JPH0430170A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance electrostatic characteristics by using 2 kinds of specified binder resins. CONSTITUTION:One of the binder resins is an A-B graft copolymer having a weight average molecular weight of 1X10<3> - 2X10<4> and comprising A blocks each composed of at least one kind of repeating unit having an acid group, such as -PO3H2, -COOH, -SO3H, phenolic OH, and cyclic acid anhydrides, and B blocks each composed of at least one kind of repeating unit represented by formula I, and monofunctional macromonoers (MA) each having a weight average molecular weight of 1X10<3> - 2X10<4> and a polymerizable double bond and combined with the terminal of polymer chain of each B block of the A-B block copolymer. In formula I, each of a1 and a2 is H, halogen, cyano, or a hydrocarbon group, and A1 is -COO-, -OCO-, -O-, -SO2-, -CO-, -CONHCOO-, or -CONHCONH-, thus permitting electrostatic characteristics to be enhanced.

Description

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

[Prior art] Particularly related to CPC photoreceptors with excellent performance Electrophotographic photoreceptors take various configurations in order to obtain predetermined characteristics or depending on the type of electrophotographic process to which they are applied.

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

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

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

The binder resin used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film-forming properties itself and ability to disperse photoconductive powder into the binder resin. The photoconductive layer of the recording layer has excellent adhesion to the base material, and the photoconductive layer of the recording layer has excellent charging ability, has low dark decay, large light decay, and low pre-exposure fatigue, and is highly resistant to changes in humidity during photographing. It is necessary to have various electrostatic properties such as the need to stably maintain these properties and excellent imaging performance.

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

However, conventionally known binder resins have many problems, particularly in electrostatic properties such as chargeability, dark charge retention, photosensitivity, and smoothness of the photoconductive layer.

In order to solve these problems, 0.05 to 1 liters of a copolymer component containing an acidic group in the side chain of the polymer was used as a binder resin.
A low molecular weight resin containing 0% by weight or a low molecular weight resin that binds an acidic group to the end of the polymer main chain (Frw103-1
04), the smoothness and electrostatic properties of the photoconductive layer are improved, and image quality without background smear is obtained, as disclosed in JP-A-63-217354 and JP-A-64-1, respectively.
No. 70761 and JP-A-2-67563.

In addition, as a binder resin, a resin containing a polymeric component containing an acidic group in the side chain of the copolymer, or bonded to the end of the main chain of the polymer, and containing a thermally and/or photocurable functional group. The technique using this is disclosed in Japanese Patent Application Laid-open No. 1-100554 and Japanese Patent Application No. 1983-3.
9690, and JP-A-1-102573 and JP-A-2-874 disclose a technique of using a resin containing an acidic group in the side chain of the copolymer or bonding to the end of the main chain of the polymer in combination with a crosslinking agent. Furthermore, the low molecular weight form of Vk resin (weight average molecular weight 10'' to 104) is mixed with high molecular weight form (weight average molecular weight 10'').
The technology used in combination with resins of 4 or more is disclosed in JP-A-64-5
No. 64, No. 63-220149, No. 63-22014
No. 8, JP-A No. 1-280761, JP-A No. 1-116643
JP-A No. 1-211766 and JP-A No. 2-34859 disclose techniques for using such low molecular weight materials in combination with heat and/or photo-curable *m. By a trick, I! Furthermore, the film strength of the photoconductive layer is made sufficient without impeding the above-mentioned properties due to the use of a resin containing an acidic group at the l chain or terminal,
It is stated that mechanical strength is increased.

(Issues to be solved by the invention) However, even when these resins are used, the environment is high temperature and
It has been found that it is still insufficient to maintain stable performance when the temperature fluctuates significantly from high temperature to low temperature and low humidity. In particular, scanning exposure methods using semiconductor laser light require longer exposure times than conventional simultaneous exposure methods using visible light across the entire surface, and there are restrictions on exposure intensity. , higher performance is required in terms of photosensitivity.

Furthermore, when a scanning exposure method using semiconductor laser light is adopted in an electrophotographic lithographic printing original plate, actual tests using a conventional photoreceptor show that the electrostatic properties described above are unsatisfactory. Especially El/! and E...
The large difference between the gradation 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.Also, even when printed as an offset master, This has resulted in serious problems such as the appearance of pasted marks from printed manuscripts on printed matter.

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

An object of the present invention is to provide an electrophotographic photoreceptor that stably maintains 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. It is to provide.

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

Another object of the present invention is to provide 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), reproduces a copy image that is faithful to the original image, and is capable of covering the entire surface of a printed matter. It is an object of the present invention to provide a lithographic printing original plate which does not generate not only such background stains but also dotted background stains and which has excellent rigidity resistance.

(Means for Solving the Problems) The above object is an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, wherein the binder resin is a binder resin represented by the following: It has been found that this can be achieved by an electrophotographic photoreceptor characterized by containing at least one type of binder resin [A] and at least one type of binder resin [B].

Resin [A]; Polymer containing at least one acidic group selected from POJm group, -coon group, -801 group, phenolicity (R' is a hydrocarbon group), and cyclic acid anhydride-containing group The polymer main chain of the B block of an A-B block copolymer composed of an A block containing at least one component and a B block containing at least a polymer component represented by the following general formula (1). A weight average molecular weight lXIO3-2X containing at least one monofunctional i-character macromonomer (hereinafter sometimes referred to as macromonomer (MA)) having a polymerizable double bond group bonded to the terminal as a copolymerization component.
10' graft copolymer.

General formula (1) % formula % [In formula (1), al and phantom each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group.

A, -coo--oco-1→C11ghas-oco
-t -5O, N--CONHCOO- -CONHCONII- or a hydrogen chloride group).

When R1 represents a hydrogen atom or a hydrocarbon group, Binder resin [B]: Weight average molecular weight lXl0'' to 1. A copolymer having a weight average molecular weight of 3X1O' to 1x106 and containing at least one of 5X10' polyester type macromonomers (MB) as at least a polymer component.

General formula (Ia) X, -Yl -COG +w+ -oco-111g
-COO+-R61 general formula (Ifib) Xz-Yx COO+Ws Coo) Rat formula (l
In la) and (Illb), represents the unit.

[ ] repeats fl and f2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-T+, or a carbonization group having 1 to 8 carbon atoms. -C00-Tz (T+ and T each represent a hydrocarbon group having 1 to 18 carbon atoms) via a hydrogen group.

Xl is a single bond or -coo--oco-+CHz
rare rCOO-1+C' both 70CO(" +, U, is 1
d.

represents a hydrocarbon group having 1 to 12 carbon atoms), or -3o
Represents w-.

Yl represents a group connecting X and -000-.

W and h may be the same or different, and each is a divalent aliphatic group or a divalent aromatic group (-0--3-- in the bond of each 2d-valent organic residue). N- (di represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms),
-5on Coo -0CO0NHCO -NHCONH -CON (ds is the same as d2 - d.

may include one bonding group) or a combination of these residues.

R&l represents a hydrogen atom or a hydrocarbon group.

fl, f4, Xz, Yz, and Y in general formula (11b) are respectively fl, ft,
Represents the same content as 1sY1 and R41.

, represents a divalent aliphatic group.

That is, the binder resin provided in the present invention is an AB block copolymer of an A block containing the above specific acidic group-containing component and a B block containing the polymer component represented by the above general formula (1). A monofunctional macromonomer (MA
) as a copolymerization component, and a macromonomer (1'lB) represented by the general formula (n[a) or (Illb)].
and a high molecular weight graft copolymer resin [B] containing at least one of the following.

Among the acidic group-containing binder resins known to improve the smoothness and electrostatic properties of the photoconductive layer mentioned above, low molecular weight polymers are used, and acidic group-containing polymeric components are randomly present in the polymer main chain. Examples include resins in which an acidic group is bonded only to one end of the polymer main chain. On the other hand, in the binder resin [A] of the present invention, the acidic groups contained in the resin are
It is a highly specific chemical structure of the polymer molecular chain, which is present in the graft portion and in the form of a block (ie, A block) at a location away from the polymer main chain.

In the resin [A] of the present invention, the acidic groups unevenly distributed in the terminal region of the graft portion in the polymer sufficiently adsorb to the stoichiometric defects of the inorganic photoconductor, and the other acid groups constituting the main chain of the polymer It is estimated that the block portion loosely and sufficiently covers the surface of the inorganic photoconductor. Compared to known resins, this resin has sufficient adsorption to the surface of the inorganic photoconductor and coating effect near the surface.
Even if the stoichiometric defect area of the inorganic photoconductor varies slightly, the inorganic photoconductor and resin are always stable because they have a sufficient adsorption area.
It is inferred that the interaction between the photoconductor and the photoconductor is maintained, and the present invention can sufficiently compensate for traps in the photoconductor and improve the humidity characteristics, compared with conventionally known acidic group-containing resins. It was found that the particles were sufficiently dispersed and aggregation was suppressed.

Therefore, if a photoreceptor with a rough surface of the photoconductive layer is used as an electrophotographic planographic printing original plate, the dispersion state of the zinc oxide particles that are the photoconductor and the binder resin is not appropriate, resulting in the presence of aggregates. Since a photoconductive layer is formed on the sandals, even if the non-image areas are made hydrophilic even if treated with a desensitizing liquid, the non-image areas will not be made uniformly and sufficiently hydrophilic, causing printing ink to adhere during printing, resulting in As a result, background stains occur in non-image areas of printed matter.

Resin [B] does not impede the high performance electrophotographic properties obtained by using resin [A], and provides sufficient mechanical strength to the photoconductive layer, which is insufficient with resin [A] alone. It has been found that sufficiently good imaging performance can be obtained even when the environment changes as described above or when a low-output laser beam is used.

This is achieved by specifying the weight average molecular weight of resin [A] and resin [B] as the binder resin of the inorganic photoconductor, as well as the content and bonding position of acidic groups in the resin. This is presumed to be due to the ability to appropriately change the strength of the interaction between the photoconductor and the resin. That is, resin [A] with stronger interaction is selectively and appropriately adsorbed to the inorganic photoconductor, while resin C with weaker interaction than resin [A]
In B), it is presumed that by interacting gently with the inorganic photoconductor to the extent that the electrophotographic properties are not inhibited, both the electrophotographic properties and the mechanical strength can be significantly improved as described above. When a resin is used, the adsorption/coating interaction between the photoconductor and the binder resin is properly performed, and the film strength of the photoconductive layer is maintained.

Even when only the low molecular weight resin [A] in the present invention is used as the binder resin, the photoconductor and the binder resin can sufficiently adsorb and coat the particle surface, which improves the smoothness of the photoconductive layer. It has good electrostatic properties, provides image quality without background staining, and has sufficient film strength to be used as a CPC photoreceptor or as an offset original plate for printing several tens of sheets. However, according to the present invention (by coexisting with resin [B], the resin I can be used without alienating the function of resin [A] at all)
I [A] alone was able to further improve the mechanical strength of the photoconductive layer, which was still insufficient. Therefore, the photoreceptor of the present invention has excellent electrostatic properties even under fluctuating environmental conditions, has sufficient film strength, and has excellent electrostatic properties even under harsh printing conditions (e.g.
It is now possible to print more than 10,000 sheets even when using large printing presses that require strong printing pressure.

The macromonomer (MA) in the resin [A] of the present invention
The polymer component therein is composed of A-block and B-block as described above, and the ratio of A-block/B-block is preferably 1 to 70/99 to 30.
(weight ratio), more preferably 3-50/97-5
0 (weight ratio).

In the graft copolymer [A) of the present invention, the ratio of the macromonomer (MA) to other monomers (for example, the monomer of formula (It)) is 1 to 60/99 to 40 (weight ratio). and preferably 5-40/95-60 (weight ratio).

Macromonomer (MA) in the resin [A] of the present invention
The amount of the acidic group-containing component contained in the resin [A]
It is 1 to 30 parts by weight in 100 parts by weight, preferably 5 parts by weight.
~20 parts by weight. That is, the proportion of acidic groups present in the resin [A] is the same as that of A- in the macromonomer (PI^).
Block composition ratio and macromonomer in resin [A] (
The ratio can be adjusted to a preferable value depending on the copolymerization ratio of MA).

Furthermore, in this resin [A], macromonomer (MA)
As the component to be copolymerized with, a monomer represented by the following general formula (II) is preferable, and a monomer selected from the following general formula (na) and/or (I[b) is particularly preferable.

oo-Rg [In formula (It), R2 represents a hydrocarbon group.

[In the formula, xl and x2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -COZ3 or -COOZs (Zs each has 1 carbon number
~10 hydrocarbon groups), with the proviso that Xl and x
Both 2 do not represent a hydrogen atom.

L, and each represent a single bond or a linking group with 1 to 4 linking atoms that connects -C00- to the benzene ring.] Monomer copolymerized with the macromonomer (MA) in the resin [A] The above general formula (na) and/or general formula (
A resin containing a small amount of a copolymer with a substituent-containing methacrylate monomer containing a substituted benzene ring or a naphthalene ring represented by I[b) (hereinafter, this resin [A] will be referred to as a resin (A')) ), further improvement in electrophotographic properties (especially Vto, D, R, R, E+z+*) is achieved.

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

When the molecular weight of the binder resin [A] is smaller than 1XIO3, the film forming ability decreases and sufficient film strength cannot be maintained.On the other hand, when the molecular weight is larger than 2X10', even the resin of the present invention is susceptible to high temperature - Fluctuations in electrophotographic characteristics (particularly initial potential and dark decay retention) under harsh conditions of low humidity become large, and the effect of the present invention in obtaining stable copied images is diminished.

If the macromonomer (monomer) content in the binder resin [A] is less than 1.0% by weight, electrophotographic properties (especially dark decay rate and light sensitivity) will decrease, and electrophotographic properties will fluctuate depending on environmental conditions. becomes particularly large in combination with a near-infrared to infrared spectral sensitizing dye.

This is thought to be due to the fact that the amount of the macromonomer that forms the graft portion is small, resulting in a composition that is almost the same as that of conventional homopolymers or random copolymers.

If the content of the macromonomer (MA) exceeds 60%, the copolymerizability of the macromonomer according to the present invention with monomers corresponding to other copolymerization components will not be sufficient, and even when used as a binder resin. It becomes impossible to obtain sufficient electrophotographic characteristics.

Furthermore, the high molecular weight resin [B] contains the above macromonomer (
MB) and -POJz group, -5O3H group, COOH group, -O
A graft-type copolymer formed by bonding at least one polar group selected from H group, -P-11, group, and cyclic acid anhydride H anastomotic group (this polymer is especially suitable for use with resin [B']). ) is preferred.

In particular, the general formula (lla) and/or (Il
In the macromonomer (MB) of lb), R1 or R
When th represents a hydrocarbon group, a resin in which the polar group is bonded to the main chain of the polymer is particularly preferable.

Among resins [B], in particular, resins [B'] that bond a specific polar group to the end of the polymer main chain have weaker interactions than resins [A]. A polar group bonded to the terminal position of the polymer main chain is more preferable because it interacts gently with the inorganic photoconductor to the extent that the electrophotographic properties are not adversely affected.

The ratio of the binder resin [A] and the polymer (resin CB) is 5 to 60 parts by weight - 95 to 40 parts by weight, preferably 10 to 40 parts by weight to 90 to 60 parts by weight.

Next, the binder resin [A] and the binder tree Ml used in the present invention
[B] will be explained in detail.

The monofunctional macromonomer (HA) used in the graft copolymer of the present invention will be explained in more detail.

The acidic groups contained in the components constituting the A-block of the macromonomer (MA) include POJz group, -Co
ol group, -801 group, phenolic OH group, Rinli hydrocarbon group) and/or cyclic acid anhydride-containing group, preferably -C0OH group, -5O3H (R
'represents a hydrocarbon group), and R and R' preferably represent an aliphatic group having 1 to 22 carbon atoms (for example, a methyl group,
Ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, Cyclohexyl group, benzyl group, phenethyl group, 3-phenylproyl group, methylbenzyl group, chlorobenzyl group,
fluorobenzyl group, methoxybenzyl group, etc.), or an optionally substituted aryl group (e.g., phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro -methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

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

Examples of aliphatic dicarboxylic anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic anhydride ring, and cyclohexane-1,2-dicarboxylic acid anhydride ring. Examples include anhydride ring, cyclohexene-1,2-dicarboxylic acid anhydride ring, 2,3-bicyclo(2,2,2)octane dicarboxylic acid anhydride ring, etc., and these rings include, for example, chlorine atom, bromine atom A halogen atom such as an atom, an alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group, etc. may be substituted.

Examples of aromatic dicarboxylic anhydrides include phthalic anhydride rings, naphthalene-dicarboxylic anhydride rings, pyridine-dicarboxylic anhydride rings, thiophene-dicarboxylic anhydride rings, etc. For example, halogen atoms such as chlorine atom and bromine atom, methyl group, ethyl group,
It may be substituted with an alkyl group such as a propyl group or a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (for example, a methoxy group, an ethoxy group, etc.).

The above “polymer component containing a specific acidic group” is
For example, the polymer component constituting the other block components of the macromonomer (MA) of the present invention, that is, the acidic group that copolymerizes with the corresponding vinyl compound such as the methacrylate component represented by the general formula (1) Any vinyl compound that can be used can be used.

For example, see the Polymer Data Handbook published by the Polymer Science Society of Japan.
Basic Edition] Baifukan (published in 1986), etc.

Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-amino)methyl form, α-chloro form, α-bromo form, α -fluoro form, α-tributylsilyl form, α-
Cyano form, β-chloro form, β-bromo form, α-chloro-
β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (
For example, 2-pentenoic acid, 2-methyl-2-hexenoic acid,
2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amide, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, Examples include half-ester derivatives of vinyl or allyl groups of vinyl sulfonic acid, vinylphosphonic acid, dicarboxylic acids, and ester derivatives and amide derivatives of these carboxylic acids or sulfonic acids, and compounds containing the acidic group in a substituent thereof.

Specific examples of these compounds include the following. However, on each side below, a is -H, -C
H3, -C1, -Br, -CN-1-CHtCOOC
H3 or cozcoou, b represents -H or -○L, represents an integer of 2 to 18, m represents an integer of 1 to 12, l represents an integer of 1 to 4.

(a oon 0OH (a-3) (a-4) (a-5) (a-6) (a-7) 〒 (a-8) de (a-9) (a-10) 〒 (a-11) 0NHCH cttzcoo.

(a-13) (a (m may be the same or different) (a-15) CHz=CHCHzOCO(CHz)mcOOH(a-
16) CH2= CH+ cut +-coon (a-17) C00CHzCHCHz00C(CHz)-COOH(
a-18) (a-19) (a 〒 (a-21) (a-22) (a-23) H (a-24) (a-25) (a-26) (a-27) H H H (a-28) (a (a-30) (a-31) (a-32) (a-33) (a-34) (a-35) (a-36) CON (CHgGHzcOOH) t(a -37) C00 (CHz) I C0N (CH2CH2COOH)
z (a-38) 03H (a-39) (a-40) UOH (a-41) (a-42) (a-43) (a-44) (a-45) OH Acidic group as above Two or more types of components may be contained in the A block, and these two or more types of acidic group-containing components may be contained in the A block by either random copolymerization or block copolymerization. Furthermore, together with the acidic group-containing component, a component not containing an acidic group (for example, a component represented by formula (1) described below) may be contained in the A block, but the acidic group-containing component is Preferably it is present at 100% by weight.

Next, the components constituting the B-block in the macromonomer, ie, the repeating unit represented by general formula (1), will be explained.

In general formula (1), A1 is -000-1-OCO-+
CH! Length 0CO-1000CH, pigeon coo-C1+,
lx represents an integer from 1 to 3), -0-1-5Offi
Here, in addition to a hydrogen atom, ZI preferably includes 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). , 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 4-1
8 optionally substituted alkenyl groups (e.g., 2-methyl l-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group,
1-hexenyl group, 2-hexenyl group, 4-methyl-2
-hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., 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.)
, an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example,
Cyclohexyl group, 2-cyclohexylethyl group, 2-
cyclopentylethyl group, etc.), or an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group) 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 group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

R1 represents a hydrocarbon group, preferably the same as those listed as preferred hydrocarbon groups in zl above.

Furthermore, the benzene ring may have a substituent. Examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy group (e.g. methoxy group,
ethoxy group, propioxy group, butoxy group, etc.).

al and a may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -cooz, or CC00Z via hydrocarbons
(Z! represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, or an aryl group, which may be substituted. Specifically, regarding the above zl) represents the same content as that described).

Examples of the hydrocarbon in one Coo-Zz group via the hydrocarbon include a methylene group, an ethylene group, a propylene group, and the like.

More preferably, the general formula (1) may be a hydrogen atom, a methyl group, -COOZ, or C
HzCOOZz (Z is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group,
represents a propyl group, a butyl group, a hexyl group, etc.). Even more preferably, one of al+az represents a hydrogen atom.

Furthermore, the B-block may contain a polymer component other than the monomer of formula (1), which corresponds to another repeating unit that can be copolymerized with the polymer component represented by formula (1). Examples of monomers include acrylonitrile, methacrylonitrile, heterocyclic vinyls (e.g. vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene,
vinyl pyrazole, vinyl dioxane, vinyl oxazine, etc.). These other monomers are used in an amount not exceeding 20 parts by weight based on 100 parts by weight of the total polymer components of B-block. In addition, it is preferable that the B block does not contain a polymer component containing an acidic group, which is a constituent component of the A-block. When two or more types of copolymer components are present in the B block, These two or more types of copolymerization components may be contained in the B block by either random copolymerization or block copolymerization, but it is preferable to contain them randomly for ease of synthesis.

Next, in the macromonomer (M) of the present invention, the A block consisting of the component containing the above-mentioned acidic group and the general formula (1)
A description will be given of the polymerizable double group that connects the B block containing the polymer component represented by the formula in an AB type and is connected to the other end of the B block that is connected to the A-block.

Specifically, a polymerizable double bond group represented by the following general formula (IV) can be mentioned as an example.

General formula (IV) b+ bz CH=C A, - [In formula (IV), ^ represents the same content as A1 in formula (1). b,, b! may be the same or different from each other, and represent the same contents as al and ag in formula (1).

] That is, the polymerizable double bond group C represented by the general formula (IV)
Hz=CH+CL)gC0O-C1(,=C)I-CO-CHz=CH-(CTo)20C-, and the like.

The macromonomer (M) used in the present invention is B as described above.
- It has a chemical structure in which a polymerizable double bond group as represented by general formula (IV) is directly bonded to one end of the block or bonded by an arbitrary linking group. Linking groups include carbon-carbon bonds (-double bonds or double bonds), carbon-heteroatom bonds (heteroatoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), heteroatoms, etc. It is composed of any combination of atomic groups of teloatomic bonds. That is, specifically, a simple bond or -f-1-(as+ R, each represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxy/L4, an alkyl group (for example, methyl group, ethyl group, propyl group, etc.)], R1 SO□ C0N--5o□N--NHCOO Rs Rs R1 R also represents the same content as R1 in the above formula (1) represents a single linking group or a linking group composed of any combination selected from atomic groups such as [indicating hydrocarbon groups, etc.].

If the weight average molecular weight of the macromonomer (M) exceeds 2 x 104, the copolymerizability with other monomers (for example, formula (It)) will decrease, which is undesirable. On the other hand, if the weight average molecular weight is too small, the photosensitive layer Since the effect of improving electrophotographic properties becomes small, it is preferable that it is lXl0' or more.

The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. For example, in the monomer corresponding to the polymer component containing the specific acidic group, the acidic group is previously protected as a functional group, and the organometallic compound (
Ionic polymerization reactions using hydrogen iodide, iodine, etc.), photopolymerization reactions using porphyrin metal complexes as catalysts, or group transfer polymerization reactions. In the so-called living polymerization reaction of A
After synthesizing the -B block copolymer, various reagents are reacted at the ends of this living polymer to introduce polymerizable double bond groups. Thereafter, the functional group with the protected acidic group is deprotected by hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, photolysis reaction, etc. to form an acidic group. One example is shown in reaction scheme (1) below.

For example, P, Lutz, P, Masson et al.
, Polym, Bull.

1i+ 79 (1984) B, C, Anderso
n, G, D, Andrews eta1Macron
+olecules, 14. 1601 (1981
) K, Hatada, KUte, etal,
Po1y+++, J, 17.977 (1985), 18
．． 1037 (1986).

Hiroshi Migashi-1 Ko Hatada-1 Polymer processing, plate, 366 (19
87) Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, 46.18
9 (1989) M, Niuroki, T, ^ida
, T,Am,Chem,Soc, 1094737
(1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 4
3, 300 (1985) D, Y., Sogah, W.
, R. Hertler et al.

Macromolecules, separate, 1473 (1
Living polymers can be easily synthesized according to the synthesis method described in 987) and others. In addition, as a method for introducing a polymerizable double bond group to the terminal of the living polymer,
The macromonomer of the present invention can be easily prepared according to the conventionally known macromonomer synthesis method.

Specifically, P, Dreyfuss & R, P, Qu
irk, EncyclePolym, Sci, Eng,
, 1L551 (1987), P.F. Rempp.

E, Franta, Adu, Polym, Sci.
, l, 1 (1984), V, Per-cec, App.
l, Polym, Sci, Limb 95 (1984),
R, ^samiM-TakaRit Makva*o
1. Che+a, 5upp1.12.163 (19B5
LP, Rempp, etal, phylum akvamo1.
Yuji Kami for chem, 5upp1.8 3 (1984),
Chemical Industry, Kawa, 56 (1987), Yuya Yamashita, Polymer, 31.988 (1982), Yobe Kobayashi, Polymer, 625 (1981), Toshinobu Higashimura, Japan Adhesive Association Visit 1
8,536 (1982), Hiroshi Ito-1 Polymer processing, peeling,
262 (1986), Tosaku Shibu, Takashi Tsuda, Functional Materials, 1
It can be synthesized according to the methods described in reviews such as 987 No. 10.5 and the literature/patents cited therein.

Furthermore, the protecting group that protects the specific acidic group of the present invention and the removal (deprotection reaction) of the protecting group can be easily carried out using conventionally known knowledge. For example, there are various descriptions in the cited literature mentioned above, and furthermore, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" ■ Published by Kodansha (197
7 years), T, W, GreenerProtectiv.
e Groups in Organic 5ynth
John Wiley & 5ous (1
(981), J., F., W., McOmie.

'Protective Groups in
Organic Che+n1stry” Plenu
This can be carried out by appropriately selecting a method described in detail in a review article such as M Press, (1973).

As for other methods of synthesizing AB type block copolymers, they can also be synthesized by a photoiniferter polymerization method using a dithiocarbament compound as an initiator. For example, Yoshiyuki Otsu, Polymer, Nail, 248 (1988), Shun Himori-1 Takashi Otsu-1 Polym, Rep, Jap, 37.3508
(1988), JP-A-64-111, JP-A-64-2
It is synthesized according to the synthesis method described in No. 6619 and the like. The macromonomer of the present invention can be obtained using the macromonomer synthesis method described above.

Specific examples of the macromonomer (MA) of the present invention include the following compounds. However, the scope of the present invention is not limited to these. However, in the following compound examples, c, d and e are respectively -H,
-C1 (3 or -CH2COOCH3, f is -H
or -CH, and R1 is -CJp++ (p is 1 to 1
8 integer) , -(CHz)acJs (q is 1 to -C
H,, -0CH3 or -COCH3) or R8 is C5H2s-+ (s is an integer of 1 to 8) or (CH2), C,ll, v2 is OH.

C0OH.

5O3H.

CH CH show, t represents an integer from 2 to 12, U is from 2 to 6 Indicates an integer.

(MA-1) (MA-2) (11A (MA-6) (M8-7) (M8-8) H@ Shiou Beer しυU(Lllth-Y3 (M8 CI(2 (MA-10) (MA-11) (M8-12) CH.

(M^ (MA-14) (MA (MA) The monomer copolymerized with the macromonomer (MA) described above is represented by, for example, the general formula (It). In the formula (It), R2 is the one in the formula (1). Represents the same content as R1.

Further, it is preferable that the main chain of the polymer does not contain copolymerization components containing acidic groups such as -P03H2 group, 5O3H group, Coon group, -OH group, -5H group and -PO3RH group.

Furthermore, the low molecular weight resin [A] of the present invention has the general formula (Il
a) and/or the 2-position or 2-position represented by the general formula (I[b)
．． A graft copolymer [A'] containing as a copolymer component a methacrylate having a specific substituent containing a benzene ring or a naphthalene ring at the 6-position is preferable.

In the general formula (Ila), in addition to hydrogen, chlorine, and bromine atoms as preferable xl and x2, preferable hydrocarbon groups include alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group). , butyl group, etc.), aralkyl group having 7 to 9 carbon atoms (e.g. hensyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl L bromohensyl group, methylhensyl group, methoxybenzyl group, chloro-methylbenzyl group) etc.), aryl groups (e.g. phenyl group, tolyl group, silyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group, etc.), -COZ, and -COOZ3 (preferable 2. is the above-mentioned preferred hydrocarbon group) ) can be mentioned. However, ×1 and
Both 2 do not represent a hydrogen atom.

In formula 1), Ll is a single bond or +CH2±[(-1 represents an integer from 1 to 3), CHtCHzOCO, -(CHzO) that connects 1000- to the benzene ring.
tT (-2 represents an integer of 1 or 2), -CH2C
) 120 etc. represents a linking group having 1 to 4 linking atoms.

L2 in formula (II b) represents the same content as .

Specific examples of the monomer represented by formula (Ila) or (It b) used in the resin [A'] of the present invention are listed below. However, the scope of the present invention is not limited thereto.

■-1) CH3 ■-2) ■ ■-4) ■-6) CHl CH.

CH3 CH3 C,H.

■ CH3 CH2=C death! ■ CH3 r ■ CH3 If-10) CH.

■ ■ II-13) n-14) CH.

r CH3 C.O.

CH.

■ ■ ■ ■ CH.

C.I.

CI(.

Shil ■ ■ ■ ■ L C) +3 C.I. CH.

■ ■ ■ ■ CH3 CH3 I CH.

■ CH3 ■ CH3 It-29) CI(.

■ CH.

■ CH3 ■ CH3 CH,=c If-33) II-34) CH3 CH,=c ■ ■ U-37) ■ CH.

CH3 CH.

H3 ■ CHl ■ C)+3 Furthermore, as a component to be copolymerized with the above macromonomer (MA) in the graft copolymer of the present invention, monomers other than general formula (II), (na) or (Ilb) For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls [e.g. It is a 5- to 7-membered heterocyclic ring containing 1 to 3 nonmetallic atoms (oxygen atoms, sulfur atoms, etc.), and specific examples include vinylthiophene, vinyl dioxane, vinylfuran, etc. It will be done.

Preferred examples include vinyl or allyl alkanoates having 1 to 3 carbon atoms, acrylonitrile, methacrylonitrile, styrene, and styrene m1 (for example, vinyltoluene, butylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromo styrene, ethoxystyrene, etc.).

The binder resin of the present invention includes the macromonomer (MA) and other monomers (for example, a monomer represented by general formula (II)).
It can be produced by copolymerizing at least one compound selected from among these in a desired ratio. As the polymerization method, it can be produced by using known methods such as solution polymerization, suspension polymerization, precipitation polymerization, and emulsion polymerization. For example, in solution polymerization, a copolymer solution can be obtained by adding monomers at a predetermined ratio in a solvent such as benzene or toluene, and polymerizing with an azobis compound, a peroxide compound, or a radical polymerization initiator. A desired copolymer can be obtained by drying it or adding it to a negative solvent. In suspension polymerization, monomers are suspended in the presence of a dispersant such as polyvinyl alcohol or polyvinylpyrrolidone, and copolymerized in the presence of a radical polymerization initiator to obtain a copolymer.

In the resin [A], the amount of the polymer component containing the specific acidic group in the AB type block copolymer is:
Preferably 1 to 30% by weight in 100 parts by weight of resin [A]
The content is more preferably 5 to 20% by weight.

The weight average molecular weight of the resin [A) is preferably 3 x 103~
lXl0'.

The glass transition point of the resin [A] is preferably −40″C to 1
10°C, preferably -20°C to 90°C.

Next, resin CB) used in the present invention will be explained.

The weight average molecular weight of resin [B] is 3 x 10' to 1 x 106
, preferably 5X10' to 5X10S.

The abundance ratio of the macromonomer represented by the -C formula (I[la) and/or (I[Ib)] in the polymer is 0.5
It is preferable that the amount is 80% by weight, especially for general formula (I[
In la) and (nlb), in the case of a macromonomer in which R61 or R64 is a hydrogen atom, the proportion thereof is preferably 0.5 to 30% by weight.

The glass transition point of the resin CB) is preferably 0°C to 11°C.
The temperature is more preferably 20°C to 90°C than 0″C1.

Furthermore, if the molecular weight of the binder resin [B] is smaller than 3X10', the film strength cannot be maintained sufficiently, while if the molecular weight is larger than 106, the dispersibility decreases and the film smoothness deteriorates, resulting in poor quality of the copied image. The image quality (particularly the reproducibility of fine lines and characters deteriorates) deteriorates, and furthermore, when used as an offset master, background stains become significant.

Macromonomer content in binder resin CB) is 0.5
If it is less than % by weight, electrophotographic properties (especially dark decay law, photosensitivity) will deteriorate, and fluctuations in electrophotographic properties under environmental conditions will become large, especially in combination with near-infrared to infrared spectral-enhancing dyes. . This is thought to be due to the fact that the amount of macromonomer that becomes the graft portion is small, resulting in a composition that is almost the same as that of conventional homopolymers or random copolymers.

If the content of the macromonomer exceeds 80%, the copolymerizability of the macromonomer according to the present invention with monomers corresponding to other copolymerization components will not be sufficient, and even when used as a binder resin, the copolymerizability will be insufficient. Electrophotographic characteristics cannot be obtained.

Furthermore, when R61 or RhZ in the general formulas (I[[a) and (I[lb)] is a hydrogen atom, if the amount of the macromonomer exceeds 30% by weight, the dispersibility decreases, the film smoothness deteriorates, and copying This results in deterioration of image quality and increase in scumming of printed matter when used as an offset master. This is thought to be because the macromonomer contains more Cool groups, which strengthens its dispersibility and interaction with the inorganic photoconductor, causing aggregation of the inorganic photoconductor.

The amount of the specific polar group-containing bonding component present in the resin [B'] is 0.1 to 100 parts by weight of the resin CB').
The amount is 10% by weight, preferably 0.5 to 5% by weight.

If the polar group content is less than 0.1%, the effect of improving the film strength of the photoconductive layer will be reduced, and if it exceeds 5%, agglomeration of the inorganic conductor dispersion will occur.

The ratio of binder resin [A] and resin [B] used is 5 to 60 parts by weight -95 to 40 parts by weight, preferably 10 to 40 parts by weight.
parts by weight versus 90 to 60 parts by weight.

The resin CB) of the present invention has the formula (I[la) and/or the formula (
I[[b] Weight average molecular weight 1.0X103~
Contains a macromonomer (MB) of 1.5X10' as a copolymerization component, weight average molecular weight 5X10' to lXl0
It is a graft copolymer of
(e represents the same content as R) and at least one acidic group selected from cyclic acid anhydride-containing groups [B'].

A macromonomer having a polyester structure with a polymerizable double bond group bonded to one end and a carboxyl group bonded to the other end, which is provided as a copolymerization component of iM resin [B].
(MB) will be explained more specifically.

In the general formulas (I[Ia) and (II[b)], []H represents the weight average molecular weight of the macromonomer (?IB) of the formula (I[Ia) and/or (Ilb) from 1XIO3 to 1.5
x10' represents enough repeating units.

In the macromonomer (MB) of general formula (I [[a)], preferably f and f may be the same or different, and each is a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, a fluorine atom). ), cyano group, carbon number 1-3
an alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), -COOT, or -cutcoor (T and T2 are each an alkyl group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group) group, pentyl group,
hexyl group, octyl group, etc.), aralkyl group having 7 to 9 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, etc.), or optionally substituted phenyl group (e.g., phenyl group, tolyl group, xylyl group, methoxyphenyl group, etc.).

More preferably, either fl or f2 represents a hydrogen atom.

X is preferably -COO-1-OCO-1-C)
12COO-1CH,0CO-1-CONH-1-CO
NHCONH-2-CONHCOO- or d is a hydrogen atom or 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, hensyl group, methylhensyl group, chlorobenzyl group, methoxyhensyl group, phenethyl group, phenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, butylphenyl (base, etc.).

YI represents a group that connects χ1 and -COO-, and represents a single bond or a group that connects.

N--CON--5o□N-2-NHCOO--NHC as a connecting group
ONH- and es e6
e? represents a linking group selected from C- or a linking group formed by a combination of these linking groups (herein, 81
~e4 may be the same or different, and each represents a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, a methyl group) , ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-methoxyethyl group, 2
-methoxycarbonylethyl group, benzyl group, methoxyhensyl group, phenyl group, methoxyphenyl group, methoxycarbonylphenyl group, etc.), and e5 to e7 are the same as the above d).

1 and -2 may be the same or different and each represents a divalent organic residue, -0--5-, -NSO-1-5
O□--COO--0CO--CONHCO-1d3d
a d3 NHCONH-1-CON--5o□N- and -3i
- represents an organic residue composed of a divalent aliphatic group, a divalent aromatic group, or a combination of these divalent residues, which may include a bonding group selected from -.

Here, d2 to d4 represent the same content as d.

Examples of divalent aliphatic groups include +C+-1e8 and e
9 may be the same or different, and each represents a hydrogen atom,
Halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.) or alkyl groups having 1 to 12 carbon atoms (e.g. methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group,
decyl group, etc.). 0 is -0--S- or -NR6
:l-, and R6ff represents an alkyl group having 1 to 4 carbon atoms, -CHz6' or CH, Br.

Examples of the divalent aromatic group include a Hensen ring group, a naphthalene ring group, and a 5- or 6-membered heterocyclic group (the hetero atom constituting the heterocycle is a hetero atom selected from an oxygen atom, a sulfur atom, and a nitrogen atom). (containing at least one kind of). These aromatic groups may have a substituent, such as a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, propyl group, etc.). Examples of substituents include C1-C6 alkoxy groups (eg, methoxy, ethoxy, propoxy, butoxy, etc.).

Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1.3-
Examples include oxazoline rings.

R61 preferably represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and specific examples of the hydrocarbon group include fl, r2
The same examples as those mentioned above can be mentioned.

Formula (I [lb), preferably f3, r4, x2,
Y2 and RbZ are fls ft, xl of the formula (I[la)
, Y+ and R61 each represent the same contents as those described as preferable.

-3 represents a divalent aliphatic residue, specifically 1" +CH, →TT (n+ is an integer from 2 to 18), -cL-
c (g+ and g2 each represent a hydrogen atom or an alkyl group such as a methyl group, ethyl group, or propyl group, and neither gl nor 8□ represents a hydrogen atom), CH + CH2
-+-i-2 (g3 represents an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, etc.), and n2 represents an integer of 1 to 16 ) etc.

Ma f in general formula (II[a) and general formula (I[b)]
+ fz CH=C and x, -y in chromomonomer (MB)
.

x, -y, - Examples include, but are not limited to, the following.

However, on each side below, Ql is one ■, -CH,, -
CHzCOOCH3, -6', -Br or -CN, Q2 represents -H or -CH, n represents an integer of 2 to 12, and m represents an integer of 1 to 12.

(Z ■) CI(2=C (Z CH.

C.I. (Z HI C00(CHz)- (Z CH.

C0NH(CHri, 1 (Z CH.

CH2=C C0NIC0NH (CHz), (Z CH.

CH2 C0NHCOO(CH2) 1l (Z CH2 Coo (C)l z) , 1OCO(CHz) 11
(Z CH2=C CONH(CI(2)llOCO(CH2).

(Z (Z-11) CHz=C OCO(CHri, 1- (Z CH2 C00(CHz)nOcOcH C) I (Z CH2 CH CH2 (Z CH2 CFI-CH, CH2 (Z CB ! = CH CH2 C0O( CHz)-0CO(CHz)-(Z 口2 CI(,=C C00(CHz)l, So□N) I(CHz)TI(Z CH,=C C00(CH2)3NHCOO(CuI2), 1(Z X cnz=c COO(CHz) 3NH (Z-22) coz=c COOCHzCHCHzOOC(CHz)ll=CH (Z CI(2=CH CHzOcO(CHz) - CH,=CH-5o□(CIZ)ll ( Z CH2 -CH CON(CHz), 1-C)13 (Z (Z -27) (Z t Specific examples of CH -1 and -2 include the following organic residues, but the present invention It is not limited to.

However, on each side below, R64 represents an alkyl group having 1 to 4 carbon atoms, -CH2 (J or -CH, Br, and R6
S is an alkyl group having 1 to 8 carbon atoms, →cot- to -OR,, (R,, represents the above meaning, l represents an integer of 2 to 8), -CH2C1 or -
CHJr, R6 & represents -H or -CH3, R
6? represents an alkyl group having 1 to 4 carbon atoms, and Q is -0-1
-5- or N (R&4 represents the above meaning), p represents an integer of 1 to 26, q represents an integer of 0 or 1 to 4, r represents an integer of 1 to 10, J is O or 1~
An integer of 4 is shown, and k is an integer of 2 to 6.

(W-1) →CH2→1- (W-2) CH=　CH (W-3) (enemy-5) CH- A4 (L6) 1←CH Hz%- (jl-8) CH2 C-CH.

R&4 (R,4 may be the same or different) (R5° may be the same or different) (W-11) +CHzC1hOCH2CH2→ynOcHzcH2+
V (W-12) +CHzCHtS CH2CHz→7-(W-13) +CHzCHzSC1bCHzOCHtCHz→7-C
H3 CH3 N,N The macromonomer (MB) represented by the general formula (nla) is described in Polymer Science Yoshin, [Polymer Data Handbook (Basic W
) J (published in 1986) Baifukan et al.
Only in the hydroxyl group at one end of a polyester oligomer with a weight average molecular weight of 1 x 103 to 1.5 x 104 synthesized by a polycondensation reaction of diols and dicarboxylic acids, dicarboxylic acid anhydrides, or dicarboxylic acid esters, high It can be easily produced by introducing a polymerizable double bond group through a molecular reaction.

Polyester is synthesized by a conventionally known polycondensation reaction, but specifically, Eibe Takiyama, "Polyester Resin Handbook," Nikkan Kogyo Shimbunsha (published in 1986)
, Polymer Science Extra Line “Polycondensation and Polyaddition” Imori Publishing (1980
Annual), 1. Goodman rEncyclop
edia of Polymer 5science
and Engineering VOI 12J p
i, John Wiley & 5ons (19
It can be synthesized according to the method described in 1985).

The method of introducing a polymerizable double bond group only into the hydroxyl group at one end of a polyester oligomer is to synthesize it by using a conventionally known reaction of esterifying an alcohol from a low-molecular compound or a reaction of converting an alcohol into a urethane. be able to.

That is, a method in which a macromonomer is synthesized by esterification by reaction with carboxylic acids, carboxylic acid esters, carboxylic acid halides, or carboxylic acid anhydrides containing a polymerizable double bond group in the molecule; This can be achieved by a method in which a macromonomer is synthesized by reacting with a monoisocyanate containing a polymerizable double bond group to form a urethane.

Specifically, Nippon Kagaku Yoshin's ``New Experimental Chemistry Course ■''.

Synthesis and Reactions of Organic Compounds [■], Chapter 5, Maruzen■, (
(published in 1977), “Synthesis and Reactions of Organic Compounds [■]
, p. 1652, Maruzen (published in 1978).

-Macromonomer (MB) represented by formula (I[lb)
is a method in which a polyester oligomer is synthesized by a self-polycondensation reaction of carbonic acids containing hydroxyl groups in the molecule, and then a macromonomer is synthesized by a polymer reaction similar to the macromolecular synthesis of the general formula ([[la)]. can be produced by a living polymerization reaction of carboxylic acids containing a polymerizable double bond group and lactones. Specifically, T, Yasuda, T, Aida
and S, Inoue J, Macromol, S
ci.

Chem, A, 21.1035 (1984),
T, Yasuda, T, Aida and S, I
noue, Macromolecules, 17.2
217 (1984LS, Sosnowski, S.
5ton+kowski and S, Penczek
Makroa+o1. CheIll, +Mon 3f1
．． 1347 (1987), Y, Gnanou an
dP, Rempp, Makromol, Chem.
, 188 2267 (1987).

T, 5hiota and Y, Goto, J, Ap.
pl, Polya+, Sci,, u.

753 (1967) and the like.

Specific examples of the macromonomer (MB) represented by formula (Iota) or (Illb) that can be used in the present invention are shown below.

However, in each side below, [ ] indicates a repeating unit sufficient to make the weight average molecular weight of the macromonomer IXIO3 to 1.5X10', Q indicates the same content as above, o3 indicates -H or -fi13, l?
thI+ and R69 may be the same or different and each -C
R'IO and R1 may be the same or different and each represents -ct, -Br, -CH2 (J or -CHzBr, S represents an integer from 1 to 25,
t represents an integer of 2 to 12, U represents an integer of 2 to 12, X represents an integer of 2 to 4, y represents an integer of 2 to 6,
2 represents an integer from 1 to 4.

(MB-1) Q.

(MB-2) (MB-3) Q.

CH.

C00(CI(z)zOcO(CHz700(MB-
4) (MB-5) R, (MB-6) l CH,=C C00(CHz+v-NFICOO-car (MB-8) CHz=CH-C1hCHz COO-* (MB-9) (MB (MB ( MB (MB-13) CH,=C C00(CHz)i-Coo-* (MB-14) Mouth.

Q.

CH,=C CONH(CHz)-0CO(CHz)r-COO-Ning (MB-16) (MB-17) (MB-18) (MB-19) I (MB-20) Q.

(MB-21) (A B-22) Q.

(?1B-23) Q.

H3 (MB-24) The resin CB used in the binder resin of the present invention is a copolymerization component containing at least one macromonomer selected from the general formulas (I[la) and (I[Ib)]. The other copolymerization components may be any monomer that satisfies the physical properties of the binder resin described above and can be radically copolymerized with the macromonomer.

Preferably, the copolymer contains 30% to 99.5% by weight of a monomer corresponding to the copolymerization component represented by the general formula (1) shown in the resin [A) as a copolymerization component.

The resin [B] may contain other copolymerization components other than the copolymerization component represented by the general formula (1), and specifically, the resin [B] may contain other copolymerization components other than the copolymerization component shown in the general formula (1). Each corresponding monomer etc. are mentioned.

The proportion of these other monomers as copolymer components is
It is preferable that at most 30% by weight of the total polymer components of the resin CB) be present, and more preferably 20% by weight or less.

Further, in some cases, the electrophotographic photoreceptor of the present invention is desired to have greater mechanical strength while maintaining its excellent electrophotographic properties. For this purpose, the same method as described for resin [A] of introducing heat-curable and/or photo-curable functional groups into the main chain of the graft copolymer can be applied.

That is, also in resin CB), the above formula (I[la)
and/or (llb) macromonomer (MB) and preferably a monomer containing at least one heat-curable and/or photo-curable functional group together with a heptamer corresponding to the repeating unit represented by general formula (1) It is preferable to contain as a copolymerization component. Such heat-curable and/or photo-curable functional groups suitably crosslink the polymers, thereby strengthening the interaction between the polymers and improving the strength of the film. Therefore, the resin of the present invention further containing such a heat-curable and/or photo-curable functional group can prevent the interaction between the binder resin and the zinc oxide particle surface without hindering the adsorption and coating of the binder resin. This has the effect of further improving the film strength.

The resin [B'] of the present invention, which has a specific acidic group bonded only to one end of the polymer main chain, can be obtained by reacting various reagents at the end of a living polymer obtained by conventionally known anionic or cationic polymerization. method (ionic polymerization method), radical polymerization method using a polymerization initiator and/or chain transfer agent containing a specific acidic group in the molecule (radical polymerization method), or the above ionic polymerization method Alternatively, a method of converting a polymer containing a reactive group (for example, an amino group, a halogen atom, an epoxy group, an acid halide group, etc.) at the end obtained by a radical polymerization method into the specific acidic group of the present invention by a polymer reaction. It can be easily produced by the following synthesis method.

Specifically, P, Kano eyfuss + R, P, Quir
k+ Encycle.

Polym, Sci, Eng, +7.551
(1987), Yoshiki Nakajo, Yuya Yamashita “Dye and Medicine j, a
, 232 (1985), Akira Ueda and Susumu Nagai, "Science and Industry" Deaf, 57 (1986), and other reviews and documents cited therein.

Specifically, the chain transfer agent to be used is, for example, a mercapto compound containing the acidic group or the above-mentioned reactive group (i.e., a group that can be induced into the acidic group) (for example, thioglycolic acid, thiomalic acid, thioglycolic acid, etc.). Salicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3- (N (2-
Mercaptoethyl)carbamoyl]propionic acid, 3C
N-C2-mercaptoethyl) aminocopropionic acid,
N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto- 2-propatol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole,
2-mercapto-3 pyridinol, 4(2-mercaptoethyloxycarbonyl)phthalic anhydride, 2-mercaptoethylphosphonoic acid, 2-mercaptoethylphosphonoic acid monomethyl ester, etc.), or the above polar groups or substituents. iodized alkyl compounds (e.g. iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanol,
iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

Specific examples of the polymerization initiator containing the acidic group or a specific reactive group include 4,4'-azobis(4-cyanovaleric acid) and 4,4'-azobis(4-cyanovaleric acid). grass acid chloride), 2.2'-azobis(2cyatuburobanol), 2.2'-azobis(2-cyanopentanol), 2.2''-azobis(2-methyl-N-
(2-hydroxyethyl)-propioamide), 2
．． 2'-Azobis(2-methyl-N-[1,1-bis(
hydroxymethyl)-2-hydroxyethyl]propioamide), 2,2'-azobis(2-[1-(2-hydroxyethyl)-2-imidacillin-2-yl]propane), 2,2'-azobis(2 -(2imidacylin-2-yl)propane) 2.2'-Azobis[2-(
4,5,6,7-tetrahydro-18-,1,3-diazopin-2-yl)propane] and the like.

The amount of each of these chain transfer agents or polymerization initiators is 0.05 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total monomers.

In the present invention, resin [A] and resin [B] (
(B') can also be used in combination with other resins. Examples of such resins include alkyd resins, polybutyral resins, polyolefins, ethylene-vinyl acetate copolymers, styrene resins, styrene-butadiene resins, acrylate-butadiene resins, vinyl alkanoate resins, and the like.

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

In addition, when the resin [A] and/or [B] of the present invention contains the thermosetting functional group, in order to promote the crosslinking reaction in the photosensitive layer film, reaction promotion may be performed as necessary. Agents may also be added. In the case of a reaction mode that forms a chemical bond between functional groups, examples thereof include organic acids (acetic acid, propionic acid, butyric acid, henzensulfonic acid, P-)luenesulfonic acid, etc.), crosslinking agents, and the like.

As a crosslinking agent, specifically, Shinzo Yamashita and Tosuke Kaneko ed.
Compounds described in "Crosslinking Agent Handbook" published by Taiseisha (1981) and the like can be used. For example, commonly used crosslinking agents such as organic silanes, polyurethanes, and polyisocyanates, and curing agents such as epoxy resins and melamine resins can be used.

In the case of a polymerizable reaction mode, a polymerization initiator (peroxide, azobis-based compound, etc., preferably an azobis-based polymerization initiator), a monomer containing a polyfunctional polymerizable group (for example, vinyl Methacrylate, allyl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinate, divinyl adipate, diallyl succinate,
2-methylvinyl methacrylate, divinylhenzen, etc.)
etc.

Further, in the present invention, when using a binder resin containing such a thermosetting functional group, a thermosetting treatment is performed. This heat curing treatment can be carried out by tightening the drying conditions during conventional photoreceptor production. For example, from 60°C to
What is necessary is just to process at 120 degreeC for 5 minutes - 120 minutes. When the above-mentioned reaction accelerator is used in combination, it becomes possible to perform the treatment under milder conditions.

The ratio of the amount of resin [A] (including (A')) and resin [B] (including (B')) used in the present invention depends on the type, particle size, and surface condition of the inorganic photoconductive material used. Although it varies depending on the situation, the ratio of resin [A] and resin [B] used is generally 5 to 5.
60:95-40 (weight ratio), preferably 10-40
The ratio is 40 to 90 to 60 (weight ratio).

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

The total amount of binder resin used for the inorganic photoconductive material is 10 to 1 (10
It is used in a proportion of 15 to 50 parts by weight, preferably 15 to 50 parts by weight.

In the present invention, various dyes can be used in combination as spectral sensitizers, if necessary. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (No. 8) p. 12,
C, J, Young et al. RCA Review 15.
469 (1954) Wataru Kiyota, Transactions of the Institute of Electrical Communication Engineers J 63-C (No, 2) 97 (1980), Yuji Harasaki et al., Industrial Chemistry Journal, 7B and 188 (1963)
), Tadaaki Tani, Journal of the Photographic Society of Japan, 208 (1972), etc., carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, phthalein dyes, polymethine dyes (e.g., oxonol dyes, merocyanine dyes) , cyanine dye, logocyanine dye, styryl dye, etc.), phthalocyanine dye (which may contain metal), and the like.

More specifically, examples of those mainly using carbonium dyes, triphenylmethane dyes, xanthine dyes, and phthalein dyes include Japanese Patent Publication No. 452/1983, Japanese Patent Application Laid-open No. 90334/1983, and Japanese Patent Application Laid-Open No. 50-90334. -114227, JP 53-39130, JP 53-82353,
U.S. Patent No. 3,052,540, U.S. Patent No. 4.05
Examples thereof include those described in No. 4,450, JP-A-57-16456, and the like.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as logcyanine dyes include F, M
,Harm+*ar rThe Cyanine D
yes and Related Compounds
” etc., and more specifically, U.S. Pat. Nos. 3.047.384 and 3,110,5
No. 91, No. 3,121,008, No. 3,125, 44
No. 7, No. 3.128.179, No. 3,132.942
No. 3,622,317, British Patent No. 1,226,
No. 892, No. 1,309.274, No. 1,405,8
No. 98, Special Publication No. 48-7814, No. 55-18892
Examples include the dyes described in No.

Furthermore, as a polymethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A-47840, JP-A-47-44180, and JP-B-Sho 51-41061 are used.
No., JP-A-49-5034, JP-A-49-45122
No., JP-A-5746245, JP-A-56-35141
No., JP-A-57-157254, JP-A-61-260
No. 44, JP-A No. 61-27551, U.S. Patent No. 3,6
No. 19.154, U.S. Pat. No. 4,175,956, r
Research Disclosure J 19B
2, 216, pp. 117-118.

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

Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers, such as chemical sensitizers, may be used in combination.
8) Electron-accepting compounds (e.g., halogens, benzoquinone, chloranil, acid anhydrides, organic carboxylic acids, etc.) cited in the review on page 12, Hiroshi Komon et al., ``Recent development of photoconductive materials and photoreceptors. ``Practical Applications'' Chapters 4 to 6 2 Nippon Scientific Information Co., Ltd. Publishing Department (1986) Review Cited Boaryl Alkane Compounds, Hindered Phenol Compounds, p-
Examples include fluorine diamine compounds and the like.

The amount of these various additives added is not particularly limited, but
Usually 0.0001 to 2.0 parts per 100 parts by weight of photoconductor.
It is 0 parts by weight.

The thickness of the photoconductive layer is preferably 1 to 100 microns, particularly 10 to 50 microns.

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

In some cases, an insulating layer is added mainly for the purpose of protecting the photoreceptor, improving its 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 between 5 and 70μ, in particular 1
It is set to 0 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 μm, particularly 10 to 3 μm.
0μ is suitable.

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

The photoconductive layer according to the invention can be provided on a conventionally known support. Generally speaking, the support for the electrophotographic photosensitive layer is preferably electrically conductive.As the electrically conductive support, for example, a base material such as metal, paper, or plastic sheet impregnated with a low-resistance substance is used in the same manner as in the past. those that have been subjected to conductive treatment, such as those that have been coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and also to prevent curling, and those that have been coated with at least one layer for the purpose of preventing curling, etc. Those with a water-resistant adhesive layer on the surface of the body, those with at least one or more pre-coated layers provided on the surface layer of the support as required, and those with a conductive plastic base coated with Affi, etc., laminated on paper. You can use the ones that have been prepared.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, "Electronic Photography", 14, (No. 1), 22~
11 (1975), Hiroyuki Moriga, “Introductory Special Paper Chemistry”
Kobunshi Publishing Association (1975), M, F, Hoover+J
, Macrosol, Sci, Che++, A 4
(6), pages 1327 to 1417 (1970), etc. are used.

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

Synthesis example 1 of macromonomer (MA): (MM-1)
A mixed solution of 30 g of triphenylmethyl methacrylate and 100 g of toluene was thoroughly degassed under a nitrogen stream and heated to 120 g.
Cooled to ℃. 1,1-diphenylbutyllithium 1.
0g was added and reacted for 10 hours.

Further, a mixed solution of 70 g of ethyl methacrylate and 100 g of toluene was added to this mixed solution after sufficiently degassing under a nitrogen stream, and the mixture was reacted for further 10 hours.

After bringing this mixture to 0°C, add 60m of carbon dioxide gas! /si
Aeration was performed for 30 minutes at a flow rate of n to stop the polymerization reaction.

The resulting reaction solution was brought to a temperature of 25°C with stirring, and 6 g of 2-hydroxyethyl methacrylate was added, followed by 12 g of dicyclohexylcarbodiimide, 1.0 g of 4-N,N-dimethylaminopyridine, and 20 g of methylene chloride. The mixed solution was added dropwise over 30 minutes, and the mixture was stirred as it was for 3 hours.

After filtering off the precipitated insoluble matter, 10IIi of a 30% hydrogen chloride ethanol solution was added to this mixed solution 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 l of petroleum ether. The polymer obtained by collecting the precipitate and drying it under reduced pressure is FSw
The yield was 56 g at 6.5 x 10'.

(MM-1>L Synthesis example 2 of macromonomer (MA): (MM-2
) A mixed solution of 5 g of benzyl methacrylate, 0.1 g of aluminum methyl (tetraphenylborufinate) 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 251 cm through a glass filter, and reacted for 12 hours. After further adding 45 g of butyl methacrylate to this mixture and irradiating it with light for 8 hours, the reaction mixture was added with 45 g of butyl methacrylate.
- 10 g of bromomethylstyrene was added 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, it was reprecipitated in petroleum ether 500-
The precipitate was collected and dried. The yield of the obtained polymer was 33g.
″cF1117×103 Tea Tsuta.

(MM-2) Synthesis Example 3 of Macromonomer (MA): (MM-3) A mixed solution of 20 g of 4-vinylphenyloxytrimethylsilane and 100 g of toluene was sufficiently degassed under a nitrogen stream and heated to 0°C. Cooled. 2 g of 1.1-diphenyl 3-methylpentyllithium was added and stirred for 6 hours. Further, a mixed solution of 80 g of 2-chloro-6 methylphenyl methacrylate and 100 g of toluene was added to this mixture after thorough degassing under a nitrogen stream, and the mixture was reacted for 8 hours. Add 3 ethylene oxide to this reaction mixture with thorough stirring.
After venting for 30 minutes at a flow rate of 0 d/min, the temperature was 15°.
C., 12 g of methacrylic acid chloride was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours.

Next, add 1 part of 30% hydrogen chloride ethanol solution to this reaction mixture.
After adding 0g of the mixture and stirring at 25°C for 1 hour, it was reprecipitated in petroleum ether If, and the collected precipitate was washed twice with 300ml of diethyl ether and dried. The resulting polymer was ˜7.8×10′ with a yield of 55 g.

(MM-3) Synthesis example 4 of CH3 macromonomer (MA): (MM-4
) A mixed solution of 40 g of triphenylmethyl methacrylate and 100 g of toluene was thoroughly degassed under a nitrogen stream, and -
Cooled to 20°C.

2 g of 5ec-butyllithium was added and reacted for 10 hours.

Next, add 60 g of styrene and 1 gram of toluene to this mixed solution.
After fully deaerating 00 g of the mixed solution under a nitrogen stream, it was added and reacted for 12 hours. After the mixture was cooled to 0°C, 1 g of benzyl bromide was added and reacted for 1 hour.
The reaction was continued for an additional 2 hours at °C.

To this reaction mixture was added 10% of a 30% hydrogen salt solution in ethanol.
g and stirred for 2 hours. After filtering off the insoluble matter, it was reprecipitated in n-hegyusan 11, and the precipitate was collected and dried under reduced pressure.

The yield of the obtained polymer was 58g and 4.5XIO” Met.

(MM-4) Synthesis example 5 of macromonomer (MA): (MM-5
) phenyl methacrylate 70g, hensyl-N-hydroxylethyl-N-ethyldithiocarbame-) 4.8
g of the mixture was sealed in a container under nitrogen flow and kept at a temperature of 60°C.
It was heated to This was irradiated with light for 10 hours using a 40 cm high pressure mercury lamp from a distance of 10C11 through a glass filter for photopolymerization. After adding 30 g of acrylic acid and 180 g of methyl ethyl ketone to this, the mixture was replaced with nitrogen and irradiated with light for 10 hours again.

To the obtained reaction mixture, 12 g of 2-isocyanatoethyl methacrylate was added dropwise at a temperature of 30° C. over 1 hour, and the mixture was further stirred for 2 hours.

The obtained reaction product was reprecipitated in 1.5f hexane, collected and dried. The resulting polymer weighed 68 g and measured ~6.0 x 10''.

(MM-5) CH.

Synthesis example 1 of resin [A]: (A-1) 80 g of ethyl methacrylate, macromonomer (MM-
1) A mixed solution of 120 g and 150 g of toluene was heated to 95° C. under a nitrogen stream. 2. Add 6 g of 2'-azobis(isobutyronitrile) (^IBN) and react for 3 hours, then add A, 1. B and 2 g of N were added to react.

~ of the obtained copolymer was 9X103.

(A-13 Synthesis example 1 of resin [A] (A-2) 2-chlorophenyl methacrylate 70 g, Mac 1:l
Mo/? A mixed solution of 30 g of -(MM-2), 2 g of n-dodecylmercaptan, and 100 g of toluene was heated to 80° C. under a nitrogen stream. 2. Add 3 g of 2'-azobis(isovaleronitrile) (AIVN) and react for 3 hours, and then add A, 1. V, N, and Ig were added and reacted for 2 hours. Next, A.1. 1 g of B and N were added, heated to 90'C, and reacted for 3 hours. ~ of the obtained copolymer was 7.6 x 103.

(A-2) Synthesis examples 3 to 18 of resin [A]: [A-3] to [A-
18] Copolymers shown in Table 1 below were synthesized under the same polymerization conditions as in Synthesis Example 1 of Resin [A), except that ethyl methacrylate was replaced with another monomer. ~ of each obtained polymer was 5X10' to 9X10'.

Table-1 x + y + 20 = 100 (weight ratio) Synthesis Examples 19 to 35 of Resin [A]: [A-19] to [A-35] In Synthesis Example 2 of Resin [A], Macro Seven Tour (MM -2
) The copolymers shown in Table 2 below were synthesized under the same polymerization conditions as in Synthesis Example 2, except that another macromonomer (MA) was used instead of . The Fl- of each obtained polymer is 2X10'~l
It was Xl0'.

Maromo Mar MB: M-1,4-butanediol 90.1g, succinic anhydride 10
5.1 g, p-) A mixture of 1.6 g of luenesulfonic acid monohydrate and 200 g of hydrene was added to a Dean-3tarR
4 hours under reflux with stirring in a flask equipped with a reflux device.
heated for an hour. The amount of water distilled off azeotropically with the toluene solvent was 17.5 g.

Next, a mixture of 17.2 g of acrylic acid and 150 g of toluene and 1.0 g of t-butylhydroquinone were added to the above reaction mixture, and the mixture was reacted under reflux for 4 hours with further stirring. After cooling to room temperature, it was reprecipitated into methanol 21, and the precipitated solid was collected by filtration and dried under reduced pressure.

The yield was 135 g, and the obtained macromonomer (M-1)
The weight average molecular weight was 6.8 x 10''.

(M-1) C1, -CH-COO-CH! srOco(CH*ter
cOo +H malomer MB: M- 1i6-hexanediol 120L geltanic anhydride 11
A mixture of 3.0 g of 4.1 g5p-) luenesulfonic acid monohydrate and 250 g of toluene was added to the macromonomer (MB
) was reacted under the same conditions as in Synthesis Example 1. The amount of water distilled off azeotropically was 17.5 g.

After cooling to room temperature, n-hexane 2I! , and the liquid was collected after decantation and dried under reduced pressure.

The above reaction product was dissolved in toluene and 0.0% was dissolved in toluene. When the carboxyl group content was measured by neutralization titration with IN potassium hydroxide methanol solution, it was found to be 500 μmol/g.
It became.

A mixture of 100 g of the above solid, 88.6 g of methacrylic, 1.0 g of 5L-butylhydroquinone, and 200 g of methylene chloride was dissolved at room temperature with stirring.

Dicyclohexylcarbodiimide (D, C, C,) 20
．． 3g, 4-(N,N-dimethyl)aminopyridine 0.
A mixed solution of 5 g and 100 g of methylene chloride was titrated into the above mixture under stirring for 1 hour. The mixture was further stirred for 4 hours.

D, C, C. As the solution was added dropwise, insoluble crystals precipitated. The reaction mixture was filtered to remove insoluble matter through a 200 mesh nylon cloth.

Hexane 2j for the filtrate! The powder was collected by filtration. After adding acetone 50 (1+d) and stirring for 1 hour, the insoluble fraction was gravity filtered using filter paper.The total volume of the filtrate was η
After concentrating under reduced pressure until the solution was dissolved, the solution was added to 1 liter of ether and stirred for 1 hour. The precipitated solid was collected by filtration and dried under reduced pressure.

The weight average molecular weight of the macromonomer (M-2) obtained in a yield of 53 g was 8.2 x 10'.

(M-2) 500 g of 12-hydroxystearic acid was heated to an external temperature of 150 g.
The mixture was stirred in an oil bath at 10° C. under reduced pressure of 10 to 15 smHg for 10 hours while distilling off the water produced.

The carboxyl group content of the obtained liquid was 600 μmol.
/g. A mixed solution of 100 g of the above liquid, 18.5 g of methacrylic anhydride, 1.5 g of St-butylhydroquinone, and 200 g of tetrahydrofuran was mixed at a temperature of 40 g.
The reaction mixture was stirred for 6 hours at ~45°C in 1 liter of water.
The mixture was added dropwise over 1 hour while stirring, and further stirred for 1 hour. Leave it to stand, remove the settled liquid with decanty silane, and remove it.
It was dissolved in 200 g of IF and reprecipitated in 1 liter of methanol. The precipitated liquid material was taken out using decanthisilane and dried under reduced pressure.

The weight average molecular weight of the macromonomer (M-3) obtained in a yield of 62 g was 6.7 x 10'.

(M-3) S, Penczek et al, Makro
mol, Chem, +188+ 1347 (1987
), a macromonomer (M-4) having the following structure was synthesized.

(M-4) Weight average molecular weight: ? , 3X10” Macromonomer: M- Macromonomer (M-4) 50g, methanol 3g.

t ~ 0.5 g of butylhydroquinone and 1 part of methylene chloride
To 50 g of mixed solution, [1, C, C, 6 g, 4-N
A mixed solution of 0.1 g of N-dimethylaminopyridine and 10 g of methylene chloride was stirred at a temperature of 20 to 25°C for 3 hours.
The mixture was added dropwise over a period of 0 minutes, and the mixture was further stirred for 4 hours. After adding 5 g of formic acid to this reaction mixture and stirring for 1 hour, the precipitated insoluble matter was filtered off. The filtrate was reprecipitated into 1 liter of methanol, the solvent was removed with decanethisilane, and the precipitate was collected and dried under reduced pressure. The yield of the obtained viscous substance was 28 g, and what was the weight average molecular weight (Frw)? , 5 x 10'.

(M-5) CHl ot-c COO-HCCoo-HCH+cHs B A, B Ethyl methacrylate-1-85g, macromonomer (MB
) 15 g of compound (M-1) of Synthesis Example 1 and toluene 2
00 g of the mixture was heated to a temperature of 75° C. under nitrogen flow.

1.0.6 g of 1'-azobis(cyclohexane-1-carbonitrile) (abbreviation ^, B, C, C,) was added and stirred for 4 hours. Further, 0.3 g of A, B, C, and C were added for 3 hours, and then 0.2 g of A, B, C, and C were added and stirred for 4 hours. The weight average molecular weight (~) of the obtained copolymer was 9.1 x 104.

(B-1) 95 g of benzyl methacrylate, macromonomer (MB
) A mixture of 5 g of the compound (M-4) of Synthesis Example 4 and 7200 g of Torx was heated to 75°C under a nitrogen stream.
It was heated to

4.4°-azobis(2-cyanovaleric acid) (abbreviation: ^,
c.

V,) 0.6 g was added and stirred for 4 hours.
,c.

0.3g of V was added and stirred for 3 hours, and then 0.2g of A, C, and V were added and stirred for 3 hours. The weight average molecular weight of the obtained copolymer was 1.2 x 10'.

(B-23 Under the same polymerization conditions as in Synthesis Example 1 of Resin [B], Table 3 below
Each of the resins [B-3] to [B-13] were synthesized.

The weight average molecular weight of each resin obtained was 8.5 x 10'
~1. It was OX 10'.

(Blank below) Person B 4-3: In Synthesis Example 1 of B-1 to B-2 resin [B], the following mercapto compound was used as a chain transfer agent and the polymerization conditions shown in Table 4 below were carried out under the same polymerization conditions. Each resin (
B-14] to [B-23] were produced.

The weight average molecular weight of each resin obtained was 8. OX 10'～
It was 1.0×10'.

(Blank below) A of B ~1: B- ~ B-3 In Synthesis Example 2 of Resin [B], similar polymerization was carried out by replacing A, C, and ν with other azobis compounds as the azobis compounds. Resin CB) shown in Table 5 was produced under the following conditions.

The weight average molecular weight of each resin [B] obtained was 8.0×10
It was 4-2X10'.

(Hereinafter, blank spaces) A to 2B- to B-4 of B Each resin [B] in Table 6 below was synthesized under the same polymerization conditions as in Synthesis Example 1 of Resin [B].

The weight average molecular weight of the obtained copolymer is 9.0XlO'~
It was 1.2XlO'.

(Leaving space below) A mixture of 80 g of benzyl methacrylate, 20 g of the compound (M-5) of Synthesis Example 5 of macromonomer (MB), and 200 g of toluene was added to the resin [B]. ] The reaction was carried out under the same polymerization conditions as in Synthesis Example 2 to synthesize resin (B-42).

The weight average molecular weight of the obtained copolymer was 9.8 x 10
'Met.

(B-423 Resin (A-2) 6g (as solid content), Resin (B-1
A mixture of 334 g (as solid content), 0.018 g of cyanine dye (1) having the following structure, and 300 g of toluene was dispersed in a ball mill for 4 hours to prepare a photosensitive layer-forming product, and this was applied to conductive-treated paper. Apply with a wire bar so that the dry coating weight is 25g, and heat it at 110°C for 30 minutes.
An electrophotographic light-sensitive material was prepared by drying for a second and then leaving it in a dark place under conditions of 20"C and 65% RH for 24 hours.

Cyanine dye (1) 1 uIN: Instead of the binder resin used in Example 1, 6 g of resin (R-1) with the following structure and poly(ethyl methacrylate) (ffw 2.4 x 10ゝ): Resin (R -2)
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that 34 g was used.

(R-1) COOCzHs CC00 Hf 6.5X10' This 1 tfu: Except for using 6 g of resin (R-3) and 34 g of resin (R-2) having the following structure instead of the binder resin used in Example 1. An electrophotographic material was prepared in the same manner as in Example 1.

(R-3) H3 HOOC-CHg-3-(CI rich-α to CC00Cz
ll sff 6.5X10 1u1q: Instead of the binder resin used in Example 1, resin
-3) An electrophotographic light-sensitive material was produced in the same manner as in Example 1, except that 6 g and a resin [R-434 g] having the following structure were used.

(R-4)] (Weight ratio) Frw 8.0X10' Film properties (surface smoothness), electrostatic properties, imaging properties, and imaging when the environmental conditions are 30°C and 80% RH of these photosensitive materials I looked into gender. Furthermore, when these photosensitive materials are used as original plates for offset masters, the photoconductive non-greasing property (expressed as the contact angle with water of the photoconductive layer after desensitizing treatment)
and printability (scumming, rigidity resistance, etc.) were investigated.

The above results are summarized in Table-7.

(The following is a blank space) The manner in which the evaluation items shown in Table 7 are implemented is as follows.

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

Note 2) Mechanical strength of photoconductive layer: The surface of the photosensitive material obtained was tested using a Hayton-14 type surface test material (
Abrasion powder was removed by repeated probing with emery paper (11000) 500 times at a load of 70 g/c+6 using a photosensitive layer (manufactured by Shinrai Kagaku ■), and the residual film rate (%) was determined from the weight loss of the photosensitive layer, which was taken as the mechanical strength.

Note 3) Electrostatic properties: In a dark room at a temperature of 20°C and 165% RH, each photosensitive material was subjected to corona discharge at -6 kV for 20 seconds using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Denki ■), and then Leave it for 10 seconds, and at this time the surface potential v1
The potential v13° was measured after being allowed to stand still for 120 seconds in the dark.
)) was determined by (V+3o/V+o)X100(%).

In addition, after the surface of the photoconductive layer was charged to -500 V by corona discharge, it was irradiated with monochromatic light with a wavelength of 785 na+, and the time required for the surface potential (V + O) to attenuate to 1/10 was determined.
From now on, exposure amount E17. . (erg/cd) is calculated.

Furthermore, E1/. -500 by corona discharge as in the measurement
After being charged to ■, irradiating it with monochromatic light with a wavelength of 785 nm,
The time required for the surface potential (V+.) to attenuate to 1/100 is determined, and from this the exposure amount is E171°. (erg/cd)
Calculate.

Note 4) Imaging performance: Each photosensitive material was left for one day and night under the following environmental conditions.

Next, the surface of the photosensitive material was charged at -5 kV, and using a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 785 nm) with an output of 2.8 mW as a light source, a 50 erg
A copy obtained by developing and fixing using ELP-7 (manufactured by Fuji Photo Film) as a liquid developer after exposure at a pitch of 25 pl and a scanning speed of 300 cm/sec under an irradiation dose of /cj. Images (capri, image quality) were visually evaluated.

Environmental conditions during imaging were 20°C65%R11 and 30°C8
It was carried out at 0% R11.

Note 5) Contact angle with water: Each photosensitive material is exposed to light by passing it through an etching processor once using a solution prepared by diluting the fat-free processing liquid EPL-EX (manufactured by Fuji Photo Film) twice with distilled water. After desensitizing the surface of the conductive layer, droplets of distilled water 23' are placed on it.
The formed contact angle with water is measured with a goniometer.

Note 6) Printing durability: Each photosensitive material is plate-made under the same conditions as Note 4) above to form a toner image, desensitized under the same conditions as Note 5) above, and this is used as an offset master. , offset printing a
(Sakurai Seisakusho Oliver Model 52) indicates the number of sheets that can be printed without causing problems with background stains in the non-image areas of the printed matter and image quality in the image areas (the higher the number of prints, the better the rigidity resistance) .

As shown in Table 7, in the photosensitive material of the present invention, the smooth film of the photoconductive layer had good strength and electrostatic properties, and the actual copied images had no ground blur and the quality of the copied images was clear. This is presumed to be due to the photoconductor and the binder resin being sufficiently adsorbed and covering the particle surface. For the same reason, even when used as an offset master original, the desensitizing treatment with the degreasing 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 I actually examined and observed the background stains on the printed matter, no background stains were observed.

Moreover, the electrostatic properties of Comparative Examples A to C were lower than those of the photosensitive materials of the present invention. In Comparative Example C, the film strength was improved and the electrostatic properties were also V. ,D,R,R,,E17
A value of 1° was quite satisfactory.

but,[! 17. . . Looking at the value, the value was higher than that of the photosensitive material of the present invention. E171°.

In actual imaging performance, the value indicates how much potential remains in the non-image area (already exposed area) after exposure. Indicates that stains will no longer occur.

Specifically, it is necessary to make the residual potential below -10V, that is, how much exposure is required to actually make it below -10V?Scanning with semiconductor laser light In the exposure method, it is very important to reduce vl 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.).

From the above, when an image was actually captured using an apparatus with a slightly lower exposure dose, Comparative Example A could not obtain a satisfactory copy image because D, R, and R were extremely low.

In Comparative Example B, the image deteriorated significantly under conditions of high temperature and high humidity, resulting in a decrease in density in the image area, fading of thin lines and characters, and occurrence of soil retention in the non-image area. In Comparative Example C, the image was quite satisfactory under room temperature and room temperature conditions, but under high temperature and high temperature conditions, ground blurring, fading of fine lines in the image area, etc. occurred. In addition, even when used as an offset master original plate, under printing conditions that allow the photosensitive material of the present invention to print 10,000 sheets or more, in all of Comparative Examples A to C, background stains occurred in the non-image areas of the printed matter at the beginning of printing. have done. This means that a clear copy image cannot be obtained.
This was caused by the fact that the soil was unable to be removed even with desensitization treatment.

From the above, an electrophotographic photoreceptor that satisfies electrostatic properties and printability can be obtained only when the resin of the present invention is used.

Resin (A-2) and Resin (B-1) in Example 1
In place of, each resin [A] and each resin [B] in Table 8 below
Each electrophotographic photoreceptor was produced in the same manner as in Example I, except that .

Electrostatic properties were measured in the same manner as in Example 1. Display the results -
8.

(Margins below) The surface electrostatic properties are measured values under the conditions (30°C, %R11), and when printed in the same manner as in Example 1 using as an offset master original, both values were 10,000 yen. I was able to print more than one page.

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 [A'].

In Example 1, the resin shown in Table 9 below was used as the binder resin [A
]6.5. Electrophotography was carried out under the same conditions as in Example 1, except that 33.5 g of resin [B] was replaced with 0.019 g of dye (II) having the following structure in place of 0.2 g of cyanine dye (1) G. A photosensitive material was produced.

Dye (II) (Cl1g) asOs” (C1,)
asOJ table The photosensitive materials of the present invention all have chargeability, dark charge retention,
It has excellent photosensitivity, and the actual copied images can be used even at high temperatures (30℃).
, 80% RH), it provided clear images with no soil blurring.

Furthermore, when this was used as an original plate for an offset master, more than 10,000 copies of clear image quality prints with no background blur were printed.

and D 6.5 g of either resin (A-13 (Example 34) or resin (A-83 (Example 35)), resin (B-2333,
5g, zinc oxide 200g, uranine 0.02g, methine dye (III) with the following structure 0.035g, methine dye (IV) with the following structure 0.02g, phthalic anhydride 0.2
0g and 300g of toluene using a homogenizer (
Made by Nippon Seiki ■) Medium, I x 10'r, p, s, 15
Disperse for 1 minute to prepare a photosensitive layer formed product, apply it to conductive treated paper with a wire bar so that the dry coating weight is 25 g/rd, dry for 1 minute at 110°C, and then dry in the dark for 20 minutes. Each electrophotographic photoreceptor was produced by leaving it for 24 hours under the conditions of 'C and 65% RH.

Methine dye (I[l) Methine dye (IV) In Example 34, resin (A-136, 5g, resin (
B-2) Instead of 33.5 g, the above resin [R3
] A photosensitive material was produced in the same manner as in Example 34, except that 6.5 g of the resin (R-4) and 33.5 g of the resin (R-4) were used.

In the same manner as in Example 1, the characteristics of each photosensitive material were investigated. The results are summarized in Table 10 below.

In the measurements shown in the table above, the electrostatic properties and imaging properties were carried out in the same manner as in Example 1, except that the following procedures were followed.

Note 7) Electrostatic characteristics El/+6 and E, 7. . . Measuring method: After the surface of the photoconductive layer is charged to -400V by corona discharge, the surface of the photoconductive layer is irradiated with visible light at an illuminance of 2.0 lux, and the surface potential (V+.) is 1/10 or E, 71
゜. Find the time it takes for the light to attenuate, and then calculate the exposure amount El
/l. Or E, /,. . Calculate (looks/seconds).

Note 8) Imaging properties After leaving each photosensitive material for one day and night under the following environmental conditions, use a fully automatic plate making machine 1! A copy image (fogging, image quality) obtained by plate making using EPL-T as a toner with PL-404V (manufactured by Fuji Photo Film ■) was visually evaluated. The environmental conditions during imaging were 20°C, 65% R11(1) and 30°C.
It was carried out at 80% RH (It). 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. However, in terms of electrostatic properties, the comparative example has a particularly high photosensitivity E17. . . The value of has increased. The photosensitive material of the present invention has good electrostatic properties,
Furthermore, Example 35 using the resin [A] having a specific substituent group had very good results, especially the value of El/I11° was small.

When examining the actual imaging performance, it was found that in the comparative example, in addition to the original, the frame of the cut out and pasted portion (i.e. pasting trace) was observed as background stains in the non-image area.

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 smudge were obtained for all of the products of the present invention. However, in the comparative example, the above-mentioned pasting marks were not removed even with the desensitizing 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.

In Example 34, in place of 6.5 g of resin (A I) and 33.5 g of resin [B-2], 1 was added to Table 11 below.
Each photosensitive material was produced in the same manner as in Example 34, except that 6.5 g of resin [A] and 33.5 g of resin [B] were used.

Table 11 All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention, and photosensitivity.
Even under the harsh conditions of "C180%RH", it provided clear images with no occurrence of ground blur or fine line skipping.

Furthermore, when printed as an offset master original plate, clear prints with no background staining were obtained even after printing 10,000 sheets.

6 g of resin (A-36) with the following structure, resin (B-40)
) 30g, zinc oxide 200g, uranine 0.02g,
Rose Bengal 0.04 g, Bromphenol Blue 0.03 g.

A mixture of 0.20 g of phthalic anhydride and 300 g of toluene was dispersed in a ball mill for 3 hours.
．． 2.5 g of 3-xylylene diisocyanate was added and further dispersed in a ball mill for 5 minutes.

The dry adhesion amount is 20g/rd on conductive treated paper.
It was coated with a wire bar so that Next, each electrophotographic photoreceptor was prepared by leaving it for 24 hours in a dark place at 20° C. and 65% RH.

Resin [A 36] When these photosensitive materials were examined for electrostatic properties and imaging properties in the same manner as in Example 34, they showed good performance.

Furthermore, when printed as an original plate for offset printing, it became possible to print more than 10,000 sheets.

(Effects of the Invention) According to the present invention, an electrophotographic photoreceptor having excellent electrostatic properties and mechanical strength even under severe conditions can be obtained. Further, the photoreceptor of the present invention is effective in a scanning exposure method using semiconductor laser light.

Claims (1)

[Scope of Claims] (1) An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material and a binder resin, wherein the binder resin includes at least one of the following resins [A] and the following resins: [
An electrophotographic photoreceptor comprising at least one of B). Resin [A]; -PO_3H_2 group, -COOH group, -SO_3H group,
At least one selected from phenolic OH group, ▲mathematical formula, chemical formula, table, etc.▼ group {R represents a hydrocarbon group or -OR' group (R' is a hydrocarbon group)}, and a cyclic acid anhydride-containing group. An A-B block copolymer composed of an A block containing at least one polymer component containing one acidic group and a B block containing at least a polymer component represented by the following general formula (I) containing as a copolymerization component at least one monofunctional macromonomer (MA) formed by bonding a polymerizable double bond group to the end of the main chain of the polymer main chain of the B block, with a weight average molecular weight of 1 x 10^3 to 2 ×1
0^4 graft copolymer. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In formula (I), a_1 and a_2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group. A_1 is -COO-, -OCO-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (
l_1, l_2 represent integers from 1 to 3), -O-, -SO_2-, -CO-, -CON
-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CONHC
Represents OO-, -CONHCONH- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (here, Z_1 represents a hydrogen atom or a hydrocarbon group). R_1 represents a hydrocarbon group, provided that A_1 is ▲ formula,
There are chemical formulas, tables, etc. When representing ▼, R_1 represents a hydrogen atom or a hydrocarbon group. ] Binder resin [B]; represented by the following general formula (IIIa) and general formula (IIIb),
A weight average molecular weight of 3 x 10^4 to 1 x 10 containing at least one polyester type macromonomer (MB) having a weight average molecular weight of 1 x 10^3 to 1.5 x 10^4 as a polymer component. ^6 copolymer. General formula (IIIa) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIIb) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In formulas (IIIa) and (IIIb), the brackets [ ] represent repeating units. f_1 and f_2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
hydrocarbon group, -COO-T_1 or -COOT_2 (T_1 and T_2
each represents a hydrocarbon group having 1 to 18 carbon atoms. X_2 is a single bond or -COO-, -OCO-, ▲
There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (u_1u_2 represents an integer from 1 to 3), -CON- (d_1 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms ), -CON
HCONH-, -CONHCOO-, -O-, ▲ Formula,
There are chemical formulas, tables, etc. Represents ▼ or -SO_2-. Y_1 represents a group connecting X_1 and -COO-. W_1 and W_2 may be the same or different from each other,
Each divalent aliphatic group, divalent aromatic group {-O-, -S-, ▲mathematical formula, chemical formula, table, etc. are present in the bond of each divalent organic residue▼(d_2 is a hydrogen atom or carbon number 1-12
represents a hydrocarbon group), -SO_2-, -COO-, -
OCO-, -CONHCO-, -NHCONH-, ▲Mathematical formulas, chemical formulas, tables, etc.▼(d_3 represents the same content as d_2), -SO_2N-(d_4 represents the same content as d_2), and ▲Mathematical formulas , chemical formula, table, etc.) (which may include at least one bonding group selected from ▼) or an organic residue composed of a combination of these residues. R_6_1 represents a hydrogen atom or a hydrocarbon group. f_3, f_4, X_2, Y in general formula (IIIb)
_2 and R_6_2 are each f in general formula (IIIa)
It represents the same content as _1, f_2, X_1, Y_1 and R_6_1. W_3 represents a divalent aliphatic group. (2) In the resin [A], the macromonomer (MA
) and at least one monomer represented by the following general formula (II) as a copolymerization component. General formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼ [In formula (II), R_2 represents a hydrocarbon group. ]
(3) In the resin [A], the macromonomer (M)
Claim (2) characterized in that it contains at least 30% by weight of at least one of the monomers represented by the following general formulas (IIa) and (IIb) as a copolymerization component.
The electrophotographic photoreceptor described above. General formula (IIa) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIb) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X_1 and ~10 hydrocarbon group, chlorine atom, bromine atom, -COZ_3 or -COOZ_3 (Z_3 each represents a hydrocarbon group having 1 to 10 carbon atoms). However, both X_1 and X_2 do not represent hydrogen atoms. L_1 and L_2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- to the benzene ring. ] (4) The resin [B] has -PO_3H_2 groups, -SO_
There are 3H groups, -COOH groups, -OH groups, ▲mathematical formulas, chemical formulas, tables, etc.▼ groups (R_0 represents the same content as R)
and at least one selected from cyclic acid anhydride-containing groups
The electrophotographic photoreceptor according to any one of claims 1 to 3, which is a resin in which a polar group of a species is bonded to an end of a polymer main chain portion of the copolymer.