JP6526286B2 - Electrophotographic photosensitive member, process cartridge and electrophotographic apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

  In recent years, as an organic electrophotographic photosensitive member (hereinafter referred to as "electrophotographic photosensitive member"), an electrophotographic photosensitive member comprising an undercoating layer containing metal oxide particles and a photosensitive layer formed on the undercoating layer The body is used.

  Various metal oxide particles have been proposed as the metal oxide particles contained in the undercoat layer of the electrophotographic photosensitive member. Patent Document 1 discloses strontium titanate particles as metal oxide particles contained in the undercoat layer from the viewpoint of electrical properties.

JP 2007-279620 A

  When the present inventors examined, when strontium titanate particles having a specific X-ray diffraction pattern are used as metal oxide particles in the undercoat layer of the electrophotographic photosensitive member, it is possible to obtain more electric characteristics such as residual potential and charging characteristics. It turned out that it can be improved to a superior one.

  The object of the present invention is to achieve both residual potential and charging characteristics at an excellent level when strontium titanate particles having a specific X-ray diffraction pattern are used as metal oxide particles in the undercoat layer of an electrophotographic photosensitive member. An electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus are provided.

The present invention relates to an electrophotographic photosensitive member having a support, an undercoat layer, and a photosensitive layer in this order:
The undercoat layer contains a binder resin and strontium titanate particles,
The strontium titanate particle has a maximum peak at a position of 2θ = 32.20 ± 0.20 in the CuKα characteristic X-ray diffraction pattern (θ is a Bragg angle),
The half width of the maximum peak is 0.10 deg or more and 0.50 deg or less
The present invention relates to an electrophotographic photosensitive member characterized by

  According to the present invention, residual potential is suppressed and charging characteristics are excellent by using strontium titanate particles having a specific X-ray diffraction pattern as metal oxide particles in the undercoat layer of an electrophotographic photosensitive member. An electrophotographic photosensitive member can be provided.

FIG. 2 is a view showing an example of the layer configuration of the electrophotographic photosensitive member of the present invention. FIG. 1 is a view showing an example of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention. It is a figure showing one example of the polisher which used the polish sheet. (A): It is a top view which shows the mold used in the manufacture example of an electrophotographic photosensitive member. (B): It is BB sectional drawing of the convex part in the mold shown by FIG. 4 (a). (C): It is CC sectional drawing of the convex part in the mold shown by FIG. 4 (a). FIG. 2 is a view showing an example of a pressure contact shape transfer processing apparatus for forming a recess on the circumferential surface of an electrophotographic photosensitive member.

  In the electrophotographic photosensitive member of the present invention, the process cartridge having the electrophotographic photosensitive member, and the electrophotographic apparatus, the undercoat layer of the electrophotographic photosensitive member has 2θ = 32.20 ± 0.20 in the CuKα characteristic X-ray diffraction pattern. And Strontium titanate particles having a maximum peak at the position of θ (θ is a Bragg angle), and a half width of the maximum peak is 0.10 deg or more and 0.50 deg or less.

  As a result of intensive investigations by the present inventors, in order to achieve the effect of achieving both good charging characteristics and suppression of residual potential, 2θ = 32.20 ± 0.20 (θ that the strontium titanate particles have) It was found that it is very important to control the half width of the X-ray diffraction peak at the Bragg angle) to 0.10 deg or more and 0.50 deg or less.

Generally, the half value width of the diffraction peak in powder X-ray diffraction is related to the crystallite diameter of the inorganic fine particles. One grain of primary particles is constituted by a plurality of crystallites, and the crystallite diameter is the size of individual crystallites constituting the primary particles.
In the present invention, the term “crystallites” refers to individual crystal grains constituting particles, and the crystallites are gathered into particles. The size of the crystallites and the size of the particles are irrelevant.
In general, when the crystallite diameter of the inorganic fine particles is small, the half width of the diffraction peak in powder X-ray diffraction is large, and when the crystallite diameter of the inorganic fine particles is large, the half width of the diffraction peak in powder X-ray diffraction is small.

When the crystallite diameter of the inorganic fine particles is reduced, the grain boundaries (crystal grain boundaries) of crystallites and crystallites present in primary particles increase. Grain boundaries are considered to be points at which charge is trapped.
Therefore, when the undercoat layer of the electrophotographic photosensitive member contains strontium titanate particles, the crystallite diameter of the crystallites of the strontium titanate particles is sufficiently small to have many crystal grain boundaries and trap charges. The charging characteristics are improved because the points are increased.
On the other hand, the inside of the crystallite of the inorganic fine particle is easy to flow the charge. When the undercoat layer of the electrophotographic photoreceptor contains strontium titanate particles, the crystal grain diameter of the crystallites of the strontium titanate particles is sufficiently large, so that the grain boundaries are reduced, and the charge is excessively stored. As a result, residual potential can be reduced.
Therefore, in order to achieve both good charging characteristics and suppression of residual potential, it is important to appropriately adjust the grain boundaries of the strontium titanate particles.
The present inventors believe that by controlling the half width of the strontium titanate particles to 0.10 deg or more and 0.50 deg or less, it was possible to obtain the effect of achieving both good charging characteristics and suppression of residual potential. There is.

The strontium titanate particle of the present invention has a maximum peak at a position of 2θ = 32.20 ± 0.20 in the CuKα characteristic X-ray diffraction pattern (θ is a Bragg angle), and the half width of the maximum peak is 0. 10 deg or more and 0.50 deg or less.
If the half width is less than 0.10 deg, as described above, the grain boundaries of the strontium titanate particles are small, so the charging characteristics are degraded.
When the half width is larger than 0.50 deg, as described above, since the strontium titanate particles do not have crystallites of a sufficient size, the residual potential increases.
In particular, when the half value width is 0.23 deg or more, the effect of achieving both the better charging characteristics and the suppression of the residual potential can be obtained.

  The number average particle diameter of primary particles of the strontium titanate particles of the present invention is not particularly limited, but is preferably 10 nm or more and 150 nm or less, and more preferably 10 nm or more and 95 nm or less from the viewpoint of electrical characteristics.

  The strontium titanate particles of the present invention may be surface-treated with a surface treatment agent, and preferably surface-treated with a silane coupling agent. In particular, it is more preferable from the viewpoint of the electrical properties that the silane coupling agent has at least one functional group selected from the group consisting of an alkyl group, an amino group and a halogen group.

[Electrophotographic photosensitive member]
The electrophotographic photosensitive member of the present invention, for example, as shown in FIG. 1, has an undercoat layer on a support, and further has a photosensitive layer on the undercoat layer. In FIG. 1, 1-1 is a support, 1-2 is an undercoat layer, and 1-3 is a photosensitive layer.

  As a method of producing the electrophotographic photosensitive member of the present invention, there may be mentioned a method of preparing a coating solution for each layer to be described later, coating the layers in the order of desired layers, and drying it. At this time, examples of the coating method of the coating liquid include dip coating, spray coating, ink jet coating, roll coating, die coating, blade coating, curtain coating, wire bar coating, ring coating and the like. Among these, dip coating is preferable from the viewpoint of efficiency and productivity.

<Support>
The electrophotographic photosensitive member of the present invention preferably has a support, and the support is preferably a conductive support having conductivity. Moreover, as a shape of a support body, cylindrical shape, belt shape, a sheet shape, etc. are mentioned. Among them, a cylindrical support is preferable. The surface of the support may be subjected to electrochemical treatment such as anodization, blast treatment, cutting treatment, etc. However, it is preferable to carry out blast treatment or cutting treatment.

As a material of a support body, metal, resin, glass etc. are preferable.
Examples of the metal include aluminum, iron, nickel, copper, gold, stainless steel and alloys thereof. Among them, an aluminum support using aluminum is preferable.
In addition, the resin or glass may be provided with conductivity by a process such as mixing or coating of a conductive material.

<Conductive layer>
In the present invention, a conductive layer may be provided on the support. By providing the conductive layer, it is possible to conceal scratches and irregularities on the surface of the support and to control the reflection of light on the surface of the support.
The conductive layer preferably contains conductive particles and a resin.

Examples of the material of the conductive particles include metal oxides, metals, carbon black and the like. Examples of metal oxides include zinc oxide, aluminum oxide, indium oxide, silicon oxide, zirconium oxide, tin oxide, titanium oxide, magnesium oxide, antimony oxide, bismuth oxide and the like. Examples of the metal include aluminum, nickel, iron, nichrome, copper, zinc, silver and the like.
Among these, it is preferable to use a metal oxide as the conductive particles, and in particular, it is more preferable to use titanium oxide, tin oxide, or zinc oxide.
When a metal oxide is used as the conductive particles, the surface of the metal oxide may be treated with a silane coupling agent or the metal oxide may be doped with an element such as phosphorus or aluminum or an oxide thereof.
In addition, the conductive particles may have a laminated structure including core material particles and a coating layer that covers the particles. The core particles include titanium oxide, barium sulfate, zinc oxide and the like. The covering layer may, for example, be a metal oxide such as tin oxide.
When a metal oxide is used as the conductive particles, the volume average particle diameter is preferably 1 nm or more and 500 nm or less, and more preferably 3 nm or more and 400 nm or less.

Examples of the resin include polyester resin, polycarbonate resin, polyvinyl acetal resin, acrylic resin, silicone resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, alkyd resin and the like.
In addition, the conductive layer may further contain a masking agent such as silicone oil, resin particles, titanium oxide and the like.
The average film thickness of the conductive layer is preferably 1 μm or more and 50 μm or less, and particularly preferably 3 μm or more and 40 μm or less.

  The conductive layer can be formed by preparing a coating solution for a conductive layer containing the above-described respective materials and a solvent, forming the coating on a support, and drying it. Examples of the solvent used for the coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents and the like. As a dispersion method for dispersing conductive particles in the coating liquid for conductive layer, a method using a paint shaker, a sand mill, a ball mill, or a liquid collision type high speed disperser can be mentioned.

<Subbing layer>
In the present invention, an undercoat layer is provided on the support or the conductive layer.
The undercoat layer of the electrophotographic photosensitive member of the present invention contains the above-mentioned strontium titanate particles and a binder resin.

As the binder resin, polyester resin, polycarbonate resin, polyvinyl acetal resin, acrylic resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, polyvinyl phenol resin, alkyd resin, polyvinyl alcohol resin, polyethylene oxide resin, polypropylene oxide resin, A polyamide resin, a polyamic acid resin, a polyimide resin, a polyamidoimide resin, a cellulose resin etc. are mentioned.
The binder resin may be a binder resin by polymerizing a composition containing a monomer having a polymerizable functional group. As a polymerizable functional group which a monomer having a polymerizable functional group has, an isocyanate group, a blocked isocyanate group, a methylol group, an alkylated methylol group, an epoxy group, a metal alkoxide group, a hydroxyl group, an amino group, a carboxyl group, a thiol group, A carboxylic anhydride group, a carbon-carbon double bond group, etc. are mentioned.

（式（Ｎ）中、Ｎｂはニオブ原子、Ｏは酸素原子、Ｎは窒素原子であり、０．００＜Ｙ＜Ｘ≦４．００である。）
導電性高分子としては、ポリアニリン、ポリピロール、ポリチオフェンなどが挙げられる。 In addition, the undercoat layer of the present invention may further contain an electron accepting substance, an electron transporting substance, a metal oxide, a metal, a conductive polymer and the like for the purpose of enhancing the electrical properties.
Examples of the electron accepting substance include quinone compounds, anthraquinone compounds, phthalocyanine compounds, porphyrin compounds, triphenylmethane compounds, fluorenylidene malononitrile compounds, and benzalmalononitrile compounds.
Electron transport materials include quinone compounds, imide compounds, benzimidazole compounds, cyclopentadienylidene compounds, fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, halogenated aryl compounds, silole compounds, boron compounds and the like. . The undercoat layer may be formed as a cured film by copolymerizing with the above-described monomer having a polymerizable functional group, using an electron transport material having a polymerizable functional group as the electron transporting substance.
Examples of the metal oxide include indium tin oxide, tin oxide, indium oxide, titanium oxide, zinc oxide, aluminum oxide, silicon dioxide, ammonia reduced niobium oxide and the like. Examples of the metal include gold, silver and aluminum.
As the ammonia-reduced niobium oxide, particles represented by the general formula described below are preferable.

(In the formula (N), Nb is a niobium atom, O is an oxygen atom, N is a nitrogen atom, and 0.00 <Y <X ≦ 4.00).
Examples of the conductive polymer include polyaniline, polypyrrole and polythiophene.

（式（１）中、Ｒ_ａ１〜Ｒ_ａ８は、それぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、アルキル基、アルコキシ基、フェニル基、または、アミノ基を示す。）

（式（２）中、Ｒ_ｂ１〜Ｒ_ｂ１０は、それぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、アルキル基、アルコキシ基、フェニル基、または、アミノ基を示す。） The subbing layer of the present invention particularly preferably contains a compound represented by the following formula (1) or (2) from the viewpoint of electrical properties. These may be used alone or in combination of two or more.

(In formula (1), R _{a1 to} R _a8 each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, or an amino group.)

(In formula (2), R _{b1 to} R _b10 each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, or an amino group.)

The undercoat layer of the present invention may further contain organic resin particles and a leveling agent. Examples of the organic resin particles include hydrophobic organic resin particles such as silicone particles, and hydrophilic organic resin particles such as crosslinkable polymethacrylate resin (PMMA) particles.
The average film thickness of the undercoat layer of the present invention is preferably 0.1 μm or more and 50 μm or less, and more preferably 0.2 μm or more and 40 μm or less.

  The undercoat layer of the present invention is formed by preparing a coating solution for the undercoat layer containing the above-described materials and a solvent, forming this coating film on a support or a conductive layer, and drying and / or curing it. can do. Examples of the solvent used for the coating solution include alcohol solvents, ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents and the like.

<Photosensitive layer>
The electrophotographic photosensitive member of the present invention has a photosensitive layer on the undercoat layer.
The photosensitive layer of the electrophotographic photosensitive member is mainly classified into (1) laminated type photosensitive layer and (2) single layer type photosensitive layer. (1) The laminated photosensitive layer has a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance. (2) The single-layer type photosensitive layer is a photosensitive layer containing both the charge generating substance and the charge transporting substance.

(1) Stacked Photosensitive Layer The stacked photosensitive layer has a charge generation layer and a charge transport layer.

(1-1) Charge Generating Layer The charge generating layer preferably contains a charge generating substance and a resin.

Examples of the charge generating material include azo pigments, perylene pigments, polycyclic quinone pigments, indigo pigments, and phthalocyanine pigments. Among these, azo pigments and phthalocyanine pigments are preferable. Among the phthalocyanine pigments, oxytitanium phthalocyanine pigments, chlorogallium phthalocyanine pigments and hydroxygallium phthalocyanine pigments are preferable.
The content of the charge generation material in the charge generation layer is preferably 40% by mass to 85% by mass, and more preferably 60% by mass to 80% by mass, with respect to the total mass of the charge generation layer. preferable.

  As resin, polyester resin, polycarbonate resin, polyvinyl acetal resin, polyvinyl butyral resin, acrylic resin, silicone resin, epoxy resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, polyvinyl alcohol resin, cellulose resin, polystyrene resin, polyvinyl acetate resin And polyvinyl chloride resin. Among these, polyvinyl butyral resin is more preferable.

The charge generation layer may further contain an additive such as an antioxidant and an ultraviolet light absorber. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds and the like can be mentioned.
The average film thickness of the charge generation layer is preferably 0.1 μm or more and 1 μm or less, and more preferably 0.15 μm or more and 0.4 μm or less.

  The charge generation layer can be formed by preparing a coating solution for charge generation layer containing the above-mentioned respective materials and a solvent, forming this coating film on the undercoat layer, and drying it. Examples of the solvent used for the coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents and the like.

(1-2) Charge Transport Layer The charge transport layer preferably contains a charge transport material and a resin.

Examples of the charge transport material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having a group derived from these materials. Be Among these, triarylamine compounds and benzidine compounds are preferable.
The content of the charge transport material in the charge transport layer is preferably 25% by mass to 70% by mass, and more preferably 30% by mass to 55% by mass, with respect to the total mass of the charge transport layer. preferable.

Examples of the resin include polyester resin, polycarbonate resin, acrylic resin, polystyrene resin and the like. Among these, polycarbonate resin and polyester resin are preferable. As the polyester resin, a polyarylate resin is particularly preferable.
The content ratio (mass ratio) of the charge transport substance to the resin is preferably 4:10 to 20:10, and more preferably 5:10 to 12:10.

  The charge transport layer may also contain additives such as an antioxidant, an ultraviolet light absorber, a plasticizer, a leveling agent, a slipperiness imparting agent, and an abrasion resistance improver. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane modified resins, silicone oils, fluorine resin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles Etc.

  The average film thickness of the charge transport layer is preferably 5 μm or more and 50 μm or less, more preferably 8 μm or more and 40 μm or less, and particularly preferably 10 μm or more and 30 μm or less.

  The charge transport layer can be formed by preparing a coating solution for charge transport layer containing the above-described respective materials and a solvent, forming the coating on the charge generation layer, and drying it. Examples of the solvent used for the coating solution include alcohol solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents. Among these solvents, ether solvents or aromatic hydrocarbon solvents are preferable.

(2) Single-Layer Type Photosensitive Layer A single-layer type photosensitive layer is prepared by preparing a coating solution for a photosensitive layer containing a charge generating substance, a charge transporting substance, a resin and a solvent, and forming this coating on the undercoat layer, It can be formed by drying. The charge generating substance, the charge transporting substance, and the resin are the same as the examples of the material in the above-mentioned “(1) laminated type photosensitive layer”.

<Protective layer>
In the present invention, a protective layer may be provided on the photosensitive layer. By providing the protective layer, the durability can be improved.
The protective layer preferably contains a conductive particle and / or a charge transport substance, and a resin. The conductive particles include particles of metal oxides such as titanium oxide, zinc oxide, tin oxide and indium oxide.
Examples of the charge transport material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having a group derived from these materials. Among these, triarylamine compounds and benzidine compounds are preferable.
Examples of the resin include polyester resin, acrylic resin, phenoxy resin, polycarbonate resin, polystyrene resin, phenol resin, melamine resin, epoxy resin and the like. Among them, polycarbonate resin, polyester resin and acrylic resin are preferable.

  In addition, the protective layer may be formed as a cured film by polymerizing a composition containing a monomer having a polymerizable functional group. The reaction at that time may, for example, be a thermal polymerization reaction, a photopolymerization reaction or a radiation polymerization reaction. As a polymerizable functional group which the monomer which has a polymerizable functional group has, an acryl group, methacryl group, etc. are mentioned. As a monomer having a polymerizable functional group, a material having a charge transporting ability may be used.

The protective layer may contain additives such as an antioxidant, an ultraviolet light absorber, a plasticizer, a leveling agent, a slipperiness imparting agent, and an abrasion resistance improver. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane modified resins, silicone oils, fluorine resin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles Etc.
The average film thickness of the protective layer is preferably 0.5 μm to 10 μm, and more preferably 1 μm to 7 μm.

  The protective layer can be formed by preparing a coating solution for a protective layer containing the above-described respective materials and a solvent, forming the coating on the photosensitive layer, and drying and / or curing. Examples of the solvent used for the coating solution include alcohol solvents, ketone solvents, ether solvents, sulfoxide solvents, ester solvents, and aromatic hydrocarbon solvents.

<Surface processing of electrophotographic photosensitive member>
In the electrophotographic photosensitive member of the present invention, a concave portion or a convex portion may be provided on the surface layer of the electrophotographic photosensitive member for the purpose of further stabilizing the behavior of the cleaning means (cleaning blade) brought into contact with the electrophotographic photosensitive member. The surface layer can be polished to provide roughness.
In the case of forming a recess, the recess can be formed on the surface of the electrophotographic photosensitive member by pressing a mold having the corresponding protrusion to the surface of the electrophotographic photosensitive member and performing shape transfer.
When forming a convex portion, the convex portion can be formed on the surface of the electrophotographic photosensitive member by pressing a mold having a concave portion corresponding to the convex portion to the surface of the electrophotographic photosensitive member and performing shape transfer. .

  When the surface layer of the electrophotographic photosensitive member is polished to give roughness, a polishing tool is brought into contact with the electrophotographic photosensitive member and either one or both are moved relatively to polish the surface of the electrophotographic photosensitive member Roughness can be given by doing. Examples of the polishing tool include a polishing member in which a layer in which polishing abrasives are dispersed in a binder resin is provided on a base material.

<Method of forming a recess on the circumferential surface of the electrophotographic photosensitive member>
A concave portion can be formed on the peripheral surface of the electrophotographic photosensitive member by pressing a mold having a convex portion corresponding to the concave portion to be formed onto the peripheral surface of the electrophotographic photosensitive member and performing shape transfer.

FIG. 5 shows an example of a pressure transfer shape transfer processing apparatus for forming a recess on the peripheral surface of the electrophotographic photosensitive member.
According to the pressure transfer type transfer processing apparatus shown in FIG. 5, the mold 5-2 is continuously brought into contact with the peripheral surface of the electrophotographic photosensitive member 5-1 which is a workpiece while being rotated, while being pressed. Recesses and flat portions can be formed on the circumferential surface of the electrophotographic photosensitive member 5-1.
Examples of the material of the pressure member 5-3 include metals, metal oxides, plastics, glass and the like. Among these, stainless steel (SUS) is preferable from the viewpoint of mechanical strength, dimensional accuracy, and durability. The mold 5-2 is installed on the upper surface of the pressure member 5-3. Further, a mold 5-2 is formed on the circumferential surface of the electrophotographic photosensitive member 5-1 supported by the support member 5-4 by a support member (not shown) and a pressure system (not shown) installed on the lower surface side. The contact can be made at a predetermined pressure. The support member 5-4 may be pressed against the pressure member 5-3 with a predetermined pressure, or the support member 5-4 and the pressure member 5-3 may be pressed against each other.

In the example shown in FIG. 5, by moving the pressing member 5-3 in a direction perpendicular to the axial direction of the electrophotographic photosensitive member 5-1, the electrophotographic photosensitive member 5-1 is driven or rotated while being driven. It is an example which processes a surrounding surface continuously. Further, the pressure member 5-3 is fixed, and the support member 5-4 is moved in a direction perpendicular to the axial direction of the electrophotographic photoreceptor 5-1, or the support member 5-4 and the pressure member 5 are used. The peripheral surface of the electrophotographic photosensitive member 5-1 can also be processed continuously by moving both of -3.
In addition, it is preferable to heat the mold 5-2 and the electrophotographic photosensitive member 5-1 from the viewpoint of efficiently performing shape transfer.

For example, the mold 5-2 has a fine surface processed metal or resin film, a pattern obtained by patterning a resist on the surface of a silicon wafer or the like, a resin film in which fine particles are dispersed, or a fine surface shape. What gave metal coating to the resin film etc. are mentioned.
Further, from the viewpoint of making the pressure applied to the electrophotographic photosensitive member 5-1 uniform, it is preferable to place an elastic body between the mold 5-2 and the pressing member 5-3.
The concave portions, flat portions, convex portions, and the like of the peripheral surface of the electrophotographic photosensitive member can be observed using a microscope such as a laser microscope, an optical microscope, an electron microscope, or an atomic force microscope.

<Abrasive tool used for mechanical polishing>
Mechanical polishing can use known means. Generally, the polishing tool is brought into contact with the electrophotographic photosensitive member, and either one or both are moved relatively to polish the surface of the electrophotographic photosensitive member. The polishing tool is a polishing member provided with a layer in which polishing abrasives are dispersed in a binder resin on a base material.

  As the abrasive grains, for example, particles of aluminum oxide, chromium oxide, diamond, iron oxide, cerium oxide, corundum, silica, silicon nitride, boron nitride, molybdenum carbide, silicon carbide, tungsten carbide, titanium carbide, silicon oxide, etc. It can be mentioned. The particle diameter of the abrasive grains is preferably 0.01 μm or more and 50 μm or less, and more preferably 1 μm or more and 15 μm or less. When the particle diameter of the abrasive grains is too small, the polishing power becomes weak, and it becomes difficult to increase the F / C ratio of the outermost surface of the electrophotographic photosensitive member. These abrasive grains can be used alone or in combination of two or more. In the case of mixing two or more kinds, the material and the particle diameter may be different or the same.

  As a binder resin for dispersing abrasive grains used in a polishing tool, known thermoplastic resins, thermosetting resins, reactive resins, electron beam curing resins, ultraviolet curing resins, visible light curing resins and flameproof resins It can be used. Examples of the thermoplastic resin include vinyl chloride resin, polyamide resin, polyester resin, polycarbonate resin, amino resin, styrene-butadiene copolymer, urethane elastomer and polyamide-silicone resin. Examples of the thermosetting resin include phenol resin, phenoxy resin, epoxy resin, polyurethane resin, polyester resin, silicone resin, melamine resin and alkyd resin. In addition, an isocyanate-based curing agent may be added to the thermoplastic resin.

  The film thickness of the layer formed by dispersing the abrasive grains in the binder resin of the polishing tool is preferably 1 μm or more and 100 μm or less. If the film thickness is too thick, the film thickness unevenness tends to occur, and as a result, the unevenness of the surface roughness of the object to be polished becomes a problem. On the other hand, if the film thickness is too thin, falling off of the abrasive grains tends to occur.

  The shape of the substrate of the polishing tool is not particularly limited. In the embodiment of the present example, a sheet-like substrate is used to efficiently polish a cylindrical electrophotographic photosensitive member, but other shapes may be used. The material of the base of the polishing tool (hereinafter, the polishing tool of this example is also described as a polishing sheet) is not particularly limited. For example, as a material of a sheet-like base material, paper, woven fabric, non-woven fabric, plastic film, etc. may be mentioned.

  The polishing tool can be obtained by applying and drying a coating liquid obtained by mixing and dispersing the above-mentioned abrasive grains, a binder resin, and a solvent capable of dissolving the binder resin on a substrate.

<Polishing device>
An example of the apparatus for polishing an electrophotographic photosensitive member of this embodiment is shown in FIG.
FIG. 3 shows an apparatus for polishing a cylindrical electrophotographic photosensitive member using a polishing sheet. In FIG. 3, the polishing sheet 301 is wound around a hollow shaft 306, and a motor (not shown) is arranged to apply tension to the polishing sheet 301 in the direction opposite to the direction in which the polishing sheet 301 is fed. ing. The polishing sheet 301 is fed in the direction of the arrow, passes through the backup roller 303 via the guide rollers 302a and 302b, and the polishing sheet 301 after polishing is taken up by the motor (not shown) via the guide rollers 302c and 302d. It is taken up. Polishing is performed by always pressing the polishing sheet 301 against the object to be processed (electrophotographic photosensitive member before polishing) 304. Since the polishing sheet 301 is often insulating, it is preferable to use a material that is grounded to the ground or that has conductivity at a portion in contact with the polishing sheet 301.

  The feed speed of the polishing sheet 301 is preferably 10 mm / min or more and 1000 mm / min or less. If the feed amount is small, adhesion of the binder resin to the surface of the polishing sheet 301 may result in deep scratches on the surface of the object to be treated 304.

  The object to be treated 304 is placed at a position facing the backup roller 303 via the polishing sheet 301. The backup roller 303 is preferably an elastic body from the viewpoint of improving the uniformity of the surface roughness of the object to be treated 304. At this time, the object to be treated 304 and the backup roller 303 are pressed with a desired set value for a predetermined time through the polishing sheet 301, and the surface of the object to be treated 304 is polished. The rotation direction of the object to be processed 304 may be the same as or opposite to the direction in which the polishing sheet 301 is sent. In addition, the rotation direction may be changed in the middle of polishing.

Pressing pressure to the target object 304 of backup roller 303, depending on the hardness and polishing time of the backup roller 303, 0.005 N / ^{m 2} or more 15N / ^{m 2} or less.

  As for the surface roughness of the electrophotographic photosensitive member, the feed speed of the polishing sheet 301, the pressing pressure of the backup roller 303, the abrasive grain type of the polishing sheet, the film thickness of the binder resin of the polishing sheet, the thickness of the substrate, etc. are appropriately selected. It can adjust by doing.

[Process cartridge, electrophotographic apparatus]
The process cartridge of the present invention integrally supports the above-described electrophotographic photosensitive member and at least one unit selected from the group consisting of a charging unit, a developing unit, a transfer unit, and a cleaning unit. It is characterized in that it is detachable from the main body.
An electrophotographic apparatus according to the present invention is characterized by including the electrophotographic photosensitive member, the charging unit, the exposure unit, the developing unit, and the transfer unit described above.
Furthermore, in the electrophotographic apparatus according to the present invention, as the charging means, the charging roller disposed so as to abut on the above-described electrophotographic photosensitive member, and by applying only a DC voltage to the charging roller The electrophotographic photosensitive member is characterized by comprising means for charging.

FIG. 2 shows an example of a schematic configuration of an electrophotographic apparatus having a process cartridge provided with an electrophotographic photosensitive member.
A cylindrical electrophotographic photosensitive member 1 is rotationally driven around an axis 2 in the direction of the arrow at a predetermined peripheral speed. The surface of the electrophotographic photosensitive member 1 is charged by the charging unit 3 to a predetermined positive or negative potential. Although the roller charging system using a roller type charging member is shown in the drawing, a charging system such as a corona charging system, a proximity charging system, or an injection charging system may be employed. In the case of the roller charging method, there are DC charging method in which the voltage applied to the roller type charging member is only DC voltage and AC / DC charging method in which AC voltage is superimposed on DC voltage. From the viewpoint of the above, the DC charging method is preferable. Exposure light 4 is irradiated from the exposure means (not shown) on the charged surface of the electrophotographic photosensitive member 1 to form an electrostatic latent image corresponding to the target image information. The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed by the toner contained in the developing means 5, and a toner image is formed on the surface of the electrophotographic photosensitive member 1. The toner image formed on the surface of the electrophotographic photosensitive member 1 is transferred to the transfer material 7 by the transfer means 6. The transfer material 7 to which the toner image has been transferred is conveyed to the fixing means 8, subjected to the fixing process of the toner image, and printed out of the electrophotographic apparatus. The electrophotographic apparatus may have a cleaning means 9 for removing deposits such as toner remaining on the surface of the electrophotographic photosensitive member 1 after transfer. In addition, a so-called cleaner-less system may be used in which the attached matter is removed by a developing means or the like without separately providing a cleaning means. The electrophotographic apparatus may have a diselectrification mechanism for diselectrifying the surface of the electrophotographic photosensitive member 1 with pre-exposure light 10 from a pre-exposure means (not shown). Further, in order to attach and detach the process cartridge 11 of the present invention to the electrophotographic apparatus main body, a guide means 12 such as a rail may be provided.
The electrophotographic photosensitive member of the present invention can be used for a laser beam printer, an LED printer, a copying machine, a facsimile, a composite machine of these, and the like.

  Hereinafter, the present invention will be described in more detail using examples and comparative examples. The present invention is not limited at all by the following examples unless the gist is exceeded. In the following description of the examples, "part" is on a mass basis unless otherwise noted.

[Method of producing strontium titanate particles]
<Production Example of Particle S-1>
A hydrous titanium oxide slurry obtained by hydrolyzing an aqueous solution of titanyl sulfate was washed with an aqueous alkali solution.
Next, hydrochloric acid was added to the water-containing titanium oxide slurry to adjust its pH to 0.7 to obtain a titania sol dispersion.
A 1.1-fold molar amount of an aqueous solution of strontium chloride was added to 2.2 mol (converted to titanium oxide) of the titania sol dispersion, and the mixture was charged into a reaction vessel and purged with nitrogen gas.
Furthermore, pure water was added so as to be 1.1 mol / L in terms of titanium oxide.
Next, after stirring and mixing and heating to 90 ° C., 440 mL of a 10 N aqueous solution of sodium hydroxide was added over 15 minutes while applying ultrasonic vibration, and then reaction was performed for 20 minutes.
Pure water of 5 ° C. was added to the slurry after the reaction to rapidly cool it to 30 ° C. or less, and then the supernatant liquid was removed.
Furthermore, after adding hydrochloric acid aqueous solution of pH 5.0 to the said slurry and stirring for 1 hour, washing with pure water was repeated. Furthermore, it was neutralized with sodium hydroxide, filtered with a Nutche, and washed with pure water. The obtained cake was dried to obtain particles S-1.

<Production Example of Particle S-2>
A 1.0-fold molar amount of a strontium chloride aqueous solution was added to 2.6 mol (in terms of titanium oxide) of the titania sol dispersion, and the mixture was placed in a reaction vessel and purged with nitrogen gas. Furthermore, pure water was added so that the titanium oxide concentration would be 1.3 mol / L.
Next, after stirring and mixing and heating to 95 ° C., 300 mL of a 15 N aqueous solution of sodium hydroxide was added over 5 minutes while applying ultrasonic vibration, and then reaction was performed for 20 minutes. Pure water of 5 ° C. was added to the slurry after the reaction to rapidly cool it to 30 ° C. or less, and then the supernatant liquid was removed. Furthermore, after adding hydrochloric acid aqueous solution of pH 5.0 to the said slurry and stirring for 1 hour, washing with pure water was repeated. Furthermore, it was neutralized with sodium hydroxide, filtered with a Nutche, and washed with pure water. The obtained cake was dried to obtain particles S-2.

<Production Example of Particle S-3>
A 1.1-fold molar amount of an aqueous solution of strontium chloride was added to 2.0 mol (in terms of titanium oxide) of the titania sol dispersion, and the mixture was placed in a reaction vessel and purged with nitrogen gas. Furthermore, pure water was added so that the titanium oxide concentration would be 1.0 mol / L.
Next, after stirring and mixing and heating to 85 ° C., 800 mL of a 5 N aqueous solution of sodium hydroxide was added over 20 minutes while applying ultrasonic vibration, and then reaction was performed for 20 minutes. Pure water of 5 ° C. was added to the slurry after the reaction to rapidly cool it to 30 ° C. or less, and then the supernatant liquid was removed. Furthermore, after adding hydrochloric acid aqueous solution of pH 5.0 to the said slurry and stirring for 1 hour, washing with pure water was repeated. Furthermore, it was neutralized with sodium hydroxide, filtered with a Nutche, and washed with pure water. The obtained cake was dried to obtain particles S-3.

<Production Example of Particle S-4>
A 1.1-fold molar amount of a strontium chloride aqueous solution was added to 1.8 moles (in terms of titanium oxide) of the titania sol dispersion, and the mixture was charged into a reaction vessel and purged with nitrogen gas. Furthermore, pure water was added so that the titanium oxide concentration would be 0.9 mol / L.
Next, after stirring and mixing and heating to 85 ° C., 576 mL of a 5 N aqueous solution of sodium hydroxide was added over 5 minutes while applying ultrasonic vibration, and then reaction was performed for 20 minutes. Pure water of 5 ° C. was added to the slurry after the reaction to rapidly cool it to 30 ° C. or less, and then the supernatant liquid was removed. Furthermore, after adding hydrochloric acid aqueous solution of pH 5.0 to the said slurry and stirring for 1 hour, washing with pure water was repeated. Furthermore, it was neutralized with sodium hydroxide, filtered with a Nutche, and washed with pure water. The obtained cake was dried to obtain particles S-4.

<Production Example of Particle S-5>
A 1.1-fold molar amount of a strontium chloride aqueous solution was added to 1.8 moles (in terms of titanium oxide) of the titania sol dispersion, and the mixture was charged into a reaction vessel and purged with nitrogen gas. Furthermore, pure water was added so that the titanium oxide concentration would be 0.9 mol / L.
Next, after stirring and mixing and heating to 80 ° C., 792 mL of a 5 N aqueous solution of sodium hydroxide was added over 40 minutes while applying ultrasonic vibration, and then reaction was performed for 20 minutes. After the reaction slurry was cooled to 30 ° C. or lower, the supernatant was removed. Furthermore, after adding hydrochloric acid aqueous solution of pH 5.0 to the said slurry and stirring for 1 hour, washing with pure water was repeated. Furthermore, it was neutralized with sodium hydroxide, filtered with a Nutche, and washed with pure water. The obtained cake was dried to obtain particles S-5.

<Production Example of Particle S-6>
A 1.2-fold molar amount of a strontium chloride aqueous solution was added to 1.4 mol (in terms of titanium oxide) of the titania sol dispersion, and the mixture was charged into a reaction vessel and purged with nitrogen gas. Furthermore, pure water was added so that the titanium oxide concentration would be 0.7 mol / L.
Next, after stirring and mixing and heating to 80 ° C., 1100 mL of a 3N aqueous solution of sodium hydroxide was added over 40 minutes while applying ultrasonic vibration, and then reaction was performed for 20 minutes. After the reaction slurry was cooled to 30 ° C. or lower, the supernatant was removed. Furthermore, after adding hydrochloric acid aqueous solution of pH 5.0 to the said slurry and stirring for 1 hour, washing with pure water was repeated. The obtained cake was dried to obtain particles S-6.

<Production Example of Particle S-7>
A 1.2-fold molar amount of an aqueous solution of strontium chloride was added to 1.0 mol (in terms of titanium oxide) of the titania sol dispersion, and the mixture was placed in a reaction vessel and purged with nitrogen gas. Further, pure water was added so that the concentration of titanium oxide was 0.5 mol / L.
Next, after stirring and mixing and heating to 70 ° C., 1100 mL of 2N aqueous sodium hydroxide solution was added over 40 minutes while applying ultrasonic vibration, and then reaction was performed for 20 minutes. After the reaction slurry was cooled to 30 ° C. or lower, the supernatant was removed. Furthermore, after adding hydrochloric acid aqueous solution of pH 5.0 to the said slurry and stirring for 1 hour, washing with pure water was repeated. The obtained cake was dried to obtain particles S-7.

<Production Example of Particle S-8>
A 1.2-fold molar amount of an aqueous solution of strontium chloride was added to 1.0 mol (in terms of titanium oxide) of the titania sol dispersion, and the mixture was placed in a reaction vessel and purged with nitrogen gas. Further, pure water was added so that the concentration of titanium oxide was 0.5 mol / L.
Next, after stirring and mixing and warming to 70 ° C., 1200 mL of 2N aqueous sodium hydroxide solution was added over 240 minutes, and then reaction was performed for 60 minutes. After the reaction slurry was cooled to 30 ° C. or lower, the supernatant was removed. Further, a hydrochloric acid aqueous solution having a pH of 5.0 was added to the slurry, and the mixture was stirred for 1 hour, then washed with pure water and dried to obtain particles S. The half value width of the particles S was 0.15. Further, the particles S were put into an automatic discharge ball mill (manufactured by Eishin Co., Ltd.) together with alumina balls of 4 mm, and stirred for 200 hours. Thereafter, alumina balls were removed and washed to obtain particles S-8.

<Production Example of Particle S-9>
A 1.2-fold molar amount of an aqueous solution of strontium chloride was added to 0.6 mol (in terms of titanium oxide) of the titania sol dispersion, and the mixture was placed in a reaction vessel and purged with nitrogen gas. Furthermore, pure water was added so that the titanium oxide concentration would be 0.3 mol / L.
Next, after stirring and mixing and warming to 80 ° C., 750 mL of 2N aqueous sodium hydroxide solution was added over 480 minutes, and then reaction was performed for 20 minutes. After the reaction slurry was cooled to 30 ° C. or lower, the supernatant was removed. Furthermore, the slurry was washed with pure water, and the obtained cake was dried to obtain particles S-9.

<Production Example of Particle S-10>
A 1.2-fold molar amount of an aqueous solution of strontium chloride was added to 0.6 mol (in terms of titanium oxide) of the titania sol dispersion, and the mixture was charged into a reaction vessel and purged with nitrogen gas. Furthermore, after 0.05 mol of aluminum sulfate was added, pure water was added so that the titanium oxide concentration would be 0.3 mol / L.
Next, after stirring and mixing and heating to 80 ° C., 450 mL of 2N aqueous solution of sodium hydroxide was added over 5 minutes while applying ultrasonic vibration, and then reaction was performed for 20 minutes. Pure water of 5 ° C. was added to the slurry after the reaction to rapidly cool it to 30 ° C. or less, and then the supernatant liquid was removed. Furthermore, the slurry was washed with pure water, and the obtained cake was dried to obtain particles S-10.

<Production Example of Particle S-11>
A 1.2-fold molar amount of an aqueous solution of strontium chloride was added to 0.6 mol (in terms of titanium oxide) of the titania sol dispersion, and the mixture was placed in a reaction vessel and purged with nitrogen gas. Furthermore, pure water was added so that the titanium oxide concentration would be 0.3 mol / L.
Next, after stirring and mixing and warming to 80 ° C., 750 mL of 2N aqueous sodium hydroxide solution was added over 540 minutes, and then reaction was performed for 20 minutes. After the reaction slurry was cooled to 30 ° C. or lower, the supernatant was removed. Furthermore, the slurry was washed with pure water, and the obtained cake was dried to obtain particles S-11.

<Production Example of Particle S-12>
A 1.2-fold molar amount of an aqueous solution of strontium chloride was added to 0.4 mol (in terms of titanium oxide) of the titania sol dispersion, and the mixture was placed in a reaction vessel and purged with nitrogen gas. Furthermore, pure water was added so that the titanium oxide concentration would be 0.2 mol / L.
Next, after stirring and mixing and warming to 70 ° C., 600 mL of 2N aqueous sodium hydroxide solution was added over 660 minutes, and then reaction was performed for 20 minutes. After the reaction slurry was cooled to 30 ° C. or lower, the supernatant was removed. Furthermore, the slurry was washed with pure water, and the obtained cake was dried to obtain particles S-12.

<Production Example of Particle S-13>
A 1.2-fold molar amount of an aqueous solution of strontium chloride was added to 0.6 mol (in terms of titanium oxide) of the titania sol dispersion, and the mixture was placed in a reaction vessel and purged with nitrogen gas. Furthermore, pure water was added so that the titanium oxide concentration would be 0.3 mol / L.
Next, after stirring and mixing and warming to 80 ° C., 750 mL of 2N aqueous sodium hydroxide solution was added over 600 minutes, and then reaction was performed for 20 minutes. After the reaction slurry was cooled to 30 ° C. or lower, the supernatant was removed. Furthermore, the slurry was washed with pure water, and the obtained cake was dried to obtain particles S-13.

<Production Example of Particle S-14>
A 1.3-fold molar amount of an aqueous solution of strontium chloride was added to 0.6 mol (in terms of titanium oxide) of the titania sol dispersion, and the mixture was placed in a reaction vessel and purged with nitrogen gas. Further, pure water was added so as to have a titanium oxide concentration of 0.1 mol / L.
Next, after stirring and mixing and warming to 70 ° C., 750 mL of 2N aqueous sodium hydroxide solution was added over 900 minutes, and then reaction was performed for 20 minutes. After the reaction slurry was cooled to 30 ° C. or lower, the supernatant was removed. Furthermore, the slurry was washed with pure water, and the obtained cake was dried to obtain particles S-14.

<X-ray diffraction measurement of particles>
The X-ray diffraction measurement of the produced particles S-1 to S-14 was performed using MiniFlex 600 (manufactured by RIGAKU Co., Ltd.) under the following conditions.
The measurement sample was mounted while being lightly pressed on a non-reflection sample plate (made by RIGAKU) having no diffraction peak in the measurement range so that the powder remains flat. When flat, the sample plate was set in the apparatus and measured.
[Measurement conditions of X-ray diffraction]
Tube: Cu
Parallel beam optics voltage: 40kV
Current: 15 mA
Starting angle: 3 °
End angle: 60 °
Sampling width: 0.02 °
Scanning speed: 10.00 ° / min
Divergence slit: 0.625 deg
Scattering slit: 8.0 mm
Light receiving slit: 13.0 mm (Open)
In the X-ray diffraction pattern obtained from the measurement, the half width of the peak appearing at the position of 2θ = 32.20 ± 0.20 was calculated (θ is a Bragg angle). The calculation of the half width of the peak was performed using Rigaku analysis software "PDXL". The results are shown in Table 1.

<Measurement of Average Particle Size of Primary Particles>
The average particle diameter (number average particle diameter) of the primary particles of the particles S-1 to S-14 manufactured as described above is observed with a transmission electron microscope “H-800” (manufactured by Hitachi, Ltd.) and is up to 2,000,000 times In the enlarged field of view, the major diameter of 100 primary particles was measured to determine the average particle diameter of the primary particles. The results are shown in Table 1.

[Production example of surface-treated strontium titanate particles]
<Production example of surface-treated particle S-1A>
100 parts of the particle S-1 produced above is stirred and mixed with 500 parts of toluene, to which N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (trade name: KBM602, Shin-Etsu) as a silane coupling agent 2 parts of Chemical Industry Co., Ltd. product) was added and it was made to stir for 6 hours. Thereafter, toluene was distilled off under reduced pressure, and the residue was heated and dried at 130 ° C. for 6 hours to obtain surface-treated particles S-1A.

<Production example of surface-treated particle S-1B>
In the production example of the surface-treated particle S-1A, the surface-treated particle S- is the same as the production example of the particle S-1A except that the addition amount of the silane coupling agent is changed to 0.75 parts. Manufactured 1B.

<Production example of surface-treated particles S-1C>
In the production example of the surface-treated particle S-1A, the surface-treated particle S-1C is prepared in the same manner as the production example of the particle S-1A except that the addition amount of the silane coupling agent is changed to 5 parts. Manufactured.

<Production example of surface-treated particles S-1D>
In the production example of surface-treated particles S-1A, the silane coupling agent was changed to N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (trade name: KBM 603, Shin-Etsu Chemical Co., Ltd. product) The surface-treated particles S-1D were produced in the same manner as in the production example of the particles S-1A except for the above.

<Production example of surface-treated particles S-1E>
In the production example of the surface-treated particle S-1A, the particle S- is used except that the silane coupling agent is changed to 5 parts of isobutyltrimethoxysilane (trade name: Z-2306, manufactured by Toray Dow Corning Co., Ltd.). Surface-treated particles S-1E were produced in the same manner as in Production Example 1A.

<Production example of surface-treated particles S-1F>
In the production example of surface-treated particles S-1A, particles S- were obtained except that the silane coupling agent was changed to 5 parts of trifluoropropyl methoxysilane (trade name: KBM-7103, manufactured by Shin-Etsu Chemical Co., Ltd.). Surface-treated particles S-1F were produced in the same manner as in Production Example 1A.

<Production example of surface-treated particles S-1G>
Example of preparation of particle S-1A, except that in the preparation example of surface-treated particle S-1A, the silane coupling agent is changed to 4.6 parts of isobutyltrimethoxysilane and 4.6 parts of trifluoropropylmethoxysilane Similar to the above, surface-treated particles S-1G were produced.

<Production example of surface-treated particles S-2A to S-14A>
In the production example of the surface-treated particle S-1A, the surface-treated particle S is the same as the production example of the particle S-1A except that the particle S-1 is changed to the particle S-2 to S-14. -2A to S-14A were manufactured.

Example A1
As a support (conductive support), an aluminum cylinder having a length of 357.5 mm, a thickness of 0.7 mm and an outer diameter of 30 mm was prepared. The surface of the prepared aluminum cylinder was cut using a lathe.
As cutting conditions, using a cutting tool of R0.1, machining was performed by continuously changing the spindle rotational speed = 10000 rpm and the feeding speed of the cutting tool in the range of 0.03 to 0.06 mm / rpm.

Next, 15 parts of butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 15 parts of blocked isocyanate (trade name: Sumidure 3175, manufactured by Sumika Bayer Urethane Co., Ltd.) as a polyol resin It was dissolved in a mixed solution of 300 parts of methyl ethyl ketone and 300 parts of 1-butanol.
To this solution, 120 parts of particle S-1A as strontium titanate particles and 1.2 parts of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) as an additive are added, and the diameter is set to 0 Dispersed for 3 hours under an atmosphere of 23 ± 3 ° C. in a sand mill using glass beads of 8 mm.
After dispersion, 0.01 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.) was added to the dispersion and stirred to obtain a coating liquid for undercoat layer.
The obtained undercoat layer coating solution was dip-coated on the support and dried for 30 minutes at 160 ° C. to form an undercoat layer having a thickness of 2.0 μm.

Next, 20 parts of hydroxygallium phthalocyanine crystal (charge generation material) having a strong peak at Bragg angles 2θ ± 0.2 °, 7.4 ° and 28.2 ° in CuKα characteristic X-ray diffraction, 0.2 parts of calixarene compound shown in A), 10 parts of polyvinyl butyral resin (trade name: S-Lec BX-1, manufactured by Sekisui Chemical Co., Ltd.), and 600 parts of cyclohexanone, using 1 mm diameter glass beads After being placed in a sand mill and dispersed for 4 hours, 600 parts of ethyl acetate was added to prepare a coating solution for charge generation layer.
The coating solution for charge generation layer was dip-coated on the undercoat layer, and the obtained coating film was dried at 80 ° C. for 15 minutes to form a charge generation layer having a film thickness of 0.19 μm.

Next, 60 parts of a compound (charge transport substance) represented by the following formula (B), 30 parts of a compound (charge transport substance) represented by the following formula (C), 10 parts of a compound represented by the following formula (D) 100 parts of resin (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics Co., Ltd., bisphenol Z type polycarbonate), 0.02 part of polycarbonate (viscosity average molecular weight Mv: 20000) represented by the following formula (E) A charge transport layer coating solution was prepared by dissolving in a mixed solvent of 600 parts of xylene and 200 parts of dimethoxymethane.
The coating solution for charge transport layer was dip-coated on the charge generation layer to form a coating film, and the obtained coating film was dried at 100 ° C. for 30 minutes to form a charge transport layer having a film thickness of 18 μm. .

この保護層用塗布液を上記電荷輸送層上に浸漬塗布し、得られた塗膜を５分間４０℃で乾燥させた。乾燥後、窒素雰囲気下にて、加速電圧７０ＫＶ、吸収線量１５ｋＧｙの条件で１．６秒間電子線を塗膜に照射した。その後、窒素雰囲気下にて、塗膜の温度が１３５℃になる条件で１５秒間加熱処理を行った。なお、電子線の照射から１５秒間の加熱処理までの酸素濃度は１５ｐｐｍであった。次に、大気中において、塗膜が１０５℃になる条件で１時間加熱処理を行い、膜厚５μｍである保護層を形成した。このようにして凹部形成前の電子写真感光体を作製した。 Next, a resin having a repeating structural unit represented by the following formula (M1) and a repeating structural unit represented by the following formula (M2) (weight average molecular weight: 130,000, copolymerization ratio (M1) / (M2) = 1 / 1 (molar ratio): 1.65 parts, 40 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeorora H, manufactured by Nippon Zeon Co., Ltd.) and 1 -It melt | dissolved in the mixed solvent of 55 parts of propanol. Thereafter, a solution obtained by adding 30 parts of tetrafluoroethylene resin powder (trade name: Rubron L-2, manufactured by Daikin Industries, Ltd.) was added to a high-pressure disperser (trade name: Microfluidizer M-110EH, US Microfluidics ) To obtain a dispersion.
Thereafter, 52.0 parts of a hole transporting compound represented by the following formula (F), 16.0 parts of a compound represented by the following formula (G) (Alonix M-315, manufactured by Toagosei Co., Ltd.), H) 2.0 parts of a compound (manufactured by Sigma-Aldrich), 0.75 parts of a siloxane-modified acrylic compound (BYK-3550, manufactured by Big Chemie Japan KK), 1,1,2,2,3,3, 3 Then, 35 parts of 4-heptafluorocyclopentane and 15 parts of 1-propanol are added to the dispersion, followed by filtration with a polyflon filter (trade name: PF-040, manufactured by Advantec Toyo Co., Ltd.), and a coating solution for a protective layer Was prepared.

The coating solution for protective layer was dip-coated on the charge transport layer, and the obtained coating film was dried at 40 ° C. for 5 minutes. After drying, the coating film was irradiated with an electron beam for 1.6 seconds under conditions of an acceleration voltage of 70 KV and an absorbed dose of 15 kGy in a nitrogen atmosphere. After that, heat treatment was performed for 15 seconds under the condition that the temperature of the coating film becomes 135 ° C. in a nitrogen atmosphere. The oxygen concentration from the electron beam irradiation to the heat treatment for 15 seconds was 15 ppm. Next, in the air, heat treatment was performed for 1 hour under the condition that the coating film reached 105 ° C., and a protective layer having a film thickness of 5 μm was formed. Thus, an electrophotographic photosensitive member before the formation of the concave portion was produced.

[Formation of concave portion by mold pressure transfer shape transfer]
Next, a die member (mold) was placed in a pressure contact shape transfer processing apparatus, and surface processing was performed on the produced electrophotographic photosensitive member before the formation of the concave portion.
Specifically, the mold shown in FIG. 4 was placed in the press-contact transfer apparatus having the configuration shown generally in FIG. 5, and the surface processing was performed on the produced electrophotographic photosensitive member before forming the concave portion. FIG. 4 is a view showing molds used in Examples and Comparative Examples. FIG. 4 (a) is a top view schematically showing a mold, and FIG. 4 (b) is a schematic cross-sectional view in the axial direction of the electrophotographic photosensitive member of the convex portion of the mold ). FIG. 4C is a cross-sectional view of the convex portion of the mold in the circumferential direction of the electrophotographic photosensitive member (cross-sectional view taken along the line C-C in FIG. 4A). The mold shown in FIG. 4 has a maximum width (the maximum width in the axial direction of the electrophotographic photosensitive member when the protrusions on the mold are viewed from above) X: 50 μm, maximum length (convex on the mold When viewed from above, Y: 75 μm, area ratio 56%, height H: 4 μm. The area ratio is the ratio of the area of the convexes to the entire surface when the mold is viewed from above. At the time of processing, the temperatures of the electrophotographic photosensitive member and the mold were controlled such that the temperature of the surface of the electrophotographic photosensitive member was 120 ° C. Then, while pressing the electrophotographic photosensitive member and the pressing member against the mold at a pressure of 7.0 MPa, the electrophotographic photosensitive member is rotated in the circumferential direction, and the concave portion is formed on the entire surface layer (circumferential surface) of the electrophotographic photosensitive member. It formed.

As described above, one electrophotographic photosensitive member of Example A1 was produced for each of evaluation of electrical characteristics and X-ray diffraction measurement.
[Evaluation of electrophotographic photosensitive member]
<Electrical Characteristic Evaluation 1 of Electrophotographic Photoreceptor>
As the electrical property evaluation 1 of the electrophotographic photosensitive member, a modified machine of an electrophotographic apparatus imageRUNNER ADVANCE C3330 manufactured by Canon Inc. was used. The evaluation was performed using a method of applying a DC voltage to a roller-type contact charging member (charging roller) as the charging means.
The evaluation device was installed in an environment of temperature 23 ° C. and humidity 50% RH. The measurement of the surface potential of the electrophotographic photosensitive member was performed by removing the developing cartridge from the evaluation device and inserting the potential measuring device therein. The potential measuring device is configured by disposing a potential measuring probe at the developing position of the developing cartridge, and the position of the potential measuring probe is at the center of the electrophotographic photosensitive member in the generatrix direction.

As the evaluation of the chargeability, the surface potential (dark area potential) Vd1 of the electrophotographic photosensitive member when a DC voltage of -1500 V was applied to the charging member (charging roller) was evaluated. The results are shown in Table 2.
The chargeability is ranked A if the absolute value | Vd1 | of the dark portion potential Vd1 measured under the above evaluation conditions is 750 V or more; Rank B if it is 700 V or more; Rank C if it is 650 V or more; The case was evaluated as rank D.

Next, the voltage applied to the charging member (charging roller) was adjusted so that the dark area potential Vd1 was −700V. The amount of laser light was adjusted so that the bright part potential Vl1 was -200 V when irradiated with a laser beam having a wavelength of 780 nm, and the residual potential Vr1 after continuous output of 10 sheets of solid black images was evaluated. The results are shown in Table 2.
The residual potential is evaluated as rank A if the absolute value | Vr1 | of residual potential Vr1 measured under the above evaluation conditions is 70 V or less, rank B if it is 100 V or less, and rank C if it is larger than 100 V did.

<X-ray diffraction measurement of undercoat layer>
First, the layers above the charge generation layer were removed from the photosensitive member prepared for X-ray diffraction measurement using methyl ethyl ketone and methanol.
Next, the subbing layer is cut out using a cutter knife, and the cut out subbing layer is powdered using a mortar and then placed on a non-reflective sample plate (made by RIGAKU) while lightly pressing so as to make the powder flat. The The flattened sample was set with the sample plate into the apparatus.
The measurement was performed using MiniFlex 600 (manufactured by RIGAKU Co., Ltd.) under the following conditions.
In the X-ray diffraction pattern obtained from the measurement, the half width of the peak appearing at the position of 2θ = 32.20 ± 0.20 was calculated (θ is a Bragg angle). The calculation of the half width of the peak was performed using Rigaku analysis software "PDXL". The results are shown in Table 2.
[Measurement conditions of X-ray diffraction]
Tube: Cu
Parallel beam optics voltage: 40kV
Current: 15 mA
Starting angle: 3 °
End angle: 60 °
Sampling width: 0.02 °
Scanning speed: 10.00 ° / min
Divergence slit: 0.625 deg
Scattering slit: 8.0 mm
Light receiving slit: 13.0 mm (Open)

Example A2
Example A1, except that 1.2 parts of 2,3,4-trihydroxybenzophenone added to the undercoat layer coating solution were changed to 1.2 parts of alizarin (manufactured by Tokyo Chemical Industry Co., Ltd.) In the same manner as in Example A1, an electrophotographic photosensitive member of Example A2 was produced, and electrical property evaluation and X-ray diffraction measurement were performed. The results are shown in Table 2.

Example A3
In Example A1, except that 1.2 parts of 2,3,4-trihydroxybenzophenone added to the coating solution for undercoat layer is changed to 1.2 parts of 9-fluorenone (manufactured by Tokyo Chemical Industry Co., Ltd.) In the same manner as in Example A1, an electrophotographic photosensitive member of Example A3 was produced, and electrical property evaluation and X-ray diffraction measurement were performed. The results are shown in Table 2.

Example A4
In Example A1, an electrophotographic photosensitive member of Example A4 was produced in the same manner as in Example A1, except that 1.2 parts of 2,3,4-trihydroxybenzophenone to be added to the undercoat layer coating solution was not added. The body was made and electrical characterization and X-ray diffraction measurements were performed. The results are shown in Table 2.

[Examples A5 to A10]
Electrons of Examples A5 to A10 in Example A1 in the same manner as Example A1, except that the strontium titanate particles S-1A used for the undercoating layer coating liquid were changed to particles S-1B to 1G. A photosensitive member was produced and subjected to electrical property evaluation and X-ray diffraction measurement. The results are shown in Table 2.

Example A11
The electrophotographic photosensitive member of Example A11 is prepared in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 are changed to particles S-1. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A12
The electrophotographic photosensitive member of Example A12 is prepared in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 are changed to particles S-4A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A13
The electrophotographic photosensitive member of Example A13 is prepared in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 are changed to particles S-5A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A14
The electrophotographic photosensitive member of Example A14 was produced in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 were changed to particles S-7A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A15
The electrophotographic photosensitive member of Example A15 is the same as Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 are changed to particles S-2A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A16
An electrophotographic photosensitive member of Example A16 was produced in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 were changed to particles S-3A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A17
The electrophotographic photosensitive member of Example A17 was produced in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 were changed to particles S-6A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A18
The electrophotographic photosensitive member of Example A18 is produced in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 are changed to particles S-8A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A19
An electrophotographic photosensitive member of Example A19 is produced in the same manner as in Example A1 except that the silicone oil used for the undercoat layer coating solution is not used in Example A1, and the electric characteristics are evaluated and the X-rays are obtained. Diffraction measurements were made. The results are shown in Table 2.

Example A20
In Example A1, 15 parts of butyral resin and 15 parts of blocked isocyanate used in the coating liquid for undercoat layer are changed to 25 parts of butyral resin and 25 parts of blocked isocyanate, and 120 parts of particle S-1A is converted to 100 parts An electrophotographic photosensitive member of Example A20 was produced in the same manner as in Example A1 except for the change, and the electrical property evaluation and the X-ray diffraction measurement were performed. The results are shown in Table 2.

Example A21
In Example A1, 15 parts of butyral resin and 15 parts of blocked isocyanate used in the coating liquid for undercoat layer are changed to 19 parts of butyral resin and 18.5 parts of blocked isocyanate, and 120 parts of particle S-1A An electrophotographic photosensitive member of Example A21 was produced in the same manner as in Example A1 except that the number of parts was changed to 5 parts, and the electric characteristic evaluation and the X-ray diffraction measurement were performed. The results are shown in Table 2.

Example A22
The electrophotographic photosensitive member of Example A22 was prepared in the same manner as in Example A1, except that 300 parts of methyl ethyl ketone and 300 parts of methyl ethyl ketone used for the undercoat layer coating solution were changed to 600 parts of THF. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A23
An electrophotographic photosensitive member of Example A23 is produced in the same manner as in Example A1, except that the film thickness of 2.0 μm of the undercoat layer in Example A1 is changed to 1.0 μm, and the electric characteristics are evaluated. X-ray diffraction measurement was performed. The results are shown in Table 2.

Example A24
An electrophotographic photosensitive member of Example A24 is produced in the same manner as in Example A1, except that the film thickness of 2.0 μm of the undercoat layer in Example A1 is changed to 5.0 μm, and the electric characteristics are evaluated. X-ray diffraction measurement was performed. The results are shown in Table 2.

Example A25
In Example A1, an electrophotographic photosensitive member of Example A25 is produced in the same manner as in Example A1, except that the undercoat layer is formed by the method described below, and the electrical characteristics are evaluated and the X-ray diffraction measurement is performed. went. The results are shown in Table 2.
27 parts of butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) as a polyol resin, 27 parts of blocked isocyanate (trade name: SUMIDUR 3175, manufactured by Sumika Bayer Urethane Co., Ltd.) 115 parts of methyl ethyl ketone And 1 part of 1-butanol was dissolved in a mixed solution.
To this solution, 135 parts of particle S-1A as strontium titanate particles and 1.35 parts of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) as an additive are added, and the diameter is set to 0 Dispersed for 3 hours under an atmosphere of 23 ± 3 ° C. in a sand mill using glass beads of 8 mm.
After dispersion, 0.02 parts of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.), crosslinked poly (methyl methacrylate) (PMMA) particles (trade name: TECHPOLYMER SSX-103, Sekisui Plastics Co., Ltd.) 9.5 parts was added to the dispersion and stirred to obtain a coating liquid for undercoat layer.
The obtained undercoat layer coating solution was dip-coated on the support and dried for 30 minutes at 160 ° C. to form an undercoat layer having a thickness of 18.0 μm.

Example A26
An electrophotographic photosensitive member of Example A26 is produced in the same manner as in Example A25 except that the film thickness of 18 μm of the undercoat layer is changed to 30.0 μm in Example A25, and the electric characteristics are evaluated and X-rays are obtained. Diffraction measurements were made. The results are shown in Table 2.

Example A27
An electrophotographic photosensitive member of Example A27 was produced in the same manner as Example A1, except that the drying conditions 30 minutes at 160 ° C. for the undercoating layer coating liquid in Example A1 were changed to 20 minutes at 170 ° C. Electrical characterization and X-ray diffraction measurements. The results are shown in Table 2.

Example A28
An electrophotographic photosensitive member of Example A28 was produced in the same manner as Example A1, except that the drying conditions 30 minutes at 160 ° C. for the undercoat layer coating liquid in Example A1 were changed to 50 minutes at 150 ° C. Electrical characterization and X-ray diffraction measurements. The results are shown in Table 2.

Example A29
An electrophotographic photosensitive member of Example A29 was produced in the same manner as in Example A1 except that an aluminum cylinder processed by the method described below was used as a support in Example A1, and the electrical characteristics were evaluated. Evaluation and X-ray diffraction measurements were performed. The results are shown in Table 2.
A cylindrical aluminum cylinder (diameter 30 mm, length 357.5 mm, thickness 0.7 mm) was mounted on a lathe, and with a diamond sintered tool, outer diameter 30.0 ± 0.02 mm, runout accuracy 15 μm, surface roughness Cutting was performed so that Rz = 0.2 μm. At this time, the spindle rotational speed was 3000 rpm, the feed rate of the cutting tool was 0.3 mm / rev, and the processing time was 24 seconds except for the attachment and detachment of the work.
The surface roughness was measured according to JIS B 0601 using a Kosaka Research Institute surface roughness meter surf coder SE3500 with a cutoff of 0.8 mm and a measurement length of 8 mm.
Liquid honing was performed on the obtained aluminum cutting tube under the following conditions using a liquid (wet) honing apparatus.

<Liquid honing conditions>
Abrasive material abrasive particle = spherical alumina bead average particle diameter 30 μm
(Brand name: CB-A30S, manufactured by Showa Denko KK)
Suspension medium = water abrasive / suspension medium = 1/9 (volume ratio)
Rotation speed of aluminum cutting tube = 1.67S ^-1
Air blowing pressure = 0.15 MPa
Gun moving speed = 13.3 mm / sec.
Distance between gun nozzle and aluminum tube = 200 mm
Honing abrasive discharge angle = 45 °
Polishing fluid number of times = 1 (one way)

The cylinder surface roughness after honing was Rmax 2.53 μm, Rz 1.51 μm, Ra 0.23 μm, and Sm 34 μm. Immediately after the wet honing treatment was performed as described above, the aluminum cylinder was once immersed in a dip tank covered with pure water, pulled up, and subjected to pure water shower washing before the cylinder was dried. Thereafter, hot water at 85 ° C. was discharged from the discharge nozzle onto the inner surface of the substrate, and the outer surface was dried. Thereafter, the inner surface of the substrate was dried by natural drying.
The aluminum cylinder surface-treated as described above was used as a support of the electrophotographic photosensitive member.

Example A30
An electrophotographic photosensitive member of Example A30 was produced in the same manner as in Example A1 except that an aluminum cylinder processed by the method described below was used as a support in Example A1, and the electrical characteristics were evaluated. Evaluation and X-ray diffraction measurements were performed. The results are shown in Table 2.
A cylindrical aluminum cylinder was mounted on a lathe, and cutting was performed using a single crystal diamond cutting tool (tip R 20 mm). At this time, the spindle rotational speed was 3000 rpm, and the cutting speed of the cutting tool was 5 mm / sec.

Example A31
An electrophotographic photosensitive member of Example A31 is produced in the same manner as in Example A1 except that the following conductive layer is provided between the support and the undercoat layer in Example A1, and the electric characteristics are evaluated and X Line diffraction measurement was performed. The results are shown in Table 2.
57 parts of titanium oxide particles having a covering layer (trade name: Pastelan LRS, manufactured by Mitsui Mining & Smelting Co., Ltd.), 35 parts of resol-type phenolic resin (trade name: Phenolite J-325, DIC Corporation (old: Dainippon Ltd.) A dispersion was prepared by dispersing 33 parts of 2-methoxy-1-propanol in a sand mill using glass beads with a diameter of 1 mm for 3 hours, manufactured by Ink Chemical Industry Co., Ltd. (methanol solution with solid content of 60%). . The average particle diameter of the powder contained in this dispersion was 0.30 μm.
In this dispersion, 8 parts of silicone resin (trade name: Tospearl 120, Momentive Performance Materials Japan LLC (formerly Toshiba Silicone Co., Ltd.)) was dispersed in 8 parts of 2-methoxy-1-propanol The solution was added. Furthermore, 0.008 part of silicone oil (trade name: SH28PA, Toray Dow Corning Co., Ltd. (old: Toray Silicone Co., Ltd.)) was added.
The dispersion prepared in this manner is applied onto an aluminum cylinder by a dipping method, and the coating is cured by heating for 30 minutes in a hot air dryer adjusted to 150 ° C. to cure the coated film of the dispersion. A 30 μm thick conductive layer was formed.

Example A32
Example A1 was carried out in the same manner as Example A1, except that in the formation of the surface layer (protective layer), the surface layer coating solution (protective layer coating solution) prepared by the method described below was used. The electrophotographic photosensitive member of Example A32 was produced and subjected to electrical property evaluation and X-ray diffraction measurement. The results are shown in Table 2.
100 parts of a compound represented by the above formula (F), 200 parts of 1-propanol, 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeoror H, manufactured by Nippon Zeon Co., Ltd.) 100 parts were mixed and stirred.
Thereafter, the solution was filtered with a polyfluorocarbon filter (trade name: PF-020, manufactured by Advantec Toyo Kaisha, Ltd.) to prepare a coating solution for surface layer (coating solution for protective layer).

Example A33
Example A1 was carried out in the same manner as Example A1, except that in the formation of the surface layer (protective layer), the surface layer coating solution (protective layer coating solution) prepared by the method described below was used. The electrophotographic photosensitive member of Example A33 was produced and subjected to electrical property evaluation and X-ray diffraction measurement. The results are shown in Table 2.
1.5 parts of a fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.), 1,1,2,2,3,3,3,4-heptafluorocyclopentane (trade name: Zeorora H, It was dissolved in a mixed solvent of 45 parts of Nippon Zeon Co., Ltd. and 45 parts of 1-propanol.
Thereafter, a high-pressure dispersing machine (trade name: Microfluidizer M-) is a mixed solution obtained by adding 30 parts of tetrafluoroethylene resin powder (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) to the above solution. A dispersion was obtained by passing through 110EH (manufactured by Microfluidics, Inc.).
Thereafter, 70 parts of the compound represented by the above formula (F), 30 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane and 30 parts of 1-propanol are added to the dispersion, and a polyfluorocarbon filter is obtained. (Brand name: PF-040, manufactured by Advantec Toyo Kaisha, Ltd.) The solution was filtered to prepare a coating solution for surface layer (coating solution for protective layer).

Example A34
In Example A1, an electrophotographic photosensitive member of Example A34 is produced in the same manner as in Example A1, except that the surface processing of the electrophotographic photosensitive member is changed to processing using a polishing apparatus described below. Electrical characterization and X-ray diffraction measurements were performed. The results are shown in Table 2.
The surface of the electrophotographic photosensitive member before surface polishing was polished. Polishing was performed using the polishing apparatus of FIG. 3 under the following conditions.
Feeding speed of polishing sheet: 400 mm / min
Number of revolutions of electrophotographic photosensitive member; 450 rpm
Pushing the electrophotographic photosensitive member to the backup roller; 3.5 mm
Rotation direction of abrasive sheet and electrophotographic photosensitive member; With backup roller; Outer diameter 100 mm, Asker C hardness 25
The polishing sheet A attached to the polishing apparatus was prepared by mixing polishing abrasives used in GC3000 and GC2000 manufactured by Riken Corundum Co., Ltd.
GC 3000 (abrasive sheet surface roughness Ra 0.83 μm)
GC 2000 (abrasive sheet surface roughness Ra 1.45 μm)
Polishing sheet A (abrasive sheet surface roughness Ra 1.12 μm)
The polishing time using the polishing sheet A was 20 seconds.

（式（Ｉ）中、ｍおよびｎは共重合比を示し、ｍ：ｎ＝７：３） Example A35
In Example A1, an electrophotographic photosensitive member of Example A35 is produced in the same manner as in Example A1, except that the surface layer (protective layer) is not provided, and the charge transport layer is formed by the method described below. Electrical characterization and X-ray diffraction measurements were performed. The results are shown in Table 2.
72 parts of a compound represented by the above formula (B) (charge transporting substance),
8 parts of a compound represented by the above formula (D) (charge transport material),
100 parts of a resin having a structure represented by the following formula (I),
1.8 parts of a resin having a structure represented by the following formula (J), 360 parts of o-xylene,
160 parts of methyl benzoate, and
270 parts of dimethoxymethane (methylal) were mixed to prepare a coating solution for charge transport layer.
Next, the coating solution for charge transport layer was dip-coated on the charge generation layer, and the obtained coated film was dried at 125 ° C. for 50 minutes to form a charge transport layer with a film thickness of 20 μm.

(In the formula (I), m and n represent a copolymerization ratio, and m: n = 7: 3)

Example A36
In Example A1, 15 parts of butyral resin and 15 parts of blocked isocyanate used in the coating liquid for undercoat layer are changed to 30 parts of a phenol resin (trade name: Priofen J-325, manufactured by DIC Corporation), An electrophotographic photosensitive member of Example A36 was produced in the same manner as Example A1, except that 300 parts of methyl ethyl ketone and 300 parts of 1-butanol were changed to 300 parts of methanol and 300 parts of 1-methoxy-2-propanol. Electrical characterization and X-ray diffraction measurements. The results are shown in Table 2.

Example A37
In Example A1, 15 parts of butyral resin and 15 parts of blocked isocyanate used for the coating liquid for undercoat layer are changed to 30 parts of alcohol-soluble copolyamide (trade name: Amilan CM 8000, manufactured by Toray Industries, Inc.), An electrophotographic photosensitive member of Example A37 was produced in the same manner as in Example A1 except that 300 parts of methyl ethyl ketone was changed to 300 parts of methanol, and the electric characteristics were evaluated and the X-ray diffraction measurement was performed. The results are shown in Table 2.

Example A38
The electrophotographic photosensitive member of Example A38 was produced in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 were changed to particles S-9A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A39
The electrophotographic photosensitive member of Example A39 was produced in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 were changed to particles S-11A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A40
The electrophotographic photosensitive member of Example A40 is produced in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 are changed to particles S-12A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Example A41
In Example A1, an electrophotographic photosensitive member of Example A41 is produced in the same manner as in Example A1, except that the undercoat layer is formed by the method described below, and the electrical characteristics are evaluated and the X-ray diffraction measurement is performed. went. The results are shown in Table 2.

<Production example of ammonia-reduced niobium oxide particles N-1>
The niobium pentoxide fine powder having an average primary particle diameter of 60 nm was subjected to reduction treatment at 700 ° C. for 6 hours in an ammonia gas flow at a linear flow rate of 3 cm / sec. Subsequently, 10% hydrochloric acid aqueous solution was added to the obtained powder, and the mixture was stirred and allowed to stand. The resulting supernatant was removed, decanted with water twice, and the filtered material was dried. The obtained filtrate was subjected to a grinding treatment step to obtain a powder of particles N-1 having an average primary particle diameter of 60 nm. The elemental ratio of the obtained particles N-1 was analyzed by the following ESCA analysis. The measurement conditions are as follows.
<ESCA analysis>
Device used: ULVAC-PHI VersaProbe II
X-ray source: Al K α 1486.6 eV (25 W 15 kV)
Measurement area: φ 100 μm
Spectral region: 300 × 200 μm, angle 45 °
Pass Energy: 58.70 eV
Step Size: 0.125 eV

From the peak intensity of each element measured under the above conditions, the surface atom concentration (atoms%) is calculated using the relative sensitivity factor provided by ULVAC-PHI. The measurement peak top range of each element adopted is as follows.
O: Energy of photoelectrons derived from electron orbital 1s: 525 to 545 eV
N: energy of photoelectrons derived from electron orbital 1s: 390 to 410 eV
Nb: energy of photoelectrons derived from electron orbit 2p: 197 to 217 eV
In addition, in order to remove the influence of surface contamination, after performing Ar ion sputter | spatter with the intensity | strength of 0.5-4.0 kV, it measured.
As a result of the measurement, in the particle N-1, the value of X in the general formula (N) was 1.16, and the value of Y was 0.78.

Next, 15 parts of butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 15 parts of blocked isocyanate (trade name: Sumidur 3175, manufactured by Sumika Bayer Urethane Co., Ltd.) as a polyol resin It was dissolved in a mixed solution of 115 parts of methyl ethyl ketone and 115 parts of 1-butanol.
In this solution, 94.5 parts of particles S-3A as strontium titanate particles, 40.5 parts of particles N-1 described above, and 2,3,4-trihydroxybenzophenone as an additive (Tokyo Chemical Industry Co., Ltd. 1.35 parts were added and dispersed for 3 hours under an atmosphere of 23 ± 3 ° C. in a sand mill apparatus using glass beads with a diameter of 0.8 mm.
After dispersion, 0.02 parts of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.), crosslinked poly (methyl methacrylate) (PMMA) particles (trade name: TECHPOLYMER SSX-103, Sekisui Plastics Co., Ltd.) 9.5 parts was added to the dispersion and stirred to obtain a coating liquid for undercoat layer.
The obtained undercoat layer coating solution was dip-coated on the above support, and dried at 160 ° C. for 30 minutes to form an undercoat layer having a thickness of 30.0 μm.

Example A42
Example A41 shows that 94.5 parts of particles S-3A and 40.5 parts of particles N-1 used in the undercoat layer coating solution, 67.5 parts of particles S-3A and particles N- An electrophotographic photosensitive member of Example A42 was produced and evaluated in the same manner as in Example A41 except that the amount was changed to 1, 67.5 parts. The results are shown in Table 2.

Example A43
Example A41 shows that 94.5 parts of particles S-3A and 40.5 parts of particles N-1 used in the undercoat layer coating solution, 128.25 parts of particles S-3A and particles N- An electrophotographic photosensitive member of Example A43 was produced and evaluated in the same manner as in Example A41 except that the number of copies was changed to 1, 6.75 parts. The results are shown in Table 2.

Example A44
In Example A41, an electrophotographic photosensitive member of Example A44 was produced and evaluated in the same manner as in Example A41 except that the film thickness of 30.0 μm of the undercoat layer was changed to 15.0 μm. The results are shown in Table 2.

Example A45
In Example A42, an electrophotographic photosensitive member of Example A45 was produced and evaluated in the same manner as in Example A42 except that the film thickness of 30.0 μm of the undercoat layer was changed to 15.0 μm. The results are shown in Table 2.

Example A46
An electrophotographic photosensitive member of Example A46 was produced and evaluated in the same manner as in Example A43, except that the film thickness of 30.0 μm of the undercoat layer in Example A43 was changed to 15.0 μm. The results are shown in Table 2.

Example A47
The electrophotographic photosensitive member of Example A47 is prepared in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 are changed to particles S-14A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Comparative Example A1
An electrophotographic photosensitive member of Comparative Example A1 was produced in the same manner as in Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 were changed to particles S-13A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

Comparative Example A2
An electrophotographic photosensitive member of Comparative Example A2 was prepared in the same manner as Example A1, except that the strontium titanate particles S-1A used for the undercoat layer coating solution in Example A1 were changed to particles S-10A. They were fabricated and subjected to electrical characterization and x-ray diffraction measurements. The results are shown in Table 2.

  Next, in Examples A1 to A47 and Comparative Examples A1 to A2, an aluminum cylinder having a length of 370.0 mm, a thickness of 1.0 mm, and an outer diameter of 30.5 mm was used as a support (conductive support). In the same manner as in Examples A1 to A47 and Comparative Examples A1 to A2, electrophotographic photosensitive members of Examples B1 to B47 and Comparative Examples B1 to B2 were produced, and the electric characteristic evaluation 2 shown below was performed. . The results are shown in Table 3.

[Evaluation of electrophotographic photosensitive member]
<Electrical characteristic evaluation 2 of electrophotographic photosensitive member>
As the electrical property evaluation 2 of the electrophotographic photosensitive member, a cyan station of a modified machine of an electrophotographic apparatus imagePRESS C850 manufactured by Canon Inc. was used for the evaluation.
As the charging means, evaluation was performed using a system in which a voltage obtained by superimposing an AC voltage on a DC voltage is applied to a roller type contact charging member (charging roller).
The evaluation device was installed in an environment of temperature 23 ° C. and humidity 50% RH. The measurement of the surface potential of the electrophotographic photosensitive member was performed by removing the developing cartridge from the evaluation device and inserting the potential measuring device therein. The potential measuring device is configured by disposing a potential measuring probe at the developing position of the developing cartridge, and the position of the potential measuring probe is at the center of the electrophotographic photosensitive member in the generatrix direction.
As the evaluation of the chargeability, the surface potential (dark area potential) Vd2 of the electrophotographic photosensitive member when a voltage of DC voltage -830 V on which an AC voltage of 2000 Hz 1500 Vpp was superimposed was applied to the charging member (charging roller) was evaluated. The results are shown in Table 3.

  The chargeability is ranked A if the absolute value | Vd2 | of the dark portion potential Vd2 measured under the above evaluation conditions is 750 V or more; Rank B if it is 700 V or more; Rank C if it is 650 V or more; The case was evaluated as rank D.

  Next, the DC voltage applied to the charging member (charging roller) was adjusted so that the dark area potential Vd2 was −700V. The amount of laser light was adjusted so that the bright part potential V12 when irradiated with a laser beam having a wavelength of 680 nm was -200 V, and the residual potential Vr2 after continuous output of 10 sheets of solid black images was evaluated. The results are shown in Table 3.

  The residual potential is evaluated as rank A if the absolute value | Vr2 | of residual potential Vr2 measured under the above evaluation conditions is 70 V or less, rank B if it is 100 V or less, and rank C if it is greater than 100 V did.

  Next, in Examples A1 to A47 and Comparative Examples A1 to A2, an aluminum cylinder having a length of 370.0 mm, a thickness of 3.0 mm, and an outer diameter of 84.0 mm was used as a support (conductive support). The electrophotographic photosensitive members of Examples C1 to C47 and Comparative examples C1 to C2 were produced in the same manner as in Examples A1 to A47 and Comparative Examples A1 to A2, and the electrical characteristic evaluation 3 shown below was performed. The The results are shown in Table 4.

[Evaluation of electrophotographic photosensitive member]
<Evaluation of electrical characteristics of electrophotographic photosensitive member 3>
As the electrical property evaluation 3 of the electrophotographic photosensitive member, a black station of a modified machine of an electrophotographic apparatus imagePRESS C850 manufactured by Canon Inc. was used for the evaluation.
As a charging means, evaluation was performed using a corona charging system in which a voltage is applied to a grid and a wire not in contact with the photosensitive member.
The evaluation device was installed in an environment of temperature 23 ° C. and humidity 50% RH. The measurement of the surface potential of the electrophotographic photosensitive member was performed by removing the developing cartridge from the evaluation device and inserting the potential measuring device therein. The potential measuring device is configured by disposing a potential measuring probe at the developing position of the developing cartridge, and the position of the potential measuring probe is at the center of the electrophotographic photosensitive member in the generatrix direction.

As the evaluation of the chargeability, the surface potential (dark area potential) Vd3 of the electrophotographic photosensitive member when a wire current of -1000 μA and a grid voltage of -850 V were applied was evaluated. The results are shown in Table 4.
The chargeability is ranked A if the absolute value | Vd3 | of the dark portion potential Vd3 measured under the above evaluation conditions is 750 V or more; Rank B if it is 700 V or more; Rank C if it is 650 V or more; The case was evaluated as rank D.

Next, the grid voltage was adjusted so that the dark portion potential Vd3 was −700V. The amount of laser light was adjusted so that the bright part potential V13 when irradiated with a laser beam having a wavelength of 680 nm was -200 V, and the residual potential Vr3 after continuous output of 10 sheets of solid black images was evaluated. The results are shown in Table 4.
The residual potential is evaluated as rank A if the absolute value | Vr3 | of residual potential Vr3 measured under the above evaluation conditions is 70 V or less, rank B if it is 100 V or less, and rank C if it is greater than 100 V. did.

  As shown in Table 2, Table 3 and Table 4, it is possible to use an electrophotographic photosensitive member having a subbing layer containing the strontium titanate particles of the present invention, a process cartridge provided with the electrophotographic photosensitive member, and an electrophotographic apparatus For example, the residual potential is suppressed, and the charging characteristics are further excellent.

1-1 Support 1-2 Undercoating layer 1-3 Photosensitive layer 1 Electrophotographic photosensitive member 2 Axis 3 Charging means 4 Exposure light 5 Development means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process Cartridge 12 guide means

Claims (12)

In an electrophotographic photosensitive member having a support, an undercoat layer, and a photosensitive layer in this order,
The undercoat layer contains a binder resin and strontium titanate particles,
The strontium titanate particle has a maximum peak at a position of 2θ = 32.20 ± 0.20 in the CuKα characteristic X-ray diffraction pattern (θ is a Bragg angle),
The half width of the maximum peak is 0.10 deg or more and 0.50 deg or less
An electrophotographic photosensitive member characterized by   The electrophotographic photosensitive member according to claim 1, wherein the number average particle diameter of primary particles of the strontium titanate particles is 10 nm or more and 150 nm or less.   The electrophotographic photosensitive member according to claim 1, wherein the half width is 0.23 deg or more.   The electrophotographic photosensitive member according to any one of claims 1 to 3, wherein a number average particle diameter of primary particles of the strontium titanate particles is 10 nm or more and 95 nm or less.   The electrophotographic photosensitive member according to any one of claims 1 to 4, wherein the strontium titanate particles are surface-treated with a surface treatment agent.   The electrophotographic photosensitive member according to claim 5, wherein the surface treatment agent is a silane coupling agent.   The electrophotographic photosensitive member according to claim 6, wherein the silane coupling agent is a silane coupling agent having at least one functional group selected from the group consisting of an alkyl group, an amino group and a halogen atom.   The electrophotographic photosensitive member according to any one of claims 1 to 7, wherein the undercoat layer contains an electron accepting substance. The electrophotographic photosensitive member according to any one of claims 1 to 8, wherein the undercoat layer contains at least one compound selected from the group represented by the following formulas (1) and (2).

(In formula (1), R _{a1 to} R _a8 each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, or an amino group.)

(In formula (2), R _{b1 to} R _b10 each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, or an amino group.)   An electrophotographic photoreceptor according to any one of claims 1 to 9 and at least one means selected from the group consisting of charging means, developing means, transfer means and cleaning means are integrally supported, and electrophotography A process cartridge characterized by being removable from an apparatus body.   An electrophotographic apparatus comprising the electrophotographic photosensitive member according to any one of claims 1 to 9, a charging unit, an exposure unit, a developing unit, and a transfer unit. As the charging means, a charging roller arranged to be in contact with the electrophotographic photosensitive member, and a charging means for charging the electrophotographic photosensitive member by applying only a DC voltage to the charging roller,
The electrophotographic apparatus according to claim 11, characterized in that:

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