JPH04328750A - Processing method of photosensitive copying material - Google Patents

Abstract

PURPOSE:To obtain the above copying material capable of conducting the long time maintenance of the processing capacity of a developer and produces a waste liquid in a lesser amt. by removing org. coating layers by a washing stage. CONSTITUTION:The photosensitive copying material successively having the 1st photosensitive org. coating layer which is changed in solubility by photoirradiation and the 2nd org. coating layer contg. a water insoluble and org. solvent soluble high-polymer compd. having film formability on a base is subjected to development processing after image exposing. The 2nd org. coating layer of the non-image parts is removed in the washing stage after immersion in the developer in this method.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing photosensitive copying materials, and more particularly to a method for processing photosensitive copying materials that uses a small amount of developer and is suitable for environmental conservation.

0002

[Prior art and its problems] Photosensitive copying materials containing o-quinonediazide compounds, diazonium salts, photopolymerizable photosensitive materials, and photocrosslinkable photosensitive materials as photosensitive components include photosensitive lithographic printing plates, photosensitive resist materials, and Photosensitive proof materials and the like are known. Among these, a positive-working photosensitive lithographic printing plate that has been widely used conventionally is one in which a photosensitive layer made of an o-quinonediazide compound is provided on an aluminum plate as a support. It is known that an o-quinonediazide compound is converted into a carboxylic acid by exposure to ultraviolet rays. Therefore, when this compound is developed with an alkaline aqueous solution, only the exposed portion of the photosensitive layer is removed and the surface of the support is exposed. Since the surface of the aluminum support is hydrophilic, the exposed areas (non-image areas) of the support during development retain water and repel oil-based ink. On the other hand, the areas (image areas) of the photosensitive layer that are not removed by development are oleophilic, so they repel water and accept ink.

Various alkaline aqueous solutions are known to be used as developing solutions for such positive photosensitive lithographic printing plates, but the most preferred are aqueous solutions of silicates such as sodium silicate and potassium silicate. It is. The reason for this is the ratio of silicon oxide, SiO2, which is a component of silicate, and alkali metal oxide, M2O (generally [SiO2]/[M2O
This is because it is possible to adjust the developability to some extent by changing the molar ratio of

These silicates are used not only in the above-mentioned positive-working photosensitive lithographic printing plates, but also in reversible negative-working photosensitive lithographic printing plates using an o-quinonediazide photosensitive layer described in Japanese Patent Publication No. 56-14970, and dimethyl It is also preferably used as a developer for negative photosensitive lithographic printing plates using a photosensitive layer containing a resin containing a maleimide group in its side chain as a photocrosslinking agent. As mentioned above, the conventional development of these photosensitive copying materials is
The process consists of eluting the photosensitive layer corresponding to the non-image area with a developer to expose the support. Therefore, the concentration of the photosensitive layer components eluted into the developer gradually increases, resulting in the generation of sludge and sludge and a decrease in the processing ability (elution ability) of the developer.

Furthermore, in recent years, automatic developing machines for photosensitive lithographic printing plates have been widely used in the plate-making and printing industries in order to rationalize and standardize plate-making operations. This automatic developing machine generally consists of a device for conveying the photosensitive planographic printing plate, a developer tank, and a spray device.While the exposed photosensitive planographic printing plate is conveyed horizontally, the developer pumped up by a pump is sprayed into the spray nozzle. It is developed by spraying it on.

[0006] Even in the method of developing positive-working photosensitive planographic printing plates using such an automatic developing machine, when a larger amount of photosensitive planographic printing plates are processed, insoluble sludge and sludge are generated at the bottom of the developing tank. Moreover, there were other problems such as clogging of spray pipes and nozzles. As a technique for improving these drawbacks, as disclosed in Japanese Patent Application Laid-Open No. 54-62004 and Japanese Patent Publication No. 57-7427, processing ability is maintained by using a developer replenisher, and the generation of sludge and sludge is prevented. There are techniques to suppress this. Although this made it possible to reduce the generation of insoluble matter, it had the disadvantage that a large amount of waste liquid was discharged. As a technique for improving this drawback, there is a technique disclosed in Japanese Patent Application Laid-Open No. 2-3065,
There is still a strong demand for reducing running costs and waste liquid volume. Particularly today, when environmental conservation is being discussed on a global scale, the reduction of industrial waste is increasingly required.

On the other hand, a typical negative photosensitive copying material includes a photosensitive lithographic printing plate having a photosensitive layer made of a diazonium salt. In addition, in recent years, negative-working photosensitive lithographic printing plates having a photopolymerizable photosensitive layer made of a polymerizable monomer and a photopolymerization initiator, and negative-working photosensitive lithographic printing plates having a photocrosslinkable photosensitive layer made of cinnamic acid, dimethylmaleimide, etc. It has been known.

[0008] In the development of these negative photosensitive lithographic printing plates, as in the case of the above-mentioned positive type, there is a limit to the throughput of the developer, and a large amount of replenisher is required. Moreover, when a large amount of processing is carried out, sludge and sludge are deposited due to the eluted components of the photosensitive layer, and long-term stable processing is still difficult. Apart from this, Special Publication No. 54-21089, No. 37-
Japanese Patent No. 11558 discloses a multilayer photosensitive copying material in which an organic coating layer hardly soluble in a developer is provided on a photosensitive layer made of an o-quinonediazide compound or a photosensitive diazo resin. Such a photosensitive copying material is preferable because it has fewer components eluted into the developer and therefore causes less fatigue of the developer during processing. However, the swollen residue of the organic coating layer scraped off in the developer re-adheres to the copying material or accumulates in the developer, making stable processing over a long period of time impossible.

[0009]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an improved method for processing photosensitive copying materials which allows for the reduction of industrial waste. Another object of the present invention is to provide an improved method for processing photosensitive copying materials, which does not generate insoluble substances even when processing a large amount of photosensitive copying materials for a long period of time, and can stably process the materials. That's true.

0010

[Means for Solving the Problems] As a result of extensive studies to achieve the above object, the present inventors have discovered a method for processing photosensitive copying materials that can minimize the elution of the photosensitive layer into the developer, and the present invention has been made. This is what we have come to realize. That is, the present invention comprises, in order, on a support: (1) a photosensitive first organic coating layer whose solubility changes upon irradiation with light; and (2) a water-insoluble and organic solvent-soluble polymer compound having film-forming ability. In a method in which a photosensitive copying material having a second organic coating layer is imagewise exposed and then developed, the first and second organic coating layers in non-image areas are removed by a step of immersing in the developer and a subsequent washing step. A method of processing photosensitive copying material, characterized in that:

The present invention will be explained in detail below. Support The support used in the photosensitive copying material of the present invention is a dimensionally stable plate-like material. Such supports include paper, paper laminated with plastics (e.g., polyethylene, polypropylene, polystyrene, etc.), e.g.
Aluminum (including aluminum alloys), zinc, iron,
Metal plates such as copper, such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate,
Plastic films such as cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., paper or plastic films laminated with or vapor-deposited with the above metals, and glass plates are used, but in particular, photosensitive When the copying material is a photosensitive printing plate, aluminum plates are preferred.

[0012] In the photosensitive lithographic printing plate as an example of the present invention, an aluminum plate is basically used as a support. Suitable aluminum plates are pure aluminum plates and alloy plates containing aluminum as a main component and a trace amount of other elements, and may also be plastic films laminated or vapor-deposited with aluminum. Different elements contained in aluminum alloys include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by weight
It is as follows. Aluminum suitable for the present invention is pure aluminum, but since completely pure aluminum is difficult to produce due to scouring technology, it may contain a slight amount of a different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly used materials can be used as appropriate. The thickness of the aluminum plate used in the present invention is approximately 0.1
It is about mm to 0.6 mm.

[0013] The aluminum plate is roughened in order to improve its surface water retention and adhesion with the photosensitive layer, but before that, if desired, it may be treated with a surfactant, an organic Degreasing treatment using a solvent or alkaline aqueous solution is performed. The photosensitive lithographic printing plate of the present invention may be usable on only one side, or may be usable on both sides by the same treatment. The following explanation will be limited to the case of single-sided printing, but when producing a photosensitive lithographic printing plate that can be used on both sides, similar treatments may be applied to both sides.

First, the surface of the aluminum plate is roughened, and the methods include mechanical roughening, electrochemical dissolving and roughening, and chemical surface roughening. There is a method of selective dissolution. As a mechanical method, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, etc. can be used. Further, as an electrochemical surface roughening method, there is a method in which alternating current or direct current is used in a hydrochloric acid or nitric acid electrolyte. Furthermore, a method that combines both methods can also be used, as disclosed in Japanese Patent Application Laid-Open No. 54-63902.

[0015] The aluminum plate thus roughened is subjected to alkali etching treatment and neutralization treatment as required, and then subjected to anodization treatment in order to improve the water retention and abrasion resistance of the surface. As the electrolyte used for anodizing the aluminum plate, any electrolyte that forms a porous oxide film can be used, and generally sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of those electrolytes is appropriately determined depending on the type of electrolyte.

The processing conditions for anodic oxidation vary depending on the electrolyte used, so they cannot be specified, but generally the electrolyte concentration is 1 to 80% by weight solution, the liquid temperature is 5 to 70°C, and the current density is 5 to 80%. A range of 60 A/dm2, voltage of 1 to 100 V, and electrolysis time of 10 seconds to 5 minutes is suitable. The amount of the anodic oxide film is preferably 1.0 g/m2 or more, more preferably in the range of 2.0 to 6.0 g/m2. If the anodic oxide film is less than 1.0 g/m2, the printing durability may be insufficient, and the non-image areas of the lithographic printing plate may be easily scratched, resulting in so-called "scratches" where ink adheres to the scratched areas during printing. "dirt" is more likely to occur.

After the anodic oxidation treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. The hydrophilic treatment used in the present invention includes U.S. Patent No. 2,714,0
No. 66, No. 3,181,461, No. 3,280,
There are alkali metal silicate (e.g., aqueous sodium silicate) processes, such as those disclosed in No. 734 and No. 3,902,734. In this method, the support is immersed in an aqueous sodium silicate solution or electrolytically treated.

In particular, potassium fluorozirconate disclosed in Japanese Patent Publication No. 36-22063 and US Pat. Nos. 3,276,868, 4,153,461 and 4,689,272 A method such as treatment with polyvinylphosphonic acid, such as that described in Organic Undercoat Layer The aluminum plate is optionally provided with an organic undercoat layer before coating the photosensitive layer. Examples of organic compounds used in this organic undercoat layer include carboxymethyl cellulose,
It is selected from dextrin, gum arabic, amino acids such as glycine and β-alanine, organic phosphonic acids such as phenylphosphonic acid, and hydrochlorides of amines with hydroxyl groups such as triethanolamine hydrochloride, but two or more types are mixed. It may also be used as

This organic undercoat layer can be provided by the following method. That is, a method in which the above-mentioned organic compound is dissolved in water or an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof is coated on an aluminum plate and dried. An aluminum plate is immersed in a solution of the above organic compound dissolved in an organic solvent or a mixed solvent thereof to adsorb the above organic compound, and then washed with water etc. and dried to form an organic undercoat layer. It's a method. In the former method,
Solutions of the above-mentioned organic compounds at concentrations of 0.005 to 10% by weight can be applied in various ways. For example, any method such as bar coater coating, spin coating, spray coating, curtain coating, etc. may be used. In addition, in the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight.
% by weight, and the immersion temperature is 20-90°C, preferably 2
The temperature is 5 to 50°C, and the immersion time is 0.1 seconds to 20 minutes, preferably 2 seconds to 1 minute.

The pH of the solution used for this is adjusted with a basic substance such as ammonia, triethylamine, potassium hydroxide, etc., or an acidic substance such as hydrochloric acid, phosphoric acid, etc. to a pH of 1 to 1.
A range of 12 can also be used. Further, a yellow dye may be added to improve the tone reproducibility of the photosensitive planographic printing plate. The coating amount of the organic undercoat layer after drying is 2 to 20
0mg/m2 is suitable, preferably 5-100mg
/m2. If the above coating amount is less than 2 mg/m2, sufficient printing durability cannot be obtained. Also, 200mg/m
The same applies even if it is larger than 2.

Back coat layer The back surface of the support layer of the photosensitive planographic printing plate used in the present invention includes:
Even if a coating layer made of an organic polymer compound (hereinafter this coating layer is referred to as a back coat layer) is provided to suppress the elution of the aluminum anodic oxide film and to prevent the photosensitive layer from being damaged when stacked. good. As the material for the back coat layer, an organic polymer compound that is insoluble in an alkaline developer is used, such as polyethylene, polypropylene,
Polybutene, polybutadiene, nylon, polyurethane, polyurea, polyimide, polysiloxane, polycarbonate, epoxy resin, aldehyde condensation resin of alkylphenol, acetal resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylic resin, and copolymer resins thereof, etc. Are suitable.

In addition to these organic polymer compounds, plasticizers, surfactants, and other additives may be added to the backcoat layer, if necessary, for the purpose of imparting flexibility or adjusting slipperiness. The plasticizer is contained up to about 30% by weight based on the resin used for the back coat layer. A surfactant is further added to the back coat layer of the present invention for the purpose of improving slipperiness, coating surface condition, adhesion to the support, etc. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants.

Basically, the thickness of the back coat layer used in the present invention is sufficient as long as it can suppress the elution of the anodic oxide film of aluminum during development, and is 0.01 to 50 μm.
The range is preferably 0.05 to 10 μm, more preferably 0.05 to 10 μm.
is preferred. Various methods can be used to coat the back surface of the aluminum support with the back coat layer. For example, a method of coating and drying a solution in a suitable solvent or an emulsified dispersion, a method of forming a film in advance and bonding it to an aluminum support using an adhesive or heat, and a method of forming a molten film using a melt extruder. Examples include a method of forming the solution and bonding it to a support, but the most preferable method for ensuring the above-mentioned coating amount is a method of applying the solution as a solution and drying it.

First Organic Coverage A first organic coating layer of a positive-working photosensitive composition or a negative-working photosensitive composition is provided on the aluminum plate having a hydrophilic surface thus obtained. Positive-type photosensitive composition The main component of the positive-type photosensitive composition includes an o-naphthoquinone diazide compound. As such o-naphthoquinone diazide compounds, Japanese Patent Publication No. 43-2840
The ester of 1,2-diazonaphthoquinone sulfonic acid and pyrogallol acetone resin described in Publication No. 3 is preferred. Other suitable orthoquinone diazide compounds include, for example, 1,2-diazonaphthoquinone-5-sulfonic acid and phenol- There is an ester with formaldehyde resin,
There are esters of 1,2-diazonaphthoquinone-4-sulfonic acid and phenol-formaldehyde resin described in JP-A-2-96163, JP-A-2-96165, and JP-A-2-96761. Other useful o-naphthoquinone diazide compounds include those known from numerous patents and the like. for example,
JP-A-47-5303, JP-A No. 48-63802, JP-A No. 4
No. 8-63803, No. 48-96575, No. 49-3
No. 8701, No. 48-13354, Special Publication No. 37-18
No. 015, No. 41-11222, No. 45-9610, No. 49-17481, U.S. Patent No. 2,797,
No. 213, No. 3,454,400, No. 3, 5
44,323, British Patent No. 3,573,917, British Patent No. 3,674,495, British Patent No. 3,785,825, British Patent No. 1,227,602, British Patent No. 1,251
, No. 345, No. 1,267,005, No. 1,
Examples include those described in German Patent No. 329,888, German Patent No. 1,330,932, and German Patent No. 854,890.

The o-naphthoquinone diazide compound particularly preferred in the present invention is a compound obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinone sulfonic acid. Specific examples of such compounds are disclosed in JP-A-51-139402 and JP-A-51-139402.
No. 8-150948, No. 58-203434, No. 59
-165053, 60-121445, 60-
No. 134235, No. 60-163043, No. 61-1
No. 18744, No. 62-10645, No. 62-106
No. 46, No. 62-153950, No. 62-17856
No. 2, No. 64-76047, U.S. Patent No. 3,102,
No. 809, No. 3,126,281, No. 3,1
No. 30,047, No. 3,148,983, No. 3,184,310, No. 3,188,210, No. 4,639,406, etc. I can list things that I have.

When synthesizing these o-naphthoquinone diazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-diazonaphthoquinone sulfonic acid chloride to the hydroxyl group of the polyhydroxy compound.
It is more preferable to react in an amount of 0.3 to 1.0 equivalents. 1
, 2-diazonaphthoquinone sulfonic acid chloride, 1,2-diazonaphthoquinone-5-sulfonic acid chloride or 1,2-diazonaphthoquinone-4-sulfonic acid chloride can be used.

The o-naphthoquinone diazide compound obtained is a mixture of compounds having various positions and amounts of 1,2-diazonaphthoquinone sulfonic acid ester groups, but all of the hydroxyl groups are 1,2-diazonaphthoquinone sulfonic acid ester groups. The proportion of the acid esterified compound in this mixture (the content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%.

Normally, the amount of these positive-acting photosensitive compounds (including the above-mentioned combinations) is suitably 10 to 50% by weight, but in the present invention, the photosensitive compound is added to the lower photosensitive layer. It is preferable for the photosensitive layer to be present at a high density in order to make the photosensitive layer thinner and to reduce the amount of substances eluted into the developer. Therefore, the preferred amount of o-quinonediazide compound added is 3
It is 0% by weight or more, more preferably 40% by weight or more.

In addition, as a photosensitive compound that acts in a positive manner without using an o-naphthoquinonediazide compound, for example, a polymer compound having an orthonitrocarbinol ester group described in Japanese Patent Publication No. 56-2696 can also be used in the present invention. can do. Furthermore, a compound that generates an acid upon photolysis, and a -C-O-C group or -C that dissociates with an acid.
Combination systems with compounds having -O-Si groups can also be used in the present invention. For example, a combination of a compound that generates an acid by photolysis and an acetal or an O,N-acetal compound (JP-A-48-89003), a combination with an orthoester or an amide acetal compound (JP-A-51-1998),
No. 120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429)
No.), combination with enol ether compound (Unexamined Japanese Patent Publication No. 1983)
-12995), a combination with an N-acylimino carbon compound (JP-A-55-126236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-1
7345), combinations with silyl ester compounds (JP-A-60-10247) and combinations with silyl ether compounds (JP-A-60-37549, JP-A-60-1)
No. 21446).

Binder Although a photosensitive compound such as an o-quinonediazide compound can constitute the photosensitive layer alone, it is preferable to use a resin soluble in alkaline water as a binder. Such alkaline water-soluble resins include novolac type resins, such as phenol formaldehyde resins, o-, m-, and p-cresol formaldehyde resins, m/p-mixed cresol formaldehyde resins, and phenol/cresol ( o-, m-, p-, m
/p- and o/m-mixtures) mixed formaldehyde resins, and the like.

Also usable are phenol-modified xylene resins, polyhydroxystyrene, polyhalogenated hydroxystyrene, and acrylic resins containing phenolic hydroxyl groups such as those disclosed in JP-A-51-34711. Other suitable binders include copolymers having a molecular weight of usually 10,000 to 200,000 and having the monomers shown in (1) to (13) below as their constituent units. (1) Acrylamides, methacrylamides, acrylic esters, methacrylic esters and hydroxystyrenes having an aromatic hydroxyl group, such as N-(4-hydroxyphenyl)acrylamide or N-(4-hydroxyphenyl)methacrylamide , o-, m- and p-hydroxystyrene, o-
, m- and p-hydroxyphenyl acrylate or methacrylate, (2) acrylic esters and methacrylic esters having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (3) acrylic acid, Unsaturated carboxylic acids such as methacrylic acid, maleic anhydride, itaconic acid, (4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate , (substituted) acrylic esters such as phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 4-hydroxybutyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, methacrylic acid Ethyl, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate,
(Substituted) methacrylic acid esters such as 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylol acrylamide, N-sotylol methacrylate Amide, N-ethylacrylamide, N-
Ethyl methacrylamide, N-hexyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, N-phenylacrylamide, N-phenyl methacrylamide, Acrylamides or methacrylamides such as N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide, ( 7)
Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether; (8) vinyl esters such as vinyl acetate, vinyl chloroacetate, bityl butyrate, and vinyl benzoate; (9) Styrenes such as styrene, methylstyrene, chloromethylstyrene, (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, (1
1) Olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, (12) N
-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc., (13) N-(o-aminosulfonylphenyl)
Acrylamide, N-(m-aminosulfonylphenyl)acrylamide, N-(p-aminosulfonylphenyl)acrylamide, N-[1-(3-aminosulfonyl)naphthyl]acrylamide, N-(2-aminosulfonylethyl)acrylamide, etc. Acrylamides of ) naphthyl] methacrylamide, N-(2-aminosulfonylethyl)methacrylamide, o-aminosulfonylphenyl acrylate,
Unsaturated sulfonamides such as acrylic acid esters such as m-aminosulfonylphenyl acrylate, p-aminosulfonylphenyl acrylate, 1-(3-aminosulfonylphenylnaphthyl)acrylate, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl unsaturated sulfonamides such as methacrylic acid esters such as methacrylate, p-aminosulfonylphenyl methacrylate, and 1-(3-aminosulfonylphenylnaphthyl) methacrylate;

Furthermore, a monomer that can be copolymerized with the above monomer may be copolymerized. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with glycidyl acrylate, glycidyl methacrylate, and the like. The above copolymer preferably contains an unsaturated carboxylic acid listed in (3), and the copolymer preferably has an acid value of 0.
~10meq/g, more preferably 0.5-5meq
/g.

The preferred molecular weight of the above copolymer is 10,000 to 1
It is 00,000. Moreover, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, and an epoxy resin may be added to the above copolymer as necessary. There are one or two kinds of alkaline water-soluble polymer compounds.
More than 8 kinds of photosensitive compositions can be combined.
It is used in an amount of 0% by weight or less.

The positive photosensitive composition of the present invention contains cyclic acid anhydrides, phenols,
It is preferable to add organic acids. Examples of cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 3,6-endoxy-Δ4 described in U.S. Pat. No. 4,115,128.
-Tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride, etc. can be used.

[0035] As a phenol, bisphenol A
, p-nitrophenol, p-ethoxyphenol, 2
, 4,4'-trihydroxybenzophenone, 2,3,
4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4',4''-trihydroxy-triphenylmethane, 4,4',3'',4''-tetrahydroxy-3,5,3',5'- Examples include tetramethyltriphenylmethane.

Furthermore, as organic acids, JP-A-60-8
These include sulfonic acids, sulfinic acids, alkyl sulfuric acids, phosphonic acids, phosphoric esters, and carboxylic acids, which are described in JP-A No. 8942 and JP-A-2-96755, and specifically p-toluenesulfone. Acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,
4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1
, 4-cyclohexene-2,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like.

The proportion of the above cyclic acid anhydrides, phenols and organic acids in the positive photosensitive composition is 0.
．． 05 to 15% by weight is preferable, more preferably 0.1
~5% by weight. In addition, in the positive photosensitive composition of the present invention, in order to widen the processing stability (so-called development latitude) with respect to development conditions,
Nonionic surfactants such as those described in Japanese Patent Application No. 1740 and Japanese Patent Application No. 181248/1989,
Ampholytic surfactants such as those described in Japanese Patent Application No. 121044 and Japanese Patent Application No. 115992/1999 can be added.

Specific examples of nonionic surfactants include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, and polyoxyethylene nonylphenyl ether. Specific examples of amphoteric surfactants include alkyl di(
aminoethyl)glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-
N-hydroxyethylimidazolinium betaine and N-
Tetradecyl-N,N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and alkylimidazoline type (for example, trade name Levon 15, manufactured by Sanyo Chemical Co., Ltd.)
(manufactured by).

The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive composition is 0.05 to 15
It is preferably 0.1 to 5% by weight, more preferably 0.1 to 5% by weight. A print-out agent for obtaining a visible image immediately after exposure, and a dye or pigment as an image coloring agent can be added to the positive photosensitive composition of the present invention. A representative example of the printout agent is a combination of a compound that releases an acid upon exposure to light (photoacid release agent) and an organic dye that can form a salt. Specifically, Japanese Patent Publication No. 50-3620
No. 9 and No. 53-8128.
-A combination of naphthoquinone diazide-4-sulfonic acid halide and a salt-forming organic dye, and JP-A-53-36223
No. 54-74728, No. 60-3626, No. 6
Combinations of trihalomethyl compounds and salt-forming organic dyes described in Japanese Patent Publications No. 1-143748, No. 61-151644, and No. 63-58440 can be mentioned. Such trihalomethyl compounds include oxazole compounds and triazine compounds, both of which have excellent stability over time and provide clear printed images.

In addition to the above-mentioned salt-forming organic dyes, other dyes can be used as image coloring agents. Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic dyes. Specifically, oil yellow #101, oil yellow #103, oil pink #312, oil green BG, oil blue BOS,
Oil Blue #603, Oil Black BY, Oil Black BS, Oil Black T-505 (manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201
5), etc. Also, JP-A-62-2
The dyes described in Japanese Patent No. 93247 are particularly preferred.

These print-out agents and dyes may be added to the second organic coating layer, which will be described later, or to both the first and second layers. The positive photosensitive composition in the present invention is
The above components are dissolved in a solvent and applied onto an aluminum plate as a support. As the solvent used here, organic solvents such as those described in JP-A-62-251739 may be used alone or in combination.

The positive photosensitive composition of the present invention has a photosensitive composition of 0.2 to
It is dissolved and dispersed at a solid content concentration of 20% by weight, coated on a support, and dried. The coating amount of the positive photosensitive composition layer (photosensitive layer) coated on the support varies depending on the application, but
Generally, the weight after drying is 0.03 to 2.0 g/
m2 is preferred. More preferably 0.2 to 1.5 g/m
It is 2. As the coating amount decreases, the amount eluted into the developer decreases, but it becomes difficult to remove the second organic coating layer, which will be described later, from the support. On the other hand, as the coating amount increases, the second organic coating layer becomes easier to remove, but the amount eluted into the developer increases, promoting fatigue of the developer.

The positive photosensitive composition of the present invention may contain a surfactant for improving the coated surface quality, such as a fluorine-containing surfactant as described in JP-A-62-170950. can be added. The amount added is preferably 0.001 to 1.0% by weight, more preferably 0.005 to 0.5% by weight of the total photosensitive composition. Negative photosensitive composition Examples of the negative photosensitive composition used in the present invention include a photosensitive composition containing a photosensitive diazo compound, a photopolymerizable photosensitive composition, a photocrosslinkable photosensitive composition, etc. However, among these, a photocurable photosensitive composition comprising a photosensitive diazo compound will be explained in detail by giving an example.

The photosensitive diazo compound used in the negative photosensitive copying material of the present invention is an aromatic diazonium salt and a reactive carbonyl group-containing organic condensing agent, particularly aldehydes or acetals such as formaldehyde and acetaldehyde. A diazo resin condensed in a medium is preferably used. The most typical example is a condensate of p-diazodiphenylamine and formaldehyde. Synthesis methods for these diazo resins are described, for example, in U.S. Pat.
No. 679,498, No. 3,050,502, No. 3,311,605 and No. 3,277,074
It is stated in the specification of No.

There are diazo resins using inorganic anions such as mineral acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, and phosphoric acid or double salts with zinc chloride as the counter anions of these diazonium salts, but they do not contain water substantially. Diazo resins that are insoluble and soluble in organic solvents are particularly preferred. Such preferred diazo resins are disclosed in Japanese Patent Publication No. 47-1167 and U.S. Pat. No. 3,300,30.
Details are described in Publication No. 9.

Furthermore, Japanese Patent Application Laid-open No. 54-98613 and 56
Diazo resins containing halogenated Lewis acids such as tetrafluoroboric acid and hexafluorophosphoric acid and perhalogen acids such as perchloric acid and periodic acid as counteranions as described in Japanese Patent No. 121031 are preferably used. It will be done. Also, JP-A-58-209733, JP-A No. 62-1757
Diazo resins having a sulfonic acid having a long chain alkyl group as a counter anion, which are described in Japanese Patent No. 31 and No. 63-262643, are also suitably used.

[0047] The photosensitive diazo compound is usually contained in the photosensitive layer.
It is contained in an amount of 50% by weight, generally in the range of 8 to 20% by weight, but in the photosensitive copying material used in the present invention, the photosensitive material is present at high density in the underlying photosensitive layer, which makes the photosensitive layer thin. It is preferable because it can be layered and the amount of substances eluted into the developer can be reduced. Therefore, the amount of the diazo compound added is preferably 30% by weight or more, more preferably 50 to 100% by weight based on the total solid content of the photosensitive layer.

In the photosensitive diazo compound used in the present invention, it is preferable to use a lipophilic polymer compound that is soluble or swellable in alkaline water as a binder. As such lipophilic polymer compounds, compounds (1) to (
13) Usually 10,000~
Although a copolymer having a molecular weight of 200,000 can be used, polymer compounds obtained by copolymerizing the monomers shown in (14) and (15) as constituent units can also be used. (14)
maleimide, N-acryloyl acrylamide, N
-acetylacrylamide, N-propionylacrylamide, N-(p-chlorobenzoyl)acrylamide, N-acetylacrylamide, N-acryloylmethacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N-(p-chlorobenzoyl) unsaturated imides such as methacrylamide, (15)
N-[2-(acryloyloxy)-ethyl]-2
, 3-dimethylmaleimide, N-[2-(methacryloyloxy)-ethyl]-2,3-dimethylmaleimide,
Unsaturated monomers with crosslinking groups in their side chains, such as vinyl cinnamate.

Furthermore, a monomer that can be copolymerized with the above monomer may be copolymerized. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with glycidyl acrylate, glycidyl methacrylate, and the like. The above copolymer preferably contains an unsaturated carboxylic acid listed in (3), and the copolymer preferably has an acid value of 0.
~10meq/g, more preferably 0.2-5.0m
eq/g.

The preferred molecular weight of the above copolymer is 10,000 to 1
It is 00,000. Moreover, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, and an epoxy resin may be added to the above copolymer as necessary. Further, novolak type resins, phenol-modified xylene resins, polyhydroxystyrene, polyhalogenated hydroxystyrenes, and alkali-soluble resins containing phenolic hydroxyl groups such as those disclosed in JP-A-51-34711 can also be used. can.

[0051] Such alkali-soluble polymer compounds can be used alone or in combination of two or more types,
It is contained in the solid content of the total photosensitive composition in a range of 0 to 50% by weight. A plasticizer is added to the negative photosensitive composition of the present invention to impart flexibility and abrasion resistance to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate,
Dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate,
Mention may be made of oligomers and polymers of acrylic acid or methacrylic acid, of which tricresyl phosphate is particularly preferred.

In addition, in the negative photosensitive composition of the present invention, for example, phosphoric acid,
Phosphorous acid, citric acid, oxalic acid, dipicolinic acid, benzenesulfonic acid, naphthalenesulfonic acid, sulfosalicylic acid,
4-methoxy-2-hydroxybenzophenone-5-sulfonic acid, tartaric acid, etc. are added. A printing-out agent for obtaining a visible image immediately after exposure, and pigments such as dyes and pigments as image coloring agents can be added to the negative photosensitive composition of the present invention.

[0053] As the pigment, those that change color tone by reacting with free radicals or acids are preferably used. For example, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical), Oil Yellow #101, Oil Yellow #103
, Oil Pink #312, Oil Red, Oil Green BG, Oil Blue BOS, Ocle Blue #603,
Oil Black BY, Oil Black BS, Oil Black T-505 (manufactured by Orient Chemical Industry Co., Ltd.)
, Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI1451701B), Malachite Green (CI42000), Methylene Blue (CI52015)
), triphenylmethane type, diphenylmethane type represented by brilliant blue, methylene green, erythricin B, basic fuchsin, m-cresol purple, auramine, 4-p-diethylaminophenyl iminaphthoquinone, cyano-p-diethylaminophenyl acetanilide, etc. Examples include oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes that change from colored to colorless or a different colored tone.

On the other hand, examples of discoloration that changes from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3
-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p,p'-bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p,p
',p''-tris-dimethylaminotriphenylmethane, p,p'-bis-dimethylaminodiphenylmethylimine, p,p',p''-triamino-o-methyltriphenylmethane, p,p'-bis- Dimethylaminodiphenyl-4-anilinonaphthylmethane, p, p', p''-
Examples include primary or secondary arylamine dyes represented by triaminotriphenylmethane.

Particularly preferred are triphenylmethane-based and diphenylmethane-based dyes, and even more preferred are triphenylmethane-based dyes, particularly Victoria Pure Blue BOH. The above dye is usually contained in the negative photosensitive composition in an amount of about 0.5 to 10% by weight, more preferably about 1 to 5% by weight.

These print-out agents and dyes may be added to the second organic coating layer, which will be described later, or to both the first and second layers. Cyclic acid anhydrides, phenols, organic acids, and higher alcohols can be added to the negative photosensitive composition of the present invention in order to improve developability. The negative photosensitive composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto an aluminum plate as a support. The solvent used here is JP-A No. 6
Organic solvents such as those described in Japanese Patent No. 2-251739 may be used alone or in combination.

[0057] The negative photosensitive composition of the present invention has a
It is dissolved and dispersed at a solid content concentration of 20% by weight, coated on a support, and dried. The coating amount of the negative photosensitive composition layer (photosensitive layer) coated on the support varies depending on the application, but
As in the case of positive type, the weight after drying is generally preferably 0.03 to 2.0 g/m2. More preferably, it is 0.2 to 1.5 g/m2. As the coating amount decreases, the amount eluted into the developer decreases, but the second organic coating layer becomes more difficult to remove from the support. On the other hand, as the coating amount increases, the second organic coating layer becomes easier to remove, but the amount eluted into the developer increases, promoting fatigue of the developer.

The negative photosensitive composition of the present invention also contains a surfactant for improving the coated surface quality, such as a fluorine-containing surfactant as described in JP-A-62-170950. can be added. The amount added is preferably 0.001 to 1.0% by weight, more preferably 0.005 to 0.5% by weight of the total photosensitive composition. Second Organic Coating Layer The photosensitive copying material used in the present invention has a second organic coating layer, which is hardly soluble in a developer and permeable to the developer, provided on the photosensitive layer described above. This second organic coating layer is made of a water-insoluble, organic solvent-soluble polymer compound that has film-forming ability.

The polymer compound useful for forming the second organic coating layer of the present invention is a homopolymer of monomers selected from the following group A, a copolymer of two or more monomers selected from the following group A, or A polymer compound obtained by copolymerizing at least one monomer selected from Group A and Group B, or a polymer compound obtained by combining them with at least one monomer from Group C. Group A: Monomer CHX=CYZ represented by the following general formula [wherein, X: hydrogen atom, methyl group, or -COOR1 group Y: hydrogen atom, methyl group, or -(CH2)nCOOR2,
Halogen, nitrile, Z: aryl group, -COOR3, -OR3,
-O-COR3, -CONR3, halogen, nitrile R1, R2, R3: these may be the same or different, aliphatic group or aromatic group n: integer from 0 to 3] Group B: free carboxylic acid An ethylene monomer having at least one group, a sulfonic acid group, a phosphoric acid group, or a salt thereof.

A hydroxyalkyl ester or amide of the carboxylic acid. Group C: divinyl monomer. In the general formula of Group A, among the groups represented by R1 to R3, aliphatic groups include direct or branched alkyl groups (including cyclic ones) and substituted alkyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 12.

Examples of the substituent of the substituted alkyl group include an aryl group, an aryloxy group, a halogen atom, a cyano group, an acyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, and an amino group (including a substituted amino group. Alkyl group, aryl group, etc.The number of substituents is 1 to
2), hydroxy group, alkoxy group, heterocyclic residue (heteroatoms include, for example, oxygen atom, nitrogen atom,
such as sulfur atoms. The number of members in the ring is preferably 5 to 6, and the ring may be unsaturated or saturated. An aromatic ring may be further fused to the heterocycle. ), etc.

Of the groups represented by R1 to R3, the aryl group naturally includes substituted phenyl groups and naphthyl groups, and the substituents include the substituents listed above with respect to the substituted alkyl groups. Examples include alkyl groups. Examples of monomers in Group A include monofunctional monomers such as acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, and styrenes.

Further, specific monomers include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-
Butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2
-Phenoxyethyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2
-Acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl- 3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxyethyl acrylate, 2-
Butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of moles added n = 9), 1-bromo-2-methoxyethyl acrylate , 1,1-dichloro-2-ethoxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate,
Octyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate , 2-hydroxyethyl methacrylate,
3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, acetoacetoxyethyl methacrylate,
2-Ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy) Ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (additional mole number n = 6), vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl dimethyl propionate, vinyl ethyl butyrate, vinyl valerate, Vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzyl Styrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorstyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlor Styrene, bromstyrene, dibromstyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, vinylbenzoic acid methyl ester, crotonic acid Butyl, hexyl crotonate, glycerin monocrotonate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dihexyl fumarate, dibutyl methyl acrylamide fumarate, ethyl Acrylamide, propylacrylamide, isopropylacrylamide, butylacrylamide, t
ert-butylacrylamide, heptylacrylamide, tert-octylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethyl acrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, hydroxyethylacrylamide, phenylacrylamide, hydroxyphenylacrylamide, tolylacrylamide, naphthylacrylamide, dimethyl acrylamide,
Diethylacrylamide, dibutylacrylamide, diisobutylacrylamide, N-(1,1-dimethyl-
3-oxobutyl) acrylamide, methylbenzylacrylamide, benzyloxyethylacrylamide,
β-cyanoethyl acrylamide, acryloylmorpholine, N-methyl-N-acryloylpiperazine, N-
Acryloylpiperidine, N-(1,1-dimethyl-3
tert
-Butylmethacrylamide, tert-octylmethacrylamide, benzylmethacrylamide, cyclohexylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, dipropylmethacrylamide, hydroxyethyl-N-methylmethacrylamide, N-methyl-N -Phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide, methacrylhydrazine, etc.; Allyl compounds: For example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate , allyl acetoacetate, allyl lactate, allyloxyethanol, allyl butyl ether, allyl phenyl ether, etc.; vinyl ethers:
For example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, Hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl ketones:
For example, methyl vinyl ketone, phenyl vinyl ketone,
Methoxyethyl vinyl ketone, etc.; Olefins: for example, dicyclopentadiene, ethylene, propylene, 1
-butene, 1-pentene, 1-hexene, 4-methyl-
1-pentene, 1-heptene, 1-octene, 1-decene, 5-methyl-1-nonene, 5,5-dimethyl-1-
Octene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 5-methyl-1-hexene, 4-methyl-1-heptene, 5-methyl-1-heptene, 4,
Unsubstituted hydrocarbons such as 4-dimethyl-1-hexene, 5,5,6-trimethyl-1-heptene, 1-dodecene and 1-octadecene; diene compounds such as butadiene, isoprene, and chloroprene; vinyl heterocyclic compounds ( The heteroatoms include, for example, nitrogen atoms, oxygen atoms, sulfur atoms, etc., and the number of members of the heterocyclic ring is, for example, 5 to 6, and an aromatic ring may be further bonded to this ring.): For example, N
-Vinyloxazolidone, vinylpyridine, vinylpicoline, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyltriazole, N-vinyl-3,5-dimethyltriazole, N-vinylpyrrolidone, N-vinyl-3 , 5-dimethylpyrazole, N-vinylcarbazole, vinylthiophene, N-vinylsuccinimide, N-vinylglutarimide, N-vinyladipimide, N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinyl- 2
-pyridone, etc.; unsaturated nitriles; for example, acrylonitrile, methacrylonitrile, etc.; halogenated vinyl compounds; vinyl chloride, vinylidene chloride, vinyl bromide, vinyl iodide, etc.

Specific examples of monomers of group B include the following monofunctional monomers. acrylic acid,
Methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (e.g. monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.), monoalkyl maleate (e.g. monomethyl maleate, monoethyl maleate, monobutyl maleate, monomaleate) octyl, etc.), citraconic acid, styrene sulfonic acid,
Vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, (e.g., acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, acryloyloxybutylsulfonic acid, etc.), methacryloyloxyalkylsulfonic acid ( For example, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, methacryloyloxybutylsulfonic acid, etc.)
Acrylamidoalkylsulfonic acids (e.g. 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.), methacrylamidealkylsulfonic acids (e.g. 2-acrylamidoalkylsulfonic acid) methacrylamide-2-methylethyl sulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.), acryloyloxyalkyl phosphates (e.g. acryloyloxyethyl phosphate, 3-acryloyl oxypropyl phosphate, etc.), methacryloyloxyalkyl phosphates (eg, methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl phosphate, etc.), and the like.

The alkyl group in the acid monomer has, for example, about 1 to 8 carbon atoms. These acids contain alkali metal ions (preferably Na+, K+
) or a salt of ammonium ion. Specific examples of monomers of group C include unsaturated esters of polyols, especially esters such as α-methylenecarboxylic acid, such as ethylene di(meth)acrylate, diethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, glycerol triacrylate, etc. (meth)acrylate, 1,3-propylene di(meth)acrylate, 1
, 4-cyclohexanediol (meth)acrylate,
1,4-benzenediol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,
3-propylene glycol di(meth)acrylate, 1
, 5-pentanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate. Unsaturated amides, especially those of α-methylenecarboxylic acid and especially those of α,ω-diamines and ω-diamines with intermediate oxygen, such as methylene bis(meth)acrylamide, ethylene bis(meth)acrylamide, 1,6- hexamethylene bis(meth)acrylamide and diethylenetriamitris(meth)acrylamide, divinyl succinate, divinyl adipate, divinyl phthalate,
Divinyl terephthalate, divinylbenzene-1,3-
Vinyl esters such as disulfonate and divinylbutane-1,4-disulfonate, unsaturated aldehydes such as sorbaldehyde or 2,4-hexadienal.

Neutral α-methylene carboxylic acid polyesters such as (meth)acrylates, (meth)acrylamides, polyamides and/or primary and secondary amino alcohols, aminopolyols or polyamino alcohols or esteramides of polyols and the above. Similar derivatives of alcohols, such as β-methacrylamidoethyl (
meth)acrylamide, N-(β-hydroxyethyl)
-β-(methacrylamide)ethyl acrylate, N
, N-bis(β-methacryloxyethyl)acrylamide, and other urethane compounds from divinylbenzene, xylylene diisocyanate, and hydroxyethyl (meth)acrylate, such as those having the chemical structure below.

[0067]

[Chemical formula 1]

Urethane compounds made from isocyanates and hydroxyalkyl compounds such as ##STR1## are useful. In addition, in the above, "(meth)acrylate" means both "acrylate" and "methacrylate",
"(Meth)acrylamide" also means the same thing. The ratio of Group A, Group B, and Group C in the above-mentioned polymer compound can be appropriately selected in consideration of the performance of the applied second organic coating layer, such as developability, ink receptivity, and printing durability. . The monomer components of group A mainly control ink receptivity and printing durability. Therefore, the amount of the Group A monomer component is preferably 20 to 100% by weight, particularly preferably 60 to 100% by weight, based on the solid content of the polymer compound.

The amount of the group B monomer component is preferably 0 to 25% by weight, particularly 0 to 10% by weight of the solid content of the polymer compound.
is suitable. The C group monomer component is preferably 0 to 80% by weight, particularly preferably 0 to 40% by weight. In addition to the above-mentioned copolymerizable polymer compounds, for example, acetal resins such as formal resins or butyral resins, cellulose esters such as cellulose acetate, cellulose propionate, cellulose butyrate, and cellulose crotonate, and combinations of these ester compounds with phthalic acid, succinic acid, etc. acid, coester compounds with dicarboxylic acids such as sebacic acid and maleic acid, methylcellulose, ethylcellulose, propylcellulose, butylcellulose, allylcellulose, benzylcellulose,
Examples include cellulose ether compounds such as cyclohexylcellulose and cyanoethylcellulose, polyesters, polyamides, polyurethanes, polyureas, polyimides, epoxy resins, aldehyde condensation resins of alkylphenols, and shellac. These polymer compounds have hydroxyl, amino, amide,
Those containing at least one group selected from imino, imido, nitrilo, carboxyl, sulfonyl, sulfonoxy, isocyanate, urethane, azoimide, azo, hydrazino, carbamide, carbamyl, epoxy, mercapto, thio, and sulfonamido groups are preferred. .

The polymer compound used in the present invention can range from oligomers to high molecular weight compounds, ranging from about 2,000 to about 200,000 in molecular weight. These polymer compounds may be used alone, but by mixing a plurality of them, it is possible to adjust the permeability and swelling property of the second organic coating layer to the developer, and to adjust the film properties. can.

The degree of solubility of the second organic coating layer in the developer described above is relative to the strength of the developer. As is well known, the strength of the developer for an o-quinonediazide photosensitive layer varies depending on its composition, and it is possible to select a developer having a strength suitable for the photosensitive layer. Therefore,
The polymer compound that can be used for the second organic coating layer is difficult to limit due to general solubility and swelling properties, and the polymer compound used for the second organic coating layer is determined according to the selected components of the first organic coating layer and the components of the developer. The polymeric compound of the layer is also suitably selected.

[0072] The second organic coating layer also contains o
- A quinonediazide compound can be added as a developer penetration enhancer, but if the amount added is too large, the amount of components eluted into the developer increases, which is not suitable for the purpose of the present invention. Therefore, the amount of the o-quinonediazide compound added is preferably 20% or less. Furthermore, various organic and inorganic additives can be added to the second organic coating layer as desired. For example, dyes or pigments as image colorants, print-out agents, fillers such as titanium dioxide or clay to improve the physical strength of the coating, or plasticizers to accelerate development, and The mentioned acid anhydrides, organic acids and phenols, etc. can be added.

Furthermore, stabilizers, surfactants, plasticizers and the like can be added as appropriate. In particular, it is preferable to add a surfactant to improve the coated surface quality, for example, a fluorine-based surfactant as described in JP-A-62-170950. The amount added is preferably 0.001 to 1.0% by weight, more preferably 0.005 to 0.5% by weight, based on the total organic coating layer.

The second organic coating layer is applied onto the photosensitive layer using a coating technique such as solution coating, casting, transfer or simultaneous multilayer coating and is dried. As the solvent used here, organic solvents such as those described in JP-A No. 62-251739 are used, but among these, alcohols and hydrocarbons, which are poor solvents for o-quinonediazide compounds, are particularly useful. be.

Alternatively, methods such as melt lamination and film heat fusion may also be used. The preferred coating amount of the second organic coating layer is 0.1 to 5.0 g/m in weight after drying.
2, more preferably 0.5 to 3.0 g/m2. If the coating amount of the second organic coating layer is smaller than this range, the strength of the image on the photosensitive copying material will be inferior, and if it is larger than this range, it will take time for the developer to penetrate, making it impossible to obtain a desirable image.

Matte layer The surface of the second organic coating layer provided as described above is coated with a matte layer in order to shorten the evacuation time during contact exposure using a vacuum printing frame and to prevent printing blur. Preferably, a layer is provided. Specifically, JP-A-50-125805
A method of providing a matte layer as described in Japanese Patent Publication No. 57-6582 and Japanese Patent Publication No. 61-28986,
Examples include a method of heat-sealing solid powders as described in Japanese Patent Publication No. 62-62337.

Actinic rays The photosensitive copying material thus obtained is exposed to active rays from a carbon arc lamp, mercury lamp, metal halide lamp, xenon lamp, tungsten lamp, etc. as a light source through a transparent original, and then developed. Developer: A conventional aqueous alkali solution can be used as the developer for the photosensitive copying material. For example, sodium silicate, potassium, tertiary sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium,
Inorganic alkaline agents such as ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium can be mentioned. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkaline agents such as ethyleneimine, ethylenediamine, and pyridine are also used.

These alkaline agents may be used alone or in combination of two or more. Among these alkaline agents, the most preferred are aqueous solutions of silicates such as sodium silicate and potassium silicate. The reason is that the ratio of silicon oxide (SiO2), which is a component of silicate, and alkali metal oxide (M2O) (generally [SiO2]/[M2O
This is because it is possible to adjust the developability to some extent by changing the molar ratio of ) and the concentration.
SiO2 as disclosed in Publication No. 2004
/Na2O molar ratio of 1.0 to 1.5 (i.e. [SiO
2]/[Na2O] is 1.0 to 1.5),
An aqueous solution of sodium silicate with an SiO2 content of 1 to 4% by weight, or a solution with [SiO2]/[M] of 0.5 to 0.
75 (i.e. [SiO2]/[M2O] is 1.0~
1.5), and the concentration of SiO2 is 1 to 4% by weight
Alkali metal silicates are preferably used, wherein the developer solution contains at least 20% potassium, based on the total alkali metal gram atoms present therein.

When developing the photosensitive copying material using an automatic processor, by adding an aqueous solution (replenisher) with a higher alkaline strength than the developer to the developer, the developer in the developer tank can be kept for a long time. It is known that large quantities of photosensitive copying material can be processed without having to be replaced. This replenishment method is also preferably applied in the present invention. For example, the molar ratio of SiO2/Na2O in a developer as disclosed in JP-A-54-62004 is 1.
0 to 1.5 (that is, [SiO2]/[Na2O] is 1
．． 0 to 1.5), and the SiO2 content is 1 to 1.5).
An aqueous solution of 4% by weight of sodium silicate is used, and depending on the throughput of the positive-working photosensitive lithographic printing plate, the molar ratio of SiO2/Na2O is 0.5 to 1.
5 (that is, [SiO2]/[Na2O] is 0.5 to 1
．． 5) The method of adding an aqueous sodium silicate solution (replenisher) to the developer, and the method disclosed in Japanese Patent Publication No. 57-7427, in which [SiO2]/[M] is 0.5 to 0
．． 75 (that is, [SiO2]/[M2O] is 1.
0 to 1.5), and the concentration of SiO2 is 1 to 4% by weight.
[M] is 0.25 to 0.75 (i.e. [SiO2]/
[M2O] is from 0.5 to 1.5, and both the developer and the replenisher contain at least 20% potassium based on the total alkali metal gram atoms present therein. A developing method comprising the following steps is preferably used. Furthermore, in order to reduce running costs and waste liquid volume,
As a highly active developer, an aqueous solution of an alkali metal silicate with a SiO2/M2O molar ratio of 0.7 to 1.5 and an SiO2 concentration of 1.0 to 4.0% by weight is used. A system in which the replenisher is an aqueous solution of an alkali metal silicate with a SiO2/M2O molar ratio of 0.3 to 1.0 and an SiO2 concentration of 0.5 to 4.0% by weight is also suitable. used for.

[0080] Various surfactants and organic solvents can be added to the developer and replenisher used in the present invention, if necessary. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyrylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, and sorbitan. Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters,
Polyoxyethylene sorbitan fatty acid partial esters,
Polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylene castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N,N-bis-2 -Nonionic surfactants such as hydroxyalkylamines, polyoxyethylenealkylamines, triethanolamine fatty acid esters, trialkylamine oxides, fatty acid salts, abietates, hydroxyalkanesulfonates, alkanesulfonates, dialkyl Sulfosuccinic acid ester salts, linear alkylbenzene sulfonates, branched chain alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylphenoxypolyoxyethylene propyl sulfonates,
Polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt,
N-alkylsulfosuccinic acid monoamide disodium salt,
Petroleum sulfonates, sulfated tallow oil, sulfate ester salts of fatty acid alkyl esters, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, fatty acid monoglyceride sulfate ester salts, polyoxyethylene alkyl phenyl ether sulfate ester salts, polyoxy Ethylene styryl phenyl ether sulfate ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkyl phenyl ether phosphate ester salts, partially saponified products of styrene/maleic anhydride copolymer, olefins /Anionic surfactants such as partially saponified maleic anhydride copolymers, naphthalene sulfonate formalin condensates, alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, etc. Cationic surfactants, carboxybetaines, aminocarboxylic acids,
Examples include amphoteric surfactants such as sulfobetaines, aminosulfate esters, and imidazolines. Among the surfactants listed above, polyoxyethylene can be read as polyoxyalkylene such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc., and these surfactants are also included.

A more preferred surfactant is a fluorine-based surfactant containing a perfluoroalkyl group in the molecule. Such fluorine-based surfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates, amphoteric types such as perfluoroalkyl betaines,
Cationic type and perfluoroalkylamine oxides such as perfluoroalkyltrimethylammonium salts, perfluoroalkylethylene oxide adducts, oligomers containing perfluoroalkyl groups and hydrophilic groups,
Nonionic types include oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic and lipophilic groups, and urethanes containing perfluoroalkyl groups and lipophilic groups.

The above-mentioned surfactants can be used alone or in combination of two or more, and can be used in a developer solution containing 0.
It is added in an amount of 0.001 to 10% by weight, more preferably 0.01 to 5% by weight. Suitable organic solvents are those having a solubility in water of about 10% by weight or less, preferably 5% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1
-butanol, 2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4 - methylcyclohexanol,
Examples include N-phenylethanolamine and N-phenyldiethanolamine. The content of the organic solvent is 0.1 to 5% by weight based on the total weight of the liquid used. The amount used is closely related to the amount of surfactant used.
Preferably, as the amount of organic solvent increases, the amount of surfactant increases. This is because the amount of surfactant is small, and if a large amount of organic solvent is used, the organic solvent will not be completely dissolved.
Therefore, ensuring good developability cannot be expected.

A reducing agent is further added to the developer and replenisher used in the present invention. This prevents staining of printing plates, and is particularly effective when developing negative photosensitive lithographic printing plates containing photosensitive diazonium salt compounds. Preferred organic reducing agents include thiosalicyl, hydroquinone, metol, methoxyquinone, resorcinol,
- Phenol compounds such as methylresorcin, amine compounds such as phenylenediamine and phenylhydrazine. More preferred inorganic reducing agents include sodium salts, potassium salts, and ammonium salts of inorganic acids such as sulfite, hydrogen sulfite, phosphorous acid, hydrogen phosphite, dihydrogen phosphite, thiosulfate, and dithionite. Examples include salt. Among these reducing agents, sulfites are particularly effective in preventing staining. These reducing agents are preferably contained in the developing solution in an amount of 0.05 to 5% by weight.

[0084] An organic carboxylic acid can also be added to the developer and replenisher used in the present invention. Preferred organic carboxylic acids are aliphatic carboxylic acids and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of aliphatic carboxylic acids include caproic acid, enantylic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, and stearic acid, with those having 8 carbon atoms being particularly preferred.
~12 alkanoic acids. Further, it may be an unsaturated fatty acid having a double bond in the carbon chain or a branched carbon chain.

Aromatic carboxylic acids include compounds in which a carboxyl group is substituted on a benzene ring, naphthalene ring, anthracene ring, etc. Specifically, o-chlorobenzoic acid,
p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6- Dihydroxybenzoic acid, 2
, 3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, erosic acid, 1-hydroxy-2-naphthoic acid,
3-hydroxy-2-naphthoic acid, 2-hydroxy-1
-Naphthoic acid, 1-naphthoic acid, 2-naphthoic acid, etc., and hydroxynaphthoic acid is particularly effective.

[0086] The above aliphatic and aromatic carboxylic acids are preferably used as sodium salts, potassium salts or ammonium salts in order to improve water solubility. The content of organic carboxylic acid in the developer used in the present invention is not particularly limited, but if it is lower than 0.1% by weight, the effect will not be sufficient;
If the amount is more than % by weight, not only will the effect not be improved any further, but it may also hinder dissolution when other additives are used together. Therefore, the preferred amount of addition is 0 to the developer used.
．． The content is 1 to 10% by weight, more preferably 0.5 to 4% by weight.

[0087] The developer and replenisher used in the present invention may further contain an antifoaming agent, a water softener, and the like, if necessary. Examples of water softeners include:
Polyphosphoric acid and its sodium, potassium and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and 1,3-diamino -Aminopolycarboxylic acids such as 2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), triethylenetetramine Mention may be made of hexa(methylenephosphonic acid), hydroxyethylethylenediaminetri(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid and their sodium, potassium and ammonium salts.

The optimum value of such a water softener varies depending on its chelating power, the hardness of the hard water used, and the amount of hard water used, but the general usage amount is 0.00% in the developer when used. 01-5% by weight, more preferably 0.01-0
．． It is in the range of 5% by weight. If the amount added is less than this range, the intended purpose will not be fully achieved, and if the amount added is more than this range, adverse effects such as color loss will occur on the image area.

The remaining component of the developer and replenisher of the present invention is water, and may further contain various additives known in the art, if necessary. The developer used in the present invention is determined depending on various factors such as whether the photosensitive copying material is positive type or negative type, and whether or not the second organic coating layer is easily permeable to alkaline water. The amount of agent is determined, and in some cases it is possible to process positive-working and negative-working photosensitive copying materials with the same developer.

[0090] It is advantageous for transportation of the developer and replenisher of the present invention to be in the form of a concentrated solution with a lower water content than at the time of use, and to be diluted with water at the time of use. In this case, the appropriate degree of concentration is such that each component does not separate or precipitate. Development Treatment The method for processing photosensitive copying materials which characterizes the present invention comprises the step of immersing the exposed photosensitive copying material in the developer and then removing the second organic coating layer in the non-image areas in a water washing step. The processing method of the present invention can also be applied to so-called plate printing, which consists of immersing the photosensitive copying material in a plate filled with a developing solution. is the most suitable.

[0091] In the automatic processing, the exposed photosensitive copying material is immersed in a developer using an automatic developing machine comprising a device for horizontally conveying the photosensitive copying material, a developer tank, and a spray device. In general, a developer pumped up by a pump is sprayed from a spray nozzle to form a thin film of the developer on the copy material while the copy material is being conveyed horizontally. Furthermore, a method of developing the photosensitive copying material by immersing it in a developing tank filled with a developer using a submerged guide roll or the like can also be suitably applied.

[0092] In the development process according to the present invention, the developer is
Sufficient time and temperature (developer temperature) are required to penetrate the organic coating layer, reach the photosensitive layer, and dissolve the first organic coating layer in areas that are to become non-image areas. The development conditions are determined by the ease of development of the photosensitive copying material and the strength of the developer, but the preferred development time is 3 to 90 seconds, more preferably 5 to 30 seconds. Also, the developing temperature is 10~
The temperature is preferably 50°C, more preferably 20 to 40°C. At shorter times and at lower temperatures than this range, development tends to be insufficient, and at longer and higher temperatures, part of the second organic coating layer is eluted into the developer, which is not compatible with the purpose of the present invention. .

The photosensitive copying material immersed in the developer is removed from the developer by a pair of rollers, and then conveyed to the subsequent washing section. The water washing section includes a spray nozzle that supplies water, a film removal device such as a rotating brush that physically removes the second organic coating layer in the non-image area, a filter that collects the residue of the removed second organic coating layer, and a filter that collects the residue of the second organic coating layer that has been removed. It consists of an overflow that releases water out of the system.

The amount of fresh water supplied is preferably such that it can dilute the developer brought into the washing section to a concentration that does not cause environmental pollution even if it is released as is, and the amount is 5 to 3 per minute.
0 liters is preferred. In this case, it is preferable in terms of washing efficiency and water saving to store the once-used washing water and use it for preliminary washing. The second organic coating layer can be removed by using various types of brushes such as a rotating or sliding cylindrical brush, a flat brush that slides left and right, a flat brush that moves horizontally back and forth, or by spraying compressed air or high-pressure water. is used.

Recovery of the residue of the second organic coating layer is carried out by a filter attached to the water circulation system. A copying material is obtained by the above-described treatment, but if this is a lithographic printing plate, it can be further protected from scratches and surrounding contaminants by coating it with a commonly used protective gum solution.

[0096]

Effects of the Invention: The second organic coating layer, which is poorly soluble in the developer, is the main component of the photosensitive copying material, and the second organic coating layer is removed in the subsequent water washing section without being removed in the developer. By doing so, the processing ability of the developer is significantly improved. Therefore, even when processing a large number of sheets, the amount of replenisher is sufficient to compensate for the amount carried out by the copying material, and the amount of waste liquid can be significantly reduced.

[0097] Furthermore, since the scraps of the second organic coating layer scraped off in the water washing section are collected by a filter, post-treatment is also easy. The pollution of the washing water is low, and it can be released without treatment or with simple post-treatment.

[0098]

EXAMPLES The present invention will be explained in detail with reference to Examples below. Example 1 Naphthoquinone-1,2-, a polyhydroxy compound obtained by polycondensation of acetone and pyrogallol, as described in Example 1 of U.S. Pat. No. 3,635,709.
A photosensitive liquid for the first organic coating layer was prepared by dissolving 3 parts by weight of diazide-5-sulfonic acid ester and 1 part by weight of novolac type cresol formaldehyde resin in 20 parts by weight of 2-methoxyethyl acetate and 20 parts by weight of methyl ethyl ketone. Prepared. An aluminum plate with a thickness of 0.3 mm and grained on one side was anodized in sulfuric acid to form an oxide film of approximately 3 g/m2, washed well, dried, and the above photosensitive solution was applied to the grained side by dry weight. It was coated at a concentration of about 0.4 g/m2 and dried.

Next, a mixed solution of n-propyl alcohol and methyl alcohol at a mixing ratio of 1:1 was prepared, and it was confirmed that the photosensitive layer was hardly soluble in this mixed solution. To 100 parts by weight of this alcohol mixture, 8 parts by weight of styrene-maleic anhydride copolymer half ester (trade name, Styrite HS, manufactured by Daido Kogyo Co., Ltd.), dye (trade name, Oil Blue #)
603 (manufactured by Orient Chemical Co., Ltd.) was dissolved and applied onto the o-quinone diazide photosensitive layer at a dry weight of 2.0 g/m2, and dried to form a second organic coating. A two-layer coating type photosensitive lithographic printing plate was obtained by forming layers.

[0100] A positive image original film was brought into close contact with the two-layer coated positive photosensitive lithographic printing plate thus obtained.
A printer that uses a 3kW metal halide lamp as a light source (
Exposure was performed for 40 seconds using a product name: Eye Rotary Printer P-311X (manufactured by Eye Graphics Co., Ltd.). Separately, an automatic developing machine with a device for automatically conveying the plate material, an immersion type developing section with an air shield plate on the liquid surface, and a water washing/film removal section equipped with a rotating sliding brush was prepared, and the developing tank was prepared. , [SiO2]/[M2O] ratio 1.2, Si
Consisting of an aqueous solution of potassium silicate containing 1.5% by weight of O2,
A developer containing 0.04% by weight of N-alkyl-N,N-dihydroxyethylbetaine amphoteric surfactant was charged, and 3
The temperature was kept at 0°C.

Next, the exposed photosensitive planographic printing plate described above was transported at such a speed that it was immersed in the developer for 25 seconds. In the exposed areas of the photosensitive lithographic printing plate, penetration of the developer was observed in the developing tank, but the second organic coating layer did not elute. The second organic coating layer was scraped off by a rotating sliding brush in a subsequent water wash, exposing the aluminum surface of the substrate.

[0102] A protective gum liquid (trade name: GU-7, Fuji Photo Film) was applied to the surface of the lithographic printing plate thus obtained.
After applying a 2-fold diluted solution (manufactured by Co., Ltd.), printing was performed using an offset printing machine, and more than 100,000 good-quality prints were obtained. On the other hand, similar development processing was performed using a replenisher (composition [SiO
2]/[M2O] ratio of 1.2 and a silicate aqueous solution containing 3.1% by weight of SiO2) using a large number of photosensitive lithographic printing plates.

As a result, it was found that the amount of replenishment was only about 8 cc/m2, and it was confirmed that this photosensitive material and processing method caused significantly less developer fatigue.・No sludge was observed. Also, in the water washing section, the scraps of the second organic coating layer that were scraped off did not adhere to the printing plate being processed, and were gradually collected by a filter installed in the circulation system.

Comparative Example 1 An automatic processor was prepared in the same manner as in Example 1, except that a submerged rotating brush was provided in the latter half of the immersion developing section, the brush was removed from the washing section, and a filter was provided in the developer circulation system. The same treatment was carried out using the photosensitive lithographic printing plate, developer and replenisher described in Example 1.

At the beginning of the process, a good printing plate similar to that of Example 1 was obtained, but as the process progressed, the swollen residue of the second organic coating layer scraped off in the developer was removed from the printing plate. It started to adhere to the . Furthermore, as the residue of the organic coating layer gradually dissolved, the activity of the developer decreased with 8 cc/m2 of replenisher, resulting in insufficient development, so when the amount of replenishment was increased, the activity decreased to 33 cc/m2. was maintained, resulting in approximately 25 cc/m2 of overflow waste.

Example 2 Naphthoquinone-1,2-, a polyhydroxy compound obtained by the condensation polymerization of acetone and pyrogallol, as described in Example 1 of US Pat. No. 3,635,709.
A photosensitive solution for the first organic coating layer was prepared by dissolving 3 parts by weight of diazide-5-sulfonic acid ester in 20 parts by weight of 2-methoxyethyl acetate and 20 parts by weight of methyl ethyl ketone. The surface of an aluminum plate having a thickness of 0.3 mm was grained using a nylon brush and a water suspension of 400 mesh pumice stone, and then thoroughly washed with water. After etching by immersing in 10% sodium hydroxide at 70°C for 60 seconds, and washing with running water, this was etched in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of VA = 12.7V. Electrolytic surface roughening treatment was performed with an anode electricity amount of coulomb/dm2. When the surface roughness was measured, it was found to be 0.
It was 6 μ (in Ha). Subsequently, it was immersed in a 30% aqueous sulfuric acid solution and desmutted at 55°C for 2 minutes.
It was anodized in a 0% sulfuric acid aqueous solution at a current density of 2 A/dm2 to a thickness of 2.7 g/m2.

[0107] The above-mentioned photosensitive liquid was applied onto the surface-treated substrate in a dry weight of about 0.3 g/m2 and dried. Next, 100 parts by weight of a mixed solution of n-propyl alcohol and methyl alcohol at a mixing ratio of 1:1, 8 parts by weight of alcohol-soluble nylon (trade name, Toray Milan 4000CM, manufactured by Toray Industries, Inc.), and dye (trade name, Oil Blue #603, manufactured by Orient Chemical Co., Ltd.) 0
．． A second organic coating layer was formed by dissolving 0.5 parts by weight of the o-quinone diazide photosensitive layer and applying the solution to a dry weight of 1.5 g/m<2> on the o-quinonediazide photosensitive layer, followed by drying.

When the photosensitive lithographic printing plate thus obtained was treated in exactly the same manner as in Example 1, the image formed had the high abrasion resistance characteristic of nylon. As a result, more than 200,000 good prints were obtained. Example 3 A two-layer photosensitive copying material was prepared in the same manner as in Example 1 except that a 0.1 mm thick transparent polyethylene terephthalate film was used in place of the aluminum support used in Example 1. A transparent sheet having a blue image was obtained by the same exposure and development treatments as in Example 1. This could be used as a manuscript for an overhead projector.

Example 4 An aluminum plate with a thickness of 0.2 mm was used with a nylon brush.
The surface was grained using a water suspension of 00 mesh pumice stone, and then thoroughly washed with water. After etching by dipping in 10% sodium hydroxide at 70°C for 60 seconds, washing with running water, etching in 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of VA = 12.7V.
Electrolytic surface roughening treatment was performed with an anode electricity amount of 0 coulomb/dm2. Subsequently, immersion in a 30% sulfuric acid aqueous solution,
After desmutting for 2 minutes at 55°C, the thickness was 2.7 g/m at a current density of 2 A/dm2 in a 20% sulfuric acid aqueous solution.
2, then anodized at 70°C and 2% 3
Hydrophilic treatment was performed using aqueous solution of sodium silicate.

Next, hexafluorophosphate 2 of a condensate of p-diazodiphenylamine and paraformaldehyde
A solution prepared by dissolving 40 parts by weight of 2-methoxyethanol was coated and dried on the aluminum plate having a hydrophilic surface to a dry weight of 0.2 g/m2 to form a diazo photosensitive layer (first An organic coating layer) was formed. Furthermore, 60 parts by weight of 2-methoxyethyl acetate and 40 parts by weight of methyl ethyl ketone were mixed with a polyurethane resin (trade name: Estane #5).
715, manufactured by Monsanto Co., Ltd.) 8 parts by weight, dye (trade name, Oil Blue #603, manufactured by Orient Chemical Co., Ltd.) 0.0
A second organic coating layer was formed by dissolving 5 parts by weight and drying the solution on the diazo photosensitive layer at a dry weight of 2 g/m2 to obtain a negative photosensitive lithographic printing plate.

[0111] A large number of sheets of the photosensitive lithographic printing plate obtained in this way were cut to a size of 1003 mm x 800 mm, and a negative original film was passed through them to form a 1 m long sheet.
Using a 3kW metal halide lamp from a distance of 3
Exposure was made for 0 seconds. Next, we prepared an automatic developing machine consisting of a device that automatically conveys the plate material horizontally, a developing section that sprays developer solution, and a washing and film-removing section that has a rotating brush. A developing solution consisting of an aqueous solution containing 4.5% by weight of alcohol, 1.5% by weight of triethanolamine, 1.5% by weight of sodium isopropylnaphthalene sulfonate, and 0.3% by weight of sodium sulfite was charged and kept at 30°C.

Next, the exposed photosensitive lithographic printing plate was transported at such a speed that it passed through the developing section in 25 seconds, and a developer was supplied onto the printing plate. Although the unexposed areas of the photosensitive lithographic printing plate were seen to be penetrated by the developer in the developing tank,
The second organic coating layer did not elute. The second organic coating layer was scraped off by a rotating sliding brush in a subsequent water wash, exposing the hydrophilic aluminum surface.

[0113] A protective gum liquid (trade name: GU-7, Fuji Photo Film) was applied to the surface of the lithographic printing plate thus obtained.
After applying a 2-fold diluted solution (manufactured by Co., Ltd.), printing was performed using an offset printing machine, and more than 100,000 good-quality prints were obtained. On the other hand, a similar development process was carried out using a large number of photosensitive lithographic printing plates while supplementing the decreased amount of developer taken out by the plate material with a replenisher (same composition as the developer).

As a result, it was found that the amount of replenishment was only about 8 cc/m2, and it was confirmed that this photosensitive material and processing method caused significantly less developer fatigue. - No sludge was observed. Furthermore, in the water washing section, the scraps of the second organic coating layer that were scraped off did not adhere to the printing plate being processed, but were gradually collected by a filter installed in the circulation system.

Claims (1)

[Claims] Claim 1: A first photosensitive organic coating layer whose solubility changes upon irradiation with light; and (2) a water-insoluble and organic solvent-soluble polymer compound having film-forming ability are deposited on a support in this order. A method of imagewise exposing and developing a photosensitive copying material having a second organic coating layer containing the first and second organic coating layers in non-image areas by a step of immersing in the developer and a subsequent washing step with water. 1. A method for processing photosensitive copying material, which comprises removing.