JP2684435B2 - Electrophotographic photoreceptor - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more particularly, to an electrophotographic photoreceptor excellent in electrostatic characteristics and moisture resistance. In particular, it relates to a CPC photosensitive member having excellent performance.

[Conventional technology]

The electrophotographic photosensitive member has various configurations in order to obtain predetermined characteristics or according to the type of an applied electrophotographic process.

Representative electrophotographic photoreceptors include a photoreceptor having a photoconductive layer formed on a support and a photoreceptor having an insulating layer on the surface, and are widely used.

Photoreceptors composed of a support and at least one photoconductive layer are used for image formation by the most common electrophotographic processes, i.e. charging, image exposure and development, and, if necessary, transfer.

Further, a method using an electrophotographic photosensitive member as an offset master for direct plate making has been widely used. In particular, in recent years, direct electrophotographic lithographic printing has become important as a method for printing high-quality printed matter with a print number of several hundreds to several thousands.

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

Furthermore, research on a lithographic printing original plate using an electrophotographic photoreceptor has been earnestly conducted, and a binder resin for a photoconductive layer having both electrostatic characteristics as an electrophotographic photoreceptor and printing characteristics as a printing original plate. is required.

However, conventionally known binder resins include, in particular, chargeability,
There are many problems in dark charge retention, electrostatic characteristics such as photosensitivity, and smoothness of the photoconductive layer.

In order to solve these problems, a low molecular weight resin containing 0.05 to 10% by weight of a copolymer component containing an acidic group in the side chain of the polymer as a binder resin or an acidic group at the end of the polymer main chain By using a low-molecular-weight resin (w10 ³ to 10 ⁴ ) that binds to, it is possible to improve the smoothness and electrostatic properties of the photoconductive layer and to obtain image quality free of background stains. And JP-A-64-70761.

Further, as a binder resin, a resin containing a polymerization component containing an acidic group in the side chain of the copolymer or bonded to the end of the polymer main chain and containing a heat and / or photocurable functional group. JP-A-1-100554 and Japanese Patent Application No. 63-39690 disclose a technique of using a resin containing an acidic group in the side chain of the copolymer or a resin bonded to the end of the polymer main chain together with a crosslinking agent. Are disclosed in JP-A-1-102573 and Japanese Patent Application No. 63-39691, respectively. Further, a low molecular weight product of the resin (weight average molecular weight 10 ³ to 1
0 ⁴ ) in combination with a resin having a high molecular weight (weight average molecular weight of 10 ⁴ or more) is disclosed in JP-A 64-564 and 63-220149.
No. 63-220140, Japanese Patent Application No. 62-273547, JP-A-1-
No. 116643 and JP-A No. 1-169455 disclose the techniques of using such a low molecular weight compound in combination with a heat-curable and / or photo-curable resin, respectively, in JP-A No. 1-211766 and Japanese Patent Application No. 63-26561. . According to these techniques, the film strength of the photoconductive layer is further sufficiently leveled and the mechanical strength is increased without impairing the above properties due to the use of a resin containing an acidic group at a side chain or at a terminal. Have been.

(Problems to be Solved by the Invention) However, even if these resins are used, it is still insufficient to maintain stable performance when the environment fluctuates remarkably from high temperature and high humidity to low temperature and low humidity. Was. In particular, in the scanning exposure method using a semiconductor laser beam, the exposure time is longer and the exposure intensity is limited as compared with the conventional simultaneous exposure method using visible light. Higher performance is required for light sensitivity.

Furthermore, in the electrophotographic lithographic printing plate precursor, when the scanning exposure method using the semiconductor laser light is adopted, when the conventional photoconductor is actually tested, the above electrostatic characteristics are unsatisfactory, In particular, the difference between E _1/2 and E _1/10 is large, the tone of the copied image becomes soft, and it becomes difficult to further reduce the residual potential after exposure, and the fog of the copied image becomes remarkable, In addition, even when printing is performed as an offset master, a serious problem such as sticking traces of a printed original appears on a printed material has appeared.

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

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor having stable and good electrostatic characteristics and having a clear and high-quality image even when the environment at the time of forming a copy image fluctuates such as low temperature and low humidity or high temperature and high humidity. To provide.

Another object of the present invention is to provide a CPC electrophotographic photoreceptor having excellent electrostatic characteristics and low environmental dependency.

Another object of the present invention is to provide an electrophotographic photosensitive member effective for a scanning exposure method using a semiconductor laser beam.

A further object of the present invention is to provide an electrophotographic lithographic printing plate precursor having excellent electrostatic properties (particularly dark charge retention and light sensitivity),
By providing a lithographic printing original plate that reproduces a copy image that is faithful to the original image, does not cause spot stains as well as uniform stains on the entire surface of the printed matter, and has excellent printing durability. is there.

(Means for Solving the Problems) An object of the present invention is to provide an electrophotographic photosensitive member 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 an electrophotographic photoreceptor characterized in that it contains at least one kind of A) and at least one kind of binder resin [B].

Resin (A); -PO ₃ H ₂ group, -COOH group, -SO ₃ group, phenolic OH groups, At least one polymer component containing at least one acidic group selected from {R represents a hydrocarbon group or an --OR 'group (R' is a hydrocarbon group) and a cyclic acid anhydride-containing group is contained. A polymerizable double bond is added to the end of the polymer main chain of the B block of the A / B block copolymer composed of the A block and the B block containing at least the polymer component represented by the following general formula (I). Graft-type copolymer having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ containing at least one monofunctional macromonomer (hereinafter sometimes referred to as macromonomer (MA)) having a group bonded thereto as a copolymerization component. Polymer.

General formula (I) [In the 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−, (L ₁ and l ₂ represent an integer of 1 to 3), -O-, -SO
_2- , -CO-, -CONHCO-, -CONHCONH- or (Wherein Z ₁ represents a hydrogen atom or a hydrocarbon group) R ₁ represents a hydrocarbon group. Where A ₁ is When R ₁ represents R ₁ represents a hydrogen atom or a hydrocarbon group. Binder resin [B]; The following general formula (III) is provided only at one end of the polymer main chain containing at least one of the polymer components represented by the following general formulas (IV a) and (IV b). ) Monofunctional macromonomers (hereinafter sometimes referred to as macromonomers (MB)) having a weight average molecular weight of 2 × 10 ⁴ or less formed by engaging a polymerizable double bond group represented by the following general formula (V) A resin which is a copolymer comprising at least a monomer represented by:

General formula (III) Wherein (III), V ₀ is -COO -, - OCO -, - CH 2 OCO-,
_{-CH 2 COO -, - O -} , - SO 2 -, - CO -, - CONHCOO-,
−CONHCONH−, −CONHSO ₂ −, Or (P ₃ represents a hydrogen atom or a hydrocarbon group).

c ₁ and c ₂ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-
Z'or -COO-Z 'through a hydrocarbon (Z' represents a hydrogen atom or a hydrocarbon group which may be substituted) is represented. General formula (IVa) General formula (IV b) [In the formula (IV a) or (IV b), V ₁ is V ₀ in the formula (III).
Represents the same content as.

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

d ₁ and d ₂ may be the same or different from each other;
Represents the same contents as c ₁ and c _{2 in} I).

Q ₀ is -CN-, -CONH ₂ or Represents

Here, T represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group or -COOZ "(Z" represents an alkyl group, an aralkyl group or an aryl group). General formula (V) [In the formula (V), V ₂ represents the same content as V ₁ in the formula (IV a).

Q ₂ has the same meaning as Q ₁ in formula (IV a).

e ₁ and e ₂ may be the same or different from each other, and have the formula (III)
Represents the same content as c ₁ and c _{2 in} . That is, the binder resin used in the present invention has an AB block copolymerization of an A block containing the specific acidic group-containing component and a B block containing the polymer component represented by the general formula (I). Monofunctional macromonomer (MA) in which a polymerizable double bond group is bonded to the end of the polymer main chain of the combined B block
[A] comprising a graft-type copolymer containing at least one as a copolymerization component, and one end of a polymer main chain containing at least a polymer component of the general formula (IV a) or (IV b) Resin comprising a comb-type copolymer containing at least one monofunctional macromonomer (MB) having a polymerizable double bond group and at least one monomer represented by the general formula (V).
At least.

The acidic group-containing polymer component is randomly present in the polymer main chain as a low molecular weight polymer among the acidic group-containing binder resins known to improve the smoothness and electrostatic characteristics of the photoconductive layer. And a resin in which an acidic group is bonded only to one end of the polymer main chain. In contrast,
In the binder resin [A] of the present invention, the acidic groups contained in the resin are present in the graft portion and in two blocks (that is, A block) at a position distant from the polymer main chain, It remarkably specifies the chemical structure of the polymer molecular chain.

In the resin [A] of the present invention, the acidic groups which are unevenly distributed in the terminal region of the graft portion in the polymer are sufficiently adsorbed to the stoichiometric defects of the inorganic photoconductor to form the polymer main chain. It is presumed that the block portion gently and sufficiently covers the surface of the inorganic photoconductor. This inorganic photoconductor is sufficiently adsorbed on the surface and the effect of coating near the surface is more effectively performed as compared with the known resin, so that the stoichiometric defects of the inorganic photoconductor are somewhat reduced. It is inferred that a stable interaction between the inorganic photoconductor and the resin [A] is always maintained because it has a sufficient adsorption region even if it fluctuates, and according to the present invention, the conventionally known acidic group-containing resin is used. It has been found that the photoconductor is sufficiently dispersed and the humidity characteristics are improved, while the photoconductor is sufficiently dispersed and aggregation is suppressed.

Therefore, when a photoconductor having a rough surface of the photoconductive layer is used as the electrophotographic lithographic printing plate precursor, the dispersion state of the zinc oxide particles as the photoconductor and the binder resin is not appropriate, and aggregates are present. Since the photoconductive layer is formed in the state, even if the desensitizing treatment with the desensitizing solution is performed, the non-image portion is not sufficiently and sufficiently hydrophilized, causing adhesion of the printing ink during printing, and as a result, The background stain on the non-image portion of the printed matter occurs.

The resin [B] does not hinder the high performance of the electrophotographic properties due to the use of the resin [A] at all, and the resin [A] alone provides sufficient mechanical strength of the photoconductive layer, which is insufficient. It has been found that a sufficiently good imaging performance can be obtained even when the environment fluctuates as described above or a low output laser beam is used.

This is a resin [A] as a binder resin for the inorganic photoconductor.
And the resin [B] by specifying the weight average molecular weight of the resin and the content and bonding position of the acidic group in the resin,
It is presumed that the strength of the interaction between the inorganic photoconductor and the resin was appropriately changed. That is, the resin [A] having a stronger interaction selectively and appropriately adsorbs to the inorganic photoconductor, while the resin [B] having a weaker interaction than the resin [A] inhibits the electrophotographic properties. It is presumed that by gently interacting with the inorganic photoconductor to such an extent that both the electrophotographic characteristics and the mechanical strength were remarkably improved as described above.

When the resin of the present invention is used, the interaction between the adsorption and coating of the photoconductor and the binder resin is appropriately performed, and the film strength of the photoconductive layer is maintained.

When only the low molecular weight resin [A] of the present invention is used as the binder resin, the photoconductor and the binder resin are sufficiently adsorbed and the particle surface can be covered. It also has good electrostatic characteristics, and provides image quality without scumming. Furthermore, it has sufficient film strength as a CPC photoconductor or an offset master plate for printing several thousand sheets. However, by coexisting the resin [B] as in the present invention, the mechanical strength of the photoconductive layer which is still insufficient with the resin [A] alone without further alienating the function of the resin [A] is further improved. I was able to. Accordingly, the photoreceptor of the present invention has excellent electrostatic characteristics even when environmental conditions fluctuate, has sufficient film strength, and is subjected to severe printing conditions (for example,
Even when the printing pressure is increased with a large printing press), it is possible to print more than 10,000 sheets.

Furthermore, the resin (B), said comb copolymer mainly at one end of the chain only -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -OH group, -SH
Group and {R ₀ represents a hydrocarbon group or a —OR ₀ ′ (R ₀ ′ represents a hydrocarbon group) group} and a resin (hereinafter referred to as resin [B ′]) further bound with at least one acidic group selected from (Sometimes referred to)).

When the resin [B '] is used, the electrostatic characteristics, particularly DRR and E _1/10 are improved, and the excellent characteristics due to the use of the resin [A] are not hindered at all. It is preferable because there is almost no change even in environmental changes such as humidity, low temperature and low humidity. Further, the film strength is further improved, and the printing durability is improved.

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

In the graft copolymer [A] of the present invention, a macromonomer (MA) and another monomer (for example, a monomer of the formula (II))
Is 1 to 60/99 to 40 (weight ratio), preferably 5 to 40/95 to 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]
1 to 30 parts by weight in 100 parts by weight, preferably 3 to 20 parts
Parts by weight. That is, the abundance ratio of the acidic groups in the resin [A] is preferably determined by the composition ratio of the A-block in the macromonomer (MA) and the copolymerization ratio of the macromonomer (MA) in the resin [A]. It can be adjusted to the ratio.

Furthermore, in this resin [A], macromonomer (MA)
As the component that copolymerizes with, a monomer represented by the following general formula (II) is preferable, and a monomer selected from the following general formulas (IIa) and / or (IIb) is particularly preferable.

[In the formula (II), R ₂ represents a hydrocarbon group. ] Wherein X ₁ and X ₂ are each independently a hydrogen atom,
Hydrocarbon group having 1 to 10 carbon atoms, chlorine atom, bromine atom, -CO
Z ₃ or —COOZ ₃ (Z ₃ each represents a hydrocarbon group having 1 to 10 carbon atoms) is represented. However, X ₁ and X ₂ are never both represent a hydrogen atom.

L ₁ and L ₂ each represent a single bond or a linking group having 1 to 4 linking atoms, each linking —COO— and a benzene ring. In the resin [A], a substituent containing a substituted benzene ring or naphthalene ring represented by the above general formula (IIa) and / or general formula (IIb) as a monomer copolymerizable with the macromonomer (MA) In the case of a resin containing at least the copolymer of the methacrylate monomer with (the resin [A] is referred to as a resin [A '] hereinafter), more excellent electrophotographic characteristics (particularly V ₁₀ , DRRE _{1) are obtained. / 10} ) improvement is achieved.

Although the reason for this is unknown, one reason is that the ester component of methacrylate, a planar benzene ring having a substituent at the ortho-position, or the effect of a naphthalene ring at the zinc oxide interface in the film. It is considered that the arrangement of these polymer molecular chains is properly performed.

When the molecular weight of the binder resin [A] is smaller than 1 × 10 ³ , the film-forming ability is lowered and sufficient film strength cannot be maintained. On the other hand, when the molecular weight is larger than 2 × 10 ⁴ , even if the resin of the present invention is used. Under the severe conditions of high temperature, high humidity, low temperature, and low humidity, the fluctuation of electrophotographic characteristics (particularly, initial potential and dark decay retention) becomes large, and the effect of the present invention that a stable copied image can be obtained is weakened. .

When the content of the macromonomer (MA) in the binder resin [A] is less than 1.0% by weight, the electrophotographic characteristics (especially dark decay rate and photosensitivity) are deteriorated, and the variation of the electrophotographic characteristics under environmental conditions is particularly close. In the combination with infrared to infrared spectral sensitizing dyes, it becomes large. It is considered that this is because the composition of the macromonomer serving as the graft portion becomes small, resulting in almost the same composition as the conventional homopolymer or random copolymer.

On the other hand, when the content of the macromonomer (MA) exceeds 60%, the copolymerizability of the monomer corresponding to the other copolymerization component and the macromonomer according to the present invention becomes insufficient, and even when it is used as a binder resin. Sufficient electrophotographic characteristics cannot be obtained.

The use ratio of the binder resin [A] and the high molecular weight polymer: resin [B] is 5 to 80 parts by weight to 95 to 20 parts by weight, preferably 10 to
60 to 90-40 parts by weight.

Next, the details of the binder resin [A] and the binder resin [B] used in the present invention will be described.

The monofunctional macromonomer (MA) used in the graft copolymer of the present invention will be described more specifically.

The acidic groups contained in the components making up the A- block of the macromonomer (MA), -PO ₃ H ₂ group, -COOH
Group, --SO ₃ H group, phenolic OH group, {R is a hydrocarbon group or -OR 'group (R' is a hydrocarbon group),} and / or include cyclic acid anhydride-containing group, preferably, -COOH group, -SO ₃ H group, a phenolic OH group, or It is.

In the formula, R represents a hydrocarbon group or an -OR 'group (R' represents a hydrocarbon group), and R and R 'are preferably an aliphatic group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group) , Propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, 2-chloroethyl, 2-methoxyethyl, 3-ethoxypropyl,
Allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc.), or an optionally substituted aryl group (For example, phenyl, tolyl, ethylphenyl, propylphenyl, chlorophenyl,
Fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

Further, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride contained include aliphatic dicarboxylic anhydride and aromatic dicarboxylic anhydride. Can be

Examples of the aliphatic dicarboxylic anhydride include a succinic anhydride ring, a glutaconic anhydride ring, a maleic anhydride ring,
Cyclopentane-1,2-dicarboxylic anhydride ring, cyclohexane-1,2-dicarboxylic anhydride ring, cyclohexene-1,2-dicarboxylic anhydride ring, 2,3-bicyclo [2.2.
2] octanedicarboxylic anhydride rings and the like, and these rings are substituted with, for example, halogen atoms such as chlorine atom and bromine atom, and alkyl groups such as methyl group, ethyl group, butyl group and hexyl group. Is also good.

Examples of the aromatic dicarboxylic anhydride include a phthalic anhydride ring, a naphthalene-dicarboxylic anhydride ring, a pyridine-dicarboxylic anhydride ring, a thiophene-dicarboxylic anhydride ring, and the like. Is, for example, a chlorine atom, a halogen atom such as a bromine atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (for the alkoxy group, for example, Methoxy group, ethoxy group, etc.) may be substituted.

As described above, “polymer component containing specific acidic group”
Is, for example, a polymer component that constitutes another block component of the macromonomer (MA) of the present invention, that is, the acidic group that is copolymerized with a corresponding vinyl compound such as a methacrylate component represented by the general formula (I). Any vinyl-based compound containing can be used.

For example, it is described in “Polymer Data Handbook [Basic Edition]” edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form,
α- (2-amino) methyl, α-chloro, α-bromo, α-fluoro, α-tributylsilyl, α-cyano, β-chloro, β-bromo, 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 (eg 2-pentenoic acid, 2-methyl- 2-hexenoic acid, 2-octenoic acid, -methyl-2-hexenoic acid, 4-
Ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acid vinyl group or allyl group Examples thereof include half-ester derivatives, and ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the acidic group in the substituents of amide derivatives.

The following are specific examples of these compounds. However, in each of the following examples, a is -H,-
_{CH 3, -Cl, -Br, -CN} -, - CH 2 COOCH 3 or -CH ₂ COOH
Are shown, b represents -H or -CH _3, n is an integer of 2 to 18, m represents an integer of 1 to 12, l is an integer of 1-4.

_{(A-15) CH 2 =} CHCH 2 OCO (CH 2) mCOOH (a-16) CH 2 = CHCH 2 l COOH Two or more kinds of the acidic group-containing components as described above may be contained in the A block, and these two or more kinds of acidic group-containing components may be contained in the A block by random copolymerization or block copolymerization. Good. Further, together with the acidic group-containing component, a component that does not contain an acidic group (for example, a component represented by the formula (I) described later) may be contained in the A block, but the acidic group-containing component is 30 in the A block.
It is preferably present at .about.100% by weight.

Next, in the above-mentioned micromonomer, the component constituting the B-block, that is, the repeating unit represented by the general formula (I) will be described.

In the general formula (I), A ₁ is -COO-, -OCO-, (L ₁ , l ₂ represents an integer of 1 to 3), -O-, -SO _2- ,
-CO-, -CONHCOO-, -CONHCONH- or Represents

Here, in addition to the hydrogen atom, Z ₁ is preferably a hydrocarbon group which may be substituted and has 1 to 18 carbon atoms, such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group). Group, octyl group, decyl group,
Dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), having 4 to 18 carbon atoms An optionally substituted alkenyl group (e.g., 2-methyl-1
-Propenyl group, 2-butenyl group, 2-pentenyl group,
3-methyl-2-pentenyl group, 1-pentenyl group, 1
-Hexenyl group, 2-hexenyl group, 4-methyl-2-
Hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-
Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.),
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 (For example, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl) , Dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamidophenyl, dodecylylamidophenyl, etc.) can give.

R ₁ represents a hydrocarbon group, and preferably the same as those listed as the preferable hydrocarbon group for Z ₁ above.

A ₁ is In the formula, R ₁ represents a hydrogen atom other than the above-mentioned hydrocarbon, and the benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group, Ethoxy groups,
And a propoxy group and a butoxy group).

a ₁ and a ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
A bromine atom), a cyano group, an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, etc.), - COOZ COOZ ₂ (Z ₂ via the ₂ or hydrocarbons, hydrogen An 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, and specifically, the same as those described for Z ₁ above. Represents the contents of).

Examples of the hydrocarbon in the —COO—Z ₂ group via the above hydrocarbon include a methylene group, an ethylene group, and a propylene group.

More preferably, in the general formula (I), A ₁ is —CO
O -, - OCO -, - CH 2 OCO -, - CH 2 COO -, - O -, - CO
NH -, - SO ₂ NH- or And a ₁ and a ₂ may be the same or different from each other, and are a hydrogen atom, a methyl group, —COOZ ₂ or —CH ₂ COOZ ₂ {Z is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms ( For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.). Even more preferably,
One of a ₁ and a ₂ represents a hydrogen atom.

Furthermore, the B-block may contain a polymer component other than the monomer of the formula (I), and corresponds to another repeating unit copolymerizable with the polymer component of the formula (I). Examples of the monomer to be used include acrylonitrile, methacrylonitrile, and heterocyclic vinyls (eg, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.). These other monomers are used in an amount not exceeding 20 parts by weight per 100 parts by weight of the total polymer components of the B-block. Further, it is preferable that the B block does not contain a polymer component containing an acidic group which is a component of the A-block. When two or more copolymer components are present in the B block, these two or more copolymer components may be contained in the B block by either random copolymerization or block copolymerization. More preferably, it is contained at random.

Next, in the macromonomer (M) of the present invention, an A block comprising the above-mentioned component containing an acidic group and a B block containing the polymer component represented by the general formula (I)
The polymerizable dipolymer group that connects the blocks in an AB type and is connected to the other end of the B block that connects to the A-block will be described.

Specifically, a polymerizable double bond group represented by the following general formula (VII) is exemplified.

General formula (VII) [In formula (VII), A ₂ has the same meaning as A ₁ in formula (I). b ₁ and b ₂ may be the same or different from each other and represent the same contents as a ₁ and a ₂ in the formula (I). That is, as the polymerizable double bond group represented by the general formula (VII), more specifically, _{CH 2 = CHCH 2 2 -COO-,} CH 2 = CH-CO-, And the like.

In the macromonomer (M) used in the present invention, a polymerizable double bond group represented by the general formula (VII) is directly bonded to one end of the B-block as described above, or any linking is carried out. It has a chemical structure bonded by a group.
Examples of the linking group include a carbon-carbon bond (single bond or double bond), a carbon-hetero atom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.), a hetero atom-hetero atom. It is composed of any combination of bonding atomic groups. That is, specifically,
Mere union or [R ₃ and R ₄ are each a hydrogen atom and a halogen atom (eg,
A fluorine atom, a chlorine atom, a bromine atom, etc., a cyano group, a hydroxyl group, an alkyl group (for example, a methyl group, an ethyl group,
Propyl group etc.), CH = CH, -O-, [R ₅ and R ₆ are each a hydrogen atom, and R ₁ in the above formula (I)
And a weight average molecular weight of the macromonomer (M) that represents a linking group selected from atomic groups such as] and a linking group composed of any combination of 2 × 10 5. ^If it exceeds ⁴ , it is not preferable because the copolymerizability with other monomers (for example, the formula (II) decreases). On the other hand, if the weight average molecular weight is too small, the effect of improving the electrophotographic properties of the photosensitive layer decreases. It is preferably 1 × 10 ³ or more.

The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. For example, in a monomer corresponding to the polymer component containing the specific acidic group, the acidic group is preliminarily protected as a functional group, and an organometallic compound (eg, alkyllithium, lithium diisopyramide, alkylmagnesium halide) is used. Or the like) or an ionic polymerization reaction with hydrogen iodide, an iodine system or the like, a photopolymerization reaction using a porphyrin metal complex as a catalyst, or a known so-called living polymerization reaction such as a group transfer polymerization reaction to form an AB block copolymer. After synthesis, various reagents are reacted with the ends of this living polymer to introduce a polymerizable double bond group. Thereafter, a method in which a functional group protecting the acidic group is subjected to a deprotection reaction by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photolysis reaction, or the like to form an acidic group is used. One example is shown in the following reaction scheme (1).

For example, P. Lutz, P. Masson etal, Polym. Bull., 12 , 79
(1984) BCAnderson, GDAndrews etal, Mecromolecul
es, 14 , 1601 (1981) K. Hatada, K. Ute. et al., Polym. J. 17 , 9,
77 (1985), 18 , 1037 (1986), Koichi Ute, Koichi Hatada,
Polymer Processing, 36, 366 (1987) Higashimura Satoshinobe, Mitsuo Sawamoto, polymer Collected Papers, 46, 189 (1989) M.Kuroki , T.Aida, T.Am.Che
m.Soc. 109 , 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43 , 300 (1985) DYSogah, WRHertler et al, M
A living polymer can be easily synthesized according to the synthetic method described in acromolecules, 20 , 1473 (1987) and the like. As a method for introducing a polymerizable double bond group into the terminal of the living polymer, the macromonomer of the present invention can be easily obtained according to a conventionally known synthesis method of a macromonomer method.

Specifically, P.Dreyfuss & R.P.Quirk, Encycl, Polym.S
ci.Eng., 7 , 551 (1987), PFRempp, E.Franta, Adu., Pol
ym.Sci. 58 , 1 (1984), V. Percec, Appl., Polym. Sci., 285 ,
95 (1984), R. Asami, M. TakaRi, Makvamol. Chem. Suppl. 1
2, 163 (1985), P.Rempp.etal , Makvamol.Chem.Suppl. 8,
3 (1984) Yusuke Kawakami, Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 31 , 988 (1982), Shiro Kobayashi, Polymer, 30 ,
625 (1981), Higashi-son Toshinobu, Journal of the Adhesion Society of Japan 18, 536 (198
2), Koichi Ito, Polymer Processing, 35 , 262 (1986), Higashi Kishiro, Takashi Tsuda, Functional Materials, 1987 No.10,5, etc. can do.

Further, the protecting group for protecting the specific acidic group of the present invention and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing conventionally known knowledge. For example, various references are given in the cited document, and further, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer", published by Kodansha Ltd. (1977
), TWGreene "Protective Groups in Organic Syn
thesis ", John Wiley & Sous (1981), JFW McOmi
e, `` Protective Groups in Organic Chemistry '' Plenum
Press, (1973) and the like can be carried out by appropriately selecting a method described in detail.

As another method for synthesizing an AB block copolymer, it can be synthesized by a photoiniferter polymerization method using a diciocarbamate compound as an initiator. For example, Takayuki Otsu, polymeric, 37, 248 (1988), Hinokimori Shunichi, Ryuichi Otsu,
Jap. 37 , 3508 (1988), JP-A-64-111, JP-A-64-26619, and the like. The macromonomer of the present invention can be obtained by utilizing the above-mentioned macromonomer synthesis method.

Specific examples of the macromonomer (M) of the present invention include the following compounds. However, the scope of the present invention is not limited to these. However, in the following compound examples, c, d and e are respectively -H, -C
H ₃ or indicates -CH ₂ COOCH _3, f represents -H or -CH _3,
R ₇ is -C _p H _{2p +} 1 _(p is 1 to 18 _{integer), - (CH 2) q} C 6 H 5
(Q is an integer of 1 to 3), (YC represents _{-H, -Cl, -Br, -CH 3} , a -OCH ₃ or -COCH ₃₎ or (R is an integer of 0 or 1 to 3) shows a, R ₈ is -C _S H _{2S +} 1 (s is an integer of 1 to 8) or - (C
H ₂₎ shows the _q C ₆ H _5, Y ₂ is -OH, -COOH, -SO ₃ H, Are shown, Y ₃ is -COOH, -SO ₃ H, Is shown, t shows the integer of 2-12, u shows the integer of 2-6.

The monomer copolymerizable with the macromonomer (MA) is represented by the general formula (II). In the formula (II), R ₂ has the same contents as R ₁ in the formula (I).

Moreover, in the polymer main chain, -PO ₃ H ₂ group, -SO ₃ H group, -COO
Those which do not contain a copolymer component containing an acidic group such as H group, -OH group, -SH group and -PO ₃ RH group are preferred.

Further, the low-molecular-weight resin [A] of the present invention has the general formula (II)
a) and / or 2-position or 2,6 represented by general formula (IIb)
It is preferable that the graft copolymer [A '] contains, as a copolymer component, methacrylate having a specific substituent having a benzene ring or a naphthalene ring having a specific substituent at the -position.

In the general formula (IIa), as preferred X ₁ and X ₂ , in addition to a hydrogen atom, a chlorine atom, and a bromine atom, as a preferred hydrocarbon group, an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group) , A propyl group, a butyl group, etc.), an aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group) , A chloro-methyl-benzyl group, etc.) and an aryl group (for example, a phenyl group,
Tolyl, silyl, bromophenyl, methoxyphenyl, chlorophenyl, dichlorophenyl, etc.),
And (Preferred Z ₃ may be mentioned those described as the preferred hydrocarbon groups) -COZ ₃ and -COOZ ₃ can be exemplified. However, X ₁ and X ₂ are never both represent a hydrogen atom.

In the formula (IIa), L ₁ is a single bond or —CH _{2 m1} (m ₁ represents an integer of ₁ to 3), —CH ₂ CH ₂ OCO—, CH ₂ O, which connects —COO— to a benzene ring. _{m @ 2} (m ₂ represents an integer of 1 or _{2), - CH 2 CH 2} O- number such linking atom, such as 1
Represents 4 linking groups.

L ₂ in formula (II b) is the same meaning as L _1.

Specific examples of the monomer represented by the formula (IIa) or (IIb) used in the resin [A '] of the present invention are shown below. However, the scope of the present invention is not limited to these.

Furthermore, as the component copolymerizable with the macromonomer (MA) in the graft copolymer of the present invention, a monomer other than the general formula (II), (IIa) or (IIb) may be used. Well, for example, α-olefins, alkanes vinyl or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls (for example, non-metal atoms other than nitrogen atom ( It is a 5- to 7-membered heterocyclic ring containing 1 to 3 oxygen atoms, sulfur atoms and the like), and specific compounds include vinylthiophene, vinyldioxane, vinylfuran and the like]. Preferred examples include, for example, vinyl or allyl esters having 1 to 3 carbon atoms, acrylonitrile, methacrylonitrile, styrene and styrene derivatives (for example, vinyltoluene, butylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene). , Ethoxystyrene, etc.).

The binder resin of the present invention contains at least one compound selected from the macromonomer (MA) and another monomer (for example, a monomer represented by the general formula (II)) at a desired ratio. It can be produced by copolymerization.
As the polymerization method, it can be produced by using a known method such as solution polymerization, suspension polymerization, precipitation polymerization, and emulsion polymerization. For example, in solution polymerization, a monomer can be added in a predetermined ratio in a solvent such as benzene or toluene, and polymerized with an azobis compound, a peroxide compound, and a radical polymerization initiator to obtain a copolymer solution. The desired copolymer can be obtained by adding this to a drying or loading agent. In the suspension polymerization, a monomer can be suspended in the presence of a dispersant such as polyvinyl alcohol and polyvinylpyrrolidone, and then copolymerized in the presence of a radical polymerization initiator to obtain a copolymer.

In the resin [A], the amount of the specific acidic group-containing polymer component in the AB type block copolymer is preferably in the range of 1 to 20% by weight in 100 parts by weight of the resin [A].
And more preferably 3 to 15% by weight.

The weight average molecular weight of the resin [A] is preferably 3 × 10 ³ to
It is 1 × 10 ⁴ .

The glass transition point of the resin [A] is preferably -40 ° C to 110 ° C.
C, preferably -20 to 90 ° C.

Next, the resin [B] used in the present invention will be described.

The resin [B] is a resin which is a graft type copolymer that satisfies the above-mentioned physical properties and contains at least a monofunctional macromonomer (MB) and a monomer represented by the general formula (V). Characterize.

The resin [B] preferably has a weight average molecular weight of 3 × 10 ⁴
The above is a graft copolymer resin. More preferably, the weight average molecular weight is from 5 × 10 ^{4 to} 3 × 10 ⁵ .

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

The monofunctional macromonomer (MB) has a polymerizable double bond group represented by the general formula (III), a general formula (IV a) or (IV
It has a weight-average molecular weight of 2 × 10 ⁴ or less which is bonded to only one end of a polymer main chain containing at least one polymer component represented by b).

In the general formulas (III), (IVa) and (IVb),
The hydrocarbon groups contained in c ₁ , c ₂ , V ₀ , d ₁ , d ₂ , V ₁ , Q ₁ and Q ₀ each have the indicated carbon number (as an unsubstituted hydrocarbon group), These hydrocarbon groups may have a substituent.

Formula showing the macromonomer (MB) in (III), V ₀ is -COO -, - OCO -, - CH 2 OCO -, - CH 2 COO-,
_{-O -, - SO 2 -,} - CO -, - CONHCOO -, - CONHCONH
−, −CONHSO ₂ −, Represents Here, P ₃ is, in addition to a hydrogen atom, a preferable hydrocarbon group as an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group). Group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2
-Chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group: 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-promopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, , 2-methyl-
1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), An optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group,
-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 (E.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or C6-C6.
12 optionally substituted aromatic groups (for example, phenyl group,
Naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl Group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.).

V ₀ In the case where is represented, the benzene ring may have a substituent.
Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group, Ethoxy group, propoxy group, butoxy group, etc.).

c ₁ and c ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
Bromine atom, etc.), cyano group, alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.), -COO-Z 'or -COO-Z' via hydrocarbon.
(Z 'represents a hydrogen atom or an alkyl group, alkenyl group, aralkyl group, alicyclic group or aryl group having 1 to 18 carbon atoms, which may be substituted, and specifically,
It represents the same contents as those described for P ₃ above).

Examples of the hydrocarbon in the -COO-Z 'group through the hydrocarbon include a methylene group, an ethylene group, a propylene group and the like.

More preferably, in the general formula (III), V ₀ is -C
OO -, - OCO -, - CH 2 OCO -, - CH 2 COO -, - O -, - C
ONHCOO -, - CONHCONH -, - CONH -, - SO 2 NH- or And c ₁ and c ₂ may be the same or different from each other, and are a hydrogen atom, a methyl group, —COO—Z ′ or —CH ₂ COOZ ′ (Z ′.
Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.). Even more preferably, one of c ₁ and c ₂ always represents a hydrogen atom.

That is, as the polymerizable double bond group represented by the general formula (III), specifically, And the like.

In general formula (IV a), V ₁ has the same meaning as V ₀ in formula (III).

d ₁ and d ₂ may be the same or different from each other, and have the formula (III)
Represents the same content as c ₁ and c _{2 in} .

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

Specifically, an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, an octyl group, a decyl group,
Dodecyl group, tridecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group,
2-hydroxyethyl group, 2-methoxyethyl group, 2
-Ethoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2- (trimethoxysilyl) ethyl group, 2
-Tetrahydrofuryl group, 2-thienylethyl group, 2-
N, N-dimethylaminoethyl group, 2-N, N, -diethylaminoethyl group, etc.), cycloalkyl group having 5 to 8 carbon atoms (eg, cycloheptyl group, cyclohexyl group, cyclooctyl group, etc.), 7 carbon atoms 12 optionally substituted aralkyl groups (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, dichlorobenzyl group, methylbenzyl group, chloro group -Methyl-benzyl group, dimethylbenzyl group, trimethylbenzyl group,
Aliphatic groups such as methoxybenzyl group).

Further, an optionally substituted aryl group having 6 to 12 carbon atoms (eg, phenyl, tolyl, xylyl, chlorophenyl, bromophenyl, dichlorophenyl, chloro-methyl-phenyl, methoxyphenyl, methoxycarbonylphenyl) , A naphthyl group, a chloronaphthyl group, etc.).

In the formula (IVa), preferably V ₁ is -COO-, -OCO.
_{-, - CH 2 COO -,} - CH 2 OCO -, - O -, - CO -, - CONH
COO -, - CONHCONH -, - CONH -, - SO 2 NH-, or Represents

Preferred examples of d ₁ and d ₂ represent the same contents as those of c ₁ and c ₂ described above.

In formula (IV b), Q ₀ is —CN, —CONH ₂ or Represents a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a hydrocarbon group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, phenyl group, etc.), an alkoxy group (eg, Methoxy group, ethoxy group, etc.) or --COO--Z ″ (Z ″ is preferably 1 to 1 carbon atoms.
8 represents an alkyl group, an aralkyl group having 7 to 12 carbon atoms or an aryl group).

The macromonomer (MB) may contain two or more polymer components represented by the formula (IV a) or (IV b). When Q ₁ is an aliphatic group in formula (IV a), it has 6 to 12 carbon atoms.
It is preferable to use the aliphatic group in a range not exceeding 20% by weight based on the total polymer components in the macromonomer (MB).

Furthermore, when V ₁ in the general formula (IV a) is —COO—, in all the polymer components in the macromonomer (MB),
At least 30% by weight of the polymer component of the formula (IVa)
It is preferable to contain the above.

Further, in the macromonomer (MB), acrylonitrile, methacrylonitrile, acrylamides as monomers corresponding to repeating units that can be copolymerized with the polymer component represented by the formula (IV a) and / or (IV b) , Methacrylamides, styrene and derivatives thereof (eg vinyltoluene, chlorostyrene, dichlorostyrene, bromostyrene, hydroxymethylstyrene, N, N-dimethylaminomethylstyrene etc.), heterocyclic vinyls (eg vinylpyridine, vinylimidazole, Vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.) and the like.

The macromonomer (MB) provided in the resin [B] of the present invention has the general formula (IV a) and / or (IV
The polymerizable double bond group represented by the general formula (III) is directly bonded to only one less than one of the polymer main chains composed of the repeating unit represented by b) or engaged with any linking group. It has a defined chemical structure. The group connecting the formula (III) component and the formula (IV a) or (IV b) component includes a carbon-carbon bond (single bond or double bond), a carbon-heteroatom bond (as a hetero atom, for example, oxygen). atom,
Sulfur atom, nitrogen atom, silicon atom, etc.), hetero atom-
It is composed of any combination of heteroatom-bonded atomic groups.

Preferred among the macromonomers (MB) of the present invention are those represented by the formula (VI a) or (VI b).

In formula (VI a) or (VI b), c ₁ , c ₂ , d ₁ , d ₂ , V ₀ ,
V ₁ , Q ₁ and Q ₀ are the formula (III), the formula (IV a) and the formula (IV
Represents the same content as described in b).

W ₀ is a simple bond or [H ₁ and h ₂ represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.) ], CH = CH, -O-, -S-, −COO−, −SO ₂ , -NHCOO-, -NHCONH-, [H ₃ and h ₄ each represent a hydrogen atom, a hydrocarbon group having the same content as Q ₁ in the above formula (IV a)] or the like, and a single linking group selected from atomic groups or any combination thereof. Represents a linked group.

When the weight average molecular weight of the macromonomer (MB) exceeds 2 × 10 ⁴ , the copolymerizability with the monomer represented by the formula (V) decreases. On the other hand, if the molecular weight is too small, the effect of improving the electrophotographic properties of the photosensitive layer will be small, so that it is preferably 1 × 10 ³ or more.

The macromonomer (MB) used for the resin [B] in the present invention can be produced by a conventionally known synthesis method. For example, a method by an ionic polymerization method in which various reagents are reacted with the ends of a living polymer obtained by anionic polymerization or cationic polymerization to form a macromer,
Oligomers of terminal reactive group bond obtained by radical polymerization using a polymerization initiator and / or chain transfer agent containing a reactive group such as carboxyl group, hydroxyl group, amino group in the molecule and various reagents By a radical polymerization method of reacting with a polymer to form a macromer, a polyaddition condensation method of introducing a polymerizable double bond group into the oligomer obtained by a polyaddition or polycondensation reaction in the same manner as the above radical polymerization method. Is mentioned.

Specifically, P.Dreyfuss & R.P.Quirk, Encycl.Polym.S
ci.Eng., 7 , 551 (1987), PFRempp, E.Franta, Adv.Poly
m.Sci., 58 , 1 (1984), V.Percec, Appl.Polym.Sci., 285 , 9
5 (1984), R. Asami, M. TakaRi, Makvamol. Chem. Suppl., 1
2 , 163 (1985), P. Rempp et al, Makvamol. Chem. Suppl.,
8 , 3 (1984), Yusuke Kawakami, Chemical Industry, 38 , 56 (1987),
Yuya Yamashita, polymer, 31, 988 (1982), Shiro Kobayashi, polymer, 30, 625 (1981), Higashimura Satoshinobe, Journal of the Adhesion Society of Japan, 18, 536
(1982), Koichi Ito, polymer processing, 35, 262 (1986), AzumaTakashi Shiro, Takashi Tsuda, functional materials, according to the method described in the review, such as 1987 Nanba10,5 and it references the literature, patents, etc. Can be synthesized.

The macromonomer (MB) of the present invention is specifically,
The following compounds may be mentioned as examples: However, the scope of the present invention is not limited to these.

However, in the following examples, c ₁ represents -H or -CH _3, d ₁ represents -H or -CH _3, d ₂ is -H, -CH ₃ or -
CH ₂ COOCH ₃ indicates, R ₁₁ is _{-C d H 2d + 1, -CH} 2 C 6 H 5, -C 6 H 5
Or Are shown, R _{12 is, -C d H 2d + 1,} CH 2 e C 6 H 5 or Are shown, R ₁₃ is -C _d H _{2d +} 1, shows a -CH ₂ C ₆ H ₅ or -C ₆ H _5, R ₁₄ represents a -C _d H _{2d + 1} or -CH ₂ C ₆ H ₅ , R ₁₅ is -C _d H
_{2d + 1, -CH 2 C 6} H 5 or R ₁₆ represents -C _d H _{2d + 1} , R ₁₇ represents -C _d H _{2d + 1} , -CH
₂ C ₆ H ₅ or Wherein R ₁₈ is -C _d H _{2d + 1} , -CH ₂ C ₆ H ₅ or V ₁ represents -COOCH ₃ , -C ₆ H ₅ or -CN, and V ₂ represents-
OC _d H _{2d + 1} , -OCOC _d H _{2d + 1} , -COOCH ₃ , -C ₆ H ₅ or -CN, and V ₃ is -COOCH ₃ , -C ₆ H ₅ , Or indicates -CN, V ₄ is _{-OCOC d H 2d + 1, -CN} , shows a -CONH ₂ or -C ₆ H _5, V ₅ represents -CN, a -CONH ₂ or -C ₆ H _5, V ₆ is -COOCH ₃ , -C ₆ H ₅ or And T ₁ represents -CH ₃ , -Cl, -Br or -OCH ₃ , and T ₂
Represents a -CH _3, -Cl or -Br, T ₃ is -H, -Cl, -B
r, -CH _3, shows a -CN or -COOCH _3, T ₄ is -CH _3, -Cl
Or indicates -Br, T ₅ is -Cl, -Br, -F, -OH or -CN
Wherein T ₆ is -H, -CH ₃ , -Cl, -Br, -OCH ₃ or -C
Indicates OOCH _3, d is an integer of 1 to 18, e is an integer of 1 to 3, f is an integer of 2-4.

The monomer copolymerized with the macromonomer (MB) is represented by the general formula (V). In the formula (V), e ₁ ,
e ₂ may be the same or different from each other;
Represents the same content as c ₁ and c ₂ . V ₂ is V ₁ of the formula (IV a),
Q ₂ has the same contents as Q _{1 in} formula (IV a).

Further, the resin [B] of the present invention may contain other monomers as copolymer components in addition to the above-mentioned macromonomer (MB) and the monomer of the general formula (V).

For example, vinyl compounds containing an acidic group, α-olefins, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, vinyl group-containing naphthalene compounds (for example, vinyl-naphthalene,
-Isoperopenylnaphthalene, etc.) vinyl group-containing heterocyclic compounds (for example, vinylpyridine, vinylpyrrolidone, vinylthiophene, vinyl-tetrahydrofuran, vinyl-
Compounds such as 1,3-dioxolan, vinylimidazole, vinylthiazole, and vinyloxazoline).

In the resin [B], the composition ratio of the copolymer component having a macromer (MB) as a repeating unit and the copolymer component having a monomer represented by the general formula (V) as a repeating unit is 1 to 80/9.
9-20 (weight composition ratio), preferably 5-60 / 95-40
It is a weight composition ratio.

The above-mentioned vinyl compound containing an acidic group is described, for example, in “Polymer Data Handbook [Basic Edition]” edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α-acetoxy form)
(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, α, β-dichloro), methacrylic acid,
Itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl-2-hexenoic acid,
-Octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinyl Examples include half-ester derivatives of vinyl or allyl groups of sulfonic acids, vinylphosphonic acids and dicarboxylic acids, and ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing an acidic group in the substituents of the amide derivatives.

When the "vinyl compound containing an acidic group" is contained as a repeating unit as another copolymerization component, the acidic group-containing copolymerization component preferably does not exceed 10% by weight in the copolymer.

When the content of the acidic group-containing component exceeds 10% by weight, the interaction with the inorganic photoconductor particles becomes remarkable, and the smoothness of the photoreceptor surface is impaired. As a result, electrophotographic properties (particularly, chargeability, charge in the dark) (Retention) is deteriorated.

Further, the resin [B '] which can be used as a preferred embodiment of the present invention contains at least one kind of a repeating unit represented by the general formula (V) and at least one kind of a repeating unit represented by a macromonomer (MB). at one end of the polymer main chain only, -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -OH
Group, -SH group and (R ₀ represents a hydrocarbon group or a —OR ₀ ′ (R ₀ ′ represents a hydrocarbon group) group}, and is a polymer having at least one acidic group bonded thereto.

Here, R ₀ , as the hydrocarbon group represented by R ₀ ′, an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group,
Octyl, decyl, dodecyl, tetradecyl,
Octadecyl group, 2-methoxyethyl group, 3-methoxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, etc.) and aralkyl groups having 7 to 9 carbon atoms and which may be substituted (for example, benzyl group, phenethyl group, 3 -Phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), carbon number 5-8
Alicyclic group (eg, cyclopentyl group, cyclohexyl group, etc.), and optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, tolyl group, xylyl group, naphthyl group, chlorophenyl group, bromophenyl group) , An alkoxyphenyl group (as an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group,
Nonyl group, decyl group, dodecyl group, etc.), acetoxyphenyl group, methyl-chloro-phenyl group, propylphenyl group, butylphenyl group, decylphenyl group, etc.).

When the above acidic group is bonded to one end of the polymer main chain, the polymer main chain should not contain a copolymerization component containing an acidic group such as a carboxyl group, a sulfo group, a hydroxyl group or a phosphono group. Is preferred.

In the resin [B '], the acidic group has a chemical structure in which it is directly bonded to one end of the polymer main chain or is bonded via an arbitrary linking group.

Examples of the bonding group include a carbon-carbon bond (single bond or double bond), a carbon-heteroatom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom), and a heteroatom-heteroatom bond. It is composed of any combination of atomic groups. For example, [H _5, h ₆ represents h _1, h ₂ same contents as the) CH =
CH, (Where h ₇ and h ₈ represent the same contents as h ₃ and h ₄ above)
And the like, or a single linking group selected from an atomic group such as the above, or a linking group composed of an arbitrary combination.

The content of the acidic group bonded to only one end of the polymer main chain in the resin [B '] is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on parts by weight of the resin [B'].
It is. If the amount is less than 0.1% by weight, the effect of improving the film strength is small, and if the amount is 15% by weight or more, the photoconductor is not uniformly dispersed at the time of preparing the photoconductor dispersion, so that aggregation occurs, and a uniform coating film is not formed.

The resin [B '] of the present invention comprising a specific acidic group bonded to only one terminal of the polymer main chain is prepared by reacting various reagents with the terminal of a living polymer obtained by conventionally known anionic or cationic polymerization. Method (method by ionic polymerization), method of radical polymerization using a polymerization initiator and / or chain transfer agent containing a specific acidic group in the molecule (method by radical polymerization), or ionic polymerization as described above Alternatively, it can be easily produced by a synthesis method such as a method of converting a polymer having a terminal reactive group obtained by a radical polymerization method into a specific acidic group of the present invention by a polymer reaction.

Specifically, P. Dreyfuss, RPQuirk, Encycl.Polym.Sc
i.Eng., ₇ : 551 (1987), Yoshiki Nakajo, Yuya Yamashita "Dyes and Drugs" ₃₀ , 232 (1985), Akira Ueda, Susumu Nagai "Chemistry and Industry" ₆₀ , 57 (1986) and others. In addition, it can be manufactured by the method described in the cited documents.

The ratio of the resin [A] and the resin [B] (including [B ']) used in the present invention varies depending on the type, particle size and surface condition of the inorganic photoconductive material used, but the resin [A] is generally used.
And the resin [B] are used in a ratio of 5 to 80 to 95 to 20 (weight ratio).
And preferably 10 to 60 to 90 to 40 (weight ratio).

Examples of the inorganic photoconductive material used in the present invention include zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, and lead sulfide. Preferably, zinc oxide, titanium oxide and the like are used.

The total amount of the binder resin used for the inorganic photoconductive material is 10 to 100 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the photoconductor.

In the present invention, various dyes can be used as spectral sensitizers as needed. For example, Harumiya Miyamoto, Hidehiko Takei, Imaging ₁₉₇₃ (No.8) page 12, CJ Young, R
CA Review ₁₅ , 469 (1954), Kouhei Kiyota, The Institute of Electrical Communication, J63-C (No.2), 97 (1980), Yuji Harasaki, etc.,
Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, which are cited as references in industrial chemistry magazines ₆₆ , 78 and 188 (1963), Tadaaki Tani, Japan Photographic Society magazine ₃₅ , 208 (1972), etc. Examples thereof include polymethine dyes (for example, oxonol, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes), phthalocyanine dyes (which may contain a metal), and the like.

More specifically, those using mainly carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes are described in JP-B-51-452,
0-90334, JP-A-50-114227, JP-A-53-39130
And JP-A-53-82353, U.S. Pat. No. 3,052,540, U.S. Pat. No. 4,054,450, and JP-A-57-16456.

Polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes are FM
Hammer, "The Cyanine Dyes and Ralated Compounds"
Can be used, more specifically, more specifically,
U.S. Patent No. 3047384, U.S. Patent No.3110591, U.S. Patent No.3121008, U.S. Patent No.3125447, U.S. Patent No.
No. 9, U.S. Patent No. 3,129,342, U.S. Patent No. 3,622,317, U.K. Patent No. 1,228,892, U.K. Patent No. 1,309,274, U.K. Patent No.
Dyes described in JP 1405898, JP-B-48-7814, JP-B-55-18892 and the like can be mentioned.

Further, as a polymethylene dye that spectrally sensitizes the near infrared to infrared light region having a long wavelength of 700 nm or more, JP-A-47-840,
JP-A-47-44180, JP-B-51-41061, JP-A-49-50
No. 34, JP-A-49-45122, JP-A-57-46245, JP-A
No. 56-35141, JP-A-57-157254, JP-A-61-26044
No., JP-A-61-27551, U.S. Pat.No. 3,619,154, U.S. Pat.No. 4,175,596, `` Research Disclosure '' 1982, 21
6, pages 117 to 118 and the like.

The photoreceptor of the present invention is also excellent in that even when various sensitizing dyes are used in combination, the performance is not easily changed by the sensitizing dye.

Furthermore, various conventionally known additives for an electrophotographic photosensitive layer such as a chemical sensitizer can be used in combination, if necessary. For example, the review mentioned above: Imaging ₁₉₇₃ (No. 8)
"Recent development and commercialization of photoconductive materials and photoreceptors", e.g., electron accepting compounds (eg, halogen, benzoquinone, cranyl, acid anhydride, organic carboxylic acid, etc.) described in the reviews on page 12, etc. Chapters 4 to 6: Polyarylalkane compounds, which are reviewed in Japanese Science Information Publishing Co., Ltd. (1986)
Hindered phenol compounds, p-phenylenediamine compounds, and the like.

The amount of these various additives is not particularly limited,
Usually, it is 0.001 to 2.0 parts by weight based on 100 parts by weight of the photoconductor.

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

When a photoconductive layer is used as the charge generation layer of the photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is preferably 0.01 to 1 μm, particularly preferably 0.05 to 0.5 μm.

In some cases, an insulating layer is provided for the main purpose of protecting the photoreceptor, improving durability, and improving dark attenuation characteristics. At this time, the insulating layer is set relatively thin, and the insulating layer provided when the photosensitive member is used in a specific electrophotographic process is set relatively thick.

In the latter case, the thickness of the insulating layer is between 5 and 70 μm, especially 10
Set to ~ 50μ.

Examples of the charge transport material of the laminated photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, and triphenylmethane dyes. The thickness of the charge transport layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.

As the resin used for forming the insulating layer or the charge transport layer, typical ones are polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-copolymer resin, A thermoplastic resin and a curable resin such as a polyacryl resin, a polyolefin resin, a urethane resin, an epoxy resin, a melamine resin, and a silicone resin are appropriately used.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, just as in the conventional case, for example, a metal, paper, a plastic sheet or the like substrate having a low resistance property is used. Those that have been subjected to a conductive treatment such as impregnation, those that are coated with at least one layer for the purpose of imparting conductivity to the back surface of the base (the surface opposite to the surface on which the photosensitive layer is provided) and further preventing curling, Paper having a water-resistant adhesive layer provided on the surface of the support, one having at least one precoat layer provided on the surface layer of the support, if necessary, and a conductive electroconductive plastic substrate on which Al or the like is deposited. Those laminated to can be used.

Specifically, as examples of the conductive substrate or the conductive material, Yukio Sakamoto, “Electrophotography”, 14, (No. 1), Nos. 2 to 11
Page (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry" Polymer Publishing (1975), MF Hoover, J. Macromol. Sci. Chm. A-4
(6), and those described in pages 1327 to 1417 (1970) and the like are used.

(Examples) Examples of the present invention will be described below, but the contents of the present invention are not limited thereto.

Synthesis example of macromonomer (MA) 1: (MM-1) 30 g of triphenylmethyl methacrylate and toluene 1
00 g of the mixed solution was sufficiently degassed under a nitrogen stream and cooled to -20 ° C. 1.0 g of 1,1-diphenylbutyllithium was added and 10
Reacted for hours.

Further, to this mixed solution, a mixed solution of 70 g of ethyl methacrylate and 100 g of toluene was sufficiently degassed under a nitrogen gas stream, and then added, followed by further reacting for 10 hours. After the mixture was heated to 0 ° C., it was bubbled with carbon dioxide at a flow rate of 60 ml / min for 30 minutes to stop the polymerization reaction.

The obtained reaction solution was stirred at a temperature of 25 ° C., 6 g of 2-hydroxyethyl methacrylate was added, and a mixed solution of 12 g of dicyclohexylcarbodiimide, 1.0 g of 4-N, N-dimethylaminopyridine and 20 g of methylene chloride was further added to 30 g. Then, the mixture was added dropwise for 3 minutes and stirred for 3 hours.

After filtering the precipitated insoluble matter, 10 ml of 30% hydrogen chloride methanol solution was added to this mixed solution, and the mixture was stirred for 1 hour. next,
The solvent was distilled off under reduced pressure until the total amount of the reaction mixture was reduced to half, and then reprecipitated in petroleum ether 1. The precipitate was collected, and dried under reduced pressure to obtain a polymer having a weight of 6.5 × 10 ³ and a yield of 56 g.

Macromonomer (MA) Synthesis Example 2: (NM-2) benzyl methacrylate 5 g, (tetraphenylporphinato) aluminum methyl 0.1 g and methylene chloride 60
g of the mixed solution was adjusted to a temperature of 30 ° C. under a nitrogen stream. 300 for this
W-xenon lamp light 25cm through glass filter
And irradiated for 12 hours. 45 g of butyl methacrylate was further added to this mixture, and the mixture was similarly irradiated with light for 8 hours, and then 4-bromomethylstyrene was added to the reaction mixture.
10 g was added, and the mixture was stirred for 30 minutes to stop the reaction.

Next, Pd-C was added to the reaction mixture, and a catalytic reduction reaction was performed at a temperature of 25 ° C. for 1 hour.

After filtering off the insoluble matter, the precipitate was reprecipitated in 500 ml of petroleum ether,
The precipitate was collected and dried. The obtained polymer was obtained in a yield of 33 g.
It was w7 × 10 ³ .

Macromonomer (MA) Synthesis Example 3: (NM-3) A mixed solution of 20 g of 4-vinylphenyloxytrimethylsilane and 100 g of toluene was thoroughly degassed under a nitrogen stream and cooled to 0 ° C. 2 g of lithium 1,1-diphenyl-3-methylpentyl was added, and the mixture was stirred for 6 hours. Furthermore, 2-chloro-6-methylphenyl methacrylate is added to this mixture.
A mixed solution of 80 g and 100 g of toluene was sufficiently degassed under a nitrogen stream, and then added and reacted for 8 hours. Ethylene oxide was bubbled through the reaction mixture at a flow rate of 30 ml / min for 30 minutes with sufficient stirring, then cooled to a temperature of 15 ° C., 12 g of methacrylic acid claroids was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours.

The reaction mixture is then added to a 10% 30% hydrogen chloride ethanol solution.
g and stirred at 25 ° C. for 1 hour.
Re-precipitated in, the collected precipitate was diethyl ether 300ml
And dried twice. The obtained polymer was obtained in a yield of 55 g.
w 7.8 × 10 ³

Synthesis Example 4 of Macromonomer (MA): (NM-4) 40 g of triphenylmethyl methacrylate and toluene 1
00 g of the mixed solution was sufficiently degassed under a nitrogen stream and cooled to -20 ° C.

2 g of sec-butyllithium was added and reacted for 10 hours. Next, to this mixed solution, a mixed solution of 60 g of styrene and 100 g of toluene was sufficiently degassed under a nitrogen stream, and then added, followed by a reaction for 12 hours. After the mixture was cooled to 0 ° C., 11 g of benzyl bromide was added and reacted for 1 hour, and further reacted at a temperature of 25 ° C. for 2 hours.

10 g of a 30% salt hydrogen-containing ethanol solution was added to the reaction mixture.
Was added and stirred for 2 hours. After filtering off the insoluble matter, the precipitate was reprecipitated in n-hexane 1, and the precipitate was collected and dried under reduced pressure. The yield of the obtained polymer was 58 g and w 4.5 × 10 ³ .

Macromonomer (MA) Synthesis Example 5: (NM-5) Phenylmethacrylate 70 g, benzyl-N-hydroxyethyl-N-ethyldithiocarbamate 4.8 g mixture was sealed in a container under a nitrogen stream, and the temperature was raised to 60 ° C. Heated. This was subjected to photopolymerization by irradiating with light for 10 hours through a glass filter from a distance of 10 cm with a high pressure mercury lamp of 400 W. After 30 g of acrylic acid and 180 g of methyl ethyl ketone were added thereto, the atmosphere was replaced with nitrogen and light irradiation was performed again for 10 hours.

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

The obtained reaction product was reprecipitated in hexane 1.5, collected, and dried. The obtained polymer was 68 g and had a weight of 6.0 × 10 ³ .

Synthesis Example of Resin [A] 1: [A-1] 80 g of ethyl methacrylate, macromonomer (MM-
1) Heat a mixed solution of 120 g and 150 g of toluene under a nitrogen stream.
Heated to 95 ° C. 6 g of 2,2'-azobis (isobutyronitrile) (AIBN) was added and reacted for 3 hours.
IBN2g was added and reacted.

W of the obtained copolymer was 9 × 10 ³ .

Synthesis Example 2 of Resin [A]: [A-2] A mixed solution of 70 g of 2-chlorophenyl methacrylate, 30 g of macromonomer (MM-2), 2 g of n-dodecyl mercaptan and 100 g of toluene was heated to a temperature of 80 ° C. under a nitrogen stream. Warmed. 2,2'-azobis (isovaleronitrile) (AIV
N) 3 g was added and reacted for 3 hours, and 1 g of AIVN was further added and reacted for 2 hours. Next, 1 g of AIBN was added, and the mixture was heated to a temperature of 90 ° C. and reacted for 3 hours. W of the obtained copolymer was 7.6 × 10 ³ .

Synthetic Examples 3 to 18 of Resin [A]: [A-3] to [A-18] The following table was used under the same polymerization conditions as in Synthetic Example 1 of Resin [A], except that ethyl methacrylate was replaced by another monomer. -1 was synthesized. The w of each polymer obtained is 5 × 10 ^{3 to} 9
× was 10 ^3.

Synthesis Examples 19 to 35 of Resin [A]: [A-19] to [A-35] In Synthesis Example 2 of Resin [A], the macromonomer (MM
The copolymers shown in Table 1 below were synthesized under the same polymerization conditions as in Synthesis Example 2 except that another macromonomer (MA) was used instead of -2). W of each of the obtained polymers is 2 × 10 ³ to 1 × 1
It was 0 ² .

(Production Example of Macromonomer Used in Resin [B]) Production Example of Macromonomer (MB) 1: (M-1) While stirring a mixed solution of 95 g of methyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene under a nitrogen stream. ,
Heated to a temperature of 75 ° C. 1.0 g of 2,2'-azobis (cyanovaleric acid) (abbreviated as ACV) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to the reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in methanol 2 to give a white powder.
I got 82g. The number average molecular weight of the polymer (M-1) was 6,500.

Production Example 2 of Macromonomer (MB): (M-2) A mixed solution of 95 g of methyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was heated to 70 ° C while stirring under a nitrogen stream. 1.5 g of 2,2'-azobis (isobutyronitrile) (abbreviation: AIBN) was added and reacted for 8 hours.
Next, to this reaction solution, 7.5 g of glycidyl methacrylate,
1.0 g of N, N-dimethyldodecylamine and 0.8 g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in methanol 2 to obtain 85 g of a colorless and transparent viscous substance. The number average molecular weight of the polymer (M-2) was 2,400.

Macromonomer (MB) Production Example 3: (M-3) Propyl Methacrylate 94g, 2-Mercaptoethanol 6g, Toluene 200g Mixed solution at 70 ° C under nitrogen stream
Was heated. 1.2 g of AIBN was added and reacted for 8 hours.

Next, the reaction solution was cooled in a water bath to a temperature of 20 ° C., 10.2 g of triethylamine was added, and 14.5 g of methacrylic acid chloride was added dropwise with stirring at a temperature of 25 ° C. or lower. After the addition, the mixture was further stirred for 1 hour. Thereafter, 0.5 g of t-butylhydroquinone was added, the mixture was heated to a temperature of 60 ° C., and stirred for 4 hours. After cooling, the precipitate was reprecipitated in methanol 2 to obtain 79 g of a colorless and transparent viscous substance. The number average molecular weight of the polymer (M-3) was 4.500.

Production Example 4 of Macromonomer (MB): (M-4) A mixed solution of 95 g of ethyl methacrylate and 200 g of toluene was heated to 70 ° C. under a nitrogen stream. 5 g of 2,2'-azobis (cyanoheptanol) was added and reacted for 8 hours.

After cooling, the temperature of the reaction solution was adjusted to 20 ° C. in a water bath, 1.0 g of triethylamine and 21 g of methacrylic anhydride were added, and the mixture was stirred for 1 hour and then at 60 ° C. for 6 hours.

After cooling the obtained reaction product, it was reprecipitated in methanol 2 to obtain 75 g of a colorless and transparent viscous substance. The number average molecular weight of the polymer (M-4) was 6.200.

Production Example 5 of Macromonomer (MB): (M-5) A mixture of 93 g of benzyl methacrylate, 7 g of 3-mercaptopropionic acid, 170 g of toluene and 30 g of isopropanol was heated to 70 ° C. under a nitrogen stream to obtain a uniform solution. . 2.0 g of AIBN was added and reacted for 8 hours. After cooling, the precipitate was reprecipitated in methanol 2 and heated to 50 ° C. under reduced pressure to distill off the solvent. The obtained viscous substance was dissolved in 200 g of toluene, and glycidyl methacrylate 16 was added to the mixed solution.
g, N, N-dimethyldodecyl methacrylate 1.0 g and t-
1.0 g of butyl hydroquinone was added, and the mixture was stirred at 110 ° C. for 10 hours. This reaction solution was reprecipitated in methanol 2 again. The number average molecular weight of the obtained pale yellow viscous substance (M-5) was 3,400.

Production Example 6 of Macromonomer (MB): (M-6) A mixed solution of 95 g of propyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was heated to 70 ° C. while stirring under a nitrogen stream. 1.0 g of AIBN was added and reacted for 8 hours. Next, glycidyl methacrylate 13 g, N, N
1.0 g of -dimethyldodecylamine and 1.0 g of t-butylhydroquinone were added, and the mixture was stirred at 110 ° C for 10 hours. After cooling, the reaction solution was reprecipitated in methanol 2 to obtain 86 g of a white powder. The number average molecular weight of the polymer (M-6) was 3,5
00.

Production Example 7 of Macromonomer (MB): (M-7) 40 g of methyl methacrylate, 54 of ethyl methacrylate
g, a mixture of 6 g of 2-mercaptoethylamine, 150 g of toluene and 50 g of tetrahydrofuran were heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 2.0 g of AIBN was added and reacted for 8 hours. Next, the reaction solution was heated to a temperature of 20 ° C. in a water bath, and 23 g of methacrylic anhydride was added dropwise thereto so that the temperature did not exceed 25 ° C., followed by further stirring for 1 hour. 2,
0.5 g of 2'-methylenebis (6-t-butyl-p-cresol) was added, and the mixture was stirred at a temperature of 40 ° C for 3 hours. After cooling,
This solution was reprecipitated in methanol 2 to obtain 83 g of a viscous substance. The number average molecular weight of the polymer (M-7) was 2,200.

Production Example 8 of Macromonomer (MB): (M-8) 2-chlorophenyl methacrylate 95 g, toluene 150
g and ethanol 150 g in a nitrogen stream at a temperature of 75
Warmed to ° C. 5 g of ACV was added and reacted for 8 hours. Next, 15 g of glycidyl acrylate, 1.0 g of N, N-dimethyldodecylamine and 1.0 g of 2,2′-methylenebis- (6-t-butyl-p-cresol) were added, and the mixture was stirred at a temperature of 100 ° C. for 15 hours. After cooling, the reaction solution was reprecipitated in methanol 2 to obtain 83 g of a transparent viscous substance. The number average molecular weight of the polymer (M-8) was 3,600.

Macromonomer (MB) Production Examples 9-18: (M-9)-
(M-18) A macromonomer (MB) was prepared in the same manner as in Production Example 3 except that the acid halide compounds shown in Table 2 below were used instead of methacrylic acid chloride in Production Example 3. Monomers (M-9) to (M-18) were produced.

The weight average molecular weight (w) of the macromonomers (M-9) to (M-18) was 4.000 to 5,000.

Macromonomer (MB) Production Examples 19-27: (M-19)-
(M-27) A macromonomer (M-) was produced in the same manner as in Production Example 2 except that the monomers shown in Table 3 below were used instead of methyl methacrylate in Production Example 2 of macromonomer (MB).
19) to (M-27) were produced.

(Production Example of Resin [B]) Production Example 1 of Resin [B] 1: Resin [B-1] 70 g of ethyl methacrylate, macromonomer (M-
1) A mixed solution of 30 g and 150 g of toluene was heated under a nitrogen stream at a temperature of 7
Warmed to 0 ° C. Next, 0.5 g of AIBN was added and reacted for 4 hours. Further, 0.3 g of AIBN was added and reacted for 6 hours.
The weight average molecular weight of the obtained copolymer [B-1] is 9.8 × 1
0 Glass transition point ⁴ was 72 ° C..

Production Examples 2 to 15 of Resin [B]: Resins [B-2] to [B-1]
5] Under the same polymerization conditions as in Production Example 1 of Resin [B], the following Table-
Resin No. 4 [B] was produced. The w of each resin is 8 × 10 ⁴ ~
The range was 1.5 × 10 ⁵ .

Production Example 16 of Resin [B]: Resin [B-16] 70 g of ethyl methacrylate, macromonomer (M-
2) A mixed solution of 30 g, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 70 ° C. under a nitrogen stream. Next, 4,4 '
0.8 g of -azobis (4-cyanovaleric acid was added and reacted for 10 hours. The weight average molecular weight (w) of the obtained copolymer was
The glass transition point was 72 ° C. at 9.8 × 10 ⁴ .

Production Examples 17 to 24 of Resin [B]: Resins [B-17] to [B-2]
4] In Production Example 16 of Resin [B], the macromonomer (M
Each resin [B] was produced in the same manner as in Production Example 16 except that macromonomers shown in Table 5 below were used instead of -2). The w of each resin was 9 × 10 ^{4 to} 1.2 × 10 ⁵ .

Production Examples 25 to 31 of Resin [B]: Resins [B-25] to [B-3]
1] In Production Example 16 of Resin [B], instead of ACV,
The production examples except that the azobis compounds shown in Table 6 below were used.
By operating in the same manner as in 16, each polymer was produced.

Production Example 32 of Resin [B]: Resin [B-32] 80 g of butyl methacrylate, macromonomer (M-
8) A mixed solution of 20 g, 1.0 g of thioglycolic acid, 100 g of toluene and 50 g of isopropanol was heated to 80 ° C. under a nitrogen stream.
Was heated. 1,1'-azobis (cyclohexane-1-
0.5 g of carbonitrile) (abbreviation ACHN) was added and stirred for 4 hours, and 0.3 g of ACHN was further added and stirred for 4 hours. The w of the obtained polymer was 8.0 × 10 ⁴ and the glass transition point was 41 ° C.

Production Examples 33 to 39 of Resin [B]: Resins [B-33] to [B-3]
9] A polymer was produced in the same manner as in Production Example 32 of Resin [B] except that the compounds shown in Table 7 below were used instead of thioglycolic acid.

Production Examples 40 to 48 of Resin [B]: Resins [B-40] to [B-4]
8] The following Table 8 was used under the same polymerization conditions as in Production Example 26 of Resin [B].
Was produced.

The w of each resin was in the range of 9.5 × 10 ^{4 to} 1.2 to 10 ⁵ .

Production Examples 49 to 56 of Resin [B]: Resins [B-49] to [B-5]
6] Under the same polymerization conditions as in Production Example 16 of resin [B],
The resins shown in Table 9 below were produced. Each resin obtained [B]
W was 9.5 × 10 ^{4 to} 1.1 × 10 ⁵ .

Example 1 and Comparative Examples AC Resin [A-2] 6 g (as solid content), Resin [B-
1] A mixture of 34 g (as solid content), cyanine dye [I] of the following structure 0.018 g, and toluene 300 g was dispersed in a ball mill for 4 hours to prepare a photosensitive layer-forming material, which was applied to a conductive-treated paper. Then, apply it with a wire bar so that the dry adhesion amount becomes 25 g / m ² , dry at 110 ° C for 30 seconds, and then 2 in the dark.
An electrophotographic light-sensitive material was prepared by being left at 0 ° C. and 65% RH for 24 hours.

Comparative Example A: Instead of the binder resin used in Example 1, 6 g of resin [R-1] having the following structure and poly (ethyl methacrylate) (w2.4 × 10 ⁵ : 34 g of resin [R-2] are used. An electrophotographic photosensitive material was produced in the same manner as in Example 1 except for the above.

Comparative Example B: The procedure of Example 1 was repeated, except that 6 g of the resin [R-3] and 34 g of the resin [R-2] having the following structure were used instead of the binder resin used in Example 1. A photographic light-sensitive material was prepared.

Comparative Example C: The procedure of Example 1 was repeated, except that 6 g of resin [R-3] and 34 g of resin [R-4] having the following structure were used instead of the binder resin used in Example 1. A photographic light-sensitive material was prepared.

The film properties (surface smoothness), electrostatic properties, image pick-up properties and image pick-up properties when the environmental conditions were 30 degrees and 80% RH were examined. Furthermore, the photoconductivity when these photosensitive materials are used as a source plate for an offset master is desensitized (expressed by the contact angle of the photoconductive layer after desensitization treatment with water) and printability (background stain). , Printing durability, etc.).

 Table 10 summarizes the above results.

The modes of implementation of the evaluation items shown in Table 10 are as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was measured for its smoothness (sec / cc) using a Beck smoothness tester (manufactured by Kumagaya Riko Co., Ltd.) under the condition of an air capacity of 1 cc. It was measured.

Note 2) Mechanical strength of the photoconductive layer: The surface of the obtained light-sensitive material was coated with Haydon-14 type surface test material (manufactured by Shinto Chemical Co., Ltd.) under a load of 60 g / cm ² and emery paper (# 1000) was repeated 1000 times to remove the abrasion powder, and the residual film rate (%) was calculated from the reduction in the weight of the photosensitive layer to obtain the mechanical strength.

Note 3) Electrostatic properties: Paper analyzer (Kawaguchi Electric Co., Ltd. paper analyzer) in a dark room at a temperature of 20 ° C and 65% RH.
After 20 seconds corona discharge -6kV with SP-428 type), allowed to stand for 10 seconds to measure the surface potential V ₁₀ at this time.
Then the potential V ₁₈₀ after being left for 180 seconds in it the dark
Of the potential after dark decay for 180 seconds, that is, the dark decay retention rate [DRR (%)] is (V ₁₈₀ / V ₁₀ ) × 100.
(%).

After charging the surface of the photoconductive layer to −500 V by corona discharge, the surface is irradiated with monochromatic light having a wavelength of 785 nm, and the surface potential (V ₁₀ ) is reduced.
The time required to decay to 1/10 is determined, and the exposure E
Calculate _1/10 (erg / cm ² ). Furthermore, after charging to -500 V by corona discharge in the same manner as in E _1/10 measurement, irradiation with monochromatic light having a wavelength of 785 nm was performed, and the time until the surface potential (V ₁₀ ) attenuated to 1/100 was determined. The quantity E _1/100 (erg / cm ² ) is calculated.

Note 4) Image-capturability: Each photosensitive material was allowed to stand for one day under the following environmental conditions. Next, gallium-aluminum-arsenic of 2.8 mW output and semiconductor laser (oscillation wavelength 785 nm) charged at −5 kV were used, and the pitch μm and scanning speed were applied on the surface of the photosensitive material under the irradiation amount of 50 erg / cm ^2. ELP-T (Fuji Photo Film Co., Ltd.) as a liquid developer after speed exposure of 330 m / sec
Image) and the image quality) of the copied image obtained by developing and fixing the image.

The environmental conditions during shooting were 20 ° C 65% RH and 30 ° C 80% RH.

Note 5) Contact angle with water: Each light-sensitive material was passed through an etching processor once using a desensitizing solution EPL-EX (manufactured by Fuji Photo Film Co., Ltd.) diluted twice with distilled water. After desensitizing the surface of the photoconductive layer with water, a drop of distilled water 2III- is placed on the surface, and the contact angle with the formed water is measured with a goniometer.

Note 6) Printing durability: Each light-sensitive material is subjected to plate making under the same conditions as in Note 4) above to form a toner image, and desensitized under the same conditions as in Note 5) above, and this is used as an offset master. The number of sheets that can be printed on an offset printing machine (Oliver 52 type, Sakurai Seisakusho Co., Ltd.) without causing stains on the non-image area of the printed matter and on the image quality of the image area. It means that the property is good).

As shown in Table-10, the light-sensitive material of the present invention was excellent in the strength and electrostatic property of the smooth film of the photoconductive layer, and the actual copied image was free of background fog and the copied image quality 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 master, the desensitizing treatment with the desensitizing solution proceeds sufficiently, the contact angle with water of the non-image area is as small as 10 degrees or less, and the hydrophilicity is sufficiently increased. You can see that Even when the printed matter was actually examined and the background stain was observed, no background stain was observed.

Comparative Examples A to C are compared with the photosensitive material of the present invention.
The electrostatic characteristics have deteriorated. In Comparative Example C, the film strength was improved, and the values of V ₁₀ , DRR, and E _1/10 were almost satisfactory in electrostatic characteristics. However, looking at the E _1/100 value, it was more than twice as large as that of the light-sensitive material of the present invention. The E _1/100 value indicates how much potential remains in the non-image area (exposed area) after exposure in the actual imaging performance. This indicates that background contamination of the image portion will not occur.

Specifically, it is necessary to set the residual potential to -10 V or less, that is, scanning with a semiconductor laser beam depends on how much exposure is required in order to actually make V _R -10 V or less. With the exposure method, a small exposure
To the V _R below -10V, the (cost of the device, the accuracy of an optical system an optical path) optical system design of the copying machine is very important.

From the above, when an image was actually taken with an apparatus having a slightly reduced exposure dose, Comparative Example A had a remarkably low DRR, so that a satisfactory copied image could not be obtained. In Comparative Example B, the image was remarkably deteriorated under the conditions of high temperature and high humidity, the density of the image part was decreased, fine lines and letters were scraped, and the background fog was generated in the non-image part. . Comparative Example C is at room temperature
The image was almost satisfactory under normal humidity conditions, but at high temperatures and
Under high-humidity conditions, the occurrence of background fog and thin lines in the image area have occurred. Further, even when used as an offset master, under the printing conditions that the photosensitive material of the present invention can print 10,000 sheets or more, in each of Comparative Examples A to C, non-image area stains are generated from printed printouts. have done. This was because a clear copied image was not obtained, and ground fog could not be removed by the desensitizing treatment.

As described above, an electrophotographic photosensitive member that satisfies electrostatic characteristics and printability only when the resin of the present invention is used is obtained.

Examples 2 to 17 In Example 1, the resin [A-7] and the resin [B-
1] was replaced with each of the resins [A] and [B] shown in Table 11 below, and the same operation as in Example 1 was carried out to produce each electrophotographic photosensitive member.

The electrostatic characteristics were measured in the same manner as in Example 1. The results are shown in Table-11.

Example 1 was used as an offset master master.
When printing was performed in the same manner as described above, all of them could print 10,000 sheets or more.

From the above, each photosensitive material of the present invention, the smoothness of the photoconductive layer,
The film strength, electrostatic properties, and printability were all favorable.

Furthermore, it was found that the use of the resin [A '] further improved electrostatic characteristics.

Examples 18 to 33 In Example 1, the binder resin was replaced by 7.6 g of resin [A] and 34 g of resin [B] shown in Table 12 below, and instead of 0.02 g of cyanine dye [I], a dye having the following structure [ II) 0.019g
An electrophotographic photosensitive material was produced under the same conditions as in Example 1 except that the above was changed to.

The photosensitive materials of the present invention are all excellent in chargeability, dark charge retention, and photosensitivity.
(80 ° C., 80% RH), a clear image without fog was obtained.

Furthermore, when this was used as an offset master master, 10,000 or more printed materials with clear image quality without background fog could be printed.

Examples 34 and 35 and Comparative Example D 6.5 g of either resin [A-15] (Example 34) or resin [A-20] (Example 35), 33.5 g of resin [B-16], 200 g of zinc oxide. , Uranine 0.02 g, rose bengal 0.04 g, bromphenol bull-0.03 g, phthalic anhydride 0.20 g and toluene 300 g were dispersed in a ball mill for 4 hours to prepare a photosensitive layer-forming material, which was subjected to conductive treatment. Then, it was coated with a wire bar so that the dry adhesion amount was 20 g / m ^2, and dried at 110 ° C. for 1 minute. Then, in the dark, at 20 ° C and 65% RH
Each electrophotographic photoreceptor was prepared by being left for 24 hours.

Comparative Example D In Example 34, 6.5 g of resin [A-2] and 6.5 g of resin [B-
16] A light-sensitive material was prepared in the same manner as in Example 34 except that 6.5 g of resin [R-3] and 33.56 g of resin [R-4] were used instead of 33.5 g.

As in Example 1, each characteristic of each photosensitive material was examined. The results are summarized in Table 13 below.

In the above measurement, the same operation as in Example 1 was performed, except that the following operation was performed for the electrostatic characteristics and the image capturing property.

Note 7) Method for measuring E _1/10 and E _1/100 of electrostatic characteristics After charging the surface of the photoconductive layer to −400 V by corona discharge, irradiating the surface of the photoconductive layer with visible light having an illuminance of 2.0 lux. The time required for the surface potential (V ₁₀ ) to decay to 1/10 or E _1/100 is determined, and the exposure amount E _1/10 or E _1/100 (lux seconds) is calculated from this.

Note 8) Imaging characteristics After each photosensitive material is left for one day and night under the following environmental conditions, E is used with a fully automatic plate making machine EPL-404V (Fuji Photo Film Co., Ltd.).
A copy image (fog, image quality) obtained by making a plate using PL-T as a toner was visually evaluated. Environmental conditions at the time of imaging were 20 ° C. and 65% RH (I) and 30 ° C. and 80% RH (II). However, a copy original (that is, a copy original) was prepared by cutting and pasting another original.

In each photosensitive material, no difference was observed in the smoothness and strength of the photoconductive layer. However, in Comparative Example D, the value of the light sensitivity E _1/100 was particularly large in the electrostatic characteristics. The photosensitive material of the present invention has good electrostatic characteristics, and furthermore, the photosensitive material of Example 35 using the resin [A] having a specific substituent was used.
Was very good, and the value of E _1/100 was particularly small.

Investigation of the actual imaging performance revealed that in Comparative Example D, in addition to the original as a copy image, the frame of the cut and pasted portion (that is, the pasted trace) was recognized as background stain in the non-image portion. However, in each case of the present invention, clear images without background stains were obtained.

Further, when these were subjected to desensitization processing as an offset printing original plate and then printed, 10,000 sheets of clear images having no background stain were obtained in any of the present invention. However, in Comparative Example D, the sticking marks were not removed even by the desensitizing treatment, and were generated from the printed material.

As described above, only the photosensitive material of the present invention was able to give good characteristics.

Examples 36 to 49 In Example 34, the resin [A-15] 6.5 g and the resin [B
-16] Instead of 33.5g, resin [A] 6.5g in Table -14 below
Each photosensitive material was produced in the same manner as in Example 34 except that 33.5 g of the resin [B] was used.

All photosensitive materials of the present invention are chargeable, dark charge retention,
Excellent light sensitivity, real copy image is high temperature and humidity (30 ℃, 80%
Even under severe conditions (RH), a clear image was obtained without occurrence of ground fogging or fine line skipping.

Further, when printing was performed as an offset master plate, a printed matter of clear image quality free of background stain was obtained even after printing 10,000 sheets.

Examples 50 and 51 6.5 g of either resin [A-14] (Example 50) or resin [A-15] (Example 51), resin [B-2] 33.5 g, zinc oxide 200 g, uranine 0.02 g. A mixture of 0.04 g of rose bengal, 0.03 g of bromphenol blue, 0.20 g of phthalic anhydride and 300 g of toluene was dispersed in a ball mill for 3 hours. Next, 0.6 g of glutaric acid (Example 50) or 1,6-
Hexanediol (0.5 g, Example 51) was added and further dispersed in a ball mill for 10 minutes.

This was applied to a conductive treated paper with a wire bar so that the dry adhesion amount was 20 g / m ² , dried at 110 ° C. for 1 minute, and further heated at 120 ° C. for 1.5 hours. Then, each electrophotographic photosensitive member was produced by leaving it in the dark at 20 ° C. and 65% RH for 24 hours.

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

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

(Effects of the Invention) According to the present invention, it is possible to obtain an electrophotographic photosensitive member having excellent electrostatic characteristics and mechanical strength even under severe conditions. Further, the photoreceptor of the present invention is effective for a scanning exposure method using a semiconductor laser beam.

Claims (4)

(57) [Claims] 1. An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material and a binder resin, wherein the binder resin is at least one of the following resins [A] and the following resin [B]: An electrophotographic photosensitive member comprising at least one kind. Resin (A); -PO ₃ H ₂ group, -COOH group, -SO ₃ H groups, phenolic OH groups, At least one polymer component containing at least one acidic group selected from {R represents a hydrocarbon group or an --OR 'group (R' is a hydrocarbon group) and a cyclic acid anhydride-containing group is contained. A polymerizable double bond is added to the end of the polymer main chain of the B block of the A / B block copolymer composed of the A block and the B block containing at least the polymer component represented by the following general formula (I). A graft-type copolymer having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , containing at least one monofunctional macromonomer having a group bonded thereto as a copolymerization component. General formula (I) [In the 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−, (L ₁ and l ₂ represent an integer of 1 to 3), -O-, -SO
_2- , -CO-, -CONHCOO-, -CONHCONH- or Wherein Z ₁ represents a hydrogen atom or a hydrocarbon group. R ₁ represents a hydrocarbon group. Where A ₁ is When R ₁ represents R ₁ represents a hydrogen atom or a hydrocarbon group. Binder resin [B]; The following general formula (III) is provided only at one end of the polymer main chain containing at least one of the polymer components represented by the following general formulas (IV a) and (IV b). ) A resin which is a copolymer comprising at least a monofunctional macromonomer having a weight average molecular weight of 2 × 10 ⁴ or less and a monomer represented by the following general formula (V). . General formula (III) Wherein (III), V ₀ is -COO -, - OCO -, - CH 2 OCO-,
_{-CH 2 COO -, - O -} , - SO 2 -, - CO -, - CONHCOO-,
−CONHCONH−, −CONHSO ₂ −, Or (P ₃ represents a hydrogen atom or a hydrocarbon group). c ₁ and c ₂ may be the same or different from each other, and represent a hydrogen atom,
It represents a halogen atom, a cyano group, a hydrocarbon group, -COO-Z 'or a hydrocarbon-mediated -COO-Z' (Z 'represents a hydrogen atom or an optionally substituted hydrocarbon group). General formula (IVa) General formula (IV b) [In the formula (IV a) or (IV b), V ₁ is V ₀ in the formula (III).
Represents the same content as. Q ₁ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. d ₁ and d ₂ may be the same or different from each other, and have the formula (III)
Represents the same content as c ₁ and c _{2 in} . Q ₀ is -CN, -CONH ₂ or Represents Here, T represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group or -COOZ "(Z" represents an alkyl group, an aralkyl group or an aryl group). General formula (V) [In the formula (V), V ₂ represents the same content as V ₁ in the formula (IV a). Q ₂ has the same meaning as Q ₁ in formula (IV a). e ₁ and e ₂ may be the same or different and represent the same contents as c ₁ and c _{2 in} formula (III). ] 2. The resin [A] contains at least one monomer represented by the following general formula (II) together with the macromonomer (M) as a copolymerization component (1). ) The electrophotographic photosensitive member according to [1]. General formula (II) [In the formula (II), R ₂ represents a hydrocarbon group. ] 3. In the resin [A], together with the macromonomer (M), the following general formula (IIa) and general formula (II)
3. The electrophotographic photoreceptor according to claim 2, wherein at least one of the monomers represented by b) is contained as a copolymer component in an amount of 30% by weight or more. General formula (IIa) General formula (IIb) Wherein X ₁ and X ₂ are each independently a hydrogen atom,
Hydrocarbon group having 1 to 10 carbon atoms, chlorine atom, bromine atom, -CO
Z ₃ or —COOZ ₃ (Z ₃ each represents a hydrocarbon group having 1 to 10 carbon atoms) is represented. However, X ₁ and X ₂ are never both represent a hydrogen atom. L ₁ and L ₂ each connect -COO- and a benzene ring,
It represents a single bond or a linking group having 1 to 4 linking atoms. ] 4. The copolymer in resin [B] further comprises-
PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -OH group, and -SH group At least one acidic group selected from {R ₀ represents a hydrocarbon group or a --OR ₀ ′ group (R ₀ ′ represents a hydrocarbon group)} is bonded to one end of the main chain of the copolymer. The electrophotographic photosensitive member according to any one of claims (1) to (3), wherein