JPH07281451A - Processing method of photosensitive planographic printing plate and device therefor - Google Patents

Abstract

PURPOSE:To effectively prevent remaining of components which are the cause for printing staining to a plate surface by constituting a cleaning means as a filtering means which is formed of multilayered films obtd. by laminating filters varying in pore sizes successively from the filters having the coarser pore sizes. CONSTITUTION:Printing plates PS are washed in a washing section C by supplying the washing water preped. in a washing water tank 20 by a magnet pump 21 and discharging the washing water to the plate surfaces of the printing plates PS existing between nip transporting rollers 3E, 3F via nozzles 22, 23 for discharging the washing water. The once utilized washing water is purified and recycled. Namely, a washing water purifying tank 24 is arranged in the front on sear stage of the magnet pump 21 for circulating the washing water. The purification of the washing water by the multilayered filters is executed in this tank. The multilayered filters which are composed of >=2 layers of the filters varying in mesh and are finer in the mesh of the filters arranged on the downstream side are used for the multilayered filters in such a case.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for treating a photosensitive lithographic printing plate, and more specifically, it is possible to effectively prevent, at a low cost, from adhering or remaining on a plate surface a component which causes printing stains. The present invention relates to a method and apparatus for processing a photosensitive lithographic printing plate that can be used.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication No. 57-158643 discloses
Disclosed is a plate making method and apparatus in which the washing water that has been subjected to the washing treatment is filtered and purified and then reused as the washing water.

The above publication discloses disposing a filtering / purifying means in the circulation system of the washing water, utilizing a plurality of washing tanks, and the like, and as the means for filtering the washing water, a filter paper, a filter cloth. , Using an organic filter medium such as a net, sand, silica sand, anthracite (anthracite), and using a mesh having a mesh size of 10 to 100 μm as a preferable filter medium. It is disclosed that as a purification means for washing water for removing the fatigue developing solution, an ion exchange membrane, an ion exchange resin, activated carbon, zeolite, silicate, a molecular sieve adsorbent, a reverse osmosis method, or the like is used. ing.

[0004]

A photosensitive lithographic printing plate (hereinafter simply referred to as a printing plate in the present specification) is subjected to imagewise exposure, followed by development treatment with an alkali developer, and further rinse treatment and washing treatment. -It is a printing plate that is used for printing only after it is dried, but of course the printing plate itself
Various ideas have been made regarding the composition of the processing liquid, the development processing method, the mechanism of the developing device, and the like. For example, a method in which no washing treatment is performed is disclosed in JP-A-54-8002 and JP-A-55-1.
No. 2921, No. 55-115045 and the like, which are used for post-treatment of a printing plate after development with a rinse solution containing a surfactant as a main component instead of washing with water. From the viewpoint of preventing the above, a method of performing both the rinse treatment and the water washing treatment is widely used.

Although it is ideal that the washing process should be performed with a large amount of running water, the large amount of washing water itself causes high cost, depletion-prone water resources, pollution prevention, compact equipment, etc. It will come up as a difficult problem from the problem of. Then, as shown in the above-mentioned publication, the idea of purifying the washing water and reusing it appears.

The stains on the printing plate are mainly caused by the components of the developing solution and the components of the eluted photosensitive layer which are brought in from the developing tank when the printing plate is conveyed, and when these are not sufficiently removed from the plate surface by the rinsing treatment and the water washing treatment. Occurs in Therefore, in order to reuse the wash water that has been purified after washing, it is necessary to sufficiently separate these developing solution components and elution photosensitive layer components washed out in the washing water until washing is insufficient. This means that the stain on the printing plate cannot be eliminated. Further, even if the efficiency of purifying the washing water is high, it is a problem that maintenance takes too much time. For example, in the washing water filtering means as shown in the above publication, when a filter having a fine mesh is used, the filter is clogged quickly, so it is not practical considering the cost of the filter and the labor of replacement, and the coarse mesh is used. There is a dilemma that the above filter cannot perform sufficient filtration.

As is apparent from the above, the present invention provides a method for treating a printing plate having an improved washing step capable of efficiently removing components causing a printing stain brought from a developing tank at low cost. The purpose is to clarify the device.

[0008]

A method of treating a printing plate according to the present invention comprises developing an image-exposed photosensitive lithographic printing plate with an alkaline developer and then rinsing with rinsing water and drawing out the rinsing water. In the method for treating a photosensitive lithographic printing plate having a cleaning means in the middle of the system of circulating again to the water washing section, the cleaning means is formed of a multilayer filter in which filters having different pore sizes are sequentially stacked from coarse ones. That the cleaning means is a filtration means using activated carbon based coal, and the cleaning means is a filtration means formed by at least two ultrafiltration membranes having a molecular weight cut off of 1000 to 20000. That the cleaning means is configured to discharge carbon dioxide gas into the wash water, and the cleaning means is configured to contain an acid or an acid salt in the wash water, The purifying means is at least one of a filter, a coal-based activated carbon, or an ultrafiltration membrane, and the purifying means is a filtration formed by a multilayer filter in which filters having different pore diameters are sequentially stacked in order from coarser pore diameters. Means, filtration means using coal-based activated carbon, filtration means formed by at least two kinds of ultrafiltration membranes having a molecular weight cut off of 1000 to 20000, carbon dioxide gas being discharged into the wash water, acid in the wash water Or at least one of the constitutions containing an acidic salt, and the imagewise exposed photosensitive lithographic printing plate is developed with an alkaline developer and then rinsed with rinse water, and the rinse water is drawn out and circulated again to the rinse part. In the middle of the system, the washing water is filtered using a coal-based activated carbon, which is a filtration means formed by a multi-layer filter in which filters having different pore sizes are sequentially stacked from coarse ones. Means, or passed through a filtration means formed with an ultrafiltration membrane, further, possible to discharge carbon dioxide to the water washing water,
And / or adding an acid or acid salt, the coarse filter initially placed as a multilayer filter is 200μ
A mesh having a size of more than 2 m and not more than m, the second and subsequent filters having a mesh of 200 μm or less, particularly at least one having a mesh of 100 to 200 μm and at least one having a mesh of 2 to less than 100 μm
It is characterized by being used.

The printing plate processing apparatus according to the present invention is
A photosensitive lithographic printing plate having a cleaning means in the middle of the system in which the imagewise exposed photosensitive lithographic printing plate is developed with an alkaline developer and then washed with rinsing water, and the rinsing water is drawn out and circulated again in the rinsing section. That the cleaning means is a filtration means formed by a multi-layer filter in which filters having different pore sizes are sequentially stacked from a coarse pore size filter, and the cleaning means is a filter using coal-based activated carbon. Means, the cleaning means has a molecular weight cutoff of 1000
No. 20,000 to at least two kinds of ultrafiltration membranes, the cleaning means is configured to discharge carbon dioxide gas into the washing water, and the cleaning means is acid in the washing water. Or, the cleaning device is configured to contain an acidic salt, the cleaning means is at least one of a filter, activated carbon or an ultrafiltration membrane, and the cleaning means is a filter having different pore diameters in order from a coarse pore diameter. Filtration means formed by layered multi-layer filters, filtration means using coal-based activated carbon, filtration means formed by at least two ultrafiltration membranes having a cut-off molecular weight of 1,000 to 20,000, and carbon dioxide gas is discharged into the washing water. If so, at least one of the constitution, the constitution in which an acid or an acid salt is contained in the washing water, a developing section for developing the image-exposed printing plate with an alkaline developing solution, and a washing treatment It is a processing device having a washing section, and is equipped with a washing water circulation system that draws out the washing water from the washing section and circulates it again in the washing section with a pump.In the middle of this washing water circulation system, a filter with a different pore size is used. The carbon dioxide gas in the washing water is disposed together with the washing water filtering means including the filtering means formed by a multilayer filter sequentially stacked from the ones, the filtering means using the coal-based activated carbon or the filtering means formed by the ultrafiltration membrane. A means for ejecting and / or a means for adding an acid or an acid salt is arranged. As a multilayer filter, the coarse filter that is initially arranged is a mesh having a mesh of more than 200 μm and 2 mm or less, and the second and subsequent elements are arranged. There are at least one filter with a mesh of 200 μm or less, especially with a mesh of 10 to 200 μm, and few with a mesh of 2 to 100 μm Both are used.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Next, a specific structure of the present invention will be described in detail. Prior to this, an example of an automatic developing machine to which the present invention can be applied will be schematically described with reference to FIG.

The automatic processor of the embodiment shown in FIG.
An inserting section A for inserting a printing plate, a developing section B for performing a developing process,
It is composed of a rinsing unit C for rinsing, a rinsing unit D for rinsing, and a drying unit E for rinsing. The area of the printing plate inserted, the driving state of the transport system, the amount and supply state of the treating liquid. It includes various sensors that detect such things, and a control mechanism that controls the operation according to the information detected by the sensors. In the figure, the symbol PS indicates a printing plate or its carrying 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 automatic developing machine to which the present invention is applied can be implemented with a mode in which a fixed amount of replenisher is replenished per unit time regardless of the total area of the inserted printing plate PS.

The printing plate PS sent to the developing section B by the nip conveying roller 3A is guided by the conveying roller 4, the nip conveying rollers 3B and 3C, etc., and slightly in the processing tank 5 in which the developing treatment liquid is stored. It is conveyed in a curved state, and is immersed in the course of the conveyance. In the processing tank 5, for the purpose of accelerating and stabilizing the development processing, the processing liquid discharge nozzles 6A and 6B (the processing liquid circulated by the magnet pump 7 is used) and the surface of the printing plate PS are rubbed. A brush roller 8, a pressing roller 9, and a heater 10 for maintaining the temperature of the developing solution within a predetermined temperature range are arranged.

Reference numerals 11 to 13 are bellows pumps, respectively, and the bellows pump 11 is provided with a bellows pump 12 for returning the overflowed processing liquid to the processing tank 5.
Is used to supply the concentrated replenisher solution prepared in the replenisher tank 14 to the treatment tank 5, and the bellows pump 13 is used to supply the diluted water prepared in the tank 15 to the treatment tank 5. It Reference numeral 16 is a tank for a concentrated rinse replenisher used in a rinse section D described later, and 17 is a waste tank for the development processing solution.

In the rinsing section C, the rinsing water prepared in the rinsing water tank 20 is supplied by the magnet pump 21, and the printing plate PS located between the nip conveying rollers 3E and 3F is supplied through the nozzles 22 and 23 for discharging the rinsing water. The water washing process is performed by discharging the water onto the printing plate.

In the rinsing section D, the rinsing liquid prepared in the rinsing liquid tank 30 is supplied by the magnet pump 31, and the rinsing liquid discharging nozzles 32 and 33 are used to supply the rinsing liquid between the nip conveying rollers 3G and 3H. A rinsing process is performed by discharging the ink onto the plate surface.

As described above, the concentrated rinse replenisher is prepared in the tank 16, is supplied to the rinse solution tank 30 by the bellows pump 34, and is diluted in the tank 15 by the dilution water supplied by the bellows pump 35. Mixed and diluted. The automatic developing machine to which the present invention is applied also includes a mode in which a concentrated rinse replenisher and diluted water are mixed and diluted and then supplied to the rinse tank 30.

In the drying section E, the nozzles 40.4 are formed on the plate surface of the printing plate PS being conveyed by the nip conveying roller 3I.
The drying process is performed by blowing heated dry air ejected from No. 1 onto the plate surface, and all the steps of the developing process are completed. The automatic processor described above shows an example of an apparatus to which the present invention is applicable, and from the insertion section A to the drying section E within a range that does not impede 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-mentioned automatic processor will be described in detail. As described above, in the rinsing unit C, the rinsing water prepared in the rinsing water tank 20 is supplied by the magnet pump 21 and the printing between the nip conveying rollers 3E and 3F is performed via the nozzles 22 and 23 for discharging the rinsing water. The rinsing treatment is performed by discharging the rinsing water onto the plate surface of the plate PS. In the present invention, the rinsing water used once is purified and reused. That is, the wash water purification tank 24 is arranged before or after the magnet pump that circulates the wash water, the multi-layer filter is used in the first mode, and the wash water is purified by activated carbon in the second mode, and the third mode is used. Then, the washing water is purified by the ultrafiltration membrane.

In another embodiment of the present invention, the carbon dioxide gas prepared in the cylinder 25 is adjusted into the flush water stored in the flush water tank 20 or the flush water purification tank while the discharge amount is adjusted by the valve 26. Discharge into the washing water stored in 24. When the carbon dioxide gas is discharged into the wash water, it is preferable to make the bubbles of carbon dioxide gas fine. To make the bubbles fine, for example, a filter 27 is interposed in front of the discharge port or a stirring blade is used. Things can be adopted. Reference numeral 28 indicates a waste liquid tank.
In still another aspect of the present invention, an acidic salt is added to the wash water to be purified.

As the multi-layer filter arranged in the flush water purification tank 24, for example, those made of nylon, polyester, polyethylene, polypropylene or the like can be used, and the shape thereof can be a known shape such as a flat membrane, a pole or a bag. it can. The multi-layer filter is composed of two or more layers of different meshes, and the one arranged on the downstream side has a finer mesh. That is, a coarse mesh is used on the upstream side where a large amount of dust and elution photosensitive layer components are contained in the processing liquid, and a fine mesh is used on the downstream side where these coarse suspended matters are removed. By doing so, the filter is prevented from being clogged in a short time.

The first coarse filter placed is 200 μ
A mesh having a size of more than m and 2 mm or less is preferable, and a filter having a mesh of 20 μm or less is preferable among the filters arranged after the second. Particularly preferably, at least one mesh having a mesh size of 100 to 200 μm and at least one mesh having a mesh size of less than 2 to 100 μm are included in the second and subsequent meshes. When stacking filters with different mesh diameters in order,
You may make it arrange | position above.

As the activated carbon for adsorbing the developing solution component and the eluted photosensitive layer component in the wash water, various forms such as granules and powders can be used, but the average particle size is preferably 10 to 10.
100 items are used. The activated carbon is coal-based, and various shapes such as powdered coal, granular coal, granulated coal, granular coal, and fibrous coal can be used. The coal-based activated carbon may be used by interposing it in a sandwich form between the above-mentioned filters, or may be arranged independently as one or more activated carbon layers.

The ultrafiltration membrane for purifying the wash water is for filtering the developer component and the photosensitive component carried into the wash water, and the fractionated molecular weight is 1,000 to 1,000 when estimated from the molecular weight of these components. 20,000 is preferably used,
In particular, one or more from 15,000 or more, 5000 to 1
It is preferable to use a combination of one or more from less than 5,000.

As the ultrafiltration membrane, for example, known ones such as hollow fiber, flat membrane single layer and flat membrane laminated can be used. There are various materials such as inorganic materials of metal oxides, zirconium dioxide-based materials, polyolefin-based materials, polysulfone-based materials, polyimide-based materials, polyacrylonitrile-based materials, and polyimide-based materials having good chemical resistance are preferable. When the ultrafiltration membrane and the above-mentioned multilayer filter are used in combination, the ultrafiltration membrane is arranged on the downstream side of the multilayer filter.

In the present invention, the carbon dioxide gas is discharged into the wash water to be purified by lowering the pH of the wash water to precipitate the components of the photosensitive layer dissolved in the wash water and purifying means such as filtration. This is to enhance the effect of. The carbon dioxide gas does not have to be 100% carbon dioxide gas, and may be a mixture of other gas such as nitrogen or oxygen, or may be air. Further, the object can be achieved even by adding a block of dry ice to the washing water. The amount of carbon dioxide gas discharged is 20 ml / mi
It is preferably n or more.

In the present invention, the acid or acid salt is added to the washing water to be purified in the same manner as carbon dioxide gas,
This is because it has the effect of promoting the precipitation of solids. The acid or acid salt used for purifying the wash water is not particularly limited, and a known acid or acid salt that is soluble in an aqueous solution having a pH of 10 to 12 can be used. Acidic salts such as hydrogen carbonate, hydrogen sulfate and hydrogen phosphate are preferable, and hydrogen sulfate is particularly preferable. The concentration or amount of the acid or acid salt to be added is not particularly limited, and an appropriate addition amount is
It can be added in the range of 0.1 to 40.0 g / liter, though it varies greatly depending on the processing conditions such as the time from the exchange of the developing solution and the number of processed sheets per day.

The support used in the printing plate to be treated according to the present invention is preferably one that can be set in an ordinary lithographic printing plate and can withstand the load applied during printing, for example, aluminum, magnesium, zinc, chromium, iron. Examples of the metal plate include copper, nickel, and the like, alloy plates of these metals, and the like. 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, etc., which are commonly used in this technical field. At least the graining treatment and the anodizing treatment are performed in this order. It is preferable to use the body.

Degreasing treatment for removing rolling oil on the aluminum surface includes solvent degreasing with trichlene, thinner, etc., emulsion degreasing with kerosene and triethanol, etc. Further, in order to remove stains and natural oxide film which cannot be removed only by degreasing, an alkaline solution such as caustic soda having a concentration of 1 to 10% is added at 20 to 70 ° C. for 5 seconds to 10 seconds.
Examples include a method of dipping for a minute and then dipping in an acidic solution such as nitric acid or sulfuric acid having a concentration of 10 to 20% at 10 to 50 ° C. for 5 seconds to 5 minutes to neutralize and remove smut after alkali etching.

As a graining treatment method carried out for improving the adhesion to the photosensitive layer and improving 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 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 layer is obtained by coating a photosensitive layer made of a photosensitive composition on the surface-treated support. The photosensitive substance used in this photosensitive layer is not particularly limited, and various substances generally used for printing plates, for example, the following various substances 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.

[0037]

[Chemical 1]

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 methyl methacrylate, a composition containing methyl methacrylate and polymethyl methacrylate, a composition containing methyl methacrylate, polymethyl methacrylate and polyethylene glycol methacrylate monomers, methyl methacrylate, 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 the photosensitive composition containing an o-quinonediazide compound, it is preferable to use an o-quinonediazide compound and an alkali-soluble resin in combination. 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 above-mentioned 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, and furfural. 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. 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, as the o-quinonediazide compound, the following compounds described in JP-A-58-43451 can also be used. That is, for example, known 1,2-benzoquinone diazide sulfonic acid ester, 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, etc. Quinone diazide compounds, more specifically J. Kosal
r) "Light-Sensitive Systems" (Lig
ht-Sensitive Systems) No. 339
Pp. 352 (1965), John Willy & Sons (New York) and W. S. De Forest, "Photoresist".
(Photoresist) Volume 50 (1975),
1,2-Benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2,1 described by McGraw Hill Company (New York).
′, 2′-Di- (benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, 1,2-benzoquinonediazide-4- (N-ethyl-M-β-naphthyl) -sulfonamide, 1,2-naphthoquinonediazide- 5-sulfonic acid cyclohexyl ester, 1- (1,2-naphthoquinonediazide-5-sulfonyl) -3,5-dimethylpyrazole, 1,2-naphthoquinonediazide-5-sulfone-4'-hydroxydiphenyl-4'-azo -Β
-Naphthol-ester, N, N-di- (1,2-naphthoquinonediazide-5-sulfonyl) -aniline, 2 '
-(1,2-naphthoquinonediazide-5-sulfonyloxy) -1-hydroxy-anthraquinone, 1,2-naphthoquinonediazide-5-sulfone-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonodiazide-5 -Sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid chloride 2 mol and 4,4'-diaminobenzophenone 1 mol condensate, 1,2-naphthoquinonediazide -5-sulfonic acid chloride 2 mol and 4,4
Condensation product with 1 mol of ′ -dihydroxy-1,1′-diphenylsulfone, Condensation product with 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of purpurogallin, 1,2-naphthoquinonediazide-5 An example is a 1,2-quinonediazide compound such as (N-dihydroabietyl) -sulfonamide. In addition, Japanese Examined Patent Publication Nos. 37-1953, 37-3627, and 37-13.
No. 109, No. 40-26126, No. 40-3801
No. 45, No. 45-5604, No. 45-27345, No. 5
1-13013, JP-A-48-96575, 48
The 1,2-quinonediazide compounds described in JP-A-63802 and JP-A-48-63803 can also be mentioned.

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 the weight average molecular weight Mw is 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 above novolak resins may be used alone or in combination of two or more.

The proportion of the novolak resin in the photosensitive composition is preferably 5 to 95% by weight. The vinyl copolymer having a phenolic hydroxyl group preferably used is a polymer having a unit having a phenolic hydroxyl group in its molecular structure, and has the following general formulas [I] to [V]
Polymers containing at least one structural unit of are preferred.

[0051]

[Chemical 2]

[In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R ₃ 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. R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an optionally substituted alkylene group connecting a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B represents
Represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. ]

The polymer used is preferably one having a copolymer type structure, and as a monomer unit which can be used in combination with the structural units represented by the above general formulas [I] to [V], respectively. Are, for example, ethylene, propylene, isobutylene, butadiene, isoprene, and other ethylenically unsaturated offylenes, such as styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene, and other styrenes, such as acrylic acid and methacrylic acid. Acrylic acids, for example, unsaturated aliphatic dicarboxylic acids such as itacone, maleic acid, maleic anhydride, etc., such as methyl acrylate, ethyl acrylate, acrylate n-butyl, isobutyl acrylate, dodecyl acrylate, acrylate-2 -Chloroethyl, phenyl acrylate, α
Esters of α-methylene aliphatic monocarboxylic acids such as methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, ethyl methacrylate, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, such as acryl Anilides such as anilide, p-chloroacrylanilide, m-nitroacrylanilide, and m-methoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate, such as methyl vinyl ether, ethyl vinyl ether. , Isobutyl vinyl ether, vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1, 1-dimethoxyethylene, 1,2
Ethylene derivatives such as -dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene, N- There are N-vinyl monomers such as vinylpyrrolidone. These vinyl-based monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved.

Of the above-mentioned monomers, aliphatic monocarboxylic acid esters and nitriles are preferable because they exhibit excellent performance for the purpose of the present invention. These monomers may be bound to the polymer used in either a block or random state.

The proportion of the vinyl polymer in the photosensitive composition is 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.

As the organic dye, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), Oil Blue # 603 (manufactured by Orient Chemical Co., Ltd.) ), Sudan blue II (manufactured by BASF), crystal violet, malachite green, fuchsin, methyl violet, ethyl violet, methyl orange, brilliant green, congo red, eosin, rhodamine 6
6 etc. can be mentioned. In addition to the above materials, a plasticizer, a surfactant, an organic acid, an acid anhydride and the like can be added to the photosensitive composition, if necessary.

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

Solvents that can be used when dissolving the photosensitive composition include methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether,
Propylene glycol, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dicarboxylic acid methyl ether, dipropylene glycol methyl ethyl ether, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate , Ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate,
Examples thereof include ethyl butyrate, dimethylformamide, dimethylsulfoxide, dioxane, acetone, methylethylketone, cyclohexanone, methylcyclohexanone, diacetone alcohol, acetylacetone, and γ-butyrolactone. These solvents may be used alone or in combination of two or more.

As the coating method used for coating the surface of the support with the photosensitive composition, there are conventionally known methods 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, and a developer used for the development is preferably an alkaline aqueous solution, for example, sodium silicate or potassium silicate. , Aqueous solutions of sodium hydroxide, potassium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate and the like. The concentration of the alkaline aqueous solution at this time varies depending on the type of the photosensitive composition and the alkali, but is generally in the range of 0.1 to 10% by weight, and the acid-alkaline aqueous solution may contain a surfactant or alcohol if necessary. It is also possible to add an organic solvent such as 0.1 to 20% by weight.

The negative-type and positive-type developers used in the present invention contain an alkaline agent, an organic solvent, an anionic surfactant, a water-soluble reducing agent and a nonionic surfactant and / or a cationic surfactant. contains.

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, 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 present invention is 20
It is preferable that the solubility in water at 10 ° C. is 10% by weight or less. Examples of such an organic solvent include ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate and butyl lactate. , Carboxylic acid esters such as butyl levulinate; ketones such as ethyl butyl ketone, methyl isobutyl ketone, cyclohexane; ethylene glycol monobutyl ether, ethylene glycol benzyl monophenyl ether, benzyl alcohol, ethylphenyl carbinol, n-amyl alcohol , Alcohols such as methylamyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene, halogenated carbonization such as methylene dichloride, ethylene dichloride, monochlorobenzine There is such as iodine. 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 0.0001% by weight.
To 20% by weight is preferred.

The organic solvent is an excellent additive for improving the developability for both negative type and positive type printing plates.

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.

[0066]

[Chemical 3]

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 developer used in the present invention contains a water-soluble reducing agent, and the water-soluble reducing agent includes organic and inorganic reducing agents.

Examples of the organic reducing agent include phenol compounds such as hydroquinone, metol and methoxyquinone, amine compounds such as phenylenediamine and phenylhydrazine, and examples of the inorganic reducing agent include sodium sulfite, potassium sulfite and sulfite. Sulfites such as ammonium sulfate, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite, sodium dihydrogen phosphite, dipotassium hydrogen phosphite, etc. Examples thereof include phosphite, hydrazine, sodium thiosulfate, and sodium dithionite, and the reducing agent particularly excellent in the present invention is sulfite.

The above-mentioned meaning of "water-soluble" of the water-soluble reducing agent also includes alkali-soluble, and these water-soluble reducing agents are contained in an amount of 0.1 to 10% by weight, more preferably 0. It is contained in the range of 5 to 5% by weight.

Further, the developer used in the present invention preferably contains a nonionic and / or cationic surfactant.

As the nonionic surfactant, various compounds can be used, but they can be roughly classified into a polyethylene glycol compound and a polyhydric alcohol compound, and the polyethylene glycol compound is more preferably used. It Among them, the oxyethylene unit has a repeating structure of 3 or more and has an HLB value (Hydroph
A nonionic surfactant having an ile-Lipophile Balance) of 5 or more, more preferably 10 to 20, is suitable. That is, the above-mentioned preferable nonionic surfactant is represented by the following chemical formula 2 as a general formula.

[0072]

[Chemical 4] Here, n, m, a, b, c, x, y represents an integer of 1-40.

Specific examples of the compound represented by the above general formula are as follows. For example, ethylene glycol, polyoxyethylene lauryl ether, polyoxyethylene nonyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, polyoxyethylene polyoxypropylene cetyl ether. , Polyoxyethylene polyoxypropylene behenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene stearyl amine, polyoxyethylene oleyl amine, polyoxyethylene stearic acid amide, polyoxyethylene castor oil, polyoxyethylene abiethyl ether, poly Oxyethylene lanolin ether, polyoxyethylene monolaurate, polyoxyethylene monostearate Rate, polyoxyethylene glyceryl monooleate, polyoxyethylene glyceryl monostearate, polyoxyethylene propylene glycol monostearate, oxyethylene oxypropylene block polymer, distyrenated phenol polyethylene oxide adduct, tribenzylphenol polyethylene oxide adduct, octylphenol Examples thereof include polyoxyethylene polyoxypropylene adduct, glycerol monostearate, sorbitan monolaurate, and polyoxyethylene sorbitan monolaurate.

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 50,000. In the present invention, the above-mentioned nonionic surfactants may be used alone or in combination of two or more.

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. Examples of the organic amine compound include polyoxyethylene alkylamine, N-alkyl propylene diamine, N-alkyl polyethylene polyamine, N-alkyl polyethylene polyamine, N-alkyl polyethylene polyamine dimethyl sulfate, alkyl biguanide, long chain amine oxide, There are alkyl imidazoline, 1-hydroxyethyl-2-alkyl imidazoline, 1-acetylaminoethyl-2-alkyl imidazoline, 2-alkyl-4-methyl-4-hydroxymethyl oxazoline and the like.

Examples of the quaternary ammonium salt compound include long-chain primary amine salt, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylmethylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridinium salt, and alkylquinone. Norinium salt, alkylisoquinolinium salt, alkylviridinium sulfate, steamidomethylpyridinium salt,
Acylaminoethyldiethylamine salt, acylaminoethylmethyldiethylammonium salt, alkylamidopropyldimethylbenzylammonium salt, aliphatic polyethylene polyamide acylaminoethylviridinium salt,
Acyl colaminoformylmethylviridinium salt, stearooxymethylviridinium salt, fatty acid triethanolamine, fatty acid triethanolamine formate salt, trioxyethylene fatty acid triethanolamine, fatty acid dibutylaminoethanol, cetyloxymethylviridinium Salt, p-isooctylphenoxyethoxyethyl dimethylbenzylammonium salt and the like.

Among these compounds, a water-soluble quaternary ammonium salt cationic surfactant is particularly effective, and examples thereof include alkyl trimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, and ethylene oxide addition 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 copolymerizing with a lipophilic monomer can be preferably used.

The addition amount of the above-mentioned cationic surfactant 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 effects of the invention can be obtained even when a nonionic surfactant and a cationic surfactant are used in combination.

The following additives may be added to the developing solution used in the present invention in order to further enhance the developing property. For example, NaC described in JP-A-58-75152
1, neutral salts such as KCl and KBr, JP-A-58-190
952, chelating agents such as EDTA and NTA described in JP-A-59-121336, [Co (NH ₃ ) ₆
] A complex such as Cl _3, an anionic or amphoteric surfactant such as sodium alkylphthalenesulfonate described in JP-A-50-51324, N-tetradecyl-N, N-dihydroxyethylbetaine, JP-A-55-9594.
Cationic polymer such as methyl chloride quaternary compound of p-dimethylaminomethyloristyrene described in No. 6,
An amphoteric polymer electrolyte such as a copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142528, JP-A-57-19.
Reducing inorganic salts described in 2952, JP-A-58-5944
No. 4, an inorganic lithium compound such as lithium chloride, an organic lithium compound such as lithium benzoate described in JP-B No. 50-34442, an organometallic surfactant containing Si, Ti, etc. described in JP-A-59-75255, JP 59
Examples thereof include organic boron compounds described in No. 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.

[0081]

EXAMPLES The present invention will be illustrated with reference to the following examples. Example 1 Using the automatic processor shown in FIG. 1, a washing water purification means using a multilayer filter was arranged in the washing treatment section C. The multilayer filter was arranged on the granule side of the magnet pump 21 for circulating the wash water. The filter is made of nylon, NGG20, N
-NO125T, N-NO420T (both are trade names, N
BC industrial filter, first mesh 1
000 μm, second one 133 μm, third one 2
5 μm) and arranged in this order in a stacked state to form 20 × 3
A 0 cm bag type multilayer filter was formed.

The processed printing plate is an exposed positive PS.
Plate KM (trade name, manufactured by Konica), processing speed 50 cm ²
/ H, the following processing solution A (developing solution) is prepared in a 20-liter processing tank, and the following processing solution B (replenishing solution) is replenished in a volume of 20 ml / m ² while 30
Development was performed at a liquid temperature of ° C, and 10 liters of prepared washing water was used to treat a printing plate of 30 m ² / l liter, that is, 300 m ² . The flow rate of the shower pipe having the washing water discharge nozzles 22 and 23 was 15 liters / minute and remained unchanged from the beginning to the end of the treatment.

By the above treatment, the treatment property (proper supply condition of washing water, occurrence of filter clogging, etc.) was evaluated,
Printing was performed with the treated printing plate to evaluate the printability (stainability and inking property). The results are shown in Table 1. Carcass is
◯: No problem, Δ: Slightly bad, ×: Bad, and the two symbols are intermediate evaluations of both.

Example 2 The processed printing plate was used as a negative PS plate SW whose image lines were exposed.
NX (trade name, manufactured by Konica Corporation), replacing the processing liquid A (developing liquid) and the processing liquid B (replenishing liquid) with a replenishing amount of 40 ml.
/ M ² was treated under the same conditions as in Example 1, except that
Evaluation of processability and generation of print stains were verified. The results are shown in Table 1. The flow rate of the shower pipe having the washing water discharge nozzles 22 and 23 was 15 liters / minute, and did not change from the beginning to the end of the treatment.

Example 3 An exposed positive PS plate KM (trade name, manufactured by Konica) and an exposed negative PS plate SWN-X (trade name, manufactured by Konica) were treated at a ratio of 8: 2. Example 1 except that the treatment liquid A (developer) was replaced with the treatment liquid D (developer), the treatment liquid B (replenisher) was replaced with the treatment liquid E (replenisher), and the replenishment rate was 40 ml / m ^2. Processing was carried out under the same conditions as above, and the evaluation of processability and the occurrence of print stains were verified. The results are shown in Table 1. The flow rate of the shower pipe having the washing water discharge nozzles 22 and 23 was 15 liters / minute, and did not change from the beginning to the end of the treatment.

Example 4 As a means for purifying washing water, granular activated carbon CAL (coal diameter activated carbon manufactured by Toyo Calgon Co., Ltd., particle size 12 × was used instead of the multilayer filter.
40) was used under the same conditions as in Example 1 except that 200 g was used to evaluate the processability and verify the occurrence of print stains. The results are shown in Table 1. The flush water discharge nozzle 22.2
The flow rate of the shower pipe with 3 was 15 l / min and remained unchanged from the beginning to the end of the treatment.

Example 5 Using the automatic processor shown in FIG. 1, instead of the multilayer filter used in Example 1, a chewable UF module N was used.
TU4220 and NTU-4208 (an ultrafiltration membrane manufactured by Nitto Denko Co., Ltd., with a molecular weight cutoff of 20,000 for the former and 80 for the latter.
The treatment was carried out under the same conditions as in Example 3 except that the value (00) was used, and the processability was evaluated and the occurrence of print stain was verified.
The results are shown in Table 1. The flow rate of the shower pipe having the washing water discharge nozzles 22 and 23 was 15 liters / minute, and did not change from the beginning to the end of the treatment.

Example 6 The process was carried out under the same conditions as in Example 1 except that the automatic developing machine used in Example 1 was used and carbon dioxide gas was discharged at 30 ml / min into the washing water stored in the washing water tank. Then, the processability was evaluated and the occurrence of print stain was verified. The results are shown in Table 1. The flow rate of the shower pipe having the washing water discharge nozzles 22 and 23 was 15 liters / minute, and did not change from the beginning to the end of the treatment.

Example 7 Treatment was carried out under the same conditions as in Example 3 except that 100 g (10.0 g per liter) of sodium hydrogensulfate was added to the washing water tank of the automatic processor used in Example 3, and the processability was improved. And the occurrence of print stains was verified. The results are shown in Table 1. The flow rate of the shower pipe having the washing water discharge nozzles 22 and 23 was 15 liters / minute, and did not change from the beginning to the end of the treatment.

Example 8 Carbon dioxide gas was added in an amount of 30 m in the wash water stored in the wash water tank.
Processing was performed under the same conditions as in Example 4 except that the ink was ejected at a rate of 1 / min to evaluate the processability and verify the occurrence of print stains.
The results are shown in Table 1. The flow rate of the shower pipe having the washing water discharge nozzles 22 and 23 was 15 liters / minute, and did not change from the beginning to the end of the treatment.

Example 9 Treatment was carried out under the same conditions as in Example 4 except that 100 g (10.0 g per liter) of sodium hydrogensulfate was added to the washing water tank to evaluate the processability and verify the occurrence of print stains. . The results are shown in Table 1. The flush water discharge nozzle 22
The flow rate of the shower pipe with 23 was 15 l / min and remained unchanged from the beginning to the end of the treatment.

Comparative Example 1 A single-layer filter NGG20 (trade name, NBC Kogyo Co., Ltd., mesh: 1000 μm) was used in place of the multilayer filter, and the treatment was carried out under the same conditions as in Example 3 to evaluate the processability and The occurrence of print stains was verified. The results are shown in Table 2. When the processing amount of the printing plate reached 23 m ² / liter, printing stains occurred due to poor washing with water.

Comparative Example 2 A single layer filter N-NO420T was used instead of the multilayer filter.
(Trade name, NBC Kogyo Co., Ltd., mesh 25 μm) was used under the same conditions as in Example 3 to evaluate the processability and verify the occurrence of print stains. The results are shown in Table 2.
When the processing amount of the printing plate reached 10 m ² / liter, the filter was clogged, and unless the filter was replaced, the flow rate of washing water decreased and printing stains occurred due to poor washing.

Comparative Example 3 Except that 200 g of granular activated carbon Zeocole Y-M (manufactured by Japan Age Co., Ltd., coconut shell activated carbon, particle size 8 to 32) was used, the treatment was carried out under the same conditions as in Example 4, evaluation of the processability and printing. The generation of dirt was verified. The results are shown in Table 2.

Comparative Example 4 Chewable UF Modules NTU4220 and NT
Processing was performed under the same conditions as in Example 5 except that only the former NTU4220 was used instead of U-4208, and the evaluation of processability and the occurrence of print stains were verified. The results are shown in Table 2.
Shown in.

Comparative Example 5 In Example 6, the processing was performed except that the use of the multilayer filter was stopped, and the processing property was evaluated and the occurrence of print stain was verified. The results are shown in Table 2.

Comparative Example 6 In Example 7, the processing was performed except that the use of the multilayer filter was stopped, and the processing property was evaluated and the occurrence of print stain was verified. The results are shown in Table 2.

Example 10 In Comparative Example 1, the treatment was performed except that carbon dioxide gas of 30 ml / min was discharged into the washing water stored in the washing water tank, and the treatment was evaluated and the print stain was generated. Verified. The results are shown in Table 2. The flow rate of the shower pipe having the washing water discharge nozzles 22 and 23 was 15 liters / minute, and did not change from the beginning to the end of the treatment.

Example 11 In Comparative Example 3, the treatment was performed except that carbon dioxide gas of 30 ml / min was discharged into the washing water stored in the washing water tank, and the treatment performance was evaluated and print stain was generated. Verified. The results are shown in Table 2. The flow rate of the shower pipe having the washing water discharge nozzles 22 and 23 was 15 liters / minute, and did not change from the beginning to the end of the treatment.

Example 12 In Comparative Example 1, 1 part of sodium hydrogen carbonate was added to the washing water tank.
Processing was carried out with the difference that only 100 g was charged to evaluate the processability and verify the occurrence of print stains. The results are shown in Table 2. The flow rate of the shower pipe having the washing water discharge nozzles 22 and 23 was 15 liters / minute, and did not change from the beginning to the end of the treatment.

Example 13 In Comparative Example 3, 1 part of sodium hydrogen carbonate was added to the washing water tank.
Processing was carried out with the difference that only 100 g was charged to evaluate the processability and verify the occurrence of print stains. The results are shown in Table 2. The flow rate of the shower pipe having the washing water discharge nozzles 22 and 23 was 15 liters / minute, and did not change from the beginning to the end of the treatment.

Treatment liquid A (Developer) A Potassium silicate 120 parts by weight Potassium hydroxide 13 parts by weight Water 620 parts by weight

Treatment liquid B (replenisher) A Potassium silicate 70 parts by weight Potassium hydroxide 30 parts by weight Water 350 parts by weight

Treatment liquid C (Developer) Benzyl alcohol 72 parts by weight Diethanolamine 42 parts by weight Perex NBL (manufactured by Kao Corporation) 18 parts by weight Potassium sulfite 9 parts by weight Water 300 parts by weight

Treatment Solution D (Developer) Propylene glycol 7 parts by weight pt-butylbenzoic acid 4 parts by weight 50% potassium hydroxide 30 parts by weight Emulgen 147 1 part by weight A potassium silicate 31 parts by weight Triethanolamine 6 parts by weight Water 159 parts by weight

Treatment Solution E (Replenisher) Propylene Glycol 7 parts by weight pt-butylbenzoic acid 4 parts by weight 50% potassium hydroxide 60 parts by weight Emulgen 147 1 part by weight A potassium silicate 31 parts by weight Triethanolamine 6 parts by weight Water 159 parts by weight

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

According to the method and apparatus for treating a printing plate of the present invention, it is possible to effectively prevent, at a low cost, components that cause printing stains from remaining on the plate surface, and the above-mentioned problems can be solved. Is.

[Brief description of drawings]

FIG. 1 is a schematic view of an automatic processor to which the present invention is applied.

[Explanation of symbols]

 A-insertion part B-developing part C-washing part D-rinsing part E-drying part PS-printing plate (photosensitive planographic printing plate) 1-insertion table 2-optical sensor 3A-nip conveying roller 3B-nip conveying roller 3C -Nip conveying roller 3D-Nip conveying roller 3E-Nip conveying roller 3F-Nip conveying roller 3G-Nip conveying roller 3H-Nip conveying roller 3I-Nip conveying roller 4-Conveying roller 5-Processing tank 6A-Processing liquid discharge nozzle 6B- Treatment liquid discharge nozzle 7-Magnet pump 8-Brush roller 9-Holding roller 10-Heater 11-Bellows pump 12-Bellows pump 13-Bellows pump 14-Replenisher tank 15-Diluting water tank 16-Rinse replenisher tank 17-Waste liquid Tank 20-Washing water tank 21-Magnet pump 22-Washing water discharge nozzle 23-Washing Discharge nozzle 24-Washing water purification tank 25-Cylinder 26-Valve 27-Filter 28-Waste liquid tank 30-Rinse liquid tank 31-Magnet pump 32-Rinse liquid discharge nozzle 33-Rinse liquid discharge nozzle 34-Bellows pump 35 Bellows pump 40 -Dry air jet nozzle 41-Dry air jet nozzle

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C02F 9/00 H G 503 G 504 B G03F 7/00 503 7/32 501 (72) Inventor Hattori Ryoji Tokyo No. 1 Sakuramachi, Hino City, Konica Stock Company (72) Inventor Akio Kasakura 1000 Kamoshidacho, Midori-ku, Yokohama 1000 Kamoshida-cho, Ward Sanryo Kasei Co., Ltd.

Claims (18)

[Claims] 1. A cleaning means is provided in the middle of a system in which an image-exposed photosensitive lithographic printing plate is developed with an alkaline developer and then washed with washing water, and the washing water is drawn out and circulated again in the washing section. In the method for processing a photosensitive lithographic printing plate, the cleaning means is a filtering means formed by a multilayer filter in which filters having different pore diameters are sequentially stacked in order from coarser pore diameters. Processing method. 2. A cleaning means is provided in the middle of a system in which an imagewise exposed photosensitive lithographic printing plate is developed with an alkaline developer and then rinsed with rinse water, and the rinse water is drawn out and circulated again in the rinse section. A method for treating a photosensitive lithographic printing plate, characterized in that the cleaning means is a filtration means utilizing coal-based activated carbon. 3. A cleaning means is provided in the middle of the system in which the imagewise exposed photosensitive lithographic printing plate is developed with an alkaline developer and then rinsed with rinsing water, and the rinsing water is drawn out and circulated again in the rinsing section. In the method for processing a photosensitive lithographic printing plate, the cleaning means has a molecular weight cutoff of 1,000 to 200.
00 is a filtration means formed of at least two types of ultrafiltration membranes of No. 00. 4. A cleaning means is provided in the middle of a system in which an imagewise exposed photosensitive lithographic printing plate is developed with an alkaline developer and then rinsed with rinse water, and the rinse water is drawn out and circulated again in the rinse section. A method for treating a photosensitive lithographic printing plate, wherein the cleaning means is configured to discharge carbon dioxide gas into the washing water. 5. A cleaning means is provided in the middle of the system in which the photosensitive lithographic printing plate subjected to image exposure is developed with an alkali developing solution and then washed with washing water, and the washing water is drawn out and circulated again in the washing section. A method for treating a photosensitive lithographic printing plate, characterized in that the cleaning means has a constitution in which an acid salt is contained in the washing water. 6. The method of treating a photosensitive lithographic printing plate as claimed in claim 4, wherein the cleaning means is at least one of a filter, a coal-based activated carbon and an ultrafiltration membrane. 7. The cleaning means comprises a filtration means formed by a multilayer filter in which filters having different pore diameters are successively stacked in order of coarse pore diameter, filtration means using coal-based activated carbon, and a molecular weight cutoff of 1,000 to 20,000. At least one of a filtering means formed of at least two kinds of ultrafiltration membranes, a structure in which carbon dioxide gas is discharged into the wash water, and a structure in which an acid or an acid salt is contained in the wash water. Claim 4
Alternatively, the method of processing the photosensitive lithographic printing plate as described in 5 above. 8. An imagewise exposed photosensitive lithographic printing plate is developed with an alkaline developer and then rinsed with rinse water, and the rinse water is removed in the middle of a system in which the rinse water is drawn out and circulated again in the rinse section. , A filter having different pore diameters, a filtration means formed by a multilayer filter sequentially stacked from a coarse pore diameter, a filtration means using coal-based activated carbon, or a filtration means formed by an ultrafiltration membrane, Further, a method for treating a photosensitive lithographic printing plate characterized by discharging carbon dioxide gas into the washing water and / or adding an acid or an acid salt. 9. As a multilayer filter, a coarse filter arranged first has a mesh of more than 200 μm and 2 mm or less, and a second arranged filter has a thickness of 200 μm.
8. The photosensitive material according to claim 1, 6 or 7, wherein at least one mesh having a size of m or less, particularly 100 to 200 μm, and at least one having a mesh of 2 to less than 100 μm are used. How to process planographic printing plates. 10. A cleaning means is provided in the middle of a system in which a photosensitive lithographic printing plate subjected to image exposure is developed with an alkali developing solution and then washed with rinsing water, and the rinsing water is drawn out and circulated again in the rinsing section. A photosensitive lithographic printing plate processing apparatus, characterized in that the cleaning means is a filtering means formed by a multilayer filter in which filters having different pore diameters are sequentially stacked from coarser ones. Plate processing equipment. 11. A photosensitizer having a cleaning means in the middle of a system in which a photosensitive lithographic printing plate subjected to image exposure is developed with an alkali developing solution and then rinsed with rinsing water, and the rinsing water is drawn out and circulated again in the rinsing section. An apparatus for processing a photosensitive lithographic printing plate, wherein the cleaning means is a filtering means utilizing activated carbon of coal type. 12. A cleaning means is provided in the middle of a system in which a photosensitive lithographic printing plate subjected to image exposure is developed with an alkali developing solution and then washed with rinsing water, and the rinsing water is drawn out and circulated again in the rinsing section. A processing apparatus for a photosensitive lithographic printing plate, wherein the cleaning means has a molecular weight cutoff of 1,000 to 2,000.
A processing device for a photosensitive lithographic printing plate, which is a filtration means formed of at least two types of ultrafiltration membranes of No. 0. 13. A cleaning means is provided in the middle of a system in which a photosensitive lithographic printing plate subjected to image exposure is developed with an alkali developing solution and then washed with washing water, and the washing water is drawn out and circulated again in the washing section. A processing apparatus for a photosensitive lithographic printing plate, wherein the cleaning means is configured to discharge carbon dioxide gas into the washing water. 14. A cleaning means is provided in the middle of the system in which the imagewise exposed photosensitive lithographic printing plate is developed with an alkaline developer and then washed with washing water, and the washing water is drawn out and circulated again in the washing section. A processing apparatus for a photosensitive lithographic printing plate, wherein the cleaning means is configured to contain an acidic salt in the washing water. 15. The processing apparatus for the photosensitive lithographic printing plate as claimed in claim 13, wherein the cleaning means is at least one of a filter, a coal-based activated carbon and an ultrafiltration membrane. 16. The cleaning means comprises a filtering means formed by a multi-layer filter in which filters having different pore diameters are sequentially stacked from one having a coarse pore diameter, a filtration means using coal-based activated carbon, and a molecular weight cutoff of 1,000 to 20,000. At least one of a filtering means formed of at least two kinds of ultrafiltration membranes, a structure in which carbon dioxide gas is discharged into the wash water, and a structure in which an acid or an acid salt is contained in the wash water. The photosensitive lithographic printing plate processing apparatus according to claim 13. 17. A processing apparatus comprising a developing section for developing an image-exposed photosensitive lithographic printing plate with an alkaline developing solution and a rinsing section for rinsing with water, and rinsing water from the rinsing section is drawn out and washed again with a pump. Equipped with a washing water circulation system to circulate in the part, and a filtering means formed by a multi-layer filter in which filters having different pore diameters are sequentially stacked from a coarse pore diameter in the middle of this washing water circulation system, a filtration means using coal-based activated carbon Alternatively, a washing water filtering means including a filtering means formed of an ultrafiltration membrane is arranged, and a means for discharging carbon dioxide gas into the washing water and / or a means for adding an acid or an acid salt are arranged. Characteristic photosensitive lithographic printing plate processing device. 18. As a multilayer filter, a coarse filter arranged first is a mesh having a size of more than 200 μm and not more than 2 mm, and a filter arranged second or later is 200.
18. The photosensitive lithographic plate according to claim 10, 16 or 17, wherein at least one mesh having a size of less than or equal to μm, particularly 100 to 200 μm, and at least one having a size of 2 to 100 μm are used. Printing plate processing equipment.