JP2009015121A - Electrophotographic device and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic device and a process cartridge capable of suppressing stripe image defects and stably achieving favorable picture quality for a long period of time even when the device or the process cartridge is equipped with an electrophotographic photoreceptor having a long life suppressing scratches or wear and with a charging member to be in contact with the photoreceptor to charge. <P>SOLUTION: The electrophotographic device 100 and the process cartridge 20 are equipped with an electrophotographic photoreceptor 1 and a charging member 21 to be in contact with the photoreceptor to charge and are characterized in that: the electrophotographic photoreceptor includes a conductive support and a photosensitive layer formed on the conductive support; the photosensitive layer is made of a cured product of a curable resin composition containing a curable resin and a polyether compound; and the charging member has a surface layer containing a resin having an amide group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrophotographic apparatus and a process cartridge including an electrophotographic photosensitive member and a charging member.

  A so-called xerographic image forming apparatus includes an electrophotographic photosensitive member (hereinafter, simply referred to as “photosensitive member”), a charging device, an exposure device, a developing device, a transfer device, and the like, and an electrophotographic process using them. To form an image.

  2. Description of the Related Art In recent years, xerographic image forming apparatuses (electrophotographic apparatuses) have been further increased in speed and life due to technological progress of each member and system. Accordingly, demands for high-speed compatibility and high reliability of each subsystem are higher than ever. In particular, there is a strong demand for high-speed compatibility and high reliability for a photoconductor used for image writing and a cleaning member for cleaning the photoconductor. In addition, the photosensitive member and the cleaning member receive more stress than the other members due to their mutual sliding. Therefore, the photoconductor is scratched or worn, which causes image defects.

  Therefore, in order to extend the life of the electrophotographic photosensitive member, it is extremely important to suppress the occurrence of scratches and abrasion, and the use of a curable resin has been studied from the viewpoint of improving the mechanical strength of the photosensitive layer. For example, Patent Document 1 below discloses an electrophotographic photoreceptor having an outermost surface layer having a cross-linked structure including a specific silane compound and having a charge transporting ability. Patent Documents 2 to 6 below disclose electrophotographic photoreceptors having an outermost surface layer having a cross-linked structure constituted by using a phenol resin and having a charge transporting ability.

Japanese Patent Laid-Open No. 11-38656 JP 2002-6527 A JP 2002-82466 A JP 2002-82469 A JP 2003-186215 A JP 2003-186234 A

However, even in an electrophotographic photosensitive member that uses a curable resin to suppress the occurrence of scratches and abrasion, a charging member that performs charging by contacting the photosensitive member, such as a charging roll, is used as a charging unit. In this case, streak-like image defects are likely to occur at the contact position of the electrophotographic photosensitive member due to contact and friction with the charging member.
On the other hand, streaky image defects may occur at the contact position of the charging roll due to contact with the electrophotographic photosensitive member.

  The present invention has been made in view of the above-described problems, and includes a long-life electrophotographic photosensitive member in which generation of scratches and wear is suppressed, and a charging member that is charged in contact with the electrophotographic photosensitive member. Another object of the present invention is to provide an electrophotographic apparatus and a process cartridge that can suppress the occurrence of streak-like image defects and can stably obtain good image quality over a long period of time.

  In order to achieve the above object, the present invention provides the following electrophotographic apparatus and process cartridge.

The invention according to claim 1 forms an electrostatic latent image by exposing the electrophotographic photosensitive member, a charging member that contacts and charges the electrophotographic photosensitive member, and the electrophotographic photosensitive member charged by the charging member. Electrostatic latent image forming means for developing, developing means for developing the electrostatic latent image with toner to form a toner image, and transfer means for transferring the toner image to a transfer medium,
The electrophotographic photosensitive member has a conductive support and a photosensitive layer provided on the conductive support, and the photosensitive layer is a cured curable resin composition containing a curable resin and a polyether compound. It has a layer consisting of things,
The electrophotographic apparatus is characterized in that the charging member has a surface layer containing a resin having an amide group.

  The invention according to claim 2 is the electrophotographic apparatus according to claim 1, wherein the polyether compound is a polyether-modified silicone oil.

  The invention according to claim 3 is the electrophotographic apparatus according to claim 1 or 2, wherein the resin having an amide group is nylon.

  The invention according to claim 4 is the electrophotographic apparatus according to any one of claims 1 to 3, wherein the resin having an amide group is methoxymethylated nylon.

The invention according to claim 5 includes an electrophotographic photosensitive member and a charging member that is charged in contact with the electrophotographic photosensitive member,
The electrophotographic photosensitive member has a conductive support and a photosensitive layer provided on the conductive support, and the photosensitive layer is a cured curable resin composition containing a curable resin and a polyether compound. It has a layer consisting of things,
The charging member has a surface layer including a resin having an amide group.

  The invention according to claim 6 is the process cartridge according to claim 5, wherein the polyether compound is a polyether-modified silicone oil.

  The invention according to claim 7 is the process cartridge according to claim 5 or 6, wherein the resin having an amide group is nylon.

  The invention according to claim 8 is the process cartridge according to any one of claims 5 to 7, wherein the resin having an amide group is methoxymethylated nylon.

  According to the present invention, even when a long-life electrophotographic photosensitive member in which generation of scratches and wear is suppressed, and a charging member that is charged in contact with the photosensitive member, generation of streak-like image defects is suppressed, An electrophotographic apparatus and a process cartridge capable of stably obtaining a good image quality over a long period of time can be provided.

DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.
FIG. 1 is a schematic view showing an electrophotographic apparatus according to this embodiment. An electrophotographic apparatus 100 shown in FIG. 1 mainly includes a process cartridge 20, an electrostatic latent image forming apparatus (exposure apparatus) 30, a transfer apparatus 40, and an intermediate transfer body 50. It has. In the process cartridge 20, the electrophotographic photosensitive member 1, the charging member (charging roll) 21, the developing device 25, the cleaning device 27, and the fibrous member (flat brush shape) 29 are combined in a case by a mounting rail. It has become. The process cartridge 20 is detachable from the apparatus main body, and constitutes an electrophotographic apparatus together with the apparatus main body.

  An opening for exposure is provided in the case of the process cartridge 20, and the exposure device 30 is disposed at a position where the electrophotographic photosensitive member 1 can be exposed from the opening of the process cartridge 20. The transfer device 40 is disposed at a position facing the electrophotographic photosensitive member 1 via the intermediate transfer member 50, and a part of the intermediate transfer member 50 is disposed so as to contact the electrophotographic photosensitive member 1.

  In this embodiment, the electrophotographic photoreceptor 1 has a conductive support and a photosensitive layer provided on the conductive support, and the photosensitive layer includes a curable resin and a polyether compound. It has a layer made of a cured product of the curable resin composition. The charging roll 21 has a surface layer containing a resin having an amide group. By providing the electrophotographic photoreceptor 1 and the charging roll 21 as described above, the occurrence of streak-like image defects can be suppressed, and good image quality can be stably obtained over a long period of time.

The reason why the occurrence of streak-like image defects is improved by the electrophotographic apparatus and the process cartridge of the present embodiment is not necessarily clear, but the present inventors speculate as follows.
Since the functional layer of the electrophotographic photosensitive member contains a polyether compound, the polarity of frictional charging with the charging roll is changed, the electrostatic influence on the photosensitive member is suppressed, and no history is left on the photosensitive member. It is considered that the generation of pitch streaky defects can be suppressed.
On the other hand, it is considered that streaky defects in the charging roll pitch are generated when the polyether compound adheres to the charging roll. However, the resin having an amide group has a low permeability to the polyether compound, It is considered that the occurrence of streaky defects in the charging roll pitch can be suppressed by suppressing the penetration of the ether compound into the charging roll.
Hereinafter, each component will be described more specifically.

<Electrophotographic photoreceptor>
FIG. 2 is a schematic cross-sectional view illustrating an example of the electrophotographic photosensitive member according to the present embodiment. An electrophotographic photoreceptor 1 shown in FIG. 2 includes a function-separated type photosensitive layer 3 in which a charge transport layer 6 and a charge generation layer 5 are separately provided. More specifically, the electrophotographic photoreceptor 1 has a structure in which an undercoat layer 4, a charge generation layer 5, a charge transport layer 6, and a protective layer 7 are laminated in this order on a conductive support 2. Yes. And the protective layer 7 is comprised by the layer which consists of hardened | cured material of curable resin composition containing curable resin and a polyether compound.

  Examples of the conductive support 2 include a metal plate, a metal drum, a metal belt, or a conductive metal 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, plastic film, belt and the like coated, vapor-deposited, or laminated with a conductive polymer, a conductive compound such as indium oxide, or a metal or alloy such as aluminum, palladium, or gold.

  In addition, in order to prevent interference fringes generated when the laser beam is irradiated, the surface of the conductive support 2 is preferably roughened. The degree of roughness is preferably 0.04 μm or more and 0.5 μm or less in terms of centerline average roughness Ra. If Ra is smaller than 0.04 μm, it may be close to a mirror surface, so that the effect of preventing interference may not be obtained. If Ra is larger than 0.5 μm, the image quality may be rough even if a film according to this embodiment is formed. Therefore, the above range is preferable.

  As a method for roughening the surface of the conductive support 2, wet honing is performed by suspending an abrasive in water and spraying the support, or by pressing the support against a rotating grindstone and continuously Centerless grinding with grinding, anodization, etc. are preferred. A layer in which conductive or semiconductive powder is dispersed in a resin layer without roughening the support surface itself is formed on the support surface. A method of roughening with particles formed and dispersed in the layer is also preferably used.

  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 anodized film is preferably 0.3 μm or more and 15 μm or less. When the thickness is less than 0.3 μm, the barrier property against injection is poor and the effect may be insufficient. On the other hand, if it is thicker than 15 μm, there is a risk of increasing the residual potential due to repeated use.

  The treatment with an acidic treatment liquid comprising phosphoric acid, chromic acid and hydrofluoric acid can be performed as follows. 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 mass, chromic acid is in the range of 3 to 5% by mass, hydrofluoric acid Is in the range of 0.5% by mass or more and 2% by mass or less, and the concentration of these acids is preferably in the range of 13.5% by mass or more and 18% by mass or less. The processing temperature is 42 ° C. or higher and 48 ° C. or lower, but by keeping the processing temperature high, a thicker film can be formed more quickly. The film thickness is preferably 0.3 μm or more and 15 μm or less. If the thickness is less than 0.3 μm, the barrier property against injection is poor and the effect may not be sufficiently obtained. Moreover, when the film is thicker than 15 μm, there is a possibility that the residual potential is increased by repeated use.

  The boehmite treatment is immersed in pure water at 90 ° C. or higher and 100 ° C. or lower for 5 minutes or longer and 60 minutes or shorter, or is contacted with heated steam at 90 ° C. or higher and 120 ° C. or lower for 5 minutes or longer and 60 minutes or shorter. Can be performed. The film thickness is preferably 0.1 μm or more and 5 μm or less. 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.

  When non-interfering light is used for the light source, it is not particularly necessary to roughen the interference fringes, and it is possible to prevent the occurrence of defects due to the irregularities on the surface of the conductive support 2, which is suitable for longer life.

  The undercoat layer 4 is provided as necessary. Particularly, when the conductive support 2 is subjected to an acidic solution treatment or boehmite treatment, the conductive support 2 has insufficient defect concealing power. Therefore, it is preferable to form the undercoat layer 4.

  Materials used for the undercoat layer 4 include 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, and 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 And organic metal compounds such as, in particular an 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 4 may further contain a silane coupling agent. As silane coupling agents, 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 , 4-epoxycyclohexyltrimethoxysilane and the like. These mixing ratios can be appropriately set as necessary.

  The undercoat layer 4 may further contain a binder resin. As binder resin, 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, phenol resin , Vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, polyacrylic acid, and other known binder resins can also be used. These mixing ratios can be appropriately set as necessary.

  The undercoat layer 4 may further contain an electron transporting pigment from the viewpoint of lowering the residual potential and improving the environmental stability. 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. In addition, 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 transportability. If the amount of the electron transporting pigment is too large, the strength of the undercoat layer is lowered and a coating film defect may occur. Therefore, the amount is preferably 95% by mass or less, more preferably 90% by mass or less.

  The undercoat layer 4 may further contain fine powders of various organic compounds or fine powders of inorganic compounds from the viewpoint of improving electrical characteristics and light scattering properties. In particular, white pigments such as titanium oxide, zinc oxide, zinc white, zinc sulfide, lead white and lithopone, inorganic pigments as extender pigments such as alumina, calcium carbonate and barium sulfate, polyethylene terephthalate resin particles, benzoguanamine resin particles, styrene resin Particles are effective. The added fine powder has a particle size of 0.01 μm or more and 2 μm or less. The fine powder is added as necessary, but the addition amount is preferably 10% by mass or more and 90% by mass or less, and 30% by mass with respect to the total mass of the solid content of the undercoat layer 4. % Or more and 80% by mass or less is more preferable.

  The undercoat layer 4 can be formed by applying a coating solution containing the constituent material of the undercoat layer 4 on the conductive support 2 and drying it. As the solvent used in the coating solution for forming the undercoat layer 4, as the organic solvent, an organic metal compound or a resin is dissolved, and when an electron transporting pigment is mixed / dispersed, gelation or aggregation occurs. Anything that does not cause the problem can be used. 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. Further, as a dispersion treatment method for the coating liquid, methods such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, a paint shaker, and an ultrasonic wave can be used. Furthermore, as a coating method of the coating solution, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like can be used. Drying after coating is performed at a temperature at which the solvent can be evaporated and a film can be formed. In general, the thickness of the undercoat layer 4 is preferably 0.01 μm or more and 30 μm or less, and more preferably 0.05 μm or more and 25 μm or less.

  The charge generation layer 5 includes a charge generation material and a binder resin. Examples of charge generation materials include azo pigments such as bisazo pigments and trisazo pigments, 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. Known materials such as pigments can be used. In particular, when exposure light having a wavelength of 380 nm or more and 500 nm or less is used for image formation, metal and metal-free phthalocyanine pigments, trigonal selenium, dibromoanthanthrone, and the like are preferable. 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 5 can be selected from a wide range of insulating resins. It can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane. 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 mixing ratio of the charge generating material and the binder resin (mass ratio) is preferably in the range of 10: 1 to 1:10. Here, “insulating” preferably has a volume resistivity of 10 ¹³ Ωcm or more.

  The charge generation layer 5 can be formed by applying a coating liquid containing the above constituent materials onto the undercoat layer 4 and drying it. Solvents used in the coating solution for forming the charge generation layer 5 are methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate. Ordinary organic solvents such as n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene and toluene can be used alone or in admixture of two or more. In addition, as a dispersion method when preparing the coating liquid, 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. Conditions that do not change the crystal form are required. Further, at the time of this dispersion, it is effective to make the pigment particles have a particle size of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less. Furthermore, as a coating method of the coating solution, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like can be used. Drying after coating is performed at a temperature at which the solvent can be evaporated and a film can be formed. In general, the thickness of the charge generation layer 5 is preferably 0.1 μm or more and 5 μm or less, more preferably 0.2 μm or more and 2.0 μm or less.

  The charge transport layer 6 includes a charge transport material and a binder resin, or includes a polymer charge transport material.

  Charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds , Electron transport compounds such as cyanovinyl compounds and ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include, but are not limited to, hole transporting compounds. These charge transport materials can be used singly or in combination of two or more.

  Moreover, as a charge transport material, the compound shown by the following general formula (a-1), (a-2) or (a-3) from a viewpoint of charge mobility is preferable.

In the above formula (a-1), R ³⁴ represents a hydrogen atom or a methyl group, and k10 represents 1 or 2. Ar ⁶ and Ar ⁷ are each a substituted or unsubstituted aryl group, —C ₆ H ₄ —C (R ³⁸ ) ═C (R ³⁹ ) (R ⁴⁰ ), or —C ₆ H ₄ —CH═CH—. CH = C (Ar) ₂ is shown, and the substituent is a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. And a substituted amino group substituted with. R ³⁸ , R ³⁹ and R ⁴⁰ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group.

In the formula (a-2), R ³⁵ and R ^{35 ′} 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, R ³⁶ R ^{36 ′} , R ³⁷ and R ^{37 ′} are each independently substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 or 2 carbon atoms. Amino group, substituted or unsubstituted aryl group, —C (R ³⁸ ) ═C (R ³⁹ ) (R ⁴⁰ ), or —CH═CH—CH═C (Ar) ₂ , R ³⁸ , R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group. M4 and m5 each independently represents an integer of 0 or more and 2 or less.

Here, in the formula (a-3), R ⁴¹ is 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 is shown. Ar represents a substituted or unsubstituted aryl group. R ⁴² , R ^{42 ′} , R ⁴³ , and R ^{43 ′} each independently represent 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 alkoxy group having 1 carbon atom. Or an amino group substituted with 2 alkyl groups, or a substituted or unsubstituted aryl group.

  Examples of the binder resin used for the charge transport layer 6 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, and the like. These binder resins can be used individually by 1 type or in mixture of 2 or more types. The blending ratio (mass ratio) of the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  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. Although the polymer charge transport material alone can be used as a constituent material of the charge transport layer 6, it may be mixed with the binder resin to form a film.

  The charge transport layer 6 can be formed by applying a coating solution containing the above constituent materials on the charge generation layer 5 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, methylene chloride, chloroform and ethylene chloride. And usual organic solvents such as halogenated aliphatic hydrocarbons such as cyclic ethers such as tetrahydrofuran and ethyl ether. These can be used individually by 1 type or in mixture of 2 or more types. As a coating method of the coating solution for forming the charge transport layer, a usual method such as a blade coating method, a wire 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 should be used. Can do. Drying after coating is performed at a temperature at which the solvent can be evaporated and a film can be formed. The film thickness of the charge transport layer 6 is preferably 5 μm or more and 50 μm or less, more preferably 10 μm or more and 30 μm or less.

  Further, for the purpose of preventing deterioration of the photoreceptor due to ozone, oxidizing gas, light, or heat generated in the copying machine, an antioxidant, a light stabilizer, Additives such as heat stabilizers can be added. 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.

  The photosensitive layer 3 can contain at least one electron accepting substance for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use.

Examples of the electron acceptor include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, Examples include chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, and phthalic acid. Of these, fluorenone-based, quinone-based, and benzene derivatives having an electron-withdrawing substituent such as Cl, CN, NO ₂ are particularly preferable.

  The protective layer 7 is comprised from the hardened | cured material of the curable resin composition containing curable resin and a polyether compound as above-mentioned.

  Specifically, as the “curable resin” constituting the protective layer 7, a curable resin that can be dissolved in 1% by mass or more in an alcohol having 5 or less carbon atoms can be suitably used. Specific examples of such alcohol-soluble curable resins are preferably thermosetting resins such as phenol resins, thermosetting acrylic resins, thermosetting silicone resins, epoxy resins, melamine resins, guanamine resins, and urethane resins. Particularly, phenol resin, melamine resin, guanamine resin, siloxane resin, urethane resin and the like can be mentioned. Among these curable resins, phenol resins are used from the viewpoint of effectively suppressing the occurrence of streak-like defects in terms of mechanical strength, electrical properties, and deposit removability of the cured product of the curable resin composition. A guanamine resin is preferred. In particular, by using a phenol resin or a guanamine resin, sufficient mechanical strength can be imparted to the functional layer.

  Examples of the phenol resin include resorcin, bisphenol, substituted phenols containing one hydroxyl group such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, substituted phenols containing two hydroxyl groups such as catechol, resorcinol, hydroquinone, and bisphenol. A, a compound having a phenol structure, such as bisphenols such as bisphenol Z, biphenols, and the like, and formaldehyde, paraformaldehyde, etc. are reacted in the presence of an acid or alkali catalyst to produce monomethylolphenols, dimethylolphenols, trimethylolphenol Class of monomers, and mixtures thereof, or oligomerized thereof, and mixtures of monomers and oligomers. Among these, a relatively large molecule having about 2 to 20 repeating molecular structural units is an oligomer, and a smaller molecule is a monomer.

As the acid catalyst used at this time, sulfuric acid, paratoluenesulfonic acid, phenolsulfonic acid, phosphoric acid and the like are used. Further, as the alkali catalyst, hydroxides or oxides of alkali metals and alkaline earth metals such as NaOH, KOH, Ca (OH) ₂ , Mg (OH) ₂ , Ba (OH) ₂ , CaO, MgO, or the like, or Amine-based catalysts and acetates such as zinc acetate and sodium acetate are used.

  Examples of the amine catalyst include, but are not limited to, ammonia, hexamethylenetetramine, trimethylamine, triethylamine, and triethanolamine.

When a basic catalyst is used, carriers may be significantly trapped by the remaining catalyst, which may deteriorate electrophotographic characteristics. In such a case, it is preferable to inactivate or remove by distilling off under reduced pressure, neutralizing with an acid, or contacting with an adsorbent such as silica gel or an ion exchange resin. A curing catalyst can also be used for curing. The catalyst used at that time is not particularly limited as long as it does not adversely affect the electrical characteristics and the like.
As the guanamine resin, those obtained by crosslinking a guanamine compound are preferable, and examples of the guanamine compound include acetoguanamine, benzoguanamine, formoguanamine, steroguanamine, spiroguanamine, cyclohexylguanamine and the like.
The guanamine compound is particularly preferably at least one of a compound represented by the following general formula (A) and a multimer thereof. Here, the multimer is an oligomer polymerized using the compound represented by the general formula (A) as a structural unit, and the degree of polymerization thereof is, for example, 2 or more and 200 or less (preferably 2 or more and 100 or less). In addition, the compound shown by general formula (A) may be used individually by 1 type, but may use 2 or more types together. In particular, when the compound represented by the general formula (A) is used as a mixture of two or more kinds, or used as a multimer (oligomer) having the structural unit as a structural unit, the solubility in a solvent is improved.

In general formula (A), R ₁ is a linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and 4 to 10 carbon atoms. Or a substituted or unsubstituted alicyclic hydrocarbon group. R _{2 to} R ₅ each independently represent hydrogen, —CH ₂ —OH, or —CH ₂ —O—R ₆ . R ₆ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. )

In the general formula (A), the alkyl group representing R ₁ has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms. . The alkyl group may be linear or branched.
In general formula (A), the phenyl group represented by R ₁ has 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms. Examples of the substituent substituted with the phenyl group include a methyl group, an ethyl group, and a propyl group.
In general formula (A), the alicyclic hydrocarbon group representing R ₁ has 4 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms. Examples of the substituent substituted with the alicyclic hydrocarbon group include a methyl group, an ethyl group, and a propyl group.
In the general formula (A), in “—CH ₂ —O—R ₆ ” representing R _{2 to} R ₅ , the alkyl group representing R ₆ has 1 to 10 carbon atoms, and desirably has carbon atoms. 1 or less and 8 or more, and more preferably 1 or more and 6 or less. The alkyl group may be linear or branched.
In general formula (A), R ₆ is preferably selected from a methyl group and an n-butyl group.
As the compound represented by the general formula (A), it is particularly desirable that R ₁ represents a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and R _{2 to} R ₅ are each independently —CH ₂ —O. It is a compound represented by —R ₆ .

  The compound represented by the general formula (A) is synthesized by a known method using, for example, guanamine and formaldehyde (for example, synthesized in the same manner as the melamine resin in Experimental Chemistry Course 4th edition, Volume 28, page 430). Is done.

  Specific examples of the compound represented by the general formula (A) are shown below, but are not limited thereto. Moreover, although the following specific examples show the thing of a monomer, the multimer (oligomer) which uses these as a structural unit may be sufficient.

  Moreover, as the “polyether compound” in the present embodiment, a polyether compound that can be dissolved in an alcohol having 5 or less carbon atoms in an amount of 1% by mass or more can be suitably used. Examples of the alcohol include methanol. Specific examples of the polyether compound soluble in alcohol include polyethylene glycol having an average molecular weight of 2000 or less, a polyether antifoaming agent, and a polyether-modified silicone oil.

  Examples of polyethylene glycol having an average molecular weight of 2000 or less include polyethylene glycol 2000 (average molecular weight 2000), polyethylene glycol 600 (average molecular weight 600), polyethylene glycol 400 (average molecular weight 400), polyethylene glycol 200 (average molecular weight 200), and the like. .

  As the polyether antifoaming agent, PE-M, PE-L (above, manufactured by Wako Pure Chemical Industries, Ltd.), antifoaming agent No. 1. Antifoaming agent No. 1 5 (above, manufactured by Kao Corporation).

  Polyether-modified silicone oils include KF351 (A), KF352 (A), KF353 (A), KF354 (A), KF355 (A), KF615 (A), KF618, KF945 (A), KF6004 (and above, Shin-Etsu) (Made by Chemical Industry Co., Ltd.), TSF4440, TSF4445, TSF4450, TSF4446, TSF4452, TSF4452, TSF4460 (above, GE Toshiba Silicon Corporation), Granol 400, Granol 410, Granol 420, Granol 440, Granol 450, Polyflow KL-260 (above , Manufactured by Kyoeisha Chemical Co., Ltd.).

  Among the above polyether compounds, polyether-modified silicone oil is preferable from the viewpoint of more effectively suppressing the occurrence of streak-like defects. Further, during image formation, discharge products such as NOx and ozone gas may be generated due to residual toner after the transfer process and charging stress in the electrophotographic process, but a curable resin composition containing a polyether-modified silicone oil It is possible to improve the deposit removability of the cured product with respect to the discharge product. For example, in the case of a protective layer made of a cured product of a curable resin composition containing a phenol resin or a guanamine resin and a polyether-modified silicone oil, the outermost surface layer of the electrophotographic photosensitive member (farthest from the conductive support) Particularly suitable as a layer provided on the side).

  The content of the polyether compound is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, based on the total solid content of the protective layer 7. If content of a polyether compound is 0.01 mass% or more, the coating-film defect prevention effect can fully be acquired. In addition, if the content of the polyether compound is 10% by mass or less, it is possible to reliably prevent the strength of the resulting cured product from being lowered and the peripheral members from being contaminated by the bleeding out of the polyether compound. Can do.

  It is preferable that the protective layer 7 further contains conductive inorganic particles and / or a charge transporting organic compound in order to improve electrical characteristics in addition to the above-described constituent materials.

  Examples of the conductive inorganic particles include metals, metal oxides, and carbon black. Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, and stainless steel, or those obtained by depositing these metals on the surface of plastic particles. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony and tantalum-doped tin oxide, and antimony-doped zirconium oxide. . These can be used alone or in combination of two or more. When two or more types are used in combination, they may be simply mixed, or may be in the form of a solid solution or fusion. The average particle diameter of the conductive particles used in the present embodiment is preferably 0.3 μm or less, and particularly preferably 0.1 μm or less in terms of the transparency of the protective layer. Moreover, in this embodiment, it is especially preferable to use a metal oxide from the viewpoint of transparency among the conductive inorganic particles described above. Further, it is preferable to treat the surface of the particles for controlling dispersibility. Examples of the treating agent include silane coupling agents, silicone oils, siloxane compounds, and surfactants. These preferably contain a fluorine atom.

  Moreover, as a charge transportable organic compound, what is compatible with the curable resin to be used is preferable, and what forms a chemical bond with the curable resin to be used is more preferable.

  Examples of the charge transporting organic compound having a reactive functional group include compounds represented by the following general formulas (I), (II), (III), (IV), (V), and (VI). It is preferable because of its excellent mechanical strength and stability.

F-[(X ¹ ) _n1 R ¹ -Z ¹ H] _m1 (I)
[In Formula (I), F represents an organic group derived from a compound having a hole transporting ability, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, a sulfur atom, NH or COO, and X ¹ Represents an oxygen atom or a sulfur atom, m1 represents an integer of 1 or more and 4 or less, and n1 represents 0 or 1. ]

^{_{F - [(X 2) n2}} - (R 2) n3 - (Z 2) n4 G] n5 (II)
[In Formula (II), F represents an organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z ² represents an oxygen atom, S represents a sulfur atom, NH or COO, G represents an epoxy group, n2, n3 and n4 each independently represents 0 or 1, and n5 represents an integer of 1 or more and 4 or less. ]

F [—D—Si (R ³ ) _(3-a) Q _a ] _b (III)
[In Formula (III), F represents a b-valent organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, and R ³ represents a hydrogen atom, substituted or unsubstituted. An alkyl group or a substituted or unsubstituted aryl group, Q is a hydrolyzable group, a is an integer of 1 to 3, and b is an integer of 1 to 4. ]

[In Formula (IV), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ⁴ , R ⁵ and R ⁶ independently represents a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m 2 represents 0 or 1, and n 6 represents an integer of 1 or more and 4 or less. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (V), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, R ⁸ represents a monovalent organic group, and m3 represents 0 or 1 N7 represents an integer of 1 or more and 4 or less. ]

[In formula (VI), F represents an organic group derived from a compound having a hole transporting property, L represents an alkylene group, R ⁹ represents a monovalent organic group, and n8 represents 1 or more and 4 or less. Indicates an integer. ]

  The F in the compounds represented by the general formulas (I) to (VI) is preferably a group represented by the following general formula (VII).

[In formula (VII), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or an arylene group, and Ar ^{1 to} 4 of ^{1 to} Ar ⁵ are a moiety represented by the following general formula (VIII) in the compound represented by the above general formula (I), a general formula (IX) in the compound represented by the above general formula (II), ), A site represented by the following general formula (X) in the compound represented by the above general formula (III), a site represented by the following general formula (XI) in the compound represented by the above general formula (IV), In the compound represented by the above general formula (V), a site represented by the following general formula (XII) or the following general formula (XIII) in the compound represented by the above general formula (VI) Has a joint to join. ]
_{^{- (X 1) n1 R 1}} -Z 1 H (VIII)
_{^{- (X 2) n2 - (}} R 2) n3 - (Z 2) n4 G (IX)
-D-Si (R ³ ) _(3-a) Q _a (X)

In addition, as the substituted or unsubstituted aryl group represented by Ar ^{1 to} Ar ⁴ in the general formula (VII), specifically, aryl groups represented by the following general formulas (1) to (7) are preferable. .

In the above formulas (1) to (7), R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, A substituted or unsubstituted phenyl group, or an aralkyl group having 7 to 10 carbon atoms; R ^{11 to} R ¹³ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carbon atom; An alkoxy group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted or unsubstituted with them, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom , Ar represents a substituted or unsubstituted arylene group, D represents any one of the structures represented by the general formulas (VIII) to (XIII), c and s each represents 0 or 1, and t represents 1 more than An integer of 3 or less is shown.

  Moreover, as Ar in the aryl group represented by the above formula (7), an arylene group represented by the following formula (8) or (9) is preferable.

In the above formulas (8) and (9), R ¹⁴ and R ¹⁵ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. A phenyl group substituted by an alkoxy group, or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom, and t represents an integer of 1 to 3.

  Moreover, as Z 'in the aryl group represented by the above formula (7), divalent groups represented by the following formulas (10) to (17) are preferable.

In formulas (10) to (17), R ¹⁶ and R ¹⁷ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. A phenyl group substituted by an alkoxy group or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom, W represents a divalent group, and q and r are each 1 or more, An integer of 10 or less is shown, and t represents an integer of 1 or more and 3 or less, respectively.

  In the above formulas (16) to (17), W represents a divalent group represented by the following formulas (18) to (26). In formula (25), u represents an integer of 0 or more and 3 or less.

In addition, the specific structure of Ar ⁵ in the general formula (VII) is as follows. When k = 0, the structure of c = 1 in the specific structure of Ar ^{1 to} Ar ⁴ and when Ar = 1, the Ar 5 ^The structure of c = 0 in the specific structure of ^{1 to} Ar ⁴ is given.

  Specific examples of the compound represented by the general formula (I) include the following compounds (I-1) to (I-37). In addition, in the following table | surface, although the bond is described, the thing in which the substituent is not described shows a methyl group.

  Specific examples of the compound represented by the general formula (II) include the following compounds (II-1) to (II-47). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

Specific examples of the compound represented by the general formula (III) include the following compounds (III-1) to (III-61). In addition, the following compounds (III-1) to (III-61) combine Ar ^{1 to} Ar ⁵ and k of the compound represented by the general formula (VI) as shown in the following table, and an alkoxysilyl group. (S) is the specific one shown in the table below.

  Specific examples of the compound represented by the general formula (IV) include the following compounds (IV-1) to (IV-40). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

  Specific examples of the compound represented by the general formula (V) include the following compounds (V-1) to (V-55). In the following table, Me or a bond is described but a substituent is not described indicates a methyl group.

  Specific examples of the compound represented by the general formula (VI) include the following compounds (VI-1) to (VI-17). In the following table, Me represents a methyl group, and Et represents an ethyl group.

The charge transporting organic compound having a reactive functional group that is preferable when combined with a guanamine resin is desirably a compound represented by the following general formula (B).
_{F - ((- R 7 -X} ) n1 R 8 -Y) n2 (B)

In general formula (B), F is an organic group derived from a compound having a hole transporting ability, R ₇ and R ₈ are each independently a linear or branched alkyl group having 1 to 5 carbon atoms. N1 represents 0 or 1, and n2 represents an integer of 1 or more and 4 or less. X represents an oxygen, NH, or sulfur atom, and Y represents —OH, —NH ₂ , —SH, or —COOH.

  In general formula (B), as the compound having a hole transporting ability in an organic group derived from a compound having a hole transporting ability representing F, an arylamine derivative is preferably exemplified. Preferred examples of the arylamine derivative include a triphenylamine derivative and a tetraphenylbenzidine derivative.

The compound represented by the general formula (B) is preferably a compound represented by the following general formula (C). The compound represented by the general formula (C) is particularly excellent in charge mobility, stability against oxidation and the like.

In general formula (C), Ar ^{1 to} Ar ⁴ may be the same or different and each independently represents a substituted or unsubstituted aryl group, and Ar ⁵ represents a substituted or unsubstituted aryl group or substituted or unsubstituted. D represents — (— R ₇ —X) _n1 R ₈ —Y, c represents 0 or 1 independently, k represents 0 or 1, and the total number of D is 1 or more and 4 It is as follows. R ₇ and R ₈ each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms, n1 represents 0 or 1, X represents an oxygen, NH, or sulfur atom. , Y represents —OH, —NH ₂ , —SH, or —COOH.

In the general formula (C), “— (— R ₇ —X) _n1 R ₈ —Y” representing D is the same as in the general formula (B), and R ₇ and R ₈ each independently have 1 or more carbon atoms. It is a linear or branched alkyl group having 5 or less. N1 is preferably 1. X is preferably oxygen. Y is preferably a hydroxyl group. Note that the total number of D in the general formula (C) corresponds to n2 in the general formula (B), preferably 2 or more and 4 or less, and more preferably 3 or more and 4 or less. That is, in the general formula (B) and the general formula (C), when the molecular weight is desirably 2 or more and 4 or less, and more desirably 3 or more and 4 or less in one molecule, the crosslinking density increases and a crosslinked film with higher strength can be obtained. .

In general formula (C), Ar ^{1 to} Ar ⁴ are preferably any of the following formulas (1) to (7). Incidentally, the following equation (1) to (7) can be coupled to each Ar ¹ to Ar ⁴ - shown with _{"(D) C".}

In Formulas (1) and (2), R ⁹ is a phenyl substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Represents one selected from the group consisting of a group, an unsubstituted phenyl group, and an aralkyl group having 7 to 10 carbon atoms, wherein R ^{10 to} R ¹² are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, carbon Selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom. 1 represents one, Ar represents a substituted or unsubstituted arylene group, D and c are the same as “D” and “c” in the general formula (C), s represents 0 or 1, and t represents 1 to 3 It represents an integer. ]

  Here, as Ar in Formula (7), what is represented by following formula (8) or (9) is desirable.

In formulas (8) and (9), R ¹³ and R ¹⁴ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. This represents one selected from the group consisting of a substituted phenyl group or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, and t represents an integer of 1 to 3. ]

  Further, Z ′ in the formula (7) is preferably represented by any one of the following formulas (10) to (17).

[In the formulas (10) to (17), R ¹⁵ and R ¹⁶ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Represents a phenyl group substituted with a group or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, W represents a divalent group, q and Each r represents an integer of 1 to 10, and t represents an integer of 1 to 3. ]

  W in the formulas (16) to (17) is preferably any one of divalent groups represented by the following (18) to (26). However, in formula (25), u represents an integer of 0 or more and 3 or less.

In general formula (C), Ar ⁵ is an aryl group exemplified in the description of Ar ^{1 to} Ar ⁴ when k is 0, and when k is 1, a predetermined hydrogen atom is taken from the aryl group. Excluded arylene group

  Specific examples of the compound represented by the general formula (B) include the following compounds (B-1) to (B-25). In addition, the compound shown by the said general formula (B) is not limited at all by these.

  In addition, a compound represented by the following general formula (XIV) is added to the curable resin composition for forming the protective layer 7 in order to control various physical properties such as strength and film resistance of the protective layer 7. You can also.

Si (R ⁵⁰ ) _(4-c) Q _c (XIV)
[In the formula (XIV), R ⁵⁰ 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 (XIV) include the following silane coupling agents. Examples of silane coupling agents include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane (c = 4); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl L) Triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H , 1H, 2H, 2H-perfluorodecyltriethoxysilane, trifunctional alkoxysilanes such as 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (c = 3); dimethyldimethoxysilane, diphenyldimethoxysilane, methyl And bifunctional alkoxysilanes such as phenyldimethoxysilane (c = 2); monofunctional alkoxysilanes such as trimethylmethoxysilane (c = 1), and the like. Trifunctional and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and monofunctional and bifunctional alkoxysilanes are preferable for improving the flexibility and film formability.

  In addition, a silicon-based hard coat agent produced mainly 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). Etc.) can be used.

  Moreover, in order to raise the intensity | strength of the protective layer 7, the compound which has a 2 or more silicon atom as shown to the following general formula (XV) is used for the curable resin composition for forming the protective layer 7 Is also preferable.

B- (Si (R ⁵¹ ) _(3-d) Q _d ) ₂ (XV)
[In the above formula (XV), B is a divalent organic group, R ⁵¹ is a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q is a hydrolyzable group, d is 1 or more and 3 or less. Indicates an integer. ]

  More specific examples of the compound represented by the general formula (XV) include the following compounds (XV-1) to (XV-16).

Furthermore, various resins can be added for the purpose of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life extension, and the like.
In the present embodiment, it is preferable to further add a resin that dissolves in alcohol. Examples of resins soluble in alcohol solvents include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal or acetoacetal (for example, manufactured by Sekisui Chemical Co., Ltd.). ESREC B, K, etc.), polyamide resin, cellulose resin and the like. In particular, polyvinyl acetal resin is preferable from the viewpoint of improving electrical characteristics.

  The molecular weight of the resin is preferably 2,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less. If the molecular weight is less than 2000, the desired effect tends not to be obtained. If the molecular weight is more than 100,000, the solubility tends to be low and the addition amount is limited, or the film formation tends to be poor during coating. The addition amount is preferably 1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 30% by mass or less, and most preferably 5% by mass or more and 20% by mass or less. When the addition amount is less than 1% by mass, it is difficult to obtain a desired effect. When the addition amount is more than 40% by mass, there is a risk of image blurring at high temperature and high humidity. Moreover, said resin may be used independently and may be used in mixture.

  In order to prolong pot life and control film properties, it is preferable to contain a cyclic compound having a repeating structural unit represented by the following general formula (XVI) or a derivative thereof.

[In the above formula (XVI), A ¹ and A ² each independently represent a monovalent organic group. ]

  Examples of the cyclic compound having the repeating structural unit represented by the general formula (XVI) include commercially available cyclic siloxanes. 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, (3,3,3-trifluoropropyl) methylcyclotrisiloxane and other fluorine atom-containing Cyclosiloxanes and methylhydrosiloxane blends Things, pentamethylcyclopentasiloxane include a phenyl hydrosilyl group-containing cyclosiloxanes of hydrocyclosiloxane like, cyclic siloxanes and vinyl group-containing cyclosiloxanes such as penta vinyl pentamethylcyclopentasiloxane like. These cyclic siloxane compounds may be used alone or in combination of two or more.

  Further, various particles may be added to the curable resin composition for forming the protective layer 7 in order to control the contamination resistance adhesion, lubricity, hardness and the like on the surface of the electrophotographic photosensitive member.

  An example of the particles may include silicon atom-containing particles. The silicon atom-containing particles are particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone particles. The colloidal silica used as the silicon atom-containing particles has a volume average particle diameter of preferably 1 nm or more and 100 nm or less, more preferably 10 nm or more and 30 nm or less, and an acidic or alkaline aqueous dispersion, alcohol, ketone, ester or the like. Those which are selected from those dispersed in an organic solvent and which are generally commercially available can be used. The solid content of colloidal silica in the curable resin composition is not particularly limited, but is preferably based on the total solid content in the curable resin composition in terms of film formability, electrical characteristics, and strength. Can be used in the range of 0.1 mass% or more and 50 mass% or less, more preferably in the range of 0.1 mass% or more and 30 mass% or less.

  Silicone particles used as silicon atom-containing particles are spherical and have a volume average particle diameter of preferably 1 nm or more and 500 nm or less, more preferably 10 nm or more and 100 nm or less. Silicone resin particles, silicone rubber particles, and silicone surface-treated silica Those selected from particles and generally commercially available can be used.

  Silicone particles are small particles that are chemically inert and excellent in dispersibility in resins, and since the content required to obtain more sufficient properties is low, the crosslinking reaction is not hindered. The surface properties of the photographic photoreceptor can be improved. In other words, in a state in which it is uniformly incorporated into a strong cross-linked structure, it improves the lubricity and water repellency of the surface of the electrophotographic photosensitive member, and maintains good wear resistance and contamination resistance adhesion over a long period of time. Can do. The content of the silicone particles in the curable resin composition is preferably in the range of 0.1% by mass to 30% by mass based on the total solid content in the curable resin composition, and more preferably 0.00%. It is the range of 5 mass% or more and 10 mass% or less.

Other particles include fluorine-based particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and the 8th Polymer Materials Forum Lecture Proceedings p89. 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 , MgO Examples thereof include semiconductive metal oxides such as —Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO.

  Silicone oils other than polyether-modified silicone oils can also be added to control the antifouling substance adhesion, lubricity, hardness and the like on the surface of the electrophotographic photosensitive member. 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 include reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes. These may be added in advance to the curable resin composition for forming the protective layer 7, or may be impregnated under reduced pressure or increased pressure after producing the photoreceptor.

  Moreover, the curable resin composition for forming the protective layer 7 can also contain additives, such as a plasticizer, a surface modifier, antioxidant, and a photodegradation inhibitor. 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 curable resin composition for forming the protective layer 7, and the potential stability when the environment changes It is effective for improving image quality.

  Examples of the antioxidant include the following compounds. For example, as the hindered phenol type, “Sumizer BHT-R”, “Sumizer MDP-S”, “Sumizer BBM-S”, “Sumizer WX-R”, “Sumizer NW”, “Sumizer BP-76”, “ Sumilizer BP-101 "," Sumilizer GA-80 "," Sumilizer GM "," Sumilizer GS "or more manufactured by Sumitomo Chemical Co., Ltd.," IRGANOX1010 "," IRGANOX1035 "," IRGANOX1076 "," IRGANOX1098 "," IRGANOX1098 "," 114 " ”,“ IRGANOX1222 ”,“ IRGANOX1330 ”,“ IRGANOX1425WL ”,“ IRGANOX1 20L "," IRGANOX 245 "," IRGANOX 259 "," IRGANOX 3114 "," IRGANOX 3790 "," IRGANOX 5057 "," IRGANOX 565 "or more, manufactured by Ciba Specialty Chemicals," ADK STAB AO-20 "," ADK STAB AO-30 "," ADEKA 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 system, “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744” or more manufactured by Sankyo Lifetech Co., Ltd. "Mark LA57", "Mark LA67", "Mark LA62", "Mark LA68", "Mark LA63" or more manufactured by Asahi Denka, "Sumilyzer TPS" or more manufactured by Sumitomo Chemical Co., Ltd. As a phosphite system manufactured by Sumitomo Chemical Co., Ltd., "Mark 2112", "Mark PEP 8", "Mark PEP 24G", "Mark PEP 36", "Mark 329K", "Mark HP 10" or more Asahi Denka products, especially hindered phenol, hindert Min antioxidants are preferred. Furthermore, these may be modified with a substituent such as an alkoxysilyl group capable of undergoing a crosslinking reaction with the material forming the crosslinked film.

  Moreover, a catalyst can be added at the time of the curable resin composition for forming the protective layer 7, or its preparation. Catalysts include inorganic acids such as hydrochloric acid, acetic acid and sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, benzoic acid, phthalic acid and maleic acid, potassium hydroxide, sodium hydroxide, calcium hydroxide, ammonia and triethylamine Further, an alkali catalyst such as the following, and a solid catalyst insoluble in the system as shown below can also be used.

Examples of solid catalysts insoluble in the system include Amberlite 15, Amberlite 200C, Amberlyst 15E (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR- W2 (above, manufactured by Dow Chemical Co.); Lebatit SPC-108, Lebatit SPC-118 (above, manufactured by Bayer); Diaion RCP-150H (manufactured by Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C , Duolite C-433, Duolite-464 (manufactured by Sumitomo Chemical Co., Ltd.); Cation exchange resins such as Nafion-H (manufactured by DuPont); Amberlite IRA-400, Amberlite IRA-45 (above, Anion exchange resin such as Rohm &Haas); Zr (O ₃ PCH ₂₎ An inorganic solid in which a group containing a protonic acid group such as CH ₂ SO ₃ H) ₂ or Th (O ₃ PCH ₂ CH ₂ COOH) ₂ is bonded to the surface; a protonic acid such as a polyorganosiloxane having a sulfonic acid group Group-containing polyorganosiloxanes; heteropolyacids such as cobalt tungstic acid and phosphomolybdic acid; isopolyacids such as niobic acid, tantalum acid and molybdic acid; monometallic oxides such as silica gel, alumina, chromia, zirconia, CaO and MgO Composite metal oxides such as silica-alumina, silica-magnesia, silica-zirconia, zeolites; clay minerals such as acid clay, activated clay, montmorillonite, kaolinite; metal sulfates such as LiSO ₄ and MgSO ₄ ; phosphorus acid zirconia, metal phosphates such as lanthanum phosphate; LiNO _3, Mn NO _{3) 2} and the like of a metal nitrate; inorganic solid by reacting aminopropyltriethoxysilane on silica gel containing amino groups such as the resulting solid which group is attached to the surface; amino and amino-modified silicone resin And polyorganosiloxane containing a group.

  In preparing the curable resin composition, it is preferable to use a solid catalyst that is insoluble in a photofunctional compound, a reaction product, water, a solvent, or the like 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 the charge transporting organic compound having the reactive functional group, other additives, water, solvent and the like.

  The amount of the solid catalyst insoluble in these systems is not particularly limited, but is preferably 0.1 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the charge transporting organic compound having the reactive functional 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 ° C. or higher and 100 ° C. or lower, preferably 10 ° C. or higher and 70 ° C. or lower, More preferably, it is 15 degreeC or more and 50 degrees C or less, Reaction time becomes like this. Preferably it is 10 minutes or more and 100 hours or less. When the reaction time exceeds the above upper limit, gelation tends to occur.

  When preparing a curable resin composition, when a catalyst that is insoluble in the system is used, it is preferable to use a catalyst that is further dissolved in the system for the purpose of improving strength, liquid storage stability, and the like. 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.

  In addition to organoaluminum compounds, organotin 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.

  The amount of the catalyst dissolved in these systems is not particularly limited, but is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the charge transporting organic compound having the reactive functional group. 3 parts by mass or more and 10 parts by mass or less are particularly preferable.

  Moreover, when using an organometallic compound as a catalyst when forming the protective layer 7, it is preferable to add a multidentate ligand from the viewpoint of pot life and curing efficiency. Examples of such multidentate ligands include, but are not limited to, those shown below and those derived therefrom.

  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 specific examples include a bidentate ligand represented by the following general formula (XVII) in addition to the above.

[In the formula (XVII), R ⁵¹ and R ⁵² each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, or an alkoxy group having 1 to 10 carbon atoms. ]

As the multidentate ligand, a bidentate ligand represented by the above general formula (XVII) is preferably used, and those in which R ⁵¹ and R ⁵² in the above general formula (XVII) are the same are particularly preferable. By making R ⁵¹ and R ^{52 the} same, the coordination power of the ligand near room temperature becomes strong, and further stabilization of the curable resin composition can be achieved.

  The compounding amount of the polydentate ligand can be arbitrarily set, but is preferably 0.01 mol or more, more preferably 0.1 mol or more, relative to 1 mol of the organometallic compound to be used. It is preferably 1 mol or more, particularly preferably.

  The protective layer 7 is formed using the curable resin composition containing each constituent material described above as a coating liquid for forming a protective layer.

  Preparation of the curable resin composition containing the above components is carried out in the absence of a solvent, or alcohols such as methanol, ethanol, propanol and butanol as necessary; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, diethyl ether, It can carry out using solvents, such as ethers, such as a dioxane. Such solvents can be used singly or in combination of two or more, but preferably have a boiling point of 100 ° C. or lower. The amount of the solvent used can be arbitrarily set, but if the amount of the solvent is too small, the charge transporting organic compound having the reactive functional group is likely to be precipitated, and therefore 1 mass of the charge transporting organic compound having the reactive functional group. The solvent is preferably used in an amount of 0.5 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less.

  The reaction temperature and reaction time for curing the curable resin composition are not particularly limited, but the reaction temperature is preferably 60 ° C. or more from the viewpoint of the mechanical strength and chemical stability of the protective layer 7 to be formed. Preferably it is 80 degreeC or more and 200 degrees C or less, and reaction time becomes like this. Preferably it is 10 minutes or more and 5 hours or less. In addition, maintaining the protective layer 7 obtained by curing the curable resin composition in a high humidity state is effective in stabilizing the characteristics of the protective layer 7. Further, depending on the application, the protective layer 7 may be subjected to a surface treatment using hexamethyldisilazane, trimethylchlorosilane, or the like to make it hydrophobic.

  When the curable resin composition is applied onto the charge transport layer 6, the application methods are blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating method. A usual method such as can be used.

  In addition, in the case of application | coating, when a required film thickness cannot be obtained by one application | coating, a required film thickness can be obtained by apply | coating several 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 thickness of the protective layer 7 may be determined according to the required mechanical strength, etc., but is usually preferably 0.5 μm or more and 15 μm or less, more preferably 1 μm or more and 10 μm or less, and more preferably 1 μm or more and 5 μm or less. Further preferred.

  The electrophotographic photosensitive member used in this embodiment is not limited to the above. For example, in the electrophotographic photosensitive member according to the present embodiment, the undercoat layer 4 is not necessarily provided.

  The electrophotographic photosensitive member shown in FIG. 2 includes a protective layer 7 made of a cured product of a curable resin composition containing a curable resin and a polyether compound, and the curable resin composition reacts. In the case of containing a charge transporting organic compound having a functional functional group, the resulting cured product has excellent mechanical strength and sufficient photoelectric properties, so that it can be used as it is as a charge transporting layer of a multilayer photoreceptor. You can also. An example of such an electrophotographic photoreceptor is shown in FIG. The electrophotographic photoreceptor 1 shown in FIG. 3 has a structure in which an undercoat layer 4, a charge generation layer 5 and a charge transport layer 6 are sequentially laminated on a conductive support 2. It becomes the surface layer comprised with the hardened | cured material of the curable resin composition containing curable resin and a polyether compound. The undercoat layer 4 and the charge generation layer 5 on the conductive support 2 are the same as those of the electrophotographic photosensitive member shown in FIG. 2 (hereinafter the same).

  The order of stacking the charge generation layer 5 and the charge transport layer 6 may be the reverse of the case of the above embodiment. An example of such an electrophotographic photoreceptor is shown in FIG. The electrophotographic photoreceptor shown in FIG. 4 has a structure in which an undercoat layer 4, a charge transport layer 6, a charge generation layer 5 and a protective layer 7 are sequentially laminated on a conductive support 2. Is the outermost surface layer made of a cured product of a curable resin composition containing a curable resin and a polyether compound.

  Each of the electrophotographic photoconductors shown in FIGS. 2 to 4 is a function-separated type photoconductor, but the electrophotographic photoconductor used in this embodiment is a layer containing both a charge generating substance and a charge transporting substance ( (Charge generation / charge transport layer) may be provided. An example of an electrophotographic photoreceptor having a single-layer type photosensitive layer is shown in FIGS.

  The electrophotographic photoreceptor 1 shown in FIG. 5 has a structure in which an undercoat layer 4 and a charge generation / charge transport layer 8 are sequentially laminated on a conductive support 2. It is a surface layer. The charge generation / charge transport layer 8 is formed by adding a charge generation material and a charge transport material (preferably a compound having a reactive functional group) to the curable resin composition containing a curable resin and a polyether compound, and as necessary. And a coating solution containing a binder resin other than the curable resin, other additives, and the like. The charge generation material is the same as that used for the charge generation layer in the function-separated type photosensitive layer, and the binder resin other than the curable resin is polyvinyl butyral resin, polyvinyl formal resin, or part of butyral is formal or Polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins modified with acetoacetal or the like (for example, Sleksui B or K manufactured by Sekisui Chemical Co., Ltd.), polyamide resins, cellulose resins, or the like can be used. The content of the charge generation material in the charge generation / charge transport layer 8 is preferably 10% by mass or more, 85% by mass or less, more preferably 20% by mass or more, based on the total solid content in the charge generation / charge transport layer 8. 50 mass% or less. A charge transport material or a polymer charge transport material may be added to the charge generation / charge transport layer 8 for the purpose of improving photoelectric characteristics. The addition amount is preferably 5% by mass or more and 50% by mass or less based on the total solid content in the charge generation / charge transport layer 8. Moreover, the solvent and coating method used for coating can be the same as those for the above layers. The film thickness of the charge generation / charge transport layer 8 is preferably about 5 to 50 μm, and more preferably 10 μm to 40 μm.

  The electrophotographic photoreceptor 1 shown in FIG. 6 has a structure in which an undercoat layer 4, a charge generation / charge transport layer 8 and a protective layer 7 are sequentially laminated on a conductive support 2. Becomes a surface layer made of a cured product of a curable resin composition containing a curable resin and a polyether compound.

<Charging member>
Next, the charging member used in this embodiment will be described. As the charging member 21, a member that charges the electrophotographic photosensitive member 1 by a contact charging method is used. The charging member used in the present embodiment is of a type that charges the surface of the photosensitive member by applying a voltage to a conductive member (charging member) that is in contact with the surface of the photosensitive member (contact charging method). The charging member is not particularly limited, and a charging member of a charging member such as a roll, a brush, or a blade can be used, but a roller-shaped charging member (charging roll) is preferable.

FIG. 7 is a schematic cross-sectional view illustrating an example of the charging member according to the present embodiment. The charging member 21 is formed in a roller shape and is a contact charging charging roll 21.
As shown in FIG. 7, the charging roll 21 in the electrophotographic apparatus 100 according to the present embodiment has a conductive elastic layer 12 and a surface resin layer (resistance) concentrically formed on the outer peripheral surface of the roll shaft body (core material) 10. Layer) 14 may be formed sequentially.

  The charging roll 21 rotates at the same peripheral speed as that of the photosensitive member 1 by contacting the photosensitive member 1 without any driving means, and functions as a charging unit. However, some driving means may be attached to the charging roll 21, and the photosensitive member 1 may be charged by rotating at a peripheral speed different from that of the photosensitive member 1.

  The material of the core material 10 is conductive, and generally iron, copper, brass, stainless steel, aluminum, nickel or the like is used. In addition, a resin molded product in which conductive particles are dispersed can also be used.

The elastic layer 12 is made of a material having conductivity or semiconductivity, and generally a conductive material or semiconducting particles are dispersed in a rubber material. Moreover, a foam may be sufficient.
EPDM (ethylene-propylene-diene rubber), polybutadiene, natural rubber, polyisobutylene, SBR (styrene butadiene rubber), CR (chloroprene rubber), NBR (nitrile rubber), silicon rubber, urethane rubber, epichlorohydrin rubber, SBS (styrene-butadiene-styrene block copolymer), thermoplastic elastomer, norbornene rubber, fluorosilicone rubber, ethylene oxide rubber and the like are 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 may be used alone or in combination of two or more.

As the material of the resistance layer 14, conductive particles or semiconductive particles are dispersed in a binder resin to control the resistance, and the resistivity is 10 ³ Ωcm or more, 10 ¹⁴ Ωcm or less, preferably 10 ^5. Ωcm or more and 10 ¹² Ωcm or less, more preferably 10 ⁷ Ωcm or more and 10 ¹² Ωcm or less. The film thickness is 0.01 μm or more and 1000 μm or less, preferably 0.1 μm or more and 500 μm or less, more preferably 0.5 μm or more and 100 μm or less.

The binder resin for forming the resistance layer 14 to be the surface layer may be any resin having an amide group, and examples thereof include nylon resins and aramid resins.
Nylon is preferable from the viewpoint of effectively suppressing the occurrence of streak-like defects, and since the formation of the surface layer can use a coating method, nylon soluble in alcohol, modified nylon, or amine group, ether group, Modified water-soluble nylon having a carboxyl group and the like is preferable. For example, nylon soluble in alcohol, such as nylon 6, copolymer nylon such as Nineron 6-66-10, nylon 6-66-10-12, alkoxymethylated nylon such as methoxymethylated nylon, ethoxymethylated nylon, etc. is suitable From the viewpoint of effectively suppressing the occurrence of streak-like defects, methoxymethylated nylon is particularly preferable.

  As the conductive particles or semiconductive particles, the same carbon black, metal, and metal oxide as the elastic layer are used. If necessary, an antioxidant such as hindered phenol and hindered amine, a filler such as clay and kaolin, and a lubricant such as silicone oil can be added. 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, or the like can be used.

  As a means for forming these layers 12 and 14 relating to the charging roll 21, a blade coating method, a Mayer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like is used. Can do.

  When charging the photoreceptor 1 using such a charging roll 21, a voltage is applied to the charging roll 21 in contact with the surface of the photoreceptor 1. The applied voltage is preferably a DC voltage or a DC voltage superimposed with an AC voltage. As the range of the voltage to be applied, the DC voltage is preferably positive or negative 50 V or more and 2000 V or less, particularly preferably 100 V or more and 1500 V or less, depending on the required photoreceptor charging potential. When the AC voltage is superimposed, the peak-to-peak voltage is preferably 400 V or higher and 1800 V or lower, preferably 800 V or higher and 1600 V or lower, more preferably 1200 V or higher and 1600 V or lower. The frequency of the AC voltage is 50 Hz or more and 20,000 Hz or less, preferably 100 Hz or more and 5,000 Hz or less.

  The charging roll according to the present embodiment is not limited to the configuration shown in FIG. 7 as long as it has a surface layer containing a resin having an amide group. For example, as shown in FIG. 8, a conductive elastic layer 12, an intermediate layer 13, and a surface resin layer 14 may be sequentially formed on the outer peripheral surface of the roll shaft body 10 in a concentric manner. In this case, the intermediate layer 13 can be formed of, for example, a resin in which conductive particles are dispersed. As specific examples, resins such as polyester, phenol, acrylic, polyurethane, epoxy resin, and cellulose can be used.

  The configuration of the electrophotographic apparatus 100 (process cartridge 20) according to the present embodiment is not particularly limited except for the photoreceptor 1 and the charging member 21, and a known one can be used.

<Developing device and toner>
The developing device (developing unit) 25 develops the electrostatic latent image on the electrophotographic photosensitive member 1 to form a toner image.
The toner used in the developing device 25 has an average shape factor (ML ² / A) of preferably 100 or more and 150 or less, and more preferably 100 or more and 140 or less. Further, the toner preferably has an average particle size of 2 μm or more and 12 μm or less, more preferably 3 μm or more and 12 μm or less, and further preferably 3 μm or more and 9 μm or less. By using a toner satisfying such an average shape factor and average particle size, an image with high development, transferability and high image quality can be obtained.

  The toner is not particularly limited by the production method as long as it satisfies the above average shape factor and average particle diameter, and examples thereof include a binder resin, a colorant, and a release agent. A kneading and pulverizing method in which a charge control agent is added, if necessary, kneading, pulverizing, and classifying; a method of changing the shape of particles obtained by the kneading and pulverizing method with mechanical impact force or thermal energy; The polymerizable monomer is emulsion-polymerized, and the formed dispersion is mixed with a dispersion of a colorant, a release agent, and a charge control agent, if necessary, and agglomerated and heat-fused to form toner particles. Emulsion polymerization aggregation method to be obtained: Suspension weight for polymerization by suspending a polymerizable monomer for obtaining a binder resin, a colorant, a release agent, and a charge control agent as necessary in an aqueous solvent. Legal; binder resin, colorant and release agent, and if necessary charge control agent The toner and liquid are suspended in an aqueous solvent is prepared by dissolution suspension method or the like granulation is used.

  Further, a known method such as a production method in which the toner obtained by the above method is used as a core, and agglomerated particles are further adhered and heat-fused to give a core-shell structure can be used. The toner production method is preferably a suspension polymerization method, an emulsion polymerization aggregation method, or a dissolution suspension method in which an aqueous solvent is used from the viewpoint of shape control and particle size distribution control, and an emulsion polymerization aggregation method is particularly preferable.

  The toner base particles are composed of a binder resin, a colorant, and a release agent, and include silica and a charge control agent as necessary.

  Binder resins used for toner base particles include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. Α-methylene aliphatics such as vinyl esters, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Homopolymers and copolymers of monocarboxylic acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone Polyester resins by copolymerization of dicarboxylic acids and diols.

  Particularly representative binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. A polymer, polyethylene, polypropylene, a polyester resin, etc. can be mentioned. In addition, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like can also be mentioned.

  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.

  Typical examples of the release agent include low molecular weight polyethylene, low molecular weight polypropylene, Fischer tropic wax, montan wax, carnauba wax, rice wax, and candelilla wax.

  As the charge control agent, known ones can be used, and azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups can be used. When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. The toner may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  The toner used in the developing device 25 can be manufactured by mixing the toner base particles and the external additive with a Henschel mixer or a V blender. In addition, when the toner base particles are produced by a wet method, external addition can also be performed by a wet method.

  Lubricating particles may be added to the toner used in the developing device 25. 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 Minerals such as system waxes, montan waxes, ozokerites, ceresins, paraffin waxes, microcrystalline waxes, Fischer-Tropsch waxes, etc., petroleum waxes, and modified products thereof can be used. These can be used individually by 1 type or in combination of 2 or more types. However, the average particle size is preferably in the range of 0.1 μm or more and 10 μm or less, and those having the above chemical structure may be pulverized to make the particle sizes uniform. The amount of the lubricating particles added to the toner is preferably 0.05% by mass or more and 2.0% by mass or less, more preferably 0.1% by mass or more and 1.5% by mass or less.

  To the toner used in the developing device 25, inorganic particles, organic particles, composite particles obtained by attaching inorganic particles to the organic particles, and the like can be added for the purpose of removing the adhered matter and deteriorated matter on the surface of the electrophotographic photosensitive member. .

  Inorganic 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.

  In addition, the inorganic particles may be mixed with titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzene sulfonyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, γ- (2- Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxy Silane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane The treatment may be performed with a silane coupling agent such as run, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, and p-methylphenyltrimethoxysilane. In addition, those hydrophobized with higher fatty acid metal salts such as silicone oil, aluminum stearate, zinc stearate and calcium stearate are also preferably used.

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

  The average particle size is preferably 5 nm or more and 1000 nm or less, more preferably 5 nm or more and 800 nm or less, and still more preferably 5 nm or more and 700 nm or less. If the average particle size is less than the lower limit, the polishing ability tends to be lacking. On the other hand, if the average particle size exceeds the upper limit, the surface of the electrophotographic photoreceptor tends to be damaged. Moreover, it is preferable that the sum of the addition amount of the particle | grains mentioned above and lubricity particle | grains is 0.6 mass% or more.

  Other inorganic oxides added to the toner are small-diameter inorganic oxides with a primary particle size of 40 nm or less for powder flowability, charge control, etc. It is preferable to add a larger-diameter inorganic oxide. These inorganic oxide particles can 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 particles increases the dispersibility and increases the effect of increasing the powder fluidity. Furthermore, it is also preferable to add carbonates such as calcium carbonate and magnesium carbonate and inorganic minerals such as hydrotalcite in order to remove the discharge purified product.

  In addition, the color toner for electrophotography is used by mixing with a carrier. As the carrier, iron powder, glass beads, ferrite powder, nickel powder, or those having a resin coating on the surface thereof are used. The mixing ratio with the carrier can be set as appropriate.

<Cleaning device>
The cleaning device 27 in this embodiment includes a fibrous member (roll shape) 27a and a cleaning blade (blade member) 27b. Note that the cleaning device may be provided with either one.
The fibrous member 27a may have a flat brush shape in addition to the roll shape. Further, the fibrous member 27a may be fixed to the cleaning device main body, may be supported so as to be rotatable, and may be supported so as to be capable of oscillating in the photosensitive member axial direction. As the fibrous member 27a, polyester, nylon, acrylic, etc., cloth-like ones made of ultrafine fibers such as Toraysee (made by Toray Industries), resin fibers such as nylon, acrylic, polyolefin, polyester, etc. are used as a substrate or carpet. The brush-like thing etc. which were flocked to can be mentioned. Further, as the fibrous member 27a, a conductive powder or an ionic conductive agent is added to the above-described material to impart conductivity, or a conductive layer is formed inside or outside of each fiber. Can also be used. When conductivity is imparted, the resistance value of the single fiber is preferably 10 ² Ω or more and 10 ⁹ Ω or less. The fiber thickness of the fibrous member 27a is preferably 30 d (denier) or less, more preferably 20 d or less, and the fiber density is preferably 20,000 fibers / inch ² or more, more preferably 30,000 fibers / inch. inch ² or more.

  The cleaning device 27 is required to remove deposits (for example, discharge products) on the surface of the photoreceptor with a cleaning blade and a cleaning brush. In order to achieve this purpose over a long period of time and stabilize the function of the cleaning member, the cleaning member may be supplied with a lubricating substance (lubricating component) such as metal soap, higher alcohol, wax, silicone oil or the like. preferable.

  For example, when a roll-shaped member is used as the fibrous member 27a, it is preferable to supply a lubricating component to the surface of the electrophotographic photosensitive member by bringing it into contact with a lubricating substance such as metal soap or wax. A normal rubber blade is used as the cleaning blade 27b. As described above, when a rubber blade is used as the cleaning blade 27b, supplying a lubricating component to the surface of the electrophotographic photosensitive member is particularly effective in suppressing chipping and wear of the blade.

<Electrostatic latent image forming apparatus>
The electrostatic latent image forming device (exposure device) 30 may be any device that exposes the electrophotographic photosensitive member 1 charged by the charging member 21 to form an electrostatic latent image. As a light source of the electrostatic latent image forming apparatus 30, a multi-beam surface emitting laser can be preferably used.

<Transfer device>
The transfer device (transfer means) 40 may be any device that transfers the toner image on the electrophotographic photosensitive member 1 to a transfer medium (intermediate transfer member 50). For example, a normal roll-shaped one may be used. Can do.

As the intermediate transfer member 50, a belt-like member (intermediate transfer belt) such as polyimide, polyamideimide, polycarbonate, polyarylate, polyester, rubber or the like having semiconductivity can be used. Further, as the form of the intermediate transfer member 50, a drum-like member can be used in addition to the belt-like member.
Although there is a direct transfer type electrophotographic apparatus that does not include the intermediate transfer member 50, the present embodiment can also be suitably applied to such a direct transfer type electrophotographic apparatus. In the direct transfer type electrophotographic apparatus, paper dust, talc, and the like are generated from the print paper, and they are likely to adhere to the electrophotographic photosensitive member, and image quality defects due to the attached matter tend to occur. However, since the electrophotographic photosensitive member according to the present embodiment has excellent cleaning properties, it is easy to remove paper dust, talc, and the like, and includes a charging member having a surface layer containing a resin having an amide group. Therefore, the occurrence of streak-like image defects is suppressed, and a good image quality can be stably obtained over a long period of time even with a direct transfer type electrophotographic apparatus.

  The medium to be transferred in the present embodiment is not particularly limited as long as it is a medium to which a toner image formed on the electrophotographic photosensitive member 1 is transferred. For example, when transferring directly from the electrophotographic photosensitive member 1 to paper or the like, paper or the like is a transfer medium, and when the intermediate transfer member 50 is used, the intermediate transfer member is a transfer medium.

  FIG. 9 is a schematic view showing another electrophotographic apparatus according to this embodiment. The electrophotographic apparatus 120 is a tandem-type full-color electrophotographic apparatus equipped with four process cartridges 20. In the electrophotographic apparatus 120, four process cartridges 20 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photosensitive member and a charging member can be used for one color. The electrophotographic apparatus 120 has the same configuration as the electrophotographic apparatus 100 shown in FIG. 1 except that it is a tandem system.

  In the tandem electrophotographic apparatus 120, the wear amount of each electrophotographic photosensitive member varies depending on the use ratio of each color, and thus the electric characteristics of each electrophotographic photosensitive member tend to be different. Along with this, the toner development characteristics gradually change from the initial state, and the hue of the print image changes, so that a stable image cannot be obtained. In particular, in order to reduce the size of the electrophotographic apparatus, a small-diameter electrophotographic photosensitive member tends to be used, and this tendency becomes prominent when one having a diameter of 30 mm or less is used. Here, when the electrophotographic photosensitive member and the charging member according to the present embodiment are employed, even when the diameter of the electrophotographic photosensitive member is set to 30 mm or less, wear on the surface is sufficiently suppressed, and a streak-like image defect is generated. Is suppressed, and good image quality can be stably obtained over a long period of time. Therefore, this embodiment is particularly effective for a tandem type electrophotographic apparatus.

In the electrophotographic apparatuses shown in FIGS. 1 and 9, the process cartridge 20 including the electrophotographic photosensitive member 1, the charging member 21 and the like is detachably provided. However, the electrophotographic apparatus according to this embodiment is not necessarily limited to the above. It is not necessary to have a detachable process cartridge.
FIG. 10 is a schematic configuration diagram showing a basic configuration of another embodiment according to the electrophotographic apparatus of the present embodiment. An electrophotographic apparatus 220 shown in FIG. 10 is an intermediate transfer type electrophotographic apparatus. In the housing 420, four electrophotographic photoreceptors 401a to 401d (for example, the electrophotographic photoreceptor 401a is yellow and the electrophotographic photoreceptor 401b is magenta). The electrophotographic photosensitive member 401c can form an image of cyan and the electrophotographic photosensitive member 401d can form a black color) are arranged in parallel along the intermediate transfer belt 409.

  The electrophotographic photoreceptors 401a to 401d and the charging rolls 402a to 402d mounted on the electrophotographic apparatus 220 are the electrophotographic photoreceptor and the charging member according to the present embodiment, respectively. That is, each of the electrophotographic photoreceptors 401a to 401d has a conductive support and a photosensitive layer provided on the conductive support, and the photosensitive layer includes a curable resin and a polyether compound. It has a layer made of a cured product of the resin composition. The charging rolls 402a to 402d have a surface layer containing a resin having an amide group.

  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 rolls 410a to 410a to the rotation direction. 410d and cleaning blades 415a to 415d are respectively disposed. 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 (electrostatic latent image forming means) 403 is disposed at a predetermined position in the housing 420, and the surfaces of the electrophotographic photosensitive members 401a to 401d after charging the laser light emitted from the laser light source 403. It is possible to irradiate. 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 medium tray) 411 is provided at a predetermined position in the housing 420, and the transfer medium 500 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.
Also in the electrophotographic apparatus 220 having such a configuration, by providing the electrophotographic photosensitive member and the charging member as described above, generation of streak-like image defects can be suppressed, and good image quality can be stably obtained over a long period of time. Can do.

  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.

-Production of electrophotographic photoreceptor-
[Preparation 1 of Photoconductor]
The cylindrical aluminum substrate was polished by a centerless polishing apparatus, and the surface roughness was set to Rz = 0.6 μm. In order to clean the aluminum substrate subjected to the centerless polishing treatment, a degreasing treatment, an etching treatment with a 2% by mass sodium hydroxide solution for 1 minute, a neutralization treatment, and a pure water washing were performed in this order. Next, an anodic oxide film (current density: 1.0 A / dm ² ) was formed on the surface of the base material with a 10% by mass sulfuric acid solution with respect to the aluminum base material. After washing with water, sealing treatment was performed by dipping in a 1 mass% nickel acetate solution at 80 ° C. for 20 minutes. Further, pure water washing and drying treatment were performed. In this way, a conductive support having a 7 μm anodic oxide film formed on the surface was obtained.

  Next, 1 mass 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. 1 part by weight of polyvinyl butyral (ESREC BM-S, Sekisui Chemical) and 100 parts by weight of n-butyl acetate are mixed with glass beads for 1 hour with a paint shaker and dispersed to form a charge generation layer A coating solution was obtained. This coating solution was dip-coated on the outer peripheral surface of the conductive support and heat-dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts by mass of a benzidine compound represented by the following formula (XVIII-1) and a polymer compound having a structural unit represented by the following formula (XIX-1) (viscosity average molecular weight 30,000) 2.5 masses A part was dissolved in 20 parts by mass of chlorobenzene to obtain a coating solution for forming a charge transport layer.

  The obtained coating solution was applied onto the charge generation layer by a dip coating method and dried by heating at 120 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

Next, 3 parts by mass of the compound (III-16), 0.5 parts by mass of methyltrimethoxysilane, 0.2 parts by mass of colloidal silica, Me (MeO) ₂ Si— (CH ₂ ) ₄ -SiMe (OMe) ₂ ( In the formula, Me is a methyl group) 0.5 part by mass, methyl alcohol 5 parts by mass, and ion exchange resin (Amberlyst 15E) 0.5 part by mass were mixed and stirred to carry out a protective group exchange reaction for 3 hours. . Thereafter, 10 parts by mass of n-butanol and 0.3 parts by mass of distilled water were added to the reaction solution, followed by hydrolysis for 15 minutes. The ion exchange resin was separated by filtration from the reaction solution after hydrolysis, and 0.1 parts by mass of aluminum trisacetylacetonate (Al (aqaq) ₃ ), 0.1 part by mass of acetylacetone, and 3,5-dithiol were added to the filtrate. -T-butyl-4-hydroxytoluene (BHT) 0.4 parts by mass, phenol resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.) 3 parts by mass, and polyether-modified silicone oil (KF353 (A), Shin-Etsu Chemical Co., Ltd.) (Product) 0.12 part by mass was added to obtain a coating solution for forming a protective layer.

  The obtained coating liquid for forming a protective layer was 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 130 ° C. for 1 hour. As a result, a protective layer having a thickness of about 3 μm was formed, and an intended electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-1”) was obtained.

[Production of Photoreceptor 2]
First, a cylindrical aluminum substrate subjected to a honing treatment was prepared as a conductive support. Next, 100 parts by mass of a zirconium compound (Olgatix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts by mass of a silane compound (A1100, manufactured by Nihon Unicar Company), 3 parts by mass of polyvinyl butyral (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) 380 parts by mass of isopropanol and 200 parts by mass of butanol were mixed to obtain a coating solution for forming an undercoat layer. 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 about 0.17 μm.

  Next, the Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum are 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 °, and 28. 1 part by weight of hydroxygallium phthalocyanine having a strong diffraction peak at 3 °, 1 part by weight of polyvinyl butyral (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.), and 100 parts by weight of n-butyl acetate are mixed, and glass beads At the same time, it was dispersed by treatment with a paint shaker for 2 hours 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 mass of a compound represented by the following formula (XVIII-2) and 3 parts by mass of a polymer compound having a structural unit represented by the following formula (XIX-2) (viscosity average molecular weight 50,000) are added to chlorobenzene. Dissolved in 20 parts by mass, a coating liquid for forming a charge transport layer was obtained.

  The obtained coating solution was applied onto the charge generation layer by a dip coating method and heated at 120 ° C. for 45 minutes to form a charge transport layer having a thickness of 20 μm.

Next, 3 parts by mass of the compound (III-3), 0.5 parts by mass of Me (MeO) ₂ Si— (CH ₂ ) ₄ —SiMe (OMe) ₂ (wherein Me is a methyl group), hexamethylcyclotrisiloxane 0.3 parts by mass, 5 parts by mass of butyl alcohol and 0.3 part of an ion exchange resin (Amberlyst 15E) were mixed and stirred to carry out a protective group exchange reaction for 5 hours. Thereafter, the ion exchange resin was separated by filtration from the reaction solution, and 0.1 parts by mass of aluminum trisacetylacetonate (Al (aqaq) ₃ ), 0.1 part by mass of acetylacetone, 3,5-di-t with respect to the filtrate. -0.4 part by mass of butyl-4-hydroxytoluene (BHT), 3 parts by mass of phenol resin (PR-51206, manufactured by Sumitomo Bakelite), and polyether-modified silicone oil (KF355 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) 0 .1 part by mass was added to obtain a coating solution for forming a protective layer.

  The obtained coating solution for forming a protective layer is applied onto the above charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, cured by heat treatment at 130 ° C. for 1 hour, and a film thickness of about 3 μm. The target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-2”) was obtained.

[Production of Photoreceptor 3]
First, an undercoat layer was formed in the same manner as the photoreceptor-2.

  Next, 1 part by mass of titanyl phthalocyanine having a strong diffraction peak at 27.2 ° in the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is added by 1 part by mass of polyvinyl butyral (ESREC BM-S, Sekisui Chemical) and acetic acid. The mixture was mixed with 100 parts by mass of n-butyl and dispersed with a glass shaker for 1 hour using a paint shaker to obtain a coating solution for forming a charge transport 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 mass of a benzidine compound represented by the above formula (XVIII-1) and 2.5 parts of a polymer compound (viscosity average molecular weight 79,000) having a structural unit represented by the above formula (XIX-1) Was dissolved in 25 parts of chlorobenzene to obtain a coating solution for forming a charge transport layer. This coating solution was applied onto the charge generation layer by dip coating, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Next, 3 parts by mass of the compound (I-1), 3 parts by mass of a phenol resin (PL-2215, manufactured by Gunei Chemical Co., Ltd.), 0.1 mass of a polyether-modified silicone oil (KF615 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) Parts were mixed 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 heating at 130 ° C. for 1 hour to form a protective layer having a thickness of about 3 μm. The intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-3”) was obtained.

[Production of Photoreceptor 4]
First, a cylindrical aluminum substrate was prepared as a conductive support.

Next, 100 parts by mass of zinc oxide (SMZ-017N, manufactured by Teica) was mixed with 500 parts by mass of toluene, and 2 parts by mass 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 ratio of Si element strength to zinc element strength was 1.8 × 10 ⁻⁴ .

  35 parts by mass of the surface-treated zinc oxide, 15 parts by mass of a curing agent (blocked isocyanate Sumijoule 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.), 6 parts by mass of butyral resin (BM-1, manufactured by Sekisui Chemical Co., Ltd.) and methyl ethyl ketone The dispersion was obtained by mixing with 44 parts by mass and carrying out a dispersion treatment for 2 hours in a sand mill using glass beads of 1 mmφ. As a catalyst, 0.005 parts by mass of dioctyltin dilaurate and 17 parts by mass of silicone particles (Tospearl 130, manufactured by GE Toshiba Silicone) were added to the resulting dispersion to obtain an undercoat layer coating solution. This coating solution was applied onto an Al base material by a dip coating method, followed by drying and curing at 160 ° C. for 100 minutes to obtain an undercoat layer having a thickness of 20 μm. The surface roughness of the undercoat layer was measured using a surface roughness profile measuring device Surfcom 570A manufactured by Tokyo Seimitsu Co., Ltd. at a measurement distance of 2.5 mm and a scanning speed of 0.3 mm / sec. The Rz value was 0.24. It was.

  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 °, 28. 1 part by mass of hydroxygallium phthalocyanine having a strong diffraction peak at 3 ° is mixed with 1 part by mass of polyvinyl butyral (Esreck BM-S, Sekisui Chemical) and 100 parts by mass of n-butyl acetate, and the glass shaker is used for 1 hour. Dispersion treatment was performed 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 mass of the benzidine compound represented by the above formula (XVIII-1) and a polymer compound having a structural unit represented by the above formula (XIX-1) (viscosity average molecular weight 79,000) 2.5 mass A part was dissolved in 25 parts by mass of chlorobenzene to obtain a coating solution for forming a charge transport layer. This coating solution was applied onto the charge generation layer by dip coating, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Subsequently, 3 parts by mass of the compound (I-19), 3 parts by mass of a phenol resin (PL-2211, manufactured by Gunei Chemical Co., Ltd.), 0.1 mass of a polyether-modified silicone oil (KF353 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) Parts were mixed 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 130 ° C. for 1 hour to form a protective layer having a thickness of about 3 μm. The intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-4”) was obtained.

[Preparation of Photoconductor 5]
First, the charge transport layer was formed in the same manner as the photoconductor-4.

  Subsequently, 3 parts by mass of the compound (I-1), 3 parts by mass of a phenol resin (PR-50404, manufactured by Sumitomo Bakelite Co., Ltd.), 0.1 parts by mass of a polyether-modified silicone oil (KF355 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) Were mixed 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 130 ° C. for 1 hour to form a protective layer having a thickness of about 3 μm. The intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-5”) was obtained.

[Production of Photoconductor 6]
First, the charge transport layer was formed in the same manner as the photoreceptor-3.
Next, 3 parts by mass of the compound (I-25), 3 parts by mass of a phenol resin (PR-51206, manufactured by Sumitomo Bakelite Co., Ltd.), and 0.1 part by mass of polyethylene glycol 400 (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. A coating solution for forming a protective layer was obtained. This coating solution is applied onto the above 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 160 ° C. for 1 hour to form a protective layer having a thickness of about 3 μm. The intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-6”) was obtained.

[Preparation of Photoconductor 7]
First, the charge transport layer was formed in the same manner as the photoconductor-4.
Subsequently, 3 parts by mass of the compound (IV-11), 3 parts by mass of a phenol resin (PL-2215, manufactured by Gunei Chemical Co., Ltd.), and a polyether antifoaming agent No. 5 (manufactured by Kao) 0.1 parts by mass was mixed to obtain a coating solution for forming a protective layer. This coating solution is applied onto the above 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 160 ° C. for 1 hour to form a protective layer having a thickness of about 3 μm. The intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-7”) was obtained.

[Production of Photoreceptor 8]
First, the charge transport layer was formed in the same manner as the photoreceptor-3.

  Next, 3 parts by mass of the compound (II-15), 3 parts by mass of a phenol resin (BLS-3122, Showa Polymer Co., Ltd.), 0.1 part of triethylphosphine, and polyether-modified silicone oil (KF353 (A), Shin-Etsu) (Chemical Co., Ltd.) 0.1 parts by mass was mixed to obtain a coating solution for forming a protective layer. This coating solution is applied onto the above 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 160 ° C. for 1 hour to form a protective layer having a thickness of about 3 μm. The intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-8”) was obtained.

[Preparation of Photoconductor 9]
First, the charge transport layer was formed in the same manner as the photoconductor-4.

  Next, 3 parts by mass of the compound (IV-6), 3 parts by mass of a phenol resin (CKM-2400, manufactured by Showa Polymer Co., Ltd.), and polyether-modified silicone oil (KF355 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 Mass parts were mixed to obtain a coating solution for forming a protective layer. This coating solution is applied onto the above 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 160 ° C. for 1 hour to form a protective layer having a thickness of about 3 μm. The intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-9”) was obtained.

[Production of Photoconductor 10]
First, the charge transport layer was formed in the same manner as in the photoreceptor-5.

  Next, 3 parts by mass of the compound (V-47), 3 parts by mass of a phenol resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.), and polyether-modified silicone oil (KF355 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 Mass parts were mixed to obtain a coating solution for forming a protective layer. This coating solution is applied onto the above 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 160 ° C. for 1 hour to form a protective layer having a thickness of about 3 μm. The intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-10”) was obtained.

[Production of Photoreceptor 11]
First, the charge transport layer was formed in the same manner as in the photoreceptor-5.

  Next, 100 parts by mass of tin oxide particles (S-1, manufactured by Mitsubishi Materials Corporation), which are conductive inorganic particles, together with 20 parts by mass of heptadecafluorodecyltrimethoxysilane (TSL8233, manufactured by Toshiba Silicone) and 300 parts of methanol The mixture was stirred with a ball mill for 24 hours. The mixed solution after stirring was filtered, and the tin oxide particles on the filter were washed with methanol, and then dried at 150 ° C. for 2 hours to treat the surface of the tin oxide particles. 11 parts by mass of the tin oxide particles subjected to this surface treatment and 10 parts by mass of a phenol resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.), 5 parts by mass of a polyvinyl butyral resin (ESREC BH-S, manufactured by Sekisui Chemical Co., Ltd.), In addition, 0.2 parts by mass of a polyether-modified silicone oil (KF355 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) is added to a solution of 150 parts of n-butyl alcohol, and dispersed for 1 hour in a sand mill to form a protective layer. A liquid was obtained. The obtained coating solution is dip-coated on the above charge transport layer and dried and cured at 170 ° C. for 1 hour to form a protective layer having a thickness of 4 μm. -11 ").

[Production of Photoreceptor 12]
First, the charge transport layer was formed in the same manner as in the photoreceptor-5.

  Next, 8 parts by mass of the compound (II-15), 60 parts by mass of cyclohexanone, 10 parts by mass of block type polyisocyanate (Sumidur BL3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.), 0.1 part by mass of dibutyl Sn dilaurate, and poly 0.2 parts by mass of ether-modified silicone oil (KF355 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed to obtain a coating solution for forming a protective layer. This coating solution is applied onto the above 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 160 ° C. for 1 hour to form a protective layer having a thickness of about 3 μm. The intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-12”) was obtained.

[Production of Photoconductor 13]
First, the charge transport layer was formed in the same manner as in the photoreceptor-5.

  Next, 3 parts by mass of the compound (VI-3), 2.5 parts by mass of a phenol resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.), and a polyether-modified silicone oil (TSF 4440, manufactured by Toshiba Silicone) 0. 05 parts by mass and 5 parts by mass of butanol were mixed to prepare a coating solution for forming a protective layer. This coating solution is ring-dip-coated on the charge transport layer, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 150 ° C. for 1 hour to form a protective layer having a thickness of 3 μm. A photoreceptor (hereinafter referred to as “photoreceptor-13”) was obtained.

[Preparation of Photoconductor 14]
First, the charge transport layer was formed in the same manner as in the photoreceptor-5.

  Next, 3 parts by mass of the compound (VI-6), 3.5 parts by mass of a phenol resin (PR-50404, manufactured by Sumitomo Bakelite Co., Ltd.), and a polyether-modified silicone oil (TSF 4452, manufactured by Toshiba Silicon Co., Ltd.) 0.05 A coating solution for forming a protective layer was prepared by mixing 6 parts by mass and 6 parts of butanol. This coating solution is ring-dip-coated on the charge transport layer, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 150 ° C. for 1 hour to form a protective layer having a thickness of 3 μm. A photoreceptor (hereinafter referred to as “photoreceptor-14”) was obtained.

[Preparation of Photoconductor 15]
The electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-15”) is the same as the photosensitive member-1 except that the polyether-modified silicone oil (KF353 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) is not used when forming the protective layer. ").

[Production of Photoconductor 16]
The electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-16”) is the same as the photosensitive member-5 except that polyether-modified silicone oil (KF355 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) is not added when forming the protective layer. ").

[Preparation of Photoconductor 17]
Photoreceptor-3 except that, in forming the protective layer, unmodified silicone oil (KP354, manufactured by Shin-Etsu Chemical) was used instead of polyether-modified silicone oil (KF615 (A), manufactured by Shin-Etsu Chemical). In the same manner, an electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-17”) was produced.

[Preparation of Photoconductor 18]
First, the charge transport layer was formed in the same manner as in the photoreceptor-4.
Subsequently, 500 parts by mass of Super Becamine (R) L-148-55 (Butylated Benzoguanamine Resin: manufactured by Dainippon Ink Co., Ltd.) was dissolved in 500 parts by mass of xylene, and each was washed five times with 300 ml of distilled water. The conductivity of the final wash water was 6 μS / cm. The solvent was distilled off from the solution under reduced pressure to obtain 250 parts by weight of a candy-like resin. 3 parts by mass of this resin, 3 parts by mass of the compound (B-2), 0.3 parts by mass of colloidal silica (trade name: PL-1, manufactured by Fuso Chemical Industries), polyvinylphenol resin (weight average molecular weight of about 8000, Aldrich) 0.2 parts by mass, 1-methoxy-2-propanol 8 parts by mass, 3,5-di-t-butyl-4-hydroxytoluene (BHT) 0.2 parts by mass, p-toluenesulfonic acid 0. 01 parts by mass and 0.12 parts by mass of polyether-modified silicone oil (KF353 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) were added to prepare a coating solution for a protective layer. This coating solution is applied onto the charge transport layer by a dip coating method, air-dried at room temperature (25 ° C.) for 30 minutes, and then cured by heat treatment at 150 ° C. for 1 hour to form a protective layer having a thickness of about 7 μm. Hereinafter, the photoconductor is referred to as “photoconductor-18”. ) Was produced.

[Preparation of Photoconductor 19]
An electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-19”) was prepared in the same manner as the photosensitive member-18 except that the polyether-modified silicone oil (KF353 (A), manufactured by Shin-Etsu Chemical Co., Ltd.) was not used when forming the protective layer. ").

-Production of charging roll-
[Preparation of Charging Roll 1]
In order to form an elastic layer, the following mixture was kneaded with an open roll, and the surface of a conductive support (core material) having a diameter of 8 mm made of SUS416 was coated in a cylindrical shape so as to have a thickness of 3 mm. This is put into a cylindrical mold having an inner diameter of 14.0 mm, vulcanized at 170 ° C. for 30 minutes, taken out from the mold, polished, and cylindrical, the thickness of the central portion being thinner than the thickness of the end portion. An elastic layer was obtained. The difference in the outer diameter between the central portion and the end portion was 85 μm.

・ Rubber material ・ ・ ・ ・ ・ ・ ・ ・ ・ 100 parts by mass (Epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymer rubber, Gechron 3106: manufactured by Nippon Zeon Co., Ltd.)
-Conductive agent (Carbon Black Asahi Thermal: manufactured by Asahi Carbon Co., Ltd.) ... 25 parts by mass-Conductive agent (Ketjen Black EC: manufactured by Lion)-... 8 parts by mass-Ionic conductive agent (lithium perchlorate) ··· 1 part by mass · Vulcanizing agent (sulfur) 200 mesh: manufactured by Tsurumi Chemical Co., Ltd. · · · 1 part by mass · Vulcanization accelerator (Noxeller DM: Ouchi Shinsei Chemical Co., Ltd.) ··· 2 .0 part by mass / Vulcanization accelerator (Noxeller TT: Ouchi Shinsei Chemical Co., Ltd.) ・ ・ ・ 0.5 part by mass

  Next, in order to form a surface layer, a dispersion obtained by dispersing the following mixture in a bead mill was diluted with methanol to obtain a surface layer coating solution. This coating solution is applied to the surface of the elastic layer by a dip coating method, and then heated and dried at 150 ° C. for 15 minutes to form a 10 μm surface layer, which is referred to as a charging roll (hereinafter referred to as “charging roll-1”). )

-Polymer material: 100 parts by mass (copolymerized nylon) Alamine CM8000: manufactured by Toray Industries, Inc.-Conductive agent: 20 parts by mass (carbon black) MONARCH1000: manufactured by Cabot, pH 2.0
・ Solvent (methanol): 500 parts by mass ・ Solvent (butanol): 240 parts by mass

[Production of Charging Roll 2]
The elastic layer was formed by the same method as in the production 1 of the charging roll.
In order to form a surface layer, the following mixture was dispersed with a bead mill, and the obtained dispersion was diluted with MEK. This was dip-coated on the surface of the elastic layer, and then dried by heating at 150 ° C. for 30 minutes. Thus, a surface layer was formed to obtain a charging roll (hereinafter referred to as “charging roll-2”).

-Polymer material: 100 parts by mass (Methoxymethylated nylon) Toresin F30K: manufactured by Nagase ChemteX Corporation-Conductive agent: 17 parts by mass (carbon black) MONARCH1000: manufactured by Cabot Corporation pH 2.0
・ Solvent (methanol): 500 parts by mass ・ Solvent (butanol): 150 parts by mass

[Production of Charging Roll 3]
The elastic layer was formed by the same method as in the production 1 of the charging roll.
In order to form a surface layer, the following mixture was dispersed with a bead mill, and the obtained dispersion was diluted with MEK. This was dip-coated on the surface of the elastic layer, and then dried by heating at 150 ° C. for 30 minutes. Thus, a surface layer was formed to obtain a charging roll (hereinafter referred to as “charging roll-3”).

Polymer material: 100 parts by weight (copolymerized nylon) Alamine CM8000: manufactured by Toray Industries, Inc. Conductive agent: 35 parts by weight (antimony-doped tin oxide) SN-100P: manufactured by Ishihara Sangyo Co., Ltd. Solvent (methanol)・ ・ 500 parts by mass ・ Solvent (butanol) ・ ・ ・ 240 parts by mass

[Production of Charging Roll 4]
The elastic layer was formed by the same method as in the production 1 of the charging roll.
In order to form a surface layer, the following mixture was dispersed with a bead mill, and the obtained dispersion was diluted with MEK. This was dip-coated on the surface of the elastic layer, and then dried by heating at 170 ° C. for 30 minutes. Thus, a surface layer was formed, and a charging roll (hereinafter referred to as “charging roll-4”) was obtained.

-Polymer material-100 parts by mass (saturated copolymer polyester resin solution) Byron 30SS: manufactured by Toyobo Co., Ltd.-Curing agent ... 26.3 parts by mass (amino resin solution, Super Becamine G-821-60 : Dainippon Ink & Chemicals, Inc.)
-Conductive agent: 24 parts by mass (carbon black) MONARCH1000: manufactured by Cabot Corporation

[Preparation of Charging Roll 5]
The elastic layer was formed by the same method as in the production 1 of the charging roll.
In order to form a surface layer, the following mixture was dispersed with a ball mill, and the obtained dispersion was diluted with MEK. This was applied to the surface of the elastic layer with a roll coater, and then dried by heating at 160 ° C. for 30 minutes. As a result, a surface layer of 20 μm was formed to obtain a charging roll (hereinafter referred to as “charging roll-5”).

・ Polymer material ・ ・ ・ ・ 100 parts by mass (solution of polyurethane resin in toluene and MEK) NIPPOLAN 3113: manufactured by Nippon Polyurethane Co., Ltd. ・ Conductive agent: 35 parts by mass (carbon black) Special Black 4: manufactured by Degussa, Germany ・Solvent (MEK): 100 parts by mass

Drum cartridges were prepared by combining the electrophotographic photosensitive member and the charging roll shown in Table 1, respectively. As the drum cartridge, the same elements as those of the copying machine “Docucenter color a450CP” manufactured by Fuji Xerox Co., Ltd. were used except for the electrophotographic photosensitive member and the charging roll.
After this drum cartridge was stored for one month in an environment of 40 ° C./humidity of 95%, a uniform image with an image density of 30% was formed using a Fuji Xerox copier “Docucenter color a450CP”. After the image formation, streak-like image defects were evaluated by dividing them into a photoreceptor pitch and a charging roll pitch. The obtained results are shown in Table 1.

The presence or absence of streak-like image defects was determined visually and evaluated based on the following evaluation criteria.
◎: Not generated ○: Slightly generated acceptable range ×: Strongly generated (There is a problem with image quality)

As can be seen from the results shown in Table 1, in the cartridges of Examples 1 to 18, both the photosensitive member pitch and the charging roll pitch did not cause streak-like image defects, or they did not cause any problems. .
On the other hand, in the cartridges of Comparative Examples 1 to 8, a streak-shaped image defect that caused an image problem occurred in either the photoreceptor pitch or the charging roll pitch.

1 is a schematic configuration diagram illustrating an example of an electrophotographic apparatus including a process cartridge according to the present invention. 1 is a schematic cross-sectional view illustrating an example of a configuration of an electrophotographic photoreceptor according to the present invention. It is a schematic sectional drawing which shows the other example of a structure of the electrophotographic photoreceptor which concerns on this invention. It is a schematic sectional drawing which shows the other example of a structure of the electrophotographic photoreceptor which concerns on this invention. It is a schematic sectional drawing which shows the other example of a structure of the electrophotographic photoreceptor which concerns on this invention. It is a schematic sectional drawing which shows the other example of a structure of the electrophotographic photoreceptor which concerns on this invention. It is a schematic sectional drawing which shows an example of a structure of the charging roll which concerns on this invention. It is a schematic sectional drawing which shows the other example of a structure of the charging roll which concerns on this invention. It is a schematic block diagram which shows the other example of the electrophotographic apparatus of this invention. It is a schematic block diagram which shows the other example of the electrophotographic apparatus of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photosensitive member, 2 ... Conductive support body, 3 ... Photosensitive layer, 4 ... Undercoat layer, 5 ... Charge generation layer, 6 ... Charge transport layer, 7 ... Protective layer, 8 ... Charge generation / charge transport layer , 20 ... process cartridge, 21 ... charging roll, 100, 120, 220 ... electrophotographic apparatus.

Claims (8)

An electrophotographic photosensitive member; a charging member that is charged in contact with the electrophotographic photosensitive member; and an electrostatic latent image forming unit that exposes the electrophotographic photosensitive member charged by the charging member to form an electrostatic latent image. Developing means for developing the electrostatic latent image with toner to form a toner image; and transfer means for transferring the toner image to a transfer medium;
The electrophotographic photosensitive member has a conductive support and a photosensitive layer provided on the conductive support, and the photosensitive layer is a cured curable resin composition containing a curable resin and a polyether compound. It has a layer consisting of things,
The electrophotographic apparatus, wherein the charging member has a surface layer containing a resin having an amide group.   The electrophotographic apparatus according to claim 1, wherein the polyether compound is a polyether-modified silicone oil.   The electrophotographic apparatus according to claim 1, wherein the resin having an amide group is nylon.   The electrophotographic apparatus according to claim 1, wherein the resin having an amide group is methoxymethylated nylon. An electrophotographic photoreceptor, and a charging member that is charged in contact with the electrophotographic photoreceptor,
The electrophotographic photosensitive member has a conductive support and a photosensitive layer provided on the conductive support, and the photosensitive layer is a cured curable resin composition containing a curable resin and a polyether compound. It has a layer consisting of things,
A process cartridge, wherein the charging member has a surface layer containing a resin having an amide group.   The process cartridge according to claim 5, wherein the polyether compound is a polyether-modified silicone oil.   7. The process cartridge according to claim 5, wherein the resin having an amide group is nylon.   The process cartridge according to any one of claims 5 to 7, wherein the resin having an amide group is methoxymethylated nylon.

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