JPH02251966A - Method for developing photosensitive material containing photopolymerization initiator - Google Patents

Abstract

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

Description

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

[Background of the invention]

Conventionally, photosensitive compositions have been coated with supports such as hydrophilic metals,
It is applied to paper, preferably aluminum (particularly grained aluminum), etc., 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, such photosensitive materials were usually 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 may not achieve the desired development, resulting in poor developability or deterioration in developability after the photosensitive material is stored over time. That is,
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. This tendency is particularly noticeable in photographic materials after storage. 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 remove the organic solvent and raise the pH to accelerate the progress of development, but this alone will not solve the developability problems such as the stains mentioned above or similar developability problems after storage.

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 photosensitive material that does not cause stains or the like even when the photosensitive material is used, has good developability after storage, and does not cause stains or the like.

[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 compound having a polymerizable unsaturated bond and a photopolymerization initiator on a support has a pH of 12 at 25°C.
．． It has been discovered that the above-mentioned problems can be solved by a method for developing a photosensitive material containing a photopolymerization initiator, which is developed with a developer containing a photopolymerization initiator of 0 or more and substantially free of organic solvents, leading to the present invention.

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

The present invention will be explained in more detail below.

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

The photosensitive material according to the present invention has a photosensitive layer containing a compound having a polymerizable unsaturated bond and a photopolymerization initiator on a support.

In the present invention, the following compounds can be preferably used as the compound having a polymerizable unsaturated bond in the molecule.

That is, as such a compound, Japanese Patent Application Laid-Open No. 59-538
Allyl (meth)acrylate/(meth)acrylic acid/other addition-polymerizable vinyl septamer copolymers as described in No. 36, JP-A-59-7104
Copolymers such as those described in No. 8, in which pentaerythritol triacrylate is added to the maleic anhydride copolymer by half-esterification, can be mentioned.

Synthesis examples of compounds having polymerizable unsaturated bonds that can be preferably used in the present invention are illustrated below.

Synthesis Example 1: Synthesis of poly(allyl methacrylate/methacrylic acid) copolymer 113.4 g of allyl methacrylate and 8.6 g of methacrylic acid were mixed with 1.2-dichloroethane 2! 1.8 g of 2,2'-abysis (2,4-dimethylvaleronitrile) was added as a polymerization initiator, and the mixture was refluxed for 5 hours. After refluxing, the reaction solution was concentrated under reduced pressure, and the concentrated solution was poured into hexane. The resulting precipitate was dried under vacuum to obtain Compound 1.

Synthesis Example 2: Synthesis of poly(allyl methacrylate/p-hydroxyphenyl methacrylamide/methyl acrylate acrylonitrile/methacrylic acid) copolymer Allyl methacrylate 59.2 g, p-hydroxyphenyl methacrylamide 17.7 g, methyl acrylate 15.0 g, acrylonitrile 10.6 g,
6.9 g of methacrylic acid was dissolved in a mixed solvent of 400 m1 of acetone and 400 m2 of methanol, 1.6 g of azobisisobutyronitrile was added as a polymerization initiator, and the mixture was refluxed for 6 hours to react. Concentrate the reaction solution to 400%
After concentration, the precipitate obtained by pouring into 22 water was vacuum dried to obtain Binder 2.

In the present invention, the compound having a polymerizable unsaturated bond in its molecule is preferably contained in an amount of 99 to 70%, particularly preferably 97 to 50%, in the total photosensitive composition.

In addition, in the present invention, as a compound having a polymerizable unsaturated bond in the molecule, a compound having a boiling point of 100 ° C or more at normal pressure,
It is also possible to use hexamers or oligomers having a molecular weight of 10,000 or less and having at least one addition-polymerizable unsaturated group in one molecule.

Specifically, as an oligomer, such nanatsumer is
Polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate,
Monofunctional acrylates and methacrylates such as phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)acrylate, polypropylene di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaethane Ristryl tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,
dipentaerythryl hexa(meth)acrylate,
Hexanediol di(meth)acrylate, tri(acryloyloxyethyl)isocyanurate, polyhydric alcohol such as glycerin or trimethylolethane added with ethylene oxide or propylene oxide and then converted into (meth)acrylate, 1977- 41708
No., Special Publication No. 50-6034, Japanese Patent Publication No. 51-37193
Urethane acrylates as described in each specification, JP-A No. 48-64183, JP-B No. 49-431
Examples include polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates prepared by reacting an epoxy resin with (meth)acrylic acid, which are described in Japanese Patent Publication No. 91 and Japanese Patent Publication No. 52-30490.

For more details, see the Japan Adhesive Association Vol. 1.20. No,
7.

Polymerizable compounds introduced as 300 to 308 photocurable polymers and oligomers can also be used.

Next, the photopolymerization initiator used in the present invention will be described.

In the present invention, as the photopolymerization initiator, any known initiator can be used without particular limitation, but trihalomethyloxadiazole compounds or S-)lyazine trihalomethyl compounds are particularly preferred. Examples of the photopolymerization initiator include the following compounds.

In the present invention, the photopolymerization initiator is preferably contained in an amount of 0.91 to 20% in the total photosensitive composition, and 0.5 to 10%.
It is particularly preferable that the content is %.

As a photopolymerization initiator, it is preferable to use a diazo resin alone or in combination with other photopolymerization initiators. When a diazo resin is used in combination, good results can be obtained especially in terms of sensitivity.

Although the diazo resin itself can function as a photosensitive resin, it also functions as a photopolymerization initiator. Particularly preferred is to use the above trihalomethyloxadiazole compound or S-triazine trihalomethyl compound and a diazo resin in combination as a photopolymerization initiator.

The above-mentioned diazo resin that can be used in the present invention is arbitrary.

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-methylresorcinol, (o, m, p)-methoxyphenol, m-ethoxyphenol, catechol, fluoro glycine, 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-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-)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-( O-hydroxybenzoyl)benzoic acid, 4-(2,4-dihydroxybenzoyl)benzoic acid, 4-(p-hydroxyphenoxy)benzoic acid, 4-(p-hydroxyanilino)benzoic acid, bis(3-carboxy- 4-hydroxyphenyl)amine, 4-(p-hydroxyphenylsulfonyl)
Examples include benzoic acid, 4-(p-hydroxyphenylthio)benzoic acid, and the like. Particularly preferred among these are salicylic acid, p-hydroxybenzoic acid, p-methoxybenzoic acid, and metachlorobenzoic acid.

As the aromatic diazonium compound used as a constitutional unit of the co-condensed diazo resin, diazonium salts such as those listed in Japanese Patent Publication No. 49-48 (No. 101) can be used, but diphenylamine-4-diazonium salts are particularly preferred. Diphenylamine-4-diazonium salts are derived from 4-amino-diphenylamines, but
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-
Examples include amino-diphenylamine-2-carboxylic acid and 4-amino-diphenylamine-2'-carboxylic acid. Particularly preferred are 3-methoxy-4-amino-diphenylamine and 4-amino-diphenylamine.

As the co-condensed diazo resin that can be used in the present invention, those represented by the following general formula (I) are preferred.

In the general formula (I), 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, R, and R3 represent a hydrogen atom, an alkyl group, or a phenyl group, R represents a hydrogen atom, an alkyl group, or a phenyl group, X represents a counter anion, and n is preferably a number from 1 to 200. shows.

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 30-70,770-30 from the viewpoint of providing excellent sensitivity and developability.

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

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

The molar ratio of the aromatic compound having at least one of a carboxyl group and a hydroxyl group to the aromatic diazonium compound is preferably 1:0.1 to 0.1:1,
The ratio is more preferably i:o, s to 0.2:1, and even more preferably 1:1 to 0.2:1. In this case, the molar ratio of the sum of aromatic compounds and aromatic diazonium compounds having at least one of a carboxyl group and a hydroxyl group to aldehydes or ketones is usually preferably t:o, 6 to 1.2, more preferably t:o. is t:o, 7-1.
A co-condensed diazo resin can be obtained by charging the mixture in step 5 and reacting at a low temperature for a short period of time, for example, about 3 hours.

The counter anion of the diazo resin includes an anion that stably forms a salt with the diazo resin and makes the resin soluble in an organic solvent. Those that form such anions include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and sulfonic acids; typical examples include methanesulfonic acid, Chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, and anthraquinonesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroxysulfonic acid, 4-acetylbenzenesulfonic acid, Aliphatic and aromatic sulfonic acids such as dimethyl-5-sulfoisophthalate, 2°2',4,4'-tetrahydroxybenzophenone, 1,2,3-trihydroxybenzophenone, 2.2',4-trihydroxy Aromatic compounds containing hydroxyl groups such as benzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, Cl
Examples include perhalogen acids such as O, 104, and the like. However, it is not limited to this. Among these, particularly preferred are hexafluorophosphoric acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic 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 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 &
Engineer Link (Photo.

Sci, Eng.), Vol. 17, p. 33 (1973), and U.S. Patent No. 2,063,631, 2.679.4.
No. 98, Specifications of No. 3,050,502, JP-A-59
A diazo resin obtained by condensing a diazo compound and an active carbonyl compound, such as formaldehyde, acetaldehyde or benzaldehyde, etc., in an acidic medium such as sulfuric acid, phosphoric acid, or hydrochloric acid, the manufacturing method of which is described in Publication No. 78340, etc. Examples include diazo compounds and diphenyl resins whose production methods are described in Japanese Patent Publication No. 49-4001.

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

At that time, when polycondensing the diazonium salt and the aldehyde, the molar ratio of both is usually 1:0.6 to 1:
2, preferably 1:0.7 to t:1. A highly sensitive diazo resin can be obtained by charging with S and reacting at a low temperature for a short time, for example, 10° C. or less for about 3 hours.

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

In the present invention, a polymerization inhibitor such as hydroquinone, p-methoxyphenol, di-
t-Butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4.4'-thiobis(3
-methyl-6-t-butylphenol), 2.2' -
Methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, etc. may be used in combination.

A polymer compound can be contained in the photosensitive layer of the photosensitive material according to the present invention. This polymer compound can function as a binder when forming a photosensitive composition.

In the present invention, the photosensitive layer contains, as a polymer compound,
It is possible to contain an alkali-soluble/swellable polymer compound, that is, a polymer compound that is alkali-soluble, alkali-swellable, or has both properties.

Here, the term "alkali-soluble" refers to a substance that dissolves into an alkaline solution, particularly an alkaline solution having a pH of 12.0 or higher at 25°C. Also,
The term "alkali swelling property" refers to a material exhibiting volumetric expansion due to the intrusion of a liquid component into the above-mentioned alkaline solution.

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 C, PC (gel permeation chromatography method), and the number average molecular weight Mn and weight average molecular weight MW can be calculated according to Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka. “Journal of the Chemical Society of Japan”
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 type of polymer compound that can be used in the present invention is arbitrary, and for example, the following 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, shellac, epoxy resin, phenol resin, acrylic resin, etc. can be mentioned.

Preferably, monomer copolymers shown in the following (1) to (12) are used, which are alkali-soluble and swellable polymer compounds.

(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, 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, N
-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide,
Acrylamides or methacrylamides such as 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,
More preferred are copolymers having aromatic hydroxyl groups.

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) a structural unit having an alcoholic hydroxyl group and/or
or 1 to 50 structural units having a phenolic hydroxyl group.
Mol%, Φ) Following general formula IA 11 -CH, -C- IAN (wherein, RI' represents a hydrogen atom or an alkyl group.

) 5 to 40 mol% of the structural unit represented by (C) the following general formula nA R1! -Cl A polymer compound containing 25 to 60 mol% of a structural unit represented by ), which represents a group or an alkyl-substituted aryl group, is preferable. and its weight average molecular weight is 20.000 to 200,
000 is more preferred.

Specific examples of the monomer forming the structural unit having an alcoholic hydroxyl group in (a) above include Japanese Patent Publication No. 52-736
Examples thereof include (meth)acrylic esters and acrylamides such as the compounds shown in the following general formula 11 [A] as described in No. 4.

I4 CHt -C-...I[IACOO+C
HzclIo→, H In the formula, RI4 represents a hydrogen atom or a methyl group, 11715 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-hydroxypentyl (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 monomers forming the structural unit having a phenolic hydroxyl group (a) 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 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 the general formula IA include acrylonitrile, methacrylonitrile, 2-pentenenitrile, and 2-pentenenitrile.
Examples include methyl-3-butenenitrile, 2-cyanoethyl acrylate, o+, m-P-cyanostyrene, and the like. Preferred are acrylonitrile and methacrylonitrile.

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

Examples of monomers having a carboxy ester group in the side chain that form the structural unit represented by the general formula IIA include ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate, amyl methacrylate, and hexyl acrylate. 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.

Examples of the material forming the structural unit having a carboxyl group include methacrylic acid, acrylic acid, maleic anhydride, and maleic acid. 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.

When a polymer compound such as an alkali-soluble/swellable polymer compound is contained in the photosensitive material of the present invention, it is preferably usually 40 to 99% by weight in the solid content of the photosensitive composition constituting the photosensitive layer. , more preferably 50 to 95% by weight. In addition, when the photosensitive material according to the present invention contains a photosensitive diazo resin, the same (preferably usually 1 to 6
The content is preferably 0% by weight, more preferably 3 to 30% by weight.

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

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

When containing an acid anhydride, the type of acid anhydride is arbitrary, such as acetic anhydride, propionic anhydride, benzoic anhydride, 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, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Pesic Tsuksin, Malachite Green, Oil Red, m-Cresol Purple, Rhodamine B1 Auramine, 4-P-dimethylaminophenylimino naphthoquine, 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 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.

In addition, alkyl ethers (e.g., ethyl cellulose, methyl cellulose), fluorosurfactants, nonionic surfactants (e.g., Pluronic L-64 (manufactured by Asahi Denka Corporation)) to improve coating properties, and Plasticizers for imparting flexibility and abrasion resistance (e.g. butylphthalyl, polyethylene glycol, tributyl citrate,
diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid), oil sensitivity of image area sensitizing agents (e.g. half-esterified styrene-maleic anhydride copolymer with alcohol as disclosed in JP-A-55-527), stabilizers [e.g. phosphoric acid, phosphorous acid, , organic acids (citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2hydroxybenzophenone-5-sulfonic acid, tartaric acid, etc.)
] 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, etc.). 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/nl.

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. 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 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
0mg/drrf is preferable, more preferably 5~
30■/dryf.

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 for 10 seconds to 2 minutes at 0-95°C. More preferably, it is then treated by immersing it in water at 40 to 95°C for 10 seconds to 2 minutes.

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

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 produced using a developer having a pH of 12.0 or higher at 25°C and containing substantially no organic solvent (hereinafter referred to as the "developing solution according to the present invention"). It is visualized in the image.

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

The developer according to the present invention has a pH of 12.0 at 25°C.
This is the above alkaline aqueous solution. 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. Examples include sodium, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, 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 most preferable because it has good development gradation, and the composition of the alkali silicate is (SiO□)/ (M:l=0.5~1.5(here (S
tow) and CM) indicate the molar concentration of 5 iOt and the molar concentration of total alkali metals, respectively. ) and Sing
A developing solution containing 0.8 to 8% by weight of is particularly preferably used.

Of this alkali silicate composition, especially in terms of molar ratio (SiO
□)/(M)=0.5~0.75, and Si
A developer having n of 0.8 to 4% by weight is preferably used because it is easy to neutralize the developer waste due to its low concentration.
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 Sin is preferably used because it has a high buffering power (high processing capacity).

The pH of the developer according to the present invention at 25°C is 12.0.
Although it is above, preferably it is 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-60-2139
By containing at least one kind of nonionic surfactants such as those described in Japanese Patent Application Laid-open No. 55-95946 and Japanese Patent Application Laid-open No. 56-1425.
As described in Japanese Patent No. 28, by containing a polymer electrolyte, the wettability to the photosensitive composition can be improved and the gradation can be further improved, and it is preferably used. There is no particular limit to the amount of surfactant added, but 0.00
A concentration of 3 to 3% by weight is preferred, particularly a concentration of 0.006 to 1% by weight. 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. and most preferably 100 mol% potassium
This is the case.

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

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

After imagewise exposure, the photosensitive material according to the present invention can be brought into contact with the developer according to the present invention, or by rubbing with the developer, the photosensitive material can be exposed to light at a temperature of about 10 to 40°C.
After 0 seconds, the photosensitive composition in the non-exposed areas of the photosensitive composition layer is completely removed without adversely affecting the exposed areas of the photosensitive composition layer. In this case, the developing ability is high and no stains occur. The developability after storage is also good. Furthermore, since substantially no organic solvents are used, pollution and occupational health problems are solved.

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

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

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

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

〔Example〕

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

Prior to specific descriptions of Examples, some of the photosensitive materials (photosensitive printing plates) used in Examples use alkali-soluble resins as polymer compounds, so these alkali-soluble resins will be explained. Further, the diazo resin used in the examples will be explained.

Alkali Solubility '1 person N-(4-hydroxyphenyl)-methacrylamide 58.1 g Acrylonitrile 19.2 g Ethyl acrylate 82.2 g Methacrylic acid 11.3 g Azobisisobutylnitrile 4.1 g It was dissolved in 240 d of acetone-methanol 1:1 mixed solution, purged with nitrogen, and then heated at 60'C for 6 hours.

After the reaction was completed, the reaction solution was poured to 2.5 mL with water while stirring, and the resulting white precipitate was filtered and dried to obtain 110 g of alkali-soluble resin (1), which is a lipophilic polymer compound.

This lipophilic polymer compound is an alkali-soluble resin (1
) was measured for molecular weight by gel permeation chromatography (hereinafter abbreviated as GPC) using a polystyrene standard, and the weight average molecular weight was 65,000.

Alkali (2) 2-hydroxyethyl methacrylate 50g acrylonitrile 20g methyl methacrylate 25g methacrylic acid
5g benzoyl peroxide
1.2g of the above mixture was heated to 100°C. 300g ethylene glycol monomethyl ether
It was added dropwise over a period of 2 hours. After the dropwise addition was completed, 300 g of ethylene glycol monomethyl ether and 0.3 g of benzoyl peroxide were added, and the mixture was allowed to react for 4 hours.

After the reaction was completed, the mixture was diluted with methanol and poured into water 51 with stirring, and the resulting white precipitate was filtered and dried to obtain 90 g of alkali-soluble resin (2), which is a lipophilic polymer.

This lipophilic polymer compound is an alkali-soluble resin (2
) was measured for molecular weight by GPC in the same manner as above, and the weight average molecular weight was 65.000.

Diazo 81 4-diazodiphenylamine sulfate (50 g) was dissolved in 150 g of concentrated sulfuric acid under water cooling. After dissolution, 4.6 g of paraformaldehyde was slowly added.

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 poured into 1.21 t of ethanol under water cooling, and the resulting precipitate was collected by filtration. After washing with ethanol, dissolve this precipitate in 200% pure water and add 20g to this solution.
A cold concentrated aqueous solution of zinc chloride was added. The resulting precipitate was collected by filtration, washed with ethanol, and washed with 500
was dissolved in pure water. To this liquid was added a cold concentrated aqueous solution in which 26 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was filtered, washed with water, and then dried at 30°C for one day and night to obtain diazo resin 1.

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

Mudiazo resin 2 of Diazo 52 can be synthesized by the same method as above, after dissolving 25 g of 4-diazodiphenylamine sulfate and 12 g of per-hydroxybenzoic acid in concentrated sulfuric acid.

Synthesis of diazo resin 3 Diazo resin 3 can be synthesized by the same method as above after dissolving 25 g of 4-diazodiphenylamine sulfate and 15 g of N-(4-hydroxyphenyl)-methacrylamide in concentrated sulfuric acid. I can do it.

Next, examples will be specifically described.

Example-1 An aluminum plate was degreased with a 3% aqueous sodium hydroxide solution, electrolytically etched in a 2% hydrochloric acid bath at a current density of 13 A/dnf at 25°C, and after washing with water, etched at 30° in a 30% sulfuric acid bath. Anodizing was performed for 2 minutes under the conditions of C11,5A/dn.

Next, using 1% sodium metasilicate aqueous solution, 85°C
The pores were sealed for 130 seconds, washed with water, and dried to obtain an aluminum plate for planographic printing. Each photosensitive solution with the following composition was applied to this aluminum plate so that the film weight after drying was 1.7 g/drr.
The photosensitive planographic printing plates 1 to 8 were obtained as shown in Table 1 below.

Photosensitive liquid composition 1 Photosensitive liquid composition 2 Photosensitive liquid composition 3 Photosensitive liquid composition 6 Photosensitive liquid composition 4 Photosensitive liquid composition 7 Photosensitive liquid composition 5 Photosensitive liquid composition 8 The obtained photosensitive planographic printing plate was brought into close contact with a negative transparent original image, and a 2KW plate was applied. 3 from a distance of 60cm with a metal halide lamp
The film was exposed to light for 0 seconds, immersed in developer solution (1) or (n) having the following composition at 27°C for 20 seconds, and then developed by rubbing with absorbent cotton.

Developer (I) composition (pH 13.0 at 25°C) On the other hand, the photosensitive planographic printing plate obtained above was subjected to forced storage (
After heating at 55°C for 3 days, plate making was performed in the same manner as described above.

The developability was evaluated by printing using the above plate and visually determining the degree of staining on the paper surface.

The results are shown in Table-1.

As understood from Table 1, according to the present invention, high-sensitivity lithographic printing with excellent developability and storage developability (pH at 25°C is 12.8). [Effects] As described above, the method for developing the diazo resin-containing window light material of the present invention uses a developer that does not contain an organic solvent, so it can solve the problems associated with the use of organic solvents, and improves developability, especially long-term storage. It has excellent developability when used for printing, and has the effect of not causing stains even when used for printing, for example, when applied to a developing method for photosensitive lithographic printing plates.

value ○: No stains observed, good developability.

△: Slight stains are visible.

: A condition in which dirt is visible on the entire surface of the printed matter.

Claims (1)

[Claims] 1. A photosensitive material having a photosensitive layer containing a compound having a polymerizable unsaturated bond and a photopolymerization initiator on a support,
A method for developing a photosensitive material containing a photopolymerization initiator, which comprises developing with a developer having a pH of 12.0 or higher at 25° C. and containing substantially no organic solvent.