JPH0268561A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve electrostatic characteristics and to obtain a sharp and good-quality image even if the environment at the time of formation of a copied image fluctuates e.g. between low temp., low humidity and high temp., high humidity by incorporating a resin A of specific components, a thermosetting resin B contg. a crosslinkable functional group and a crosslinking agent into the binder resin to be contained in the electrophotographic sensitive body having a photoconductive layer. CONSTITUTION:The photoconductive layer contg. an inorg. photoconductive material and the binder resin is provided to the electrophotographic sensitive body. At least one kind of the resin A and at least one kind of the thermosetting resin B having the crosslinkable functional group and the crosslinking agent are incorporated into this binder resin. The resin A has 1X10<3> to 2X10<4> weight average mol. wt. and contains >=30wt.% at least one repeating unit expressed by the formula I or the formula II. In the formulas, X1, X2 respectively independently denote a hydrogen atom, 1 to 10C hydrocarbon group, chlorine atom, carbon atom, -COY1 or -COOY2 (Y1 and Y2 are respectively 1 to 10C hydrocarbon group). However, there is no case when both the X1 and X2 denote the hydrogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having excellent electrostatic properties and moisture resistance.

In particular, it relates to a CPC photoreceptor with excellent performance.

(Prior Art) Electrophotographic photoreceptors have various configurations in order to obtain predetermined characteristics or depending on the type of electrophotographic process to which they are applied.

As representative electrophotographic photoreceptors, there are photoreceptors having a photoconductive layer formed on a support and photoreceptors having an insulating layer on the surface, which are widely used.

Photoreceptors, consisting of a support and at least one photoconductive layer, are used for imaging by most common electrophotographic processes, ie, charging, imagewise exposure and development, and optionally transfer.

Furthermore, a method of using an electrophotographic photoreceptor as an offset original plate for direct plate making is widely used. Particularly in recent years, direct electrophotographic lithography has become important as a method for printing high-quality printed matter with a print count of several hundred to several dozen sheets.

The binder used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film-forming properties and the ability to disperse photoconductive powder into the binder, and also has excellent properties in the formation of the formed recording layer. It has good adhesion to the substrate, and the photoconductive layer of the recording layer has excellent charging ability, low dark decay, large light decay, and little pre-exposure fatigue. It is necessary to have various electrostatic properties such as stable properties and excellent imaging performance.

Examples of resins that have been known for a long time include silicone resin (Japanese Patent Publication No. 34-6670), styrene-butadiene resin (
(Japanese Patent Publication No. 35-1960), alkyd resin, maleic acid resin, polyamide (Japanese Patent Publication No. 11219-197), vinyl acetate resin (Japanese Patent Publication No. 2425-1977), vinyl acetate copolymer (Japanese Patent Publication No. 2426-197) ,acrylic resin(
(Japanese Patent Publication No. 35-11216), acrylic acid ester copolymers (e.g., Japanese Patent Publication No. 11219/1971, Japanese Patent Publication No. 36/1982)
No. 8510, Japanese Patent Publication No. 41-13946, etc.) are known.

However, electrophotographic photosensitive materials using these resins have problems such as (1) insufficient affinity with the photoconductive powder, resulting in poor dispersibility of the coating solution, and (2) poor charging properties of the photoconductive layer. low, 3
) The quality of the image area of the copied image (especially halftone reproducibility and resolution) is poor; 4) The environment at which the copied image was created (e.g. high temperature,
The problem was that the image quality was easily affected by low temperatures (low temperature, low humidity, etc.).

Various methods have been proposed to improve the electrostatic properties of the photoconductive layer, and one such method is to use a compound containing a carboxyl group or a nitro group in an aromatic ring or a furan ring, or a dicarboxylic acid anhydride. A method of further combining materials and making them coexist in the photoconductive layer is disclosed in Japanese Patent Publications No. 42-6878 and No. 45-3073. but,
Even with photosensitive materials improved by these methods, their electrostatic properties are still insufficient, and none particularly excellent in light attenuation properties has been obtained. Therefore, in order to improve the lack of sensitivity of this photosensitive material, a method of adding a large amount of aggravating dye to the photoconductive layer has been conventionally used, but the photosensitive materials produced by this method have a significant deterioration in whiteness. However, there is a problem in that the quality of the recording medium deteriorates, and in some cases, the dark decay of the photosensitive material deteriorates, making it impossible to obtain a sufficient copy image.

On the other hand, Japanese Patent Laid-Open No. 10254/1983 discloses a method of adjusting the average molecular weight of a resin as a binder resin for use in a photoconductive layer. That is, an acrylic resin with an acid value of 4 to 50 and an average molecular weight distribution of 103 to 104;
A technique is described for improving electrostatic properties (particularly repeatability as a PPC photoreceptor), moisture resistance, etc. by using together components having a distribution of 4 to 2 x 104.

Furthermore, research is being carried out on lithographic printing original plates using electrophotographic photoreceptors, and a binder resin for the photoconductive layer that has both the electrostatic properties of an electrophotographic photoreceptor and the printing properties of a printing original plate has been developed. For example, in Japanese Patent Publication No. 50-31011, a (meth)acrylate monomer and other monomers are copolymerized in the presence of fumaric acid.
A combination of a resin with a TglO~80°C at O' and a copolymer consisting of a (meth)acrylate monomer and a monomer other than fumaric acid, and JP-A-53-5402
No. 7 uses 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, and JP-A No. 54-20735, In JP-A-57-202544, a quaternary or quintuple copolymer containing acrylic acid and hydroxyethyl (meth)acrylate is used, and in JP-A-58-68046, an alkyl group having 6 to 12 carbon atoms is used. It is described that a terpolymer containing a (meth)acrylic ester and a carboxylic acid-containing vinyl monomer as a substituent is effective in improving the repellency of the photoconductive layer.

(Problems to be Solved by the Invention) However, even if the resin is said to be effective in the above-mentioned electrostatic properties and moisture resistance properties, when actually evaluated, it shows that it is particularly effective in charging properties, dark charge retention properties, and photosensitivity. There were problems with electrostatic properties such as , smoothness of the photoconductive layer, etc., and it was not practically satisfactory.

Furthermore, when actually evaluating the binder resin which is said to have been developed as an original plate for electrophotographic planographic printing, there were problems with the electrostatic properties, background smearing of printed matter, moisture resistance, etc.

The present invention is intended to improve the problems of conventional electrophotographic photoreceptors as described above.

An object of the present invention is to provide a high-quality electrophotographic photoreceptor that has improved electrostatic properties (particularly dark charge retention and photosensitivity) and reproduces copied images that are faithful to original images.

Another object of the present invention is to provide an electrophotographic photoreceptor that produces clear, high-quality images even when the environment during copy image formation fluctuates, such as low temperature and low humidity, or high temperature and high humidity.

Another object of the present invention is to provide a CPC electrophotographic photoreceptor with excellent electrostatic properties and low environmental dependence.

Another object of the present invention is to provide a lithographic printing plate which can be used as an electrophotographic lithographic printing original plate and which can produce printed matter that does not cause any scumming.

Another object of the present invention is to provide an electrophotographic photoreceptor that is less susceptible to the effects of the types of sensitizing dyes that can be used in combination.

(Means for Solving the Problem) The above problem is an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material and a binder resin, wherein the binder resin is at least one of the following resins [A]. It has been found that the problem can be solved by an electrophotographic photoreceptor comprising a thermosetting resin [B] containing a crosslinkable functional group, and at least one of a crosslinking agent. Ta.

Resin [A] A resin having a weight average molecular weight of IXIO' to 2×10 4 and containing the following repeating units (i) and (ii) as copolymerization components.

(i) At least one represented by formula (I) or formula (II)
W and W2 each represent a direct bond or a linking group having 1 to 4 linking atoms that connects -000- to a benzene ring. ) (+i) POzHz group, -3O3H group, -COOH
Formula (II) C++3 (where xl and X2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -coy, or -cooy, (y).

and Y2 each represent a hydrocarbon group having 1 to 10 carbon atoms. However, both X and X2 do not represent hydrogen atoms.

At least one of an acidic group such as a base group or an OR' group (R' represents a hydrocarbon group having 1 to 10 carbon atoms), a -3H group, a phenolic OH group, and a cyclic acid anhydride-containing group.
at least one repeating unit containing 0 substituents
．． 1 to 20% by weight, that is, the binder resin used in the present invention is
A methacrylate copolymer component having a specific substituent and an acidic group and/or a cyclic acid anhydride-containing group (hereinafter, the term "acidic group" includes a cyclic acid anhydride-containing group unless otherwise specified). It is composed of at least a low molecular weight resin [A] containing a copolymer component, and a thermosetting resin [B] and/or a crosslinking agent that forms a crosslinked structure between the polymers.

The conventionally known acidic group-containing binder resins as described above are mainly used for offset masters, and have a large molecular weight (for example, 5×10 4 or more) in order to improve rigidity resistance by maintaining membrane strength.

On the other hand, the acidic group-containing resin [A] containing a methacrylate copolymer component having a specific substituent used in the present invention has a stoichiometry in which the acidic group contained in the resin has inorganic photoconductivity. Because it adsorbs to the defects of the photoconductor and has a low molecular weight, it improves the coverage of the surface of the photoconductor, compensating for the trap of the photoconductor and dramatically improving the humidity characteristics. It was found that the particles were sufficiently dispersed and aggregation was suppressed.

Furthermore, the surface of the photoconductor becomes smooth.

When a photoreceptor with a rough surface of the photoconductive layer is used as an electrophotographic lithographic printing original plate, the dispersion state of the photoconductor particles and the binder resin may not be appropriate, and the photoconductive layer may be damaged in the presence of aggregates. As a result, even if desensitization treatment is performed using a desensitization treatment liquid, the non-image area cannot be made uniformly and sufficiently hydrophilic.
This causes adhesion of printing ink during printing, resulting in background smudges in non-image areas of printed matter.

Even when only the low molecular weight resin [A] in the present invention is used as the binder resin, the photoconductor and the binder resin can sufficiently adsorb and coat the particle surface, which improves the smoothness of the photoconductive layer. It has good electrostatic properties, provides image quality without background staining, and has sufficient film strength to be used as a CPC photoreceptor or as an offset original plate for printing several tens of sheets. However, by coexisting a thermosetting resin CB) or a crosslinking agent as in the present invention, a crosslinking structure is created (preferably between resin [A] and resin C83 when resin CB is used). was formed, and the mechanical strength of the photoconductive layer, which is still insufficient with resin [A] alone, could be further improved without detracting from the function of the resin (Al). Therefore, the photoreceptor of the present invention It has excellent electrostatic properties even when environmental conditions change, and has sufficient film strength, making it possible to print more than 10,000 sheets as an offset master plate.

A catalyst may be added to promote the above-mentioned crosslinking reaction, or both the thermosetting resin [B] and the crosslinking agent may be used together with the resin [A].

In resin [A], the weight average molecular weight is 1 x 103 to 2
×104, preferably 3X103 to 1×104, formula (I
) or the copolymer component corresponding to the repeating unit (i) of formula (n) is 30% or more, preferably 50 to 9
7% by weight, the proportion of copolymerized components containing acidic groups is 0.
．． It is 5 to 15% by weight, preferably 1 to 10% by weight.

Further, the glass transition point of the resin [A] is preferably -10°.
C to 100°C, more preferably -5°C to 80°C.

When the molecular weight of the resin [A] is less than 1×10 3 , the film-forming ability decreases and sufficient film strength cannot be maintained. On the other hand, if the molecular weight is greater than 2×10 4 , electrophotographic properties (especially initial potential and dark decay retention) deteriorate, which is not preferable.

Particularly in the case of such a high molecular weight material, if the content of acidic groups exceeds 3%, the electrophotographic properties deteriorate significantly, and when used as an offset master, background smudge becomes noticeable.

If the acidic group content in the resin (Al) is less than 0.1% by weight, the initial potential is low and sufficient image density cannot be obtained. On the other hand, if the acidic group content is more than 20% by weight, the dispersion The film smoothness and high-temperature electrophotographic properties are reduced, and when used as an offset master, background smearing increases.

The resin [A] of the present invention contains a repeating unit (i) represented by formula (I) or formula (II) and a repeating unit (ii) containing an acidic group as copolymerization components. Two or more types of each repeating unit (i) and (ii) may be contained in the resin [A].

In formula (I), preferable examples of XI and X2 include a hydrogen atom, a chlorine atom, and a bromine atom, respectively, and preferable hydrocarbon groups include an alkyl group having 1 to 4 carbon atoms (for example, a methyl group and an ethyl group).

propyl group, butyl group), aralkyl group having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorohensyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group) , chloro-methylbenzyl group, etc.) and aryl groups (e.g., phenyl group, tolyl group, silyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group, etc.), and -COY, and -C00Y2
(As preferred Y and Y2, those described as the above-mentioned preferred hydrocarbon groups can be mentioned). However, both X and X2 do not represent hydrogen atoms.

In formula (I), W is a direct bond connecting -COO- and a benzene ring or 1+cH (n represents an integer from 1 to 3), CHz
CHz ○C0 -(-CH,O)-(m represents an integer of 1 or 2),
Represents a linking group having 1 to 4 linking atoms, such as CHzCHzO-1.

W2 in formula (II) represents the same content as WI.

Formula (I) or (II) used in resin [A] of the present invention
Specific examples of the repeating unit (i) represented by are listed below. However, the scope of the present invention is not limited thereto.

CH3 i-2) H3 ! i-5) i-11) CH.

CH3 CH.

C1(+ CH.

CH3 i-6) i-8) i-12) i-14) CH3 cr-r.

CH3 r CH3 CH3 CH.

CH.

CH3 CH3 i-21) CH3 CH.

CH.

CH3 CH.

CH.

■ CH3 i-25) CH3 i-26) H3 CH.

! 2 days) CH3 CB(3 i-33) CH:1 CH3 i-35) CH.

CH3 →CHz C--1-÷- H3 →CH2-C-1→- CH3 CH.

CH.

CH.

0CH3 i-40) CH:l In addition, in the "acidic group-containing repeating unit (ii)" in the resin [A] of the present invention, the preferred acidic group is -
P Ox H2 group, SO3H group, -OH group, -P-
Examples include an OH group and a cyclic acid anhydride-containing group such as OR'.

R'(R' represents a hydrocarbon group), and R and R' are preferably aliphatic groups having 1 to 22 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group). group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 3
-ethoxypropyl group, 71J group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylfurohyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group), or Aryl groups that may be substituted (e.g., phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyano phenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

In addition, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride include aliphatic dicarboxylic acid anhydride and aromatic dicarboxylic acid anhydride. It will be done.

Examples of aliphatic dicarboxylic anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclobencune-1,2-dicarboxylic anhydride ring, and cyclohexane-1,2-dicarboxylic anhydride ring. cyclohexene-1,2-dicarboxylic acid anhydride ring, 2,3-bicyclo[2,2゜2]octanedicarboxylic acid anhydride ring, etc. These rings include, for example, chlorine atom, bromine atom, etc. may be substituted with a halogen atom, an alkyl group such as a methyl group, an ethyl group, a butyl group, or a hexyl group.

Examples of aromatic dicarboxylic anhydrides include phthalic anhydride rings, naphthalene-dicarboxylic anhydride rings, pyridine-dicarboxylic anhydride rings, and thiophene-dicarboxylic anhydride rings. , for example, halogen atoms such as chlorine atom and bromine atom, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hydroxyl group,
Cyano group, nitro group, alkoxycarbonyl group (as an alkoxy group, for example, methoxy group, ethoxy group, etc.)
etc. may be replaced.

The copolymer component corresponding to the "acidic group-containing repeating unit (ii)" of the present invention is, for example, -form (I) or (n
) Any vinyl-based compound containing an acidic group that can be copolymerized with the methacrylate monomer corresponding to the repeating unit represented by the above formula may be used. ” Baifukan (I98
6 years) etc. Specifically, acrylic acid,
α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-amino)methyl 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-
dichloroform, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid,
2-alkenylcarboxylic acids (e.g. 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, vinyl Benzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid,
Examples include half-ester derivatives of vinyl or allyl groups of dicarboxylic acids, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the acidic group in the substituent of amide derivatives.

“The acidic group-containing repeating unit (ii) J will be exemplified.

ii-1) b.

One child CH, -C-+ 0OH bl: H, CH3 (bl' below) ii -2
) CH3 (CH-CH--) 0OH ii -3) b.

1÷CH, -C-+ Coo(CH2)llCOOH n: integer from 2 to 11 ii-4) b.

1,000 CH, -C-)- CONH(CH2), 1COOH n: integer from 1 to 11 b, b2 -(-CH-C+ Co0(CH2)ZOCO(CH2)I, C00Hn:
Integer b from 1 to 3, b2 → CH-C-+ Coo(CHz)zOcOcH=CHC0OHtz
bz - 1,000 CH-C→ COO (CHz), SOz H n: integer from 2 to 4/OOH H3 -(-CH, -CH-+ Co0H ii -12) ii -18) b.

0OH -+cH2-C+ CH,C00R R: C, ~4 alkyl group 1i-14) Coo(CH2)20-P CH CH CH 1+CH CH-) OOH 0OH ii-21) z ii-22) +1 1÷CH, -CH-t O3H 1i-24) ii-28) −(CH, −−CH−+− CH2COOH ! ! b.

ii-29) 1i-26) One ÷ CH C+ C0NH(CH,)zsOffH ii-27) 1i-30) -(-CH-CH+ 07°＼. 10\.

m: integer from 2 to 10 1i-31) b.

-H group, -NH, group, -NHR, group (R1 has 1 to 8 carbon atoms
Dissociative groups such as alkyl groups (e.g. methyl, ethyl, propyl, butyl, hexyl, etc.) or aryl groups (e.g. phenyl, tolyl, methoxyphenyl, butylphenyl, etc.) 1i-32) b, bz -÷CH-C-+ m: an integer of 2 to 10 R: an alkyl group of C, to 6, a benzyl group having at least one type of hydrogen atom;

Further, the resin [A] of the present invention preferably contains, in addition to the acidic group, a functional group that enhances the crosslinking effect between the resin [A] and the crosslinking agent and/or resin CB). Examples include -OH group, -S phenyl group (R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group)), and the like.

The copolymer component containing these functional groups is
Similarly to the copolymer component containing an acidic group, any vinyl-based compound containing a functional group that can be copolymerized with, for example, type (I) or (II) may be used.

Specifically, compounds containing the functional group in the substituent of each of the above-mentioned derivatives may be mentioned. The proportion of copolymer components containing these functional groups is 1 to 20% in resin [A].
% by weight, preferably 3 to 10% by weight.

Furthermore, the resin [A] of the present invention contains a monomer corresponding to the repeating unit of general formula (r) or (II) described above, a monomer containing the acidic group, and an optional functional group that enhances the crosslinking effect. Along with the monomer containing , other monomers other than these may be contained as copolymerization components.

For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylic esters, methacrylic esters, acrylamides, methacrylamides, styrenes, heterocyclic vinyls (e.g. Vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidacillin, vinylpyrazole, vinyl-dioxane, vinylkyrin, vinylthiazole,
vinyl-oxazine, etc.).

The binder resin of the present invention may contain two or more types of resins CA) as described above.

The resin [B] is a thermosetting resin containing a crosslinkable functional group, that is, a functional group that generates a crosslinking reaction by heat and forms a bridge between polymers, and is preferably It reacts with the functional group that can be used to form a crosslinked structure.

That is, it utilizes a reaction mode in which bonding between molecules by condensation reaction, addition reaction, etc., or crosslinking by polymerization reaction, etc. is caused by heat.

Specifically, a functional group having a dissociable hydrogen atom (for example -
CH group, -3H group, NHR:l group (R3 is a hydrogen atom, an optionally substituted aliphatic group having 1 to 12 carbon atoms, or an optionally substituted aryl group) or -CON ) (CHz ORa (Ra is a hydrogen atom or a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group having 1 to 6 carbon atoms) (representing an alkyl group) or a polymerizable double bond group.

The functional group having a dissociable hydrogen atom is preferably -O
Examples include H group, -SH group, and -NHR3 group.

Specifically, the polymerizable double bond group is CH2=CH
-2CHz-CHCHz-OCHff CH2=CH-C-0-1CH, =C-C-0-CH,
0 CH-CH-C-0-1CH2=CH-CONH-CH
3CH.

CH2=C-C0NH-1CH,=CH-C0NH-C
H2=CHCHHz OC-1CH2=CH-NHCO
-2CHz=CHCHz NHC0CH2=CH-3
o□-1CHz=CH5o-1CH,=CH-0-1C
H, =CH-3-, etc. can be mentioned.

Examples of the resin CB) of the present invention include polymers or copolymers containing the above functional groups.

Specifically, Tsuyoshi Endo [Refinement of thermosetting polymers (C0M
, C■, 1986), Yuji Harasaki, "Latest Binder Technology Handbook" Chapter ■-1 (General Technology Center, 1985)
), Otsu Attendance [Synthesis, design and development of new applications of acrylic resin] (Published by Chubu Business Development Center Publishing Department, 1985)
, Eizo Omori, "Functional Acrylic Resins" (Technosystem, 1985), etc., conventionally known resins are used. For example, polyester resin, unmodified epoxy resin, polycarbonate resin, vinyl alkanoate resin, modified polyamide resin, phenolic resin,
Modified alkyd resins, melamine resins, acrylic resins, styrene resins, etc. may be mentioned, as long as these resins contain the functional groups that form the crosslinking reaction described above. Preferably, these resins that do not contain the acidic group represented by resin [A] or have been modified can be used as the resin of the present invention.

Specific examples of monomers corresponding to military components containing these functional groups include, for example, vinyl compounds containing these functional groups.

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-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, 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, In the substituents of vinyl sulfonic acid, vinylphosphonic acid, half-ester derivatives of vinyl or allyl groups of dicarboxylic acids, and the ester derivatives and amide derivatives of these carboxylic acids or sulfonic acids, or in the substituents of styrene derivatives, the above-mentioned Examples include vinyl compounds containing functional groups.

More specifically, a (meth)acrylic copolymer containing a total of 30% by weight or more of a monomer represented by the following format (III) as a copolymerization component is cited as an example of resin CB). Can be done.

-Form (I[[)%Formula% In the general formula (III), ■ represents a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom), a cyano group, or an alkyl group having 1 to 4 carbon atoms.

R3 is an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group,
dodecyl group, tridecyl group, tetradecyl group, 2-methoxyethyl group, 2-ethoxyethyl group, etc.), carbon number 2~
18 optionally substituted alkenyl groups (e.g. vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), carbon number 7
~12 optionally substituted aralkyl groups (e.g. benzyl group, phenethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), optionally substituted cycloalkyl groups having 5 to 8 carbon atoms (e.g. cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.)
, aryl group (eg, phenyl group, tolyl group, xyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, chlorophenyl group, dichlorophenyl group, etc.).

In resin CB), the "copolymer component containing a crosslinkable (crosslinkable) functional group" is 0.5 to 4 in resin [B].
0 mol% is preferred.

The weight average molecular weight of the resin [B] is preferably 1 x 103~
lXl0', more preferably 5 x 103 to 5 x 1
It is 04.

The ratio of resin [A] and resin [B] used in the present invention varies depending on the type, particle size, and surface condition of the inorganic photoconductive material used, but in general, the ratio of resin [A] and resin (Bl) used is The ratio is 5 to 80 to 95 to 20 (weight ratio), preferably 10 to 50 to 90 to 50 (weight ratio).

On the other hand, as the crosslinking agent used in the present invention, compounds commonly used as crosslinking agents can be used. Specifically, compounds described in Shinzo Yamashita, Tosuke Kaneko, "Crosslinking Agent Handbook" published by Taiseisha (1981), Polymer Data, "Polymer Data Handbook Basic Edition" Baifukan (1986), etc. are used. be able to.

For example, silane coupling agents such as organic silane compounds (e.g., vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropinitriethoxysilane, γ-aminopropyltriethoxysilane) etc.), polyisocyanate compounds (e.g. toluylene diisocyanate, 〇-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, isocyanate, high-molecular polyisocyanate, etc.), polyol-based compounds (e.g., 1.4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1°1-trimethylolpropane, etc.), polyamine-based compounds (e.g., , ethylenediamine, T-hydroxypropylated ethylenediamine, phenylenediamine,
hexamethylene diamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds and epoxy resins (for example, "New Epoxy Resin" edited by Hiroshi Kakiuchi, published by Shokodo (1985), "Epoxy Compounds described in "Resin" Nikkan Kogyo Shimbun (published in 1969), etc.), melamine resin (for example, "Uria Melamine Resin" edited by Kazube Miwa and Hideo Matsunaga) Nikkan Kogyo Shimbun (1969), etc.
(1969), poly(meth)acrylate compounds (for example, "Oligomer" edited by Makoto Okawara, Takeo Saegusa, and Toshinobu Higashimura, Kodansha (1976),
Eizo Omori “Functional Acrylic Resin” Technosystem (I)
985), and specifically, polyethylene glycol diacrylate, neopentyl glycol cyacrylate, 1. 6-hesanodiol acrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate, oligoester acrylate: methacrylates of these are included. ) etc.

The amount of crosslinking agent used in the present invention is preferably 0.5 to 30% by weight, particularly 1 to 10% by weight based on the total amount of binder resin.

In the present invention, a reaction accelerator may be added to the binder resin as necessary in order to promote the crosslinking reaction in the photosensitive layer.

When the crosslinking reaction is a reaction mode in which a chemical bond is formed between functional groups, examples thereof include organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.).

When the crosslinking reaction is a polymerizable reaction mode, a polymerization initiator (peroxide, azobis compound, etc.) may be used, and preferably,
azobis polymerization initiator), polyfunctional polymerizable monomers (e.g. vinyl methacrylate, allyl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinate, divinyl succinate, diallyl succinate) , 2-methylvinyl methacrylate, divinylbenzene, etc.).

Furthermore, in the present invention, resins other than the resin of the present invention can also be used in combination. Examples of these resins include:
Examples include alkind resins, polybutyral resins, polyolefins, ethylene-vinyl acetate copolymers, styrene resins, styrene-butadiene resins, acrylate butadiene resins, vinyl alkanoate resins, and the like.

If the above-mentioned other resin exceeds 30% (weight ratio) of the total binder resin amount using the resin of the present invention, the effects of the present invention (especially improvement in electrostatic properties) will be lost.

The binder resin of the present invention is crosslinked or thermally cured after applying the photosensitive layer forming material. To perform crosslinking or thermosetting,
For example, the drying conditions are made stricter than those used in conventional photoreceptor production. For example, the drying conditions are high temperature and/or long time. Alternatively, after drying the coating solvent, it is preferable to further perform a heat treatment. For example, 5~ at 60″C~120″C
Process for 120 minutes. When used together with the reaction accelerators mentioned above,
Can be processed under milder conditions.

Further, although crosslinking should be carried out at least between the resins of the present invention, it may also be carried out between other resins. It is preferable that the resin of the present invention and a resin having a weight average molecular weight of 2×10 4 or more are crosslinked.

Inorganic photoconductive materials used in the present invention include zinc oxide,
Examples include titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide, and the like.

Preferable examples include zinc oxide and titanium oxide. The total amount of binder resin used for the inorganic photoconductive material is 10 to 100 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the photoconductor.

In the present invention, various dyes can be used in combination as spectral sensitizers, if necessary. For example, Harumi Miyamoto: Hidehiko Takei; Imaging 1973 (Nα8) p. 12, C0J,
Young et al., RCA Review 15°46
9 (I954L Wataru Kiyota, Journal of the Institute of Electrical and Communication Engineers J6
3-C (No, 2), 97 (I980), Yuji Harasaki et al., Industrial Chemistry Magazine - Glass - 178 and 188 (I963)
, Tadaaki Tani, Journal of the Photographic Society of Japan 35.208 (I972)
Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, phthalein dyes, polymethine dyes (e.g. oxonol, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes), phthalocyanine dyes (metal ), etc.

More specifically, examples using mainly carbonium dyes, triphenylmethane dyes, xanthine dyes, and phthalein dyes include Japanese Patent Publication No. 51-452, Japanese Patent Application Laid-open No. 50-90334, and Japanese Patent Application Laid-open No. 50-90334. No. 50-114227,
JP 53-39130, JP 53-82353, U.S. Patent No. 3052540, U.S. Patent No. 40544
50, JP-A-57-16456, and the like.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as logcyanine dyes include F, M
, Hammer, rThe Cyantne
Dyes and Related Compound
It is possible to use the pigments described in "S" etc., and more specifically, the pigments described in US Pat. No. 3,047,384 and US Pat. No. 3,110
No. 591, U.S. Patent No. 3,121,008, U.S. Patent No. 3
125447, U.S. Patent No. 3128179, U.S. Patent No. 3132942, U.S. Patent No. 3622317,
British Patent No. 1226892, British Patent No. 130927
No. 4, British Patent No. 1405898, Special Publication No. 1978-78
14, Japanese Patent Publication No. 55-18892, and the like.

Furthermore, as a polymethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A-47-840
No., JP-A No. 47-44180, JP-A No. 51-4106
No. 1, JP-A-49-5034, JP-A-49-4512
No. 2, JP-A-57-46245, JP-A-56-351
No. 41, JP-A-57-157254, JP-A-61-2
No. 6044, JP-A No. 61-27551, U.S. Patent No. 3
619154, U.S. Patent No. 4175956, rRe
Examples include those described in Search Disclosure J 1982, 216, pages 117-118.

The photoreceptor of the present invention is also excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together.

Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example, the review mentioned above: Imaging 1973 (N
o, 8) Electron-accepting compounds (e.g. halogens, benzoquinone, cranyl, acid anhydrides, organic carboxylic acids, etc.) cited in the review, p. 12, etc., Hiroshi Komon et al., ``Recent Developments of Photoconductive Materials and Photoreceptors''・Practical Application'' Chapters 4 to 6 2 Japanese Scientific Information (
Examples include polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, etc. cited in the review published by Shuppan Co., Ltd. (1986).

The additives for these various additives are not particularly limited, but are usually 0.0001 to 2.0 parts by weight per 100 parts by weight of the photoconductor.
Parts by weight.

The thickness of the photoconductive layer is preferably 1-100 .mu.m, particularly 10-50 .mu.m.

In addition, when a photoconductive layer is used as a charge generation layer in a laminated photoreceptor consisting of a charge generation layer and a charge transport layer, the thickness of the charge generation layer is preferably 0.01 to 1μ, particularly 0.05 to 0.5μ. suitable.

Charge transport materials for the laminated photoreceptor include polyvinylcarbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes, and the like.

The thickness of the charge transport layer is 5 to 40 μm, particularly 10 to 3 μm.
0μ is suitable.

Typical resins used to form the absolute 8i layer or charge transport layer include polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, and divinyl chloride copolymer resin. Thermoplastic resins and curable resins such as polyacrylic resins, polyolefin resins, urethane resins, polyester resins, epoxy resins, melamine resins, and silicone resins are used as appropriate.

The photoconductive layer according to the invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably electrically conductive.As the electrically conductive support, for example, a low-resistance material is added to the base material such as metal, paper, or plastic sheet. Those that have been subjected to conductive treatment such as impregnating them, those that have been coated with at least one layer to impart conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and further to prevent curling, etc. To those with a water-resistant adhesive layer provided on the surface of the support, and those with at least one precoat layer provided on the surface layer of the support as required! A material made by laminating electrically conductive plastic onto paper or the like can be used.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, Electrophotography, 14, (No. 1), No. 2~
11 pages (I975L Hiroyuki Moriga, "Introductory Special Paper Chemistry" Kobunshi Publishing Association (I975), M, F.

Hoover, J., Macromol, Sci.
Chem, A-4(6) pp. 1327-1417 (
I970) etc. are used.

(Examples) The present invention will be illustrated below by examples, but the content of the present invention is not limited to these.

Example 1 and Comparative Examples A-C 2,6-cyclophenyl methacrylate 85 g, 6-
After heating a mixed solution of log hydroxyhexamethylene methacrylate, 5 g of acrylic acid, and 200 g of toluene to a temperature of 90°C under a nitrogen stream, 2. 6 g of 2'-azobis(isobutyronitrile) was added and reacted for 8 hours.

The weight average molecular weight (hereinafter n) of the obtained copolymer (A-1)
(abbreviated as w) was 7,800.

Resin (A-1) - Dispersed in Lumil for 10 minutes.

This was applied to electrically conductive treated paper using a wire bar so that the dry adhesion amount was 22 g/bore, heated at 100°C for 15 seconds, and then heated at 120°C for 2 hours. Next, an electrophotographic light-sensitive material was prepared by leaving it in a dark place at 20° C. and 265% RH for 24 hours.

(Cyanine dye) ShiL 40 g of the above copolymer (A-1) (as solid content),
A mixture of 200 g of zinc oxide, 0.02 g of heptamethine cyanine dye represented by the following structural formula, 0.05 g of phthalic anhydride, and 300 g of toluene was dispersed in a ball mill for 2 hours, and then 2 g of 1,3-xylylene diisocyanate was dispersed. In addition, Comparative Example A In Example 1, 40 g of copolymer (A-1) (as solid content), 200 g of zinc oxide, and 0.0 cyanine dye.
2g, phthalic anhydride 0.05g and toluene 300g
The mixture was dispersed in a ball mill for 2 hours.

This was applied to electrically conductive treated paper using a wire bar so that the dry adhesion amount was 22 g/po, and heated at 100°C for 15 seconds.

Next, an electrophotographic light-sensitive material was prepared by leaving it in a dark place under conditions of 20"C and 65% RH for 24 hours.

Comparative Example B Copolymer (A-1) except that in the synthesis example of copolymer (A-1), 85 g of ethyl methacrylate-t was used instead of 85 g of 2.6 dichlorophenyl methacrylate.
A copolymer (R-1) was produced in the same manner as in Example.

The obtained copolymer (R-1) had an iw of 7,500.

In Comparative Example A, an electrophotographic light-sensitive material was produced in the same manner as in Comparative Example A, except that 40 g of copolymer CR-1) was used instead of copolymer (A-1).

Comparative Example C In Comparative Example A, an electrophotographic light-sensitive material was prepared in the same manner as in Comparative Example A, except that a copolymer (R-2340g) having the following structure was used instead of copolymer (A-1). was created.

Copolymer (R-2) H3 1+CH, -C--→Go'-ElectricHCH,-CH-Te'-
COOC2H, COCo oH: 34,000 The film properties (surface smoothness), electrostatic properties, imaging properties, and imaging properties of these photosensitive materials were examined at 30°C, 980% R)-I. . Furthermore, when these photosensitive materials are used as original plates for offset masters, the photoconductive desensitization property (represented by the contact angle with water of the photoconductive layer after desensitization treatment) and printability (background smudge, The printing durability, etc.) were investigated.

The above results are summarized in Table-1.

Back-1 The implementation aspects of the evaluation items shown in Table-1 are as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was tested using a Beck smoothness tester (Kumagai Riko ■
The smoothness (
sec/cc) was measured.

Note 2) Mechanical strength of photoconductive layer: The surface of the photosensitive material obtained was measured using emery paper (#1000) at a load of 50 g/C using Hayton-14 type surface property test material (Shinraikagaku ■!!). ) was repeated 1000 times to remove abrasion powder, and the residual film rate (%) was determined from the weight loss of the photosensitive layer, which was taken as the mechanical strength.

Note 3) Electrostatic properties: In a dark room at a temperature of 20°C and 165% 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 ■). After that, leave it for 10 seconds, and the surface potential at this time is
,. was measured. Then, the potential after leaving it for 90 seconds in the dark was 1°.

The retention of the potential after dark decay for 90 seconds, that is, the dark decay retention rate (D, R, R (%)), is measured as (V+.

/V+. )X100(%). Further, after the surface of the photoconductive layer is charged to -400 μm by corona discharge, the surface of the photoconductive layer is irradiated with light from a gallium-aluminum-arsenide semiconductor laser (oscillation wavelength: 830 nm) to increase the surface potential (
V+. ) is attenuated to 1/10, and from this the exposure IEI is determined.

Calculate (erg/cTA).

The environmental conditions at the time of measurement were 20°C, 265%RH (I) and 3
The test was carried out at 0°C and 180%RH (n).

Note 4) Imaging properties: After leaving each photosensitive material for one day and night under the following environmental conditions, each photosensitive material was charged at -6 kV, and a gallium-aluminum-arsenide semiconductor laser (oscillation wavelength: 830 mW) with an output of 2.8 mW was used as a light source. 6 nm) on the surface of the photosensitive material.
After exposure under an irradiation dose of 4 erg/c+It at a pitch of 25 μm and a scanning speed of 300 m/sec, the image was developed and fixed using ELP-T (manufactured by Fuji Photo Film ■) as a liquid developer. The copied images (fogging, image quality) were visually evaluated. The environmental conditions during imaging were 20°C, 65% RH (I) and 30°C, 80%.
It was carried out at RH(n).

Note 5] Contact angle with water: After passing each photosensitive material once through an etching processor using a fat-free processing liquid ELP-E (manufactured by Fuji Photo Film ■) to desensitize the photoconductive layer surface, A droplet of 2 μ2 of distilled water is placed on this, and the contact angle with the water formed is measured using a goniometer.

Note 6) Printing durability After making the plate in the same manner as for imaging performance in Note 3) above, it was desensitized under the same conditions as Note 4) above, and this was used as an offset master on an offset printing machine (Oliver manufactured by Sakurai Seisakusho ■). 52 type) and using high-quality paper as the printing paper, it indicates the number of sheets that can be printed without causing background smudges in the non-image areas of the printed matter and problems with the image quality of the image areas (the higher the number of sheets printed, the better the rigidity resistance. ).

As shown in Table 1, in the photosensitive material of the present invention, the smooth film of the photoconductive layer had good strength and electrostatic properties, and the actual copied images had no ground blur and the quality of the copied images was clear. This is presumed to be due to the photoconductor and the binder resin being sufficiently adsorbed and covering the particle surface. For the same reason, even when used as an offset master original, the desensitization treatment with the desensitization treatment liquid progresses sufficiently, the contact angle with water in the non-image area is as small as 20 degrees or less, and it is sufficiently hydrophilic and water-resistant. It can be seen that it has been modified. Even after actually printing 7,000 sheets, no background smudge was observed when observing the printed matter for background smudge.

Comparative Example A using only the resin [A] of the present invention had extremely good electrostatic properties, but when printed using it as an offset master original, the image quality of the printed matter deteriorated after 3000 sheets.

In addition, in Comparative Example B, adhesiveness decreased for 90 seconds, R and R decreased, and E
It has increased by 171 degrees.

Furthermore, in Comparative Example C, in which the weight average molecular weight was increased using a copolymer exhibiting the chemical structure of the resin of Comparative Example B, the electrostatic properties were significantly deteriorated. This is presumed to be due to an increase in the molecular weight of the binder resin, which causes adsorption to the photoconductor particles and aggregation between the particles, resulting in an adverse effect.

As a result of the above, an electrophotographic window light material that satisfies electrostatic properties and printability can be obtained only when the resin of the present invention is used.

Examples 2 to 22 As resins, copolymers shown in Table 2 were manufactured under the same manufacturing conditions as in Synthesis Example 1.

The weight average molecular weight of each of the obtained resins (2) to (22) was 7,000 to s, ooo.

Table 2 Table 3 Each photosensitive material was prepared in the same manner as in Example 1, except that 40 g (as solid content) of each resin shown in Table 2 was used instead of copolymer (I) used in Example 1. A body was manufactured and each characteristic was measured in the same manner as in Example 1. The surface smoothness of the photoconductive layer of each photoreceptor was all 80 (Sec/cc) or more.

Furthermore, the membrane strength was 85% or more, indicating sufficient strength. The results regarding electrostatic properties and imaging properties are shown in Table 3.

All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention, and photosensitivity, and the actual copied images are also produced at high temperatures and high humidity (30'C18
Even under the harsh conditions of 0% RH), clear images were produced without any occurrence of ground blur or fine line skipping.

Example 23 8 g of the following resin (A-23), 32 g of resin CB-1),
Zinc oxide 200g Cyanine dye (A) used in Example 1
0.02g, phthalic anhydride 0゜01g and toluene 3
00 g of the mixture was dispersed in a ball mill for 2 hours.

This was applied to electrically conductive treated paper using a wire bar so that the dry adhesion amount was 22 g/bore, heated at 100°C for 15 seconds, and then heated at 120°C for 2 hours.

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

Resin (A-233 Resin CB-1) CH3 C11:1 Mw 41,000 Each characteristic was measured in the same manner as in Example 1.

Smoothness of photoconductive layer: 88 (cc/5ec) Strength of photoconductive layer 2 88% Electrostatic properties C-Vo (V) D, RoR (χ)
E+z+o(erg/cffl)■(20°C965χ
RH) -5708342■(30°C180χR1
()-5508043 Imaging properties: (20°C, 65XR
)I) and (30°C, 980χRH), good copied images were obtained.

Printing durability: Good printed images were obtained up to 6000 sheets.

As described above, the photosensitive material of the present invention was able to obtain excellent electrophotographic properties and high stiffness resistance.

Examples 24 to 31 6.5 g of the following resin (A-24), resin C of the following Table-4
A mixture of 33.5 g of B), 200 g of zinc oxide, 0.018 g of the following cyanine dye [B], 0.02 g of maleic anhydride, and 300 g of toluene was dispersed in a ball mill for 2 hours.

A predetermined amount of the crosslinking agent shown in Table 4 below was added to this, and the mixture was further dispersed in a ball mill for 10 minutes. This was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 22 g/n, heated at 100°C for 15 seconds, and then heated at 120°C for 2 hours.
Heated further for an hour. Next, an electrophotographic light-sensitive material was prepared by leaving it for 24 hours at 20° C. and 165% RH.

Resin (A-24) tUt ratio j The electrostatic properties of these photosensitive materials were measured using a paper analyzer in the same manner as in Example 1. However, a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) was used as the light source.

Each of the photosensitive materials of the present invention has chargeability, dark charge retention,
It has excellent light sensitivity, and the actual copied images can be produced even under high temperature and high humidity (30'C1).
Even under the harsh conditions of 80% RH), clear images were obtained without any occurrence of ground force blur or thin line skipping.

When each photosensitive material is used as an offset master original plate, the desensitization treatment with the desensitization treatment liquid progresses sufficiently, and the contact angle with water in the non-image area of each master original plate is as small as 15 degrees or less, which is sufficient. It had been made hydrophilic. 60 prints with clear images without blurring when actually printed.
I was able to print between 00 and 7000 sheets.

Examples 32 to 36 8 g of the following resin (A-25) and resin CB of the following Table-5
), 200 g of zinc oxide, a mixture of 30.02 g of the cyanine dye (A) used in Example 1, 0.01 g of phthalic anhydride, and 300 g of toluene was dispersed in a ball mill for 2 hours. The amount is 18g/
Apply it with a wire bar so that it becomes rd, and
After heating for seconds, it was heated at 110°C for 2.5 hours. Next, an electrophotographic light-sensitive material was prepared by leaving it in a dark place at 20° C. and 165% RH for 24 hours.

All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention, and photosensitivity, and the actual reproduced images are produced at high temperatures (30°C, 18°C).
Even under the harsh conditions of 0% RH), clear images were produced without any occurrence of ground blur or fine line skipping.

Further, when plate making was carried out in the same manner as in the example process, the density of the obtained master plate for offset printing was 1.0 or more and the image quality was clear. Further, when etching was performed and printed on a printing press, the printed matter after printing 7000 sheets had clear image quality with no fogging.

Examples 37 to 42 7 g of the following resin (A-26), 20 g of resin of group X of resin [B] in Table 6 below, 200 g of zinc oxide, 0.50 g of rose bengal, 0.25 g of tetrabromophenol blue
, uranine 0. A mixture of 30 g of phthalic anhydride, 0.01 g of phthalic anhydride, and 240 g of toluene was dispersed in a ball mill for 2 hours.

Next, resin 13 of group Y of resin [B] in Table 6 below is added to this.
A solution prepared by dissolving 1.0 g of 100 g in 80 g of toluene was added thereto, and the mixture was further dispersed in a ball mill for 10 minutes. This is then placed on conductive treated paper.
It was applied with a wire bar so that the dry coating weight was 18 g/bo, heated at 110"C for 30 seconds, and then further heated at 120°C for 2 hours. Then, it was left at 20°C and 165% RH for 24 hours. An electrophotographic light-sensitive material was prepared by doing this.

Resin (A-26) Mw 7,800 The photosensitive material of the present invention has good chargeability, dark charge retention,
It has excellent light sensitivity, and the actual copied images can be used even under high temperature and high humidity conditions (30°).
Even under the harsh conditions of (C-80% RH), clear images were produced with no soil blurring.

Furthermore, when this was used as an original plate for an offset master for printing, prints with clear image quality were obtained even after 6,000 to 7,000 copies.

However, the plate making of photosensitive materials is done using a fully automatic plate making machine ELP404V.
(manufactured by Fuji Photo Film ■) using ELP-T as a toner to form a toner image.

Claims (1)

[Scope of Claims] An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material and a binder resin, the binder resin comprising:
An electrophotographic photoreceptor comprising at least one of the following resins [A], a thermosetting resin containing a crosslinkable functional group [B], and a crosslinking agent. Resin [A] has a weight average molecular weight of 1 x 10^3 to 2 x 10^4,
and a resin containing the following repeating units (i) and (ii) as copolymerization components. (i) At least one represented by formula (I) or formula (II)
30% or more of repeating units by weight Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X_1 and X_2 each independently represent a hydrogen atom. , a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -COY_1 or -COOY_2 (Y_1 and Y
_2 each represents a hydrocarbon group having 1 to 10 carbon atoms. However, both X_1 and X_2 do not represent hydrogen atoms. W_1 and W_2 each represent a direct bond or a connecting group having 1 to 4 connected atoms that connects -COO- and the benzene ring. ) (ii) -PO_3H_2 group, -SO_3H group, -CO
OH group, ▲ Numerical formula, chemical formula, table, etc. ▼ group {R represents a hydrocarbon group having 1 to 10 carbon atoms or OR' group (R' represents a hydrocarbon group having 1 to 10 carbon atoms)}, 0.1 to 20% by weight of at least one repeating unit containing at least one substituent among the acidic group and cyclic acid anhydride-containing group of -SH group and phenolic OH group