JPH0442164A - Planographic printing original plate for electrophotographic plate making - Google Patents

Abstract

PURPOSE:To obviate the staining of edge parts by printing by providing layers contg. a polymer having a polysiloxane structure on the end faces of the planographic printing original plate. CONSTITUTION:This planographic printing original plate is constituted by forming a photoconductive layer 2 on a conductive base 1 having a hydrophilic surface 3. The layers 4 contg. the polymer having the polysiloxane structure are provided on the end faces of the plate. The provision of the layers 4 on the end faces after a soln. contg. the silicate expressed by general formula mSiO2/nM2O (M is an alkaline metal atom, m/n=0.5 to 8.5) and a hydrophilic reson is applied on the end faces is also preferable. The provision of the layers 4 after the end faces is subjected to desensitization treatment is equally preferable.

Description

[Detailed description of the invention] [Industrial application field] This E! A is a lithographic printing original plate for electrophotographic platemaking, in which a lithographic printing plate is produced by obtaining a toner image by electronic 4-tone toner development, especially a reversal development method, and then eluting the photosensitive layer in the blue image area other than the toner image area; In particular, the present invention relates to a planographic printing original plate for electrophotographic plate making that provides a planographic printing plate that is prevented from printing stains.

[Conventional technology]

Today, as lithographic offset printing plates, PS plates that use positive-working photosensitizers whose main components are diazo compounds and phenolic resins, and negative-working photosensitizers whose main components are acrylic monomers and prepolymers are in practical use. However, all of these methods have low sensitivity, so plate making is performed by densely exposing a film original plate on which an image has been recorded in advance. - In recent years, advances in computer image processing, large-capacity data storage, and data communication technology have meant that everything from manuscript input, correction, editing, and page layout to page layout is now computer-operated, and high-speed communications networks and satellite communications have enabled Immediate remote terminal terminal a
An electronic editing system that can output to vines has been put into practical use. In particular, electronic editing systems are in high demand in the field of newspaper printing, which requires immediacy. Furthermore, even in fields where originals are stored in the form of original film and printed plates are reproduced as needed, with the development of ultra-high capacity recording media such as optical discs, the originals are stored on these recording media as digital data. It is thought that K will be preserved.

However, it has hardly been put to practical use in direct printing plates where the entire printing plate is created directly from the output of the terminal plotter.
Even in places where electronic editing systems are in operation, the output is done on a button-shield photographic film, and based on this, PS is indirectly created.
In reality, printing plates are created by exposing the plate to light. This is the output plotter's light source (for example, He-
Another reason was that it was difficult to develop a direct printing plate with high enough sensitivity to make a printing plate within a practical time using Ne laser, semiconductor laser, etc.

An electrophotographic photoreceptor can be considered as a photoreceptor having high photosensitivity that can provide all direct printing plates. After toner image formation,
Many lithographic printing original plates for electrophotographic platemaking are already known in which the photoconductive layer in non-image areas is removed. For example, Special Publication No. 37-17112, No. 3l-62t/No. 3! −
77jr issue, same issue/-2≠2 issue, same≠6-3 free Or
No., JP-A-ShojO-19!02, same! 0-/ri No. 570, same! Cor No. 24137, same! Hiro-7≠! No. 331.

Same l1l-/34tt,? No. 2, same No. 1! -/1173 coj≠ issue, same j! -/63ri ≠ issue, direction j1-/bu72S
O, same! 7-l Gua A jj No. 7-16716
Examples include the lithographic printing original plate for electrophotographic platemaking described in No. 3, etc.

In order to make a lithographic printing plate (printing plate for offset printing) 2 using such a lithographic printing original plate for electrophotographic plate making, after image exposure, development is first performed by toner development to completely form a toner image. The toner development K performed here is known to include a normal development method that develops the portion where the electrostatic latent image remains, and a reversal development method that develops the portion where the electrostatic latent image does not remain. Generally, when scanning exposure is performed using a light source such as a laser beam, a reversal development method is often used. Thereafter, after fixing the toner image, the non-image area other than the toner image area is eluted with an eluent to expose the hydrophilic substrate and form a lithographic printing plate.

However, when printing using a printing plate obtained in this way, the portion corresponding to the edge of the printing plate is There is no problem if the surface is not printed, but when printing on a roll of paper using a rotary press, such as in newspaper printing, printing stains occur at locations corresponding to the edges of the printing plate. This stain is significant when toner development is performed by reversal development.

Notification of printing plate for electrophotographic plate making 1j An insulating resin layer is provided on the end surface (side surface) of the planographic printing original plate for electrophotographic plate making in order to prevent edge staining caused by the planographic printing plate obtained by reverse development of the original plate. has been proposed (Unexamined Japanese Patent Publication No. 43-1971 JaO
Publication No.). In other words, one of the causes of printing stains caused by the lithographic printing plate obtained by reversing the lithographic printing original plate for electrophotographic platemaking as described above is that toner also adheres to the end surface of the lithographic printing original plate for electrophotographic platemaking during reversal development. However, it is believed that ink also adheres to this area during printing, causing printing stains. Therefore, an insulating resin is applied to the end surface of the lithographic printing original plate for electrophotographic platemaking, and toner is applied to this area during reversal development. Based on the idea of preventing the adhesion of water-soluble polymer layers. In particular, it has been proposed to provide a resin layer on the edge surface, which has a higher solubility in an alkaline solution than the resin of the photosensitive layer.However, the edge surface of the lithographic printing original plate is often cut with a cutter, and the cut surface is smooth. Generally, the resin tends to remain undissolved because it does not dissolve, and since the remaining resin is ink receptive, printing stains occur at the edges.To prevent this, An effective proposal has already been made by the present applicant (Japanese Patent Application No. Hei/-/J ri+0, Patent Application No. 1-Cocoa 3) The present invention is a further development of this. .

[Problem to be solved by the invention]

Even if the above-mentioned measures were taken, the present inventors were unable to print newspapers, etc. using a lithographic printing plate obtained by forming a toner image through reversal development and removing the photoconductive layer in the non-exposed areas. We found that printing stains were still observed on the edges when printing was done, and as a result of investigating the cause, we found that even if an insulating resin layer is provided as described above, toner hardly adheres to the edges;
It has been found that because the insulating resin layer itself remains on the end face, ink adheres to this area and causes printing stains. That is, by providing an insulating resin layer on the end surface, toner adhesion to the end surface during reversal development has certainly been improved, but the newly provided insulating resin layer itself has lipophilic properties (
In other words, since it is ink-receptive, it was found that if it remained, ink would adhere to the end surface and printing stains could not be prevented.

[Means to solve the problem]

As a result of extensive research in order to solve the above-mentioned drawbacks, the inventors of the present invention discovered a resin that does not cause printing stains even if it remains on the edge surface.This makes it possible to completely prevent printing stains on the edge surface. achieved.

That is, in the present invention, (1) a photoconductive layer is provided on a conductive support having a hydrophilic surface, and after a toner image is formed by imagewise exposure and toner development, a non-image area other than the toner image area is formed; In a planographic printing original plate for electrophotographic plate making which is made into a planographic printing plate by completely removing the photoconductive layer, a layer containing at least a polymer having a polysiloxane structure is provided on the end face of the planographic printing original plate for electrophotographic plate making. A lithographic printing original plate for electrophotographic platemaking, which is characterized by the following.

(2) After applying a photoconductor to the entire layer on a conductive support having a hydrophilic surface, exposing the image to light, and developing a toner image to form a toner image, the entire photoconductive layer in non-image areas other than the toner image area is removed. In the lithographic printing original plate for electrophotographic plate making which is thereby made into a lithographic printing plate, the end surface of the planographic printing original plate for electrophotographic plate making has the following formula: m S i 02 / n M 2
O (MH alkali metal atom, m/n-0, j~
Electrophotography characterized in that a solution containing a silicate represented by r, j) and a hydrophilic resin is coated, and a layer containing at least a polymer having a polysiloxane structure is further provided thereon. Planographic printing original plate for type plate making.

(3) A photoconductive layer is provided on a conductive support having a hydrophilic surface, and after imagewise exposure and toner development to form a toner image, the photoconductive layer in non-image areas other than the toner image area is removed. In the lithographic printing original plate for electrophotographic plate making which is thereby made into a lithographic printing plate, the end surface of the planographic printing original plate for electrophotographic plate making is subjected to a desensitization treatment, and further a polymer having at least a polysiloxane structure is applied thereon. This is a lithographic printing original plate for electrophotographic platemaking, characterized by being provided with a layer containing:

The present invention will be explained in detail below.

As the 411 substrate of the electrophotographic printing original plate of the present invention,
All types of supports can be used. For example, plastic sheets with an electrically conductive surface or papers made particularly solvent-impermeable and electrically conductive, aluminum plates, zinc plates, but also copper-aluminum plates, copper-stainless steel plates, chrome-
Conductive substrates with hydrophilic surfaces such as bimetallic plates such as copper plates, trimetallic plates such as chromium-copper-aluminum plates, chromium-lead-iron plates, and chromium-copper-stainless steel plates are used. The diameter is preferably o, i to J mm, particularly preferably O67 to 0.1 mm. Among these substrates, aluminum plates are preferably used. The aluminum plate used in the present invention is a plate-shaped body such as pure aluminum whose main component is aluminum or an aluminum alloy containing a small amount of foreign atoms, and whose composition is not specified (previously known or publicly used materials). can be used as appropriate.

This aluminum plate can be used after being grained and anodized using a conventionally known method. Prior to the graining treatment, in order to remove rolling fat from the surface of the aluminum plate, degreasing treatment is performed using a surfactant or an alkaline aqueous solution, if desired, and then the graining treatment is performed. Graining treatment methods include a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the entire surface chemically. As a method for mechanically roughening the surface, known methods such as ball polishing, brush polishing, blast 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 solution of hydrochloric acid or nitric cRt. Furthermore, a method combining both methods can also be used, as disclosed in Japanese Patent Application Laid-Open No. 5≠-63°PO2.

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

The thus treated aluminum plate is anodized. As the electrolyte used in the anodizing treatment, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used, and is appropriately determined depending on the electrolyte, its concentration, and the order in which the electrolyte moves. Since it varies depending on the electrolyte used in the anodizing treatment conditions, it is impossible to specify the general condition, but the concentration of electrolyte in boat fishing is /-10% by weight solution, and the temperature of the solution is... ~7Q
QC1 current density j ~60A/dm, pressure/-10
It is preferable that the voltage is 0 V and the electrolysis time is in the range of io seconds to 10 minutes. 0 for the amount of anodic oxide film. /~/O97m2 is suitable, but the range of 2/~All/m2 is more preferable.

A known electrophotographic photosensitive layer (photoconductive layer) is provided on the conductive substrate thus obtained.

Many conventionally known compounds can be used as photoconductive materials for the photoconductive layer of the lithographic printing original plate for electrophotographic platemaking of the present invention.

1) U.S. Patent No. 3. //2. Triazole derivatives described in /RI No. 7 FIA specifications, etc., 2) U.S. Patent No. 3
．． ≠Oxadiazole derivatives described in Japanese Patent Publication No. 7, etc., 3) Imidazole derivatives described in Japanese Publication No. 37-/1, No. 0, etc., 4) U.S. Patent Document No. 7, etc. ,l,/! , No. 0-, 3. rkoo
, Riri issue, same 3. jdaλ,! Hiro≠ issue, special public Akira Fj-j
! J No., J/-10, Ri No. 13, JP-A-Shozi-ta 3.
Coco≠ issue, same! J-101,637, same tt-izt
Polyarylalkane conductors described in the specifications and publications of No. 53, No. J4-34゜tzt, and the like.

5) US tjffy'r 3rd. /10.729, Dokei. λ7r, 7t14, JP5r-rr, ottt, 5j-rr, otj, tty-iot, s37
No., same jj-yo/, Olt No., same 5t-to.

No. 017, No. jl, -rr, No. /Q/, No. j 7-1!
, j4# issue, same j hiro-7/ko, 637 issue, same j-74
Pyrazoline derivatives and pyrazolone derivatives described in J414, Publications, etc.

6 U.S. Patent No. 3. Bu/J', 4tOV issue, special public Akij/
-10, 10t, Mukai 4LJ-j, 7/ko, 417
-Kor, No. 334, Tokukai Sho! Gu IJ, 4'Jj No. 41-//0, IJA No. 747-//
Ri, Ri 2! 1114 phenylene diamines described in the specifications, publications, etc., 7) US Pat. j Otsu No. 7.4160, No. 3,710
．． No. 703, J, No. 2110.617, No. 3゜tj
t, z ko 0, same gu, ko 3, 103, same ≠, /71
．． ri No. 57, same≠, 0/2. ．． No. 37, West German patent (
DAS) / , /10,111, Tokuko Sho ≠ Tar 3! ,
No. 702, same 3ter 27. ! No. 77, Tokukai Sho! ! -/+
4/-, No. 210, same evening, No. 732, same j otsu-22. ≠ Arylamine derivatives described in the specification and publications of No. 37, etc. 8) Amino-substituted chalcone derivatives described in the specification of US Patent No. J, Jco J, jθ/, 9) US Special Edition No. ! Hiroko, N,N-bicalpadil derivatives where j≠ is described in the specification etc., 10) US Patent No. j
, oxazole derivatives described in 237.2O3 specification etc., 11) JP-A-Sho! 6-≠Styrylanthracene derivatives described in J, 2J4', etc., 12) Fluorenone derivatives described in JP-A-5≠-/10,137, etc., 13) U.S. Patent No. 3,7/7 ．． ≠6λ, Tokukai Sho! ≠−
No. 14Ls (U.S. Pat. No. 1, /jO.

Corresponds to No. 17), same! ! -j co, O6J issue, same! ! −
! Ko, 06≠ issue, is-≠t, 740 issue, same rr-r
s-sled! No. 17-//, No. 3jθ, same! -7-/
4tlr, 74t number, 57-104t.

/4'≠Hydrazone derivatives described in specifications, publications, etc. 14) U.S. Patent No. G, O≠7. ri ≠ No. 1, Dokei.

04c7, ri≠ri issue, 41,241. Tata O, Same ≠, Core 3.14It, Same 4t12PF, rri No. 7,
Benzidine derivatives described in the specifications of the same +, 3ot, oor, etc., 15) f# Kaisho! t-/RiQ, Ri No. 53, same j Tata! ≠θ No. 27. ／≠ No., same! Tar/rij
, No. 631, No. 62-36.67, and the like.

Further, in addition to the above-mentioned low-molecular photoconductive compounds, the following high-molecular compounds can also be used.

16) Polyvinylcarbazole and its derivatives described in Japanese Patent Publication No. 3≠-70, 6), 17) % disclosure≠j-/
1. Polyvinylpyrene, polyvinylanthracene, borikovinylugu(≠'-dimethylaminophenyl)-1-phenyloxazole, polyJ-vinyl-s-ethylcarbazole described in t7 No., ≠3-/ri, 772 Publication 18) Polymers such as polyacenaphthylene, polyindene, and copolymers of acenaphthylene and styrene described in Japanese Patent Publication No. 173.

19)% Kosho t4-/3. Condensation resins such as pyrene-formaldehyde resin, brompyrene-formaldehyde, ethylcarpane-formaldehyde resin, etc., described in Rihiro θ, etc., 2O) JP-A-40,113
No., direction r7-/A/,! Various triphenylmethane polymers described in Publication No. 30 are also used for purposes such as improving the sensitivity of photoconductors and giving them a desired photosensitive wavelength range, as well as various pigments and sensitizing dyes. I can do it. Examples of these are: 21) US special liver No. a, a36. roo, France.

Gu3ri, No. 604, JP-A-Sho Gua-3714LJ, same j
lr-/23, j17/issue, same! I-/ri2. Ou
No. 2, same! I-2/ri, No. 243, same! Turf 1.3/
No. 4, No. 40-/7ri, No. 74tj, No. Δ/-/lit
, No. 1733, t/-231. OtJ issue, special public Akira+o
Monoazo, bisazo, trisazo pigments described in -rri≠No. 1, No. 60-Data, No. 66μ, etc. 22) Phthalocyanine pigments (A) such as metal phthalocyanines and metal-free phthalocyanines illustrated below! Public 4
t4t-/14101. No., Dokei J-304tA No.,
Dokei A-42j/ko issue, Dokei≠1-3≠/r issue, Tokukai Sho! l'-/r Koro 3rd issue, 6th Koro 4170! Hirogo, same A,? -,! To 1! ! Hirogo, 63-/, t'1tl1
No. 1? -/l09t2 issue, to-, zp3or issue, Journal Op Chemical Physics, jj
Volume (J, Chem, Phys,.

VoJ-jj) J/71 (/ri7/) fi
Metal-free phthalocyanine pigments such as type, τ type, α type, etc. and their derivatives (B) JP-A No. Shoto-3rzaJ, same! /-23731
Issue, same ri-ioyrai issue, same! ! -! No. 214, same! 7-! Geta 4t3g+, same 7-7rzo4L4L, same t2-/ko l≠! No. ri, No. j6-4t6ko3j,
α type, β type, ε described in 62-7μ/No. 143 etc.
Copper phthalo-7-anine pigments such as molds and their derivatives (C) JP-A-Sho! Tar μ Tata ≠ Hiro issue, same! Tar/A6rij
ri issue, same Aj-//l/! ! No. 63-/910t7
No., same tλ-core! Core λ No., same t/-17rtJ No.,
Mukai t/-2/7 OjO issue, 7/-2/7030 issue, same! 9-2/1 IOJ4 No., AJ-3AII- No. 43-36! Various titanyl 7ta-a7-anine pigments and their derivatives described in JP-A No. 63-37163 and the like (D) JP-A No. 2003-111003-1! 6/ issue, same! 7-7≠Otoko!
! No. j7-/≠76≠1, No. 6/-21117, Applied Fixtures Letter Volume 31 (Appl,
Phys, Left, Vol-Jj)4'
Vanadyl phthalocyanine pigments and their derivatives (E) as described in 4(j(/rif/) etc.)
///Hori issue, 6λ-/63040, same 1-/7
No. 706, same Aj-173/! ! No., Same Jter, 2/
≠03≠ issue, same j7-2O0! No. r, Applied Fixtures Letter, Ko08 (App 1-Phys, L
Aluminum phthalocyanine pigments and derivatives thereof (F) described in JP-A-4/-117413, Vol-KO) 27 RiharitS), et al. ter4t4/
.

O! Gu issue! Tarkot ≠ da issue, same 60-! Ri3! j
No. 63-37163, sameyo Tar/Jr! II No. 1, No. 43-27411; No. 2, No. ≦3-! ≦jj4<l
23) Indium phthalocyanine pigments and their derivatives as described in U.S. Pat. 5-thioindigo derivatives 25) Quinacridone pigments described in British Patent No. λ, 237,672, etc. 26) British Patent No. 2. Ko No. 37,471, Tokukai Sho! Polycyclic quinone pigments described in 1t4L, 34tt, 4J-1ff, 731, etc. 27) JP-A Akihiro 7-30.33! Bisbenzimidazole pigments described in No. 28) U.S. %E No. 4', JPj, No. 1G10, same ta.

Squarium-based pigments described in 6μμ, orλ, etc. 29)% Kaishoj? -jJ, rjO No. 4/-,2
/2. ! ≠Azulenium-based pigments described in No. λ, etc.

In addition, as a sensitizing agent, "sensitizer" /-! Page Kodansha 1
1917, "Electrophotography J/2 Tahari 73)"
Organic Synthetic Chemistry” 2hiro A//1010(/’?tt
), etc. can be used. For example, 30 U.S. Pat.

ko r3. Byrylium-based dyes described in Kokoku No. 7J, Special Publication Sho No. AT-2Z, TRY No., JP-A No. 4.2-7/, No. 45, etc. 31) "Applied Optics Supplements"
”' (Applied 0ptics S
UPLEMENT)J! 0(／rittri), Tokukai Sho! o-32,! Triarylmethane dyes described in No. V1 etc. 32) U.S. Patent No. 3. ! 7. Cyanine dyes described in JP-A No. 6, etc. 33) JP-A-Sho JO-/Δ3. θ4t7, same! Tar it
a, try, same AO-252,! Styryl yarn dyes described in /7q etc. These can be used alone or in combination of two or more. In addition, when these charge generation agents have not only charge generation ability but also charge transport ability, as a basic material,
A photosensitive metal bar can be produced by dispersing and coating the charge generating agent in a binder. That is, organic photoconductive compounds known as charge transport agents (for example, (1) above)
- (Compound described in (2O)) does not necessarily need to be used in combination.

All known compounds can be added to the photoconductive layer of the lithographic printing original plate for electrophotographic platemaking of the present invention for the purpose of improving sensitivity. Examples of such compounds include electron-withdrawing compounds such as trinitrofluorenone, chloranil, and tetracyanoethylene; ri,≠3
Examples include compounds described in No. 2, No. 62-7/, No. 246, and the like.

In an electrophotographic photoreceptor, 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 used in the photoconductive layer of the lithographic printing original plate for electrophotographic plate making of the present invention, resins known in the field of electrophotography can be used. In order to create a printing plate using an electrophotographic photoreceptor, it is necessary to finally remove the photoconductive layer in the non-image area. It cannot be generalized because it depends on the relative relationship between the image and the eluent, such as the resistivity. As the binding resin, a polymer compound that is soluble or dispersible in the eluate described below is preferred.

Examples of polymers 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 polymers, acrylic acid/methacrylic ester copolymers, styrene/acrylic acid/methacrylic ester copolymers, vinyl acetate/crotonic acid ester copolymers, vinyl acetate/crotonic acid/methacrylic ester copolymers, etc. Combination of esters, methacrylic acid esters, styrene, vinyl acetate, etc. with carboxylic acid-containing monomers or acid anhydride group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid anhydride, fumaric acid, etc. Polymers, methacrylic acid amide, vinyl pyrrolidone, copolymers containing monomers with phenolic hydroxyl groups, sulfone dispersion groups, sulfonamide groups, sulfonimide groups, phenolic resins, partially saponified vinyl acetate resins, xylene resins, Examples include vinyl acetal resins such as polyvinyl butyral.

A copolymer containing a monomer having an acid anhydride group and a carboxylic acid group as a copolymerization component, and a phenol resin have a charge retention ability of a photoconductive insulating layer when used as a printing plate for electrophotographic engraving. High (, can be used with good results.

Among the copolymers containing acid anhydride-based monomers as copolymerization components, copolymers of styrene and maleic anhydride are preferred. Half esters of this copolymer can also be used.

A copolymer containing a monomer having a carboxylic acid group tOW as a copolymerization component is a monomer of acrylic acid or methacrylic acid and an alkyl ester, aryl ester, or aralkyl ester of acrylic acid or methacrylic acid. The above copolymers are preferred. Further, preferable examples include a copolymer of vinyl acetate and crotonic acid, and a terpolymer of vinyl acetate, a vinyl ester of a carboxylic acid having carbon number λ~/I, and crotonic acid. Among the phenolic resins, phenol, 0-cresol, m
Examples include novolac resins obtained by condensing -cresol or p-cresol with formaldehyde or acetaldehyde under acidic conditions.

When a photoconductive compound and a binding resin are used, the t of the photoconductive compound is determined by adding t to the photoconductive compound per 1 part by weight of the binding resin, since sensitivity decreases when the content of the photoconductive compound is small. It can be used in a range of from 0.02 parts by weight to 1-parts by weight, more preferably from 0.02 parts by weight to 0 parts by weight.

In addition, if the film thickness of the light guide shield of the present invention is too thin, it will not be possible to charge the entire surface potential required for development, and conversely, if the film thickness is too thin, a flat surface called side etch will occur when removing the photoconductor. This causes directional etching and makes it impossible to obtain a good printing plate.
0. /~30μ, preferably 0. Can be used with j-10μ.

The electrophotographic printing plate of the present invention can be obtained by coating a photoconductive layer on a conductive substrate according to a conventional method. When creating a photoconductive layer, what are the components that make up the photoconductive layer? A method in which the charge carrier generating substance and a charge carrier transporting substance are contained in the same layer, and a method in which the charge carrier generating substance and the charge carrier transporting substance are separated into different layers are known, and it can be produced by either method.

The coating solution is prepared by dissolving each component constituting the photoconductive layer in an appropriate solvent. When using components that are insoluble in solvents such as pigments, the particle size can be adjusted using a ball mill, a dispersing machine such as an Indian shaker, Dyno Mill, or Attrital. It is used by dispersing it in μ to Q, lμ. Addition of pigments, etc. to the binder resin and other additives used in the photoconductive layer during or after dispersion.
The coating solution prepared in this way is coated on a substrate by a known method such as spin coating, grade coating, knife coating, reverse roll coating, dip coating, rod bar coating, or spray coating, and then dried. A printing plate for electrophotographic engraving can be obtained.Solvents for preparing the coating solution include nohalocarbonated hydrocarbons X such as dichloromethane, dichloroethane, and chloroform, alcohols such as methanol and ethanol, acetone, methyl ethyl ketone, cyclohexanone, etc. Examples include ketones such as ethylene, glycol monomethyl ether, glycol ethers such as comethoxyethyl acetate, ethers such as tetrahydroctane and dioxane, and esters such as ethyl acetate and methyl acetate.

In addition to a photoconductive compound and a binding resin, the photoconductive layer of the lithographic printing original plate for electrophotographic platemaking of the present invention contains a plasticizer and an interface, if necessary, in order to improve the flexibility of the photoconductive layer and the condition of the coated surface. Various additives such as activators, matting agents, and others can be added to the blade. These additives can be contained within a range that does not deteriorate the electrostatic properties and etching properties of the photoconductive layer.

In the lithographic printing original plate for electrophotographic platemaking of the present invention, an intermediate layer is provided, if necessary, for the purpose of improving the adhesion between the conductive substrate and the photoconductive layer, the electrical properties of the photoconductive layer, the etching properties, the printing properties, etc. be able to.

Examples of the intermediate layer include casein, polyvinyl alcohol, ethyl cellulose, phenolic resin, styrene-maleic anhydride resin, polyacrylic acid, monoethanolamine, jetanolamine, triethanolamine, triproparturamine, triethylamine, and the like. hydrochloride, oxalate, phosphate, aminoacetic acid, monoamino monocarboxylic acid such as alanine, serine, threonine,
Oxyamino acids such as dihydroxyethylglycine, sulfur-containing amino acids such as cysteine and cystine, monoaminodicarmenic acids such as aspartic acid and glutamic acid,
diaminomonocarboxylic acids such as p-hydroxyphenylglycine, phenylalanine, anthranilic acid, amino acids with an aromatic nucleus such as p-hydroxyphenylglycine, phenylalanine, anthranilic acid, 7/acids with multiple repeating rings such as tryptophan, proline, sulfamic acid, cyclohexylsulfamic acid, etc. Aliphatic aminosulfonic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminediacetic acid, cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol ether diamine tetraacetic acid (Polyaminopolyacetic acid such as acetic acid) and salts in which all or all of the acid groups of these compounds are sodium salts, potassium salts, ammonium salts, etc. can be mentioned.

In addition, if necessary, an overcoat layer that can be removed during etching of the photoconductive layer is provided on the photoconductive layer for the purpose of improving the electrical properties of the photoconductive layer, the adhesion with the toner during toner development, etc. 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, resin particles (for example, polymethyl methacrylate, polystyrene, phenolic resin, etc.) and US%E Cocoa No. 024A, No. 22
The matting agents described in US Pat. No. 22,101 are included. Two or more of these can be used in combination.

It is appropriately selected depending on the combination with the etching liquid used for the resin used in the resin layer containing the matting agent. For example, gum arabic, glue, gelatin, casein, cellulose (eg, hiscose, methylcellulose, ethylcellulose, ethylcellulose, hydroquinepropylmethylcellulose, carboxymethylcellulose, etc.), Starches (e.g. soluble starch, modified starch, etc.), polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyacrylamide,
Borivinylimethyl ether, epoxy resin, phenolic resin (especially preferred is novolak type phenolic resin),
Polyamide, polyvinyl butyral, etc. can be mentioned. Two or more of these can be used in combination.

A polymer having at least a polysiloxane structure formed at the end portion (hereinafter referred to as a polysiloxane polymer), which is a feature of the present invention, will be explained.

The polysiloxa 71 combination referred to in the present invention has silicon/silicone in the main chain.
It is a polymer having a repeating structure of oxygen bonds (-8i-0- bonds), and the polymer generally called silicone belongs to this category.

That is, it may be a homopolymer, a copolymer, or a crosslinked structure as long as it contains at least the above structure. If it is a copolymer,
Copolymers such as block and graft copolymers of polymers other than polysiloxane and polysiloxane polymers may also be used. These are generally known as silicone oil, organically modified silicone oil, silicone grease, silicone rubber, and silicone resin.

The polysiloxane polymer will be explained in more detail below. Chemically, it belongs to a family of polysiloxane polymers known as silicone oils and silicone greases, which are called edge-shaped organopolysiloxanes.

The linear organopolysiloxane mentioned here is a linear polymer having repeating units as shown in the following formula.
R1 and R2H are hydrogen atoms, or alkyl, vinyl, aryl, or aralkyl groups having a carbon number of up to IO, and may have appropriate substituents. R1 and R2 [may be the same or different, and the repeating units may be different along the polymer main chain. That is, it may be a copolymer.

The above substituents are not particularly limited, but include amino groups,
Examples include an epoxy group, a carboxy group, a mercapto group, a hydrosilylated group, a halogen atom, a polyhaloalkyl group, a vinyl group, and a group having a polyether structure.

It is a polymer that is three-dimensionally crosslinked with a silicone polymer known as silicone rubber or silicone resin, and is synthesized by crosslinking the above-mentioned linear organopolysiloxane. Known crosslinking methods include peracid individual crosslinking, condensation crosslinking, hydrosilylation, addition reaction, ultraviolet crosslinking, and electron beam crosslinking. I don't mind if you use something.

Peracid individual crosslinking refers to crosslinking linear organopolysiloxane using a peracid individual as an initiator.

Linear organoporin loxanes do not have special functional groups (although they can be crosslinked, but polysiloxanes with vinyl-based side chains that are highly reactive to radicals are usually used).

For condensation crosslinking, a condensation type crosslinking agent or a condensate thereof is added to a linear organopolysiloxane having hydroxyl groups at both ends,
If necessary, a catalyst is added to carry out crosslinking by a condensation reaction. The condensation type crosslinking agent mentioned above is preferably one represented by the following general formula.

Rm-8i-Xn (m+n-ren, an integer of n≧/) Rd has the same meaning as Rt explained above, and xh is a substituent as shown below.

(1) C1,Br,I7'xdo(r)haO'J7N child (
210H Also, organic functional groups such as OCO3, OR4, etc.

Here, R3 to R511 alkyl or substituted alkyl groups are shown.

Catalysts used for such condensation-type crosslinking include organic carboxylates of metals such as tin, zinc, lead, calcium, and manganese, such as diptyltin laurate, tin octylate, and lead naphthenate. Alternatively, something like platinum chloride is used.

Crosslinking by hydrosilylation creates 8iH groups and -CH=C
A linear organopolysiloxane which gives a silicone rubber by an addition reaction with H-, and which contains two or more vinyl groups as a substituent, is used as a crosslinking agent, using cloxane oligo7-, which has three or more 5i-H groups, as a crosslinking agent. It is used as a catalyst, and if necessary, a catalyst is added to perform crosslinking by a hydrosilylation reaction. For example, (1) 7 parts by weight of an organopolysiloxane having at least 2 alkenyl groups (more preferably vinyl groups) directly bonded to silicon atoms (2) 7 parts by weight of organopolysiloxane having at least 2 alkenyl groups (more preferably vinyl groups) bonded directly to silicon atoms (2) having a small number (2 SiH bonds) per molecule Organohydrodiene polysiloxane with 0.1 to 1000
Parts by Weight (3) Edge Catalyst There are compositions consisting of o, ooooi to 10 parts by weight. The alkenyl group of component (1) may be located either at the end or in the middle of the molecular chain, and organic groups other than the alkenyl group include substituted or unsubstituted alkyl groups and aryl groups.

Component (1) may contain a trace amount of hydroxyl group.

The hydrogen group in component <27 may be located either at the end or in the middle of the molecular chain, and examples of organic groups other than hydrogen include those similar to component (1).

Examples of component (1) include α,ω-divinylborodimethylroxane, a copolymer of (methylvinylsiloxane) (dimethylsiloxane) having methyl groups at both ends, and the like.
Component (2) includes polydimethylcloxane having hydroxyl groups at both ends, α,ω-dimethylpolymethylhydrodiene 7
Examples include 0xane, (methylhydrodienesiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, and cyclic polymethylhydrodienesiloxane.

The addition catalyst for component (3) may be arbitrarily selected from known ones, but platinum-based compounds are particularly preferred, and examples include platinum, platinum chloride, chloroplatinic acid, and olefin-coordinated platinum. For the purpose of controlling the curing rate of these compositions, vinyl group-containing organopolysiloxanes such as tetracyclo(methylvinyl)cyclohexane, carbon-carbon 311L
Binding metal alcohol, acetone, methyl ethyl ketone,
Crosslinking inhibitors such as methanol, ethanol, propylene glycol monomethyl ether can also be added.

The three-dimensionally cross-linked polysiloxane polymers exemplified above are prepared by mixing the components for cross-linking to form a three-dimensional polymer, applying a silicone rubber precursor, and then heating it to room temperature or 3-dimensionally. A dimensionally crosslinked polysiloxane polymer.

In the present invention, a polysiloxane polymer or its precursor is applied to the cut surface of the planographic printing original plate for electrophotographic platemaking obtained as described above, which is cut into a required size and stacked in large numbers. Apply a liquid containing the body. It is preferable for mass production to stack a large number of sheets in this way, but
- It may be applied to the end face of each sheet.

Polysiloxane polymer or precursor of polysiloxane polymer? The coating can be applied using a brush, a sponge, a roller, etc., or by a conventionally known method such as spray coating.

In addition, the edge surface to be coated varies depending on the usage pattern of the printing plate, and if only one end surface of the printing plate will be the printing surface, it is fine to apply the coating to only that one end surface, but if various usage patterns are assumed, , preferably two opposing end faces, most preferably (outer end 1i1o (i.e., the entire μ side end face).

In the present invention, below the layer containing the polysiloxane polymer, - formula m5i02/n M2O (M
U alkali metal atom, m/(r-0.

! An aqueous solution containing a silicate represented by ~t and ri and a hydrophilic resin gold may be applied.

Further, in the present invention, the end face may be desensitized by applying a desensitizing treatment liquid under the layer containing the polysiloxane polymer.

By carrying out these treatments, even if the upper layer containing a polysiloxane polymer should fall off during printing, printing stains on the edges can be prevented.

The aqueous solution containing a silicate and a water bath resin and its application in the present invention will be explained below.

In the present invention, sodium silicate, potassium silicate, lithium silicate, etc. can be used as the silicate. The molar ratio m/n of m S+ 02 / n M 2 Q used in the present invention is preferably o, tr, or t.

In the silicate and hydrophilic resin solution or silicate aqueous solution used in the present invention, the silicate is about O1 of the total composition weight.
μ weight t% ~ about ≠ O weight %, preferably about o, r weight % ~
About 2! It is preferable to use it within a range of % by weight.

Further, examples of hydrophilic resins that can be used in the present invention include the following.

For example, natural polymers include starches such as kansho starch, potato starch, tapioca starch, wheat starch, and corn starch; , Troro mallow, mannan,
Plant mucilages such as quince seed, pectin, tragacanth gum, karaya gum, xanthine gum, guarbing gum, locust bingham gum, gum arabic, calops gum and benzoin gum, homopolysaccharides such as dextran, glucan and levan, and heteropolysaccharides such as succinoglucan and santhanum gum Examples include mucilage, glue, and proteins such as gelatin, casetin, and collagen that have been denatured by the fermentation of microorganisms such as Spears. In addition to alginate propylene glycol ester, which is a semi-thermodynamic (semi-synthetic product), viscose, methylcellulose, ethylcellulose, methylethylcellulose, carboquine methylcellulose, hydroquineprobylcellulose, hydroxypropylmethylcellulose, hydroxypropylethylcellulose and hydroxypropylmethylcellulose phthalate. and modified starch. Processed starches include roasted starches such as white dextrin, yellow dextrin, and Gritish gum, enzyme-modified dextrins such as enzyme dextrin and Nyardinger dextrin, acid-decomposed starches as solubilized starches, and oxidized starches as dialdehyde starch. , pregelatinized starch such as modified pregelatinized starch and unmodified pregelatinized starch, esterified starch such as phosphate starch, fatty starch, sulfuric acid starch, nitrate starch, xanthate starch and carbamate starch, carboxylalkyl starch, hydroxyalkyl starch Starch, etherified starch such as sulfoalkyl starch, anoethyl starch, allyl starch, benzyl starch, carbamylethyl starch and dialkylamino starch, methylol cross-linked starch, hydroxyalkyl starch starch, phosphoric acid cross-linked starch and dicarboxylic acid cross-linked starch, etc. Cross-linked starch, starch polyacrylamide copolymer, starch polyacrylic acid copolymer,
Starch polyvinyl acetate copolymer, starch polyacrylny l-
IJ Le copolymer, cationic starch polyacrylic acid ester copolymer, cationic starch vinyl polymer-11i,
Examples include starch graft copolymers such as starch polystyrene maleic acid copolymers and starch polyethylene oxide copolymers. In addition to polyvinyl alcohol, synthetic products include partially acetalized polyvinyl alcohol, 71Jruf
- Polyvinyl alcohol, vinyl methyl ether, modified polyvinyl alcohol such as polyvinyl alcohol and polyvinyl imbutyl ether, sodium polyacrylate, partially saponified polyacrylic ester, partially saponified polyacrylic ester copolymer monster,
polyacrylic acid derivatives and polymethacrylic acid derivatives such as polymethacrylate and polyacrylamide;
Polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, copolymer of polyvinylpyrrolidone and vinyl acetate, carboxyl vinyl polymer,
These include styrene maleic acid copolymer and styrene crotonic acid copolymer.

In the aqueous solution of silicate and hydrophilic resin used in the present invention, the water-soluble resin is used in an amount ranging from about 1% to about 30% by weight, preferably from about 3% to about 2J% by weight of the total composition weight. It is better. When the content is less than 7% by weight, the effectiveness of use decreases, and when it is more than 30% by weight, the viscosity increases and handling becomes difficult. These hydrophilic resins may be used alone (or may be used in combination of two or more types).

The desensitization treatment using gAK- of the present invention is carried out by applying the desensitization treatment solution ti described below to the end surface of the aqueous support. As a desensitizing treatment liquid, what has been known as a desensitizing treatment liquid for hydrophilic supports of lithographic printing plates can be effectively used. It consists of an aqueous solution containing an organic polymer compound gold. Specific hydrophilic organic polymer compounds include gum arabic, dextrin, alginates such as sodium alginate, water-soluble celluloses such as carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylmethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylamide. , water-soluble copolymers containing acrylamide units, polyacrylic acid, copolymers containing acrylic acid units, polymethacrylic acid, copolymers containing methacrylic acid units, copolymers of vinyl methyl ether and maleic anhydride, Copolymer of vinyl acetate and maleic anhydride,
Examples include phosphoric acid-modified starch, among which gum arabic is preferred because it has a strong desensitizing effect. Two or more of these hydrophilic polymer compounds can be used in combination if necessary, and are used at a concentration of about 10% by weight, more preferably 1 to 30% by weight.

It is preferable that the desensitizing liquid consisting of an aqueous solution of a hydrophilic polymer compound used in the present invention further contains a metal salt of a strong acid, whereby the desensitizing effect can be enhanced. Specific metal salts of strong acids include sodium salts, potassium salts, magnesium salts, calcium salts, and zinc salts of nitric acid, sodium salts, potassium salts, magnesium salts, calcium salts, and zinc salts of sulfuric acid, sodium salts of chromic acid, Mention may be made of potassium, magnesium, calcium and zinc salts, as well as sodium and potassium fluoride. Two or more of these metal salts of strong acids can be used in combination, and the amount thereof is preferably about 0.07-7% by weight based on the total weight of the desensitizing solution.

When the hydrophilic polymer compound contained in the desensitizing liquid used in the present invention is gum arabic, the PU value should be in the acidic range, more preferably in the acidic range, more preferably in the range of /~j, most preferably in the range of λ~6,! is adjusted to Therefore, if the pH of the aqueous phase is not acidic, more acid is added to the aqueous phase. Examples of acids that can be used as such pH adjusters include mineral acids such as phosphoric acid, sulfuric acid, and nitric acid; Examples include organic acids such as phosphonic acid. Among these, phosphoric acid has a pH
It is particularly excellent because it not only functions as a regulator but also has the effect of strengthening the desensitizing effect. 0.0/~1% by weight based on the total weight of the desensitizing liquid, most preferably o,/
~! It is preferable to include it in a range of t% by weight.

It is preferable that the desensitizing liquid Kfl used in the present invention contains a wetting agent and/or a surfactant, thereby improving the applicability of the desensitizing liquid. Specific wetting agents include lower polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol, bentanediol, hexylene glycol, tetraethylene glycol, polyethylene glycol, diethylene glycol, and tripropylene. glycol,
Examples include glycerin, nrubitol, pentaerythrol, etc., with glycerin being particularly preferred.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl phenyl ether and polyoxyethylene polyoxypropylene block copolymer, and fatty acid salts.

Anionic surfactants such as alkyl sulfuric acid ester hydrochloric acid, alkylbenzenesulfonic acid salts, alkylnaphthalene sulfonic acid salts, dialkyl sulfosuccinic acid ester salts, alkyl phosphoric acid ester salts, naphthalene sulfonic acid formalin condensate, etc.1 For example, betaine type, glycine type, Alanine type and sulfobetaine type amphoteric surfactants can be used.

These wetting agents and/or surfactants are about 0.0% based on the total weight of the desensitizing liquid. j~10 times 'IkaID, more preferably /~! It can be contained within a certain range.

In addition to the desensitizing liquid Vr- used in the present invention, a filler such as silicon dioxide, Merck, clay, etc. is added in an amount of 10% by weight,
It is also possible to contain dyes, pigments, etc. in amounts up to /Mt%.

In order to desensitize the entire end surface of an electrophotographic photoreceptor using the desensitizing liquid as described above, it is possible to apply the desensitizing liquid to the end surfaces seven times at a time, but preferably, a large number of sheets (for example,
, ooo photoreceptors) are stacked and coated onto their end surfaces.

In the present invention, as described above, a desensitizing treatment liquid or a liquid containing a silicate and a water-bathable resin is coated on the end face of a lithographic printing original plate for electrophotographic platemaking, and after drying, polyester is applied thereon. Scale coating containing siloxane polymer.

The amount of the desensitizing treatment liquid or the liquid containing the silicate and water-soluble resin applied to the end surface is preferably in the range of approximately 5θ to /309/m 2 .

Thickness Bo of the layer containing the polysiloxane polymer of the present invention,
iμ~30μ/m is preferable, more preferably 0. j
~10μ/m2.

FIG. 1 is a schematic cross-sectional view of the lithographic printing original plate for electrophotographic platemaking of the present invention, in which a photoconductive layer is provided on the hydrophilic surface 3 of the support 1, and a polysiloxane polymer is coated on the end surface of the photoconductive layer. Containing layer ≠ is coated. FIG. 1 shows another embodiment of the present invention, in which a photoconductive layer 6 is provided on a hydrophilic surface 7 of a support j, and a desensitized layer l and a polysiloxane polymer are coated on the end faces of the photoconductive layer 6. It is coated with a layer of Confucianism.

FIG. 3 shows another embodiment of the present invention, in which a photoconductive layer/l is provided on the hydrophilic surface 12 of a support 10, and a photoconductive layer/l containing silicate and water-soluble resin, and a layer/4' containing a polysiloxane polymer.

A lithographic printing plate can be produced using the lithographic printing original plate for electrophotographic engraving of the present invention by a process known in the art. That is, it is charged substantially uniformly in the dark,
An electrostatic latent image is formed by imagewise exposure. Examples of the exposure method include reflection image exposure using a scanning tube tip using a semiconductor laser, He--Ne laser, etc., or using a total light source such as a xenon lamp, tungsten lamp, or fluorescent nail, and contact exposure using a transparent positive film. Next, the latent image is developed with toner. As the developing method, conventionally known methods such as cascade development, magnetic brush development, powder cloud development, and liquid development can be used. Among these, it is possible to form a fine image on liquid inkjet g, and it is suitable for creating a printing plate. The formed toner image can be fixed by a known fixing method, such as heat fixing, pressure fixing, solvent fixing, or the like.

A lithographic printing plate can be prepared by allowing the toner image ffl' thus formed to act as a resist and removing the electrophotographic photosensitive layer in the non-image area with an etching solution.

As the etching solution for removing the photoconductive insulating layer in the non-toner image area after toner image formation, any solvent can be used as long as it can remove the entire photoconductive insulating layer, and there are no particular limitations. However, preferably alkaline solvents are used. The alkaline solvent referred to herein is an aqueous solution containing an alkaline compound, an organic solvent containing an alkaline compound, or a mixture of an aqueous solution containing an alkaline compound and an organic solvent.

Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, potassium silicate, and sodium metasilicate.

Any organic or inorganic alkaline compounds can be mentioned, such as potassium metasilicate, sodium phosphate, potassium phosphate, ammonia, and amino alcohols such as monoethanolamine, jetanolamine, and triethanolamine. The solvent for the etching solution is as described above.

Water or a large amount of organic solvent can be used, but
From the viewpoint of odor and pollution, an etching solution mainly containing water is preferably used.

If necessary, various organic solvents can be added to the etching solution using water as a living body. Preferred organic solvents include lower alcohols and aromatic alcohols such as methanol, ethanol, propatool, phthanol, benzyl alcohol, and phenethyl alcohol; Amino alcohols such as tanolamine and triethanolamine can be mentioned.

Further, the etching liquid may contain a surfactant, an antifoaming agent, and various other additives as required.

In the present invention, the toner forming the image area may be used as long as it has resistivity to the etching solution (although it is not particularly limited, it generally contains a resin component that has resistivity to the etching solution). It is preferable that you do so.

Examples of resin components include acrylic resins using methacrylic acid, acrylic acid, and their esters, vinyl acetate resins, copolymer resins such as vinyl acetate and ethylene or vinyl chloride, vinyl chloride resins, vinylidene chloride resins, and polyvinyl butyral resins. Vinyl acetal resins such as polystyrene, copolymer resins of styrene and getadiene, methacrylic acid esters, polyethylene, polypropylene and their chlorinated products, polyester resins (e.g., polyethylene terephthalate, polyethylene isoheptalate, polycarbonate of bisphenol A, etc.), phenol Resin, xylene resin, alkyd resin, vinyl modified alkyd resin, gelatin, cellulose ester conductor such as carboquine methylcellulose, wax, polyolefin,
Examples include 臘etc.

〔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 of the present invention is exceeded.

The surface of the JIS 10!0 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 0.2μ
Met. After washing with water, it was immersed in a 700C aqueous solution of 10% caustic soda and etched so that the amount of aluminum dissolved was 4g7m2. 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 aqueous solution, using a square wave alternating waveform with an anode special voltage of 3 volts and a cathode special voltage of 6 volts (Tokuko Shojj
-/ri/ri No. 1) Perform electrolytic surface treatment for 0 seconds, and
O% of sulfuric acid! After cleaning the surface by immersing it in 09C solution, it was washed with water. Further, the substrate was anodized in an aqueous solution of 0 clJ sulfuric acid so that the weight of the anodized film was 3,097 m2, washed with water, and dried to prepare a substrate.

On this substrate, the following photoconductive layer coating solution (1) was applied using a bar coater and dried for 70 minutes to prepare a printing plate for electrophotographic printing.

Coating liquid for photoconductive layer (1) Zeta type steel phthalocyanine/(Liophoto on-ERPC manufactured by Jl Ink)/
, 0 parts copolymer of benzyl methacrylate and methacrylic acid (30 moles of methacrylic acid) io, o part tetrahydro7 run titr, o part cyclohexanone /A, 0 parts or more in a 3001 glass container with glass beads, in a paint shaker (
Toyo Seiki Seisakusho ■) was used for several minutes to prepare a photoconductive layer dispersion.

The dry film thickness of the electrophotographic printing plate thus prepared was ≠μ.

This electrophotographic photoreceptor was stacked by sandwiching and stacking paper with a weight of 3097 m on which 10 μm of polyethylene was laminated on one side so that the polyethylene side of the mount was in contact with the photosensitive layer. After cutting with a guillotine cutter, 1. Apply an addition reaction silicone solution (1) of /
It was dried for 2θ0Cj minutes to provide a 3μ thick layer of polysiloxane polymer.

Addition reaction type licone solution (1) (1) 8 D 7.2 pieces 10
Part 0 (2) 5fLx-λ/ko
Made by Toray 7 Recon ■ (3) Toluene 230 parts (4)
n-Hexane cojO part Next, this sample was charged in a completely dark place with a corona charger to a surface potential of 1000 V, and then a negative image was exposed to tungsten light, and this was charged in Ainno ξ-H (Esso Standard Co., Ltd.) 17i medium. Polymethyl methacrylate particles (particle size 0.3μ)!
Using a liquid developer prepared by dispersing it as toner particles and adding zirconium naphthenate fO, 0/9f as a charge control agent, a bias voltage of +3 ooV is applied to the counter electrode and reverse development is performed to produce a clear positive image. I was able to obtain Further, the created image was heated for 2 minutes at /O0C to completely fix the toner image.

This non-image area was removed with an etching solution diluted with potassium silicate ≠ O parts, potassium hydroxide 10 parts, ethanol / 00 parts f water 100 parts, thoroughly washed with water, and then a gum solution (for PS plates made by Fuji Photo Film) was removed. An offset printing plate was prepared using Gum GU-716 cloth.

When this printing plate was set in an offset printing machine and printing was performed, all of the obtained prints were good prints with no stains at all even in the portions corresponding to the edges of the printing plate.

Comparative Example 1 A printing plate was prepared in exactly the same manner as in Example 1 except that the dove containing the polysiloxane polymer was not provided on the end face.

When printing was carried out using this printing plate in the same manner as in Example 1, the resulting printed matter was in good condition with no stains in the image area, but there were streaks in the portions corresponding to the edges of the printing plate. This resulted in staining and was not suitable for practical use.

Comparative Example 2 In Example 1, in place of not providing I-, which completely impregnates the end face of borine loxane, inbutyl methacrylate and methacrylic acid (molar ratio: r:x) were used as insulating resins.
A printing plate was prepared in exactly the same manner except that a 3μ layer containing the copolymer of

When printing was carried out using this printing plate in the same manner as in Example 1, the obtained printed matter was a good printed image with no stains, but there were streaks in the portions corresponding to the edges of the printing plate. This resulted in staining and was not suitable for practical use.

Example 2 In Example 1, addition reaction type silicone solution (1)?
Instead of using it, apply a condensation reaction type silicone solution (2) with the following composition, and! A lithographic printing original plate for electrophotographic plate making was prepared in the same manner as in Example 1, except that a layer having a polysiloxane polymer of yμ was formed by drying for 09 C, j' minutes, and plate making was carried out in the same manner as in Example 1. When I went to print and printed it,
All of the obtained printed matter were good printed matter, with no stains at all even in the portions corresponding to the edges of the printing plate.

Example 3 Weighed the electrophotographic photoreceptor on which the entire photoconductive layer was formed in the same manner as in Example 1! The polyethylene side of the mount, which is made by laminating 10μ polyethylene on one side of Op/m paper, is exposed to light/I
After sandwiching and stacking them so that they are in contact with each other and cutting them with a guillotine cutter, a hydrophilic resin solution (A) containing the following silicate is applied to the outer peripheral end surface of the silicate in a length of about 7,097 m.
The coating was applied at a coverage of 100% and dried at room temperature.

Hydrophilic resin solution containing silicate (A) Hydroxypropyl etherified starch (image resolution 0,0
tO part Potassium silicate melt (!2Be :2O 'C) IIf part Potassium hydroxide<ar, zchi) part Pure water
Next, apply a silicone gum solution (3) with the following composition to the end surface of the to'c
Dry for io minutes! A polysiloxane polymer layer of μ was provided.

Noricone gum solution (3) (1) Dimethylpolysiloxane (number average molecule 1 to 10,000) ioo part (2) Vinyltri(methylethylketooquine)silane
70 parts (3) digtyltin acetate o, z parts (4) n-hexane
4too parts Next, this sample was plate-made in the same manner as in Example 1, and the obtained printing plate was set in an offset printing machine and printing was performed. The print was in good condition with no stains even in the areas where it was printed.

Example 4 Instead of applying the entire silicate-containing hydrophilic resin in Example 1, the following desensitizing treatment liquid (B)k was applied with a coating amount of approximately 7097 m2 and dried at room temperature. .

Desensitizing treatment liquid (B) 30% aqueous gum arabic solution 1 part water
30 parts Sodium hexametaphosphate 0.7 parts Sodium nitrate 7.0 parts Magnesium sulfate
1.2 part r! Chirin M
-2・μ parts Polyoxyethylene polyoxypropylene block copolymer (trade name Pluronic) 10.2 parts On top of this, a silicone bath with the following composition! (4) Complete coating to provide a layer containing μμ polysiloxane polymer.

Silicone solution (4) (1) Dimethylpolysiloxane (number average molecular weight 20,000) 100 parts (2) Vinyltriacetoxysilane 75 parts (3) Dibutyl acetate 8 parts (4) n-hexane
1ooo section Next, this sample was plate-made in the same manner as in Example 1, and the obtained printing plate was set in an offset printing machine and printing was performed. The printed matter was also in good condition with no stains at all.

Example 5 A printing original plate for electrophotographic platemaking was prepared in exactly the same manner as in Example 1 except that the following photoconductive coating liquid (2) was used instead of the photoconductive coating liquid (1).

Coating liquid for photoconductive layer (2) Trisazo compound i, o Oxadiazole compound λ shown in E below! 1 part: Copolymer of vinyl acetate and crotonic acid (RESYN Aco I-/J10 manufactured by Kanebo NSC Co., Ltd.) io part: Tetrahydrofuran 700 parts f! 001 in a glass container with glass peas and a paint shaker (
Toyo Seiki Seisakusho ■) was used for dispersion for several minutes to prepare a photoconductive layer dispersion.

The thickness of this photoelectric layer was approximately μμ. In the same manner as in Example 3, apply the following hydrophilic resin solution (C) containing silicate to the outer peripheral end face! It was coated in an area of 6 y 7 m 2 .

Hydrophilic resin solution containing silicate (C) Cream dextrin with a water-soluble content of Pj weight or more (Cream Dext J Non #3, Matsutani Chemical ■@l) / 00 parts Potassium silicate (!2Be:, 2O °C) 20 parts Potassium hydroxide<tr, ztin 10 parts Sodium inpropylnaphthalene sulfonate! pure water
Next, a silico/rubber solution (5) with the following composition was applied on top of this and dried to a film thickness of 3.
! A layer containing μ polysiloxane was formed.

Silicone rubber solution (5) 100 parts of dimethylpolyrinloxane containing vinyl groups at both ends (molecular weight: approx. 33,000) 100 parts Methylhydrodiene polysiloxane having trimethylsilyl groups at both ends (molecular weight: approx. 2.00) 3 parts Olefin-platinum chloride Acid catalyst (10% toluene bath liquid) Kobe Ein・ξ
-G (Esso Chemical Co., Ltd.!!) Next, this sample was charged to a surface potential of 10 μOOV using a corona belt in a dark place, and then a positive image was exposed to tungsten light using Ricoh MR liquid developer.
By developing with P (Ricoh ■) (bias voltage + SOV), a clear positive image could be obtained. Furthermore,
The created image was heated at 0C for 1 minute to fix the toner image.

This non-image area 4DN-JC (Fuji Photo Film PS plate developer) was diluted with water to a ratio of 1:2.
After being immersed for a second, it was thoroughly washed with water, and then applied to a gum solution (Fuji Photo Film's PS plate gum GTJ-7) to prepare an offset printing plate.

When this printing plate was placed in an offset printing machine and printing was carried out, all of the obtained prints were good prints with no stains at all even in the portions corresponding to the edges of the printing plate.

Example 6 Hydrophilic resin solution containing silicate in Example 5 (
Instead of C), use the following desensitizing treatment liquid water bath resin solution (D
), printing plates were prepared using the same procedure as above. All of the obtained prints were good prints with no stains at all even in the portions corresponding to the edges of the printing plates.

Desensitizing treatment solution (D) Carboxine methylated starch (carboxine methyl group introduction rate 0.2) 100 parts Potassium silicate <rsBe:zo 0c) So part Potassium hydroxide (μr, j%) 10 parts Isopropyl naphthalene Sodium sulfonate J part pure water
145 parts (Effects of the Invention) By using the lithographic printing original plate for electrophotographic platemaking of the present invention, all printing stains caused by toner adhesion to the edge surface of the plate during reversal development are completely prevented, and printing stains on the edge portions are completely prevented. It is possible to create lithographic printing plates that give high-quality prints.

[Brief explanation of drawings]

Section 1 to FIG. 3 show three different configurations of the present invention. FIG. 1 shows a lithographic printing original plate for electrophotographic platemaking in which only a layer containing a polymer having a V-shaped polyoloxane structure on the end surface is provided. FIG. 1 shows a lithographic printing original plate for electrophotographic platemaking in which a desensitized layer is provided on the end face, and only a layer containing a polymer having a polysiloxane structure is further provided thereon. FIG. 3 shows a lithographic printing original plate for electrophotographic platemaking in which a silicate/hydrophilic resin layer is provided on the end face, and only a layer containing a polymer having a polysiloxane structure is further provided thereon. 1st % liver applicant Fuji Photo Film Co., Ltd. March 3, 1991

Claims (3)

[Claims] (1) A photoconductive layer is provided on a conductive support having a hydrophilic surface, and after imagewise exposure and toner development to form a toner image, the photoconductive layer in non-image areas other than the toner image area is removed. A lithographic printing original plate for electrophotographic plate making, which is used as a lithographic printing plate, is characterized in that a layer containing at least a polymer having a polysiloxane structure is provided on an end surface of the lithographic printing original plate for electrophotographic plate making. Planographic printing original plate for electrophotographic platemaking. (2) A photoconductive layer is provided on a conductive support having a hydrophilic surface, and after a toner image is formed by image exposure and toner development, the photoconductive layer in non-image areas other than the toner image area is removed. In a lithographic printing original plate for electrophotographic plate making which is thereby made into a lithographic printing plate, a general formula mSiO_2/nM_2O (M is an alkali metal atom, m/n=0.5 to 8.5) Electrophotography characterized by being coated with a solution containing a silicate and a hydrophilic resin, and further provided with a layer containing at least a polymer having a polysiloxane structure. Planographic printing original plate for type plate making. (3) A photoconductive layer is provided on a conductive support having a hydrophilic surface, and after imagewise exposure and toner development to form a toner image, the photoconductive layer in non-image areas other than the toner image area is removed. In the lithographic printing original plate for electrophotographic plate making which is thereby made into a lithographic printing plate, the end surface of the planographic printing original plate for electrophotographic plate making is subjected to a desensitization treatment, and further a polymer having at least a polysiloxane structure is applied thereon. A lithographic printing original plate for electrophotographic platemaking, characterized in that the layers it contains can be explained.