JPH01185668A - Printing plate for electrophotographic plate making - Google Patents

Abstract

PURPOSE:To obtain a printing plate which is free from staining in the non-image part by using a compd. contg. at least one group selected from an amino group, carboxyl group and the salt thereof, sulfo group and the salt thereof to constitute the intermediate layer of the printing plate consisting of a conductive substrate, the intermediate layer and an electrophotographic sensitive layer. CONSTITUTION:The surface of the conductive substrate consisting of aluminum, zinc plate, etc., imparted with solvent impermeability and electrical conductivity is subjected to sand dressing. Such surface is coated with an anodized film. The intermediate layer is then formed thereon and is constituted of the hydrophilic compd. contg. at least one amino group, carboxyl group and the salt thereof, sulfo group and the salt thereof, etc. This compd. is, for example, glycine, aniline, valine, leucine, isoleucine, etc. The concn. of the compd. at the time of coating is selected at 0.001-10wt.%, the temp. at 10-30 deg.C and the pH at 1-13. The layer of an ordinary photoconductive material consisting of an inorg. or org. compd., for example, selenium, amorphous silicon, polyvinyl carbazole or polyvinyl anthracene is laminated thereon.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a printing plate for electrophotographic platemaking having an electrophotographic photosensitive layer.

In particular, it relates to a printing plate for electrophotographic plate making that does not stain non-image areas during printing.

[Conventional technology]

Today, as lithographic offset printing plates, 28 plates that use positive-working photosensitizers whose main components are diazo compounds and phenolic resins, and negative-working W& base agents whose main components are acrylic monomers and prepolymers have been put into practical use. However, all of these have low sensitivity, so plate making is performed by deep latent exposure of a silver halide photographic film master plate on which an image has been recorded in advance. On the other hand, advances in computer image processing, large-capacity data storage, and data communication technology have led to advances in manuscript input,
Electronic machinery systems have been put into practical use in which everything from correction, editing, layout to page setting is controlled by a computer, and can be instantly delivered to a terminal plotter in a remote location using high-speed digital communication or satellite communications. In particular, electronic editing systems are in high demand in the field of newspaper printing, which requires immediacy. Well, even in fields where originals are preserved in the form of original film and printed versions are reproduced as needed based on this, with the development of ultra-high capacity recording media such as original disks, these records are no longer the same as originals. It is thought that information will be stored as digital data on media.

However, direct printing plates that create printing plates directly from the output of terminal plotters have hardly been put into practical use.
Even in places where electronic editing systems are in operation, the current situation is that output is performed on silver halide photographic film, and based on this, printing plates are indirectly created by contact exposure to PS plates. This is the light source of the output plotter (for example)
This is because it is difficult to develop a direct printing plate with a sensitivity high enough to make a printing plate within a practical time using Ne laser, semiconductor laser, etc.).

An electrophotographic M photoreceptor is considered as a photoreceptor having high photosensitivity that can be provided by direct printing.

Conventionally, as printing plate materials (printing original plates) using electrophotographic gold, for example, Tokko Akihiro 7-Hiro 76IQ, Tokko Sho ψg
−≠No.0002, Tokuko Sho≠za-7za 32j, Tokuko Sho 3
/-/J761s, Japanese Patent Publication No. 31-2371, 1, etc., zinc oxide-resin dispersion offset printing plate materials are known, and after forming a toner image by electrophotography, the non-image area It is used after being wetted with a desensitizing solution (for example, an aqueous wave solution with a ferrocyan salt or a gold ferricyanide salt) to render it non-greasy. Offset printing plates treated in this way have a printing durability of about 3,000 to 70,000 sheets, and are not suitable for printing beyond this, and if the composition is made suitable for desensitization, the electrostatic properties deteriorate. However, there are drawbacks such as deterioration of image quality. In addition, there is a drawback that all harmful cyanide compounds are used as a desensitizing solution.

Special Publication No. 37-/7/62, Special Publication No. 3g-77jg
No., Special Public Sho≠6-39≠Oj No., Special Public Shoj2-! Hiro 37
In the organic optical 41jL body-resin printing plate material described in the above publications, for example, a photoconductive insulating layer bonded with an oxazole compound or an oxadiazole compound and a total styrene-maleic anhydride copolymer is used. An electrophotographic photoreceptor is used, which is provided on an aluminum plate, and after a toner image is formed on this photoreceptor by an electrophotographic method, a printing plate is formed by dissolving and removing the image with an alkaline organic solvent.

In addition, the present inventors disclosed a photosensitive printing plate material containing a hydrazone compound and barbylic acid or thiobarbylic acid in Japanese Patent Application Laid-Open No. 37-7636. In addition, JP-A No. 3 Taichi/≠733j, JP-A No. 39-/32≠56, JP-A Showj Turf 6 ≠ 62
Dye-sensitized printing plates for electrophotographic platemaking are known, such as No. 1 and Japanese Patent Application Publication No. 2003-100003. however,
Substances in the electrophotographic photosensitive layer are adsorbed to the non-image area of the printing plate for electrophotographic plate making, contaminating the non-image area, and ink adheres to the non-image area of printed matter, causing "stains". Therefore, there was a problem that it could not be used as a printing plate. In order to solve all of these problems, a method of physically or chemically making a conductive substrate hydrophilic, for example, an anodized aluminum substrate surface, as described in US Patent No. 3. Although methods such as immersion in an alkali metal silicate described in the specification of iri, ≠ No. 67 are known, none of them are fully satisfactory.

[Purpose of the invention]

An object of the present invention is to provide a printing plate for electrophotographic platemaking that is free from stains in non-image areas during printing.

Another object of the present invention is to provide sufficient sensitivity to directly create printing plates using lasers, etc.! An object of the present invention is to provide a printing plate for electrophotographic plate making.

Another object of the present invention is to provide a printing plate for an electrophotographic exhibition plate having excellent electrostatic properties.

[Friendly means to solve all problems]

As a result of intensive studies, the present inventors found that at least a conductive substrate,
In a printing plate for electrophotographic plate making consisting of an intermediate layer and an electrophotographic photoreceptor, the intermediate layer has at least one solid amino group and at least one selected from the group consisting of a carboxyl group and a salt thereof, and a sulfo group and a salt thereof. The above object can be achieved by a printing plate for electrophotographic plate making which is characterized in that it consists of a compound having one group.

Hereinafter, the present invention will be explained in detail step by step.

The conductive substrate used in the present invention has conductivity i[f
Plastic sheets or especially solvent-impermeable and electrically conductive paper, aluminum plates, zinc plates, or bimetallic plates such as steel-aluminum plates, steel-stainless steel plates, copper copper plates, or copper-copper plates. A conductive substrate having a hydrophilic surface such as a tri-metal plate such as an aluminum plate, a lead-iron plate, a chromium-copper-stainless steel plate, etc. is used, and its thickness is preferably n, o, i to 3as, particularly 0 , /~0.1 m is preferred. Among these substrates, an aluminum plate having an anodic oxide film on it is preferably used.

The aluminum plate used in the present invention is a plate-shaped body made of pure aluminum whose main component is aluminum or an aluminum alloy containing a trace amount of foreign atoms. These foreign atoms include silicon, iron, manganese, steel, magnesium, chromium, zinc, bismuth, nickel, and titanium. The alloy composition has a content of at most 70% by weight or less.

Aluminum suitable for the present invention is pure aluminum, but since completely pure aluminum is difficult to produce due to smelting technology, it is preferable to use aluminum that contains as few foreign atoms as possible.

Furthermore, any aluminum alloy having the above-mentioned content can be said to be a material that can be applied to the present invention. As described above, the composition of the aluminum plate applied to the present invention is not specified; conventionally known and publicly used materials can be used as appropriate.

Prior to the graining treatment, in order to remove rolling oil from the surface of the aluminum plate, a degreasing treatment using a surfactant or an alkaline aqueous solution is performed, if desired.

Thereafter, the aluminum plate is subjected to a graining treatment.

The graining treatment method includes a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. As a method for mechanically roughening the surface, known methods such as ball polishing, brush polishing, plastic polishing, puff polishing, 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. It is also possible to use a method that combines both methods, as disclosed in Japanese Patent Application Laid-Open No. 4-3702.

The thus roughened aluminum plate is subjected to alkali etching treatment and neutralization treatment as required.

The aluminum plate thus treated is subjected to anodizing treatment. As the electrolyte used in the anodizing treatment, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used, and the electrolyte and its concentration are determined as appropriate depending on the type of electrolyte. The processing conditions for anodic oxidation vary depending on the electrolyte used, so it is impossible to specify them.
Generally, the electrolyte concentration is 1 to 0% by weight solution, the liquid temperature is 3 to 70°C, the current density is J-AOA/dze, and the voltage is 1 to 10%.
oV electrolysis time 7 Electrolysis time 7 is appropriate.

The amount of anodized film is o. i~1011/lr? is preferably in the range of /-497-.

By dissolving the following hydrophilic compound in water or an organic solvent on the anodic oxide film of the aluminum plate treated as described above, applying the solution and drying it to form an intermediate layer,
A printing plate support of the present invention is obtained.

The compound used in the intermediate layer of the present invention has at least 7 groups selected from (11) at least 7 amiZ groups, (2) carboxyl groups and salt groups thereof, and sulfo groups and salt groups thereof. Furthermore, this hydrophilic compound has a hydrophilic group other than the groups (1) and (2) mentioned above.
You may.

Such a hydrophilic compound is suitably a compound having a molecular weight of /,000 or less.

Specific hydrophilic compounds include, for example, chrysine, alanine, valine, leucine, inleucine, serine, threonine, cysteine, cystine, methionine, alapartic acid, glutamic acid, lysine, arginine, ornithine phenylalanine, tyrosine, histidine, tryptophan. , amino acids such as proline, oxyproline, parahydroxyphenylglycine, dihydroxyethylglycine, aliphatic aminosulfonic acids such as sulfamic acid, cyclohexylsulfamic acid, and their sodium salts, potassium salts, ammonium salts, hydrochlorides, etc. Useful. Among these, dihydroxyethylglycine and alanine are the most useful.

The concentration of the intermediate layer liquid is 0.00/~IO weight %, the temperature is 70
It is suitable if it is in the range of ℃ to jQ ℃, p ) i / to /3.

As a method for applying the liquid for the intermediate layer, any of dip coating, spin coating, spray coating, curtain coating, etc. may be used.

Application 1i has a coating amount after drying of /~10089/rr?
is preferable, and more preferably in the range of j-30 cape/d.

As the above-mentioned coating amount becomes less than 1g9/rr/, the effect of preventing stains on the non-painted area becomes less and
0019/rr? As the amount increases, the adhesion between the photosensitive layer and the support deteriorates, and only lithographic printing plates with low printing durability can be obtained.

Before or after providing such an intermediate layer, the anodized aluminum plate may be treated with an aqueous solution of an alkali metal silicate (e.g. sodium silicate) as described in U.S. Pat. No. 3.7 Zahar 67. Can be done.

On the intermediate layer on the conductive substrate thus obtained, a conventionally known electrophotographic photosensitive layer can be provided to obtain the printing plate for an electrophotographic cleavage plate of the present invention. As the photoconductive material, many conventionally known inorganic or organic compounds can be used. For example, inorganic photoconductive materials include selenium and selenium alloys, amorphous silicon, Cd, Cd8e, Cd88e, ZnO1
Examples include Zn8. Next, as organic photoconductive materials, (1) polyvinylcarbazole and its derivatives described in Japanese Patent Publication No. 341-10-66, (2) % Koko Akihiro 3-
Polyvinylpyrene, polyvinylanthracene, polyvinylpyrene, polyvinyl anthracene, polyvinyl anthracene, etc. described in /za 67≠ publication, Tokko Sho≠3-/ri 192 publication
2-vinyl-hiro-(μ'-dimethylaminophenyl)-
j-phenyl-oxazole, poly-3-vinyl-
Vinyl polymers such as ethyl carbazole, (3) Polymers such as polyacenaphthylene, polyindene, and copolymerization of acenaphthylene and styrene described in Tokko Sho 36-/3?4LO issue all 4
Condensation resins such as pyrene-formaldehyde resin, brompyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin described in L.
Various triphenylmethane polymers described in No.-36-7Q and JP-A No. 36-itijjo, as well as low molecular weight ones, (6) U.S. Pat. (7) Oxadiazole derivatives described in US Pat. No. 37g7μμ7, etc.;
/1,076 publication etc., (9) US@Patent No. 36/ J≠02, Patent No. 3za 20 Rizari No., Mukai 3jμ2jμ≠, Special Publication No. 4Lj-333, Special Publication Showa 3/-109g3, Japanese Patent Publication Showa J/-9322≠
No., JP-A-33-1011s67, JP-A-JJ-/3
6ri No. 53, Tokukai Sho! ;l, -31゜146 specification,
Polyarylalkane derivatives described in publications, α1 US 1% Patent No. 3/107λ, US Patent No. 427
g7≠6, JP-A-33-ZAROB≠, JP-A-J! −
Zal063, Tokukai Akihiro Terio, 5jj7, Tokukai Sho3! -31016, JP-A-56-ZA003/, JP-A-56-g♂l-Hiroshi 7, JP-A-37-μ33≠j, JP-A-Sho 34! -ii, No. 2637, JP-A-33-7 Hiroj4
Pyrazoline # described in L6 specification, gazette, etc.
! j4 body and pyrazolone rust conductor, αυ U.S. Patent No. 36131AO≠, Special Publication Shoj/-1
010! No., JP-A Shoj Hiro-g3≠3j No., JP-A Sho-j≠-
Phenyldiamine derivatives described in Japanese Patent Publication No. 10♂36, Japanese Patent Application Publication No. 7/723, Japanese Patent Publication No. Sho Als-37/λ, Japanese Patent Publication No. 447-2g336, publications, etc., 0 U.S. patents. No. 3367μJO, special public Akira≠? -347
No. 0,2, West German Patent (DAS) ///.

No. 57g, U.S. Patent No. 3/0703, U.S. Patent No. 3
2≠0377, U.S. Patent No. 363-320, U.S. Patent No. 232103, U.S. Patent No. ≠/73 L? 6
/ issue, U.S. Patent No. ≠ 012376, JP-A-33-/μ
μ2jO, JP-A-36-//RI-732, JP-A-Sho 3
No. 9-27377, Japanese Unexamined Patent Application Publication No. 1973-. Arylamine derivatives described in 12 μ37 specification, publications, etc. (13 Amino-substituted chalcone derivatives described in U.S. Patent No. 33.21,30/I) N as described in U.S. Pat. , N-bicalbasil derivatives, α9 Oxyazole derivatives described in US Pat. Fluorenone derivatives described in Jμ-/10g No. 37, etc., α US Pat.
32/Hiroshi No. 3 (corresponding to U.S. Patent No. ttijori g7)
, JP-A-33-32063, JP-A-33-3206≠
No., ¥f Kaisho jj-Hiroshi 67AO No., JP 33-13≠
No. 9j, JP-A-37-11330, IV! Kaisho 37-
Hydrazone derivatives are disclosed in JP-A No. 37-1986/θ≠/μ≠, JP-A-60-7G6ZA4L7 Specification 4, and publications.

α 罎 U.S. Patent @≠0≠77 Hong, U.S. Patent No. 410
Benzidine derivatives described in Ko 72μri, US Patent Wb≠J6j Tata No. 0, US Patent≠273g4t6, US Patent≠λ Tataza No. 27, US Patent No. 304001, and the like.

■ Unexamined Japanese Patent Publication No. 3, 7, No. 33, No. 351-23
3≠θ, JP-A Shoj Tartuffugu G, JP-A Shoj Tar/
31.31, JP-A No. 62-3667q, etc. U.S. Pat. No. 369g0Q, U.S. Pat.

Ko 3ri, No. 306, JP-A-Sho≠7-373≠3, J-Za-/233≠-1, J-ZA-1/92Q≠2, JP-A-60-
/7!77416 No. 6/-/Hirof44j No. 3, No. 6
No. 1-23g063, Special Publication No. 60-39≠/No. 60
- Monoazo, bisazo, etc. described in Hiroj, No. 66, etc.
Trisazo pigment■ U.S. Patent No. 3,397,0g6,
Same scripture.

Phthalocyanine pigments such as metal phthalocyanine or metal-free phthalocyanine described in US Pat. Indigo and thioindigo derivatives (to) described in British Patent No. 2.237. Quinacridone pigments described in No. 1, No. 7, etc., British Patent No. 2,237,157g, Japanese Patent Application Publication No. 111,3≠g, I'ff16.2-λza, 73
Polycyclic quinone pigments described in No. g, etc. Bisbenzimidazole pigments described in U.S. Pat.

6t≠, squaliwam salt-based face described in 0za No. 2, etc. @ JP-A No. 39-! 13. Za No. 30, 6/-, 2/2.3
The azulenium salt pigments described in No. 4'2, etc. These organic photoconductive materials may be used in combination in combinations of two or more.

Furthermore, as a sensitizing agent, triallylmethane dyes such as brilliant green, Victoria blue B1 methyl violet, crystal violet, acid violet 6B, O-damine B10-damine 6G, rhodamine G extra, eosin 8. Erythrosine, rose bengal, xanthine dyes such as fluorescein, thiazine dyes such as methylene blue, C,1,Ba5ic
Anthracene dyes such as Violet 7, cyanine dyes, co,6-diphenyl-μm(?'l,N-dimethylaminophenyl)thiapyriliwaum velchlorate,
Examples include biryllium dyes such as penzopyrilliwam salt.

In the printing plate for electrophotographic platemaking of the present invention, the photoconductive compound itself may have film properties, but if the photoconductive compound does not have film properties, a binding resin can be used. As the binding resin, resins commonly known in electrophotography can be used. In the present invention, it is necessary to remove the gold from the photoconductive layer in non-image areas using a liquid junction, but this process is difficult due to the relative properties of the photoconductive layer, such as the solubility of the photoconductive layer in the etching solution or the resistivity of the toner image to the etching solution. It is not possible to generalize because it depends on the relationship between However, in consideration of environmental safety and the like, it is desirable to use as the etching solution an aqueous solution or a mixed solution with an organic solvent that is miscible with the aqueous solution, which will be described later. Therefore, the binding resin used in the present invention is preferably a polymer compound that is soluble or dispersible in the etching solution described below.

Examples of the binding resin include copolymers of styrene and maleic anhydride, copolymers of styrene and monoalkyl maleic anhydride, methacrylic acid/methacrylic ester copolymers, and styrene/methacrylic acid/methacrylic ester copolymers. Acrylic acids such as acrylic acid/methacrylic acid ester copolymer, styrene/acrylic acid/methacrylic acid ester copolymer, vinyl acetate/crotonic acid copolymer, vinyl acetate/croton II/methacrylic acid ester copolymer, etc. Co-operation of esters, methacrylic esters, styrene, vinyl acetate, etc. with carboxylic acid-containing monomers or fII anhydride group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid anhydride, fumaric acid, etc. Polymers, methacrylic acid amide, vinylbiolidone, phenolic hydroxyl groups, sulfonic acid groups,
Copolymers containing monomers having sulfonamide groups or sulfonimide groups, phenol resins, partially saponified vinyl acetate resins, xylene resins, vinyl acetal resins such as polyvinyl butyral can be used.

A copolymer containing a moamer having an acid anhydride group and a carboxylic acid group as a copolymer and a phenol resin are used as a printing plate for electrophotolithography to retain charge in the photoconductive insulating layer when used as a printing plate. It is powerful and can be used with good results.

A copolymer of styrene and maleic anhydride is preferred as a copolymer containing a heptamer having an acid anhydride group as a copolymerization component. Further, a half ester of this copolymer can also be used.

A copolymer containing a heptamer having a carboxylic acid group 't- as a copolymerization component is a copolymer containing two or more elements of acrylic acid or methacrylic acid and an alkyl ester, aryl ester or aralkyl ester of acrylic acid or methacrylic acid. Copolymers are preferred. In addition, vinyl acetate and O-ton acid copolymer, vinyl acetate and carbon number 2-7g
A terpolymer of vinyl ester of carboxylic acid and crotonic acid is also a preferred example. Particularly preferred among the phenolic resins are phenol, 0-cresol,
Novolac resins obtained by condensing m-cresol or p-cresol with formaldehyde and acetaldehyde under completely acidic conditions can be mentioned. The binding resin may be used alone or in combination of two or more.

When using a photoconductive compound and a binding resin, the sensitivity decreases if the content of the photoconductive compound is small, so there is no need to worry! The photoconductive compound can be used in an amount of 0.03 parts by weight or more, more preferably 0.7 parts by weight or more, per 1 part by weight of the resin. If the film thickness of the photoconductive layer is too thin, it will not be able to charge the charge necessary for development, and if it is too thick, etching will occur in the plane direction called side etching, making it impossible to obtain a good image. It can be used in a range of 0.7 to 30μ, more preferably 0.3 to 70μ.

The electrophotographic printing plate of the present invention is obtained by applying a light guiding layer onto a conductive substrate.

The coating solution is obtained by dissolving each component constituting the entire photoconductive layer in a suitable solvent and coating the solution on a conductive substrate.

When using a component that is insoluble in a solvent such as a pigment, the particle size is jμ~0. /μ will be distributed and used. The binder resin and other additives used in the photoconductive layer can be added during or after dispersing the pigment. The coating liquid prepared in this way can be applied by spin coating, blade coating, knife coating, reverse roll coating,
A printing plate for electrophotolithography can be obtained by coating and drying on a substrate by a known method such as dip coating, O-Radbur coating, or spray coating. As a solvent for creating a coating solution,
Halogenated hydrocarbons such as diglomethane, dichloroethane, and ri00 foam, alcohols such as methanol and ethanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and glycol nityl such as ethylene glycol monomethyl ether and d-methoxyethyl acetate. ethyl acetate, ethyl acetate, butyl acetate, and the like.

The printing plate for electrophotographic platemaking of the present invention can be produced by a generally known process. That is, it is charged substantially uniformly in a dark place, and an electrostatic latent image is formed by imagewise exposure.

Examples of the exposure method include scanning U source using a semiconductor laser, )ie-Ne laser, etc., reflection image exposure using a xenon lamp, tungsten lamp, fluorescent lamp, etc. as a light source, and contact exposure using a transparent positive film 1r. Next, the entire electrostatic latent image is developed with toner. As the developing method, various conventional methods such as cascade development, magnetic brush development, powder cloud development, and liquid development can be used. Among these, liquid development can form fine images and is suitable for creating printing plates. The formed toner image can be fixed by known fixing methods, such as heated mud layers, pressure mud layers, solvent fixing, and the like. A printing plate can be prepared by allowing the toner image thus formed to act as a resist and removing the electrophotographic photosensitive layer in non-image areas with an etching solution.

Etching solutions used in the present invention include organic and inorganic acids,
It is preferable to use a mixture of an aqueous solution of one group or a salt thereof with an organic solvent that is miscible with the aqueous solution. Specifically, sodium hydroxide, potassium hydroxide, sodium carbonate,
Sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, sodium phosphorus, potassium phosphate, ammonia, and monoethanolamine,
Amino alcohols such as jetanolamine and triethanolamine are well known. Examples of organic solvents that are miscible with the aqueous solution include alcohols, ketones, esters, and ethers. Alcohols include lower alcohols and aromatic alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol, and phenethyl alcohol, cellosolves such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol, monoethanolamine, and jetanol. Examples include amino alcohols such as amines and triethanolamine.

Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.

Examples of ester fields include ethyl acetate, isopropyl acetate, n-propyl acetate, 5ec-butyl acetate, imbutyl acetate, n-butyl acetate, l-acetoxy 2-methoxyethane, ethylene glycol diacetate, and the like. Examples of the ethers include ethyl ether, tetrahydrofuran, dioxane, 2-methoxyethanol, and ethylene glycol dimethyl ether. These organic solvents can be mixed with the aqueous solution in any range and used, but are preferably mixed and used in a range of 0% by weight or less in the heating solution. A surfactant, an antifoaming agent, a coloring agent, etc. may be added to this etching liquid as necessary.

The toner used in the present invention preferably contains a resin component having resist properties to the etching solution. Examples of resin components include acrylic resins using methacrylic acid esters, vinyl acetate resins, copolymers of vinyl acetate and ethylene or vinyl chloride, vinyl chloride resins, vinylidene chloride resins, and vinyls such as polyvinyl butyral. Acetal resin, polystyrene, copolymers of styrene and butadiene, methacrylic acid esters, etc., polyethylene, polypropylene and its chlorinated products, polyester resins (e.g., polyethylene terephthalate, polyethylene isophthalate, polycarbonate of bisphenol A), polyamide resins (e.g. , polycapramide, polyhexamethylene adiboamide, polyhexamethylene sebamide), phenolic resins, xylene resins, alkyd resins, vinyl-modified alkyd resins, gelatin, cellulose ester derivatives such as carboxymethylcellulose, waxes, polyolefins, and waxes. and so on.

In the present invention, in many cases, the relationship between the toner and the conductive substrate having an oil-repellent or ink-resistant surface is such that the former is oleophilic and the latter surface is hydrophilic; in this case, oleophilic and hydrophilic The degree of oleophobic printing ink on the surface of the substrate is relative, and the oil-based printing ink must not be retained on the substrate surface when the toner image area and the exposed substrate surface are adjacent. This means that the hydrophilicity of the substrate surface is 11! This means that when two substrate surfaces are adjacent to each other, the substrate surface must not be so repellent to water that it is impossible to retain water, and the lipophilicity of the toner means that it must be highly repellent to oil-based printing inks. This means that it should not be impossible to retain oil-based printing inks. The surface of the conductive substrate may have oil-repellent printing ink properties and may also be water-repellent (hydrophobic).

In the present invention, in addition to the original tetraelectric compound and the binding resin, the purpose is to improve the electrical properties such as sensitization and charge retention of the photoquadraconic layer, or the physical properties of the film such as flexibility and coated surface condition, as necessary. Sensitizers, plasticizers, surfactants, and other additives can be added. For example, as a sensitizer, JP-A No. 63≠39, JP-A No. 2.237, 3g-
/, 2'? Examples include amide compounds described in μ32, 6.2-7/'#j, and the like. Examples of the plasticizer include biphenyl, chlorinated biphenyl, o-terphenyl, p-luphenyl, dibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, and the like.

In the present invention, the electrostatic properties of the electrophotographic photosensitive layer, the development properties during toner development, or the image IJ! For the purpose of improving properties, an overcoat layer that can be dissolved when the electrophotographic photosensitive layer is removed can be provided.

This overcoat layer may be mechanically matted or a resin layer containing a matting agent. As matting agents, silicon dioxide, zinc oxide, titanium oxide, zirconium oxide, glass particles, alumina, starch, electrolyte particles (for example, particles of polymethyl methacrylate, polystyrene, phenol resin, etc.) and US special liver i
@j, 710. ．． No. 24j, U.S. Patent No. 2. The matting agents described in Tata λ, 1O1 are included. Two or more of these can be used in combination. The resin used for Resin I-, which coats the matting agent, is appropriately selected depending on the combination with the etching solution used. Specifically, for example, gum arabic, glue, gelatin, casein, celluloses (for example, viscose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, etc.), starches (for example, soluble starch, Modified starch, etc.), polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyacrylamide, polyvinyl methyl ether, epoxy resin, phenol resin (preferably novolac type phenol resin), polyamide, polyvinyl butyral, etc. Two or more of these can be used in combination.

〔Example〕

The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In addition, in the examples, all parts indicate weight 1.

Example 1 JIS10! The surface of the aluminum sheet was grained using a rotating nylon brush using a water suspension as an abrasive. The surface roughness at this time (center line average roughness) is 0.3
μ at nine. After washing with water, it is immersed in a 70% caustic soda aqueous solution at 70°C, and the melting mt of aluminum is 6/rr? I etched it to make it look like this.

After washing with water, it was neutralized by immersing it in a 30% nitric acid aqueous solution for 7 minutes, and was thoroughly washed with water. After that, in a 0.7% nitric acid water bath solution, using a rectangular wave alternating waveform with an anode dark voltage of 3 volts and a cathode voltage of 6 volts (described in % Kosho! J-/RI, RI No. 7), Electrolytic coarsening was performed for 2Q seconds, and 20% sulfuric acid was heated at 30°C.
The surface was washed by immersing it in a solution, and then washed with water. Furthermore,
The weight of the anodized film in 10% sulfuric acid aqueous solution is 3. Op/-
After Illllll oxidation treatment metalwork, washing with water and drying,
A substrate (1) was created.

A solution having the following composition was applied to the surface of the bare substrate (1) treated in this way, and dried at 0° C. for 30 seconds.

The amount of film after drying is IO'9/? Met. A substrate (it) was created in this manner.

Intermediate layer coating liquid dihydroxyethylglycine 0.03 parts methanol Tahiro, ? j part water
! , 0 parts then the board (
]), (II) was coated with the following photoconductive layer coating solution using a bar coater and dried at 120° C. for 10 minutes to prepare a printing plate for electrophotographic platemaking.

Coating liquid for photoconductive layer Shimezu hydrazone compound shown below 2j parts Copolymer of benzyl methacrylate and methacrylic acid (methacrylic flj 30 mol%) 73 parts Thiopyrilliwam salt compound shown below /, / part Methylene chloride 310 parts Methylcellosolve acetate The dry film thickness of 730 copies of the thus prepared printing plate for electrophotographic engraving was 10 μm.

Next, this sample was charged with a Corona Teiden machine in a dark place to a surface potential of 1000 OO■, exposed to tungsten light, and developed with a liquid developer Ricoh MRP (17K) to produce a clear positive image. I don't think I'll be able to get the money. Further, the created image was heated at U.degree. C. for 1 minute, and the toner image was inspected.

This non-lfI image area is removed with an etching solution diluted with potassium silicate Os1 potassium hydroxide 70 parts, ethanol 100@f water g OQ parts, thoroughly washed with water, fc, and gummed to create an offset printing plate. I was able to do it.

This printing plate was printed using a conventional method, and when the 20,000th print was compared, the printing plate using the substrate ([1)'t- did not have any stains, but the printing plate using the substrate (1) If this happens, the non-image areas will become smudged, making it unsuitable for practical use.

Example λ The following intermediate layer coating liquid was applied to the substrate (1) in Example 1 to create a substrate CM).

Coating liquid for intermediate layer β-alanine 0.03 parts Methanol ? ≠, 9j part water
S, O parts, then the board (+),
The following photoconductive layer coating solution was applied to (1) using a bar coater and dried at 120°C for 70 minutes to prepare a printing plate for electrophotographic engraving.

Dispersion liquid for photoconductive layer Trisazo compound /, 0 parts Oxazole compound shown below 2, 3 parts Copolymer of vinyl acetate and crotonic acid (RE8YN rotary lambda g-1310 Kanepois Nisniscy @ 4-fiber) io part Tetrahydro 7ran 100 parts Put it in a 300m glass container with the glass beads, and put it in a paint shaker (
Toyo Seiki Seisakusho @) was dispersed for 60 minutes to prepare a photoconductive layer dispersion.

The thickness of this photovoltaic layer was approximately ≠μ. These are examples/
A printed version was created in a similar manner.

This printing plate was printed using a conventional method, and compared with the printed matter of the cane pattern, the printing plate using the substrate (1) did not have any stains, but the printing plate using the substrate (1) did not have any stains. Please note that the non-image area becomes dirty and is not suitable for practical use.

Example 3 A substrate (
IV) K was prepared and the photoconductive layer of Example/was applied. When a planographic printing plate was prepared using this printing plate for electrophotographic plate making, it was possible to print clearly and without stains in the non-image areas.

Example≠ A substrate (v) was prepared in exactly the same manner as in Example except that lysine was used instead of β-alanine, and the entire photoconductive layer of Example 2 was coated. When a planographic printing plate was prepared using this printing plate for electrophotographic plate making, it was possible to print clearly and without stains in the non-image areas.

Example! A substrate (vl) was prepared in exactly the same manner as in Example 2, except that asnolaginic acid was used instead of β-alanine, and the photoconductive layer of Example 2 was coated thereon. A lithographic printing plate was prepared using this printing plate for electrophotographic plate making, and it was possible to print clearly and without stains in the non-image areas.

Example 6 Substrate (■) was prepared in exactly the same manner except that ornithine hydrochloric acid @gold was used instead of β-alanine in Example 2.
was prepared, and the photoconductive layer of Example λ was applied. When a lithographic printing plate was created using this electrophotographic printing plate,
It was possible to print clearly and without stains in the non-image areas.

Example 7 The following photoconductive layer dispersion was applied to the substrate (1) using β-alanine in Example 2 and the substrate (1) to which no intermediate layer was applied, to create a printing plate for electrophotolithography. .

Dispersion liquid for photoconductive layer C-type steel phthalocyanine / 0 parts Hydrazone compound shown below 2. Part J: Copolymer of benzyl methacrylate and methacrylic acid (0 mol qb of benzyl methacrylate) 70 parts Tetrahydro 7ran 100 parts were placed in a 300 td glass container with glass beads, and mixed in a paint shaker (Toyo Seiki Seisakusho @ 4). Dispersed for 60 minutes. When a lithographic printing plate was created using this printing plate for electrophotography, it was possible to print clearly using the substrate (1) with no stains on the non-image area, but with the substrate (1). In printing plates using this method, the non-image areas are smeared and are not suitable for practical use.

Patent applicant: Fuji Photo Film Co., Ltd. May 7-2, 1988 2, Title of the invention: Printing plate for electrophotographic platemaking 3, Relationship with the amendr case: 1'l? Applicant address
210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 2-26-30 Nishiazabu, Minato-ku, Tokyo 106 Fujisha 1゛ (Film Co., Ltd. Tokyo Head Office' IL story (406) 2537 4 , Target of amendment The description in the "Detailed Description of the Invention" column 5 of the specification and the "Detailed Description of the Invention" section of the Statement of Contents of Amendment 11al is amended as follows.

l) ``90'' on page J, Hiro line l, ``Friend.'' In so-called lithographic printing plates (28th edition), in order to improve staining and printing durability, U.S. Patent 3゜rto, t2
No., British patent λ, 0ri? , No. 627, Special Publication Akihiro 44-
6. Many proposals have been made, as shown in I/L No. 10, JP-A-60-44F, No. 4cP/, and JP-A-60-232, No. 5'.

However, the formation of the 28-plate image formation is carried out by changing the dissolution column of the photosensitive layer itself using an 0-quinone diazide compound, a diazo compound, a photopolymerization system, etc. The printing plate forms an entire image by making the toner 11' formed by electrophotography act as a resist and removing it with a photoconductive gold etching solution.It uses a method essentially different from the conventional 28 plate. It is something. Several proposals have been made as methods for improving stains on printing plates for electrophotographic platemaking. Tokukai Showa J7-
/μ7. The Ajj specification proposes the use of compounds such as casein, polyvinyl alcohol, ethyl cellulose, phenol resin, styrene-maleic anhydride copolymer, and polyacrylic acid for the purpose of improving adhesiveness and electronic properties. ing. In general, the hydrophilicity and printing durability of the substrate (
Adhesion a) between the photosensitive layer and the substrate has been criticized as being contradictory, but wait! ? −μ! , μsr describes the use of a specific amount of polyacrylic acid as an intermediate layer in order to improve both of these properties at the same time. Furthermore, in the specification of Machikai ShojA-/2.063, a method for preventing staining by coating a photoconductive pigment with a resin is shown, but this method is insufficient. ” he corrected.

2) Page 20! row "No maleic acid" "Maleic acid, no" and correct it.

3) 2nd line of page λ “Not obtained”? "Ninth thing you can't get." and correct it.

4) Page 2 IIL, line 76 "acid," Delete.

5) Lines 76-77 of Hiroshi 2 ``With an organic solvent that is miscible with this'' "Organic solvents and these" and correct it.

6) Page 27/row From “Invention” 2nd line on page 7 "I don't mind." Okidai.

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Claims (1)

[Claims] An electrophotographic printing plate comprising at least a conductive substrate, an intermediate layer, and an electrophotographic photosensitive layer, wherein the intermediate layer is selected from the group consisting of at least one amino group, a carboxyl group and its salt, and a sulfo group and its salt. 1. A printing plate for electrophotographic platemaking, comprising a compound having at least one selected group.