JP2002091021A - Method for producing electrophotographic photoreceptor and electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the dispersibility of a filler in a coating liquid for forming a surface layer containing a resin binder, the filler and, optionally, an electric charge transferring material disposed on a photosensitive layer and to obtain a high durability electrophotographic photoreceptor. SOLUTION: In the method for producing the electrophotographic photoreceptor by disposing at least a photosensitive layer on an electrically conductive substrate and a surface layer containing a resin binder, a filler and, optionally, an electric charge transferring material on the photosensitive layer, a coating liquid for forming the surface layer is prepared with a dispersing machine using media, and the amount of powder of the media mixed in the coating liquid by abrasion in the dispersing step is 0.2-20 wt.% of the amount of the filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a durable electrophotographic photosensitive member used in a copying machine, a facsimile, a laser printer, a direct digital plate making machine, etc., and more particularly, to form a surface layer of the photosensitive member. The present invention relates to a production method in which the dispersion stability of a coating liquid is improved.

[0002]

2. Description of the Related Art In recent years, as the speed, size, and image quality of electrophotographic copying machines, electrophotographic printers, and the like increase, photoconductors have been required to have high durability. The photoreceptor is deteriorated by mechanical and chemical actions during repeated charging, exposure, development, transfer and cleaning in an electrophotographic process. The mechanical deterioration causes wear and damage of the photoconductor, and the chemical deterioration causes deterioration of image quality due to oxidative deterioration of the binder resin and the charge transporting substance due to the generated ozone and deposits. As described above, the diameter of the photoreceptor is reduced as the speed and the size are reduced, and the use conditions in the electrophotographic process are severe. In particular, a rubber blade is used in the cleaning section, and for sufficient cleaning, an increase in rubber hardness and an increase in abutment pressure are inevitable, which promotes abrasion of the photoreceptor, causing potential fluctuations and sensitivity fluctuations. There are problems such as abnormal images, color balance of color images being broken, and problems in color reproducibility. For this purpose, a technique of adding a filler to the surface layer of the photoconductor has been proposed.

[0003] As a method of adding a filler to the surface layer, a method of dissolving a binder resin in a solvent and dispersing the filler in the solution, or a method of dissolving the binder resin and a charge transporting material in a solvent and adding the filler to the solution. It is common to prepare a coating liquid by a method of dispersing, apply it on the photosensitive layer using a coating method such as dip coating, ring coating, spray coating, roll coating, etc., and form it by drying. is there. The surface layer containing the filler formed in this way requires a uniform film thickness and a uniform filler concentration. When the film is mounted on a copying machine, a printer, or the like, a non-uniform film causes uneven film thickness in a halftone image. The problem occurs. In addition, when the particle size of the filler in the film increases to 2 μm or more, the coating film becomes rough and the light transmittance decreases, so that sufficient sensitivity cannot be obtained, and the gradation of the image deteriorates, And other problems occur. The problems such as the non-uniformity of the coating film and the aggregation of the filler particles are caused by the poor dispersion state of the filler in the coating liquid, and are solved by improving the dispersibility of the filler in the coating liquid. can do.

Heretofore, there have been many proposals for improving the dispersibility of a coating liquid. For example, Japanese Unexamined Patent Publication No. 6-273962 aims to prevent deterioration of chargeability under low temperature and low humidity by using titania or zirconia as a dispersion medium of a coating liquid for an intermediate layer containing a filler. However, if the mixing amount of the abrasion powder is excessively increased, adverse effects appear on the contrary, and there is a risk that the charging property may be deteriorated in this proposal having no upper limit.

[0005] Japanese Patent No. 2797266, Japanese Unexamined Patent Application Publication No. 3-1
No. 23045, Japanese Unexamined Patent Publication No. 9-212873,
By using glass as the dispersion medium of the coating liquid for the charge generation layer, the amount of abrasion powder mixed is reduced to prevent image defects and deterioration of charging characteristics. However, the dispersion stability is poor unless 0.2% by weight or more of media abrasion powder is mixed. In order to realize these proposals, a binder resin effective for dispersion stability is selected or a dispersant is added. There is a need. In most cases, the electrical characteristics deteriorate due to the change of the binder resin or the addition of the acid dispersing agent. Therefore, it is very difficult to achieve both the dispersion stability and the charging characteristics by a method of suppressing the media abrasion powder.

JP-A-11-038652 discloses that a coating liquid for a charge generation layer is dispersed using a circulation type dispersing machine, and zirconia and silicon carbide are used in a liquid contact portion for driving to prevent mixing of metal wear powder. The purpose is to prevent image defects due to a local decrease in chargeability. Japanese Patent Laid-Open No. Hei 2
Japanese Patent Application Laid-Open No. 000-056484 aims to produce a uniform dispersion by dispersing a coating solution for a surface protective layer while circulating the coating solution. Japanese Patent Application Laid-Open No. 11-27205 discloses that a sand mill is used for dispersing a coating liquid for a surface protective layer. However, none of these proposals can improve dispersion stability and charging characteristics because a dispersion medium is not specified. I can't control it.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and provides a surface layer containing a binder resin and a filler or a binder resin, a filler and a charge transport material on a photosensitive layer. An object of the present invention is to improve the dispersibility of a coating liquid for forming the surface layer of the electrophotographic photoreceptor, thereby providing a highly durable electrophotographic photoreceptor.

[0008]

Means for Solving the Problems In order to optimize the coating solution for the surface layer, the present inventors have conducted intensive studies on the physical properties of the dispersing medium and the coating solution. The abrasion powder is adsorbed on the surface of the filler due to the abrasion of the dispersion medium into the liquid, and the dispersion stability of the coating liquid for the surface layer is improved by modifying the filler surface with the abrasion powder. I found that. Further, when the media abrasion powder is mixed in an amount of 0.2% by weight or more with respect to the filler, the coating liquid is remarkably hard to settle, and the sedimentation prevention effect tends to increase as the amount of mixed media increases. By using alumina balls, the effect of preventing sedimentation is further increased.
If the media wear powder in the surface layer is excessively increased, the surface in the wear powder particles acts as a charge trap site and inhibits the charge transfer of the surface layer, resulting in an increase in residual potential and a decrease in sensitivity. It was also clarified that an amount of the media abrasion powder exceeding 20% by weight with respect to the filler was not preferable in terms of charging characteristics, and the present invention was completed. That is, according to the present invention, first, at least a photosensitive layer on a conductive support, and a binder resin and a filler on the photosensitive layer, or a surface layer containing a binder resin, a filler and a charge transport material was provided. In the method for producing an electrophotographic photoreceptor, the coating liquid for forming the surface layer is produced by a disperser using a medium, and the amount of the media abrasion powder mixed with the filler in the dispersion step of the coating liquid is 0. There is provided a method for producing an electrophotographic photoreceptor, which is in a range from 2% by weight to 20% by weight.

Secondly, there is provided a method of manufacturing an electrophotographic photosensitive member according to the first aspect, wherein the medium is an alumina ball.

Third, in the method for producing an electrophotographic photosensitive member according to the first or second aspect, the charge transport material contained in the surface layer is a polymer charge transport material. A method for manufacturing a photoreceptor is provided.

Fourthly, in the method for producing an electrophotographic photosensitive member according to the first, second or third aspect, the filler contained in the surface layer is an inorganic pigment. Is provided.

Fifth, in the method for producing an electrophotographic photosensitive member according to the fourth aspect, the inorganic pigment is at least one selected from titanium oxide, alumina and silica. A method for manufacturing a photoreceptor is provided.

Sixth, there is provided an electrophotographic photosensitive member manufactured by any one of the above-described methods for manufacturing an electrophotographic photosensitive member.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The present invention has a photosensitive layer on a conductive support directly or via an intermediate layer, and a surface layer containing at least a binder resin and a filler, or a binder resin, a filler and a charge transport material is laminated on the photosensitive layer. In the method for producing an electrophotographic photoreceptor, the amount of abrasion of the dispersion medium mixed in the surface layer coating liquid is 0.2
By defining the content in the range of 20% by weight to 20% by weight, the dispersibility of the filler in the coating liquid is improved, and a uniform coating film without unevenness in film thickness, roughness of the film, and uneven filler concentration can be obtained. Since there is no image unevenness or image defect, and there is no deterioration in chargeability, a highly durable electrophotographic photoreceptor having no background stain can be obtained.

The filler used in the present invention includes organic pigments such as melamine resin particles and silicone resin particles, titanium oxide, silica, tin oxide, alumina, zirconium oxide, indium oxide, silicon nitride, calcium oxide, and the like.
Inorganic pigments such as magnesium oxide, zinc oxide and barium sulfate are mentioned, and particularly preferable ones are silica, alumina and titanium oxide.

The filler whose surface has been subjected to a hydrophobic treatment is preferably used. In general, those treated with a silane coupling agent as a hydrophobizing treatment, those treated with a fluorine-based silane coupling agent, those treated with a higher fatty acid, those treated with alumina, zirconia, tin oxide, and silica as the inorganic surface treatment. Are known.

Examples of the binder resin include acrylic resins, polyesters, polycarbonates, polyamides, polyurethanes, polystyrenes, epoxy resins, and the like. Particularly preferred binder resins are the polycarbonates represented by the following general formulas 1 and 2.

[0018]

Embedded image

[0019]

Embedded image In Formulas 1 and 2, R ₄ , R ₅ , R ₆ , and R ₇ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom, or a substituted or unsubstituted aryl group. X represents an aliphatic divalent group or a cycloaliphatic divalent group;
Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-,
_{-SO 2 -, - CO -,} - CO-O-Z-O-CO-
(Z represents an aliphatic divalent group) or a group represented by the following general formula 3.

[0020]

Embedded image (In the general formula 3, a is an integer of 1 to 20, b is 1 to 2,000
And R ₈ and R ₉ represent a substituted or unsubstituted alkyl group or aryl group. ). Where R ₆ and R ₇ ,
R ₈ and R ₉ may be the same or different.
p and q represent compositions, and 0.1 ≦ p ≦ 1, 0 ≦ q ≦ 0.
9, n represents a repeating unit and is an integer of 5 to 5000. These polycarbonates have high toughness and good film properties. In addition, it is important that the filler layer has good compatibility with a charge transporting substance in order to have a charge transporting function. And polycarbonates 2 are preferred.

It is preferable to add a charge transport material to the outermost surface layer containing the filler in order to provide a charge transport function. Examples of the charge transport material to be added include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9- (p-diethylaminostyrylanthracene), 1,1-bis- (4-dibenzylaminophenyl) propane, and styryl. Anthracene,
Examples include styrylpyrazolin, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. These charge transport materials
They can be used alone or as a mixture of two or more. In particular, a charge transporting material represented by the following general formula 4 has a high mobility and is preferably compatible with the binder resin.

[0022]

Embedded image In Formula 4, R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom, or a substituted or unsubstituted aryl group. R ₂ and R ₃ represent a substituted or unsubstituted aryl group.

Specific examples of R ₁ include the following. As the alkyl group, C ₁ to C ₁ are preferably used.
C ₁₂ , in particular C ₁ -C ₈ , more preferably C ₁ -C ₄ linear or branched alkyl, which further comprises fluorine, hydroxyl, cyano, C ₁ -C ₄ alkoxy Group, phenyl group or halogen atom, C _1-
It may contain a phenyl group substituted with a C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t
-Butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group,
2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4
-Methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R ₂ and R ₃ represent a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different. Examples of the aromatic hydrocarbon group include a styryl group, a phenyl group, and a condensed polycyclic group such as a naphthyl group, a pyrenyl group, a 2-fluorenyl group,
9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group as a non-condensed polycyclic group And a terphenylyl group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group.

The above-mentioned aryl group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) Examples of the alkyl group include the same as those described above for R ₁ , R ₂ and R ₃ . (3) As the alkoxy group (—OR ₁₀₅ ), R ₁₀₅ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-hydroxyethoxy
Examples include a cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group. (4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. This is C ₁ -C ₄
Or a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, an i-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, and a 6-methyl-2-naphthyloxy group. . (5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

For the surface layer containing the filler, a high molecular charge transporting material having both a function as a charge transporting material and a function as a binder resin can be used. it can. As the polymer charge transport substance, known materials can be used, and particularly, a polycarbonate containing a triarylamine structure in a main chain and / or a side chain is preferably used. Among them, polymer charge transport materials represented by the following formulas (I) to (X) are preferably used, and these are exemplified below.

Formula (I)

Embedded image (I) In the formula, R ₁ , R ₂ , and R ₃ are each independently a substituted or unsubstituted alkyl group or a halogen atom, R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, R ₅ ,
R ₆ is a substituted or unsubstituted aryl group, o, p, and q each independently represent an integer of 0 to 4, k and j each represent a composition,
0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9, n represents the number of repeating units, and is an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula 5.

Embedded image In Formula 5, R ₁₀₁ and R ₁₀₂ each independently represent a substituted or unsubstituted alkyl group, aryl group, or halogen atom. l, m is an integer of 0 to 4, Y is a single bond, a linear or branched or cyclic alkylene group having 1 to 12 carbon atoms, -O -, - S -, - SO -, - SO 2 - , -CO
-, -CO-O-Z-O-CO- (wherein Z is an aliphatic 2
Represents a valence group. ) Or general formula 6

Embedded image (In the general formula 6, a is an integer of 1 to 20, b is 1 to 2,000
And R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group. ). Where R ₁₀₁
And R ₁₀₂ and R ₁₀₃ and R ₁₀₄ may be the same or different.

Equation (II)

Embedded image (II) In the formula, R ₇ and R ₈ represent a substituted or unsubstituted aryl group, and Ar ₁ , Ar ₂ and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (I).

Formula (III)

Embedded image (III) In the formula, R ₉ and R ₁₀ represent a substituted or unsubstituted aryl group, and Ar ₄ , Ar ₅ and Ar ₆ represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (I).

Equation (IV)

Embedded image (IV) In the formula, R ₁₁ and R ₁₂ represent a substituted or unsubstituted aryl group, and Ar ₇ , Ar ₈ and Ar ₉ represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (I).

Equation (V)

Embedded image (V) In the formula, R ₁₃ and R ₁₄ are substituted or unsubstituted aryl groups, Ar ₁₀ , Ar ₁₁ , and Ar ₁₂ are the same or different arylene groups; X ₁ and X ₂ are substituted or unsubstituted ethylene groups or substituted Alternatively, it represents an unsubstituted vinylene group. X, k, j and n are the same as in the case of the formula (I).

Equation (VI)

Embedded image (VI) In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are a substituted or unsubstituted aryl group, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ are the same or different arylene groups, Y ₁ , Y ₂ , Y ₃ represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group. You may. X, k, j and n are the same as in the case of the formula (I).

Formula (VII)

Embedded image (VII) In the formula, R ₁₉ and R ₂₀ represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ and Ar ₁₉ represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (I).

Formula (VIII)

Embedded image(VIII) wherein R_{twenty one}Is a substituted or unsubstituted aryl
Group, Ar₂₀, Ar_{twenty one}, Ar_{twenty two}, Ar _{twenty three}Are the same or different
Represents a group. X, k, j and n are the same as in the case of the formula (I)
It is.

Equation (IX)

Embedded image(IX) where R_{twenty two}, R_{twenty three}, R_{twenty four}, R_{twenty five}Is replaced or
Unsubstituted aryl group, Ar _{twenty four}, Ar_{twenty five}, Ar₂₆, Ar₂₇, Ar₂₈Is
Represents the same or different arylene groups. X, k, j and n
Is the same as in the case of the formula (I).

Equation (X)

Embedded image (X) wherein, R _26, R ₂₇ is a substituted or unsubstituted aryl _{group, Ar 29, Ar 30, Ar} 3 1 represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (I).

The content ratio of the charge transport material (D), the binder resin (R) and the filler (F) in the surface layer containing the filler is (D) :( R) :( F) = 10 to 40: 3.
The range of 5-55: 5-40 is good. When the amount of the charge transporting substance is 10% by weight or less, the potential of the light portion is considered to be increased due to a decrease in the charge transporting property. When the amount is 40% by weight or more, the film strength is reduced. The binder resin is used to fix the charge transport material and the filler. If the content is 35% by weight or less, the filler layer is embrittled. If the content is 55% by weight or more, the balance between the charge transport material and the filler amount is reduced. Is not preferred in terms of electrical characteristics and film strength. If the amount of the filler is 5% by weight or less, it is not preferable in terms of abrasion resistance.
When the content is more than the weight%, image deterioration such as background contamination due to opacity of the film occurs. As the dispersing solvent, methyl ethyl ketone, acetone, methyl isobutyl ketone, ketones of cyclohexanone, ethers such as dioxane, tetrahydrofuran, ethyl cellosolve, aromatics such as toluene and xylene, halogens such as chlorobenzene and dichloromethane, ethyl acetate, acetic acid Esters such as butyl are used, and are dispersed and pulverized by a disperser using media such as a ball mill, a sand mill, and a vibration mill. The dispersion state of the filler has a volume average particle size of 0.05 to 1.5 μ.
m, preferably 0.2 to 1.0 μm. When the volume average particle size is smaller than 0.2 μm, there is a disadvantage that the wear resistance is reduced. When the volume average particle size is larger than 1.0 μm, the resolution is reduced due to scattering of the writing light, and A cleaning defect that protrudes and damages the cleaning blade occurs.

The thickness of the outermost layer containing the filler is 0.5
It is 10 to 10 μm, preferably 1 to 6 μm. As a coating method, a dipping method, a spray coating method, a ring coating method, a roll coater method, a gravure coating method, a nozzle coating method, a screen printing method, or the like is employed.

When a surface layer containing a filler is provided on a charge transport layer composed of a charge transport substance and a binder resin, the structures of the binder resin used for the charge transport layer and the binder resin used for the filler layer may be the same or different. May be.

An example of the structure of an electrophotographic photosensitive member manufactured according to the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view of an electrophotographic photoreceptor. A single-layer photosensitive layer 31 mainly composed of a charge generating substance and a charge transporting substance is provided on a conductive support 30, and a surface layer containing a filler is provided thereon. 32 are provided. FIG. 2 shows another configuration example, in which a charge generation layer 33 containing a charge generation substance as a main component is formed on a conductive support 30.
And a charge transport layer 34 containing a charge transport material as a main component, and a surface layer 32 containing a filler is provided thereon.

As the conductive support 30, a volume resistance 10
Those exhibiting conductivity of ¹⁰ Ωcm or less, such as aluminum, nickel, chromium, nichrome, copper, silver, gold, platinum,
Metals such as iron, oxides such as tin oxide and indium oxide coated on film or cylindrical plastics or paper by vapor deposition or sputtering, or plates made of aluminum, aluminum alloy, nickel, stainless steel, etc. . I. , I. I. , Extrude,
Pipes that have been surface-treated by cutting, superfinishing, polishing, or the like can be used after the pipes are formed by a method such as drawing.

The photosensitive layer in the present invention may be a single layer type or a laminated type, but here, for convenience of explanation, the laminated type will be described first. First, the charge generation layer will be described. The charge generation layer is a layer containing a charge generation substance as a main component, and a binder resin may be used as necessary. As the charge generation substance, an inorganic material and an organic material can be used. Inorganic materials include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, amorphous silicon, and the like. As amorphous silicon, a material obtained by terminating a dangling bond with a hydrogen atom or a halogen atom, or a material doped with a boron atom, a phosphorus atom, or the like is preferably used.

On the other hand, as the organic material, a known material can be used. For example, metal phthalocyanine, phthalocyanine pigments such as metal-free phthalocyanine, azulhenium salt pigment, methine squaric acid pigment, azo pigment having a carbazole skeleton, azo pigment having a triphenylamine skeleton, azo pigment having a diphenylamine skeleton, dibenzothiophene skeleton Azo pigment having a fluorenone skeleton, azo pigment having an oxadiazole skeleton, azo pigment having a bisstillene skeleton, azo pigment having a distyryl oxadiazole skeleton, azo pigment having a distyryl carbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinone imine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, i Jigoido based pigments, and bisbenzimidazole pigments. These charge generating substances can be used alone or as a mixture of two or more kinds.

The binder resin optionally used for the charge generation layer 33 includes polyamide, polyurethane,
Epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene,
Poly-N-vinylcarbazole, polyacrylamide, and the like are used. These binder resins can be used alone or as a mixture of two or more. Further, a charge transport material may be added as needed.

Examples of the charge transporting material include the following electron donating materials, which are preferably used. For example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9- (p-diethylaminostyrylanthracene), 1,1-bis (4
-Dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives and the like. . These charge transport materials can be used alone or as a mixture of two or more.

As the method for forming the charge generation layer 33, a vacuum thin film preparation method and a casting method from a solution dispersion system can be mentioned. The former methods include vacuum deposition, glow discharge decomposition, ion plating, sputtering,
Reactive sputtering, CVD, or the like is used, and the above-described inorganic and organic materials can be formed favorably. In addition, in order to provide the charge generation layer 33 by a casting method described later, if necessary, the above-mentioned inorganic or organic charge generation substance is used together with a binder resin in tetrahydrofuran,
It can be formed by dispersing using a solvent such as cyclohexanone, dioxane, dichloroethane, butanone or the like with a ball mill, an attritor, a sand mill or the like, diluting the dispersion liquid appropriately, and coating. The coating can be performed by a dip coating method, a spray coating method, a bead coating method, or the like. The thickness of the charge generation layer provided as described above is
About 0.01 to 5 μm is appropriate, and preferably about 0.0 to 5 μm.
5 to 2 μm.

Next, the charge transport layer will be described. The charge transport layer dissolves both the charge transport material and the binder resin,
It is formed by coating. Polycarbonate with good film properties (bisphenol A type,
Bisphenol Z type, bisphenol C type, or copolymers thereof), polyarylate, polysulfone, polyester, methacrylic resin, polystyrene,
Polyvinyl acetate, epoxy resin, phenoxy resin and the like are used. These binder resins can be used alone or as a mixture of two or more.

The charge transport material used in the charge transport layer is
Oxazole derivatives, oxadiazole derivatives (JP-A-52-139065, 52-139066), imidazole derivatives, triphenylamine derivatives (JP-A-1-77839), benzidine derivatives (Japanese Patent Publication No.
8-32372), α-phenylstilbene derivatives (JP-A-57-73075), hydrazone derivatives (JP-A-55-154555, 55-156954,
55-52063, 56-81850, etc.), triphenylmethane derivatives (JP-B-51-10983), anthracene derivatives (JP-A-51-94829), styryl derivatives (JP-A-56-29245, and JP-A-56-29245).
JP-A-1198043), carbazole derivatives (JP-A-58-58552), pyrene derivatives and the like can be used.

For the charge transporting layer, the above-mentioned polymer charge transporting material having both the function as a charge transporting material and the function as a binder resin is preferably used. Are excellent in wear resistance. The thickness of the charge transport layer is about 5 to 100 μm,
Preferably it is 10 to 40 μm.

In the present invention, a plasticizer or a leveling agent may be added to the charge transport layer. As a plasticizer,
Those generally used as plasticizers for resins, such as dibutyl phthalate and dioctyl phthalate, can be used as they are, and the amount of use is suitably about 0 to 30 parts by weight with respect to 100 parts by weight of the binder resin.

Next, the case where the photosensitive layer has a single-layer structure will be described. When a single-layer photosensitive layer is provided by a casting method or the like, in many cases, a function-separated type comprising a charge generating substance, a charge transporting substance, and a binder resin is used. That is, the above-described materials can be used as the charge generating substance and the charge transporting substance. If necessary, a plasticizer or a leveling agent may be added. Further, as the binder resin that can be used as necessary, the binder resin described above for the charge transport layer may be used as it is, or the binder resin described for the charge generation layer may be mixed and used.
The thickness of the single-layer photoreceptor is about 5 to 100 μm, preferably 10 to 40 μm.

The electrophotographic photosensitive member used in the present invention includes:
An intermediate layer can be provided between the conductive support and the photosensitive layer (the charge generation layer in the case of a laminated type). The intermediate layer is provided for the purpose of improving adhesiveness, preventing moire, improving the coating property of the upper layer, and reducing residual potential. The intermediate layer generally contains a resin as a main component. However, considering that these resins are coated on the photosensitive layer with a solvent, it is desirable that the resin be a resin having high solubility resistance to a general organic solvent. . Examples of such a resin include water-soluble resins such as polyvinyl alcohol, casein and sodium polyacrylate, alcohol-soluble resins such as copolymerized nylon and methoxymethylated nylon, polyurethane, melamine resin, alkyd-melamine resin, epoxy resin, and tertiary resin. A curable resin that forms a primary network structure may be used.
Further, a fine powder of a metal oxide such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide, or a metal sulfide or a metal nitride may be added. These intermediate layers can be formed using a suitable solvent and a coating method as in the case of the above-mentioned photosensitive layer.

In addition, the intermediate layer is provided with Al ₂ O ₃ by anodic oxidation, an organic substance such as polyparaxylylene (parylene), SiO, SnO ₂ , TiO ₂ , ITO, CeO ₂
And the like provided with an inorganic substance by a vacuum thin film production method can also be used favorably. The thickness of the intermediate layer is suitably from 0 to 8 μm.

In the present invention, an antioxidant can be added for the purpose of improving environmental resistance, especially for the purpose of preventing a decrease in sensitivity and an increase in residual potential. The antioxidant may be added to any layer containing an organic substance,
Good results are obtained when added to the layer containing the charge transport material.

The antioxidants that can be used in the present invention include the following. Monophenolic compound 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t −
(Butyl-4-hydroxyphenyl) propionate and the like. Bisphenolic compounds 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-
Ethyl-6-t-butylphenol), 4,4'-thiobis- (3-methyl-6-t-butylphenol),
4,4'-butylidenebis- (3-methyl-6-t-butylphenol) and the like. High molecular phenolic compound 1,1,3-tris- (2-methyl-4-hydroxy-
5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-
4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy -3'-t-butylphenyl) butyric acid] glycol esters, tocophenols and the like. Paraphenylenediamines N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-
Phenylenediamine, N, N'-di-isopropyl-p
Phenylenediamine, N, N'-dimethyl-N, N '
-Di-t-butyl-p-phenylenediamine and the like. Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t
-Octyl-5-methylhydroquinone, 2- (2-octadecenyl) -5-methylhydroquinone and the like. Organic sulfur compounds Dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate and the like. Organophosphorus compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like. These compounds are known as antioxidants for rubber, plastics, oils and the like, and commercially available products can be easily obtained. The addition amount of the antioxidant in the present invention is 0.1 to 1 with respect to 100 parts by weight of the charge transporting substance.
00 parts by weight, preferably 2 to 30 parts by weight.

[0055]

Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited by the following examples. In the examples, all parts are parts by weight.

Example 1 A coating liquid for an intermediate layer, a coating liquid for a charge generation layer, and a coating liquid for a charge transport layer having the following composition were sequentially applied to an aluminum cylinder of φ30 mm and dried to 3.5 μm. , A 0.2 μm charge generation layer, and a 25 μm charge transport layer. Using a ball mill containing zirconia balls having a diameter of 2 mm, the mixture was pulverized for 2 hours to prepare a coating liquid (1) -A for a surface layer in which the following organic filler was dispersed.
Similarly, using a ball mill containing glass beads having a diameter of 2 mm, the mixture was pulverized for 48 hours to prepare a coating liquid (1) -B for a surface layer in which the following organic filler was dispersed. 2mm in diameter
Using a ball mill containing alumina balls, pulverized for 48 hours to disperse the following organic filler and disperse a coating liquid for a surface layer
(1) -C was prepared. These liquids were applied by spraying to provide a surface layer of about 3.0 μm, and after drying, the electrophotographic photoreceptor of the present invention was obtained. Table 1 shows the media mixing amount, the volume average particle size of the dispersed filler, the sedimentation evaluation result, the initial image, the image after the 10,000-sheet passing test, and the abrasion loss of the photoconductor.

[Coating Liquid for Intermediate Layer] Alkyd resin (Veccosol 1307-60-EL manufactured by Dainippon Ink and Chemicals) 6 parts Melamine resin (Super Beckamine G-821-60 manufactured by Dainippon Ink and Chemicals) 4 parts Oxidation Titanium (CREL manufactured by Ishihara Sangyo Co., Ltd.) 40 parts Methyl ethyl ketone 200 parts [Coating liquid for charge generation layer layer] Oxotitanium phthalocyanine pigment 2 parts Polyvinyl butyral (XYHL manufactured by UCC) 0.2 part Tetrahydrofuran 50 parts [Charge transport layer layer Coating Liquid] Polycarbonate resin (Z-Polyka, Teijin Chemicals, Mv 50,000) 10 parts Dichloromethane 100 parts 1% silicone oil (KF50, Shin-Etsu Silicone Co., Ltd.) 1 part Charge transporting material represented by the following structural formula a 12 parts

Embedded image [Coating liquid for filler-containing surface layer] Spherical melamine (Nippon Shokubai Co., Ltd. Eposter S) 2 parts Polycarbonate resin (Z-Polyka, Teijin Chemicals, Mv50,000) 5 parts Tetrahydrofuran 120 parts Cyclohexanone 80 parts

Example 2 In the same manner as in Example 1, an intermediate layer, a charge generation layer, and a charge transport layer were provided, and a bead mill containing alumina balls having a diameter of 0.5 mm was ground for 10 minutes. A coating liquid (2) -A for a surface layer in which the same organic filler was dispersed was prepared.
Similarly, the mixture was pulverized for 2 hours using a bead mill to prepare a surface layer coating liquid (2) -B in which the same organic filler as in Example 1 was dispersed. Using these coating solutions, a surface layer was provided in the same manner as in Example 1. Table 1 shows the media mixing amount, the volume average particle size of the dispersed filler, the sedimentation evaluation result, the initial image, the image after the 10,000-sheet passing test, and the abrasion loss of the photoconductor.

Example 3 In the same manner as in Example 1, the following organic filler was dispersed by pulverizing for 8 hours using a ball mill provided with an intermediate layer, a charge generation layer, and a charge transport layer and alumina balls having a diameter of 2 mm. A coating solution (3) for a surface layer was prepared. Using this coating solution, a surface layer was provided in the same manner as in Example 1. Table 1 shows the media mixing amount, the volume average particle size of the dispersed filler, the sedimentation evaluation result, the initial image, the image after the 10,000-sheet passing test, and the abrasion loss of the photoconductor. [Coating liquid for filler-containing surface layer] Spherical melamine (Nippon Shokubai Co., Ltd. Eposter S) 2 parts Polycarbonate resin (Z-Polyka, Teijin Chemicals, Mv50,000) 5 parts Tetrahydrofuran 120 parts Cyclohexanone 80 parts Represented by the following structural formula b Charge transport material 3 parts

Embedded image

Example 4 In the same manner as in Example 1, the following organic filler was dispersed by pulverizing for 8 hours using a ball mill provided with an intermediate layer, a charge generation layer, and a charge transport layer and alumina balls having a diameter of 2 mm. A coating solution (4) for a surface layer was prepared. Using this coating solution, a surface layer was provided in the same manner as in Example 1. Table 1 shows the media mixing amount, the volume average particle size of the dispersed filler, the sedimentation evaluation result, the initial image, the image after the 10,000-sheet passing test, and the abrasion loss of the photoconductor. [Coating liquid for filler-containing surface layer] Spherical melamine (Nippon Shokubai Co., Ltd. Eposter S) 2 parts Tetrahydrofuran 120 parts Cyclohexanone 80 parts Polymer charge transport material represented by the following structural formula c 8 parts

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Example 5 In the same manner as in Example 1, the following inorganic pigment was dispersed by pulverizing for 8 hours using a ball mill in which an intermediate layer, a charge generation layer and a charge transport layer were provided and alumina balls having a diameter of 2 mm were put. A coating solution (5) for a surface layer was prepared. Using this coating solution, a surface layer was provided in the same manner as in Example 1. Table 1 shows the media mixing amount, the volume average particle size of the dispersed filler, the sedimentation evaluation result, the initial image, the image after the 10,000-sheet passing test, and the abrasion loss of the photoconductor. [Coating liquid for filler-containing surface layer] Zinc oxide (Sazex 4000, Sakai Chemical Co., Ltd.) 2 parts Polycarbonate resin (Z-Polyka, Teijin Chemicals, Mv 50,000) 5 parts Tetrahydrofuran 120 parts Cyclohexanone 80 parts Represented by the following structural formula b Charge transport material 8 parts

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Example 6 In the same manner as in Example 1, an intermediate layer, a charge generation layer, and a charge transport layer were provided, and a ball mill containing alumina balls having a diameter of 2 mm was crushed for 8 hours. , Silica-dispersed surface layer coating liquid (6) -A, (6)-
B, (6) -C were prepared. Using these coating solutions, a surface layer was provided in the same manner as in Example 1. Table 1 shows the media mixing amount, the volume average particle size of the dispersed filler, the sedimentation evaluation result, the initial image, the image after the 10,000-sheet passing test, and the abrasion loss of the photoconductor. [Coating liquid for filler-containing surface layer (6) -A] Titanium oxide (CR-EL manufactured by Ishihara Sangyo Co., Ltd.) 2 parts Polycarbonate resin (Z-Polyka manufactured by Teijin Chemicals, Mv 50,000) 5 parts Tetrahydrofuran 120 parts Cyclohexanone 80 parts 8 parts of a charge transport material represented by the structural formula b

Embedded image [Coating liquid for filler-containing surface layer (6) -B] Alumina (AKP-50 manufactured by Sumitomo Chemical Co., Ltd.) 2 parts Polycarbonate resin (Z-Polyka, Mv50,000, Teijin Chemicals Ltd.) 5 parts Tetrahydrofuran 120 parts Cyclohexanone 80 parts 8 parts of a charge transport material represented by the structural formula b

Embedded image [Coating liquid for filler-containing surface layer (6) -C] Silica (KMPX-100, manufactured by Sumitomo Chemical Co., Ltd.) 2 parts Polycarbonate resin (Z-Polyka, Teijin Chemicals, Mv 50,000) 5 parts Tetrahydrofuran 120 parts Cyclohexanone 80 parts 8 parts of a charge transport material represented by the structural formula b

Embedded image

Comparative Example 1 An intermediate layer, a charge generation layer and a charge transport layer were provided in the same manner as in Example 1. A coating solution for a filler-containing surface layer in which the organic filler of Example 1 was dispersed by grinding for 1 hour using a ball mill containing the same zirconia balls as in Example 1
(7) -A was produced. Similarly, a ball mill containing the glass beads used in Example 1 was pulverized for 72 hours to prepare a filler-containing surface layer coating liquid (7) -B in which the organic filler of Example 1 was dispersed. Similarly, using a ball mill containing the alumina balls used in Example 1, pulverized for 72 hours to disperse the following organic filler and disperse the following coating liquid for a surface layer.
(7) -C was produced. Example 1 using these coating solutions
An electrophotographic photoreceptor was produced in the same manner as described above. Media mixing amount, volume average particle size of dispersed filler, sedimentation evaluation result,
Table 2 shows the initial image, the image after the 10,000-sheet passing test, and the wear amount of the photoconductor.

Comparative Example 2 An intermediate layer, a charge generation layer and a charge transport layer were provided in the same manner as in Example 2. Using an ultrasonic dispersing device, the mixture was pulverized for 4 hours to prepare a coating liquid (8) for a filler-containing surface layer in which the same organic filler was dispersed as in Example 2, and the coating liquid was used in Example. A surface layer was formed in the same manner as in Example 2 to produce an electrophotographic photosensitive member. Table 2 shows the media mixing amount, the volume average particle diameter of the dispersed filler, the sedimentation evaluation result, the initial image, the image after the 10,000-sheet passing test, and the abrasion loss of the photoconductor.

Comparative Example 3 An intermediate layer, a charge generation layer and a charge transport layer were provided in the same manner as in Example 3. Using a ball mill containing the same alumina balls as in Example 3 thereon, the mixture was pulverized for 96 hours to prepare a filler-containing surface layer coating liquid (9) in which the charge transporting substance and the organic filler of Example 3 were dispersed. Using this coating solution, a surface layer was formed in the same manner as in Example 3 to produce an electrophotographic photosensitive member. Table 2 shows the media mixing amount, the volume average particle diameter of the dispersed filler, the sedimentation evaluation result, the initial image, the image after the 10,000-sheet passing test, and the abrasion loss of the photoconductor.

Comparative Example 4 An intermediate layer, a charge generation layer and a charge transport layer were provided in the same manner as in Example 4. Using a ball mill containing the same alumina balls as in Example 4, the mixture was pulverized for 96 hours to obtain a coating liquid (10) for a filler-containing surface layer in which the polymer charge transport material of Example 4 and an organic filler were dispersed. A surface layer was formed in the same manner as in Example 4 using this coating solution, and an electrophotographic photosensitive member was manufactured. Table 2 shows the media mixing amount, the volume average particle diameter of the dispersed filler, the sedimentation evaluation result, the initial image, the image after the 10,000-sheet passing test, and the abrasion loss of the photoconductor.

Comparative Example 5 An intermediate layer, a charge generation layer and a charge transport layer were provided in the same manner as in Example 6. A ball mill containing the same alumina balls as in Example 6 was further crushed for 1 hour to prepare a coating liquid (11) -A for a filler-containing surface layer in which the charge transport material of Example 6 and alumina were dispersed. did. Similarly, a ball containing the alumina ball used in Example 6 was pulverized for 72 hours to prepare a filler-containing surface layer coating liquid (11) -B in which alumina was dispersed in Example 6. Using these coating solutions, a surface layer was formed in the same manner as in Example 6 to produce an electrophotographic photosensitive member. Table 2 shows the media mixing amount, the volume average particle diameter of the dispersed filler, the sedimentation evaluation result, the initial image, the image after the 10,000-sheet passing test, and the abrasion loss of the photoconductor.

Comparative Example 6 An electrophotographic photosensitive member was provided in the same manner as in Example 1 except that an intermediate layer, a charge generation layer, and a charge transport layer were provided and no filler-containing surface layer was laminated. Table 2 shows Comparative Example No. The evaluation result was described as (12).

[0069]

[Table 1]

[0070]

[Table 2] (Note)-The amount of media mixed was calculated by the following method. Incorporation amount (%) = (media weight before dispersion−media weight after dispersion) / filler weight × 100 The volume average particle diameter was measured with CAPA500 manufactured by Horiba, Ltd. -Sedimentability evaluation criteria ：: No sedimentation of dispersed particles after standing for 2 days, ： １: No sedimentation of dispersed particles after standing for one day, Δ: Partial sedimentation of dispersed particles after standing for one day, ×: After standing for one day, all the dispersed particles settle.・ Image and abrasion amount are measured by using Ricoh Imagio MF2
00, the dark part potential was set to 800 V, the light part potential was set to 100 V, an image (initial) was taken out, and then a 10,000-sheet passing test was performed. Amount (1
The difference in film thickness before and after passing a million sheets) was measured. -The film thickness was measured with an eddy current film thickness meter Fischer Corp. MMS manufactured by Fischer.

[0071]

As described above, according to the first aspect of the present invention, there is provided a method for producing an electrophotographic photoreceptor having a surface layer containing a binder resin and a filler, or a binder resin, a filler and a charge transport material, on a photosensitive layer. In, a coating liquid for forming a surface layer is produced by a disperser using a medium,
Since the amount of the media abrasion powder mixed in the coating liquid dispersion step is in the range of 0.2% by weight to 20% by weight with respect to the filler, the dispersibility of the filler in the coating liquid is improved, and A uniform coating film without unevenness in thickness, roughness of the film, and uneven filler concentration can be obtained. Therefore, there is no image unevenness or image defect, and the chargeability is not degraded, so that a highly durable electrophotographic photoreceptor without background contamination can be obtained.

According to a second aspect of the present invention, since the medium is an alumina ball, the effect of preventing the sedimentation of the filler is further increased by mixing in the abrasion powder of the alumina ball, and a surface layer coating liquid having more excellent dispersion stability is provided. Can be made.

According to the third aspect of the present invention, since the charge transport material contained in the surface layer is a polymer charge transport material, it has not only a function as a charge transport material but also a function as a binder resin. By adding to the surface layer, a surface layer having excellent wear resistance can be formed.

According to the fourth aspect of the present invention, since the filler contained in the surface layer is an inorganic pigment, a surface layer harder than other fillers is formed, and the amount of abrasion of the surface layer is reduced.

According to a fifth aspect of the present invention, any one of titanium oxide, alumina and silica is used as the inorganic pigment.
Compared with other inorganic pigments, the coating dispersion has a greater effect of preventing sedimentation due to the mixing of media abrasion powder.

According to a sixth aspect of the present invention, there is provided an electrophotographic photoreceptor manufactured by any one of the above-described manufacturing methods, wherein a surface layer having excellent filler dispersibility is formed on the photosensitive layer, so that high durability and repetition can be obtained. An electrophotographic photosensitive member capable of forming a high-quality image stable for use can be obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a configuration example of an electrophotographic photosensitive member manufactured according to the present invention.

FIG. 2 is a cross-sectional view showing another configuration example of the electrophotographic photosensitive member manufactured according to the present invention.

[Explanation of symbols]

 Reference Signs List 30 conductive support 31 photosensitive layer 32 surface layer 33 charge generation layer 34 charge transport layer

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Nozomu Tamoto 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Satoshi Kurimoto 1-3-6 Nakamagome, Ota-ku, Tokyo In Ricoh Co., Ltd. (72) Inventor Eritoshi Paper 1-3-6 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Co., Ltd. (Reference) 2H068 AA04 BA12 BA13 CA06 CA29 CA33 EA13

Claims (6)

[Claims] At least a photosensitive layer on a conductive support,
In a method for producing an electrophotographic photoreceptor having a surface layer containing a binder resin and a filler, or a binder resin, a filler and a charge transport material on the layer, a dispersing machine wherein a coating liquid for forming the surface layer uses a medium Wherein the amount of the media abrasion powder mixed in the dispersion step is in the range of 0.2% by weight to 20% by weight with respect to the filler. 2. The method for manufacturing an electrophotographic photosensitive member according to claim 1, wherein said medium is an alumina ball. 3. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the charge transporting substance contained in the surface layer is a polymer charge transporting substance. 4. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the filler contained in the surface layer is an inorganic pigment. 5. The method according to claim 4, wherein the inorganic pigment is at least one selected from titanium oxide, alumina, and silica. Production method. 6. An electrophotographic photosensitive member produced by the method for producing an electrophotographic photosensitive member according to claim 1.