JPH08123039A - Processing method of photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE: To stabilize liquid sensitivity in, what is called, two-bath developing for a printing plate. CONSTITUTION: In a processing method of a photosensitive planographic printing plate by dividing a development processing part into a 1st developing vessel 5 and a 2nd developing vessel 6 and passing the planographic printing plate successively through the 1st developing vessel 5 and the 2nd developing vessel 6, (1) a processing solution is used while purifying by ultrafiltration in the 2nd developing vessel 6 or both of the 1st and 2nd developing vessels 5, 6, (2) at least a part of the solution in the 2nd developing vessel 6 is used for the 1st developing vessel 5 and the processing solution is used while purifying by ultrafiltration in the 2nd developing vessel 6 or both of the 1st and 2nd developing vessel 5, 6, and (3) the solution of the 2nd developing vessel 6 is purified by ultrafiltration and the permeated solution is supplied to the 1st developing vessel 5 to be used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing plate for carrying out development, washing with water, gum treatment, etc. by supplying a processing solution while conveying a photosensitive lithographic printing plate (hereinafter also referred to as printing plate). The present invention relates to a processing method, and more specifically, to improvement of a so-called two-bath development method in which development processing is performed in a first developing tank and a second developing tank.

[0002]

2. Description of the Related Art In a printing plate processing method, a so-called two-bath development method in which development processing is carried out in a first developing tank and a second developing tank is disclosed in, for example, Japanese Patent Publication No. 63-61659.

Although it relates to the production of a printed circuit board, not to the processing of a printing plate, the developing solution or stripping solution used once is separately ultrafiltered to replenish the dissociated and consumed components and reused. It is special fair 6-1507
No. 8 publication.

[0004]

The above-mentioned so-called two-bath developing method has a certain degree of effectiveness in producing a stain-free printing plate with a small amount of waste liquid, but the first and second baths. However, it is difficult to control the liquid sensitivity because the amount of dissolved resin is different.

Further, when a mixed bath of a wide variety of printing plates and a negative-positive common development are carried out, the dissolution rate varies depending on the types of printing plates, and the balance of the resin amounts of the 1st and 2nd baths becomes unstable, so that the sensitivity can be controlled. It gets more difficult.

As is obvious from the above, it is an object of the present invention to stabilize the liquid sensitivity in so-called two-bath development of a printing plate.

[0007]

In the method for processing a printing plate according to the present invention, the development processing section is divided into a first developing tank and a second developing tank, and the first and second developing tanks are photosensitive. In a method for treating a photosensitive lithographic printing plate that sequentially passes through a lithographic printing plate, the treatment liquid is used while being purified by ultrafiltration in the second developing tank or both the first developing tank and the second developing tank. In the method for processing a photosensitive lithographic printing plate, the developing processing section is divided into a first developing tank and a second developing tank, and the photosensitive lithographic printing plate is sequentially passed through these first and second developing tanks. At least a part of the liquid in the second developing tank is used for the first developing tank, and the processing liquid is purified by ultrafiltration in the second developing tank or both the first and second developing tanks. While using it, the development processing section is divided into a first developing tank and a second developing tank. In the processing method of the photosensitive lithographic printing plate for sequentially passing the photosensitive lithographic printing plate in an image tank, the liquid of the second developing tank ultrafiltered, the permeate first
It is characterized in that it is supplied to a developing tank and used.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Next, a printing plate processing method according to the present invention will be described in detail with reference to a processing apparatus to which the printing plate is applied.

The processing apparatus shown in FIG. 1 has an insertion section A into which a printing plate to be processed is inserted, a first development section B1 to perform a development process, a second development section B2, a finisher section C to perform post-processing, and not shown. It is composed of a drying unit, and includes various sensors that detect the area of the inserted printing plate, the drive state of the transport system, the amount and supply state of the processing liquid, and the mechanism that controls the operation according to the detection information of the sensor. There is.

In the finisher section C, washing treatment,
Rinsing treatment, gumming treatment and the like are appropriately selected or combined depending on the type of printing plate.

In the figure, the symbol PS indicates a printing plate or its transport path.

In the insertion section A, an insertion table 1 for guiding the insertion of the printing plate PS into the apparatus, an optical sensor 2 for detecting the inserted printing plate PS by reflected light, and a pair of rollers for the inserted printing plate PS. A nip conveying roller 3A for nipting and taking in and loading the device into the apparatus is provided.

The optical sensor 2 is a printing plate PS to be inserted.
Is detected, and the operation of various mechanisms is automatically controlled by the detected information. For example, by arranging a large number of optical sensors 2 at right angles to the insertion direction of the printing plate PS at equal intervals, the width of the printing plate PS is detected by reflected light, and the detection information and the conveyance speed are used for insertion. Printing plate PS
Area can be calculated, and the supply of the replenishment processing liquid and the rinse liquid can be controlled by this calculation information.

The printing plate PS sent to the first developing section B1 by the nip carrying roller 3A is guided by the carrying roller 4, the nip carrying rollers 3B and 3C, and the first bath developing solution is stored therein. 1) The development processing tank 5 is conveyed in a slightly curved state, and an immersion treatment is performed during the conveyance.

In the treatment in the first developing treatment tank 5, in addition to the above dipping treatment, or in place of the dipping treatment, the treatment liquid is supplied to the plate surface side of the printing plate PS by a shower ejected from a nozzle. So-called shower development may be performed, or a mode in which a brush roller for rubbing the surface of the printing plate PS is arranged may be used.

The second developing section B2 includes nip rollers 3D and 3D.
So-called shower development is carried out by pumping up the second bath development processing solution stored in the second development processing tank 6 on both the front and back surfaces of the printing plate PS being conveyed between E by the pump and supplying it through the nozzle 7. Even in the second developing section B2, a brush roller for rubbing the surface of the printing plate PS or the like can be arranged.

In the finisher section C, the finisher liquid stored in the finisher liquid tank 8 is pumped up by a pump and supplied to both front and back surfaces of the printing plate PS through the nozzle 8 for processing.

The apparatus described above shows one example of the apparatus to which the present invention is applicable, and from the insertion section A to the drying section within the range not impeding the application of the present invention described below. The design of each mechanism can be changed.

Next, how the present invention is applied to the above apparatus will be described.

Second overflow from second developing tank 6
The bath developing solution is collected in the overflow storage tank 111 through the guide pipe 110. When the overflow liquid reaches a certain amount, the valve 112 opens and is sent to the ultrafiltration tank 113 for processing. Ultrafiltration tank 113
The permeated liquid from (1) is sent to the ultrafiltration membrane module 115 by the pump 114 for processing, the permeated liquid is returned to the replenisher liquid adjusting tank 116, and the liquid not permeated and concentrated is returned to the ultrafiltration tank 113 again. . Several times ultrafiltration tank 113
The liquid that has been returned to and concentrated to reach a certain concentration rate is discharged to the waste liquid tank 118 by opening the valve 131.

A concentrated replenisher having a high pH and water are added to the permeate introduced into the replenisher adjusting tank 116 to adjust it to a constant pH, and the pump is pumped according to the degree of deterioration of the second bath developing solution. It is supplied to the second developing tank 6 by the operation of 117.

The first bath developing solution stored in the first developing tank 5 is also treated in the same manner as above. That is, the first developing tank 5
The first bath developing solution overflowed from the guide tube 1
01 to the overflow storage tank 102. When the overflow liquid reaches a certain amount, valve 1
03 opens and is sent to the ultrafiltration tank 104 for processing. The permeated liquid from the ultrafiltration tank 104 is pump 1
By 05, the liquid is sent to the ultrafiltration membrane module 106 for processing, the permeated liquid is returned to the replenisher liquid adjusting tank 107, and the liquid not permeated and concentrated is returned to the ultrafiltration tank 104 again.
The liquid that has been returned to the ultrafiltration tank 104 several times and concentrated to reach a certain concentration rate is discharged to the waste liquid tank 109 by opening the valve 130.

In the permeate introduced into the replenisher adjusting tank 107, together with the concentrated replenisher having a high pH and water, the overflow solution of the second bath developing solution which is stored in the overflow storage tank 111 and is introduced by the pump 119. It is added and adjusted to a constant pH, and is supplied to the first developing tank 5 by the operation of the pump 108 according to the degree of deterioration of the first bath developing solution.

The second bath developing solution used in the second developing tank 6 has a higher liquid sensitivity than the first bath developing solution and a small amount of resin. Can be used as a part of the replenisher used in. By having such a liquid circulation path, the developer in the second developing tank can be kept in a state in which the amount of resin is smaller, which prevents re-adsorption of the resin component on the plate in the second developing tank. Further, it is possible to suppress the generation of a residual film that causes printing stains.

The method of the present invention can be carried out except for the ultrafiltration device (reference numerals 101 to 109, 130) relating to the first developing tank shown in FIG. In this case, the overflow solution from the second developing tank, which is guided by the pump 119, is supplied to a tank similar to the replenisher solution adjusting tank 107, and the concentrated replenisher solution having high pH and water are added to adjust the pH to a constant value. Is supplied to the first developing tank 5 according to the degree of deterioration of the first bath developing solution.

The embodiment shown in FIG. 2 is characterized in that the overflow solution from the second developing tank 6 is ultrafiltered and used as a part of the replenisher for the first bath development processing solution. In the apparatus indicated by reference numerals 101 to 111 · 130 in FIG. 1, the overflow solution from the second developing tank 6 is used as it is as a part of the first bath development processing solution, but in the apparatus shown in FIG. 2 The overflow liquid from the developing tank 6 is subjected to ultrafiltration and used. That is, the second bath development processing liquid overflowing from the second developing tank 6 is collected in the overflow storage tank 121 through the guide pipe 120. When the overflow liquid reaches a certain amount, the valve 122 opens and is sent to the ultrafiltration tank 123 for processing. The permeated liquid from the ultrafiltration tank 123 is sent to the ultrafiltration membrane module 125 by the pump 124 to be processed, and the permeated liquid is passed to the replenisher liquid adjusting tank 126, and the liquid not permeated and concentrated is again ultrafiltered. It is returned to the tank 123. The liquid that has been returned to the ultrafiltration tank 123 several times and concentrated to reach a certain concentration rate is discharged to the waste liquid tank 128 by opening the valve 132.

A concentrated replenisher having a high pH and water are added to the permeate introduced into the replenisher adjusting tank 126 to adjust it to a constant pH, and the pump is pumped according to the degree of deterioration of the first bath developing solution. It is supplied to the first developing tank 5 by the operation of 127.

The material of the filtration membrane used in the ultrafiltration tanks 104, 113 and 123 is preferably zirconium dioxide, polysulfone type, polyimide type, acrylonitrile type, and particularly preferably polysulfone type polyether sulfone. Yes, and molecular weight cutoff of 3000 to 10
Those of 000 are preferably used.

It is also preferable to use a prefilter in front of the above ultrafiltration membrane. The prefilter may be a single filter or a combination of several types, but the minimum mesh type is preferably 50 μm or less.

Ultrafiltration membrane module 106 / 115.1
25 uses a hollow fiber, a flat membrane, a tubular membrane, or the like, and it is particularly preferable to use a hollow fiber, but a conventionally known one can be used without any special limitation.

The printing plate to be treated according to the present invention may be any one, but it is effective when the following planographic printing plate and developing solution are used in terms of achieving the object of the present invention. As the support used in the printing plate,
A flexible plate that can be set in a normal planographic printing plate and one that can withstand a load applied at the time of printing are preferable, and examples thereof include metal plates of aluminum, magnesium, zinc, chromium, iron, copper, nickel, and alloy plates of these metals. Further, a metal plate coated with chromium, zinc, copper, nickel, aluminum, iron, or the like by plating or vapor deposition may be used. Of these, the preferred support is aluminum or its alloy.

The support is subjected to degreasing treatment, graining treatment, anodizing treatment and the like which are commonly used in this technical field. At least the graining treatment and the anodizing treatment are carried out in this order. It is preferable to use the body.

As a graining treatment method carried out to improve the adhesion to the photosensitive layer and to improve the water retention,
There are a so-called mechanical surface-roughening method for mechanically roughening the surface and a so-called electrochemical surface-roughening method for electrochemically roughening the surface. Examples of the mechanical surface roughening method include ball polishing, brush polishing, blast polishing, buff polishing and the like. The electrochemical surface-roughening method includes, for example, a method of electrolytically treating the support with an alternating current or a direct current in an electrolytic solution containing hydrochloric acid, nitric acid, or the like. The support can be grained by using any one of these methods or a combination of two or more methods.

Since smut is generated on the surface of the support obtained by the graining treatment as described above, it is generally necessary to appropriately perform washing with water or alkali etching to remove the smut. preferable. Examples of such a treatment include the alkaline etching method described in Japanese Patent Publication No. 48-28123 and Japanese Patent Laid-Open No. 53-53.
Examples thereof include a treatment method such as a sulfuric acid desmutting method described in 12739.

The support usually has abrasion resistance, chemical resistance,
An oxide film is formed by anodic oxidation in order to improve water retention. In this anodic oxidation, generally, a method of electrolyzing with an aqueous solution containing sulfuric acid and / or phosphoric acid or the like at a concentration of 10 to 50% at a current density of 1 to 10 A / dm ² is preferably used. Patent No. 1,41
There are a method of electrolyzing in sulfuric acid at a high current density described in 2,768, a method of electrolyzing using phosphoric acid described in US Pat. No. 3,511,661, and the like.

After the anodizing treatment, the support is preferably subjected to a pore-sealing treatment with hot water or the like, or a surface treatment such as immersion in an aqueous solution of potassium fluorozirconate.

Next, a printing plate is obtained by coating a photosensitive layer made of a photosensitive composition on the surface-treated support. The photosensitive substance used in the photosensitive layer is not particularly limited, and various kinds of substances generally used for a printing plate such as those described below are used.

1) Photocrosslinking-type photosensitive resin composition The photosensitive component in the photocrosslinking-type photosensitive resin composition is composed of a photosensitive resin having an unsaturated double bond in the molecule. For example, US Pat. No. 030,208, No. 3,4
No. 35,237 and No. 3,622,320, etc., the photosensitive group in the polymer main chain is used as a photosensitive group.

[0039]

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Examples thereof include a photosensitive resin containing, and polyvinyl cinnamate having a photosensitive group on the side chain of the polymer.

2) Photopolymerizable Photosensitive Resin Composition A photopolymerizable composition containing an addition polymerizable unsaturated compound, which comprises a monomer having a double bond or a monomer having a double bond. A typical example of such a composition comprising a polymer binder is disclosed in, for example, US Pat. No. 2,760,8.
No. 63 and No. 2,791,504.

As an example, a composition containing methylmethacrylate, a composition containing methylmethacrylate and polymethylmethacrylate, a composition containing methylmethacrylate, polymethylmethacrylate and polyethyleneglycolmethacrylate monomers, methylmethacrylate, an alkyd resin. A photopolymerizable composition such as a composition containing a polyethylene glycol dimethacrylate monomer is used.
This photopolymerization type photosensitive resin composition includes a photopolymerization initiator usually known in this technical field (for example, benzoin derivative such as benzoin methyl ether, benzophenone derivative such as benzophenone, thioxanthone derivative, anthraquinone derivative, acridone derivative, etc. ) Is added.

3) Photosensitive Composition Containing Diazo Compound The diazo compound in the photosensitive composition is, for example, preferably a diazo resin represented by a condensation product of an aromatic diazonium salt and formaldehyde or acetaldehyde. Particularly preferably, a salt of a condensate of p-diazophenylamine and formaldehyde or acetaldehyde,
For example, a diazo resin inorganic salt which is a reaction product of hexafluoroborophosphate, tetrafluoroborate, perchlorate or periodate and the condensate, and US Pat.
Examples thereof include a diazo resin organic salt, which is a reaction product of the condensate and a sulfonic acid, as described in Japanese Patent No. 300,309. Furthermore, diazo resins are preferably used with binders. As the binder, various polymer compounds can be used, but preferably, a monomer having an aromatic hydroxyl group as described in JP-A-54-98613, such as N- (4 -Hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, or p-hydroxystyrene, o-, m-, or p-hydroxyphenylmethacrylate and the like with other monomers Copolymers, polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as main repeating units as described in US Pat. No. 4,123,276, natural resins such as shellac and rosin, polyvinyl Alcohol, US Pat. No. 3,75
1,257, including linear polyurethane resins, phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin, cellulose derivatives such as cellulose acetate and cellulose acetate phthalate. It

4) Photosensitive composition containing o-quinonediazide compound In a photosensitive composition containing an o-quinonediazide compound, it is preferable to use an o-quinonediazide compound in combination with an alkali-soluble resin. Examples of the o-quinonediazide compound include ester compounds of o-naphthoquinonediazidesulfonic acid and a polycondensation resin of phenols and aldehydes or ketones.

Examples of the phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol and thymol, and dihydric compounds such as catechol, resorcinol and hydroquinone. Examples include trihydric phenols such as phenol, pyrogallol, and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, furfural and the like. Preferred of these are formaldehyde and benzaldehyde. 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- and p-mixed cresol / formaldehyde resin, resorcin / benzaldehyde resin, pyrogallol / acetone resin and the like. To be OH of phenols of the o-naphthoquinonediazide compound
The condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the group (reaction rate with respect to one OH group) is preferably 15 to 80%, and more preferably 20 to 45%. Further o
-As a quinonediazide compound, JP-A-58-4345
The compounds described in JP-A-1 can also be used.

Of the above o-quinonediazide compounds,
An o-quinone diazide ester compound obtained by reacting 1,2-benzoquinone diazide sulfonyl chloride or 1,2-naphthoquinone diazide sulfonyl chloride with pyrogallol-acetone condensation resin or 2,3,4-trihydroxybenzophenone is particularly preferable. As the o-quinonediazide compound used in the present invention, the above compounds may be used alone or in combination of two or more kinds.

The proportion of the o-quinonediazide compound in the photosensitive composition is preferably 6 to 60% by weight, and particularly preferably 10 to 50% by weight. Examples of the alkali-soluble resin include novolac resins, vinyl polymers having a phenolic hydroxyl group, and condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841.

Examples of the novolac resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolymer resin as described in JP-A-55-57841, JP-A-55- Examples thereof include copolymer resins of p-substituted phenol and phenol or cresol and formaldehyde as described in 127553.

The novolak resin preferably has a number average molecular weight Mn of 3.00 × (polystyrene standard).
10 ^{2 to} 7.50 × 10 ³ , and a weight average molecular weight Mw of 1.
00 × 10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn
Is 5.00 × 10 ^{2 to} 4.00 × 10 ³ , and Mw is 3.0.
It is 0 × 10 ^{3 to} 2.00 × 10 ⁴ . The novolak resins may be used alone or in combination of two or more.

The ratio of the novolak resin in the photosensitive composition is preferably 5 to 95% by weight. The vinyl copolymer having a phenolic hydroxyl group that is preferably used is a polymer having a unit having the phenolic hydroxyl group in the molecular structure.

The proportion of the vinyl polymer in the photosensitive composition is preferably 0.5 to 70% by weight.
As the vinyl polymer, the above polymers may be used alone or in combination of two or more kinds. It can also be used in combination with other polymer compounds.

A printout material capable of forming a visible image upon exposure can be added to the photosensitive composition.
The printout material comprises an organic dye which changes its color tone by interacting with a compound which forms an acid or a free radical upon exposure. Examples of the compound which forms an acid or a free radical upon exposure include, for example, JP-A-50- Three
O-naphthoquinonediazide-4 described in Japanese Patent No. 6209
-Sulfonic acid halogenide, o-naphthoquinonediazide-4-sulfonic acid chloride described in JP-A-53-36223 and phenols having an electron-withdrawing substituent, or an ester compound or amide compound of aniline acid, JP-A-55-77742, JP-A-5
Examples thereof include halomethylvinyloxadiazole compounds and diazonium salts described in JP-A No. 7-148784.

The photosensitive composition may contain, for example, p-tert-butylphenol formaldehyde resin or pn-octylphenol formaldehyde resin, or these resins may be o-quinonediazide in order to improve the oil sensitivity of the photosensitive composition. It is also possible to add a resin which is partially esterified with a compound. By dissolving each of these components in a solvent and coating and drying on the surface of the support, a photosensitive layer is provided and a printing plate can be produced.

The coating method used for coating the surface of the support with the photosensitive composition is a conventionally known method such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating and curtain coating. Coating or the like is used. At this time, the coating amount varies depending on the application, but for example, a coating amount of 0.05 to 5.0 g / m ² as a solid content is preferable. In using the printing plate thus obtained, a conventionally used method can be applied. For example, a transparent original image having a line image, a halftone dot image or the like is exposed in close contact with the photosensitive surface, and then this is exposed. The relief image is obtained by removing the photosensitive layer in the non-image area with an appropriate developing solution. As a light source suitable for exposure, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp or the like is used.

The negative-working and positive-working developers preferably used in the present invention are alkali agents, organic solvents, anionic surfactants, water-soluble reducing agents and nonionic surfactants and / or cationic surfactants. Can be included.

As the alkaline agent used in the developing solution of the present invention, sodium silicate, potassium silicate, sodium hydroxide, lithium hydroxide, sodium triphosphate, dibasic sodium phosphate, tribasic potassium phosphate and dibasic sodium Inorganic alkaline agents such as potassium phosphate, ammonium triphosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, sodium carbonate, potassium carbonate, ammonium carbonate, mono-, di- or triethanolamine and Organic alkali agents such as tetraalkylammonium hydroxide and organic ammonium silicates are useful. Of these, alkali silicates are most preferred. The content of the alkaline agent in the developing solution is preferably used in the range of 0.05 to 20% by weight, and more preferably,
It is 0.1 to 10% by weight.

The organic solvent used in the developer of the present invention preferably has a solubility in water at 20 ° C. of 10% by weight or less. Examples of such an organic solvent include ethyl acetate, propyl acetate and acetic acid. Butyl,
Carboxylic esters such as amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate; ketones such as ethyl butyl ketone, methyl isobutyl ketone, cyclohexane; ethylene glycol monobutyl ether, ethylene glycol benzyl monophenyl Alcohols such as ether, benzyl alcohol, ethylphenylcarbinol, n-amyl alcohol, methylamyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as methylene dichloride, ethylene dichloride and monochlorobenzine. and so on. One or more of these organic solvents may be used. Among these organic solvents, ethylene glycol monophenyl ether, ethylene glycol benzyl ether and benzyl alcohol are particularly preferable. The content is generally 0.000.
1% to 20% by weight is preferred.

The anionic surfactants used in the present invention include higher alcohol (C ₈ -C ₂₂ ) sulfate ester salts [eg, sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, lauryl alcohol sulfate]. Ammonium salt, "Teabol B-81" (trade name, manufactured by Shell Chemical Co., Ltd., secondary sodium alkyl sulfate, etc.), aliphatic alcohol phosphate ester salts (for example,
Cetyl alcohol phosphate sodium salt, etc., alkylaryl sulfonates (eg, dodecylbenzine sulfonic acid sodium salt, isopropylnaphthalene sulfonic acid sodium salt, dinaphthalene disulfonic acid sodium salt, metanitrobenzene sulfonic acid sodium salt, etc. ), Alkylamide sulfonates (for example, compounds represented by the following chemical formula 1, dibasic aliphatic ester sulfonates (for example, sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.)). Of these, alkylnaphthalene sulfonates are particularly preferably used.

[0060]

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The concentration of the above-mentioned anionic surfactant is preferably 0.2 to 10% by weight, particularly preferably 1 to 5% by weight. Further, the developing solution used in the present invention may contain a water-soluble reducing agent.

The above-mentioned meaning of "water-soluble reducing agent" includes water-soluble reducing agent, and the water-soluble reducing agent also contains 0.1 to 10% by weight, more preferably 0.1% by weight or less. It is contained in the range of 5 to 5% by weight. Furthermore, the developing solution used in the present invention may contain a nonionic and / or cationic surfactant.

As the nonionic surfactant, various compounds can be used, but they can be roughly classified into polyethylene glycol compounds and polyhydric alcohol compounds, and polyethylene glycol compounds are more preferably used. It Among them, the oxyethylene unit has a repeating structure of 3 or more and has an HLB value (Hydrophi).
A non-ionic surfactant having a le-Lipophile Balance) of 5 or more, and more preferably 10 to 20 is suitable.

The amount of these nonionic surfactants added is preferably 0.001 to 1.0% by weight, more preferably 0.01 to 1.0% by weight. The weight average molecular weight of these nonionic surfactants is
300 to 50,000 is preferable, and 50 is particularly preferable.
It is in the range of 0 to 5000. In the present invention, the above-mentioned nonionic surfactant may be used alone,
Two or more kinds may be used in combination. On the other hand, as the cationic surfactant used in the present invention, there are various compounds, and examples thereof include organic amine compounds and quaternary ammonium salt compounds.

Among these compounds, a water-soluble quaternary ammonium salt cationic surfactant is particularly effective, and examples thereof include alkyltrimethylammonium salt, alkyldimethylbenzylammonium salt, and ethylene oxide-added ammonium salt. be able to. Also,
A polymer having a cation component as a repeating unit is also generally a cationic surfactant and is effective in achieving the object of the present invention. In particular, a polymer containing a quaternary ammonium salt obtained by copolymerization with a lipophilic monomer can be suitably used.

The amount of the above cationic surfactant added is preferably 0.001 to 5 as in the case of the nonionic surfactant.
%, More preferably 0.01 to 1.0% by weight. The weight average molecular weight is 300 to 50,000.
It is in the range of 0, particularly preferably in the range of 500 to 5,000. These cationic surfactants are used alone, but two or more kinds may be used in combination.

Furthermore, according to the present invention, the effect of the present invention can be obtained even when a nonionic surfactant and a cationic surfactant are used in combination. The developer used in the present invention includes
The following additives can be added to further improve the developability.

For example, neutral salts such as NaCl, KCl and KBr described in JP-A-58-75152, JP-A-58-58
190952, chelating agents such as EDTA and NTA described in JP-A-59-121336, [Co (N
Complexes such as H _{3) 6]} Cl _3, Sho 50-51324
Alkyl phthalene sulfonate described in No. 3, N-
Anionic or amphoteric surfactants such as tetradecyl-N, N-dihydroxyethylbetaine, JP-A-55-95
Cationic polymers such as quaternary methyl chloride of p-dimethylaminomethyloristyrene described in JP-A 946, and amphoteric polymers such as copolymers of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142528. Electrolyte, JP-A-57-
Reducing inorganic salts described in 192952, JP-A-58-59
Inorganic lithium compounds such as lithium chloride described in JP-A-444, organic lithium compounds such as lithium benzoate described in JP-B-50-34442, organometallic surfactants containing Si, Ti, etc. described in JP-A-59-75255, Examples thereof include organic boron compounds described in JP-A-59-84241.

The image forming layer of the printing plate to which the present invention can be applied contains a photosensitive substance, and its physical and chemical properties are changed by exposure as a photosensitive substance or subsequent development treatment. For example, one that causes a difference in solubility in a developing solution by exposure, one that causes a difference in adhesive force between molecules before and after exposure, one that causes a difference in affinity for water and oil due to exposure or development treatment, and one that uses an electrophotographic method. Those which can form an image portion, and those having a multilayer structure described in JP-A-55-166645 are included.

[0070]

EXAMPLES Next, a method for treating a printing plate according to the present invention will be described through examples. Example 1 Using the apparatus shown in FIG. 1, Konica PS plate developer KCT-10 (trade name, manufactured by Konica Corporation) was placed in the first development processing tank 5.
0 liters, 8 liters of the same developing solution in the second developing tank 6, Konica gum solution SGW-in the tank of finisher section C
5 liters of 3 (trade name, manufactured by Konica Corporation) were charged and the device was set. Each liquid was diluted with a standard dilution ratio.

Overflow storage tank 102/111
Each of them was set to store 45 ml / m ^{2 on} average. When the storage amount in this tank reached 5 liters, the valves 103 and 112 were opened, and the ultrafiltration treatment was set. In the ultrafiltration tank, FB02-CC-FUST653 (manufactured by Daicel Corp., cut-off molecular weight 6000) using a hollow fiber membrane of polyether sulfone was used as a membrane module, and the operating pressure was 3 kg.
/ Cm ^{2 The} liquid temperature was set to 20 ° C and the concentration ratio was set to 20 times, and the filtration device was operated. The concentrated liquid was discarded in the waste liquid tanks 109 and 118 when it became 20 times as set. It was prepared by mixing 1 part of the overflow liquid introduced by the pump 119 with 8 parts of the permeate of the ultrafiltration membrane module 106, and further adjusting the pH to 13.37 with 50% KOH solution.
It was used as a replenisher for the developing tank. Further, 1 part of KCT-10 was mixed with 8 parts of the permeate of the ultrafiltration membrane module 115, and the pH was adjusted to 13.3 with 50% KOH solution.
It was adjusted to 7 and used as a replenisher for the second developing tank.

Under the above conditions, the Konica Positive PS plate KM was 15000 m ² , and the Konica Negative PS plate SWN-X was 500.
When 0 m ² treatment was performed, good treatment could be performed without problems such as dirt and film loss. The amount of waste liquid at this time was 5 millitorr / m ² .

Example 2 Using the apparatus shown in FIG. 1, Konica PS plate developer KCT-10 (trade name, manufactured by Konica Corporation) was placed in the first development processing tank 5.
0 liters, 8 liters of the same developing solution in the second developing tank 6, Konica gum solution SGW-in the tank of finisher section C
5 liters of 3 (trade name, manufactured by Konica Corporation) were charged and the device was set. Each liquid was diluted with a standard dilution ratio.

The overflow storage tank 121 was set to store an average of 45 ml / m ² . When the storage amount of this tank reached 5 liters, the valve 122 was opened to perform the ultrafiltration process. FB02-CC-F using a polyethersulfone hollow fiber membrane as a membrane module in the ultrafiltration tank.
Using UST653 (manufactured by Daicel, molecular weight cutoff 6000), the operating pressure was set to 3 Kg / cm ^{2, the} liquid temperature was 20 ° C., and the concentration ratio was 20 times to operate the filtration device. The concentrated liquid was discarded in the waste liquid tank 128 when it became 20 times as set. The permeate of the ultrafiltration membrane module 125 was adjusted to pH 13.37 with a 50% KOH solution and used as a replenisher for the first developing tank. In the second developing tank, KCT-11 diluted with a standard dilution ratio was used as a replenisher.

Under the above-mentioned conditions, Konica positive PS plate KM was 15000 m ² , and Konica Negative PS plate SWN-X was 500.
When 0 m ² treatment was performed, good treatment could be performed without problems such as dirt and film loss. The amount of waste liquid at this time was 60 millitorr / m ² .

Example 3 In Example 1, the pump 119 was not operated, and water and a KOH solution were added to the development replenisher of the first and second baths to the permeate from the ultrafiltration device of each tank. An experiment was conducted under the same conditions as in Example 1 except that a liquid whose pH was adjusted was used. As a result, the gradation increased by 1.25 steps at the end of the treatment, but it can be treated without causing any problems in practice. did it.

Comparative Example 1 In Example 1, the ultrafiltration device of the second developing tank was not used, and the second developing tank was used.
When the PS plate was processed under the same conditions as in Example 1 except that KCT-11 was used as the replenisher for the developing tank, the residual film gradually increased, and stains during printing were confirmed during 17,000 m ² processing.

[0078]

According to the method of the present invention, even if a so-called two-bath treatment is performed, it is possible to perform a favorable treatment without impairing the stability of the liquid sensitivity, and the above-mentioned problems are solved.

Further, according to the method of the present invention, in addition to the above-mentioned effects, by removing the photosensitive layer component in the liquid, the deterioration of the liquid sensitivity due to the hydrolysis of the binder is prevented, and the decomposition and adsorption of the diazo compound is caused. The effect of preventing red stains on the printing plate can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of an apparatus to which the present invention is applied.

FIG. 2 is a schematic diagram showing another example of an apparatus to which the present invention is applied.

[Explanation of symbols]

 A-insertion part B1-first development part B2-second development part C-finisher part PS-printing plate or its transport path 1-insertion table 2-optical sensor 3A-nip transport roller 3B-nip transport roller 3C-nip transport Roller 3D-nip transport roller 3E-nip transport roller 4-transport roller 5-first developing tank 6-second developing tank 7-processing liquid discharge nozzle 8-finisher tank 9-nozzle 101-overflow liquid guide pipe 102-overflow Liquid storage tank 103-Valve 104-Ultrafiltration tank 105-Pump 106-Ultramembrane module 107-Replenisher liquid adjustment tank 108-Pump 109-Waste liquid tank 110-Overflow liquid guide pipe 111-Overflow liquid storage tank 112 -Valve 113-Ultrafiltration Tank 114-Pump 115-Limit Membrane Module 116-Replenisher Adjusting Tank 117-Pump 118-Waste Liquid Tank 119-Valve 120-Overflow Liquid Guide Tube 121-Overflow Liquid Storage Tank 122-Valve 123-Ultrafiltration Tank 124-Pump 125-Ultramembrane Module 126-Replenisher adjusting tank 127-Pump 128-Waste liquid tank 130-Valve 131-Valve

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryoji Hattori 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company (72) Inventor Akio Kasakura 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa (72) Inventor Kenshi Kaneda 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Chemical Co., Ltd.

Claims (3)

[Claims] 1. A method of processing a photosensitive lithographic printing plate, wherein the developing processing section is divided into a first developing tank and a second developing tank, and the photosensitive lithographic printing plate is sequentially passed through these first and second developing tanks. 2. The method for treating a photosensitive lithographic printing plate as described in (1) above, wherein the treatment liquid is used while being purified by ultrafiltration in the second developing tank or both the first developing tank and the second developing tank. 2. A method for processing a photosensitive lithographic printing plate, wherein the developing processing section is divided into a first developing tank and a second developing tank, and the photosensitive lithographic printing plate is sequentially passed through these first and second developing tanks. At least a part of the liquid in the second developing tank is used for the first developing tank, and the second developing tank or the first developing tank and the second developing tank are used.
The method for treating a photosensitive lithographic printing plate as described above, wherein the treating solution is purified by ultrafiltration in both developing tanks. 3. A method of processing a photosensitive lithographic printing plate, wherein the developing processing section is divided into a first developing tank and a second developing tank, and the photosensitive lithographic printing plate is sequentially passed through these first and second developing tanks. In the second developing tank, the liquid in the second developing tank is ultrafiltered, and the permeated liquid is
The method for treating a photosensitive lithographic printing plate, which comprises supplying the lithographic printing plate to a developing tank for use.