JPH02217860A - Method for developing photosensitive materials containing diazo resin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 light of recent pollution control problems, it is not preferable for the waste liquid to contain organic solvents, and if organic solvents are used, it will take time and money to process the waste liquid.

[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 found that a photosensitive material having a photosensitive layer containing a diazo resin, a polymer compound with an acid value of less than 100, and an acid and/or an acid anhydride on a support at 25°C.
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 having a pH of 12.0 or higher and containing substantially no aqueous solvent, and has thus arrived at 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, the 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 less than 100 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 2. 3 is preferred. When a carboxyl group or a hydroxyl group is bonded to an aromatic ring via a bonding group, the bonding group includes, for example, a group having 1 to 4 carbon atoms.
Examples include alkylene groups.

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, O-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 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, 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-dihydroxy-6-methylbenzoic acid, 2゜6-dihydroxy Benzoic acid, 2,6-cyhydroxy-4-benzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2
, 6-dioxybenzoic acid, gallic acid, phloroglucincarboxylic acid, 2,4.5-)dihydroxybenzoic acid, m-
Galloyl gallic acid, tannic acid, m-benzoyl gallic acid, m-(p-)ruyl) gallic acid, protocatechoyl gallic acid, 4,6-cyhydroxyphthalic acid, (2,
4-dihydroxyphenyl)acetic acid, (236-cyhydroxyphenyl)acetic acid, (3,4,5-trihydroxyphenyl)acetic acid, p-hydroxymethylbenzoic acid, p~hydroxyethylbenzoic acid H14-(p-hydroxyphenyl) Methylbenzoic acid, 4-(o-hydroxybenzoyl)benzoic acid, 4-(2,4-dihydroxybenzoyl)
Benzoic acid, 4-(p-hydroxyphenoxy)benzoic acid, 4-(p-hydroxyanilino)benzoic acid, bis(3
-carboxy-4-hydroxyphenyl)amine, 4-
(p-hydroxyphenylsulfonyl)benzoic acid, 4-
(p-hydroxyphenylthio)benzoic acid and the like can be mentioned. Particularly preferred among these are salicylic acid, p-hydroxybenzoic acid, P-methoxybenzoic acid, and metachlorobenzoic acid.

For the aromatic diazonium compound used as the structural 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.
In particular, diphenylamine-4-diazonium salts are preferred. Diphenylamine-4-diazonium salts are
Although derived from 4-amino-diphenylamines, such 4-7minodiphenylamines 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-ethoxydiphenylamine, 4-amino-3-β-hydroxy-ethoxydiphenylamine, 4
-Amino-diphenylamine-2-sulfonic acid, 4-aminodiphenylamine-2-carboxylic acid, 4-amino-
Diphenylamine-2°-carboxylic acid and the like can be mentioned. Particularly preferred are 3-methoxy-4-amino-diphenylamine and 4-amino-diphenylamine.

The co-condensed diazo resin that can be used in the present invention is preferably one represented by the following general formula (1).

General formula C1) In general formula (1), A is a group derived from an aromatic compound having at least either a carboxyl group or a hydroxyl group, and examples of such aromatic compounds include those listed above. Can be done.

In the formula, R1, R2 and R3 represent a hydrogen atom, an alkyl group or a phenyl group, R represents a hydrogen atom, an alkyl group or a phenyl group, X represents a counter anion, and n preferably represents a number from 1 to 200. show.

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 combination 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. It is obtained by polycondensation of salts, aromatic compounds having carboxyl and hydroxyl groups and aldehydes such as paraformaldehyde, acetaldehyde, benzaldehyde or ketones such as acetone and acetophenone.

Furthermore, 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. 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 1:0.1 to o, i:t,
More preferably 1:O,S to 0.21, still more preferably 1:l to 0.2:l. 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.
:0.6-1.2, more preferably 1:0.7-1.5
A co-condensed diazo resin can be obtained by reacting at a low temperature for a short 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 a-containing 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, 22°, 4.4°-tetrahydroxybenzophenone, 1.2.3-trihydroxybenzophenone, 2.2',4-)lihydroxybenzo Aromatic compounds containing hydroxyl groups such as phenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, CeO2,
Examples include perhalogen acids such as 104, but are not limited thereto. 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, in general, 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.

Sci, 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 (n), and the resin in which n in each formula is 5 or more is 20 mol% or more, more preferably 20 mol% or more. In the formula 0 containing ~60 mol%, R
3 to R1, R, X, and n are represented by the general formula [! ] has the same meaning as that in ). In general formula (If), R1, R2
Examples of the alkyl group and alkoxy group of R1 include an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms, and examples of the alkyl group of R1 include an alkyl group having 1 to 5 carbon atoms. can be mentioned.

General formula (n) 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 U.S. 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.

As the counter anion of the diazo resin represented by the general formula (II), the same counter anions as mentioned for the co-condensed diazo resin can be mentioned.

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 less than 100.

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 was diluted 50 times with methyl cellosolve and o. Titrate with a specified aqueous potassium hydroxide 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 CPC 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. This can be carried out by leveling the peaks of the oligomer region (connecting the center lines of the peaks and valleys) according to the method described in "Journal of Japan," pages 800 to 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 less than 100 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, shrink, epoxy resin, phenol resin, acrylic resin, and the like.

Preferably, a copolymer of the monomers shown in (1) to (12) below is used, and the copolymer has an acid value within the range of the present invention.

(1) Hetamine-1 having an aromatic hydroxyl group, e.g.
-hydroxyphenyl)acrylamide or N-(4
-hydroxyphenyl) methacrylamide, o-! -,
m-, p-hydroxystyrene, o +, m-, p-
Hydroxyphenyl-acrylate or -methacrylate.

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

(3) α1 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 acrylate, octyl acrylate, acrylic acid-
(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-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylamide, etc.

Furthermore, a heptamer that can be copolymerized with the above-mentioned heptamer 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.

More specifically, a copolymer having a hydroxyl group containing the heptamers listed in (1) and (2) above is preferred, and a copolymer having an aromatic hydroxyl group 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 less than 100 used in the present invention are the following copolymers.

That is, in the molecular structure, (a) a structural unit having an alcoholic hydroxyl group and/or
or 1 to 50 structural units having a phenolic hydroxyl group.
Mol%, (b) General formula IA-CI! -C-......IA (in the formula,
R11 represents a hydrogen atom or an alkyl group. ) 5 to 40 mol% of the structural unit represented by (C) the following general formula 11A Rls -c n t -c-...■AC0OR
' Co (in the formula, R1! 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). Polymer compounds containing 25 to 60 mol % are preferred. Copolymers of such compounds whose acid value is less than 100 are preferred.

Specific examples of the monomer forming the structural unit having an alcoholic hydroxyl group in (a) above include Japanese Patent Publication No. 52-736
Examples include (meth)acrylic acid esters and acrylamides such as the compounds shown in the following General 2 mA as described in No. 4.

CIl□-C-・・・・・・・・・mACOO+CIL
zCHO→1-H 1171% In the formula, RI4 represents a hydrogen atom or a methyl group, Rls represents a hydrogen atom, a methyl group, an ethyl group, or a chloromethyl group, and n represents an integer of 1 to 10.

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

Preferably it is 2-hydroxyethyl (meth)acrylate.

In addition, examples of the seven polymers forming the structural unit having a phenolic hydroxyl group in (a) above include N-(4-hydroxyphenyl)-(meth)acrylamide, N-(
2-hydroxyphenyl)-(meth)acrylamide,
Monomers of (meth)acrylamides such as N-(4-hydroxynaphthyl)-(meth)acrylamide SO-,
Examples include m- or p-hydroxyphenyl (meth)acrylate monomers; o-, m- or p-hydroxystyrene monomers. Preferably they are o-, m- or P-hydroxyphenyl (meth)acrylate monomers, N-(4-hydroxyphenyl)-(meth)acrylamide monomers, and more preferably N-(4-
Hydroxyphenyl)-(meth)acrylamide monomer.

The structural unit having an alcoholic hydroxyl group and/or the structural unit having a phenolic hydroxyl group is 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 methachloronitrile.

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 monomers having a carboxy ester group in the side chain forming the structural unit represented by the general 2〇A include ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, Octyl acrylate, 2-chloroethyl acrylate,
Examples include 2-hydroxyethyl acrylate and glycidyl acrylate. The unit formed from the hexamer is preferably selected from the range of 25 to 60 mol%, more preferably 35 to 60 mol% in the polymer compound.

In addition, the above-mentioned preferred polymer compound has, in its molecular structure,
It may also contain a structural unit having a carboxyl group.

Examples of the monomer forming the structural unit having a carboxyl group include methacrylic acid, acrylic acid, maleic anhydride, and maleic acid. The gynomer is preferably selected from the range of 2 to 30 mol%, more preferably 5 to 15 mol% in the polymer compound.

In addition, each of the above-mentioned structural units 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 the present invention, the acid contained in the photosensitive layer can be arbitrarily selected from any organic acid or inorganic acid. As the organic acid, acids having at least one carboxyl group such as monocarboxylic acids and polycarboxylic acids are preferred, such as malic acid, tartaric acid, and polyacrylic acid (
Those commercially available under the trade name Jurimer, etc.) can be preferably used. As the inorganic acid, phosphoric acid or the like can be used. These acids are preferably contained in the photosensitive layer in an amount of 0.05 to 10% by weight, more preferably 0.1 to 10% by weight.
The content is preferably 8% by weight.

In the present invention, any acid anhydride can be used as the acid anhydride contained in the photosensitive layer. For example, all known various acid anhydrides can be used, but cyclic acid anhydrides are preferred, Examples of such substances include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-nindooxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, glutaric anhydride,
Examples include maleic anhydride, talol maleic anhydride, α-phenyl maleic anhydride, succinic anhydride, pyromellitic acid, and the like. These acid anhydrides are contained in the photosensitive layer in an amount of 0.05 to
It is preferably contained in an amount of 10% by weight, particularly 0.1 to 5% by weight.

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 colored to colorless or changes color upon processing.

Preferably, a pigment that changes from colored to colorless is contained.

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 4603 (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, Pesic Tsuksin, Malachite Green, Oil Red, m-Cresol Purple, Rhodamine B1 Auramine, 4-p-dimethylaminophenyl imino naphthoquine , triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based pigments such as cyano-p-diethylaminophenyl acetanilide change color from colored to colorless or to a different color. Examples of pigments include:

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 added in the photosensitive composition from 0.5 to about 1O
It is preferable to contain the amount 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.

Additionally, 1 liter of alkyl ether to improve coating properties.
(e.g. ethyl cellulose, methyl cellulose), fluorine surfactants, nonionic surfactants [e.g. Pluronic L-64 (manufactured by Asahi Denka Corporation)], plasticizers to impart flexibility and abrasion resistance to the coating film. agents (e.g. butyl phthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, diethyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylate) (acid oligomers and polymers), oil-sensitizing agents for improving the oil-sensitivity of image areas (e.g., half-esterification of styrene-maleic anhydride copolymer with alcohol as disclosed in JP-A No. 55-527) , stabilizers [e.g. phosphoric acid, phosphorous acid, organic alts (citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5-sulfonic acid,
tartaric acid, etc.)]. The amount of these additives added varies depending on the object and purpose of use, but is generally preferably from o, oi 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 liquid 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 the coating solution may be applied onto a support or special holiday and dried. The concentration of the photosensitive composition during coating is preferably in the range of 1 to 50% by weight. In this case, the coating amount of the photosensitive composition is preferably about 0.2 to 10 g/rrf.

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 1:1 schemes have been proposed.

For example, a method in which the surface of an aluminum plate is grained and then treated with a silicate (US Pat. No. 2,714.066), a method in which the surface of an aluminum plate is treated with an organic acid salt (US Pat. No. 2,714.
066), treatment with phosphonic acids and their derivatives (U.S. Pat. No. 3,220,832), treatment with hexafluorodino (potassium conate (U.S. Pat. No. 2,946,683), anodes There are a method of oxidation, a method of treating with an aqueous solution of an anosikalic metal silicate after anodization (US Pat. No. 3,181,461), and the like.

In a preferred embodiment of the present invention, after degreasing the surface of the aluminum plate (including an alumina laminate; the same applies hereinafter), the aluminum plate (including an alumina laminate) is subjected to grain removal by a brush polishing method, a ball polishing method, a chemical polishing method, an electrolytic etching method, etc. The grains are preferably etched using an electrolytic etching method which produces deep and uniform grains.

The anodizing treatment is carried out, for example, in an aqueous solution of an inorganic salt such as phosphoric acid, chromic acid, boric acid, or 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. The amount of anodic oxide film is 5 to 6, which is done by passing electric current through an aluminum plate as an anode.
0 ■/drd is preferable, more preferably 5 to 30 m/drd.
drrf.

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 10 seconds to 2 minutes.

More preferably, it is then soaked in water at 40 to 95°C for lθ 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 "developing solution 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 12.0 or more at 25°C. The developing solution according to the present invention can contain an alkaline agent to adjust the pH to the above range, but the alkaline agent to be contained is preferably potassium silicate, sulfur silicate, etc. , sodium silicate, sodium hydroxide, 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 to, ) / (M) = 0.5 to 1.5 (here (S
ing) and (M) indicate the molar concentration of sto and the total alkali metal concentration, respectively. ), and SiO□
A developing solution containing 0.8 to 8% by weight of is particularly preferably used.

Of this alkali silicate composition, especially in terms of molar ratio (S 5
0− ) / (M) = 0.5 to 0.75,
A developing solution with a Sin content of 0.8 to 4% by weight is preferably used because it is easy to neutralize the developing waste solution due to its low concentration. A developer having a 5iOffi of 1 to 8% by weight 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
The amount is preferably 0.1-1% by weight.

Furthermore, 1.-The developing solution according to the present invention contains JP-A-50-5
Anionic surfactants and amphoteric surfactants as described in JP-A-1324, JP-A-59-75255
No. 60-111246 and No. 60-21
By containing at least one kind of nonionic surfactants such as those described in JP-A-55-95946 and JP-A-56-14.
As described in Japanese Patent No. 2528, by incorporating a polymer electrolyte, the wettability of the photosensitive composition can be increased,
It is preferably used because it can further improve gradation. There is no particular limit to the amount of such surfactant added, but 0.
0 (preferably 13 to 3% by weight, particularly preferably 0.006 to 1% by weight. Furthermore, as the alkali metal of the alkali silicate, 20 mol% of potassium is added to the total alkali metals.
It is preferable to contain 90 mol% of potassium in terms of less generation of insoluble matters in the developer, and more preferably 90 mol% of potassium.
or more, most preferably potassium is 100% or more.
This is a case of mol%.

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" means that the present invention covers cases in which the substance is contained in a small amount 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 printing durability 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 descriptions of the examples, the polymer compound (in this example, a lipophilic polymer compound was particularly used), diazo resin, and grained plate used in each example will be described.

t Human ■ N-(4-hydroxyphenyl)-methacrylamide 18g acrylonitrile 16g ethyl acrylate 75g methacrylic acid 9.2g azobisisobutyronitrile 4.1g Dissolve the above in acetone-methanol 1:1 mixed solution 240g. After purging with nitrogen, the mixture was heated at 60° C. for 6 hours.

After the reaction is complete, add 2.5 liters of water to the reaction solution. The resulting white precipitate was collected by filtration and dried to obtain 110 g of lipophilic polymer compound (1).

This lipophilic polymer compound (1) was subjected to polystyrene standard gel vermicion chromatography (hereinafter referred to as GPC).
The weight average molecular weight was 58,000.

Further, when this lipophilic polymer compound (1) was titrated with a 0.1N aqueous potassium hydroxide solution, the acid value was 62.
It was 0.

A (2) 2-Hydroxyethyl methacrylate I 3.0 g Methacrylic acid 8.6 g Acrylonitrile 10.6 g Ethyl acrylate 60. After dissolving 1.64 g of Og azobisisobutyronitrile in a 1:1 mixed solution of acetone and methanol and purging with nitrogen,
Heated at 60"C for 6 hours.

Hereinafter, in the same manner as the method for lipophilic polymer compound (1),
83.0g of lipophilic polymer compound (2) was obtained.

This lipophilic polymer compound (2) was subjected to GPC in the same manner as above.
When the molecular weight was measured, the weight average molecular weight was 67.000.

Furthermore, when this lipophilic polymer compound (2) was titrated with an aqueous solution of normal potassium hydroxide, the acid value was 74.6.
Met.

Add 50 g of 4-diazodiphenylamine sulfate to 1 ml under water cooling.
Dissolved in 70g of concentrated sulfuric acid. After dissolution, 4.6 g of rose formaldehyde was slowly added. At this time, the addition was made so that the reaction temperature did not exceed 10°C.
Stirring was continued for 2 hours under water cooling.

This reaction mixture was poured into 1.21 ethanol under water cooling, and the resulting precipitate was collected by filtration. After washing with ethanol, this precipitate is 200111! Dissolve in pure water and add 2 to this solution.
A cold concentrated aqueous solution of 0 g of zinc chloride was added.

The resulting precipitate was collected by filtration, washed with ethanol, and dissolved in 500 d of pure water. To this liquid was added a cold concentrated aqueous solution in which 26 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was filtered, washed with water, and then dried at 30° C. day and night to obtain diazo resin 1.

When the molecular weight of this diazo resin 1 was measured by GPC, the weight average molecular weight was about 2,300.

The main diazo resin 2 can be synthesized by the same method after dissolving 25 g of 4-diazodiphenylamine sulfate and 12 g of parahydroxybenzoic acid in concentrated sulfuric acid.

Next, an example will be described.

Example 1 An aluminum plate was degreased with a 3% aqueous sodium hydroxide solution, electrolytically etched in a 2% hydrochloric acid bath at a current density of 53 A/dnf at 25°C, washed with water, and etched in a 30% sulfuric acid bath for 30 minutes.
Anodizing was carried out for 2 minutes at 0° C. and 1.5 A/dn.

Next, using a 1% sodium metasilicate aqueous solution,
The pores were sealed for 30 seconds, washed with water, and dried to obtain an aluminum plate for planographic printing.

A photosensitive liquid having the following composition was applied to this aluminum fist plate so that the film volume after drying was 1.7 g/nf.

photosensitive liquid This was done based on how dirty the paper was.

The results are shown in Table-1.

As understood from Table 1, according to the developing method of the present invention, it is possible to develop a lithographic printing plate with excellent developability and storage developability.

The resulting photosensitive lithographic printing plate was exposed to light for 30 seconds from a distance of 60 cm using a metal halide lamp with a negative transparent original image in close contact with it, and a developer having the following composition (PS plate developer 5DR-1 (Konica (manufactured by ■) diluted 6 times), 2
The film was immersed at 7° C. in 12 O for 2 seconds and developed by rubbing lightly with absorbent cotton.

Developer Composition (pH at 25°C: 12.8) Next, the above photosensitive lithographic printing plate was forcibly stored (55°C for 3 days), and then plate-making was performed in the same manner as above.

Evaluation of developability was carried out by printing using the above-mentioned plate. [Effects of the Invention] As mentioned above, since the method for developing the diazo resin-containing fluorescent material of the present invention uses a developer that does not contain an organic solvent, It solves the problems associated with the use of organic solvents, and has excellent developability, especially when stored for a long period of time. It has the effect of not causing stains even when

Claims (1)

[Claims] 1. A photosensitive material having a photosensitive layer containing a diazo resin, a polymer compound with an acid value of less than 100, and an acid and/or an acid anhydride on a support has a pH of 12.0 or more at 25° C. A method for developing a diazo resin-containing photosensitive material, which involves developing with a developer that does not substantially contain an organic solvent.