JPH02219060A - Method of developing photosensitive material containing diazo resin - Google Patents

Abstract

PURPOSE:To enable desired development to be attained with good developability by developing a photosensitive material containing a diazo resin having anions, such as PF6<->, BF4<-> organic anions, or a mixture of them, with a specified developer. CONSTITUTION:The photosensitive layer formed on a substrate contains the diazo resin having anions, such as PF6<->, BF4<->, organic anions, or a mixture of them, and an alkali soluble and swellable polymer compound. This photosensitive material is developed with the developer having a pH of >=2.0 at 25 deg.C and substantially not containing an organic solvent, thus permitting problems caused by the use of the organic solvents to be solved and desired development to be attained with good developability.

Description

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

[Background of the invention]

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

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

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

[Problem that the invention seeks to solve]

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

However, simply removing the organic solvent does not achieve the desired development. If development is simply carried out using a developing solution that does not contain an organic solvent, portions that should be removed by development remain, which will become stains when used for printing. Such stains are unacceptable and cannot be put to practical use, especially when used as a photosensitive material for printing. Further, 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. It is also an object of the present invention to provide a method for developing a diazo resin-containing photosensitive material that has good storage stability.

[Means for solving problems]

As a result of various studies, the present inventors have found that the support has a photosensitive layer containing a diazo resin and an alkali-soluble/swellable polymer compound, and the anions of the diazo resin are PF, -, B
A photosensitive material containing P, -, an organic anion, or a mixture thereof is developed with a developer having a pH of 12.0 or more at 25° C. and containing substantially no organic solvent.
The inventors have discovered that the above-mentioned problems can be solved by a method for developing a photosensitive material containing a diazo resin, 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.

The diazo resin that can be used in the present invention has anions such as PF, -(hexafluorophosphate ion), BF4
- (tetrafluoroborate ion), an organic anion, or a mixture thereof, but the others are arbitrary. It is preferable to use an organic anion (such as benzophenone sulfonate ion) as a counter anion from the viewpoint of improving storage stability.

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

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

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

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

Specific examples of the aromatic compound containing a carboxyl group and/or hydroxyl group as a constitutional unit of the co-condensed diazo resin include benzoic acid, 0-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, phthalate. Acid, terephthalic acid, diphenylacetic acid, phenoxyacetic acid, p-methoxyphenylacetic acid, p-methoxybenzoic acid, 2.4-dimethoxybenzoic acid, 2.4-dimethylbenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid , 4-(m-methoxyanilino)benzoic acid, 4-(p-methylbenzoyl)benzoic acid, 4-(p-methylanilino)benzoic acid,
4-phenylsulfonylbenzoic acid, phenol, (o,
m,p)-cresol, xylenol, resorcinol, 2
-Methylresorcin, (o,m,p)-methoxyphenol, m-ethoxyphenol, catechol, phloroglycin, p-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone, P-hydroxybenzyl alcohol, 4-chlororesorcin, biphenyl- 4
, 4°-diol, 1,2.4 benzenetriol, bisphenol 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-゜dihydroxybenzoic acid, 2,6-cyhydroxy-4-benzoic acid, 4-
Chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2,6-dioxybenzoic acid, gallic acid, phloroglucincarboxylic acid, 2,4.5-1-dihydroxybenzoic acid, m-galloyl gallic acid, tannic acid , m-benzoyl gallic acid, m-(p-toluyl) gallic acid, protocatechoyl gallic acid, 4,6-cyhydroxyphthalic acid,
(2,4-dihydroxyphenyl)acetic acid, (2,6-dihydroxyphenyl)acetic acid, (3,4,5-trihydroxyphenyl)acetic acid, p-hydroxymethylbenzoic acid,
P-hydroxyethylbenzoic acid, 4-(p-hydroxyphenyl)methylbenzoic acid, 4-(0-hydroxybenzoyl)benzoic acid, 4-(2,4-dihydroxybenzoyl)benzoic acid, 4-(p-hydroxyphenoxy) ) benzoic acid, 4-(p-hydroxyanilino)benzoic acid, bis(3-lupoxy-4-hydroxyphenyl)amine, 4-(p-hydroxyphenylsulfonyl)benzoic acid, 4-(p-hydroxyphenylthio) ) benzoic acid, etc.

Particularly preferred among these are salicylic acid, p-hydroxybenzoic acid, p-methoxybenzoic acid, and metachlorobenzoic acid.

As the aromatic diazonium compound used as the structural 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
Although derived from 4-amino-diphenylamines, such 4-amino-diphenylamines include 4-amino-diphenylamines.
-Amino-diphenylamine, 4-amino-3-methoxy-diphenylamine, 4-amino-2-methoxydiphenylamine, 4'-amino-2-methoxy-diphenylamine, 4''-amino-4-methoxydiphenylamine, 4-amino-3 -methyldiphenylamine, 4-amino-3-ethoxydiphenylamine, 4-amino-
3-β-hydroxy-ethoxydiphenylamine, 4-
Examples include aminodiphenylamine-2-sulfonic acid, 4-amino-diphenylamine-2-carboxylic acid, 4-amino-diphenylamine-2''-carboxylic acid, etc. Particularly preferred are 3-methoxy-4-amino-diphenylamine, 4-aminodiphenylamine.

As the co-condensed diazo resin that can be used in the present invention, those represented by the following structure (1) are preferable.

-S In formula (1), A is a group derived from an aromatic compound having at least one of a carboxyl group and a hydroxyl group, and examples of such aromatic compounds include those exemplified above.

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, and X represents a counter anion. n preferably represents a number from 1 to 200.

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

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

Furthermore, in this case, the weight percent ratio of co-condensed diazo resin to condensed diazo resin is particularly preferably 30 to 70: 70 to 30 in terms of achieving both excellent anger 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.
In sulfuric acid, phosphoric acid, or hydrochloric acid according to the method described in U.S. Pat. It is obtained by polycondensing diazonium 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 0.1:1,
The ratio is more preferably i:o, s to 0.2:1, and even more preferably 1:l to 0.2:1. In this case, the molar ratio of the sum of aromatic compounds and aromatic diazonium compounds having at least one of a carboxyl group and a hydroxyl group to aldehydes or ketones is usually preferably 1:0.6 to 1.2, more preferably 1:0.6 to 1.2. is 1:0.7~
Prepare at 1.5 and cook at low temperature for a short time.

A co-condensed diazo resin can be obtained by reacting for a period of time, for example, about 3 hours.

The counter anions of the diazo resin are PF, -, and BF.

Organic anions, or mixtures thereof2, include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenyl phosphoric 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-sulfo-isophthalate, 2.2゜4.4''-tetrahydroxybenzophenone, 1゜2.3-)lihydroxybenzophenone, 2 , 2゜4-trihydroxybenzophenone and other hydroxyl group-containing aromatic compounds, but are not limited to these.Among these,
Preferred is the ion of benzophenone sulfonic acid or its derivatives, particularly preferred is the ion of 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 structure (II) and contains 20 mol% or more of a resin in which n in each formula is 5 or more, more preferably, It contains 20 to 60 mol%. During the ceremony,
R1 to R,, R,
As the alkyl group and alkoxy group of Rz and R1,
Examples 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.

General formula [''] Such photosensitive diazo resins can be produced according to known methods, such as those 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 at a ratio of 1:0.7 to 1:1.5, and a high anger diazo resin is obtained by reacting at a low temperature for a short period of time, for example, at 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 whose p J (at 25°C is 12.0 or more). means that the volume expands due to the permeation of liquid in the above alkaline solution,
When coated on a support, it is easily peeled off from the support.

Any alkali-soluble/swellable polymer compound 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 molecule i1Mn and the weight average molecule IMW can be calculated according to the book written by Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka, “Japan Chemical society journal”
This can be carried out by leveling the peaks of the oligomer region (by connecting the center lines of the peaks and valleys of the peaks) according to the method described on 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 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 formal resin, polyvinyl formal resin, shellac, 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) Hetamine-1 having an aromatic hydroxyl group, for example, N(4-
hydroxyphenyl)acrylamide or N-(4-
hydroxyphenyl) methacrylamide, o -, m
-, p-hydroxystyrene, o-, m-, p-hydroxyphenyl-acrylate or monomethacrylate.

(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, 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, tono-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylamide, Acrylamides or methacrylamides such as 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 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 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 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 structure IA (in the formula, R11 is a hydrogen atom) or represents an alkyl group.) 5 to 40 mol% of the structural unit represented by (c) the following -Structure 11A It -CHt-C-... IIACOOR+! (In the formula, R1ff1 represents a hydrogen atom, a methyl group, or an ethyl group, and R13 represents an alkyl group having 2 to 12 carbon atoms or an alkyl-substituted aryl group.) A polymer compound containing is preferable. and its weight average molecular weight is 20.000~
Even more preferred are copolymers with a molecular weight of 200,000.

As a specific example of the seven-termer forming the structural unit having an alcoholic hydroxyl group in (a) above, Japanese Patent Publication No. 52-736
Examples include (meth)acrylic acid esters and acrylamides, such as the compounds shown in the following Mechanism 111A as described in No. 4.

Rth CH2-C-・・・・・・・・・I [[AC00+CI
l□C110→1-II R1% In the formula, R14 represents a hydrogen atom or a methyl group, RI5 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, N-hydroxyethyl (meth)acrylamide, and the like.

Preferably it is 2-hydroxyethyl (meth)acrylate.

In addition, examples of monomers forming the structural unit having a phenolic hydroxyl group (a) include N-(4-hydroxyphenyl)-(meth)acrylamide, N-(
2-hydroxyphenyl)-(meth)acrylamide,
(meth)acrylamides such as N-(4-hydroxynaphthyl)-(meth)acrylamide,
Examples include m- or p-hydroxyphenyl (meth)acrylate monomers; o-, m- or p-hydroxystyrene monomers. Preferably, o-, m- or p-hydroxyphenyl (meth)acrylate monomers, N-(4-hydroxyphenyl)-(meth)acrylamide monomers, 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 preferably 1 to 50 mol%, more preferably 5 to 50 mol%, in the polymer compound.
It is selected from a range of 30 mol%.

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

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

Examples of monomers having a carboxy ester group in the side chain that form the structural unit represented by structure A above include ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate, amyl methacrylate, and hexyl acrylate. , octyl acrylate, 2-chloroethyl acrylate,
Examples include 2-hydroxyethyl acrylate and glycidyl acrylate. The unit formed from the monomer 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 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 of the present invention is preferably usually 40 to 99% by weight, more preferably 40% to 99% by weight in the solid content of the photosensitive composition constituting the photosensitive layer is contained in an amount of 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. As the inorganic acid, phosphoric acid or the like can be used.

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

The photosensitive material composition for forming the photosensitive layer of the photosensitive material according to the present invention may contain a dye, particularly a dye that changes color from 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 violet, flilliant green, ethyl violet, methyl violet, methyl green, erythrosin B1 basic tsuksin, malachite green, oil red, m-cresol purple, rhodamine B1 auramine, 4-p-dimethylaminophenylimino naphthoquine, cyano - Triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes such as p-diethylaminophenylacetanilide are pigments that change color from colored to colorless or to a different color. This can be cited as an example.

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

The above-mentioned color changing agent is generally added in the photosensitive composition from 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.

Also, alkyl ether to improve coating properties! (e.g. ethyl cellulose, methyl cellulose), fluorine surfactants, nonionic surfactants [e.g. Bluronic L-64 (manufactured by Asahi Denka Corporation)], plasticizers to impart flexibility and abrasion resistance to the coating film. agents (e.g. butylphthalyl, polyethylene glycol, tributyl citrate,
diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid), oil sensitivity of image area Sensitizers (for example, half esters of styrene-maleic anhydride copolymer with alcohol as described in JP-A No. 55-527), stabilizers [for example, phosphoric acid, phosphorous acid, etc.] , organic acids (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 0.01 to 30% by weight based on the total solid content.

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

For example, a method in which the surface of an aluminum plate is grained and then treated with a silicate (US Pat. No. 2,714°066), a method in which the surface is treated with an organic acid salt (US Pat.
No. 066), treatment with phosphonic acids and their derivatives (U.S. Patent Box 3,220.832), treatment with potassium hexafluorozirconate (U.S. Patent Box 2)
．． No. 946i6B3), a method of anodizing, and a method of treating with an aqueous solution of alkali metal silicate after anodizing (US Pat. No. 3,181,461).

In a preferred embodiment of the present invention, the surface of the aluminum plate (including the alumina laminate; the same applies hereinafter) is degreased and then grained by a brush polishing method, a ball polishing method, a chemical polishing method, an electrolytic etching method, etc. The grain is preferably grained 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. This is done by passing an electric current through an aluminum plate as an anode. The amount of anodic oxide film is 5-6
Preferably 0 ■/d, more preferably 5 to 30 ■/d
It is rrf.

When carrying out sealing treatment in carrying out the present invention, preferably a sodium silicate aqueous solution with a concentration of 0.1 to 3% is added at a temperature of 8.
This treatment is carried out by immersion at 0 to 95°C for 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 for the original image by exposing it to light through a standard original image having a line image, a halftone image, etc., and then developing it 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 referred to as "developing solution j according to the present invention etc."). 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 agent to be contained is 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)=0.5~1.5 (where (StO
□], (M) respectively indicate the molar concentration of sio, and the molar concentration of total alkali metal), and 5iO7 is 0.
．． A developer containing 8 to 8% by weight is particularly preferably used.

Of this alkali silicate composition, especially in terms of molar ratio (S i
Ox : l / CM) = 0.5 to 0.75, and a developer with a sin of 0.8 to 4% has a low concentration, making it easy to neutralize the developer waste. On the other hand, a developer having a molar ratio of more than 0.75 to 1.3 and containing 1 to 8% by weight of 5int 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 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 as described in JP-A No. 24, JP-A No. 59-75255, JP-A No. 60.111246, and JP-A No. 60-2139.
．． By containing at least one type of nonionic surfactant as described in Publication No. 43, 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 property can be further improved, and thus 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, particularly 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 heated to a temperature of about 10 to 60°C at room temperature to 40°C.
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 referred to as “2
The method for developing the 8th edition) with the developer according to the present invention is arbitrary, and for example, various conventionally known methods can be used.

Specifically, there is a method of immersing the image-exposed 28th plate in a developer, a method of jetting the developer from a number of nozzles onto the photosensitive layer of the 28th plate, and a method of exposing the PS plate with 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 28th plate in this manner, the surface of the photosensitive layer can be lightly rubbed with a brush or the like.

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

〔Example〕

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

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

Under nitrogen flow, 130 g of acetone and 130 g of methanol
P-hydroxyphenylmethacrylamide (8yPMA) 7.52g, ethyl acrylate)
(HA) 30.25 g, acrylonitrile (AN)
6.36 g.

3.01 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 (polystyrene standard), the weight average molecular weight was 41,000.

12.5 p-hydroxyphenyl methacrylamide was added to a mixed solvent of 300 g of acetone and 300 g of methanol.
g, 28.2 g of ethyl acrylate, 6.9 g of acrylonitrile, 1.67 g of methacrylic acid, and 1.23 g of abbisisobutyronitrile were dissolved, and the mixture was heated at 60° C. for 6 hours under a nitrogen stream. It refluxed.

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 of the obtained polymer compound was measured by GPC in the same manner as above, the weight average molecular weight was 18.000.

Both polymer compounds (1) and (2) were alkali-soluble.

Diazo '31 person p-diazodiphenylamine sulfate 145 g (0,
5 mol) was dissolved in 400 g of concentrated sulfuric acid under water cooling.

10.5 g (0.35 mol) 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. after that,
Stirring was continued for 2 hours under water cooling. This reaction mixture was added dropwise to 0.52 ethanol under water cooling, and the resulting precipitate was filtered off. After washing the precipitate with ethanol, the precipitate was dissolved in 12 pure water, and an aqueous solution in which 68 g of zinc chloride was dissolved was added to this solution.

After filtering the resulting precipitate, it was washed with ethanol and heated at 25°C.
After drying for 3 days, a diazo resin (1) was obtained.

I have heard of the poor and investigated.

35 g (0.25 mol) of p-hydroxybenzoic acid,
and p-diazodiphenylamine sulfate 217.5 g
(0.75 mol) was dissolved in 900 g of concentrated sulfuric acid under water cooling.

27 g (0.9 mol) of paraformaldehyde were slowly added to this solution. At this time, the reaction temperature was 1°C.
I added it so as not to exceed. Thereafter, stirring was continued for 2 hours under water cooling. This reaction solution was added dropwise to 0.5° C. ethanol under water cooling, and the resulting precipitate was filtered off. After washing the precipitate with ethanol, the precipitate was dissolved in 11 pure water, and to this solution was added an aqueous solution in which 68 g of zinc chloride was dissolved. After filtering the resulting precipitate, it was washed with ethanol and
Diazo resin (2) was obtained by drying at °C for 3 days.

Diazo tlJJM (contains 3) Mix 5% aqueous solution of diazo resin (1) and 50d of 10% ammonium hexafluorophosphate solution at room temperature,
The precipitate that immediately formed was filtered with suction and dried at 30° C. for 3 days.

Adding diazo resin (4) A 5% aqueous solution of diazo resin (1) and a 10% ammonium tetrafluoroborate solution are mixed at room temperature,
The precipitate that immediately formed was filtered with suction and dried at 30° C. for 3 days.

Combination of diazo resin (5) 5% aqueous solution of diazo resin (1) and 10% 2-
Ammonium oxy-4-methoxybenzophenone-5-sulfonate solution 50#11! The precipitate immediately formed was suction filtered and dried at 30° C. for 3 days.

5% aqueous solution of diazo resin (2) and 10% ammonium hexafluorophosphate solution 50af were mixed at room temperature, and the precipitate that formed immediately was suction filtered and dried at 30°C for 3 days. .

Mixing 5% aqueous solution of diazo resin (2) and 50 d of 10% ammonium tetrafluoroborate solution at human room temperature of Diazo 157,
The precipitate that immediately formed was filtered with suction and dried at 30° C. for 3 days.

Diazo 1 to 58 A Mix 5% aqueous solution of diazo resin (2) and 10% ammonium 2oxy-4-methoxybenzophenone-5-sulfonate solution 50 In 1 at room temperature, and immediately filter the resulting precipitate with suction. , and dried at 30°C for 3 days.

Among the above, diazo resins (3) to (8) whose anions are PFb-, BF, -, or organic anions are all almost insoluble in water and soluble in organic solvents such as ethylene glycol monomethyl ether. It was melting.

Diazo resins (1) and (2) other than the present invention, in which the anion is other than those mentioned above, are insoluble in organic solvents, cannot be used, and cannot be evaluated.

Next, an example will be described.

Example 1 Photosensitive lithographic printing plate samples A-L were prepared as follows. That is, for each sample A-L, a photosensitive solution having the composition shown in Table 1 below was applied to an anodized aluminum plate in a grain room until the coating weight after drying was 16 μ/dn. Each photosensitive lithographic printing plate sample was prepared by applying the following coatings.

Each photosensitive lithographic printing plate sample A- prepared as above
A negative transparent original was placed on L, and exposed for 30 seconds from a distance of 60c+++ using a 2KW metal halide lamp.

After exposure, each sample was placed in a developer having the following composition I at 27°C for 20 minutes.
It was immersed for a second, rubbed lightly with absorbent cotton, and developed. Separately, each sample after exposure was developed in exactly the same manner using a developer having the following composition (1).

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

That is, no stains were observed in any of the samples A-L, no matter whether they were developed with either developer I or II.

Developer solution IA Potassium silicate 1160g5
0% potassium hydroxide aqueous solution 266g water
6430
g (pH at 25°C is 12.8) Developer ■ A Potassium silicate 387g50
% potassium hydroxide aqueous solution 100 g water
80
30 g (pH 13.0 at 25°C) [Effect of the invention] As described above, according to the developing method of the present invention, a developer containing no organic solvent is used, so problems associated with the use of organic solvents are solved. In addition, the desired development can be achieved with good developability, and even when used for printing, there is an effect that stains and the like do not occur.

Claims (1)

[Claims] 1. A photosensitive layer containing a diazo resin and an alkali-soluble/swellable polymer compound is provided on the support, and the anion of the diazo resin is PF_6^-, BF_4^-, an organic anion, or any of these. A photosensitive material that is a mixture of
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.