JPH04358156A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide the electrophotographic sensitive body which is improved in electrostatic characteristics and characteristic and has the excellent reproducibility of highly fine images by using a liquid developer in particular and the excellent image pickup characteristic by a scanning exposing system using a low-output laser beam. CONSTITUTION:This photosensitive body contains a is a low-mol.wt. copolymer of a macromer bonded with the group of formula II at one terminal of the main chain of a polymer contg. the component of formula I and the monomer equiv. to the formula I and is further bonded with a polar group at the terminal of the main chain or a resin A2 contg. this group in the macromer component and a resin B of a high-mol.wt. AB block copolymer of an A block contg. a polar group and the B block contg. the component of the formula I as a binder resin. [In the formula I, a<1>, a<2> denote hydrogen, halogen, cyano group or hydrocarbon group; R<3> denotes a hydrocarbon group; in the formula II, G denotes a bivalent combination group; b<1>, b<2> denote hydrogen, halogen, cyano group, hydrocarbon group,-COOR<12>(R<12>; hydrocarbon group)].

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to an electrophotographic photoreceptor.
Specifically, the present invention relates to an electrophotographic photoreceptor having excellent electrostatic properties and moisture resistance.

0002

2. Description of the Related 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.

Typical electrophotographic photoreceptors include 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 master 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 on the order of several hundred to several thousand sheets. Under these circumstances, the binder resin 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 resin. The formed recording layer has good adhesion to the base material, and the photoconductive layer of the recording layer has excellent charging ability, low dark decay, large light decay, little pre-exposure fatigue, and is easy to photograph. It is necessary to have various electrostatic properties and excellent imaging performance, such as the need to maintain these properties stably depending on changes in humidity.

Furthermore, research is being carried out on lithographic printing original plates using electrophotographic photoreceptors, and a photoconductive layer material that has both the electrostatic properties of an electrophotographic photoreceptor and the printing properties of a printing original plate has been developed. A binder resin is required.

It has been found that in a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye, and a binder resin, not only smoothness but also electrostatic properties are greatly affected by the chemical structure of the binder resin. Ta. In particular, in terms of electrostatic properties, the dark charge retention rate (D.R.R.) and photosensitivity are greatly affected.

On the other hand, according to the techniques described in JP-A-63-217354, JP-A-64-70761, JP-A-2-67563 and JP-A-2-247656, the acidic group-containing polymerization component is a polymer. A low molecular weight resin that exists randomly in the main chain, a low molecular weight resin that has an acidic group bonded to one end of the polymer main chain, or a low molecular weight resin that has an acidic group bonded to one end of the polymer main chain. It has become possible to improve smoothness and electrostatic properties by using a graft copolymer resin, a low molecular weight graft copolymer resin containing an acidic group in the graft portion, etc. as a binder resin. These low molecular weight resins have the effect of sufficiently dispersing the photoconductor and suppressing aggregation of the photoconductors, and the inorganic resin does not interfere with the adsorption of the photoconductor and the spectral sensitizing dye. This is presumed to be due to sufficient adsorption to the stoichiometric defects of the photoconductor and a loose and sufficient coating of the surface of the photoconductor.

Due to its mechanism of action, the inorganic photoconductor, spectral sensitizing dye, and resin are relatively stable because they have a sufficient adsorption area even if the stoichiometric defect portion of the inorganic photoconductor varies slightly. It is inferred that peer interaction is preserved.

[0009] In order to make the mechanical strength of the photoconductive layer sufficient, which is insufficient with these low molecular weight resins alone, a technique of using other medium to high molecular weight resins in combination or a resin containing a curable group has been developed. Techniques for curing after film formation by using in combination are disclosed in JP-A-64-564, JP-A-63-220149, JP-A-63-220148, JP-A-1-280761, JP-A-1-116643, and JP-A-1-169455. , 1-2
No. 11766, No. 2-34859, No. 2-53064
No. 2-56558, Japanese Patent Application No. 1-163796,
No. 1-212994, No. 1-229379, No. 1-
It is described in No. 189245, etc.

0010

[Problem to be Solved by the Invention] However, even if these resins or combinations of resins are used, it is still insufficient to maintain stable performance when the environment changes significantly from high temperature and high humidity to low temperature and low humidity. I found out something. The scanning exposure method using semiconductor laser light requires longer exposure time than the conventional simultaneous exposure method using visible light across the entire surface, and there are restrictions on the exposure intensity, so electrostatic properties, especially dark charge retention properties , for light sensitivity,
Higher performance is required.

[0011] In particular, when a scanning exposure method using semiconductor laser light is adopted in an original plate for electrophotographic planographic printing, actual tests using a conventional photoreceptor show that
The above electrostatic properties are not fully satisfactory, especially E
The difference between 1/2 and E1/10 is large, and the gradation of the copied image becomes soft, and furthermore, it becomes difficult to reduce the residual potential after exposure, resulting in noticeable fogging of the copied image.
Further, even when printing as an offset master, problems such as pasting marks of the printed original appear on the printed matter.

Furthermore, in recent years, there has been a desire to realize a technology that faithfully reproduces not only copies of images consisting of line drawings and halftone dots, but also high-definition images consisting of continuous gradation using liquid developers. However, the above-mentioned known techniques could not fully satisfy these demands.

In conventionally known techniques, medium to high molecular weight resins that are used in combination with low molecular weight resins may deteriorate the electrostatic properties that have been improved by the low molecular weight resins, and in fact the above-mentioned An electrophotographic photoreceptor having a photoconductive layer using a combination of these known resins has the advantage of achieving faithful reproduction of high-definition images (particularly continuous-tone images) as described above, or of low-output images. It has become clear that problems may arise in imaging performance using a scanning exposure method using laser light.

The present invention is intended to improve the problems of conventionally known electrophotographic photoreceptors as described above. An object of the present invention is to provide an electrophotographic photoreceptor that always maintains stable and good electrostatic properties and produces clear, high-quality images even when the environment during copy image formation changes such as low temperature and low humidity or high temperature and high humidity. The goal is to provide the following.

Another object of the present invention is to provide a CPC electrophotographic photoreceptor that has excellent electrostatic properties and less environmental dependence. Another object of the present invention is to provide an electrophotographic photoreceptor that is effective in a scanning exposure method using semiconductor laser light.

A further object of the present invention is to use an electrophotographic lithographic printing original plate that has excellent electrostatic properties (particularly dark charge retention and photosensitivity) and is faithful to original images (particularly high-definition continuous tone images). To provide a lithographic printing original plate which reproduces a copy image, does not cause not only uniform background smearing on the entire surface of printed matter but also dotted smearing, and has excellent printing durability.

[0017]

[Means for Solving the Problems] The above object is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye, and a binder resin, wherein the binder resin is the following resin [A1]. ] and at least one of the resins [A2] and at least one of the following resins [B]
It has been found that this can be achieved by an electrophotographic photoreceptor characterized by containing seeds. Resin [A1] has a weight average molecular weight of 1 x 103 to 2 x 104,
A polymerizable double bond group represented by the following general formula (II) is bonded only to one end of the main chain of a polymer containing 30% by weight or more of repeating units represented by the following general formula (I) as a polymer component. A copolymer consisting of at least a monofunctional macromonomer (M1) having a weight average molecular weight of 2 x 104 or less, and a monomer corresponding to a repeating unit represented by the general formula (I), -PO3 H2, -SO3 H, -COOH, -P at one end of the combined main chain
(=O)(OH)R1 [R1 is a hydrocarbon group or -O
R2 (R2 represents a hydrocarbon group)] and a cyclic acid anhydride group. Resin [A2] has a weight average molecular weight of 1 x 103 to 2 x 104,
A polymer component containing 30% by weight or more of repeating units represented by the following general formula (I) as a polymer component and at least one polar group selected from the specific polar groups represented by the resin [A1] above. A weight average molecular weight 2× consisting of a polymerizable double bond group represented by the following general formula (II) bound only to one end of a polymer main chain containing 1 to 50% by weight.
104 or less monofunctional macromonomer (M2),
A resin which is a copolymer comprising at least a monomer corresponding to the repeating unit represented by the general formula (I).

[0018]

embedded image [In formula (I), a1 and a2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group. R3 represents a hydrocarbon group. Preferably, a1 is a hydrogen atom, a2
is the case of a methyl group. ]

[0019]

[In formula (II), G1 is -COO-, -OCO-, -
CH2 OCO-, -CH2 COO-, -O-, -S
O2-, -CO-, -CONR11-, -SO2N
R11- (here R11 represents a hydrogen atom or a hydrocarbon group), -CONHCOO-, -CONHCONH- or -C6H4-.

b1 and b2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group,
-C via hydrocarbon group, -COOR12 or hydrocarbon
OOR12 (here, R12 represents an optionally substituted hydrocarbon group). ] Resin [B] has a weight average molecular weight of 2 x 104 to 1 x 106,
The A block containing at least one kind of polymer component containing at least one kind of polar group selected from the specific polar groups shown in the above resin [A1] and the above resin [A]
An AB block copolymer comprising a B block containing at least a polymer component represented by the general formula (I).

That is, the binder resin of the present invention is formed by bonding a specific polar group to one end of a copolymer containing the above macromonomer (M1) and a monomer corresponding to the above general formula (I). Resin [A1] and/or resin [A2] which is a copolymer containing the above macromonomer (M2) containing a specific polar group-containing component and a monomer corresponding to the above general formula (I) (hereinafter referred to as macromonomer) Monomers (M1) and (M2) are collectively called macromonomers (M), and resin [
A1] and [A2] may be collectively referred to as resin [A]), an A block containing the above specific polar group-containing component, and B containing a polymer component represented by the above formula (I).
The resin [B] is an AB block copolymer with the block.

As a result of various studies, as mentioned above, in the technique of using a known low molecular weight polar group-containing resin in combination with a medium to high molecular weight resin, the medium to high molecular weight resin used in combination,
It has been found that the electrostatic properties improved by the low molecular weight resin described above may deteriorate. It is also more important than expected that these medium to high molecular weight resins can interact more appropriately with the photoconductor, spectral sensitizing dye, and low molecular weight resins in the photoconductive layer. It has become clear that this is the cause.

As a result of repeated studies, we found that the polar group-containing block A according to the present invention and the polar group-free block were selected as medium to high molecular weight resins to be used in combination with the low molecular weight resin [A] containing polar groups. It has been found that the above problem can be effectively solved by using an AB block copolymer having B.

[0024] This means that the binder resin [A] and [
Due to the synergistic effect of [B], the photoconductor particles are sufficiently dispersed and exist in a non-condensed state, and the spectral sensitizing dye is sufficiently adsorbed on the surface of the photoconductor particles, and the excess on the photoconductor surface is This is presumed to be due to the fact that the binding resin sufficiently adsorbs the active sites and compensates for the trapping.

That is, the low molecular weight graft copolymer resin [A] containing a specific polar group sufficiently adsorbs to the photoconductor particles and uniformly disperses the particles, and the polymer chains are extremely It has important effects such as suppressing aggregation due to its short length and preventing adsorption and alienation of spectral sensitizing dyes.

[0026] Furthermore, a medium to
By using the high molecular weight AB block copolymer, the mechanical strength of the photoconductive layer was sufficiently maintained. This is thought to be due to the fact that the interaction of the block A part of this resin with the photoconductor particles is weaker than that of the resin [A], and the entanglement effect between the polymer chains of the block B part. .

Furthermore, the fact that the electrostatic properties are more improved than the known medium to high molecular weight resins used in combination is that the block A portion that interacts with the photoconductor particles has a polar group. Therefore, it is thought that it functions to suppress the adsorption and alienation of spectral sensitizing dyes.

This effect was particularly remarkable with polymethine dyes or phthalocyanine pigments, which are particularly effective as dyes for spectral sensitization of near-infrared to infrared light. On the other hand, when the electrophotographic photoreceptor of the present invention using photoconductive zinc oxide as a photoconductor is used as a conventionally known direct printing plate, it exhibits excellent imaging properties and extremely good water retention.

That is, the photoreceptor of the present invention, on which a copy image has been formed through an electrophotographic process, is chemically treated to desensitize the non-image areas using a conventionally known desensitizing treatment liquid, and this is used as a printing original plate. It shows excellent performance as a printing original plate when printed by offset printing.

When the photoreceptor of the present invention was desensitized, the non-image area was sufficiently made hydrophilic and the water retention property was improved, resulting in a dramatic increase in the number of prints. This is because the above-mentioned zinc oxide particles are uniformly dispersed and the binder resin present on the surface of the zinc oxide particles is in an appropriate state, so that the desensitization reaction with the desensitization treatment solution does not occur and is rapid. This is thought to be due to the effective progression of the disease.

Furthermore, in the present invention, a low molecular weight resin [A]
In, the general formula (I) contained in the macromonomer
and/or as the general formula (I) copolymerized with the macromonomer, a specific substituent at the 2-position and/or at the 2-position and the 6-position shown in the following general formula (Ia) and general formula (Ib). The resin is preferably a resin containing a methacrylate component having a specific substituent, which contains a benzene ring or an unsubstituted naphthalene ring (hereinafter, this low molecular weight product is particularly referred to as resin [AA]).

[0032]

[C7]

[0033]

[Formula (Ia) and (Ib), A1 and A2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -COR4 or -COO
R4 (here, R4 represents a hydrocarbon group having 1 to 10 carbon atoms).

B1 and B2 each represent a single bond or a linking group having 1 to 4 linking atoms, which connects -COO- to the benzene ring. ] When the above-mentioned specific resin [AA] is used, electrophotographic properties (particularly V10, D.R.R., and E1/10) can be further improved than in the case of resin [A].

The reason for this is unknown, but one reason is that the zinc oxide interface in the film is caused by the effect of the planar benzene ring or naphthalene ring having a substituent at the ortho position, which is the ester component of methacrylate. This is thought to be due to proper alignment of these polymer molecular chains.

The binder resin of the present invention will be explained in detail below. First, the resin [A] of the present invention will be explained. The resin [A] is a graft copolymer containing at least a monomer corresponding to the polymer component represented by the general formula (I) and a monofunctional macromonomer (M), and further contains a specific polar group. at one end of the main chain of the polymer (resin [A1])
Alternatively, the weight average molecular weight of each contained in the graft portion (resin [A2]) is 1 x 103 to 2.
*104 It is a low molecular weight resin.

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, whereas when the molecular weight is greater than 2×10 4 , even the resin of the present invention In particular, for photoreceptors using near-infrared to infrared spectral sensitizing dyes, fluctuations in dark decay retention and light sensitivity become somewhat large under harsh conditions of high temperature, high humidity, low temperature and low humidity, resulting in stable copying. When an image is obtained, the effect of the present invention is diminished.

The glass transition point of the resin [A] is preferably -
The temperature is 30°C to 110°C, more preferably -20°C to 90°C. The proportion of the polymer component corresponding to the repeating unit of general formula (I) in the resin [A] is 30% by weight or more, preferably 50% by weight or more in the resin [A], and the total amount of components containing polar groups is 0.5 to 15% by weight, preferably 1 to 10% by weight in resin [A].

[0039] The polar group content in resin [A] is 0.5
If it is less than % by weight, the initial potential will be low and sufficient image density will not be obtained. On the other hand, if the polar group content is more than 15% by weight, the dispersibility decreases no matter how low the molecular weight is, and furthermore, background smudge increases when used as an offset master.

Macromonomer (M) in resin [A]
The content of is 1 to 70% by weight, preferably 5 to 50% by weight in the resin [A]. If the copolymerization component corresponding to the macromonomer (M) is less than 1% by weight, the characteristics of the graft type copolymer will be lost, the electrostatic properties (especially dark charge retention, sensitivity) will decrease, and it will be difficult to use for offset printing. Water retention is also reduced when used as an original plate. When the content exceeds 70% by weight, it becomes difficult for the copolymerization of the graft copolymer to proceed sufficiently, resulting in the deterioration of electrostatic properties and water retention as described above.

Next, 30% by weight in the copolymer of resin [A]
The repeating units represented by the general formula (I) contained above will be further explained. a1 and a2 each represent a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom), a cyano group, or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.).

R3 represents a hydrocarbon group, specifically an alkyl group, an aralkyl group or an aromatic group, preferably an aralkyl group or an aromatic group which is a hydrocarbon group containing a benzene ring or a naphthalene ring. .

Furthermore, R3 preferably has 1 to 18 carbon atoms.
represents an optionally substituted hydrocarbon group. The substituent may be any substituent other than the polar group contained in the polar group-containing polymer component of the resin [A], such as a halogen atom (e.g. fluorine atom,
chlorine atom, bromine atom, etc.), -OR5, -COOR5
, -OCOR5 (R5 represents an alkyl group having 1 to 22 carbon atoms, such as a methyl group, an ethyl group, a propyl group,
butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.). Preferred hydrocarbon groups include optionally substituted alkyl groups having 1 to 18 carbon atoms (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 (e.g., 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group) group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group) , 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), carbon number 5 ~
8 optionally substituted alicyclic groups (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or optionally substituted aromatic groups 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, dodecoylamidophenyl group, etc.).

In the hydrocarbon group represented by R3, R3
When is an aliphatic group, it is preferable that the component represented by formula (I) preferably contains 60% by weight or more of a hydrocarbon group having 1 to 5 carbon atoms.

[0045] Among the repeating units of general formula (I) which are components having such a substituent R3, polymer components of repeating units represented by general formula (Ia) and/or general formula (Ib) are more preferable. can be mentioned.

In formula (Ia), preferred A1 and A2 are, independently of each other, a hydrogen atom, a chlorine atom and a bromine atom, as well as a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Alkyl groups (e.g. methyl group, 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, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloromethylbenzyl group) and aryl groups (e.g. phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group) , chlorophenyl group,
dichlorophenyl group), and -COR4 and -CO
OR4 (preferably R4 has 1 to 1 carbon atoms as described above)
Examples of preferable hydrocarbon groups include those described above.

In formulas (Ia) and (Ib), B1
and B2 are each a single bond connecting -COO- and a benzene ring, or -(CH2)a- (a represents an integer of 1 to 3), -CH2OCO-, -CH2CH2OCO
-, -(CH2)b - (b represents an integer of 1 or 2), -CH2CH2O-, etc., with 1 to 4 connected atoms
, and more preferably a single bond or a linking group having 1 to 2 bonded atoms.

Formula (Ia) used in the resin [A] of the present invention
) or (Ib) are listed below. However, the scope of the present invention is not limited thereto. In addition, in the following (a-1) to (a-20), c is an integer of 1 to 4, d is 0 or an integer of 1 to 3,
e is an integer from 1 to 3, R6 is -CcH2c+1
or -(CH2)d-C6H5 (however, c,
d is the same as above), and D1 and D2 may be the same or different and represent a hydrogen atom, -Cl, -Br, or -I.

[0049]

[Chemical formula 9]

[0050]

[Chemical formula 10]

[0051]

[Chemical formula 11]

[0052]

[Chemical formula 12]

[0053]

embedded image Next, the polar groups contained in the low molecular weight resin [A] will be explained. The polar group is -PO3 H2, -SO3 H
, -COOH, -P(=O)(OH)R1 -, and a cyclic acid anhydride-containing group.

Here, -P(=O)(OH)R1 is
Indicates a group represented by the following chemical formula 14, where the R1
represents a hydrocarbon group or -OR2 group (R2 represents a hydrocarbon group), specifically R1 represents an optionally substituted hydrocarbon group having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group). group, butyl group, 2-chloroethyl group, 2
-bromoethyl group, 2-fluoroethyl group, 3-chloropropyl group, 3-methoxypropyl group, 2-methoxybutyl group, benzyl group, phenyl group, propenyl group, methoxymethyl group, ethoxymethyl group, 2-ethoxyethyl group) etc., and R2 represents the same content as R1.

[0055]

embedded image 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 anhydride, aromatic dicarboxylic acid anhydride, Examples include anhydrides.

Examples of aliphatic dicarboxylic anhydrides include:
Succinic anhydride, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic anhydride ring, cyclohexane-1,2-dicarboxylic anhydride ring, cyclohexene-1,2- Dicarboxylic anhydride ring, 2
, 3-bicyclo[2.2.2]octadicarboxylic acid anhydride rings, etc., and these rings include, for example, halogen atoms such as chlorine atoms and bromine atoms, methyl groups, ethyl groups, butyl groups, hexyl groups, etc. The alkyl group, etc. may be substituted.

Examples of aromatic dicarboxylic anhydrides include phthalic anhydride ring, naphthalene-dicarboxylic anhydride ring, pyridine-dicarboxylic anhydride ring, thiophene-dicarboxylic anhydride ring, etc. These rings are
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 (alkoxy groups include, for example, methoxy group, ethoxy groups) etc. may be substituted.

In the case of resin [A1], the polar group is contained and bonded to the end of the polymer main chain. The content of the polar group is not particularly limited, but is preferably 0.5 to 15% by weight. The polar group may be directly bonded to the end of the polymer main chain or may be bonded via a linking group. Such a linking group may be any bonding group, but specific examples include -CR21R22-
[Here, R21 and R22 may be the same or different, and each represents a hydrogen atom, a halogen atom (chlorine atom, bromine atom, etc.), an OH group, a cyano group, an alkyl group (methyl group, ethyl group, 2-chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group, hexyl group, etc.), aralkyl group (
(benzyl group, phenethyl group, etc.), phenyl group, etc.]
, -(CHR21-CHR22)-, -C6 H10-
, -C6 H4 -, -O-, -S-, -NR23-[
Here, R23 is a hydrogen atom or a hydrocarbon group {specifically, a hydrocarbon group having 1 to 12 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group) , dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, phenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, butylphenyl group, etc.) ], −C
O-, -COO-, -OCO-, -CONR23-, -
SO2 NR23-, -SO2-, -NHCONH-
, -NHCOO-, -NHSO2-, -CONHCOO
-, -CONHCONH-, heterocycle (any 5- or 6-membered ring containing at least one of O, S, N, etc. as a heteroatom, or a condensed ring thereof, such as a thiophene ring, a pyridine ring, a furan ring, imidazole ring, piperidine ring, morpholine ring, etc.) or -
Si R24R25 [Here, R24 and R25 may be the same or different, and each represents a hydrocarbon group or -OR26 (
Here, R26 represents a hydrocarbon group. Examples of these hydrocarbon groups include those similar to those listed for R23.

On the other hand, in the case of resin [A2], the above polar group is contained in the polymer component in the monofunctional macromonomer (M2). The copolymerization component containing a polar group in the resin [A2] can be copolymerized, for example, with a monomer corresponding to a repeating unit represented by general formula (I) [including general formulas (Ia) and (Ib)]. Any vinyl compound containing the polar group may be used, and is described in, for example, "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science and Technology, Baifukan (1986). in particular,
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 body, α-tributylsilyl body, α-cyano body, 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 (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, vinylbenzenecarboxylic acid,
Half ester derivatives of vinyl or allyl groups of vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids, and ester derivatives and amide derivatives of these carboxylic acids or sulfonic acids, compounds containing said polar group in the substituent group etc.

Examples of copolymerizable components containing polar groups are shown below. Here, b1 represents H or CH3, and b2
represents H, CH3 or CHCOOCH3, R7
represents an alkyl group having 1 to 4 carbon atoms, R8 represents an alkyl group having 1 to 6 carbon atoms, a benzyl group, or a phenyl group, f represents an integer of 1 to 3, and g represents an integer of 2 to 11. , h represents an integer of 1 to 11, i represents an integer of 2 to 4, and j represents an integer of 2 to 10.

[0061]

[Chemical formula 15]

[0062]

[Chemical formula 16]

[0063]

[Chemical formula 17]

[0064]

[Chemical formula 18]

[0065]

[Chemical formula 19]

[0066]

[C20]

[0067]

[C21]

[0068]

[C22]

[0069]

[C23]

[0070]

[C24]

[0071]

[C25]

[0072]

embedded image In the present invention, the resin [A2] containing a polar group in the macromonomer may further have at least one of the above polar groups bonded to the terminal of the polymer main chain ( Such resin is sometimes referred to as resin [A12])
.

In the resin [A12], the polar group contained as a copolymerization component in the macromonomer and the polar group bonded to one end of the polymer main chain may be the same or different, and their abundance ratio varies depending on the type and amount of other binder resins, spectral sensitizing dyes, chemical sensitizers, or other additives constituting the photoconductive layer of the present invention, and it is preferable to adjust the ratio arbitrarily. What is important is that the total amount of both polar groups is used within the range of 0.5 to 15% by weight.

Furthermore, a monofunctional macromonomer (M
) will be explained in detail. Monofunctional macromonomer (M1
) is a polymerizable double bond group represented by general formula (II),
A weight average compound formed by bonding only to one end of a polymer main chain containing at least one of the polymer components represented by the above general formula (I) [including general formulas (Ia) and (Ib)] The macromonomer (M2) has a molecular weight of 2 x 104 or less, and the macromonomer (M2) is a polymer component that is a repeating unit of the macromonomer (M1) and further contains a specific polar group as described above. It contains at least one of the following.

[0075]

[In formula (II), G1 is -COO-, -OCO-, -
CH2 OCO-, -CH2 COO-, -O-, -S
O2-, -CO-, -CONR11-, -SO2N
R11- (here R11 represents a hydrogen atom or a hydrocarbon group), -CONHCOO-, -CONHCONH- or -C6H4-.

b1 and b2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group,
-C via hydrocarbon group, -COOR12 or hydrocarbon
OOR12 (here, R12 represents an optionally substituted hydrocarbon group). ] If the weight average molecular weight of the macromonomer (M) exceeds 2×10 4 , copolymerizability with the monomer corresponding to formula (I) decreases, which is not preferable. On the other hand, if the weight average molecular weight is too small, the effect of improving the electrophotographic properties of the photosensitive layer will be reduced, so it is preferably 1×10 3 or more.

The polymer components constituting the repeating unit of the monofunctional macromonomer (M) having the polymerizable double bond group bonded to one end thereof include general formulas (I), (Ia) and/or
or (Ib), and its content is 30% by weight or more, preferably 50% by weight or more in the macromonomer.

These general formulas (I), (Ia) and (I
The specific description of the polymer component represented by b) is as described above as a copolymerization component that can be copolymerized with the macromonomer, and specific examples thereof include the same ones as above. In the resin [A], the component of formula (I) contained as a copolymer component of the resin [A] and the macromonomer (M)
The component of formula (I) contained as a polymerization component therein may be the same or different.

Furthermore, the macromonomer (M) may contain other polymer components other than those mentioned above. For example, as monomers corresponding to other polymerizable repeating units, acrylonitrile, methacrylate, etc. lonitrile, acrylamides, methacrylamides, styrene and its derivatives (e.g. vinyltoluene, chlorostyrene, bromostyrene, hydroxymethylstyrene, N,N-dimethylaminomethylstyrene, etc.), heterocyclic vinyls (e.g. vinylpyridine, vinyl imidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.).

[0080] When these other monomers are contained,
1 to 30% by weight of the macromonomer (M) in the total polymer components
It is preferable that In addition, macromonomer (M2
) The specific polar group-containing component further contained in the macromonomer is preferably 1 to 50% by weight, more preferably 3 to 30% by weight.

On the other hand, in the general formula (II), the specific content of the hydrocarbon group is the same as that described for R3 in the general formula (I). G1 is -C6
When representing H4-, the benzene ring may have a substituent. Examples of substituents include halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, propioxy group, butoxy group, etc.).

b1 and b2 may be the same or different, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom), a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group). , propyl group,
(butyl group, etc.), -COOR12 or - via hydrocarbon
COOR12 (R12 preferably represents an alkyl group, alkenyl group, aralkyl group, alicyclic group, or aryl group having 1 to 18 carbon atoms, and these may be substituted, specifically as explained in R3 above. Something similar to this can be mentioned.

The hydrocarbon group in the -COOR12 group via the hydrocarbon mentioned above includes a methylene group, an ethylene group,
Examples include propylene group. More preferably, in general formula (II), G1 is -COO-, -OCO-,
-CH2 OCO-, -CH2 COO-, -O-, -
CONH-, -SO2 NH- or -C6 H4 -, b1 and b2 may be the same or different, and each represents a hydrogen atom, a methyl group, -COOR12 or -CH2 COOR12 [R12 is more preferably a carbon number of 1 to 6 alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.)]. More preferably, one of b1 and b2 represents a hydrogen atom.

The macromonomer used in the present invention includes repeating units represented by general formulas (I), (Ia) and/or (Ib) as described above, and in the case of the macromonomer (M2), more specific repeating units. A polymerizable double bond group represented by the general formula (II) is bonded directly to only one end of a random polymer main chain consisting of at least repeating units containing a polar group, or is bonded by an arbitrary linking group. It has a chemical structure.

The linking group connecting the formula (II) component and the polymer component moiety is a carbon-carbon bond (single bond or double bond), a carbon-heteroatom bond, and a heteroatom-heteroatom bond (in the above, heteroatom For example, it is composed of any combination of atomic groups such as oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.

More specific linking groups include the resin [
A1] The same linking groups as those described in [A1] for linking the polymer main chain and the polar group can be mentioned, and these linking groups may be used alone or in combination of two or more linking groups.

The macromonomer (M) used in the present invention can be produced by a conventionally known synthesis method. Specifically, radical polymerization is performed using a polymerization initiator and/or chain transfer agent containing a reactive group such as a carboxyl group, a carboxyhalide group, a hydroxyl group, an amino group, a halogen atom, or an epoxy group in the molecule. It is synthesized by a method such as a radical polymerization method by reacting the obtained oligomer with terminal reactive group bonding with various reagents to form a macromer.

Specifically, P. Dreyfuss a
nd R. P. Quirk, Encycle. Poly
m. Sci. Eng. , 7, 551 (1987), P.
F. Rempp, E. Franta, Adu. Poly
m. Sci, 58, 1 (1984), Yuji Kawakami, Chemical Industry, 38, 56 (1987), Yuya Yamashita, Polymer, 31
, 988 (1982), Shiro Kobayashi, Polymers, 30, Koichi Ito, Polymer Processing, 35, 262 (1986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987, No. It can be synthesized according to the methods described in reviews such as No. 10, No. 5, and the literature and patents cited therein.

However, the macromonomer (M2) of the present invention
contains the above-mentioned polar group as a component of its repeating unit, so it is synthesized with the following considerations in mind, for example. As one method, for example, as shown in reaction formula (A), a monomer containing the polar group in the form of a protected functional group is used to carry out radical polymerization and terminal reactive group formation by the above method. This is to be introduced.

[0090]

embedded image The protection reaction and deprotection reaction (for example, hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, etc.) of the polar groups randomly contained in the macromonomer (M2) of the present invention are known in the art. This can be done by the following method. Specifically, J. F. W. McOmie, “Protective
e Groups in OrganicChe
mistry” Plenum Press (1973
), T. W. Greene, “Protective
Groups in Organic Syn
John Wiley and
Sous (1981), Ryohei Oda "Polymer Fine Chemicals" Kodansha (1976), Yoshio Iwakura and Keisuke Kurita "Reactive Polymers" Kodansha (1977), G. Berner
etal, J. Radiation Curing
, 1986, No. 10, p10, JP-A-62-212
No. 669, No. 62-286064, No. 62-2104
No. 75, No. 62-195684, No. 62-25847
No. 6, No. 63-260439, patent application No. 62-2205
It can be synthesized using the method described in No. 20, No. 62-226692, and the like.

As another method, for example, the reaction formula (
As shown in B), after synthesizing the oligomer as described above, it is possible to synthesize the oligomer by utilizing the difference in reactivity between the specific reactive group bonded to one end of the oligomer and the polar group contained in the oligomer. , is a method of synthesis by reacting with a reagent containing a polymerizable double bond group that reacts only with a specific reactive group.

[0092]

embedded image As shown in reaction formula (B), specific examples of combinations of specific functional groups are shown in Table 1 below. However, the present invention is not limited thereto, and the important thing is that macromonomerization can be achieved without protecting the polar groups in the oligomer by utilizing the reaction selectivity in ordinary organic chemical reactions. It would be good if it were done.

[0093]

[Table 1] Chain transfer agents that can be used include, for example, mercapto compounds containing the polar group or a substituent that can later be induced into the polar group (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid). , 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-
Mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl) ) Alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-
Mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3
-pyridinol, etc.) or disulfide compounds which are oxidized products of these mercapto compounds, or iodized alkyl compounds containing the above polar groups or substituents (e.g. iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanol, etc.)
-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred is a mercapto compound.

Specific reactive group-containing polymerization initiators that can be used include, for example, 2,2'-azobis(2
-cyanopropanol), 2,2'-azobis(2-cyanopentanol), 4,4'-azobis(4-cyanovaleric acid), 4,4'-azobis(4-cyanovaleric acid chloride), 2, 2'-azobis[2-(5-methyl-2
-imidazolin-2-yl)propane], 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane], 2,2'-azobis{2-
[1-(2-hydroxyethyl)-2-imidazoline-
2-yl]propane}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]
or derivatives thereof.

The amount of these chain transfer agents or polymerization initiators is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomers.

The macromonomer (M) of the present invention can be specifically exemplified by the following compounds. however,
The macromonomer (M1) may be similar to the following specific example as one that does not contain a polar group-containing component.

Furthermore, in each of the following examples, e1 is -H
or -CH3, e2, e3 or e4 each represent -H, -CH3 or -CH2COOCH3, R10 is -Ck H2k+1 (k represents an integer from 1 to 18), -CH2 C6 H5, -C6 H4 (E
1) (E2), (E1 and E2 are -H and -Cl, respectively)
, -Br, -CH3 or -COOCH3),
-C10H7 or -CH2 -C10H7,
F1 represents -CN, -OCOCH3, -CONH2 or -C6H5, and F2 represents -Cl, -Br, -
CN or -OCH3, l represents an integer of 2 to 18, m represents an integer of 2 to 12, and n represents an integer of 2 to 4.

[0098]

[C30]

0099

[Chemical formula 31]

[0100]

[C32]

[0101]

[Chemical formula 33]

[0102]

[C34]

[0103]

[Chemical Formula 35] In addition, the resin [A] of the present invention contains monomers corresponding to the general formula (I) and the macromonomer (M) described above, as well as monomers other than these as further copolymerization components. You can.

Examples of such other copolymerization components include, for example, methacrylic esters, acrylic esters, and crotonic esters containing substituents other than those described in general formula (I), as well as α-olefins. esters, vinyl carboxylates or allyl esters (for example, carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalene carboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic esters (
(e.g. dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (e.g. styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N,N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinyl naphthalene, etc.), vinyl sulfone-containing compounds, vinyl ketone-containing compounds, heterocyclic vinyls (
For example, vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline,
vinyltetrazole, vinyloxazine, etc.). However, it is preferable that the amount of these other monomers does not exceed 20% by weight in the copolymer of resin [A].

[0105] In the resin [A] used in the present invention, the resin [A1
] or resin [A12], at least the polar group or a specific reactive group that can be derived therefrom during the polymerization reaction of the macromonomer (M) described above and the monomer corresponding to general formula (I). This can be achieved by using a polymerization initiator or a chain transfer agent containing in the molecule.

Specifically, it can be obtained in the same manner as the method for oligomers with reactive bonding at one end as described above in the synthesis of macromonomers. Next, the resin [B] of the present invention will be explained.

The resin [B] is an AB block copolymer, and the amount of the specific polar group-containing component in the block copolymer [B] is preferably 0.
It is contained in a proportion of 1 to 5% by weight, more preferably 0.2 to 3% by weight.

[0108] The polar group content in the binder resin [B] is 0
．． If it is less than 1% by weight, the initial potential will be low and sufficient image density cannot be obtained, and if the polar group content is more than 5% by weight, dispersibility will decrease and film smoothness and electrophotographic properties will deteriorate. This is undesirable because the characteristics of high temperature and high humidity are reduced, and when used as an offset master, background smudge increases.

In addition, in the resin [B], the total amount of the specific polar group-containing polymer component contained in the entire copolymer is 10 to 10% of the total amount of the specific polar group-containing polymer component contained in the resin [A]. Preferably it is 50% by weight.

[0110] If the total amount in resin [B] is less than 10% by weight of that in resin [A], the electrophotographic properties (particularly charge retention in the dark and photosensitivity) will be significantly reduced, and the strength of the film will also be reduced. . Moreover, if it exceeds 50% by weight, uniformity of dispersion becomes insufficient, electrophotographic properties deteriorate, and water retention as an offset original plate deteriorates.

[0111] The weight average molecular weight of copolymer [B] is 2×1
04 to 1×106, preferably 3×104 to 5×
It is 105. When the molecular weight of the resin [B] is smaller than 2 x 104, the film forming ability is reduced and sufficient film strength cannot be maintained, and when the molecular weight is larger than 1 x 106, the effect of the resin [B] of the present invention is reduced. However, the electronic properties are comparable to those of conventionally known resins.

[0112] The glass transition point of the resin [B] is -10°C
The temperature range is preferably 100°C to 100°C, more preferably 0°C to 90°C. AB block copolymer of the present invention (
As a specific example of the polymerization component containing a specific polar group constituting the A block of resin [B]), the above-mentioned resin [A]
The same polymer components as those containing specific polar groups can be mentioned.

[0113] Two or more kinds of polymer components containing specific polar groups as described above may be contained in the A block, and in this case, the two or more kinds of polar group-containing components are the same as the A block.
It may be contained in the block in either random copolymerization or block copolymerization.

[0114] Further, the block A may contain a polymer component other than the above polar group-containing polymer component, and such polymer component is preferably represented by the following general formula (III).
A polymer component corresponding to the repeating unit of is mentioned.

[0115]

embedded image [In formula (III), X1 is -COO-, -OCO-,
-(CH2)p-OCO-, -(CH2)p-
COO- (p represents an integer of 1 to 3), -O-, -S
O2 -, -CO-, -CON-Q2 -, -SO2
N-Q2-, -CONHCOO-, -CONHCON
It represents H- or -C6H4- (where Q2 represents a hydrogen atom or a hydrocarbon group).

Q1 represents a hydrocarbon group. m1 and m2 may be the same or different from each other, and m1 and m2 may be the same or different from each other, and
) respectively represent the same content as a1 and a2. ] Here, in addition to a hydrogen atom, Q2 is preferably a hydrocarbon group such as an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group). 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.), carbon number 4-18
An optionally substituted alkenyl group (e.g., 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group) group, 2-hexenyl group, 4-methyl-
2-hexenyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromo benzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexylethyl group) base, 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 group, ethoxycarboxyphenyl group, butoxycarbonylphenyl group, acetamidophenyl group,
propioamidophenyl group, dodecoylamidophenyl group, etc.).

[0117] When X1 represents -C6H4-,
The benzene ring may have a substituent. As substituents,
Halogen atoms (e.g. chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, propioxy group) , butoxy group, etc.).

Q1 represents a hydrocarbon group, and preferred hydrocarbon groups include optionally substituted alkyl groups having 1 to 22 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group,
Decyl group, dodecyl group, tridecyl group, tetradecyl 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 (e.g., 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group), group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group) , 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), carbon number 5
~8 optionally substituted alicyclic groups (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), optionally substituted aromatic groups 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, dodecoylamidophenyl group, etc.).

More preferably, in general formula (III), X1 is -COO-, -OCO-, -CH2OC
O-, -CH2 COO-, -O-, -CONH-, -
Represents SO2 NH- or -C6 H4 -.

Furthermore, as a polymer component that can be contained in the A block together with the polymer component represented by formula (III), a polymer component corresponding to another repeating unit that can be copolymerized with the polymer component of formula (III) is also added. monomers such as acrylonitrile, methacrylonitrile, heterocyclic vinyls (such as vinylpyridine, vinylimidazole, vinylpyrrolidone,
vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.). These other monomers are contained in an amount of 20 parts by weight in 100 parts by weight of the total polymer components of the A block.
It is used within a range not exceeding parts by weight.

Next, in the AB block copolymer [B], the polymerization components constituting the B block component will be explained in detail. The B block component has at least the general formula (I
), and the component represented by formula (I) preferably accounts for 30 to 100% by weight, more preferably 50 to 10% by weight of the B block component.
Contains 0% by weight.

The specific contents of the components of general formula (I) are the same as those explained for resin [A]. Other polymer components that may be contained include the same components as those described as the component represented by general formula (III) or other components that may be contained in block A. However, block B is characterized in that it does not contain the specific polar group-containing component contained in block A.

The AB block copolymer [B] of the present invention is:
It can be produced by a conventionally known polymerization reaction method. Specifically, in the monomer corresponding to the polymer component containing the specific polar group, the polar group is previously protected as a functional group, and an organometallic compound (for example, alkyl lithiums, lithium diisopropylamide, alkyl magnesium After synthesizing an AB block copolymer using a known so-called living polymerization reaction such as an ionic polymerization reaction using a hydrogen iodide/iodine system (halides, etc.), a photopolymerization reaction using a porphyrin metal complex as a catalyst, or a group transfer polymerization reaction. , a method of forming a polar group by deprotecting a functional group with a protected polar group by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photolysis reaction, etc. can be mentioned. One example is shown in reaction scheme (1) below.

[0124]

embedded image These include, for example, P. Lutz, P. Masson
etal, Polym. Bull. 12. ,79(1
984), B. C. Anderson, G. D. And
rews etal, Macromolecules
, 14, 1601 (1981), K. Hatada, K.
．． Ute. etal, Polym. J. 17,977(
1985), 18, 1037 (1986), Koichi Migitari,
Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, 46, 189 (19
89), M. Kuroki, T. Aida, J. Am.
Chem. Soc. 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (19
85), D. Y. Sogah, W. R. Hertler
etal. Macromolecules, 20, 14
73 (1987) and others.

Furthermore, the AB block copolymer [B] uses a monomer with its polar group unprotected and uses a compound containing a dithiocarbament group and/or a compound containing a xanthate group as an initiator. It can also be synthesized by performing a polymerization reaction under light irradiation. For example, Takayuki Otsu, Kobunshi, 37, 248 (1988), Shunichi Himori, Ryuichi Otsu, P.
olym. Rep. Jap. 37.3508 (1988
), JP-A-64-111, JP-A-64-26619, Higashi Nobuyuki et al., Polymer Preprints,
Japan, 36, (6), 1511 (1987), M
．． Niwa, N. Higashi, etal, J. Ma
cromol. Sci. Chem. A24(5), 56
7 (1987) and others.

[0126] Regarding the protection of a specific polar group of the present invention with a protecting group and the removal of the protecting group (deprotection reaction),
This can be easily done using conventionally known knowledge. For example, there are various descriptions in the cited documents, and furthermore,
Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" Kodansha Co., Ltd. (1977), T. W. Greene, “Prote
Active Groups in Organi
John Wiley
& Sons (1981), J. F. W. Mc
Omie, “Protective Groups
in Organic Chemistry”Ple
num Press, (1973) and the like can be suitably selected.

Furthermore, block A is equivalent to synthesizing an azobis compound containing any part of block B (that is, a polymeric azobis initiator) and using this as an initiator to form the other block. A method of synthesizing monomers by radical polymerization reaction can also be used.

[0128] Specifically, it can be synthesized by the method described in Akira Ueda, Susumu Nagai, Collection of Kobunshi Ronsen, 44, 469 (1987), Akira Ueda, Osaka City Industrial Research Institute Report, 84 (1989), etc. Can be done.

When synthesizing using this reaction, the weight average molecular weight of the polymeric azobis initiator is 2 104 or less is preferable. On the other hand, the resin of the present invention [
B], it is preferable that block B has a longer polymer chain than block A.

From the above, when synthesized by this reaction,
A method using a block A-containing polymeric initiator is preferred. For example, the reaction can be carried out using the reaction scheme (2) shown below.

[0131]

[Chemical Formula 38] As the binder resin provided for the photoconductive layer of the present invention, in addition to the resin [A] and resin [B] of the present invention, the above-mentioned known resins for inorganic photoconductors can also be used in combination. . However, the proportion of these other resins used is 3 out of 100 parts by weight of the total binder resin.
Preferably, it does not exceed 0% by weight. If this ratio is exceeded, the effect of the present invention will be significantly reduced.

Typical examples of other resins that can be used in combination include vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, and acrylate copolymer. , vinyl acetate copolymer, polyvinyl butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin, polyester resin, etc.

Specifically, Ryuji Shibata and Jiro Ishiwata, "Polymer" Vol. 17, p. 278 (1968), Harumi Miyamoto and Hidehiko Takei, "Imaging", 1973 (No. 8), p. 9,
Edited by Koichi Nakamura "Practical technology of binders for insulating materials" No. 10
Chapter, C. H. C. Publishing (1985), D. D. Ta
tt, S. C. Heidecker, Tappi, 49
(No. 10), 439 (1966), E. S. Bal
tazzi, R. G. Blanclotte eta
l, Photo. Sci. Eng. 16 (No. 5),
354 (1972), Nguyen Tranh Khe, Shimizu
Isamu, Eiichi Inoue, Journal of the Electrophotography Society 18 (No. 2), 28
(1980), JP-B No. 50-31011, JP-A-53
-54027, 54-20735, 57-20
Examples include resins disclosed in Publications No. 2544 and No. 58-68046.

The total amount of binder resin used in the photoconductive layer of the present invention is 1 part by weight based on 100 parts by weight of the inorganic photoconductor.
It is preferably 0 parts by weight to 100 parts by weight, more preferably 15 parts by weight to 50 parts by weight.

[0135] The ratio of resin [A] and resin [B] used in the present invention is 0.05 to 0 in weight ratio of resin [A]/resin [B].
．． The ratio is preferably 8/0.95 to 0.20, more preferably 0.10 to 0.50/0.90 to 0.50.

If the total amount of the binder resin is less than 10 parts by weight, the film strength of the photoconductive layer cannot be maintained. If the amount exceeds 100 parts by weight, the electrostatic properties will deteriorate, resulting in deterioration of copied images in actual imaging performance.

[0137] Furthermore, in the ratio of resin [A] and resin [B] used in the present invention, if the weight ratio of resin [A] is less than 0.05, the effect of improving electrostatic properties will be diminished. On the other hand, 0.8
If this is the case, the film strength of the photoconductive layer may not be maintained sufficiently (especially as an original plate for electrophotographic lithographic printing).

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

Spectral sensitizing dyes used in the present invention include:
Various dyes may be used alone or in combination as necessary. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (N
o. 8) Page 12, C. J. Young et al., R.C.A.
Review 15, 469 (1054), Wataru Kiyota, Transactions of the Institute of Electrical Communication Engineers J63-C (No. 2),
97 (1980), Yuji Harasaki et al., Industrial Science Magazine 6678
and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35
Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, cited in reviews such as , 208 (1972), etc.
Examples include xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain metals), and the like.

More specifically, as for those mainly using carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes, Japanese Patent Publication No. 51-45
No. 2, JP-A-50-90334, JP-A No. 50-11422
No. 7, No. 53-39130, No. 53-82353,
U.S. Patent Nos. 3,052,540 and 4,054,45
Examples include those described in No. 0, JP-A-57-16456, and the like.

Polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes include F. M. Hammer “The Cya”
nine Dyes and Related C
It is possible to use the pigments described in ".
More specifically, U.S. Pat. No. 3,047,384, U.S. Pat.
, No. 125,447, No. 3,128,179, No. 3,
132,942, British Patent No. 3,622,317, British Patent No. 1,226,892, British Patent No. 1,309,274, British Patent No. 1,405,898, Japanese Patent Publication No. 48-7814, British Patent No. 5
Examples include dyes described in No. 5-18892 and the like.

Furthermore, as a polymethine dye that spectrally sensitizes in the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A No. 4
No. 7-840, No. 47-44180, Special Publication No. 51-4
No. 1061, JP-A-49-5034, JP-A No. 49-451
No. 22, No. 57-46245, No. 56-35141, No. 57-157254, No. 61-26044, No. 61-27551, U.S. Patent No. 3,619,154, No. 4,175,956 , “Research D.
isclosure” 1982, 216, No. 117~
Examples include those described on page 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,
Review mentioned above: Imaging 1973 (No. 8) No. 1
Electron-accepting compounds (e.g., halogens, benzoquinones, chloranil, acid anhydrides, organic carboxylic acids, etc.) cited in reviews such as page 2, Hiroshi Komon et al., “Development and practical application of bacterial photoconductive materials and photoreceptors,” Vol. Examples include polyarylalkane compounds, hindered phenol compounds, and p-phenylenediamine compounds cited in Chapters 4 to 6 of the review published by Nihon Kagaku Information Co., Ltd. (1986).

The amount of these various additives added is not particularly limited, but is usually 0.0 parts by weight per 100 parts by weight of the photoconductor.
001 to 2.0 parts by weight. The thickness of the photoconductive layer is 1 to 1
00μ, especially 10 to 50μ is suitable.

When a photoconductive layer is used as the charge generation layer of a photoreceptor with a stacked charge generation layer and charge transport layer, the thickness of the charge generation layer is 0.01 to 1μ, particularly 0.05 to 0.0μ. 5
μ is preferred.

[0145] In some cases, an insulating layer is added mainly for the purpose of protecting the photoreceptor, improving durability, dark decay characteristics, etc. 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 5 to 70 μm.
In particular, it is set to 10 to 50μ. 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
μ, particularly 10 to 30 μ is suitable.

Typical resins used for forming the insulating layer or charge transport layer include polystyrene resin, polyester resin, cellulose resin, polyether resin,
Thermoplastic resins and effective resins such as vinyl chloride resin, vinyl acetate resin, vinyl chloride acid vinyl copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, epoxy resin, melamine resin, and silicone resin are used as appropriate. .

The photoconductive layer according to the present 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, metal, paper, plastic sheet, etc. are basically impregnated with a low-resistance substance, just as in the conventional case. Those that have been subjected to conductive treatment such as by applying a conductive coating, those that have been coated with at least one layer for the purpose of imparting conductivity to the back side of the base (the opposite side to the side on which the photosensitive layer is provided) and preventing curling, etc.
One in which a water-resistant adhesive layer is provided on the surface of the support, one in which at least one or more pre-coated layer is provided on the surface layer of the support as required, and one in which the conductive plastic substrate is vapor-deposited with Al, etc. You can use a laminated one.

[0149] Specifically, as an example of a conductive substrate or a conductive material, see Yukio Sakamoto, Electrophotography, 14 (No. 1).
, P2-11 (1975), Hiroyuki Moriga, "Introductory Chemistry of Special Papers" Kobunshi Publishing (1975), M. F. Hoove
r, J. Macromol. Sci. Chem. A-4
(6), pages 1327 to 1417 (1970), etc. are used.

The electrophotographic photoreceptor of the present invention can be used in applications using all conventionally known electrophotographic processes. That is, the photoreceptor of the present invention can be used for both the PPC method and the CPC method, and
As the developer, any combination of a dry developer or a liquid developer can be used.

In particular, since it is possible to form a high-definition faithful copy image of the original, the effects of the present invention are more effectively achieved when used in combination with a liquid developer. In addition, by combining it with a color developer, it is possible to produce not only black and white copies, but also
It can also be applied to color copies (for example, Kuro Takizawa, "Photography Industry" 33, 34 (1975), Masayasu Anzai, "IEICE Technical Research Report 77, 17 (1975),
7 years) etc.).

[0152] Furthermore, it is also effective in systems for other uses using recent electrophotographic processes. For example, the photoreceptor of the present invention using photoconductive zinc oxide as a photoconductor can be used as an original plate for offset lithographic printing, and can also be used as a photoconductive zinc oxide or photoconductive titanium oxide, which is non-polluting and has good whiteness. The photoreceptor can be used as a marking material for a printing plate or a color proof used in an offset printing process.

[0153]

[Synthesis of macromonomer (M)]

Macromonomer Synthesis Example 1: (MM-1) A mixed solution of 75 g of methyl methacrylate, 25 g of methyl acrylate, 5 g of thioglycolic acid, and 200 g of toluene was heated to 75° C. with stirring under a nitrogen stream. 2,2'
-Azobisisobutyronitrile (abbreviated as A.I.B.N.
) 1.0 g was added and reacted for 8 hours. Next, this reaction solution was added with 8 g of glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine, and 0 g of t-butylhydroquinone.
．． 5 g was added and stirred at a temperature of 100°C for 12 hours. After cooling, this reaction solution was reprecipitated into 2 liters of n-hexane to obtain 82 g of white powder. Weight average molecular weight of the polymer (M
w) was 3.8×103.

[0154]

embedded image Synthesis Example 2 of Macromonomer (MM-2) A mixed solution of 90 g of butyl methacrylate, 10 g of methacrylic acid, 4 g of 2-mercaptoethanol, and 200 g of tetrahydrofuran was heated to 70° C. under a nitrogen stream. A. I. B. N. 1.2 g was added and reacted for 8 hours.

Next, the reaction solution was cooled in a water bath to a temperature of 20
℃, 10.2 g of triethylamine was added, and 14.5 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, 0.5g of t-butylhydroquinone was added and the temperature was 60°C.
and stirred for 4 hours. After cooling, the mixture was added dropwise to 1 liter of water while stirring (about 10 minutes), stirred for 1 hour and allowed to stand, and then the water was removed by decantation. After two more washes with water, 10 ml of tetrahydrofuran
0 ml and reprecipitated into 2 liters of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure. The yield of the obtained viscous material was 65 g, Mw 3.3 x 10
It was 3.

[0156]

embedded image Synthesis Example 3 of Macromonomer: (MM-3) A mixture of 95 g of benzyl methacrylate, 5 g of 2-phosphonoethyl methacrylate, 6 g of 2-aminoethyl mercaptan, and 200 g of tetrahydrofuran was heated at a temperature of 70° C. with stirring under a nitrogen stream. It was heated to

A. I. B. N. 1.5g was added and reacted for 4 hours, and then A. I. B. N. 0.5 g was added and reacted for 4 hours. Next, this reaction solution was cooled to a temperature of 20°C, 10g of acrylic anhydride was added, and the temperature was 20-25°C.
The mixture was stirred for 1 hour. Next, t-butylhydroquinone 1.
0 g was added and stirred at a temperature of 50 to 60°C for 4 hours. After cooling, the reaction mixture was added dropwise to 1 liter of water while stirring over about 10 minutes, and after stirring for 1 hour, the mixture was allowed to stand, and the water was removed by decantation. After repeating the washing with water two more times, it was dissolved in 100 ml of tetrahydrofuran and reprecipitated in 2 liters of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure. The yield of the viscous material obtained was 70 g, and the Mw was 6 x 103.

[0158]

Synthesis Example 4 of Macromonomer: (MM-4) A mixed solution of 90 g of 2-chlorophenyl methacrylate, 10 g of the monomer having the following structure (I), 4 g of thioglycolic acid, and 200 g of toluene was heated at 70°C under a nitrogen atmosphere. Warmed to ℃. A. I
．． B. N. 1.5g was added and reacted for 5 hours, and then A.
I. B. N. 0.5 g was added and reacted for 4 hours. Next, 12.4 g of glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine, and 1.5 g of t-butylhydroquinone were added and reacted at a temperature of 110° C. for 8 hours. After cooling, the reaction mixture was mixed with 3 g of p-toluenesulfonic acid, 90
The solution was added to 100 ml of vol% tetrahydrofuran aqueous solution and stirred at a temperature of 30 to 35°C for 1 hour. The above mixture was reprecipitated into 2 liters of a water/ethanol [(1/3) volume] mixed solution, and the precipitate was collected by decantation. This precipitate was mixed with 200 g of tetrahydrofuran.
ml and reprecipitated in 2 liters of n-hexane to obtain 58 g of powder. Mw was 7.6×103.

[0159]

[C42]

[0160]

embedded image Macromonomer synthesis example 5: (MM-5) 95 g of 2,6-dichlorophenyl methacrylate, 5 g of 3-(2'-nitrobenzyloxysulfonyl)propyl methacrylate, 150 g of toluene, and 5 g of isopropyl alcohol.
0 g of the mixed solution was heated to a temperature of 80° C. under a nitrogen stream. 2,2'-azobis(2-cyanovaleric acid) (abbreviation: A.
C. V. ) was added and reacted for 5 hours, and further A. C.
V. 1.0 g was added and reacted for 4 hours. After cooling, the reaction product was reprecipitated into 2 liters of methanol, and the powder was collected by filtration and dried under reduced pressure. A mixture of 50 g of the above powder, 14 g of glycidyl methacrylate, 0.6 g of N,N-dimethyldecylamine, 1.0 g of t-butylhydroquinone, and 100 g of toluene was stirred at a temperature of 110° C. for 10 hours. After cooling to room temperature, the mixture was irradiated with light for 1 hour under stirring using an 80 W high-pressure mercury lamp. Thereafter, the reaction mixture was reprecipitated into 1 liter of methanol, and the powder was collected by filtration and dried under reduced pressure. The yield was 34 g and the Mw was 7.3 x 103.

[0161]

Synthesis Example 6 of Macromonomer: (MM-6) A mixed solution of 80 g of ethyl methacrylate, 5 g of N-vinylpyrrolidone, 29 g of trimethylsilyl methacrylate, 3 g of β-mercaptoethanol, and 200 g of tetrahydrofuran was heated while stirring under a nitrogen stream. It was heated to 70°C. A. I. B. N. 1 g was added and reacted for 4 hours, and then A. I. B. N. 0.5 g was added and reacted for 4 hours. After cooling the reaction mixture and setting the temperature to 25°C, 6.6 g of methacrylic acid was added, and to this was added 8 g of dicarboxylcarbondiimide (D.C.C.) and 4-(N,N-dimethylamino)pyridine. 0.2g and methylene chloride 20
A mixed solution of g was added dropwise at a temperature of 25 to 30°C, and the mixture was further stirred for 4 hours. Next, 10 g of formic acid was added to this reaction mixture and stirred for 1 hour. After filtering out the precipitated insoluble matter, the filtrate was reprecipitated into 1 liter of methanol, and the oily matter was collected by filtration. Furthermore, this oily substance was dissolved in 200 g of tetrahydrofuran, and after filtering off insoluble matter, it was reprecipitated again in 1 liter of methanol, and the oily substance was collected and dried. Yield 65g, Mw 7x
It was 103.

[0162]

[Synthesis of resin [A]] Synthesis example 1 of resin [A]: [A-1] 70 g of benzyl methacrylate, macromonomer (MM
-1) A mixed solution of 30 g of toluene, 150 g of toluene, and 50 g of isopropanol was heated to a temperature of 80° C. under a nitrogen stream. To this A. C. V. 5g was added and reacted for 4 hours, and then A. C. V. 0.5 g was added and reacted for 4 hours. The weight average molecular weight (Mw) of the obtained copolymer was 1.0×
It was 104.

[0163]

[Chemical formula 46] Synthesis example 2 of resin [A]: [A-2] 80 g of 2-chlorophenyl methacrylate, 20 g of a macromonomer (Mw 5 x 103) corresponding to the following structure,
β-mercaptopropionic acid 3g and toluene 200g
The mixed solution was heated to a temperature of 75° C. under a nitrogen stream. In addition to this, A. I. B. N. 1.5 g was added and reacted for 4 hours, and further 0.5 g was added and reacted for 4 hours. The Mw of the obtained copolymer was 8.8 x 103.

[0164]

[Chemical Formula 47] Synthesis Examples 3 to 9 of Resin [A]: [A-3] to [A-9] In the Synthesis Examples of Resin [A], instead of 80 g of 2-chloromethacrylate and 20 g of macromonomer, the following table was used. -A
Each copolymer was produced in the same manner as in Synthesis Example 2 of Resin [A] except that the corresponding monomers and macromonomers were replaced. The Mw of each polymer was in the range of 7.5 x 103 to 9 x 103.

[0165] The Mw of each macromonomer used was 3.
It was in the range of 5×10 3 to 5×10 3 .

[0166]

[Table 2]

[0167]

[Table 3] Synthesis Example 10 of Resin [A]: [A-10] A mixed solution of 70 g of benzyl methacrylate, 30 g of macromonomer (MM-4) and 200 g of toluene was heated at a temperature of 80 g under a nitrogen stream.
Warmed to ℃. 2,2'-azobisvaleronitrile (A
．． I. V. N. ) was added and reacted for 3 hours, and then A. I
．． V. N. 1 g was added and reacted for 4 hours.

Mw of the obtained polymer is 8.5×103
Met.

[0169]

Synthesis Example 11 of Resin [A]: [A-11] 60 g of 2-chlorophenyl methacrylate, macromonomer (MM-2
), 5 g of 2-methoxyethyl methacrylate, 3 g of octadecyl methacrylate, and 200 g of toluene were heated to 75° C. under a nitrogen stream. A. I.
B. N. 1.0 g was added and reacted for 3 hours, and then A.
I. B. N. The operation of adding 0.5 g and reacting for 3 hours was repeated twice.

After cooling, the reaction product was reprecipitated in 1 liter of ether, the precipitate was collected and dried, and the Mw was 6.5×10
63g of the viscous material of No. 3 was obtained.

[0171]

[Chemical formula 49] Synthesis examples 12 to 19 of resin [A]: [A-12] to [A-
19] Synthesis Example 11 of Resin [A] except that each monomer and macromonomer were replaced with each monomer and macromonomer corresponding to the polymerization components shown in Table-B below. Each polymer was produced by reacting in the same manner as in No. 11.

Mw of each copolymer is 6×103 to 8×1
It was in the range of 0.03.

[0173]

[Table 4]

[0174]

[Table 5] Synthesis example 20 of resin [A]: [A-20] 70 g of 2-chlorophenyl methacrylate, macromonomer (MM-3
) 30g, thioglycolic acid 3.0g and toluene 15
0 g of the mixed solution was heated to a temperature of 80° C. under a nitrogen stream. A. I. B. N. 1.0g was added and reacted for 4 hours, and then A. I. B. N. Add 0.5g and continue for 2 hours.
I. B. N. 0.3g was added and reacted for 3 hours.

Mw of the obtained copolymer is 8.5×103
Met.

[0176]

[Chemical formula 50] Synthesis examples 21 to 28 of resin [A]: [A-21] to [A-
28] In the same manner as in Synthesis Example 20 of Resin [A], 60 g of monomer and 40 g of macromonomer corresponding to the components shown in Table-C below were added.
A polymerization reaction was carried out using 0.04 mol of a mercapto compound.

[0177] The Mw of the obtained copolymer is 6 x 103 ~
It was 9×103.

[0178]

[Table 6]

[0179]

[Table 7]

[0180]

[Table 8] Synthesis example 29 of resin [A] of the present invention: [A-29] 60 g of 2-chloro-6-methylphenyl methacrylate, 25 g of macromonomer (MM-4), 1 methyl acrylate
A mixed solution of 5g of toluene, 150g of toluene, and 50g of isopropanol was heated to 80°C under a nitrogen stream. A. C. V. 5g was added and reacted for 5 hours, and then A. C.
V. 1.0 g was added and reacted for 4 hours. The Mw of the obtained copolymer was 9.8 x 103.

[0181]

[Synthesis of Resin [B]] Synthesis Example 1 of Resin [B]: [B-1] A mixed solution of 100 g of methyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream, and -2
Cooled to 0°C. 1,1-diphenylbutyllithium 0
．． 8 g was added and reacted for 12 hours. Further, a mixed solution of 60 g of methyl acrylate, 6 g of triphenylmethyl methacrylate, and 5 g of tetrahydrofuran was added to this mixed solution after sufficient degassing under a nitrogen stream, and the mixture was reacted for further 8 hours. After bringing the mixture to 0°C, add 10ml of methanol.
was added and reacted for 30 minutes to stop the polymerization. The resulting polymer solution was brought to a temperature of 30° C. under each condition, and 3 ml of a 30% hydrogen chloride ethanol solution was added thereto and stirred for 1 hour. Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total volume was reduced to half, and then reprecipitated into 1 liter of petroleum ether.

[0182] The precipitate was collected and dried under reduced pressure to obtain a polymer, which had an Mw of 7.3 x 104 and a yield of 73 g.

[0183]

[Chemical formula 52] Synthesis example 2 of resin [B]: [B-2] 70 g of methyl methacrylate, 30 g of methyl acrylate
A mixed solution of 0.5 g of aluminum methyl (tetraphenylporphinate), and 60 g of methylene chloride was brought to a temperature of 30° C. under a nitrogen stream. This was irradiated with 300 W xenon lamp light from a distance of 25 cm through a glass filter, and reacted for 12 hours. In addition to this mixture,
After adding 60 g of methyl acrylate and 3.2 g of benzyl methacrylate and irradiating with light for 8 hours, 3 g of methanol was added to the reaction mixture and stirred for 30 minutes to stop the reaction. Next, Pd-C was added to this reaction mixture, and a catalytic reduction reaction was carried out at a temperature of 25° C. for 1 hour.

After filtering out insoluble matter, 500 m of petroleum ether
The precipitate was collected and dried. The obtained polymer had a yield of 133 g and a Mw of 8 x 104.

[0185]

embedded image Synthesis Example 3 of Resin [B]: [B-3] A mixed solution of 100 g of ethyl methacrylate and 200 g of toluene was sufficiently degassed under a nitrogen stream and cooled to 0°C. Then, 2.5 g of 1,1-diphenyl-3-methylpentyllithium was added and stirred for 6 hours. Further, 60 g of methyl methacrylate and 46 g of 4-vinylphenyloxytrimethylsilane were added to this mixture and stirred for 6 hours.
3 g of methanol was added and stirred for 30 minutes.

Next, 10 g of a 30% hydrogen chloride ethanol solution was added to this reaction mixture, and the mixture was stirred at 25° C. for 1 hour. The precipitate was reprecipitated into 1 liter of methanol and the collected precipitate was washed twice with 300 ml of methanol and dried. . The obtained polymer had a yield of 127 g and a Mw of 6.5 x 104.

[0187]

[Chemical formula 54] Synthesis example 4 of resin [B]: [B-4] A mixture of 67 g of methyl methacrylate and 6.4 g of benzyl N,N-diethyldithiocarbamate was sealed in a container under a nitrogen stream and heated to a temperature of 50°C. Warmed. For this, 40
Light was irradiated for 6 hours using a 0W high-pressure mercury lamp from a distance of 10 cm through a glass filter for photopolymerization.

After adding 32 g of methyl acrylate, 1 g of acrylic acid, and 180 g of methyl ethyl ketone, the mixture was purged with nitrogen and irradiated with light for 10 hours again. The obtained reaction product was reprecipitated in 1.5 liters of methanol, collected and dried. The resulting polymer weighed 70 g and had a Mw of 5.5 x 104.

[0189]

[Chemical formula 55] Synthesis example 5 of resin [B]: [B-5] Methyl methacrylate 50 g, ethyl methacrylate 2
A mixture of 5 g and 1.0 g of benzyl isoprusanthate was sealed in a container under a nitrogen stream and heated to a temperature of 50°C. This was irradiated with light from a 10 cm distance through a glass filter for 6 hours using a 400 W high-pressure mercury lamp for photopolymerization.

[0190] This polymer was diluted with tetrahydrofuran to a concentration of 4.
A 0% solution was made, 22 g of methyl acrylate was added thereto, the atmosphere was replaced with nitrogen, and the mixture was irradiated with light for 10 hours again. Next, 3 g of 2-(2'-carboxyethyl)carbonyloxyethyl methacrylate was added to this mixture, the atmosphere was again purged with nitrogen, and the mixture was again irradiated with light for 8 hours.

The obtained reaction product was reprecipitated in 2 liters of methanol, and the collected powder was dried. The obtained polymer had a yield of 63 g and a Mw of 6 x 104.

[0192]

Synthesis Example 6 of Resin [B]: [B-6] 97 g of ethyl acrylate, 3 g of methacrylic acid, 2 g of 2-mercaptoethanol, and 200 g of tetrahydrofuran.
The mixed solution of g was heated to 60° C. with stirring under a nitrogen stream. To this, 1.0 g of 2,2'-azobisisovaleronitrile (A.I.V.N.) was added and reacted for 4 hours.
Furthermore, A. I. V. N. 0.5 g was added and reacted for 4 hours.

After bringing the reaction mixture to a temperature of 20°C, 4
, 8.6 g of 4'-azobis(cyanovaleric acid), 12 g of dicyclohexyldicarbodiimide, 0.2 g of 4-(N,N-dimethyl)pyridyl, and 30 g of tetrahydrofuran.
A mixed solution of was added dropwise over 1 hour. After further stirring for 2 hours, 5 g of 85% formic acid aqueous solution was added and further stirred for 30 minutes. Next, after separating the precipitated crystals by filtration, the filtrate was collected at a temperature of 25
The solvent was distilled off under reduced pressure at °C. The Mw of the obtained polymer was 6.3 x 103.

[0194]

embedded image A mixed solution of 70 g of methyl methacrylate and 170 g of toluene was heated to 70° C. with stirring under a nitrogen stream. A solution prepared by dissolving 30 g of the above polymer in 30 g of toluene was added to the solution after previously purging with nitrogen, and the mixture was reacted for 8 hours.

The obtained polymer was reprecipitated in 2 liters of methanol, and the collected powder was dried. The yield of the obtained polymer was 72 g, and the Mw was 4 x 104.

[0196]

[Chemical formula 58] Synthesis examples 7 to 16 of resin [B]: [B-7] to [B-16
] Using the same reaction method as in Synthesis Example 3 of Resin [B], the following Table-D
Resin [B] shown below was synthesized. The Mw of each of the obtained polymers was in the range of 5 x 104 to 9 x 104.

[0197]

[Table 9]

[0198]

[Table 10]

[0199]

[Table 11] Synthesis examples 17 to 23 of resin [B]: [B-17] to [B-
23] Using the same reaction method as in Synthesis Example 6 of Resin [B], the following Table-E
Resin [B] shown below was synthesized. Mw of each polymer obtained
was in the range of 4 x 104 to 8 x 104.

[0200]

[Table 12]

[0201]

[Table 13] Example 1 and Comparative Examples 1 and 2 Resin [A-2] 6 g (as solid content), Resin [B-1
] 34g (as solid content), photoconductive zinc oxide 200
g A mixture of 0.018 g of cyanine dye [I] having the following structure, 0.45 g of phthalic anhydride, and 300 g of toluene was heated in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a rotation speed of 6 x 103.
rpm for 10 minutes to prepare a photosensitive layer-forming product, which was coated on electrically conductive treated paper with a wire bar so that the dry adhesion amount was 22 g/m2, and dried at 110°C for 10 seconds. Then, in a dark place at 20°C and 65% RH,
By leaving it for 4 hours, an electrophotographic light-sensitive material was produced.

[0202]

Comparative Example 1: Electrophotography was carried out in the same manner as in Example 1, except that 34 g of resin [R-1] having the following structure was used instead of 34 g of resin [B-1]. A photosensitive material was produced.

[0203]

Comparative Example 2: Example 1 except that 34 g of resin [R-2] having the following structure was used instead of 34 g of resin [B-1].
An electrophotographic material was prepared in the same manner as in Example 1.

[0204]

[Chemical formula 61] These photosensitive materials have electrostatic properties, imaging properties, and environmental conditions (20°C, 65% RH) and (30°C, 80% RH).
H) The imaging performance was investigated.

The above results are shown in Table F.

[0206]

[Table 14] The implementation mode of the evaluation items shown in Table-F is as follows. Note 1) Electrostatic properties: In a dark room at a temperature of 20°C and 65% RH.
-6k using a paper analyzer (Paper Analyzer SP-428 model manufactured by Kawaguchi Electric Co., Ltd.) for each photosensitive material.
After performing corona discharge at V for 20 seconds, it was left to stand for 10 seconds, and the surface potential V10 at this time was measured. Next, the potential V100 was measured after leaving it to stand still in the dark for 90 seconds.
The retention of the potential after dark decay for 0 seconds, that is, the dark decay retention rate [DRR (%)] is (V100 /V10) x 10
It was calculated as 0 (%).

[0207] Furthermore, the surface of the photoconductive layer is heated to -40 by corona discharge.
After charging to 0V, the surface of the photoconductive layer is heated with a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm).
Irradiate with light, find the time until the surface potential (V10) attenuates to 1/10, and calculate the exposure amount E1/10 (erg
/cm2). Also, similar surface potential (V10
) is attenuated to 1/100, and the exposure amount E1/100 (erg/cm2) is calculated from this. The environmental conditions at the time of measurement were 20°C, 65% RH (I), and 3
The test was carried out at 0° C. and 80% RH (II). Note 2) 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-arsenic semiconductor laser (oscillation wavelength 780 nm) with a 2.8 mW output was used as a light source. ) with a pitch of 25 on the surface of the photosensitive material under an irradiation dose of 64 erg/cm2.
After exposure at a scanning speed of 300 m/sec, the liquid developer was developed using ELP-T (manufactured by Fuji Photo Film Co., Ltd.), and the rinse solution of isoparaffin Isopar G (manufactured by Esso Chemical Co., Ltd.) solvent was used. Copied images that were obtained after being washed and fixed (fogging, image quality)
was visually evaluated.

[0208] The environmental conditions during imaging were 20°C, 65% RH (I
) and 30°C and 80% RH (II). As shown in Table F, the photosensitive material of the present invention had good electrostatic properties, and the actual copied images had no background fog and the quality of the copied images was clear. On the other hand, Comparative Examples 1 and 2 have photosensitivity (E1/10 and E1/10).
100), and even in actual copied images, faint fading of thin lines and letters, and background fog remained unremoved even after rinsing.

[0209]Also, although not consistent with the electrostatic characteristics, unevenness occurred in the intermediate density of the continuous tone portion of the copied original. E1/1 between the photoreceptor of the present invention and the photoreceptor of the comparative example
00 Values are significantly different. In actual imaging performance, the E1/100 value indicates how much potential remains in the non-image area (already exposed area) after exposure, and the smaller the value, the more the non-image after development. Indicates that scumming will no longer occur in the area.

[0210] Specifically, it is necessary to make the residual potential below -10V, that is, how much exposure is required to actually make VR below -10V? In the scanning exposure method, it is very important to reduce the VR to −10 V or less with a small exposure amount in terms of the design of the optical system of the copying machine (device cost, precision of the optical system optical path, etc.).

[0211] From the above, it is possible to obtain an electrophotographic photoreceptor that satisfies electrostatic properties and imaging performance only when the resin of the present invention is used, which is particularly advantageous for photoreceptor systems using semiconductor laser light scanning exposure method. It became clear that Example 2 Resin [A-10] 5g (as solid content), resin [B-
2] 35g (as solid content), photoconductive zinc oxide 20
0g, methine dye (II) with the following structure 0.020g, N
- 0.20 g of hydroxymaleimide and 3 toluene
00g of the mixture was operated in the same manner as in Example 1 to produce an electrophotographic light-sensitive material.

[0212]

embedded image The film properties (surface smoothness), electrostatic properties, imaging properties, and environmental conditions of this photosensitive material were 30° C. and 80% RH. The electrostatic properties and imaging properties were investigated. Furthermore, the printability when used as an original plate for electrophotographic planographic printing was investigated. These results are shown in Table-G.

[0213]

[Table 15] The implementation aspects of the evaluation items shown in Table-G are as follows. Note 3) Smoothness of surface layer: The obtained photosensitive material was measured using a Beck smoothness tester (manufactured by Kumagai Riko Co., Ltd.) with an air capacity of 1 c.
The smoothness (sec/cc) was measured under the conditions of c. Note 4) Contact angle with water: Desensitizing treatment liquid EP for each photosensitive material
Using a solution prepared by diluting L-EX (manufactured by Fuji Photo Film Co., Ltd.) twice with distilled water, apply it to an etching processor.
After the surface of the photoconductive layer is desensitized by passing it through, a drop of 2 μl of distilled water is placed on it, and the contact angle with the water formed is measured using a goniometer. Note 5) Printing durability: Make a plate under the same conditions as the imaging performance in Note 2) above to form a toner image, desensitize it under the same conditions as Note 4) above, and use this as an offset master. This indicates the number of sheets that can be printed using an offset printing machine (Oliver Model 52 manufactured by Sakurai Seisakusho Co., Ltd.) without causing problems with background stains in non-image areas or image quality in image areas (the higher the number of sheets printed, the longer the printing durability As shown in Table G, the photosensitive material of the present invention has good mechanical strength and electrostatic properties of the smooth film of the photoconductive layer, and there is no ground fog in actual copied images. The quality of the copied image was also 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 desensitizing treatment with the desensitizing treatment liquid progresses sufficiently, and the contact angle with water in the non-image area is as small as 10 degrees or less, making it sufficiently hydrophilic. It can be seen that When actually printing and observing the background smear on the printed matter, no background smudge was observed, and 10,000 printed matter with clear image quality were obtained.

[0214] The above means that the resin [A] and resin [B] of the present invention interact appropriately with the zinc oxide particles, and the desensitization reaction by the desensitization treatment liquid can easily and sufficiently proceed. This shows that a remarkable improvement in film strength has been achieved due to the formation of this condition and the action of resin [B]. Examples 3 to 18 In Example 2, resin [A-10] and resin [B-2]
] Instead of each resin [A] and each resin [B] in Table-H below
] Each electrophotographic photoreceptor was produced in the same manner as in Example 1, except that

[0215] Electrostatic properties were measured in the same manner as in Example 2. The results are also shown in Table H.

[0216]

[Table 16] Furthermore, when we investigated the actual operability of these photosensitive materials, we were able to obtain clear reproduced images with good reproducibility of fine lines and characters, no unevenness in halftones, and no background fog. It was done.

[0217] Furthermore, when printing was performed in the same manner as in Example 2 using the original offset master plate, at least 10,000 sheets or more could be printed in each case. From the above, each of the photosensitive materials of the present invention was good in all respects of the smoothness of the photoconductive layer, film strength, electrostatic properties, and printability.

Furthermore, it was found that the electrostatic properties were further improved by using resin [AA]. Examples 19 to 22 Electrophotographic materials were produced under the same conditions as in Example 1, except that the methine dye [I] used in Example 1 was replaced with the dyes shown in Table I below.

[0219]

[Table 17]

[0220]

[Table 18] The photosensitive materials of the present invention all have chargeability, dark charge retention,
It has excellent light sensitivity, and the actual copied images can be used even in high temperature and high humidity conditions (30℃).
, 80% RH), it provided clear images without background fog. Examples 23 and 24 and Comparative Example 3 6.5 g of either resin [A-1] (Example 23) or resin [A-2] (Example 24), resin [B-8] 33.
5 g, 200 g of zinc oxide, 0.02 g of uranine, 0.03 g of methine dye [VII] with the following structure, 0.03 g of methine dye [VIII] with the following structure, 0.18 g of p-hydroxybenzoic acid, and 300 g of toluene in a homogenizer. Inside rotation speed 7×103 r. p. m. The photosensitive layer was dispersed for 10 minutes to prepare a photosensitive layer-formed product, which was coated on electrically conductive treated paper with a wire bar so that the dry adhesion amount was 20 g/m 2 and dried at 110° C. for 20 seconds. Next, each electrophotographic photoreceptor was prepared by leaving it for 24 hours in a dark place at 20° C. and 65% RH.

[0221]

[C63]

[0222]

Comparative Example 3 A photosensitive material was prepared in the same manner as in Example 23, except that resin [R-3] g having the following structure was used instead of resin [B-2] g. Created.

[0223] In the same manner as in Example 1, the characteristics of each photosensitive material were investigated. The results are summarized in Table J below.

[0224]

[C65]

[0225]

[Table 19] In the above measurements, the electrostatic properties and imaging properties were performed in the same manner as in Example 1, except that the following operations were followed. Note 6) Method for measuring electrostatic properties E1/10 and E1/100 After the surface of the photoconductive layer was charged to -400 V by corona discharge, the surface of the photoconductive layer was irradiated with visible light at an illuminance of 2.0 lux. , the surface potential (V10) is 1/10 or E1/
The time required for the light to attenuate to 100 is determined, and the exposure amount E1/10 or E1/100 (lux/second) is calculated from this. Note 7) Imaging properties After each photosensitive material was left for one day and night under the following environmental conditions, it was obtained by making a plate using a fully automatic plate making machine EPL-404V (manufactured by Fuji Photo Film Co., Ltd.) using EPL-T as a toner. The copied images (fogging, image quality) were visually evaluated. The environmental conditions during imaging were 20°C, 65% RH (I) and 30°C, 80°C.
%RH(II). However, the manuscript for copying (ie, the draft manuscript) was created by cutting out and pasting other manuscripts.

No difference was observed in the smoothness and strength of the photoconductive layer among the photosensitive materials. but,
In terms of electrostatic properties, Comparative Example 3 particularly has a photosensitivity E1/10.
The value of 0 was large, and this was further exacerbated by high temperature and high humidity, resulting in deterioration. The electrostatic properties of the photosensitive material of the present invention are good, and the resin having a specific substituent [
Example 24 using E
The value of 1/100 has become smaller.

[0227] When examining the actual imaging performance, in Comparative Example 3, in addition to the original as a copy image, the frame of the cut out and pasted part (that is, the pasting trace) was recognized as background stains in the non-image area. Ta. However, in all cases of the present invention, clear images without background stains were obtained.

Furthermore, when these were desensitized and printed as offset printing original plates, 10,000 prints with clear image quality and no background smear were obtained for all of the products of the present invention. However, in Comparative Example 3, the above-mentioned pasting marks were not removed even with the desensitization treatment, and were generated from the printed matter.

From the above, only the photosensitive material of the present invention was able to provide good characteristics. Example 25 5 g of resin [A-22] and 35 g of resin [B-11], 200 g of zinc oxide, 0.02 g of uranine, 0.04 g of rose bengal, 0.03 g of bromophenol blue, 0.40 g of phthalic anhydride, and 300 g of toluene. a mixture of
A photosensitive material was produced by the following operations in the same manner as in Example 23.

[0230] The photosensitive materials of the present invention were operated in the same manner as in Example 23, and their respective properties were examined. All of them had excellent chargeability, dark charge retention, and photosensitivity, and the actual copied images were also stable at high temperatures and high humidity. of(
Even under harsh conditions (30° C., 80% RH), clear images without background fog were provided.

Furthermore, when printing was performed using this as an original plate for an offset master, prints with clear image quality were obtained even after printing 10,000 sheets. Examples 26 to 37 In Example 25, 5 g of resin [A-22] and resin [
B-11] Instead of 35g, use the resin [A] in Table-K below.
Each photosensitive material was produced in the same manner as in Example 23, except that 5 g of resin [B] and 35 g of resin [B] were used.

[0232]

Table 20 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°C, 80°C).
%RH), it provided clear images without background fog.

[0233] Furthermore, when printing was performed as an offset master original plate, printed matter with clear image quality and no scumming was obtained even after printing 10,000 sheets. Furthermore, the photoreceptor of resin [A] containing methacrylate having a specific aryl group as a substituent showed better performance.

[0234]

Effects of the Invention According to the present invention, an electrophotographic photoreceptor is provided which has excellent electrostatic properties (especially electrostatic properties under severe conditions), has clear and high-quality images, and also has excellent mechanical strength. can be obtained. It is particularly effective for scanning exposure methods using semiconductor laser light.

By using a repeating unit containing a specific methacrylate component represented by formula (Ia) or (Ib) in the resin of the present invention, the electrostatic properties are further improved.

Claims (4)

[Claims] Claim 1. An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye, and a binder resin, wherein the binder resin is one of the following resins [A1] and [A2]. An electrophotographic photoreceptor comprising at least one of the above resins and at least one of the following resins [B]. Resin [A1] has a weight average molecular weight of 1 x 103 to 2 x 104,
A polymerizable double bond group represented by the following general formula (II) is bonded only to one end of the main chain of a polymer containing 30% by weight or more of repeating units represented by the following general formula (I) as a polymer component. A copolymer consisting of at least a monofunctional macromonomer (M1) having a weight average molecular weight of 2 x 104 or less, and a monomer corresponding to a repeating unit represented by the general formula (I), -PO3 H2, -SO3 H, -COOH, -P at one end of the combined main chain
(=O)(OH)R1 [R1 is a hydrocarbon group or -O
R2 (R2 represents a hydrocarbon group)] and a cyclic acid anhydride group. Resin [A2] has a weight average molecular weight of 1 x 103 to 2 x 104,
A polymer component containing 30% by weight or more of repeating units represented by the following general formula (I) as a polymer component and at least one polar group selected from the specific polar groups represented by the resin [A1] above. A weight average molecular weight 2× consisting of a polymerizable double bond group represented by the following general formula (II) bound only to one end of a polymer main chain containing 1 to 50% by weight.
104 or less monofunctional macromonomer (M2),
A resin which is a copolymer comprising at least a monomer corresponding to the repeating unit represented by the general formula (I). [In formula (I), a1 and a2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group. R3 represents a hydrocarbon group. ] [Formula (II), G1 is -COO-, -OCO-, -
CH2 OCO-, -CH2 COO-, -O-, -S
O2-, -CO-, -CONR11-, -SO2N
R11- (here R11 represents a hydrogen atom or a hydrocarbon group), -CONHCOO-, -CONHCONH- or -C6H4-. b1 and b2 may be the same or different, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COOR12, or -COOR12 via a hydrocarbon (here, R12 is an optionally substituted hydrocarbon group) represents). ] Resin [B] has a weight average molecular weight of 2 x 104 to 1 x 106,
The A block containing at least one kind of polymer component containing at least one kind of polar group selected from the specific polar groups shown in the above resin [A1] and the above resin [A]
An AB block copolymer comprising a B block containing at least a polymer component represented by the general formula (I). 2. The resin [A2] further has at least one polar group selected from the specific polar groups shown in the resin [A1] bonded to the end of the copolymer main chain. The electrophotographic photoreceptor according to claim 1, characterized in that: 3. The resin [A1] or [A2] is a methacrylate component containing an aryl group represented by the following general formula (Ia) or the following general formula (Ib) as a polymer component represented by the general formula (I). The electrophotographic photoreceptor according to claim 1 or 2, characterized in that it contains at least one of the following. [Formula (Ia) and (Ib), A1 and A2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms,
Chlorine atom, -COR4 or -COOR4 (where R
4 represents a hydrocarbon group having 1 to 10 carbon atoms), and B
1 and B2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- and the benzene ring. ] 4. In the resin [B], the total amount of the specific polar group-containing polymer component contained in the entire copolymer is
10% to 50% by weight based on the total amount of specific polar group-containing components contained in the above resins [A1] and [A2]
The electrophotographic photoreceptor according to any one of claims 1 to 3, characterized in that: