JPS63167366A - Replenishing method developing replenisher in automatic developing machine - Google Patents

Abstract

PURPOSE:To omit the necessity of draining of washing water and to reduce the generation environmental pollution by using a part of washing water used in a washing process as a diluting water of a developing replenisher. CONSTITUTION:In a processing method for developing, washing and desensitizing processing a photosensitive lithographic plate (PS) exposed at its image by using an automatic developing machine connected to a developing replenisher replenishing device, at least a part of the washing water used in the washing process is used as the diluting water of the developing replenisher. Preferably, water is newly replenished to the washing process circulating the washing water continuously after development in according with the processing quantity of the PS plate and at least a part of the washing water flowing out at the time of replenishment is used as the diluting water of the developing replenisher. Consequently, the washing water containing toxic substances does not flow out, the generation of environmental polluiton can be suppressed as low as possible, the processing valume of drained water can be reduced, and the processing cost can be also reduced.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for replenishing a developer replenisher when developing a large number of photosensitive lithographic printing plates using an automatic developing device. , in the water washing process that follows the development process that occurs when a large number of photosensitive lithographic printing plates are processed in an automatic developing machine, water is newly replenished according to the amount of the photosensitive lithographic printing plates processed, and at that time. The present invention relates to a developer replenisher replenishment method that makes it possible to reduce processing wastewater by using at least a part of the washing water flowing out of the developer replenisher as dilution water for the developer replenisher.

[Conventional technology]

In recent years, photosensitive planographic printing plates (Pre-3ensitiz
It is called edplate, and is hereinafter referred to as PS version. ) is used as an excellent plate material because of its stability, ease of plate-making process, and high reproducibility.

Conventionally, in order to obtain a printing original plate from a PS plate, the PS plate is imagewise exposed, then developed with a developer, washed with a large amount of running water, and then treated with a rinse solution containing a surfactant or the like as the case may be. A method of treating with a protective agent (so-called gumming) is generally known.

However, using a large amount of washing water not only increases costs, but also because such washing water contains harmful components such as synthetic resins eluted from developer compositions and PS plates, environmental pollution due to wastewater is caused. This includes many issues that are of great concern.

For this reason, as a method to solve the above problems,
As disclosed in Japanese Patent No. 2507, a method has been proposed in which washing water after development is used as dilution water for the developer.

[Problem that the invention seeks to solve]

However, when washing is performed using circulating water as in the above method, as the number of PS plates processed increases, the pH of the washing water increases due to the developer brought in, and the rinsing water increases. And the gum liquid gradually becomes fatigued. The term "fatigue" as used here refers to developer components in the developer, dissolved resin components, atmospheric components, developer replenisher, antifoaming agent, fatigue developer, etc. brought in and mixed in by the PS plate being processed. This indicates that the processing capacity is decreasing. If the fatigue of the rinsing liquid or gum liquid exceeds a certain limit, unexpected problems such as staining during printing or poor ink adhesion in the printed area may occur. If such stains occur, stop normal printing and, depending on the severity, either treat the plate surface with a treatment liquid containing phosphoric acid or hydrofluoric acid, or make a new plate using a different PS plate. The need also arises. Even if poor ink adhesion occurs, it can be recovered by interrupting printing and washing with water depending on the severity, or by reproducing the image and washing with water, but there are cases where recovery is impossible.

As described above, with the method of circulating and repeatedly using the washing water, it has been impossible to use the washing water continuously for a long period of time.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for replenishing a developer replenisher for an automatic processor, which eliminates the need for draining washing water and minimizes pollution.

Another object of the present invention is to provide a method for replenishing a developer replenisher for an automatic processor, which can reduce processing costs.

Furthermore, another object of the present invention is to suppress the deterioration of the processing solutions used in the post-development processing steps, ie, the rinsing step and the gumming step, to extend the service life of the processing solutions, thereby providing stable processing over a long period of time. An object of the present invention is to provide a method for replenishing a developer replenisher for an automatic processor.

[Means for solving problems]

The above-mentioned object of the present invention is to provide a processing method in which an image-exposed photosensitive lithographic printing plate is developed, washed with water, and subjected to rinsing or desensitization using an automatic developing machine connected to a developer replenisher replenisher. This is achieved by using at least a part of the washing water used in step 1 as dilution water for the developer replenisher.

In a preferred embodiment of the present invention, water is newly replenished according to the amount of PS plate processed in the washing process in which washing water is continuously circulated after development, and the washing water that flows out at that time is It is characterized in that at least a part of the developer replenisher is used as dilution water for the developer replenisher.

In order to carry out the present invention more effectively, it is preferable that the rinsing liquid and the gum liquid be replenished with a newly prepared processing liquid in accordance with the amount of PS plates to be processed, similarly to the washing water.

The automatic developing machine used in the present invention is preferably one that conveys a photosensitive printing plate and has a developing zone, a washing zone, a rinsing zone, a cam coating zone, and a drying zone. Conventionally known automatic developing machines can also be used.

Since the rinsing water used in the present invention is continuously circulated, all or most of it is water that has been previously used for rinsing at least once.

For this reason, as mentioned above, if you bring in a developer, etc., the pH will change.
Inconveniences such as an increase in water and contamination may occur, but to prevent this, new water is added. This replenishment amount is determined depending on the amount of PS plate processed, especially its area, and is preferably 3 to 300 cc, more preferably 10 to 100 cc, based on the PS plate area l m'. Further, this replenishment can be performed based on the area detection signal of the PS plate to be processed, and of course it is also possible to perform replenishment based on determining the replenishment amount by calculation. In addition, the above-mentioned washing methods include immersing the PS plate in a washing tank, spraying washing water from multiple nozzles, and applying and washing with a roller. Since the purpose is to remove residual developer and the like from the PS plate, it is preferable to perform the washing with a high flow rate of washing water, such as by spraying water from a number of nozzles. The flow rate of this washing water is determined as appropriate depending on the number of nozzles and the developing state of the PS plate. Once used, the rinsing water is returned to the rinsing tank and circulated again by a commonly known circulation pump or the like, and is used for repeated rinsing. Such water washing can also be carried out continuously in two or more substantially separated tanks in multiple stages. Furthermore, it is also possible to use a method of purifying the circulating water using a conventionally known solid matter filtering device or a device for separating charged substances.

Further, the overflow waste liquid generated by replenishing the new washing water is used as dilution water for the developer replenisher when replenishing the developer replenisher in response to exhaustion of the developer. The washing water waste liquid is added as dilution water at a predetermined ratio to the developer replenisher depending on the exhaustion of the developer. The overflow waste liquid may be stored in a separate tank or may be directly added to the developer replenisher using a circulation pump or the like. The fatigue of the developer mentioned above usually includes processing fatigue deterioration due to 23-plate processing and aging fatigue deterioration in which the developing ability decreases over time, but replenishment for processing fatigue deterioration and aging fatigue deterioration must be performed separately. You can do both at the same time. Furthermore, a method for replenishing together with the throughput of the PS plate, and a method for measuring the degree of elution of the photosensitive layer in the non-image area of the PS plate during the development process or physical property values of the liquid,
A variety of methods are possible for replenishing the developer replenisher based on the signal.

The developer used for processing such a PS plate may vary depending on the type of photosensitive composition used for the PS plate, but preferably contains at least one of an alkaline agent and an organic solvent.

Examples of alkali agents include sodium silicate, potassium silicate, lithium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic potassium phosphate, Inorganic alkaline agents such as potassium diphosphate, tertiary ammonium phosphate, ammonium diphosphate, sodium mesilicate, sodium bicarbonate, sodium carbonate, potassium carbonate, ammonium carbonate, etc., mono-, di-, or triethanolamine, mono- Organic amine compounds such as -, di-, or trimethylamine, mono-, di-, or triethylamine, mono-1- or di-isopropylamine, n-butylamine, mono-, di-, or triisopropylamine, ethyleneimine, ethylenediimine, etc. Can be mentioned.

Various conventionally known methods can be used to develop the PS plate that has been imagewise exposed with the developer described above. Specifically, methods include immersing an image-exposed PS plate in a developer, squirting the developer from a number of nozzles onto the photosensitive layer of the PS plate, and using a sponge moistened with the developer to remove the photosensitive layer.
Examples include a method of wiping the photosensitive layer of the S plate, and a method of applying a developer to the surface of the photosensitive layer of the PS plate using a roller. Further, after applying the developer to the photosensitive layer of the PS plate in this manner, the surface of the photosensitive layer can be lightly rubbed with a brush or the like. The developing conditions can be appropriately selected depending on the developing method. - For example, in the development method by immersion, a method of immersing the material in a developer solution at about 10 to 35° C. for about 20 to 80 seconds is selected.

As described above, a lithographic printing plate obtained by imagewise exposure and development of a PS plate and washing with water is treated with a rinsing liquid or a gum liquid containing a surfactant. Surfactants contained in such a base liquid include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyrylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and glycerin fatty acid moiety. Esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbicun fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol Fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenized castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid jetanolamides, N,N-bis-2-hydroxyalkylamines, polyoxyethylene alkyl Nonionic surfactants such as amines, triethanolamine fatty acid esters, trialkylamine oxides, fatty acid salts, abietates, hydroxyalkanesulfonates, -alkanesulfonates, dialkylsulfosuccinates salts, linear alkylbenzenes Sulfonates, branched alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylphenoxypolyoxyethylene propyl sulfonates, polyoxyethylene alkylsulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkyl Sulfosuccinic acid monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef leg oil, sulfate ester salts of fatty acid alkyl esters, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, fatty acid monoglyceride sulfate ester salts ,
Polyoxyethylene alkyl phenyl ether sulfate ester salts, polyoxyethylene styryl phenyl ether sulfate ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkyl phenyl ether phosphate salts, styrene - Partially saponified maleic anhydride copolymers, partially saponified olefin-maleic anhydride copolymers, anionic surfactants such as naphthalene sulfonate formalin condensates, alkylamine salts, quaternary Examples include cationic surfactants such as ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives, and amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfate esters, and imidacillins. Among the surfactants listed above, polyoxyethylene can also be read as polyoxyalkylene such as polyoxymethylene, polyoxypropylene, and polyoxybutylene, and these surfactants are also included, and the following The same applies to the explanation of .

The above surfactants can be used alone or in combination of two or more, and are approximately 0.01% by weight in the aqueous solution.
from about 10% by weight, more preferably from 0.1% to 1% by weight
Used in a range of %.

In the present invention, the pH of the rinsing liquid, ie, the aqueous solution containing a surfactant, is preferably 1 to 12. In order to adjust the aqueous solution to this pH, it is preferable to contain either or both of an acid and a water-soluble salt as a buffer. As a result, when the aqueous solution is applied to a lithographic printing plate, the developer components remaining on the plate are neutralized, and the non-image areas become more hydrophilic.

Details of buffering agents are described in, for example, "Chemical Handbook [inj Chemical Society of Japan Silk, February 20, 1971, 5th edition, published by Maruzen Co., Ltd., pages 1312 to 1320], and these can be applied as is. Suitable acids and water-soluble salts include inorganic acids such as molybdic acid, boric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, acetic acid, oxalic acid, tartaric acid, benzoic acid, succinic acid, citric acid, malic acid, Examples include acids such as water-soluble organic acids such as lactic acid and p-)luenesulfonic acid, and their salts.

More preferred salts are water-soluble alkali metal salts and ammonium salts, and particularly preferred are molybdates such as ammonium molybdate, phosphates such as IJium, polyphosphoric acids such as potassium tetrapolyphosphate, and sodium trimetaphosphate. salt, oxalates such as sodium oxalate,
These are tartrates such as potassium tartrate, succinates such as sodium succinate, and citrates such as ammonium citrate. These acids and water-soluble salts can be used alone or in combination.

The more preferable pH of the aqueous solution containing the surfactant is 2 to 8.
It is. The most preferable pH is 2.5 to 6.5, in which case the desensitization performance of the non-image areas of the lithographic printing plate becomes higher. In addition, in the plate making method of the present invention, developer components are brought into the aqueous solution, so in order to neutralize this, an amount of salt and/or acid is added in advance according to the planned treatment area of the PS plate. It is preferable to leave it there. The amounts of acids and salts added to the aqueous solution are not particularly limited, but the total amount of acids and salts is preferably about 10% by weight or less based on the total weight of the aqueous solution. More preferably, it is used in a range of 0.01 to 6% by weight.

In the present invention, the aqueous solution containing the surfactant further includes sorbic acid, preservatives such as ethyl p-oxybenzoate, fungicides, propyl gallate, 2.6-di-t-butyl-4-ethylphenol, 2. It is possible to contain antioxidants such as 6-di-t-butyl-4-methylphenol.Adding small amounts of preservatives, fungicides, and antioxidants as preservatives can It can prevent deterioration etc. due to storage of aqueous solution, but the preferable addition amount is 0.
．． 001 to 5% by weight.

It is preferable that the aqueous solution containing the surfactant in the present invention contains a lipophilic substance. As a result, the image area of the lithographic printing plate shows higher oil sensitivity, which not only makes it easier to build up the developing ink, but also makes it easier to apply the plate surface protectant after treatment with the aqueous solution. It is possible to strongly suppress the decrease in oil sensitivity. Preferred lipophilic substances include, for example, oleic acid, lauric acid, valeric acid,
Examples include organic carboxylic acids having 5 to 25 carbon atoms such as nonylic acid, capric acid, myristic acid, palmitic acid, and castor oil. These lipophilic substances can be used alone or in combination of two or more. The lipophilic substance contained in the surfactant-containing aqueous solution in the present invention ranges from 0.005% to about 1% by weight based on the total weight.
0% by weight, more preferably 0.05-5% by weight.

In the present invention, it is preferable to squeegee the surface of the lithographic printing plate after development and washing so that the amount of developer and washing water used repeatedly is as small as possible. This is because the squeegee is used to reduce developer fleas on the lithographic printing plate, which prevents contamination by the developer from washing water.
Similarly, by squeegeeing so that the amount of washing water on the plate is small, contamination of the aqueous solution containing the surfactant by the washing water is prevented as much as possible, and the processing capacity with the washing water and the aqueous solution containing the surfactant is increased. Therefore, the amount of residual developer and washing water on the lithographic printing plate after squeegeeing is preferably 5Q+t+j!/m' or less, more preferably 3Q+++j!/m" or less. Most preferably 15mβ/m1 It is as follows.

Various methods of treatment with an aqueous solution containing a surfactant are possible, such as immersion in the same way as washing with water, application with a roller, and spraying from multiple nozzles onto a lithographic printing plate or roller. By repeatedly using an aqueous solution containing the surfactant, the plate-making process is performed.
It becomes possible to greatly reduce the amount of the aqueous solution containing the surfactant per S plate.

Similar to the replenishment of washing water, the rinsing liquid is replenished according to the amount of PS plates to be treated, preferably the area to be treated, and preferably in the range of 1 to 400 cc per PS plate.

The gum liquid also contains a polymer compound, a lipophilic substance, a surfactant, and water.

Natural polymers include starches such as Japanese starch, potato starch, corn starch, wheat starch, and corn starch; those obtained from algae such as carrageenan, laminaran, seaweed mannan, funori, Irish moss, agar, and sodium alginate; Vegetable mucilages such as mannan, quince seed, pectin, tragacanth gum, karaya gum, xanthine gum, guarving gum, low strength, stobbing gum, gum arabic, carob gum and benzoin gum, dextran,
Examples include microbial mucilages such as homopolysaccharides such as glucan and levan, and heteropolysaccharides such as succinoglucan and xanthan gum, and proteins such as glue, gelatin, casein, and collagen. In addition to alginate propylene glycol ester, semi-natural products (semi-synthetic products) include viscose, methyl cellulose, ethyl cellulose, methyl ethyl cellulose, hydroxyethyl cellulose, carboxin methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxypropylethyl cellulose, and hydroxypropyl cellulose. Examples include cellulose derivatives such as bill methyl cellulose phthalate and modified starches. white dextrin for processed starch)
IJ-n, yellow dextrin) IJ-n,
Acid-degraded starches such as solubilized starch, oxidized starches such as dialdehyde starch, pregelatinized starches such as modified pregelatinized starches and unmodified pregelatinized starches, phosphate starches, fatty starches, sulfate starches, nitrate starches, xanthogenic acids Esterified starches such as starch and carbamic acid starch, etherified starches such as carboxyalkyl starch, hydroxyalkyl starch, sulfoalkyl starch, cyanoethyl starch, allyl starch, benzyl starch, carbamylethyl starch and dialkylamino starch, methylol cross-linked starch , crosslinked starches such as hydroxyalkyl crosslinked starches, phosphoric acid crosslinked starches and dicarboxylic acid crosslinked starches, starch polyacrylamide copolymers, starch polyacrylic acid copolymers, starch polyvinyl acetate copolymers, starch polyacrylonitrile copolymers Examples include starch graft copolymers such as cationic starch polyacrylic acid ester copolymers, cationic starch vinyl polymer copolymers, starch polystyrene maleic acid copolymers, and starch polyethylene oxide copolymers. Synthetic products include polyvinyl alcohol (7), partially acecooled polyvinyl alcohol, allyl-modified polyvinyl alcohol, modified polyvinyl alcohols such as polyvinyl methyl ether, polyvinylethyl ether and polyvinyl isobutyl ether, sodium polyacrylate, partially saponified polyvinyl esters, Partially saponified polyacrylic acid ester copolymers, polyacrylic acid derivatives and polymethacrylic acid derivatives such as polymethacrylate and polyacrylamide, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate , carboxyvinyl polymer, styrene maleic acid copolymer, styrene crotonic acid copolymer, and the like. Among these, those obtained from algae, vegetable mucilages, cellulose derivatives, modified starches, alginate propylene glycol esters, and synthetic products are preferably used because they have good film-forming properties on printing plates. Lipophilic substances include lipophilic agents, fatty acids, fatty oils, -hydric alcohols, waxes, and lipophilic resins used as vehicles for lithographic printing inks. Preferred lipophilic resins include phenol formaldehyde resins, cresol formaldehyde resins, t-butylphenol formaldehyde resins, and other seven-volume phenolic resins, xylene resins obtained by condensing phenol and xylene with formaldehyde, and condensing phenol and mesitylene with formaldehyde. Resin, polyhydroxystyrene, brominated polyhydroxystyrene, cashew resin, partially esterified copolymer of styrene and maleic anhydride, melamine resin, alkyd resin, polyester resin, epoxy resin, rosin, hydrogenated rosin, rosin ester, etc. Examples include petroleum resins such as modified rosin and Giltonite.

Preferred plasticizers include, for example, dibutyl phthalate, di-n
-octyl phthalate, di(2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate,
Phthalic acid diesters such as dilauryl tucrate and butylbenzyl phthalate, such as dioctyl azelate, dioctyl adipate, dibutyl glycol adipate, dibutyl sebacate, di(2-ethylhexyl)
aliphatic dibasic acid esters such as sebacate and dioctyl sebacate, epoxidized triglycerides such as epoxidized soybean oil, phosphoric acid esters such as tricresyl phosphate, trioctyl phosphate, and trichloroethyl phosphate; Examples include benzoic acid esters such as benzyl benzoate. Preferred fatty acids include caproic acid, enanthic acid, caprylic acid, herargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, valmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, Saturated fatty acids such as behenic acid, lignoceric acid, cerotic acid, heptacanoic acid, montanic acid, melisic acid, roughceric acid, isovaleric acid, acrylic acid, crotonic acid, isocrotonic acid, undecyl acid, oleic acid,
Elaidic acid, cetoleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linuric acid, arachidonic acid,
Propiolic acid, stearolic acid, sardine acid, IJ
There are unsaturated fatty acids such as IJ acid and lycanic acid. -hydric alcohols are aliphatic saturated -hydric alcohols, aliphatic unsaturated -
It is classified into hydric alcohols, aromatic alcohols, fatty FF1 type alcohols, double AM type alcohols, etc. Further, the -hydric alcohol may have a substituent, and examples of the substituent include a halogen atom such as chlor and brome, an alkoxy group such as methquine and propoxy, and an aryloquine group such as phenokine.

The gum liquid used in the present invention can be manufactured in any way, such as emulsion type cam liquid, suspension type gum liquid, non-emulsion type non-suspension type gum liquid, etc. by appropriately selecting the surfactant, lipophilic substance, etc. to be contained. However, emulsion-type gum liquids and suspension-type gum liquids are preferably used because they have a high ability to prevent a decrease in oil sensitivity in the image area of a lithographic printing plate. Furthermore, emulsion type gum liquid is preferable because it strongly suppresses the generation of 62 substances and generates less insoluble substances in the plate making method of the present invention.

There are various methods for treating with the gum liquid, such as dipping in the same way as the cleaning method, applying with a roller, and spraying it from multiple nozzles onto the PS plate or roller. By using it, it becomes possible to greatly reduce the amount of gum liquid used per PS plate subjected to plate-making processing. The amount used in the processing method for supplying the plate surface protectant onto the lithographic printing plate is 0.1 fl/l.
More than the quantity! /min or less is preferable. More preferably 3~
201/min. In addition, a method in which the lithographic printing plate is treated with high agitation, such as a method in which jets are ejected from multiple nozzles, has the advantage that it is possible to wash away residual adhesion on the lithographic printing plate with the gum liquid. This method is more preferable because the liquid can be made uniform.

The replenishment of the gum solution, like the replenishment of the rinsing solution, is carried out in accordance with the amount of PS plate to be processed, preferably the area to be processed, and is carried out in the range of 1 to 400 cc per 1 m' of PS plate.

The photosensitive composition provided on the hydrophilic surface of the support includes a diazo compound, British Patent No. 1.23.
5.281 and 1.495.861, and photosensitive compositions containing azide compounds as described in U.S. Pat. No. 3.860.426. Photosensitive compositions containing photocrosslinkable photopolymers, U.S. Pat. Nos. 4.072.528 and 4.0
No. 72.527: Photosensitive composition containing a photopolymerizable photopolymer as described in each specification, JP-A-56-1
9063 and 56-29250; JP-A-52-6250;
Examples include silver halide emulsion compositions as described in No. 1 and No. 56-29250.

Among these photosensitive compositions, photosensitive compositions containing diazo compounds have excellent properties such as the storage stability of the photosensitive layer, development performance such as development latitude, image performance such as image quality, ink receptivity, oil sensitivity, abrasion resistance, etc. printing performance, low-pollution properties of the developer used, etc.
It is preferably used because of its comprehensive properties.

Photosensitive compositions containing diazo compounds are classified into negative type and positive type.

The negative photosensitive composition containing a diazo compound contains a photosensitive diazo compound and preferably a polymer compound. Conventionally known photosensitive diazo compounds can be used, but organic solvents are preferably used. Examples include salts of soluble diazo resins, such as salts of p-diazodiphenylamine, formaldehyde or acetaldehyde condensates, and hexafluorophosphates, and 2-hydroxy-4-methoxybenzophenone-5-sulfonate salts. .

Examples of polymeric compounds include acrylic acid or methacrylic acid copolymers, crotonic acid copolymers, itaconic acid copolymers, maleic acid copolymers, cellulose derivatives having carboxyl groups in their side chains, and cellulose derivatives having carboxyl groups in their side chains. Polyvinyl alcohol derivatives having carboxyl groups, hydroxyalkyl acrylate or methacrylate copolymers having carboxyl groups in side chains, unsaturated polyester resins having carboxyl groups, etc. are preferably used.

Conventionally known diazo compounds can be used as the diazo compound used in the positive photosensitive composition, but typical examples include 0-quinonediazides, and preferably 0-naphthoquinonediazide compounds. Among the 0-naphthoquinonediazide compounds, in particular, Q-naphthoquinonediazide sulfonic acid esters or O-naphthoquinonediazide carboxylic acid esters of various hydroquine compounds, and 0-naphthoquinonediazide sulfonic acid amide or O-naphthoquinonediazide carboxylic acid ester of aromatic amino compounds. Acid amides are preferred. Preferred hydroxyl compounds include condensation resins of phenols and carbonyl group-containing compounds. Examples of the phenols include phenol, cresol, resorcinol, and pyrogallol, and examples of the carbonyl group-containing compound include formaldehyde, benzaldehyde, and acetone.

Preferred hydroxyl compounds include phenol and
Examples include formaldehyde, cresol/formaldehyde resin, pyrogallol/acetone resin, and resorcinol/benzaldehyde resin.

Typical specific examples of 0-quinonediazide compounds include:
Benzoquinone-(1,2)-diazide sulfonic acid or naphthoquinone-(1,2)-diazide sulfonic acid ester with tophenol-pot formaldehyde resin or cresol-formaldehyde resin, JP-A-56-1044
Esters of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid and resorcinol-benzaldehyde resin, as described in US Pat. No. 3,635.
Naphthoquinone-(1
,2)-Ester of diazide sulfonic acid and pyrogallol acetone resin, naphthoquinone-(1,2)-diazide-(
2) Esters of -5-sulfonic acid and resolun-pyrogallol-heptadone copolycondensate can be mentioned. Other useful O-quinonediazide compounds include:
117503, in which a polyester having a hydroxyl group at the end is subjected to an esterification reaction with 0-naphthoquinonediazide sulfonyl chloride, and p-hydroxystyrene as described in JP-A-50-113305, Homopolymers or copolymers with other copolymerizable monomers are esterified with 0-naphthoquinonediazide sulfonyl chloride, bisphenol formaldehyde resins described in JP-A-54-29922, and O - Esters with quinonediazide sulfonic acid, U.S. Pat. No. 3,859.
Condensation product of a copolymer of alkyl acrylate, acryloyloxyalkyl carbonate and hydroxyalkyl acrylate described in No. 099 and 0-quinonediazide sulfonyl chloride, Japanese Patent Publication No. 49-1
7481, a reaction product of a copolymerization product of styrene and a phenol derivative with O-quinonediazide sulfonic acid, and p-amino- as described in U.S. Pat. No. 3,759,711. Amides of copolymers of styrene and other copolymerizable monomers and 0-naphthoquinonediazide sulfonic acid or O-naphthoquinonediazidecarboxylic acid, and ester compounds of polyhydroxybenzophenone and 0-naphthoquinonediazide sulfonyl chloride. etc.

Although these O-quinonediazide compounds can be used alone, it is preferable to mix them with an alkali-soluble resin and provide this mixture as a photosensitive layer. Suitable alkali-soluble resins include novolac type phenolic resins, specifically phenol formaldehyde resins, cresol formaldehyde resins, and phenol/cresol formaldehyde copolycondensation resins as described in JP-A-55-57841. Includes body resin, etc.

Furthermore, as described in JP-A No. 50-125806, in addition to the above-mentioned phenol resins, t-butylphenol formaldehyde resins having 3 to 3 carbon atoms,
It is even more preferable to use a condensate of formaldehyde and phenol substituted with an alkyl group of 8 or cresol in combination.

The content of the O-quinonediazide compound is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, based on the total solid content of the photosensitive composition. The content of the alkali-soluble resin is preferably 30 to 90% by weight, particularly preferably 50 to 85% by weight, based on the total solid content of the photosensitive composition.

The photosensitive composition layer can be provided in multiple layers, and additives such as dyes, plasticizers, and components imparting printout performance can also be added as necessary.

The coating amount of the photosensitive composition provided on the support is 0.
1-7 g/m' is preferred, more preferably 0.
5 to 4 g/m''.

The PS plate thus obtained is exposed through a transparent original to a light source rich in actinic radiation, such as a carbon arc lamp, mercury lamp, metal halide lamp, tungsten lamp, or xenon lamp, and then developed.

As mentioned above, the developer replenisher replenishment method of the present invention is characterized by using the overflowing wash water as dilution water for the developer replenisher when replenishing the circulating wash water with new water. By reusing water and wastewater, it is possible to minimize the release of harmful substances into the environment. Furthermore, according to such a method, it is possible to recycle the washing water by replenishing new water according to the amount of PS plate processed, eliminating the need to use large amounts of water, and further reducing wastewater treatment. The amount can be reduced and processing costs can be reduced. Furthermore, since the deterioration of the washing water can be suppressed in this way, the deterioration of the treatment liquids used in the subsequent rinsing process and gumming process can be prevented, extending the life of the product, thereby providing stable treatment over a long period of time. I can do it.

Also, replenishing the rinse solution and gum solution with new solution is
Furthermore, it has the effect of promoting this stabilization.

In addition, since the life of the rinsing liquid and gum liquid is extended, it is possible to perform stable processing without causing problems such as stains or poor ink adhesion in printed areas when printing PS plates. . A preferred embodiment of an automatic processor for carrying out the method of the present invention is shown in FIG. This is development zone A1 washing zone B1 rinsing or gum zone C
The 28 plate 1 is guided to a developer tank 3 by a conveyance roller 2 and developed, and then led to a washing zone, where it is circulated from a washing tank 6 by a circulation pump 5a and washed. It is washed with water sprayed from the water spray device 4.

This washing water is returned to the washing tank and used for circulation. P
When the washing water is replenished by the pump 8C which operates in accordance with the S-plate processing area detection signal 7, overflow waste water flows out. Developer fatigue detection signal 9 due to PS plate processing
Accordingly, the developer replenisher is replenished from the developer replenisher tank 10 by the pump 8a, and the developer tank 3 is replenished with the washing water overflow liquid at a predetermined ratio by the pump 8b. Washed P
The S version is further directed to the rinse or gum zone C.

The rinsing (gum) liquid is guided from the rinsing (gum) liquid tank 12 to the rinsing (gum) liquid injection device 11 by the pump 5b and is injected to process the PS plate. Like the washing water, this rinsing (gum) liquid is also replenished by a pump 8d activated by the PS plate processing area detection signal 7, and the overflow liquid 13 is discharged. The rinsed (gummed) PS plate is finally introduced into drying zone D and dried.

[Example] Hereinafter, the method for replenishing a developer replenisher for an automatic processor of the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited in any way by the following specific examples.

Example 1 A grained IS material aluminum plate was immersed for 1 minute in a 2% by weight hydroxide solution kept at 40°C to perform etching treatment. Next, after washing with water, it was immersed in a sulfuric acid-chromic acid mixture for about 1 minute to expose the pure aluminum surface. This was immersed in 20% by weight sulfuric acid kept at 30°C, and the DC voltage was 1.5cm and the current density was 2A/dm'.
Anodizing was carried out for 2 minutes, followed by washing with water and drying. A photosensitive composition solution having the following composition was coated on a comb-treated aluminum plate at a weight of 2 g/m' (dry weight) and dried to obtain a PS plate.

Methyl ethyl ketone ・・・・・・・・・50
g Cyclohexanone ・・・・・・40g
The positive PS plate obtained in this way was passed through a transparent positive film for 60 minutes using a 3kw metal halide lamp.
Exposure for seconds. This was developed using an automatic developing machine shown in FIG.

The developer tank 3 was charged with 201 mm of a developer consisting of a 3.0% by weight aqueous solution of potassium silicate (20 molar ratio to SI02/=1.24). The developer replenishment stock solution tank 10 contains 39% by weight of potassium silicate (20 molar ratio to S10□7 = 1.24)
30 f of a developer replenishment stock solution consisting of an aqueous solution was charged. The washing water tank 6 was filled with 101 ml of water, and 55 cc of new water was added to the circulating washing water every time 1 ml of the PS plate was processed according to the PS plate processing area detection signal 7. The pumps 8a and 8b are activated by the developer fatigue detection signal 9, and the washing water tank 6 is activated.
The ratio of 5 parts water and 1 part developer replenishment solution from the developer replenishment stock solution tank 10 is approximately 55c, converted to the amount of replenishment per 1 m'' of PS plate processing.
The developer tank 3 was replenished in an amount of c as a developer replenisher. The rinsing liquid tank 12 contains 10 parts by weight of sodium dihydrogen phosphate, 3 parts by weight of sodium dipolyethylene oxide polystyrylether sulfosuccinate, 1 part by weight of sodium dioctyl sulfosuccinate, 11 parts by weight of sodium alkyl diphenyl ether disulfonate, and 11 parts by weight of sodium alkyl diphenyl ether disulfonate. An aqueous solution containing 0.9 parts by weight of foaming agent TSA-731 (manufactured by Toshiba Silicone) was charged at 101 cm, and a PS plate of 1 m'' was prepared in the same way as in the water washing section.
60 cc of new rinse solution was added each time. Overflow liquid 13 was collected as waste liquid.

As described above, a PS version of l m x l m size is made into 1
Even after processing 700 sheets, a good original printing plate was obtained. In addition, a printing original plate similar to that obtained by using fresh water as the dilution water of the conventional developer replenishment stock solution was obtained. Also, conventionally, the amount of waste liquid from the washing tank was approximately 90! In contrast, in the present invention, the amount of waste liquid was 101, which was a small amount.

Comparative Example 1 PS plate used in Example 1, developer, developer replenisher stock solution, rinse solution, and PS exposed using an automatic developer having a water washing section in place of Example 1, which washes with water running at 5β/min. A total of 1,700 PS plates were processed with a processing time of 50 seconds per PS plate. Although a good original printing plate was obtained, the amount of waste liquid from the washing water tank was about 7000 J2, and it was necessary to collect a very large amount of waste liquid.

Comparative Example 2 The PS plate, developer, developer replenisher stock solution, rinse solution, and developing section used in Example 1 were used, fresh water was used for diluting the developer replenisher stock solution, and water was added to the washing section. When an exposed PS plate was processed using an automatic developing machine that circulates the 101-prepared rinsing liquid and processes the rinsing liquid by adding 10β rinsing liquid to the rinsing section, it was found that as the number of PS plates processed increased, the rinsing water decreased. When the pH increased and 400 PS plates were processed, only printing original plates with stains were obtained. The amount of waste liquid from the washing tank was 101.

As described above, according to the method of the present invention, the life of the rinsing liquid was similar to that obtained when rinsing was performed with running water. In the case of washing with running water, the pH exceeds the standard and recovery is required, and as mentioned above, there is a disadvantage that a large amount of water is required and the cost is high.

〔Effect of the invention〕

As described above in detail, by the method of the present invention, it was possible to suppress the occurrence of pollution as much as possible without causing washing water containing harmful substances to flow out. In addition, there is no need to use large amounts of washing water, reducing wastewater treatment fireflies and reducing treatment costs.

Furthermore, deterioration of the rinsing liquid and gum liquid has been prevented and the service life has been extended, making it possible to carry out stable processing over a long period of time. Therefore, it was possible to prevent inconveniences such as staining and poor ink adhesion in the image area that occur during printing of the PS plate.

[Brief explanation of the drawing]

Figure 1 shows one of the automatic processors for carrying out the method of the present invention.
It is a schematic sectional view showing an example. 1...PS plate, 2...Transport roller, 3...Developer tank, 4...Washing water injection device, 5... Circulation pump, 6...
...Washing water tank, 7...PS plate processing area detection signal, 8...Pump, 9...Developer fatigue detection signal, 10...Development Replenishment liquid tank, 11...Rinse (gum) liquid injection device, 12...
... Rinse (gum) liquid tank, 13 ... Rinse (cam) liquid overflow liquid.

Claims (1)

[Claims] In a processing method in which an image-exposed photosensitive lithographic printing plate is developed, washed, and rinsed or desensitized using an automatic developing machine connected to a developer replenisher replenisher, the washing water used in the washing step is A method for replenishing a developer replenisher for an automatic processor, characterized in that at least a part of the developer replenisher is used as dilution water.