JP2018017887A - Electrophotographic photoreceptor, method for manufacturing electrophotographic photoreceptor, process cartridge, electrophotographic device and method for extracting filling member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having high wear resistance and showing little variation in electric characteristics in repeated use.SOLUTION: The electrophotographic photoreceptor has a surface layer comprising a cured product of a triphenylamine compound having at least two chain polymerizable functional groups, polytetrafluoroethylene particles, a fluorine atom-containing graft polymer, and 4-methoxyphenol, in which the content of the polytetrafluoroethylene particles in the surface layer is 5 mass% or more and 75 mass% or less with respect to the whole mass of the surface layer, and the content of the 4-methoxyphenol in the surface layer is 0.001 mass% or more and 5 mass% or less with respect to the polytetrafluoroethylene particles in the surface layer.SELECTED DRAWING: None

Description

  The present invention relates to an electrophotographic photosensitive member, a method for manufacturing an electrophotographic photosensitive member, a process cartridge and an electrophotographic apparatus, and a method for taking out a filling member.

  In recent years, electrophotographic apparatuses are required to produce a large amount of high-quality printed matter.

  Therefore, an electrophotographic photoreceptor that is repeatedly used in an electrophotographic apparatus is required to have a surface layer that is excellent in wear resistance and has stable electrical characteristics during repeated use.

  In Patent Document 1, the electrophotographic photoreceptor is provided with a surface layer containing a cured product obtained by polymerizing a charge transport material having two or more chain-polymerizable functional groups. A technique for improving the performance is disclosed.

  Patent Document 2 discloses a technique in which a surface layer of an electrophotographic photoreceptor contains polytetrafluoroethylene particles as a lubricant and a fluorine atom-containing graft polymer as a dispersant for the polytetrafluoroethylene particles. Yes.

JP 2000-066425 A JP 2005-043818 A

  In the surface layer containing the polytetrafluoroethylene particles and the fluorine atom-containing graft polymer, the inventors have changed the electrical characteristics of the electrophotographic photoreceptor during repeated use if the content of the fluorine atom-containing graft polymer is too large. Found that it will grow.

  If the content of the fluorine atom-containing graft polymer in the surface layer is reduced to improve the fluctuation of the electric characteristics, the wear resistance of the surface layer is reduced in certain cases, resulting in high wear resistance and fluctuations in the electric characteristics. In some cases, coexistence with suppression of the above cannot be achieved.

  An object of the present invention is to provide an electrophotographic photosensitive member having high wear resistance and small variation in electrical characteristics during repeated use, and a method for producing the same.

  Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  As a result of intensive studies, the inventors have further included 4-methoxyphenol in the surface layer of the electrophotographic photosensitive member, so that even if the content of the fluorine atom-containing graft polymer in the surface layer is reduced, the surface layer It was found that the wear resistance was maintained.

That is, the present invention relates to an electrophotographic photosensitive member having a support and a photosensitive layer on the support.
The surface layer of the electrophotographic photoreceptor is
A cured product of a triphenylamine compound having two or more chain polymerizable functional groups,
Polytetrafluoroethylene particles,
A fluorine atom-containing graft polymer, and
Contains 4-methoxyphenol,
The content of the polytetrafluoroethylene particles in the surface layer is 5% by mass to 75% by mass with respect to the total mass of the surface layer,
The electrophotographic photoreceptor, wherein the content of 4-methoxyphenol in the surface layer is 0.001% by mass to 5% by mass with respect to the polytetrafluoroethylene particles in the surface layer. It is.

  Further, the present invention integrally supports the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means, a transfer means and a cleaning means, and is attached to and detached from the main body of the electrophotographic apparatus. It is a process cartridge characterized by being free.

  The present invention also provides an electrophotographic apparatus comprising the above-described electrophotographic photosensitive member, and a charging unit, an exposing unit, a developing unit, and a transfer unit.

Further, the present invention is a method for producing an electrophotographic photosensitive member for producing an electrophotographic photosensitive member having a support and a photosensitive layer on the support,
The manufacturing method comprises:
A step of preparing a coating solution for the surface layer,
Forming a coating film of the coating solution for the surface layer, and
Having a step of forming a surface layer of the electrophotographic photosensitive member by curing the coating film,
The surface layer coating solution is
A triphenylamine compound having two or more chain polymerizable functional groups,
Polytetrafluoroethylene particles,
A fluorine atom-containing graft polymer, and
Contains 4-methoxyphenol,
The content of the polytetrafluoroethylene particles in the surface layer is 5% by mass to 75% by mass with respect to the total mass of the surface layer,
The electrophotographic photoreceptor, wherein the content of 4-methoxyphenol in the surface layer is 0.001% by mass to 5% by mass with respect to the polytetrafluoroethylene particles in the surface layer. It is a manufacturing method.

  According to the present invention, it is possible to provide an electrophotographic photosensitive member having high wear resistance and small variation in electrical characteristics during repeated use, and a method for producing the same.

  In addition, according to the present invention, a process cartridge and an electrophotographic apparatus having such an electrophotographic photosensitive member can be provided.

It is a figure which shows an example of the laminated constitution of the electrophotographic photoreceptor of this invention. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention. It is a figure which shows an example of the method of taking out a filling member from the inside of an electrophotographic photoreceptor. It is a figure which shows another example of the method of taking out a filling member from the inside of an electrophotographic photoreceptor.

  As described above, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a support and a photosensitive layer on the support.

And the surface layer of the electrophotographic photoreceptor is
A cured product of a triphenylamine compound having two or more chain polymerizable functional groups,
Polytetrafluoroethylene particles,
A fluorine atom-containing graft polymer, and
Contains 4-methoxyphenol,
The content of the polytetrafluoroethylene particles in the surface layer is 5% by mass to 75% by mass with respect to the total mass of the surface layer,
The content of 4-methoxyphenol in the surface layer is 0.001% by mass to 5% by mass with respect to the polytetrafluoroethylene particles in the surface layer.

  As described above, the electrophotographic photosensitive member of the present invention has high wear resistance, small variation in electrical characteristics during repeated use, and stable electrical characteristics. The present inventors presume the reason why the fluctuation of the electric characteristics during repeated use is small and the electric characteristics are stable as follows.

A cured product of a triphenylamine compound having two or more chain polymerizable functional groups,
Polytetrafluoroethylene particles, and
The surface layer containing the fluorine atom-containing graft polymer is
A triphenylamine compound having two or more chain polymerizable functional groups,
Polytetrafluoroethylene particles, and
Generally, it is formed by forming a coating film of a coating solution for a surface layer containing a fluorine atom-containing graft polymer and curing the coating film.

  The fluorine atom-containing graft polymer tends to be oxidatively deteriorated in the surface layer coating solution.

  Therefore, conventionally, a large amount of the fluorine atom-containing graft polymer has been added to the surface layer coating liquid in anticipation of a decrease in the dispersant function due to oxidative degradation of the fluorine atom-containing graft polymer.

  The fluorine atom-containing graft polymer contained in a large amount in the coating solution for the surface layer is contained in a large amount in the surface layer. The fluorine atom-containing graft polymer in the surface layer is modified (electric current modification) due to the influence of energization due to repeated use of the electrophotographic photosensitive member, and the modified fluorine atom-containing graft polymer tends to inhibit the movement of carriers in the surface layer. It is in. The larger the amount of fluorine atom-containing graft polymer in the surface layer, the more easily the movement of carriers in the surface layer is inhibited. As a result, the present inventors presume that fluctuation (deterioration) of the electrical characteristics of the electrophotographic photosensitive member is caused.

  The present invention is characterized in that 4-methoxyphenol is further contained in the surface layer / surface layer coating solution of the electrophotographic photosensitive member. Since 4-methoxyphenol suppresses the oxidative deterioration of the fluorine atom-containing graft polymer, it is not necessary to allow the surface layer / surface layer coating solution to contain a large amount of the fluorine atom-containing graft polymer in anticipation of the oxidative deterioration. As a result, in the surface layer, the amount of the fluorine-containing graft polymer denatured product that inhibits carrier movement is reduced, and fluctuation (deterioration) in electrical characteristics when the electrophotographic photoreceptor is repeatedly used is suppressed. The present inventors speculate.

  Examples of the triphenylamine compound having two or more chain polymerizable functional groups include a compound represented by the following formula (1).

  The average particle diameter of the polytetrafluoroethylene particles used in the present invention is preferably 50 μm or less, more preferably 10 μm or less, and more preferably 1 μm or less, from the viewpoint of the stability of the surface layer coating solution. Is more preferable.

The fluorine atom-containing graft polymer used in the present invention is
A triphenylamine compound having two or more chain polymerizable functional groups, and
It is preferable to have a structural unit highly compatible with each of the polytetrafluoroethylene particles in the same resin molecule, and the molecular weight is preferably several hundred to several hundred thousand.

  The electrophotographic photoreceptor of the present invention has a support and a photosensitive layer on the support.

  The photosensitive layer is preferably a laminated type (functional separation type) photosensitive layer having a charge generation layer on a support and a charge transport layer on the charge generation layer.

  FIG. 1 is a view showing an example of the layer structure of the electrophotographic photosensitive member of the present invention.

  In FIG. 1, 101 is a support, 102 is a charge generation layer, 103 is a charge transport layer, and 104 is a surface layer (protective layer).

  In the present invention, a conductive layer and undercoat layer described later may be provided between the support and the photosensitive layer as necessary.

  The support used in the electrophotographic photosensitive member of the present invention is preferably a conductive one (conductive support), and examples thereof include a support made of a metal (alloy) such as aluminum, aluminum alloy, and stainless steel. It is done. In the case of a support made of aluminum or aluminum alloy, an ED tube, an EI tube, or a tube obtained by cutting, electrolytic composite polishing, wet or dry honing treatment of these can also be used as the support. In addition, a metal support or a resin support on which a thin film of a conductive material such as aluminum, an aluminum alloy, or an indium oxide-tin oxide alloy is formed can also be used as the support.

  In addition, a support obtained by impregnating a resin or the like with conductive particles such as carbon black, tin oxide particles, titanium oxide particles, or silver particles, or a support made of conductive resin can also be used.

  The surface of the support may be subjected to cutting treatment, roughening treatment, alumite treatment, or the like.

  A conductive layer having conductive particles and a binder resin may be provided between the support and the photosensitive layer or the undercoat layer described below.

  The conductive layer is formed by coating a conductive layer coating solution obtained by dispersing conductive particles together with a binder resin and a solvent to form a coating film, and drying and / or curing the coating film. Can do.

  Examples of the conductive particles used in the conductive layer include carbon black, acetylene black, metal particles such as aluminum, nickel, iron, nichrome, copper, zinc, silver, tin oxide, zinc oxide, titanium oxide, Examples thereof include particles of metal oxides such as ITO.

  Examples of the resin used for the conductive layer include acrylic resin, alkyd resin, epoxy resin, phenol resin, butyral resin, acetal resin, urethane resin, melamine resin, polyester, and polycarbonate. These resin may use only 1 type and may use 2 or more types together as a mixture or a copolymer.

  Examples of the solvent used in the conductive layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents. These solvents may be used alone or in combination of two or more.

  The thickness of the conductive layer is preferably 0.2 μm or more and 40 μm or less, and more preferably 5 μm or more and 40 μm or less.

  An undercoat layer may be provided between the support or the conductive layer and the photosensitive layer.

  The undercoat layer can be formed by applying a coating solution for an undercoat layer containing a resin to form a coating film, and drying or curing the coating film.

  Examples of the resin used for the undercoat layer include polyacrylic acid, methylcellulose, ethylcellulose, polyamide, polyimide, polyamideimide, polyamic acid, melamine resin, epoxy resin, and polyurethane. These resin may use only 1 type and may use 2 or more types together as a mixture or a copolymer.

  The undercoat layer may contain the above-described conductive particles, semiconductive particles, electron transporting material, and electron accepting material.

  Examples of the solvent used in the coating solution for the undercoat layer include ether solvents, alcohol solvents, ketone solvents, aromatic hydrocarbon solvents, and the like. These solvents may be used alone or in combination of two or more.

  The thickness of the undercoat layer is preferably 0.05 μm or more and 40 μm or less, and more preferably 0.1 μm or more and 20 μm or less.

  A photosensitive layer is formed on the support, the conductive layer or the undercoat layer.

  When the photosensitive layer is a laminate type photosensitive layer, the charge generation layer is formed by applying a charge generation layer coating solution obtained by dispersing a charge generation material together with a binder resin and a solvent to form a coating film. It can be formed by drying the membrane. The charge generation layer may be a vapor generation film of a charge generation material.

  Examples of the charge generation material used in the charge generation layer include pyrylium, thiapyrylium dyes, phthalocyanine pigments, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, azo pigments, indigo pigments, quinacridone pigments, and quinocyanine pigments. It is done.

  Among these, gallium phthalocyanine is preferable. Furthermore, hydroxygallium phthalocyanine is preferable from the viewpoint of high sensitivity. Among hydroxygallium phthalocyanines, hydroxygallium phthalocyanine crystals having strong peaks at 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° of the Bragg angle 2θ in CuKα characteristic X-ray diffraction are preferable.

  Examples of the binder resin used for the charge generation layer include butyral resin, acrylic resin, urea resin, polycarbonate, polyester, polyvinyl acetal, and polyvinyl acetate. Among these, a butyral resin is preferable. These resin may use only 1 type and may use 2 or more types together as a mixture or a copolymer.

  In the charge generation layer, the ratio of the charge generation material to the binder resin is preferably 0.3 parts by mass or more and 4 parts by mass or less for the binder resin with respect to 1 part by mass of the charge generation material.

  Examples of the dispersion treatment method include a method using a homogenizer, ultrasonic waves, a ball mill, a sand mill, an attritor, a roll mill, and the like.

  Examples of the solvent used in the charge generation layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents. These solvents may be used alone or in combination of two or more.

  The thickness of the charge generation layer is preferably from 0.01 μm to 5 μm, and more preferably from 0.1 μm to 1 μm.

  Moreover, various sensitizers, antioxidants, ultraviolet absorbers, plasticizers, and the like can be added to the charge generation layer as necessary.

  When the photosensitive layer is a laminated type photosensitive layer, the charge transport layer is formed by applying a charge transport layer coating solution obtained by dissolving a charge transport material and a binder resin in a solvent to form a coating film. It can be formed by drying the membrane.

  Examples of the charge transport material used in the charge transport layer include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, triarylmethane compounds, and the like.

  Examples of the binder resin used for the charge transport layer include cellulose resin, urethane resin, epoxy resin, agarose resin, cellulose resin, acrylic resin, butyral resin, phenoxy resin, polyarylate, polycarbonate, polyester, polyvinyl acetate, poly Examples include acrylamide, polyamide, polyvinyl pyridine, casein, polyvinyl alcohol, and polyvinyl pyrrolidone. These resin may use only 1 type and may use 2 or more types together as a mixture or a copolymer.

  The ratio of the charge transport material is preferably 30% by mass to 70% by mass with respect to the total mass of the charge transport layer.

  Examples of the solvent used in the charge transport layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents. These solvents may be used alone or in combination of two or more.

  The thickness of the charge transport layer is preferably 5 μm or more and 40 μm or less.

  The charge transport layer can contain additives such as various sensitizers, antioxidants, ultraviolet absorbers, and plasticizers as necessary.

  The surface layer in the electrophotographic photoreceptor can be formed, for example, as follows. First, polytetrafluoroethylene particles, a fluorine atom-containing graft polymer, 4-methoxyphenol and a solvent are dispersed with an ultrahigh pressure disperser to obtain a dispersion mother liquor. A surface layer coating solution is prepared by adding a triphenylamine compound having two or more chain polymerizable functional groups to the dispersion mother liquor. A surface layer can be formed by forming a coating film of this surface layer coating solution and polymerizing a triphenylamine compound having two or more chain polymerizable functional groups contained in the coating film. The surface layer thus formed becomes a three-dimensional crosslinked film.

  In this invention, content of the polytetrafluoroethylene particle | grains in a surface layer is 5 mass% or more and 75 mass% or less with respect to the total mass of a surface layer. Moreover, content of 4-methoxyphenol in a surface layer is 0.001 mass% or more and 5 mass% or less with respect to the polytetrafluoroethylene particle | grains in a surface layer.

  When the content of 4-methoxyphenol is too large, the electrical characteristics of the electrophotographic photosensitive member are likely to deteriorate. When the content of 4-methoxyphenol is too small, it is difficult to obtain the effect of improving the abrasion resistance of the electrophotographic photosensitive member.

Examples of the solvent used in the surface layer coating solution include:
Alcohol solvents such as methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 1-methoxy-2-propanol,
Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone,
Ester solvents such as ethyl acetate and butyl acetate,
Ether solvents such as tetrahydrofuran and dioxane,
Halogen solvents such as 1,1,2,2,3,3,4-heptafluorocyclopentane, dichloromethane, dichloroethane, chlorobenzene,
Aromatic solvents such as benzene, toluene, xylene,
Examples include cellosolve solvents such as methyl cellosolve and ethyl cellosolve. These solvents may be used alone or in combination of two or more.

  The film thickness of the surface layer is preferably 2 μm or more and 20 μm or less.

  The surface layer can contain various additives as required.

  Examples of the additive to be contained in the surface layer include a deterioration inhibitor such as an ultraviolet absorber, a polymerization controller such as a polymerization reaction initiator and a polymerization reaction stopper, a leveling agent such as silicone oil, and a surfactant. .

  In the present invention, a benzophenone derivative is preferably contained in the surface layer of the electrophotographic photosensitive member from the viewpoint of improving the electrical characteristics of the electrophotographic photosensitive member. Among the benzophenone derivatives, a benzophenone derivative represented by the following formula (2) is more preferable.

  The content of the benzophenone derivative in the surface layer of the electrophotographic photoreceptor is preferably 0.001% by mass to 5% by mass with respect to the total mass of the surface layer.

  In the present invention, polymerization of a triphenylamine compound having two or more chain-polymerizable functional groups can be performed using heat, light (such as ultraviolet rays), radiation (such as electron beams) and the like. Among these, polymerization using radiation is preferable, and among these radiation, an electron beam is more preferable.

  When polymerized using an electron beam, a very dense (high density) three-dimensional crosslinked structure is obtained, and a surface layer having high durability is obtained. Further, since the polymerization reaction is efficient in a short time, productivity is also increased.

  When irradiating an electron beam to the coating film of the surface layer coating liquid, examples of the accelerator include a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type accelerator.

  When an electron beam is used, the acceleration voltage of the electron beam is preferably 120 kV or less from the viewpoint of suppressing deterioration of material properties due to the electron beam without impairing the polymerization efficiency. Further, the electron beam absorbed dose on the surface of the coating film of the surface layer coating solution is preferably 5 kGy or more and 50 kGy or less, and more preferably 1 kGy or more and 10 kGy or less.

  When polymerizing a triphenylamine compound having two or more chain-polymerizable functional groups using an electron beam, it is inert after irradiation with an electron beam in an inert gas atmosphere from the viewpoint of suppressing polymerization inhibition by oxygen. Heating in a gas atmosphere is preferred. Examples of the inert gas include nitrogen gas, argon gas, and helium gas.

  When applying the coating liquid for each of the above layers, a coating method such as a dip coating method (dipping method), a spray coating method, a spinner coating method, a bead coating method, a blade coating method, or a beam coating method can be used.

  The surface of the surface layer of the electrophotographic photosensitive member may be subjected to surface processing using various methods to form an arbitrary shape.

  FIG. 2 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

  In FIG. 2, reference numeral 1 denotes a cylindrical (drum-shaped) electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in the direction of an arrow with a predetermined peripheral speed (process speed).

  The surface (circumferential surface) of the electrophotographic photosensitive member 1 is positively or negatively charged by a charging unit (primary charging unit) 3 during the rotation process. Next, the surface of the electrophotographic photoreceptor 1 is irradiated with exposure light (image exposure light) 4 output from an exposure means (image exposure means) (not shown). The exposure light 4 is intensity-modulated corresponding to the time-series electric digital image signal of the target image information. Examples of exposure means include slit exposure and laser beam scanning exposure. Thus, an electrostatic latent image corresponding to the target image information is formed on the surface of the electrophotographic photoreceptor 1.

  The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is then developed (regular development or reversal development) with toner contained in the developing means 5 to form a toner image. The toner image formed on the surface of the electrophotographic photoreceptor 1 is transferred to the transfer material 7 by the transfer means 6. Here, when the transfer material 7 is paper, it is taken out from a paper feeding unit (not shown) in synchronization with the rotation of the electrophotographic photosensitive member 1 and fed between the electrophotographic photosensitive member 1 and the transfer means 6. Is done. Further, a bias voltage having a polarity opposite to the charge held in the toner is applied to the transfer means 6 from a bias power source (not shown). The transfer means may be an intermediate transfer type transfer means having a primary transfer member, an intermediate transfer member, and a secondary transfer member.

  The transfer material 7 onto which the toner image has been transferred is separated from the surface of the electrophotographic photosensitive member 1, transported to a fixing unit 8, and subjected to a fixing process of the toner image, whereby an electronic image forming product (print, copy) is obtained. Printed out of photographic device.

  The surface of the electrophotographic photosensitive member 1 after the toner image is transferred is cleaned by the cleaning means 9 to remove deposits such as transfer residual toner. The transfer residual toner can also be collected by a developing means or the like. Further, if necessary, the surface of the electrophotographic photosensitive member 1 is subjected to charge removal treatment by irradiation with pre-exposure light 10 from a pre-exposure unit (not shown), and then repeatedly used for image formation. When the charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure unit is not always necessary.

  In the present invention, a plurality of components selected from the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, the transfer unit 6, the cleaning unit 9, and the like may be housed in a container to form a process cartridge. Further, the process cartridge may be detachable from the main body of the electrophotographic apparatus. For example, the electrophotographic photoreceptor 1 and at least one means selected from the group consisting of charging means 3, developing means 5, transfer means 6 and cleaning means 9 are integrally supported to form a cartridge. Then, the process cartridge 11 can be detachably attached to the main body of the electrophotographic apparatus using the guide means 12 such as a rail of the main body of the electrophotographic apparatus.

  In addition, a filling member may be inserted into the electrophotographic photosensitive member (inside the cylindrical support) in order to prevent squeal due to charging noise or friction with the cleaning blade. Examples of the filling member include a rubber filling member. The filling member can be reused because there is no abrasion due to rubbing, such as the electrophotographic photosensitive member (the surface thereof) and the flange (including the gear flange) provided at the end thereof.

  Hereinafter, a method for taking out the filling member from the inside of the electrophotographic photoreceptor will be described. An electrophotographic photosensitive member having flanges attached to both ends (both ends) is taken as an example.

As shown in FIG.
(A) An electrophotographic photosensitive member is fixed, and a shaft is inserted into the shaft hole of the flange at one end.
(B) Tilt the shaft.
(C) Remove the flange from the electrophotographic photosensitive member, and then remove the flange at the other end in the same manner.
(D) An extrusion jig having a shape corresponding to the shape of the filling member is inserted into the support of the electrophotographic photosensitive member, and a part of the filling member is pressed to take out the filling member from the inside of the support of the electrophotographic photosensitive member. .

  Further, as shown in FIG. 4, (b) it is possible to tilt the shaft inserted into the flange and turn the shaft to remove the flange.

  The filling member taken out by the above method is less likely to be scratched or soiled and can be easily reused.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples, “part” means “part by mass”.

<Example 1>
An aluminum cylinder having a diameter of 30 mm, a length of 357.5 mm, and a thickness of 0.7 mm was used as a support (conductive support).

Next, 100 parts of zinc oxide particles (specific surface area: 19 m ² / g, powder resistance: 4.7 × 10 ⁶ Ω · cm) as metal oxide particles were stirred and mixed with 500 parts of toluene. To this, 0.8 part of a silane coupling agent (compound name: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) is added for 6 hours. Stir. Then, toluene was distilled off under reduced pressure, and the surface-treated zinc oxide particles were obtained by drying (heating drying) at 130 ° C. for 6 hours.

  Next, 15 parts of butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) as a polyol and 15 parts of blocked isocyanate (trade name: Sumijoule 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.) are added to methyl ethyl ketone 73. A solution was obtained by dissolving in a mixed solvent of 5 parts and 73.5 parts of 1-butanol. In this solution, 80.64 parts of the surface-treated zinc oxide particles, 0.8 part of a compound (benzophenone derivative) represented by the following formula (2) (manufactured by Tokyo Chemical Industry Co., Ltd.)

Was added to a sand mill using glass beads having a diameter of 0.8 mm, and dispersed in an atmosphere of 23 ± 3 ° C. for 3 hours.

  After the dispersion treatment, 0.01 parts of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone), crosslinked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMERSSX-102, manufactured by Sekisui Plastics Co., Ltd.) An undercoat layer coating solution was prepared by adding 5.6 parts of (average primary particle size: 2.5 μm) and stirring.

  This undercoat layer coating solution is dip-coated on the support to form a coating film, and this coating film is dried at 160 ° C. for 40 minutes (heat drying) to form an undercoat layer having a thickness of 18 μm. did.

  Next, 11 parts of a crystalline hydroxygallium phthalocyanine crystal (charge generating substance) having strong peaks at 7.4 ° and 28.2 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction, polyvinyl 5 parts of butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 130 parts of cyclohexanone are mixed, 500 parts of glass beads having a diameter of 1 mm are added thereto, and cooled with cooling water at 18 ° C. However, the dispersion treatment was performed for 2 hours under the condition of 1800 rpm.

  After the dispersion treatment, 300 parts of ethyl acetate and 160 parts of cyclohexanone were added and diluted to prepare a charge generation layer coating solution.

  This coating solution for charge generation layer is dip-coated on the undercoat layer to form a coating film, and this coating film is dried at 110 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.16 μm. did.

  The average particle size (median) of the hydroxygallium phthalocyanine crystals in the prepared coating solution for charge generation layer is determined based on the centrifugal particle size measuring device (trade name: CAPA700, manufactured by HORIBA, Ltd.) based on the liquid phase precipitation method. ) Was 0.18 μm.

  Next, 2 parts of a compound (charge transport material) represented by the following formula (3):

7 parts of a compound (charge transport material) represented by the following formula (4):

1 part of a compound (charge transport material) represented by the following structural formula (5),

10 parts of polycarbonate (trade name: Iupilon Z400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and a polycarbonate having a structural unit represented by the following formula (6-1) and a structural unit represented by the following formula (6-2) ( Viscosity average molecular weight: Mv: 20000) 0.002 part

(0.95 and 0.05 in the formulas (6-1) and (6-2) mean the copolymerization ratio of both.)
Was dissolved in a mixed solvent of 70 parts of monochlorobenzene and 30 parts of dimethoxymethane to prepare a charge transport layer coating solution.

  The charge transport layer coating solution was dip coated on the charge generation layer to form a coating film, and the coating film was dried at 100 ° C. for 30 minutes to form a charge transport layer having a thickness of 18 μm.

  Next, 0.35 part of 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 1,1,2,2,3,3,4-heptafluorocyclopentane (trade names: Zeolora H, Nippon Zeon ( A 4-methoxyphenol diluted solution was prepared by dissolving in 10,000 parts.

  Next, 100 parts of the 4-methoxyphenol diluted solution, 30 parts of polytetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd.), and a fluorine atom-containing graft polymer (trade name: GF300) are vacuum-dried. A dispersion mother liquor of Example 1 was prepared by dispersing 1.5 parts of the dried product thus obtained with a high-pressure disperser. GF300 (trade name) is a fluorine atom-containing graft polymer manufactured by Toa Gosei Co., Ltd.

  Next, 70 parts of a triphenylamine compound (triphenylamine compound having two chain polymerizable functional groups (acryloyloxy group)) represented by the following formula (7)

Was dissolved in 100 parts of n-propanol and mixed with 130 parts of the dispersion mother liquor to prepare a surface layer coating solution of Example 1.

  This coating solution for surface layer was dip coated on the charge transport layer to form a coating film, and the coating film was heat-treated at 50 ° C. for 5 minutes. Thereafter, the coating film was irradiated with an electron beam for 1.6 seconds under the conditions of an acceleration voltage of 70 kV and an absorbed dose of 50000 Gy in a nitrogen atmosphere. Then, it heat-processed for 25 second on the conditions which this coating film becomes 130 degreeC in nitrogen atmosphere. The oxygen concentration from the electron beam irradiation to the heat treatment for 25 seconds was 18 ppm. Next, in the air, a surface layer having a thickness of 5 μm was formed by heat-treating the coating film at 115 ° C. for 12 minutes.

  In this manner, the electrophotographic photosensitive member of Example 1 having a support, a conductive layer, an undercoat layer, a charge generation layer, a charge transport layer, and a surface layer was produced.

<Example 2>
In Example 1, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.7 parts. Other than that was carried out similarly to Example 1, and prepared the coating liquid for surface layers of Example 2. FIG.

  An electrophotographic photoreceptor of Example 2 was produced in the same manner as in Example 1 except that the surface layer was formed using the surface layer coating solution of Example 2.

<Example 3>
In Example 1, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.07 parts. Other than that was carried out similarly to Example 1, and prepared the coating liquid for surface layers of Example 3. FIG.

  An electrophotographic photoreceptor of Example 3 was produced in the same manner as in Example 1 except that the surface layer was formed using the surface layer coating solution of Example 3.

<Example 4>
One part of the compound represented by the above formula (2) (benzophenone derivative) is mixed with 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) 1000 A benzophenone diluted solution of Example 4 was prepared by dissolving in a portion.

  To the surface layer coating solution prepared in the same manner as in Example 1, 2 parts of the benzophenone diluted solution of Example 4 was further added to prepare the surface layer coating solution of Example 4.

  An electrophotographic photosensitive member of Example 4 was produced in the same manner as in Example 1 except that the surface layer was formed using the coating solution for the surface layer of Example 4.

<Example 5>
In Example 1, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.7 parts, and the amount of polytetrafluoroethylene particles used was changed from 30 parts to 60 parts. Moreover, the usage-amount of the dried product which vacuum-dried the fluorine atom containing graft polymer (brand name: GF300) was changed from 1.5 parts to 3 parts. A dispersion mother liquor of Example 5 was prepared in the same manner as Example 1 except for the above.

  Next, in Example 1, the amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 40 parts, and the dispersion mother liquor was changed from 130 parts of the dispersion mother liquid of Example 1 to the dispersion of Example 5. Changed to 160 parts mother liquor. A surface layer coating solution of Example 5 was prepared in the same manner as Example 1 except for the above.

  An electrophotographic photoreceptor of Example 5 was produced in the same manner as in Example 1 except that the surface layer was formed using the surface layer coating solution of Example 5.

<Example 6>
In Example 1, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.12 parts, and the amount of polytetrafluoroethylene particles used was changed from 30 parts to 10 parts. Moreover, the usage-amount of the dried product which vacuum-dried the fluorine atom containing graft polymer (brand name: GF300) was changed from 1.5 parts to 0.5 parts. A dispersion mother liquor of Example 6 was prepared in the same manner as Example 1 except for the above.

  Next, in Example 1, the amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 90 parts, and the dispersion mother liquor was changed from 130 parts of the dispersion mother liquid of Example 1 to the dispersion of Example 6. Changed to 110 parts mother liquor. A surface layer coating solution of Example 6 was prepared in the same manner as Example 1 except for the above.

  An electrophotographic photoreceptor of Example 6 was produced in the same manner as in Example 1 except that the surface layer was formed using the surface layer coating solution of Example 6.

<Example 7>
A surface layer coating solution of Example 7 was prepared by adding 3 parts of pure water to the surface layer coating solution prepared in the same manner as in Example 1.

  An electrophotographic photoreceptor of Example 7 was produced in the same manner as in Example 1 except that the surface layer was formed using the surface layer coating solution of Example 7.

<Example 8>
To the surface layer coating solution prepared in the same manner as in Example 1, 1 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone) was further added to prepare the surface layer coating solution of Example 8. did.

  An electrophotographic photosensitive member of Example 8 was produced in the same manner as in Example 1 except that the surface layer was formed using the surface layer coating solution of Example 8.

<Example 9>
In Example 1, an electrophotographic photosensitive member of Example 9 was produced in the same manner as Example 1 except that the film thickness of the surface layer was changed to 10 μm.

<Example 10>
In Example 1, the amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 58 parts, and further 12 parts of the compound represented by the following formula (8).

Was added to prepare a surface layer coating solution of Example 10.

  An electrophotographic photoreceptor of Example 10 was produced in the same manner as in Example 1 except that the surface layer was formed using the coating solution for the surface layer of Example 10.

<Example 11>
In Example 1, the amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 35 parts, and 35 parts of the compound represented by the above formula (8) was further added. A surface layer coating solution was prepared.

  An electrophotographic photoreceptor of Example 11 was produced in the same manner as in Example 1 except that the surface layer was formed using the surface layer coating solution of Example 11.

<Example 12>
In Example 1, the amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 58 parts, and further 12 parts of the compound represented by the following formula (9).

Was added to prepare a coating solution for the surface layer of Example 12.

  An electrophotographic photoreceptor of Example 12 was produced in the same manner as in Example 1 except that the surface layer was formed using the surface layer coating solution of Example 12.

<Example 13>
In Example 1, 1.5 parts of a dried product obtained by vacuum drying a fluorine atom-containing graft polymer (trade name: GF300) and another dried product obtained by vacuum drying another fluorine atom-containing graft polymer (trade name: GF400). Changed to 1.5 parts. GF400 (trade name) is also a fluorine atom-containing graft polymer manufactured by Toa Gosei Co., Ltd. Other than that was carried out similarly to Example 1, and prepared the coating liquid for surface layers of Example 13. FIG.

  An electrophotographic photosensitive member of Example 13 was produced in the same manner as in Example 1 except that the surface layer was formed using the surface layer coating solution of Example 13.

<Example 14>
To the surface layer coating solution prepared in the same manner as in Example 7, 1 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone) was further added to prepare the surface layer coating solution of Example 14. did.

  An electrophotographic photoreceptor of Example 14 was produced in the same manner as in Example 7, except that the surface layer was formed using the coating solution for surface layer of Example 14.

<Example 15>
In Example 14, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.7 parts. Other than that was carried out similarly to Example 14, and prepared the coating liquid for surface layers of Example 15. FIG.

  An electrophotographic photosensitive member of Example 15 was produced in the same manner as in Example 14 except that the surface layer was formed using the surface layer coating solution of Example 15.

<Example 16>
In Example 14, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.07 parts. Other than that was carried out similarly to Example 14, and prepared the coating liquid for surface layers of Example 16. FIG.

  An electrophotographic photoreceptor of Example 16 was produced in the same manner as in Example 14 except that the surface layer was formed using the surface layer coating solution of Example 16.

<Example 17>
To the surface layer coating solution prepared in the same manner as in Example 14, 2 parts of the benzophenone diluted solution in Example 17 prepared in the same manner as in Example 4 was further added to prepare the surface layer coating solution in Example 17. Prepared.

  An electrophotographic photosensitive member of Example 17 was produced in the same manner as in Example 14 except that the surface layer was formed using the surface layer coating solution of Example 17.

<Example 18>
In Example 14, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.7 parts, and the amount of polytetrafluoroethylene particles used was changed from 30 parts to 60 parts. Moreover, the usage-amount of the dried product which vacuum-dried the fluorine atom containing graft polymer (brand name: GF300) was changed from 1.5 parts to 3 parts. A dispersion mother liquor of Example 18 was prepared in the same manner as Example 14 except for the above.

  Next, in Example 14, the usage amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 40 parts, and the usage amount of the dispersion mother liquor was changed from 130 parts to 160 parts. A surface layer coating solution of Example 18 was prepared in the same manner as Example 14 except for the above.

  An electrophotographic photoreceptor of Example 18 was produced in the same manner as in Example 14 except that the surface layer was formed using the surface layer coating solution of Example 18.

<Example 19>
In Example 14, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.12 parts, and the amount of polytetrafluoroethylene particles used was changed from 30 parts to 10 parts. Moreover, the usage-amount of the dried product which vacuum-dried the fluorine atom containing graft polymer (brand name: GF300) was changed from 1.5 parts to 0.5 parts. A dispersion mother liquor of Example 19 was prepared in the same manner as Example 14 except for the above.

  Next, in Example 14, the usage amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 90 parts, and the usage amount of the dispersion mother liquor was changed from 130 parts to 110 parts. A surface layer coating solution of Example 19 was prepared in the same manner as Example 14 except for the above.

  An electrophotographic photoreceptor of Example 19 was produced in the same manner as in Example 14, except that the surface layer was formed using the surface layer coating solution of Example 19.

<Example 20>
In Example 14, the electrophotographic photosensitive member of Example 20 was produced in the same manner as in Example 14, except that the film thickness of the surface layer was changed to 10 μm.

<Example 21>
In Example 14, the amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 58 parts, and 12 parts of the compound represented by the above formula (8) was further added. A surface layer coating solution of Example 21 was prepared in the same manner as Example 14 except for the above.

  An electrophotographic photosensitive member of Example 21 was produced in the same manner as in Example 14 except that the surface layer was formed using the surface layer coating solution of Example 21.

<Example 22>
In Example 14, the amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 35 parts, and 35 parts of the compound represented by the above formula (8) was further added. A surface layer coating solution of Example 22 was prepared in the same manner as Example 14 except for the above.

  An electrophotographic photoreceptor of Example 22 was produced in the same manner as in Example 14 except that the surface layer was formed using the surface layer coating solution of Example 22.

<Example 23>
In Example 14, the amount of the triphenylamine compound represented by the above formula (7) was changed to 58 parts, and 12 parts of the compound represented by the above formula (9) was further added. A surface layer coating solution of Example 23 was prepared in the same manner as Example 14 except for the above.

  An electrophotographic photoreceptor of Example 23 was produced in the same manner as in Example 14 except that the surface layer was formed using the surface layer coating solution of Example 23.

<Example 24>
In Example 14, 1.5 parts of a dried product obtained by vacuum drying a fluorine atom-containing graft polymer (trade name: GF300) and another dried product obtained by vacuum drying another fluorine atom-containing graft polymer (trade name: GF400). Changed to 1.5 parts. Other than that was carried out similarly to Example 14, and prepared the coating liquid for surface layers of Example 24. FIG.

  An electrophotographic photoreceptor of Example 24 was produced in the same manner as in Example 14 except that the surface layer was formed using the surface layer coating solution of Example 24.

<Example 25>
In Example 17, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.7 parts. Other than that was carried out similarly to Example 17, and prepared the coating liquid for surface layers of Example 25. FIG.

  An electrophotographic photosensitive member of Example 25 was produced in the same manner as in Example 17 except that the surface layer was formed using the coating liquid for surface layer of Example 25.

<Example 26>
In Example 17, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.07 parts. Other than that was carried out similarly to Example 17, and prepared the coating liquid for surface layers of Example 26. FIG.

  An electrophotographic photoreceptor of Example 26 was produced in the same manner as in Example 17, except that the surface layer was formed using the coating solution for the surface layer of Example 26.

<Example 27>
In Example 17, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.7 parts, and the amount of polytetrafluoroethylene particles used was changed from 30 parts to 60 parts. Moreover, the usage-amount of the dried product which vacuum-dried the fluorine atom containing graft polymer (brand name: GF300) was changed from 1.5 parts to 3 parts. A dispersion mother liquor of Example 27 was prepared in the same manner as Example 17 except for the above.

  Next, in Example 17, the usage amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 40 parts, and the usage amount of the dispersed mother liquor was changed from 130 parts to 160 parts. A surface layer coating solution of Example 27 was prepared in the same manner as Example 17 except for the above.

  An electrophotographic photoreceptor of Example 27 was produced in the same manner as in Example 17, except that the surface layer was formed using the coating liquid for surface layer of Example 27.

<Example 28>
In Example 17, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.12 parts, and the amount of polytetrafluoroethylene particles used was changed from 30 parts to 10 parts. Moreover, the usage-amount of the dried product which vacuum-dried the fluorine atom containing graft polymer (brand name: GF300) was changed from 1.5 parts to 0.5 parts. A dispersion mother liquor was prepared in the same manner as Example 17 except for the above.

  Next, in Example 17, the usage amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 90 parts, and the usage amount of the dispersion mother liquor was changed from 130 parts to 110 parts. A surface layer coating solution of Example 28 was prepared in the same manner as Example 17 except for the above.

  An electrophotographic photoreceptor of Example 28 was produced in the same manner as in Example 17, except that the surface layer was formed using the surface layer coating solution of Example 28.

<Example 29>
In Example 17, the electrophotographic photosensitive member of Example 29 was produced in the same manner as in Example 17, except that the film thickness of the surface layer was changed to 10 μm.

<Example 30>
In Example 17, the amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 58 parts, and 12 parts of the compound represented by the above formula (8) was further added. A surface layer coating solution of Example 30 was prepared in the same manner as Example 17 except for the above.

  An electrophotographic photoreceptor of Example 30 was produced in the same manner as in Example 17, except that the surface layer was formed using the coating solution for the surface layer of Example 30.

<Example 31>
In Example 17, the amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 35 parts, and 35 parts of the compound represented by the above formula (8) was further added. A surface layer coating solution of Example 31 was prepared in the same manner as Example 17 except for the above.

  An electrophotographic photosensitive member of Example 31 was produced in the same manner as in Example 17 except that the surface layer was formed using the surface layer coating solution of Example 31.

<Example 32>
In Example 17, the amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 58 parts, and 12 parts of the compound represented by the above formula (9) was further added. A surface layer coating solution of Example 32 was prepared in the same manner as Example 17 except for the above.

  An electrophotographic photoreceptor of Example 32 was produced in the same manner as in Example 17, except that the surface layer was formed using the surface layer coating solution of Example 32.

<Example 33>
In Example 17, 1.5 parts of a dried product obtained by vacuum drying a fluorine atom-containing graft polymer (trade name: GF300) and another dried product obtained by vacuum drying another fluorine atom-containing graft polymer (trade name: GF400) Changed to 1.5 parts. Other than that was carried out similarly to Example 17, and prepared the coating liquid for surface layers of Example 33. FIG.

  An electrophotographic photoreceptor of Example 33 was produced in the same manner as in Example 17, except that the surface layer was formed using the coating solution for the surface layer of Example 33.

<Example 34>
In Example 30, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.7 parts. Other than that was carried out similarly to Example 30, and prepared the coating liquid for surface layers of Example 34. FIG.

  An electrophotographic photoreceptor of Example 34 was produced in the same manner as in Example 30, except that the surface layer was formed using the surface layer coating solution of Example 34.

<Example 35>
In Example 30, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.07 parts. Other than that was carried out similarly to Example 30, and prepared the coating liquid for surface layers of Example 35. FIG.

  An electrophotographic photoreceptor of Example 35 was produced in the same manner as in Example 30, except that the surface layer was formed using the surface layer coating solution of Example 35.

<Example 36>
In Example 30, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.7 parts, and the amount of polytetrafluoroethylene particles used was changed from 30 parts to 60 parts. Moreover, the usage-amount of the dried product which vacuum-dried the fluorine atom containing graft polymer (brand name: GF300) was changed from 1.5 parts to 3 parts. A dispersion mother liquor of Example 36 was prepared in the same manner as Example 30 except for the above.

  Next, in Example 30, the amount of the triphenylamine compound represented by the above formula (7) was changed from 58 parts to 33 parts, and the amount of the compound represented by the above formula (8) was changed from 12 parts to 7 parts. The amount of the dispersion mother liquor used was changed from 130 parts to 160 parts. A surface layer coating solution of Example 36 was prepared in the same manner as Example 30 except for the above.

  An electrophotographic photosensitive member of Example 36 was produced in the same manner as in Example 30, except that the surface layer was formed using the surface layer coating solution of Example 36.

<Example 37>
In Example 17, the amount of 4-methoxyphenol used was changed from 0.35 parts to 0.12 parts, and the amount of polytetrafluoroethylene particles used was changed from 30 parts to 10 parts. Moreover, the usage-amount of the dried product which vacuum-dried the fluorine atom containing graft polymer (brand name: GF300) was changed from 1.5 parts to 0.5 parts. A dispersion mother liquor of Example 37 was prepared in the same manner as Example 17 except for the above.

  Next, in Example 17, the amount of the triphenylamine compound represented by the above formula (7) was changed from 70 parts to 75 parts, and the dispersion mother liquor was changed from 130 parts of the dispersion mother liquid of Example 17 to the dispersion of Example 37. Changed to 110 parts mother liquor. Further, 15 parts of the compound represented by the above formula (8) was added. A surface layer coating solution of Example 37 was prepared in the same manner as Example 17 except for the above.

  An electrophotographic photoreceptor of Example 37 was produced in the same manner as in Example 30, except that the surface layer was formed using the coating solution for the surface layer of Example 37.

<Example 38>
In Example 30, the electrophotographic photoreceptor of Example 38 was produced in the same manner as in Example 30, except that the thickness of the surface layer was changed to 10 μm.

<Example 39>
In Example 30, the amount of the triphenylamine compound represented by the above formula (7) was changed from 58 parts to 50 parts, and the amount of the compound represented by the above formula (8) was changed from 12 parts to 10 parts. Further, 10 parts of the compound represented by the above formula (9) was added. A surface layer coating solution of Example 39 was prepared in the same manner as Example 30 except for the above.

  An electrophotographic photoreceptor of Example 39 was produced in the same manner as in Example 30, except that the surface layer was formed using the surface layer coating solution of Example 39.

<Example 40>
In Example 30, 1.5 parts of a dried product obtained by vacuum drying a fluorine atom-containing graft polymer (trade name: GF300) was dried from another dry atomized product obtained by vacuum drying another fluorine atom-containing graft polymer (trade name: GF400). Changed to 1.5 parts. Other than that was carried out similarly to Example 30, and prepared the coating liquid for surface layers of Example 40. FIG.

  An electrophotographic photosensitive member of Example 40 was produced in the same manner as in Example 30 except that the surface layer was formed using the coating solution for the surface layer of Example 40.

<Evaluation>
About the coating liquid for surface layers of Examples 1-40 and the evaluation method of an electrophotographic photoreceptor, it is as follows. The surface layer coating solution of Example 9 is the same as the surface layer coating solution of Example 1. The surface layer coating solution of Example 20 is the same as the surface layer coating solution of Example 14. The surface layer coating solution of Example 29 is the same as the surface layer coating solution of Example 17. The surface layer coating solution of Example 38 is the same as the surface layer coating solution of Example 30.

(Evaluation of coating solution for surface layer)
The dispersibility of the surface layer coating liquids of Examples 1 to 40 was evaluated as follows. After preparing the coating solution for the surface layer, the coating solution for the surface layer is allowed to stand for 3 days in an environment of a temperature of 23 ° C./humidity of 30% RH, and aggregation / precipitation of polytetrafluoroethylene particles in the coating solution for the surface layer The presence or absence of was evaluated by checking visually.

(Evaluation of electrical characteristics)
Evaluation of the electrical characteristics of the electrophotographic photosensitive member was performed as follows.

  A copying machine (trade name: iR-ADVC5255) manufactured by Canon Inc., which is an electrophotographic apparatus, was used as an evaluation apparatus. The copying machine has a charging roller as charging means. The modification was made so that power could be supplied to the charging roller from outside the copier.

  As a power source for supplying electric power for the charging roller from the outside of the copying machine, a high voltage power source control system (trade name: Model 615-3) manufactured by Trek was used.

Then, the amount of discharge current is adjusted to 100 μA by constant voltage control, the initial dark portion potential (Vd ₀ ) of the electrophotographic photosensitive member is −700 [V], and the initial bright portion potential (Vl ₀ ) is −200 [V. The conditions of the DC voltage applied to the charging roller and the amount of exposure light were set so that

  During the evaluation, the power supply to the environmental heater was turned off consistently.

The electrophotographic photosensitive members of Examples 1 to 40 were mounted on the process cartridge for the copying machine (evaluation apparatus), and this was mounted on the evaluation apparatus. Thereafter, 1000 images with an image ratio of 3% were output on A4 vertical size paper in an environment of temperature 23 ° C./humidity 30% RH. The bright part potential (Vl) after outputting 1000 images was measured, and the fluctuation (ΔVl) from the initial value (Vl ₀ ) was calculated.

ΔVl = | Vl−Vl ₀ | (V)
If ΔVl was within 10V, it was determined that the variation in electrical characteristics was small.

(Evaluation of wear resistance)
The abrasion resistance of the electrophotographic photosensitive member was evaluated as follows.

A copying machine (trade name: iR-ADVC5255) manufactured by Canon Inc. was used as an evaluation apparatus. The DC voltage applied to the charging roller and the amount of exposure light are applied so that the initial dark portion potential (Vd ₀ ) of the electrophotographic photosensitive member is −700 [V] and the initial bright portion potential (Vl ₀ ) is −200 [V]. The conditions of were set.

  During the evaluation, the power supply to the environmental heater was kept off.

  The electrophotographic photosensitive members of Examples 1 to 40 were mounted on the process cartridge for the copying machine (evaluation apparatus), and this was mounted on the evaluation apparatus, and then an image was obtained in an environment of temperature 23 ° C./humidity 30% RH. 200000 images with a ratio of 3% were output on A4 vertical size paper. The film thickness of the surface layer before image output and after output of 200000 sheets was measured with an interference film thickness meter (trade name: MCPD-3700) manufactured by Otsuka Electronics Co., Ltd. Then, the difference in the thickness of the surface layer before and after the image output was evaluated as the amount of wear of the electrophotographic photosensitive member (surface layer).

  If the amount of wear was 2.0 μm or less, it was judged that the electrophotographic photosensitive member had high wear resistance.

(Evaluation results)
Even if the surface layer coating solutions of Examples 1 to 40 were allowed to stand for 3 days after preparation, no aggregation or precipitation of polytetrafluoroethylene particles in the surface layer coating solution was observed, and the dispersibility was good. It was judged.

  Table 1 shows the evaluation results of the electrical characteristics and abrasion resistance of the electrophotographic photoreceptors of Examples 1 to 40.

DESCRIPTION OF SYMBOLS 101 Support body 102 Charge generation layer 103 Charge transport layer 104 Surface layer (protective layer)
DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means 201 Electrophotographic photoreceptor 202 Flange 203 Shaft 204 Filling member 205 Extrusion jig

Claims (8)

In an electrophotographic photosensitive member having a support and a photosensitive layer on the support,
The surface layer of the electrophotographic photoreceptor is
A cured product of a triphenylamine compound having two or more chain polymerizable functional groups,
Polytetrafluoroethylene particles,
A fluorine atom-containing graft polymer, and
Contains 4-methoxyphenol,
The content of the polytetrafluoroethylene particles in the surface layer is 5% by mass to 75% by mass with respect to the total mass of the surface layer,
The electrophotographic photoreceptor, wherein the content of 4-methoxyphenol in the surface layer is 0.001% by mass to 5% by mass with respect to the polytetrafluoroethylene particles in the surface layer. . The surface layer further contains a benzophenone derivative;
2. The electrophotographic photosensitive member according to claim 1, wherein the content of the benzophenone derivative in the surface layer is 0.001% by mass to 5% by mass with respect to the total mass of the surface layer.   The electron according to claim 1, wherein the support is a cylindrical support, a filling member is inserted into the support, and a flange is attached to an end of the electrophotographic photosensitive member. Photoconductor.   The electrophotographic photosensitive member according to claim 3, wherein the filling member is a rubber filling member.   An electrophotographic photosensitive member according to any one of claims 1 to 4 and at least one means selected from the group consisting of a charging means, a developing means, a transfer means and a cleaning means are integrally supported, A process cartridge which is detachable from a main body of a photographic apparatus.   An electrophotographic apparatus comprising: the electrophotographic photosensitive member according to claim 1; and a charging unit, an exposing unit, a developing unit, and a transferring unit. An electrophotographic photoreceptor production method for producing an electrophotographic photoreceptor having a support and a photosensitive layer on the support,
The manufacturing method comprises:
A step of preparing a coating solution for the surface layer,
Forming a coating film of the coating solution for the surface layer, and
Having a step of forming a surface layer of the electrophotographic photosensitive member by curing the coating film,
The surface layer coating solution is
A triphenylamine compound having two or more chain polymerizable functional groups,
Polytetrafluoroethylene particles,
A fluorine atom-containing graft polymer, and
Contains 4-methoxyphenol,
The content of the polytetrafluoroethylene particles in the surface layer is 5% by mass to 75% by mass with respect to the total mass of the surface layer,
The electrophotographic photoreceptor, wherein the content of 4-methoxyphenol in the surface layer is 0.001% by mass to 5% by mass with respect to the polytetrafluoroethylene particles in the surface layer. Manufacturing method. A method of taking out a filling member for taking out the filling member from the inside of the support of the electrophotographic photosensitive member according to claim 3 or 4,
Inserting a shaft into the shaft hole of the flange, tilting and / or pivoting the shaft, and removing the flange; and
After the flange is removed, the filling member has a step of inserting an extrusion jig into the support and taking out the filling member from the inside of the support by pushing a part of the filling member. How to take out.

Images