JPS59128559A - Printing plate material for electrophotographic plate making - Google Patents

Abstract

PURPOSE:To enhance printing resistance by using a specified photoconductive compd. CONSTITUTION:A layer contg. an org. photoconductive compd. represented by the formula shown here and an alkali-soluble resin is formed on a conductive substrate. In the formula, R is lower alkyl or benzyl; Y is H, lower alkyl, lower alkoxy, halogen, nitro, amino, or lower alkylamino, or benzylamino; and n is 1 or 2.

Description

[Detailed description of the invention]

The present invention relates to a new printing plate that can be made by electrophotography. More specifically, a new printing plate containing a specific photoconductive substance is charged, and an electrostatic latent image obtained by image exposure is developed with toner and fixed to obtain a toner image. This invention relates to a printing plate that is made by dissolving and removing a photosensitive layer in an image area. Traditionally, photosensitive resins have been used as master plates for lithographic printing. , those using silver halide photosensitive materials are known. However, although lithographic printing plates using photosensitive resin have high printing durability, they have low sensitivity, and so-called direct plate making is not possible, and it is necessary to create negatives or positives from the original using silver halide film 11. Therefore, there are drawbacks such as requiring large-scale equipment and requiring time for plate making. In addition, printing plates using diffusion transfer development or hardening development methods of silver halide photosensitive materials (direct plate making in stores are possible, but they have the drawbacks of low printing durability and high cost per sheet. Electrophotography) As a printing plate for direct plate making using the method, for example, Tokko Sho/I 7-47610° Tokko Sho 48
-40002. Tokuko Sho 48-18325, Tokuko Sho 51-
15766 and Japanese Patent Publication No. 51-25761, printing plates having a zinc oxide-resin dispersion system are known. After forming a toner image on this printing plate using electrophotography,
In order to make the non-image area hydrophilic, it is treated with, for example, an acidic aqueous solution containing ferrocyanate. The printing plate made in this way will peel off due to the mechanical pressure applied during printing and the penetration of dampening water into the photosensitive layer and conductive treatment layer.
Because the hydrophilic layer on the surface is destroyed, its printing durability is 5,
It was approximately 000 to 10', 000 sheets. The purpose of the present invention is to
The objective is to provide a new printing plate that works effectively and has very high printing durability. As a result of studying printing plates having layers made of various photoconductive compounds and alkali-soluble resins, the present inventors found that the above object can be achieved when a photoconductive compound represented by the following general formula is used. I discovered that. That is, the present invention provides a printing plate for electrophotolithography having a layer containing an organic photoconductive compound and an alkali-soluble resin on an electroconductive support.
The present invention provides a printing plate for electrophotographic engraving characterized by using a compound represented by the following general formula. In formula C, R represents a lower alkyl group, ' or a benzyl group, and Y represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, or an amino group. or an amino group substituted with a lower alkyl group or a Hensyl group; +1 represents 1 or 2; ] The photoconductive compound represented by the above general formula used in the present invention is represented by the following general formula (1) [wherein Y' is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom or a nitro group, represents a halogen ion) or a dialkyl phosphorous group represented by -PO(OR')2 (where R' represents a lower alkyl group). ] It can be obtained by reacting a phenyl derivative represented by the following with an altehyde derivative represented by the following general formula (b) (wherein R is a lower alkyl group or a benzyl group). In addition, in the general formula of the photoconductive compound used in the present invention, Y is an amino group. Alternatively, in the case of an amino group substituted with a lower alkyl group or a benzyl group, Y obtained by the above synthesis method
By ring-forming a compound having a nitro group as
Further, if necessary, it can be obtained by alkylation or benzylation. Here, one example of the photoconductive compound used in the present invention is shown in the table below. (Hereinafter, blank spaces) The alkali-soluble resin used in the present invention refers to a resin that becomes soluble in an aqueous or alcoholic solvent by adding an alkali. For the purposes of the present invention, in addition to properties such as film-forming properties, electrical properties, and adhesion strength to a support, solubility properties are particularly important for these resins. Examples of resins having such characteristics include styrene/maleic anhydride copolymers, styrene/methacrylic acid/methacrylate copolymers, methacrylic acid/methacrylate copolymers, and phenol resins. Examples of phenolic resins include phenol and 0-cresol. rrl-cresol, P-cresol, ethylphenol, isopropylphenol, t-butylphenol,
t-amylphenol, hexylphenol, t-octylphenol, cyclohexylphenol, 3-methyl-4-lyro-6-1-butylphenol, isobrobycresol, (-butylcresol, t-amylcresol, hexylphenol,

[-A novolak type resin obtained by condensing at least one substituted phenol such as octyl cresol and cyclohexyl furesol with an aldehyde such as formaldehyde, acetaldehyde, acrolein, crotonaldehyde, and furfural under acidic conditions is used. In the electrophotographic printing plate of the present invention, a dye sensitizer or a chemical sensitizer can be used. Examples of dye sensitizers include brilliant green,
Victoria Blue B, Methyl Violet, Crystal Violet, Rhodamine B, Rhodamine FB. Rhodamine G Extra, Sulforhodamine B, Fast Acid Eosin G, Rose Bengal, Fluorescein, Methylene Blue. Acridine Niro, Acridine Orange, Tribaflavin, Cryptocyanin, Alizarin, Astrason Yellow 3G. Basic Yellow 52115, As 1 to Razon Orange R, Malachite Clean, etc. are used. Examples of chemical sensitizers include quinones such as P-pentuquinone and chloranil, aldehydes such as 4-nitrobenzaldehyde, 2-ethoxy-1-nandoldehyde, anthracene-9-aldehyde, and 4-nitrophenol. Nitrophenols. For example, acid anhydrides such as phosuccinic anhydride, maleic anhydride, and phthalic anhydride. For example, benzophenone benzoin, 9-
Examples include ketones such as acetyl-anthracene, phosphoric acids, and boron halide compounds. Furthermore, the printing plate of the present invention can contain a gH-enabler. Examples of plasticizers include dimethyl phthalate,
Phthalate esters such as diethyl phthalate and dibutyl phthalate. Glycol esters such as dimethyl glycol phthalate and ethyl phthalyl ethyl glycolate are effective. These plasticizers can be contained within a range that does not deteriorate the electrostatic properties and alkali solubility of the photoconductive layer. The conductive substrate used in the present invention is an aluminum plate, a zinc plate, a bimetallic plate such as a copper-aluminum plate, a copper-stainless steel plate, a chrome-copper plate, or a chrome-copper-aluminum plate. A conductive substrate having a wood-loving surface such as a tri-metal plate such as a chrome-button-iron plate or a chrome-copper-stainless steel plate is used, and its thickness is preferably 0.1 to 1 mm. Also, especially in the case of supports with an aluminum surface, a grain chamber treatment, sodium silicate. Preferably, the material has been subjected to surface treatment such as immersion treatment in an aqueous solution of potassium fluorozirconate or phosphate, or anodization treatment. Also, U.S. Patent No. 271
As shown in No./1066. After processing in a grain chamber, the aluminum plate was immersed in an aqueous solution of sodium silicate, and after being anodized as shown in JP-A No. 47-5125, it was immersed in an aqueous solution of an alkali metal silicate. Also preferable. The anodic oxidation treatment is performed using, for example, an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or oxalic acid. Electron M, consisting of a solution of organic acids such as sulfamic acid or their salts, ? 132, by passing a current through the aluminum plate as an anode. Further, in the present invention, casein, polyvinyl alcohol, ethyl cellulose, or phenol resin is optionally provided between the conductive substrate and the photoconductive layer. An alkali-soluble interlayer such as a styrene/maleic anhydride copolymer, polyacrylic acid, etc. can be provided to improve the adhesion of the photoconductive layer to the substrate or the electrostatic properties of the photoconductive layer. To produce the electrophotographic printing plate of the present invention, the photoconductive compound represented by the above general formula and additives such as the alkali-soluble resin and dye sensitizer are mixed with toluene, tetrahydrofuran, ethylene glycol monoethyl ether, etc. , methyl ethyl quinone. It is dissolved in a suitable solvent such as halogenated hydrocarbon or ethyl acetate, coated on the fluorescent substrate, and dried. The leading fli layer has a thickness of 1 to 30 μm, preferably 2 μm to 30 μm.
It is created to have a thickness of 5μ. The appropriate proportion of the photoconductive compound in the photoconductive layer is 10 to 60%. The printing plate of the present invention is charged with a conventional electrophotographic method, and then charged with a light source such as a halogen lamp, a tank stencil lamp, or a fluorescent lamp.
Alternatively, a toner image is obtained by exposing to laser light such as an argon laser and then developing with a hydrophobic and ink-receptive toner. After development, the image is fixed by heating using a heat roller, heat wire, or the like. Next, use alkaline water such as sodium silicate aqueous solution or sodium phosphate aqueous solution, or an alkaline water containing an alkaline salt or an organic amine such as ethanolamine. j
, a solvent, or a mixture thereof to dissolve the non-image area (the area to which toner is not attached). If the support is then washed with water and dried, only the image area (toner-attached area) remains on the surface of the support, and a good printing plate can be obtained. Additives such as surfactants can be added to the eluate. Further, the printing plate of the present invention may contain a quinonediazide compound such as 〇-naphthoquinonediazide for the purpose of increasing the solubility of the recording layer by exposing the entire surface to light after forming the toner image. The printing plate of the present invention prepared by the method described above has particularly high stability during printing operations and excellent printing durability. The photosensitive layer of the printing plate of the present invention can also be used for manufacturing printed wiring boards. The present invention will be specifically explained below using examples. Example 1 10g Compound No. 7 photoconductive compound 10g Styrene/maleic anhydride copolymer 0.5g Rhodamine FB 180g Tetrahydrofuran The above solution was applied to a 0.25nnn thick material whose surface was grained and anodized. It was coated on an aluminum plate using a wire bar and dried at 100° C. for 20 minutes to produce a printing plate with a photosensitive layer about 5 μm thick. This printing plate was charged to about -400 V by corona discharge, exposed to light using a plate-making camera using a halogen lamp as a light source, and then developed and fixed with toner to obtain a toner image. Next, the pieces were immersed in a 1% aqueous sodium silicate solution for 1 minute, and then washed with a stream of water while being lightly brushed. The non-image area was removed in this way and the dried printing plate was run on an offset printing machine, 1
00,000 good prints were obtained. Example 2 10g Photoconductive compound of metal compound No. 9 10g Styrene/maleic anhydride copolymer 0.5g Astrason Orange R 180g Tetrahydrofuran The above solution was applied to an aluminum plate whose surface was grained and anodized. A printing plate having a photosensitive layer with a thickness of about 5 μm was prepared. This printing plate was charged to about -400 .mu. by corona discharge, exposed to 488 nm light using a 10 m'W argon laser, developed and fixed with toner, and a toner image was obtained. Next, after removing the non-image area in the same manner as in Example 1, it was printed on an offset printing machine for 10 minutes.
0,000 good prints were obtained. Example 3 Log Compound N012 Photoconductive Compound 10g Methyl methacrylate (80%)/Methyllic Acid (20%)
Copolymer 0.5 g Rhodamine FB 180 g Tetrahydrofuran The same procedure as in Example 1 was carried out except that the photosensitive layer was formed using the above solution, and 100,000 good prints were made in 7.
l). Example 4 10g Compound N015 photoconductive compound
m-cresol formaldehyde resin 0.5 g Astrazone Orange R 180 g Ethylene glycol 7-noethyl ether The same procedure as in Example 2 was carried out except that the photosensitive layer was formed using the above solution, and 100,000 good prints were obtained. 1;
)Ta. Patent applicant Ricoh Co., Ltd.

Claims (1)

[Claims] In an electrophotographic printing plate having a layer containing an organic photoconductive compound and an alkali-soluble resin on a conductive support, a compound represented by the following general formula is used as the organic photoconductive compound. A printing plate for electrophotographic engraving characterized by the following. In the general formula, 艮 represents a lower alkyl group or a benzyl group, and Y represents a hydrogen atom, a lower alkyl group, a lower alkoxy group,
Haloken atom, nitro group, amino group. or an amino group substituted with a lower alkyl group or a benzyl group; n represents 1t or 2;