JPH02262148A - Method for developing photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain always stable developability even when development is carried out over a long period of time with an automatic developing machine and a developing soln. repeatedly used under replenishment with a replenisher by incorporating a specified surfactant into at least one of the rear surface and overcoat layer of a positive type photosensitive planographic printing plate. CONSTITUTION:When a positive type PS plate is imagewise exposed and developed with a repeatedly used developing soln., at least one of nonionic and cationic surfactants is incorporated into at least one of the rear surface and overcoat layer of the PS plate. The stability of the finish of the developed PS plate is improved even when development is carried out over a long period of time with an automatic developing machine and a developing soln. repeatedly used under replenishment with a replenisher. In the case where positive and negative PS plates are developed with the same developing soln., both the PS plates can be developed with stable finish.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for developing a photosensitive lithographic printing plate (hereinafter referred to as "23rd plate"), and more specifically, the present invention relates to a method for developing a photosensitive lithographic printing plate (hereinafter referred to as "23rd plate"), and more specifically, the present invention relates to a method for developing a photosensitive lithographic printing plate (hereinafter referred to as "23rd plate"), and more specifically, it relates to a method for developing a photosensitive lithographic printing plate (hereinafter referred to as "23rd plate"). The present invention relates to a method for developing a positive type 23 plate with a developing solution. [Background of the Invention] When 23 plates are processed continuously using an automatic developing machine that circulates the developer, the activity of the developer decreases. In order to prevent this decrease, it is known to replenish the developer replenisher to maintain the developability at a certain level. Developer replenisher is usually
A solution having a higher alkaline strength than the mother solution (a developing solution that is repeatedly used and is to be replenished) is used. However, when developing the positive 23rd plate, including cases where the positive 23rd plate and the negative PS plate are commonly developed with the same developer,
Even if the alkaline strength is kept constant by adding a developer replenisher, the development result of the positive type 23 plate tends to be soft. In order to improve this softening phenomenon, the present inventors have found that it is effective to add a nonionic or cationic surfactant to the developer replenisher. It has been found that there are problems in that a stable development finish cannot be obtained due to difficulty in dissolving the surfactant or an excess or deficiency in the amount of the surfactant. [Problems to be Solved by the Invention] The present invention attempts to solve the above-mentioned technical problems, and an object of the present invention is to replenish the developer replenisher using an automatic developing machine and use the developer repeatedly for a long period of time. To provide a developing processing method for a positive type 23 plate, which can always obtain stable developing performance even when processing is repeated. Another object of the present invention is that when the negative 28th plate and the positive 23rd plate are developed with a common developer that can be used repeatedly by replenishing a developer replenisher, both can be developed with a stable finish. An object of the present invention is to provide a method for developing a plate. [Means for Solving the Problems] The object of the present invention is to provide a development processing method in which a positive type 23 plate is processed with a repeatedly used developer after image exposure.
This is achieved by a method for developing a photosensitive planographic printing plate in which at least one of the back surface or overcoat layer of a positive WPS plate contains at least one selected from nonionic surfactants and cationic surfactants. The present invention will be explained in detail below. Various nonionic surfactants can be used as the nonionic surfactant to be contained in the back surface or overcoat layer of the positive adjusted PS plate of the present invention. Nonionic surfactants can be broadly classified into polyethylene glycol type and polyhydric alcohol type, and both can be used in the present invention, but polyethylene glycol type nonionic surfactants are preferred from the viewpoint of the large effect. , among which ethyleneoxy group (-CH2CH20-
) of 3 or more, and ) HLB value (HLB is Hydro
A nonionic surfactant having a phile-Lipophile Balance of 5 or more (more preferably 8 to 2o) is more preferable. Moreover, among nonionic surfactants, those having both an ethyleneoxy group and a propyleneoxy group are particularly preferable, and among these, those having an HLB value of 8 or more are more preferable. Preferred examples of the nonionic surfactant used in the positive type 23rd plate of the present invention include compounds represented by Noshiro (1) to [8] below. (1) RO(CH2CH20)nH(3) R-
0-(CH3COO)m (CH2CH20)nH(
7) H(OCsH4)y(ocsue)x \/(
C3H60)X (C2H40)yH[l]~[8]
In the formula, R represents a hydrogen atom or a monovalent organic group. The organic group is, for example, a straight chain or branched group having 1 to 1 carbon atoms.
3o, an alkyl group that may have a substituent (for example, an aryl group (phenyl, etc.)), an alkylcarbonyl group whose alkyl moiety is the above alkyl group, a substituent (for example, a hydroxyl group, an alkyl group as described above, etc.) ), etc., which may have a phenyl group. alb, c, mS
n, X and y each represent an integer of 1 to 40. Next, specific examples of nonionic surfactants used in the present invention will be shown. Polyethylene glycol, polyoxyethylene lauryl ether, polyoxyethylene nonyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxy Ethylene polyoxypropylene behenyl ether, polyoxyethylene nonylphenyl ether, holoxyethylene octylphenyl ether, polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide, polyoxyethylene castor oil, polyoxyethylene abiethyl ether, polyoxyethylene lanolin ether, polyoxyethylene monolaurate, polyoxyethylene monostearate,
Polyoxyethylene glyceryl monooleate, polyoxyethylene glycer monostearate, polyoxyethylene propylene glycol monostearate, oxyethylene oxypropylene block polymer, distyrenated phenol polyethylene oxide adduct, tribenzylphenol polyethylene oxide adduct, octylphenol polyoxyethylene Polyoxypropylene adduct, glycerol monostearate, sorbitan monolaurate, polyoxyethylene sorbicun monolaurate, etc. The weight average molecular weight of the nonionic surfactant used in the present invention is preferably in the range of 300 to 10,000, and preferably in the range of 500 to 500.
A range of 0 is particularly preferred. One type of nonionic surfactant may be contained alone, or two or more types may be used in combination. Various cationic surfactants can be used to contain the back surface or overcoat layer of the positive type 13 plate. Cationic surfactants are broadly classified into amine type and quaternary ammonium salt type, and any of these can be used in the present invention. Examples of amine types include polyoxyethylene alkylamine, N-alkylpropylene amine, N-alkyl polyethylene polyamine ethylene polyamine dimethyl biguanide, long chain amine oxide, alkylimidacilline, 1-hydroxyethyl-2-alkylimidacilline, Examples include 1-acetylaminoethyl-2-alkylimidacilline and 2-alkyl-4-methyl-4-hydroxymethyloxazoline. Examples of quaternary ammonium salts include long chain primary amine salts, alkyltrimethylammonium salts, dialkyldimethylethylammonium salts, alkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, and alkylquinolinium salts. salt, alkylisoquinolinium salt, alkylpyridinium sulfate, stearamidemethylpyridinium salt, acylaminoethyldiethylamine methyldiethylammonium salt, alkylamidopropyldimethylbenzylammonium salt, fatty acid polyethylene polyamide, acylaminoethylpyridinium salt, acylcolamino Formylmethylpyridinium salt, stearoxymethylpyridinium salt, fatty acid triethanolamine, fatty acid triethanolamine formate, trioxyethylene fatty acid triethanolamine, fatty acid dibutylaminoethanol, cetyloxymethylpyridinium salt, p-inoctylphenoxyethoxyethyl There are dimethylbenzylammonium salts, etc. (In the above compound examples, "alkyl" refers to a straight-chain or partially substituted alkyl having 6 to 20 carbon atoms, and specifically, straight-chain alkyl such as hexyl, octyl, cetyl, stearyl, etc.) (Preferably used.) Among these, water-soluble quaternary ammonium salt-based cationic surfactants are particularly effective, and among these, alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, ethylene oxide addition ammonium salts, etc. are preferable. be. Further, a polymer having a cationic component as a repeating unit is also a cationic surfactant in a broad sense, and the cationic surfactant of the present invention has a golden color. In particular, a polymer containing a quaternary ammonium salt obtained by copolymerizing with a lipophilic hexamer can be suitably used. The weight average molecular weight of the polymer is in the range of 300 to 50,000, particularly preferably in the range of 500 to 5,000. These cationic surfactants can be used alone or in combination with
You may use more than one species in combination. The amount of nonionic surfactant and/or cationic surfactant to be contained in the back surface and/or overcoat layer of the positive type 13 plate is 0.001 to 0.1 g in total of nonionic surfactant and cationic surfactant. /m2 is preferred. Alternatively, an amount corresponding to the amount consumed by the positive PS plate during development may be determined experimentally, and such an amount may be determined. In order to contain the surfactant on the back surface of the positive PS plate, a layer containing a water-soluble or alkali-soluble polymer compound as a binder is provided on the back surface, and the surfactant is contained in the layer. is preferred. In addition, in order to incorporate it into the overcoat layer, as in the case of the back side above, an overcoat layer containing a water-soluble or alkali-soluble polymer compound as a binder is coated on the photosensitive layer, and the overcoat layer is coated on the photosensitive layer. The surfactant may be contained in the layer. Examples of the water-soluble or alkali-soluble polymer compound include polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylpyrrolidone, polysodium-L-glutamate, water-soluble polyvinyl butyral, a copolymer of vinyl alcohol and maleic acid, copolymer of vinyl alcohol and acrylamide,
Copolymer of vinylpyrrolidone and vinyl acetate, (meth)
Synthetic polymer compounds such as copolymers of acrylic esters and (meth)acrylic acid; methylcellulose, carboxymethylcellulose, hydroxyethylcellulose,
Cellulose ethers such as hydroxypropyl methylcellulose; natural polymer compounds such as casein, albumin, gelatin (including acylated gelatin), and gum arabic are included, and these can be used alone or in combination of two or more. The amount of the binder in the back layer and overcoat layer containing the surfactant is not particularly limited, but each is suitably in the range of 0.1 to 5.0 g/m'. In a preferred embodiment of the present invention, the layer containing the surfactant is formed by using an alkali-soluble polymer as a binder.
An example is an embodiment in which the coating is applied to the back side of the plate. The positive hard PS plate according to the present invention is formed by coating a photosensitive composition containing an O-quinonediazide compound as a photosensitive component on a support commonly used as a support for PS plates. As the support, for example, JP-A-62-175
Supports such as those described in JP-A No. 757, page 6, lower right column, line 15 to page 7, upper right column, line 11, are exemplified. Examples of the 0-quinonediazide compound in the present invention include ester compounds of 0-naphthoquinonediazide sulfonic acid and polycondensation resins of phenols and aldehydes or ketones. Examples of the phenols include phenol, 0-
Cresol, l-cresol, p-cresol, 3.5
Examples include m-phenols such as xylenol, carvacrol, and thymol, dihydric phenols such as catechol, resorcinol, and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred among these are formaldehyde and benzaldehyde. Further, examples of the ketone include acetone and methyl ethyl ketone. Specific examples of the polycondensation resin include phenol formaldehyde resin, m-cresol formaldehyde resin, m-9p-mixed cresol formaldehyde resin, resorcinol benzaldehyde resin, pyrogallol acetone resin, and the like. The condensation rate of 0-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol of the 0-su7toquinonediazide compound (reaction rate with respect to one OHiI!i) is 15 to
It is preferably 80%, more preferably 20-45%. Furthermore, it is used in the present invention. - As the quinonediazide compound, the following compounds described in JP-A-58-43451 can also be used. That is, for example, known 1,2-quinonediazides such as 1,2-benzoquinonediazide sulfonic acid ester, 1,2-naphthoquinonediazide sulfonic acid ester, 1,2-benzoquinonediazide sulfonic acid amide, 1,2-naphthoquinonediazide sulfonic acid amide, etc. compounds, more specifically J. Kosar (J, [o
``Light Sensitive Systems'' by Sar) (
“Light-Sensitive Systems”
) pp. 339-352 (1965), John Wiley & Sons
N.S.) company (knee York) and dubliny varnish day-.
“Photoresist” Volume 50 by W.S. De Forest,
(1975), McGraw-Hill (Me Gray-
1, 2-
Benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2.1',2'-di(benzoquinonediazide-4-sulfonyl)-dihydroxybiphenyl, 1
, 2-benzoquinonediazide-4-(N-ethyroot β
・Naphthyl)-sulfonamide, 1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, l
-(1,2-NaphthoquinonediaziF -5-sulfonyl)-3,5-dimethylpyrazole, 1,2-7toquinonediazido-5-sulfonic acid-4'-hydroxydiphenyl-4'-azo-β- Naphthol ester, N, N-
Di(1,2-naphthoquinonediazide-5-sulfonyl)-aniline, 2'-(1,2-naphthoquinonediazide-5-sulfonyloxy)-1-hydroxy-anthraquinone, 1,2-naphthoquinonediazide 5-sulfonic acid -2,4-dihydroxybenzophenone ester, 1
．． 2-naphthoquinonediazide-5-sulfonic acid-2,3
,4-)lyhydroxybenzophenone ester, 112
- Condensate of 2 moles of naphthoquinonediazide-5-sulfonic acid chloride and 1 mole of 4°4'-diaminobenzophenone, 2 moles of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4.4'-dihydroxy-1,1 '-Condensate of 1 mole of diphenylsulfone, ■, 2-naphthoquinone diazide, condensate of 1 mole of 5-sulfonic acid chloride and 21 moles of purpurogasa, 1.2-naphthoquinone diazide-
Mention may be made of 1,2-quinonediazide compounds such as 5-(N-dihydroabiethyl)-sulfonamide. Also, Special Publication No. 37-1953, No. 37-3627,
No. 37-1310Q, No. 40-26126, No. 40
-3801, 45/5604, 45-2734
No. 5, No. 51-13013, JP-A-48-96575
Also included are l,2-quinonediazide compounds described in Japanese Patent Nos. No. 48-63802 and No. 48-63802. Among the 0-quinonediazide compounds, 0-quinonediazide obtained by reacting l,2-benzoquinonediazide sulfonyl chloride or 1,2-naphthoquinonediazide sulfonyl chloride with pyrogallol acetone condensation resin or 2,3,4-trihydroxybenzophenone. Ester compounds are particularly preferred. In the present invention, each of the above compounds may be used alone as the O-quinonediazide compound, or two or more thereof may be used in combination. The proportion of the 0-quinonediazide compound in the photosensitive layer of the positive 23 plate of the present invention is 5 to 60.
% by weight is preferred, particularly preferably 10-50% by weight
It is. The photosensitive layer of the positive PS plate of the present invention can contain an organic acid. Preferred organic acids include p at 25°C.
Examples include organic acids having a ka value of 2 or more. Organic acids having the above pka value include, for example, Chemical Handbook Basic Edition ■, Maruzen Co., Ltd., 1966, No. 1054-1.
The organic acids listed on page 058 have a pka value of 2.
All the compounds mentioned above can be mentioned. Examples of compounds having a pka value of 2 or more include benzoic acid, adipic acid, azelaic acid, isophthalic acid, p-toluic acid, β-ethylglutaric acid, rhooxybenzoic acid, p-oxybenzoic acid, and 3.5-dimethyl. Benzoic acid, 3
, 4-dimethoxy acid, glyceric acid, glutaconic acid, glutaric acid, p-anisic acid, succinic acid, sepacic acid, β,
β-diethylglutaric acid, 1,1-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1.1-
Cyclopenkune dicarboxylic acid, 1゜2-cyclopenkune dicarboxylic acid, 1,3-cyclopenkune dicarboxylic acid,
β, β-dimethylglutaric acid, dimethylmalonic acid, α-
Tartaric acid, superric acid, terephthalic acid, pimelic acid, phthalic acid, hepmalic acid, β-propylglutaric acid, propylmalonic acid, mandelic acid, meso-sake soap, β-methylglutaric acid, β, β-methylpropylglutaric acid, Methylmalonic acid, malic acid, ■, 1-cyclohexanedicarboxylic acid,
1.2-cyclohexanedicarboxylic acid, 1.3-cyclohexanedicarboxylic acid, 1.4-cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, erucic acid, undecenoic acid, lauric acid, n-capric acid , pelargonic acid, n-undecanoic acid, and the like. Other organic acids having an enol structure such as Meldrum's acid and ascorbic acid can also be preferably used. The proportion of the organic acid in the photosensitive layer is 0.05
~10% by weight is suitable, preferably 0.1-5% by weight. The photosensitive layer of the positive ff1Ps plate of the present invention may contain an acid anhydride. Preferred are cyclic acid anhydrides, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-nindooxy-△4tetrahydroheptalic anhydride, tetrachlorophthalic anhydride, and glutaric anhydride. acid, maleic anhydride,
Talol maleic anhydride, a-phenyl maleic anhydride,
Examples include succinic anhydride and pyromellitic acid. These acid anhydrides are contained in the photosensitive layer in an amount of 0.05 to 10% by weight, especially 0.
．． It is preferably contained in an amount of 1 to 5% by weight. In the positive PS plate of the present invention, it is preferable that the photosensitive layer containing the 0-quinonediazide compound contains an alkali-soluble resin. Examples of the alkali-soluble resin include novolac resin, vinyl polymer having a phenolic hydroxyl group, and JP-A No. 55
Examples include condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-57841. Examples of the novolak resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensate resin as described in JP-A-55-57841, and JP-A-55-127553. Examples include copolycondensate resins of p-substituted phenol and phenol or cresol and formaldevit as described in publications. The molecular weight (polystyrene standard) of the novolak resin is:
Preferably, the number average molecular weight Mn is 3. OOX 102~7
．． 50X 103, weight average molecular weight My is 1.00X
103 to 3.00X 10', more preferably Mn is 5
．． OOX 102-4.008IQ”%My is 3.00
X 10"-2,00
Weight % is appropriate. It is preferable that the photosensitive layer contains a vinyl polymer having a phenolic hydroxyl group. This vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having a phenolic hydroxyl group in its molecular structure, and the following - Noshiro

Polymers containing at least one structural unit of [9] to [13] are preferred. General formula [12] General formula [13] General formula

[9] General formula [IO] General formula (11) general formula

In [9] to [13], R and R2 each represent a hydrogen atom, an alkyl group or a carboxyl group,
Preferably it is a hydrogen atom. R8 represents a hydrogen atom, a halogen atom, or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,
Preferably it is a hydrogen atom. A represents an alkylene group which may have a substituent and which connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, ■ represents an integer from 0 to 1o, and B may have a substituent. Represents a phenylene group or a naphthylene group which may have a substituent. The polymer used in the photosensitive layer preferably has a copolymer type structure, and

[9] ~ [13]
Examples of monomer units that can be used in combination with the structural units shown in ] include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, isoprene,
Styrenes such as methylstyrene, p-methylstyrene, and p-chlorostyrene; acrylic acids such as acrylic acid and methacrylic acid; unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride; e.g. acrylic acid; Methyl, ethyl acrylate, n-acrylate
Butyl, isobutyl acrylate, dodecyl acrylate,
2-chloroethyl acrylate, phenyl acrylate, α
- Esters of α-methylene aliphatic monocarboxylic acids such as methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, ethyl ethagrylate, nitriles such as acrylonitrile, methacrylonitrile, amides such as acrylamide, e.g. acrylic Anilides such as anilide, p-chloroacrylanilide, m-ditroacrylanilide, l-methoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, such as methyl vinyl ether, ethyl Vinyl ethers such as vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as l-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, l,2-
Ethylene derivatives such as dimethoxyethylene, 1,1-dimethoxycarbonylethylene, l-methyl-1-ditroethylene, such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolene, N- There are vinyl monomers such as N-vinyl compounds such as vinylpyrrolidone. These vinyl monomers exist in polymer compounds with a structure in which an unsaturated double bond is cleaved. Among the above monomers, aliphatic monocarboxylic acid esters and nitriles exhibit excellent performance for the purpose of the present invention and are therefore preferred. These monomers may be bound in the polymer either in a block or random manner. The proportion of the vinyl polymer in the photosensitive layer is from 0.5 to
70% by weight is preferred. The above vinyl polymers may be used alone or in combination of two or more. Moreover, it can also be used in combination with other polymer compounds. It is preferable that the photosensitive layer of the present invention further contains a substituted phenol represented by the following Noshiro [14] as a fat-sensitizing agent. Furthermore, it is preferable that the photosensitive layer of the present invention contains a condensation resin of a substituted phenol and an aldehyde represented by the following Noshiro [14] and/or an 0-quinonediazide sulfonic acid ester compound of the resin. General formula [14] H In general formula [14], R1 and R7 each represent a hydrogen atom, an alkyl group, or a halogen atom, and R3 represents an alkyl group or a cycloalkyl group having 2 or more carbon atoms. In the general formula [14], the alkyl group represented by R1 and R2 is preferably an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 to 2 carbon atoms is particularly useful. The halogen atom represented by R□ and R2 is, for example, fluorine, chlorine, bromine, iodine, etc., and chlorine atom and bromine atom are particularly preferred. The alkyl group represented by R8 preferably has 15 or less carbon atoms, particularly preferably an alkyl group having 3 to 8 carbon atoms, and the cycloalkyl group preferably has 3 to 15 carbon atoms, and preferably has 3 to 8 carbon atoms. are particularly useful. Examples of substituted phenols represented by -Noshiro [14] include isopropylphenol, tert-butylphenol, tert-amylphenol, hexylphenol, tert-octylphenol, cyclohexylphenol, 3-methyl-4-chloro-5-tert -butylphenol, isopropylcresol, tert-
Examples include butyl cresol, tert-amyl cresol, hexyl cresol, tert-octyl cresol, and cyclohexyl cresol, among which tert-octylphenol and tert-butylphenol are particularly preferred. Examples of the aldehydes include aliphatic and aromatic aldehydes such as formaldehyde, benzaldehyde, acetaldehyde, acrolein, crotonaldehyde, and furfural, including those having 1 to 6 carbon atoms. Among them, formaldehyde and benzaldehyde are preferred. The content of the substituted phenol represented by the general formula [14] in the photosensitive layer is preferably in the range of 0.05 to 15% by weight. The resin obtained by condensing the substituted phenol and aldehyde is synthesized by polycondensing the substituted phenol represented by -Noshiro [14] and an aldehyde in the presence of an acidic catalyst. The acidic catalysts used are inorganic acids and organic acids such as hydrochloric acid, oxalic acid, sulfuric acid, and phosphoric acid. is used in an amount of 0.7 to 1.0 mole part. Alcohols, acetone, water, tetrahydrofuran, etc. are used as the reaction solvent. After reaction at a predetermined temperature (-5 to 120° C.) for a predetermined period of time (3 to 48 hours), the reaction product is obtained by pressurizing under reduced pressure and washing with water to dehydrate, or by allowing water to precipitate. 0 of the condensation resin of the above substituted phenols and aldehydes
-The naphthoquinonediazide sulfonic acid ester compound is
The above condensation resin is dissolved in a suitable solvent such as dioxane, 0-naphthoquinonediazide sulfonic acid chloride is added thereto, and an alkali such as alkali carbonate is added dropwise to the equivalence point while stirring under pressure. Obtained by converting In the esterified product, the condensation rate of 0-su7toquinonediazide sulfonic acid chloride with respect to the hydroxyl group of the phenol (reaction rate % with respect to one hydroxyl group) is 5 to 80%.
is preferable, more preferably 20 to 70%, still more preferably 30 to 60%. The condensation rate is calculated by determining the content of sulfur atoms in the sulfonyl group by elemental analysis. A resin obtained by condensing a substituted phenol represented by -Noshiro [14] with an aldehyde, which occupies the photosensitive layer, and an 0-naphthoquinone cyacytosulfonic acid ester compound of the resin (hereinafter referred to as a "sensitizing agent") The amount of B) is preferably 0.05 to 15% by weight, particularly preferably 1 to 10% by weight. The fat sensitizing agent (B) preferably has a weight average molecular weight My,
5. OX 102~5. OX 103, more preferably 7. The range is OX 10" to 3.OX 10". Its number average molecular weight Mn is 3. OX102
It is preferably in the range of ~2.5X103, more preferably in the range of 4.0X102-2, OX10''. Examples of the compound of the oil sensitizing agent (B) are listed below. -i 30w (m : n = 50: 50. Mw of the resin before reacting with Q' = 1500) (m: n = 50: 50, Mw of the resin before reacting with Q -1300) H In the photosensitive layer In addition to the above-mentioned materials, dyes, pigments, photochromic dyes, plasticizers, surfactants, fluorine-based surfactants, compounds capable of generating acids upon exposure to light, etc. can be added as necessary. In order to improve the oil sensitivity of the photosensitive layer, for example, p-tert-butylphenol formaldehyde resin, p-n-octylphenol formaldehyde resin, or a resin partially esterified with an 0-quinonediazide compound is used in the photosensitive layer. These components can be dissolved in a commonly used solvent, and 28
A positive WPS plate can be manufactured by providing a photosensitive layer by coating the surface of a plate support and drying it. The coating amount is preferably 0.5 to 7 g/m' in weight after drying.
is within the range of In order to provide the back layer containing the surfactant according to the present invention, a coating solution in which the polymer compound and the surfactant are dissolved in a solvent is applied by spin coating, wire bar coating, dip coating, air knife coating, or roll coating. It may be applied to the back side of the 28 plate by coating, blade coating, curtain coating, or the like. To provide an overcoat layer containing a surfactant according to the present invention, a coating solution containing the polymer compound and the surfactant is applied on the photosensitive layer of the 28th plate in the same manner as in the case of the back side. It should be applied to. As the coating solvent, a solvent that does not dissolve the photosensitive layer, such as water, methanol, ethanol, or propylene glycol, can be preferably used. Next, in the present invention, the developing solution used repeatedly (hereinafter simply referred to as "developing solution") is preferably an alkaline solution containing water as the main solvent (specifically, 50% by weight or more of the solvent is water). It is a developer. Examples of the alkali agents include alkali silicate (potassium silicate, sodium silicate, etc.), potassium hydroxide,
Sodium hydroxide, lithium hydroxide, sodium triphosphate, sodium diphosphate, potassium triphosphate, potassium diphosphate, ammonium diphosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, carbonic acid Examples include inorganic alkaline agents such as sodium, potassium carbonate, ammonium carbonate, etc., organic alkaline agents such as mono- or triethanolamine and tetraalkyl hydroxide, and organic ammonium silicate. The content of the alkaline agent in the developer is preferably in the range of 0.05 to 20% by weight, more preferably in the range of 0.1 to 10% by weight. The developing solution contains at least one selected from nonionic surfactants and cationic surfactants from the start of repeated use.
Preferably, seeds are included. As the surfactant, the surfactants mentioned above as nonionic surfactants and cationic surfactants that are contained in the back surface or overcoat layer of the positive type 28 plate can be used. The concentration of the surfactant in the developer is 0.001 to 0.001 in total amount of nonionic surfactant and cationic surfactant.
10% by weight is preferred, more preferably 0.01-1% by weight. It is preferable that the developer contains an organic carboxylic acid. The organic carboxylic acid preferably has 6 to 6 carbon atoms.
20 aliphatic carboxylic acids, and aromatic carboxylic acids in which a benzene ring or naphthalene ring is substituted with a carboxyl group. The aliphatic carboxylic acid is preferably an alkanoic acid having 6 to 20 carbon atoms, and specific examples include caproic acid, enantylic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, mystylic acid, valmitic acid, and stearic acid. etc., and particularly preferred are alkanoic acids having 6 to 12 carbon atoms. Also, fatty acids with double bonds in their carbon chains,
It may also have a branched carbon chain. In order to improve water solubility, the aliphatic carboxylic acid is preferably used as a sodium or potassium salt or an ammonium salt. Specific compounds of aromatic carboxylic acids include benzoic acid, 0-chlorobenzoic acid, p-chlorobenzoic acid, 0-hydroxybenzoic acid, p-hydroxybenzoic acid, p-ter
t-Butylbenzoic acid, 0-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2゜5-dihydroxybenzoic acid, 2.3-dihydroxybenzoic acid, 2
, 3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, l-hydroxy-2-7toic acid,
3-hydroxy-2-naphthoic acid, 2-hydroxy-■
-su7toic acid, -su7toic acid, 2-naphthoic acid, etc. Among these, benzoic acids are particularly effective. The above aromatic carboxylic acid is preferably used as a sodium or potassium salt or an ammonium salt in order to improve water solubility. There is no particular limit to the content of aliphatic carboxylic acid or aromatic carboxylic acid added to the developer, but if it is less than 1% by weight, the effect will not be sufficient, and if it is more than 10% by weight, the effect will be insufficient. Not only can it not be measured, but it can also hinder dissolution when used in combination with other additives. Therefore, the amount added is preferably 0.1-10% by weight, more preferably 0.5-4% by weight. Additives can be added to the developer, but among them, additives with a solubility in water of 10% by weight at 20°C
The following organic solvents are particularly effective for the purposes of this invention. Examples of organic solvents having a solubility in water of 10% by weight or less include carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, and butyl levulinate; Ketones such as butyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monobutyl ether, methylphenyl carbinol, n-amyl alcohol, and methyl amyl alcohol;
These include alkyl-substituted aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, and monochlorobenzene. One or more of these organic solvents may be used. The organic solvent is an excellent additive for improving the developability of both negative and positive PS plates, but at the same time it has the disadvantage of deteriorating the film in the image area for positive type 23 plates. It also has Since the positive 23rd plate does not undergo a crosslinking reaction like the negative 28th plate during exposure, the film deteriorates significantly when development is excessive, and the degree of deterioration becomes even greater in the presence of organic solvents. As mentioned above, it prevents the deterioration of the film during development of the positive type 23 plate, and
In order to develop the 8th plate well, it is effective to include a nonionic surfactant and/or a cationic surfactant in the developer. When the developer according to the present invention is a developer for both negative and positive uses, the pH of the developer mother solution is preferably 12 or more, more preferably in the range of 12.5 to 13.5. When developing a negative 28 plate at such a high pH (pH 12 or higher), some types of plates may be smudged during printing even though they are developed. The degree of staining is dependent on pH; the higher the pH, the more likely it is to stain. In order to develop the negative type 28 plate well at such a high pH and eliminate stains when opening the plate, it is very effective to include sulfite in the developer, and anionic surfactant. The addition of
It is highly effective in accelerating plate development. The developer of the present invention can contain water-soluble or alkali-soluble organic and inorganic reducing agents. Examples of organic reducing agents include phenolic compounds such as hydroquinone, methol, and methoxyquinone, and amine compounds such as phenylenediamine and phenylhydrazine. Examples of inorganic reducing agents include sodium sulfite, potassium sulfite, ammonium sulfite, and hydrogen sulfite. Sulfites such as sodium and potassium hydrogen sulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite,
Examples include phosphates such as potassium hydrogen phosphite, sodium dihydrogen phosphite, and potassium hydrogen sulfite, hydrazine, sodium thiosulfate, and sodium dithionite. The reducing agent may be contained in a range of at least 0.1 to 10% by weight. Further, the following additives can be added to the developer in the present invention in order to further improve the developing performance. For example, NaCLKC (2
Neutral agents such as Br, etc., chelating agents such as EDTA and NTA described in JP-A-59-190952, JP-A-59-1909-
(Co(NHs)) aC(
complexes such as 2s, ampholytic polymer electrolytes such as the copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142528;
Inorganic lithium compounds such as lithium chloride described in JP-A No. 58-59444, organic lithium compounds such as lithium benzoate described in JP-A-50-34442, Si, Ti, etc. described in JP-A-59-75255. and organoboron compounds described in JP-A-59-84241. The developer replenisher in the present invention suffers from fatigue due to the development process itself and fatigue due to aging (due to absorption of carbon dioxide gas in the air).
It may be of a composition that can restore the activity of the developer by replenishing the components in the developer that are consumed by the developer. In the present invention, since the surfactant is replenished from the PS plate by making the positive PS plate contain the surfactant as described above, it is not necessary to contain the surfactant in the developer replenisher. The concentration of the alkaline agent in the developer replenisher is preferably higher than the concentration of the alkaline agent in the developer. Its concentration preferably ranges from 0.2 to 30% by weight, more preferably from 0.5 to 10% by weight. It is preferable that the 5i02 concentration is equal to or higher than that of the developer. When using additives such as organic carboxylic acids, organic solvents, and reducing agents, their respective concentrations in the developer replenisher are preferably higher than those in the developer. Specifically, the concentration in the developer replenisher is suitably 1.2 to 1090 times the concentration in the developer. In the method of the present invention, a positive-hard PS plate having a back layer and/or overcoat layer containing the surfactant and a PS plate other than the PS plate that can be developed in common with the same developer include diazo as a photosensitive component. A negative WPS plate containing a compound, a compound that causes a photodimerization reaction with a compound having an ethylenically unsaturated double bond as a photosensitive component, a compound that causes a photopolymerization reaction, and a compound that has a C-0-C group that decomposes with an acid. Includes negative PS version using . A negative WPS plate containing the above-mentioned diazo compound as a photosensitive component is a negative WPS plate such as that described in JP-A-62-175757, page 6, upper right column, line 8 to page 6, lower right column, line 14. It is a version. [Example] The present invention will be specifically described below with reference to Examples. Example 1 An aluminum plate with a thickness of 0.31 mm was electrochemically roughened in a nitric acid solution, thoroughly washed, and then anodized in a sulfuric acid solution to form an oxide film of 2.5 g/m'' on the aluminum plate. After washing with water and drying, 3 parts by weight of an esterified product of resorcin benzaldehyde resin and naphthoquinone-1,2-diazido-5-sulfonyl chloride synthesized according to the example of JP-A-56-1044, Talesol formaldehyde novolac resin 9 parts by weight, 2-trichloromethyl-
0.09 parts by weight of 5-(β-(2-benzofuryl)vinyl)-1,3,4-oxadiazole,
A photosensitive solution prepared by dissolving 0.12 parts by weight of Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd.) in 100 parts of 2-methoxyethanol was applied onto the above support and dried, resulting in a photosensitive layer of 2.8 g/a''. Next, on this photosensitive layer, an overcoat layer having the following composition was coated so that the dry weight was 1-5 g/n+''. (Overcoat layer composition) Swanol CA-1000.01 parts by weight (cationic surfactant manufactured by Nikko Chemicals Co., Ltd.) Polyvinyl alcohol 10 parts by weight Water
200 parts by weight of the thus obtained PS plate was exposed to light for 30 seconds using a 2 kW metal halide lamp through a step tablet (Kodak Company) No. 2). This PS plate was processed using an automatic processor PSK-910 (Konica Corporation).
Using developer solution 5DR-1 for positive PS plate (Konica Co., Ltd.)
Co., Ltd.) was continuously processed with a developer diluted six times with water. In addition, 5RC-3 (Konica Corporation) is used as a replenishment device.
The replenisher was 5DR-IR (manufactured by Konica Corporation).
I used it to replenish the development. When the 28 plates were processed for 500 plates over one week and the tonality (difference between the number of clear steps and the number of solid steps) was investigated, the tonality at the start of the process was 7.5 steps and at the end of the process one week later. At 7.0 steps, the variation in gradation was small, and no particular problem occurred during printing. Comparative Example 1 28 plate produced in Example 1 without overcoat layer 2
An 8th plate was prepared, exposed and developed in the same manner as in Example 1, and the gradation at the start of processing and after the 500th plate was examined.The gradation at the start of processing was 7.5 steps. In contrast,
The gradation after the 500 plate processing was as soft as 9.0 steps, and there were problems with halftone dot reproducibility during printing, after embedding, and film loss. Example 2 2% sealing 31050 aluminum plate with a thickness of 0.24 mm
After being immersed in an aqueous sodium hydroxide solution and degreased, the surface was electrochemically roughened in a dilute hydrochloric acid solution, thoroughly washed, and then anodized in a diluted hydrochloric acid solution.
．． An oxide film of 5 g/m2 was formed on the surface of the aluminum plate. After washing the obtained aluminum plate with water and drying, a photosensitive liquid having the following composition was applied to the dry weight of 2.5 g/n+''.
Furthermore, a back layer composition having the following composition was added with a dry weight of 1.2 g/+
”, and dry it to form a positive W with a back layer.
I got the PS version. The dimensions of the plate were 1003 mm and 10 O3. (Photosensitive liquid) Naphthoquinone-1,2-diazide(2)-5-sulfonic acid ester of resorcinol-benzaldehyde resin (described in Example 1 of JP-A-56-1044) ... 1 weight Part cresol-phenol-formaldehyde resin...3 parts by weight ter
Naphthoquinone 1,2-diazide(2)-5-sulfonic acid ester of t-butylphenol-benzaldehyde resin (as described in Example 1 of JP-A-60-31138) 0.1 parts by weight Crystal Violet ( B, A, S, F, manufactured dyes)...0.05
Part by weight Ethylene glycol monomethyl ether...
20 parts by weight (back layer composition) Niracol BO-500, 1 part by weight (nonionic surfactant manufactured by Nikko Chemicals Co., Ltd.) Gelatin 10 parts by weight Water
200 parts by weight Silicon oxide particles (diameter 5-10 μm) 0.3 parts by weight Meanwhile, a JIS1050 aluminum plate with a thickness of 0.24IllIIl was degreased by immersing it in a 20% aqueous sodium phosphate solution, and electrochemically treated in a dilute nitric acid solution. After roughening the surface and washing it thoroughly, it was anodized in a dilute sulfuric acid solution to produce 1.5 g.
/m'' was formed on the surface of the aluminum plate. =44- The obtained aluminum plate was further immersed in an aqueous solution of sodium metasilicate for pore sealing treatment, washed with water, dried, and then subjected to the following process. A photosensitive solution was applied to give a dry weight of 2.0 g/m2 and dried to obtain a negative PS plate.The dimensions of the plate were 10010O3800mm. (Photosensitive solution) A combination of p-diazodiphenylamine and paraformaldehyde. Hexafluorophosphate of condensate... 1 part by weight N-
(4-Hydroxyphenylmethacrylamide copolymer (described in Example 1 of JP-A-57-43890)...10 parts by weight Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) dye)...0.2 parts by weight ethylene glycol monomethyl ether...100
Parts by weight A transparent original film was brought into close contact with the positive 2ffl PS plate and the negative PS plate, and exposure was performed for 30 seconds from a distance of 70 cm using a 2 kilowatt metal halide lamp. On the other hand, the following developing mother liquor was charged into an automatic developing machine PSK-910 (manufactured by Konica Corporation). (Development mother liquor) β-anilinoethanol 5 parts by weight Propylene glycol 5 parts by weight 2-hydroxy-3-naphthoic acid lo parts by weight p-tert-butylbenzoic acid 2 o parts by weight 50% aqueous potassium hydroxide solution 50 parts by weight Eyalgen 147
0.3 parts by weight (nonionic surfactant manufactured by Kao Corporation) Potassium silicate 36 parts by weight (manufactured by Nihon Kagaku Kogyo Co., Ltd.) Potassium sulfite 12 parts by weight Water
1500 parts by weight Finally, the pH was adjusted to 12.90 at 25°C. In addition, a developer replenisher having the following composition was used and was replenished every time 5 m2 of the PS plate was processed. (Developer replenisher) β-anilinoethanol 5 parts by weight Propylene glycol 5 parts by weight 2-hydroxy-3-naphthoic acid 10 parts by weight p-tert-butylbenzoic acid 20 parts by weight 50% aqueous potassium hydroxide solution 60 parts by weight Potassium sulfite
12 parts by weight A potassium silicate
100 parts by weight (manufactured by Nihon Kagaku Kogyo Co., Ltd.) Water 1500 parts by weight Finally, the pH was adjusted to 13.30 at 25°C. In this way, a large number of 23 negative and positive plates were randomly processed. As a result, the negative type 28 version also turned into a positive PS.
The plate was also able to be developed stably. Furthermore, since the content of nonionic surfactant in the developer was constant, there was almost no variation in gradation for both plates. Comparative Example 2 In Example 2, the nonionic surfactant was not added to the back layer of the positive type 23 plate, but the same nonionic surfactant as that added to the back layer was added to the developer replenisher. Similarly, when continuous processing is performed, the amount of nonionic surfactant consumed differs when processing a negative PS plate and when processing a positive PS plate, but the developer replenisher is replenished according to the processed area of the plate. Depending on the processing ratio between the negative PS plate and the positive 23 plate, variations occurred in the development finish, especially in the gradation. [Effects of the Invention] According to the present invention, in the development processing of a positive type 23 plate, in the development processing in which processing is performed alternately over a long period of time using a developer that is refilled with a developer replenisher and used repeatedly using an automatic developing machine. The stability of the developed finish has been improved, and positive ff1Ps
When the plate and the negative 28th plate are commonly developed with the same developer, both the positive 23rd plate and the negative 28th plate can be developed with a stable finish. The above effect is that the replenishment amount can be refilled according to the area of the PS plate to be processed, there is no excess or deficiency of surfactant in the developer, and that one developer can handle negative
When developing the positive type 23rd plate in common, nonionic surfactants and/or cationic surfactants that are not necessary for the negative type 28th plate are replenished even when the negative type 28th plate is processed, and the positive type This solves the problem that the development finish of the 23rd plate becomes inconsistent. Furthermore, according to the present invention, a nonionic surfactant and a cationic surfactant, which have the effect of improving the softening phenomenon of a positive WPS plate, are added to the developer replenisher, or are added to the PS plate and dissolved into the developer to be replenished. By doing so, it is also possible to obtain the effect that even a surfactant that is difficult to dissolve in the developer replenisher can be used.

Claims (1)

[Claims] In a development processing method in which a positive photosensitive lithographic printing plate is treated with a repeatedly used developer after image exposure, a nonionic surfactant and/or 1. A method for developing a photosensitive lithographic printing plate, characterized by containing a cationic surfactant.