer. When used in photosensitive planographic printing plates, aluminum plates are particularly preferred.

However, if an aluminum plate is used without treatment, there are problems in that the adhesion of the photosensitive composition is poor and the photosensitive composition decomposes. In order to eliminate this problem, various proposals have been made in the past.

For example, a method in which the surface of an aluminum plate is grained and then treated with a silicate (U.S. Pat. No. 2,714.066), and a method in which the surface of an aluminum plate is treated with an organic acid salt (U.S. Pat. No. 2,714.066).
066), treatment with phosphonic acids and their derivatives (U.S. Pat. No. 3,220.832), treatment with potassium hexafluorozirconate (U.S. Pat. No. 2,220,832),
, 946.683), a method of anodic oxidation, and a method of treating with an aqueous solution of alkali metal silicate after anodization (US Pat. No. 3,181.461).

In a preferred embodiment of the present invention, the surface of the aluminum plate (including the alumina laminate; the same applies hereinafter) is degreased, and then sanded by a brush polishing method, a ball polishing method, a chemical polishing method, an electrolytic polishing/nitching method, etc. Graining is applied, preferably by an electrolytic etching method which produces deep and uniform grains.

The anodizing treatment is carried out in an aqueous solution of an inorganic salt such as phosphoric acid, chromic acid, boric acid, sulfuric acid, or an organic acid such as oxalic acid, or a mixture of two or more of these acids, preferably in an aqueous sulfuric acid solution. This is done by passing an electric current through an aluminum plate as an anode. The amount of anodic oxide film is 5-6
0 ■/d% is preferable, more preferably 5 to 30 ■/d
It is rrf.

When carrying out sealing treatment in carrying out the present invention, preferably a sodium silicate aqueous solution with a concentration of 0.1 to 3% is added at a temperature of 8.
This treatment is carried out by immersion at 0 to 95° C. for lθ seconds to 2 minutes.

More preferably, it is then soaked in water at a temperature of 40 to 95°C for 10 seconds to 2
Soak and process for a minute.

The photosensitive material according to the present invention can be exposed and developed by conventional methods. That is, for example, a negative leaf image can be obtained with respect to the original image by exposing the transparent original image having a line image, halftone image, etc. to light, and then developing with an aqueous developer.

Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, and the like.

In the present invention, the photosensitive material according to the present invention is prepared using a developer having a pH of 12.0 or higher at 25° C. and containing substantially no organic solvent (hereinafter appropriately referred to as "developer according to the present invention"). Developed.

The developer according to the present invention will be explained below.

The developer according to the present invention is an alkaline aqueous solution having a pH of 12.degree. or more at 25.degree. The developer according to the present invention can contain an alkaline agent to adjust the pH to the above range, but the alkaline agents to be contained are preferably potassium silicate, lithium silicate, sodium silicate, hydroxide, etc. Sodium, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate,
Examples include tribasic potassium phosphate, 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 the most preferable because it has good development gradation, and the composition of the alkali silicate is (
S tow ) / CM) -0.5 to 1.5 (here [
SiO□] and (M) indicate the molar concentration of SiO2 and the molar concentration of total alkali metals, respectively. ), and 5tO
A developer containing 0.8 to 8% by weight of z is particularly preferably used.

Of this alkali silicate composition, especially in terms of molar ratio (S i
Ox ) / (M) = 0.5 to 0.75,
A developing solution containing 0.8 to 4% by weight of SiO is preferably used because it is easy to neutralize the developing waste solution due to its low concentration. A developer containing 1 to 8% by weight of SiO2 is preferably used because it has a high buffering power and a high throughput.

The pH of the developer according to the present invention at 25° C. is 12.0 or more, preferably 12.5 to 14.0.

Furthermore, water-soluble sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite can be added to the developer. The preferred content of sulfite in the developer composition is 0.05 to 4
It is more preferably 0.1 to 1li1% by weight.

Furthermore, the developer according to the present invention contains Japanese Patent Application Laid-Open No. 50-513
Anionic surfactants and amphoteric surfactants such as those described in JP-A-59-75255, JP-A-60-111246 and JP-A-60-2139
By containing at least one kind of nonionic surfactants such as those described in Japanese Patent Application Laid-open No. 55-95946 and Japanese Patent Application Laid-open No. 5644252.
As described in Japanese Patent No. 8, by incorporating a polymer electrolyte, the wettability to the photosensitive composition can be improved and the PJ tonality can be further improved, and thus it is preferably used. There is no particular limit to the amount of surfactant added, but 0.00
A concentration of 3 to 3% by weight is preferred, particularly a concentration of 0.006 to 1% by weight. Furthermore, it is preferable that the alkali silicate contains 20 mol% or more of potassium as the alkali metal out of all the alkali metals, from the viewpoint of less generation of insoluble matter in the developer, and more preferably 90 mol% or more of potassium. and most preferably 100 mol% potassium
This is the case.

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

The developer according to the present invention is substantially free of organic solvents. "Substantially free of" means that the present invention includes the presence of a small amount of the component without impairing the effects of the present invention.

After imagewise exposure, the photosensitive material according to the present invention can be brought into contact with the developer according to the present invention, or by rubbing with the developer, the photosensitive material can be exposed to 10 to 60%
After a few seconds, the photosensitive composition in the non-exposed areas of the photosensitive composition layer is completely removed without adversely affecting the exposed areas of the photosensitive composition layer. In this case, the developing ability is high (and the rigidity resistance is particularly good).

Furthermore, since substantially no organic solvents are used, pollution and occupational health problems are solved.

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

In this case, an image-exposed photosensitive lithographic printing plate (rP
The method for developing the S plate (sometimes referred to as "S plate") with the developer according to the present invention is arbitrary, and for example, various conventionally known methods can be used.

Specifically, methods include immersing an image-exposed PS plate in a developer, spraying the developer from multiple nozzles onto the photosensitive layer of the PS plate, and exposing the PS plate using a sponge moistened with the developer. Various methods can be used, such as wiping the layer and applying a developer to the surface of the photosensitive layer of the PS plate with a roller. Further, after applying the developer to the photosensitive layer of the PS plate in this manner, the surface of the photosensitive layer can be lightly rubbed with a brush or the like.

The developing conditions can be appropriately selected depending on the developing method. - For example, in the development method by immersion, a method of immersing the film in a developer solution at about 10 to 40° C. for about 10 to 80 seconds can be used.

(Example) Examples of the present invention will be described below. As a matter of course, the present invention is not limited to the following examples.

Prior to specific description of Examples, the polymer compound and diazo resin used in each Example will be explained.

8 (11) N-(4-hydroxyphenyl)methacrylamide 17.7 g Methacrylic acid 12.9 g Acrylonitrile 10.6 g Ethyl acrylate 55.0 g Azobisisobutyronitrile 1.64 g or more was added to acetone-methanol. After the reaction was completed, the reaction solution was poured into water 51 with stirring, and the resulting white precipitate was filtered and dried. 86g of polymer compound [1,) was obtained.

When the molecular weight of this polymer compound (1) was measured by gel permeability chromatography (hereinafter abbreviated as GPC) using a polystyrene standard, the weight average molecular weight was 35.000.

Further, the acid value of this polymer compound (1) was determined to be 104 by titration as explained above.

Examples 2 to 9 Polymer compounds (2) to (9) were synthesized in the same manner as above.

Table 1 shows the monomer composition ratio, average molecular weight, and acid value of each polymer compound.

Since polymer compounds (1) to (7) have an acid value of 100 or more, they fall within the scope of the present invention, but polymer compounds (8) (
9) is 14.5 g (50
IJ mol) was dissolved in 40 g of concentrated sulfuric acid under water cooling.

To this reaction solution, 1.05 g (35 mmol) of rose formaldehyde was slowly added dropwise. At this time, the addition was made so that the reaction temperature did not exceed 10'C. Thereafter, the mixture was stirred for 2 hours under water cooling. This reaction mixture was added dropwise to 500 d of ethanol under water cooling, and the resulting precipitate was filtered off. After washing the precipitate with ethanol, it was dissolved in 100 d of pure water, and 6. An aqueous solution in which 8 g of zinc chloride was dissolved was added. The resulting precipitate was filtered, washed with ethanol, and dissolved in 150 d of pure water. To this solution, 8 g
An aqueous solution in which ammonium hexafluorophosphate was dissolved was added, and the resulting precipitate was filtered off, washed with water and ethanol, and then dried at 25° C. for 3 days to obtain diazo resin (1).

Diazo 1 (2) A p-hydroxybenzoic acid 3.5 g (25 mmol)
, and P-diazodiphenylamine sulfate 21.75
g (75 mmol) was dissolved in 90 g of concentrated sulfuric acid under water cooling.

To this solution, 2.7 g (90 mmol) of paraformaldehyde was slowly added.
It was added so as not to exceed ℃. After stirring the reaction solution for 2 hours, it was added dropwise to ethanol in step 11, and the resulting precipitate R;
It was filtered and washed with ethanol. The precipitate was dissolved in 2007 pure water, and an aqueous solution containing 10.5 g of zinc chloride was added. The resulting precipitate was filtered, washed with ethanol, and then dissolved in 300 d of pure water. To this solution, add 13.7g
An aqueous solution of ammonium hexafluorophosphate was added. The resulting precipitate was filtered, washed with water and ethanol, and dried at 25°C for - days to obtain diazo resin (2).
I got it.

A of Diazo resin (3) In the synthesis of diazo resin (2), 4.2 g of P-methoxybenzoic acid (25
A diazo resin (3) was obtained by synthesizing in the same manner using (mmol).

Next, an example will be described.

Example 1 A photosensitive solution having the following composition-1 was applied onto an anodized aluminum plate in a grained chamber until the coating weight after drying was 201.
A photosensitive lithographic printing plate sample, which is a sample according to the present invention, was prepared by coating at a concentration of 1 g/drrf.

Composition-1 As Comparative Example-1, a photosensitive lithographic printing plate was prepared using the polymer compound (8) instead of the polymer compound (1) of the photosensitive liquid composition-1, and otherwise coated in the same manner as above. A sample was prepared and used as a comparison sample.

A negative transparent original image was placed on each of the obtained samples, exposed for 30 seconds from a distance of 60 cm using a 2KW metal halide lamp, then immersed in developer (1) with the following composition at 27°C for 220 seconds, and then rubbed lightly with absorbent cotton. Developed.

Composition of developer (1) (pH at 25°C: 12.8) When the obtained lithographic printing plate was printed with a Heidelberg GTO printing machine, in the sample according to the present invention, there was no stain at all on the non-image area of the paper surface. However, in the comparative sample, stains were observed on a part of the paper surface.

Next, each coated sample was forcibly stored at 55° C. and 20% R11 humidity, and then exposed, developed, and printed in the same manner as described above.

The comparison sample had stains all over the printed matter after 3 days of forced storage, but the sample according to the present invention had no stains at all even after 5 days of forced storage.

Examples-2 to 9 and Comparative Example-2 The diazo resin (1) and polymer compound (11) of the photosensitive liquid of composition-1 above were replaced with those shown in Table-2, and the other conditions were the same. Samples were prepared and evaluated in the same manner as described above.

Example-10 and Comparative Example-3 The diazo resin (11) and polymer compound (1, 1) of the photosensitive liquid of composition-1 above were replaced with those shown in Table-2, and the other conditions were the same. It was created.

The obtained sample was exposed in the same manner as described above, and then developed in the same manner with developer (II) having the following composition, and evaluated in the same manner as described above.

Developer solution (II) composition table 2 (pH at 25°C is 13.0) From Table 2, the sample obtained in the comparative example was partially stained even if it was not stored, and after being stored with forced deterioration. While stains occur on the entire surface of the paper, the samples according to the present invention obtained by each of the examples of the present invention are either completely free of stains even when unstored or after storage, or are only partially stained after storage. , it turns out to be excellent.

0: The non-print area is not stained at all.

△　2　Partial staining occurs.

×　;　The entire paper surface is stained.

[Effects of the Invention] As described above, since the method for developing a photosensitive material containing a diazo resin of the present invention uses a developer that does not contain an organic solvent, it is possible to solve the problems associated with the use of organic solvents, and it also improves developability, especially long-term development. It has excellent developability when stored for a period of time, and has the effect of not causing stains even when used for printing, for example when applied to a developing method for photosensitive planographic printing plates.

Claims (1)

[Claims] 1. A photosensitive material having a photosensitive layer containing a diazo resin and a polymer compound with an acid value of 100 or more on a support,
A method for developing a diazo resin-containing photosensitive material, which comprises developing with a developer having a pH of 12.0 or higher at °C and substantially containing no organic solvent.