JPH02220062A - Method for developing photosensitive material containing diazo resin - Google Patents

Abstract

PURPOSE:To enhance ability of a developer and to avoid environmental pollution due to organic solvents by developing a photosensitive material having a photosensitive layer containing a diazo resin and an alkali-soluble and -swellable polymer with a developer adjusted in pH and not containing any organic solvent. CONSTITUTION:The polycondensed diazo resin composed of structural units derived from an aromatic compound having at least one of carboxylic or hydroxyl group and an aromatic diazonium compound is used as the diazonium resin. The alkali-soluble and -swellable polymer functions as a binder at the time of constituting a photosensitive composition. Such a photosensitive material is developed with the developer having a pH of >=12.0 at 25 deg.C and containing substantially no organic solvent, and the developer is embodied by an alkaline agent, preferably, such as an aqueous solution of potassium, lithium, or sodium silicate.

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 lithographic 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, the desired development cannot be achieved simply by removing the organic solvent. If development is simply performed using a developer that does not contain an organic solvent, a portion that should be removed by development remains, and this is used for printing. If you do so, it will become dirty. Such stains are unacceptable and cannot be put to practical use, especially when used as a photosensitive material for printing. Further, film peeling may occur, which is also an unacceptable problem. It is conceivable to increase the progress of development by increasing the pH while removing the organic solvent, but this alone will not solve the problems such as the above-mentioned stains.

The present invention solves the above problems and uses 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 making it suitable for printing. 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 or the like even when exposed to light-sensitive materials.

[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 an alkali-soluble/swellable polymer compound on a support has a pH of 12.
It has been discovered that the above-mentioned problems can be solved by a method for developing a photosensitive material containing a diazo resin, which involves developing with a developer containing a diazo resin of 0 or more and substantially free of organic solvents, leading to the present invention.

In the present invention, the alkali-soluble/swellable polymer compound refers to an alkali-soluble and/or swellable polymer compound, and includes an alkali-soluble polymer compound, an alkali-swellable polymer compound, and an alkali-soluble and alkali-swellable polymer compound. This is a general term for the concept that includes chemical polymer compounds.

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 an alkali-soluble/swellable polymer compound 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, O-chlorobenzoic acid, m-
Chlorobenzoic acid, p-chlorobenzoic acid, phthalic acid, terephthalic acid, diphenylacetic acid, phenoxyacetic acid, p-methoxyphenylacetic acid, p-methoxybenzoic acid, 2.4-dimethoxybenzoic acid, 2.4-dimethylbenzoic acid, 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-stialylsalicylic acid, 4.6-dimethylsalicylic acid, p-hydroxybenzoic acid, 2-methyl -4-hydroxybenzoic acid, 6-methyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2
．． 4-dihydroxy-6-methylbenzoic acid, 2゜6-dihydroxybenzoic acid, 2,6-cyhydroxy-4-benzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 4
-Methoxy-2,6-dioxybenzoic acid, gallic acid, phloroglucincarboxylic acid, 2,4.5-trihydroxybenzoic acid, m-galgallic acid, tannic acid, m-benzoyl gallic acid, m- (p-)ruyl) gallic acid, protocatechuo-gallic acid, 4,6-cyhydroxyphthala, (2,4-dihydroxyphenyl)acetic acid, (2
,6-dihydroxyphenyl)acetic acid, (3,4,5-)
dihydroxyphenyl)acetic acid, p-hydroxymethylbenzoic acid, p-hydroxyethylbenzoic acid, 4-(p-
Hydroxyphenyl)methylbenzoic acid, 4-(o-hydroxybenzoyl)benzoic acid, 4-(2,4-dihydroxybenzoyl)benzoic acid, 4(p-hydroxyphenoxy)benzoic acid, 4-(p-hydroxyanilino) Examples include benzoic acid, bis(3-carboxy-4-hydroxyphenyl)amine, 4-(p-hydroxyphenylsulfonyl)benzoic acid, and 4-(p-hydroxyphenylthio)benzoic acid. Among these, particularly preferred are salicylic acid, p-hydroxybenzoic acid,
p-methoxybenzoic acid and metachlorobenzoic acid.

For the aromatic diazonium compound used as a constitutional unit of the co-condensed diazo resin, 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 derived from 4-amino-diphenylamines,
Such 4-amino-diphenylamines include:
4-amino-diphenylamine, 4-amino-3-methoxy-diphenylamine, 4-amino-2-methoxy-
Diphenylamine, 4'-amino-2-methoxy-diphenylamine, 4'-amino-4-methoxydiphenylamine, 4-amino-3-methyldiphenylamine, 4-amino-3-ethoxy-diphenylamine, 4-
Amino-3-β-hydroxy-ethoxydiphenylamine, 4-amino-diphenylamine-2-sulfonic acid,
4-amino-diphenylamine-2-carboxylic acid, 4-
Amino-diphenylamine-2°-carboxylic acid and the like can be mentioned. Particularly preferably 3-methoxy-4-
Amino-diphenylamine and 4-amino-As the co-condensed diazo resin that can be used in the present invention, those represented by the following formula (1) are preferred.

-III In formula CI), A is a group derived from an aromatic compound containing at least one of a carboxyl group and a hydroxyl group, and examples of such aromatic compounds include those exemplified above.

In the formula, R,, R1 and R5 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 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 the co-condensed diazo resin to the m-condensed diazo resin is particularly preferably 30-70, nia 0-30, from the viewpoint of providing excellent sensitivity and developability.

The above-mentioned co-condensed diazo resins and the condensed diazo resins used in combination with these or independently as diazo resins can be prepared by known methods (41, for example, Photo Ink Science and Engineering Co., Ltd.). , Sc.
i, Eng,) Volume 17, Page 33 (1973), U.S. National Patent No. 2.063.631, National Patent No. 2,679,4
According to the methods described in each specification of No. 98, diazonium salts, aromatic compounds having carboxyl and hydroxyl groups, and aldehydes, such as paraformaldehyde, acetaldehyde, benzaldehyde, or ketones, such as acetone and acetophenone, in sulfuric acid, phosphoric acid, or hydrochloric acid. It is obtained by polycondensation of

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 0.1:1,
More preferably t:O,S~0.2:1, still more preferably 1:1~0.2:1.

In this case, the molar ratio of the total of aromatic compounds and aromatic diazonium compounds having a small amount (both of which have one of carboxyl groups and hydroxyl groups) to aldehydes or ketones is usually preferably 1; 0.6 to 1.2; A co-condensed diazo resin can be obtained by mixing more preferably at a ratio of 1:0.7 to 1.5 and 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 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-)lihydroxybenzophenone, 2.2',4 -) Hydroxyl group-containing aromatic compounds such as hydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, C
Examples include perhalogen acids such as ZO4,10, and the like. However, it is not limited to this.

Among these, particularly preferred are hexafluorophosphoric acid and tetrafluoroboric 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 s, ooo
O is appropriate.

In addition, in the present invention, other than the above-mentioned co-condensed diazo resins, those which can be preferably used as diazo resins include, for example, the above-mentioned Photographic Ink Science & Co., Ltd.
Engineer Link (Photo.

Sci, Eng.) Vol. 17, p. 33 (1973), and U.S. Pat.
No. 98, Specifications of No. 3゜050, No. 502, JP-A No. 1973
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. 9-78340, etc. , in Special Publication No. 49-4001,
Examples include diazo compounds and diphenyl resins whose production methods are described.

Among the above, the diazo resin that can be preferably used in the present invention is represented by the following 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. In formula 0, which contains ~60 mol%,
R1-R2, R, X, and n have the same meanings as in formula (1) above. - In formula (n), R,, Rt
Examples of the alkyl group and alkoxy group for R8 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 for R include an alkyl group having 1 to 5 carbon atoms. can be mentioned.

General 2(n) Such a photosensitive diazo resin can be produced by a known method, for example, the method described in the above-mentioned Photographic Ink Science and Engineering and other U.S. patent specifications cited above. can.

At that time, when polycondensing the diazonium salt and the aldehyde, the molar ratio of both is usually 1:0.6 to 1:
2. A highly sensitive diazo resin can be obtained by charging preferably at a ratio of 11.7 to 1:1.5 and reacting at a low temperature for a short time, for example, 10° C. or less for about 3 hours.

Examples of the counter anion of the diazo resin represented by the general formula (n) 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 an alkali-soluble/swellable polymer compound, that is, a polymer compound that is alkali-soluble, alkali-swellable, or has both properties. .

In the present invention, alkali-soluble refers to a substance that dissolves into an alkaline solution, particularly an alkaline solution with a pH of 12.0 or more at 25°C, and alkali-swellable refers to a substance that dissolves into the solution. , refers to a substance whose volume expands due to penetration of liquid in the alkaline solution, and when it is coated on a support, it becomes easy to peel off from the support.

Any alkali-soluble/swellable polymerized metal material as described above can be used in the present invention.

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 according to Morio Tsuge, Tatsuya Miyabayashi, Masayuki Tanaka, "Japan Chemical Society Journal 8
By the method described on pages 00 to 805 (1972),
This can be done by leveling the peaks of the oligomer region (connecting the center lines of the peaks and valleys).

The polymer compound that can be used in the present invention may be of any type as long as it is alkali-soluble and swellable as described above, and for example, the following compounds can be used. That is, the polymer compounds that can be used include polyamide, polyether, polyester, polycarbonate, polystyrene, polyurethane, polyvinyl chloride and its copolymers, polyvinyl butyral resin, polyvinyl formal resin, sielank, epoxy resin, phenol resin, acrylic resin, etc. can be mentioned.

Preferably, copolymers of the monomers shown in (1) to (12) below, which are alkali-soluble and swellable polymer compounds, are preferred.

(1) Monomers having aromatic hydroxyl groups, such as N-(4
-hydroxyphenyl)acrylamide or N-(4
-hydroxyphenyl) methacrylamide, o+, m+
, p-hydroxystyrene, o+, m-, p-hydroxyphenyl-acrylate or -methacrylate.

(2) Monomers having aliphatic hydroxyl groups, such as 2-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 acrylate, octyl acrylate, acrylic acid-
(substituted) alkyl acrylates such as 2-chloroethyl, 2-hydroxyethyl acrylate, glycidyl acrylate), 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, 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.

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 copolymer which is the alkali-soluble/swellable polymer compound used in the present invention are the following copolymers.

That is, in the molecular structure, (a) 1 to 50 mol% of a structural unit having an alcoholic hydroxyl group and/or a structural unit having a phenolic hydroxyl group, (b) the following formula IA (wherein, R is a hydrogen atom) or represents an alkyl group.) 5 to 40 mol% of the structural unit represented by
” (wherein, R12 represents a hydrogen atom, a methyl group, or an ethyl group, and RI3 represents an alkyl group having 2 to 12 carbon atoms or an alkyl-substituted aryl group) at 25 to 60 mol%. A polymer compound containing is preferred, and its weight average molecular weight is 20.000 to
Even more preferred are copolymers with a molecular weight of 200.000.

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 of the compounds shown in formula 1 [IA] as described in No. 4 include (meth)acrylic acid esters and acrylamides.

R eye C11t C-・・・・・・・・・mACOO+C
ToCHO7-H RIs In the formula, R14 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, 2-bitroxypentyl (meth)acrylate, and examples of acrylamides include , 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,
(meth)acrylamide monomers such as N-(4-hydroxynaphthyl)-(meth)acrylamide; O-,
Examples include m- or p-hydroxyphenyl (meth)acrylate monomers; o-, m- or p-hydroxystyrene monomers. Preferably, O-m- or p-hydroxyphenyl (meth)acrylate monomer, N-(4-hydroxyphenyl)-(meth)acrylamide monomer, more preferably N-(4-hydroxyphenyl)-(meth) It is an acrylamide monomer.

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

The monomers having a cyano group in the side chain and forming the structural unit represented by formula IA include acrylonitrile, methacrylonitrile, 2-pentynitrile, 2-
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 forming the structural unit represented by formula nA include ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate, amyl methacrylate, hexyl acrylate,
Examples include octyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, and glycidyl acrylate. The unit formed from the monomer preferably accounts for 25 to 60 mol% in the polymer compound,
More preferably, it is selected from the range of 35 to 60 mol%.

In addition, the above-mentioned preferred polymer compound has, in its molecular structure,
It may contain, for example, 2 to 30 mol% of a structural unit having a carboxyl group.

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

Note that each of the above structural units is not limited to units formed from the monomers listed as specific examples.

The alkali-soluble/swellable polymer compound contained in the photosensitive material according to the present invention is preferably usually 40 to 99% by weight, more preferably 40% to 99% by weight, based on the solid content of the photosensitive composition constituting the photosensitive layer. The content is 50 to 95% by weight. The photosensitive diazo resin contained in the photosensitive material according to the present invention is also preferably 1 to 60% by weight, more preferably 3% by weight.
Contain up 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. Moreover, organic acids (citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5-sulfonic acid, etc.) can also be used.

As the inorganic acid, phosphoric acid, phosphorous acid, etc. can be used. These acids can also function as stabilizers.

When containing an acid anhydride, the type of acid anhydride is arbitrary, such as acetic anhydride, propionic anhydride, benzoic anhydride, etc.
Examples include those derived from aliphatic/aromatic monocarboxylic acids, and those derived from aliphatic/aromatic dicarboxylic acids such as cohelic 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 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 #603 (manufactured by Orient Chemical Industry Co., Ltd.), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.)
, Crystal Bioref), brilliant green, ethyl violet, methyl violet, methyl green, erythrosin B1 basic tsuksin, malachite green, oil red, m-cresol purple, rhodamine B1 auramine, 4-p-dimethylaminophenyl imino naphthokin, A triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dye represented by cyano-p-diethylaminophenyl acetanilide, which changes 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 usually added in the photosensitive composition from about 0.5 to about 10
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.

In addition, alkyl ethers (e.g., ethyl cellulose, methyl cellulose), fluorosurfactants, nonionic surfactants (e.g., Bluronic 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), oiliness in the image area For example, a sensitizing agent for improving the sensitization properties (for example, a half ester of a styrene-maleic anhydride copolymer disclosed in JP-A No. 55-527 with alcohol) and the like. The amount of these additives added varies depending on the object and purpose of use, but is generally preferably 0.01 to 3% of the total solid content.
It is 0% by weight.

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% by weight. In this case, the coating amount of the photosensitive composition is preferably approximately 0.
．． It may be about 2 to 10 glcd.

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 is a problem 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. being done.

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.
No. 066), treatment with phosphonic acids and their derivatives (U.S. Pat. No. 3,220,832), treatment with potassium hexafluorozirconate (U.S. Pat. No. 2
, 946.683), a method of anodizing, and a method of treating with an aqueous solution of alkali metal silicate after anodization (US Pat. No. 3,181,461).

In preferred embodiment B of the present invention, the surface of the aluminum plate (including the alumina laminate, the same shall apply hereinafter) is degreased and then grained by a brush polishing method, a ball polishing method, a chemical polishing method, an electrolytic etching method, etc. It is preferably grained using an electrolytic etching method that 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. 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 mg/drrf is preferable, more preferably 5 to 30
w/dnf.

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 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 "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 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 (
SiO! ) / (M) = 0.5 to 1.5 (where (Sin and (M) represent the molar concentration of Sing and the molar concentration of total alkali metals, respectively), and Si
A developing solution containing 0.8 to 8% by weight of ng is particularly preferably used. Among this alkali silicate composition, especially the molar ratio "C' (S i O! ) / CM) = 0.
5 to 0.75, and S i O-t is 0.8 to 4
A developer solution with a molar ratio of more than 0.75 to 1.3 and a Sing of 1 to 8 is preferably used because it is easy to neutralize the developer waste solution due to its low concentration.
% by weight developer is preferably used because it has a high buffering power (high processing ability).

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 to 1% 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-60-213
By containing at least one type of nonionic surfactant as described in Publication No. 943, etc.,
or JP-A No. 55-95946, No. 56-142
As described in Japanese Patent Application No. 528, by incorporating a polymer electrolyte, the wettability to the photosensitive composition can be improved and the gradation can be further improved, so it is preferably used.

The amount of such surfactant added is not particularly limited, but 0.0
0.03 to 3% by weight is preferred, especially 0.006 to 1% by weight
A concentration of is preferred. Further, it is preferable that the alkali silicate contains 20 mol% or more of potassium as the alkali metal among 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. Most preferably, the potassium content is 100 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 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, stains do not occur, and since organic solvents are not substantially used,
Pollution and occupational health problems will be 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 (hereinafter "P
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.

\"Me:1 [Examples] Examples of the present invention will be described below. It goes without saying that the present invention is not limited to the following Examples.

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

A (1) under a nitrogen stream, 130 g of acetone and 130 g of methanol
In a mixed solvent of 7.97 g of p-hydroxyphenylmethacrylamide (H31PMA), 28.5 g of ethyl acrylate (E^), and acrylonitrile (AN
)6.36 g.

4.3 g of methacrylic acid (MAA) and 1.23 g of azobisisobutyronitrile were dissolved, and the mixture was refluxed at 60° C. for 6 hours with stirring. After the reaction was completed, the reaction solution was poured into water to precipitate the polymer compound. This was filtered and vacuum-dried at 50°C overnight.

The obtained polymer compound was dissolved in tetrahydrofuran (THF).
and gel permeation chromatography (
When the molecular weight was measured by GPC (folystyrene standard), the weight average molecular weight was 41.000.

(2) Under a nitrogen stream, add 130 g of acetone and 130 g of methanol.
g of mixed solvent, 7.97 g of p-hydroxyphenylmethacrylamide, 25.5 g of ethyl acrylate)
Acrylonitrile 5.3 g, methyl acrylate) 4
．． 3g of methacrylic acid, 5.3g of methacrylic acid, and 1.23g of azobisisobutyronitrile were dissolved, and the mixture was refluxed at 60°C for 6 hours with stirring. After the reaction was completed, the reaction solution was poured into water to precipitate the polymer compound.

This was filtered and vacuum-dried at 50°C overnight.

When the molecular weight was similarly measured by GPC, the weight average molecular weight was 45.000.

(3) Under a nitrogen stream, 130 g of acetone and 130 g of methanol.
13.3 g of p-hydroxyphenylmethacrylamide and 30 g of ethyl acrylate in the mixed solvent.

Acrylonitrile 5.3g, methacrylic acid 2.15g.

Then, 1.23 g of azobisisobutyronitrile was dissolved, and the mixture was refluxed at 60° C. for 6 hours with stirring.

After the reaction was completed, the reaction solution was poured into water to precipitate the polymer compound. This was filtered and vacuum-dried at 50°C overnight.

When the molecular weight was similarly measured by GPC, the weight average molecular weight was 38,000.

A (4) under nitrogen flow, 130 g of acetone and 130 g of methanol.
Hydroxyethyl methacrylate 11.
05g of ethyl acrylate, 25g of ethyl acrylate, 5.3g of acrylonitrile, 5.6g of methacrylic acid, and 1.23g of azobisisobutyronitrile were dissolved, and the mixture was refluxed at 60°C for 6 hours with stirring. After the reaction was completed, the reaction solution was poured into water to precipitate the polymer compound. This was filtered and vacuum-dried at 50°C overnight.

When the molecular weight was similarly measured by GPC, the weight average molecular weight was 43.000.

A of (5) Under a nitrogen stream, add 1 p-hydroxyphenyl methacrylamide to a mixed solvent of 60 g of acetone and 60 g of methanol.
3.3 g, 30 g of ethyl acrylate, 5.3 g of acrylonitrile, 2.15 g of methacrylic acid, and
After the completion of the reaction, 1.23 g of azobisisobutyronitrile was dissolved and the mixture was refluxed at 60°C for 6 hours with stirring.
The reaction solution was poured into water to precipitate the polymer compound. This was filtered and vacuum-dried at 50°C overnight.

When the molecular weight was similarly measured by GPC, the weight average molecular weight was 90,000.

14.5 g (5
0 mmol) was dissolved in 40 g of concentrated sulfuric acid under water cooling.

1.05 g (35 mmol) of paraformaldehyde was slowly added dropwise to this reaction solution. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C.

Thereafter, stirring was continued for 2 hours under water cooling. This reaction mixture was added dropwise to 500 ml of ethanol under water cooling, and the resulting precipitate was filtered off. After washing the precipitate with ethanol,
It was dissolved in pure water at 0 mA, and to this solution was added an aqueous solution in which 6.8 g of zinc chloride was dissolved. After filtering out the resulting precipitate,
It was washed with ethanol and dissolved in 150ml of pure water.

An aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved was added to this solution, and the resulting precipitate was filtered off, washed with water and ethanol, and dried at 25°C for 3 days to obtain the diazo resin (1). Obtained.

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

2.7 g (90 mmol) of paraformaldehyde was slowly added to this solution. At this time, the reaction temperature is 1
It was added so that the temperature did not exceed 0°C. After stirring the reaction solution for 2 hours, it was added dropwise to ethanol (11), and the resulting precipitate was filtered out and washed with ethanol. The precipitate was dissolved in 200 ml of pure water, and an aqueous solution containing 10.5 g of zinc chloride was added. After filtering the resulting precipitate and washing with ethanol,
It was dissolved in 300ml of pure water. In this solution, 13.7
An aqueous solution containing g of ammonium hexafluorophosphate was added. The resulting precipitate was filtered, washed with water and ethanol, and dried at 25°C for - days to obtain a diazo resin (2
) was obtained.

In the synthesis of diazo resin (2), 4.2 g (25 mmol) of p-methoxybenzoic acid was used instead of p-hydroxybenzoic acid to synthesize diazo resin (3). Obtained.

In the synthesis of diazo resin containing diazo (4) + 1), 16 g (50 mmol) of 3-methoxy-4-diazodiphenylamine sulfate was used instead of p-diazodiphenylamine sulfate to synthesize the diazo resin (4). 4) was obtained.

In the synthesis of human diazo resin (2) of diazo 1'' (5), 24 g (75 mmol) of 3-methoxy-4-diazodiphenylamine sulfate was used instead of p-diazodiphenylamine sulfate. , diazo resin (5) was obtained.

The coated aluminum plate was degreased with a 3% aqueous sodium hydroxide solution, electrolytically etched in a 2% hydrochloric acid bath at 25°C and at a current density of 3A/drr, and washed with water. % sulfuric acid bath for 2 minutes at 30°C and 1.5 A/dnl.Next, it was anodized in a 1% sodium metasilicate aqueous solution at 85°C.
, sealed for 30 seconds, washed with water and dried.

Sand 1'' Jioi Co., Ltd. 1 Aluminum plate was degreased with a 3% aqueous sodium hydroxide solution, electrolytically etched in a 1% hydrochloric acid bath at 25°C for 5 minutes at a current density of 3A/dITr, and washed with water. , immersed in a 0.9% aqueous sodium hydroxide solution, washed with water, and anodized at 1.5 A/dm in a 40% sulfuric acid aqueous solution at 30°C.

Next, the pores were sealed with a 1% aqueous sodium metasilicate solution at 85° C. for 30 seconds, washed with water and dried.

The surface of the aluminum plate was grained using a nylon brush and an aqueous suspension of 400 mm of pumice stone, and then thoroughly washed with water. After etching this by immersing it in a 10% sodium hydroxide aqueous solution at 70°C for 60 seconds,
Wash with running water, then neutralize with 20% nitric acid, and remove Va.
-12.7V, vc =9. Electrolytic surface roughening treatment was performed using an IV sinusoidal alternating waveform current and an anodic current of 160 coulombs/dn in a 1% nitric acid aqueous solution.

Subsequently, after being immersed in a 30% sulfuric acid aqueous solution and desmutted, the coating amount of aluminum oxide was 2% in a 7% sulfuric acid aqueous solution.
．． Anodic oxidation treatment was performed so that the concentration was 0 g/rrr. Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70° C. for 1 minute, washed with water and dried.

Next, an example will be explained.

Example 1 A photosensitive liquid having the following composition (A) was applied and the weight of the coating after drying was 1.
Samples were obtained by coating each of grained plates (11 to (3)) with a Whaler so that the concentration was 6 mg/dnf.

Composition (A) 90 g A negative transparent original image was placed on each photosensitive lithographic printing plate sample obtained, and exposed for 30 seconds from a distance of 60 cm using a 2KW metal halide lamp.

After exposure, each sample was placed in a developer having the following composition 1 at 27°C for 25 minutes.
It was immersed for a second, rubbed lightly with a degreased surface, and developed. Separately, each sample after exposure was developed in exactly the same manner using a developer having the following composition H.

When each sample after development was printed using a Heidelberg GTO printing machine, there was no stain on the non-image area on the paper surface of each sample.

Developer I A Potassium silicate 1160g 50% potassium hydroxide aqueous solution 266g Water
6430 g (pH at 25°C is 12.8) Developer solution A Potassium silicate 387 g 50% potassium hydroxide aqueous solution 100 g Water
8030 g (pH at 25° C. is 13.0) Example 2 Photosensitive solutions having the following compositions (B) to (1) were coated and dried to a coating film weight of 16 mg/drr? Whaler was applied to the grained board (1) so that 8 types of samples were obtained.

Compositions (B) to (E) Compositions (F) to (1) Table 1 Table 2 190.0 g 190.0 g A negative transparent original image was placed on each of the obtained lithographic printing plate samples, and then heated to 5Qcm with a - metal halide lamp. (7;) Exposure for 30 seconds from a distance. For each sample after exposure, Example-
Similarly to 1, add 2 to developer ■ and ■ at 27℃ independently.
The film was immersed for 5 seconds and developed by rubbing lightly with a degreased surface. When each sample after development was printed using a Heidelberg GTO printing machine, there was no stain on the non-image area on the paper surface of each sample.

〔Effect of the invention〕

As described above, according to the developing method of the present invention, since a developer that does not contain an organic solvent is used, the problems associated with the use of organic solvents can be solved, and the desired development can be achieved with good developability, making it suitable for printing. The effect is that no staining occurs even when exposed to water.

Claims (1)

[Claims] 1. A photosensitive material having a photosensitive layer containing a diazo resin and an alkali-soluble/swellable polymer compound on a support,
A method for developing a diazo resin-containing photosensitive material, comprising developing with a developer having a pH of 12.0 or higher at 25° C. and containing substantially no organic solvent.