JP7080739B2 - Electrophotographic photosensitive members, their manufacturing methods, process cartridges and electrophotographic equipment - Google Patents

Description

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

In recent years, the electrophotographic photosensitive member used in an electrophotographic apparatus has mainly been configured by laminating an intermediate layer and a photosensitive layer on a support in this order.
The intermediate layer has functions such as covering defects of the support, improving the coatability of the photosensitive layer, improving the adhesiveness between the photosensitive layer and the support, improving the charge injection property from the support to the photosensitive layer, and improving the chargeability.
As the intermediate layer, a resin single film having no conductive compound or a resin film containing a conductive compound has been proposed. Patent Document 1 describes a polyamide resin, a phenol resin, a (meth) acrylic resin, a polyurethane resin, an epoxy resin, a polyester resin, a melamine resin, and a polyvinyl alcohol resin used for a conventional intermediate layer.
Further, there is a technique of dispersing metal oxide particles in the intermediate layer resin in order to hide scratches and irregularities on the surface of the support. Patent Document 2 describes a technique of using titanium oxide particles in the intermediate layer.
Further, Patent Document 3 describes a method of adding silicone oil to the intermediate layer to improve the coatability.

Japanese Unexamined Patent Publication No. 4-213462 Japanese Unexamined Patent Publication No. 2010-271705 JP-A-2002-341569

In recent years, there has been a demand for higher image quality and higher speed processes for electrophotographic devices, and electrophotographic photosensitive members that can provide images with more stable image density for all environments from low temperature and low humidity to high temperature and high humidity. Is required. The electrophotographic photosensitive member described in Patent Document 1 has room for improvement due to fluctuations in image density due to changes in electrical resistance in a low-temperature low-humidity to high-temperature high-humidity environment due to moisture absorption of the intermediate layer resin in a high-speed process. It was a thing. Further, the electrophotographic photosensitive member having an intermediate layer containing a metal oxide of Patent Document 2 has a problem that the image density becomes thin due to repeated use under high temperature and high humidity conditions.

It is presumed that the environmental dependence of the electrical characteristics and the image density in the electrophotographic photosensitive member is caused by the adsorption of water on the intermediate layer and the change in the electrical resistance of the intermediate layer. When the resin-only intermediate layer is used in a high-temperature and high-humidity environment, the electrical resistance of the intermediate layer decreases, making it easier for charges to flow from the photosensitive layer to the support, and the bright potential (sensitivity) when undergoing an exposure process. Will improve. As a result, the image density becomes darker than when used in a low humidity environment. Further, in the intermediate layer containing the metal oxide and the resin, when used in a high humidity environment, the resistance of the resin decreases due to the adsorption of water on the intermediate layer, but the conductivity of the metal oxide is also water. It decreases due to the influence. As a result, it is considered that the electric resistance of the intermediate layer becomes high in repeated use and the bright potential (sensitivity) when subjected to the exposure process deteriorates, so that the image density in a high humidity environment becomes thin.

Therefore, an object of the present invention is to provide an electrophotographic photosensitive member having a small change in sensitivity in a low temperature low humidity to high temperature high humidity environment.

The above object is achieved by the following invention. That is, the present invention is an electrophotographic photosensitive member having a conductive support, an intermediate layer, and a photosensitive layer in this order.
The intermediate layer is characterized by containing at least a urethane resin and a siloxane-modified (meth) acrylic polymer which is a graft polymer having a polymer of (meth) acrylate as a main chain and a siloxane structure as a side chain. Regarding the body.

Further, the present invention is a method for producing an electrophotographic photosensitive member having a conductive support, an intermediate layer, and a photosensitive layer in this order, wherein a polymer of at least a urethane resin and a (meth) acrylate is used as a main chain and a siloxane is used. A step of forming a coating film of an intermediate layer coating solution in which a siloxane-modified (meth) acrylic polymer, which is a graft polymer having a structure as a side chain, is dissolved in a solvent, and a step of forming the coating film on the support, and drying or curing the coating film. The present invention relates to a method for producing an electrophotographic photosensitive member, which comprises a step of forming an intermediate layer.

Further, the present invention integrally supports the electrophotographic photosensitive member and at least one means selected from the group consisting of charging means, developing means, and cleaning means, and is detachable to the main body of the electrophotographic apparatus. With respect to a process cartridge characterized by.

Furthermore, the present invention relates to an electrophotographic apparatus having the electrophotographic photosensitive member and at least one means selected from the group consisting of charging means, exposure means, developing means, and transfer means.

According to the present invention, it is possible to provide an electrophotographic photosensitive member having a small change in sensitivity in all environments from low temperature and low humidity to high temperature and high humidity.

Further, according to the present invention, it is possible to provide an electrophotographic apparatus and a process cartridge having the above electrophotographic photosensitive member.

It is a figure which shows one example of the layer structure of the electrophotographic photosensitive member of this invention. It is a figure which shows an example of the electrophotographic apparatus provided with the process cartridge which has the electrophotographic photosensitive member of this invention. It is a figure which shows an example of the polishing machine using a polishing sheet. (A) is a top view showing an outline of the mold, (b) is a schematic cross-sectional view in the axial direction of the electrophotographic photosensitive member of the convex portion of the mold (cross-sectional view in the BB cross section of FIG. 4A), (c). ) Is a sectional view in the circumferential direction of the electrophotographic photosensitive member of the convex portion of the mold (cross-sectional view taken along the line CC of FIG. 4A). It is a figure which shows the example of the pressure contact shape transfer processing apparatus for forming a recess on the peripheral surface of an electrophotographic photosensitive member.

Hereinafter, the present invention will be described in detail with reference to suitable embodiments.
The electrophotographic photosensitive member of the present invention has a conductive support, an intermediate layer, and a photosensitive layer in this order, and the intermediate layer has at least a urethane resin and a polymer of (meth) acrylate as a main chain and has a siloxane structure. It is characterized by containing a siloxane-modified (meth) acrylic polymer which is a graft polymer having a side chain.

In addition, in this specification, "(meth) acrylic group" means "acrylic group" and / or "methacrylic group". Further, the "(meth) acrylic polymer" includes a polymer obtained by polymerizing an "acrylic group", a polymer obtained by polymerizing a "methacrylic group", and a polymer obtained by polymerizing a "acrylic group" and a "methacrylic group".

The present inventors have solved the above problems by incorporating a siloxane-modified (meth) acrylic polymer, which is a graft polymer having a polymer of urethane resin and (meth) acrylate as a main chain and a siloxane structure as a side chain, in an intermediate layer. The reason why it can be solved is speculated as follows.
In the intermediate layer, the resin in the intermediate layer absorbs or desorbs moisture depending on the temperature and humidity of the usage environment, the electrical resistance changes, and the amount of charge flowing from the photosensitive layer to the support changes, causing a change in the sensitivity of the electrophotographic photosensitive member. Let me.
The urethane bond (NHCOO group) of the urethane resin and the ester bond (COO group) of the main chain of the siloxane-modified (meth) acrylic polymer have good compatibility. Therefore, by containing both in the intermediate layer, the siloxane-modified (meth) acrylic polymer can be present on the surface of the intermediate layer and inside the depth direction of the layer. As a result, the water-repellent effect of the siloxane structure is obtained in the intermediate layer, and the absorption of moisture of the resin in a high-temperature and high-humidity environment is suppressed, so that it is considered that the resistance change of the intermediate layer due to the change in temperature and humidity becomes small.

Patent Document 3 describes adding silicone oil to the intermediate layer. However, the silicone oil has high surface transferability and transfers to the upper photosensitive layer. Therefore, it is difficult to continue to exist inside the intermediate layer, and it is presumed that the water-repellent effect of the intermediate layer as in the present invention is difficult to obtain.

Further, when the metal oxide particles are contained in the intermediate layer, the absorption of moisture in the intermediate layer is suppressed for the above reason in a high temperature and high humidity environment, so that the adsorption of water to the metal oxide particles is reduced, and the use is repeated. It is presumed that the deterioration of conductivity is suppressed.

As described above, the effects of the present invention can be achieved by synergistically exerting the effects of each configuration.

[Electrophotophotoconductor]
As shown in FIG. 1, the electrophotographic photosensitive member of the present invention has an intermediate layer on a support and a photosensitive layer on the intermediate layer. In FIG. 1, 1-1 is a support, 1-2 is an intermediate layer, and 1-3 is a photosensitive layer.

Examples of the method for producing the electrophotographic photosensitive member of the present invention include a method of preparing a coating liquid for each layer described later, applying the coating liquid in the order of desired layers, and drying the coating liquid. At this time, examples of the coating method of the coating liquid include immersion coating, spray coating, inkjet coating, roll coating, die coating, blade coating, curtain coating, wire bar coating, and ring coating. Among these, dip coating is preferable from the viewpoint of efficiency and productivity.
Hereinafter, each layer will be described.

<Middle layer>
In the present invention, an intermediate layer is provided on the support.
By providing the intermediate layer, it is possible to cover defects of the support, to apply the photosensitive layer, to provide adhesiveness between the photosensitive layer and the support, and to prevent charge injection from the support to the photosensitive layer.

The intermediate layer contains at least a siloxane-modified (meth) acrylic polymer which is a graft polymer having a polymer of urethane resin and (meth) acrylate as a main chain and a siloxane structure as a side chain.

Examples of the urethane resin include polyurethane or a cured urethane resin produced by the reaction of a polyol with a blocked isocyanate compound. A cured urethane resin is preferable from the viewpoint of preventing elution to other layers in the production of the electrophotographic photosensitive member. These resins and compounds can be synthesized by a known method, or commercially available ones may be used.

Examples of the polyol include polyvinyl acetal, polyphenol, polyethylene diol, polycarbonate diol, polyether polyol, poly (meth) acrylic polyol and the like. Of these, polyvinyl acetal is preferable. Among the polyvinyl acetals, polyvinyl butyral is particularly preferable. Only one kind of these polyols may be used, or two or more kinds thereof may be used in combination.

As the isocyanate compound, any compound can be used as long as it has an isocyanate group, but the blocked isocyanate compound obtained by reacting the isocyanate group with a blocking agent is used from the viewpoint of the stability of the coating liquid in the production of the intermediate layer. preferable. Examples of the isocyanate compound to be blocked include aliphatic diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate. Of these, those having an isocyanurate as the central skeleton are preferable. Only one kind of these isocyanate compounds may be used, or two or more kinds thereof may be used in combination.

Examples of the blocking agent include methyl ethyl keto oxime, acetone oxime, dialkyl malonate, and acetoacetic ester, and methyl ethyl keto oxime is preferable.

In the present invention, the siloxane-modified (meth) acrylic polymer, which is a graft polymer having a polymer of (meth) acrylate as a main chain and a siloxane structure as a side chain, is commercially available such as BYK-3550 manufactured by Big Chemie Japan Co., Ltd. Examples include compounds.

で示される構造と、式（２）

（式（１）および式（２）中、Ｒ^１は水素原子またはメチル基であり、Ｒ^２は水素原子または炭素数１～５のアルキル基であり、Ｒ^３はメチル基またはメトキシ基であり、ａは１以上５以下の整数であり、ｂは１０以上５０以下の整数であり、ｃは０または１である。）
で示される繰り返し構造単位を有する（メタ）アクリル樹脂である。シロキサン変性（メタ）アクリルポリマーにおける式（１）で示される構造の含有比率は５質量％以上２０質量％以下が好ましい。式（１）で示される構造の含有比率が５質量％以上である場合、本発明の効果が得られやすくなり好ましい。また、式（１）で示される構造の含有比率が２０質量％以下である場合は、シロキサン変性（メタ）アクリルポリマーの表面移行性を低くすることができ、本発明の効果が得られやすくなる。 Furthermore, equation (1)

The structure represented by and equation (2)

(In formulas (1) and (2), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ is a methyl group or a methoxy group. , A is an integer of 1 or more and 5 or less, b is an integer of 10 or more and 50 or less, and c is 0 or 1.)
It is a (meth) acrylic resin having a repeating structural unit indicated by. The content ratio of the structure represented by the formula (1) in the siloxane-modified (meth) acrylic polymer is preferably 5% by mass or more and 20% by mass or less. When the content ratio of the structure represented by the formula (1) is 5% by mass or more, the effect of the present invention can be easily obtained, which is preferable. Further, when the content ratio of the structure represented by the formula (1) is 20% by mass or less, the surface transferability of the siloxane-modified (meth) acrylic polymer can be lowered, and the effect of the present invention can be easily obtained. ..

Table 1 below shows structural examples of the siloxane-modified (meth) acrylic polymer.

These siloxane-modified (meth) acrylic polymers can be synthesized by known methods. For example, it can be synthesized by the method described in JP-A-58-167606 and JP-A-62-75462.

The content of the siloxane-modified (meth) acrylic polymer is preferably 0.1% by mass or more and 5% by mass or less with respect to the content of the urethane resin in the intermediate layer. When it is contained in an amount of 0.1% by mass or more, the effect of the present invention is obtained, and when it is 5% by mass or less, the adhesion to the photosensitive layer is good.

Further, the intermediate layer of the present invention may further contain other resins, electron transporting substances, metal oxides, metals, conductive polymers and the like, if necessary. Among these, it is preferable to use a metal oxide.

Examples of the metal oxide include indium tin oxide, tin oxide, indium oxide, titanium oxide, zinc oxide, aluminum oxide, silicon dioxide, and strontium titanate. Of these, titanium oxide, zinc oxide, aluminum oxide, and strontium titanate are preferable from the viewpoint of hiding defects in the support and electrical properties.
The content of the metal oxide is preferably 10 to 500% by mass, more preferably 50 to 400% by mass, based on the binder resin.

The surface of the metal oxide may be treated with a silane coupling agent or the like, or the metal oxide may be doped with an element such as phosphorus or aluminum or an oxide thereof.

Further, the metal oxide particles may have a laminated structure having core material particles and a coating layer covering the particles. Examples of the core material particles include titanium oxide, barium sulfate, zinc oxide and the like. Examples of the coating layer include metal oxides such as tin oxide.

The volume average particle size of the metal oxide particles 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 electron transporting substance include a quinone compound, an imide compound, a benzimidazole compound, a cyclopentadienylidene compound, a fluorenone compound, a xanthone compound, a benzophenone compound, a cyanovinyl compound, an aryl halide compound, a silol compound, and a boron-containing compound. .. An intermediate layer may be formed as a cured film by using an electron transporting substance having a polymerizable functional group as the electron transporting substance and copolymerizing it with the above-mentioned monomer having a polymerizable functional group.
Further, the intermediate layer may further contain additives such as silicone oil and resin particles.

The average film thickness of the intermediate layer is preferably 0.1 μm or more and 50 μm or less, more preferably 0.2 μm or more and 40 μm or less, and particularly preferably 0.3 μm or more and 30 μm or less. Any method may be used for measuring the film thickness, and for example, a film thickness meter using an eddy current method can be used. Examples of the film thickness meter using the eddy current method include Fisherscopy manufactured by Helmut Fisher. The average film thickness of the intermediate layer was calculated as the difference before and after film formation.

The intermediate layer of the present invention is composed of only one layer containing a siloxane-modified (meth) acrylic polymer, which is a graft polymer having a polymer of the above-mentioned urethane resin and (meth) acrylate as a main chain and a siloxane structure as a side chain. May be done. When the intermediate layer of the present invention is composed of a plurality of layers, at least one layer is a layer containing a urethane resin and a siloxane-modified (meth) acrylic polymer.

The intermediate layer can be formed by preparing a coating liquid for an intermediate layer containing each of the above materials and a solvent, forming this coating film on a conductive support, and drying and / or curing it. Examples of the solvent used for the coating liquid include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents and the like.

When the intermediate layer contains metal oxide particles, a method using a paint shaker, a sand mill, a ball mill, or a liquid collision type high-speed disperser is used as a dispersion method for dispersing the metal oxide particles in the coating liquid for the intermediate layer. Can be mentioned.

<Support>
In the present invention, the electrophotographic photosensitive member has a support. In the present invention, the support is preferably a conductive support having conductivity. Further, examples of the shape of the support include a cylindrical shape, a belt shape, a sheet shape, and the like. Above all, a cylindrical support is preferable. Further, the surface of the support may be subjected to an electrochemical treatment such as anodization, a blast treatment, a cutting treatment or the like.
As the material of the support, metal, resin, glass or the like is preferable.
Examples of the metal include aluminum, iron, nickel, copper, gold, stainless steel, and alloys thereof. Above all, it is preferable that the support is made of aluminum using aluminum.
Further, the resin or glass may be imparted with conductivity by a treatment such as mixing or coating a conductive material.

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

(1) Laminated Photosensitive Layer The laminated 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 substance include azo pigments, perylene pigments, polycyclic quinone pigments, indigo pigments, phthalocyanine pigments and the like. 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 generating substance in the charge generating layer is preferably 40% by mass or more and 85% by mass or less, and more preferably 60% by mass or more and 80% by mass or less with respect to the total mass of the charge generating layer. preferable.

Resins include polyester resin, polycarbonate resin, polyvinyl acetal resin, polyvinyl butyral resin, (meth) acrylic resin, silicone resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, polyvinyl alcohol resin, cellulose resin, polystyrene resin, and poly. Examples thereof include vinyl acetate resin and polyvinyl chloride resin. Among these, polyvinyl butyral resin is more preferable.

Further, the charge generation layer may further contain additives such as an antioxidant and an ultraviolet absorber. Specific examples thereof include hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds and the like.

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 liquid for a charge generation layer containing each of the above materials and a solvent, forming the coating film, and drying the coating film. Examples of the solvent used for the coating liquid include alcohol-based solvents, sulfoxide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents and the like.

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

Examples of the charge transporting substance include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having a group derived from these substances. Be done. Among these, triarylamine compounds and benzidine compounds are preferable.

The content of the charge transporting substance in the charge transport layer is preferably 25% by mass or more and 70% by mass or less, and more preferably 30% by mass or more and 55% by mass or less, based on the total mass of the charge transport layer. preferable.

Examples of the resin include polyester resin, polycarbonate resin, (meth) 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 transporting substance and the resin is preferably 4:10 to 20:10, more preferably 5:10 to 12:10.

Further, the charge transport layer may contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a leveling agent, a slipperiness imparting agent, and an abrasion resistance improving agent. Specifically, hindered phenol compound, hindered amine compound, sulfur compound, phosphorus compound, benzophenone compound, siloxane modified resin, silicone oil, fluororesin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles. And so on.

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 liquid for a charge transport layer containing each of the above materials and a solvent, forming the coating film, and drying the coating film. Examples of the solvent used for the coating liquid include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents. Among these solvents, ether-based solvents or aromatic hydrocarbon-based solvents are preferable.

(2) Single-layer type photosensitive layer The single-layer type photosensitive layer is formed by preparing a coating liquid for a photosensitive layer containing a charge generating substance, a charge transporting substance, a resin and a solvent, forming this coating film, and drying the coating film. can do. The charge generating substance, the charge transporting substance, and the resin are the same as the examples of the materials in the above “(1) Laminated photosensitive layer”.

<Protective layer>
In the present invention, a protective layer may be provided on the photosensitive layer. By providing a protective layer, durability can be improved.

The protective layer preferably contains conductive particles and / or a charge transporting material and a resin.

Examples of the conductive particles include particles of metal oxides such as titanium oxide, zinc oxide, tin oxide, and indium oxide.

Examples of the charge transporting substance include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having a group derived from these substances. Among these, triarylamine compounds and benzidine compounds are preferable.

Examples of the resin include polyester resin, (meth) acrylic resin, phenoxy resin, polycarbonate resin, polystyrene resin, phenol resin, melamine resin, epoxy resin and the like. Of these, polycarbonate resin, polyester resin, and (meth) acrylic resin are preferable.

Further, the protective layer may be formed as a cured film by polymerizing a composition containing a monomer having a polymerizable functional group. Examples of the reaction at that time include a thermal polymerization reaction, a photopolymerization reaction, and a radiation polymerization reaction. Examples of the polymerizable functional group of the monomer having a polymerizable functional group include a (meth) acrylic group. As the monomer having a polymerizable functional group, a material having a charge transporting ability may be used.

The protective layer may contain additives such as antioxidants, UV absorbers, plasticizers, leveling agents, slippery imparting agents, and abrasion resistance improving agents. Specifically, hindered phenol compound, hindered amine compound, sulfur compound, phosphorus compound, benzophenone compound, siloxane modified resin, silicone oil, fluororesin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles. And so on.

The average film thickness of the protective layer is preferably 0.5 μm or more and 10 μm or less, and preferably 1 μm or more and 7 μm or less.

The protective layer can be formed by preparing a coating liquid for a protective layer containing each of the above materials and a solvent, forming this coating film, and drying and / or curing it. Examples of the solvent used for the coating liquid include alcohol-based solvents, ketone-based solvents, ether-based solvents, sulfoxide-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents.
The surface of the protective layer may be roughened, blasted, pressure-welded shape transfer, or the like.

FIG. 3 shows an example of using a polishing machine using a polishing sheet as a roughening means as an example of roughening the surface of the protective layer of the electrophotographic photosensitive member of the present invention. The polishing sheet 101 is a sheet-shaped polishing member provided with a layer in which polishing abrasive grains are dispersed in a binder resin on a sheet-shaped base material. The polishing sheet 101 is wound around a hollow shaft 106, and a motor (not shown) is arranged so that tension is applied to the polishing sheet 101 in a direction opposite to the direction in which the polishing sheet 101 is sent to the shaft 106. The polishing sheet 101 is fed in the direction of the arrow, passes through the backup roller 103 via the guide rollers 102a and 102b, and the polished polishing sheet 101 is taken up by a motor (not shown) via the guide rollers 102c and 102d to the winding means 105. It is taken up. Polishing is performed by constantly pressing the polishing sheet 101 against the electrophotographic photosensitive member 104, which is the object to be treated, to roughen the peripheral surface of the electrophotographic photosensitive member 104, which is the object to be processed. The electrophotographic photosensitive member 104, which is the object to be treated, is the electrophotographic photosensitive member 104 before roughening (polishing) the peripheral surface, or before roughening (polishing) and cleaning the peripheral surface. The electrophotographic photosensitive member 104 of the above. Since the polishing sheet 101 is often insulating, it is preferable to use a portion that is grounded to the ground or has conductivity as the portion in contact with the polishing sheet 101.

The electrophotographic photosensitive member 104, which is the object to be processed, is placed at a position facing the backup roller 103 via the polishing sheet 101. At this time, the backup roller 103 is pressed against the electrophotographic photosensitive member 104, which is the object to be processed, from the substrate side of the polishing sheet 101 at a desired set value (pressure) for a predetermined time, and the electrophotograph, which is the object to be processed. The peripheral surface of the photoconductor 104 is roughened. The rotation direction of the electrophotographic photosensitive member 104, which is the object to be processed, may be the same as the feeding direction of the polishing sheet 101, or may be opposite to each other. Further, the rotation direction of the electrophotographic photosensitive member 104, which is the object to be processed, may be changed during the roughening.

[Method for forming the surface shape of electrophotographic photosensitive member]
For the purpose of further stabilizing the behavior of the cleaning blade in contact with the electrophotographic photosensitive member, it is more preferable to provide a concave-shaped portion or a convex-shaped portion on the surface layer of the electrophotographic photosensitive member.

The concave or convex portion may be formed on the entire surface of the electrophotographic photosensitive member, or may be formed on a part of the surface of the electrophotographic photosensitive member. When the concave or convex portion is formed on a part of the surface of the electrophotographic photosensitive member, it is preferable that the concave or convex portion is formed at least in the entire contact area with the cleaning blade. ..
For example, when forming a concave portion, a mold having a convex portion corresponding to the concave portion to be formed is pressed against the surface of the electrophotographic photosensitive member and shape transfer is performed to form the concave portion. Can be done.

FIG. 5 shows an example of a pressure contact shape transfer processing device for forming a concave shape portion on the surface of an electrophotographic photosensitive member.
According to the pressure contact shape transfer processing apparatus shown in FIG. 5, while rotating the electrophotographic photosensitive member 5-1 which is the workpiece, the mold 5-2 is continuously brought into contact with the surface (peripheral surface) thereof and pressed. Thereby, a concave portion or a flat portion can be formed on the surface of the electrophotographic photosensitive member 5-1.

Examples of the material of the pressure member 5-3 include metals, metal oxides, plastics, and glass. Among these, stainless steel (SUS) is preferable from the viewpoint of mechanical strength, dimensional accuracy, and durability. A mold 5-2 is installed on the upper surface of the pressure member 5-3. Further, a mold 5-2 is specified on the surface of the electrophotographic photosensitive member 5-1 supported by the support member 5-4 by the support member (not shown) and the pressurizing system (not shown) installed on the lower surface side. Can be contacted with the pressure of. Further, the support member 5-4 may be pressed against the pressurizing member 5-3 with a predetermined pressure, or the support member 5-4 and the pressurizing member 5-3 may be pressed against each other.

In the example shown in FIG. 5, the pressure member 5-3 is moved in a direction perpendicular to the axial direction of the electrophotographic photosensitive member 5-1 so that the electrophotographic photosensitive member 5-1 is driven or driven and rotated. This is an example of continuously processing the surface. Further, by fixing the pressurizing member 5-3 and moving the support member 5-4 in the direction perpendicular to the axial direction of the electrophotographic photosensitive member 5-1 or by moving the support member 5-4 and the pressurizing member 5 By moving both of -3, the surface of the electrophotographic photosensitive member 5-1 can be continuously processed.

From the viewpoint of efficient shape transfer, it is preferable to heat the mold 5-2 and the electrophotographic photosensitive member 5-1.
The mold 5-2 includes, for example, a metal or resin film having a fine surface processed, a resin film having a pattern on the surface of a silicon wafer or the like with a resist, a resin film in which fine particles are dispersed, or a resin film having a fine surface shape. For example, a metal coating is applied to the film.
Further, from the viewpoint of making the pressure pressed against the electrophotographic photosensitive member 5-1 uniform, it is preferable to install an elastic body between the mold 5-2 and the pressurizing member 5-3.

[Process cartridge, electrophotographic equipment]
The process cartridge of the present invention integrally supports the electrophotographic photosensitive member described above and at least one means selected from the group consisting of charging means, developing means, and cleaning means, and is used in the main body of the electrophotographic apparatus. It is characterized by being removable.

Further, the electrophotographic apparatus of the present invention is characterized by having the electrophotographic photosensitive member described above and at least one means selected from the group consisting of charging means, exposure means, developing means and transfer means. do.

FIG. 2 shows an example of a schematic configuration of an electrophotographic apparatus having a process cartridge including an electrophotographic photosensitive member.
The cylindrical electrophotographic photosensitive member 1 is rotationally driven at a predetermined peripheral speed in the direction of the arrow about the axis 2. The surface of the electrophotographic photosensitive member 1 is charged to a predetermined positive or negative potential by the charging means 3. Although the roller charging method using the roller type charging member is shown in the figure, a charging method such as a corona charging method, a proximity charging method, or an injection charging method may be adopted. The surface of the charged electrophotographic photosensitive member 1 is irradiated with exposure light 4 from an exposure means (not shown), and an electrostatic latent image corresponding to the target image information is formed. The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed with the toner contained in the developing means 5, and the 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 is transferred is conveyed to the fixing means 8, undergoes the fixing process of the toner image, and is 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. Further, a so-called cleanerless system may be used in which the cleaning means 9 is not separately provided and the deposits are removed by a developing means or the like. The electrophotographic apparatus may have a static elimination mechanism for statically eliminating the surface of the electrophotographic photosensitive member 1 with the preexposure light 10 from the preexposure means (not shown). Further, in order to attach / detach the process cartridge 11 of the present invention to / from the main body of the electrophotographic apparatus, a guide means 12 such as a rail may be provided.

The electrophotographic photosensitive member of the present invention can be used in a laser beam printer, an LED printer, a copying machine, a facsimile, a multifunction device thereof, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In the description of the following examples, the term "part" is based on mass unless otherwise specified.

(Example 1)
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 machined using a lathe.
As the cutting conditions, a cutting tool of R0.1 was used, and the spindle rotation speed was 10000 rpm, and the feeding speed of the cutting tool was continuously changed in the range of 0.03 to 0.06 mm / rpm for processing.

Next, as the polyol resin, 15 parts of butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.), 15 parts of blocked isocyanate (trade name: Sumijour 3175, manufactured by Sumika Bayer Urethane Co., Ltd.) and 15 parts. 0.15 parts of a siloxane-modified acrylic polymer (exemplified compound 2) was dissolved in a mixed solution of 300 parts of methyl ethyl ketone and 300 parts of 1-butanol to obtain a coating liquid for an intermediate layer.
The obtained coating liquid for an intermediate layer was dipped and coated on the support and dried at 160 ° C. for 30 minutes to form an intermediate layer having an average film thickness of 2.0 μm.
The film thickness was measured with an eddy current type film thickness meter (Fischerscoppe, manufactured by Helmut Fisher). Five points were measured evenly in the generatrix direction of the cylindrical electrophotographic photosensitive member, and the average value was adopted as the average film thickness.

Next, 20 parts of crystalline hydroxygallium phthalocyanine crystals (charge generator) having strong peaks at 7.4 ° and 28.2 ° of the Bragg angle of 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction, formula (A). ), 0.2 parts of the calix-alene compound, 10 parts of polyvinyl butyral resin (trade name: Eslek BX-1, manufactured by Sekisui Chemical Industry Co., Ltd.), and 600 parts of cyclohexanone, sand mill using glass beads with a diameter of 1 mm. After 4 hours of dispersion treatment, 600 parts of ethyl acetate was added to prepare a coating liquid for a charge generation layer.
This coating liquid for a charge generation layer was immersed and coated on the intermediate layer, and the obtained coating film was dried at 80 ° C. for 15 minutes to form a charge generation layer having an average film thickness of 0.19 μm.

next,
60 parts of the compound (charge transport material) represented by the formula (B),
30 parts of the compound (charge transport material) represented by the formula (C),
10 parts of the compound (charge transport material) represented by the formula (D),
100 parts of polycarbonate resin (trade name: Iupiron 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 formula (E),
A coating liquid for a charge transport layer was prepared by dissolving in a mixed solvent of 600 parts of o-xylene and 200 parts of dimethoxymethane.
This coating liquid for a charge transport layer is immersed and coated on the charge generation layer to form a coating film, and the obtained coating film is dried at 100 ° C. for 30 minutes to form a charge transport layer having an average film thickness of 18 μm. did.

next,
Resin having a repeating structural unit represented by the formula (F1) and a repeating structural unit represented by the formula (F2) (weight average molecular weight: 130,000, copolymerization ratio (F1) / (F2) = 1/1 (molar ratio). )) 1.65 copies,
It was dissolved in a mixed solvent of 40 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeorora H, manufactured by Nippon Zeon Co., Ltd.) and 55 parts of 1-propanol.
After that, 30 parts of tetrafluoroethylene resin powder (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) was added to a high-pressure disperser (trade name: Microfluidizer M-110EH, US Microfluidics). A dispersion was obtained by passing through (manufactured by Co., Ltd.).
after that,
52.0 parts of the hole transporting compound represented by the formula (G),
16.0 parts of the compound represented by the formula (H),
2.0 parts of the compound represented by the formula (I),
0.75 parts of siloxane-modified acrylic compound (BYK-3550, manufactured by Big Chemie Japan Co., Ltd.),
Add 35 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane and 15 parts of 1-propanol to the dispersion.
Filtration was performed with a polyfluorocarbon filter (trade name: PF-040, manufactured by Advantech Toyo Co., Ltd.) to prepare a paint for a protective layer.
The coating liquid for the protective layer was immersed and 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 the conditions of an acceleration voltage of 70 KV and an absorption dose of 15 kGy under a nitrogen atmosphere. Then, the heat treatment was performed for 15 seconds under the condition that the temperature of the coating film became 135 ° C. under a nitrogen atmosphere. The oxygen concentration from the irradiation of the electron beam to the heat treatment for 15 seconds was 15 ppm. Next, a protective layer having an average film thickness of 5 μm was formed by heat treatment in the air for 1 hour under the condition that the coating film became 105 ° C. In this way, the electrophotographic photosensitive member was manufactured.

[Formation of recesses by mold pressure welding shape transfer]
Next, a mold member (mold) was installed in the pressure contact shape transfer processing apparatus, and the surface of the prepared electrophotographic photosensitive member before forming the recess was processed.
Specifically, the mold shown in FIG. 4 was placed in the pressure-welded shape transfer processing apparatus having the configuration generally shown in FIG. 5, and the surface of the prepared electrophotographic photosensitive member before forming the recess was processed. FIG. 4 is a diagram showing molds used in Examples and Comparative Examples. 4 (a) is a top view showing an outline of the mold, and FIG. 4 (b) is a schematic sectional view in the axial direction of the electrophotographic photosensitive member of the convex portion of the mold (cross-sectional view taken along the line BB of FIG. 4 (a)). ). FIG. 4C is a circumferential cross-sectional view of the electrophotographic photosensitive member of the convex portion of the mold (cross-sectional view taken along the line CC of 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 convex portion on the mold is viewed from above) X: 50 μm, and a maximum length (the convex portion on the mold). The maximum length of the electrophotographic photosensitive member in the circumferential direction when viewed from above.) Y: 75 μm, area ratio 56%, maximum height H: 4 μm. The area ratio is the ratio of the area of the convex portion to the entire surface when the mold is viewed from above. During processing, the temperatures of the electrophotographic photosensitive member and the mold were controlled so that the temperature of the surface of the electrophotographic photosensitive member was 120 ° C. Then, while pressing the electrophotographic photosensitive member and the pressurizing member against the mold at a pressure of 7.0 MPa, the electrophotographic photosensitive member is rotated in the circumferential direction to form a recess on the entire surface layer (peripheral surface) of the electrophotographic photosensitive member. Formed.
As described above, the electrophotographic photosensitive member of Example 1 was produced.

[Evaluation of electrophotographic photosensitive member]
As an electrophotographic apparatus for evaluation, a modified machine of a copying machine imageRUNNER ADVANCE C5560 manufactured by Canon Inc. was used. As the charging means, a method of applying a DC voltage to a roller-type contact charging member (charging roller) was used, and the process speed was modified to 320 mm / sec (cycle time 0.3 seconds) for evaluation.

The surface potential of the electrophotographic photosensitive member was measured by removing the developing cartridge from the evaluation device and inserting the potential measuring device into the cartridge. The potential measuring device is configured by arranging the potential measuring probe at the developing position of the developing cartridge, and the position of the potential measuring probe is centered in the bus direction of the electrophotographic photosensitive member.

The evaluation device was first installed in an environment with a temperature of 15 ° C. and a humidity of 10% RH. The voltage Vc applied to the charging member (charging roller) is adjusted so that the dark potential Vd is -700V, and the amount of laser light is adjusted so that the bright potential Vl when irradiated with laser light having a wavelength of 780 nm is -200V. did. Then, an evaluation device was installed in an environment of a temperature of 32 ° C. and a humidity of 85% RH, and the bright potential Vl of the electrophotographic photosensitive member was measured without changing the applied voltage and the amount of laser light.

Further, in each environment, a printing job of continuously outputting 5 sheets with an image having a printing rate of 5% was repeated 10,000 times, and the bright potential Vl of the electrophotographic photosensitive member was measured without changing the applied voltage and the amount of laser light. The bright potential difference between the temperature of 15 ° C. and the humidity of 10% RH and the temperature of 32 ° C. and the humidity of 85% RH was determined at the initial stage and after the durability of 50,000 sheets. The results are shown in Table 2.

[Preparation of sheet sample]
In Example 1, instead of the aluminum cylinder, an aluminum cylinder wound with an aluminum sheet having a thickness of 50 μm is used as a support. An intermediate layer, a charge generation layer, and a charge transport layer are sequentially formed on the support in the same manner as in the method for producing the electrophotographic photosensitive member of Example 1. Then, the aluminum sheet from which the aluminum sheet was peeled off was used as the sheet sample of Example 1, and the film peeling test described later was carried out.

[Membrane peeling test]
The produced sheet sample was allowed to stand for 72 hours in a high temperature and high humidity environment with a temperature of 50 ° C. and a humidity of 90% RH. This sheet sample was taken out. After that, in order to dry the wet intermediate layer sheet surface so that the tape used for the following film peeling test adheres firmly, it is allowed to stand in a normal temperature and humidity environment with a temperature of 23 ° C. and a humidity of 50% RH, and after 24 hours, it is intermediate. A film peeling test of the layer was performed.

The film peeling test was carried out by the grid tape method based on JIS-K5400. Items not specified are subject to JIS regulations. The measurement procedure is shown below.
1: Fix the sheet sample, make cuts that reach the aluminum sheet at 2 mm intervals in the intermediate layer using a cross cut guide, and make cuts on the grid. A grid pattern with 100 grids was formed.
2: Always use a new utility knife when making cuts and keep it at a constant angle in the range of 35-45 degrees to the coated surface. Further, the cut is pulled at a constant speed for about 0.5 seconds for each cut so as to penetrate the intermediate layer and reach the aluminum sheet.
3: Attach cellophane adhesive tape to the surface of the cut intermediate layer, rub it with an eraser to attach the tape to the intermediate layer, and then 1 to 2 minutes after attaching the tape, hold one end of the tape and hold the middle. Keep at right angles to the coated surface of the layer and instantly peel off the tape.
4: Observe the coated surface and the tape, determine the number of peeled grids, and calculate the ratio of the peeled area. In the film peeling test, the above sheet sample was subjected to a grid test by the method described in JIS, and the number of remaining grids out of 100 was counted. The ratio of the grid with the remaining intermediate layer was counted. Adhesive rate (%) = number of cells not peeled off (mass) / total number (100 cells). A adhesion rate of 90% or more was designated as A, an adhesion rate of 80% or higher was defined as B, and an adhesion rate of 70% or higher was defined as C.
The evaluation results are shown in Table 2.

(Example 2)
In Example 1, an electrophotographic photosensitive member and a sheet sample were prepared and evaluated in the same manner as in Example 1 except that the intermediate layer was changed as follows. The results are shown in Table 2.
As an intermediate layer, 15 parts of butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.), 15 parts of blocked isocyanate (trade name: Sumijour 3175, manufactured by Sumika Bayer Urethane Co., Ltd.) and siloxane-modified acrylic. 0.15 parts of the polymer (exemplified compound 2) was dissolved in a mixed solution of 300 parts of methyl ethyl ketone and 300 parts of 1-butanol.
60 parts of titanium oxide having an average particle size of 35 nm was added as metal oxide particles, and 1.2 parts of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added as an additive, and this was added to a diameter of 0. The mixture was dispersed in a sand mill device using 8 mm glass beads in an atmosphere of 23 ± 3 ° C. for 3 hours to obtain a coating liquid for an intermediate layer.
The obtained coating liquid for an intermediate layer was dipped and coated on the support and dried at 160 ° C. for 30 minutes to form an intermediate layer having an average film thickness of 2.0 μm.

(Examples 3 to 9)
In Example 2, an electrophotographic photosensitive member and a sheet sample were prepared and evaluated in the same manner as in Example 2 except that the amount of the siloxane-modified acrylic polymer added to the intermediate layer was changed to the amount shown in Table 2. .. The results are shown in Table 2.

(Examples 10 to 12)
In Example 2, an electrophotographic photosensitive member and a sheet sample were prepared and evaluated in the same manner as in Example 2 except that the structure and the amount of the siloxane-modified acrylic polymer added in the intermediate layer were changed as shown in Table 2. gone. The results are shown in Table 2.

(Example 13)
In Example 2, an electrophotographic photosensitive member and a sheet sample were prepared and evaluated in the same manner as in Example 2 except that the following aluminum oxide particles were used instead of the titanium oxide particles used for the intermediate layer. rice field.
100 parts of aluminum oxide particles having an average particle size of 13 nm were stirred and mixed with 500 parts of toluene, 25 parts of octylsilane was added, and the mixture was stirred for 2 hours. Then, toluene was distilled off by vacuum distillation and baked at 120 degreeC for 3 hours to obtain surface-treated aluminum oxide particles.
The results are shown in Table 2.

(Example 14)
In Example 2, an electrophotographic photosensitive member and a sheet sample were prepared and evaluated in the same manner as in Example 2 except that the following strontium titanate particles were used instead of the titanium oxide particles used for the intermediate layer. gone.
100 parts of strontium titanate particles having an average primary particle size of 50 nm were stirred and mixed with 500 parts of toluene, 1 part of N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane was added, and the mixture was stirred for 2 hours. Then, toluene was distilled off by vacuum distillation and baked at 120 degreeC for 3 hours to obtain surface-treated strontium titanate particles.
The results are shown in Table 2.

(Example 15)
In Example 2, an electrophotographic photosensitive member and a sheet sample were prepared and evaluated in the same manner as in Example 2 except that the following zinc oxide particles were used instead of the titanium oxide particles used for the intermediate layer. rice field.
100 parts of zinc oxide particles having an average primary particle size of 35 nm were stirred and mixed with 500 parts of toluene, 1 part of N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane was added, and the mixture was stirred for 2 hours. Then, toluene was distilled off by vacuum distillation and baked at 120 degreeC for 3 hours to obtain surface-treated zinc oxide particles.
The results are shown in Table 2.

(Example 16)
In Example 15, 0.001 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.) and crosslinked polymethyl methacrylate particles (trade name: TECFORMIER SSX-102, Sekisui Plastics Co., Ltd.) were added to the intermediate layer. Co., Ltd., primary average particle size (2.5 μm) was added in 3 parts, and an electrophotographic photosensitive member and a sheet sample were prepared in the same manner as in Example 15 except that the average film thickness of the intermediate layer was 20 μm, and evaluated. gone. The results are shown in Table 2.

(Example 17)
In Example 2, the electrophotographic photosensitive member and the sheet sample of Example 17 were prepared in the same manner as in Example 1 except that the surface treatment of the electrophotographic photosensitive member was performed by using the polishing apparatus described below. , Evaluated. The results are shown in Table 2.
The surface was processed using the polishing apparatus shown in FIG. 3 under the following conditions.
Polishing sheet feed speed; 400 mm / min
Rotational speed of electrophotographic photosensitive member; 450 rpm
Pushing the electrophotographic photosensitive member into the backup roller; 3.5 mm
Rotation direction of polishing sheet and electrophotographic photosensitive member; with backup roller; outer diameter 100 mm, Asker C hardness 25
As the polishing sheet attached to the polishing device, GC3000 (polishing sheet surface roughness Ra 0.83 μm) manufactured by Riken Corundum Co., Ltd. was used.
The polishing time was 20 seconds.

（式（Ｊ）中、ｍおよびｎは共重合比を示し、ｍ：ｎ＝７：３）

(Example 18)
In Example 2, the electrophotographic photosensitive member and the sheet sample of Example 18 were prepared in the same manner as in Example 2 except that the surface layer (protective layer) was not provided and the charge transport layer was formed by the method described below. It was prepared and evaluated. The results are shown in Table 2.
72 parts of the compound (charge transport material) represented by the formula (B),
8 parts of the compound (charge transport material) represented by the formula (D),
100 parts of the resin having the structure represented by the formula (J),
1.8 parts o-xylene 360 parts of the resin having the structure represented by the formula (K),
160 parts of methyl benzoate and 270 parts of dimethoxymethane (methylar) were mixed to prepare a coating liquid for a charge transport layer.
Next, the coating liquid for the charge transport layer was immersed and coated on the charge generation layer, and the obtained coating film was dried at 125 ° C. for 50 minutes to form a charge transport layer having an average film thickness of 20 μm.

(In formula (J), m and n indicate a copolymerization ratio, m: n = 7: 3).

(Comparative Example 1)
In the intermediate layer of Example 1, 15 parts of butyral resin and 15 parts of blocked isocyanate were changed to 30 parts of alcohol-soluble copolymerized polyamide (trade name: Amylan CM8000, manufactured by Toray Industries, Inc.), and 300 parts of methyl ethyl ketone was changed to methanol. An electrophotographic photosensitive member and a sheet sample were prepared and evaluated in the same manner as in Example 1 except that the number was changed to 300 parts. The results are shown in Table 2.

(Comparative Example 2)
An electrophotographic photosensitive member and a sheet sample were prepared and evaluated in the same manner as in Example 1 except that the siloxane-modified acrylic polymer was not used in the intermediate layer of Example 1. The results are shown in Table 2.

(Comparative Example 3)
The electrophotographic photosensitive member of Comparative Example 2 was obtained in the same manner as in Example 1 except that dimethylpolysiloxane (KF96, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed in place of the siloxane-modified acrylic polymer in the intermediate layer of Example 1. A sheet sample was prepared and evaluated. The results are shown in Table 2.

(Comparative Example 4)
In the intermediate layer of Example 2, 15 parts of butyral resin and 15 parts of blocked isocyanate were changed to 30 parts of alcohol-soluble copolymerized polyamide (trade name: Amylan CM8000, manufactured by Toray Industries, Inc.), and 300 parts of methyl ethyl ketone was changed to methanol. An electrophotographic photosensitive member and a sheet sample were prepared and evaluated in the same manner as in Example 2 except that the number was changed to 300 parts. The results are shown in Table 2.

(Comparative Example 5)
An electrophotographic photosensitive member and a sheet sample were prepared and evaluated in the same manner as in Example 2 except that the siloxane-modified acrylic polymer was not used in the intermediate layer of Example 2. The results are shown in Table 2.

表２中、含有量はウレタン樹脂に対するシロキサン変性アクリルポリマーの含有量を表す。

In Table 2, the content represents the content of the siloxane-modified acrylic polymer with respect to the urethane resin.

As shown in Table 2, electrons containing a siloxane-modified (meth) acrylic polymer, which is a graft polymer having a polymer of the urethane resin of the present invention and a (meth) acrylate as a main chain and a siloxane structure as a side chain, in an intermediate layer. The sensitivity change of the photographic photosensitive member was suppressed from low temperature and low humidity to high temperature and high humidity.

Furthermore, in the intermediate layer containing the metal oxide particles, it was possible to suppress the change in sensitivity from low temperature and low humidity to high temperature and high humidity after repeated use.

1-1 Support 1-2 Intermediate layer 1-3 Photosensitive layer

1 Electrophotographic photosensitive member 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means

101 Polishing sheet 102a Guide roller 102b Guide roller 103 Backup roller 104 Processed object (electrophotograph photosensitive member before polishing)
105 Winding means 106 Hollow shaft

H Maximum height of mold X Maximum width of mold Y Maximum length of mold

5-1 Subject to be treated (electrophotograph photosensitive member before processing)
5-2 Mold type 5-3 Pressurizing member 5-4 Supporting member

Claims (8)

An electrophotographic photosensitive member having a conductive support, an intermediate layer, and a photosensitive layer in this order.
The intermediate layer is characterized by containing at least a urethane resin and a siloxane-modified (meth) acrylic polymer which is a graft polymer having a polymer of (meth) acrylate as a main chain and a siloxane structure as a side chain. body The electrophotographic photosensitive member according to claim 1, wherein the content of the siloxane-modified (meth) acrylic polymer is 0.1% by mass or more and 5% by mass or less with respect to the urethane resin. The siloxane-modified (meth) acrylic polymer has a structure represented by the formula (1) and a structural unit represented by the formula (2), and the structure represented by the formula (1) in the siloxane-modified (meth) acrylic polymer. The electrophotographic photosensitive member according to claim 1 or 2, wherein the content ratio of the unit is 5% by mass or more and 20% by mass or less.

(In formulas (1) and (2), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ is a methyl group or a methoxy group. , A is an integer of 1 or more and 5 or less, b is an integer of 10 or more and 50 or less, and c is 0 or 1.) The electrophotographic photosensitive member according to any one of claims 1 to 3, wherein the intermediate layer contains metal oxide particles. The electrophotographic photosensitive member according to claim 4, wherein the metal oxide particles are at least one selected from the group consisting of titanium oxide particles, zinc oxide particles, aluminum oxide particles, and strontium titanate particles. .. There is a method for manufacturing an electrophotographic photosensitive member having a conductive support, an intermediate layer, and a photosensitive layer in this order.
At least a coating film of a coating liquid for an intermediate layer in which a siloxane-modified (meth) acrylic polymer, which is a graft polymer having a polymer of urethane resin and (meth) acrylate as a main chain and a siloxane structure as a side chain, is dissolved in a solvent. The step of forming on the conductive support and
A method for producing an electrophotographic photosensitive member, which comprises a step of drying or curing the coating film to form an intermediate layer. The electrophotographic photosensitive member according to any one of claims 1 to 5 and at least one means selected from the group consisting of charging means, developing means, and cleaning means are integrally supported, and the electrophotographic apparatus main body is supported. A process cartridge that is removable. An electrophotographic apparatus having the electrophotographic photosensitive member according to any one of claims 1 to 5 and at least one means selected from the group consisting of charging means, exposure means, developing means, and transfer means.

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