JPH01262556A - Master plate for planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain the master plate for printing which reproduces the copied image faithful to an original picture, does not generate not only the scumming uniform over the entire surface but also dotty scumming as an offset master plate and has an excellent desensitization characteristic by incorporating at least two kinds of specific resins as the essential component of a surface layer. CONSTITUTION:This master plate contains at least two kinds of the resin A and resin B as the essential components of the surface layer. The resin A: A resin contg. at least one kind of the functional group which forms at least one hydroxyl group by decomposition. The resin B: A thermal-/or photosetting resin. The ratio of the resin A and resin B to be used is generally 40-95:60-5 (by weight). This resin B has the effect to prevent the resin A from becoming soluble in water and eluting from a non-image part. The copied image faithful to the original picture is thereby reproduced and since the hydrophilicity of the non-image part is good, the summing is not generated; further, the excellent plate wear is obtd. by the improved power to sustain the hydrophilicity of the non-image part.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to an electrophotographic lithographic printing original plate made by an electrophotographic method, and in particular, a surface having specific properties on a photoconductive layer. This invention relates to a lithographic printing original plate having layers.

(Prior art and its problems) Currently, various types of offset original plates for direct plate making have been proposed and put into practical use. A photoreceptor with a photoconductive layer mainly composed of A widely used technique is to obtain an offset master plate by selectively making non-image areas hydrophilic.

In order to obtain good printed matter, first, the original image is faithfully copied onto the offset master plate, the surface of the photoreceptor is easily compatible with the desensitizing treatment liquid, and the non-image area is made sufficiently hydrophilic, while at the same time it is water resistant. In addition, during printing, the photoconductive layer with the image does not separate, has good compatibility with dampening water, and has sufficient hydrophilicity in the non-image area to prevent staining even if a large number of prints are made. It is necessary to have performance such as the ability to maintain

In particular, as an offset master plate, background smearing due to insufficient desensitizing properties is a major problem, and in order to improve this problem, various studies have been conducted on the development of zinc oxide binding resins that improve desensitizing properties. , for example, Special Publication No. 50-3101
No. 1, JP-A-53-54027, JP-A-54-207
No. 35, JP-A-57-202544, JP-A-58-6
It is disclosed in the specification of No. 8046 and the like. However, even if these resins are said to be effective in improving desensitization properties, when actually evaluated, they are still unsatisfactory in terms of scumming and stiffness resistance.

On the other hand, using an organic photoconductive compound as the photoconductive particle,
It is also possible to use an electrophotographic body in which a photoconductive layer and a binder resin are provided on a grained aluminum substrate.

To make this type of master plate, as described above, a toner image is formed on the photosensitive layer by a normal electrophotographic method, and then the non-image area is dissolved and removed using a processing liquid. As a result, the non-image area becomes an aluminum substrate, which becomes hydrophilic.
-39405, JP-A-52-2437, JP-A-56
When using a photosensitive layer in which an oxadiazole compound or an oxazole compound is bound with an alkali-soluble resin such as a styrene-maleic anhydride copolymer, as shown in Japanese Patent Application Laid-open No. 105254-10724, etc.
No., JP-A-55-16125, JP-A-58-1509
It is known that a photosensitive layer comprising a phthalocyanine pigment or an azo pigment and an alkali-soluble phenol resin is used, as shown in Japanese Patent Application Laid-Open No. 58-162961.

However, in this plate-making process, the photosensitive layer in the non-image area must be dissolved and removed, which requires a large-scale apparatus, and this takes time, resulting in a slow plate-making speed. Furthermore, since ethylene glycol, glycerin, methanol, ethanol, etc. are used as processing liquids (organic solvents),
This plate-making method still poses problems in terms of cost, safety, pollution, and occupational health.

Furthermore, Japanese Patent Publication No. 5606/1983 discloses a method of preparing a printing plate of the type in which the surface of the non-image area is hydrophilized, which is easy to make by providing a specific resin layer on an ordinary electrophotographic photoreceptor. That is, vinyl ether is deposited on the electrophotographic photoreceptor.
A printing plate provided with a surface layer comprising a maleic anhydride copolymer and a hydrophobic resin compatible therewith is disclosed.

This layer is a layer that can be made hydrophilic (hydrophilicizable layer) by treating the non-image area with an alkali to open the acid anhydride ring portion with water after the toner image is formed.

The vinyl ether-maleic anhydride copolymer used there becomes water-soluble when the ring is opened and made hydrophilic, so even if it is compatible with other hydrophobic resins, a layer may not be formed. Even if it were, its water resistance was extremely poor, and its printing life was limited to 500 to 600 sheets at most.

Furthermore, JP-A-60-90343, JP-A-60-159
No. 756, JP-A No. 61-217292, etc.,
A method of providing a surface layer (hydrophilicizable layer) containing silylated polyvinyl alcohol as a main component and also using a crosslinking agent is disclosed.

That is, in this layer, silylated polyvinyl alcohol is hydrolyzed in a non-image area after toner image formation to make it hydrophilic. In order to maintain the film strength after hydration, the degree of silylation of polyvinyl alcohol is adjusted and the remaining hydroxyl groups are crosslinked using a crosslinking agent.

It is stated that these improve the scumming resistance of printed matter and increase the number of printed sheets. However, when evaluated in reality, it is still unsatisfactory, especially in terms of background stains. Furthermore, silylated polyvinyl alcohol is produced by silylating polyvinyl alcohol to a desired ratio with a silylating agent, but since it is a polymer reaction, it is difficult to produce it stably. Furthermore, since the chemical structure of the hydrophilic polymer is limited, it is important to ensure that 1) charging properties, 2) quality of copied images (halftone reproducibility/resolution of image areas, There were problems such as it was difficult to prevent the surface layer from affecting the image area (ground blur, etc.), 3) exposure sensitivity, etc.

Furthermore, as the surface layer resin, resins containing functional groups that generate hydrophilic groups upon decomposition are being considered; for example, resins containing functional groups that generate hydroxyl groups upon decomposition (Japanese Patent Application No. 1982 No. 106417, patent application No. 106417
No. 2-151507) and those containing functional groups that generate carboxyl groups upon decomposition (Japanese Patent Application No. 62-22669)
No. 4, Japanese Patent Application No. 62-28345), etc. are disclosed.

These resins are resins that generate hydrophilic groups by being hydrolyzed or hydrolyzed by the unfattening liquid or dampening water used during printing, and when used as the surface layer resin of a lithographic printing original plate, they can be decomposed by decomposition. The generated hydrophilic group improves the hydrophilicity of the non-image area, makes the lipophilicity of the image area and the hydrophilicity of the non-image area clear, and prevents printing ink from adhering to the non-image area during printing. It is stated that as a result, it becomes possible to print a large number of prints with clear image quality and no background smear.

However, even when these resins are used, they are still not satisfactory in terms of stain resistance and rigidity, and even when using resins containing hydrophilic group-forming functional groups as mentioned above, it is difficult to further improve the hydrophilicity in non-image areas. If the content is increased to increase the content, the hydrophilicity increases due to the hydrophilic groups generated by decomposition, and the surface layer resin becomes water-soluble, which may cause problems, especially in its sustainability. understood.

Therefore, it is desired to develop a technique that further improves the effect of hydrophilicity in non-image areas and further improves durability.

Further, in the conventional technology, there were problems such as a narrow allowable range of material composition when achieving a comprehensive balance of electrophotographic properties, film properties, etc.

The present invention is intended to improve the problems of electrophotographic lithographic printing original plates as described above.

The purpose of the present invention is to reproduce a copy image that is faithful to the original image, and to produce a lithographic printing plate with excellent desensitization properties that does not cause not only uniform background smudges on the entire surface but also dotted smudges as an offset original plate. The purpose is to provide the original version.

Another object of the present invention is to provide a lithographic printing original plate which maintains sufficient hydrophilicity in non-image areas even when the number of printed sheets increases, does not cause scumming, and has high stiffness resistance.

Another object of the present invention is to provide a lithographic printing original plate having a resin that can be used in the surface layer, can be made hydrophilic in non-image areas, and is easy to manufacture.

Another object of the present invention is to provide a lithographic printing original plate having a wide range of material composition tolerances when achieving a comprehensive balance of electrophotographic properties, film properties, etc.

(Means for Solving the Problems) The above-mentioned method is based on lithographic printing using an electrophotographic photoreceptor comprising at least one photoconductive layer on a conductive support and a surface layer on the top layer. The problem is solved by an electrophotographic lithographic printing original plate characterized by containing a small amount (both of the following resins [A] and resin [B] as the main components of the surface layer). was discovered.

(i) Resin (A); Resin containing at least one functional group that produces at least one hydroxyl group upon decomposition (ii) Resin [B]; Heat and/or photocurable resin The present invention is a lithographic printing original plate. The present invention is characterized in that a resin containing at least one functional group that decomposes to produce at least one hydroxyl group and a thermosetting and/or photocurable resin are used as main components of the surface layer of the invention. The original plate for lithographic printing reproduces a copy image that is faithful to the original image, and because the non-image area has good hydrophilicity, it does not cause background smearing. Furthermore, the long-lasting hydrophilicity of the non-image area has improved durability. It has the advantage of being superior.

Furthermore, the lithographic printing original plate of the present invention is not affected by the environment during plate-making processing and has excellent storage stability before processing.

Below, at least one functional group that decomposes to produce at least one hydroxyl group used in the present invention will be described.
The seed-containing resin (hereinafter sometimes simply referred to as "hydroxyl group-generating functional group-containing resin") will be explained in detail.

The functional group contained in the hydroxyl group-generating functional group-containing resin of the present invention generates a hydroxyl group by decomposition.
The number of hydroxyl groups generated from one functional group may be one or two or more.

According to one preferred embodiment of the present invention, the hydroxyl group-generating functional group-containing resin is a resin containing at least one functional group represented by the general formula (1): (-0-L).

In general formula (1) (-0-L), L is -5 i-R
" , -Co-Y', -Co-Z'-Y", however, R
I SRz and R3 may be the same or different and represent a hydrogen atom, a hydrocarbon group, or ORIO (RIo represents a hydrocarbon group), Yl and Y'' represent a hydrocarbon group, and Zl is It represents an oxygen atom, a sulfur atom or an -NH- group, and Xl represents a sulfur atom or an oxygen atom.

The above-mentioned -fune type (-0-L) functional group generates a hydroxyl group by decomposition, and will be explained in more detail below.

In the case where L represents -3i-R'', RI, R2,
R3 may be the same or different and represents a hydrogen atom, a hydrocarbon group, or -0-R10 (RIO represents a hydrocarbon group). The hydrocarbon groups represented by R1, R1, and R3 are preferably straight-chain or branched alkyl groups having 1 to 1 carbon atoms that may be substituted (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group). , octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic groups (e.g. cyclopentyl group, cyclohexyl group, etc.), Good aralkyl groups having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, fluorobenzyl group, chlorobenzyl group, methylbenzyl group,
methoxybenzyl group, 3-phenylpropyl group, etc.), an optionally substituted aromatic group (e.g. phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.) The hydrocarbon group represented by R1 (1) has the same meaning as the hydrocarbon group represented by R1, R1, and R3 above.

When L represents -Co-Y', the hydrocarbon group represented by Yl preferably has a carbon number of 1 which may be substituted.
~6 straight-chain or branched alkyl groups (e.g. methyl group,
Trichloromethyl group, trifluoromethyl group, methoxymethyl group, phenoxymethyl group, 2. 2. 2-1-
Lifluoroethyl group, t-butyl group, hexafluoro-
1-propyl group, etc.), optionally substituted aralkyl groups having 7 to 9 carbon atoms (e.g., benzyl group, phenethyl group, methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group, methoxybenzyl group, etc.), substituted Aryl groups having 6 to 12 carbon atoms (e.g. phenyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group, methoxyphenyl group, butoxyphenyl group,
(chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.).

When L represents -Co-Z'-Y'', Zl represents an oxygen atom, a sulfur atom or a -NH- group, and Y2 has the same meaning as Yl described above.

In these cases, Xl represents an oxygen atom or a sulfur atom.

The resin used in the present invention containing at least one functional group selected from the group of formulas (-0-L) can be obtained by converting hydroxyl groups contained in the polymer into a polymer having the general formula (-0-L). -L), or -1 containing one or more functional groups of -0-L)
It is produced by a method of polymerizing one or more monomers, or by a polymerization reaction of the monomer and another monomer that can be copolymerized therewith.

For example, as a production method for the above polymer reaction, Yoshiyu Iwakura
Publicly known literature cited in reviews such as "Reactive Polymers" by Keisuke Kurita, page 158 (published by Kodansha), and the production method of converting the hydroxyl group of the monomer into a functional group of the general formula (-0-L) These are described in detail in the well-known literature cited in reviews such as the Chemical Society of Japan's "New Experimental Chemistry Course, Volume 14, Synthesis and Reactions of Organic Compounds [■)", page 2497 (published by Maruzen Co., Ltd.). It can be manufactured according to the method.

The polymer contains a functional group of the general formula (-0-L) in advance for reasons such as being able to arbitrarily adjust the functional group of the general formula (-0-L) or preventing the inclusion of impurities. A method of manufacturing by a polymerization reaction from monomers is preferable. Specifically, a method of producing a compound containing a polymerizable double bond and at least one hydroxyl group, for example, as described in the above-mentioned known literature, etc. is preferable. According to the method described above, the hydroxyl group is converted to a functional group of the general formula (-0-L), or a compound containing a functional group of the general formula (-0-L) is converted into a compound containing a polymerizable double bond. It can be produced by a reaction method.

As mentioned above, to describe more specifically the monomer containing the functional group of general formula (-0-L) used in the method of producing a desired resin by polymerization reaction, for example, the following -
Examples include compounds such as Monken (It). However, it is not limited to these compound examples.

General formula (II) X''-Y'-0-L In formula (I[), X2 is -〇-1-CO-1-CH,C
OO-1-CH, 0CO-1-(-C)-, a divalent aromatic group, or a divalent heterocyclic group.

However, Q', Q'', Q3, and Q' are hydrogen atoms, respectively.
represents a hydrocarbon group or +Y'-0-L) in formula (II), b+, 1. ! may be the same or different,
Hydrogen atom, hydrocarbon group or +Y'-0- in formula (II)
L), where n is an integer from 0 to 18, Q'%Q
The hydrocarbon group represented by ' has the same meaning as the hydrocarbon group represented by R1-R3 in formula (I), and the hydrocarbon group represented by b+ and bz has the same meaning as the hydrocarbon group represented by R1 and R3 in 2N). is synonymous with

Y3 connects the bonding group Xt and the general formula (-0-L),
(represents a divalent linking group which may be connected via a heteroatom; the heteroatom is an oxygen atom, a sulfur atom, or a nitrogen atom), for example, O+! -(CH=CH)-, -0-1-S-1-N-1-CO
O-1-CONH-5S Oz-1-3O,NH-1-
NHCOO-1 -NHCONH-1, etc., are composed of bonding units singly or in combination (however, b' and b' each represent the above-mentioned b
I, b! Q' has the same meaning as Q1 to Q4 above. ) L has the same meaning as in formula (I).

a I and at may be the same or different, and are a hydrogen atom, a hydrocarbon group (for example, an alkyl group having 1 to 12 carbon atoms, an aryl group, etc. which may be substituted with -COOH, etc.), -COOH or - coo-w' (W+ is a general formula (-0-L'')) an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, an aromatic represents a group group).

More specifically, the following examples of compounds can be cited as monomers containing the -Momona (-0-L) functional group, but the scope of the present invention is not limited thereto. do not have.

Chang CHs CHz=　CM　e COOCH, CH, 0-S t-C, H.

Me Hs CHz-COMe COOCHzCHzO3i OMe OMe Hz CH,=C C00CH, CHCH, 0COCH2CF.

0 COCHHz CF 5 CH.

CH.

CHz=CHMe CH20S iMe ■ Me bHs CH3 bush CH! OS i (M e) 3 ChzCOOC-H9 ■ Hz = C C00(CHz)　z　OCH=　CHCH5CH3 CH,=C C0NH(CHz)+oOCOOCL CH.

CH3 CH.

CH,=C 謳Coo(CHz)zOco(CHz)sO3i(Me)
zCH.

CH3 CH’s CH.

CH3 CH.

C,H.

(However, Me represents a methyl group) These monomers may be polymerized alone, or
A copolymer may be prepared by combining these monomers with other monomers that can be copolymerized. Other monomers to be copolymerized include, for example, vinyl aliphatic carboxylates or allyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, allyl propionate, acrylic acid, methacrylic acid, crotonic acid, etc. , unsaturated carboxylic acids such as itaconic acid, maleic acid, and fumaric acid, and esters or amides of these unsaturated carboxylic acids, styrene, vinyltoluene, styrene derivatives such as α-methylstyrene, α-olefins, acrylonitrile, Examples include vinyl group-substituted heterocyclic compounds such as methacrylonitrile and N-vinylpyrrolidone.

According to another preferred embodiment of the present invention, the hydroxyl group-generating functional group-containing resin has at least two functional groups in which at least two hydroxyl groups located sterically close to each other are simultaneously protected with one protecting group. It is a resin containing one type. Examples of functional groups having at least two hydroxyl groups in a protected form that are sterically close to each other include the following - Monken (II), (TV
) and (V).

- Monna (I[I) In formula (III), R4 and R5 may be the same or different from each other, and may be a hydrogen atom, a hydrocarbon group, or -0-R1'
(R'' represents a hydrocarbon group), and U represents a carbon-carbon bond which may be via a heteroatom (provided that the number of atoms between oxygen atoms is 5 or less).

General formula (IV) In formula (IV), U is as defined above.

- Monna (V) In formula (V), R4, R5 and U are as defined above.

A more detailed explanation of the functional group is as follows.

In the above formulas (III) to (V), R' and R' may be the same or different and represent a hydrogen atom, a hydrocarbon group, or -OR11 (R11 represents a hydrocarbon group). The hydrocarbon group represented by R4 and R5 is preferably an optionally substituted alkyl group having 1 to 12 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-methoxyethyl group, octyl group). groups, etc.), carbon number 7~
9 optionally substituted aralkyl groups (e.g. benzyl group, phenethyl group, methylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), alicyclic groups having 5 to 7 carbon atoms (
For example, it represents a cyclopentyl group, a cyclohexyl group, etc.), or an optionally substituted aryl group (for example, a phenyl group, a chlorophenyl group, a methoxyphenyl group, a methylphenyl group, a cyanophenyl group, etc.). The hydrocarbon group represented by R1+ has the same meaning as the hydrocarbon group for R' and R' above.

U represents a carbon-carbon bond which may be via a heteroatom, and the number of atoms between oxygen atoms is 5 or less.

The resin containing at least one kind of functional group used in the present invention can be obtained by a method in which hydroxyl groups contained in a polymer and located in positions sterically close to each other are protected with a protecting group by a polymer reaction, Or produced by a method of polymerizing a monomer containing at least two hydroxyl groups that has been previously protected with a protecting group, or by a polymerization reaction of the monomer and another monomer that can be copolymerized with it. .

The former polymer reaction production method includes, for example, polymer components (i) (ii) which have at least two hydroxyl groups in close proximity or can have at least two hydroxyl groups in close proximity after polymerization, such as those listed below as specific examples. (RI! is H
or substituents such as CH, etc.) (iii) (iv) (v) CH,OH (vi) (vi)C
By reacting a polymer containing H,OH CH,0H (X) CH 1+CH, -C← CH,OH with a compound such as a carbonyl compound, orthoester compound, halogen-substituted formate, dihalogen-substituted silyl, etc. A functional group having at least two desired hydroxyl groups simultaneously protected with one protecting group can be formed. Specifically, the Chemical Society of Japan, “New Experimental Chemistry Course, Volume 14, Synthesis and Reactions of Organic Compounds [■]”, page 2505 (published by Maruzen Co., Ltd.), J, F, H, Mc, 0m1e,
rProtective groups in Org
antc Chemistry” Chapters 3 and 4 (
It can be produced by a method described in a known literature cited in a review such as Plencuw Press (published by Plencuw Press).

In the latter method, a monomer with at least two hydroxyl groups protected in advance is synthesized by a known method cited in the above-mentioned review, and then, if necessary, other monomers that can be copolymerized with the monomer are synthesized. A homopolymer or a multi-component copolymer can be produced by carrying out polymerization using a conventional polymerization method in the presence of monomers.

More specifically, examples of polymer components containing the functional group include the following. However, the scope of the present invention is not limited to the following.

■ CH.

CH3 CH3 0C,H.

CHz 1+CH, -C→- (CH, -C-masu/H,C0 ti3 U IJ U Shin 5CHl Hot CH3 CHzCOOCHs -(-CH, -C-← Hydroxyl group-forming functionality in the resin [A] of the present invention When the resin [A] is a copolymer, the group-containing polymer component accounts for 20 to 100% of the total polymer, especially 40%
It is preferably 90% by weight. In addition, resin [A
] The molecular weight of the polymer is between 10" and 10", especially 5XlO"
It is preferable that it is 5XIO'.

Furthermore, the resin [A] of the present invention preferably contains a functional group that undergoes a crosslinking reaction with the resin [B] by heating, light irradiation, or the like. These crosslinkable functional groups include resins [B] described below.
The same functional groups as those contained therein that exhibit a crosslinking reaction can be mentioned.

Monomers corresponding to copolymer components containing these crosslinkable functional groups include polymer components containing hydroxyl group-forming functional groups in resin [A] (for example, if
Examples include vinyl compounds containing the crosslinkable functional group that can be copolymerized with the compound).

For example, see the Polymer Data Handbook [Polymer Data Handbook]
Basic Edition] Baifukan (published in 1986), etc.

Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-aminomethyl form, α-chloro form, α-
Bromo form, α-fluoro form, α-tributylsilyl form, α
-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form, α, β-dichlorochloro), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, croton acids, 2-alkenylcarboxylic acids MC such as 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4
-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, vinyl group or allyl group. Examples include half ester derivatives of dicarboxylic acids, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the crosslinkable functional group in the substituent of amide derivatives.

As described above, when the resin [A] of the present invention contains the above-mentioned crosslinkable functional group, the "content of the copolymer component containing the crosslinkable functional group" in the resin [A] is preferably 20-100% by weight, more preferably 40-95% by weight
It is.

On the other hand, the resin [B] used in the present invention is a curable resin that undergoes a crosslinking reaction with heat and/or light, and preferably performs a crosslinking reaction with the crosslinkable functional group in the resin [A) described above. It is something.

Specifically, as a thermosetting resin, Tsuyoshi Endo [Refinement of Thermosetting Polymers J (C, M, C, @, published in 1986),
Yuji Harasaki [Latest Binder Technology Handbook] Chapter 11-1 (General Technology Center, published in 1985), Yoshiyuki Otsu, “Synthesis, Design and Development of New Applications of Acrylic Resins (Chubu Management Development Center Publishing Department, published in 1985), Omori Conventionally known resins are used as thermosetting resins cited in reviews such as Eizo's "Functional Acrylic Resins" (Techno System, 1985).For example, polyester resins, epoxy resins that may be modified, Polycarbonate resin, vinyl alkanoate resin, modified polyamide resin, phenolic resin,
Modified alkyd resins, melamine resins, acrylic resins, isocyanate resins, etc. are used.

Specifically, the photocurable resins include Hideo Inui, Gentabe Nagamatsu,
"Photosensitive polymer" (Kodansha, published in 1977); Takahiro Tsunoda, "Photosensitive resin" (Printing Society Publishing Department, published in 1981); G, E, Green and B,
P.

5tark+ J, Macro, Sct, Rev
s, Macro Chem, + C21(2), 1
87-273 (1981-82); C, G,
Raffey.

rPhotopolymerizat: on of 5
Surface Coatings” (A, Wile
Conventionally known photosensitive resins are used as photocurable resins, such as those cited in reviews such as ``Y Interscience Pub, 1982.

More specifically, for example, polymers containing functional groups that undergo a crosslinking reaction by heating or light irradiation can be mentioned, and examples of the crosslinkable functional groups include (i) (For example, at least one of the functional groups A and B in the table below reacts in combination); or (ii) a self-crosslinkable functional group type [specifically,
(ii-a) -CONHCHzOR'(R' is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, hexyl group), (i
ib) a double bonding group having polymerization reactivity represented by the following formula [A]].

In formula [A], X4 is -COO-1-OCO-1-co
-, -so, -1-CONH-1-3O, NH-1-〇-1-S-1 represents a divalent aromatic group or a divalent heterocyclic group, and dl and dZ may be the same or different. Often, each hydrogen atom or an optionally substituted hydrocarbon group (e.g.
Methyl group, ethyl group, propyl group, butyl group, hexyl group, carboxymethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2-chloroethyl group, 2-methoxyethyl group,
Ethoxymethyl group, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, phenyl group, tolyl group, xylyl group, methoxyphenyl group, chlorophenyl group, bromophenyl group group, etc.), and r is 0
or represents an integer of 1.

Examples of the monomer corresponding to the copolymer component containing these functional groups include vinyl compounds containing the crosslinkable functional group (specifically, the same as those described in resin [A]). can be mentioned. In addition, specific examples of monomers corresponding to other components that can be copolymerized with the copolymerization component containing the crosslinkable functional group include those similar to resin [A].

The content of the "copolymer component containing a crosslinkable functional group" in the resin [B] is particularly preferably from 1 to 80% by weight.

The weight average molecular weight of the resin [B] is preferably 103 to 5X
10', more preferably 5XIO' to 5x10'.

In the present invention, resin [A] and resin [B] can be combined by using heat and/or photocurable resin as resin [B].
and/or crosslinks between resins [B].

The ratio of the amounts of resin [8] and resin CB used in the present invention is generally 40 to 95 to 60 to 5 (weight ratio).

In the present invention, a reaction accelerator may be added as necessary. For example, if the resin CB) is a resin containing a thermosetting functional group, an acid (eg acetic acid).

Organic acids such as propionic acid, butyric acid, etc.) or a crosslinking agent may be added.

As the crosslinking agent used, compounds commonly used as crosslinking agents can be used. Specifically, Shinzo Yamashita and Tosuke Kaneko ed. “Crosslinking Agent Handbook” published by Taiseisha (19
1981); Compounds described in Polymer Data "Polymer Data Handbook [Basic Edition]" Baifukan (1986) etc. can be used. For example, organic silane compounds (e.g. vinyltrimethoxysilane, Silane coupling agents such as vinyltributoxysilane, T-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc.), polyisocyanate compounds (e.g. isocyanate, 0-)ylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.), polyols system compounds (e.g. 1,4
-butanediol, polyoxypropylene glycol,
Polyoxyalkylene glycol, 1. 1. 1-trimethylolpropane, etc.), polyamine compounds (e.g., ethylenediamine, T-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds, and Epoxy resins (for example, "New Epoxy Resins" edited by Hiroshi Kakiuchi, Shokodo (
(published in 1985), compounds described in "Epoxy Resin" edited by Kuniyuki Hashimoto, Nikkan Kogyo Shimbun (published in 1969), etc.
Melamine resin (for example, compounds described in "Uria Melamine Resin" edited by Kazu Miwa and Hideo Matsunaga, published by Nikkan Kogyo Shimbunsha (1969)), polyfunctionality containing two or more polymerizable double bond groups Monomer compounds [for example, compounds described in Makoto Okawara, Takeo Saegusa, and Toshinobu Higashimura, "Oligomer J Kodansha (published in 1976)," Eizo Omori, "Functional Acrylic Resins J Techno System (published in 1985), etc. Specifically, divinylbenzene, divinylglutaconic acid diester, vinyl methacrylate, acrylic methacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, neopentyl glycol cyacrylate, 1,6-hexanethioldia Acrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A
- diglycidyl ether diacrylate, oligoester acrylate, methacrylate forms thereof, etc.).

Further, when the resin [B] is a resin containing a photocrosslinkable functional group, a sensitizer, a photopolymerizable monomer, etc. may be added. Specifically, the compounds cited in the review on photosensitive resins mentioned above can be used.

When a thermosetting resin is used as the resin CB) of the present invention, it is crosslinked by heating after the surface layer forming material is applied. In order to perform crosslinking, it is preferable, for example, to set the drying conditions to a high temperature and/or for a long time, or to further heat-treat after drying the coating solvent.
C for 5-120 minutes.

In addition, in the case of a surface layer formed product in which a photocurable resin is used as resin [B], after coating, it is crosslinked by irradiation with electron beams, X-rays, ultraviolet rays, or plasma light, and not only during drying, but also during drying. Either before or after that is fine.
The reaction is further accelerated by heating under the above drying conditions.

In both cases of heat crosslinking and light irradiation crosslinking, the treatment can be carried out under milder conditions if the above-mentioned reaction accelerator is used in combination.

Conventionally known resins can also be used together with the resins [A] and CB) used in the present invention. Examples include silicone resins, alkyd resins, vinyl acetate resins, polyester resins, styrene-butadiene resins, acrylic resins, etc. Specifically, Ryuji Kurita and Tsugube Ishiwata, "Polymers", Vol. 17, No. 278 Page (1968); Harumi Miyamoto,
Hidehiko Takei, "Imaging", 1973 (Na8) No. 9
Examples include well-known materials such as review citations such as pages.

The resin used in the present invention and known resins can be mixed in any proportion, but the content of the resin containing a hydroxyl group-forming functional group in the total amount of resin should be about 40 to 90% by weight. It is appropriate that

The resin [A] containing at least one type of hydroxyl group-forming functional group of the present invention is hydrolyzed or hydrogenolyzed by a fat-fixing liquid or a dampening solution used during printing to generate a hydroxyl group. Therefore, in the present lithographic printing original plate containing the resin in the surface layer (hydrophilicizable layer), the non-image area is made hydrophilic by the hydroxyl groups generated in the resin, and is clearly distinguished from the lipophilicity of the image area. This prevents printing ink from adhering to non-image areas during printing.

By further using the resin [B] of the present invention in combination with such resin [A], a crosslinking reaction with the resin [A] of the present invention occurs.

On the other hand, the hydroxyl group-containing resin [A
] becomes hydrophilic, and when its content is large, it usually becomes water-soluble. At this time, because the resin [A] forms a crosslinked structure with the non-aqueous resin [B] used in combination according to the present invention, its solubility in water is significantly reduced while maintaining hydrophilicity, resulting in a poorly soluble Or it becomes insoluble. That is, resin [B
] has the effect of preventing the resin [A] from becoming water-soluble and eluting from the non-image area.

Therefore, it is inferred that the hydrophilicity of the non-image area is further enhanced by the hydroxyl groups generated in the resin, and the durability is improved.

In terms of more specific effects, the effect of improving hydrophilicity can be maintained unchanged, or prints with clear image quality without background smudges even when printing conditions become harsher, such as when the printing machine becomes larger or printing pressure fluctuates. It becomes possible to print a large number of sheets.

In order to improve the strength of the hydrophilic surface layer itself, adhesion with the electrophotographic photosensitive layer, electrophotographic properties, etc., resins other than the resins of the present invention described above may be added, crosslinking agents, plasticizers, etc. may be added.

As the crosslinking agent, commonly used crosslinking agents such as organic peroxides, metal soaps, organic silanes, and polyurethanes, and curing agents such as epoxy resins can be used. Specifically, they are described in "Crosslinking Agent Handbook" edited by Fuzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981).

Furthermore, the surface layer that can be made hydrophilic may have its surface mechanically matted or layered for the purpose of improving development characteristics during toner development, adhesion of toner images, or water retention after hydrophilic treatment. Matting agents may contain fillers such as silicon dioxide, zinc oxide, titanium oxide, zirconium oxide, glass particles, alumina, clay, polymethyl methacrylate, polystyrene, phenol resin, etc. When constituting the surface layer, it is important that the non-image area becomes sufficiently hydrophilic after the degreasing treatment, as described above.

That is, this hydrophilicity can be confirmed, for example, by measuring the contact angle with respect to water.

The contact angle of surface N (hydrophilic layer) with water before the desensitizing treatment is approximately 60° to 120″, but after the desensitizing treatment, it decreases to approximately 5° to 20°. Therefore, the printing plate has an image area made of lipophilic toner and a highly hydrophilic non-image area on its surface. The surface layer after the fatening treatment may have a contact angle with water of 20 degrees or less.

The present invention is particularly superior in that its hydrophilicity is even better than conventional ones.

The electrophotographic photosensitive layer (leading tN) used in the present invention includes:
Any photoconductive substance can be used, regardless of whether it is an inorganic photoconductive compound or an organic photoconductive compound. Examples of inorganic photoconductive substances include zinc oxide, titanium oxide, zinc sulfide, selenium, selenium alloys, and sulfide. Cadmium, cadmium selenide, silicon, etc. may be used to form a photoconductive layer together with a binding resin, or may be used alone to form a photoconductive layer by vapor deposition or sputtering. As the photoconductive substance, for example, among polymeric substances, the following (1) to (5) can be mentioned.

(1) Polyvinylcarbazole and its derivatives described in Japanese Patent Publication No. 34-10966, (2) Japanese Patent Publication No. 43-1
Polyvinylpyrene, polyvinylanthracene, poly-2 described in JP-A No. 8674 and Japanese Patent Publication No. 43-19192
-vinyl-4-(4'-dimethylaminophenyl)-5
-vinyl polymers such as phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole; (3) polyacenaphthylene, polyindene, and copolymers of acenaphthylene and styrene described in Japanese Patent Publication No. 19193-1973; (4) Condensation resins such as pyrene-formaldehyde resin, brompyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin described in Japanese Patent Publication No. 56-13940, (5) Japanese Patent Publication No. 56-90833, 56-16155
Various triphenylmethane polymers described in Publication No. 0.

Examples of low molecular weight compounds include the following (6) to (18).

(6) Triazole derivatives described in US Pat. No. 3,112,197, etc.; (7) Oxadiazole derivatives, described in US Pat. No. 3,189,447, etc.;
Imidazole derivatives described in Publication No. 16096, etc. (9) U.S. Patent No. 3615402, U.S. Patent No. 382098
No. 9, No. 3542544, Special Publication No. 45-555, No. 10983-1983, Japanese Patent Publication No. 93224-1971,
JP-A-55-17105, JP-A-56-4148,
JP-A-55-108667, JP-A-55-15695
No. 3, polyarylalkane derivatives described in JP-A-56-36656, publications, etc. (10) U.S. Pat. No. 3180729, U.S. Pat. No. 42787
No. 46, JP-A-55-88064, JP-A-55-88
No. 065, JP-A-49-105537, JP-A-55-
No. 51086, JP-A-56-80051, JP-A-56
-88141, JP-A-57-45545, JP-A-5
Pyrazoline derivatives and pyrazolone derivatives described in No. 4-112637, JP-A-55-74546, publications, etc., (11) U.S. Pat. -83
No. 435, JP-A-54-110836, JP-A-54-
No. 119925, Special Publication No. 1971-3712, Special Publication No. 1977
Phenyldiamine derivatives described in -28336 specification, gazette, etc.
No. 5702, West German Patent (DAS) No. 1110518,
U.S. Patent No. 3180703, U.S. Patent No. 324059
No. 7, U.S. Patent No. 3,658,520, U.S. Patent No. 423
No. 2103, U.S. Patent No. 4175961, U.S. Patent No. 4012376, JP 55-144250, JP 56-119132, JP 39-27577,
Arylamine derivatives described in JP-A-56-22437, publications, etc., (13) amino-substituted chalcone derivatives described in U.S. Pat. No. 3,526,501, (14) U.S. Pat. No. 3,542,546, etc. (15) Oxazole derivatives described in U.S. Pat. No. 3,257,203, Saimei 11II, etc.; (Engineering 6) Styryl anthracene derivatives, described in JP-A-56-46234, etc.; (17) Fluorenone derivatives described in JP-A-54-110837, etc., (18) U.S. Patent No. 3717462, JP-A-54-5
No. 9143, JP-A-55-52063, JP-A-55-
No. 52064, JP-A-55-46760, JP-A-55
-85495, JP-A-57-11350, JP-A-57-11350
Hydrazone derivatives disclosed in Patent No. 7-148749 and other publications.

Two or more of these photoconductive substances may be used in combination depending on the case.

Among these photoconductive materials are poly-N-vinylcarbazole; triarylamines such as tri-p-)lylamine and triphenylamine; 4,4'-bis(diethylamine)-2°2'-dimethyltriamine; Boarylmethane such as phenylmethane: and 3-(4
-dimethylaminophenyl)-1,5-diphenyl-2
-Unsaturated heterocycle-containing compounds represented by pyrazoline derivatives such as pyrazoline are preferably used.

As the binder that can be combined, all conventionally known binders can be used. Typical examples include vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-butyl meccrylate copolymer, These include polymethacrylate, polyacrylate, polyvinyl acetate, polyvinyl butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin, polyester resin, and the like.

It is also possible to combine it with an aqueous acrylic emulsion or an acrylic ester emulsion.

For examples of specific polymeric materials useful as binders, see
Research Disclosure
Disclosure), Vol. 109, pp. 61-67.
under the title ``Electrophotographic Elements, Materials and Methods''.

-a, the amount of binder present in the photoconductive composition used in the present invention can vary. Typically useful amounts of binder range from about 10 to about 90% by weight, based on the total amount of the photoconductive material and binder mixture.

Furthermore, conventionally known compounds can be added as spectral sensitizers. For example, xanthine dyes, triphenylmethane dyes, azine dyes, phthalocyanine dyes (
Examples include metal-containing), polymethine dyes, etc. Specifically, examples include Harumi Miyamoto and Hidehiko Takei, “Imaging, 1973
(8), IC, J, Young, R, C, A R
View top 5. 469 (1954); Wataru Kiyota, Journal of the Institute of Electrical Communication J63-C (Nα2), 97 (
1980); Yuji Harasaki et al., Industrial Chemistry Journal, 66.78 and 188 (1963); Tadaaki Tani, Journal of the Photographic Society of Japan, 3
5.208 (1972);Re5earch D
isclosure, Saturday, 1982, 117-11
8; Comprehensive technical data collection ``Recent Development and Practical Application of Photoconductive Materials and Photoreceptors'' Nippon Kagaku Information ■Publishing Department Series (1986), etc. Publicly known materials cited as review articles.

The photoconductive layer may be formed from -i, but may also be formed from two or more multilayers.

In the case of a multilayer structure, for example, a charge generation layer comprising the above-mentioned inorganic photoconductor or an organic pigment such as a phthalocyanine pigment or an azo pigment, and a binding resin added as necessary;
A so-called functionally separated photoconductive layer may be considered, in which the above-described high molecular compound or low molecular compound and a charge transport layer made of a binding resin are laminated.

The photoconductive layer used in the present invention can be provided on a commonly used and known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably electrically conductive, and examples of the electrically conductive support include metal, paper, etc.
A substrate such as a plastic sheet that has been treated to conductivity by impregnating it with a low-resistance substance, etc. The purpose is to impart conductivity to the back side of the substrate (the side opposite to the side on which the photosensitive layer is provided) and to prevent curling. A water-resistant adhesive layer is provided on the surface of the support, and at least one layer of Brenault+-i is provided on the surface layer of the support as necessary. ,A! A material made by laminating a plastic substrate onto paper, etc., can be used.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, “Electronic Photography J 14. (N(11).

pp. 2-11 (1975) i Hiroyuki Moriga "Introductory Chemistry of Special Papers" Kobunshi Publishing (1975); M, F.

Hoover, J., Macromol, Sci.
CheIll, A-4(6), No. 1327-1
417 (1970) and the like can be used.

The coating thickness of the photoconductive composition on a suitable support can vary widely. Usually about 10 microns to about 300 microns
It can be applied within the range of microns (before drying). A preferred range of coating thickness before drying has been found to be within the range of about 50 microns to about 150 microns. However, useful results can be obtained even outside this range. The dry thickness of this coating may range from about 1 micron to about 50 microns.

The thickness of the hydrophilic surface layer of the present invention is 10 μm or less, particularly 0.1 to 5 μm for Carlson process.
It is preferable that

If it is thicker than 5 μm, disadvantages may occur such as a decrease in sensitivity of the lithographic printing original plate as an electrophotographic window light material and an increase in residual potential.

In order to actually make the lithographic printing original plate of the present invention, generally,
First, an electrophotographic photosensitive layer (photoconductive layer) is formed on a conductive support according to a conventional method. Next, on this layer, the resin of the present invention and, if necessary, the above-mentioned additives, etc., are added to a boiling point of 20.
It can be produced by dissolving or dispersing it in a volatile hydrocarbon solvent at 0°C or lower, coating it, and drying it. The organic solvent used is preferably a C1-3 rhodanized hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, dichloropropane or trichloroethane. Other aromatic hydrocarbons such as chlorobenzene, toluene, xylene or benzene, ketones such as acetone or 2-butanone, ethers such as tetrahydrofuran, and methylene chloride, etc.
Various solvents used in coating compositions and mixtures of the above solvents can also be used.

A toner image is formed on the original plate obtained as described above in accordance with a conventional electrophotographic method. A printing plate can be obtained by treating this with a desensitizing treatment liquid (for example, an acidic or alkaline aqueous solution or an aqueous solution containing a reducing agent) to make the non-image area hydrophilic.

In this way, if the hydrophilic layer of the present invention is used,
Any conventionally known electrophotographic photoreceptor can be used as a high-quality lithographic printing original plate.

The hydrophilizable layer is a film that exhibits both high hydrophilicity and water resistance after hydrophilic treatment, and also has extremely good adhesion to the substrate and toner image. In addition to extremely suppressing generation, it has high durability.

Furthermore, since the printing plate of the present invention can maintain almost the original sensitivity of the electrophotographic photosensitive layer, it is possible to obtain a printing original plate with significantly higher sensitivity than conventional printing original plates for electrophotographic engraving. In addition, conventionally, a single layer must have the properties of photoconductivity and hydrophilicity, so
Previously, only limited materials such as zinc oxide could be used, but in the printing original plate of the present invention, the functions are separated into a photoconductive layer and a hydrophilizable layer, so the range of selection of the photoconductive layer is expanded, and therefore, for example, By selecting a material that is highly sensitive to long wavelength light, it becomes possible to write with a He-Ne laser or a semiconductor laser, which was previously impossible.

In addition, in the printing original plate of the present invention, the non-image area can be made hydrophilic by simply immersing it in a hydrophilic treatment solution for a few seconds, so it is small and
Plate making becomes possible with a simple device.

(The following is a blank space) (Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

Example 1 5 g of 4,4'-bis(diethylamino)-2,2'-dimethyltriphenylmethane as an organic photoconductive substance
5 g of 1-bisphenol A polycarbonate (manufactured by GE, trade name Lexan 121), 40 cm of spectral sensitizing dye [A] with the following structural formula, and 0.2 g of an anilide compound with the following structural formula [B] as a chemical sensitizer. and methylene chloride 30
It was dissolved in a mixture of ml and 30 ml of ethylene chloride to obtain a liquid solution.

(Spectral sensitizing dye [A]) (Anilide compound [B]) This photosensitive solution was transferred using a wire round rod to a conductive transparent support (100 um polyethylene terephthalate support, a 0.0-100% carbon dioxide film having a vapor-deposited film of indium oxide on it. An organic thin film was obtained which formed a photosensitive layer of about 4 μm by coating on a surface with a surface resistance of 10″Ω.

On the other hand, 5 g of 2- and dolokidiethyl methacrylate, 45 g of the monomer shown in specific example (2), and 150 g of toluene.
After heating the mixed solution to a temperature of 70°C under a nitrogen stream,
Azobisisobutyronitrile (A, T, B, N,) 1
．． 0g was added and reacted for 8 hours.

The weight average molecular weight of the obtained copolymer was 43,000. :Resin [A]-1 Butyl methacrylate 40g, monomer 10 of the following structural formula
The reaction was carried out in the same manner as the above resin [A]-1 except that a mixed solution of 100 g of g and toluene was used, and the weight average molecular ff
138,000 copolymers were obtained. :Resin [B]-1? 113 A 5% by weight toluene solution of the copolymer obtained above, Resin [A]-1/Resin (B,)-1 (5/1 weight ratio), was applied to the surface of the electrophotographic photoreceptor obtained earlier. It was applied with a doctor blade to form a surface layer of about 2 μm. The photosensitive material was passed through an etching processor twice using a desensitizing treatment liquid (ELP-EX, manufactured by Fuji Photo Film ■) to be desensitized.

A 2μr water droplet of distilled water was placed on this, and the contact angle with the water formed was measured with a goniometer and was less than 10".The contact angle before desensitization was 83°, clearly , indicating that the surface layer of this photosensitive material was made very well hydrophilic.

The original plate obtained in this way was processed using a fully automatic plate making machine ELP404V (Fuji Photo Film ■) using a negatively charged liquid developer.
(manufactured by Sakurai Seisakusho, Ltd.) to form a toner image, which was desensitized under the same conditions as above, used as an offset master, and printed on high-quality paper using an offset printing machine (manufactured by Sakurai Seisakusho ■, model 52).

The number of prints that could be printed without causing problems with scumming in the non-image areas and image quality in the image areas was 10,000.

Example 2 5 g of bisazo pigment with the following structural formula, 9 g of tetrahydrofuran
A mixture of 5 g of polyvinyl butyral resin (manufactured by Denki Kagaku Kogyo Co., Ltd.: Denka Butyral #4000-1) of 30 g of a 5% by weight tetrahydrofuran solution was sufficiently ground in a ball mill.Then, this mixture was taken out, and 520 g of tetrahydrofuran was added thereto while stirring. Ta. This dispersion was coated onto the conductive transparent support used in Example 1 using a wire round rod, and the dispersion was coated with a wire round rod to give a coating of approximately 0.00%. A charge generating HE layer of 7 μm was formed.

(Bisazo pigment) Next, 20 g of a hydrazone compound having the following structural formula, 20 g of a polycarbonate resin (manufactured by GE, trade name: Lexan 121)
A mixed solution of 160 g of tetrahydrofuran and 160 g of tetrahydrofuran was applied onto the charge generation layer using a wire round rod to form a charge transport layer of about 18 μm, thereby obtaining an electrophotographic photoreceptor having a photosensitive layer made of 2N.

(Hydrazone compound) On the other hand, 5 g of 2-hydroxyethyl methacrylate, 45 g of the monomer shown in specific example (9), and 150 g of toluene.
A copolymer having a weight average molecular weight of 42,000 was obtained by carrying out the reaction in the same manner as the resin [A]-1 except that a mixed solution of g was used. : Resin [A]-2 Obtained copolymer, resin [
5% by weight of A]-2/resin [B]-1 (5/1 weight ratio)
A toluene solution was applied onto the photosensitive layer using a doctor blade to form a surface layer of about 2 μm.

The photosensitive material prepared in this way was charged to -6 kV with a paper analyzer (Kawaguchi Denki model, 5P-428), and the initial potential (■.), dark charge retention rate (D, R, R,) and light attenuation exposure were measured. When the amount (E1/l.) was measured, each was ■. =-
560V, D, R, R, = 85% and El/1610
．． 2 (Iux-sec).

Furthermore, in the same manner as in Example 1, a fully automatic plate making machine ELP4 was used.
When the plate was made using ELP-T)ner at 0.04 V, the density of the obtained offset printing master plate was 1.
The image quality was clear when it was 0 or higher.

Furthermore, when etching was performed and printed using a printing press, the printed matter after cane printing had no fog in the non-image area and the image was clear.

The method for measuring the evaluation items of the electrostatic properties described above is as follows.

In a dark room at a temperature of 20°C and 565% RH, each photosensitive material was subjected to corona discharge for 20 seconds at -6 and ■ using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Denki ■), and then left for 10 seconds. , the surface potential at this time■
1° was measured. Then, the potential was left undisturbed for 60 seconds in a dark room.

was measured, and the potential retention after dark decaying for 60 seconds, that is, the dark decay retention rate (D, R, R, (%)) was expressed as (V, ./
V+. )X100(%).

After the surface of the photoconductive layer was charged to -400 V by corona discharge, the surface of the photoconductive layer was irradiated with visible light at an illuminance of 2.0 lux until the surface potential (Vl(1) attenuated to 1/10). , and calculate the exposure iE, /+.(lux seconds) from this time.

Example 3 [Methyl methacrylate/ethyl methacrylate/acrylic acid (39/60/1 weight ratio)] copolymer (weight average molecular weight 42,000) 45 g, zinc oxide 200 g, rose bengal 0.03 g, tetrabromophenol blue 0
．． 02g, phthalic anhydride 0.05g and toluene 300g
g of the mixture was dispersed in a ball mill for 2 hours to prepare a photosensitive layer-forming product, and this was applied to conductive-treated paper with a dry adhesion amount of 2.
Apply with a wire bar so that it is 5g/rrT,
Dry at 0°C for 1 minute.

On the other hand, resin [A]-1 used in Example 1 and resin [
B]-1 (5/1 weight ratio) toluene solution for surface layer coating was applied to the photosensitive layer with a doctor blade to a thickness of approximately 2 μm.
A surface layer was formed.

Then, an electrophotographic light-sensitive material was prepared by leaving it for 24 hours in a dark place at 20° C. and 165% RH.

This photosensitive material was charged to -6 to ■ using a paper analyzer, the initial potential (■.) was -540V, the dark charge retention rate (D,
R, R, ) 84%, and light attenuation exposure (El/10)
A value of 10.0 (1ux-sec) was obtained for each.

Further, this was plate-made in the same manner as in Example 2, and the density of the obtained offset printing master plate was 1.0 or more and the image quality was clear.

Furthermore, when etching was performed and printed using a printing press, the printed matter after cane printing had no fog in the non-image area and the image was clear.

Examples 4 to 11 The copolymer resin [A] of the present invention (see Table 1 below) was
Each photosensitive material was produced in the same manner as in Example 3, except that resin (A)-1 of the present invention used in Example 3 was used instead.

Table-1 Table-1 (Continued 1) Table-1 (Continued 2) When this was plate-made using the same equipment as in Example 3, the density of the obtained offset printing master plate was 1.0 or more and the image quality was clear. Met. Further, when etching was performed and printed using a printing press, the printed matter after printing 10,000 sheets had clear image quality with no fogging.

Further, this photosensitive material was left under environmental conditions (45° C., 275% RH) for two weeks and then subjected to exactly the same treatment, but there was no difference at all from before aging.

Examples 12 to 13 A copolymer [weight average molecular weight 36.000] consisting of the following copolymer composition ratio (weight ratio) was used as the resin [A], and a copolymer shown in Table 2 was used as the resin [B] in 6/ 1(
A 5% by weight toluene solution (weight ratio) was applied to the surface layer of the photoreceptor obtained in Example 1 using a doctor blade, and heated at a temperature of 110''C for 2 hours.

Then, an electrophotographic light-sensitive material was prepared by leaving it in a dark place at 20° C. and 165% RH for 24 hours.

Table 2 When this was plate-made using the same apparatus as in Example 1, the density of the obtained offset printing master plate was 1.0 or more and the image quality was clear. After further etching and printing on a printing press, the printed matter after printing 10,000 sheets had clear image quality with no capri.

(Effects of the Invention) From the above, the electrophotographic lithographic printing original plate having a hydrophilic layer containing the resin of the present invention in its surface layer has both high hydrophilicity and water resistance after the hydrophilic treatment. It is a membrane,
Moreover, it has extremely good adhesion with toner images, so
The resulting lithographic printing original plate has excellent quality in both scumming and rigidity resistance.

Furthermore, the resin of the present invention is easy to manufacture.

Claims (1)

[Scope of Claims] A lithographic printing original plate using an electrophotographic photoreceptor comprising at least one photoconductive layer provided on a conductive support and a surface layer provided on the uppermost layer. An original plate for electrophotographic planographic printing, characterized in that it contains at least two of the following resins [A] and resin [B] as main components. (i) Resin [A]; Resin containing at least one functional group that generates at least one hydroxyl group upon decomposition (ii) Resin [B]; Heat and/or photocurable resin