JPH0256558A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve electrostatic characteristics and moisture resistance by incorporating a specific resin into a binder resin. CONSTITUTION:The binder resin contains the resin contg. 1 to 20wt.% copolymer component which has lX10<3> to l.5X10<4> weight average mol. wt. and contains an acidic group selected from a -PO3H2 group, -COOH group, -SO3H group, -OH group, -SH group, etc. and the resin expressed by formula I or formula II. In formulas, X0 denotes -COO-, -OCO-, CH2OCO-, -CH2COO-, -O-, -SO2-, etc.; Q0, Q denote 1 to 18C aliphat. group, or 6 to 12C arom. group; b1, b2 denote a hydrogen atom, halogen atom, cyano group, hydrocarbon group, -COO-Z or -COO-Z (Z denotes a hydrogen atom or hydrocarbon group) via the hydrocarbon. The electrostatic characteristics and moisture resistance are improved in this way.

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. Equipped with various electrostatic properties such as the need to maintain stable properties and poor imaging performance,
There is a need to.

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, in electrophotographic photosensitive materials using these resins, 1) the affinity with the photoconductive powder is insufficient, resulting in poor dispersibility of the coating liquid, and 2) the charging property of the photoconductive layer is poor. 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 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. Japanese Patent Publication No. 42-6878 and Japanese Patent Publication No. 45-3073 disclose a method of further combining materials to coexist in a photoconductive layer. However, even with the photosensitive materials improved by these methods, is it still stable? The S characteristics are not sufficient, and no material with particularly excellent light attenuation characteristics has been obtained. Therefore, in order to improve the lack of sensitivity of this photosensitive material, a conventional method has been used to add a large amount of sensitizing dye to the photoconductive layer. However, the light-sensitive materials produced by this method have a marked deterioration in whiteness, a deterioration in quality as a recording medium, and in some cases, a deterioration in the dark decay of the light-sensitive materials, making it difficult to reproduce images with sufficient quality. The problem was that it became impossible to obtain.

On the other hand, Japanese Patent Laid-Open No. 6010254 discloses a method of adjusting the average molecular weight of a resin used as a binder resin for 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 has been described for improving electrostatic properties (particularly reproducibility of retardation as a PPC photoreceptor), moisture resistance, etc. by using together components having a distribution of 4 to 2.times.10@4.

Furthermore, research into lithographic printing original plates using electrophotographic photoreceptors is being carried out, and a binding agent for the photoconductive layer that has both the electrostatic properties of an electrophotographic photoreceptor and the printing properties of a printing original plate is being actively researched. As a resin, for example, in Japanese Patent Publication No. 31011/1983, M 18 to 10 x 10
A combination of a resin with a T g of 10 to 80°C and a copolymer consisting of a (meth)acrylate monomer and a monomer other than fumaric acid, and JP-A-53-54027
In the No. 1, a ternary copolymer containing a <meth)acrylic acid ester with a substituent having a carboxylic acid group separated by at least 7 atoms from an ester bond is used, and JP-A No. 5
No. 4-20735, JP-A No. 57-202544,
Those using quaternary or penta-component copolymers containing acrylic acid and hydroxyethyl (meth)acrylate, and those using JP-A No. 5
No. 8-68046 discloses that a terpolymer containing a (meth)acrylic acid ester having an alkyl group having 6 to 12 carbon atoms as a substituent and a carboxylic acid-containing vinyl monomer is used as an insensitive resin for a photoconductive layer. It is stated that it is effective in improving the chemical properties.

(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 the electrostatic properties, the smoothness of the photoconductive layer, etc., and the results were not substantially satisfactory.

Furthermore, even in the case of a binder resin which is said to have been developed as an original plate for electrophotographic lithographic printing, when actually evaluated, there were problems with the above-mentioned electrostatic properties, scumming of printed matter, and the like.

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 and 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.

(Means for Solving the Problem) The above problem is achieved by an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material and a binder resin 3.
It has been found that the problem can be solved by an electrophotographic photoreceptor characterized in that the binder resin contains at least one of each of the following resins [A] and resin [B].

(i) Resin [A] has a weight average molecular weight of 1x1o' to 1.5x104,
KaP Os H2 group, -COOI-1 group, -SO3H
0.1 to 20 times more % weight of resin.

(ii) Resin (B) Only one end of the polymer main chain containing at least one of the polymer components represented by the following general formulas (na) and (■b) is expressed by the following general formula (1). A comb-shaped copolymer comprising at least a monofunctional macromonomer having a weight average molecular weight of 2×10 4 or less and a monomer represented by the following general formula (III), in which the shown polymerizable double bond group is bonded. polymer), and only at one end of the main chain of the copolymer,
P O3H2 group, -8O,H group, -COOH group, -O
A resin formed by bonding at least one acidic group selected from H group, -SH group, and °-P-OR group (R represents a hydrocarbon group).

CI-1=C ■− In formula (1), v bar c o o -- o c.

CH2 CO- H2CO0 O2 -CON-1-8O2N- or (R+ represents a hydrogen atom or a hydrocarbon group) alr8
2 may be the same or different, and 2 may be a hydrogen atom, a halogen atom, a cyan group, a hydrocarbon group, coo-z, or 1 coo-z via a hydrocarbon (Z is a hydrogen atom or an optionally substituted hydrocarbon group). ).

sauce Xo Q.

In formula ([Ia) or (IIb), Xo is V in formula (1)
represents the same content as . Q represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. b, ,b
2 may be the same or different, and "I" in formula (1)
Represents the same content as +a2.

Y is a hydrogen atom, a halogen atom, an alkoxy group, or -CO
OZ'(Z' represents an alkyl group, an aralkyl group or an aryl group).

CH=C X+ Q+ In formula (III), Xl is X in formula (Ila). represents the same content as Q in formula (na). el and e2 may be the same or different, and represent the same content as a+ and a2 in formula (1).

The vas deferens resin used in the present invention consists of a low molecular weight resin [A] containing 0.1 to 20% by weight of a copolymer component containing at least one of the above acidic groups, the above macromonomer (M), and a general At least one monomer represented by formula (III)
It is composed of at least a resin [B] which is a comb-shaped copolymer containing seeds and has an acidic group bonded to the end of the polymer main chain.

The amount of the acidic group present in the polymer is 1.0 to 20% by weight in the resin [A], more preferably 1.0 to 20% by weight.
10% heavy weight. Weight average molecular weight G, t of resin [A]
1. Ox 103~1.5x 10'tealka, preferably 3x10~1. Ox 10’t”Al.

The glass transition point of the resin [A] is preferably -20"C to 1
00°C, more preferably -10''C to 85°C.

The resin [B] is preferably a resin composed of a comb-shaped copolymer having an acidic group attached to the terminal end of the main chain and having a weight average molecular weight of 2×10 4 or more.

More preferably, the weight average molecular weight is 5 x 104 to 3 x 10
It is 5.

The glass transition point of resin [B] is preferably 0°C to 120°C
, more preferably from 10°C to 90°C.

In the present invention, the acidic groups contained in the resin [A] are adsorbed to the stoichiometric defects of the inorganic photoconductor, and since it is a low molecular weight substance, the resin [A] has good coating properties on the surface of the photoconductor. This improves photoconductor trapping and improves humidity characteristics, while allowing free dispersion of the photoconductor and suppressing agglomeration. And resin [B] is resin (A'
This resin 1:B) f! provides sufficient mechanical strength to the photoconductive layer, which is insufficient with l alone. :Characterized in that the electrophotographic properties are not deteriorated at all even when used together.

If the acidic group content in the resin [A] is less than 1% by weight, the initial potential will be low and it will not be possible to obtain sufficient image density. On the other hand, if the content of the acidic group is more than 20% by weight, dispersibility decreases, film smoothness and high-temperature electrophotographic properties decrease, and background smear increases when used as an offset master, so it is preferable. do not have.

When a photoreceptor with a rough photoconductive layer surface is used as an electrophotographic lithographic printing original plate, the dispersion state of the zinc oxide particles and the binder resin, which is the photoconductor, is not appropriate, and the photoreceptor is exposed to light in the presence of aggregates. Because a conductive layer is formed, even if desensitization treatment is performed using a desensitization treatment liquid, the hydrophilicity of the a part is not uniformly and sufficiently carried out, causing printing ink to adhere during printing, and as a result, the printed matter deteriorates. This causes background stains in non-image areas.

Furthermore, 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, resulting in a smooth photoconductive layer. Although it is possible to obtain image quality that is good in terms of electrostatic properties and electrostatic properties and is free from background smudges, the film strength is still insufficient and satisfactory results cannot be obtained in terms of durability.

When the resin of the present invention is used, the adsorption/covering interaction between the inorganic photoconductor and the binder resin is properly performed, and the film strength of the photoconductive layer is maintained.

In the -P-OR group H in resins [A] and [B], R more specifically has a carbon number of 1 to 12, for example.
an optionally substituted alkyl group (e.g. methyl group,
Ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, 2-chloroethyl group, 2
-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, methyl benzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, etc.)
or an optionally substituted aryl group (e.g. phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group,
(chlorophenyl group, methoxyphenyl group, etc.).

The resin [A] may be any conventionally known resin as long as it has the physical properties described above, such as polyester resin, modified epoxy resin, silicone resin, olefin copolymer,
Examples include polycarbonate resin, vinyl alkanoate resin, allyl alkanoate resin, modified polyamide resin, phenol resin, fatty acid-modified alkyd resin, and acrylic resin.

More specifically, as an example of the resin of the present invention, a (meth)acrylic copolymer containing a total amount of 30% by weight or more of a monomer shown in the following (IV) as a copolymer component is used as an example of the resin of the present invention. It can be mentioned as follows.

-Clothing cost <IY) CH2H2 CO0-R' -a In formula (IV), d represents a hydrogen atom, a halogen atom, an atom (e.g. a chloro atom, a bromo atom), a cyan group, or an alkyl group having 1 to 4 carbon atoms. represent. R' is carbon number 1
~18 optionally substituted alkyl groups (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-chloroethyl group, 2-
bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-hydroxy 10-byr group, etc.), optionally substituted alkenyl group having 2 to 18 carbon atoms (e.g. vinyl group,
allyl group, impropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), carbon number 7-1z
an optionally substituted aralkyl group (e.g. benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), a substituted aralkyl group having 5 to 8 carbon atoms; optionally substituted cycloalkyl groups (e.g., cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), optionally substituted aryl groups (e.g., phenyl group, tolyl group, xyl group, mesityl group, naphthyl group, methoxyphenyl group, (ethoxyphenyl group, chlorophenyl group, dichlorophenyl group, etc.).

The "acidic group-containing copolymer component" used in the resin [A] of the present invention may be any vinyl compound containing an acidic group that can be copolymerized with -maximum (IV), for example. , for example, polymer data [polymer data/
It is described in "Handbook [Basic Edition]" Baifukan (1986), etc. Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-amine)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-dichloro form, etc.), methacrylic acid, itaconic acid, itacone Acid half esters, itacone amide, crotonic acid, 2-alkenylcarboxylic acids such as 2-pentenoic acid, 2-methyl-
2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.>, maleic acid, maleic acid half esters, maleic acid derivatives, vinylbenzene carboxylate Acids, vinyl benzene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid, half ester derivatives of vinyl or allyl groups of dicarboxylic acids, and ester derivatives and amide derivatives of these carboxylic acids or sulfonic acids. Compounds contained therein can be mentioned.

Furthermore, the resin [A] of the present invention has the general formula (1'/
) and the acidic group-containing monomer, other monomers other than these may be contained as copolymer components.

For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylnitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls (e.g. vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene) , vinylimidacillin, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.).

The resin (B) is a comb-shaped copolymer that satisfies the physical properties described above, contains at least a -functional macromer (M) and a monomer represented by -maximum (II[), and has a polymer main chain. It is characterized by having a specific acidic group bonded only to one end.

The monofunctional macromonomer (M) first has the general formula (1)
A polymerizable double bond group represented by -at least one of the heavy components represented by (Ila) and (llb)
It has a weight average molecular weight of 2×10 4 or less and is formed by bonding only to one end of the polymer main chain containing seeds.

In the general formula (1) showing the macro-natsuma (M), ■
is -coo--oco-1-CH20CO-CH2CO
O1-〇-1-SO, -1-CON- where R1 is not only a hydrogen atom, but also a preferable hydrocarbon group having 1 to 1 carbon atoms.
18 optionally substituted alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (for example, 2-methyl 1-propenyl group, 2-
butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), carbon number 7 to 12 optionally substituted aralkyl groups (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxy benzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, cyclohexyl group, 2
-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), or an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group,
xylyl group, propylphenyl group, butylphenyl group,
octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group,
Decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobushilo ylamidophenyl group, etc.).

It may have a substituent. As a substituent, a halogen atom (
For example, chlorine atom, bromine atom, etc.), alkyl group (for example,
Methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy group (13
``Methoxy group, ethoxy group, propioxy group,
butoxy group, etc.).

a and a2 may be the same or different from each other,
Preferably hydrogen atoms, halogen atoms (e.g. chlorine atoms,
bromine atom, etc.), cyano group, alkyl group having ~4 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group), -coo-z or C00Z via hydrocarbon (Z is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, a fatty acid group, etc.) Represents a cyclic group or an aryl group, which may be substituted, specifically, the above R
1).

Examples of the hydrocarbon in the -coo-z group via a hydrocarbon include a methylene group, an ethylene group, a propylene group, and the like.

More preferably, in -maximum (1), ■ is -COO
-, -0CO-, -CH20CO-CH2COO1-0
-1-CON N-1-802 may be the same or different, hydrogen atom, methyl group, -cooz or -c T-12
c OOZ (Z represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, 10-biru group, butyl group, hexyl group, etc.), even more preferably "l+&2") Either one always represents a hydrogen atom.

That is, the polymerizable double bond group represented by -ffi formula (1) is specifically CH2C00CH3 CH= CH-C-0-, 0=C-O-CH2COO
H C1l□200=C-O-1CH2= CHCON HCI-T□=
C-CONH-1CH=CH-CONHCH2=CH-
〇 -C-, CH2=CH-C1-t20
COOI-10-
C-1CH2=CHO, CH2=CCH2-C-○-1
CH2-C'-C1 (2-C-Q -- maximum (Ila)
In, Xo represents the same content as V in formula (1). b+ and bz may be the same or different from each other, and the formula (
Represents the same content as al+”2 in 1).

Qo is an aliphatic group having 1 to 18 carbon atoms or 6 to 12 carbon atoms
represents an aromatic group.

Specifically, an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, an octyl group, a decyl group,
Dodecyl group, tridecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2
-hydroxylethyl group, 2-methoxyethyl group, 2-
Ethoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2-(trimethodoxysilyl)ethyl group, 2
-tetrahydrofuryl group, 2-thienylethyl group, 2-
N,N-dimethylaminoethyl group, 2-N,N-diethylaminoethyl group, etc.), cycloalkyl group having 5 to 8 carbon atoms (e.g. cycloheptyl group, cyclohexyl group, cyclooctyl group, etc.), 7 to 12 carbon atoms optionally substituted aralkyl group (e.g. benzyl group, phenethyl group, 3-
Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, dichlorobenzyl group, methylbenzyl group, chloro-methyl-
Examples include aliphatic groups such as benzyl group, dimethylbenzyl group, trimethylbenzyl group, methoxybenzyl group, etc.).

Furthermore, an optionally substituted aryl group having 6 to 12 carbon atoms (e.g. phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, dichlorophenyl group, chloro-methyl-phenyl group, methoxyphenyl group, methoxycarbonylphenyl group) , naphthyl group, chloronaphthyl group, etc.). In formula (■a), preferably X. -COO-1-OCO-1CH□COO
-1CH20CO--0--CO--CONH- A preferred example of b, , b2 represents the same content as "l+82" described above.

In formula (IIb), Q is -CN, -CON H2 or (e.g., chlorine atom, bromine atom, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), or -COOR'(R'
is preferably an alkyl group having 1 to 8 carbon atoms, 7 to 1 carbon atoms
(2) represents an aralkyl group or an aryl group.

The macromonomer (M) may contain two or more kinds of polymer components represented by formula (II).

Also, in formula (Ila), Q. When is an aliphatic group, the aliphatic group having 6 to 12 carbon atoms is preferably used in an amount that does not exceed 20% by weight of the total heavy components in the macromonomer (M).

Furthermore, when Xo at -maximum (Tla) is -COO-, at least 3 of the polymer components represented by formula (Ila) are present in all the polymer components in the macromonomer (M).
It is preferable that the content is 0% by weight or more.

In addition, in the macromonomer (M), acrylonitrile, methacrylonitrile, acrylamides, methacrylamide can be used as a monomer corresponding to a repeating unit that can be copolymerized with the polymer component represented by formula (lla) and/or (Db). styrene and its derivatives (e.g. vinyltoluene, chlorostyrene, dichlorostyrene, bromostyrene, hydroxymethylstyrene, N,N-di,
methylaminomethylstyrene, etc.), heterocyclic vinyls (eg, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.), and the like.

The macromonomer provided in t3 of the present invention has only one end of the polymer main chain consisting of a retardation unit represented by -m formula (Ila) and/or (Illt) as described above. A chemical i in which the polymerizable double bond group shown in 1) is directly bonded or bonded with an arbitrary linking group.
It has a structure. Examples of the group connecting the formula N) component and the formula (Ila) or (Irb) component include a carbon-carbon bond (-double bond or double bond), a carbon-heteroatom bond (the heteroatom includes, for example, an oxygen atom) , sulfur atom,
(nitrogen atom, silicon atom, etc.), and any combination of atomic groups of heteroatom-heteroatom bonds.

Among the macromonomers (M) of the present invention, preferred are those represented by formula (Va) or (Vb).

Formula (Va) al　　　R2 1-I X, -Q.

Formula (Vb) Q In formula (Va) and (Vll>, "I + a 2 r
b l + ])2 + V+ xO+ Q 0 and Q represent the same contents as explained in formula (f), formula (Ha), and (Ilb), respectively.

R5 W is a simple bond or -+C← (R2, R1 are R
1 hydrogen atom, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (e.g. methyl group, ethyl group, propyl group, etc.)], 0- -8- --C--N--Co.

R4L R4 N I-I COO--N I-I CON
H--S 1R1 (R< is a hydrogen atom or Q in the above formula (Ha).

represents a single linking group or a linking group composed of any combination selected from the atomic groups such as [indicates a hydrocarbon group etc. expressing the same content as]].

The weight average molecular weight of the macromonomer (M) is ZXl, O'
If it exceeds, the copolymerization with the monomer represented by the formula ([[[) will decrease. On the other hand, if the molecular weight is too small, the effect of improving the electrophotographic properties of the photosensitive layer will be small;
It is preferable that it is above.

The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. For example, a method using an ionic polymerization method in which the ends of a living polymer obtained by anionic or cationic polymerization are reacted with various reagents to form a macromer, and a method that contains reactive groups such as carboxyl groups, hydroxyl groups, and amine groups in the molecule. Using a polymerization initiator and/or a chain transfer agent, various reagents are reacted with the oligomer with a terminal reactive group bond obtained by radical polymerization to form a macromer, a radical polymerization method, a polymerization method, Examples include a method using a polyaddition condensation method in which a polymerizable double bond group is introduced into an oligomer obtained by a polycondensation reaction in the same manner as the radical polymerization method described above.

Specifically, P., Dreyfuss & R.P.
, Quirk.

Encycle, Po1y+*, Sci, IEng,, Fu', 551 (1,987), P.

F,Re鵠1) p,E',, Franta, Adu,
, PolyI1. Sci, 58.1 (1984), V.
Pcrcec,Appl,,Polym,Sci,,2
85.95 (1984), R. Asami, M. Tak.
aRi, Makva ring o1. Chem.

5upp1.1ζ, 163 (1985), P.
Repp, etal, Makvamol.

CI+em, SuppL 8, 3 (1984)
, Kawa-Hi Yuji, Chemical Industry, 38.56 (1987),
Yuya Yamashita, Polymers, η Engineering, 988 (1982), Shibe Kobayashi, Polymers, Chen-, 625 (1981), Toshinobu Higashimura, Japan Adhesive Association Journal 18, 536 (1982), Hiroshi Ito-1 Polymer processing , 35, 262 (1986), Shibu Nori, Takashi Tsuda, Functional Materials, 1987 No. 10.5, and the literature and patents cited therein.

Specific examples of the macromonomer (M) of the present invention include the following compounds. However, the scope of the present invention is not limited to these.

C11゜ b:H, Cs13゜ R; CnHzn” (n: an integer from 1 to 18).

-(CH2) CaHs (m” integer from 1 to 3).

N 0OR b=I-1, CH3 or CH2C00CHj R=-CnHtn+ (n=an integer from 1 to 18).

C11゜C00C112CIIC11200C-+CI+2-C
←Suga IIx t+:H, Ctl *.

X Knee C00CI+,.

C6111,-CM b=H, C1 (3 or CH2COOCH3 R = -CnH214, (n = integer from 1 to 18).

CH2CaHs.

Cs　Hs　.

b: H or CH.

R knee Cnl-12n+ (n (integer from 1 to 18) CI-13 N C○0R 0OR b=H, C11* or C1,12COOC1-13 coor+ R-” CnH2n+ (n: an integer from 1 to 18).

b:H, -CH=.

R: CnHzn◆+ (n = integer from 1 to 18).

CHzCsH5, Cs1(.

CI+.

C00CH2CH2 S + CH2 CH- 0OR a=H, CHs+b=H+CH*

-CeHs.

CM b = H, CI.

R = -CnH2n"l (n = integer from 1 to 18).

C00(CHz)JIfOC1000CH2 C← a” H, CHs.

b=H, CH,.

CH,=C11 502Nil(C1h±,S+CI+2-C+0OR b:H,CI(-+,R:CnH2n+(n:1~
18 integers).

(Y:C1-(,.

CI, Br).

C.N. '142CsH5, Cg Hs.

0OR a'= H, CHi, b= H, CH3R= -CnH
2n”l (n: an integer from 1 to 18).

0OR -CT-1z Cal-1s r C@)I
s.

a=H+cH3, b=H2CH** R knee Cn[-12n (n=an integer from 1 to 18).

Cl-12C, H7゜ CsH.

C00(C1h)n-SOzNll(C1lz)T'-
S0Cll1C+ 0OR n=H CHj.

b=H, CH3 11=2-4 integer.

R knee CnHtru+ (n: m number from 1 to 1s).

0OR -CH□Cs　Hs　,　　　　Ca　H.

b=H CH.

n= CnH2n++ (n: an integer from 1 to 18).

CIf 2c-H9, CsH.

17) CH3 Police station X= C.N.

CON　H2 C6H9.

a　””　tl　　,CHy　.

b=　H, CI　,.

n = CnH21+ (n: integer from 1 to 18) C112C6I
+5CnH2n+ (n=an integer of 1 to 18).

-CH2Ca■l 5. - CnH5 I Br.

-OH, -CN.

0OR n = H, CHs, b = H, CHy.

CIl□C00CI+3 n=-CnH2n÷+ (n: integer from 1 to 18).

C112C112C.

n=1-1, CH3 X= OCOCnHzn button (n: 1-18 integer), -CN CON　H2,Cs+-(s.

n=-CnH2n+ (n: an integer from l to 18), -CIl, C, l+.

n=H.

CH3゜b= H, CH3, -C112COOC113R=
CnHl+l (n: an integer from 1 to 18), -CII.

Cs1li.

a= H, CH*, b= H, CH3,X'-COOC
ll*, -Cslls+a"' H, CH*.

+(=-CnH2n+, (n: integer from L to 18)X-
■ CHff, c l, Br, OCH3, COOCHs
.

The monomer copolymerized with the macromonomer (M) described above is represented by the general formula (III) ([[[], where e
+.

c2 may be the same or different, and al+ in formula (1)
X represents the same content as a, and is X in formula (Ila).

and Q represent the same content as Qo in formula (Ila).

Furthermore, the resin (B) of the present invention may contain other monomer Ji# other than these as a copolymer component together with the above-mentioned macromonomer (M) and -maximum (III) monomer.

For example, the "vinyl compound containing an acidic group" mentioned above for resin [A], α-olefin pigment, acrylonitrile,
methacrylnitrile, acrylamide, methacrylamide, styrene, vinyl group-containing naphthalene compounds (e.g. vinyl-naphthalene, ■-yne 10-benylnaphthalene, etc.) vinyl group-containing heterocyclic compounds (e.g. vinylpyridine,
(vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyl-1,3-dioxolane, vinylimidazole, vinylthiazole, vinyloxazoline, etc.).

In the resin [B], the composition ratio of the copolymer component having the macromer (M) as a repeating unit and the copolymer component having the monomer represented by -maximum (III) as a repeating unit is 1 to 90.
/99 to 10 (weight composition ratio), preferably 5 to 6
The weight composition ratio is 0/95 to 40.

Further, it is preferable that the main chain of the polymer does not contain a copolymer component containing a polar group such as a carboxyl group, a sulfo group, a hydroxyl group, or a phosphono group.

Furthermore, the resin (B) of the present invention has at least one type of repeating unit represented by maximum (III) and at least one type of repeating unit represented by a macromonomer, only at one end of the heavy main chain, - po.

H2 group, -so*HM, -COOH group, -〇11 group, S
It is a polymer formed by bonding at least one acidic group selected from H group and PO3RH group. Here, -PO,I
R in the RH group is -PO, R) in the resin [A]
It has the same meaning as the group R. Further, the polar group has a chemical structure in which it is directly bonded to one end of the polymer main chain or bonded via an arbitrary linking group.

Bonding groups include carbon-carbon bonds (-double bonds or double bonds), carbon-hetero atom bonds (hetero atoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and hetero atoms-hetero atoms. It is composed of a combination of atomic groups of atomic bonds, such as rogene atom (for example), chlorine atom, chlorine atom, bromine atom, etc.), sia/group, hydroxyl group, alkyl group (methyl group, ethyl group, propyl, etc.], 〇- C- COO- -NHCOO- -NHCON H- i- R1 (R4 is a hydrogen atom or a hydrocarbon having the same meaning as Qo shown in -maximum (Ilg) above) Examples include a single linking group selected from atomic groups such as [indicating groups, etc.] or a linking group composed of any combination thereof.

The content of the acidic group bonded only to one end of the polymer main chain in the resin [B] is preferably 0.1 to 15!1i, 1%, more preferably 1% per 100 folded parts of the resin (B). 0.5 to 10% by weight. If it is less than 0.1% by weight, the effect of improving the film strength will be small, and if it is more than 1% by weight, the photoconductor will not be uniformly dispersed when adjusting the photoconductor content.
Coagulation occurs and a uniform coating film is no longer formed.

The resin (B) of the present invention, which has a specific acidic group bonded only to one end of the polymer main chain, can be obtained by reacting various reagents at the ends of living polymers obtained by conventionally known ayu-on polymerization or cation polymerization. (ionic polymerization method), radical polymerization method using a polymerization initiator and/or chain transfer agent containing a specific acidic group in the molecule (radical polymerization method), or the above-mentioned ionic polymerization method. It can be easily produced by a synthetic method such as a method in which a polymer containing a reactive group at the end obtained by a legal or radical polymerization method is converted into the specific acidic group of the present invention by a polymer reaction.

Specifically, P, Dreyfuss, R, P, Quir.
k.

Encycle, Polym, Sci, Eng, 7.55
1 (1987), Nakayoshiki, Shiroshita! Iya “dyes and chemicals”,
30.2:'+2 (1985), Akira Ueda and Susumu Nagai, "Science and Industry," 60.57 (1986), and other reviews and documents cited therein.

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 proportion of resin [A] and resin [B] is The ratio used is 5 to 80 to 95 to 20 (weight ratio), preferably 10 to 60 to 90 to 40 (weight ratio).

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.

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, per 100 parts by weight of the photoconductor. .

In the present invention, various dyes can be used in combination as spectral sensitizers if necessary9 For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (No. 8) p. 12, C
J. Young et al., RCA Review 15.
469 (+954), Wataru Kiyota, Journal of the Institute of Electrical Communication, T63-C (No, 2), 97 (1980), Yuji Harasaki et al., Industrial Chemistry Journal 6678 and 188 (1963),
Tadaaki Tani, Journal of the Photographic Society of Japan 35.208 (1972), etc., cited in the review of carboniurine pigments, diphenylmethane pigments, triphenylmethane pigments, xanthine pigments, phthalein pigments, polymethine pigments (e.g., oxonol pigments, merocyanine pigments, cyanine pigments) dyes, logocyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain metals), and the like.

More specifically, examples using mainly carboniurine dyes, triphenylmethane dyes, xanthine dyes, and phthalein dyes include Japanese Patent Publication No. 51452 and Japanese Patent Application Laid-open No. 51-197.
0-90334, JP 50-114227, JP 53-39130, JP 53-82353, U.S. Patent No. 3,052,540, U.S. Patent No. 4,054
, No. 450, and JP-A-57-16456.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as rhodacyanine dyes include F,
M,HarmerrThe Cyanine D
Yesand Re1ated Co＋＊pounds
It is possible to use the dyes described in "U.S. Pat. No. 3,047,384, U.S. Pat. No. 3,
No. 110,591, U.S. Patent No. 3,121,008;
U.S. Patent No. 3,125,447, U.S. Patent No. 3,12
No. 8,179, U.S. Patent No. 3,132,942, U.S. Patent No. 3,622,317, British 11il Patent Nos. 1 and 2
No. 26,892, British Patent No. 1,309,274, British Patent No. 1,405,898, Special Publication No. 1978-7814
Examples include dyes described in Japanese Patent Publication No. 55-18892.

Furthermore, as a polymethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 n- 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 57157254, JP 61-28
No. 044, JP-A No. 61-27551, U.S. Patent No. 3,
No. 619,154, U.S. Pat. No. 4,175,956;
rResercl+ D 1closureJ198
2, 216, pp. 117-118.

The photoreceptor of the present invention is 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 (
No. 8 > Electron-accepting compounds cited in reviews such as page 12 (
For example, halogens, benzoquinone, chloranil, acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon et al., [Development and practical application of near-R photoconductive materials and photoreceptors] Chapters 4 to 6, 2 Japanese Scientific Information Boaryl alkane compounds and hindered phenol compounds cited in the review published by Shuppan Co., Ltd. (1986), p.
-phenylenediamine compounds and the like.

The amount of these various additives added is not particularly limited, but
Normally o, oooi to 2.0% per 100 parts by weight of photoconductor.
It is 0 parts by weight.

The thickness of the photoconductive layer is from 1 to 100μ, in particular from 10 to 50zt
is suitable.

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 0.01 to 1μ, particularly 0.05 to 0.5μ. suitable.

In some cases, an insulating layer is added mainly for the purpose of improving the protective layer, durability, and dark decay characteristics of the photoreceptor. At this time, the insulating layer is set to be relatively thin, and when the photoreceptor is used for a specific electrophotographic process, the insulating layer provided is set to be relatively thick.

In the latter case, the thickness of the insulating layer is between 5 and 70μ, in particular 1
It is set from 0 to 50 noL.

Charge transport materials for the M-layer type 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 insulating layer or charge transport layer include polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, hydrochloric acid and 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 for the electrophotographic photosensitive layer is preferably electrically conductive.As the electrically conductive support, for example, a base material such as metal, paper, or plastic sheet impregnated with a low-resistance substance is used in the same manner as in the past. those that have been subjected to conductive treatment, such as those that have been coated with at least one layer 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 also to prevent curling, and those that have been coated with at least one layer for the purpose of preventing curling, etc. A water-resistant adhesive layer is provided on the surface of the body, a pre-coat layer of at least 1 m or more is provided as necessary on the surface layer of the support, and a base conductive plastic coated with No. 1 is laminated on paper. Things can be used.

Specifically, as an example of the conductive substrate or conductive material f1, Yukio Sakamoto, Electrophotography, 14. (No, 1), p2
~1l (1975), Hiroyuki Moriga, "Introductory chemistry of special paper" Kobunshi Publishing (1975), M, F, Hoove
r, J, Macromol, 5ciC1+em, A
-4 (6>, pages 1327 to 1417 (1970), etc.) are used.

(Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

Macromo, Tsuma's 1:M-1, methyl methacrylate 95g, thioglycolic acid 59
A mixed solution of 200 g of toluene and 200 g of toluene was heated to 75° C. while stirring under a nitrogen stream. 4.4' Azobis (4
-cyanovaleric acid) (abbreviated as A, C, V) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate and 1.0 g of N,N-dimethyldodecylamine were added to this reaction solution. Og and 0.5 g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 100°C for 12 hours.

After cooling, the reaction solution was reprecipitated into 2N methanol to obtain a white powder. Obtained. The number average molecular weight of the heavy body is 6.50
It was 0.

Preparation of macromonomer 2: M-2 Methyl methacrylate 959, thioglycolic acid 5g and toluene 200. The mixed solution was heated to 70°C while stirring under a nitrogen stream. 1.53 of 2.2'-azobis(isobutylnitrile) (abbreviated as A, 1.B, N) was added and reacted for 8 hours. Next, to this reaction solution, 1.0 g of glycidyl methacrylate (7.59, N,N-dimethyldodecylamine) and t-butylhydroquinone (o,s) were added.
g was added thereto, and the mixture was stirred at a temperature of 100°C for 12 hours. After cooling, this reaction solution was reprecipitated into methanol 2e to obtain 85 g of a colorless and transparent viscous substance. The number average molecular weight of the heavy body is 2,
It was 400.

A mixed solution of macromonomer l'': 94 g of M-3 butyl methacrylate, 6 g of 2-mercaptoethanol, and 200 g of toluene was heated to 70°C under a nitrogen stream. A, I, B, N, 1.29 was added and reacted for 8 hours.

The reaction solution was then cooled in a water bath to a temperature of 20°C,
Triethylamine 10.2. was added, and 191.5 g of methacrylic acid chloride was added dropwise with stirring at a temperature of 25° C. or lower. After the dropwise addition, the mixture was further stirred for 1 hour. Then 5. t-
Butylhydroquinone O and SFI were added and the mixture was heated to 60°C and stirred for 4 hours. After cooling, it was reprecipitated into methanol 21 to obtain a colorless and transparent viscous substance 792.

The number average molecular weight was 4,500.

Preparation of macromonomer 4: M-4 Ethyl methacrylate 951F and toluene 200. The mixed solution was heated to a temperature of 70° C. under a nitrogen stream. 2゜2
5 g of '-azobis(cyanoheptatool) was added and reacted for 8 hours.

After cooling, the reaction solution was brought to a temperature of 20°C in a water bath, and triethylamine i, og and methacrylic anhydride 212 were added thereto and stirred for 1 hour, followed by stirring at a temperature of 60°C for 6 hours.

After the obtained reaction product was cooled, it was reprecipitated in methanol 21 to obtain 75 g of a colorless and transparent viscous material. Number average molecular weight is 6
, it was Zoo.

Macromonomer 5: M-5 benzyl methacrylate 93g, 3-mercaptoaropionic acid 71? , toluene 1709, and 30 g of Improper Tool was heated to 70° C. under a nitrogen stream to form a homogeneous solution. 2.0 g of A, I, B, and N were added and reacted for 8 hours. After cooling, it was reprecipitated into 2 liters of methanol, heated under reduced pressure to a temperature of 50°C, and the solvent was distilled off. The obtained viscous flocculent was dissolved in 200 g of toluene, and glycidyl methacrylate 161, N, N
-dimethyldodecyl methacrylate], Og and t-butylhydroquinone1. O1? 1 at a temperature of 110℃.
Stirred for 0 hours. This reaction solution was reprecipitated again into methanol 21. The number average molecular weight of the pale yellow viscous material obtained was 3,400.

, of macromonomers 6: M6 proyl methacrylate 95g, thioglycolic acid 59g
A mixed solution of toluene 2002 and toluene 2002 was heated to 75° C. with stirring under a nitrogen stream. A.1. B, N! , and reacted for 8 hours. Next, 13 g of glycidyl methacrylate and 1.0 g of N,N-dimethyldodecylamine were added to the reaction solution.
0g and 1.0g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 110°C for 10 hours. After cooling, this reaction solution was reprecipitated into methanol 21 to form a white powder. Obtained. The number average molecular weight was 2,300.

A mixture of macromonomers ``7:M-7 methyl methacrylate 40 g, ethyl methacrylate 549.2-mercaptoethylamine 6 g, toluene 150 g and tetrahydrofuran 50'' was heated to 75°C with stirring under a nitrogen stream. .AI, B, N, 2.
0. was added and reacted for 8 hours. Next, this reaction solution was brought to a humidity of 20° C. in a water bath, and methacrylic anhydride 239 was added dropwise thereto so that the temperature did not exceed 25° C., followed by further stirring for 1 hour.

2.2'-methylenebis-(6-1-butyl-1)-
Cresol) 0.5g was added thereto, and the mixture was stirred at a temperature of 40°C for 3 hours. After cooling, this solution was reprecipitated into methanol 21,
A viscous substance 839 was obtained. The number average molecular weight was 2,200.

A mixed solution of 95 g of macromonomer -8:M-8 methyl methacrylate, 1509 toluene, and 50 g of ethanol was heated at a temperature of 75°C under a nitrogen stream.
It was heated to 3.5 g of A and C were added and reacted for 8 hours.

Next, 15 g of glycidyl acrylate, N.

1.0 g of N-dimethyldodecylamine and 1.0 g of 2.2'methylenebis-(6-t-butyl-〇-cresol)
g was added thereto, and the mixture was stirred at a temperature of 100°C for 15 hours. After cooling, this reaction solution was reprecipitated into methanol 21 to form a transparent viscous substance 8.
3g was obtained. The number average molecular weight was 3,600.

Macromonomer 19-18: M -9-M-18 Macromonomer % Suitable Example 3 Same as Production Example 3 except that the acid halide shown in Table 1 was used instead of methacrylic acid chloride. A macromonomer was produced by the following steps. In addition, the MW of the macromonomers M-9 to M-18 was 4,000 to 5,000.

19-27 of harmful macromonomers: M-19-M-2
In Production Example 2 of Macromonomer 7, a macromonomer was produced in the same manner as in Preparation Example 2, except that the monomers shown in Table 2 were used instead of methyl methacrylate.

Table-2 Macromonomer ゛” 28-32: M-28-M
In Production Example 2 of -32 Mac, Lomonomer, 1. Other than using the monomers in the table below instead of methyl methacrylate,
Each macromonomer was produced in the same manner as in Production Example 2.

Table 3 Production Example 1 of Resin CA) [A]-1 After heating a mixed solution of 95 g of engineered methyl methacrylate, 5 g of acrylic acid, and 200 g of toluene to a temperature of 90°C under a nitrogen stream, Nitrile (abbreviation A, I
,B,N,)7I? was added and reacted for 8 hours.

The weight average molecular weight of the obtained copolymer was 7400, and the glass transition point was 45°C.

Production example 2 of resin [A]: [A]-2 94 g of benzyl methacrylate, 5.0 g of acrylic M6y dodecyl mercaptan. A mixed solution of 200 g of toluene and 200 g of toluene was heated to a temperature of 75° C. under a nitrogen stream. f & a.

1, B, N, 1. O, was added and reacted for 8 hours. The weight average molecular weight of the obtained copolymer was 6,500, and the glass transition point was 49°C.

Production examples 3 to 10 of resin [A]: [A]-3 to [A]-1
0 Production of Resin [A] Resin [A] was produced in the same manner as in Production Example 1, except that the monomers shown in Table 4 were used in place of 95 g of ethyl methacrylate in PAl.

Resin (B'J vJ formulation example t: (B)-t ethyl methacrylate 70g, macromonomer M-2) 30glue A mixed solution of toluene 1502 and isopropanol 50g was heated to a temperature of 70°C under a nitrogen stream. .

Next, 4,4'-azobis(4-cyanovaleric acid) t, of
I was added and reacted for 10 hours. The weight average molecule F& (Mw) of the obtained copolymer was 9.8 x 10', and the glass transition point was 72°C.

([3)-1 Composition formula % Formula % Production examples 2 to 9 of resin [B]: (B)-2 to (B)-9 In production example 1 of resin [B], macromonomer (M-2
Each resin (BJ) was produced in the same manner as in Production Example 1, except that the macromonomer shown in Table 5 below was used instead of the above.

Table-5 OOR Resin (B) Production Example 10: (B) -10 Butyl methacrylate 80. , macromonomer (MS) ZO9,
A mixed solution of 1.0 g of thioglycolic acid, 100° of toluene and 50 g of isopropanol was heated to 80°C under a nitrogen stream.
Warmed to ℃. 1.1'azobis(cyclohexane-1
-carbonitrile) (abbreviations A, C, H.

Add N, >0.5g, stir for 4 hours, and then add A, C, I (
,N.

0.3 g was added and stirred for 4 hours. M of the obtained polymer
W is 8. At OX 10', the glass transition temperature was 46°C.

Composition of resin (B)-to CN C00CI! .

Production examples 11 to 17 of resin [B]: (B)-11 to (B)
-17 Ig of resin (B)! In Preparation Example 10, the following compound of coating-6 was used instead of thioglycolic acid.
A polymer was produced in the same manner as in Production Example 1O.

Production examples 18 to 24 of resin (B): (B)-18 to (:B
:1-24 Production of resin [B] In PAl, A, C,
H,N.

Each heavy body was produced in the same manner as in Production Example 1, except that the azobis-based compounds shown in Table 7 below were used instead of.

Table-7 COOCI+.

Example 1 Resin [:A)-1 produced in Production Example 1 of resin CA) was
1F (as solid content) 35 g (as solid content) of the resin (B)-1 prepared in Production Example 1 of VI4 fat [B], 200 g of zinc oxide, cyanine dye o with the following structure, otsg
, Anhydrophthalic 90.051? and toluene 300. A photosensitive layer-forming product was prepared by dispersing the mixture in a ball mill for 2 hours, and this was applied to electrically conductive treated paper with a dry weight of 22y.
/m2 using a wire bar, dried at 110°C for 30 seconds, and then left in the dark at 20°C and 65% RH for 24 hours to prepare an electrophotographic light-sensitive material.

Cyanine dye comparative example A Resin [A]-1 used as binder resin in Example 1
And instead of (B:]-1, only resin [A] 1 is used at 40
Electrophotographic light-sensitive material A was prepared in the same manner as in Example 1 of Example 81, except that g # (as the solid content) was used.

Comparative Example B Electrophotographic light-sensitive material B was produced in the same manner as in Example PA1, except that 40 g (solid content) of only Resin [B]-4 was used as the binder resin.

Comparison PAC As a binder resin, only resin (C)-1 with the following structure was used at 40%
Electrophotographic light-sensitive material C was produced in the same manner as in Example 1 except that G was used.

Resin (C)-] CI(.

Weight average molecular weight 1ii 35,000 Glass transition point 46°C Film properties (surface smoothness), film strength,
Electrostatic properties, imaging performance, and imaging performance under environmental conditions of 30° C. and 80% RH were investigated. 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 8.

Table-8 The implementation aspects of the evaluation items shown in Table-8 are as follows.

Note 1) Smoothness of leading wS84: The obtained photosensitive material was tested using a Beck smoothness tester (Kumagai Riko).
The smoothness (see/ce) was measured under the condition of air volume Ice.

Note 2) Mechanical strength of photoconductive layer: The surface of the obtained photosensitive material was subjected to a load of 50I using a Hayton-14 type surface test material (manufactured by Shinshu Kagaku Co., Ltd.). /cs+”
The film was repeatedly probed 1000 times with emery paper (#1000) to remove abrasion powder, and the remaining 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 65% RH, each photosensitive material was subjected to corona discharge at -6 kV for 20 seconds using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Electric Co., Ltd.). After allowing it to stand for 10 seconds, the surface potential at this time is V. was measured. Next, after standing in the dark for 60 seconds, the potential ■7° was measured, and the retention of the potential after 60 seconds of dark decay, that is, the dark decay retention rate (DRR (%)) was calculated as (vyo/V+oxlOO (%) ).

After the surface of the photoconductive layer was charged to -400 V by corona discharge, it was irradiated with monochromatic light with a wavelength of 780 nm to increase the surface potential (
Determine the time it takes for V+・) to decay to 1/10, and calculate the exposure acid E18 from this. (erg/cm2).

Note 4) Imaging properties: Each photosensitive material was left overnight under the following environmental conditions, charged at 15 kV, and used as a light source with a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 mW).
64erg/c on the surface of the photosensitive material using
Under the irradiation dose, pitch 25. gm and scanning speed 3
After speed exposure of 00+*/see, the copied image obtained by developing and fixing using E L PT (Fuji Photo Film Co., Ltd.) as liquid development W1 (fogging, image quality of the image) ) was visually evaluated.

The environmental conditions during imaging were 20°C 65% r (I-[ and 30°C 8
It was carried out at 0% RH.

Note 5) Contact angle with water After each photosensitive material is passed through an etching processor once using a desensitizing liquid ELP-EX (Fuji Photo Film Co., Ltd. vJ) to desensitize the photoconductive layer surface. A droplet of 2 μl of distilled water is placed on this, and the contact angle with the water formed is measured using a goniometer.

Note 6) Printing durability Each photosensitive material is plate-made to form a toner image under the same conditions as Note 4) above, desensitized under the same conditions as Note 5) above, and this is used as an offset master for offset printing. This indicates the number of sheets that can be printed using a machine (Oliver Model 52 manufactured by Sakurai Seisakusho Co., Ltd.) without causing problems with scumming in the non-image areas of the prints or problems with the image quality of the image areas (the higher the number of prints, the better the printing durability. (represents something).

Note 7> D end (image 4 degrees) The maximum value is indicated by the toner image density of the solid area (can be measured with a Macbeth reflection densitometer)°.

As shown in Table 8, the photosensitive material of the present invention and Comparative Example A had good smoothness and electrostatic properties of the photoconductive layer, 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 fact that the photoconductivity and binder resin are sufficiently adsorbed and coat the back surface of the particles.

For the same reason, even when used as an offset master original, the desensitization treatment with the desensitization treatment liquid progresses sufficiently, and the contact angle with water in the non-image area is small at 15 degrees or less, making it sufficiently hydrophilic. ing. When actually printing and observing the background stains on the printed matter, no stains were observed at all. However, in the case of Comparative Example A, when the strength test and the printing durability test of the photoconductive layer were conducted, the film strength was not sufficient and a major problem occurred in durability.

In each of the photoreceptors of Comparative Example B and Comparative Example C, the film strength was sufficient, but the electrostatic properties 1-? l), Q, R and E
l/, o (corresponding to photosensitivity) were significantly reduced, and even when an image was actually taken, a sufficient copy image could not be obtained. Comparative Example C uses a resin with a reduced amount of acid component, but a high molecular weight polymer containing the same amount of acid component as in Example 1 would aggregate when dispersed with zinc oxide. No dispersion could be formed.

From the following, only the photosensitive material of the present invention was good in all points of smoothness of the photoconductive layer, film strength, electrostatic properties, and printability.

Examples 2 to 16 Copolymers shown in Table 9 were produced as Kobunsha Resin [A] in the same manner as in the production of Resin [A]-1 in Production Example 1 of Resin rA).

Table 9 Each of these resins [A] lh (as solid content) and the resin [B] produced in Production Example 1 of resin (B) -130 g (
A light-sensitive material was produced in the same manner as in Example 1, except that (as the solid content) was used.

Each characteristic was measured in the same manner as in Example PA1. The smoothness and film strength of each light-sensitive material showed properties almost equivalent to those of the sample of Example 1.

Each of the photosensitive materials of the present invention has excellent chargeability, dark charge retention rate, and photosensitivity, and the actual copied images are also produced under high temperature and high humidity (30°C
Even under the harsh conditions of 80% RH), clear images with no soil burr were obtained.

Examples 17 to 28 Example 1 except that resin [A]-1 and resin (B) shown in Table 10 below were used in combination at a weight ratio of (1/4).
Each photosensitive material was manufactured in the same manner as described above.

In the same manner as in Example 1, the smoothness, film strength, and electrostatic properties of each photosensitive material were measured. Each of the photosensitive materials of the present invention has good photoconductive layer strength and electrostatic properties, and the actual copied images are clear and free of blur even under high temperature and high humidity (30°C, 80% RI-1). The image quality was good.

Table 10 Examples 29 to 38 Resin [A] and resin (B) shown in Table 11 below (
115,6) Each photosensitive material was produced in the same manner as in Example 1, except that they were used in combination at a weight ratio. The smoothness, film strength, and electrostatic properties of each photosensitive material were measured in the same manner as in Example 1. Each of the photosensitive materials of the present invention has good photoconductive layer strength and electrostatic properties, and the actual copied images have clear image quality without blurring even under high temperatures (30°C, 80% RH). Ta.

Claims (1)

[Scope of Claims] An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material and a binder resin, wherein the binder resin comprises at least one each of the following resins [A] and resins [B]. An electrophotographic photoreceptor comprising: (i) Resin [A] has a weight average molecular weight of 1 x 10^3 to 1.5 x 10^4, and -PO_3H_2 groups, -COOH groups, -SO_
A copolymerization component containing at least one acidic group selected from 3H group, -OH group, -SH group, and ▲ mathematical formula, chemical formula, table, etc. ▼ group (R represents a hydrocarbon group) is 0.1 Resin containing ~20% by weight. (ii) Resin [B] Only one end of the polymer main chain contains at least one of the polymer components represented by the following general formulas (IIa) and (IIb), and is represented by the following general formula (I). A copolymer consisting of at least a monofunctional macromonomer having a weight average molecular weight of 2×10^4 or less, which is formed by bonding a polymerizable double bond group, and a monomer represented by the following general formula (III), and -PO_3H_2 group, - only at one end of the copolymer main chain
A resin formed by bonding at least one acidic group selected from SO_3H group, -COOH group, -OH group, -SH group, and ▲ mathematical formula, chemical formula, table, etc. ▼ group (R represents a hydrocarbon group). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (I), V is -COO-, -OCO-, -CH_
2OCO-, -CH_2COO-, -O-, -SO_2
-, -CO-, ▲Mathematical formulas, chemical formulas, tables, etc.▼,▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_1 represents a hydrogen atom or a hydrocarbon group) a_1
, a_2 may be the same or different, and are hydrogen atoms,
It represents a halogen atom, a cyano group, a hydrocarbon group, -COO-Z, or -COO-Z via a hydrocarbon (Z represents a hydrogen atom or a hydrocarbon group which may be substituted). General formula (IIa) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIb) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In formula (IIa) or (IIb), X_0 is V in formula (I) represents the same content as . Q_0 represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. b_1
, b_2 may be the same or different from each other, and the formula (I)
It represents the same content as a_1 and a_2 inside. Q is -CN, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, where Y represents a hydrogen atom, a halogen atom, an alkoxy group, or -COOZ'(Z' represents an alkyl group, an aralkyl group, or an aryl group). General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (III), X_1 represents the same content as X_0 in formula (IIa), and Q_1 is the same as Q_0 in formula (IIa). represents the content of c_1 and c_2 may be the same or different, and represent the same contents as a_1 and a_2 in formula (I).