JPH10307414A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the electrophotographic photoreceptor free from rise of residual potential in repeating uses and high in transfer efficiency and improved in cleanability by incorporating a mixture of a polyether-modified and another modified polysiloxane in the outermost layer of the photoreceptor. SOLUTION: The mixture of the polyether-modified polysiloxane and the other polysiloxane modified by an alkyl or aliphatic acid ester or vinyl group are contained in the outermost layer of the photoreceptor, and the binder resin of thus outermost layer is a polycarbonate comprising main repeating structural units each represented by the formula in which Z is a nonmetallic atomic group necessary to form an optionally substituted C or hetero ring, and each of R<1> -R<8> is an H or halogen atom or an optionally substituted aliphatic or carbon ring group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more particularly, to a highly durable electrophotographic photoreceptor which is excellent in toner transfer efficiency, cleanability and environmental stability.

[0002]

2. Description of the Related Art Conventionally, inorganic photoconductive materials such as selenium, α-silicon, zinc oxide and the like have been mainly used as photoconductive materials for electrophotographic photosensitive members from the viewpoint of sensitivity and durability. Materials have the drawback that they are harmful and costly due to poor productivity. For this reason, organic photoreceptors that are non-polluting, can be mass-produced by coating, and can be easily reduced in cost have been actively developed in recent years.

[0003]

Although these organic photoreceptors have advantages such as no pollution and low cost, their sensitivity,
Problems remain in terms of environmental stability and durability. Among them, development of an electrophotographic photosensitive member having particularly excellent environmental stability and durability has been eagerly desired. Furthermore, recent demands for higher image quality have been directed to reducing the particle size of the toner, and an electrophotographic photoreceptor having a high transfer efficiency and a high cleaning property corresponding to this trend has been demanded.

As a method for solving these disadvantages, a method has been proposed in which a charge transport layer provided on the surface of a photoreceptor contains a silicone resin or a silicone-containing polymer (Japanese Patent Application Laid-Open No. 57-64243, Japanese Patent Application Laid-Open No. 57-64243). Kaisho 60-2
JP-A-56146, JP-A-61-95358, JP-A-61-132954, JP-A-61-2190
No. 47). However, the method of adding a silicone resin or a silicone-containing polymer has a drawback that the abrasion resistance is poor and the residual potential increases. As described above, the conventional organic photoreceptors containing a silicone-containing polymer or the like have various durability problems, and improvement thereof is eagerly desired.

[0005] As described above, in addition to the problems of various durability, the fact that high transfer efficiency and cleanability are required, but sufficient characteristics have not been obtained. is there. SUMMARY OF THE INVENTION An object of the present invention is to provide a highly durable electrophotographic photoreceptor in which the above-mentioned problems are solved, in which the residual potential does not increase during repeated use, and in which the transfer efficiency and the cleaning property are improved.

[0006]

Means for Solving the Problems The present inventors have repeatedly studied to achieve the above object, and as a result, completed the present invention. That is, according to the present invention, (1) in an electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, the outermost layer of the electrophotographic photosensitive member is a polyether-modified polysiloxane;
An electrophotographic photoreceptor characterized by containing a mixture with another modified polysiloxane selected from alkyl-modified polysiloxane and fatty acid ester-modified polysiloxane,
(2) The electrophotographic photoreceptor according to the above (1), wherein the other modified polysiloxane is a vinyl-modified polysiloxane, (3)
The electrophotographic photoreceptor according to the above (1), wherein the other modified polysiloxane is an alkoxy-modified polysiloxane, and (4) the electrophotography according to the above (1), wherein the other modified polysiloxane is a heterofunctional group-modified polysiloxane. (5) The electrophotographic photoreceptor according to the above (1), wherein the other modified polysiloxane is a fluorine-modified polysiloxane, and (6) the binder resin of the outermost layer is a structural unit represented by the following general formula: The electrophotographic photoreceptor according to any one of the above (1) to (5), wherein

[0007]

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In the formula, Z represents a group of non-metallic atoms necessary for forming a carbocyclic or heterocyclic ring which may have a substituent;
^{1 to} R ⁸ represent a hydrogen atom, a halogen atom, or an aliphatic group or a carbocyclic group, each of which may have a substituent. Next, the present invention will be described in detail with reference to the drawings.

FIG. 1 is a sectional view showing a single-layer photosensitive member used in the present invention. A single-layer photosensitive layer 15 mainly composed of a charge generating material and a charge transport material is provided on a conductive support 11. ing. 2 and 3 are cross-sectional views showing a configuration example of a laminated photoreceptor used in the present invention, in which a charge generation layer 17 mainly containing a charge generation material and a charge transport layer 19 mainly containing a charge transport material are included. It has a stacked configuration.

In the present invention, the outermost layer refers to the above (1) to
This is a layer containing the specific polysiloxane mixture shown in (5), which is a layer provided on the surface of the electrophotographic photosensitive member. Therefore, in the case of a single-layer photoreceptor, the photosensitive layer is the outermost layer, and in the case of a laminated photoreceptor, the layer provided on either one of the charge generation layer and the charge transport layer is the outermost layer. In the present invention, the polysiloxane mixture of (1) to (5) is contained in the coating liquid corresponding to the outermost layer in the present invention, but when the addition amount is increased to further enhance the effect, the above ( It is preferable to dissolve or disperse a predetermined material in a coating solution solvent containing these polysiloxane mixtures represented by 1) to (5). Further, if necessary, the coating solution may be secondarily dispersed using a paint shaker, a sand mill, a bead mill, a ball mill, or the like.

Each of the polysiloxane mixtures (1) to (5) used in the present invention alone has a high transfer efficiency when used repeatedly, a long lasting cleaning property, and an effect of lowering the surface energy. However, when these are used in combination, a synergistic effect is exhibited, and the effects are remarkably improved as compared with the case of using each alone.

Other modified polysiloxanes used together with the polyether-modified polysiloxane in the present invention include alkyl-modified polysiloxane, fatty acid ester-modified polysiloxane, vinyl-modified polysiloxane, alkoxy-modified polysiloxane, heterofunctional group-modified polysiloxane, Fluorine-modified polysiloxane is exemplified. As the polyether-modified polysiloxane used in the present invention,
It is at least one represented by the following general formula, and may have a cyclic structure.

[0013]

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In the above formula, R ^{1 to} R ¹⁰ may be different from each other, and may be an alkyl group having 1 to 3 carbon atoms, —R ¹¹ — (C
₂ H ₄ O) (represents _{C 3 H 6 O) b -R} 12 ( provided that at least one _{^{-R 11 - (C 2 H 4}} O) a is _{a (C 3 H 6 O)} b-R 12 ), R ¹¹ represents an alkylene group, R ¹² represents an alkyl group, hydrogen, or —R ¹³ —OH (R ¹³ represents an alkylene group). m, n, a, and b are 0 or a positive integer (provided that
m and n are not simultaneously 0). The alkyl-modified polysiloxane used in the present invention is at least one represented by the following general formula, and may have a cyclic structure.

[0015]

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In the above formula, R ^{1 to} R ¹⁰ may be different from each other, and may be an alkyl group having 1 to 30 carbon atoms, or an alkyl group having 1 to 30 carbon atoms.
3 represents an alkoxy group or an aralkyl group (at least one of which is an alkyl group having 4 to 30 carbon atoms or an aralkyl group). m and n are 0 or a positive integer (provided that
m and n are not simultaneously 0). The fatty acid ester-modified polysiloxane used in the present invention is at least one represented by the following general formula, and may have a cyclic structure.

[0017]

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In the above formula, R ^{1 to} R ¹⁰ may be different from each other, and may be an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.
Alkoxy group represents -OCO-R ¹¹ (provided that at least one is -OCO-R ^11), R ¹¹ represents an alkyl group. m and n are 0 or a positive integer (however, m and n are not simultaneously 0). The vinyl-modified polysiloxane used in the present invention is at least one represented by the following general formula, and may have a cyclic structure.

[0019]

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In the above formula, R ^{1 to} R ¹⁰ may be different from each other, and may be an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.
An alkoxy group, a phenyl group which may have a substituent,
CH = CH ₂ (at least one of which is -CH = C
It is a H _2). m and n are 0 or a positive integer (provided that
m and n are not simultaneously 0). The alkoxy-modified polysiloxane used in the present invention is at least one represented by the following general formula, and may have a cyclic structure.

[0021]

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In the above formula, R ^{1 to} R ¹⁰ may be different from each other, and may be an alkyl group having 1 to 3 carbon atoms or 1 to 3 carbon atoms.
0 represents an alkoxy group (at least one of which is an alkoxy group having 4 to 30 carbon atoms). m and n are 0 or a positive integer (however, m and n are not simultaneously 0). The heterofunctional group-modified polysiloxane used in the present invention is a modified polysiloxane having two or more different functional groups, is at least one represented by the following general formula, and may have a cyclic structure. .

[0023]

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R ^{1 to} R ¹⁰ in the above general formula may be different from each other, and may be an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.
Represents an alkoxy group, an amino group, an epoxy group, or a polyether group (however, at least two are selected from the group consisting of an alkoxy group having 1 to 3 carbon atoms, an amino group, an epoxy group, and a polyether group) . m and n are 0 or a positive integer (however, m and n are not simultaneously 0).
The fluorine-modified polysiloxane used in the present invention is at least one represented by the following general formula, and may have a cyclic structure.

[0025]

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R ^{1 to} R ¹⁰ in the above general formula may be different from each other, and may be an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.
Represents an alkoxy group, —R ¹¹ —CF ₃ (where at least one is —R ¹¹ —CF ₃ ), and R ¹¹ represents an alkylene group. m and n are 0 or a positive integer (however, m and n
Are not simultaneously 0).

The amount of the polysiloxane mixture represented by the above (1) to (5) used in the present invention is preferably 0.5 to 10% (weight ratio) based on the binder resin. If the amount is small, the high transfer efficiency and the durability of the cleaning property at the time of repeated use are lost. On the other hand, if the amount is too large, the film-forming property is deteriorated, and image defects such as initial background stain are likely to occur. In addition, the above (1) to (5)
The mixing ratio of the polysiloxane mixture represented by
The ratio is preferably from 5:95 to 95: 5 (weight ratio). The viscosity representing the molecular weight (degree of polymerization) of the polysiloxane represented by the above (1) to (5) used in the present invention is 100 CS
(25 ° C.) or higher is preferred, and the higher this is, the more the printing durability in actual use is improved. However, it is satisfactory if at least one of the contained components corresponds to this.

As the conductive support 11, a volume resistance 10
Those exhibiting conductivity of ¹⁰ Ωcm or less, such as aluminum, nickel, chromium, nichrome, copper, silver, gold, platinum and other metals, tin oxide, metal oxides such as indium oxide, by vapor deposition or sputtering, in the form of a film or cylinder. Plastics, paper-coated ones, or plates made of aluminum, aluminum alloy, nickel, stainless steel, etc., and tubes made by cutting them, cutting, super-finishing, polishing, etc., can be used. Next, the photosensitive layer 15 will be described. The photosensitive layer may be a single layer or a laminate, but for convenience of explanation, the case where the photosensitive layer is composed of the charge generation layer 17 and the charge transport layer 19 will be described first. The charge generation layer 17 is a layer containing a charge generation material as a main component.

Inorganic and organic materials are used as the charge generating material. Representative examples thereof include monoazo pigments, disazo pigments, trisazo pigments, perylene pigments, perinone pigments, quinacridone pigments, quinone condensed polycyclic compounds, and squaric acid compounds. Dyes, phthalocyanine-based pigments, naphthalocyanine-based pigments, azulenium salt-based dyes, selenium, selenium-tellurium, selenium-arsenic alloys, amorphous silicon and the like can be used. The charge generating materials are used alone or in combination of two or more.

The charge generation layer 17 is prepared by dispersing the charge generation material together with a binder resin as appropriate using a suitable solvent such as tetrahydrofuran, cyclohexanone, dioxane, 2-butanone, or dichloroethane using a ball mill, an attritor, a sand mill, or the like. It can be formed by coating. The coating can be performed by a dip coating method, a spray coating method, a bead coating method, or the like. Suitable binder resins include polyamide, polyurethane, polyester, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polyacrylamide, and the like. In the case where 17 corresponds to the outermost layer as shown in FIG. 3, a polycarbonate having a structural unit represented by the following general formula as a main repeating unit has an affinity with the polysiloxane mixture of the above (1) to (5). And is more preferable in terms of productivity.

[0031]

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In the formula, Z represents a group of nonmetallic atoms necessary for forming a carbocyclic or heterocyclic ring which may have a substituent;
^{1 to} R ⁸ represent a hydrogen atom, a halogen atom, or an aliphatic group or a carbocyclic group which may have a substituent. The amount of the binder resin is suitably from 0 to 2 parts by weight based on 1 part by weight of the charge generating material. Charge generation layer 17
In the case where does not correspond to the outermost layer, it can also be provided by a known vacuum thin film manufacturing method. The thickness of the charge generation layer 17 is suitably about 0.01 to 5 μm, preferably 0.1 to 5 μm.
２2 μm.

The charge transport layer 19 can be formed by dissolving or dispersing a charge transport material and a binder resin in an appropriate solvent, and applying and drying this. If necessary, a plasticizer or the like can be added. Examples of the charge transport material include materials represented by the following general formulas. These charge transport materials may be used alone or as a mixture.

The charge transport material used in the electrophotographic photoreceptor of the present invention is represented by oxazole derivatives, imidazole derivatives, triphenylamine derivatives and the following general formulas (1) to (19). Compounds and the like can be used.

[0035]

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(Wherein R ¹ is a methyl group, an ethyl group, 2-
Represents a hydroxyethyl group, or a 2-chloroethyl group,
R ² represents a methyl group, an ethyl group, a benzyl group, or a phenyl group; R ³ represents a hydrogen atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group, or Represents a nitro group. Examples of the compound represented by the general formula (1) include 9-ethylcarbazole-3-aldehyde-1-methyl-1-phenylhydrazone and 9-ethylcarbazole-3-aldehyde-1-benzyl-1-phenylhydrazone. And 9-ethylcarbazole-3-aldehyde-1,1-diphenylhydrazone.

[0037]

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(In the formula, Ar represents a naphthalene ring, an anthracene ring, a styryl ring, or a substituted product thereof, or a pyridine ring, a furan ring, or a thiophene ring, and R represents an alkyl group or a benzyl group.) )) Include, for example, 4-diethylaminostyryl-β-aldehyde-1-methyl-1-
Examples include phenylhydrazone, 4-methoxynaphthalene-1-aldehyde-1-benzyl-1-phenylhydrazone.

[0039]

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Wherein R ¹ is an alkyl group, a benzyl group,
Represents a phenyl group or a naphthyl group, R ² is a hydrogen atom,
Represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group, a diaralkylamino group, or a diarylamino group, n represents an integer of 1 to 4,
When n is 2 or more, R ² may be the same or different. R ³ represents a hydrogen atom or a methoxy group. Examples of the compound represented by the general formula (3) include 4-methoxybenzaldehyde-1-methyl-1-phenylhydrazone, 2,4-dimethoxybenzaldehyde-1-benzyl-1-phenylhydrazone, and 4-diethylaminobenzaldehyde. 1,1-diphenylhydrazone, 4-
Methoxybenzaldehyde-1-benzyl-1- (4-
Methoxy) phenylhydrazone, 4-diphenylaminobenzaldehyde-1-benzyl-1-phenylhydrazone, 4-dibenzylaminobenzaldehyde-1,1
-Diphenylhydrazone and the like.

[0041]

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(Wherein, R ¹ represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group, or a heterocyclic group; R ² and R ³ may be the same or different;
Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a chloroalkyl group, or a substituted or unsubstituted aralkyl group, and R ² and R ³ are mutually bonded to form a heterocyclic ring containing a nitrogen atom You may. R ⁴ may be the same or different and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen atom. Examples of the compound represented by the general formula (4) include 1,1-bis (4-dibenzylaminophenyl) propane, tris (4-diethylaminophenyl) methane, and 1,1-bis (4-dibenzylamino). Phenyl) propane, tris (4-diethylaminophenyl) methane, 1,1-bis (4-dibenzylaminophenyl) propane, 2,2 ′
-Dimethyl-4,4'-bis (diethylamino) -triphenylmethane.

[0043]

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(In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group and a phenyl group, and R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or a halogen atom.) Examples of the compound represented by the formula (5) include N-ethyl-3,6-tetrabenzylaminocarbazole.

[0045]

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(In the formula, R represents a hydrogen atom or a halogen atom, and Ar represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, or carbazolyl group.) Formula (6) The compound includes, for example, 9- (4-
Diethylaminostyryl) anthracene, 9-bromo-
And 10- (4-diethylaminostyryl) anthracene.

[0047]

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(Wherein R ¹ is a hydrogen atom, a halogen atom,
Cyano group, alkoxy group having 1 to 4 carbon atoms or 1 to carbon atoms
4 represents an alkyl group, wherein Ar is

[0049]

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Wherein R ² represents an alkyl group having 1 to 4 carbon atoms, and R ³ represents a hydrogen atom, a halogen atom, and a carbon atom having 1 to 4 carbon atoms.
Represents an alkyl group, an alkoxy group having 1 to 4 carbon atoms or a dialkylamino group, wherein n is 1 or 2, and when n is 2, R ³ may be the same or different, and R ⁴ and R ⁵ are hydrogen. Represents an atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted benzyl group. The compound represented by the general formula (7) includes, for example, 9- (4-
Dimethylaminobenzylidene) fluorene, 3- (9-
Fluorenylidene) -9-ethylcarbazole and the like.

[0051]

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(Wherein R is a carbazolyl group, a pyridyl group, a thienyl group, an indolyl group, a furyl group, or a substituted or unsubstituted phenyl group, a styryl group, a naphthyl group or an anthryl group. Is a dialkylamino group, an alkyl group, an alkoxy group, an alkoxy group, or an ester thereof, a halogen atom cyano group,
Represents a group selected from the group consisting of an aralkylamino group, an N-alkyl-N-aralkylamino group, an amino group, a nitro group, and an acetylamino group. Examples of the compound represented by the general formula (8) include 1,2-bis (4-diethylaminostyryl) benzene and 1,2-bis.
And bis (2,4-dimethoxystyryl) benzene.

[0053]

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[0054] (wherein, R ¹ represents a lower alkyl group, a substituted or unsubstituted phenyl group or a benzyl group, R ^2,
R ³ is a hydrogen atom, a lower alkyl group, a lower alkoxy group,
It represents a halogen atom, a nitro group, an amino group, or an amino group substituted with a lower alkyl group or a benzyl group, and n represents an integer of 1 or 2. Examples of the compound represented by the general formula (9) include 3-styryl-9-ethylcarbazole and 3- (4-methoxystyryl) -9-ethylcarbazole.

[0055]

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(Wherein, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ² and R ³ represent an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group. , R ⁴ is a hydrogen atom,
Ar represents a lower alkyl group or a substituted or unsubstituted phenyl group, and Ar represents a substituted or unsubstituted phenyl group or a naphthyl group. Examples of the compound represented by the general formula (10) include 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4-diphenylaminostyryl) naphthalene, 1- (4 -Diethylaminostyryl) naphthalene and the like.

[0057]

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Wherein n is an integer of 0 or 1, R ¹ is a hydrogen atom, an alkyl group or a substituted or unsubstituted phenyl group, Ar ¹ is a substituted or unsubstituted aryl group, and R ⁵ is Represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group,

[0059]

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Represents a 9-anthryl group or a substituted or unsubstituted carbazolyl group, wherein R ² is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or

[0061]

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(Provided that R ³ and R ⁴ represent an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, R ³ and R ⁴ may be the same or different, and R ⁴ is And m may be an integer of 0, 1, 2, or 3, and when m is 2 or more, R
² may be the same or different. When n is 0, A and R ¹ may form a ring together. Examples of the compound represented by the general formula (11) include 4′-diphenylamino-α-phenylstilbene and 4′-bis (4-methylphenyl) amino-α-phenylstilbene.

[0063]

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(Wherein, R ¹ , R ² and R ³ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a dialkylamino group, or a halogen atom, and n represents 0 or 1). Examples of the compound represented by
Phenyl-3- (4-diethylaminostyryl) -5
(4-diethylaminophenyl) pyrazolin, 1-phenyl-3- (4-dimethylaminostyryl) -5- (4
-Dimethylaminophenyl) pyrazolin and the like.

[0065]

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(Wherein R ¹ and R ² represent an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and A represents a substituted amino group, a substituted or unsubstituted aryl group or an allyl group. The compound represented by the general formula (13) includes, for example, 2,5-
Bis (4-diethylaminophenyl) -1,3,4-oxadiazole, 2-N, N-diphenylamino-5
(4-diethylaminophenyl) 1,3,4-oxadiazole, 2- (4-dimethylaminophenyl) -5
(4-diethylaminophenyl) -1,3,4-oxadiazole and the like.

[0067]

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Wherein X is a hydrogen atom, a lower alkyl group,
Or a halogen atom, R represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and A represents a substituted amino group or a substituted or unsubstituted aryl group. As the compound represented by the general formula (14), for example, 2-
N, N-diphenylamino-5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole, 2
-(4-diethylaminophenyl) -5- (N-ethylcarbazol-3-yl) 1,3,4-oxadiazole and the like.

[0069]

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(Wherein, R ¹ represents a lower alkyl group, a lower alkoxy group or a halogen atom, n represents an integer of 0 to 4, R ² and R ³ may be the same or different, and represent a hydrogen atom, Represents a lower alkyl group, a lower alkoxy group or a halogen atom.) Examples of the benzidine compound represented by the general formula (15) include N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[ 1,1′-biphenyl] -4,4′-diamine, 3,3′-dimethyl-N, N, N ′, N′-tetrakis (4-methylphenyl)-[1,1′-biphenyl] -4 , 4'-diamine and the like.

[0071]

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(Wherein R ¹ , R ³ and R ⁴ represent a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, a halogen atom or a substituted Alternatively, R ² represents a hydrogen atom, an alkoxy group, a substituted or unsubstituted alkyl group, or a halogen atom, provided that R 2 represents an unsubstituted aryl group.
¹ , R ² , R ³ and R ⁴ are all excluded when they are hydrogen atoms. K, l, m and n are integers of ¹ , ² , 3 or 4, and when each is an integer of 2, 3 or 4, the above R ¹ , R ² ,
R ³ and R ⁴ may be the same or different. The biphenylamine compound represented by the general formula (16) includes, for example, 4′-methoxy-N, N-diphenyl-
(1,1′-biphenyl) -4-amine, 4′-methyl-N, N′-bis (4-methylphenyl)-(1,1 ′
-Biphenyl) -4-amine, 4'-methoxy-N,
N'-bis (4-methylphenyl)-(1,1'-biphenyl) -4-amine and the like.

[0073]

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(Wherein, Ar represents a condensed polycyclic hydrocarbon group having 18 or less carbon atoms, and R ¹ and R ² represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, Represents a substituted or unsubstituted phenyl group, which may be the same or different.) Examples of the triarylamine compound represented by the general formula (17) include 1-phenylaminopyrene and 1-di (p-tolylamino ) Pyrene. A-CH = CH-Ar-CH = CH-A (18) [wherein, Ar represents a substituted or unsubstituted aromatic hydrocarbon group;

[0075]

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(Where Ar ¹ represents a substituted or unsubstituted aromatic hydrocarbon group, and R ¹ and R ² are a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group). Examples of the diolefin aromatic compound represented by the general formula (18) include 1,4-bis (4-diphenylaminostyryl) benzene and 1,4-bis [4-di (p-tolyl) aminostyryl] There is benzene.

[0077]

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(Wherein, Ar represents an aromatic hydrocarbon group, R represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group. N is 0 or 1, m is 1 or 2, and When n = 0 and m = 1, Ar and R may form a ring together.) As the styrylpyrene compound represented by the general formula (19), for example, 1- (4-diphenylaminostyryl) pyrene And 1- [4-di (p-tolyl) aminostyryl] pyrene.

The binder resin used in the charge transport layer 19 together with the charge transport material includes polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, and polyvinyl chloride. , Vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene,
Thermoplastic or thermosetting resins such as acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, and alkyd resin are exemplified. Among these, polycarbonates are preferable because they have excellent environmental properties and abrasion resistance when used as an electrophotographic photoreceptor, and excellent mechanical properties.In particular, polycarbonates having a structural unit represented by the following general formula as a main repeating unit are preferred. It has excellent affinity with the polysiloxane mixture shown in the above (1) to (5), and is further preferable from the viewpoint of productivity.

[0080]

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In the formula, Z represents a group of nonmetallic atoms necessary for forming a carbocyclic or heterocyclic ring which may have a substituent;
^{1 to} R ⁸ represent a hydrogen atom, a halogen atom, or an aliphatic group or a carbocyclic group which may have a substituent. Such a polycarbonate is on the market, for example, Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Company. As the solvent, tetrahydrofuran, dioxane, toluene, 2-
Butanone, monochlorobenzene, dichloroethane, methylene chloride and the like are used. The thickness of the charge transport layer 19 is 5
１００100 μm is appropriate.

In the present invention, a plasticizer may be added to the charge transport layer 19. As the plasticizer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount of the plasticizer is suitably about 0 to 30% by weight based on the binder resin. Next, the case where the photosensitive layer 15 has a single-layer structure will be described. Also in this case, a function-separated type material composed of a charge generating material and a charge transport material is often used.

That is, it can be formed by dissolving or dispersing at least the charge generating material and the charge transporting material in a suitable solvent together with a binder resin, and applying and drying this. If necessary, a plasticizer or the like can be added.
As the binder resin, the binder resin described for the charge transport layer 19 may be used as it is, or the binder resin described for the charge generation layer 17 may be mixed. The thickness of the single-layer photosensitive layer is suitably from 5 to 100 μm.

In the electrophotographic photoreceptor of the present invention, an undercoat layer can be provided between the conductive support 11 and the photosensitive layer. The undercoat layer generally contains a resin as a main component. However, considering that the photosensitive layer is coated thereon with a solvent, these resins are resins having high solubility resistance to general organic solvents. desirable. Such resins include polyvinyl alcohol, casein, water-soluble resins such as sodium polyacrylate, copolymerized nylon, alcohol-soluble resins such as methoxymethylated nylon, polyurethane, melamine resin, alkyd-melamine resin, epoxy resin, and the like.
Curable resins that form a three-dimensional network structure are exemplified.

Further, in order to prevent moire and reduce residual potential, fine powder of a metal oxide exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide, etc. may be added to the undercoat layer. Good. These undercoat layers can be formed using an appropriate solvent and a coating method as in the above-described photosensitive layer. Further, as an undercoat layer of the present invention,
A metal oxide layer formed by a sol-gel method using a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like is also useful.

In addition, the undercoat layer of the present invention is provided with Al ₂ O ₃ by anodic oxidation, an organic substance such as polyparaxylylene (parylene), SiO, SnO ₂ , TiO ₂ , IT
Those provided with an inorganic substance such as O and CeO ₂ by a vacuum thin film manufacturing method can also be used favorably. The thickness of the undercoat layer is suitably from 0 to 5 μm.

[0087]

The present invention will now be described in more detail with reference to the following Examples, which are provided only for illustrating the present invention in detail and do not limit the present invention. All parts in the examples are parts by weight.

Example 1 An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following compositions were successively applied and dried on an aluminum cylinder having an outer diameter of 100 mm. Coating layer, 0.2
A charge generating layer having a thickness of μm and a charge transporting layer having a thickness of 28 μm were formed to prepare an electrophotographic photosensitive member of the present invention.

[Undercoat layer coating solution] 15 parts of oil-free alkyd resin (manufactured by Dainippon Ink and Chemicals, Becco Light M6401) 10 parts of melamine resin (manufactured by Dainippon Ink and Chemicals, Super Beckamine G-821) 10 parts of titanium dioxide [Ishihara Sangyo Co., Ltd .: Taipaq R-670] 50 parts 2-butanone 40 parts [Charge generating layer coating solution] 5 parts of a charge generating material having the following structural formula

[0090]

Embedded image

Polyvinyl butyral resin (Denka Butyral # 5000-A, manufactured by Denki Kagaku Kogyo Co., Ltd.) 5 parts Cyclohexanone 350 parts [Coating solution for charge transport layer] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Alkyl-modified polysiloxane (BY16-846 20CS, manufactured by Dow Corning Toray Silicone Co., Ltd.) 0.25 parts 4-diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Upilon Z-200 manufactured by Mitsubishi Gas Chemical Company, Inc.) 10 parts Methylene chloride 75 parts Example 2 An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1 except that the coating solution for the charge transport layer in Example 1 was changed to the one having the following composition.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS, Shin-Etsu Silicone Co., Ltd.) 0.01 parts Alkyl-modified polysiloxane (BY16-846 20CS, Dow Corning Toray Silicone Co., Ltd.) 01 parts 4-diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 3 The charge transport layer coating solution of Example 1 was used. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1 except that the composition was as follows.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.025 parts Alkyl-modified polysiloxane (BY16-846 20CS manufactured by Dow Corning Toray Silicone Co., Ltd.) 0.025 Part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 4 The coating solution for the charge transport layer of Example 1 is as follows: An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 1 except that the composition was changed to that of Example 1.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS, Shin-Etsu Silicone Co., Ltd.) 0.5 parts Alkyl-modified polysiloxane (BY16-846 20CS, Dow Corning Silicone Toray Co., Ltd.) 0 0.5 part 4-diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Inc. Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 5 Coating solution for the charge transport layer of Example 1 Was prepared in the same manner as in Example 1 except that the following composition was used.

[Coating solution for charge transport layer] 0.75 parts of polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) BY16-846 20CS manufactured by Dow Corning Toray Silicone Co., Ltd. 75 parts 4-diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Co., Ltd. Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 6 The charge transport layer coating solution of Example 1 was used. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1 except that the composition was as follows.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 618 20CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Alkyl-modified polysiloxane (BY16-846 20CS manufactured by Dow Corning Toray Silicone Co., Ltd.) 25 parts 4-diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 7 The coating solution for the charge transport layer of Example 1 was used. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1 except that the composition was as follows.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 618 20CS, Shin-Etsu Silicone Co., Ltd.) 0.25 parts Alkyl-modified polysiloxane (KF 410 1000CS, Shin-Etsu Silicone Co., Ltd.) 0.25 parts 4-diethylaminobenzaldehyde -1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Inc. Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 8 The charge transport layer coating solution of Example 1 was made to have the following composition. An electrophotographic photoreceptor of the invention was prepared in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 351 100CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Alkyl-modified polysiloxane (KF 413 100CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts 4-diethylaminobenzaldehyde -1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 9 In the coating solution for the charge transport layer of Example 1, the binding of the charge transport layer was performed. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1 except that the following resin was changed.

10 parts of polycarbonate (Panlite K-1300 manufactured by Teijin Chemicals) Comparative Example 1 The electrophotographic photoreceptor of Comparative Example 1 was prepared in the same manner as in Example 1 except that the coating solution for the charge transport layer was changed to the one having the following composition. Produced.

[Charge Transport Layer Coating Solution] 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Company) 10 parts Methylene chloride 75 parts Comparative Example 2 Comparative Example 2 An electrophotographic photoreceptor of Comparative Example 2 was prepared in the same manner except that the charge transport layer coating liquid of No. 1 had the following composition.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.5 part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical) Comparative Example 3 An electrophotographic photoreceptor of Comparative Example 3 was prepared in the same manner as in Example 1 except that the coating solution for the charge transport layer was changed to the following composition.

[Charge Transport Layer Coating Solution] Alkyl-modified polysiloxane (BY16-846 20CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.5 part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical) Comparative Example 4 An electrophotographic photoreceptor of Comparative Example 4 was prepared in the same manner as in Example 1, except that the coating solution for the charge transport layer in Example 1 had the following composition.

[Charge Transport Layer Coating Solution] Silicone Graft Polymer (GS-30, manufactured by Toa Gosei Chemical) 0.5 part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (manufactured by Mitsubishi Gas Chemical Company, Ltd.) (Eupilon Z-200) 10 parts Methylene chloride 75 parts The following measurements were performed on each of the above photoreceptors using an evaluation device disclosed in Japanese Patent Application Laid-Open No. 60-100167. Corona discharge voltage −6.0 kV, potential V after charging for 20 seconds
_m (V), potential V _o (V) after dark decay 20 seconds, intensity 1 μW
/ Cm ² of monochromatic light (780 nm, half-value width 20 nm) residual potential after exposure 20 seconds by VR (V), the exposure amount required to further attenuate the potential V _o to 1/2 E _1/2 [.mu.J / c
m ² ] was measured.

The potential holding ratio is defined as follows. Potential holding ratio = V _o / V _m Each photoconductor of the example and the comparative example was used as a copying machine D manufactured by Ricoh Co., Ltd.
A-355 remodeling machine to copy 10,000 copies continuously
The presence or absence of an abnormal image was visually determined. After completion of the copying test, the characteristics of the photoconductors were measured by the same method as described above. Table 1 shows the test results.

[0105]

[Table 1]

Example 10 An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 1 except that the coating solution for the charge transport layer in Example 1 was changed to the one having the following composition.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Fatty acid ester-modified polysiloxane (KF910 35CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts 4-diethylaminobenzaldehyde -1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 11 The charge transport layer coating solution of Example 1 was made to have the following composition. An electrophotographic photoreceptor of the invention was prepared in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.01 part Fatty acid ester-modified polysiloxane (KF910 35CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.01 part 4-diethylaminobenzaldehyde -1-Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 12 The coating solution for the charge transport layer of Example 1 was made to have the following composition. An electrophotographic photoreceptor of the invention was prepared in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF353 400CS manufactured by Shin-Etsu Silicone Co.) 0.025 parts Fatty acid ester-modified polysiloxane (KF910 35CS manufactured by Shin-Etsu Silicone Co.) 0.025 parts 4-diethylaminobenzaldehyde- 1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Inc. Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 13 Except that the coating liquid for the charge transporting layer of Example 1 had the following composition In the same manner as in Example 1, an electrophotographic photosensitive member of the present invention was produced.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS, Shin-Etsu Silicone Co., Ltd.) 0.5 part Fatty acid ester-modified polysiloxane (KF 910 35CS, Shin-Etsu Silicone Co., Ltd.) 0.5 part 4-diethylamino Benzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 14 The charge transport layer coating solution of Example 1 was prepared to have the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.75 part Fatty acid ester-modified polysiloxane (KF910 35CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.75 part 4-diethylaminobenzaldehyde -1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 15 The coating solution for the charge transport layer of Example 1 was made to have the following composition. An electrophotographic photoreceptor of the invention was prepared in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 part Fatty acid ester-modified polysiloxane (KF910 35CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 part 4-diethylaminobenzaldehyde -1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 16 The coating solution for the charge transport layer of Example 1 was made to have the following composition. An electrophotographic photoreceptor of the invention was prepared in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] 0.25 parts of polyether-modified polysiloxane (KF 618 20CS manufactured by Shin-Etsu Silicone) 0.25 parts of fatty acid ester-modified polysiloxane (X-22-715 14800CS manufactured by Shin-Etsu Silicone) 4-diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 17 The charge transporting layer coating solution of Example 1 has the following composition. An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 1 except that the photoreceptor was changed to the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 351 100CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Fatty acid ester-modified polysiloxane (KF910 heat-treated product 100CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts 4- Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 18 The charge transport layer in the charge transport layer coating solution of Example 10 was used. The electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 10, except that the binder resin was changed to the following. Polycarbonate (Teijin Kasei's Panlite K-1300) 10 parts Comparative Example 5 An electrophotographic photoreceptor of Comparative Example 5 was produced in the same manner as in Example 10 except that the coating solution for the charge transport layer was changed to the following composition.

[Charge Transport Layer Coating Solution] Fatty acid ester-modified polysiloxane (KF 910 35CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.5 part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical) 10 parts, methylene chloride 75 parts The following measurements were performed on each of the above photoreceptors using an evaluation apparatus disclosed in Japanese Patent Application Laid-Open No. 60-100167. Corona discharge voltage −6.0 kV, potential V after charging for 20 seconds
_m (V), potential V _o (V) after dark decay 20 seconds, intensity 1 μW
/ Cm ² of monochromatic light (780 nm, half-value width 20 nm) residual potential after exposure 20 seconds by VR (V), the exposure amount required to further attenuate the potential V _o to 1/2 E _1/2 [.mu.J / c
m ² ] was measured.

The potential holding ratio is defined as follows. Potential holding ratio = V _o / V _m Each photoconductor of the example and the comparative example was used as a copying machine D manufactured by Ricoh Co., Ltd.
A-355 remodeling machine to copy 10,000 copies continuously
The presence or absence of an abnormal image was visually determined. After completion of the copying test, the characteristics of the photoconductors were measured by the same method as described above. Table 2 shows the test results.

[0117]

[Table 2]

Example 19 An electrophotographic photosensitive member of the present invention was produced in the same manner as in Example 1 except that the coating solution for the charge transport layer in Example 1 was changed to the one having the following composition.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Vinyl-modified polysiloxane (FM2231 1000CS manufactured by Chisso Corporation) 0.25 parts 4-diethylaminobenzaldehyde-1 -Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 20 The same procedure as in Example 1 was carried out except that the coating solution for the charge transport layer had the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.01 parts Vinyl-modified polysiloxane (FM2231 1000CS manufactured by Chisso Corporation) 0.01 parts 4-diethylaminobenzaldehyde-1 -Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 21 Except that the coating liquid for the charge transport layer of Example 1 was made to have the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF353 400CS manufactured by Shin-Etsu Silicone Co.) 0.025 parts Vinyl-modified polysiloxane (FM2231 1000CS manufactured by Chisso) 0.025 parts 4-diethylaminobenzaldehyde-1- Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 22 The charge transport layer coating liquid of Example 1 was changed to the one having the following composition. In the same manner as in Example 1, an electrophotographic photosensitive member of the present invention was produced.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS, Shin-Etsu Silicone Co., Ltd.) 0.5 parts Vinyl-modified polysiloxane (FM2231 1000CS, Chisso Corporation) 0.5 parts 4-diethylaminobenzaldehyde-1 -Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 23 Except that the coating liquid for the charge transport layer in Example 1 was changed to the one having the following composition An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.75 parts Vinyl-modified polysiloxane (FM2231 1000CS manufactured by Chisso Corporation) 0.75 parts 4-diethylaminobenzaldehyde-1 -Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 24 The charge transport layer coating liquid of Example 1 was changed to the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 618 20CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Vinyl-modified polysiloxane (FM2231 1000CS manufactured by Chisso Corporation) 0.25 parts 4-diethylaminobenzaldehyde-1 -Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 25 The charge transport layer coating solution of Example 1 was changed to the one having the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 618 20CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Vinyl-modified polysiloxane (FM2242 20000CS manufactured by Chisso Corporation) 0.25 parts 4-diethylaminobenzaldehyde-1 -Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 26 The charge transport layer coating liquid of Example 1 was changed to the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 351 100CS manufactured by Shin-Etsu Silicone) 0.25 parts Vinyl-modified polysiloxane (FP2241 10000CS manufactured by Chisso) 0.25 parts 4-diethylaminobenzaldehyde-1 -Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Inc. Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 27 In the coating solution for the charge transport layer of Example 19, the binder resin of the charge transport layer was used. An electrophotographic photoreceptor of the invention was prepared in the same manner as in Example 19 except that the following was changed. Polycarbonate (Panlite K-1300 manufactured by Teijin Chemicals) 10 parts Comparative Example 6 An electrophotographic photosensitive member of Comparative Example 6 was produced in the same manner as in Example 19 except that the coating solution for the charge transport layer was changed to the one having the following composition.

[Charge Transport Layer Coating Solution] Vinyl-modified polysiloxane (FM2231 1000CS, manufactured by Chisso) 0.5 part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemicals, Inc. Iupilon) Z-200) 10 parts Methylene chloride 75 parts Each of the above photoreceptors was subjected to the following measurement using an evaluation device disclosed in Japanese Patent Application Laid-Open No. 60-100167. Corona discharge voltage −6.0 kV, potential V after charging for 20 seconds
_m (V), potential V _o (V) after dark decay 20 seconds, intensity 1 μW
/ Cm ² of monochromatic light (780 nm, half-value width 20 nm) residual potential after exposure 20 seconds by VR (V), the exposure amount required to further attenuate the potential V _o to 1/2 E _1/2 [.mu.J / c
m ² ] was measured.

The potential holding ratio is defined as follows. Potential holding ratio = V _o / V _m Each photoconductor of the example and the comparative example was used as a copying machine D manufactured by Ricoh Co., Ltd.
A-355 remodeling machine to copy 10,000 copies continuously
The presence or absence of an abnormal image was visually determined. After completion of the copying test, the characteristics of the photoconductors were measured by the same method as described above. Table 3 shows the test results.

[0129]

[Table 3]

Example 28 An electrophotographic photosensitive member of the present invention was produced in the same manner as in Example 1, except that the coating solution for the charge transport layer in Example 1 was changed to the one having the following composition.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Alkoxy-modified polysiloxane (FZ 3701 18CS manufactured by Nippon Unicar) 0.25 parts 4-diethylaminobenzaldehyde -1-Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 29 Except for having the following composition for the charge transport layer coating liquid of Example 1 In the same manner as in Example 1, an electrophotographic photosensitive member of the present invention was produced.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.01 parts Alkoxy-modified polysiloxane (FZ3701 18CS manufactured by Nippon Unicar) 0.01 parts 4-diethylaminobenzaldehyde -1-Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 30 The charge transport layer coating liquid of Example 1 was changed to the following composition. In the same manner as in Example 1, an electrophotographic photosensitive member of the present invention was produced.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF353 400CS manufactured by Shin-Etsu Silicone Co.) 0.025 parts Alkoxy-modified polysiloxane (FZ3701 18CS manufactured by Nippon Unicar) 0.025 parts 4-diethylaminobenzaldehyde- 1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 31 The charge transport layer coating solution of Example 1 was changed to the one having the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS, Shin-Etsu Silicone Co., Ltd.) 0.5 parts Alkoxy-modified polysiloxane (FZ 3701 18CS, Nippon Unicar Co., Ltd.) 0.5 parts 4-diethylaminobenzaldehyde -1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 32 The charge transport layer coating solution of Example 1 was made to have the following composition. An electrophotographic photoreceptor of the invention was prepared in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.75 parts Alkoxy-modified polysiloxane (FZ3701 18CS manufactured by Nippon Unicar Co.) 0.75 parts 4-diethylaminobenzaldehyde -1-Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Company) 10 parts Methylene chloride 75 parts Example 33 Except that the coating liquid for the charge transport layer of Example 1 had the following composition In the same manner as in Example 1, an electrophotographic photosensitive member of the present invention was produced.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 618 20CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Alkoxy-modified polysiloxane (FZ 3701 18CS manufactured by Nippon Unicar) 0.25 parts 4-diethylaminobenzaldehyde -1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 34 Except that the coating liquid for the charge transporting layer of Example 1 had the following composition In the same manner as in Example 1, an electrophotographic photosensitive member of the present invention was produced.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 618 20CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 part Alkoxy-modified polysiloxane (KF 851 heat-treated product 500CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 part 4- Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 35 The coating solution of the charge transport layer of Example 1 was prepared as follows. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 351 100CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Alkoxy-modified polysiloxane (KF8580CS manufactured by Chisso Corporation) 0.25 parts 4-diethylaminobenzaldehyde-1 -Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 36 In the charge transport layer coating liquid of Example 28, the binder resin of the charge transport layer was An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 28 except that the following was changed. Polycarbonate (Panlite K-1300 manufactured by Teijin Chemicals) 10 parts Comparative Example 7 An electrophotographic photosensitive member of Comparative Example 7 was produced in the same manner as in Example 28 except that the coating solution for the charge transport layer was changed to the one having the following composition.

[Charge Transport Layer Coating Solution] Alkoxy-modified polysiloxane (Nippon Unicar FZ3701-18CS) 0.5 part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Company) 10 parts of methylene chloride 75 parts of each of the above photoreceptors was subjected to the following measurement using an evaluation apparatus disclosed in JP-A-60-100167. Corona discharge voltage −6.0 kV, potential V after charging for 20 seconds
_m (V), potential V _o (V) after dark decay 20 seconds, intensity 1 μW
/ Cm ² of monochromatic light (780 nm, half-value width 20 nm) residual potential after exposure 20 seconds by VR (V), the exposure amount required to further attenuate the potential V _o to 1/2 E _1/2 [.mu.J / c
m ² ] was measured.

The potential holding ratio is defined as follows. Potential holding ratio = V _o / V _m Each photoconductor of the example and the comparative example was used as a copying machine D manufactured by Ricoh Co., Ltd.
A-355 remodeling machine to copy 10,000 copies continuously
The presence or absence of an abnormal image was visually determined. After completion of the copying test, the characteristics of the photoconductors were measured by the same method as described above. Table 4 shows the test results.

[0141]

[Table 4]

Example 37 An electrophotographic photosensitive member of the present invention was prepared in the same manner as in Example 1 except that the coating solution for the charge transport layer in Example 1 was changed to the one having the following composition.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Heterofunctional group-modified (amino / alkoxy-modified) polysiloxane (KF857 70CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0 .25 parts 4-diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 38 The coating solution for the charge transport layer of Example 1 was used. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1 except that the composition was as follows.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS, Shin-Etsu Silicone Co., Ltd.) 0.01 part Heterofunctional group-modified polysiloxane (KF 857 70CS, Shin-Etsu Silicone Co., Ltd.) 0.01 part 4-diethylamino 7 parts of benzaldehyde-1-benzyl-1-phenylhydrazone 10 parts of polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts of 75 parts of methylene chloride Example 39 The coating solution for the charge transport layer of Example 1 was made to have the following composition. An electrophotographic photoreceptor of the invention was prepared in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF353 400CS manufactured by Shin-Etsu Silicone Co.) 0.025 parts Heterofunctional group-modified polysiloxane (KF85770CS manufactured by Shin-Etsu Silicone Co.) 0.025 parts 4-diethylamino 7 parts of benzaldehyde-1-benzyl-1-phenylhydrazone 10 parts of polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts of 75 parts of methylene chloride Example 40 The coating liquid for the charge transport layer of Example 1 was made to have the following composition. An electrophotographic photoreceptor of the invention was prepared in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS, Shin-Etsu Silicone Co., Ltd.) 0.5 part Heterofunctional group-modified polysiloxane (KF 857 70CS, Shin-Etsu Silicone Co., Ltd.) 0.5 part 4- Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 41 The charge transport layer coating solution of Example 1 has the following composition. An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 1 except that the above conditions were changed.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.75 parts Heterofunctional group-modified polysiloxane (KF 857 70CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.75 parts 4- Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Ltd. Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 42 The coating solution for the charge transport layer of Example 1 was prepared as follows. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 618 20CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 part Heterofunctional group-modified polysiloxane (KF 857 70CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 part 4- Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Inc. Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 43 The charge transport layer coating solution of Example 1 was prepared to have the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1 except for the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 618 20CS, Shin-Etsu Silicone Co., Ltd.) 0.25 parts Heterofunctional group-modified (epoxy polyether) polysiloxane (X-22, Shin-Etsu Silicone Co., Ltd.) 3667 3000CS) 0.25 part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Company) 10 parts Methylene chloride 75 parts Example 44 Charge transport layer of Example 1 An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 1 except that the coating liquid had the following composition.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 351 100CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Heterofunctional group-modified (epoxy polyether) polysiloxane (manufactured by Toray Dow Corning Silicone Co., Ltd.) BY16-845 150CS) 0.25 parts 4-diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Chemical Co., Inc. Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 45 Charge of Example 37 An electrophotographic photoreceptor of the invention was prepared in the same manner as in Example 37 except that the binder resin of the charge transport layer was changed to the following in the transport layer coating liquid. Polycarbonate (Panlite K-1300 manufactured by Teijin Chemicals) 10 parts Comparative Example 8 An electrophotographic photosensitive member of Comparative Example 8 was produced in the same manner as in Example 37 except that the coating solution for the charge transport layer was changed to the one having the following composition.

[Charge Transport Layer Coating Solution] Heterofunctional Group Modified Polysiloxane (KF 857 70CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.5 part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas) 10 parts Iupilon Z-200 manufactured by Kagaku Co., Ltd. 10 parts 75 parts methylene chloride Each of the above photoreceptors was subjected to the following measurement with an evaluation apparatus disclosed in JP-A-60-100167. Corona discharge voltage −6.0 kV, potential V after charging for 20 seconds
_m (V), potential V _o (V) after dark decay 20 seconds, intensity 1 μW
/ Cm ² of monochromatic light (780 nm, half-value width 20 nm) residual potential after exposure 20 seconds by VR (V), the exposure amount required to further attenuate the potential V _o to 1/2 E _1/2 [.mu.J / c
m ² ] was measured.

The potential holding ratio is defined as follows. Potential holding ratio = V _o / V _m Each photoconductor of the example and the comparative example was used as a copying machine D manufactured by Ricoh Co., Ltd.
A-355 remodeling machine to copy 10,000 copies continuously
The presence or absence of an abnormal image was visually determined. After completion of the copying test, the characteristics of the photoconductors were measured by the same method as described above. Table 5 shows the test results.

[0153]

[Table 5]

Example 46 An electrophotographic photosensitive member of the present invention was produced in the same manner as in Example 1 except that the coating solution for the charge transport layer in Example 1 was changed to the one having the following composition.

[Charge Transport Layer Coating Solution] 0.25 parts of polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co.) 0.25 parts of 4-diethylaminobenzaldehyde-fluorine-modified polysiloxane (FL50 50CS manufactured by Shin-Etsu Silicone) 1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 47 The charge transport layer coating liquid of Example 1 was changed to the one having the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] 0.01 part of polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co.) 0.01 part of fluorine-modified polysiloxane (FL50 50CS manufactured by Shin-Etsu Silicone Co.) 4-diethylaminobenzaldehyde- 1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 48 Except that the coating liquid for the charge transport layer of Example 1 was changed to the one having the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF353 400CS, Shin-Etsu Silicone Co., Ltd.) 0.025 parts Fluorine-modified polysiloxane (FL50 50CS, Shin-Etsu Silicone Co., Ltd.) 0.025 parts 4-diethylaminobenzaldehyde-1 -Benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 49 Example was carried out except that the coating liquid for the charge transport layer of Example 1 was changed to the one having the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.5 part Fluorine-modified polysiloxane (FL50 CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.5 part 4-diethylaminobenzaldehyde- 1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 50 Except that the coating liquid for the charge transport layer of Example 1 had the following composition In the same manner as in Example 1, an electrophotographic photosensitive member of the present invention was produced.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 353 400CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.75 part Fluorine-modified polysiloxane (FL50 50CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.75 part 4-diethylaminobenzaldehyde- 1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Inc. Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 51 Except that the coating liquid for the charge transport layer of Example 1 was changed to the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] 0.25 parts of polyether-modified polysiloxane (KF 618 20CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts of 4-diethylaminobenzaldehyde-fluorine-modified polysiloxane (FL50 50CS manufactured by Shin-Etsu Silicone Co.) 1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Inc. Iupilon Z-200) 10 parts Methylene chloride 75 parts Example 52 The charge transport layer coating solution of Example 1 was changed to the one having the following composition. An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 618 20CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 parts Fluorine-modified polysiloxane (FS1265 1000CS manufactured by Dow Corning Toray Silicone Co., Ltd.) 0.25 Part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Methylene chloride 75 parts Example 53 The charge transport layer coating liquid of Example 1 is composed as follows. An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 1 except that the photoreceptor was changed to the above.

[Charge Transport Layer Coating Solution] Polyether-modified polysiloxane (KF 351 100CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 part Fluorine-modified polysiloxane (FL100 100CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.25 part 4-diethylaminobenzaldehyde- 1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Company) 10 parts Methylene chloride 75 parts Example 54 In the coating solution for the charge transport layer of Example 46, a binder resin for the charge transport layer. The electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 46, except that the following was used. Polycarbonate (Teijin Kasei's Panlite K-1300) 10 parts Comparative Example 9 An electrophotographic photoreceptor of Comparative Example 9 was prepared in the same manner as in Example 46 except that the coating solution for the charge transport layer was changed to the one having the following composition.

[Charge Transport Layer Coating Solution] Fluorine-modified polysiloxane (FL50 50CS manufactured by Shin-Etsu Silicone Co., Ltd.) 0.5 parts 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (manufactured by Mitsubishi Gas Chemical Company, Inc.) (Eupilon Z-200) 10 parts Methylene chloride 75 parts The following measurements were performed on each of the above photoreceptors using an evaluation device disclosed in Japanese Patent Application Laid-Open No. 60-100167. Corona discharge voltage −6.0 kV, potential V after charging for 20 seconds
_m (V), potential V _o (V) after dark decay 20 seconds, intensity 1 μW
/ Cm ² of monochromatic light (780 nm, half-value width 20 nm) residual potential after exposure 20 seconds by VR (V), the exposure amount required to further attenuate the potential V _o to 1/2 E _1/2 [.mu.J / c
m ² ] was measured.

The potential holding ratio is defined as follows. Potential holding ratio = V _o / V _m Each photoconductor of the example and the comparative example was used as a copying machine D manufactured by Ricoh Co., Ltd.
A-355 remodeling machine to copy 10,000 copies continuously
The presence or absence of an abnormal image was visually determined. After completion of the copying test, the characteristics of the photoconductors were measured by the same method as described above. Table 6 shows the test results.

[0165]

[Table 6]

[0166]

According to the present invention, by using a combination of two specific polysiloxanes, it is possible to provide an electrophotographic photosensitive member which exhibits excellent stability even after repeated use without losing high sensitivity. .

[Brief description of the drawings]

FIG. 1 is an explanatory cross-sectional view of a single-layer photoreceptor.

FIG. 2 is an explanatory sectional view of a laminated photoreceptor.

FIG. 3 is an explanatory cross-sectional view of another laminated photoconductor.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Nakai 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Koji Kishida 1-3-6 Nakamagome, Ota-ku, Tokyo Share Inside the company Ricoh

Claims (6)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, wherein the outermost layer of the electrophotographic photosensitive member is selected from a polyether-modified polysiloxane, an alkyl-modified polysiloxane, and a fatty acid ester-modified polysiloxane. An electrophotographic photoreceptor comprising a mixture with another modified polysiloxane. 2. The electrophotographic photosensitive member according to claim 1, wherein the other modified polysiloxane is a vinyl-modified polysiloxane. 3. The electrophotographic photosensitive member according to claim 1, wherein the other modified polysiloxane is an alkoxy-modified polysiloxane. 4. The electrophotographic photoreceptor according to claim 1, wherein the other modified polysiloxane is a heterofunctional group-modified polysiloxane. 5. The electrophotographic photoreceptor according to claim 1, wherein the other modified polysiloxane is a fluorine-modified polysiloxane. 6. The electrophotographic photosensitive member according to claim 1, wherein the binder resin of the outermost layer is a polycarbonate having a structural unit represented by the following general formula as a main repeating unit. Embedded image In the formula, Z represents a nonmetallic atom group necessary for forming a carbocyclic or heterocyclic ring which may have a substituent, and R ^{1 to} R ⁸ represent a hydrogen atom, a halogen atom, or each having a substituent. Represents an aliphatic group or a carbocyclic group which may be substituted.