JPH0572757A - Production of electrophotographic planographic printing original plate - Google Patents

Abstract

PURPOSE:To provide the electrophotographic planographic printing original plate which is stable in spite of storage under severe conditions and can rapidly and easily develop hydrophilicity at the time of a treatment for hydrophilicity impartation by improving the process for production of the above-mentioned planographic printing original plate and more particularly a compsn. for forming the photoconductive layers of the planographic printing original plate and a desensitization processing method. CONSTITUTION:The electrophotographic sensitive body constituted by providing at least one layer of photoconductive layers contg. a photoconductive inorg. compd. and a binder resin on a conductive base and incorporating at least one kind of reins contg. at least one kind of polymer components having the functional group expressed by formula I into the binder resin is formed with a toner image by image exposing thereafter, the non-image parts of the photoconductive layers are subjected to the desensitization processing by a processing liquid contg. a hydrophilic property contg. a substituent having a value of at least >=5.5 Parsons nucleophilic constant (n), by which the printing original plate is formed. In the formula I, at least either of X, X' are an electron-withdrawing group and the sum of Hammet Vp value of both is >=0.45.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electrophotographic lithographic printing plate precursor prepared by electrophotography, and more particularly to a composition for forming a photoconductive layer of the lithographic printing plate precursor and a desensitizing oil. The present invention relates to improvement of a chemical treatment method.

[0002]

2. Description of the Related Art At present, various types of offset original plates for direct plate making have been proposed and put into practical use. Above all, photoconductive particles such as zinc oxide and a binder resin are mainly used on a conductive support. In a photoconductor provided with a photoconductive layer as a component, a highly lipophilic toner image is formed on the surface of the photoconductor through an ordinary electrophotographic process, and then the surface is treated with a desensitizing solution called an etchant. A technique is widely used in which an offset original plate is obtained by processing and selectively hydrophilizing a non-image portion.

In order to obtain a good printed matter, first, the original image is faithfully copied to the offset original plate, the surface of the photoreceptor is easily compatible with the desensitizing solution, and the non-image area is sufficiently hydrophilized, and at the same time, it is water resistant. The hydrophilicity of the non-image area is sufficient so that the surface conductive layer with the image does not come off during printing and is well compatible with fountain solution, so that stains do not occur even when the number of printed sheets increases. It is necessary to have properties such as maintaining the nature.

It is already known that these performances are affected by the ratio of zinc oxide and binder resin in the photoconductive layer.
For example, if the ratio of the binder resin to the zinc oxide particles of the photoconductive layer is reduced, the desensitizing property of the surface of the photoconductive layer is improved and scumming is reduced, but the internal cohesive force of the photoconductive layer itself is reduced. And the printing durability deteriorates due to insufficient mechanical strength. On the contrary, when the ratio of the binder resin is increased, the printing durability is improved, but the background stain is increased. It goes without saying that the background stain is a phenomenon related to the quality of the desensitizing property of the photoconductive layer surface, but the desensitizing property of the photoconductive layer surface depends on the zinc oxide and the binder resin in the photoconductive layer. It is becoming clear that not only the ratio but also the type of binder resin greatly affects.

Known binder resins have long been known, for example, silicone resin (Japanese Patent Publication No. 34-6670), styrene-butadiene resin (Japanese Patent Publication No. 35-1950),
Alkyd resin, maleic acid resin, polyamide (Japanese Patent Publication No. 35-11219), vinyl acetate resin (Japanese Patent Publication No. 4)
No. 1-2425), vinyl acetate copolymer (Japanese Patent Publication No.
No. 1-2426), acrylic resin (Japanese Patent Publication No. 35-1)
No. 1216), acrylic acid ester copolymers (for example, Japanese Examined Patent Publications 35-11219, 36-8510, 41).
-13946 publications, etc.) are known. But,
In the electrophotographic photosensitive material using these as a binder resin, 1) the photoconductive layer has a low chargeability, 2) the quality of the image portion of the copied image (particularly halftone dot reproducibility / resolution) is poor, and 3) exposure. Low sensitivity, 4) Desensitization is not performed even when desensitized for use as an offset master, and thus background stain occurs on printed matter when offset printing is performed 5)
The film strength of the photosensitive layer is not sufficient, and the offset printing causes detachment of the photosensitive layer, and the number of printed sheets cannot be increased. 6) The image quality is easily affected by the environment (for example, high temperature and high humidity) at the time of making a copy image, Etc. there was any problem.

In particular, as the offset original plate, as described above, the occurrence of background stain due to insufficient desensitizing property is a serious problem. To improve this, a zinc oxide binder resin for improving desensitizing property is used. Various developments have been studied.
For example, in Japanese Patent Publication No. 50-31011, a (meth) acrylate-based monomer is copolymerized with another monomer in the presence of fumaric acid, and the weight average molecular weight is 1.8 to 10 × 1.
0 ⁴ and 10 to 80 ° C. of the resin glass transition point Tg, the ones used in combination with a copolymer comprising a monomer other than (meth) acrylate monomer and fumaric acid, JP 53
No. 54027, a terpolymer containing a (meth) acrylic acid ester having a substituent having a carboxylic acid group separated from the ester bond by at least 7 atoms is used. 57-20254
4 each use a quaternary or quaternary copolymer containing acrylic acid and hydroxyethyl (meth) acrylate. In JP-A-58-68046, the number of carbon atoms is 6 to 6.
A terpolymer using a (meth) acrylic acid ester having an alkyl group of 12 as a substituent and a carboxylic acid-containing vinyl monomer is effective in improving the desensitizing property of the photoconductive layer. Have been described. However, even with these resins that are said to be effective in improving the desensitizing property, when actually evaluated, the background stain and the printing durability were insufficient.

Further, a binder resin using a resin containing a functional group capable of generating a hydrophilic group by decomposition has been investigated. 62-195684,
62-210475, Japanese Patent Application No. 63-8446.
Specification) and those containing a functional group capable of generating a carboxyl group by decomposition (JP-A-62-212669, JP-A-1-63977, Japanese Patent Application No. 63-14576).
No. specification) and the like. These resins are resins that are hydrolyzed or hydrolyzed by a desensitizing solution or immersion water used at the time of printing to generate a hydrophilic group, and when these are used as a binder resin for a lithographic printing original plate, a hydrophilic group is used. Various problems that may occur due to strong interaction between the hydrophilic groups and the photoconductive zinc oxide particle surface when a resin containing itself is used (deterioration of smoothness, deterioration of electrophotographic characteristics, etc.) And the hydrophilicity of the non-image area which is hydrophilized by the desensitizing solution is further enhanced by the hydrophilic group generated by decomposition in the resin, so that the lipophilicity of the image area and the non-image area can be improved. It is described that the hydrophilicity of the ink becomes clear, preventing the printing ink from adhering to the non-image area during printing, and as a result, it is possible to print a large number of prints with clear image quality without background stains. .

[0008]

The resin of the type which produces a hydrophilic group by the above-mentioned decomposition reaction is desensitized by decomposing a carboxyl group or a hydroxyl group masked with a protecting group in advance with a treatment liquid to remove the protecting group. It is something to separate. Therefore, the binder resin of this type is stably present without being hydrolyzed under the influence of atmospheric humidity (moisture) during storage, and the deprotecting group reaction rapidly proceeds during hydrophilization treatment. It is required as an important property that a hydrophilic group can be generated to improve the hydrophilicity of the non-image area. In view of such a situation, the present invention further improves the effect due to the hydrophilicity of the non-image area, and is stable even when stored under extremely severe conditions,
Another object of the present invention is to provide a method for producing an electrophotographic lithographic printing plate precursor that can easily exhibit hydrophilicity in a short time during hydrophilic treatment.

[0009]

SUMMARY OF THE INVENTION The present invention addresses the above-mentioned problems by providing an electrophotographic image on which at least one photoconductive layer containing a photoconductive inorganic compound and a binder resin is provided on a conductive support. An electrophotographic photoreceptor comprising a photoconductor, the binder resin containing at least one resin containing at least one polymer component having a functional group represented by the following general formula (I), After exposure to form a toner image, the non-image area of the photoconductive layer is desensitized with a treatment liquid containing at least a hydrophilic compound containing a substituent having a nucleophilic constant n of a person of 5.5 or more. This is solved by a method for producing an electrophotographic lithographic printing plate precursor, which is characterized in that it is made into a printing plate precursor by subjecting it to a chemical conversion treatment. General formula (I)

[Chemical 2] [However, in the above formula (I), at least one of -X and -X 'is an electron-withdrawing group, and Ha of -X and -X' is
If the sum of the values of mmet σ _P is 0.45 or more,
May be the same or different] In the present invention, a resin containing at least one kind of the polymer component having a functional group represented by the general formula (I) may be pre-crosslinked. In this case, the resin is water-resistant when it exhibits hydrophilicity by reacting with the hydrophilic treatment liquid, which is preferable. Further, the resin containing at least one kind of the polymer component having a functional group represented by the above general formula (I) of the present invention further contains at least one kind of functional group which causes a curing reaction by heat and / or light. It may be a resin.

[0010]

According to the present invention, at least a part of the binder resin of the photoconductive layer of the lithographic printing plate precursor has a resin containing at least one functional group represented by the general formula (I), and preferably the resin is The hydrophilic compound can be introduced into the resin by being partially crosslinked and treated with a treatment liquid containing at least one nucleophilic reactive hydrophilic compound, whereby the binder resin It is characterized in that it can exhibit hydrophilicity and, at the same time, has hydrophilicity and is insoluble or hardly soluble in water. As a result, the lithographic printing plate precursor according to the present invention reproduces a copy image faithful to the original image, and since the non-image area has good hydrophilicity, scumming does not occur, and the smoothness and electrostatic properties of the photoconductive layer are reduced. Has good characteristics,
Further, it has an advantage that the printing durability is excellent.

The mechanism by which the binder resin according to the present invention is made hydrophilic is shown in the following reaction formula (1). In reaction formula (1),
A nucleophilic reactive hydrophilic compound having an excellent nucleophilic property undergoes a rapid substitution reaction. However, this reaction is -X,-
When the sum of Hammet's σ _P values of X ′ is 0.45 or more, it is effective. When it is less than 0.45, sufficient reactivity cannot be obtained.

[Chemical 3] That is, in the present invention, when desensitizing the non-image area as a lithographic printing plate precursor, by using a nucleophilic reactive hydrophilic compound while suppressing the reaction with moisture in the atmosphere as compared with the conventional one. The reactivity could be improved dramatically.
It is characterized in that a hydrophilic group is introduced to make it hydrophilic by the above mechanism.

A resin [A] containing at least a copolymerization component having a functional group represented by the general formula (I) of the present invention.
Will be described in more detail. At least one of -X and -X 'shown in the general formula (I) is an electron-withdrawing group,
The sum of the Hammett σ _P values of −X and −X ′ may be 0.45 or more. Examples of the electron-withdrawing group referred to here include:
Examples thereof include an acyl group, aroyl group, formyl group, alkoxycarbonyl group, phenoxycarbonyl group, alkylsulfonyl group, aroylsulfonyl group, nitro group, cyano group, halogen atom, halogenated alkyl group and carbamoyl group. The Hammett σ _P value is usually used as an index for estimating the degree of electron withdrawing / donating of a substituent, and the larger it is on the + side, the stronger the electron withdrawing group is treated. For specific numerical values for each substituent,
Naoki Inamoto "Hammett's Rule-Structure and Reactivity" Maruzen (198)
4 years). In addition, H in this system
It is considered that additivity holds for the σ _P value of ammet, and −
Both X and -X 'need not be electron withdrawing groups. Thus, for example, when -X is an electron withdrawing group, the other-
The substituent of X ′ has a sum of σ _P values of −X and −X ′ of 0.45.
Any one may be used as long as it is above, and there is no particular limitation.

Examples of the copolymer component having a functional group represented by the general formula (I) used in the present invention include those represented by the following general formula (II). General formula (II)

[Chemical 4] [In the above formula (II), Z is -COO-, -OCO-, -O.
-, -CO-,

[Chemical 5] _{-CONHCOO -, - CONHCONH-, CH 2} C
OO-, CH ₂ OCO-,

[Chemical 6] Represents. Y represents an organic residue bonded to or directly connected to -Z- and -W _0. further

[Chemical 7]

[Chemical 8] And -W ₀ may be directly bonded. -W ₀ is the general formula (I)
Represents a functional group represented by. a ₁ and a ₂ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group or an aryl group. ]

The general formula (II) will be described in more detail. Preferably Z is

[Chemical 9] Represents. However, r ₁ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2-chloroethyl group, 2 -Bromoethyl group, 2-
Cyanoethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, 3-bromopropyl group, etc.), carbon number 7-9
An optionally substituted aralkyl group (for example, a benzyl group,
Phenethyl group, 3-phenylpropyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group, dibromobenzyl group, etc.), an aryl group which may be substituted (for example, a phenyl group, Tolyl group, xylyl group, mesityl group, methoxyphenyl group, chlorophenyl group, bromophenyl group,
Chloro-methyl-phenyl group, etc.) and the like.

Y is a direct bond for connection, or -Z- and -W ₀
Represents an organic residue linking. When Y represents an organic residue to be linked, this linking group represents a carbon-carbon bond which may be through a hetero atom (as a hetero atom, an oxygen atom,
Indicating a sulfur atom or a nitrogen atom), for example

[Chemical 10] And the like, each of which is composed of a single or a combination of bonding units (provided that r ₂ , r ₃ , r ₄ , r ₅ and r ₆ have the same contents as r ₁ ).

A ₁ and a ₂ may be the same or different and each is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group, a hydrocarbon group (eg, methyl group, ethyl group, propyl group, butyl group). , Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group,
An optionally substituted alkyl group having 1 to 12 carbon atoms such as butoxycarbonylmethyl group, aralkyl group such as benzyl group, phenethyl group, phenyl group, tolyl group, xylyl group,
And an aryl group such as a chlorophenyl group).

Furthermore, in the general formula (II)

[Chemical 11]

[Chemical formula 12] And -W ₀ may be directly linked.

Specific examples of the polymer component containing the functional group represented by the general formula (I) of the present invention are shown below. However, the scope of the present invention is not limited to these. In addition, in Examples (a-1) to (a-36), a is —H or —CH _3.
Represents.

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21]

The resin containing the polymer component having a functional group represented by the general formula (I) of the present invention as described above can be synthesized by a conventionally known synthesis method. That is,
A method of polymerizing a functional group represented by the general formula (I) and a monomer having a polymerizable double bond group in the molecule (for example, a monomer corresponding to the repeating unit of the general formula (II)). And reacting a low molecular weight compound containing a functional group of the general formula (I) with a polymer compound containing a polymer component containing a functional group that chemically reacts with the low molecular weight compound (that is, a polymer reaction).
Therefore, a method of synthesizing is possible. Examples of the carboxylic acid esterification reaction in the above-described monomer synthesis or polymer reaction synthesis include, for example, “Chemical Synthesis and Reaction of Organic Compounds” p.
1978) published by Maruzen Co., Ltd.

Shown by the general formula (I) in the resin of the present invention.
The resin component containing a functional group is a copolymer
Is 1 to 95% by weight in the total copolymer, especially
It is preferably 5 to 90% by weight. In addition, the resin
The molecular weight of the polymer is 10³-10⁶, Especially 3 × 10³~ 5
× 10 ^FiveIs preferred.

The resin of the present invention may further have at least a part thereof crosslinked in the electrophotographic lithographic printing plate precursor. As such a resin, a resin which has been crosslinked in advance at the time of coating the photosensitive layer forming material in the plate making process may be used, or a resin containing a crosslinkable functional group which causes a curing reaction by heat and / or light is used. It may be crosslinked during the lithographic printing plate manufacturing process (for example, a drying process). Further, these may be used in combination.

When a resin in which a part of the polymer is pre-crosslinked (a polymer having a crosslinked structure in the polymer) is used as the binder resin, the functional group of the above formula (I) contained in the resin is used. Is preferably a resin that is hardly soluble or insoluble in acidic and alkaline aqueous solutions when it is subjected to desensitizing treatment to exhibit hydrophilicity. Specifically, the solubility in distilled water is preferably 90% by weight at a temperature of 20 to 25 ° C.
Hereafter, the solubility is more preferably 70% by weight or less.

As a method for introducing a crosslinked structure into the polymer, a generally known method can be used. That is, in the polymerization reaction of a monomer containing a functional group of the above formula (I), a polyfunctional monomer (a monomer containing two or more polymerizable functional groups) or a polyfunctional oligomer is allowed to coexist. By a method of cross-linking between molecules by polymerizing, and a method of containing a functional group that promotes a cross-linking reaction in the polymer, and then polymerizing a compound containing a group of the above formula (I) to cross-link is there.

Specifically, a method of polymerizing a polyfunctional monomer with a monomer containing at least one functional group of the general formula (I) of the present invention, or the polyfunctional monomer is generally used. A polar group (for example, a functional group of formula (I)) (for example,

[Chemical formula 22] Etc.) to produce a copolymer, and then the resin of the present invention is produced by a method of introducing a low molecular weight compound containing a functional group of the general formula (I) by a polymer reaction. be able to.

Specifically as the polymerizable functional group,

[Chemical formula 23] Etc., but the monomer having two or more polymerizable functional groups is a monomer having two or more of the same or different polymerizable functional groups. Good.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, as monomers having the same polymerizable functional group, styrene derivatives such as divinylbenzene and trivinylbenzene: polyhydric alcohol ( For example, ethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol # 200, # 400, # 60
0, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhydroxyphenols (eg hydroquinone, resorcin, catechol and their derivatives) Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (eg malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) Vinyl esters, allyl esters, vinylamides or allylamides of:
A condensate of a polyamine (for example, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and a carboxylic acid containing a vinyl group (for example, methacrylic acid, acrylic acid, crotonic acid, allylacetic acid, etc.) Can be mentioned.

Further, as a polyfunctional monomer or oligomer having different polymerizable functional groups, for example, a carboxylic acid containing a vinyl group [eg methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propion] Acid, itaconiloyl acetic acid, itaconiloyl propionic acid, a reaction product of an alcohol or amine with a carboxylic acid anhydride (for example, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc. ) Etc. containing a vinyl group-containing ester derivative or amide derivative (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, methacryloyl). Vinyl acetate, methacryloyl propionic acid vinyl, methacryloyl propionic acid allyl, vinyl methacrylate oxycarbonyl ester, vinyl oxycarbonyl methyloxycarbonyl ethyl ester acrylate, N- allyl acrylamide, N- allyl methacrylamide, N- Ariruitakon acid amide,
Methacryloylpropionic acid allylamide etc.) or amino alcohols (eg aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol etc.) and a condensate of a carboxylic acid containing a vinyl group, etc. Can be mentioned.

The monomer or oligomer having two or more polymerizable functional groups which can be used in the present invention is polymerized by using not more than 10 mol%, preferably not more than 5 mol% of all monomers and preliminarily crosslinked. Resin can be formed.

On the other hand, in the method of cross-linking a polymer containing a functional group which promotes a cross-linking reaction by a macromolecular reaction, the functional group can be a chemical bond between molecules to form a chemical bond. Either is fine. That is, it is possible to use a reaction mode in which a bond between molecules due to a condensation reaction, an addition reaction or the like or a cross-link due to a polymerization reaction is caused by heat and / or light. Specifically, functional groups {e.g. -COOH group having a dissociative hydrogen atom, -PO ₃ H ₂ group,

[Chemical formula 24] [R _I represents an aliphatic group, preferably straight-chain or branched alkyl group (e.g. methyl group having 1 to 12 carbon atoms which may be substituted, an ethyl group, a propyl group, chloromethyl group, dichloromethyl group, A trichloromethyl group, a trifluoromethyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a hydroxyethyl group, a 3-chloropropyl group or the like or a -OR _II group (R _II is the same as the group of R _I Represents)], —OH group, —SH group, —NH · R _III group (R
_III is a hydrogen atom or a methyl group, an ethyl group, a propyl group,
Represents an alkyl group having 1 to 4 carbon atoms such as a butyl group)},

[Chemical 25] Containing at least one combination of functional groups selected from each group, or --CONHCH ₂ OR _IV
(R _IV represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group) or a polymerizable double bond group. Specific examples of the polymerizable double bond group include those mentioned above as specific examples of the polymerizable functional group.

Further, for example, Takeshi Endo, "Refinement of Thermosetting Polymers", CMC Co., Ltd. (published in 1986), Yuji Harazaki, "Latest Binder Technology Handbook", Chapter II-1, General Technology. Center (1985), Takayuki Otsu "Synthesis and design of acrylic resin and new application development" Chubu Business Development Center Publishing Department (1985), Eizo Omori "Functional acrylic resin"
Techno System (1985), Hideo Inui, Mototaro Nagamatsu "Photosensitive Polymer" Kodansha (1977), Takahiro Tsunoda "New Photosensitive Resin" Press Society Press (1981), G.
E. Green and BPStar, RJ Macro. Sci. Revs. Macro.
Chem., C21 (2), pp. 187-273 (1981-
1982), CGRoffey “Photopolymerization of Surfa
ce Cortings ", A. Wiley Interscience Pub. (198
Functional groups, compounds, etc. cited in the review articles such as 2 years) can be used.

These crosslinkable functional groups may be contained in one copolymer component together with the functional group represented by the general formula (I), or a copolymer containing the functional group of the formula (I) may be contained. It may be contained in a copolymer component separate from the coalescence component.

Specific examples of the monomer corresponding to the copolymer component containing these crosslinkable functional groups include, for example, those functional groups copolymerizable with the polymer component of the general formula (II). Any vinyl compound may be included. Such vinyl compounds are described in, for example, “Polymer Data
It is described in Handbook [Basic Edition] Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) ethyl form, α-
Chloro compound, α-bromo compound, α-fluoro compound, α-tributylsilyl compound, α-cyano compound, β-chloro compound, β-bromo compound, α-chloro-β-methoxy compound, α, β-dichloro compound, etc. ), Methacrylic acid, itaconic acid, half-esters of itaconic acid, half-amides of itaconic acid, crotonic acid, 2-alkenylcarboxylic acids (for example, 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, dicarboxylic acid salts Examples thereof include a half-ester derivative of a vinyl group or an allyl group, an ester derivative of these carboxylic acids or sulfonic acids, and a compound having the crosslinkable functional group in the substituent of the amide derivative. The proportion of the "copolymer component containing a crosslinkable functional group" in the resin of the present invention is preferably 1 to 60% by weight based on the total amount of the binder resin. More preferably, it is 5 to 40% by weight.

If necessary, a reaction accelerator may be added to the resin of the present invention in order to accelerate the crosslinking reaction. For example, acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, phenol,
Chlorophenol, bromophenol, cyanophenol, etc.), peroxides, azobis compounds, crosslinking agents, sensitizers, photopolymerizable monomers and the like.

As the cross-linking agent, a compound usually used as a cross-linking agent can be used. Specifically, Shinzo Yamashita and Tosuke Kaneko, "Handbook for Crosslinking Agents," published by Taiseisha (1
981), "Polymer Data Handbook Basic Edition" edited by The Society of Polymer Science, Japan, and Baifukan (1986), etc. can be used. For example, commonly used organic silanes, polyurethanes, crosslinking agents such as polyisocyanates, curing agents such as epoxy resins and melamine resins can be used. In the case of containing a photocrosslinking-reactive functional group, the compounds cited in the above-mentioned review article on the photosensitive resin can be used. Examples thereof include compounds having an allyl ester group, a cinnamoyl ester group, a dimethylmalenimide group and the like.

The binder resin having a crosslinked structure in the photoconductive layer can be formed by the method of forming a crosslinked structure by the above-mentioned method for producing the resin of the present invention, or by the above-mentioned functional group represented by the general formula (I). By using a resin containing a crosslinkable functional group that causes a curing reaction with heat and / or light as described above,
Crosslinking can also be performed in the process of forming the photoconductive layer or in the process of heating and / or light irradiation before the desensitizing treatment. Usually, it is preferable to carry out crosslinking by thermosetting treatment. This heat-curing treatment can be performed by tightening the drying conditions when the conventional photoreceptor is manufactured. For example, 60 ° C to 12
The treatment may be performed at 0 ° C. for 5 minutes to 120 minutes. When the above reaction accelerator is used in combination, the treatment can be performed under milder conditions.

A conventionally known resin can be used in combination with the binder resin used in the present invention described above. For example, the above-mentioned silicone resin, alkyd resin, vinyl acetate resin, polyester resin, styrene-butadiene resin, acrylic resin and the like can be mentioned. Specifically, Ryuji Kurita and Jiro Ishiwatari, Kogaku, Vol. 17, Vol. 278 Page (19
68), Harumi Miyamoto, Hidehiko Takei, Imaging, 197
3 (No. 8) page 9 and the like include cited publicly known materials. The resin according to the present invention and a known resin can be mixed in any proportion, but the content of the functional group component of the present invention in the total amount of the resin is 1 to 95% by weight, preferably 5 to 90%.
Must be contained by weight percent.

The above-mentioned binder resin of the present invention has the effect of improving the hydrophilicity of the non-image area by developing the hydrophilic group by the desensitizing treatment. Further, in the original plate of the present invention, when the binder resin has a crosslinked structure in at least a part of the polymer, the hydrophilic group-containing resin produced by the desensitizing treatment becomes water-soluble while maintaining hydrophilicity It also has a function of preventing elution from the part, that is, water resistance. Therefore, the effect of further enhancing the hydrophilicity of the non-image area by the hydrophilic group formed in the resin is improved and the durability is improved. Alternatively, even when printing conditions such as an increase in the size of a printing machine or fluctuations in printing pressure become strict, it is possible to print a large number of prints with clear image quality without scumming.

The photoconductive layer of the present invention comprises at least a photoconductive inorganic compound and the above-mentioned binder resin. As the photoconductive inorganic compound used in the present invention, conventionally known compounds can be used, but zinc oxide and titanium oxide are preferable from the viewpoint of pollution and the like, and zinc oxide is more preferable. In the lithographic printing plate precursor of the present invention, the binder resin is used in an amount of 10 to 60 parts by weight, preferably 15 to 40 parts by weight, based on 100 parts by weight of photoconductive zinc oxide. Preferably, in the desensitizing treatment of the light-sensitive material of the present invention, when a desensitizing treatment of a photoconductive compound (described later in detail) is also used, the functional group of the general formula (I) used in the present invention is The content of the functional group represented by formula (I) in the binder resin contained is 1 to 80% by weight, preferably 5 to 70% by weight. On the other hand, in the case of desensitizing only by the action of the binder resin of the present invention, the formula (I)
The functional group content of is 50 to 95% by weight, preferably 60 to 90% by weight. As the photoconductive zinc oxide of the present invention, those conventionally known in the technical field of this kind may be used, and not only so-called zinc oxide but also zinc oxide treated with an acid may be used. Absent.

In the present invention, various dyes can be used together as a spectral sensitizer, if necessary. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (No.
8) Page 12, CJYoung et al .: RCA Review 15 , 46.
9 (1954), Kyohei Kiyota: Transactions of the Institute of Electro-Communications
J63-C (No. 2), p. 97 (1980), Yuji Harasaki, et al .: Industrial Chemistry Magazines 66 , 78 and 188 (1963).
, Tadaaki Tani: Journal of the Photographic Society of Japan 35 , 208 pages (19)
1972) and the like, carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanines. Pigment
(A metal may be contained) and the like.

More specifically, those mainly containing carbonium type dyes, triphenylmethane type dyes, xanthene type dyes and phthalein type dyes are disclosed in Japanese Examined Patent Publication No. 51-4.
52, JP-A-50-90334, 50-11422.
7, JP-A-53-39130, JP-A-53-82353, US Pat. Nos. 3,052,540 and 4,054,450, and JP-A-57-16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes are FM Harmer "The Cyanine Dyes and Relat
The dyes described in "ed Compounds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,110.
591, ibid 3121008, ibid 3125447, ibid 31
No. 28179, No. 3132942, No. 3622317, British Patent No. 12268892, No. 130927.
4, No. 1405898, Japanese Patent Publication No. 48-781.
4, dyes described in JP-A-55-18892 and the like.

Furthermore, the near-infrared light with a long wavelength of 700 nm or more is used.
As polymethine dyes for spectrally sensitizing infrared light, JP-A-47-840, JP-A-47-44180 and JP-B-51-41 are known.
061, JP-A-49-5034, JP-A-49-45122,
57-46245, 56-34141, 57-1
57254, 61-26044, 61-27551
Publications, U.S. Pat. Nos. 3,619,154, 417,595
6 Specifications, "Research Disclosure" 1982
, 216, pp. 117-118, etc. The photoconductor of the present invention is excellent in that the performance thereof does not fluctuate depending on the sensitizing dye even when various sensitizing dyes are used in combination.

Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example, the above review: Imaging 1
973 (No. 8), page 12, etc., electron-accepting compounds (eg halogen, benzoquinone, chloranil,
Acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon et al., "Recent Developments and Practical Uses of Photoconductive Materials and Photoconductors", Chapters 4 to 6: Japan Science Information Publishing Co., Ltd. (1986) The polyarylalkane compound, the hindered phenol compound, the p-phenylenediamine compound, etc. The addition amount of these various additives is not particularly limited, but is usually 0.001 to 2.0 parts by weight with respect to 100 parts by weight of the photoconductor.

The thickness of the photoconductive layer is 1 to 100 μm, especially 10 μm.
˜50 μ is preferred. When a photoconductive layer is used as the charge generation layer of a laminated type photoreceptor having a charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.01 to 1 μm, particularly 0.05 to 0.5 μm. Is preferred.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, for example, a substrate such as metal, paper or plastic sheet is impregnated with a low resistance substance in the same manner as in the past. Those which have been subjected to a conductive treatment by, for example, those to which at least one layer is coated for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and further preventing curling,
Paper having a water-resistant adhesive layer provided on the surface of the support, one having at least one precoat layer provided on the surface layer of the support as necessary, and a substrate conductive plastic having vapor-deposited Al or the like on paper. A laminated product can be used.
Specifically, as an example of a conductive substrate or a conductive material,
Yukio Sakamoto, Electrophotography, 14, (No. 1), p2-11
(1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry," Polymer Publishing (1975), MF Hoover, J. Macromol. Sc
i. Chem. A-4 (6), pp. 1273-1417 (1
970) and the like are used.

A printing plate using the lithographic printing plate precursor of the present invention is prepared by forming a copied image on the electrophotographic plate having the above-mentioned structure by a conventional method and then desensitizing the non-image area. To be done. In the desensitizing treatment used in the present invention, both a desensitizing reaction of zinc oxide (hereinafter referred to as A reaction) and a desensitizing reaction of a binder resin (hereinafter referred to as B reaction) proceed. Desensitizing methods include, for example, a method of performing A reaction treatment and then B reaction treatment, a method of performing B reaction treatment and then A reaction treatment, or a method of simultaneously treating A reaction and B reaction. Either may be used.

As a method for desensitizing a photoconductor such as zinc oxide, any of the conventionally known processing liquids can be used. For example, Japanese Patent Laid-Open Nos. 62-239158 and 62-29, which use a ferrocyan compound as a main agent for desensitization.
2492, 63-99993, 63-9994, Japanese Patent Publication No. 40-7334, 45-33683, JP-A-57.
-107889, Japanese Examined Patent Publication No. 46-21244, and No. 44-9.
045, 47-32681, 55-9315, and JP-A-52-101102. Also,
Japanese Patent Publication Sho 43-using a phytic acid compound as a main agent
28408, 45-24609, and JP-A-51-103.
501, No. 54-10003, No. 53-83805,
53-83806, 53-127002, 54-
44901, 56-2189, 57-2796, 57-20394, 59-207290 and Japanese Patent Publication No. 38-9665, which uses a water-soluble polymer capable of forming a metal chelate as a main agent. 39-22
263, 40-763, 43-28404, 47
29642, JP-A-52-126302 and JP-A-52-1.
34501, 53-49506, 53-5950.
2, Japanese Patent Laid-Open No. 53-104302 and the like, and using a metal complex compound as a main agent, JP-A-53-10.
4301, JP-B-55-15313, and JP-A-54-4192.
4 Japanese Patent Publication No. 39-13702, which uses an inorganic or organic acid compound as a main agent.
40-10308, 46-26124, JP-A-51.
The thing described in each gazette of -118501, 56-11116, etc. are mentioned.

On the other hand, as a method of desensitizing the binder resin of the present invention containing a functional group represented by the general formula (I) (that is, imparting hydrophilicity), hydrophilicity that easily nucleophilically reacts with a carbonyl group is used. It is achieved by treating with a solution having a group-containing compound (aqueous solution or mixed solution of water-soluble organic solvent). Examples of the hydrophilic compound that undergoes a nucleophilic substitution reaction on the functional group represented by the general formula (I) include a nucleophilic constant n [R. G. Pearson, H. Sobel, J. Songstad, such as Pearson].
J. Amer. Chem. Soc., 90 , 319 (1968)] contains a substituent having a value of 5.5 or more, and distilled water 1
In 100 parts by weight, a hydrophilic compound capable of dissolving 1 part by weight or more can be mentioned. Specific compounds include, for example, hydrazine, hydroxylamine, sulfite (ammonium salt,
Sodium salt, potassium salt, zinc salt, etc.), thiosulfate, etc., and at least one polar group selected from a hydroxyl group, a carboxyl group, a sulfo group, a phosphono group, and an amino group in the molecule. Mercapto compounds,
Examples thereof include hydrazide compounds, sulfinic acid compounds, primary amine compounds, secondary amine compounds, and the like.

For example, as a mercapto compound, 2-mercaptoethanol, 2-mercaptoethylamine, N-
Methyl-2-mercaptoethylamine, N- (2-hydroxyethyl) 2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenedicarboxylic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethylphosphonic acid, mercapto Benzenesulfonic acid, 2-mercaptopropionylaminoacetic acid, 2-mercapto-1-aminoacetic acid, 1-mercaptopropionylaminoacetic acid, 1,2-dimercaptopropionylaminoacetic acid, 2,3-dihydroxypropylmercaptan, 2-methyl-2 -Mercapto-1-aminoacetic acid or the like as a sulfinic acid compound, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid Dicarboxybenzenesulfinic acid and the like, 2-hydrazinoethanesulfonic acid, 4-hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenedisulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid and the like as hydrazide compounds As the primary or secondary amine compound, for example, N- (2-hydroxyethyl) amine, N,
N-di (2-hydroxyethyl) amine, N, N-di (2-hydroxyethyl) ethylenediamine, tri (2
-Hydroxyethyl) ethylenediamine, N- (2,3
-Dihydroxypropyl) amine, N, N-di (2,3
-Dihydroxypropyl) amine, 2-aminopropionic acid, aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2-hydroxyethylmorpholine, 2
-Carboxyethyl morpholine, 3-carboxy piperazine etc. can be mentioned.

These nucleophilic compounds are used by being contained in the above-mentioned photoconductor desensitizing treatment liquid (the above-mentioned method), or in the treatment liquid for separately treating the binder resin. And use (or method). The amount of the nucleophilic compound present in these treatment liquids is 0.1 mol / liter to 10 mol / liter, preferably 0.5 mol / liter to 5 mol / liter. The processing condition is temperature 1
The immersion time at 5 ° C to 60 ° C is preferably 10 seconds to 5 minutes.
The treatment liquid may contain other compounds in addition to the nucleophilic compound and the pH adjuster described above. For example, a water-soluble organic solvent may be contained in 1 to 50 parts by weight in 100 parts by weight of water. As such a water-soluble organic solvent,
For example, alcohols (methanol, ethanol, propanol, propanol alcohol, benzyl alcohol,
Phenethyl alcohol, etc., ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers
(Dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.), amides (dimethylformamide, dimethylacetamide, etc.),
Esters (methyl acetate, ethyl acetate, ethyl formate, etc.)
And the like, and these may be used alone or in combination of two or more. Further, the surfactant may be contained in 0.1 to 20 parts by weight in 100 parts by weight of water. Examples of the surfactant include conventionally known anionic, cationic or nonionic surfactants. For example, compounds described in Hiroshi Horiguchi "New Surfactants" Sankyo Publishing Co., Ltd. (1975), Ryohei Oda, Kazuhiro Teramura "Synthesis of Surfactants and Their Applications" Maki Shoten (1980), etc. Can be used. The scope of the present invention is not limited to the specific compounds described above.

[0051]

EXAMPLES Examples of the present invention will be illustrated below, but the contents of the present invention are not limited thereto. Resin synthesis example: Resin [P-1] 63.5 g of benzyl methacrylate, 35 g of monomer (M-1) having the following structure, 1.5 g of acrylic acid and toluene 2
00 g of the mixed solution was heated to a temperature of 75 ° C. under a nitrogen stream. While stirring, azobisisobutyronitrile (hereinafter referred to as AIB
(Abbreviated as N.) 1.0 g was added and reacted for 4 hours, then AI
0.4 g of BN was added and reacted for 3 hours. The weight average molecular weight of the obtained polymer [P-1] was 4.3 × 10 ⁴ . Monomer (M-1)

[Chemical formula 26] Resin [P-1]

[Chemical 27]

Resin Synthesis Example 2: Resin [P-2] 52 g of phenyl methacrylate, 10 g of 2-hydroxyethyl methacrylate, monomer (M-2) 3 having the following structure.
A mixed solution of 0 g, 2.0 g of acrylic acid and 200 g of toluene was heated to a temperature of 70 ° C. under a nitrogen stream. While stirring, add 1.5 g of AIBN and react for 5 hours.
0.5 g of BN was added and reacted for 3 hours. The weight average molecular weight of the obtained polymer [P-2] was 3.5 × 10 ⁴ . Monomer (M-2)

[Chemical 28] Resin [P-2]

[Chemical 29]

Resin Synthesis Example 3: Resin [P-3] 18 g of ethyl methacrylate, a monomer (M-
3) 80 g, divinylbenzene 2.0 g and toluene 2
00 g of the mixed solution was heated to a temperature of 70 ° C. under a nitrogen stream. While stirring, azobisisovaleronitrile (ABV
(Abbreviated as N.) 1.5 g and reacted for 4 hours. Further A.
0.5 g of BVN was added and reacted for 4 hours. The weight average molecular weight of the obtained polymer [P-3] was 1.5 × 10 ⁵ . Monomer (M-3)

[Chemical 30] Resin [P-3]

[Chemical 31]

Resin Synthesis Example 4: Resin [P-4] A mixed solution of 90 g of a monomer (M-4) having the following structure, 10 g of glycicyl methacrylate and 200 g of toluene was heated to 70 ° C. under a nitrogen stream. .. ABVN under stirring
1.5 g was added and reacted for 4 hours. Furthermore, ABVN is 0.5
g and reacted for 3 hours. The weight average molecular weight of the obtained polymer [P-4] was 6.8 × 10 ⁴ . Monomer (M-4)

[Chemical 32] Resin [P-4]

[Chemical 33]

Example 1 Resin [P-1] 30 g (as solid content), [benzyl methacrylate / methyl methacrylate / acrylic acid (79/20/1) weight ratio] Copolymer (weight average molecular weight: 4.3 ×) 10 ⁴ ) Resin [R-1] 10 g, zinc oxide 200 g, rose bengal 0.05 g, uranine 0.02 g, tetrabromophenol blue 0.04
g, 0.15 g of phthalic anhydride and 300 g of toluene were dispersed in a ball mill for 3 hours. Next, 6 g of hexamethylene diisocyanate was added to this dispersion, and the mixture was further dispersed in a ball mill for 10 minutes to prepare a photosensitive layer-forming product, which had a dry adhesion amount of 25 on a conductive-treated paper.
Apply with a wire bar to obtain g / m ² and 100 ℃
At 60 ° C. and 60% RH for 24 hours in the dark to prepare an electrophotographic photosensitive material.

Comparative Example A As the binder resin for the photoconductive layer, the resin [R
-1] was used to prepare an electrophotographic photosensitive material in the same manner as in Example 1 except that 40 g was used.

Comparative Example B In Example 1, instead of 30 g of the resin [P-1],
Other than using 30 g of the comparative resin [R-2] having the following structure,
An electrophotographic photosensitive material was prepared in the same manner as in Example 1. Comparative resin [R-2]

[Chemical 34]

The film properties (smoothness of the surface), electrostatic properties, image pickup properties, desensitizing property (ie, water retention) of the photoconductive layer, and printability of these photosensitive materials were measured immediately after preparation of the photosensitive materials and after a lapse of time. Each was examined later. Summarizing the above results,
It shows in Table-1.

[0059]

[Table 1]

Embodiments of the evaluation items shown in Table 1 are as follows. Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was measured using a Beck's smoothness tester (produced by Kumagai Riko Co., Ltd.) with an air capacity of 1
The smoothness (sec / cc) was measured under the condition of cc.

Note 2) Electrostatic characteristics: temperature 20 ° C., 65% RH
Paper analyzer (Paper Analyzer-SP-428 manufactured by Kawaguchi Electric Co., Ltd.) on each light-sensitive material in the dark room
After using corona discharge for 20 seconds at -6 kV using
After allowing to stand for 2 seconds, the surface potential V ₁₀ at this time was measured. Then, the potential V ₇₀ after standing still for 60 seconds in the dark was measured, and the potential retention after dark decay for 60 seconds, that is, the dark decay retention rate [DRR (%)] was calculated as [(V ₇₀ / V ₁₀ ) × 10
0 (%)]. In addition, after the surface of the photoconductive layer was charged to -400 V by corona discharge, it was irradiated with visible light with an illuminance of 2.0 lux, and the time until the surface potential (V ₁₀ ) decayed to 1/10 was calculated. Quantity E _1/10 (lux ・ se
c) is calculated. However, for each light-sensitive material, the measurement was carried out on the sample (I) after 2 days from the preparation and the sample (II) after 2 months under the condition of [45 ° C., 75% RH].

Note 3) Imaging property: Each light-sensitive material and a fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) were left at room temperature and normal humidity (20 ° C., 65% RH) for one day and night.
A plate image is formed by plate-making, and the image (fog, image quality) of the obtained copy original plate is visually observed. This is performed for the sample (I) and sample (II) described in Note 2) above.

Note 4) Raw plate water retention: desensitizing treatment liquid ELP
-E (Fuji Photo Film Co., Ltd., pH 4.5) was diluted 5 times with distilled water to prepare a treatment liquid. This processing solution was put into an etching processor, and each photosensitive material was passed once. Next, each photosensitive material was immersed in the desensitizing solution (E-1) having the following formulation for 1 minute, and then the photosensitive material was washed with distilled water. Desensitizing treatment liquid: (E-1) 2-mercaptoethanesulfonic acid 60 g Benzyl alcohol 30 g was dissolved in distilled water 1 liter, and the pH was adjusted to 11.0 with potassium hydroxide. Next, distilled water was used as the soaking water, and it was applied to an offset printing machine (manufactured by Hamada Printing Machinery Co., Ltd., model 611XLA-II), and the degree of background stain of the 50th printed material after printing was visually evaluated. (Corresponding to a forced condition for examining the degree of water retention of the desensitized original plate).

Note 5) Printing durability: Using the sample (II) of each light-sensitive material under the same conditions as the image-taking property of Note 3) above, after plate making to form a toner image, ELP-E was distilled. After passing twice through an etching processor containing a treatment solution diluted with water twice, it was immersed in the desensitizing treatment solution (E-1) for 1 minute. This is used as an offset master on an offset printing machine (Oliver 52 type manufactured by Sakurai Seisakusho Co., Ltd.) to show the number of prints that can be made without causing scumming in the non-image area of the printed matter and image quality of the image (the number of printed sheets is large. Indicates that the printing durability is good).

As shown in Table 1, the photosensitive materials of Example 1 of the present invention and Comparative Examples A and B showed good electrostatic characteristics and good image pick-up property in Sample (I) immediately after preparation. But,
When the same evaluation was performed using each sample (II) after storage for 2 months under severe conditions of [45 ° C., 75% RH], Comparative Example B using a known hydrophilicity-expressing binder resin showed that The characteristics were deteriorated, and the image pickup property was such that the non-image area was scummed, the density of the image area was decreased, and characters and fine lines were missing. Further, in the water retention of the original plate, which represents the degree of hydrophilicity of each light-sensitive material immediately after the desensitizing treatment, in the comparative example A using the conventional binder resin, the background stain caused by the ink adhesion occurred. In addition, when printing was performed as a master plate for offset printing using the sample (II) stored for a long time, only the plate of the present invention was good as the master plate for non-image area without the occurrence of background stain. The image quality of the printed matter was good, and scumming did not occur. On the other hand, in Comparative Example A, the background stain was generated on about 3000 sheets, and in Comparative Example B, the background stain was large after the plate making, so that the background stain was not removed even by the desensitizing treatment, and the background stain was generated. The above facts show that only the light-sensitive material of the present invention can form a clear copy image at all times even after long-term storage and can obtain 10,000 or more printed materials without background stain.

Further, the photosensitive material of Example 1 of the present invention was subjected to a desensitizing treatment under the following conditions to examine the printing durability. As the desensitizing treatment, instead of the desensitizing treating liquid (E-1) in the above Note 5), the following treating liquid for comparison (E'-1) is used.
The same procedure as in Note 5) was performed except that was used. Comparative Treatment Liquid (E′-1) 30 g of benzyl alcohol was dissolved in 1 liter of distilled water, and the pH was adjusted to 11.0 with potassium hydroxide. The printing durability when processed under such conditions was 3,500 sheets. Such a decrease in printing durability is caused by the comparative treatment liquid (E'-
It is considered that 1) does not contain a nucleophilic compound, so that the binder resin of the present invention hardly hydrophilizes.

Example 2 Resin [P-4] 36 g (as solid content), [benzyl methacrylate / methyl methacrylate / acrylic acid (79/20/1) weight ratio] Copolymer (weight average molecular weight: 6.8 ×) 10 ⁴ ) Resin [R-3] 4 g, zinc oxide 200 g, rose bengal 0.05 g, uranine 0.02 g, tetrabromophenol blue 0.04
g, 0.15 g of phthalic anhydride and 300 g of toluene were dispersed in a ball mill for 3 hours. Next, 90 mg of phthalic anhydride and 3.9 mg of chlorophenol were added to this dispersion and dispersed in a ball mill for 10 minutes to prepare a photosensitive layer-formed product. This is applied to a conductively treated paper with a wire bar so that the dry adhesion amount becomes 25 g / m ² , dried at 100 ° C for 60 minutes, and then in the dark at 20 ° C and 65% RH for 24 hours. By leaving it to stand, an electrophotographic light-sensitive material was prepared. When this was subjected to plate making, desensitizing treatment and printing in the same manner as in Example 1, 1
The printed matter after printing ten thousand sheets had no fog in the non-image area and the image was clear.

Examples 3 to 9 Similar to Example 1 except that the copolymer [P] shown in Table 2 below was used in place of the resin [P-1] of the present invention. Each electrophotographic light-sensitive material was prepared by the operation. The weight average molecular weight of each copolymer [P] is 4 × 10 ⁴ to
The range was 6 × 10 ⁴ .

[0069]

[Table 2]

[0070]

[Table 3]

Each light-sensitive material was treated in the same manner as in Example 1,
The electrostatic property, the image pickup property, and the printability were examined. All showed the same performance as that of Example 1. Further, the photographic characteristics of these light-sensitive materials were similarly examined after aging for 4 weeks under [45 ° C., 75% RH], but no change from before aging was observed. The results are shown.

Examples 10 to 13 The same operation as in Example 2 except that the copolymer [P] shown in Table 3 was used in place of the resin [P-4] of the present invention. Then, each electrophotographic light-sensitive material was prepared.
The weight average molecular weight of each copolymer [P] is 5 × 10 ⁴ to 8 ×.
It was in the range of 10 ⁴ .

[0073]

[Table 4]

These are fully automatic plate-making machine E as in the first embodiment.
When plate-making with LP404V, the density of the obtained master plate for offset printing was 1.2 or more, and the image quality was clear. Furthermore, when printed with etching treatment, the printed matter after printing 10,000 sheets has no fog in the non-image area,
The image was also clear. Furthermore, this photosensitive material was
After being left under the condition of 75% RH] for 2 months, the same treatment as above was carried out, but there was no change from that before the passage of time.

Example 14 25 g (as solid content) of the resin [P-3] of the present invention obtained in Synthesis Example 3, 15 g of the resin [R-1] used in Example 1,
Zinc oxide 200g, uranine 0.02g, rose bengal 0.04g, tetrabromophenol blue 0.03
g, 0.20 g of maleic anhydride and 300 g of toluene were dispersed in a ball mill for 2 hours. Next, 4 g of allyl methacrylate and 0.4 g of AIBN were added to this dispersion.
Was added and the photosensitive layer formation was prepared by further dispersed for 10 minutes in a ball mill, which was coated with a wire bar to a dry coating weight in the conductive treated paper is 22 g / m ^2, 10
Heated at 5 ° C. for 2 hours. Then in the dark at 20 ℃, 65% R
An electrophotographic photosensitive material was prepared by leaving it under the condition of H for 24 hours. When a plate was prepared using the same apparatus as in Example 1, the density of the obtained master plate was 1.0.
With the above, the image quality was clear.

Further, 55 g of thioglycolic acid and 100 g of benzyl alcohol were dissolved in distilled water so that the total amount was 1.0 liter, and the pH was adjusted to 11.0 with sodium hydroxide (E-2). ), The ELP-E was soaked for 1 minute at a temperature of 25 ° C, and then soaked for 20 seconds in a liquid obtained by diluting ELP-E with distilled water for 20 seconds to perform an etching treatment. The obtained plate had a contact angle with water of 10 ° or less and was sufficiently hydrophilized. When this plate was printed by the same printing machine as in Example 1, the printed matter after printing 10,000 sheets had no fog in the non-image area and the image was clear. Further, this photosensitive material was left under the condition of [45 ° C., 75% RH] for 2 months, and then the same processing as the above was carried out, but there was no change from that before the passage of time.

Examples 15 to 19 In Example 1, instead of the resin [P-1] 30 g and the resin [R-1] 10 g of the present invention, a resin [P-5] 20 was used.
g, and resin [R-1] 20 g was used. Further, a light-sensitive material was prepared in the same manner as in Example 1 except that the compounds shown in Table 4 below were used instead of hexamethylene diisocyanate.

[0078]

[Table 5]

Examples 20 to 29 In Example 2, instead of 36 g of resin [P-4] and 4 g of resin [R-3] of the present invention, resin [P-13] 32 was used.
g, and resin [R-3] 8 g was used. Further, a light-sensitive material was prepared in the same manner as in Example 2 except that the compound shown in Table 5 below was used in place of phthalic anhydride as a cross-linking agent and o-chlorophenol acting as a cross-linking catalyst.

[0080]

[Table 6]

Plate-making these with the same apparatus as in Example 1,
It was then etched and printed on a printing press. The density of the master plate for offset printing obtained after plate making is 1.
At 0 or more, the image quality was clear. The image quality of the printed matter after printing 10,000 sheets was a clear image without fog.

Examples 30 to 41 Using each of the light-sensitive materials prepared in Examples 1 to 13, etching treatment was carried out as follows to prepare offset printing master plates. The nucleophilic compounds of Table 6 below.
5 mol and 100 g of organic solvent and Newcol B4SN
Distilled water was added to 10 g (manufactured by Nippon Emulsifier Co., Ltd.) to make 1 liter, and then the pH of each mixture was adjusted to 10.0. Each light-sensitive material was diluted with ELP-E by a factor of 2 with distilled water.
After soaking for 0 seconds and etching, at 25 ℃ in the above processing solution
Soak for 1 minute. The obtained plate was printed under the same printing conditions as in Example 1.

[0083]

[Table 7]

Example 42 34 g (as solid content) of resin [P-6], [benzyl methacrylate / acrylic acid (95/5) weight ratio] copolymer (weight average molecular weight: 8.5 × 10 ³ ). A mixture of 6 g of resin [R-4], 200 g of zinc oxide, 0.018 g of cyanine dye [I] having the following structure, 0.15 g of phthalic anhydride and 300 g of toluene was dispersed in a ball mill for 3 hours to form a photosensitive layer-forming material. It was prepared and applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 20 g / m ² , dried at 110 ° C. for 30 seconds, and then in the dark at 20 ° C. and 65% RH. An electrophotographic light-sensitive material was prepared by leaving it to stand for 24 hours. Cyanine dye [I]

[Chemical 35]

The surface smoothness and electrostatic characteristics of this photosensitive material
The results of measuring the image pickup property and the printability in the same manner as in Example 1 are as follows. Smoothness of photoconductive layer: 110 (sec / cc) Electrostatic characteristics Note 6): V ₁₀ ; -555 (V) DRR; 80% E _1/10 ; 53 (erg / cm ² ) Imaging ability Note 7): I (20 ° C, 65% RH); Good (○) II (30 ° C, 80% RH); Good (○) Contact angle with water: 10 ° or less Printing durability: 8000 sheets or less Excellent as above It also showed electrostatic characteristics and printability. However, the electrostatic characteristic and the image pickup property were performed by the following operations.

Note 6) Electrostatic characteristics: temperature 20 ° C., 65% RH
Paper analyzer (Kawaguchi
Denki Co., Ltd. paper analyzer-SP-428 type)
, And after corona discharge for 20 seconds at -6 kV, 1
Let it stand for 0 seconds, and then change the surface potential to V_TenWas measured. Next
And the potential V after standing still in the dark for 60 seconds₇₀Measure
Of the electric potential after dark decay for 60 seconds, that is,
Dark decay retention [DRR (%)] [(V ₇₀/ V_Ten) × 1
00 (%)]. In addition, photoconductive due to corona discharge
After charging the layer surface to -400 V, the wavelength of 780 nm
Irradiate with monochromatic light, and surface potential (V_Ten) Decays to 1/10
Until the exposure amount E_1/10 (erg / c
m²) Is calculated.

Note 7) Imaging property: Each light-sensitive material was left for one day under the following environmental conditions. Next, a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) of 2.8 mW output charged with −5 kV was used, and a pitch of 25 μm was applied on the surface of the photosensitive material under an irradiation amount of 64 erg / cm ^2.
m and a scanning speed of 330 m / sec, and then developed and fixed by using ELP-T (manufactured by Fuji Photo Film Co., Ltd.) as a liquid developer to obtain a copied image (fogging, image quality of image). ) Was visually evaluated. Environmental conditions at the time of imaging are 20 ° C, 65% RH, 30 ° C, 80%
Performed at RH.

Example 43 7 g of resin [P-8], 33 g of resin [R-5] shown below, 200 g of zinc oxide, and cyanine dye [II] 0.01 having the following structure
8 g, maleic anhydride 0.20 g and toluene 300 g
The mixture was dispersed in a ball mill for 3 hours to prepare a photosensitive layer-forming material.
Apply with a wire bar to achieve g / m ² and 110 ℃
And dried for 30 seconds. Then in the dark at 20 ℃, 65% RH
An electrophotographic light-sensitive material was prepared by leaving it to stand for 24 hours under the above condition. Resin [R-5]

[Chemical 36] Cyanine dye [II]

[Chemical 37] The surface of this photosensitive material was measured for smoothness, electrostatic properties, imaging properties and printability in the same manner as in Example 42, and the following results were obtained. Smoothness of photoconductive layer: 130 (sec / cc) Electrostatic property Note 6): V ₁₀ ; -560 (V) DRR; 80% E _1/10 ; 58 (erg / cm ² ) Imaging property Note 7): I (20 ° C, 65% RH); Good II (30 ° C, 80% RH); Good Contact angle with water: 10 ° or less Printing durability: 9000 sheets or less Excellent electronic characteristics and printability as described above showed that.

[0089]

As described above, the electrophotographic lithographic printing plate precursor of the present invention can exhibit hydrophilicity in a short time during the hydrophilic treatment, and the effect due to the hydrophilicity of the non-image area is improved. Stable even under extremely harsh conditions,
Even after long-term storage, a clear copy image is always formed, and it has excellent electrostatic characteristics, printability, and printing durability.

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Claims (3)

[Claims] 1. An electrophotographic photoreceptor comprising a conductive support and at least one photoconductive layer containing a photoconductive inorganic compound and a binder resin, the binder resin comprising: After an electrophotographic photoreceptor containing at least one resin containing at least one polymer component having a functional group represented by the following general formula (I) is image-exposed to form a toner image, A non-image area of the photoconductive layer is desensitized with a processing liquid containing a hydrophilic compound having a substituent having a nucleophilic constant n of at least 5.5 and used as a printing original plate. A method for producing an electrophotographic lithographic printing plate precursor. General formula (I): [However, in the above formula (I), at least one of -X and -X 'is an electron-withdrawing group, and Ha of -X and -X' is
If the sum of the values of mmet σ _P is 0.45 or more,
It may be the same or different] 2. The electrophotographic lithographic plate according to claim 1, wherein the resin containing at least one polymer component having a functional group represented by the general formula (I) is pre-crosslinked. Method for manufacturing printing original plate. 3. The resin containing at least one kind of the polymer component having a functional group represented by the general formula (I) further contains at least one kind of functional group which causes a curing reaction by heat and / or light. It is a resin, The manufacturing method of the electrophotographic lithographic printing plate precursor of Claim 1 or Claim 2 characterized by the above-mentioned.