JPH0534942A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic sensitive body excellent in reproducing a high-definition picture with the use of a liq. developer and image pickup property by the scanning exposure system using a low-output laser beam by incorporating specified resins (A) and (B) into a binder resin. CONSTITUTION:This electrophotographic sensitive body incorporates a resin (A) as the graft copolymer having an AB block copolymer consisting of a block A contg. a polymer component contg. a polar group and a block B contg. a polymer component of a repeating ingredient shown by formula I at its graft part and having 1X10<3>-2X10<4> weight average mol.wt. and a resin (B) as the AB block copolymer consisting of the block A contg. a polymer component contg. a polar group and a block B contg. a polymer component of the repeating ingredient shown by formula II and having 2X10<4>-1X10<6> weight average mol.wt. as the binder resin. In formulas I and II, a<1>, a<2>, b<1> and b<2> are hydrogen, halogens, etc., V<1> is a bivalent group, and R<3> and R<4> are a hydrocarbonic group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
More specifically, it relates to an electrophotographic photoreceptor having excellent electrostatic characteristics and moisture resistance.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors have various structures in order to obtain predetermined characteristics or depending on the type of electrophotographic process applied.

Typical of electrophotographic photoreceptors are a photoreceptor having a photoconductive layer formed on a support and a photoreceptor having an insulating layer on the surface thereof, which are widely used. Photoreceptors composed of a support and at least one photoconductive layer are produced by the most common electrophotographic process, namely charging,
It is used for image exposure and development and, if necessary, for image formation by transfer.

Further, a method of using an electrophotographic photosensitive member as an offset original plate for direct plate making is widely used. Particularly in recent years, the direct electrophotographic lithographic printing plate has become important as a method for printing high-quality printed matter by printing several hundred to several thousand sheets. In such a situation, the binder resin used for forming the photoconductive layer of the electrophotographic photosensitive member has excellent film-forming property of itself and dispersibility in the binder resin of the photoconductive powder, The formed recording layer has good adhesion to the substrate, and the photoconductive layer of the recording layer has excellent charging ability, small dark decay, large light decay, little pre-exposure fatigue, and shooting It is necessary to have various electrostatic characteristics such as being required to stably maintain these characteristics due to changes in humidity with time, and excellent image pickup properties.

Further, research on a lithographic printing plate precursor using an electrophotographic photosensitive member has been earnestly conducted, and a photoconductive layer for a photoconductive layer having both electrostatic properties as an electrophotographic photosensitive member and printing properties as a printing original plate has been made. Binder resin is required.

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

On the other hand, JP-A-63-217354
According to the techniques described in JP-A No. 64-70761, JP-A Nos. 2-67563 and 2-247656, a low molecular weight resin in which an acidic group-containing polymerization component is randomly present in the polymer main chain, A low molecular weight resin having an acidic group bonded to one end of the polymer main chain or a low molecular weight graft copolymer resin having an acidic group bonded to one end of the polymer main chain,
It has become possible to improve smoothness and electrostatic properties by using a low molecular weight graft copolymer resin containing an acidic group in the graft portion as a binder resin. These are such that the low molecular weight resin has an effect of sufficiently dispersing the photoconductor and suppressing the aggregation of the photoconductors, and the inorganic substance without alienating the adsorption between the photoconductor and the spectral sensitizing dye. It is presumed that this is due to the fact that the photoconductor is sufficiently adsorbed to the stoichiometric defects and the surface of the photoconductor is covered gently and sufficiently.

Due to its mechanism of action, the inorganic photoconductor, the spectral sensitizing dye, and the resin are relatively stable because they have a sufficient adsorption area even if the stoichiometric defects of the inorganic photoconductor fluctuate to some extent. It is inferred that mutual interaction is maintained.

[0009] In order to make the mechanical strength of the photoconductive layer insufficient by using only these low molecular weight resins, a technique of using another resin of medium to high molecular weight or a resin containing a curable group is used. Japanese Patent Application Laid-Open Nos. 64-564, 63-220149, and 63-220149, which are used together to cure after film formation,
63-220148, JP-A-1-280761,
No. 1-116643, No. 1-169455, No. 1-
No. 211766, No. 2-34859, No. 2-5306
No. 4, No. 2-56558, and Japanese Patent Application No. 1-163796.
No. 1-212994, No. 1-2229379, No. 1-189245, and the like.

[0010]

However, even if these resins or combinations of resins are used, they are still insufficient in maintaining stable performance when the environment changes significantly from high temperature / high humidity to low temperature / low humidity. I knew it was. The scanning exposure method that uses a semiconductor laser beam has a longer exposure time than the conventional simultaneous full-exposure method that uses visible light, and also has a limited exposure intensity, so electrostatic characteristics, especially dark charge retention characteristics, are used. , For light sensitivity,
Higher performance is required.

In particular, when the scanning exposure method using the semiconductor laser light is adopted in the electrophotographic lithographic printing plate precursor, when actually tested with a conventional photoconductor, the above electrostatic characteristics are sufficiently obtained. This is not satisfactory, and especially the difference between E _1/2 and E _1/10 is large, the gradation of the copied image becomes soft, and it becomes difficult to reduce the residual potential after exposure, causing fog in the copied image. Became noticeable, and again
Even when printing as an offset master, a problem such as a print original sticking mark on the printed matter appeared.

Further, in recent years, it has been desired to realize a technique for faithfully reproducing not only a copied image of an image composed of line drawings and halftone dots but also a high-definition image composed of continuous gradations by using a liquid developer. However, the above-mentioned known technology has not been able to sufficiently satisfy these demands.

In the conventionally known technique, the medium-to-high molecular weight resin used in combination with the low-molecular weight resin may lower the electrostatic properties of the low-molecular weight resin which have been improved in performance. The electrophotographic photosensitive member having a photoconductive layer used in combination with these known resins as described above is capable of reproducing the faithful reproduction of a high-definition image (especially continuous tone image) as described above or a low output. It was clarified that a problem can occur with respect to the imaging property of the scanning exposure method using laser light.

The present invention is to improve the problems of the above-described conventionally known electrophotographic photoreceptors. An object of the present invention is to provide an electrophotographic photosensitive member having a clear and high-quality image which constantly maintains good electrostatic characteristics even when the environment for forming a copied image changes such as low temperature and low humidity or high temperature and high humidity. Is to provide.

Another object of the present invention is to provide a CPC electrophotographic photosensitive member which is excellent in electrostatic characteristics and has little environmental dependence. Another object of the present invention is to provide an electrophotographic photosensitive member effective for a scanning exposure system using a semiconductor laser beam.

A further object of the present invention is an electrophotographic lithographic printing original plate which has excellent electrostatic properties (especially dark charge retention and photosensitivity) and is faithful to the original image (especially high-definition continuous tone image). Another object of the present invention is to provide a lithographic printing original plate that reproduces various copied images and does not generate spot stains as well as uniform stain stains on the entire surface of a printed matter, and that has excellent printing durability.

[0017]

The above object is an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor, a spectral sensitizing dye and a binder resin, and the binder resin is shown below. It has been found to be achieved by an electrophotographic photosensitive member characterized by containing at least one kind of resin [A] and at least one kind of resin [B] below. Resin [A] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ ,
O ₃ H ₂ group, -COOH group, -SO ₃ H group, a phenolic OH group, -P (= O) (OH ) R 1 [R ¹ is a hydrocarbon group or -OR ² (R ² is a hydrocarbon group A group containing at least one polymer group containing at least one polar group selected from the group and a cyclic acid anhydride group.
A polymerizable double bond group is bonded to the end of the polymer main chain of the B block of the AB block copolymer composed of the block and the B block containing at least the polymer component represented by the following general formula (I). A graft copolymer containing at least one kind of the monofunctional macromonomer (M) as a copolymerization component.

[0018]

[Chemical 5]

[In the formula (I), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. V ¹ was -COO -, - OCO-, chromatography (CH _{2) a} O
CO-, (is a represents an integer of 1-3.) Over _{(CH 2) a COO-, -} O -, - SO 2 over, over CO-, over CON
(Z ¹ )-, -SON (Z ¹ )-, -CONHCOO
Represents —, —CONHCONH— or —C ₆ H ₄ — (wherein Z ¹ represents a hydrogen atom or a hydrocarbon group). R
³ represents a hydrocarbon group. However, when V ¹ represents —C ₆ H ₄ —, R ³ represents a hydrogen atom or a hydrocarbon group. Resin [B] having an average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and having —PO ₃
H ₂ group, -SO ₃ H group, -COOH group, -P (= O) (O
H) Since it contains at least one polymer component containing at least one polar group selected from R ¹ (R ¹ has the same meaning as described above) group and cyclic acid anhydride group, An AB block copolymer comprising an A block and a B block containing at least a polymer component represented by the following general formula (II).

[0020]

[Chemical 6]

[In the formula (II), b ¹ and b ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ⁴ represents a hydrocarbon group. That is, the binder resin of the present invention is the B block side of the AB block copolymer of the A block containing the specific polar group-containing component and the B block containing the polymer component represented by the general formula (I). A graft type copolymer (resin [A]) containing a monofunctional macromonomer (M) having a polymerizable double bond group bonded to the terminal as a copolymerization component, and a specific polar group-containing component A
AB block copolymer of a block and a B block containing a polymer component represented by the general formula (II) (resin [B])
And at least consists of.

As described above, the acidic group-containing polymerization component is mainly used as the polymer in which the low molecular weight polymer is used among the acidic group-containing binder resins known to improve the smoothness and electrostatic properties of the photoconductive layer. Examples thereof include a resin randomly present in the chain, a resin in which an acidic group is bonded only to one end of the polymer main chain, or a so-called graft copolymer. On the other hand, in the low molecular weight binder resin [A] of the present invention, the polar group contained in the resin is present in the graft portion and is a block (that is, A block) at a position distant from the polymer main chain. The chemical structure of the polymer molecular chain is specified so that it exists.

In the resin [A] of the present invention, polar 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 other components that are present on the surface of the inorganic photoconductor gently and sufficiently cover the surface. The effect of sufficient adsorption to the surface of the inorganic photoconductor and the effect of coating near the surface is more effective than that of the known resin, so that the stoichiometric defect portion of the inorganic photoconductor is slightly changed. Even though it has a sufficient adsorption area, it is always stable inorganic resin and resin [A]
It is inferred that the interaction with the above is maintained, and according to the present invention, the humidity characteristics are improved and the photoconductor traps are sufficiently compensated and better compared with the conventionally known low molecular weight resin containing a polar group. , The photoconductor is sufficiently dispersed,
It was found to suppress aggregation.

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

As a result of repeated studies, a low molecular weight resin [A] containing the above-mentioned specific polar group at the tip of the graft portion and a high molecular weight AB containing the polar group in a block.
It has been found that the above problem can be effectively solved by using the resin [B] which is a block copolymer together.

This is due to the synergistic effect of the binder resins [A] and [B] of the present invention, in which the photoconductor particles are sufficiently dispersed and not condensed, and the spectral sensitizing dye is used as the photoconductive substance. It is presumed that this is due to the fact that the particles are sufficiently adsorbed on the surface of the body particles and that the binder resin sufficiently adsorbs extra active sites on the surface of the photoconductor to compensate the traps.

That is, the low molecular weight resin [A] containing a specific polar group is sufficiently adsorbed on the photoconductor particles to uniformly disperse the particles, and the polymer chains are very short, resulting in aggregation. And a block A containing a specific polar group and a block B containing no specific polar group, which have important functions such as suppressing the absorption of the spectral sensitizing dye and preventing the adsorption of the spectral sensitizing dye.
By using the medium to high molecular weight AB block copolymer composed of the above-mentioned, the compound acts more favorably and the mechanical strength of the photoconductive layer is sufficiently maintained. This is because the block A portion of the resin [B] has a weaker interaction with the photoconductor particles than the resin [A], and the entanglement effect between polymer chains of the block B portion of the resin [B]. It is thought to be due to.

Furthermore, in addition to the above-mentioned characteristics of the resin [A] itself, it has the effect of improving the electrostatic characteristics as compared with the known medium to high molecular weight resins used in combination. Since the block A portion of the resin [B] having an interaction has a polar group, it is considered that it has a function of suppressing adsorption and exclusion of the spectral sensitizing dye.

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

That is, the photoconductor of the present invention on which a copied image is formed through an electrophotographic process is desensitized by chemically treating the non-image portion with a conventionally known desensitizing treatment liquid to prepare a printing original plate. Shows excellent performance as an original plate for printing when it is printed by offset printing.

When the photosensitizer of the present invention is desensitized, the non-image areas are sufficiently hydrophilized and the water retention is improved, so that the number of printed sheets is dramatically improved. This is because the zinc oxide particles are uniformly dispersed and the presence state of the binder resin present on the surface of the zinc oxide particles is appropriate and the desensitizing reaction with the desensitizing treatment liquid is not alienated and quickly. It is considered that this is due to effective progress.

The binder resin of the present invention will be described in detail below. First, the resin [A] of the present invention will be described. The weight average molecular weight of the resin [A] is 1 × 10 ³ to 2 × 1.
0 ⁴ , preferably 3 × 10 ³ to 1 × 10 ⁴ , and the glass transition point of the resin [A] is preferably −40 ° C. to 110.
C, more preferably -20 to 90 ° C.

When the molecular weight of the resin [A] is less than 1 × 10 ³ , the film forming ability is lowered and the film strength cannot be maintained sufficiently.
On the other hand, when the molecular weight is more than 2 × 10 ⁴ , even in the case of the resin of the present invention, particularly in a photoreceptor using a near infrared to infrared spectral sensitizing dye, high temperature / high humidity, low temperature / low humidity under severe conditions. The fluctuation of the electrophotographic characteristics (particularly the initial potential, the dark decay retention rate and the photosensitivity) in the above-mentioned method becomes a little large, and the effect of the present invention that a stable copy image can be obtained is weakened.

In the graft copolymer [A] of the present invention, the abundance ratio of the macromonomer (M) and another monomer (for example, the monomer of the formula (II) represented by the resin [B]) is 1
-60 / 99-40 (weight ratio), preferably 5-
It is 40 / 95-60 (weight ratio).

When the content of the macromonomer 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 electrophotographic characteristics are fluctuated under environmental conditions. In particular, it becomes large when combined with a near infrared to infrared spectral sensitizing dye. It is considered that this is because the macromonomer that becomes the graft portion becomes fine, resulting in almost the same composition as the conventional homopolymer or random copolymer. On the other hand, when the content of the macromonomer exceeds 60% by weight, the copolymerizability of the monomer corresponding to the other copolymerization component and the macromonomer according to the present invention becomes insufficient, and the macromonomer is sufficiently used as the binder resin. The electrophotographic characteristics cannot be obtained.

The amount of the polar group-containing component contained in the macromonomer (M) in the resin [A] of the present invention is
The amount is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the resin [A]. That is, the abundance ratio of the polar group in the resin [A] depends on the composition ratio of the A block in the macromonomer (M) and the copolymerization ratio of the macromonomer (M) in the resin [A].
It can be adjusted to a preferable ratio.

When the content of the polar group in the resin [A] is less than 1% by weight, the initial potential is low and a sufficient image density cannot be obtained. On the other hand, the polar group content is 20% by weight
If the amount is larger than the above value, dispersibility of the low molecular weight compound is lowered, and scumming is increased when it is used as an offset master.

The use ratio of the binder resin [A] and the resin [B] is 5 to 60 parts by weight to 95 to 40 parts by weight, preferably 10 to 50 parts by weight to 90 to 50 parts by weight. The monofunctional macromonomer (M) used in the graft copolymer of the present invention will be described more specifically.

The copolymer component in the macromonomer (M) in the resin [A] of the present invention is composed of the A block and the B block as described above.
The existence ratio of the B block is preferably 1 to 70/99.
30 (weight ratio), and more preferably 3 to 50/97.
˜50 (weight ratio).

The polar group contained in the component constituting the A block of the macromonomer (M) includes --PO ₃ H ₂
Group, -COOH group, -SO ₃ H group, a phenolic OH
Group, -P (= O) (OH) R ¹ {R ¹ is a hydrocarbon group or-
OR ² (R ² represents a hydrocarbon group) group} and / or a cyclic acid anhydride-containing group, and preferably —COOH
Group, -SO ₃ H group, a phenolic OH group or -P (=
O) (OH) R ¹ group.

Here, -P (= O) (OH) R ¹ represents a group represented by the following chemical formula 7, wherein R ¹ is a hydrocarbon group or -O.
R ² represents a group (R ² represents a hydrocarbon group), and R ¹ and R ² are preferably an aliphatic group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, Octyl group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 3-
Ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group,
3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc.)
Or an optionally substituted aryl group (for example, phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, Cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.) and the like.

[0042]

[Chemical 7]

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and the cyclic acid anhydride to be contained is an aliphatic dicarboxylic acid anhydride or an aromatic dicarboxylic acid anhydride. Things can be mentioned. Examples of the aliphatic dicarboxylic acid anhydride ring include succinic acid anhydride ring, glutaconic acid anhydride ring, maleic acid anhydride ring, cyclopentane-1,2-dicarboxylic acid anhydride ring, cyclohexane-
1,2-dicarboxylic acid anhydride ring, cyclohexene-1,
2-dicarboxylic acid anhydride ring, 2,3-bicyclo [2.
2.2] Octanedicarboxylic acid anhydride ring and the like,
These rings may be substituted with, for example, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group or a hexyl group.

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

The "polymer component containing a specific polar group" as described above is, for example, a polymer component constituting another block component of the macromonomer (M) of the present invention, that is, represented by the general formula (I). Any vinyl compound containing the polar group, which is copolymerized with a corresponding vinyl compound such as a methacrylate component, can be used.

For example, it is described in "Polymer Data Handbook [Basic Edition]", edited by Japan 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 form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form Body, β-chloro form, β-bromo form,
α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg 2-pentenoic acid) , 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-
Hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids Examples thereof include a compound having a vinyl group or an allyl group half ester derivative, and a carboxylic acid or sulfonic acid ester derivative or amide derivative containing the polar group in the substituent.

The following can be mentioned as specific examples of these compounds. However, in each of the following examples, p
¹ is _{-H, -CH 3, -Cl, -Br} , -CN, -CH
₂ COOCH ₃ or —CH ₂ COOH, p ² is —
H or indicates -CH _3, b represents an integer of 2 to 18, c
Represents an integer of 1 to 12, and d represents an integer of 1 to 4.

[0048]

[Chemical 8]

[0049]

[Chemical 9]

[0050]

[Chemical 10]

[0051]

[Chemical 11]

[0052]

[Chemical 12]

[0053]

[Chemical 13]

[0054]

[Chemical 14]

[0055]

[Chemical 15]

[0056]

[Chemical 16]

[0057]

[Chemical 17]

Two or more kinds of the polar group-containing components as described above may be contained in the A block, and these two or more kinds of polar group-containing components are contained in the A block by either random copolymerization or block copolymerization. It may have been done. Further, together with the polar group-containing component, a component that does not contain a polar group {for example, a component represented by the formula (I) described below} may be contained in the A block, but the polar group-containing component is 30 to 30% in the A block. It is preferably present at 100% by weight.

Next, in the above-mentioned macromonomer, 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), V ¹
Is -COO -, - OCO -, - (CH 2) a OCO-,
_{- (CH 2) a COO- (} a is an integer of 1~3), - O -, - SO 2 -, - CO -, - CON
^{(Z 1) -, - SO} 2 N (Z 1) -, - CONHCOO
-, - CONHCONH or -C ₆ H ₄ - represents a. Here, Z ¹ is not only a hydrogen atom but also a preferable hydrocarbon group is an alkyl group having 1 to 18 carbon atoms which may be substituted (
For example, methyl group, ethyl group, propyl group, butyl group,
Heptyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group,
2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, and the like, alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, 2-methyl-1-propenyl group, 2-butenyl group) , 2-pentenyl group, 3-
A methyl-2-pentenyl group, a 1-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 4-methyl-2-hexenyl group, etc.) and 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,
A dimethylbenzyl group, a dimethoxybenzyl group, etc.), an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) or a C6-12 An optionally substituted aromatic group (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group). Group, decyloxyphenyl group, chlorophenyl group,
Dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.) To be

R ³ represents a hydrocarbon group, and is preferably the same as those listed as the preferable hydrocarbon group for Z ¹ . When V ¹ represents —C ₆ H ₄ —, R ³ represents a hydrogen atom in addition to the above hydrocarbon, and the benzene ring may have a substituent. As the substituent, 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, propioxy group, butoxy group, etc.) and the like.

A ¹ and a ² may be the same as or different from each other, and preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, a carbon number of 1 to 4
An alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), —COOZ ³ or COOZ ³ (Z ³ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, Represents an aralkyl group, an alicyclic group or an aryl group, which may be substituted,
Specifically, it represents the same contents as those described for Z ¹ ). COOZ via the above hydrocarbons
Examples of the hydrocarbon in the ^three groups include a methylene group, an ethylene group, a propylene group and the like.

More preferably, in the general formula (I),
V ¹ is -COO-, -OCO-, -CH ₂ OCO-,-.
_{CH 2 COO -, - O -} , - CONH -, - SO 2 NH
- or -C ₆ H ₄ - represents, a ¹ and a ^2, which may be the same or different, a hydrogen atom, a methyl group, -COO
Z ³ or —CH ₂ COOZ ³ {Z ³ is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.)
Represents}. Even more preferably, a ¹ and a
^{In 2} , one of them represents a hydrogen atom.

Further, the B block may contain a polymer component other than the monomer of the formula (I), and another repeating unit copolymerizable with the polymer component of the formula (I). Examples of the monomer corresponding to acrylonitrile, methacrylonitrile, heterocyclic vinyls (for example, vinyl pyridine, vinyl imidazole, vinyl pyrrolidone, vinyl thiophene, vinyl pyrazole, vinyl dioxane, vinyl oxazine, etc.) and the like. These other monomers are used within a range not exceeding 20 parts by weight based on 100 parts by weight of the total polymer component of the B block. Also, in the B block,
It is preferable not to include a polymer component containing a polar group, which is a component of the A block. 2 in block B
When two or more copolymerization components are present, these two or more copolymerization components may be contained in the B block by either random copolymerization or block copolymerization.
It is preferable that they are contained at random for the convenience of synthesis. Next, in the macromonomer (M) of the present invention, the B block containing the A block consisting of the above-mentioned component containing a polar group and the polymer component represented by the general formula (I) is contained.
The polymerizable dipolymerizable group that connects the blocks in the A-B type and that is connected to the other end of the B block that connects the A block will be described.

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

[0065]

[Chemical 18]

[In the formula (III), V ² has the same meaning as V ¹ in the formula (I). c ¹ and c ² may be the same as or different from each other and have the same meaning as a ¹ and a ² in the formula (I). That is, as the polymerizable double bond group represented by the general formula (III), more specifically, CH ₂ ═CH—COO
_{-, CH 2 = C (CH} 3) OCOO-, CH (CH 3)
_{= CHCOO-, CH 2 = C (} CH 2 COOCH 3) C
_{OO-, CH 2 = C (CH} 2 COOH) COO-, CH
_{2 = CHCONH-, CH 2 = C} (CH 3) CONH
_{-, CH (CH 3) =} CHCONH-, CH 2 = CHO
_{CO-, CH 2 = CHCH 2 OCO-} , CH 2 = CH-
_{O-, CH 2 = C (COOH} ) CH 2 COO-, CH 2
_{= C (COOCH 3) CH 2} COO-, CH 2 = CH-
_{C 6 H 4 -, CH 2} = CH (CH 2) 2 COO-, CH
_{2 = CH-CO-, CH 2} = CH (CH 2) 2 OCO-
Etc.

In the macromonomer (M) used in the present invention, a polymerizable double bond group represented by the general formula (III) is directly bonded to one end of the B block as described above, or an arbitrary one is used. It has a chemical structure bonded by the linking group of. As the group to be linked, carbon-carbon bond (single bond or double bond), carbon-hetero atom bond (as a hetero atom, for example, oxygen atom, sulfur atom, nitrogen atom,
Silicon atom, etc.), and any combination of heteroatom-heteroatom bond atomic groups. That is, specifically, a mere bond or -C (Z ⁴ ) (Z ⁴ )-[Z
⁴ may be the same or different, a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (for example, a methyl group,
Ethyl group, propyl group, etc.)],-(CH = C
_{H) -, - C 6 H} 10 -, - C 6 H 4 -, -O -, - S
-, - CO -, - N (Z 5) -, - COO -, - C (=
_{S) -, - SO 2 -} , - CON (Z 5) -, - SO 2 N
^{(Z 5) -, -NHCOO -} , - NHCONH -, -
A single linkage selected from atomic groups such as C (Z ⁵ ) (Z ⁵ )-[Z ⁵ represents a hydrogen atom, a hydrocarbon group having the same meaning as R ³ in formula (I)] It represents a linking group composed of groups or any combination.

When the weight average molecular weight of the macromonomer (M) exceeds 2 × 10 ⁴ , the copolymerizability with other monomers (for example, the monomer corresponding to the formula (II) described later) decreases, which is not preferable. On the other hand, if the weight average molecular weight is too small, the effect of improving the electrophotographic characteristics of the photosensitive layer becomes small, so that 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 polar group, the polar group is preliminarily protected as a functional group, and an organometallic compound (eg, alkyllithium, lithium diisopramide, alkylmagnesium halide) is used. , Etc.) or an ionic polymerization reaction with hydrogen iodide, iodine, etc., to synthesize an AB block copolymer by a known so-called living polymerization reaction such as a photopolymerization reaction using a porphyrin metal complex as a catalyst or a group transfer polymerization reaction. After that, various reagents are reacted with the ends of this living polymer to introduce a polymerizable double bond group. After this, a deprotection reaction is performed by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, or a photolysis reaction of the functional group with the polar group protected,
The method of forming a polar group is mentioned. One example thereof is shown in the following reaction scheme (1).

[0070]

[Chemical 19]

For example, P. Lutz, P. Masson et al, Polym. B
ull., 12 , 79 (1984) BCAnderson, GDAndrews eta
l, Macromolecules, 14 , 1601 (1981) K. Hatada, K. Ut
e.etal, Polym. J. 17 , 977 (1985), 18 , 1037 (1986), Koichi right hand, Koichi Hatada, Polymer processing, 36 , 366 (1987) Toshinobu Higashimura, Mitsuo Sawamoto, Polymers, 46 , 189 (1989) M. Kuro
ki, T. Aida, T. Am. Chem. Soc. 109 , 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43 , 300 (1985) DYSog
ah, WRHertler et al, Macromolecules, 20 , 1473 (198
The living polymer can be easily synthesized according to the synthetic method described in 7) and the like. Further, as a method for introducing a polymerizable double bond group to the terminal of the living polymer, the macromonomer of the present invention can be easily obtained according to a conventionally known synthesis method of a macromonomer method.

Specifically, P. Dreyfuss & RPQuirk, En
cycl, Polym.Sci.Eng., 7 , 51 (1987), PFRempp, E.
Franta, Adu., Polym.Sci. 58 , 1 (1984), V.Per-cec, Ap
pl., Polym. Sci., 285, 95 (1984), R. Asami, M. TakaR
i, Makvamol.Chem.Suppl. 12 , 163 (1985), P.Rempp.eta
l, Makvamol.Chem.Suppl. 8 , 3 (1984) Yusuke Kawakami, Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 31 , 988 (198)
2), Kobayashi Shiro, Kogaku, 30 , 625 (1981), Toshinobu Higashimura,
Journal of the Adhesion Society of Japan, 18, 536 (1982), Koichi Ito, polymer processing, 35, 262 (1986), AzumaTakashi Shiro, Takashi Tsuda, functional materials, 198
7 It can be synthesized according to the methods described in the review articles of Nos. 10 and 5 and the references and patents cited therein.

The protecting group for protecting the specific polar group of the present invention and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing the conventionally known knowledge. For example, various references are given in the above-mentioned references, and further, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" published by Kodansha Co., Ltd. (1977), TW Greene "Protective Groups in
Organic Synthesis ", John Wiley & Sous (1981),
JFWMcOmie, `` Protective Groups in Organic Che
Mistry "Plenum Press, (1973) and the like can be appropriately selected and performed from the methods described in detail in the review article.
As another method for synthesizing an AB type block copolymer, it can be synthesized by a photoiniferter polymerization method using a diciocarbamate compound as an initiator. For example, Takayuki Otsu, Polymer, 37 , 248 (1988), Shunichi Hinomori, Ryuichi Otsu, Pol.
ym.Rep.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-described macromonomer synthesis method.

Specific examples of the macromonomer (M) of the present invention can include the following compounds. However, the scope of the present invention is not limited to these. However, in the following compound examples, p ³ , p ⁴ and p ⁵
Indicates each, -H, -CH ₃ or -CHCOOCH _3, p ⁶ represents -H or -CH _3, R ¹¹ 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), - C 6 H 4 -Y} 1 (Y 1 is -
_{H, -Cl, -B r, -CH} 3, -OCH 3 or -CO
CH ₃ shows a) or _{- (CH 2) r -C 10} H 7 (r 0
Or an integer of 1 to 3) indicates, R ¹² is -C _s H _{2s +} 1 _(s is an integer of 1 to 8) or - (CH ₂₎ shows the _q C ₆ H _5, Y
² _{-OH, -COOH, -SO 3 H,} -OP (= O)
(OH) ₂ or -OP (= O) (OH) OCH ₃ ,
Y ³ is _{-COOH, -SO 3 H, -OP (} = O) (OH)
₂ or -OP (= O) (OH) OCH ₃ and t = 2
12 represents an integer, and u represents an integer of 2 to 6.

[0075]

[Chemical 20]

[0076]

[Chemical 21]

[0077]

[Chemical formula 22]

[0078]

[Chemical formula 23]

Furthermore, in this resin [A], as a component which is copolymerized with the macromonomer (M), the above-mentioned general formula (II)
The monomer represented by

In the formula (II), b ¹ and b ² are each a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom),
It represents a cyano group or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) and the like.

R ⁴ represents a hydrocarbon group, specifically an alkyl group, an aralkyl group or an aromatic group, preferably an aralkyl group or an aromatic group which is a hydrocarbon group containing a benzene ring or a naphthalene ring. is there.

Further, R ⁴ preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. During the polymer backbone, -PO ₃ H ₂ group, -SO ₃ H group, -COOH
Group, -OH group, -SH group and -PO ₃ R ¹ H group, which does not contain a copolymer component containing a polar group is preferable, and therefore, the polar group-containing one in the resin [A] is used as the substituent. Substituents other than the polar group contained in the polymer component may be mentioned, and examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), —OZ ⁶ , and —CO.
OZ ^6, -OCOZ ⁶ (Z ⁶ represents an alkyl group having 1 to 22 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl It is a base etc.)
And the like. The preferred hydrocarbon group is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, Hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2
-Methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), 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-
A hexenyl group, a 2-hexenyl group, a 4-methyl-2-hexenyl group, etc.) and an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group, a 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 alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or an aromatic group having 6 to 12 carbon atoms which may be substituted. (For example, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group. , Dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.) Can be mentioned

In the repeating unit of the general formula (II) which is a component having such a substituent R ⁴ , more preferably at the 2-position represented by the general formula (IIa) and / or the general formula (IIb), And / or containing a benzene ring or a naphthalene ring having a specific substituent at the 2- and 6-positions,
A methacrylate component having a specific substituent is preferred (hereinafter, this low molecular weight product is particularly referred to as resin [AA]).

[0084]

[Chemical formula 24]

[0085]

[Chemical 25]

[In the formulas (IIa) and (IIb), A ¹ and A
² are each independently a hydrogen atom and a carbon number of 1-10.
Hydrocarbon group, chlorine atom, bromine atom, -COZ ² or-
COOZ ² (Z ² represents a hydrocarbon group having 1 to 10 carbon atoms) is represented.

B ¹ and B ² each represent a single bond or a linking group having 1 to 4 linking atoms for linking —COO— and the benzene ring. When the above-mentioned specific resin [AA] is used, the electrophotographic characteristics (particularly V ₁₀ , DRR, E _1/10 ) can be further improved as compared with the case of the resin [A].

The reason for this is not clear, but one reason is that due to the effect of a planar benzene ring or naphthalene ring having a substituent at the ortho position, which is an ester component of methacrylate, the zinc oxide interface in the film is affected. It is considered that the arrangement of these polymer molecular chains in 1 is appropriately performed.

In formula (IIa), preferred A ¹ and A
^{As 2} , each independently of one another, a hydrogen atom, a chlorine atom and a bromine atom, as a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group,
Ethyl group, propyl group, butyl group, 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) , Chloromethylbenzyl group) and aryl groups (eg, phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and —COOZ ² and —COO.
Z ² (preferable Z ^{2 can} include those described as the above-mentioned preferable hydrocarbon group having 1 to 10 carbon atoms).

In the formulas (IIa) and (IIb), B ¹ and B ² are each a single bond connecting --COO-- and a benzene ring or-(CH ₂ ) _e-- (e represents an integer of 1 to 3). ,-
_{CH 2 OCO -, - CH 2} CH 2 OCO -, - (C
H _{2) f} - _(f is an integer of 1 or _2), - CH 2 C
A connecting group having 1 to 4 connecting atoms such as H ₂ O-,
More preferably, a single bond or a linking group having 1 to 2 bonding atoms can be mentioned.

Formula (II) used in the resin [A] of the present invention
Specific examples of the repeating unit represented by a) or (IIb) are shown below. However, the scope of the present invention is not limited to this.

[0092]

[Chemical formula 26]

[0093]

[Chemical 27]

[0094]

[Chemical 28]

[0095]

[Chemical 29]

[0096]

[Chemical 30]

[0097]

[Chemical 31]

[0098]

[Chemical 32]

[0099]

[Chemical 33]

Further, in the graft copolymer of the present invention, the component copolymerizable with the macromonomer (M) is a monomer other than the general formula (II), (IIa) or (IIb). Also, for example, in addition to methacrylic acid esters, acrylic acid esters, crotonic acid esters containing a substituent other than those explained in the general formula (II), α-olefins, vinyl carboxylates or allyl acid esters ( For example, as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides, Methacrylamides, styrenes (eg styrene, vinyltoluene, chlorostyrene, hydro Xylstyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene,
Methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compounds, vinylketone-containing compounds, heterocyclic vinyls (eg vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene,
Vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine and the like). As a preferable example, vinyl alkanoate having 1 to 3 carbon atoms or allyl ester,
Examples thereof include acrylonitrile, methacrylonitrile, styrene and styrene derivatives (for example, vinyltoluene, butylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, ethoxystyrene, etc.).

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

Next, the resin [B] of the present invention will be described. The resin [B] is an AB block copolymer, and the amount of the polymer component of the specific polar group-containing component in the block copolymer [B] is preferably 0.1 to 100 parts by weight of the copolymer [B]. The content is 5 parts by weight, more preferably 0.2 to 3 parts by weight.

When the content of the polar group in the binder resin [B] is less than 0.1% by weight, the initial potential is low and a sufficient image density cannot be obtained, and the content of the polar group is 5% by weight.
If it is more than the above range, the dispersibility is lowered, the film smoothness and the high temperature and high humidity of the electrophotographic characteristic are lowered, and further, the background stain is increased when the offset master is used, which is not preferable.

The weight average molecular weight of the copolymer [B] is 2 × 1.
0 ⁴ to 1 × 10 ⁶ , preferably 3 × 10 ^{4 to} 5 × 10 ^5.
Is. When the molecular weight of the resin [B] is less than 2 × 10 ⁴ , the film forming ability is lowered and sufficient film strength cannot be maintained, and when the molecular weight is more than 1 × 10 ⁶ , the effect of the resin [B] of the present invention is obtained. The amount is reduced, and the electronic characteristics are the same as those of conventionally known resins.

The glass transition point of the resin [B] is −10 ° C.
The temperature is preferably in the range of -100 to 100 ° C, more preferably 0 to 90 ° C. Specific examples of the polymerization component containing a specific polar group which constitutes the A block of the AB block copolymer (resin [B]) of the present invention include a polymer containing a specific polar group of the resin [A] described above. The same thing as a united component can be mentioned.

Two or more kinds of the polymerization component containing a specific polar group as described above may be contained in the A block,
In that case, the two or more kinds of polar group-containing components may be contained in the A block in any mode of random copolymerization or block copolymerization.

Further, a polymer component other than the above polar group-containing polymer component may be contained in the block A, and such a polymer component preferably corresponds to the repeating unit of the above general formula (I). Polymer components may be mentioned.

Further, as a polymer component which can be contained in the A block together with the polymer component represented by the formula (I), it corresponds to another repeating unit copolymerizable with the polymer component of the formula (I). Monomers such as acrylonitrile, methacrylonitrile, and heterocyclic vinyls (for example, vinyl pyridine, vinyl imidazole, vinyl pyrrolidone, vinyl thiophene, vinyl pyrazole, vinyl dioxane, vinyl oxazine, etc.) and the like. These other monomers are used within a range not exceeding 20 parts by weight based on 100 parts by weight of the total polymer component of the A block.

Next, the polymerization component constituting the B block component in the AB block copolymer [B] will be described in detail. The B block component contains at least a polymer component represented by the repeating unit represented by the general formula (II), and the component represented by the formula (II) is preferably 30 to 100% by weight in the B block component, Preferably 50-
100% by weight is contained.

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

The AB block copolymer [B] of the present invention is
It can be produced by a conventionally known polymerization reaction method.
Specifically, in the monomer corresponding to the polymer component containing the specific polar group, the polar group is preliminarily protected as a functional group, and an organometallic compound (eg, alkyllithium, lithium diisopropylamide, alkylmagnesium) is used. After synthesizing an AB block copolymer by a known so-called living polymerization reaction such as an ionic polymerization reaction with a halide or the like) or a hydrogen iodide / iodine system, a photopolymerization reaction using a porphyrin metal complex as a catalyst, or a group transfer polymerization reaction A method of forming a polar group by performing a deprotection reaction on a functional group having a protected polar group by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photodecomposition reaction, or the like. One example thereof is shown in the following reaction scheme (2).

[0112]

[Chemical 34]

These are, for example, P.P. Lutz, P.M. M
asson et al, Polym. Bull. 1
2 . 79 (1984), B.I. C. Anderson,
G. D. Andrews et al, Macromol
ecules, 14 , 1601 (1981), K.S. Ha
tada, K .; Ute. et al, Polym. J. 1
7 , 977 (1985), 18 , 1037 (198)
6), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36 , 366
(1987), Toshinobu Higashimura, Mitsuo Sawamoto, Transactions on Polymers, 4
6 , 189 (1989), M.S. Kuroki, T .; Ai
da, J. Am. Chem. Soc. 109 , 4737
(1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 4.
3 , 300 (1985), D.I. Y. Sogah, W.C.
R. Herretaltal. Macromolecule
It can be easily synthesized according to the synthetic method described in Les, 20 , 1473 (1987) and the like.

Further, the AB block copolymer [B] uses a monomer in which the polar group is not protected and uses a compound containing a dithiocarbamate group and / or a compound containing a xanthate group as an initiator. Alternatively, it can be synthesized by performing a polymerization reaction under irradiation with light. For example, Takayuki Otsu, Polymer, 37 , 248 (1988), Shunichi Hinomori, Ryuichi Otsu,
Polym. Rep. Jap. 37 . 3508 (198
8), JP-A 64-111, and JP-A 64-26619.
No., Nobuyuki Higashi, Polymer Preprints,
Japan, 36 , (6), 1511 (1987),
M. Niwa, N.N. Higashi, et al. M
acromol. Sci. Chem. A24 (5), 5
67 (1987) and the like.

Further, regarding the protection of a specific polar group with a protecting group and the elimination of the protecting group (deprotection reaction) of the present invention,
This can be easily performed by utilizing the conventionally known knowledge.
For example, various descriptions are given in the above cited document, and further,
Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" published by Kodansha Co., Ltd. (1977), T.S. W. Greene, "Prote
ctive Groups in Organic S
"Thesis", John Wiley & So
ns (1981), J. F. W. McOmie, "P
Protective Groups in Organ
icChemistry "Plenum Press,
The method described in detail in the review article such as (1973) can be appropriately selected and performed.

Further, the block A is equivalent to synthesizing an azobis compound (that is, a high molecular weight azobis initiator) containing any part of the block B and using this as an initiator to form the other block. It is also possible to use a method of synthesizing the above-mentioned monomers by radical polymerization reaction.

Specifically, it should be synthesized by the method described in Akira Ueda, Susumu Nagai, Kobunshi Shinbun, 44 , 469 (1987), Akira Ueda, Osaka City Institute of Industrial Research, 84 (1989), etc. You can

In the case of synthesizing using this reaction, the weight average molecular weight of the polymer azobis initiator is 2 × because of the ease of synthesis of the polymer azobis initiator and the regularity of the polymerization reaction of blocking. It is preferably 10 ⁴ or less. On the other hand, in the resin [B] of the present invention, the block B preferably has a longer polymer chain than the block A.

From the above, when synthesizing by this reaction,
A method using a block A-containing polymer initiator is preferable. For example, the reaction can be carried out according to the reaction scheme (3) shown below.

[0120]

[Chemical 35]

As the binder resin used in the photoconductive layer of the present invention, the above-mentioned known resins for inorganic photoconductors may be used in combination with the resins [A] and [B] of the present invention.
However, the proportion of these other resins used is the total amount of the binder resin 10
A range not exceeding 30% by weight in 0 part by weight is preferable. If this ratio is exceeded, the effect of the present invention will be significantly reduced.

As other resins that can be used in combination, for example, typical ones are vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer. , Vinyl acetate copolymer, polyvinyl butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin, polyester resin and the like.

Specifically, Ryuji Shibata and Jiro Ishiwata, "Polymer", Vol. 17, p. 278 (1968), Harumi Miyamoto.
Hidehiko Takei "Imaging" 1973 (No.8) 9th
Pp. Koichi Nakamura, "Practical Technology of Binders for Insulating Materials," Chapter 10, C.I. H. C. Published (1985), D.M. D.
Tatt, S. C. Heidecker, Tappi,
49 (No. 10), 439 (1966), E.I. S. B
Altazzi, R.A. G. Blanklotte et
al, Photo. Sci. Eng. 16 (No.
5), 354 (1972), Nguyen Chan Kae, Isamu Shimizu, Eiichi Inoue, The Electrophotographic Society of Japan 18 (No. 2),
28 (1980), JP-B-50-31011, JP-A-53-54027, JP-A-54-20735, and JP-A-57-57.
The resins disclosed in JP-A-202544 and JP-A-58-68046 are cited.

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

The ratio of the resin [A] and the resin [B] used in the present invention is 0.05 to 0.05 by weight ratio of resin [A] / resin [B].
It is preferably 0.8 / 0.95 to 0.20, more preferably 0.10 to 0.50 / 0.90 to 0.50.
Is.

When the total amount ratio of the binder resin is 10 parts by weight or less, the film strength of the photoconductive layer cannot be maintained. On the other hand, when the amount is 100 parts by weight or more, the electrostatic characteristics are deteriorated and the copy image is deteriorated in the actual image pickup property.

If the weight ratio of the resin [A] to the resin [A] and the resin [B] used in the present invention is 0.05 or less, the effect of improving the electrostatic characteristics is diminished. On the other hand, 0.8
If the above is the case, the film strength of the photoconductive layer cannot be sufficiently maintained (particularly as an electrophotographic lithographic printing plate precursor).

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.

The spectral sensitizing dye used in the present invention includes
If necessary, various dyes are used alone or in combination. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (N
o. 8) Page 12, C.I. J. Young et al., RCA R
view 15 , 469 (1054), Kouhei Kiyota,
IEICE Transactions J63 - C (No. 2 ), 97
(1980), Yuji Harasaki et al., Industrial Science Magazines 66 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35 , 2
08 (1972) and other general reference carbonium dyes,
Diphenylmethane dye, triphenylmethane dye, xanthene dye, phthalein dye, polymethine dye (for example, oxonol dye, merocyanine dye, cyanine dye, rhodacyanine dye, styryl dye, etc.), phthalocyanine dye (may contain metal), etc. Is mentioned.

More specifically, those mainly containing carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes are disclosed in Japanese Examined Patent Publication No. 51-45.
2, JP-A-50-90334 and JP-A-50-11422.
No. 7, No. 53-39130, No. 53-82353,
US Pat. Nos. 3,052,540 and 4,054,45
No. 0, those described in JP-A-57-16456, and the like.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Harmmer "The Cyani
neDyes and Related Compou
The dyes described in "nd" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,11.
0,591, 3,121,008, 3,12
5,447, 3,128,179 and 3,13
2,942, 3,622,317, British Patents 1,226,892, 1,309,274, 1,405,898, Japanese Patent Publication Nos. 48-7814, 5
Examples thereof include dyes described in No. 5-18892.

Further, as a polymethine dye for spectrally sensitizing a near-infrared region to an infrared light region having a long wavelength of 700 nm or more, JP-A-4 (1999) is used.
No. 7-840, No. 47-44180, and Japanese Patent Publication No. 51-4
1061, JP-A-49-5034, and JP-A-49-451.
No. 22, No. 57-46245, No. 56-35141.
No. 57-157254, No. 61-26044,
No. 61-27551, U.S. Pat. No. 3,619,154.
No. 4,175,956, "Research D
isclosure ", 1982, 216, 117-
Examples thereof include those described on page 118. The photoconductor of the present invention is excellent in that the performance thereof hardly changes depending on the sensitizing dye even when various sensitizing dyes are used in combination. Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example,
Review Article: Imaging 1973 (No. 8) No. 1
Electron-accepting compounds (eg halogen, benzoquinone, chloranil, organic carboxylic acid anhydrides, etc.) in the review article on page 2, etc., Hiroshi Komon, et al., “Development and practical application of bacterial photoconductive materials and photoconductors” Chapter 4 to Chapter 6 ・ Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds and the like, which are cited as reference articles of the Japanese Scientific Information Co., Ltd. Publishing Department (1986).

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

When the photoconductive layer is used as the charge generation layer of the laminated type photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.01 to 1 .mu.m, particularly 0.05 to 0. 5
μ is preferred.

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

In the latter case, the thickness of the insulating layer is 5 to 70.
μ, particularly 10 to 50 μ. Examples of the charge transport material for the laminated photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes and the like. The thickness of the charge transport layer is 5 to 4
0 μ, particularly 10 to 30 μ is preferable.

Typical resins used for forming the insulating layer or the charge transport layer are polystyrene resin, polyester resin, cellulose resin, polyether resin,
Vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl chloride copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, epoxy resin, melamine resin, silicone resin thermoplastic resin and effective 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, metal, paper, plastic sheet or the like is basically impregnated with a low resistance substance. Conductive treated by, for example, the basic back surface (the surface opposite to the surface on which the photosensitive layer is provided) to have conductivity, and at least one layer coated for the purpose of preventing curling,
Paper having a water-resistant adhesive layer provided on the surface of the support, paper having at least one precoat layer provided on the surface layer of the support, if necessary, and electroconductive plastic substrate having Al vapor deposited thereon. Those laminated to can be used.

Concrete examples of the conductive substrate or the conductive material are Yukio Sakamoto, Electrophotography, 14 (No.
1), P2-11 (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing (1975), M.M. F. Hoo
ver., J. Macromol. Sci. Chem. A
-4 (6), 1327 to 1417 (1970) and the like are used.

To prepare a printed matter using the electrophotographic printing original plate using the electrophotographic photosensitive member of the present invention, after forming a copy image on the electrophotographic original plate having the above-mentioned structure by a conventional method, a non-image area is formed. It is created by desensitizing treatment.

As a desensitizing method for zinc oxide, any of conventionally known processing liquids can be used. For example,
A ferrocyan compound was used as the main agent for desensitization,
JP-A-62-239158 and 62-292492.
No. 63-99993, No. 63-9994, Japanese Patent Publication No. 40-7334, No. 45-33683, and JP-A-5-39.
7-107889, Japanese Examined Patent Publication No. 46-21244, 4
4-9045, 47-32681, 55-93.
No. 15, JP-A No. 52-101102, and the like.

However, from the viewpoint of safety of the treatment liquid, the treatment liquids listed below are preferable. For example, JP-B-43-28408, JP-B-45-24609, JP-A-51-103501, JP-A-54-10003, JP-A-53-83805, and JP-A-53-53, which use a phytic acid compound as a main agent.
83806, 53-127002, 54-44.
901, 56-2189, 57-2796,
Nos. 57-20394 and 59-20729, and water-soluble polymers capable of forming metal chelates as main components, JP-B-38-9665 and 39-39.
No. 22263, No. 40-763, No. 43-28404.
No. 47-29642, JP-A-52-126302
No. 52-134501, No. 53-49506,
JP-A-53-104301 and JP-B-55-153, which are described in JP-A-53-59502 and JP-A-53-104302, and which use a metal complex compound as a main agent.
No. 13, No. 54-41924, etc.,
Alternatively, using inorganic and organic acid compounds as the main agent,
Examples include those described in JP-B-39-13702, JP-B-40-10308, JP-B-46-26124, JP-A-51-118501 and JP-A-56-111695.

The electrophotographic photosensitive member of the present invention can be used in applications using any conventionally known electrophotographic process. That is, the photoconductor of the present invention can be used for both PPC and CPC recording systems, and
As the developer, any combination of a dry developer and a liquid developer can be used.

In particular, since it is possible to form a copy image of a high-definition original faithfully, the effect of the present invention is more exerted when used in combination with a liquid developer. Also, by combining with a color developer, not only black and white copy images,
It can also be applied to color reproduction images (for example, Kuro Takizawa, “Photo Industry” 33 , 34 (1975), Masayasu Anzai, “Technical Research Report of the Institute of Electronics and Communication Engineers” 77 , 17 (19).
1977) etc.).

Further, it is also effective in a system used for other purposes using the electrophotographic process in recent years. For example, the photoconductor of the present invention using photoconductive zinc oxide as a photoconductor is used as an offset lithographic printing plate precursor and is made of photoconductive zinc oxide or photoconductive titanium oxide which is pollution-free and has a good whiteness. The photoconductor can be used as an underprinting material used in an offset printing process, a color group, or the like.

[0146]

[Synthesis of macromonomer]

Synthesis Example 1 of Macromonomer (M) 1: (M-1) A mixed solution of 30 g of triphenylmethyl methacrylate and 100 g of toluene was thoroughly degassed under a nitrogen stream-20
Cooled to ° C. 1,1-diphenylbutyllithium 1.
0 g was added and reacted for 10 hours.

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

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

After the precipitated insoluble matter was filtered off, 10 ml of 30% hydrogen chloride ethanol solution was added to this mixed solution, and the mixture was stirred for 1 hour. Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation in 1 liter of petroleum ether. The polymer obtained by collecting the precipitate and drying it under reduced pressure had an Mw of 6.5 × 10 ³ and a yield of 56 g.

[0150]

[Chemical 36]

Synthesis Example 2 of Macromonomer (M): (M-2) A mixed solution of 5 g of benzyl methacrylate, 0.1 g of (tetraphenylporphinato) aluminum methyl and 60 g of methylene chloride was heated to 30 ° C. under a nitrogen stream. .
This was irradiated with light of 300 W-xenon lamp through a glass filter from a distance of 25 cm and reacted 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.
10 g of bromomethylstyrene was added, and the reaction was stopped by stirring for 30 minutes. Next, Pd-C was added to this reaction mixture, and catalytic reduction reaction was performed at a temperature of 25 ° C. for 1 hour.

After filtering off the insoluble matter, 500 m of petroleum ether
The precipitate was collected and dried. The yield of the obtained polymer was 33 g, and the Mw was 7 × 10 ³ .

[0153]

[Chemical 37]

Synthesis Example 3 of Macromonomer (M): (M-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 1,1-diphenyl-3-methylpentyllithium was added and stirred for 6 hours. Further, a mixed solution of 80 g of 2-chloro-6-methylphenylmethacrylate and 100 g of toluene was thoroughly degassed in a nitrogen stream, added to this mixture, 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, and the temperature was 15 ° C.
After cooling, 12 g of methacrylic acid chloride was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours.

Next, 10 g of 30% hydrogen chloride ethanol solution was added to the reaction mixture, and the mixture was stirred at 25 ° C. for 1 hour,
The precipitate was reprecipitated in 1 liter of petroleum ether, and the collected precipitate was washed twice with 300 ml of diethyl ether and dried. The yield of the obtained polymer was 55 g, and the Mw was 7.8 × 10 ³ .

[0156]

[Chemical 38]

Synthesis Example 4 of Macromonomer (M): (M-4) A mixed solution of 40 g of triphenylmethyl methacrylate and 100 g of toluene was thoroughly degassed under a nitrogen stream to give -2.
Cooled to 0 ° 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 thoroughly degassed under a nitrogen stream and added, and the mixture was reacted for 12 hours. After this mixture was heated 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. 3 in this reaction mixture
10 g of an ethanol solution containing 0% hydrogen chloride was added, and the mixture was stirred for 2 hours. The insoluble matter was separated by filtration and then reprecipitated in 1 liter of n-hexane, and the precipitate was collected and dried under reduced pressure. The yield of the obtained polymer was 58 g, and the Mw was 4.5 × 10 ³ .

[0159]

[Chemical Formula 39]

Synthesis Example 5 of Macromonomer (M): (M-5) 70 g of phenyl methacrylate, 4.8 g of benzyl-N-hydroxylethyl-N-ethyldithiocarbamate
The mixture of (1) was sealed in a container under a nitrogen stream and heated to a temperature of 60 ° C. This was irradiated with light from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 10 hours to perform photopolymerization. After 30 g of acrylic acid and 180 g of methyl ethyl ketone were added thereto, the atmosphere was replaced with nitrogen, and light was again irradiated 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 1.5 l of hexane, collected, and dried. The polymer obtained had a Mw of 68 g.
It was 6.0 × 10 ³ .

[0162]

[Chemical 40]

[Synthesis of Resin [A]] Synthesis Example 1 of Resin [A] 1: [A-1] 80 g of ethyl methacrylate, macromonomer (M-
1) A mixed solution of 120 g and 150 g of toluene was heated to a temperature of 95 ° C. under a nitrogen stream. Add 6 g of 2,2'-azobis (isobutyronitrile) (AIBN) and add 3
Reacts for an hour, and after every 2 hours A. I. B. N. 2 g was added and reacted.

The Mw of the obtained copolymer was 9 × 10 ³ .

[0165]

[Chemical 41]

Synthesis Example 2 of Resin [A]: [A-2] 70 g of 2-chlorophenyl methacrylate, 30 g of macromonomer (M-2), 2 g of n-dodecyl mercaptan.
And a mixed solution of 100 g of toluene under a nitrogen stream at a temperature of 8
Warmed to 0 ° C. 3,2 g of 2,2′-azobis (isovaleronitrile) (AIVN) was added and reacted for 3 hours,
Furthermore, A. I. V. N. 1 g was added and reacted for 2 hours. Then A. I. V. N. 1 g was added and the mixture was heated to a temperature of 90 ° C and reacted for 3 hours. The Mw of the obtained copolymer was 7.6 × 10 ^3.
Met.

[0167]

[Chemical 42]

Synthesis Examples 3 to 18 of Resin [A]: [A-3]
~ "A-18" The copolymers shown in Table A below were synthesized under the same polymerization conditions as in Synthesis Example 1 of Resin [A], except that ethyl methacrylate was replaced with another monomer. Has a Mw of 5 × 10 ^{3 to} 9
It was × 10 ³ .

[0169]

[Table 1]

[0170]

[Table 2]

[0171]

[Table 3]

Synthesis Examples 19 to 35 of Resin [A]: [A-1
9] to [A-35] In Synthesis Example 2 of Resin [A], the macromonomer (M-
Copolymers shown in Table B below were synthesized under the same polymerization conditions as in Synthesis Example 2 except that another macromonomer (M) was used instead of 2). The Mw of each polymer obtained was 2 × 10 ³ to 1
It was × 10 ⁴ .

[0173]

[Table 4]

[0174]

[Table 5]

[0175]

[Table 6]

[0176]

[Table 7]

[Synthesis of Resin [B]] Synthesis Example 1 of Resin [B] 1: [B-1] A mixed solution of 100 g of methyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream to give -2.
Cooled to 0 ° C. 0.8 g of 1,1-diphenylbutyllithium was added and reacted for 12 hours. Further, to this mixed solution, a mixed solution of 60 g of methyl acrylate, 6 g of triphenylmethyl methacrylate and 5 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream and added, and the mixture was further reacted for 8 hours. After the mixture was brought to 0 ° C., methanol 10
ml was added and reacted for 30 minutes to terminate the polymerization. The temperature of the obtained polymer solution was set to 30 ° C. under stirring, and
% Ethanol solution of hydrogen chloride (3 ml) was added, and the mixture was stirred for 1 hour. Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation in 1 liter of petroleum ether.

The Mw of the polymer obtained by collecting the precipitate and drying it under reduced pressure was 7.3 × 10 ⁴ , and the yield was 72 g.

[0179]

[Chemical 43]

Synthesis Example 2 of Resin [B]: [B-2] 70 g of methyl methacrylate: 30 g of methyl acrylate
A mixed solution of 0.5 g of g (tetraphenylporphinato) aluminum methyl and 60 g of methylene chloride was heated to a temperature of 30 ° C. under a nitrogen stream. This was irradiated with light of 300 W-xenon lamp through a glass filter from a distance of 25 cm and reacted for 12 hours. This mixture was further mixed with 60 g of methyl acrylate and 3.2 g of benzyl methacrylate.
After irradiating with light for 8 hours in the same manner, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction. Then Pd-C was added to the reaction mixture at a temperature of 25
The catalytic reduction reaction was carried out at 0 ° C for 1 hour.

After filtering off the insoluble matter, petroleum ether 500 m
The precipitate was collected and dried. The yield of the obtained polymer was 118 g, and the Mw was 8 × 10 ⁴ .

[0182]

[Chemical 44]

Synthesis Example 3 of Resin [B]: [B-3] A mixed solution of 100 g of ethyl methacrylate and 200 g of toluene was thoroughly degassed under a nitrogen stream and cooled to 0 ° C.
Next, 2.5 g of 1,1-diphenyl-3-methylpentyllithium was added, and the mixture was stirred for 6 hours. Further, 60 g of methyl methacrylate and 4.6 g of 4-vinylphenyloxytrimethylsilane were added to this mixture, and the mixture was stirred for 6 hours.
3 g of methanol was added and stirred for 30 minutes.

Next, 10 g of a 30% hydrogen chloride ethanol solution was added to this reaction mixture, and the mixture was stirred at 25 ° C. for 1 hour and then reprecipitated in 1 liter of methanol to collect a precipitate.
It was washed twice with 00 ml and dried. The obtained polymer had a yield of 121 g and an Mw of 6.5 × 10 ⁴ .

[0185]

[Chemical formula 45]

Synthesis Example 4 of Resin [B]: [B-4] A mixture of 67 g of methyl methacrylate and 4.8 g of benzyl N, N-diethyldithiocarbamate was sealed in a container under a nitrogen stream and heated to a temperature of 50 g. did. For this, 40
Photopolymerization was performed by irradiating with a 0 W high-pressure water mercury lamp from a distance of 10 cm through a glass filter for 6 hours.

To this, 32 g of methyl acrylate and 1 g of acrylic acid and 180 g of methyl ethyl ketone were added, the atmosphere was replaced with nitrogen, and light irradiation was again performed for 10 hours. The obtained reaction product was reprecipitated in 1 l of methanol, collected, and dried. The obtained polymer had a yield of 73 g and an Mw of 4.8 × 10 ⁴ .

[0188]

[Chemical formula 46]

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

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

The obtained reaction product was reprecipitated in 2 l of methanol, and the collected powder was dried. The obtained polymer had a yield of 63 g and Mw of 6 × 10 ⁴ .

[0192]

[Chemical 47]

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

After bringing the reaction mixture to a temperature of 20 ° C.,
4,4'-azobis (sia) valeric acid) 8.6 g, dicyclohexyldicarbodiimide 12 g, 4- (N, N-dimethyl) pyridyl 0.2 g and tetrahydrofuran 30
The mixed solution of g was added dropwise over 1 hour. After stirring for another 2 hours as it was, 5 g of 85% formic acid aqueous solution was added and further stirred for 30 minutes. Next, the precipitated crystals are separated by filtration, and the filtrate is heated to a temperature of 2
The solvent was distilled off under reduced pressure at 5 ° C. The Mw of the obtained polymer having the following structure (polymer initiator) was 6.3 × 10 ³ .

[0195]

[Chemical 48]

A mixed solution of 70 g of methyl methacrylate and 170 g of toluene was stirred at a temperature of 70 while stirring under a nitrogen stream.
Warmed to ° C. Add 30 g of the above polymer to toluene 3
The solution dissolved in 0 g was preliminarily crushed and replaced with nitrogen, and then added and reacted for 8 hours. 2 l of the obtained polymer was added to methanol.
The re-precipitated and collected powder was dried. The yield of the obtained polymer was 72 g, and the Mw was ⁴ × 10 ⁴ .

[0197]

[Chemical 49]

Synthesis Examples 7 to 16 of Resin [B]: [B-7]
~ [B-16] In the same reaction method as in Synthesis Example 3 of Resin [B], the following Table-C was used.
The resin [B] shown in was synthesized.

The Mw of the obtained copolymer was 5 × 10 ^{4 to} 9
It was in the range of × 10 ⁴ .

[0200]

[Table 8]

[0201]

[Table 9]

[0202]

[Table 10]

Synthesis Examples 17 to 23 of Resin [B]: [B-1
7] to [B-23] In the same reaction method as in Synthesis Example 4 of Resin [B], the following Table-D is used.
The resin [B] shown in was synthesized. Mw of the obtained copolymer
Was in the range of 4 × 10 ⁴ to 8 × 10 ⁴ .

[0204]

[Table 11]

[0205]

[Table 12]

Example 1 and Comparative Examples 1 and 2 6 g (as solid content) of resin [A-2], resin [B-
1] 34 g (as solid content), optical electrode zinc oxide 20
0 g, a cyanine dye [I] having the following structure: 0.018 g, a mixture of 0.10 g of phthalic anhydride and 300 g of toluene in a homogenizer (manufactured by Nippon Seiki Co., Ltd.), the rotation speed was 6 × 10.
Disperse at ³ rpm for 10 minutes to prepare a photosensitive layer-formed product,
This was applied to a conductively treated paper with a wire bar so that the dry adhesion amount was 22 g / m ² , dried at 110 ° C. for 10 seconds, and then 2 ° C. and 65% RH in the dark.
An electrophotographic photosensitive material was produced by leaving it for 4 hours.

[0207]

[Chemical 50]

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

[0209]

[Chemical 51]

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

[0211]

[Chemical 52]

With respect to these photosensitive materials, electrostatic characteristics, image pick-up properties and environmental conditions (20 ° C., 65% RH), (30 ° C.,
The image pick-up property at 80% RH) and (15 ° C., 30% RH) was examined.

The above results are shown in Table-E.

[0214]

[Table 13]

Embodiments of the evaluation items shown in Table-E are as follows. Note 1) Electrostatic characteristics: In a dark room at a temperature of 20 ° C and 65% RH,
-6k using a paper analyzer (Paper Analyzer SP-428 manufactured by Kawaguchi Electric Co., Ltd.) for each light-sensitive material
After corona discharge for 20 seconds at V, the surface potential V ₁₀ at this time was measured after standing for 10 seconds. Then, the potential V ₁₀₀ after standing still in the dark for 90 seconds was measured, and the potential retention after dark decay for 90 seconds, that is, the dark decay retention rate [DRR (%)] was calculated as (V ₁₀₀ / V ₁₀ ) × 100 (%).

Further, the surface of the photoconductive layer was -40 by corona discharge.
After being charged to 0 V, the surface of the photoconductive layer was gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm).
The time until the surface potential (V ₁₀ ) is attenuated to 1/10 by irradiation with light is obtained. From this, the exposure amount E _1/10 (erg / cm
² ) is calculated. Environmental conditions at the time of measurement are 20 ° C and 65%
RH (I), 30 ° C., 80% RH (II) and 15 ° C.,
Performed at 30% RH (III). Note 2) Imaging property: After leaving each light-sensitive material under the following environmental conditions for one day and night, charge each light-sensitive material at −6 kV, and use gallium-aluminum-arsenic with a 2.8 mW output as a light source and a semiconductor laser (oscillation wavelength 780 nm). ) On the surface of the light-sensitive material under a dose of 64 erg / cm ² and a pitch of 25 μm.
m and a scanning speed of 300 m / sec. After speed exposure, ELP-T (manufactured by Fuji Photo Film Co., Ltd.) was used as a liquid developer, followed by development, and isoparaffin Isopar G (manufactured by Esso Chemical Co., Ltd.) solvent rinse solution. The copied image (fog, image quality of the image) obtained by fixing after washing with (1) was visually evaluated.

Environmental conditions at the time of imaging are 20 ° C. and 65% RH
(I), 30 ° C. 80% RH (II) and 15 ° C., 30%
Performed at RH (III). As shown in Table-E, the light-sensitive material of the present invention had good electrostatic characteristics even when environmental conditions changed, and the actual copy image was free of background fog and the copy image quality was clear. On the other hand, Comparative Examples 1 and 2 showed good imaging properties under the conditions of normal temperature and normal humidity (I), but under the conditions of high temperature and high humidity (II), they do not necessarily correspond to the electrostatic characteristics. , Unevenness occurred in the intermediate density of the continuous tone part of the copy document which is a high-definition copy image. Further, even after the rinsing treatment, a slight background fog remained without being removed.

Further, under the condition of low temperature and low humidity (III), minute white spots were randomly generated in the solid image portion. From the above, only when the resin of the present invention is used, the electrostatic characteristic and the image pickup property (especially high-definition image)
It has been revealed that an electrophotographic photoreceptor satisfying the above conditions can be obtained, and in particular, it is superior to a semiconductor laser light scanning exposure type photoreceptor system. Example 2 and Comparative Examples 3 and 4 5 g of resin [A-11] (as solid content), resin [B-
2] 35 g (as solid content), photoconductive zinc oxide 20
0 g, 0.020 g of methine dye (II) having the following structure, N-
Hydroxymaleinimide 0.20 g and toluene 30
An electrophotographic light-sensitive material was produced by operating 0 g of the mixture in the same manner as in Example 1.

[0219]

[Chemical 53]

Comparative Example 3: In Example 2, the resin [B-
2] Instead of 35 g, resin [R-3] 35 having the following structure
An electrophotographic photosensitive material was produced in the same manner as in Example 2 except that g was used.

[0221]

[Chemical 54]

Comparative Example 4: In Example 2, the resin [B-
2] Instead of 35 g, resin [R-4] 35 having the following structure
An electrophotographic photosensitive material was produced in the same manner as in Example 2 except that g was used.

[0223]

[Chemical 55]

When the film properties (surface smoothness) of each light-sensitive material, the mechanical strength of the photoconductive layer, the electrostatic characteristics, the image pick-up property and the environmental conditions are 30 ° C., 80% RH and 15 ° C., 30% RH. The electrostatic characteristics and imaging properties of Furthermore, the printability when used as an original plate for electrophotographic lithographic printing was examined.

[0225]

[Table 14]

Embodiments of the evaluation items shown in Table-F are as follows. Note 3) Smoothness of surface layer: The photosensitive material obtained was measured using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.) with an air capacity of 1 c.
The smoothness (sec / cc) was measured under the condition of c. Note 4) Mechanical strength of photoconductive layer: The surface of the obtained light-sensitive material was tested with Haydon-14 type surface test material (manufactured by Shinto Chemical Co., Ltd.) under a load of 75 g / cm ² with emery paper ( # 10
(00) was repeated 1000 times to remove the abrasion powder, and the residual film rate (%) was calculated from the weight reduction of the photosensitive layer to obtain the mechanical strength. Note 5) Raw plate water retention: Desensitizing solution EPL-EX (Fuji Photo Film Co., Ltd.)
Solution) was diluted with distilled water 5 times and passed through an etching processor twice to desensitize the surface of the photoconductive layer, and then distilled water was used as fountain solution to prepare an offset printing machine (( ) Hamada Printing Machine Co., Ltd., 611XLA-II
After printing, the degree of background stain of the 50th printed material after printing was visually evaluated (corresponding to a forced condition for examining the degree of water retention of the desensitized original plate). Note 6) Printing durability: Under the same conditions as in Note 2) above, after making a plate to form a toner image, it is passed twice through an etching processor using ELP-EX to desensitize. Then, using this as an offset master, it is applied to an offset printing machine (Oliver 52 type, manufactured by Sakurai Seisakusho Co., Ltd.), and the number of prints that can be printed without causing scumming in the non-image area of the printed matter and image quality of the image area The larger the number, the better the printing durability.)

As shown in Table-F, the light-sensitive material of the present invention comprises
The smooth film of the photoconductive layer had good mechanical strength and electrostatic properties, and the actual copied image had no background fog and the copied image quality was clear. It is presumed that this is because the photoconductor and the binder resin are sufficiently adsorbed and the particle surface is covered. For the same reason, even when used as an offset master original plate, the desensitizing treatment with the desensitizing treatment liquid is sufficiently advanced, and even if the water retention under a forced condition is evaluated, it is sufficiently hydrophilized, and ink adhesion is completely eliminated. I was not able to admit. Even when the print was actually printed and the print stain was observed, the print stain was not recognized at all, and 10,000 prints with clear image quality were obtained.

On the other hand, in Comparative Example 3 and Comparative Example 4, when the image capturing conditions were severe, the non-image part was slightly stained, and unevenness was generated in the high-definition continuous tone image part. Alternatively, problems such as white spots and unevenness in the solid image portion occurred.

[0229] Further, the offset master-original plate showed degreasing-treated water retention of the original plate with ink adhesion. The actual printing durability was 5 to 6,000 sheets. The above is
The resin [A] and the resin [B] of the present invention properly interact with the zinc oxide particles to form a pantry state in which the desensitizing reaction by the desensitizing solution can easily and sufficiently proceed. And that the film strength is remarkably improved by the action of the resin [B]. Examples 3 to 18 In Example 2, the resin [A-11] and the resin [B-
Each electrophotographic photosensitive member was produced in the same manner as in Example 2 except that each resin [A] and each resin [B] in the following Table-G was used instead of 2].

The electrostatic characteristics were measured in the same manner as in Example 2. The results are shown in Table-G.

[0231]

[Table 15]

The electrostatic characteristics and the image pickup property of each light-sensitive material were measured in the same manner as in Example 1. All of the photosensitive materials have good electrostatic characteristics, and when the actual imaging properties of these photosensitive materials were examined, the reproducibility of fine lines and characters was good, there was no unevenness in the halftone, and there was no clear background fog. A duplicate image was obtained.

When used as an offset master original plate and printed in the same manner as in Example 2, at least 10,000 or more sheets could be printed. From the above, each of the light-sensitive materials of the present invention was good in all aspects of smoothness, film strength, electrostatic properties and printability of the photoconductive layer. Examples 19 to 22 Electrophotographic photosensitive materials were produced under the same conditions as in Example 1 except that the methine dye [I] used in Example 1 was replaced with the dyes shown in Table H below.

[0234]

[Table 16]

[0235]

[Table 17]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copied images are high temperature / high humidity (30 ° C., 80% RH) and low temperature / low humidity (15).
Even under severe conditions (° C., 30% RH), a clear image with no background fog was provided. Examples 23 and 24 and Comparative Example 5 Resin [A-1] (Example 23) or Resin [A-18]
6.5 g of any of (Example 24), resin [B-23]
33.5 g, zinc oxide 200 g, uranine 0.02 g,
A mixture of 0.03 g of the methine dye [VII] having the following structure, 0.03 g of the methine dye [VIII] having the following structure, 0.18 g of p-hydroxybenzoic acid and 300 g of toluene was used in a homogenizer at a rotation number of 7 × 10 ³ rpm for 10 times. The photosensitive layer-formed product was prepared by dispersing for a minute, and this was coated on a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ^2, and dried at 110 ° C. for 20 seconds. Then in the dark 20
Each electrophotographic photosensitive member was prepared by leaving it to stand at a temperature of 65% RH for 24 hours.

[0237]

[Chemical 56]

[0238]

[Chemical 57]

Comparative Example 5 In the same manner as in Example 23 except that 33.5 g of the resin [R-5] having the following structure was used in place of 33.5 g of the resin [B-23] in Example 23, A light-sensitive material was prepared.

In the same manner as in Example 1, each characteristic of each photosensitive material was examined. The results are summarized in Table-I below.

[0241]

[Chemical 58]

[0242]

[Table 18]

In the above measurement, the same operations as in Example 1 were carried out except that the electrostatic properties and the image pickup properties were in accordance with the following operations. Note 7) Method of measuring E _1/10 of electrostatic characteristics After charging the surface of the photoconductive layer to −400 V by corona discharge, the surface of the photoconductive layer was irradiated with visible light with an illuminance of 2.0 lux to obtain the surface potential. The time until (V ₁₀ ) is attenuated to 1/10 is obtained, and the exposure amount E _1/10 (lux · second) is calculated from this. Note 8) Imaging property After leaving each light-sensitive material for 1 day under the following environmental conditions, fully automatic plate-making machine EPL-404V (Fuji Photo Film Co., Ltd.)
Manufactured by EPL-T as a toner, and a copy image (fog, image quality of the image) obtained by plate making was visually evaluated. Environmental conditions at the time of imaging are 20 ° C 65% RH (I), 30 ° C 8
Performed at 0% RH (II) and 15 ° C., 30% RH (III). However, the original for copying (that is, the original copy) was prepared by cutting and pasting other originals.

In each of the light-sensitive materials of the present invention, the photoconductive layer had good mechanical strength, but Comparative Example 5 had a lower mechanical strength. The electrostatic properties showed good performance at room temperature and normal humidity (I), but especially at low temperature and low humidity (II).
In I), E _1/10 decreased.

The light-sensitive material of the present invention has good electrostatic properties, and Example 24 using the resin [A] having a specific substituent is very good, and particularly, the value of E _1/100 . Became smaller. When the actual image pickup property is examined and seen, Comparative Example 5
In addition to the original as a copy image, the frame (that is, the trace of pasting) of the part cut out and stuck was recognized as the background stain of the non-image part. Furthermore, when the environmental conditions at the time of image pickup are high temperature / high humidity (II) and low temperature / low humidity (III), unevenness occurs in the halftone region of the continuous tone part of the copy image, and white spots in the solid image part are small. Occurrence of unevenness was observed.

Further, when these were subjected to desensitization treatment as offset printing original plates and printed, all of the present invention produced 10,000 printed matters with clear image quality without scumming.
However, in Comparative Example 5, the above-mentioned sticking mark was not removed even by the desensitizing treatment, and was generated from the printed matter.

From the above, only the light-sensitive material of the present invention could give good characteristics. Example 25 5 g of resin [A-23] and 35 g of resin [B-22], 200 g of zinc oxide, 0.02 g of uranine, 0.04 g of rose bengal, 0.03 g of bromphenol blue, 0.40 g of phthalic anhydride and 300 g of toluene. A mixture of
A light-sensitive material was prepared in the same manner as in Example 24 by the following operations.

The performance of the light-sensitive material of the present invention was examined in the same manner as in Example 24. As a result, all were excellent in chargeability, dark charge retention rate and photosensitivity. (30 ℃, 80% RH) and low temperature / low humidity (15 ℃, 30
% RH), a clear image with no background fog was obtained even under severe conditions.

Further, when this was used as an original plate of an offset master and printed, a printed matter having clear image quality was obtained even at 10,000 sheets. Examples 26 to 49 In Example 25, 5 g of resin [A-23] and 35 g of resin [B-22] were used in place of 5 g of resin [A-23] and 35 g of resin [B-22]. Each light-sensitive material was prepared in the same manner as in Example 23.

[0250]

[Table 19]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copied images are high temperature and high humidity (30 ° C., 80% RH) and low temperature and low humidity (15 ° C., 30).
% RH), a clear image with no background fog or fine line skipping was provided even under severe conditions.

Further, when printed as an offset master original plate, a printed matter having a clear image quality without generation of scumming was obtained even after printing 10,000 sheets.

[0253]

According to the present invention, an electrophotographic photoreceptor having a clear and high-quality image excellent in electrostatic characteristics (especially electrostatic characteristics under severe conditions) and further having excellent mechanical strength. Can be obtained. In particular, it is effective for a scanning exposure method using semiconductor laser light.

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

Claims (3)

[Claims] 1. An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, wherein the binder resin is at least one of the following resins [A] and the following: An electrophotographic photoreceptor comprising at least one resin [B]. Resin [A] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ ,
O ₃ H ₂ group, -COOH group, -SO ₃ H group, a phenolic OH group, -P (= O) (OH ) R 1 [R ¹ is a hydrocarbon group or -OR ² (R ² is a hydrocarbon group A group containing at least one polymer group containing at least one polar group selected from the group and a cyclic acid anhydride group.
A polymerizable double bond group is bonded to the end of the polymer main chain of the B block of the AB block copolymer composed of the block and the B block containing at least the polymer component represented by the following general formula (I). A graft copolymer containing at least one kind of the monofunctional macromonomer (M) as a copolymerization component. [Chemical 1] [In the formula (I), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. V ¹ is-
COO -, - OCO-, chromatography (CH _{2) a} OCO-, chromatography _{(CH 2) a COO-, (} a is an integer of 1-3.)
-O -, - SO ₂ over, over CO-, chromatography CON (Z ¹⁾ -,
Over SON (Z ¹⁾ -, over CONHCOO-, over CONH
CONH- or chromatography C ₆ H ₄ - represents a (wherein Z ¹ represents a hydrogen atom or a hydrocarbon group). R ³ represents a hydrocarbon group. However, when V ¹ represents —C ₆ H ₄ —, R ³ represents a hydrogen atom or a hydrocarbon group. Resin [B] having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ ,
O ₃ H ₂ group, -SO ₃ H group, -COOH group, -P (=
O) (OH) R ¹ (R ¹ has the same meaning as above) group and at least one polymer component containing at least one polar group selected from cyclic acid anhydride groups An AB block copolymer comprising an A block consisting of the above and a B block containing at least a polymer component represented by the following general formula (II). [Chemical 2] [In the formula (II), b ¹ and b ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ⁴ represents a hydrocarbon group. ] 2. A resin represented by the following general formula (II) as a copolymer component which is copolymerized with the macromonomer (M):
The electrophotographic photosensitive member according to claim 1, which contains at least one of a) and an aryl group-containing methacrylate component represented by the following general formula (IIb). [Chemical 3] [Chemical 4] [In the formulas (IIa) and (IIb), A ¹ and A ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, —COZ ² or —COOZ ² (Z ² is a carbon number. 1 to
10 represents a hydrocarbon group), and B ¹ and B ² each represent a single bond for connecting —COO— and the benzene ring or a connecting group having 1 to 4 connecting atoms. ] 3. In the resin [B], the total amount of the specific polar group-containing polymer component contained in all the copolymers is the specific polar group-containing polymer contained in the resin [A]. The electrophotographic photosensitive member according to claim 1 or 2, which is 10% by weight to 50% by weight based on the total amount of the components.