JPH07239556A - Processing method of photosensitive planographic printing plate and device therefor - Google Patents

Abstract

PURPOSE:To provide a processing method of a photosensitive planographic printing plate improved in prevention of deterioration of a developer, decrease of sludge, improvement in a property to suppress smells, improvement in workability in maintenance and prevention of contact between a floating cap and rollers and a device therefor. CONSTITUTION:This processing method for guiding and transporting the photosensitive planographic printing plate PS into the developer prepd. in a processing tank 5 and subjecting the plate to an immersion treatment comprises discharging an inert gas from the bottom side of the processing tank 5 to form the flow of the inert gas in a liquid surface direction and processing the planographic printing plate while covering the surface of the processing liquid with the inert gas. This processing device for the photosensitive planographic printing plate is arranged with the floating cap 50 consisting of an alkali resistant material on the surface of the processing liquid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for treating a photosensitive lithographic printing plate, and more specifically, to prevent deterioration of a developer, reduce sludge, improve odor control, improve workability in maintenance, The present invention relates to a method and an apparatus for processing a photosensitive lithographic printing plate which is improved in terms of preventing contact between a floating lid and a roller.

[0002]

2. Description of the Related Art A method for stably performing a developing process while replenishing a replenisher is disclosed in JP-A-50-144502 and JP-A-55-55.
It is disclosed in JP-A-115039, JP-A-58-95349 and the like.

An automatic developing machine equipped with a diffusion plate for a developing solution for the purpose of saving the developing solution is disclosed in JP-A-55-320.
No. 44 publication.

In order to prevent the deterioration of the developing solution, it is necessary to dispose a floating lid on the surface of the developing solution.
No. 1-310355, 2-31065, 3-
No. 87833 is disclosed. Among them, JP-A-2-3065 discloses a conveyor type automatic developing machine provided with an immersion developing section using a floating lid, Sio ₂ / M ₂ O = 0.6.
/1.5, the use of a developing solution with an organic solvent of 5% by weight or less is disclosed. JP-A-1-303440 discloses a developing treatment by blocking the contact area with the surface of the developing solution by 40% or more. A method and apparatus for doing so are disclosed, and Japanese Patent Laid-Open No. 1-33
Japanese Patent Laid-Open No. 10-355833 discloses arranging a floating lid having alkali resistance on the liquid surface of immersion development, and Japanese Patent Laid-Open No. 3-87833 has an extension member for the floating lid attached to the outer periphery of the brush. A structure is disclosed.

A processing method using a negative-type and positive-type common developing solution is disclosed in JP-A-1-223448.

[0006]

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 developer for one plate processing. By the way, in order to economically utilize the developing solution, it is being circulated and reused. The change in conductivity, the change in pH, and the like occur, and the developer often deteriorated due to these changes must be replaced, which makes management of the developing operation very complicated.

In order to solve the above-mentioned complication and maintain the stability of the development processing, a processing method in which a replenisher is added to a developing solution (developing mother solution) to be recycled and reused is disclosed in Japanese Patent Laid-Open No. 144502/1975.
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. Further, this treatment method requires a treatment liquid replenishing device, which is not only expensive, but also has problems of adjustment and maintenance of the device.

With the above-mentioned troublesome replenishment of the replenisher,
A processor for the purpose of saving developer is disclosed in Japanese Patent Laid-Open No. 55-32.
No. 044 publication. In this device, a developer diffusion plate is provided in the vicinity of the printing plate carrying path,
Although it has been attempted to improve the processing efficiency by stretching the developer supplied to the plate surface, a relatively large amount of developer (30
When it is not supplied to ~ 500 ml / m ² ), uneven development may occur and a residual film may occur due to poor development.

The floating lid is used to prevent the deterioration of the developing solution, but it is not enough although the deterioration can be prevented to some extent. Further, in an automatic developing machine using a negative type and a positive type common developing solution, the effect of using the floating lid is reduced, and the effect of reducing the sludge amount is insufficient.

Even if the floating lid is used, the organic solvent is 5
When the negative type printing plate developing solution is used in an amount of at least wt%, a large amount of sludge is generated. The organic solvent is 5
There was also a problem with odor when using a developing solution containing at least wt%.

The automatic developing machine utilizing the floating lid has a problem that the roller on the processing tank side comes into contact with the floating lid when the developer is reduced.

Further, it has been pointed out that the use of the floating lid has poor workability. That is, it is necessary to remove the floating lid when cleaning the automatic developing machine, but since the contact portion with the liquid surface of the floating lid is flat, the developing solution spreads over the entire back surface when the floating lid is removed. It was easy to get on, and the surroundings were often soiled by dripping. As is apparent from the above, the present invention prevents deterioration of the developer, reduces sludge, improves odor control, improves workability in maintenance,
It is an object of the present invention to clarify a printing plate processing method and apparatus that are improved in terms of preventing contact between a floating lid and a roller.

[0013]

A method for treating a printing plate according to the present invention is a treatment method in which a printing plate is dipped by being guided and conveyed into a developing solution prepared in a treatment tank. Inert gas is discharged from the nozzle to form a flow of the inert gas in the direction of the liquid surface, and the liquid surface of the processing liquid is covered with the inert gas to perform the processing. Is covered by a floating lid or cover lid,
The development process is performed with a negative or positive type processing solution or a processing solution for both negative and positive type processing, and the liquid surface is covered with a floating lid or cover lid made of an alkali-resistant material, and inert gas is supplied from the bottom side. In the processing method of performing the treatment while supplying the replenisher solution prepared in the discharging replenisher tank to the processing tank, and dipping the printing plate by guiding and conveying it into the developer prepared in the processing tank. A plurality of floating lids made of an alkali-resistant substance are floated on the liquid surface of the treatment liquid, and a part or all of the liquid surface of the treatment liquid is covered by the plurality of floating lids to perform the treatment, and the area of the liquid surface of the treatment liquid is 2000c.
m ^{2 to} 5000 cm ² , and the total volume of the floating lid made of the alkali-resistant substance to be floated is 50 cm ^{3 to} 3000.
cm ³ and the thickness of each floating lid is 0.1 cm to 1
0 cm, and the specific gravity of the floating lid made of the new developer / alkali resistant substance is in the range of 1.05 to 1.60, and one or a plurality of parts of the liquid surface are made of the alkali resistant substance. The replenisher tank, which is covered with the floating lid, is used for processing while supplying the replenisher solution to the processing tank, and the printing plate is dipped by guiding and conveying it into the developer solution prepared in the processing tank. In the treatment method described above, part or all of the liquid surface of the treatment liquid is covered with one or more floating lids made of an alkali-resistant substance, and printed with the treatment liquid containing 5.5 to 20% by weight of an organic solvent. The plate is developed and characterized.

The printing plate processing apparatus according to the present invention is
In an apparatus for dipping a printing plate by guiding and transporting it into a developing solution prepared in the processing tank, a mechanism for discharging an inert gas is arranged at the bottom of the processing tank, and the surface of the processing solution is resistant. A floating lid made of an alkaline substance is arranged, and the structure is such that the treatment is performed while supplying the replenisher solution prepared in the replenisher tank to the processing tank. Is provided with a floating lid made of an alkali-resistant substance, and further has a replenishing liquid facility in which a mechanism for discharging an inert gas is arranged at the bottom of the replenishing liquid tank, which is prepared in the processing tank. In a device for carrying a printing plate by immersion in a developing solution, having one or more floating lids made of an alkali-resistant substance floating on the surface of the processing solution, the area of the processing solution surface is 2000cm ² ~50 Is 0 cm ^2, the total volume of the floating lid made of alkali-resistant material which floats 50c
together with an m ³ ~3000cm ^3, the thickness of each floating lid is 0.1Cm～10cm, and specific gravity ratio of developing new chemical / alkali resistance material is in the range of 1.05 to 1.60 The replenisher tank is configured so that the treatment is performed while supplying the replenisher solution prepared in the replenisher tank to the treatment tank, and one or a plurality of floats made of an alkali-resistant substance are floated on the surface of the replenisher solution in the replenisher tank. In a processing device that has a structure in which the lid is floated, and the printing plate is dipped by being guided and conveyed in the developer prepared in the processing tank, the floating surface made of an alkali-resistant substance on the surface of the processing liquid in the processing tank. The printing plate is a negative type, in which the lid is arranged and a control mechanism for restricting swinging of the floating lid in the horizontal direction and / or the vertical direction is provided.

[0015]

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 portion 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 implemented in the automatic developing machine 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 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, which will be described later, and 17 is a waste tank for a developing 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 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 discharge 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 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 can be applied. From the insertion section A to the drying section E, the application of the present invention described below is not hindered. 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 FIG. 1, reference numeral 50 is a floating lid made of an alkali-resistant substance (including those which have been surface-treated with an alkali-resistant treatment agent, and the same applies hereinafter in the present specification), and is a liquid of the developing treatment liquid in the treatment tank 5. It is placed on the surface.

The floating lid 50 may oscillate in the horizontal direction and the vertical direction due to the shaking of the processing liquid accompanying the conveyance of the printing plate PS, and also due to the increase / decrease of the processing liquid, contacting the members forming the apparatus. May cause a malfunction,
A fixing member is attached to the inner side surface of the processing tank 5 to restrict the movement in the horizontal and vertical directions. Specifically, for example, it is preferable to use the fixing member 51 as shown in FIG. That is, the fixing member 51 is attached to the inner wall of the processing tank 5 in a state of being in contact with the corner of the floating lid 50 to prevent the floating lid 50 from moving in the horizontal direction at the vertical plate portion and to prevent the processing liquid from flowing. Even if the height position of the floating lid 50 becomes lower due to the decrease, the bottom plate portion of the fixing member 51 regulates the height so that it does not become lower than a certain level. Since the conventional floating lid has a structure in which the height position is lowered as much as the treatment liquid is reduced, there is a malfunction in which the floating lid comes into contact with the conveying roller or the like. According to this, such a situation is effectively prevented.

The floating lid 50 can be embodied as a single floating lid covering the entire liquid surface of the processing liquid, or as a plurality of floating lids floating on the liquid surface. In the latter embodiment, for example, Various shapes as shown in FIG. 2 can be implemented. The plane shape of the floating lids 50 as shown in the drawing needs to be a polygonal shape in which no voids are formed between adjacent floating lids 50, or a polygonal shape in which voids are unlikely to occur, such as a circle or an ellipse. Is not preferable.

It is preferable that the bottom surface of the floating lid 50 is inclined as shown in the drawing with a point centered on the center of gravity as a starting point in order to improve liquid drainage when lifted up, and the whole surface. It is not preferable that it is flat.

Whether the floating lid 50 is in the form of a single piece or a plurality of pieces as described above, small projections such as hemispheres, cones, and pyramids are arranged on the entire back surface thereof.
It is preferable for improving the liquid drainage.

As will be described later, in the present invention, since the processing liquid is prevented from coming into contact with oxygen in the air by discharging the inert gas, the discharged inert gas is scattered from the surface of the processing liquid. However, an inert gas layer may be formed on the surface of the processing liquid. Therefore, instead of the floating lid or in combination with this, the upper portion of the processing liquid is covered with a fixed cover. May be.

An inert gas is prepared for the tank 60, and the opening and closing of the valve 61 controls the discharge of the inert gas into the developing solution through the discharge port 62 arranged at the bottom of the processing tank 5. Done. It is preferable to provide a plurality of inert gas discharge ports 62 instead of one place, and the inert gas rising in the processing liquid is discharged to the upper space of the processing tank while contacting the back surface of the floating lid 50. Preferably there is.

Examples of the inert gas include argon, helium, neon, krypton, xenon, radon, and nitrogen. Among them, argon and nitrogen are preferable, and nitrogen is particularly preferable.

The amount of inert gas for discharging when the area of the treatment liquid liquid surface is 2000cm ² ~5000cm ^2, 5~1
The range of 000 ml / min is preferable, and the range of 10 to 300 ml / min is particularly preferable.

Ejecting an inert gas into the developing solution is effective when applied to a system in which negative and positive type printing plates are treated with a common developing solution.

The floating lid may be composed of a plurality of pieces.
In this embodiment, the processing tank 5 is provided with a plurality of floating lids made of an alkali-resistant substance, and floats near the surface of the development processing liquid.

As the alkali-resistant substance, resins such as polyvinyl chloride, polyethylene, polyamide, polyester, etc., resin foams, glass, metals and the like have good chemical resistance and are hard to be soiled or easily soiled even if soiled. The material can be preferably used.

The total volume of the floating lid made of the alkali-resistant substance to be charged is such that the surface area of the processing liquid is 2000 cm ^{2 to} 5 cm.
When it is 000 cm ² , the range of 50 to 3000 cm ³ is preferable, and 100 to 1500 cm ³ is more preferable. Further, the thickness of the floating lid is preferably 0.1 cm to 10 cm.

In the case of the treatment with the treatment liquid containing 5.5 to 20% by weight of the organic solvent, the specific gravity of the floating lid made of the alkali-resistant substance / the specific gravity of the replenishment treatment liquid is 1.00 / 1.05.
It is preferable that it is in the range of -11.60, more preferably in the range of 1.00 / 1.050-1.50.

Contact rate of the floating lid made of an alkali-resistant substance with the liquid surface of the processing liquid (coverage of the liquid surface of the processing liquid by the floating lid)
Is preferably 10% or more, more preferably 30% or more, and particularly preferably 50% or more.

When a plurality of floating lids made of an alkali-resistant substance are added to the development processing solution in the processing tank 5, they float near the surface of the processing solution, and have the same function as one floating lid. By preparing a small number of large floating lids and a large number of small floating lids, the function as a floating lid can be improved because the small floating lid also has the function of filling the gap created between the large floating lids. .

The arrangement of the floating lid 50 made of the alkali resistant material and the discharge of the inert gas are not limited to the treatment tank 5, but the tank 1 in which the replenishing treatment liquid is prepared.
It is preferable to carry out for No. 4. In addition, if the floating lid is missing in either the development processing solution or the replenishment processing solution, there is no effect, and the presence of both does not prevent deterioration of the processing solution or generation of sludge.

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

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

The support usually has abrasion resistance, chemical resistance,
An oxide film is formed by anodic oxidation in order to improve water retention. In this anodic oxidation, generally, a method of electrolyzing 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 a pore-sealing treatment with hot water or the like, or a surface treatment such as immersion in an aqueous solution of potassium fluorozirconate.

Next, a printing plate is obtained by coating a photosensitive layer made of a photosensitive composition on the surface-treated support. The photosensitive substance used in 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. 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.

[0056]

[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 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 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 and the like. To be OH of phenols of the o-naphthoquinonediazide compound
The condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the group (reaction rate with respect to one OH group) is preferably 15 to 80%, and more preferably 20 to 45%.

Further, 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.

[0070]

[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, one having a copolymer type structure is preferable, and as a monomer unit which can be used in combination with the structural unit represented by each of the above general formulas [I] to [V]. 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 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 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 dyes, 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-butylphenolformaldehyde resin or pn-octylphenolformaldehyde resin, or these resins may be o-quinonediazide in order to improve the oil sensitivity of the photosensitive composition. It is also possible to add a resin which is partially esterified with a compound. By dissolving each of these components in 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 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 and positive developing solutions 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, dibasic 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.

[0085]

[Chemical 3]

The concentration of the anionic surfactant is preferably in the range of 0.2 to 10% by weight, particularly 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-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.

[0091]

[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
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 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 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 improve 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 ]
Complexes such as Cl ₃ ; anionic or amphoteric surfactants such as sodium alkylphthalene sulfonate described in JP-A No. 50-51324; N-tetradecyl-N, N-dihydroxyethyl betaine; JP-A No. 55-95946. Of p-dimethylaminomethyloristyrene, such as a methyl chloride quaternary compound, and an amphoteric polyelectrolyte such as a copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142528. Kaisho 57-19295
No. 2, a reducible inorganic salt, an inorganic lithium compound such as lithium chloride described in JP-A No. 58-59444, JP-B-5.
Organic lithium compounds such as lithium benzoate described in 0-34442, Si described in JP-A-59-75255,
Organometallic surfactant containing Ti and the like, JP-A-59-84
Examples thereof include organic boron compounds described in No. 241.

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 or subsequent development as a photosensitive substance. 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 A1 The automatic developing machine using the floating lid 50 described with reference to FIG. 1 (opening area of the processing tank 5 was 4000 cm ² , the coverage of the processing liquid surface by the floating lid 50 was 80%, and the refill tank was also floating lid. 80% of the replenisher liquid surface was floated and the nitrogen gas was set to be discharged from the bottom of the processing tank 5 at a flow rate of 200 ml / min. Using the liquid A-2, the positive type printing plate KM and the negative type printing plate SWM-X (both trade names manufactured by Konica Corporation) were developed. The size of the printing plate is 1003mm x 800
It was processed at a ratio of positive type 4: negative type 1 with a thickness of mm. The processed amount was 200 plates per day, and the amount was processed for 3 days, and the degree of deterioration of the developing solution was detected by measuring the pH. After the completion of the treatment, 100 ml of the treatment liquid is collected and
After being stored in a dryer at ℃ for 4 days, it was filtered, and the filtered material was further dried at 100 ℃ for 3 hours, and the weight was measured to obtain the amount of sludge. The measurement results are shown in Table 1.

Treatment Liquid A-1 N-Phenylethanolamine 6.0 g Propylene glycol 50.0 g p-t-Butylbenzoic acid 150.0 g Emulgen 147 [trade name, nonionic surfactant manufactured by Kao Corporation] 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] 400.0 g Potassium hydroxide 200.0 g Water 11.5 liters Replenisher A-2 N -Phenylethanolamine 6.0 g Propylene glycol 50.0 g pt-Butylbenzoic acid 150.0 g Emulgen 147 [trade name, nonionic surfactant manufactured by Kao Corporation] 5.0 g Potassium sulfite 400.0 g Gluconic acid solution (50% Aqueous solution) 100.0 g Triethanolamine 25.0 g A silica silicate Lithium [manufactured by Nippon Kagaku Kogyo Co., Ltd.] 500.0 g Potassium hydroxide 400.0 g Water 11.5 liters Comparative Example A1 With the exception that nitrogen gas was not discharged, the other conditions were the same as in Example A1, and the pH and The amount of sludge was measured. The measurement results are shown in Table 1.

Comparative Example A2 SRD-1 as developer and SRD-1R as replenisher
(Both are the developer names of Konica Corporation), except that the development processing method as in Example A1 was used under the other conditions except that the positive type printing plate KM (trade name of Konica Corporation) was used. ). The size of the printing plate is 1003mm x 8
The amount of treatment was 200 mm per day for 3 days, and the pH and sludge amount were measured in the same manner as in Example A1. The measurement results are shown in Table 1.

[0104]

[Table 1]

From the measurement results shown in Table 1, it is possible to effectively prevent the deterioration of the developing solution and the generation of sludge by discharging the nitrogen gas into the processing liquid, as compared with the case where only the floating lid is used. It became clear that it will be done.

The above measurement results showed that the effect was not deteriorated even when the negative and positive common developing solutions were used, and the deterioration of the developing solution and the prevention of sludge could be sufficiently performed.

Example B1 An automatic developing machine using a floating lid as described with reference to FIGS. 1 and 2, in which the floating lid shown in FIG. A, composition B was used as a replenisher, and a floating lid made of an alkali-resistant substance was further charged into the developing tank and the replenisher tank to obtain a positive printing plate K.
M and the negative type printing plate SWN-X (both trade names manufactured by Konica Corporation) were developed. The floating lid shown in FIG. 2 was also used for the replenisher tank.

Polyvinyl chloride was used as the alkali resistant material, and the shape of the floating lid was 5c on each side as shown in FIG.
It has a coma-like shape having a square flat surface of m, and the specific gravity of the developing solution / floating lid made of alkali-resistant substance is 1.2.
It was set to 0. The amount of the floating lid made of the alkali-resistant substance added was 500 cm ³ and covered so that the surface of the treatment liquid was covered by 90%. The amount of nitrogen gas discharged was the same as in Example A1.

The size of the printing plate is 1003 mm × 800 m
m, and processed in the ratio of positive type 4: negative type 1. The processed amount was 200 plates per day, and the amount was processed for 3 days, and the degree of deterioration of the developing solution was detected by measuring the pH.
In addition, 100 ml of the treatment liquid after completion of the treatment is collected at 55 ° C.
After being stored in the drier for 4 days, it was filtered, and the filtered material was further dried at 100 ° C. for 3 hours, and its weight was measured to obtain the amount of sludge. The floating lid was removed and the workability was evaluated. Table 2 shows the results of the above measurement and evaluation.

Comparative Example B1 pH and sludge amount were measured and workability was evaluated under the same conditions as Example B1 except that nitrogen gas was not discharged. The results of measurement and evaluation are shown in Table 2.

Comparative Example B2 In the automatic processor used in Experimental Example B1, the floating lid as shown in FIG. 2 was used, and the specific gravity of the floating lid made of the developing solution / alkali resistant substance was 0.90 in the developing tank. When 500 cm ³ of a floating lid made of the following alkali-resistant substance was put in and used for processing, it was impossible to carry out because of contact with the conveying roller.

Comparative Example B3 The conditions of pH and sludge content were the same as those of Example B1 except that the floating lid made of an alkali-resistant substance was not charged in the replenisher tank but only in the treatment tank. The measurement and workability were evaluated. The results of measurement and evaluation are shown in Table 2.

Comparative Example B4 The conditions were the same as those of Example B1 except that an empty floating lid of the alkali resistant material was placed only in the replenisher tank.
The pH and sludge amount were measured and workability was evaluated.
The results of measurement and evaluation are shown in Table 2.

[0114]

[Table 2]

The workability was evaluated by easing the work when the floating lid was picked up from the treatment tank and the treatment liquid was well cut and did not drip around. Difficult = represented by x.

Example C1 The automatic processor using the floating lid used in Example A1
A negative type printing plate was prepared by using a processing liquid B having the following composition as a processing liquid and a replenishing liquid, using a material which does not discharge nitrogen gas, and developing processing was performed. Washing with water and desensitizing treatment were also performed.

The size of the printing plate is 1003 mm × 800 m
m, the amount processed is 200 editions per day, 3
Treatment for 100 days, 100ml of treatment liquid after treatment
It was separated and stored in a dryer at 55 ° C. for 4 days and then filtered, and the filtered material was dried at 100 ° C. for 3 hours, and the weight was measured to obtain the amount of sludge. In addition, in order to evaluate the odor, use a vacuum collection bottle and collect gas at a position 30 cm above the position of the plate pressing roller of the automatic processor before starting the process and just before the completion of the process. Then, measurement was performed by gas chromatography. Table 3 shows the results of the above measurement and evaluation.

Preparation of Negative Printing Plate The surface of an aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was degreased with 3% sodium hydroxide aqueous solution, and this was degreased in a 2% hydrochloric acid bath at 25 ° C. Electrolytic etching was performed at a current density of 3 A / dm ² . After washing with water, anodization treatment was performed for 2 minutes in a 5.3% sulfuric acid bath under the condition of 1.5 A / dm ² . Next, with a 2% sodium metasilicate aqueous solution,
After sealing at 85 ° C for 10 seconds, washing with hot water at 90 ° C,
It was dried to obtain an aluminum plate as a base.

A photosensitive solution having the following composition was applied to the above aluminum plate using a wire bar, and dried at 80 ° C. for 2 minutes. The film weight after drying was set to be 1.7 g / m ² . The negative photosensitive composition used in the present invention is not limited to the following.

Negative-type photosensitive composition N- (4-hydroxyphenyl) methacrylamide / ethyl acrylate / methyl acrylate / acrylonitrile / methacrylic acid = 10/52/15/15/8 (molar ratio) copolymer (Mw = 60000) 10.0 g Polyacrylic acid (polymerization degree 100) 0.24 g Victoria Pure Blue [made by Hodogaya Chemical Co., Ltd.] 0.1 g Ethylene glycol monomethyl ether 150.0 g Film on the surface of the positive printing plate prepared as described above 70cm with a 2KW metal halide lamp with the originals in close contact
Exposure was performed for 30 seconds from the distance.

Preparation of Positive Printing Plate Using the aluminum plate prepared as described above, a photosensitive solution having the following composition was applied using a wire bar and dried at 80 ° C. for 2 minutes. The film weight after drying was set to be 2.0 g / m ³ . The positive photosensitive composition used in the present invention is not limited to the following.

Positive-type photosensitive composition Novolak resin (phenyl / m-cresol / p-cresol molar ratio 10/54/36, Mw 4000) 6.70 g Pyrogallolacetone resin (Mw: 3000) and naphthoquinone diazide Condensation product of 5-sulfonyl chloride (esterification rate 30%) 1.50 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue [Hodogaya Chemical Co., Ltd.] 0.08 g 2,4-bis (trichloromethyl) -6- (P-Methoxystyryl) -S-triazine 0.15 g Fluorosurfactant FC-430 [Sumitomo 3M] 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.02 g Methyl Cellosolve 100 ml Prepared as described above. A transparent negative film on the surface of the positive printing plate By wearing it was exposed from a distance of 70cm for 60 seconds at a metal halide lamp of 2KW, development processing was carried out by the following treatment solution B.

Treatment liquid B [Negative type, containing 7.2% by weight in the liquid when an organic solvent is used] Benzyl alcohol 720 g Diethanolamine 420 g Perex NBL [trade name, manufactured by Kao Corporation, sodium t-butylnaphthalenesulfonate] 180 g Sulfurous acid Potassium 90 g Water 3 liters Of the above components, the ratio of the amount of components other than water: water was adjusted to 1: 3 for the mother liquor and 1: 3 for the replenisher.

Example C2 The same treatment liquid C was used as the treatment liquid, and the treatment liquid D having the following composition was used as the replenisher. I went.
Table 3 shows the measurement results.

Treatment liquid C [Common to negative type positive type, containing 6.0% by weight of organic solvent] N-phenylethanolamine 60.0 g propylene glycol 500.0 g pt-butylbenzoic acid 150.0 g Emulgen 147 [trade name , Kao company nonionic surfactant] 5.0 g potassium sulfite 300.0 g gluconic acid solution (50% aqueous solution) 100.0 g triethanolamine 250.0 g A potassium silicate [Nippon Kagaku Kogyo KK] 400.0 g potassium hydroxide 200 0.0 g Water 11.5 liter Treatment liquid D [Common to negative type positive type, containing 5.8% by weight of organic solvent] N-phenylethanolamine 60.0 g Propylene glycol 500.0 g p-t-Butylbenzoic acid 150.0 g Emulgen 147 [trade name, nonionic surfactant manufactured by Kao Corporation] 50.0 g sulfurous acid Potassium 400.0 g Gluconic acid solution (50% aqueous solution) 100.0 g Triethanolamine 250.0 g A Potassium silicate [Nippon Kagaku Kogyo] 500.0 g Potassium hydroxide 400.0 g Water 11.5 liter Comparative example C1 treatment liquid Was treated under the same conditions as in Example C1 except that the treatment liquid F described below was used and the treatment liquid G having the following composition was used as a replenisher, and the sludge amount and the odor were measured.
Table 3 shows the measurement results.

Treatment Liquid F [Negative Positive Positive Common, Containing 0.64% by Weight of Organic Solvent] N-Phenylethanolamine 60.0 g Propylene Glycol 50.0 g pt-Butylbenzoic Acid 150.0 g Emulgen 147 [Brand Name] , Kao nonionic surfactant] 5.0 g potassium sulfite 300.0 g gluconic acid solution (50% aqueous solution) 100.0 g triethanolamine 25.0 g potassium silicate [Nippon Kagaku Kogyo] 400.0 g potassium hydroxide 200.0 g Water 11.5 liters Treatment liquid G [Negative positive type common, containing organic solvent 0.0072% by weight] N-phenylethanolamine 60.0 g Propylene glycol 50.0 g pt-Butylbenzoic acid 150.0 g Emulgen 147 [trade name, nonionic surfactant manufactured by Kao Corporation] 5.0 g Potassium sulfate 400.0 g Gluconic acid solution (50% aqueous solution) 100.0 g Triethanolamine 25.0 g A Potassium silicate [Nippon Kagaku Kogyo] 500.0 g Potassium hydroxide 400.0 g Water 11.5 liter Comparative example C2 treatment The following treatment liquid E was used as the liquid, and the treatment liquid E was also used as the replenishing liquid under the same conditions as in Example C1 described above, and the amount of sludge and the odor were measured. Table 3 shows the measurement results.

Treatment liquid E [negative type, containing 3.7% by weight of organic solvent in the liquid when in use] benzyl alcohol 360 g diethanolamine 210 g Perex NBL [trade name, Kao Corporation, sodium t-butylnaphthalene sulfonate] 180 g potassium sulfite 90 g Water 3 liters Of the above components, the ratio of the amount of components other than water to the amount of water was adjusted to 1: 3 for the mother liquor and 1: 3 for the replenisher.

Comparative Example C3 The sludge amount and the odor were measured by treating under the same conditions as in Example C1 except that the floating lid was not used.
Table 3 shows the measurement results.

[0129]

[Table 3]

Embodiment D1 An automatic processor equipped with a floating lid whose swing is regulated by the horizontal direction control member and the vertical direction control member described with reference to FIG. 1 and FIG. In Example C1, the processing liquid F having the above-mentioned composition was used as a negative-working positive type developer, and the processing solution G having the above-mentioned composition was used as a negative-working positive type replenisher using a coating rate of 100%. The positive type printing plate and the negative type printing plate used were developed. The printing plate had a size of 1003 mm × 800 mm and was processed at a ratio of positive type 4: negative type 1. Washing with water and desensitizing treatment were also performed. The amount processed is 200 per day
The plate was processed for 3 days, and the degree of deterioration of the developing solution was detected by measuring the pH. Further, 100 ml of the treated liquid after completion of the treatment was taken, stored in a dryer at 55 ° C. for 4 days and then filtered, and the filtered product was further dried at 100 ° C. for 3 hours, and then its weight was measured. The amount of sludge was used. Further, the contact between the roller and the floating lid (contact property) was visually evaluated. The results of measurement and evaluation are shown in Table 4.

Comparative Example D1 The development processing was carried out under the same conditions as in Example D1 except that the coating rate of the processing liquid surface by the floating lid was 40% and no horizontal and vertical control members were used. The results of measurement and evaluation are shown in Table 4.

Comparative Example D2 Development processing was carried out under the same conditions as in Example D1 except that the function of the horizontal direction control member in the floating lid was stopped. The results of measurement and evaluation are shown in Table 4.

Comparative Example D3 Development processing was performed under the same conditions as in Example D1 except that the function of the vertical direction control member in the floating lid was stopped. The results of measurement and evaluation are shown in Table 4.

[0134]

[Table 4]

Regarding the contact (contactability) between the floating lid and the roller, those that contacted are marked with x, and those that did not contact are marked with ◯.
Displayed in.

[0136]

According to the method and apparatus for treating a photosensitive lithographic printing plate according to the present invention, effects of preventing deterioration of the developer and reducing sludge are recognized, odor control is improved, and work during maintenance is performed. It is recognized that the floating lid is prevented from coming into contact with the roller and being inoperable.

[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 perspective view showing an embodiment of a floating lid.

FIG. 3 is a schematic perspective view showing a control mechanism of a floating lid.

[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 51-Fixed Member 60-Inert gas tank 61-Valve 62-Inert gas discharge port

Front Page Continuation (72) Inventor Hideyuki Nakai 1 Konica, Ltd., Sakura-cho, Hino City, Tokyo (72) Inventor Akio Kasakura 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Sanryo Kasei Co., Ltd. (72) ) Inventor Kenshi Kaneda Sanshisei Kasei Co., Ltd.

Claims (16)

[Claims] 1. A method of dipping a photosensitive lithographic printing plate by guiding and conveying it in a developing solution prepared in a processing tank, in which an inert gas is discharged from the bottom side of the processing tank to move in the liquid level direction. A method for treating a photosensitive lithographic printing plate, which comprises forming a flow of an inert gas and covering the liquid surface of the treatment liquid with the inert gas for treatment. 2. The method for treating a photosensitive lithographic printing plate according to claim 1, wherein a part or all of the liquid surface of the treatment liquid is covered with a floating lid or a cover lid. 3. The method for processing a photosensitive lithographic printing plate as claimed in claim 1, wherein the developing treatment is carried out with a negative or positive type processing solution or a processing solution shared by the negative and positive type processing solutions. 4. A replenishing liquid prepared in a replenishing liquid tank in which an inert gas is discharged from the bottom side, the liquid surface is covered with a floating lid or a cover lid made of an alkali-resistant substance, and the replenishing liquid is supplied to the processing tank. The processing is performed while the processing is performed.
4. The method for processing the photosensitive lithographic printing plate as described in any one of 1 to 3 above. 5. A processing method in which a photosensitive lithographic printing plate is immersed by being guided and conveyed into a developing solution prepared in a processing tank, and a plurality of floating lids made of an alkali-resistant substance are floated on the surface of the processing solution. A method for treating a photosensitive lithographic printing plate, characterized in that a part or all of the liquid surface of the treatment liquid is covered with the plurality of floating lids for treatment. 6. The surface area of the processing liquid is 2000 cm ² to 50.
Is 00cm ^2, with the total volume of the floating lid made of alkali-resistant material to float is 50cm ³ ~3000cm ^3, the thickness of each floating lid is 0.1Cm～10cm, and from developing new chemical / alkali resistance material The method for treating a photosensitive lithographic printing plate as claimed in claim 5, wherein the floating lid has a specific gravity in the range of 1.05 to 1.60. 7. A treatment is carried out while supplying a replenisher solution prepared in a replenisher tank covered with one or a plurality of floating lids of which the liquid surface is partly or wholly made of an alkali-resistant substance to a processing tank. The method for treating a photosensitive lithographic printing plate according to claim 5 or 6, characterized in that. 8. A method of dipping a photosensitive lithographic printing plate by guiding and conveying it into a developing solution prepared in a processing tank, wherein a part or all of the liquid surface of the processing solution is made of an alkali resistant substance. Or cover with a plurality of floating lids and
A method for treating a photosensitive lithographic printing plate, which comprises developing the photosensitive lithographic printing plate with a treatment liquid containing 20% by weight of an organic solvent. 9. An apparatus for dipping a photosensitive lithographic printing plate by transporting it in a developer prepared in a processing tank, wherein a mechanism for discharging an inert gas is arranged at the bottom of the processing tank. Characteristic photosensitive lithographic printing plate processing device. 10. The photosensitive lithographic printing plate processing apparatus according to claim 9, wherein a floating lid made of an alkali-resistant substance is arranged on the liquid surface of the processing liquid. 11. A replenisher, which is prepared in a replenisher tank, is supplied to a treatment tank for processing, and the replenisher in the replenisher tank has a floating surface made of an alkali-resistant substance on the surface of the replenisher. 11. The photosensitive lithographic printing plate according to claim 9 or 10, further comprising a replenishing liquid facility in which a lid is disposed and a mechanism for discharging an inert gas is disposed at a bottom portion of the replenishing liquid tank. Plate processing equipment. 12. An apparatus for dipping a photosensitive lithographic printing plate by transporting it in a developing solution prepared in a processing tank, wherein one or more floating lids made of an alkali-resistant substance are provided on the surface of the processing solution. A photosensitive lithographic printing plate processing apparatus having a floating structure. 13. The surface area of the processing liquid surface is 2000 cm ^{2 to} 5
A 000Cm ^2, with the total volume of the floating lid made of alkali-resistant material to float is 50cm ³ ~3000cm ^3, the thickness of each floating lid is 0.1Cm～10cm, and developing new chemical / alkali resistance The photosensitive lithographic printing plate processing apparatus according to claim 12, wherein the ratio of the specific gravities of the substances is in the range of 1.05 to 1.60. 14. The replenisher tank is configured to perform treatment while supplying the replenisher solution prepared in the replenisher tank to the processing tank, and the replenisher tank is provided with one or more alkali-resistant substances on the surface of the replenisher tank. 14. The photosensitive lithographic printing plate processing apparatus according to claim 12, which has a structure in which a plurality of floating lids are floated. 15. A processing apparatus for dipping a photosensitive lithographic printing plate by guiding and conveying it into a developing solution prepared in a processing tank, wherein a floating lid made of an alkali-resistant substance is provided on the surface of the processing solution in the processing tank. A photosensitive lithographic printing plate processing apparatus, characterized in that it is provided with a control mechanism for restricting the horizontal and / or vertical swing of the floating lid. 16. The photosensitive lithographic printing plate processing apparatus according to claim 8, wherein the photosensitive lithographic printing plate is a negative type.