JPH04328748A - Photosensitive copying material and processing method thereof - Google Patents

Abstract

PURPOSE:To obtain the above copying material which enables the long time maintenance of the processing capacity of a developer to be conducted and produces a waste liquid in a lesser amt. by removing org. coating layers by a washing stage. CONSTITUTION:The 2nd org. coating layer of the photosensitive copying material successively having the 1st photosensitive org. coating layer which is increased in alkaline water solubility by irradiation with active rays and the 2nd org. coating layer contg. a water insoluble high-polymer compd. having film formability on a base is formed by applying and drying emulsion of the high-polymer compd. The developer penetrates into the 2nd org. coating layer after image exposing, but the non-image parts are removed by the washing stage after the material is immersed into the developer which does not dissolve this layer.

Description

[Detailed description of the invention]

0001

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

0002

BACKGROUND OF THE INVENTION Photosensitive copying materials containing an o-quinonediazide compound as a photosensitive component include photosensitive lithographic printing plates, photosensitive resist materials, and photosensitive proofing materials. 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 the reversal-type negative-working photosensitive lithographic printing plates using an o-quinonediazide photosensitive layer described in Japanese Patent Publication No. 14970/1983, and dimethyl silicates. It is also preferably used as a developer for negative photosensitive lithographic printing plates that use 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, and sprays the developer pumped up by a pump while horizontally conveying the exposed photosensitive planographic printing plate. It is developed by spraying it from a nozzle. Furthermore, recently, a method has been known in which a photosensitive planographic printing plate is immersed and conveyed in a developing tank filled with a developing solution using a submerged guide roll or the like.

[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, there is a growing need to reduce industrial waste.

Separately, Japanese Patent Publication No. 54-21089 discloses a multilayer photosensitive copying material in which an organic coating layer that is poorly soluble in a developer is provided on a photosensitive layer made of an o-quinonediazide compound. There is. 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, in many cases, such a photosensitive layer and a polymer compound useful for an organic coating layer share the same solvent, and the polymer compound used for an organic coating layer is an organic solvent in which the photosensitive layer component is a poor solvent. It was limited to some polymer compounds that dissolve in Furthermore, 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 long-term stable processing impossible.

[0008]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an improved photosensitive copying material and processing method that can reduce industrial waste. Another object of the present invention is to provide an improved photosensitive copying material and a processing method that can stably process a large amount of photosensitive copying material without generating insoluble matter even if the material is processed for a long period of time. That's true.

[0009]

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors have discovered a photosensitive copying material and a processing method that can minimize the elution of the photosensitive layer into the developer, and the present invention has been made. This is what we have achieved. That is, the present invention provides, on a support, (1) a photosensitive first organic coating layer whose solubility in alkaline water increases upon irradiation with actinic rays; and (2)
A second material having film-forming ability and containing a water-insoluble polymer compound.
The present invention provides a photosensitive copying material having an organic coating layer, wherein the second organic coating layer is formed by applying and drying an emulsion of a polymer compound. be. The present invention also provides that, after imagewise exposure of the photosensitive copying material, the first and second organic coatings in the non-image areas are immersed in a developer solution that penetrates but does not dissolve the second organic coating layer and a subsequent washing step with water. Second
The present invention provides a method for processing a photosensitive copying material, characterized in that the organic coating layer is removed.

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.

[0011] 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.

[0012] The aluminum plate is roughened to improve its surface water retention and adhesion with the photosensitive layer, but before that, if desired, it is 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.

[0014] The aluminum plate thus roughened is subjected to alkali etching treatment and neutralization treatment as required, and then anodization treatment is performed 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 and 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, a voltage of 1 to 100 V, and an 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, and 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, 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. "stains" are more likely to occur.

After the anodic oxidation treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. As the hydrophilic treatment used in the present invention, 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 addition, potassium fluorozirconate disclosed in Japanese Patent Publication No. 36-22063 and U.S. Pat. A method of treating with polyvinylphosphonic acid as disclosed is used. 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

[0018] This organic undercoat layer can be provided by the following method. That is, a method in which a solution of the above organic compound 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 side of the support of the photosensitive planographic printing plate of the present invention is coated with an organic polymer to suppress the elution of the aluminum anodic oxide film and to prevent the photosensitive layer from being scratched when stacked. A coating layer made of a compound (hereinafter this coating layer will be referred to as a back coat layer) may be provided. As the material for the back coat layer, organic polymer compounds insoluble in alkaline developers are used, such as polyethylene, polypropylene, polybutene, polybutadiene, nylon, polyurethane, polyurea, polyimide, polysiloxane, polycarbonate, epoxy resin, alkylphenol, etc. Suitable examples include aldehyde condensation resins, acetal resins, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylic resins, and copolymer resins thereof.

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.

[0022] The thickness of the back coat layer used in the present invention basically needs to be thick enough to 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 Coating Amount On the thus obtained aluminum plate having a hydrophilic surface, a photosensitive first organic coating layer whose solubility in alkali water is increased by irradiation with actinic light is provided. . Examples of such a photosensitive organic layer include a layer of a positive photosensitive composition containing an o-quinonediazide compound as a main component. Examples of such o-naphthoquinone diazide compounds include 1 described in Japanese Patent Publication No. 43-28403.
, 2-diazonaphthoquinone sulfonic acid and pyrogallol.
Esters with acetone resins are preferred. Other suitable orthoquinonediazide compounds include, for example, U.S. Pat. Nos. 3,046,120 and 3,188,21.
There is an ester of 1,2-diazonaphthoquinone-5-sulfonic acid and phenol-formaldehyde resin described in No. -967
There is an ester of 1,2-diazonaphthoquinone-4-sulfonic acid and phenol-formaldehyde resin described in Japanese Patent No. 61. Other useful o-naphthoquinone diazide compounds include those known from numerous patents and the like. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-
No. 96575, No. 49-38701, No. 48-133
No. 54, Special Publication No. 37-18015, No. 41-1122
No. 2, US Patent No. 45-9610, US Patent No. 49-17481, US Patent No. 2,797,213, US Patent No. 3,454
, No. 400, No. 3,544,323, No. 3,
No. 573,917, No. 3,674,495, No. 3,785,825, British Patent No. 1,227,6
No. 02, No. 1,251,345, No. 1,26
No. 7,005, No. 1,329,888, No. 1
, 330,932, German Patent No. 854,890
Examples include those described in each specification such as No.

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 2
It is 0% by weight or more, more preferably 30% by weight or more.

As the main component of the photosensitive first organic coating layer used in the present invention, preferable examples other than the o-quinonediazide compound include, for example, Japanese Patent Publication No. 56-2696.
Polymer compounds having an orthonitrocarbinol ester group or compounds that generate an acid by photolysis, and -C-O-C groups or -C that dissociate with an acid, as described in the No.
A combination system with a compound having an -O-Si group can also be mentioned. For example, a combination of a compound that generates an acid upon 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-51-12071)
No. 4), combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429), combination with an ethanol ether compound (JP-A-55-129)
No. 95), combination with N-acylimino carbon compound (JP-A-55-126236), combination with polymer having orthoester group in the main chain (JP-A-56-17345)
No.), combination with silyl ester compound (Unexamined Japanese Patent Publication No. 1983-
10247) and a combination with a silyl ether compound (
JP-A-60-37549, JP-A-60-121446
(No.), etc.

Binder Although a photosensitive compound such as an o-quinone diazide 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-methylol methacrylamide , N-ethyl acrylamide, 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, phenyl vinyl ether, (8) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, etc. (9) Styrenes such as styrene, methylstyrene, and chloromethylstyrene; (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and 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.

It is preferable to add cyclic acid anhydrides, phenols, and organic acids to the photosensitive composition of the present invention in order to increase sensitivity. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ4-tetrahydrophthalic anhydride, which are described in U.S. Pat. No. 4,115,128. Tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride, and the like can be used.

[0034] 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, JP-A-2-96755, etc., 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 photosensitive composition is 0.05
-15% by weight is preferred, more preferably 0.1-5% by weight. In addition, in the photosensitive composition of the present invention, in order to widen the stability of processing against development conditions (so-called development latitude), the method described in JP-A-62-251740 and Japanese Patent Application No. 2-181248 is incorporated. Nonionic surfactants such as those described in Japanese Patent Application Laid-Open No. 121044/1982 and amphoteric surfactants such as those described in Japanese Patent Application No. 115992/1998 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 above-mentioned 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 printing-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 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, JP-A-50-36209 and JP-A-53
The combination of o-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dye described in JP-A-8128, JP-A-53-36223 and JP-A-53-54-
No. 74728, No. 60-3626, No. 61-1437
No. 48, No. 61-151644 and No. 63-584
Combinations of trihalomethyl compounds and salt-forming organic dyes described in each publication No. 40 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 photosensitive composition in the present invention is dissolved in a solvent that dissolves the above-mentioned 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.

The photosensitive composition of the present invention is dissolved and dispersed at a solid content concentration of 0.2 to 20% by weight, and coated on a support.
dried. A layer of a photosensitive composition coated on a support (
The amount of coating (photosensitive layer) varies depending on the application, but in general,
The weight after drying is 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, which will be described later, 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 photosensitive composition of the present invention contains a surfactant for improving the coated surface quality, such as JP-A-62-17
A fluorosurfactant as described in Japanese Patent No. 0950 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 of the present invention has a second organic coating layer that is poorly soluble in a developer and permeable to the developer, on the photosensitive first organic coating layer. . The present invention is characterized in that the second organic coating layer is formed by applying and drying an emulsion obtained by emulsifying and dispersing a water-insoluble polymer compound having film-forming ability in water. The film of the second organic coating layer thus obtained is tough and wear-resistant, and preferably has a hydrophobic surface that easily accepts printing ink.

[0043] As the emulsion, a lipophilic resin latex can be used. The latex useful in 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 at least one type each of the monomers selected from Group A and Group B. A polymer latex obtained by copolymerizing these monomers, or a polymer latex obtained by combining them with at least one monomer of 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 includes, of course, substituted phenyl and naphthyl groups, and the substituents include the substituents listed above for the substituted alkyl group. 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-acrylamido-2-methylpropanesulfonic acid, etc.), methacrylamido-2-methylethanesulfonic 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 diethylenetriamine tris(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.

[0051]

[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. Latex polymers that can be used here include, for example, Preparative Methods of Polymer Chemistry Interscience Publishers (Prep
Arative Methods of Polyme
r Chemistry, Interscience
It can be synthesized according to the emulsion polymerization method described on pages 216 and 239 of the issue of J.Publishers). One example is as follows. Pour 420 ml of distilled water into a 1 liter three-necked flask, add 0.225 g of potassium metabisulfite, stir to dissolve, then purge with nitrogen, and add 33.37 g of acrylonitrile.
g, vinylidene chloride 145.3g, acrylic acid 14.1g
g and 14.1 g of Triton 770 (surfactant) were added thereto, and 0.45 g of potassium persulfate was added thereto, followed by reaction at a temperature of 30° C. and stirring at a rotational speed of 150 rpm.

Resins for which the emulsion polymerization method cannot be used in the preparation of latex, such as formal resins or acetal resins such as butyral resins, cellulose esters such as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose crotonate, and ester compounds thereof. and coester compounds with dicarboxylic acids such as phthalic acid, succinic acid, sebacic acid, and maleic acid; cellulose ether compounds such as methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, allyl cellulose, benzyl cellulose, silulohexyl cellulose, and cyanoethyl cellulose. Polymer compounds produced by condensation polymerization, such as polyester, polyamide, polyurethane, polyurea, and polyimide, are also useful as lipophilic resins that can be used in the present invention. This compound is disclosed in Japanese Patent Application Laid-Open No. 52-36
Emulsions can be prepared by the method disclosed in Japanese Patent No. 53.

Group A and B in the above copolymer latex
The ratio of Group C and Group C can be appropriately selected in consideration of the developability, ink receptivity, printing durability, and other performances of the second organic coating layer coated from latex. The monomer components of group A mainly control lipophilicity and wear resistance. Therefore, the amount of the Group A monomer component is preferably 20 to 100% by weight, particularly 60 to 10% by weight based on the solid content of the latex polymer.
0% by weight is preferred.

The amount of the group B monomer component is preferably 0 to 25% by weight, particularly preferably 0 to 10% by weight, based on the solid content of the latex polymer. Group C monomer component is 0 to 80% by weight
is preferred, particularly 0 to 40% by weight. A commercially available latex liquid can also be used. For example, emulsion of polyacrylic acid ester copolymer; trade name,
Julimar ET-410, Julimar SEK-301,
Julimar SEK-101, Julimar FC-30, Julimar FC-60, Julimar FC-80, Julimar SE-5101, Julimar SE-5102, Julimar SE-5103, Julimar SE-5301, Julimar SE-361, Julimar SE-363, Julimar SE-365, Julimar SE-6302, Julimar SE-6311, Julimar SE-6312 (manufactured by Nippon Pure Chemical Industries, Ltd.), Nipol LX811, Nip
ol LX814, Nipol LX841, Nipo
l LX851, Nipol LX852, Nipol
LX854, Nipol LX856, Nipol
LX860, Nipol LX874 (manufactured by Zeon Corporation), Primal AC-22, Primal AC-
33, Primal AC-3444, Primal AC-5
5, Primal AC-61, Primal AC-382,
Primal ASE-60, Primal ASE-75, Primal ASE-108, Primal B-15, Primal B-41, Primal B-74, Primal B-3
36, Primal B-505, Primal B-832,
Primal B-924, Primal C-72, Primal E-32, Primal E-358, Primal HA-
8, Primal HA-16, Primal HA-24, Primal I-94, Primal LC-40, Primal LT-76, Primal LT-87, Primal MC-
4530, Primal N-580, Primal P-6N
, Primal P-1060, Primal S-1, Primal TR-49, Primal 850 (manufactured by Nippon Acrylic Chemical Co., Ltd.), acrylonitrile-butadiene latex; Nipol 1551, Nipol 1561
, Nipol 1562, Nipol 1571, Ni
pol 1577, Nipol LX511, Nipol
LX513, Nipol LX531, Nipol
LX531B (manufactured by Nippon Zeon Co., Ltd.), styrene
Butadiene latex; Nipol LX111, N
ipol 4850, Nipol 4850A, Nip
ol LX110, Nipol LX119, Nipo
l LX204, Nipol LX206, Nipol
LX209, Nipol 2507, Nipol L
X303, Nipol 2518FS, Nipol L
X415A, Nipol LX426, Nipol L
X430, Nipol LX432A, Nipol L
X433, Nipol LX472, Nipol 25
70X5, Nipol LX407BP, Nipol
LX407C, Nipol LX407F, Nipol
LX407G (manufactured by Nippon Zeon Co., Ltd.), vinyl chloride latex; Geon150X15, Geon35
1. Geon576 (manufactured by Nippon Zeon Co., Ltd.), urethane resin emulsion; VONDIC 1041NS
, VONDIC 1050B-NS, VONDIC
1230NS, VONDIC 1250, VOND
IC 1310NSC, VONDIC 1320N
SC, VONDIC 1510, VONDIC 1
610NS, VONDIC 1512NSC, VON
DIC 1640, VONDIC 1660NS,
VONDIC 1670NS, VONDIC 19
30A-NS, VONDIC 1980NS, VON
DIC 1205, VONDIC 2220, VO
NDIC 2230 (manufactured by Dainippon Ink Chemical Co., Ltd.), Aron Neothane UE-1101, Aron Neothane UE-1200, Aron Neothane UE-13
00, Aron Neotan UE-1402, Aron
Neotan UE-2103, Aron Neotan UE-2
200, Aron Neotan UE-2600, Aron
Neotan UE-2900, Aron Neotan UE-54
04, Aron Neothane UE-5600 (manufactured by Toagosei Kagaku Kogyo Co., Ltd.), colloidal dispersion type urethane resin;
HYDRAN HW-301, HYDRAN HW-3
10, HYDRAN HW-311, HYDRAN
HW-312B, HYDRAN HW-333, H
YDRAN HW-340, HYDRAN HW-
350, HYDRAN HW-111, HYDRAN
HW-140, HYDRANNHW-910, HYD
RAN HW-920, HYDRAN HW-93
0, HYDRAN HW-940, HYDRAN
Examples include HW-950 and HYDRAN HW-960 (manufactured by Dainippon Ink and Chemicals Co., Ltd.). However, when using commercially available latex, it is necessary to take into account that performance is affected by the type of emulsion stabilizer used.

The polymer forming the second organic coating layer, including the latex prepared by a method that does not rely on emulsion polymerization, has hydroxyl, amino, amide, imino, imide, nitrilo, carboxyl, sulfonyl in the main chain or side chain of the polymer. , sulfonoxy, isocyanate, urethane, azoimide, azo, hydrazino, carbamide, carbamyl,
Those containing at least one group selected from epoxy, mercapto, thio and sulfonamide groups are preferred. There are no particular restrictions on the particle size of the lipophilic resin in the emulsion, but particles having a distribution within the range of about 0.03 to 10 μm can generally be used, and preferably about 0.05 to 5 μm. The polymers forming the emulsion particles can range from high molecular weight to oligomeric polymers, from about 2,000 to about 200,000 in molecular weight, or may be a mixture of these polymers. Further, the polymer forming the particles may itself be crosslinked, or may have the property of being cured by actinic rays or heat.

[0057] These polymer latexes may be used alone, but by mixing a plurality of them, the permeability and swelling property of the second organic coating layer to the developer can be adjusted, and the film properties can be adjusted. can do. The difficulty in solubility of the second organic coating layer in the developer described above is as follows.
It 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 second organic coating layer is selected according to the components of the first organic coating layer and the components of the developer. The polymer compound of the organic coating layer is also suitably selected.

[0058] The second organic coating layer also contains o
- A quinonediazide compound can be added as a developer penetration enhancer in the form of emulsion and dispersion in water, but if the amount added is too large, the amount of components eluted into the developer will increase, 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, etc. 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 from 0.001 to 1.0% by weight, more preferably from 0.005 to 0.5% by weight, based on the total weight of the second organic coating layer.

[0060] The additive component may be contained within the particles of the emulsion or may be contained outside the particles. The second organic coating layer is applied onto the photosensitive first organic coating layer using a coating technique such as coating from a latex solution, casting, transfer, or simultaneous multilayer coating, and is dried.

The preferred coating amount of the second organic coating layer is from 0.1 to 5.0 g/m 2 , more preferably from 0.5 to 3.0 g/m 2 based on the weight after drying. 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 A matte layer is provided on the surface of the second organic coating layer provided as described above in order to shorten the evacuation time during contact exposure using a vacuum printing frame and to prevent printing blur. It is preferable. Specifically, Japanese Patent Application Laid-Open No. 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 developing machine, 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 used 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 (i.e. [SiO2]/[Na2O] is 0.5~
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
Using a developing solution of alkali metal silicate that is % by weight, [ SiO2 of alkali metal silicate used as a replenisher]
]/[M] is 0.25 to 0.75 (i.e. [ SiO2
]/[M2O] is 0.5 to 1.5), and both the developer and the replenisher have at least 20 gram atoms of alkali metal present therein.
% of potassium is preferably used. Furthermore, in order to reduce running costs and the amount of waste liquid, SiO2 /M2 is used as a highly active developer.
The molar ratio of O is 0.7 to 1.5, and SiO2
The replenisher consists of an aqueous solution of an alkali metal silicate with a concentration of 1.0 to 4.0% by weight, and the replenisher is SiO2 /M2
The molar ratio of O is 0.3 to 1.0, and SiO2
An aqueous solution of an alkali metal silicate having a concentration of 0.5 to 4.0% by weight is also preferably used.

[0065] 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.

[0069] 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 acid, anthracene ring, etc. Specifically, o-chlorobenzoic acid, 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.

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.

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 solution and replenisher solution of the present invention is water, and may further contain various additives known in the art, if necessary. The amount of the above-mentioned additives in the developer and replenisher used in the present invention is determined depending on various factors such as whether or not the second organic coating layer is easily permeable to alkaline water. It is advantageous in terms of transportation that the developer and replenisher of the present invention are prepared as a concentrated solution with a lower water content than when used, and are diluted with water when used. In this case, the appropriate degree of concentration is such that each component does not separate or precipitate.

Development Processing The method for processing the photosensitive copying material of the present invention is to immerse the exposed photosensitive copying material in the above-mentioned developer, and then remove the second organic coating layer in the non-image area with a brush or the like. It consists of the process of This film removal step may be performed in a developer, but in particular,
After immersion in the developer, it is preferable to remove the second organic coating layer in the non-image area in a water washing step, since this can reduce the fatigue of the developer and reduce the amount of replenishment, ie, the amount of waste liquid. 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 developer solution.
In order to fully bring out the effects of the present invention, processing using an automatic processor is most suitable.

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.

[0077] 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 removing 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.

[0081]

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.

[0082] In addition, 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 washing water is low, and it can be released without treatment or with simple post-treatment. The second organic coating layer is formed by applying and drying a polymer latex containing water as a dispersion, and any desired polymer compound can be freely selected regardless of the type of solvent.

[0083]

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 2 parts by weight of diazide-5-sulfonic acid ester and 2 parts 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 about 3 g/m2, thoroughly washed and dried, and the above photosensitive solution was applied to the grained side. The coating was applied to a dry weight of approximately 0.4 g/m2 and dried. Next, polyacrylic acid ester copolymer latex (trade name, Jurimer SEK1
01, solid content concentration 40%, diluted 20 parts by weight of Nippon Pure Chemical Industries, Ltd. with 90 parts by weight of water, and further dye (trade name, Victoria Pure Blue BOH, manufactured by Hodogaya Chemical Co., Ltd.) 0.0
5 parts by weight was dissolved and coated on the o-quinone diazide photosensitive layer at a dry weight of 2.0 g/m2, and dried to form a second organic coating layer, forming a two-layer coating type photosensitive layer. A lithographic printing plate was obtained.

[0085] 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, we prepared an automatic developing machine with a device for automatically conveying the plate material, an air shield plate on the liquid surface, an immersion type developing section with a submerged rotating brush in the latter half, and a washing section following it. , [SiO2]/[M2O] ratio 1.2, S
A developing solution consisting of an aqueous potassium silicate solution containing 1.5% by weight of iO2 and containing 0.04% by weight of an N-alkyl-N,N-dihydroxyethylbetaine amphoteric surfactant was charged.
The temperature was kept at 30°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 area of the photosensitive lithographic printing plate, the second organic coating layer was scraped off by a rotating sliding brush in the developer tank, and the aluminum surface of the substrate was exposed. After coating the surface of the lithographic printing plate thus obtained with a 2-fold dilution of a protective gum solution (product name: GU-7, manufactured by Fuji Photo Film Co., Ltd.), printing was performed using an offset printing machine. More than 100,000 good prints were obtained.

On the other hand, similar development processing was performed using a replenisher (composition [Si
O2]/[M2O] ratio 1.2, SiO2 3.1
The test was carried out using a large number of photosensitive lithographic printing plates while supplementing with a silicate aqueous solution (wt%). As a result, the amount of replenishment was only about 30 cc/m2, and it was confirmed that this light-sensitive material and processing method caused little developer fatigue.

At this time, the amount of developer taken out by the copying material was about 10 cc/m2, so the amount of developer was about 20 cc/m2.
of overflow waste liquid was produced. Example 2 An automatic developing machine having a device for automatically transporting plate materials, an immersion type developing section with an air shield plate on the liquid surface, and a washing and film removing section equipped with a rotating sliding brush following the device was prepared, and the developing tank was The same developer as in Example 1 was added to the solution, and the temperature was kept at 30°C.

Next, the exposed photosensitive lithographic printing plate of Example 1 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.

A protective gum liquid (trade name: GU-7, Fuji Photo Film (trade name)) was applied to the surface of the lithographic printing plate thus obtained.
After applying a 2-fold dilution 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 decrease in developer carried out by the plate material with the replenisher of Example 1.

As a result, the replenishment amount is only about 10cc/m2.
It was found that this light-sensitive material and processing method caused significantly less developer fatigue, and no sludge or sludge was observed in the developing tank even after long-term and large-volume processing. 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.

Example 3 Naphthoquinone-1,2-, a polyhydroxy compound obtained by condensation polymerization of acetone and pyrogallol, as described in Example 1 of US Pat. No. 3,635,709.
2 parts by weight of diazide-5-sulfonic acid ester and 3 parts by weight of phenol novolak resin were mixed with 20 parts by weight of acetic acid-2-
A photosensitive solution for the first organic coating layer was prepared by dissolving it in methoxyethyl 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. 1
After etching by immersing in 0% sodium hydroxide at 70°C for 60 seconds, washing with running water, this was VA = 12.7
Electrolytic surface roughening treatment was carried out in a 1% nitric acid aqueous solution using an alternating sinusoidal waveform current under the condition of V and an anodic electricity amount of 160 coulombs/dm2. When the surface roughness was measured, it was 0.6μ (expressed in Ha). Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and desmutted at 55° C. for 2 minutes, and then anodized in a 20% sulfuric acid aqueous solution at a current density of 2 A/dm 2 to a thickness of 2.7 g/m 2 .

The above-mentioned photosensitive liquid was coated onto the surface-treated substrate at a dry weight of about 0.3 g/m 2 and dried. Next, 20 parts by weight of a colloidal dispersion type urethane resin (trade name, HYDRAN HW-312B, solid content concentration 40%, manufactured by Dainippon Ink and Chemicals Co., Ltd.) was diluted and dispersed with 80 parts by weight of water, and further dye ( Product name: Victoria Pure Blue BOH (manufactured by Hodogaya 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.

When the photosensitive lithographic printing plate thus obtained was processed in exactly the same manner as in Example 1, the image formed had the high abrasion resistance characteristic of urethane, and was printed using this. As a result, more than 200,000 good prints were obtained. Example 4 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 5 1,2-dichloroethane 300ml in a 500ml beaker
g, polyvinyl formal (degree of polymerization about 800, vinyl acetate residue 10.5 ± 1.5, polyvinyl residue 5.5
±0.5, #100 manufactured by Denki Kagaku Kogyo Co., Ltd.) was added and dissolved with stirring. Separately, prepare a 2 liter three-necked flask with a stirrer and a dropping funnel attached, and
Take 0ml of pure water and add 10g of polyvinyl alcohol (
GL-05 manufactured by Nippon Gosei Co., Ltd., saponification degree 86.5-89
(mol%, average degree of polymerization 500) and 2 g of sodium lauryl alcohol sulfate (active purity 75-80%) were added and dissolved under stirring. Then increase the rotation speed to 1000 RPM
The polyvinyl formal solution prepared earlier was added dropwise from the dropping funnel at a rate of about 50 ml/min. After completion of the dropwise addition, stirring was continued at room temperature for about 10 minutes, and then the flask was heated to about 80° C. and stirring was continued while maintaining this temperature for about 2 hours to remove 1,2-dichloroethane.

The emulsion obtained was diluted with 2000 ml of pure water and applied to an o-quinonediazide photosensitive layer coated on an aluminum support prepared in the same manner as in Example 1, with a dry weight of 1.5 g. /m2 and dried to obtain a photosensitive planographic printing plate. When this was exposed and developed in the same manner as in Example 2, a lithographic printing plate was obtained in which the second organic coating layer in the exposed areas was removed and the aluminum support was exposed, and it also showed good ink receptivity in printing. We were able to obtain approximately 100,000 prints. Comparative Example 1 In Example 5, an attempt was made to apply the polyvinyl formal directly from a 1,2-dichloroethane solution without making it into an emulsion, but the o-quinonediazide photosensitive layer was dissolved and a photosensitive lithographic printing plate with a satisfactory layer structure was obtained. was not obtained.

Claims (2)

[Claims] Claim 1: A photosensitive first organic coating layer whose solubility in alkaline water increases upon irradiation with actinic rays is formed on a support; 1. A photosensitive copying material having a second organic coating layer comprising a second organic coating layer, characterized in that the second organic coating layer is formed by applying and drying an emulsion of a polymer compound. 2. After the photosensitive copying material according to claim 1 has been imagewise exposed, the non-image is removed by a step of immersing it in a developer that penetrates but does not dissolve the second organic coating layer and a subsequent washing step. 1. A method of processing a photosensitive copying material, which comprises removing first and second organic coating layers of a portion of the photosensitive copying material.