JPH0338647A - Processing method for positive type photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To maintain stable development quality over a long period of time by using an aq. soln. contg. alkali silicate and an aq. soln. contg. a surfactant as a replenisher for development. CONSTITUTION:A replenisher for development is composed of an aq. soln. (A) contg. alkali silicate and an aq. soln. (B) contg. a surfactant or water for dilution is further added. The concn. of the alkali silicate in the soln. A is preferably regulated so that the concn. of alkali silicate required in a developing soln. can be maintained by replenishing the replenisher. The amts. of the solns. A, B used depend on the amt. of positive type PS plates developed per unit time, the temp. of the open air and the type of an automatic developing machine. For example, in accordance with the rise of the temp. of the open air surrounding the developing soln., the amt. of the soln. A used is increased. In accordance with the decrease of the amt. of the plates developed, the ratio of the soln. A is increased.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a positive type photosensitive lithographic printing plate (hereinafter referred to as "Positive Type 13").
More specifically, it relates to a processing method of processing a positive type 13 plate using an automatic developing machine, replenishing a replenisher, and developing it with a positive developer. [Prior Art] Conventionally, in the development process of a positive type 13 plate using an automatic processor, it has been known that in the case of long-term processing, the developer is supplemented with a replenisher in order to stabilize the development quality. ing. Regarding the replenisher and replenishment method for the developer, we will use replenisher tm which has a higher pH than the developer. A method of replenishing according to the size is known. However, even if such a replenishment method is adopted, the development quality will change due to long-term development. [Object of the Invention] The object of the present invention is to stably maintain the development quality over a longer period of time in a processing method for a positive 13th plate in which the positive 13th plate is developed by replenishing the replenisher with a developer exclusively for positives. It is an object of the present invention to provide a development replenishment method that can be used. [Structure of the Invention] The above-mentioned object of the present invention is to produce a positive type P using an automatic developing machine and a positive-only developer that can be used repeatedly by replenishing the developer replenisher.
This is achieved by a method for processing a positive PS plate in which the development replenisher comprises the following (A) and (B) in a development processing method for developing an S plate. (A) Aqueous solution containing alkali silicate. (B) Aqueous solution containing a surfactant. Further, in a preferred embodiment of the present invention, in the processing method, the above (A) and (B) are determined by the processing amount per unit time of the positive PS plate to be developed, the outside air temperature, and the type of automatic developing machine. This is an embodiment in which the amount is replenished. The present invention will be explained in detail below. The positive-only developer in the present invention (hereinafter simply referred to as "hair image solution")
) is preferably an alkaline developer containing water as a main solvent (specifically, 50% by weight or more of the solvent is water). Examples of the alkali agents include alkali silicates (potassium silicate, sodium silicate, sodium metasilicate, potassium metasilicate, ammonium silicate, etc.), potassium hydroxide, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, etc. , sodium diphosphate, potassium diphosphate, potassium diphosphate, ammonium diphosphate, ammonium diphosphate, sodium metasilicate,
Examples include inorganic alkaline agents such as sodium bicarbonate, sodium carbonate, potassium carbonate, ammonium carbonate, etc., organic alkaline agents such as mono- or triethanolamine and tetraalkyl hydroxide, and organic ammonium silicates. The content of alkaline agent in the developer is 0.6
The range is preferably 05 to 20% by weight, more preferably 0
．． It ranges from 1 to 10% by weight. It is preferable that the developer contains at least one selected from anionic surfactants, nonionic surfactants, and cationic surfactants from the start of repeated use. As anionic surfactants, higher alcohols (08-
C2□) Sulfuric ester salts [e.g., sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, rTeepol-81J'
(trade name, manufactured by Shell Chemical Co., Ltd.), sodium chloride alkyl sulfate, etc.], aliphatic alcohol phosphate ester salts (e.g., sodium salt of cetyl alcohol phosphate ester, etc.), alkylaryl sulfonates (e.g., dodecylbenzenesulfonic acid) sodium salt of isopropylnaphthalene sulfonic acid, sodium salt of sinaphthalene disulfonic acid, sodium salt of metanitrobenzene sulfonic acid, etc.), sulfonate salts of alkylamides (e.g., CryHssCON(C)13
)CH, 5o3Na, etc.), sulfonate salts of dibasic fatty acid esters (eg, sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.). Among these, sulfonate salts are particularly preferably used. Nonionic surfactants can be broadly classified into polyethylene glycol type and polyhydric alcohol type, both of which can be used, but polyethylene glycol type nonionic surfactants are preferred from the viewpoint of development performance, and among them, ethylene glycol type nonionic surfactants ( -CO.CH,O-), and has an HLB value (HLB is H
hydroph mouth e-Lipophile Balanc
# of e! Nonionic surfactants having I) of 5 or more (more preferably 8 to 20) are more preferred. Among nonionic surfactants, those having both an ethyleneoxy group and a propylene oquine group are particularly preferred, and among these, those having an HLB value of 8 or more are more preferred. Preferred examples of nonionic surfactants include the following general formula (1
) to [8]. CI) R-0-(CH2CH20)nH(3)
R-0-(CH,CHO)+++-(C112CO
! O) d(6) lo(C2H,O)a (C3)
1eo) b (C2H,0)cH(7) H(OC
21(a)y (OCst(6)X\/(CjIIa
O)X-(CzH,0)yHl((Oc2H4)y
(OCIH6)X/\(CJaO)x (CzH+0
)yH(8) HO-(CH2CH20)nH[1
[8] In the formulas, R represents a hydrogen atom or a monovalent organic group. Examples of the organic group include a straight-chain or branched alkyl group having 1 to 30 carbon atoms that may have a substituent (for example, an aryl group (phenyl, etc.)), and an alkylcarbonyl group in which the alkyl moiety is the above-mentioned alkyl group. groups, substituents (e.g. hydroxyl groups, alkyl groups as mentioned above, etc.)
Yes! Examples include a phenyl group which may have 2 atoms. al
l) %c, m, n, X and y each represent an integer from 1 to 40. Specific examples of nonionic surfactants are shown below. 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, polyoxyethylene octylphenyl ether, polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene stearamide, polyoxyethylene oleate 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 polymer, distyrenated phenol polyethylene oxide adduct, tribenzylphenol polyethylene oxide adduct, octylphenol Polyoxyethylene polyoxypropylene adduct, glycerol monostearate, sorbitan monolaurate, polyquine ethylene sorbitan monolaurate, etc. The weight average molecular weight of the nonionic surfactant is 300 to 100
A range of 00 is preferred, and a range of 500 to 5000 is particularly preferred. Cationic surfactants are broadly classified into amine type and quaternary ammonium salt type, and any of these can be used. Examples of amine types include polyoxyethylene alkyl amines, N-alkyl propylene amines, N-alkyl polyethylene polyamines polyethylene polyamine dimethyl sulfate, alkyl biguanides, long chain amine oxides, alkylimidacillins, l
-Hydroxyethyl-2-alkylimidacyline, ■-acetylaminoethyl-2-alkylimidacyline, 2
-alkyl-4-methyl-4-hydroxymethyloxazoline and the like. Examples of quaternary ammonium salts include long-chain primary amine salts, alkyltrimethylammonium salts, dialkyldimethylethylammonium salts, alkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, and alkylquinolinium salts. , alkylisoquinolinium salt, alkylpyridinium sulfate, stearamidemethylpyridinium salt, acylaminoethyldiethylamine salt, acylaminoethylmethyldiethylammonium salt, alkylamidopropyldimethylbenzylammonium salt, fatty acid polyethylene polyamide, acylaminoethylpyridinium salt , acylcolaminoformylmethylpyridinium salt, stearoxymethylpyridinium salt, fatty acid triethanolamine, fatty acid triethanolamine formate, trioxyethylene fatty acid triethanolamine, fatty acid dibutylaminoethanol, cetyloxymethylpyridinium salt, p
-inoctylphenoxyethoxyethyldimethylbenzylammonium salt and the like. (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 type 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 monomer 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 surfactants are preferably contained in an amount of 0.05 to IO weight %. It is preferable that the developer in the present invention contains an organic carboxylic acid. The organic carboxylic acid is preferably an aliphatic carboxylic acid having 6 to 20 carbon atoms, or an aromatic carboxylic acid in which a benzene ring or a 7talene 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 cabroic 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. The above aliphatic carboxylic acid is preferably used as a sodium or potassium salt or an ammonium salt in order to increase water solubility. 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-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-
Among these, benzoic acids are particularly effective. The above-mentioned 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 restriction on the content of aliphatic carboxylic acid and aromatic carboxylic acid added to the positive developer, but if it is lower than 0.1% by weight, the effect will not be sufficient, and if it is 10% by weight or more, the effect will be even lower. Not only is the improvement not measurable, but it may also hinder dissolution when used in combination with other additives. Therefore, the amount added is preferably 0.1 to 10% by weight, more preferably 0.5 to 4% by weight. The positive-only developer may contain an organic solvent having a solubility in water of 10% by weight or less at 20°C. Examples of organic solvents having a solubility in water of 10% by weight or less include ethyl acetate, propyl acetate, butyl acetate,
Carboxylic acid esters such as amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate; ketones such as ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene; methylene dichloride, ethylene Examples include halogenated hydrocarbons such as dichloride and monochlorobenzene. One or more of these organic solvents may be used. 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, N a CQ x described in JP-A-58-75152
Neutral agents such as Br for KCQ, chelating agents such as EDTA and NTA described in JP-A-59-190952, (Co(NH3)) as described in JP-A-59-121336
*Complexes such as CQs, amphoteric polymer electrolytes such as the copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-1425284, lithium chloride as described in JP-A-58-59444, etc. Inorganic lithium compounds, organic lithium compounds such as lithium benzoate described in Japanese Patent Publication No. 50-34442,
Examples include organometallic surfactants containing Si, Ti, etc. described in JP-A-59-75255, and organoboron compounds described in JP-A-59-84241. Next, the developer replenisher according to the present invention will be explained. The developer replenisher of the present invention is composed of an aqueous solution containing an alkali silicate (replenisher (A)) and an aqueous solution containing a surfactant (replenisher (B)), but water may also be used for dilution. There may be. Examples of the alkali silicate contained in the replenisher (A) constituting one of the developer replenishers of the present invention include the alkali silicate in the developer described above. It is preferable that the pH of the replenisher (A) is higher than that of the developer. In addition, the concentration of alkali silicate in the replenisher (A) is determined by replenishing the concentration of alkali silicate required in the developer in the composition mixed with the replenisher (B) (and water for dilution if necessary). It is best to maintain a concentration that can be maintained. As the surfactant contained in the replenisher (B), the surfactant in the developer described above can be used. The concentration of surfactant in the replenisher (B) is preferably 0.05 to 10% by weight. The concentration of the surfactant in the replenisher (B) is preferably such that the concentration of the surfactant required in the developer can be maintained. The replenisher (A) and the replenisher (B) can contain the developer additives described above, but in this case, if they are added as appropriate in consideration of solubility, stability, etc. good. Note that the additives contained in the developer are preferably also added to the replenisher in order to maintain the performance of the developer. In the present invention, the replenisher (A) and the replenisher (B) are replenished at a rate determined by the processing amount per unit time of the positive PS plate to be developed, the outside temperature, and the type of automatic processor. is preferred. For example, the higher the outside air temperature surrounding the developer, the higher the replenisher (
For example, the amount of replenishment of only A) may be increased, and the proportion of replenisher (A) may be increased as the throughput decreases. Such qualitative relationships are shown in Table 1 below. (Note) (1) ■ is a type that supplies developer to the PS plate using a shower. ■ is a type in which the PS plate is immersed in the developer. (2) /' indicates an increase, '\' indicates a decrease, and - indicates no increase or decrease. As described above, in the present invention, since the developer replenisher has the above-mentioned two-liquid composition, it is possible to appropriately replenish the replenisher according to the fluctuation factors for replenishment, and to maintain good development quality during long-term processing. This made it possible. The positive-working PS plate according to the present invention is one in which a photosensitive composition containing an 0-quinonediazide compound as a photosensitive component is coated on a support commonly used as a support for a PS plate. As the support, for example, JP-A-62-1757
Publication No. 57, page 6, lower right column, line 15 to page 7, upper right column, line 1
Supports such as those listed in line 1 may be mentioned. Examples of the 0-quinonediazide compound 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, m-cresol, p-cresol, 3.5
- Dihydric phenols such as xylenol, monohydric phenol of carvacrol, catechol, resorcinol, and hydroquinone, and trihydric phenols such as pyrogallol and 70-glucine. 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, ill-, p-mixed cresol/formaldehyde resin, resorcinol/benzaldehyde resin, pyrogallol/acetone resin, and the like. The condensation rate of 0-7toquinonediazide sulfonic acid with respect to the OH group of the phenol of the 0-naphthoquinonediazide compound (reaction rate with respect to one OH group) is 15 to 80%.
is preferable, and more preferably 20 to 45%. Furthermore, as an 0-quinonediazide compound, JP-A-58-4
The following compounds described in Publication No. 3451 can also be used. That is, for example, known 1, such as 1,2-benzoquinonediazide sulfonic acid ester, 1,2-7toquinonediazide sulfonic acid ester, 1,2-benzoquinonediazide sulfonic acid amide, 1,2-7toquinonediazide sulfonic acid amide, etc. .2. Quinonediazide compounds, more specifically, "Light-Sensitive Systems J" by J. Kosar.
339-
352 pages (1965), John Wiley & Sons (New York) and W.S. De Forest, ``7 Otresist'' (`` (1975), McGraw-Hill (Me Gray-1)
1.2-
Benzoquinonediazide-4-sulfonic acid phenyl ester, l. 2, 1'. 2'-G (benzoquinone diazide-4
-sulfonyl)-dihydroxybiphenyl, 1,2-benzoquinonediazide-4-(N-ethyl-M-β-naphthyl)-sulfonamide, 1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, I-(
1.2-naphthoquinonediazide-5-sulfonyl)-3
．． 5-dimethylpyrazole, 1,2-naphthoquinonediazide-5-sulfone*-4'-hydroxydiphenyl-
4'-azo-β-naphthol ester azido-5-sulfonyl 7toquinonediazide-5-sulfonyloxy)-l~hydroxy-anthraquinone, l,2-naphthoquinonediazide-5-sulfonic acid-2,4-dihydroxybenzophenone ester, 1.2-Naphthoquinonediazide-5-
Sulfonic acid-2.3.4-trihydroxybenzophenone ester, condensate of 2 moles of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mole of 4,4'-diaminobenzophenone, 1,2-naphthoquinonediazide 5 - condensate of 2 moles of sulfonic acid chloride and 1 mole of 4,4'-dihydroxy-L12-diphenylsulfone, 1
．． Condensate of 1 mol of 2-su7toquinonediazide/5-sulfonic acid chloride and 1 mol of purpurogalin, 1.2-su7
Toquinone diazido 5-(N-dihydroabiethyl)-
Mention may be made of 1,2-quinonediazide compounds such as sulfonamides. Also, Special Publication No. 37-1953, No. 37-3627, No. 37-13109, No. 40-2
No. 6126, No. 40-3801, No. 45-5604, No. 45-27345, No. 51-13013, JP-A-48-96575, No. 48-63802, No. 48
1,2-quinonediazide compounds described in each publication No. 63802 can also be mentioned. Among the O-quinonediazide compounds, O-quinonediazide obtained by reacting 1.2-benzoquinonediazide sulfonyl chloride or 1.2-naphthoquinonediazide sulfonyl chloride with a pyrogallol acetone condensation resin or 2,3.4-trihydroxybenzophenone. Ester compounds are particularly preferred. As the 0-quinonediazide compound, each of the above compounds may be used alone, or two or more thereof may be used in combination. The proportion of the O-quinonediazide compound in the photosensitive composition of the positive 15th plate is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight. The photosensitive layer of the positive type 15 plate can contain an organic acid. Preferred organic acids include those having a pka value of 2 or more at 25°C. Organic acids having the above pka value include, for example, Chemistry Handbook Basic Edition ■, Maruzen Co., Ltd., 1966, No. 1054-10.
Among the organic acids described on page 58, all compounds having the above pka value of 2 or more 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, ■-oxybenzoic acid, p-oxybenzoic acid, and 3.5. -dimethylbenzoic acid, 3
．． 4-dimethoxy acid, glyceric acid, glutaconic acid, curtaric acid, p-anisic acid, succinic acid, sebacic acid, β,
β-diethylglutaric acid, 1,1-cyclobutanedicarboxylic acid, l,3-cyclobutanedicarboxylic acid, 1.1
-cyclopentanedicarboxylic acid, 1゜2=cyclopentanedicarboxylic acid, l,3-cyclopentanedicarboxylic acid, β, β-dimethylglutaric acid, dimethylmalonic acid, σ
-Tartaric acid, superric acid, terephthalic acid, pimelic acid, phthalic acid, fumaric acid, β-propylglutaric acid, propylmalonic acid, mandelic acid, meso alcohol soap, β-methylglutaric acid, β, β-methylpropylglutaric acid, Methylmalonic acid, malic acid, 1. l-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 Examples include acids such as n-capric acid, pelargonic acid, and n-undecanoic acid. 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 0.0
5 to IO weight percent is suitable, preferably 0.1 to 5
Weight%. The photosensitive layer of the positive type 15 plate can contain an acid anhydride. Preferred are cyclic acid anhydrides, such as 7-thalic anhydride, tetrahydro-7-thalic anhydride, hexahydrophthalic anhydride, 3,6-nindooxy-Δ4-tetrahydrophthalic anhydride, tetrachloro-7-thalic anhydride, and hexahydrophthalic anhydride. Examples thereof include glutaric acid, maleic anhydride, talol maleic anhydride, α-phenylmaleic anhydride, conozylic anhydride, pyromellitic acid, and the like. These acid anhydrides are preferably contained in the photosensitive layer in an amount of 0.05 to 10% by weight, particularly 0.1 to 5% by weight. In the positive type 15th plate, 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 formaldehyde as described in publications. The molecular weight (polystyrene standard) of the novolak resin is:
Preferably, the number average molecular weight IJn is 3.00X 10”~
7.50X 10”, weight average molecular weight Ma: 1.OO
X 103 to 3.00X 10', more preferably Mn
is 5.00X 10'' to 4.00X 10'', and My is 3.00X 10'' to 2.00X to'. The above novolac resins may be used alone or in combination of two or more types. The proportion of the novolac resin in the photosensitive layer is 5 to 95%.
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 has the following general formula:

A polymer containing at least one structural unit of [9] to [13] is preferred. general formula

[9] general formula %formula% general formula (11) general formula general formula [13] general formula

In [9] to [13], R3 and R2 each represent a hydrogen atom, an alkyl group or a carboxyl group,
Preferably it is a hydrogen atom. R3 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, m 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 has the general formula

[9] ~ [13]
Examples of monomer units that can be used in combination with the structural units shown in ] include ethylenically unsaturated olefins M such as ethylene, propylene, imbutylene, butadiene, and isoprene, examples of which include t-styrene, α-methyl Styrenes such as styrene, 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, such as methyl acrylate , -ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, σ-
Esters of α-methylene aliphatic monocarboxylic acids such as methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide; e.g. acrylanilide; ,
Anilides such as p-chloroacrylanilide, m-nitroacrylanilide, -monomethoxyacrylanilide,
For example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, inbutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride,
Vinylidene cyanide, ethylene derivatives such as l-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, ■, 2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, ■-methyl-1-ditroethylene; Examples include vinyl monomers such as N-vinylpyrrole, N-vinylcarbazole, N-hynylindole, N-vinyl compounds such as N-1:'nylpyrrolidene, and N-vinylpyrrolidone. The monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved. Among the above monomers, esters of aliphatic monocarboxylic acids and nitriles have excellent performance for the purpose of the present invention. These monomers may be bonded in the polymer in either a block or random state.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 general formula [14] as a fat-sensitizing agent. Furthermore, the photosensitive layer of the positive type 13 plate has the following general formula [1
4] A condensation resin of a substituted phenol and an aldehyde and/or the resin. - A quinonediazide sulfonic acid ester compound can be contained. General formula [14] H In general formula [14], R1 and R8 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 R1 and R2 is, for example, fluorine, chlorine, bromine, iodine, etc., and chlorine atom and bromine atom are particularly preferred. The alkyl group represented by R1 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 the general formula [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, hekyne lucresol, tert-octyl cresol, cyclohekyne lucresol, and the like, among which tert-octylphenol and tert-butylphenol are particularly preferred. Further, examples of the aldehydes include aliphatic and aromatic fuldehydes such as formaldehyde, benzaldehyde, acetaldehyde, acrolein, crotonaldehyde, and 7-fural, which have 1 to 6 carbon atoms.
Includes 2 things. 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 0.605 to 15% by weight. The resin obtained by condensing the substituted phenol and aldehyde is synthesized by polycondensing the substituted phenol represented by the general formula [14] and the 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. The O-7-toquinonediazide sulfonic acid ester compound of the condensation resin of the substituted pheno-2t-2 and aldehydes can be obtained by dissolving the condensation resin in a suitable solvent such as dioxane, and adding O-naphtho It is obtained by adding quinonediazide sulfonic acid chloride and, while stirring under pressure, adding an alkali such as alkali carbonate dropwise to the equivalence point to cause esterification. In the esterified product, the condensation rate of 0-naphthoquinonediazide 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 the general formula [14] with an aldehyde and an O-naphthoquinonediazide sulfonic acid ester compound of the resin (hereinafter referred to as "sensitizing agent (B)") occupying the photosensitive layer. )") 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 10" to 5.OX 103, more preferably 7.OX 10" to 3.OX. It is in the range of OX 103. Its number average molecular weight Mn is 3. OX 10”
It is preferably in the range of 2.5 x 10', more preferably 4. The range is OX 10" to 2, OX 10'. Examples of compounds of the oil sensitizing agent ('B) are listed below. -1 (m: ~50: 50° m=n=50: M w = 1300) 50, -3H of the resin before reacting with Q In the photosensitive layer, in addition to the above-mentioned materials, depending on the required C, dyes and pigments are added. , a plasticizer, a surfactant, a heptadium-based surfactant, a compound capable of generating an acid upon exposure to light, etc. may be added to the photosensitive layer.Furthermore, in order to improve the oil sensitivity of the photosensitive layer, For example, it is also possible to add p-tert-butylphenol formaldehyde resin, p-n-octylphenol formaldehyde resin, or a resin partially esterified with an O-quinonediazide compound. Dissolve in solvent, PS
A positive type 13 plate can be manufactured by applying the photosensitive layer to the surface of a plate support and drying it. The coating amount is preferably in the range of 0.5 to 7 g/l by weight after drying. [Example] The present invention will be explained below with reference to Examples. Example 1 The following developer (A) 24α was put into the developer tank 4 of the automatic processor shown in FIG. 1, and the following developer replenisher (A1) and (B
,) was prepared. Developer (A) Potassium silicate aqueous solution 30 parts by weight (SiOz
(Contains 26% by weight, K, 0 content 13% by weight) Potassium hydroxide 16 parts by weight Emulgen 147
0.1 parts by weight (nonionic surfactant manufactured by Kao Corporation) Water 900 parts by weight Developer replenisher (AI) Potassium silicate aqueous solution 30 parts by weight (Sin
, content 26% by weight, KzO content 13% by weight) Potassium hydroxide 25 parts by weight water
700 parts by weight Developer replenisher (B1) Emal Def 14F 2 parts by weight Water 1000 parts Next, a JIS-1050 aluminum plate with a thickness of 0.24 mm was immersed in a 2% aqueous sodium hydroxide solution to perform a degreasing treatment. Afterwards, the surface was electrochemically roughened in a dilute nitric acid solution, thoroughly washed, and then anodized in a dilute sulfuric acid solution to form an oxide film of 2.5 g/+n'' on the surface of the aluminum plate. After washing the aluminum plate thus treated with water and drying, a photosensitive solution having the following composition was added to the dry weight of 2.
It was coated at a concentration of 5 g/m' and dried to obtain a positive type 15 plate. PS version size is 10010O3800m+a
And so. Photosensitive coating liquid composition Ester compound of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride and pyrogallol acetone resin (described in Synthesis Example 2 of JP-A-60-143345) Compound) Copolycondensation resin of 2 parts by weight of phenol, ff1-+p-mixed cresol, and formaldehyde (the molar ratio of each of phenol, -cresol, and p-cresol during synthesis was 2
0:48:32, weight average molecular weight My-7400, number average molecular weight Mn-1400) 6.5 parts by weight p-Lert-octylphenol and formaldehyde synthesized novolac resin and 7 toquinone (1,
2) Ester compound with diazide-(2)-5-sulfonic acid chloride (condensation rate: 50 mol%, M W-17
00) 0.1 parts by weight Victoria Pure Blue BOH 0.08 parts by weight (manufactured by Toko Tsuchigaya Kagaku Co., Ltd.) Ethyl cellosolve aom t parts Methyl cellosolve 20 parts by weight Prepare a large number of 15 positive-type plates obtained in this way and transparent Positive film and step tablet for sensitivity measurement (Eastman)
No. manufactured by Radatsuk. 2, 21 levels of gray scale with a density difference of 0.15) in close contact, and a 2 kW metal halide lamp (Idol Fin 2000, manufactured by Iwasaki Electric Co., Ltd.) was used as the light source at 8.0 mW/cm'' from a distance of 70c111. Exposure was carried out for seconds. Fifty positive PS plates thus obtained were processed in a prepared automatic developing machine at 27'C for 20 seconds. During the process, PS plates were inserted at 10 minute intervals. The room temperature at this time is 25°
It was C. Also, while processing, 23 plates 1 m2
Add replenisher (A +) to 59+a12. 30 taQ of replenisher (B1) was added. For electrical fatigue, a replenisher (Δl) was further added every 30 minutes at 5On+f2. After processing 50 sheets, the first step tablet and the last 50th step tablet were compared, and both had exactly the same development quality. In FIG. 1, 1 is a developing section that performs the developing process, and 2 is
3 is a water washing part, 3 is a rinse/gum part for processing with a rinsing liquid or desensitizing liquid, 4 is a developer tank, 5 to 7 are processing liquid supply nozzles, 8 to IO are pumps, and S is a PS plate or its This is the transport route. Example 2 The same positive type 15 plate, developer, developer replenisher, and automatic processor as in Example 1 were prepared. The processing was carried out at 27° for 0.20 seconds for 100 sheets at 5 minute intervals. During processing, 50 IIQ of replenisher (AI) and 30 mff of replenisher (B1) were added for every 1 m'' of 13 plate developed. Due to air fatigue, 1 additional replenisher (A,) was added every 30 minutes.
00mff was added. After processing 100 sheets, the first step tablet and the last 100th step tablet were compared, and both had exactly the same development quality. Example 3 The following developer solution (B) and developer replenisher (A, ) and (B2)
As a result, no difference was observed in the development quality between the first step tablet and the last 50th step tablet. Developer (B) Sodium silicate aqueous solution 30 parts by weight (5i02
7Na20 molar ratio 1.8, Sin content 37.5% by weight) Sodium hydroxide IO parts by weight Perex NB-LO 2 parts by weight (surfactant manufactured by Kao Corporation) Water 900 parts by weight Developer replenisher ( A.) Sodium silicate aqueous solution (same as above) 30 parts by weight Sodium hydroxide 15 parts by weight Water
900 parts by weight developer replenisher (Bri Perex NB-L 3 parts by weight water
1000 parts by weight Example 4 Using the automatic developing machine shown in FIG. 2, processing was conducted in the same manner as in Example 1 using the same developer, developer replenisher, and positive type 15 plate as in Example 1. While processing, ps version 1 m 2
For each development, 5011 IQ of replenisher (A2) and 30 ml of replenisher (B) were added. Due to air fatigue, 20 ml of replenisher (A2) was added every 30 minutes. 50
After processing the sheets, the first step tablet and the last 50th step tablet were compared, and no difference was found in the development quality. In addition, in FIG. 2, 11 is a developing section that performs a developing process;
12 is a water washing section, 13 is a rinse/gum section that performs processing with a rinsing liquid or a nonfatting liquid, 14 is a developing tank, 15.16.
17 is a processing liquid supply nozzle, 18.19.20 is a pump,
S is a positive type 15 plate or its conveyance path. In the same figure, *l
and *1 are connected by piping. Comparative Example 1 The same experiment as in Example 1 was conducted except that the following developer replenisher (C) was used, and during the processing, 60 ml (l) of replenisher (C) was added for every 1 m2 of PS plate developed. Due to air fatigue, 50mff of replenisher (C) was added every 30 minutes.After processing 50 sheets, we compared the first step tablet and the last 50th step tablet, and found that the clear sensitivity was almost the same. However, the solid sensitivity was significantly different. Developer replenisher (C) Potassium silicate aqueous solution 30 parts by weight (SiO2
(content 26% by weight, K, O content 13% by weight) Potassium hydroxide 20 parts by weight Emulgen 1471 parts by weight Water 700 parts by weight Comparative Example 2 The same treatment as in Example 4 was carried out using developer replenisher (C). . During processing, 60 m of replenisher (C) was added for every 1 m of PS#L developed. Due to air fatigue, 20 m of replenisher (C) was added every 30 minutes. After processing 50 sheets, we compared the first step tablet with the last 50th step tablet, and found that the clear sensitivity was almost the same, but the solid sensitivity was significantly different. [Effects of the invention] Book According to the invention, in a processing method of developing a positive 15th plate with a developer exclusively for the positive 13th plate, which is repeatedly used by replenishing the replenisher over a long period of time, it is possible to maintain stable development quality over a longer period of time. can.

[Brief explanation of drawings]

FIGS. 1 and 2 are cross-sectional views showing an example of the apparatus used in the example. 1%11...Developing section 2.12...Water washing section 3
．． 13...Rinse/gum part

Claims (2)

[Claims] (1) In a development processing method in which a positive-working photosensitive lithographic printing plate is developed using an automatic developing machine with a positive-only developer that is repeatedly used after replenishing a developer replenisher, the developer replenisher is one of the following (A) and (B) A method for processing a positive-working photosensitive lithographic printing plate. (A) Aqueous solution containing alkali silicate. (B) Aqueous solution containing a surfactant. (2) The above (A) and (B) are replenished at a replenishment amount determined by the processing amount per unit time of the positive photosensitive lithographic printing plate to be developed, the outside temperature, and the type of automatic processor. The processing method according to claim (1).