JPH07239557A - Processing method for photosensitive planographic printing plate, device therefor and exhaustion inhibitor for processing solution - Google Patents

Abstract

PURPOSE:To provide a processing method for a printing plate effective in preventing the deterioration of a developer and diminishing sludge by putting mono-, di- or trialkanolamine coated with an alkali-proof film in a processing soln. and specifying the pore diameter of the alkali-proof film. CONSTITUTION:Mono-, di- or trialkanolamine coated with an alkali-proof film is put in a processing soln. to restore the processing soln. exhausted by air. The alkali-proof film is, e.g. the film of arom. polyamide, polyolefin, polysulfone, polyimide, fluororesin, polypropylene, crosslinked aramide, a perfluorinated polymer or polyether sulfone, preferably a film of polyimide, polyether sulfone or arom. polyamide. The pref. pore diameter of the alkali-proof film is 10<-4>-10<-8>mum, especially 10<-4>-10<-6>mum.

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 processing a photosensitive lithographic printing plate, and more particularly to a method for processing a photosensitive lithographic printing plate improved in preventing deterioration of a developing solution and reducing sludge. And an apparatus and a treatment liquid fatigue inhibitor.

[0002]

2. Description of the Related Art JP-A-50-144502 and 55-55
Nos. 115039 and 58-95349 disclose a method of stably performing a developing process while replenishing a replenisher.

Japanese Unexamined Patent Publication No. 1-303440 discloses a method and an apparatus for carrying out development processing by blocking the contact area with the surface of a developing solution by 40% or more.

Japanese Unexamined Patent Publication No. 1-310355 discloses that a floating lid having alkali resistance is arranged on the liquid surface of immersion development.

Japanese Unexamined Patent Publication (Kokai) No. 57-114141 discloses a developer containing tetraalkylammonium hydroxide as a main component for the purpose of preventing fatigue of the developer due to air. A positive-type developing solution containing the same to 5 times mol of the mixture as the main agent is disclosed.

JP-A-63-32545, JP-A-1-17094
Japanese Patent Publication No. 1 discloses a photosensitive lithographic printing plate developing solution containing β-anilinoethanol.

Soviet SU-691799 discloses a positive photoresist developer solution containing mono- or diethanolamine.

[0008]

In an automatic developing machine which exposes a photosensitive lithographic printing plate (hereinafter, simply referred to as a printing plate in the present specification) and then develops the same, the printing plate is developed while being conveyed horizontally. A method of spraying a liquid in a spray form for development processing, and a method of curving a printing plate in a processing tank in which a large amount of developing solution is stored and transporting it for dipping are used. In such a processing method, it is necessary to prepare a large amount of developing solution for one plate processing, and it is necessary to circulate and reuse the developing solution for economical use. In addition to the liquid deterioration, the developer is deteriorated due to the absorption of carbon dioxide gas from the air, that is, the electric power of the developer is changed and the pH is changed. Due to these, the deteriorated developer must be replaced often. However, the management of the developing work became very complicated.

In order to solve the above-mentioned complication and to maintain the stability of the developing process, a processing method of adding a replenishing solution to a developing solution (developing mother solution) to be recycled and reused is disclosed in JP-A-50-144502.
Nos. 55-115039 and 58-95349. According to this processing method, although the frequency of liquid exchange is reduced, liquid exchange is still necessary, and the problem of accuracy of liquid replenishment and the problem of runout of replenishment due to quality difference of printing plates have not been solved.

Japanese Patent Laid-Open Publication No. 55-32044 discloses a processing apparatus for saving the developing solution except for the trouble of replenishing the replenishing solution. In this device, a developing solution diffusion plate is provided in the vicinity of the printing plate transport path, and the processing efficiency is improved by stretching the developing solution supplied to the plate surface. A relatively large amount (300 to 50
When it was not supplied at 0 ml / m ² ), uneven development was caused, and a residual film was sometimes caused due to defective development.

Although a floating lid is used to prevent the deterioration of the developing solution, it has some effects in preventing the deterioration of the developing solution and reducing sludge, but it is not sufficient.

Further, as disclosed in JP-A-63-32545 and JP-A-1-170941, there are known methods using alkanolamines.
With the method using anilinoethanol, it was not possible to add a sufficient required amount into the developing solution, and a sufficient effect was not obtained.

The developers containing mono-, di-, or trialkanolamines disclosed in JP-A-57-114141 were insufficient for long-term fatigue prevention.

As is apparent from the above, the present invention aims to clarify a method and apparatus for treating a printing plate, which is effective for preventing deterioration of a developing solution and reducing sludge.

[0015]

A method for treating a printing plate according to the present invention is a method of treating a printing plate coated with an alkali resistant film,
The present invention is characterized in that di- or trialkanolamine is added to the treatment liquid to prevent fatigue of the treatment liquid, and that the pore diameter of the alkali-resistant membrane is 10 ⁻⁴ to 10 ⁻⁶ μm. The printing plate processing apparatus according to the present invention is
The mono-, di-, or trialkanolamine coated on the alkali-resistant film must be added to the treatment liquid in the treatment tank, and the mono-, di-, or trialkanolamine coated on the alkali-resistant film must be Each of them is characterized in that the treatment liquid is circulated in the treatment tank, and the treatment liquid fatigue inhibitor for the printing plate according to the present invention is a mono-, di-, or monolithic film coated with an alkali-resistant film. Alternatively, it is characterized by containing a trialkanolamine.

[0016]

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 the 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.

Incidentally, a mode in which a fixed amount of replenisher is replenished per unit time can be applied to the automatic processor to which the present invention is applied, regardless of the total area of the inserted printing plate PS.

The printing plate PS sent to the developing section B by the nip transfer roller 3A is guided by the transfer roller 4, the nip transfer rollers 3B and 3C, and slightly in the processing tank 5 in which the developing processing 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 denote 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, which will be 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 printing plate PS between the nip conveying rollers 3G and 3H is supplied through the rinsing liquid discharge nozzles 32 and 33. 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 liquid tank 30 by the bellows pump 34, and is diluted by the dilution water prepared in the tank 15 and 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 above-described automatic developing machine shows an example of an apparatus to which the present invention is applicable, and the range from the insertion section A to the drying section E is not limited so long as the application of the present invention described below is not hindered. The design of each mechanism can be changed.

In FIG. 1, reference numeral 50 is a floating lid, which is arranged on the surface of the development processing liquid in the processing tank 5. As the floating lid 50, there are JP-A-1-303440 and 1-31.
Conventional floating lids disclosed in Japanese Patent Nos. 0355 and 2-3065 can be used.

The floating lid 50 is a state in which a single floating lid covers a part (40% or more) or all of the liquid surface of the processing liquid, and a plurality of floating lids (whether the same shape or different shapes are combined, Also, a combination of different sizes may be floated on the liquid surface, and in the latter mode, a structure in which no space is formed between adjacent floating lids is preferable.

Next, how the present invention is applied to the above-mentioned automatic processor will be described in detail.

A feature of the present invention is that the monoalkanolamine, dialkanolamine, and trialkanolamine are covered with an alkali-resistant film, and they are put into the treatment liquid to recover the treatment liquid fatigued by air. .

Examples of the alkali resistant film include aromatic polyamide, polyolefin, polysulfone, polyimide, fluororesin, polypropylene, polysulfone (acid?), Cross-linked aramid, perfluorinated polymer, polyether sulfone, and the like. More preferably polyimide,
Examples include polyether sulfone and aromatic polyamide.
In addition to being used as a single film, these may be a composite film.

The membrane pore diameter of the alkali resistant membrane is 10 ^-4 to 1
It is preferably 0 ^-8 μm, more preferably 10
^-4 to 10 ^-6 μm. Membrane pore size is CMW1000 (Membrane that blocks 90% or more of permeation of proteins with Mw: 1000 and particle size of 20Å) when expressed by molecular weight cutoff.
W10000 is preferable, and CMW10 is more preferable.
00 to CMW5000.

The monoalkanolamine, dialkanolamine and trialkanolamine contained in the alkali resistant film may be contained alone or in a mixed system. The amount of monoalkanolamine, dialkanolamine, and trialkanolamine contained in the film is preferably 5% to 80%, more preferably 10% to 60% in terms of density in the film.

It is preferable to use any of monoalkanolamine, dialkanolamine, and trialkanolamine, but considering that it diffuses from the film into the developing solution, the alkyl group portion of the monoalkanolamine is C3.
It is preferable that the above items are included. In dialkanolamines and trialkanolamines, at least one part of the alkyl group is preferably C3 or more.

The anti-fatigue agent for the treating solution used in the present invention is a substance which is sealed and covered with an alkali resistant film,
Although it is composed of at least di and trialkanolamine, the alkali-resistant film may further contain an additive as appropriate.
Examples include amine compounds and synthetic adsorbents.

A mode in which the monoalkanolamine, dialkanolamine, and trialkanolamine as they are still coated on the alkali-resistant film is directly added to the treatment tank is also possible. In such a mode, the alkali-resistant treatment is carried out. It is preferable to put it in a container such as a known stainless steel basket. The size and shape of the container are not particularly limited as long as they do not hinder the arrangement and operation of various devices in the processing tank or the transportation of the printing plate. Further, in such an embodiment, in order to promote contact of the treatment liquid in the treatment tank with the alkali-resistant film, it is preferable to add a mechanism for stirring or circulating the treatment liquid in the treatment tank.

A mode in which a tank or the like accommodating an alkali resistant film is arranged outside the treatment tank and the treatment liquid in the treatment tank is circulated can also be preferably carried out. Explaining with the automatic developing machine shown in FIG. 1, for example, a process described later in which an alkali resistant film is housed in a front stage or a rear stage of a magnet pump 7 which supplies the processing liquid drawn from the processing tank 5 to the processing liquid discharge nozzles 6A and 6B. A liquid fatigue preventive device may be arranged in advance to allow the treatment liquid to pass therethrough. Also, FIG.
A treatment liquid circulation system for preventing treatment liquid fatigue, which is provided with a treatment liquid fatigue preventer described later, may be provided separately from the treatment liquid circulation system shown in FIG.

In FIG. 2, an example of the processing liquid fatigue preventive device is indicated by reference numeral 60. The treatment liquid drawn out from the treatment tank 5 by the alkali-resistant pressure resistant tube 61 is fed into the treatment liquid fatigue preventer 60 by the pump 62, and after being treated,
An independent circulation system that returns to the processing tank 5 via the discharge pipe 63 is formed. The treatment liquid fatigue preventive device 60 includes the exterior body 6
4. An internal tank 65 made of stainless steel that has been subjected to alkali resistance treatment, a magnetic stirrer 66 that stirs the treatment liquid, and a sealing film 67. Inside the sealing film 67, mono, di, or tri Contains alkanolamine. The processing liquid has a structure that is introduced from the upper portion of the internal tank 65 and discharged from the lower portion.

The alkali-resistant film coated with the mono-, di-, and trialkanolamines can take various forms such as a bag shape, a capsule shape, and a tube shape. Also, such a membrane is
When the treatment liquid is introduced into the circulation system, it may be exposed in the treatment tank or the pipe, but it is preferably placed in a basket, a net, a container having a large number of pores, or the like. To do. In particular, in the aspect of charging into the processing tank, a basket,
It is preferably used in the state of being housed in a net or a container having a large number of pores.

A thing to be sealed and covered in an alkali resistant film.
The amount of di-trialkanolamine may be such that the amount of the sealed mono-, di-, or trialkanolamine that passes through the alkali-resistant film and is eluted or mixed into the processing solution is at least the same mole as the developing agent. The larger the amount, the more preferable in order to continue the effect for a long period of time.

Regardless of the bag shape, capsule shape, tube shape, or the like, it is possible to directly add the material to the processing tank by adding a weight or providing a binding means.

In the present invention, two or more alkali resistant membranes having different pore sizes are prepared, each of which is sealed and coated with a mono-, di- or trialkanolamine, and simultaneously contacted with the treatment liquid. , The effect can be measured over a long period of time.

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 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.

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, 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 perform neutralization and smut removal after alkali etching.

As a graining treatment method performed for improving the adhesion to the photosensitive layer and improving the water retention property,
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 at a current density of 1 to 10 A / dm ² using an aqueous solution containing sulfuric acid and / or phosphoric acid or the like at a concentration of 10 to 50% 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 sealing treatment with hot water or the like, or 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 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.

[0055]

[Chemical 1]

Examples thereof include a photosensitive resin containing, and polyvinyl cinnamate having a photosensitive group in 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 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 phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol and thymol, and divalent catechols, resorcinol, hydroquinone and the like. 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, and 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.

[0069]

[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. ]

As the polymer to be used, those having a copolymer type structure are preferable, 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 exhibit excellent performance for the purpose of the present invention and are preferred. 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 is composed of an organic dye which changes its color tone by interacting with a compound which produces an acid or a free radical upon exposure to light. Examples of the compound which produces 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.

The photosensitive composition may contain, for example, p-tert-butylphenol formaldehyde resin, pn-octylphenol formaldehyde resin, or 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 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 to dissolve 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 a 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 solid content is preferable. When 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 image, etc. is brought into close contact with the photosensitive surface and exposed, and then this is exposed to a non-image area by using a suitable developing solution. A relief image is obtained by removing the photosensitive layer. 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-working and positive-working developers used in the present invention contain an alkali 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.

[0084]

[Chemical 3] The concentration of the anionic surfactant is preferably 0.2.
A range of 10 to 10% by weight, particularly 1 to 5% by weight is preferable.

The developing solution used in the present invention contains a 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-solubility, 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 developing solution 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 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 (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.

[0090]

[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 addition amount of these nonionic surfactants 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 preferably 300 to 50,000, particularly preferably 500 to 50,000.

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

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 organic amine compounds 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, alkyl imidazoline, 1-
Hydroxyethyl-2-alkylimidazoline, 1-acetylaminoethyl-2-alkylimidazoline, 2-
Alkyl-4-methyl-4-hydroxymethyloxazoline 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, alkylquinone salt. 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 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,
In the range of 000, 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 if a nonionic surfactant and a cationic surfactant are used in combination.

The following additives can be added to the developing solution used in the present invention in order to further improve the developing property.

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 (NH
₃ ) ₆ ] Cl ₃ and the like, anionic or amphoteric surfactants such as sodium alkylphthalenesulfonate, N-tetradecyl-N, N-dihydroxyethylbetaine and the like described in JP-A-50-51324, JP-A-55 -959
Cationic polymers such as quaternary methyl chloride of p-dimethylaminomethyl orystyrene described in JP-A No. 46, and amphoteric polymers such as a copolymer 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.

Example 1 An automatic developing machine described with reference to FIG. 1 which does not use a floating lid is used, and an alkali resistant film (made of polyether sarpon, molecular weight cutoff CMW30) is used in the processing solution in the processing tank 5.
(A single film of 00) was directly added to the trialkanolamine (closed to a density of 30%).

The amount of trialkanolamine sealed in the polyether sulfone monolayer is such that the amount of elution is equimolar or more over 30 days or more with respect to the developing agent of the following developing solution. This trialkanolamine is contained in a spherical bag-shaped polyethersarpon monolayer so that the porosity is 70%. This bag-shaped polyethersarpon monolayer is It was housed in a porous stainless steel container that had been subjected to alkali resistance treatment, and was fixed to the bottom of the processing tank 5 so as not to float.

Using the treatment liquid A having the following composition and the treatment liquid B as a replenisher, a positive type printing plate KM (trade name, manufactured by Konica Corporation) and a negative type printing plate SWN-X (trade name, manufactured by Konica Corporation) were used. ).

Prior to the development processing, a film original was brought into close contact with the surface of the positive type printing plate and exposed for 60 seconds from a distance of 70 cm with a 2 KW metal halide lamp, and the same exposure was applied to the negative type printing plate. Was carried out for 30 seconds.

The size of the printing plate is 1003 mm × 800 m
m, the total amount processed was 200 plates per day at a ratio of negative: positive = 1: 4, and the deterioration of the developing solution was measured by measuring the pH fluctuation of the developing solution for 3 days. . In addition, the treatment liquid after treatment is 10
0 ml was taken out, stored in a drier at 55 ° C. for 4 days and then filtered, and the filtered product was further dried at 100 ° C. for 3 hours, and its weight was measured to obtain the amount of sludge. The measurement results are shown in Table 1.

Treatment Liquid A [Negative-type positive type common developer composition] Propylene glycol 50.0 g pt-Butylbenzoic acid 150.0 g Emulgen 147 [trade name, Kaosha nonionic surfactant] 5.0 g Potassium sulfite 300.0 g Gluconic acid solution (50% aqueous solution) 100.0 g A Potassium silicate [manufactured by Nippon Kagaku Kogyo Co., Ltd.] 400.0 g Potassium hydroxide 200.0 g Water 11.5 liter Treatment liquid B [Negative positive common replenishment] Liquid composition] Propylene glycol 50.0 g p-t-butylbenzoic acid 150.0 g Emulgen 147 [trade name, Kaosha nonionic surfactant] 5.0 g potassium sulfite 400.0 g gluconic acid liquid (50% aqueous solution) 100. 0 g A potassium silicate [manufactured by Nippon Kagaku Kogyo Co., Ltd.] 500.0 g Potassium hydroxide 400.0 g An automatic developing machine described in accordance with 11.5 liters Embodiment 2 FIG. 1 utilizing those without a floating lid, the treatment liquid anti-fatigue device 60 shown in FIG. 2
Incorporated. Trialkanolamine coated with a film of polyether sulfone was introduced into the treatment liquid in the internal tank 67, and the treatment liquid was circulated in the treatment tank by the pump 62. Otherwise, the development process is performed under the same conditions as in Example 1, and p
H and sludge amount were measured. The measurement results are shown in Table 1.

Example 3 Example 2 was repeated except that the following processing solution C was used as a negative type positive developing solution and the following processing solution D was used as a negative positive type replenishing solution.
The development process was carried out under the same conditions as above, and the pH and sludge amount were measured. The measurement results are shown in Table 1.

Treatment Liquid C [Negative-type positive type common developer composition] N-phenylethanolamine 6.0 g propylene glycol 50.0 g pt-butylbenzoic acid 150.0 g Emulgen 147 [trade name, Kaosha nonion interface Activator] 5.0 g Potassium sulfite 300.0 g Gluconic acid solution (50% aqueous solution) 100.0 g Triethanolamine 25.0 g A potassium silicate [Nippon Kagaku Kogyo KK] 400.0 g Potassium hydroxide 200.0 g Water 11.5 liters Treatment liquid D [Negative-type positive common replenisher composition] N-phenylethanolamine 6.0 g Propylene glycol 50.0 g pt-Butylbenzoic acid 150.0 g Emulgen 147 [trade name, Kaonsha Nonion Surfactant] 5.0 g Potassium sulfite 400.0 g Gluconic acid solution ( 0% aqueous solution) 100.0 g triethanolamine 25.0 g A potassium silicate [manufactured by Nippon Kagaku Kogyo Co., Ltd.] 500.0 g potassium hydroxide 400.0 g water 11.5 liters Example 4 Automatic developing machine described according to FIG. Then, the development processing was performed under the same conditions as in Example 3 except that the surface of the processing liquid was covered with a floating lid, and the pH and sludge amount were measured. The measurement results are shown in Table 1.

Comparative Example 1 Using the automatic processor described according to FIG. 1 without using the floating lid, in a state where the trialkanolamine coated with the alkali resistant film was not added to the processing solution in the processing tank, Other than the above, the development process was performed under the same conditions as in Example 1, and the pH was
And the amount of sludge was measured. The measurement results are shown in Table 1.

Comparative Example 2 Development was carried out under the same conditions as in Comparative Example 1 except that the above-mentioned processing solution C was used as the negative type positive developing solution and the above processing solution D was used as the negative type positive replenishing solution. , PH and sludge amount were measured. The measurement results are shown in Table 1.

Comparative Example 3 A developing process was performed under the same conditions as in Comparative Example 1 except that the automatic developing machine with a floating lid described with reference to FIG.
And the amount of sludge was measured. The measurement results are shown in Table 1.

[0117]

[Table 1]

(Note) ◯ = Trialkanolamine coated with an alkali resistant film was added to the treatment liquid in the treatment tank.

== Trialkanolamine coated with an alkali-resistant film was added to the circulating treatment liquid.

X = Trialkanolamine coated with an alkali resistant film is not added to the treatment liquid.

☆ = Use a floating lid.

* = Do not use the floating lid.

[0123]

EFFECTS OF THE INVENTION According to the method and apparatus for treating a photosensitive lithographic printing plate and the treating solution fatigue preventive agent according to the present invention, effects of preventing deterioration of a developing solution and reducing sludge are recognized, and the above-mentioned problems are solved. To be done.

[Brief description of drawings]

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

FIG. 2 is a schematic view showing an example of a treatment liquid fatigue preventive device.

[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 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 50-Floating lid 60-Processing Liquid Fatigue Preventer 61-Tube 62-Pump 63-Exhaust Pipe 64-Outer Body 65-Internal Tank 66-Magnet Stirrer 67-Sealing Membrane

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideyuki Nakai 1 Sakura-cho, Hino-shi, Tokyo Konica Co., Ltd. (72) Inventor Akio Kasakura 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa General Research Institute In-house (72) Inventor Kenshi Kaneda 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.

Claims (5)

[Claims] 1. An article coated with an alkali resistant film,
A method for treating a photosensitive lithographic printing plate, characterized in that di- or trialkanolamine is added to the treatment liquid to prevent fatigue of the treatment liquid. 2. The alkali-resistant film has a pore size of 10 ⁻⁴ to 1
The method for processing a photosensitive lithographic printing plate according to claim 1, which is 0 ^-6 μm. 3. An article coated with an alkali resistant film,
A processing device for a photosensitive lithographic printing plate, characterized in that di- or trialkanolamine is added to the processing liquid in the processing tank. 4. An article coated with an alkali resistant film,
A processing apparatus for a photosensitive lithographic printing plate, characterized in that di- or trialkanolamine is added to a processing solution circulated in a processing tank. 5. An article coated with an alkali resistant film,
A treatment solution fatigue preventive agent for a photosensitive lithographic printing plate containing di- or trialkanolamine.