JP2006047869A - Electrophotographic photoreceptor, its manufacturing method, electrophotographic apparatus and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having sufficiently high friction characteristics and capable of keeping the friction characteristics in a high level for a long time, and to provide an electrophotographic apparatus and a process cartridge using the electrophotographic photoreceptor and realizing a high operation speed, high picture quality and a long life. <P>SOLUTION: The electrophotographic photoreceptor 10 has a conductive substrate 12 and a photosensitive layer 13 formed on the conductive substrate, wherein a lubricating substance prepared by heating and melting a lubricating substance having 30°C to 200°C melting point is brought into contact with the surface in the opposite side of the photosensitive layer 13 to the conductive substrate 12 (with the surface in a layer 17 side). Thereby, while segregation (bleeding) of the lubricating substance is suppressed, the lubricating substance can be stably held in the photosensitive layer to impart sufficient friction characteristics to the surface. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrophotographic photosensitive member used for electrophotographic image formation, a method for manufacturing the same, an electrophotographic apparatus, and a process cartridge.

  In recent years, in the field of electrophotographic image forming apparatuses (electrophotographic apparatuses), there are increasing demands for speeding up of image forming processes, higher image quality, and longer life.

  However, it is not easy to satisfy all of these requirements at the same time, and in particular, when the speed is increased, image quality and life are often impaired. More specifically, when the image forming process is speeded up, the electrophotographic photosensitive member used for image writing is subjected to stress due to sliding with a charging member of a contact charging device or a cleaning member of a cleaning device. In many cases, wear causes image quality defects.

  Also, in the field of color image forming electrophotographic apparatuses, tandem (quadruple drum type) electrophotographic apparatuses are becoming widespread in order to cope with higher speeds. The problem is likely to be noticeable. That is, the frictional force between the electrophotographic photosensitive member and the cleaning device is reduced to some extent by the toner remaining on the electrophotographic photosensitive member after transfer, but in the tandem electrophotographic device, yellow, magenta, cyan, black Therefore, the amount of residual toner in each image forming unit is very small compared to the one-drum type. Therefore, particularly when the cleaning device uses a blade, the effect of reducing friction between the electrophotographic photosensitive member and the blade due to the toner is remarkably reduced, and the deterioration of both the electrophotographic photosensitive member and the blade tends to be accelerated. is there.

Therefore, methods for improving the friction characteristics of the electrophotographic photosensitive member have been studied. One of them is a technique using an electrophotographic photosensitive member in which a lubricating substance is held on the surface or inside of the photosensitive layer, and includes a long-chain barium carboxylate salt and a long-chain alkylcarboxylic acid group as the lubricating substance. The use of a transport material, silicone resin particles, fluororesin particles, or fully fluorinated oil has been proposed (see, for example, Patent Documents 1 to 5).
JP 2003-167368 A JP-A-11-109659 JP 11-218945 A JP 2000-75515 A Japanese Patent Laid-Open No. 2002-278122

  However, the conventional electrophotographic photosensitive member using a lubricating substance has room for improvement in the following points. That is, according to the study by the present inventors, among the above methods, when a photosensitive layer containing a lubricating substance is formed by a coating method, the lubricating substance and other constituent materials (binder resin, etc.) of the photosensitive layer are used. Insufficient compatibility with the coating layer tends to cause defects such as poor dispersion in the coating solution for forming the photosensitive layer, phase separation in the coating film, and repelling of the coating film during film formation.

  Further, even if no defect occurs, the lubricating substance segregates (bleeds) in the vicinity of the surface of the photosensitive layer. When such an electrophotographic photosensitive member is used for a long period of time, even if an effect due to the lubricating material is recognized in the initial stage, the effect cannot be sustained for a long period of time.

  On the other hand, in the case of the method of impregnating with a completely fluorinated oil after forming the photosensitive layer, there is no device that causes defects during the formation of the photosensitive layer, and it is possible to form a relatively uniform film. However, the degree of molecular freedom of the fully fluorinated oil is high, and the fact that it is not compatible with other constituent materials of the photosensitive layer is not essentially improved. For this reason, segregation (bleeding) of the fully fluorinated oil occurs, and it is difficult to ensure the sustainability of the effect as described above.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide an electrophotographic photosensitive member having sufficiently high friction characteristics and capable of maintaining the friction characteristics at a high level over a long period of time. It is to provide. Another object of the present invention is to provide an electrophotographic apparatus and a process cartridge which can realize high speed, high image quality and long life using the electrophotographic photosensitive member.

  In order to solve the above-mentioned problems, the present invention provides an electrophotographic photoreceptor comprising a conductive substrate and a photosensitive layer provided on the conductive substrate, the melting point being 30 ° C. or higher and 200 ° C. or lower. Provided is an electrophotographic photosensitive member characterized by heating a lubricating substance and bringing the molten lubricating substance into contact with the surface of the photosensitive layer opposite to the conductive substrate.

  As described above, the specific lubricating substance is heated, and the molten lubricating substance is exposed to the surface of the photosensitive layer opposite to the conductive substrate (that is, the contact surface with the contact charging member or the cleaning member at the time of image formation). ) Is increased, the space in the photosensitive layer for holding the lubricating substance is increased, and the lubricating substance is likely to penetrate into the photosensitive layer. Further, since the degree of freedom of the impregnated lubricating substance in the photosensitive layer is significantly reduced by cooling, the lubricating substance can be stably held in the photosensitive layer while suppressing segregation (bleeding). Therefore, according to the present invention, an electrophotographic photoreceptor having a sufficiently high friction characteristic and capable of maintaining the friction characteristic at a high level is realized.

  In addition, the electrophotographic photoreceptor of the present invention is also useful in terms of improving the image quality. For example, in recent years, in order to meet the demand for higher image quality, the toner has been reduced in particle size, made uniform in particle size distribution, and spheroidized. Development of manufactured toners, so-called chemical toners, has been actively conducted. However, in the case of a conventional electrophotographic photosensitive member, a cleaning failure such as residual toner slipping between the electrophotographic photosensitive member and the cleaning member easily occurs due to damage of the electrophotographic photosensitive member or the cleaning member. The high image quality due to use could not be fully exhibited. On the other hand, in the case of the electrophotographic photoreceptor of the present invention, since it has excellent friction characteristics as described above, damage to the electrophotographic photoreceptor or the cleaning member can be sufficiently suppressed. Even when combined, sufficient cleaning characteristics can be obtained. Therefore, by combining the electrophotographic photosensitive member of the present invention and the chemical toner, it is possible to realize a higher image quality (for example, photographic image quality).

  The electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor comprising a conductive substrate and a photosensitive layer provided on the conductive substrate, the surface of the photosensitive layer opposite to the conductive substrate. To a predetermined depth may include a lubricating substance holding portion containing a lubricating substance having a melting point of 30 ° C. or higher and 200 ° C. or lower.

  In this way, by providing the lubricating substance holding part in the specific area of the photosensitive layer, even if the photosensitive layer is worn away and the lubricating substance in the area is consumed with the use of the electrophotographic photosensitive member, the lower part thereof. Since the frictional force of the new surface is reduced by the existing lubricating substance, a high level of friction characteristics can be achieved over a long period of time.

  In the electrophotographic photosensitive member of the present invention, the photosensitive layer preferably has a layer containing a resin having a crosslinked structure on the side far from the conductive substrate. A resin having a crosslinked structure is preferable in that a space in the photosensitive layer for holding the lubricating substance is large, and the resin-containing layer is lubricated by bringing it into contact with the surface opposite to the conductive substrate. It is possible to more easily and reliably form the active substance holding portion. Further, with such a configuration, it is possible to obtain an unexpected effect that a phenomenon such as image flow due to discharge can be suppressed.

  The present invention also includes a first step of preparing a conductive substrate and an object to be processed having a photosensitive layer provided on the conductive substrate, and heating a lubricating material having a melting point of 30 ° C. or higher and 200 ° C. or lower. And a second step of bringing the molten lubricating substance into contact with the surface of the photosensitive layer of the object to be processed which is opposite to the conductive substrate, to provide a method for producing an electrophotographic photosensitive member. .

  In this way, by heating the specific lubricating substance and bringing the molten lubricating substance into contact with the surface of the photosensitive layer opposite to the conductive substrate, the lubricating substance is stably held in the photosensitive layer. The Therefore, according to the production method of the present invention, the electrophotographic photosensitive member of the present invention having excellent friction characteristics can be obtained easily and reliably.

  In the second step according to the method for producing an electrophotographic photosensitive member of the present invention, the molten lubricating material is applied to the surface of the photosensitive layer on the opposite side of the conductive substrate of the photosensitive member under reduced pressure or pressurized pressure. It is preferable to make it contact. Thereby, since the penetration of the lubricating substance into the photosensitive layer is promoted, the production efficiency and accuracy can be further improved.

  Further, the second step includes a step of bringing a molten lubricating substance into contact with the surface of the photosensitive layer on the side opposite to the conductive substrate under reduced pressure, and a molten lubricating property under pressure. And a step of bringing a substance into contact with the surface of the photosensitive layer of the object to be processed which is opposite to the conductive substrate. Thereby, since the penetration of the lubricating substance into the photosensitive layer is further promoted, the production efficiency and accuracy can be further improved.

  The present invention also provides an electrophotographic photosensitive member according to the present invention, a charging device that charges the electrophotographic photosensitive member, an exposure device that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image, and an electrostatic device. An electrophotographic apparatus comprising: a developing device that develops a latent image to form a toner image; and a transfer device that transfers the toner image from an electrophotographic photosensitive member to a transfer medium.

  The present invention also provides the electrophotographic photosensitive member of the present invention, a charging device for charging the electrophotographic photosensitive member, a developing device for developing a latent electrostatic image formed by exposure to form a toner image, and after transfer Provided is a process cartridge comprising at least one selected from a cleaning device that removes toner remaining on an electrophotographic photosensitive member.

  According to the electrophotographic apparatus and the process cartridge of the present invention, by using the electrophotographic photosensitive member of the present invention having excellent frictional characteristics, high speed, high image quality, and long life in electrophotographic image formation are achieved. Everything can be achieved at a high level and well-balanced.

  According to the present invention, it is possible to provide an electrophotographic photosensitive member that has sufficiently high friction characteristics and further suitability for chemical toners and that can maintain these characteristics at a high level for a long period of time. . In addition, according to the present invention, it is possible to provide an electrophotographic apparatus and a process cartridge that can achieve all of high speed, high image quality, and long life with a high level in a balanced manner.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be.

  FIG. 1 is a schematic sectional view showing a preferred embodiment of the electrophotographic photosensitive member of the present invention. In the electrophotographic photoreceptor 10 shown in FIG. 1, an undercoat layer 14 is provided on a conductive substrate 12, and a charge generation layer 15, a charge transport layer 16, and a protective layer 17 are further provided on the undercoat layer 14. The photosensitive layer 13 is configured by laminating in this order. Here, the protective layer 17 provided on the side far from the conductive substrate 12 of the photosensitive layer 13 is a layer containing a resin having a crosslinked structure. Further, the protective layer 17 has a lubricating substance holding part containing a lubricating substance that is solid at 30 ° C. and liquid at 200 ° C. in a region from the surface opposite to the conductive substrate 12 to a predetermined depth. .

  Hereinafter, each component of the electrophotographic photoreceptor 10 will be described.

  Examples of the conductive substrate 12 include a metal plate, a metal drum, a metal belt, or a conductive material using a metal or an alloy such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, or platinum. Examples thereof include paper, a plastic film, a belt, and the like on which a conductive compound such as a polymer or indium oxide, or a metal or alloy such as aluminum, palladium, or gold is applied, vapor-deposited, or laminated.

  When a metal pipe is used as the conductive substrate 12, the surface of the conductive substrate 12 may be a raw tube, but in order to prevent interference fringes generated when laser light is irradiated, the conductive substrate 12 is used. The surface on the photosensitive layer 13 side is preferably roughened, and the surface roughness is preferably 0.04 μm to 0.5 μm in terms of the centerline average roughness Ra. If Ra is smaller than 0.04 μm, it becomes close to a mirror surface, so that the effect of preventing interference cannot be obtained. If Ra is larger than 0.5 μm, even if a coating film according to the present invention is formed, the image quality becomes rough, which is not suitable. As a roughening method, wet honing is performed by suspending an abrasive in water and spraying it on the support, or centerless grinding in which the support is pressed against a rotating grindstone and grinding is performed continuously, an anode Treatment with an acidic treatment solution comprising oxidation, phosphoric acid, chromic acid and hydrofluoric acid, boehmite treatment and the like are preferred. When non-interfering light is used for the light source, it is not particularly necessary to roughen the interference fringes to prevent the occurrence of defects due to irregularities on the surface of the substrate, which is suitable for extending the life.

  The anodizing treatment is to form an oxide film on the aluminum surface by anodizing in an electrolyte solution using aluminum as an anode. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the intact porous anodic oxide film is chemically active, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the pores in the anodized film are sealed with pressurized water vapor or boiling water (a metal salt such as nickel may be added) by volume expansion due to a hydration reaction, and a sealing process is performed to change to a more stable hydrated oxide. . The thickness of the anodic oxide film is preferably 0.3 to 15 μm. When it is thinner than 0.3 μm, the barrier property against injection is poor and the effect is not sufficient. On the other hand, if it is thicker than 15 μm, the residual potential increases due to repeated use.

  In the case of performing treatment with an acidic treatment liquid comprising phosphoric acid, chromic acid and hydrofluoric acid, the mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is such that phosphoric acid is in the range of 10 to 11% by weight. Is in the range of 3 to 5% by weight, hydrofluoric acid is in the range of 0.5 to 2% by weight, and the concentration of these acids is preferably in the range of 13.5 to 18% by weight. The treatment temperature is preferably 42 to 48 ° C., but a thicker film can be formed faster by keeping the treatment temperature as high as possible. About the film thickness of a film, 0.3-15 micrometers is preferable. When it is thinner than 0.3 μm, the barrier property against injection is poor and the effect is not sufficient. On the other hand, if it is thicker than 15 μm, the residual potential increases due to repeated use.

  The boehmite treatment can be performed by immersing in pure water at 90 to 100 ° C. for 5 to 60 minutes or by contacting with heated steam at 90 to 120 ° C. for 5 to 60 minutes. About the film thickness of a film, 0.1-5 micrometers is preferable. This can be further anodized using an electrolyte solution with low film solubility such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate. Good.

  The constituent material of the undercoat layer 14 includes zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds such as titanate coupling agents, aluminum chelate compounds, In addition to organoaluminum compounds such as aluminum coupling agents, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum Titanium alkoxide compound, aluminum zirconium alkoxide compound , It includes organic metal compounds such as, among these, organic zirconium compound, an organic titanyl compound, since the organic aluminum compound to residual potential indicates a satisfactory electrophotographic properties lower, are preferably used.

  The undercoat layer 14 is composed of vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3 A silane coupling agent such as 1,4-epoxycyclohexyltrimethoxysilane may be contained.

  Further, the undercoat layer 14 is made of polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, A binder resin such as phenol resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, and polyacrylic acid may be further contained. The content ratio of the binder resin can be appropriately set as necessary.

  The undercoat layer 14 can also be used by mixing / dispersing an electron transporting pigment. Examples of the electron transport pigment include organic pigments such as perylene pigment, bisbenzimidazole perylene pigment, polycyclic quinone pigment, indigo pigment, and quinacridone pigment described in JP-A-47-30330, cyano group, nitro group, Examples thereof include organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as nitroso groups and halogen atoms, and inorganic pigments such as zinc oxide and titanium oxide. Among these pigments, perylene pigments, bisbenzimidazole perylene pigments and polycyclic quinone pigments, zinc oxide, and titanium oxide are preferably used because of their high electron mobility. Further, the surface of these pigments may be surface-treated with the above-mentioned coupling agent or binder for the purpose of controlling dispersibility and charge transport property. If the amount of the electron transporting pigment is too large, the strength of the undercoat layer is lowered and a coating film defect is caused.

  The undercoat layer 14 can be formed by applying a coating liquid obtained by mixing / dispersing the above-described constituent materials in a predetermined solvent onto the conductive substrate 12 and drying it. As the solvent, any solvent can be used as long as it can dissolve the term metal compound and the resin and does not cause gelation or aggregation during mixing / dispersion. For example, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene Ordinary organic solvents such as toluene can be used alone or in admixture of two or more. Examples of the mixing / dispersing method include a ball mill, a roll mill, a sand mill, an attritor, and an ultrasonic wave.

  In addition, as a method for applying the coating solution for forming the undercoat layer, conventional methods such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method can be used. Can be used. The undercoating layer 14 is obtained by drying the coating film formed in this manner. Usually, the drying is performed at a temperature at which the film can be formed by evaporating the solvent. The thickness of the undercoat layer 14 is generally 0.1 to 30 μm, preferably 0.2 to 25 μm.

  Note that when the conductive substrate 12 has been subjected to an acidic solution treatment or boehmite treatment, the defect concealing power of the conductive substrate 12 tends to be insufficient, so the undercoat layer 14 is formed as in this embodiment. It is preferable.

  The charge generation layer 15 includes a charge generation material and a binder resin. Charge generation materials include azo pigments such as bisazo and trisazo, condensed aromatic pigments such as dibromoanthanthrone, organic pigments such as perylene pigments, pyrrolopyrrole pigments, and phthalocyanine pigments, and inorganic pigments such as trigonal selenium and zinc oxide. Any conventionally known charge generating material can be used. In the exposure apparatus of the electrophotographic apparatus to which the electrophotographic photoreceptor 10 is applied, an inorganic pigment is preferable when the exposure wavelength is 380 nm to 500 nm, and when an exposure wavelength of 700 nm to 800 nm is used, metal and Metal phthalocyanine pigments are preferred. Among them, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279591, chlorogallium phthalocyanine disclosed in JP-A-5-98181, JP-A-5-140472 and special Dichlorotin phthalocyanine disclosed in Kaihei 5-140473 and titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 are particularly preferred.

  The binder resin for the charge generation layer 15 can be selected from a wide range of insulating resins. Alternatively, an organic photoconductive polymer such as poly-N-vinylcarbazole, polyvinyl anthracene, polyvinyl pyrene, or polysilane may be used as the binder resin. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin. Insulating resin such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin can be used, but is not limited thereto. These binder resins can be used alone or in admixture of two or more. The blending ratio of the charge generation material and the binder resin in the charge generation layer 15 (weight ratio) is preferably in the range of 10: 1 to 1:10.

  The charge generation layer 15 can be obtained by applying a coating solution obtained by adding the above-described constituent materials to a predetermined solvent and performing a dispersion treatment on the undercoat layer 14 and drying it. Solvents used include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, and methylene chloride. And organic solvents such as chloroform, chlorobenzene, and toluene. Among these, one kind can be used alone, or two or more kinds can be mixed and used. As a dispersion treatment method, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. At this time, a condition that the crystal type does not change by dispersion is required. In the dispersion treatment, it is effective that the average primary particle diameter of the particles made of the charge generating material is preferably 0.5 μm or less, more preferably 0.3 μm or less, and further preferably 0.15 μm or less.

  In addition, as a method for applying the coating solution for forming the undercoat layer, conventional methods such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method can be used. Can be used. The film thickness of the charge generation layer 15 thus formed is generally 0.1 to 5 μm, preferably 0.2 to 2.0 μm.

  The charge transport layer 16 is formed containing a charge transport material and a binder resin, or is formed containing a polymer charge transport material.

  As charge transport materials, quinone compounds such as p-benzoquinone, chloranilquinone, bromanylquinone, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds Compounds, electron transport compounds such as cyanovinyl compounds, ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include hole transporting compounds. These charge transport materials may be used alone or in combination of two or more, but are not limited thereto. These charge transport materials can be used alone or in combination of two or more. From the viewpoint of mobility, a compound having a structure represented by any one of the following general formulas (1) to (3) is preferable. .

一般式（１）中、Ｒ^１は水素原子又はメチル基を示し、ｎは１又は２を示す。また、Ａｒ^１及びＡｒ^２は各々独立に、置換又は未置換のアリール基、−Ｃ（Ｒ^２）＝Ｃ（Ｒ^３）（Ｒ^４）、―ＣＨ＝ＣＨ―ＣＨ＝Ｃ（Ｒ^５）_２（Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は各々独立に、水素原子、置換又は未置換のアルキル基、あるいは置換又は未置換のアリール基を示す）を示す。Ａｒ^１又はＡｒ^２が置換アリール基である場合の置換基としては、ハロゲン原子、アルキル基（好ましくは炭素数１〜５のアルキル基）、アルコキシ基（好ましくは炭素数１〜５のアルコキシ基）、又はアミノ基（好ましくは炭素数１〜３のアルキル基で置換された置換アミノ基）などが挙げられる。

In general formula (1), R ¹ represents a hydrogen atom or a methyl group, and n represents 1 or 2. Ar ¹ and Ar ² are each independently a substituted or unsubstituted aryl group, —C (R ² ) ═C (R ³ ) (R ⁴ ), —CH═CH—CH═C (R ⁵ ) _2. (R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group). As the substituent when Ar ¹ or Ar ² is a substituted aryl group, a halogen atom, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms) Or an amino group (preferably a substituted amino group substituted with an alkyl group having 1 to 3 carbon atoms).

一般式（２）中、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は各々独立に、水素原子、ハロゲン原子、炭素数１〜５のアルキル基、又は炭素数１〜５のアルコキシ基を示し、ｎ１、ｎ２、ｎ３及びｎ４は０〜２の整数である。また、Ｒ^１０及びＲ^１１は各々独立に、水素原子、ハロゲン原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、炭素数１〜２のアルキル基で置換されたアミノ基、置換又は未置換のアリール基、あるいは、−Ｃ（Ｒ^２）＝Ｃ（Ｒ^３）（Ｒ^４）、―ＣＨ＝ＣＨ―ＣＨ＝Ｃ（Ｒ^５）_２（Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は各々独立に、水素原子、置換又は未置換のアルキル基、あるいは置換又は未置換のアリール基を示す）を示す。

In General Formula (2), R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, n1, n2, n3, and n4 are integers of 0-2. R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an amino group substituted with an alkyl group having 1 to 2 carbon atoms. , A substituted or unsubstituted aryl group, or —C (R ² ) ═C (R ³ ) (R ⁴ ), —CH═CH—CH═C (R ⁵ ) ₂ (R ² , R ³ , R ⁴⁾ And R ⁵ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

一般式（３）中、Ｒ^１２は水素原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、置換又は未置換のアリール基、または、―ＣＨ＝ＣＨ―ＣＨ＝Ｃ（Ａｒ）_２（Ａｒは置換又は未置換のアリール基を示す）を示す。Ｒ^１３及びＲ^１４は各々独立に、水素原子、ハロゲン原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、炭素数１〜２のアルキル基で置換されたアミノ基、置換又は未置換のアリール基を表す。

In General Formula (3), R ¹² represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, or —CH═CH—CH═C ( Ar) ₂ (Ar represents a substituted or unsubstituted aryl group). R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group substituted with an alkyl group having 1 to 2 carbon atoms, Or an unsubstituted aryl group is represented.

  Examples of the binder resin used for the charge transport layer 16 include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, and vinylidene chloride. -Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N -Vinylcarbazole, polysilane, and polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used. These binder resins can be used alone or in admixture of two or more. The blending ratio (weight ratio) between the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  Further, as the constituent material of the charge transport layer 16, a polymer charge transport material can be used alone. As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, the polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have a high charge transporting property and are particularly preferable. The polymer charge transport material alone can be used as the charge transport layer, but it may be formed by mixing with the binder resin.

  In addition, an antioxidant, a light stabilizer, a heat stabilizer, etc. are added to the charge transport layer 16 for the purpose of preventing deterioration of the photoreceptor due to ozone, oxidizing gas, or light or heat generated in the copying machine. An agent can be added. For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds. Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine.

In addition, at least one kind of electron accepting substance can be contained in the charge transport layer 16 for the purpose of improving sensitivity, reducing residual potential, reducing fatigue during repeated use, and the like. Examples of the electron acceptor usable in the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, and o-dinitrobenzene. M-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and the like. Of these, benzene derivatives having electron-withdrawing substituents such as fluorenone-based, quinone-based, and -Cl, -CN, -NO ₂ are particularly preferable.

  The charge transport layer 16 can be formed by applying a coating liquid obtained by adding the above constituent materials to a predetermined solvent on the charge generation layer 15 and drying it. Solvents used in the coating solution for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenation such as methylene chloride, chloroform and ethylene chloride. Examples thereof include organic solvents such as aliphatic hydrocarbons, cyclic or linear ethers such as tetrahydrofuran and ethyl ether, and these may be used alone or in combination of two or more. As a coating method of the coating solution, a normal method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used. The thickness of the charge transport layer 16 thus formed is generally 5 to 50 μm, preferably 10 to 30 μm.

  The protective layer 17 is resistant to wear and scratches on the surface of the photosensitive layer 13 opposite to the conductive substrate 12 (that is, the contact surface with the contact charging member or the cleaning member during image formation), and In order to increase the transfer efficiency of the toner, it is preferable to provide a high-strength surface layer. As this high-strength surface layer, conductive fine particles are dispersed in a binder resin, lubricating fine particles such as fluororesin and acrylic resin are dispersed in a normal charge transport layer material, and a hard coat such as silicone or acrylic. An agent can be used, but from the viewpoint of strength, electrical characteristics, image quality maintenance, and the like, those having a charge transporting property and having a crosslinked structure are preferred, and those containing a charge transporting material are more preferred. Various materials can be used for forming the cross-linked structure, but phenolic resins, urethane resins, siloxane resins, and the like are preferable in terms of characteristics, and those made of siloxane resins are particularly preferable. Of these, those having structures derived from the compounds represented by the general formulas (I) and (II) are particularly preferred because of their excellent strength and stability.

F [-D-SiR ¹⁵ _3-a Q _a ] _b (I)
In general formula (I), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group, R ¹⁵ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted group. Or an unsubstituted aryl group, Q represents a hydrolyzable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4.

F [-(X) _p -R ¹⁶ -ZH] _q (II)
In general formula (II), F represents an organic group derived from a compound having a hole transport ability, R ¹⁶ represents an alkylene group, X represents an oxygen atom or a sulfur atom, Z represents an oxygen atom, a sulfur atom , —NH—, or —C (═O) —O— (carboxyl group), m represents an integer of 1 to 4, and n represents 0 or 1.

  The group represented by F in general formulas (I) and (II) is preferably a group represented by the following general formula (III).

一般式（ＩＩＩ）中、Ａｒ^１１〜Ａｒ^１４は各々独立に置換又は未置換のアリール基を示し、Ａｒ^１５は置換若しくは未置換のアリール基又はアリーレン基を示し、且つＡｒ^１１〜Ａｒ^１５のうち２〜４個は−Ｄ−ＳｉＲ^１５ _３−ａＱ_ａで表される基との結合手を有する。Ｄ、Ｒ^１５、Ｑ及びａはそれぞれ上記一般式（Ｉ）中のＤ、Ｒ^１５、Ｑ及びａと同一の定義内容を示す。

In General Formula (III), Ar ^{11 to} Ar ¹⁴ each independently represent a substituted or unsubstituted aryl group, Ar ¹⁵ represents a substituted or unsubstituted aryl group or an arylene group, and Ar ^{11 to} Ar ¹⁵ 2-4 has a bond to the group represented by _{^{-D-SiR 15 3-a Q}} a. D, R ¹⁵ , Q and a have the same definition as D, R ¹⁵ , Q and a in the general formula (I), respectively.

Ar ^{11 to} Ar ¹⁴ in the general formula (III) are preferably any of the following formulas (III-1) to (III-7).

−Ａｒ−Ｚ’_ｓ−Ａｒ−Ｚ_ｍ （ＩＩＩ−７）
［式中、Ｒ^１７は水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルキル基もしくは炭素数１〜４のアルコキシ基で置換されたフェニル基、または未置換のフェニル基、炭素数７〜１０のアラルキル基からなる群より選ばれる１種を示し、Ｒ^１８〜Ｒ^２０はそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、もしくは炭素数１〜４のアルコキシ基で置換されたフェニル基、または未置換のフェニル基、炭素数７〜１０のアラルキル基、ハロゲン原子からなる群より選ばれる１種を示し、Ａｒは置換又は未置換のアリーレン基を示し、Ｚは一般式（Ｉ）中の−Ｄ−ＳｉＲ^１５ _３−ａＱ_ａで表される基を示し、ｍ及びｓはそれぞれ０又は１を示し、ｔはそれぞれ１〜３の整数を示す。］
ここで、式（ＩＩＩ−７）中のＡｒとしては、下記式（ＩＩＩ−７−１）又は（ＩＩＩ−７−２）で表されるものが好ましい。

_{-Ar-Z 's -Ar-Z} m (III-7)
[Wherein, R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted phenyl group, represents one selected from the group consisting of an aralkyl group having 7 to 10 carbon ^atoms, R 18 ^{to R 20} each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or carbon atoms, 1 represents a group selected from the group consisting of a phenyl group substituted with 1 to 4 alkoxy groups, or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, and Ar represents a substituted or unsubstituted arylene represents a group, Z is the formula indicates _{^-D-SiR 15 ^3-a Q} group represented by _a in (I), m and s each represent 0 or 1, t is each an integer of 1 to 3 Indicates. ]
Here, as Ar in Formula (III-7), what is represented by following formula (III-7-1) or (III-7-2) is preferable.

［式中、Ｒ^２１及びＲ^２２はそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、未置換若しくは炭素数１〜４のアルコキシ基で置換されたフェニル基、炭素数７〜１０のアラルキル基又はハロゲン原子を示し、ｔは１〜３の整数を示す。］
また、式（ＩＩＩ−７）中のＺ’としては、下記式（ＩＩＩ−７−３）〜（ＩＩＩ−７−１０）のうちのいずれかで表されるものが好ましい。
−（ＣＨ_２）_ｑ− （ＩＩＩ−７−３）
−（ＣＨ_２ＣＨ_２Ｏ）_ｒ− （ＩＩＩ−７−４）

[Wherein R ²¹ and R ²² are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an unsubstituted or substituted phenyl group having 1 to 4 carbon atoms, An aralkyl group having 7 to 10 carbon atoms or a halogen atom is shown, and t is an integer of 1 to 3. ]
Moreover, as Z 'in Formula (III-7), what is represented by either of following formula (III-7-3)-(III-7-10) is preferable.
_{- (CH 2) q - (} III-7-3)
_{- (CH 2 CH 2 O)} r - (III-7-4)

［式中、Ｒ^２３及びＲ^２４はそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、未置換若しくは炭素数１〜４のアルコキシ基で置換されたフェニル基、炭素数７〜１０のアラルキル基又はハロゲン原子からなる群より選ばれる１種を示し、Ｗは２価の基を示し、ｑ及びｒはそれぞれ１〜１０の整数を示し、ｔはそれぞれ１〜３の整数を示す。］
上記式（ＩＩＩ−７−９）、（ＩＩＩ−７−１０）中のＷとしては、下記（ＩＩＩ−７−１１）〜（ＩＩＩ−７−１９）で表される２価の基のうちのいずれかであることが好ましい。

[Wherein, R ²³ and R ²⁴ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an unsubstituted or substituted phenyl group having 1 to 4 carbon atoms, 1 type chosen from the group which consists of a C7-C10 aralkyl group or a halogen atom, W shows a bivalent group, q and r show the integer of 1-10, respectively, and t shows 1-3 each. Indicates an integer. ]
W in the formulas (III-7-9) and (III-7-10) is a divalent group represented by the following (III-7-11) to (III-7-19). Either is preferable.

—CH ₂ — (III-7-11)
_{-C (CH 3) 2 - (} III-7-12)
-O- (III-7-13)
-S- (III-7-14)
_{-C (CF 3) 2 - (} III-7-15)
—Si (CH ₃ ) ₂ — (III-7-16)

［式中、ｕは０〜３の整数を表す］
一般式（Ｉ）で表される化合物の具体例として、Ａｒ^１１〜Ａｒ^１５、ｋ及びＳの組合せを表１〜８に示す。表中のＳは−Ｄ−ＳｉＲ^１５ _３−ａＱ_ａで表される基である。また、「Ｍｅ」はメチル基を意味する。

[Wherein u represents an integer of 0 to 3]
As specific examples of the compound represented by the general formula (I), combinations of Ar ^{11 to} Ar ¹⁵ , k and S are shown in Tables 1 to 8. S in the table is a group represented by -D-SiR ¹⁵ _3-a Q _a . “Me” means a methyl group.

一般式（ＩＩ）の具体例としては、下記式（ＩＩ）−１〜（ＩＩ）−２６で表される化合物を挙げることができる。

Specific examples of the general formula (II) include compounds represented by the following formulas (II) -1 to (II) -26.

また、強度、膜抵抗などの種々の物性をコントロールするために、下記一般式（ＩＶ）で示される化合物を添加することもできる。

In addition, in order to control various physical properties such as strength and film resistance, a compound represented by the following general formula (IV) can also be added.

SiR ²⁵ _4-c Q _c (IV)
(In the formula, R ²⁵ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and c represents an integer of 1 to 4.)
Specific examples of the compound represented by the general formula (IV) include the following silane coupling agents. Tetrafunctional alkoxysilane such as tetramethoxysilane and tetraethoxysilane (c = 4); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltri Methoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3, 3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoro Trifunctional alkoxysilanes such as decyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (c = 3); bifunctional alkoxy such as dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane Silane (c = 2); monofunctional alkoxysilane such as trimethylmethoxysilane (c = 1) and the like can be mentioned. Tri- and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and bi- and monofunctional alkoxysilanes are preferable for improving flexibility and film-forming properties.

  In addition, silicone-based hard coating agents mainly produced from these coupling agents can also be used. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), and AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning). Can be used.

In order to increase the strength, it is also preferable to use a compound having two or more silicon atoms as shown in the general formula (V).
B- (SiR ²⁶ _3-a Q _a ) ₂ (V)
(In the formula, B represents a divalent organic group, R ²⁶ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and a represents an integer of 1 to 3. Is shown.)
Specific examples of the compound represented by the general formula (V) include the compounds (V-1) to (V-16) shown in Table 9 below as preferable examples. It is not limited at all.

また、放電ガス耐性、機械強度、耐傷性、粒子分散性、粘度コントロール、トルク低減、磨耗量コントロール、ポットライフの延長などの目的でなどの調整のために熱可塑性樹脂を添加してもよい。熱可塑性樹脂としては、アルコール系、ケトン系溶剤に可溶な樹脂としては、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、ブチラールの一部がホルマールやアセトアセタール等で変性された部分アセタール化ポリビニルアセタール樹脂などのポリビニルアセタール樹脂（たとえば積水化学社製エスレックＢ、Ｋなど）、ポリアミド樹脂、セルロ−ス樹脂、フェノール樹脂、エポキシ樹脂、ポリイミド樹脂などがあげられる。特に、電気特性上ポリビニルアセタール樹脂、ポリアミド樹脂、フェノール樹脂が好ましい。上記樹脂の分子量は２０００〜１０００００が好ましく、５０００〜５００００がさらに好ましい。分子量は２０００より小さいと所望の効果が得られなくなり、１０００００より大きいと溶解度が低くなり添加量が限られてしまったり、塗布時に製膜不良の原因になったりする。添加量は１〜４０％が好ましく、さらに好ましくは１〜３０％であり、５〜２０％が最も好ましい。１％よりも少ない場合は所望の効果が得られにくくなり、４０％よりも多くなると高温高湿下での画像ボケが発生しやすくなる。
また、ポットライフの延長、膜特性のコントロール、トルク低減のため、下記一般式（ＶＩ）で示される繰り返し構造単位を持つ環状化合物、もしくはその化合物からの誘導体を含有させることも出来る。

In addition, a thermoplastic resin may be added for adjustments such as discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, and pot life extension. As thermoplastic resins, resins soluble in alcoholic and ketone solvents include polyvinyl butyral resins, polyvinyl formal resins, partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal, acetoacetal, etc. Examples thereof include polyvinyl acetal resins (for example, Sleksui B and K manufactured by Sekisui Chemical Co., Ltd.), polyamide resins, cellulose resins, phenol resins, epoxy resins and polyimide resins. In particular, polyvinyl acetal resin, polyamide resin, and phenol resin are preferable in terms of electrical characteristics. The molecular weight of the resin is preferably 2000-100000, more preferably 5000-50000. If the molecular weight is less than 2000, the desired effect cannot be obtained. If the molecular weight is more than 100,000, the solubility becomes low and the addition amount is limited, or the film formation is poor at the time of coating. The addition amount is preferably 1 to 40%, more preferably 1 to 30%, and most preferably 5 to 20%. When it is less than 1%, it is difficult to obtain a desired effect, and when it is more than 40%, image blurring under high temperature and high humidity tends to occur.
In addition, in order to extend pot life, control film properties, and reduce torque, a cyclic compound having a repeating structural unit represented by the following general formula (VI) or a derivative thereof can be contained.

（Ａ^１及びＡ^２は各々独立に１価の有機基を示す。）
一般式（ＶＩ）で示される繰り返し構造単位を持つ環状化合物として、市販の環状シロキサンを挙げることができる。具体的には、ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン等の環状ジメチルシクロシロキサン類、１，３，５−トリメチル−１，３，５−トリフェニルシクロトリシロキサン、１，３，５，７−テトラメチル−１，３，５，７−テトラフェニルシクロテトラシロキサン、１，３，５，７，９−ペンタメチル−１，３，５，７，９−ペンタフェニルシクロペンタシロキサン等の環状メチルフェニルシクロシロキサン類、ヘキサフェニルシクロトリシロキサン等の環状フェニルシクロシロキサン類、３−（３，３，３−トリフルオロプロピル）メチルシクロトリシロキサン等のフッ素含有シクロシロキサン類、メチルヒドロシロキサン混合物、ペンタメチルシクロペンタシロキサン、フェニルヒドロシクロシロキサンなどのヒドロシリル基含有シクロシロキサン類、ペンタビニルペンタメチルシクロペンタシロキサンなどのビニル基含有シクロシロキサン類等の環状のシロキサン等を挙げることができる。これらの環状シロキサン化合物は単独で用いても良いが、それらを混合して用いても良い。

(A ¹ and A ² each independently represents a monovalent organic group.)
A commercially available cyclic siloxane can be mentioned as a cyclic compound having a repeating structural unit represented by the general formula (VI). Specifically, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3,5-trimethyl-1,3,5- Triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7 , 9-pentaphenylcyclopentasiloxane and other cyclic methylphenylcyclosiloxanes, hexaphenylcyclotrisiloxane and other cyclic phenylcyclosiloxanes, and 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane and other fluorine Contain cyclosiloxanes and methylhydrosiloxane Things, pentamethylcyclopentasiloxane include a phenyl hydrosilyl group-containing cyclosiloxanes such hydrocyclosiloxane, cyclic siloxanes and vinyl group-containing cyclosiloxanes, such as penta vinyl pentamethylcyclopentasiloxane like. These cyclic siloxane compounds may be used alone or as a mixture thereof.

  Furthermore, various fine particles can be added to the protective layer 17 in order to control the antifouling substance adhesion prevention property, lubricity, hardness and the like on the surface of the electrophotographic photosensitive member. The fine particles can be used alone or in combination. Examples of the fine particles include silicon-containing fine particles. Silicon-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles. The colloidal silica used as the silicon-containing fine particles is selected from those having an average particle diameter of 1 to 100 nm, preferably 10 to 30 dispersed in an acidic or alkaline aqueous dispersion, or an organic solvent such as alcohol, ketone or ester. A commercially available product can be used. The solid content of colloidal silica in the outermost surface layer is not particularly limited, but is 0.1 to 50% by weight in the total solid content of the outermost surface layer in terms of film forming properties, electrical characteristics, and strength. Is used, preferably in the range of 0.1 to 30% by weight.

  Silicon fine particles, which are one type of silicon-containing fine particles, are spherical and have an average particle diameter of 1 to 500 nm, preferably 10 to 100 nm, selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and are generally commercially available. You can use what you have. Silicone fine particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain sufficient characteristics is low, the electron does not hinder the crosslinking reaction, The surface properties of the photographic photoreceptor can be improved. In other words, it is possible to improve the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly incorporated into a strong cross-linked structure, and to maintain good wear resistance and adherence to contaminants over a long period of time. it can. The content of the silicone fine particles in the outermost surface layer in the electrophotographic photosensitive member of the present invention is in the range of 0.1 to 30% by weight, preferably 0.5 to 10% by weight in the total solid content of the outermost surface layer. Range.

Other fine particles include fluorine-based fine particles such as ethylene tetrafluoride, trifluoride ethylene, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and the 8th Polymer Materials Forum Lecture Proceedings, page 89. Fine particles made of a resin obtained by copolymerizing a fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO _{2 as shown in FIG.} And semiconductive metal oxides such as ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. For the same purpose, an oil such as silicone oil can be added. Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Examples thereof include reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes. These may be added in advance to the coating solution, or may be impregnated under reduced pressure or increased pressure after producing the photoreceptor.

  In addition, additives such as plasticizers, surface modifiers, antioxidants, and photodegradation inhibitors can also be used. Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, and various fluorohydrocarbons. An antioxidant having a hindered phenol, hindered amine, thioether or phosphite partial structure can be added to the resin layer in the present invention, which is effective in improving the potential stability and image quality when the environment changes. . Antioxidants include the following compounds, such as “Sumizer BHT-R”, “Sumizer MDP-S”, “Sumizer BBM-S”, “Sumizer WX-R”, “Sumizer NW” as hindered phenols, "Sumilizer BP-76", "Sumilizer BP-101", "Sumilizer GA-80", "Sumilizer GM", "Sumizer GS" or more manufactured by Sumitomo Chemical Co., Ltd., "IRGANOX1010", "IRGANOX1035", "IRGANOX10X", "98" ”,“ IRGANOX1135 ”,“ IRGANOX1141 ”,“ IRGANOX1222 ”,“ IRGANOX1330 ”,“ IRGANOX1 25WL, "IRGANOX1520L", "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", "IRGANOX565" "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-70", "ADK STAB AO-80", "ADK STAB AO-330" or more, manufactured by Asahi Denka. As the hindered amine series, “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744”, “Tinuvin 144”, “Tinuvin 622LD”, “Mark LA57”, “Mark LA67”, “Mark LA62”, “Mark LA68”, “Mark LA63”, “Smilizer TPS”, “Smilizer TP-D” as thioether system, “Mark 2112”, “Mark PEP / 8”, “Mark PEP / 8G”, “Mark” as phosphite system PEP · 36 ”,“ Mark 329K ”,“ Mark HP · 10 ”, and hindered phenols and hindered amine antioxidants are particularly preferable. Further, they may be modified with a substituent such as an alkoxysilyl group capable of undergoing a crosslinking reaction with the material forming the crosslinked film.

  For the purpose of further improving the lubricity, a resin having a plurality of groups having active hydrogen in the side chain and having a fluorine atom or a Si—O bond may be added. Examples of this include SG204 (manufactured by Nippon Shokubai Co., Ltd.), ZX-007C, ZX022, ZX022H, ZX022G (manufactured by Fuji Kasei Kogyo Co., Ltd.), Modiper series (manufactured by Nippon Oil & Fats Co., Ltd.), Cephral coat series (Central Glass). Etc.). Moreover, it is also possible to create and synthesize appropriately according to the purpose. Discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life extension, cleaning system life extension by adding fluorine atom or Si-O bond resin Effects such as can be obtained. Furthermore, by using a compound having a plurality of active hydrogens in the side chain, chemical bonds can be formed in the crosslinked structure, so that these resins are easily dispersed uniformly in the film, and the above effects are maintained over a long period of time. In addition, it is possible to obtain an effect of reducing defects during coating. Furthermore, by using the resin, it is possible to obtain an effect that a large amount of fluorine-based material and silicone-based material, which have been added in a limited amount, can be added without causing defects in the coating film.

  A resin having a plurality of groups having active hydrogen in the side chain and having a fluorine atom or Si—O bond can exert the above-mentioned effect by simply adding it to the coating solution. Is made of a siloxane-based resin containing at least one of a compound having a silicon atom or a hydrolyzate or hydrolysis condensate thereof, it is more effective to replace the protective group in the liquid preparation step as follows. The characteristics can be exhibited.

  As the hydrolyzable substituent, a chlorosilyl group, an alkoxysilyl group, an acetoxysilyl group, an enoxysilyl group, an aminosilyl group, and the like are used. Among them, an alkoxysilyl group is most commonly used. Further, it is known that the hydrolysis reactivity of the alkoxysilyl group is derived from the number of carbon atoms of the alkoxy group, and the smaller the carbon number, the higher the reactivity of hydrolysis.

  The exchange of the protective group is carried out by reacting the organosilicon compound alone or together with the inorganic material precursor in a system containing at least the desired protective group precursor. Here, taking the case of an alkoxysilyl group as an example, the protective group precursor means an alcohol, and by using an alcohol having a small number of carbon atoms, it can be converted into a highly hydrolyzable protective group. By using an alcohol having a large carbon number, it can be converted into a protecting group having low hydrolyzability. In this case, a resin having a plurality of groups having active hydrogen in the side chain and having a fluorine atom or a silicone bond can be considered as a protecting group having a high carbon number, that is, a hydrolyzable low protecting group. By performing a group exchange reaction, the compound has a chemical bond with a compound having a charge transporting ability and the like, so that the respective affinity is increased and the film forming property is improved. Further, in the hydrolysis carried out later, the chemical bond with the compound having a charge transporting ability is hardly broken by hydrolysis because of its low hydrolyzability. Although a series of these processes can be confirmed by various analytical means, a method using GPC, NMR, TLC (thin layer chromatography) or the like is simple. In that case, the protective group can be efficiently exchanged by using an appropriate catalyst. As the catalyst to be used, the same catalysts as those used in the hydrolysis can be used. The following can be given as preferred examples, but the present invention is not limited to these.

  Resins having a plurality of active hydrogen-containing groups in the side chain and fluorine atoms or Si—O bonds are soluble in alcohol-based and ketone-based solvents, such as uniform dispersion, coating solution stability, coating properties, etc. It is preferable in terms of The molecular weight of the resin is preferably 2000-100000, more preferably 5000-50000. If the molecular weight is less than 2000, the desired effect cannot be obtained. If the molecular weight is more than 100,000, the solubility becomes low and the addition amount is limited, or the film formation is poor at the time of coating. Moreover, the addition amount of the resin is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, based on the total amount of the constituent materials of the protective layer 17. If the amount is less than 1% by weight, it is difficult to obtain a desired effect. If the amount is more than 40% by weight, image blurring under high temperature and high humidity tends to occur. The said resin may be used individually by 1 type, or may mix and use 2 or more types.

The protective layer 17 can be formed using a coating solution containing the above-described constituent materials. When preparing the coating liquid for forming the protective layer, it is preferable to add a catalyst. Catalysts used include inorganic acids such as hydrochloric acid, acetic acid, phosphoric acid and sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid and maleic acid, potassium hydroxide and hydroxide An alkali catalyst such as sodium, calcium hydroxide, ammonia, triethylamine, or a solid catalyst insoluble in the system can be used. Amberlite 15, Amberlite 200C, Amberlist 15E (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Co.); Levacit SPC-108, Levacit SPC-118 (above, Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite-464 (Above, manufactured by Sumitomo Chemical Co., Ltd.); cation exchange resins such as Nafion-H (manufactured by DuPont); shades such as Amberlite IRA-400 and Amberlite IRA-45 (above, manufactured by Rohm and Haas) Ion exchange resin; Zr (O ₃ PCH ₂ CH ₂ SO ₃ H) ₂ , Th (O ₃ PCH ₂ CH ₂ COOH) ₂ An inorganic solid in which a group containing a proton acid group such as ₂ is bonded to the surface; a polyorganosiloxane containing a proton acid group such as a polyorganosiloxane having a sulfonic acid group; cobalt tungstic acid , Heteropolyacids such as phosphomolybdic acid; isopolyacids such as niobic acid, tantalum acid, and molybdic acid; monometallic oxides such as silica gel, alumina, chromia, zirconia, CaO, and MgO; silica-alumina, silica-magnesia, silica -Complex metal oxides such as zirconia and zeolites; clay minerals such as acid clay, activated clay, montmorillonite and kaolinite; metal sulfates such as LiSO ₄ and MgSO ₄ ; metal phosphates such as zirconia phosphate and lanthanum phosphate _{salt; LiNO 3, Mn (NO 3} ) 2 Any metal nitrate; inorganic solid obtained by reacting aminopropyltriethoxysilane on silica gel with a group containing an amino group such as a solid; polyamino group containing an amino group such as an amino-modified silicone resin And organosiloxane.

Further, when preparing a coating solution for forming a protective layer, it is preferable to use a solid catalyst that is insoluble in a photofunctional compound, a reaction product, water, a solvent, etc., because the stability of the coating solution tends to be improved. . The solid catalyst insoluble in the system is not particularly limited as long as the catalyst component is insoluble in a material for forming a resin having a crosslinked structure, other additives, water, a solvent and the like. Although the usage-amount of these solid catalysts is not specifically limited, 0.1-100 weight part is preferable with respect to a total of 100 weight part of the compound which has a hydrolysable group. Further, as described above, these solid catalysts are insoluble in raw material compounds, reaction products, solvents and the like, and therefore can be easily removed after the reaction according to a conventional method. The reaction temperature and reaction time are appropriately selected according to the type and amount of the raw material compound or solid catalyst, but the reaction temperature is usually 0 to 100 ° C, preferably 10 to 70 ° C, more preferably 15 to 50. The reaction time is preferably 10 minutes to 100 hours. When the reaction time exceeds the upper limit, gelation tends to occur. When preparing a coating solution for forming a protective layer, if a catalyst that is insoluble in the system is used, strength, storage stability, etc. are improved. For this purpose, it is preferable to further use a catalyst that dissolves in the system. Such catalysts include, in addition to those described above, aluminum triethylate, aluminum triisopropylate, aluminum tri (sec-butyrate), mono (sec-butoxy) aluminum diisopropylate, diisopropoxyaluminum (ethyl acetoacetate). ), Aluminum tris (ethyl acetoacetate), aluminum bis (ethyl acetoacetate) monoacetylacetonate, aluminum tris (acetylacetonate), aluminum diisopropoxy (acetylacetonate), aluminum isopropoxy-bis (acetylacetonate) Organic aluminum compounds such as aluminum tris (trifluoroacetylacetonate) and aluminum tris (hexafluoroacetylacetonate) It is possible to use.

  Besides organic aluminum compounds, organic compounds such as dibutyltin dilaurate, dibutyltin dioctiate, and dibutyltin diacetate; titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis Organic titanium compounds such as (isopropoxy) bis (acetylacetonate); zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate), etc. Zirconium compounds; etc. can also be used, but from the viewpoints of safety, low cost, and pot life length, it is preferable to use an organoaluminum compound, particularly an aluminum chelate compound. It is more preferable. Although the usage-amount of these catalysts is not restrict | limited in particular, 0.1-20 weight part is preferable with respect to a total of 100 weight part of the compound which has a hydrolysable group, and 0.3-10 weight part is especially preferable.

In the present invention, when an organometallic compound is used as a catalyst, it is preferable to add a multidentate ligand from the viewpoint of pot life and curing efficiency. Examples of such multidentate ligands include those shown below and those derived therefrom, but the present invention is not limited to these. Specifically, β-diketones such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, and dipivaloylmethylacetone; acetoacetates such as methyl acetoacetate and ethyl acetoacetate; bipyridine and derivatives thereof; glycine and its Derivatives; ethylenediamine and derivatives thereof; 8-oxyquinoline and derivatives thereof; salicylaldehyde and derivatives thereof; catechol and derivatives thereof; bidentate ligands such as 2-oxyazo compounds; diethyltriamine and derivatives thereof; nitrilotriacetic acid and derivatives thereof And tridentate ligands such as ethylenediaminetetraacetic acid (EDTA) and derivatives thereof. In addition to the organic ligands as described above, inorganic ligands such as pyrophosphoric acid and triphosphoric acid can be exemplified. As the multidentate ligand, a bidentate ligand is particularly preferable, and a bidentate ligand represented by the following general formula (VII) is more preferable, and R ²⁷ and R ^{28 in the following} general formula (VII) are more preferable. Are particularly preferred. By making R ²⁷ and R ^{28 the} same, the coordination power of the ligand near room temperature becomes strong, and the coating agent can be further stabilized.

（式中、Ｒ^２７及びＲ^２８は各々独立に炭素数１〜１０のアルキル基、フッ化アルキル基、又は炭素数１〜１０のアルコキシ基を示す。）
多座配位子の配合量は、任意に設定することができるが、用いる有機金属化合物の１モルに対し、０．０１モル以上、好ましくは０．１モル以上、より好ましくは１モル以上とするのが好ましい。

(In the formula, R ²⁷ and R ²⁸ each independently represent an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, or an alkoxy group having 1 to 10 carbon atoms.)
The compounding amount of the polydentate ligand can be arbitrarily set, but is 0.01 mol or more, preferably 0.1 mol or more, more preferably 1 mol or more, with respect to 1 mol of the organometallic compound used. It is preferable to do this.

  The protective layer 17 can be formed in the absence of a solvent if the coating solution is liquid, but alcohols such as methanol, ethanol, propanol, and butanol; ketones such as acetone and methyl ethyl ketone as necessary. In addition to tetrahydrofuran; ethers such as diethyl ether and dioxane; and the like, various solvents may be used. As such a solvent, those having a boiling point of 100 ° C. or less are preferable, and they can be arbitrarily mixed and used. The amount of the solvent can be arbitrarily set, but if it is too small, the organosilicon compound is likely to be precipitated. Therefore, it is 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight based on 1 part by weight of the organosilicon compound. preferable.

  The reaction temperature and reaction time for curing the curable component in the coating liquid for forming the protective layer are not particularly limited, but the reaction temperature is preferably 60 ° C. from the viewpoint of mechanical strength and chemical stability of the obtained resin. As mentioned above, More preferably, it is 80-200 degreeC, and reaction time becomes like this. Preferably it is 10 minutes-5 hours. In addition, maintaining the organic layer obtained by curing the coating liquid in a high humidity state is effective in stabilizing the characteristics of the organic layer. Furthermore, the protective layer 17 obtained can be subjected to surface treatment to be hydrophobized using hexamethyldisilazane, trimethylchlorosilane, or the like depending on the application.

  A siloxane-based resin having a charge transporting property and having a cross-linked structure has excellent mechanical strength and sufficient photoelectric characteristics. Therefore, it can be used as it is as a charge transport layer of a multilayer photoreceptor. In that case, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used. However, when a required film thickness cannot be obtained by a single application, the necessary film thickness can be obtained by applying a plurality of times. When performing multiple times of repeated application, the heat treatment may be performed every time of application, or after multiple times of repeated application. The film thickness of the protective layer 17 thus formed is preferably 1 to 10 μm, more preferably 1 to 5 μm.

  The surface of the protective layer 17 thus formed on the side opposite to the conductive substrate 12 is heated and brought into contact with the molten lubricating substance, whereby the electrophotographic photosensitive member of the present invention is obtained. The lubricating substance used in the present invention has a melting point of 30 ° C. or higher and 200 ° C. or lower. Furthermore, the melting point of the lubricating material is preferably 40 ° C. or higher and 180 ° C. or lower from the viewpoints of friction characteristics and compatibility with chemical toners, stability, and productivity.

  The lubricating substance used in the present invention is not particularly limited as long as it is capable of imparting lubricity to the surface of the protective layer 17 and the melting point satisfies the above conditions. Solid lubricants such as fatty acids and fatty acid metal salts, higher alcohols such as tetradecanol and octadecanol, low molecular weight polyolefins such as polypropylene, polyethylene and polybutene, silicones having a softening point upon heating, oleic amide Aliphatic amides such as erucic acid amide, ricinoleic acid amide, stearic acid amide, etc., plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animals such as beeswax Wax, montan wax, ozokerite, ceresin, paraffin wax, my B wax, mineral such as Fischer-Tropsch wax, petroleum wax, and of a modified product thereof, satisfying the above conditions as is available. These lubricating substances may be used alone or in combination of two or more.

  A method for bringing the molten lubricating substance into contact with the surface of the protective layer 17 is not particularly limited, but it is preferable to impregnate the molten lubricating substance from the surface side with the protective layer 17. By impregnating in this way, the lubricating substance holding part can be easily and reliably formed in a region from the surface of the protective layer 17 to a predetermined depth.

  Further, the contact of the molten lubricating substance with the surface of the protective layer 17 is preferably performed under pressure or reduced pressure, and both the operation under pressure and the operation under reduced pressure can be performed. More preferred. Thereby, formation of a lubricous substance holding part can be performed more easily and reliably. The pressure at the time of pressurization is preferably 0.01 MPa or more when the atmospheric pressure is 0. On the other hand, the pressure when reducing the pressure is preferably -0.05 MPa or less. The operation under pressure and the operation under reduced pressure may be repeated a plurality of times.

  The formation of the lubricating substance holding portion can also be performed by dissolving the lubricating substance in a suitable solvent, impregnating the protective layer 17 in the solution from the surface side, and then drying. . In this case, the lubricating substance does not have to be heated to its melting point or higher to be melted. As the solvent used for the preparation of the solution, a solvent that does not substantially swell or dissolve the protective layer 17 is preferable, and alcohol, paraffin solvent, etc. are used alone, or these solvents and toluene, tetrahydrofuran, methyl ethyl ketone, etc. You may mix and use a solvent in the range which does not swell or melt | dissolve the protective layer 17 substantially.

  As described above, in this embodiment, the protective layer 17 containing a resin having a crosslinked structure is provided, and the molten lubricant is brought into contact with the surface of the protective layer 17 on the side opposite to the conductive base 12 to thereby obtain a predetermined value from the surface. The lubricating substance holding part can be easily and reliably formed in the region up to the depth. Therefore, according to the present embodiment, the electrophotographic photosensitive member 10 having a sufficiently high friction characteristic and capable of maintaining the friction characteristic at a high level is realized.

  The present invention is not limited to the above embodiment. For example, when the charge transport layer 16 has sufficient strength, the protective layer 17 may not be provided. In this case, the lubricated substance that has been heated and melted is brought into contact with the surface of the charge transport layer 16 on the side opposite to the conductive substrate 12, thereby holding the lubricant substance in a region from the surface of the charge transport layer 16 to a predetermined depth. Part is formed.

  The electrophotographic photosensitive member 10 shown in FIG. 1 is a function-separated type photosensitive member in which a charge generation layer 15 and a charge transport layer 16 are separately provided. The electrophotographic photosensitive member of the present invention is a charge generation material. A single-layer type photosensitive layer containing both of the charge transport material and the charge transport material may be provided. As the constituent material of the single-layer type photosensitive layer, the charge generation material, the charge transport material, and the binder resin exemplified in the description of the above embodiment can be used. The content of the charge generating material in the single-layer type photosensitive layer is preferably 10 to 85% by weight, more preferably 20 to 50% by weight. The content of the charge transport material is preferably 5 to 50% by weight. The single-layer type photosensitive layer may contain a compound represented by the general formula (I). The solvent and coating method used for coating are the same as in the above embodiment. The film thickness of the single-layer type photosensitive layer is preferably about 5 to 50 μm, more preferably 10 to 40 μm.

  Next, the electrophotographic apparatus of the present invention will be described. FIG. 2 is a sectional view schematically showing a basic configuration of a preferred embodiment of the electrophotographic apparatus of the present invention. An electrophotographic apparatus 200 shown in FIG. 2 includes a drum-shaped electrophotographic photosensitive member 207 that is the electrophotographic photosensitive member of the present invention, a charging device 208 that charges the electrophotographic photosensitive member 207 by a contact charging method, and a charging device 208. The connected power source 209, the exposure device 210 that exposes the electrophotographic photosensitive member 207 charged by the charging device 208 to form an electrostatic latent image, and the electrostatic latent image formed by the exposure device 210 are developed with toner. A developing device 211 that forms a toner image, a transfer device 212 that transfers the toner image formed by the developing device 211 to the transfer medium P, a cleaning device 213, a static eliminator 214, and a fixing device 215. . In this case, the static eliminator 214 may not be provided.

  The charging device 208 shown in FIG. 2 contacts a contact-type charging member (for example, a charging roll) with the surface of the photoconductor 207 to uniformly apply a voltage to the photoconductor to charge the surface of the photoconductor to a predetermined potential. Is.

  As the contact-type charging member, a roller-shaped member in which an elastic layer, a resistance layer, a protective layer and the like are provided on the outer peripheral surface of the core material is preferably used. The shape of the contact-type charging member may be any of the above-mentioned roller shape, brush shape, blade shape, pin electrode shape, film shape, etc., and can be arbitrarily selected according to the specifications and form of the electrophotographic apparatus. it can.

  As a material of the core material in the roller-shaped contact type charging member, a conductive material such as iron, copper, brass, stainless steel, aluminum, nickel or the like is used. Also, a resin molded product in which conductive particles or the like are dispersed can be used.

As the material of the elastic layer on the outer peripheral surface of the core material, a material having conductivity or semiconductivity, for example, a material in which conductive particles or semiconducting particles are dispersed in a rubber material can be used. EPDM, polybutadiene, natural rubber, polyisobutylene, SBR, CR, NBR, silicone rubber, urethane rubber, epichlorohydrin rubber, SBS, thermoplastic elastomer, norbornene rubber, fluorosilicone rubber, ethylene oxide rubber, chloroprene rubber, isoprene Rubber, epoxy rubber or the like is used. Examples of conductive particles or semiconductive particles include carbon black, zinc, aluminum, copper, iron, nickel, chromium, titanium, and other metals, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O _3. Metal oxides such as —SnO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , Sb ₂ O ₃ , In ₂ O ₃ , ZnO, and MgO can be used. . These materials can be used individually by 1 type or in mixture of 2 or more types.

  Moreover, as a material of the resistance layer and the protective layer on the outer peripheral surface of the core material, a material in which conductive particles or semiconductive particles are dispersed in a binder resin and the resistance thereof is controlled is used. Examples of the binder resin include acrylic resin, cellulose resin, polyamide resin, methoxymethylated nylon, ethoxymethylated nylon, polyurethane resin, polycarbonate resin, polyester resin, polyethylene resin, polyvinyl resin, polyarylate resin, polythiophene resin, PFA, A polyolefin resin such as FEP or PET, a styrene-butadiene resin, or the like is used. In addition, as the conductive particles or semiconductive particles dispersed in the binder resin, the same carbon black, metal, and metal oxide as the elastic layer are used. Moreover, antioxidants, such as hindered phenol and hindered amine, fillers, such as clay and kaolin, lubricants, such as silicone oil, etc. can be added as needed. As a means for forming these layers, a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, a melt molding method, an injection molding method, or the like is used. be able to.

  When charging the photoreceptor using these contact-type charging members, a voltage is applied to the contact-type charging member. The applied voltage may be either a DC voltage or a DC voltage superimposed with an AC voltage.

  Instead of the contact charging member in FIG. 2, a non-contact type corona charging device such as a corotron or a scorotron can be used. These can be arbitrarily selected according to the specifications and form of the electrophotographic apparatus.

  As the exposure apparatus 210, an optical system apparatus that can expose a light source such as a semiconductor laser, an LED (light emitting diode), and a liquid crystal shutter on the surface of the electrophotographic photosensitive member in a desired image-like manner can be used. When a laser is used as the exposure light source, the oscillation wavelength of the laser is preferably from 350 nm to 850 nm, and a shorter wavelength is more preferable because of excellent resolution.

  In recent years, high-definition image writing using a surface emitting laser (VCSEL) or a laser with a wavelength of about 380 to 450 nm has been performed for the purpose of improving image quality. In this case, high-definition image writing is required. As a result, the influence of the driving accuracy of the electrophotographic photosensitive member is remarkably increased. Therefore, in the conventional electrophotographic apparatus, when the rotational torque of the electrophotographic photosensitive member is high, image density unevenness (so-called “banding”) easily occurs due to vibration of the photosensitive member. On the other hand, in the electrophotographic apparatus of the present invention, since the rotational torque can be sufficiently reduced by using the electrophotographic photosensitive member of the present invention, a remarkable effect can be obtained in terms of banding suppression. Furthermore, the ability to reduce the rotational torque in this way is very useful because it leads to lower power consumption in the drive motor of the electrophotographic photosensitive member.

  As the developing device 211, a conventionally known developing device using a regular or reversal developer such as a one-component system or a two-component system can be used.

The shape of the toner used in the developing device 211 is not particularly limited, but a spherical toner is preferable from the viewpoint of high image quality and ecology. The spherical toner has a spherical shape having an average shape factor (ML ² / A) of 100 to 140, preferably 100 to 130, more preferably 100 to 125 in order to achieve high transfer efficiency. Toner.

Here, the average shape factor (ML ² / A) is an average value of the shape factors obtained for the toner particles. The average shape factor of each toner particle is calculated from the maximum length and area by measuring the equivalent circle diameter by taking an image obtained by observing the toner with an optical microscope into an image analyzer (for example, LUZEX III, manufactured by Nireco). :
(ML ² / A) = (maximum length) ² × π × 100 / [4 × (area)]
Can be determined according to In the case of a true sphere, ML ² / A = 100.

  The spherical toner contains at least a binder resin and a colorant. The spherical toner may preferably use particles having a size of 10 μm or less, more preferably particles having a size of 8 μm or less.

  Binder resins include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate, and methyl acrylate. , Α-methylene aliphatic monocarboxylic esters such as ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, vinyl Homopolymers and copolymers of vinyl ethers such as methyl ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone can be exemplified, Typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. Examples thereof include a polymer, polyethylene, and polypropylene. Further examples include polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like. Also, using a crystalline resin having a melting point at an appropriate temperature is effective in reducing the fixing temperature and suppressing energy consumption.

  In addition, as colorants, magnetic powders such as magnetite and ferrite, carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, Lamp Black, Rose Bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 can be exemplified as a representative one.

  The spherical toner may be internally added or externally added with a known additive such as a release agent, a charge control agent, and other inorganic fine particles.

  Typical examples of the releasing agent include low molecular polyethylene, low molecular polypropylene, Fischer-Tropsch wax, montan wax, carnauba wax, rice wax, and candelilla wax.

  As such a charge control agent, a known one can be used, but an azo metal complex compound, a metal complex compound of salicylic acid, a resin type charge control agent containing a polar group, or the like can be used.

  In the present invention, lubricating particles may be added to the toner. Lubricating particles include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids and fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene and polybutene, silicones having a softening point upon heating, oleic amides Aliphatic amides such as erucic acid amide, ricinoleic acid amide, stearic acid amide, etc., plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animals such as beeswax -Based wax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc., mineral wax, petroleum wax, and modified products thereof can be used alone or in combination. May be. However, the average particle size may be in the range of 0.1 to 10 μm, and the particles having the above chemical structure may be pulverized to have the same particle size. The amount added to the toner is preferably 0.05 to 2.0% by weight, more preferably 0.1 to 1.5% by weight.

  In addition, the toner used in the present invention may be added with inorganic fine particles, organic fine particles, composite fine particles obtained by attaching inorganic fine particles to the organic fine particles, etc. for the purpose of removing deposits and deteriorated matters on the surface of the electrophotographic photoreceptor. it can. Inorganic fine particles include silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, Various inorganic oxides such as manganese oxide, boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride, nitrides, borides, and the like are preferably used. Titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, γ- (2-aminoethyl) Aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane hydrochloride , Hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane Alternatively, the treatment may be performed with a silane coupling agent such as decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, or the like. In addition, hydrophobic treatment with a higher fatty acid metal salt such as silicone oil, aluminum stearate, zinc stearate or calcium stearate is also preferably used.

  Examples of the organic fine particles include styrene resin particles, styrene-acrylic resin particles, polyester resin particles, and urethane resin particles.

  If the particle size of the organic fine particles is too small, the polishing ability is insufficient, and if it is too large, the surface of the electrophotographic photosensitive member is likely to be damaged, so that the average particle size is 5 nm to 1000 nm, preferably 5 nm to 800 nm. Preferably, the one at 5 nm to 700 nm is used. Moreover, it is preferable that the sum of the addition amount of the organic fine particles and the addition amount of the lubricating particles is 0.6% by weight or more.

  As other components added to the toner, it is preferable to use inorganic oxide particles having an average primary particle size of 40 nm or less from the viewpoint of powder fluidity, charge control and the like. On the other hand, it is preferable to add an inorganic oxide having an average primary particle size exceeding 40 nm in order to reduce adhesion and control charging. These inorganic oxide fine particles may be known ones, but it is preferable to use silica and titanium oxide in combination for precise charge control. Further, the surface treatment of the small-diameter inorganic fine particles increases the dispersibility and increases the effect of increasing the powder fluidity.

  In addition, a surface lubricant (metal fatty acid salt) and fine particles having an abrasive effect can be added to the spherical toner.

  The spherical toner is not particularly limited by the production method, and can be obtained by a known method. Specifically, for example, a kneading and pulverizing method, a method of changing the shape of particles obtained by the kneading and pulverizing method with mechanical impact force or thermal energy, an emulsion polymerization aggregation method, a dissolution suspension method and the like can be mentioned. In addition, a manufacturing method may be performed in which the spherical toner obtained by the above method is used as a core, and aggregated particles are further adhered and heat-fused to give a core-shell structure. When the external additive is added, it can be produced by mixing the spherical toner and the external additive with a Henschel mixer or a V blender. In addition, when the spherical toner is manufactured by a wet method, it can be externally added by a wet method.

  When the toner used in the present invention is an electrophotographic color toner, the toner is mixed with a carrier and used as a carrier, such as iron powder, glass beads, ferrite powder, nickel powder or a surface thereof. A resin coating is used. The mixing ratio with the carrier can be set as appropriate.

  Examples of the transfer device 212 include a roller-type contact charging member, a contact-type transfer charger using a belt, a film, a rubber blade, or the like, a scorotron transfer charger using a corona discharge, a corotron transfer charger, or the like. .

  The cleaning device 213 is for removing residual toner adhering to the surface of the electrophotographic photosensitive member after the transfer process. The cleaned electrophotographic photosensitive member is repeatedly used for the image forming process described above. . As the cleaning device, brush cleaning, roll cleaning, and the like can be used in addition to the cleaning blade. Among these, it is preferable to use the cleaning blade.

  The material of the cleaning blade is not particularly limited. For example, a urethane prepolymer composed of a polyol such as a polyester polyol such as polyethylene adipate or polycaprolactone and an isocyanate such as diphenylmethane diisocyanate, 1,4-butanediol, or trimethylolpropane. A material using a crosslinking agent such as ethylene glycol or a mixture thereof as a raw material is preferable from the viewpoint that the obtained blade member is excellent in wear resistance and has high mechanical strength.

  As the urethane prepolymer, for example, those having an NCO group content of about 4 to 10% by weight and a viscosity at 70 ° C. of about 1000 to 3000 cP are preferably used. The thickness of the blade member is not particularly limited as long as it has sufficient strength to remove unnecessary toner on the surface of the photoreceptor, and is preferably about 1 to 3 mm. . Further, when the cleaning blade is attached to a mounting bracket, which will be described later, using an adhesive that is reactively cured by irradiation with ultraviolet rays or the like, the cleaning blade is transparent and can transmit ultraviolet rays or the like. It is preferable to have a thickness. The rubber hardness of the cleaning blade is not particularly limited as long as it has sufficient strength to remove unnecessary toner on the surface of the photoreceptor, and is usually 65 to 85 (JIS A hardness: JIS). Preferably, it is about the same as that of K7312 (1996).

  In order to obtain a cleaning blade for an electrophotographic apparatus containing fine particles, for example, the following method can be employed. First, the raw material of the blade material adjusted to have a desired blending amount is stirred and mixed for about 1 to 3 minutes using a mixing and stirring device such as an agitator. The mixture is rotated at about 120 to 160 ° C. at about 100 to 300 rpm, for example, after being injected into a molding drum mold of a centrifugal molding machine, and then the number of rotations of the molding drum mold is increased to about 600 to 1200 rpm for injection. The mixed liquid is uniformly spread on the inner surface of the molding drum mold, and a blade material in a state in which bubbles entrained at the time of injection float on the surface. Here, the amount of the liquid mixture injected into the molding drum mold may be adjusted so that a blade member having a desired thickness can be obtained. Next, while maintaining the rotational speed of the molding drum mold at about 600 to 1200 rpm and the temperature at about 120 to 160 ° C., the abrasive particles are uniformly dispersed using a spray gun or the like before the blade material is crosslinked and cured. After spraying the suspension onto the blade material, the blade material is cured while rotating the molding drum mold so that abrasive fine particles are present at least on the cleaning surface. The medium for obtaining the suspension in which the abrasive fine particles are uniformly dispersed is not particularly limited as long as it does not exhibit an interaction between the abrasive fine particles and the blade material. For example, a blade material is obtained. When using silicone oil such as dimethylpolysiloxane, methylphenylpolysiloxane, trifluoropropylmethylpolysiloxane, etc., which is usually used in the case of the present invention and has a function of promoting defoaming, fine particles of abrasive are used. This is preferable because it can be uniformly transferred to the blade material surface. Although it is sufficient that abrasive fine particles are uniformly dispersed in the abrasive, the amount of abrasive fine particles present on the cleaning surface can be adjusted by the amount of abrasive fine particles in the suspension. The abrasive fine particles are preferably blended in an amount of about 1 to 20 parts per 100 parts of the medium (parts by weight, the same applies hereinafter). Further, the desired amount of abrasive fine particles can be directly mixed and dispersed in the raw material of the blade material, and then molded.

In order to spray the suspension onto the blade material, a spray gun or the like is used, and the air pressure and the spray amount during such spraying are adjusted according to the amount of abrasive fine particles to be present on the cleaning surface. Usually, the air pressure is preferably about 1 to 10 kg / cm ² , and the spray amount is preferably about 0.5 to ⁵ mg / cm ² . The time when the suspension material is sprayed onto the blade material may be any time as long as the blade material is spread uniformly in the molding drum mold and before the blade material is cured in a state where air bubbles emerge on the surface of the blade material. However, since it depends on the desired depth when the abrasive particles are impregnated into the blade member, it cannot be determined unconditionally. However, after putting the blade material into the molding drum mold, it is usually about 2 to 10 minutes. The time has passed. In the blade member obtained in this way, the abrasive fine particles are firmly adhered at least to the cleaning surface or immersed inside, and the physical properties such as tensile strength and tear strength and adhesion to the mounting bracket do not deteriorate. It has excellent durability. Further, since the abrasive fine particles are present at least on the cleaning surface by centrifugal force, the degree of polishing performance can be adjusted by adjusting the spray amount of the suspension of the fine abrasive particles, the timing of spraying, the rotational speed of the molding drum mold, etc. The durability of polishing performance can be controlled.

  The above-mentioned blade member for an electrophotographic apparatus is integrated with a mounting bracket by using, for example, a hot melt adhesive or a double-sided tape to form a cleaning blade, and is mounted on an electrophotographic apparatus for PPC, PPP, PPF, etc. Can be used. The mounting bracket is not particularly limited. For example, a mounting bracket made of a rigid metal, an elastic metal, plastic, ceramic, or the like, which is usually used for a cleaning blade, can be used. A mounting bracket made of an untreated steel plate, a steel plate that has been subjected to a surface treatment such as zinc phosphate treatment or chromate treatment, or a steel plate that has been subjected to plating treatment is particularly preferred from the viewpoint that it does not cause changes over time such as corrosion. Further, the blade member may be a single layer or a laminate in which a plurality of materials are bonded together.

  As the blade material, any material can be used as long as it has a lower hardness than the surface of the electrophotographic photosensitive member. However, in particular, when used as a cleaning blade, the contact condition of the cleaning blade to the photosensitive member is as follows. The setting angle of the cleaning blade is preferably 5 ° or more and 50 ° or less, and preferably 10 ° or more and 35 ° or less from the viewpoint of cleaning properties and blade turning. Further, the pressure contact force of the cleaning blade is preferably 0.5 to 7 g / mm, and more preferably 1 g to 5 g / mm from the viewpoints of cleaning properties and photoreceptor torque. Further, an elastic body such as urethane rubber or silicone rubber having a hardness of 65 to 80 ° and a rebound resilience of 15 to 60% is preferable. If the elastic body is out of these ranges, the toner slips out and the blade peeling easily occurs.

  Further, the blade may be molded so that toner is easily deposited on the tip of the blade, and a thin film film of the same material or a different material such as PET film, PP film, or paper may be used as an adhesive or The pool portion may be produced by pasting together with a double-sided tape or the like.

  The toner accumulated in the toner reservoir is contaminated if it stays for a long time, and the cleaning effect is lowered. Therefore, it is preferable to remove the contaminated toner by rotating the electrophotographic photosensitive member reversely or regularly. At this time, it is also preferable to provide a mechanism or member that effectively removes toner accumulated at the same time as the reverse rotation or after the reverse rotation.

  The electrophotographic apparatus of the present invention may further include an erase light irradiation device 214 as shown in FIG. As a result, when the electrophotographic photosensitive member is repeatedly used, the phenomenon that the residual potential of the electrophotographic photosensitive member is brought into the next cycle is prevented, so that the image quality can be further improved.

  FIG. 3 is a schematic configuration diagram showing another embodiment of the electrophotographic photosensitive member of the present invention. An electrophotographic apparatus 300 shown in FIG. 3 includes a drum-shaped electrophotographic photosensitive member 312 of the present invention. The electrophotographic photosensitive member 312 is shown by an arrow A in the drawing at a predetermined rotational speed by a driving device (not shown). It is provided to be rotatable in the direction of. A charger 314 for charging the outer peripheral surface of the electrophotographic photosensitive member 312 is provided above the electrophotographic photosensitive member 312.

  An exposure device 316 including a surface emitting laser array as an exposure light source is disposed above the charger 314. The exposure device 316 modulates a plurality of laser beams emitted from a light source in accordance with an image to be formed and deflects the laser beams in the main scanning direction, so that the electrophotographic photosensitive member 312 is formed on the outer peripheral surface of the electrophotographic photosensitive member 312. It is made to scan in parallel with the axis. As a result, an electrostatic latent image is formed on the outer peripheral surface of the charged electrophotographic photosensitive member 312.

  A developing device 318 is disposed on the side of the electrophotographic photosensitive member 312. The developing device 318 includes a roller-shaped container that is rotatably arranged. Four accommodating portions are formed inside the accommodating body, and developing devices 318Y, 318M, 318C, and 318K are provided in the accommodating portions. Each of the developing devices 318Y, 318M, 318C, and 318K includes a developing roller 320, and stores Y, M, C, and K color toners therein.

  The full-color image is formed by the electrophotographic apparatus 300 while the electrophotographic photosensitive member 312 is rotated four times. That is, while the electrophotographic photosensitive member 312 is rotated four times, the charger 314 continues to charge the outer peripheral surface of the electrophotographic photosensitive member 312, the charge eliminating / cleaning device 322 continues to discharge the outer peripheral surface, and the exposure device 316 should be formed. The electrophotographic photosensitive member 312 is rotated once by scanning the outer peripheral surface of the electrophotographic photosensitive member 312 with a laser beam modulated according to any of Y, M, C, and K image data representing a color image. Each time it repeats, it repeats while switching the image data used for the modulation of the laser beam. The developing device 318 operates the developing unit corresponding to the outer peripheral surface in a state where the developing roller 320 of any of the developing units 318Y, 318M, 318C, 318K corresponds to the outer peripheral surface of the electrophotographic photosensitive member 312. The electrostatic latent image formed on the outer peripheral surface of the electrophotographic photosensitive member 312 is developed to a specific color, and a toner image of the specific color is formed on the outer peripheral surface of the electrophotographic photosensitive member 312. Every time the body 312 rotates once, the process is repeated while rotating the container so that the developing unit used for developing the electrostatic latent image is switched. Accordingly, every time the electrophotographic photosensitive member 312 rotates, toner images of Y, M, C, and K are sequentially formed on the outer peripheral surface of the electrophotographic photosensitive member 312 so as to overlap each other. When the electrophotographic photosensitive member 312 rotates four times, a full-color toner image is formed on the outer peripheral surface of the electrophotographic photosensitive member 312.

  An endless intermediate transfer belt 324 is disposed substantially below the electrophotographic photosensitive member 312. The intermediate transfer belt 324 is wound around rollers 326, 328, and 330, and is disposed so that the outer peripheral surface is in contact with the outer peripheral surface of the electrophotographic photosensitive member 312. The rollers 326, 328, and 330 are rotated by transmission of a driving force of a motor (not shown) to rotate the intermediate transfer belt 324 in the direction of arrow B in FIG.

  A transfer device (transfer device) 32 is disposed on the opposite side of the electrophotographic photosensitive member 312 with the intermediate transfer belt 324 interposed therebetween. A toner image formed on the outer peripheral surface of the electrophotographic photosensitive member 312 is transferred by the transfer device 32. The image is transferred to the image forming surface of the intermediate transfer belt 324.

  Further, on the opposite side of the developing device 318 with the electrophotographic photoreceptor 312 interposed therebetween, a lubricant supply device 21 and a cleaning device 22 are disposed on the outer peripheral surface of the electrophotographic photoreceptor 312. When the toner image formed on the outer peripheral surface of the electrophotographic photosensitive member 312 is transferred to the intermediate transfer belt 324, the area carrying the transferred toner image on the outer peripheral surface is cleaned by the cleaning device 322. The

  A tray 334 is disposed below the intermediate transfer belt 324, and a large number of sheets P as recording materials are accommodated in the tray 334 in a stacked state. In FIG. 3, a take-out roller 336 is disposed obliquely above and to the left of the tray 334, and a roller pair 338 and a roller 340 are arranged in this order on the downstream side in the take-out direction of the paper P by the take-out roller 336. The uppermost recording sheet in the stacked state is taken out of the tray 334 by rotating the take-out roller 336 and is conveyed by the roller pair 338 and the roller 340.

  A transfer device 342 is disposed on the opposite side of the roller 330 with the intermediate transfer belt 324 interposed therebetween. The sheet P conveyed by the roller pair 338 and the roller 340 is sent between the intermediate transfer belt 324 and the transfer unit 342, and the toner image formed on the image forming surface of the intermediate transfer belt 324 is transferred by the transfer device 342. . A fixing device 344 having a pair of fixing rollers is disposed downstream of the transfer device 342 in the conveyance direction of the paper P. The paper P on which the toner image is transferred is transferred by the fixing device 344. After being fused and fixed, it is discharged out of the electrophotographic apparatus 300 and placed on a discharge tray (not shown).

  FIG. 4 is a sectional view schematically showing a basic configuration of another embodiment of the electrophotographic apparatus of the present invention. An electrophotographic apparatus 400 shown in FIG. 3 is an intermediate transfer type electrophotographic apparatus, and includes four electrophotographic photoreceptors 401a to 401d (for example, the electrophotographic photoreceptor 401a is yellow and the electrophotographic photoreceptor 401b is in a housing 420). Magenta, electrophotographic photosensitive member 401c can be formed with cyan, and electrophotographic photosensitive member 401d can be formed with black.) Are arranged in parallel with each other along intermediate transfer belt 409.

  Here, the electrophotographic photoreceptors 401a to 401d mounted on the electrophotographic apparatus 400 are the electrophotographic photoreceptors of the present invention.

  Each of the electrophotographic photosensitive members 401a to 401d can be rotated in a predetermined direction (counterclockwise on the paper surface), and the charging rolls 402a to 402d, the developing devices 404a to 404d, and the primary transfer roll 410a along the rotation direction. To 410d and cleaning blades 415a to 415d are arranged. Each of the developing devices 404a to 404d can be supplied with toner of four colors of black, yellow, magenta and cyan accommodated in the toner cartridges 405a to 405d, and the primary transfer rolls 410a to 410d are respectively intermediate transfer belts. 409 is in contact with the electrophotographic photoreceptors 401a to 401d.

  Further, a laser light source (exposure device) 403 is disposed at a predetermined position in the housing 420, and the surfaces of the charged electrophotographic photoreceptors 401a to 401d are irradiated with laser light emitted from the laser light source 403. Is possible. Accordingly, charging, exposure, development, primary transfer, and cleaning are sequentially performed in the rotation process of the electrophotographic photosensitive members 401a to 401d, and the toner images of the respective colors are transferred onto the intermediate transfer belt 409 in an overlapping manner.

  The intermediate transfer belt 409 is supported with a predetermined tension by a drive roll 406, a backup roll 408, and a tension roll 407, and can rotate without causing deflection due to the rotation of these rolls. Further, the secondary transfer roll 413 is disposed so as to contact the backup roll 408 via the intermediate transfer belt 409. The intermediate transfer belt 409 passing between the backup roll 408 and the secondary transfer roll 413 is cleaned by, for example, a cleaning blade 416 disposed in the vicinity of the drive roll 406 and then repeatedly used for the next image forming process. Is done.

  A tray (transfer object tray) 411 is provided at a predetermined position in the housing 420, and a transfer medium P such as paper in the tray 411 is transferred to the intermediate transfer belt 409 and the secondary transfer roll by the transfer roll 412. The sheet is sequentially transferred between the two fixing rolls 414 that are in contact with each other and between the two fixing rolls 414, and then discharged to the outside of the housing 420.

  In the above description, the case where the intermediate transfer belt 409 is used as the intermediate transfer member has been described. However, the intermediate transfer member may have a belt shape like the intermediate transfer belt 409 or a drum shape. Also good. In the case of a belt shape, a conventionally known resin can be used as the resin material used as the base material of the intermediate transfer member. For example, polyimide resin, polycarbonate resin (PC), polyvinylidene fluoride (PVDF), polyalkylene terephthalate (PAT), ethylenetetrafluoroethylene copolymer (ETFE) / PC, ETFE / PAT, PC / PAT blend material, polyester Resin materials such as polyether ether ketone and polyamide, and resin materials using these as main raw materials. Furthermore, a resin material and an elastic material can be blended and used.

  As an elastic material, polyurethane, chlorinated polyisoprene, NBR, chloropyrene rubber, EPDM, hydrogenated polybutadiene, butyl rubber, silicone rubber, or the like can be used, or a material obtained by blending two or more kinds can be used. If necessary, a conductive agent imparting electronic conductivity or a conductive agent having ionic conductivity is added to the resin material and elastic material used for these base materials in combination of one kind or two or more kinds. Among these, it is preferable to use a polyimide resin in which a conductive agent is dispersed from the viewpoint of excellent mechanical strength. As the conductive agent, a conductive polymer such as carbon black, metal oxide, or polyaniline can be used.

  When a belt-shaped configuration such as the intermediate transfer belt 409 is employed as the intermediate transfer member, the thickness of the belt is generally preferably 50 to 500 μm and more preferably 60 to 150 μm, but is appropriately selected according to the hardness of the material. be able to.

  For example, a belt made of a polyimide resin in which a conductive agent is dispersed is 5 to 20% by weight as a conductive agent in a polyamic acid solution as a polyimide precursor, as described in JP-A-63-111263. After the carbon black is dispersed, the dispersion is cast on a metal drum and dried, and then the film peeled off from the drum is stretched at a high temperature to form a polyimide film. Can be produced.

  The film molding is generally performed by injecting a polyamic acid solution film-forming stock solution in which a conductive agent is dispersed into a cylindrical mold and, for example, heating at 100 to 200 ° C. at a rotational speed of 500 to 2000 rpm. The film was formed into a film by a centrifugal molding method while being rotated, and then the obtained film was demolded in a semi-cured state and covered with an iron core, and subjected to a polyimide reaction (polyamide acid) at a high temperature of 300 ° C. or higher. It can be carried out by proceeding a ring-closing reaction) and carrying out main curing. Also, the stock solution is cast on a metal sheet to a uniform thickness and heated to 100-200 ° C. to remove most of the solvent in the same manner as above, and then gradually raised to a high temperature of 300 ° C. or higher. There is also a method of forming a polyimide film. The intermediate transfer member may have a surface layer.

  When a drum-shaped configuration is adopted as the intermediate transfer member, it is preferable to use a cylindrical substrate formed of aluminum, stainless steel (SUS), copper, or the like as the substrate. If necessary, an elastic layer can be coated on the cylindrical substrate, and a surface layer can be formed on the elastic layer.

  The transfer target in the present invention is not particularly limited as long as it is a medium to which a toner image formed in the shape of an electrophotographic photosensitive member is transferred. For example, when transferring directly from an electrophotographic photosensitive member to paper or the like, paper or the like is a transfer target, and when an intermediate transfer member is used, the intermediate transfer member is a transfer target.

  Next, the process cartridge of the present invention will be described. FIG. 5 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of a process cartridge including the electrophotographic photosensitive member of the present invention. In addition to the electrophotographic photosensitive member 207, the process cartridge 500 includes a charging device 208, a developing device 211, a cleaning device (cleaning means) 213, an opening 218 for exposure, and an opening 217 for static elimination exposure. Are combined and integrated with each other.

  The process cartridge 500 is detachably attached to an image forming apparatus main body including a transfer device 212, a fixing device 215, and other components (not shown), and the image forming apparatus together with the image forming apparatus main body. It constitutes.

  In the above-described image forming apparatus and process cartridge, it is possible to obtain a high level of image quality by using the electrophotographic photosensitive member of the present invention which is excellent in friction characteristics, compatibility with chemical toners, and maintenance of those characteristics. In addition, even when a contact charging device with high stress on the electrophotographic photosensitive member is used, particularly excellent durability is exhibited. Specifically, the electrophotographic photosensitive member can be used for 200000 cycles or more, further 250,000 cycles, or 300000 cycles or more.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

In Examples 1 to 22 and Comparative Examples 1 to 14 shown below, two electrophotographic photoreceptors having the same laminated structure were prepared using an aluminum substrate having an outer diameter of 30 mmφ and an aluminum substrate having an outer diameter of 84 mmφ. .
[Example 1]
The outer peripheral surface of the cylindrical aluminum substrate was polished by a centerless polishing apparatus, and the surface roughness was set to Rz = 0.6 μm. As a cleaning process, this aluminum substrate was subjected to degreasing treatment, etching treatment for 1 minute with a 2 wt% sodium hydroxide solution, neutralization treatment, and pure water washing in this order. Next, as an anodizing treatment step, an aluminum substrate was treated with a 10 wt% sulfuric acid solution to form an anodized film (current density 1.0 A / dm ² ) on the outer peripheral surface. After washing with water, sealing was performed by dipping in a 1 wt% nickel acetate solution at 80 ° C. for 20 minutes. Further, pure water washing and drying treatment were performed. In this way, an anodized film having a thickness of 7 μm was formed on the surface of the aluminum substrate.

  Next, 1 weight of chlorogallium phthalocyanine having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 ° and 28.3 ° in the X-ray diffraction spectrum. A part was mixed with 1 part by weight of polyvinyl butyral (ESREC BM-S, Sekisui Chemical Co., Ltd.) and 100 parts of n-butyl acetate, and the mixture was treated with a glass bead for 1 hour and dispersed. The obtained coating solution was applied by dip coating on the outer peripheral surface of the above aluminum substrate, and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts by weight of a benzidine compound represented by the following formula (4), 3 parts by weight of a polymer compound having a structural unit represented by the following formula (5) (viscosity average molecular weight: 39,000), and 20 parts of chlorobenzene The coating solution dissolved in is dip coated on the charge generation layer and heated at 110 ° C. for 40 minutes to form a 20 μm-thick charge transport layer, and the conductive substrate / charge generation layer / charge transport layer An object to be processed having a laminated structure was obtained.

次に、耐圧容器内で、モンタン酸モノエステルワックス（Ｌｉｃｏｗａｘ Ｅ、クラリアントジャパン製、融点：７９〜８５℃）を１００℃に加熱し、溶融したモンタン酸モノエステルワックス中に、上記被処理体の電荷輸送層を浸漬した。この温度を保ちながら、耐圧容器内を−０．０８ＭＰａに減圧し、１０分間保持した後、常圧に戻した。さらに、耐圧容器内を０．１ＭＰａに加圧し、１０分間保持した後、常圧に戻した。この加圧操作及び減圧操作を３回繰り返した後、被処理体を取り出し、電荷輸送層側の表面に付着したモンタン酸モノエステルワックスをゴムブレードにて除去した。さらに、被処理体を冷却し、電荷輸送層側の表面を、ヘキサンを紙ワイパー（商品名：キムワイプ、以下同様）に染み込ませたもので十分にふき取り、目的の電子写真感光体を得た。
［実施例２］
先ず、実施例１と同様にして、導電性基体／電荷発生層／電荷輸送層の積層構造を有する被処理体を作製した。

Next, in a pressure-resistant container, a montanic acid monoester wax (Licowax E, manufactured by Clariant Japan, melting point: 79 to 85 ° C) is heated to 100 ° C, and in the melted montanic acid monoester wax, The charge transport layer was immersed. While maintaining this temperature, the pressure vessel was depressurized to -0.08 MPa, held for 10 minutes, and then returned to normal pressure. Further, the inside of the pressure vessel was pressurized to 0.1 MPa, held for 10 minutes, and then returned to normal pressure. After repeating this pressurizing operation and depressurizing operation three times, the object to be treated was taken out, and the montanic acid monoester wax adhering to the surface on the charge transport layer side was removed with a rubber blade. Further, the object to be processed was cooled, and the surface on the charge transport layer side was sufficiently wiped with a paper wiper (trade name: Kimwipe, hereinafter the same) soaked in hexane to obtain the intended electrophotographic photosensitive member.
[Example 2]
First, in the same manner as in Example 1, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer was produced.

  Next, 2 parts by weight of a compound represented by the following formula (6), 2 parts by weight of methyltrimethoxysilane, 0.5 parts by weight of tetramethoxysilane, 0.3 parts by weight of colloidal silica, and a fluorine graft polymer (ZX007C, Fuji Kasei) 0.5 parts by weight was dissolved in a mixed solvent of 5 parts by weight of isopropyl alcohol, 3 parts by weight of tetrahydrofuran and 0.3 part by weight of distilled water. To this solution, 0.5 part by weight of an ion exchange resin (Amberlyst 15E) was added, followed by hydrolysis at room temperature for 24 hours.

加水分解後の反応混合物からイオン交換樹脂を濾過分離した液に対し、アルミニウムトリスアセチルアセトナート（Ａｌ（ａｑａｑ）３）０．１重量部、及び３，５−ジ−ｔ−ブチル−４−ヒドロキシトルエン（ＢＨＴ）０．４重量部を加え、保護層形成用塗布液を得た。この塗布液を上記電荷輸送層の上にリング型浸漬塗布法により塗布し、室温で３０分風乾した後、１７０℃で１時間加熱処理して硬化させ、膜厚約５μｍの保護層を形成し、導電性基体／電荷発生層／電荷輸送層／保護層の積層構造を有する被処理体を得た。

0.1 parts by weight of aluminum trisacetylacetonate (Al (aqaq) 3) and 3,5-di-t-butyl-4-hydroxy are used for the liquid obtained by filtering and separating the ion exchange resin from the reaction mixture after hydrolysis. Toluene (BHT) 0.4 part by weight was added to obtain a coating solution for forming a protective layer. This coating solution is applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 170 ° C. for 1 hour to form a protective layer having a thickness of about 5 μm. Thus, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was obtained.

Next, in a pressure-resistant container, a montanic acid monoester wax (Licowax E, manufactured by Clariant Japan, melting point: 79 to 85 ° C) is heated to 100 ° C, and in the melted montanic acid monoester wax, The protective layer was immersed. While maintaining this temperature, the inside of the pressure vessel was pressurized to 0.1 MPa and held for 10 minutes. After returning the pressure to normal pressure, the object to be treated was taken out, and the montanic acid monoester wax adhering to the surface on the protective layer side was removed with a rubber blade. After the object to be processed was cooled, the surface on the protective layer side was sufficiently wiped with a paper wiper soaked in hexane to obtain the desired electrophotographic photosensitive member.
[Example 3]
First, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was produced in the same manner as in Example 2.

Next, paraffin wax (HNP9, manufactured by Nippon Seiwa Co., Ltd., melting point: 75 ° C.) was heated to 100 ° C. in a pressure resistant container, and the protective layer of the object to be treated was immersed in the melted paraffin wax. While maintaining this temperature, the pressure vessel was depressurized to -0.08 MPa and held for 10 minutes. After returning this to normal pressure, the object to be treated is taken out, and the paraffin wax adhering to the surface on the protective layer side is removed with a rubber blade, cooled, and hexane soaked in a paper wiper. The desired electrophotographic photosensitive member was obtained by wiping.
[Example 4]
First, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was produced in the same manner as in Example 2.

Next, in a pressure vessel, carnauba wax (RC160, manufactured by Toa Kasei Co., Ltd., melting point: 80 to 86 ° C.) was heated to 100 ° C., and the protective layer of the object to be treated was immersed in the melted carnauba wax. While maintaining this temperature, the pressure vessel was depressurized to -0.08 MPa, held for 10 minutes, and then returned to normal pressure. Further, the inside of the pressure vessel was pressurized to 0.1 MPa, held for 10 minutes, and then returned to normal pressure. After repeating this pressurizing operation and depressurizing operation three times, the object to be treated is taken out from the pressure vessel, carnauba wax adhering to the surface on the protective layer side is removed with a rubber blade, cooled, and hexane is further removed with a paper wiper. The material soaked in was sufficiently wiped off to obtain the desired electrophotographic photosensitive member.
[Example 5]
First, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was produced in the same manner as in Example 2.

Next, in the cylinder, zinc stearate (manufactured by Aldrich, melting point: 128 to 130 ° C.) was heated to 140 ° C., and the protective layer of the object to be treated was immersed in the molten zinc stearate. After maintaining this temperature for 1 hour, the object to be treated is taken out from the pressure vessel, the zinc stearate adhering to the surface on the protective layer side is removed with a rubber blade, cooled, and further hexane soaked into the paper wiper. The desired electrophotographic photosensitive member was obtained.
[Example 6]
First, an aluminum substrate on which an anodized film was formed in the same manner as in Example 1 was prepared. An anodic oxide film was formed in the same manner as the photoreceptor 1.

  Next, 1 part by weight of titanyl phthalocyanine having a diffraction peak with a Bragg angle (2θ ± 0.2 °) of 27.2 ° in an X-ray diffraction spectrum is 1 part by weight of polyvinyl butyral (ESREC BM-S, Sekisui Chemical). And 100 parts by weight of n-butyl acetate were mixed and dispersed together with glass beads with a paint shaker for 1 hour to obtain a coating solution for forming a charge generation layer. The obtained coating solution was dip-coated on the outer peripheral surface of the aluminum substrate and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts by weight of the charge transporting compound represented by the above formula (4) and 3 parts by weight of a polymer compound having a structural unit represented by the above formula (5) (viscosity average molecular weight: 39,000) were added to chlorobenzene. Dissolved in 20 parts by weight, a coating solution for forming a charge transport layer was obtained. This coating solution was dip-coated on the charge generation layer and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Next, a film is formed on the charge transport layer in the same manner as in Example 2 except that the compound represented by the following formula (7) is used instead of the compound represented by the formula (6) in Example 2. A protective layer having a thickness of about 7 μm was formed to obtain an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer.

次に、上記被処理体を用いたこと以外は実施例２と同様にして、被処理体の保護層にモンタン酸ジエステルワックスを含浸させ、目的の電子写真感光体を得た。
［実施例７］
先ず、実施例６と同様にして、導電性基体／電荷発生層／電荷輸送層／保護層の積層構造を有する被処理体を得た。

Next, in the same manner as in Example 2 except that the object to be processed was used, the protective layer of the object to be processed was impregnated with montanic acid diester wax to obtain the target electrophotographic photosensitive member.
[Example 7]
First, in the same manner as in Example 6, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was obtained.

Next, in the same manner as in Example 3 except that the object to be processed was used, the protective layer of the object to be processed was impregnated with paraffin wax to obtain the target electrophotographic photosensitive member.
[Example 8]
First, in the same manner as in Example 6, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was obtained.

Next, carnauba wax was impregnated into the protective layer of the target object in the same manner as in Example 4 except that the target object was used to obtain the target electrophotographic photosensitive member.
[Example 9]
First, in the same manner as in Example 6, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was obtained.

Next, the protective layer was impregnated with zinc stearate in the same manner as in Example 5 except that the object to be processed was used, to obtain the target electrophotographic photosensitive member.
[Example 10]
First, honing treatment was performed on the outer peripheral surface of a cylindrical aluminum substrate.

  Next, 100 parts by weight of a zirconium compound (trade name: Orgatics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts by weight of a silane compound (trade name: A1100, manufactured by Nihon Unicar), 400 parts by weight of isopropanol, and 200 parts by weight of butanol By mixing, an undercoat layer forming coating solution was obtained. This coating solution was applied by dip coating on the outer peripheral surface of the aluminum substrate and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.1 μm.

  Next, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 °, 1 part by weight of hydroxygallium phthalocyanine having a strong diffraction peak at 28.3 ° is mixed with 1 part by weight of polyvinyl butyral (ESREC BM-S, Sekisui Chemical) and 100 parts by weight of n-butyl acetate, and the glass shaker is used together with a paint shaker. Was applied for 1 hour to obtain a coating solution for forming a charge generation layer. This coating solution was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts by weight of the charge transporting compound represented by the following formula (8) and 3 parts by weight of a polymer compound having a structural unit represented by the above formula (5) (viscosity average molecular weight: 39,000) were added to chlorobenzene. Dissolved in 20 parts by weight, a coating solution for forming a charge transport layer was obtained. This coating solution is dip-coated on the charge generation layer, heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm, and lamination of conductive substrate / undercoat layer / charge generation layer / charge transport layer An object to be processed having a structure was obtained.

次に、上記被処理体を用いたこと以外は実施例１と同様にして、被処理体の電荷輸送層にモンタン酸モノエステルワックスを含浸させ、目的の電子写真感光体を得た。
［実施例１１］
先ず、実施例１０と同様にして、導電性基体／下引き層／電荷発生層／電荷輸送層の積層構造を有する被処理体を作製した。

Next, in the same manner as in Example 1 except that the object to be processed was used, the charge transport layer of the object to be processed was impregnated with montanic acid monoester wax to obtain the target electrophotographic photosensitive member.
[Example 11]
First, in the same manner as in Example 10, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer was produced.

  Next, 2 parts by weight of the compound represented by the above formula (6), 2 parts by weight of methyltrimethoxysilane, 0.5 parts by weight of tetramethoxysilane, 0.3 parts by weight of colloidal silica, fluorine graft polymer (ZX007C, Fuji Kasei) 0.5 parts by weight) and 0.2 parts by weight of a fluorine coupling agent (KBM-7803: manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts by weight of isopropyl alcohol, 3 parts by weight of tetrahydrofuran, and 0.3 parts by weight of distilled water Then, 0.5 parts by weight of an ion exchange resin (Amberlyst 15E) was further added, and the mixture was stirred at room temperature for 24 hours for hydrolysis.

0.1 parts by weight of aluminum trisacetylacetonate (Al (aqaq) ₃ ) and 3,5-di-t-butyl-4-hydroxy are obtained by filtering and separating the ion exchange resin from the reaction solution after hydrolysis. Toluene (BHT) 0.4 part by weight was added to obtain a coating solution for forming a protective layer. This coating solution is applied onto the charge transport layer of the object to be processed by a ring-type dip coating method, air-dried at room temperature for 30 minutes, cured by heating at 170 ° C. for 1 hour, and a protective layer having a thickness of about 5 μm is formed. Thus, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was obtained.

Next, in the same manner as in Example 2 except that the object to be processed was used, the protective layer of the object to be processed was impregnated with montanic acid diester wax to obtain the target electrophotographic photosensitive member.
[Example 12]
First, in the same manner as in Example 11, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was produced.

Next, in the same manner as in Example 3 except that the object to be processed was used, the protective layer of the object to be processed was impregnated with paraffin wax to obtain the target electrophotographic photosensitive member.
[Example 13]
First, in the same manner as in Example 11, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was produced.

Next, carnauba wax was impregnated into the protective layer of the target object in the same manner as in Example 4 except that the target object was used to obtain the target electrophotographic photosensitive member.
[Example 14]
First, in the same manner as in Example 11, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was produced.

Next, in the same manner as in Example 5 except that the object to be treated was used, the protective layer of the object to be treated was impregnated with zinc stearate to obtain the target electrophotographic photosensitive member.
[Example 15]
First, 100 parts by weight of zinc oxide (SMZ-017N, manufactured by Teica) was stirred and mixed with 500 parts by weight of toluene, and 2 parts by weight of a silane coupling agent (A1100, manufactured by Nihon Unicar) was added and stirred for 5 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 2 hours. As a result of analyzing the obtained surface-treated zinc oxide by fluorescent X-ray, the Si element strength was 1.8 × 10 ⁻⁴ of the zinc element strength.

  In this way, 35 parts by weight of the zinc oxide subjected to the surface treatment, 15 parts by weight of blocked isocyanate (Sumidule 3175, manufactured by Sumitomo Bayern Urethane) as a curing agent, butyral resin (BM-1 (manufactured by Sekisui Chemical Co., Ltd.) ) 6 parts by weight and 44 parts by weight of methyl ethyl ketone were mixed with a 1 mmφ glass bead for 2 hours in a sand mill to obtain a dispersion, and dioctyltin dilaurate 0.005 as a catalyst was added to the obtained dispersion. Part by weight and 17 parts by weight of silicone resin particles (Tospearl 130, manufactured by GE Toshiba Silicon Co., Ltd.) were added to obtain a coating solution for forming an undercoat layer, which was immersed in the outer peripheral surface of a cylindrical aluminum substrate. This was coated and dried and cured at 160 ° C. for 100 minutes to form an undercoat layer having a thickness of 20 μm. Using the surface roughness shape measuring device Surfcom 570A, measurement distance 2.5 mm, was measured at a scan rate of 0.3 mm / sec, Rz value was 0.24.

  Next, in the same manner as in Example 6, a charge generation layer having a film thickness of about 0.15 μm was formed on the undercoat layer. Further, in the same manner as in Example 1, a charge transport layer having a thickness of 20 μm was formed on the charge generation layer.

Furthermore, 2 parts by weight of the compound represented by the above formula (6), 2 parts by weight of methyltrimethoxysilane, Me (MeO) ₂ —Si— (CH ₂ ) ₄ —Si—Me (OMe) ₂ (Me: methyl group) ) 0.5 parts by weight of a silane compound having a structure represented by the following formula: 0.5 parts by weight of a fluorine graft polymer (ZX022, manufactured by Fuji Kasei), (heptadecafluoro-1,1,2,2-tetrahydrodecyl) methyldimethoxy 0.1 part by weight of silane, 0.3 part by weight of hexamethylcyclotrisiloxane, 0.5 part by weight of butyral resin (BX-L, manufactured by Sekisui Chemical), 5 parts by weight of n-butyl alcohol, 3 parts by weight of tetrahydrofuran and It is dissolved in a mixed solution of 0.3 parts by weight of distilled water, 0.5 parts by weight of ion exchange resin (Amberlyst 15E) is further added, and the mixture is stirred at room temperature for 0.5 hours. The water decomposition was carried out.

0.1 parts by weight of aluminum trisacetylacetonate (Al (aqaq) ₃ ) and 3,5-di-t-butyl-4-hydroxytoluene with respect to the solution obtained by filtering and separating the ion exchange resin from the reaction solution after hydrolysis (BHT) 0.4 part by weight was added to obtain a coating solution for forming a protective layer. This coating solution is applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 170 ° C. for 1 hour to form a protective layer having a thickness of about 5 μm. An object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was obtained.

Next, in the same manner as in Example 1 except that the object to be processed was used, the charge transport layer of the object to be processed was impregnated with montanic acid diester wax to obtain the target electrophotographic photosensitive member.
[Example 16]
First, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was produced in the same manner as in Example 15.

Next, in the same manner as in Example 3 except that the object to be processed was used, the protective layer of the object to be processed was impregnated with paraffin wax to obtain the target electrophotographic photosensitive member.
[Example 17]
First, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was produced in the same manner as in Example 15.

Next, carnauba wax was impregnated into the protective layer of the target object in the same manner as in Example 4 except that the target object was used to obtain the target electrophotographic photosensitive member.
[Example 18]
First, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was produced in the same manner as in Example 15.

Next, in the same manner as in Example 5 except that the object to be treated was used, the protective layer of the object to be treated was impregnated with zinc stearate to obtain the target electrophotographic photosensitive member.
[Example 19]
First, in the same manner as in Example 10, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer was produced.

Next, 30 parts by weight of a curable acrylic resin precursor represented by HOCH ₂ —C (CH ₂ OCOCH═CH ₂ ) ₃ , 5 parts by weight of a fluorine graft polymer (ZX022, manufactured by Fuji Kasei), and a photopolymerization initiator Of 2-methylthioxanthone is dissolved in butanol, and 21 parts by weight of the compound represented by the above formula (7) is dissolved as a charge transport material having a hydroxyalkyl group to prepare a coating solution for forming a protective layer. Obtained. This coating solution was dip-coated on the charge transport layer of the object to be processed, and photocured with a high-pressure mercury lamp at a light intensity of 800 mW / cm ² for 60 seconds. Thereafter, it was dried with hot air at 120 ° C. for 2 hours to form a protective layer having a thickness of 3 μm, and an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was obtained. .

Next, paraffin wax (HNP9, manufactured by Nippon Seiwa Co., Ltd., melting point: 75 ° C.) was heated to 100 ° C. in a pressure resistant container, and the charge transport layer of the object to be treated was immersed in the melted paraffin wax. While maintaining this temperature, the pressure vessel was depressurized to -0.08 MPa, held for 10 minutes, and then returned to normal pressure. Further, the inside of the pressure vessel was pressurized to 0.1 MPa, held for 10 minutes, and then returned to normal pressure. After repeating this pressurizing operation and depressurizing operation three times, the object to be treated was taken out, and the paraffin wax adhering to the surface on the charge transport layer side was removed with a rubber blade. Further, the object to be processed was cooled, and the surface on the charge transport layer side was sufficiently wiped with a paper wiper soaked in hexane to obtain the desired electrophotographic photoreceptor.
[Example 20]
First, in the same manner as in Example 10, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer was produced.

  Next, 2 parts by weight of the compound represented by the above formula (7), 3 parts by weight of a curable resin (Resitop PL4852, manufactured by Gunei Chemical), hindered phenol antioxidant (AO-80, manufactured by Asahi Denka) 0.1 part by weight, 0.2 part by weight of fluorine graft polymer (ZX007C, manufactured by Fuji Kasei) and 0.1 part by weight of fluorine coupling agent (KBM-7803, manufactured by Shin-Etsu Chemical) are dissolved in 10 parts of isopropyl alcohol. A coating solution for forming a protective layer was obtained. This coating solution is applied onto the charge transport layer of the object to be processed by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then heated and cured at 140 ° C. for 1 hour to form a protective layer having a thickness of about 5 μm. Thus, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was obtained.

Next, paraffin wax (HNP9, manufactured by Nippon Seiwa Co., Ltd., melting point: 75 ° C.) was heated to 100 ° C. in a pressure resistant container, and the protective layer of the object to be treated was immersed in the melted paraffin wax. While maintaining this temperature, the inside of the pressure vessel was pressurized to 0.1 MPa and held for 10 minutes. After returning this to normal pressure, the object to be treated was taken out, and the paraffin wax adhering to the surface on the protective layer side was removed with a rubber blade. After the object to be processed was cooled, the surface on the protective layer side was sufficiently wiped with a paper wiper soaked in hexane to obtain the desired electrophotographic photosensitive member.
[Example 21]
First, in the same manner as in Example 20, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was produced.

Next, in a pressure vessel, carnauba wax (RC160, manufactured by Toa Kasei Co., Ltd., melting point: 80 to 86 ° C.) was heated to 100 ° C., and the protective layer of the object to be treated was immersed in the melted carnauba wax. While maintaining this temperature, the pressure vessel was depressurized to -0.08 MPa and held for 10 minutes. After returning the pressure to normal pressure, the object to be treated is taken out, the carnauba wax adhering to the surface on the protective layer side is removed with a rubber blade, cooled, and further, a paper wiper soaked with hexane is sufficient. The desired electrophotographic photosensitive member was obtained by wiping.
[Example 22]
First, in the same manner as in Example 20, an object to be processed having a laminated structure of conductive substrate / undercoat layer / charge generation layer / charge transport layer / protective layer was produced.

Next, in the pressure vessel, zinc stearate (manufactured by Aldrich, melting point: 128 to 130 ° C.) was heated to 100 ° C., and the charge transport layer of the object to be treated was immersed in the molten zinc stearate. While maintaining this temperature, the pressure vessel was depressurized to -0.08 MPa, held for 10 minutes, and then returned to normal pressure. Further, the inside of the pressure vessel was pressurized to 0.1 MPa, held for 10 minutes, and then returned to normal pressure. After repeating this pressurizing operation and depressurizing operation three times, the object to be treated was taken out, and zinc stearate adhering to the surface on the charge transport layer side was removed with a rubber blade. Further, the object to be processed was cooled, and the surface on the charge transport layer side was sufficiently wiped with a paper wiper soaked in hexane to obtain the desired electrophotographic photoreceptor.
[Comparative Example 1]
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the charge transport layer was not treated with the montanic acid monoester wax.
[Comparative Example 2]
An electrophotographic photosensitive member was produced in the same manner as in Example 2 except that the protective layer was not treated with the montanic acid diester wax.
[Comparative Example 3]
An electrophotographic photosensitive member was produced in the same manner as in Example 6 except that the protective layer was not treated with the montanic acid diester wax.
[Comparative Example 4]
An electrophotographic photosensitive member was produced in the same manner as in Example 10 except that the charge transport layer was not treated with the montanic acid monoester wax.
[Comparative Example 5]
An electrophotographic photosensitive member was produced in the same manner as in Example 11 except that the protective layer was not treated with the montanic acid diester wax.
[Comparative Example 6]
An electrophotographic photosensitive member was produced in the same manner as in Example 15 except that the protective layer was not treated with the montanic acid diester wax.
[Comparative Example 7]
An electrophotographic photosensitive member was produced in the same manner as in Example 19 except that the protective layer was not treated with paraffin wax.
[Comparative Example 8]
An electrophotographic photosensitive member was produced in the same manner as in Example 20 except that the protective layer was not treated with paraffin wax.
[Comparative Example 9]
First, in the same manner as in Example 2, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was produced.

Next, a reactive silicone oil (X-22-162C, manufactured by Shin-Etsu Chemical Co., Ltd., liquid at room temperature) is heated to 100 ° C. in a pressure vessel, and the protective layer of the object to be treated is immersed in the reactive silicone oil. did. While maintaining this temperature, the pressure vessel was depressurized to -0.08 MPa, held for 10 minutes, and then returned to normal pressure. Further, the inside of the pressure vessel was pressurized to 0.1 MPa, held for 10 minutes, and then returned to normal pressure. After repeating this pressurizing operation and depressurizing operation three times, the object to be treated was taken out and the reactive silicone oil adhering to the surface on the charge transport layer side was removed with a rubber blade. Further, the object to be processed was cooled, and the surface on the charge transport layer side was sufficiently wiped with a paper wiper (trade name: Kimwipe, hereinafter the same) soaked in hexane to obtain the intended electrophotographic photosensitive member.
[Comparative Example 10]
First, in the same manner as in Example 3, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was produced.

Next, the protective layer of the object to be treated was treated with reactive silicone oil in the same manner as in Comparative Example 9 to obtain the target electrophotographic photosensitive member.
[Comparative Example 11]
First, in the same manner as in Example 4, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was produced.

Next, the protective layer of the object to be treated was treated with reactive silicone oil in the same manner as in Comparative Example 9 to obtain the target electrophotographic photosensitive member.
[Comparative Example 12]
First, in the same manner as in Example 2, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was produced.

Next, 100 g of fluororesin (Lumiflon, manufactured by Asahi Glass) was dissolved in 1500 g of n-butanol, and the solution was heated to 35 ° C. in a pressure resistant container, so that the protective layer of the object to be treated was immersed. While maintaining this temperature, the pressure vessel was depressurized to -0.05 MPa, held for 10 minutes, and then returned to normal pressure. Further, the inside of the pressure vessel was pressurized to 0.1 MPa, held for 10 minutes, and then returned to normal pressure. After repeating this pressurizing operation and depressurizing operation three times, the object to be treated is taken out from the pressure vessel, and the fluororesin-containing solution adhering to the surface of the protective layer is washed and removed with butanol, and then dried. A photographic photoreceptor was obtained.
[Comparative Example 13]
First, in the same manner as in Example 3, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was produced.

Next, the protective layer of the object to be treated was treated with a fluororesin-containing solution in the same manner as in Comparative Example 12 to obtain the target electrophotographic photosensitive member.
[Comparative Example 14]
First, in the same manner as in Example 4, an object to be processed having a laminated structure of conductive substrate / charge generation layer / charge transport layer / protective layer was produced.

  Next, the protective layer of the object to be treated was treated with a fluororesin-containing solution in the same manner as in Comparative Example 12 to obtain the target electrophotographic photosensitive member.

Next, Developers 1 to 3 were produced as follows. In the following description, the particle size distribution of the composite particles of the toner was measured using a multisizer (manufactured by Nikka Kisha Co., Ltd.) with an aperture diameter of 100 μm. Further, the average shape factor ML ² / A of the composite particles of the toner means a value calculated by the following formula. In the case of a true sphere, ML ² / A = 100. As a specific method for obtaining the average shape factor, a toner image is taken from an optical microscope into an image analyzer (LUZEX III, manufactured by Nireco), the equivalent circle diameter is measured, and the maximum length and area are used to determine individual particles. The value of ML ² / A in the above formula was determined.
ML ² / A = (maximum length) ² × π × 100 / [4 × (area)]
[Developer 1]
<Preparation of toner base particles>
(Preparation of resin fine particle dispersion)
A solution obtained by mixing 370 g of styrene, 30 g of n-butyl acrylate, 8 g of acrylic acid, 24 g of dodecanethiol, and 4 g of carbon tetrabromide was added to 6 g of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) and an anionic interface. 10 g of an activator (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was mixed with a solution dissolved in 550 g of ion-exchanged water, and emulsion polymerization was performed in a flask. While slowly mixing for 10 minutes, 50 g of ion-exchanged water in which 4 g of ammonium persulfate was dissolved was added thereto. After carrying out nitrogen substitution, it heated with the oil bath until the contents became 70 degreeC, stirring the inside of a flask, and emulsion polymerization was continued as it was for 5 hours. As a result, a resin fine particle dispersion in which resin particles of 150 nm, Tg = 58 ° C., and weight average molecular weight Mw = 11500 were dispersed was obtained. The solid content concentration of this dispersion was 40% by weight.
(Preparation of colorant dispersion (1))
Carbon black (Mogal L, manufactured by Cabot) 60 g, nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) 6 g and ion-exchanged water 240 g were mixed, and the mixture was homogenized (Ultra Turrax T50, manufactured by IKA). ) For 10 minutes. Furthermore, the mixed solution was dispersed with an optimizer to obtain a colorant dispersant (1) in which colorant (carbon black) particles having an average particle diameter of 250 nm were dispersed.
(Preparation of colorant dispersion (2))
60 g of cyan pigment B15: 3, 5 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Kasei Co., Ltd.) and 240 g of ion-exchanged water were mixed, and the mixture was used with a homogenizer (Ultra Turrax T50, manufactured by IKA). And stirred for 10 minutes. Further, the mixed solution was dispersed with an optimizer to obtain a colorant dispersant (2) in which colorant (cyan pigment) particles having an average particle diameter of 250 nm were dispersed.
(Preparation of colorant dispersion (3))
60 g of magenta pigment R122, 5 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Kasei Co., Ltd.) and 240 g of ion-exchanged water were mixed, and the mixture was mixed using a homogenizer (Ultra Turrax T50, manufactured by IKA). Stir for minutes. Further, the mixed solution was dispersed with an optimizer to obtain a colorant dispersant (3) in which colorant (magenta pigment) particles having an average particle diameter of 250 nm were dispersed.
(Preparation of colored dispersion (4))
90 g of yellow pigment Y180, 5 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and 240 g of ion-exchanged water were mixed, and the mixture was mixed using a homogenizer (Ultra Turrax T50, manufactured by IKA). Stir for minutes. Further, the mixed solution was dispersed with an optimizer to obtain a colorant dispersant (4) in which colorant (yellow pigment) particles having an average particle diameter of 250 nm were dispersed.
(Preparation of release agent dispersion)
100 g of paraffin wax (HNP0190, manufactured by Nippon Seiwa Co., Ltd., melting point 85 ° C.),
After dispersing 10 g of a cationic surfactant (Sanisol B50, manufactured by Kao Corporation) and 240 g of ion-exchanged water in a round stainless steel flask using a homogenizer (Ultra Turrax T50, manufactured by IKA) for 10 minutes. Then, dispersion treatment was performed using a pressure discharge type homogenizer, and a release agent dispersion liquid in which release agent particles having an average particle diameter of 550 nm were dispersed was prepared.
<Preparation of toner mother particles K1>
234 parts by weight of the resin fine particle dispersion, 30 parts by weight of the colorant dispersion (1), and 40 parts by weight of the release agent dispersion are mixed with 0.5 parts by weight of polyaluminum hydroxide (Paho2S, manufactured by Asada Chemical Co., Ltd.) and ions. After mixing with 600 parts by weight of exchange water and dispersing in a round stainless steel flask using a homogenizer (Ultra Turrax T50, manufactured by IKA), heat to 40 ° C. while stirring the flask in a heating oil bath. did. After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a D50 of 4.5 μm were produced. Further, the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, and D50 was 5.3 μm. Thereafter, 26 parts by weight of the resin fine particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. The dispersion containing the aggregated particles was added with 1N sodium hydroxide to adjust the pH of the system to 7.0, and then the stainless steel flask was sealed and heated to 80 ° C. while continuing stirring using a magnetic seal. And held for 4 hours. After cooling, the toner base particles were separated by filtration, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K1. The toner base particle K1 had a D50 of 5.9 μm and an average shape factor ML ² / A of 132.
<Preparation of toner mother particle C1>
Toner base particles C1 were produced in the same manner as toner base particles K1, except that the colored particle dispersion liquid (2) was used instead of the colored particle dispersion liquid (1). D50 of the toner mother particles C1 was 5.8 μm, and the average shape factor ML ² / A was 131.
<Preparation of toner mother particles M1>
Toner base particles M1 were produced in the same manner as toner base particles K1, except that the colored particle dispersion liquid (3) was used instead of the colored particle dispersion liquid (1). The toner base particles M1 had a D50 of 5.5 μm and an average shape factor ML ² / A of 135.
<Adjustment of toner base particle Y1>
Toner base particles Y1 were produced in the same manner as toner base particles K1, except that the colored particle dispersion liquid (4) was used instead of the colored particle dispersion liquid (1). D50 of the toner base particle Y1 was 5.9 μm, and the average shape factor ML ² / A was 130.
<Manufacture of carriers>
14 parts by weight of toluene, 2 parts by weight of a styrene / methacrylate copolymer (component ratio: 90/10) and 0.2 part of carbon black (R330: manufactured by Cabot) were mixed and stirred with a stirrer for 10 minutes. Next, 100 parts by weight of ferrite particles (average particle size: 50 μm) are added to this mixed solution, and the mixture is stirred for 30 minutes at 60 ° C. in a vacuum degassing kneader. A carrier was obtained by drying. This carrier had a volume resistivity of 10 ¹¹ Ωcm when an applied electric field of 1000 V / cm.

100 parts by weight of each of the toner base particles K1, C1, M1, and Y1 is 1 part by weight of rutile titanium oxide (particle diameter 20 nm, n-decyltrimethoxysilane treatment), silica (particle diameter 40 nm, silicone oil treatment, gas phase). Oxidation method) 2.0 parts by weight, 1 part by weight of cerium oxide (average particle size 0.7 μm), higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700) and zinc stearate are mixed in a ratio of 5: 1 by weight, The mixture was pulverized with a jet mill and 0.3 parts by weight having an average particle size of 8.0 μm was added. The mixture was stirred with a 5 L Henschel mixer at a peripheral speed of 30 m / s for 15 minutes, and coarse particles were removed using a sieve having an opening of 45 μm, whereby Toner 1 was obtained. Further, 100 parts by weight of the carrier described above was added to 5 parts by weight of toner 1, stirred for 20 minutes at 40 rpm in a V-blender, and sieved with a sieve having an opening of 212 μm to obtain developer 1.
[Developer 2]
<Preparation of toner mother particles K2>
234 parts by weight of the resin fine particle dispersion (prepared at the time of preparing the composite fine particles), 30 parts by weight of the colorant dispersion (1) and 40 parts of the release agent dispersion were mixed with polyaluminum hydroxide (manufactured by Asada Chemical Co., Ltd. (Paho2S) and 0.5 parts by weight of ion exchange water and 600 parts by weight of ion-exchanged water, dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then flasked in a heating oil bath. The interior was heated to 40 ° C. with stirring. After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a D50 of 4.5 μm were produced. Further, the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, and D50 was 5.3 μm. Thereafter, 26 parts by weight of the resin fine particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. The dispersion containing the aggregated particles is added with 1N sodium hydroxide to adjust the pH of the system to 5.0, and then the stainless steel flask is sealed and heated to 95 ° C. while stirring with a magnetic seal. And held for 4 hours. After cooling, the toner base particles were filtered off, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K2. The toner base particle K2 had a D50 of 5.8 μm and an average shape factor ML ² / A of 109.
<Preparation of toner mother particle C2>
Toner base particles C2 were prepared in the same manner as toner base particles K2, except that the color particle dispersion liquid (2) was used instead of the color particle dispersion liquid (1). D50 of the toner base particle C2 was 5.7 μm, and the average shape factor ML ² / A was 110.
<Preparation of toner mother particles M2>
Toner base particles M2 were prepared in the same manner as toner base particles K2, except that the colored particle dispersion liquid (3) was used instead of the colored particle dispersion liquid (1). D50 of the toner mother particles M2 was 5.6 μm, and the average shape factor ML ² / A was 114.
<Preparation of toner mother particle Y2>
Toner base particles Y2 were produced in the same manner as toner base particles K2, except that the color particle dispersion liquid (4) was used instead of the color particle dispersion liquid (1). D50 of the toner base particle Y2 was 5.8 μm, and the average shape factor ML ² / A was 108.

The toner base particles K2, C2, M2 and Y2 thus obtained were used, and aluminum oxide (average particle size 0.1 μm) was used instead of 1 part by weight of cerium oxide (average particle size 0.7 μm). Developer 2 was produced in the same manner as Developer 1, except that 1 part by weight was used.
[Developer 3]
<Preparation of toner mother particles K3>
100 parts by weight of polyester resin (linear polyester obtained from terephthalic acid-bisphenol A ethylene oxide adduct-cyclohexanedimethanol, Tg: 62 ° C., Mn 12000, Mw: 32000), 4 parts by weight of carbon black and 5 parts by weight of carnauba wax Was kneaded with an extruder and pulverized with a jet mill. The pulverized product was classified with a wind classifier to obtain toner base particles K3 having an average particle size of 5.9 μm and an average shape factor (ML ² / A) of 145.
<Preparation of toner mother particles C3>
The average particle size is 5.6 μm and the average shape factor (ML ² / A) is the same as that of the toner base particles K3 except that a cyan colorant (CI Pigment Blue 15: 3) is used instead of carbon black. 141 toner mother particles C3 were produced.
<Preparation of toner mother particles M3>
Toner mother particles M3 having an average particle diameter of 5.9 μm and an average shape factor (ML ² / A) of 149 were produced in the same manner as K3 except that a magenta colorant (R122) was used instead of carbon black.
<Preparation of toner mother particles Y3>
A toner base particle Y3 having an average particle size of 5.8 μm and an average shape factor (ML ² / A) of 144 was obtained in the same manner as K3 except that a yellow colorant (Y180) was used instead of carbon black.

Developer 3 was produced in the same manner as Developer 1, except that the toner base particles K3, C3, M3, and Y3 thus obtained were used.
[Cleaning blade 1]
As the cleaning blade 1, a urethane blade having physical properties of a hardness of 85 ° (JIS A hardness), a rebound resilience of 18% at 30 ° C., a Young's modulus of 159 kgf / cm ² , and a tear strength of 68 kgf / cm was prepared.
[Cleaning blade 2]
As the cleaning blade 2, a urethane blade having physical properties of hardness 75 ° (JIS A hardness), rebound resilience 55% at 30 ° C., Young's modulus 86 kgf / cm ² , and tear strength 84 kgf / cm was prepared.
[Cleaning blade 3]
As the cleaning blade 3, a urethane blade having physical properties of a hardness of 65 ° (JIS A hardness), a rebound resilience of 36% at 30 ° C., a Young's modulus of 50 kgf / cm ² , and a tear strength of 43 kgf / cm was prepared.
[Examples 23 to 44, Comparative Examples 15 to 28]
In Examples 23 to 44 and Comparative Examples 15 to 28, the electrophotographic photosensitive member produced in Examples 1 to 22 and Comparative Examples 1 to 14 having an aluminum base having an outer diameter of 30 mmφ was used. The electrophotographic apparatus shown in FIG. 4 (tandem type electrophotographic apparatus) was manufactured by combining the body, developer, and cleaning blade as shown in Table 10. Table 10 also shows the contact angle (setting angle) and contact force of the cleaning blade to the electrophotographic photosensitive member. Of the constituent elements of the electrophotographic apparatus, the same elements as those of the Fuji Xerox printer DocuCenter Color 400CP were used except for the electrophotographic photosensitive member, the developer, and the cleaning blade.

  Next, for each of the electrophotographic apparatuses of Examples 22 to 44 and Comparative Examples 15 to 28, 10,000 sheets of image forming tests were performed in the plain paper mode in an environment of low temperature and low humidity (10 ° C., 20% RH). The image quality was evaluated for a character image of 8 points. Table 10 shows the obtained results. In Table 10, “A” indicates that the characters are clear, “B” indicates that some characters are overweight, and “C” indicates that thin lines are broken (there is a problem in image quality). Each means.

  Furthermore, the same image formation test was carried out in the OHP mode (process speed 52 mm / sec) for each of the electrophotographic apparatuses of Examples 22 to 44 and Comparative Examples 15 to 28. Table 10 shows the obtained results. A to C in Table 10 mean the same evaluation criteria as described above.

［実施例４５〜６６、比較例２９〜４２］
実施例４５〜６６及び比較例２９〜４２においては、実施例１〜２２及び比較例１〜１４で作製した電子写真感光体のうちアルミニウム製基体の外径が８４ｍｍφのものを用い、電子写真感光体、現像剤及びクリーニングブレードをそれぞれ表１１に示す組合せとして、図３に示す構成を有する電子写真装置（４サイクル方式電子写真装置）を作製した。表１
１には、クリーニングブレードの電子写真感光体に対する当接角及び当接力を併せて示す。なお、電子写真装置の構成要素のうち、電子写真感光体、現像剤及びクリーニングブレード以外は富士ゼロックス製プリンターＤｏｃｕＣｅｎｔｒｅ Ｃｏｌｏｒ ５００ＣＰと同様の要素を用いた。

[Examples 45 to 66, Comparative Examples 29 to 42]
In Examples 45 to 66 and Comparative Examples 29 to 42, the electrophotographic photosensitive member produced in Examples 1 to 22 and Comparative Examples 1 to 14 having an aluminum base having an outer diameter of 84 mmφ was used. An electrophotographic apparatus (4-cycle electrophotographic apparatus) having the configuration shown in FIG. 3 was prepared with the combinations shown in Table 11 for the body, developer, and cleaning blade. Table 1
In FIG. 1, the contact angle and the contact force of the cleaning blade with respect to the electrophotographic photosensitive member are shown together. Of the constituent elements of the electrophotographic apparatus, the same elements as the printer DocuCenter Color 500CP manufactured by Fuji Xerox were used except for the electrophotographic photosensitive member, the developer, and the cleaning blade.

  Next, an image formation test was performed for each of the electrophotographic apparatuses of Examples 45 to 66. The test was performed under two conditions: 10,000 prints in an environment of high temperature and high humidity (28 ° C., 75% RH) and 15,000 prints in an environment of low temperature and low humidity (10 ° C., 20% RH). Table 11 shows the evaluation results for the image quality obtained under each condition. In Table 11, “A” indicates that good image quality was obtained, “B” indicates that image quality defects were partially recognized, but that there was no problem in practical use, and “C” was easily visually observed. This means that image quality defects of a level that can be found are recognized.

  Further, in an image formation test under high temperature and high humidity, the presence or absence of deposits on the surface of the charge transport layer or protective layer, toner cleaning properties (charger contamination and image quality deterioration due to poor cleaning), and cleaning blade The edge state of was evaluated. The results obtained are shown in Table 12.

  The presence or absence of deposits was determined visually. In Table 12, “A” indicates that no adhesion was observed, “B” indicates that adhesion was partially observed, but that there was no problem in image quality, and “C” indicates that adhesion was observed. This means that the image quality has become a problem.

  The cleaning property was judged visually. In Table 12, “A” indicates that the cleaning property is good, “B” indicates that image quality defects such as streaks are partially recognized, but there is no problem in image quality, and “C” indicates This means that image quality defects have been recognized extensively and have become image quality problems.

  The edge state of the blade was observed with a stereomicroscope. In Table 12, “A” means that there was no particular problem, “B” means that partial chipping was recognized, and “C” means that chipping and wear were observed everywhere.

1 is a schematic cross-sectional view showing a preferred embodiment of an electrophotographic photoreceptor of the present invention. 1 is a schematic configuration diagram showing a preferred embodiment of an electrophotographic apparatus of the present invention. It is a schematic block diagram which shows other one Embodiment of the electrophotographic apparatus of this invention. It is a schematic block diagram which shows other one Embodiment of the electrophotographic apparatus of this invention. 1 is a schematic configuration diagram showing a preferred embodiment of a process cartridge of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10,207,312, 401a-401d ... Electrophotographic photoreceptor, 12 ... Conductive base | substrate, 13 ... Photosensitive layer, 14 ... Undercoat layer, 15 ... Charge generation layer, 16 ... Charge transport layer, 17 ... Protective layer, 200 , 300, 400 ... Electrophotographic apparatus, 500 ... Process cartridge, 208, 314, 402a to 402d ... Charging device, 210, 316, 403 ... Exposure device, 211, 318, 404a-404d ... Developing device, 212, 332, 410a ˜410d, transfer device, 213, 324, 415a to 415d, cleaning device.

Claims (8)

An electrophotographic photoreceptor comprising a conductive substrate and a photosensitive layer provided on the conductive substrate,
An electrophotographic process comprising heating a lubricating substance having a melting point of 30 ° C. or higher and 200 ° C. or lower, and bringing the molten lubricating substance into contact with the surface of the photosensitive layer opposite to the conductive substrate. Photoconductor. An electrophotographic photoreceptor comprising a conductive substrate and a photosensitive layer provided on the conductive substrate,
An electron having a lubricating substance holding portion containing a lubricating substance having a melting point of 30 ° C. or higher and 200 ° C. or lower in a region from the surface opposite to the conductive substrate of the photosensitive layer to a predetermined depth. Photoconductor.   The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer has a layer containing a resin having a crosslinked structure on a side far from the conductive substrate. A first step of preparing a conductive substrate and a workpiece having a photosensitive layer provided on the conductive substrate;
A second lubricating material having a melting point of 30 ° C. or higher and 200 ° C. or lower is heated, and the molten lubricating material is brought into contact with the surface of the photosensitive layer of the object to be processed which is opposite to the conductive substrate. A process for producing an electrophotographic photosensitive member.   In the second step, the melted lubricating substance is brought into contact with the surface of the photosensitive layer of the workpiece opposite to the conductive substrate, under reduced pressure or pressure. The method for producing an electrophotographic photosensitive member according to claim 4. The second step includes
Bringing the melted lubricating substance into contact with the surface of the photosensitive layer on the opposite side of the conductive substrate under reduced pressure; and
Bringing the molten lubricating substance under pressure into contact with the surface of the photosensitive layer of the workpiece opposite to the conductive substrate;
The method for producing an electrophotographic photosensitive member according to claim 4, wherein: The electrophotographic photosensitive member according to any one of claims 1 to 3,
A charging device for charging the electrophotographic photoreceptor;
An exposure apparatus that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image;
A developing device for developing the electrostatic latent image to form a toner image;
An electrophotographic apparatus comprising: a transfer device that transfers the toner image from the electrophotographic photosensitive member to a transfer medium. The electrophotographic photosensitive member according to any one of claims 1 to 3,
A charging device that charges the electrophotographic photosensitive member, a developing device that develops an electrostatic latent image formed by exposure to form a toner image, and a cleaning device that removes toner remaining on the electrophotographic photosensitive member after transfer A process cartridge comprising at least one selected from

Images