JP2019045862A - Manufacturing method of xerographic photoreceptor and xerographic photoreceptor manufactured by the manufacturing method - Google Patents

Abstract

To provide a simple manufacturing method of xerographic photoreceptor superior in abrasion resistance and lubricity, which contains either one of acrylic resin particles and melamine resin particles in the surface layer.SOLUTION: The manufacturing method of xerographic photoreceptor comprises the steps of: applying a surface layer forming coating solution which contains organic resin particles of at least one of acrylic resin particles and melamine resin particles, and a compound having a monovalent hydrocarbon group of 7 or more carbon atoms and a polymerizable functional group in the same molecule, and hole transportable compound having polymerizable functional group; and forming a surface layer by curing the applied and formed film.SELECTED DRAWING: None

Description

  The present invention relates to a method of manufacturing an electrophotographic photosensitive member, and an electrophotographic photosensitive member manufactured by the method of manufacturing the same.

There is known a technique of adding organic fine particles to a surface layer containing a curable resin or a resin having a crosslinked structure for the purpose of improving the abrasion resistance and the cleaning property of an electrophotographic photosensitive member.
Patent Document 1 discloses a technology for producing an electrophotographic photosensitive member excellent in abrasion resistance and cleaning property by subjecting acrylic resin particles or melamine resin particles added to the surface layer containing a curable resin to a specific surface treatment. Is described.
In Patent Document 2, there is a technology for designing an electrophotographic photosensitive member having both a wear resistance and a cleaning property by designing the surface of a surface layer containing a resin having a crosslinked structure and acrylic resin particles to a desired roughness. Have been described.
In Patent Document 3, the surface of a surface layer containing a resin having a crosslinked structure, inorganic fine particles, and melamine resin particles is designed to have a desired roughness, and an electrophotographic photosensitive member having both wear resistance and cleanability is produced. Technology is described.

JP, 2016-95340, A Unexamined-Japanese-Patent No. 2006-267467 JP, 2015-114453, A

  However, the process for producing the electrophotographic photosensitive members disclosed in Patent Documents 1 and 2 requires a surface treatment process of acrylic resin particles and melamine resin particles. Moreover, the manufacturing process of patent documents 1-3 required the dispersion process of acrylic resin particles and melamine resin particles. The problem with any of the techniques is that the number of man-hours for manufacturing increases. Further, it is known that the improvement of the cleaning property of the electrophotographic photosensitive member is achieved by the improvement of the lubricity of the surface layer of the electrophotographic photosensitive member.

  Accordingly, an object of the present invention is to provide a simple method for producing an electrophotographic photosensitive member excellent in abrasion resistance and lubricity, which contains at least one of acrylic resin particles and melamine resin particles in the surface layer.

  The above object is achieved by the present invention described below. That is, in the method for producing an electrophotographic photosensitive member according to the present invention, a compound having a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule, and a hole transporting property having a polymerizable functional group A coating solution for forming a surface layer containing a compound and at least one of an acrylic resin particle and a melamine resin particle is applied, and the formed coating film is cured to form a surface layer.

  As described above, according to the present invention, there is provided a simple method for producing an electrophotographic photosensitive member excellent in wear resistance and lubricity, which contains at least one of acrylic resin particles and melamine resin particles in the surface layer. Can be provided.

FIG. 1 is a view showing an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

Hereinafter, the present invention will be described in detail by way of preferred embodiments.
In the prior art, man-hours have been increased to control the state of particles in the surface layer. In the technique of Patent Document 1, in order to suppress detachment of acrylic resin particles or melamine resin particles from the surface layer, the surface of acrylic resin particles or melamine resin particles is coated with an inorganic film and an organic component to form a surface layer. This is a technology to bond a curable resin and a coating film of particles by a curing reaction. Therefore, a surface treatment step of acrylic resin particles or melamine resin particles is required.

The technique of Patent Document 2 suppresses the aggregation of the acrylic resin particles by surface-treating the surface of the acrylic resin particles, and good cleanability can be obtained by controlling the surface roughness of the surface layer in a desired range. . Therefore, a surface treatment step is required.
In the technique of Patent Document 3, the surface treatment on the surface of the melamine resin particles suppresses aggregation of the melamine resin particles, and good cleanability is obtained by controlling the surface roughness of the surface layer in a desired range. . Therefore, a surface treatment step is required.

  As described above, in the prior art, in the process of forming the surface layer, the balance of the affinity of the other components with respect to the acrylic resin particles or the melamine resin particles is poor, and the surface treatment or dispersion treatment of the particles is performed to compensate for this. It was necessary, and man-hours had increased.

  In order to solve the subject which arose in the said prior art, the structure of the coating liquid for surface layer formation and the film forming method of surface layer were examined. As a result of examination, a hole transportable compound having a polymerizable functional group and a compound having a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule (hereinafter, also referred to as “compound b”) A surface containing at least one of (hereinafter also referred to as “compound c”), acrylic resin particles (hereinafter referred to as “acrylic particles”) and melamine resin particles (hereinafter referred to as “melamine particles”) Abrasion resistance containing at least one of acrylic particles and melamine resin particles in the surface layer by applying a layer forming coating solution and curing the formed coating film to form a surface layer, without increasing the number of steps. It has been found that an electrophotographic photosensitive member having excellent lubricity can be produced.

  The structure of the coating solution for forming a surface layer of the present invention and the mechanism by which the film forming method solves the problems are considered as follows. First, the compound b and the compound c dissolve substantially uniformly in an alcohol solvent having 3 or less carbon atoms. On the other hand, the compound b has higher affinity to the acrylic particles and the melamine particles than the compound c having a charge transporting skeleton. Therefore, the acrylic particles and the melamine particles are preferentially surrounded by the compound b. At this time, the compound b is considered to be a compound b because the polymerizable functional group is compatible with the acryl particles and the melamine particles, and the monovalent hydrocarbon group having 7 or more carbon atoms is opposite to the acryl particles and the melamine particles. The enclosed acrylic and melamine particles are somewhat hydrophobic. The slightly hydrophobic acrylic particles and melamine particles are not enough to separate from the surface layer forming coating solution, but when the surface layer forming coating solution becomes a coating film, the alcohol solvent having 3 or less carbon atoms is used. In this case, it is expected that the coating film is likely to be exposed near the free interface (interface with air). As a result, the formed surface layer has a high frequency of exposure of the thin film-covered acrylic particles and melamine particles composed of the cured product of compound b and compound c. This surface layer is that in the electrophotographic process, the unevenness due to the acrylic particles and the melamine particles reduces the frictional force, and the cured product of the compound b exposed on the surface together with the acrylic particles and the melamine particles has lubricity. Thus, the lubricity is improved. In addition, since the surface layer itself is formed of a cured product, the wear resistance is improved. Furthermore, since the acryl particles and melamine particles covered with a thin film made of a cured product are prevented from being detached from the surface layer, the lubricity and the abrasion resistance are maintained after repeated use.

  In the present invention, a coating solution for forming a surface layer containing compound b, compound c, and at least one of acrylic particles and melamine particles is applied, and the formed coating film is cured to form compound b and compound c and By forming the surface layer containing the copolymer of the above three, the three types of materials effectively work together in both the coating solution and the coating film, without increasing the number of steps for surface treatment of the acrylic particles and the melamine particles. It is possible to provide a method for producing an electrophotographic photosensitive member excellent in abrasion resistance and lubricity, which contains at least one of acrylic particles and melamine particles in the surface layer.

  As described above, it is possible to achieve the effects of the present invention by synergistically combining the effects of each configuration.

[Method of manufacturing electrophotographic photosensitive member]
The method for producing the electrophotographic photosensitive member of the present invention is shown below. First, there is a method of preparing a coating solution for each layer other than the surface layer described later, applying in the order of desired layers, and drying. As a coating method of the coating liquid of layers other than surface layer, dip coating, spray coating, inkjet coating, roll coating, die coating, blade coating, curtain coating, wire bar coating, ring coating, etc. may be mentioned. Among these, dip coating is preferable from the viewpoint of efficiency and productivity.

  Subsequently, on each layer other than the surface layer formed by the above method, a coating solution for forming a surface layer containing compound b, compound c and at least one organic resin particle of acrylic particles and melamine particles is applied and formed. This is a method of curing the coated film to form a surface layer.

The coating solution for forming the surface layer can be prepared only by mixing and stirring the material without passing through the surface treatment process or dispersion process of the acrylic resin or melamine resin particles.
The coating method of the coating solution for forming the surface layer is not particularly limited as long as the coating film can be formed. Coating methods include dip coating, spray coating, inkjet coating, roll coating, die coating, blade coating, curtain coating, wire bar coating, ring coating and the like. Among these, dip coating is preferable from the viewpoint of efficiency and productivity.

  The method of curing the coating film is a method of heating the coating film or irradiating radiation in order to cure the compound having a polymerizable functional group contained in the coating solution. As a heating method, a hot air drying furnace, an infrared heater, an IH heater or the like can be used. Examples of radiation include ultraviolet light and electron beams. At this time, if necessary, a known polymerization initiator may be used. In addition, heat treatment may be separately performed before and after curing for the purpose of improving the characteristics and the like.

  The compound b will be described below. The monovalent hydrocarbon group having 7 or more carbon atoms is a linear or branched unsubstituted alkyl group. In the case of a branched alkyl group, the total of the carbon number of the main chain and the carbon number of the branched chain is 7 or more. If the carbon number is less than 7, an electrophotographic photosensitive member having excellent lubricity can not be produced. As a polymerizable functional group which the compound b has, a vinyl group, acryloyl group, methacryloyl group, an epoxy group, a hydroxyl group, an alkoxy group, a carboxy group, an amino group, an isocyanate group, a styryl group etc. are mentioned, for example.

As the polymerizable functional group, a functional group capable of undergoing a polymerization reaction with the polymerizable functional group possessed by compound c can be optionally selected. The polymerizable functional group may be directly bonded to a hydrocarbon group, may be bonded via a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, or may be bonded via an oxycarbonyl group, a carbonyloxy group or the like. May be combined. The polymerizable functional group is more preferably an acryloyloxy group or a methacryloyloxy group in which an acryloyl group and a methacryloyl group are bonded to a hydrocarbon group via oxygen. One or more polymerizable functional groups may be contained in one molecule of the compound b. As the compound b, a compound represented by the formula (1) is more preferable.
In formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is a linear or branched unsubstituted alkyl group having 7 or more carbon atoms. In the case of a branched alkyl group, the total of the carbon number of the main chain and the carbon number of the branched chain is 7 or more. X is -OCO- (oxycarbonyl group) or -COO- (carbonyloxy group).

Examples of compound b are shown below.

  The compound c will be described below. Examples of the polymerizable functional group possessed by the compound c include vinyl group, acryloyl group, methacryloyl group, epoxy group, hydroxyl group, alkoxy group, carboxy group, amino group, isocyanate group, styryl group and the like. The polymerizable functional group may be directly bonded to a hydrocarbon group, or may be bonded via a heteroatom such as oxygen atom, nitrogen atom or sulfur atom. One or more polymerizable functional groups may be contained in one molecule of the compound c.

As a hole transportable group which compound c has, for example,
A group derived by removing a hydrogen atom of a benzene ring or an alkyl group of a triarylamine compound having an alkyl group as a substituent or not having a substituent,
A group derived by removing a hydrogen atom of a benzene ring of a hydrazone compound,
And groups derived by removing the hydrogen atom of the benzene ring of the stilbene compound.

The compound c is more preferably a compound represented by the following formula (2).
In Formula (2), P ¹ is a polymerizable functional group, and is a monovalent group represented by the following Formula (3), a monovalent group represented by the following Formula (4), the following Formula (5), or It is a group shown by Formula (6). a is an integer of 1 or more and 4 or less, and when a is 2 or more, a pieces of P1 may be the same or different.

In the above formula (2), Z is a hole transporting group. The hydride in which the bonding site of Z to P ¹ in the above formula (2) is replaced by a hydrogen atom is a compound represented by the following formula (7) or the following formula (8).
In the formula (7), R ³¹ is a phenyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, or biphenyl which may have an alkyl group having 1 to 3 carbon atoms as a substituent Indicates a group. R ³² and R ³³ each represent a phenyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent. R ³¹ , R ³² and R ³³ may be identical to or different from each other.
In formula (8), R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ each represent a phenyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent. R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ may be identical to or different from each other. R ³⁸ and R ^{39 each} represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ³⁸ and R ³⁹ may be identical to or different from each other.

The example of the hole transportable compound (compound c) which has a polymerizable functional group is shown below.

Below, the acrylic resin particle which the coating liquid for surface layer formation contains is demonstrated. The acrylic resin is a resin containing a polymer of acrylic ester or methacrylic ester. Among them, styrene acrylic resin particles are preferable. There are no particular limitations on the degree of polymerization of the acrylic resin or styrene acrylic resin, and whether the resin is thermoplastic or thermosetting.
The particle diameter of the acrylic resin particles can be arbitrarily designed, but is preferably 1.0 μm or less.

  As commercially available acrylic resin particles which can be used in the present invention, for example, Finespheres manufactured by Nippon Paint Industrial Coatings Co., Ltd .: FS-101, FS-102, FS-107, FS-201, FS-301, FS-701 MG-155, MG-351, MG-451, manufactured by Sekisui Chemical Co., Ltd. TECHPOLYMER: SSX-101, SSX-102, SSX-103, SSX-104, SSX-105, JSR Corporation highly crosslinked particles: SX 8002 Sekisui Plastics Co., Ltd. polymethyl methacrylate powder: XX-159AP, XX-160AP and the like.

  The ratio B / A of the mass B of the compound b to the mass A of the acrylic resin particles of the coating liquid for forming a surface layer can be arbitrarily designed, but 8 mass% or more is preferable.

  The ratio A / (A + B + C) of the mass A of the acrylic resin particles to the mass B of the compound (b) of the coating liquid for forming the surface layer and the mass C of the compound c and the mass A of the acrylic resin particles is arbitrarily designed Although it is possible, 10 mass% or more and 25 mass% or less are more preferable.

  Below, the melamine resin particle which the coating liquid for surface layer formation contains is demonstrated. Melamine resin particles are produced by the polycondensation of melamine and formaldehyde. Benzoguanamine may also be added to increase compatibility. Among them, particles containing a melamine / formaldehyde resin as a main component are preferable, and particles containing a melamine / formaldehyde resin are more preferable. Although the particle diameter of the particle | grains containing a melamine resin particle can be designed arbitrarily, 1.0 micrometer or less is more preferable.

  As a commercially available melamine resin particle which can be used for this invention, Nippon Shokuhin Co., Ltd. make エ poster: SS, S, FS, S6 etc. are mentioned, for example.

  Although ratio B / D of mass B of the compound b with respect to mass D of the melamine resin particle of the coating liquid for surface layer formation can be designed arbitrarily, 10 mass% or more is more preferable.

  The ratio D / (D + B + C) to the total of the mass B of the compound b of the coating liquid for forming the surface layer, the mass C of the compound c, and the mass A of the melamine resin particles of the mass D of melamine resin particles can be designed arbitrarily. 13 mass% or more and 32 mass% or less are more preferable.

  Hereinafter, the structure and each layer of the electrophotographic photosensitive member manufactured by the manufacturing method of the present invention will be described.

<Support>
The electrophotographic photosensitive member produced by the production method of the present invention has a support. The support is preferably a conductive support having conductivity. Moreover, as a shape of a support body, cylindrical shape, belt shape, a sheet shape, etc. are mentioned. Among them, a cylindrical support is preferable. In addition, the surface of the support may be subjected to electrochemical treatment such as anodization, blast treatment, cutting treatment and the like.
As a material of a support body, metal, resin, glass etc. are preferable.
Examples of the metal include aluminum, iron, nickel, copper, gold, stainless steel and alloys thereof. Among them, an aluminum support using aluminum is preferable.
In addition, the resin or glass may be provided with conductivity by a process such as mixing or coating of a conductive material.

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

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

Examples of the resin include polyester resin, polycarbonate resin, polyvinyl acetal resin, acrylic resin, silicone resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, alkyd resin and the like.
In addition, the conductive layer may further contain a masking agent such as silicone oil, resin particles, titanium oxide and the like.

  The average film thickness of the conductive layer is preferably 1 μm or more and 50 μm or less, and particularly preferably 3 μm or more and 40 μm or less.

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

<Subbing layer>
In the electrophotographic photosensitive member produced by the production method of the present invention, an undercoat layer may be provided on the support or the conductive layer. By providing the undercoat layer, the adhesion function between the layers is enhanced, and the charge injection blocking function can be imparted to the electrophotographic photosensitive member.
The undercoat layer preferably contains a resin. Alternatively, the undercoat layer may be formed as a cured film by polymerizing a composition containing a monomer having a polymerizable functional group.

  As resin, polyester resin, polycarbonate resin, polyvinyl acetal resin, acrylic resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, polyvinyl phenol resin, alkyd resin, polyvinyl alcohol resin, polyethylene oxide resin, polypropylene oxide resin, polyamide resin And polyamide acid resin, polyimide resin, polyamide imide resin, cellulose resin and the like.

  As a polymerizable functional group which a monomer having a polymerizable functional group has, an isocyanate group, a blocked isocyanate group, a methylol group, an alkylated methylol group, an epoxy group, a metal alkoxide group, a hydroxyl group, an amino group, a carboxyl group, a thiol group, A carboxylic anhydride group, a carbon-carbon double bond group, etc. are mentioned.

The undercoat layer may further contain an electron transport material, a metal oxide, a metal or the like for the purpose of enhancing the electrical properties. Among these, electron transport substances and metal oxides are preferably used.
Electron transport materials include quinone compounds, imide compounds, benzimidazole compounds, cyclopentadienylidene compounds, fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, halogenated aryl compounds, silole compounds, boron compounds . The undercoat layer may be formed as a cured film by copolymerizing with the above-described monomer having a polymerizable functional group, using an electron transport material having a polymerizable functional group as the electron transporting substance.
Examples of metal oxides include indium tin oxide, tin oxide, indium oxide, titanium oxide, zinc oxide, aluminum oxide, silicon dioxide and the like. Examples of the metal include gold, silver and aluminum.
The undercoat layer may further contain an additive.

  The average film thickness of the undercoat layer is preferably 0.1 μm to 50 μm, more preferably 0.2 μm to 40 μm, and particularly preferably 0.3 μm to 30 μm.

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

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

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

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

  Examples of the charge generating material include azo pigments, perylene pigments, polycyclic quinone pigments, indigo pigments, and phthalocyanine pigments. Among these, azo pigments and phthalocyanine pigments are preferable. Among the phthalocyanine pigments, oxytitanium phthalocyanine pigments, chlorogallium phthalocyanine pigments and hydroxygallium phthalocyanine pigments are preferable.

  The content of the charge generation material in the charge generation layer is preferably 40% by mass to 85% by mass, and more preferably 60% by mass to 80% by mass, with respect to the total mass of the charge generation layer. preferable.

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

  The charge generation layer may further contain an additive such as an antioxidant and a UV absorber. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds and the like can be mentioned.

  The average film thickness of the charge generation layer is preferably 0.1 μm or more and 1 μm or less, and more preferably 0.15 μm or more and 0.4 μm or less.

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

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

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

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

  The charge transport layer may also contain additives such as an antioxidant, a UV absorber, a plasticizer, and a leveling agent. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane modified resins, silicone oils and the like can be mentioned.

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

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

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

<Protective layer>
In the present invention, a protective layer may be provided on the photosensitive layer. By providing the protective layer, the durability can be improved.
The protective layer preferably contains a conductive particle and / or a charge transport material, and a resin.

The conductive particles include particles of metal oxides such as titanium oxide, zinc oxide, tin oxide and indium oxide.
Examples of the charge transport material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having a group derived from these materials. Among these, triarylamine compounds and benzidine compounds are preferable.

  Examples of the resin include polyester resin, acrylic resin, phenoxy resin, polycarbonate resin, polystyrene resin, phenol resin, melamine resin, epoxy resin and the like. Among them, polycarbonate resin, polyester resin and acrylic resin are preferable.

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

  The protective layer may contain additives such as an antioxidant, a UV absorber, a plasticizer, a leveling agent, and the like. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane modified resins, silicone oils and the like can be mentioned.

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

  The protective layer can be formed by preparing a coating solution for a protective layer containing the above-described respective materials and a solvent, forming the coating, and drying and / or curing. As a solvent used for a coating liquid, C3-C3 or less alcohol-type solvent is desirable. Among the alcohol solvents, if the carbon number is large, the effect of particle cueing is diminished. If 50% by mass of the alcohol solvent is contained, a ketone solvent, an ether solvent, a sulfoxide solvent, an ester solvent, or an aromatic hydrocarbon solvent may be contained.

<Surface layer>
As described above, the layer corresponding to the surface layer is a coating film formed by applying a coating solution for forming a surface layer containing the compound b, the compound c, and at least one of an acrylic resin particle and a melamine resin particle. Is cured to form a surface layer including at least one of a copolymer of compound b and compound c and acrylic resin particles and melamine resin particles.

The surface layer of the electrophotographic photosensitive member produced by the production method of the present invention is the above protective layer, or, in the case of a laminated type photosensitive member without the protective layer, a charge transport layer, single layer type without the protective layer. In the case of a photosensitive member, it is any one of a single layer type photosensitive layer.
As long as the layer corresponding to the surface layer is formed according to the production method of the present invention, it is composed of the materials described in the above (1-2) charge transport layer, (2) single layer type photosensitive layer, and <protective layer>. You may

[Process cartridge, electrophotographic apparatus]
A process cartridge having an electrophotographic photosensitive member produced by the production method of the present invention is at least one member selected from the group consisting of the electrophotographic photosensitive member described above, a charging unit, a developing unit, and a cleaning unit. And are integrally supported, and are detachable from the electrophotographic apparatus main body.

  An electrophotographic apparatus according to the present invention is characterized by including the electrophotographic photosensitive member, the charging unit, the exposure unit, the developing unit, and the transfer unit described above.

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

  The electrophotographic photosensitive member manufactured by the manufacturing method of the present invention can be used for a laser beam printer, an LED printer, a copying machine, a facsimile, a composite machine of these, and the like.

  Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. The present invention is not limited at all by the following examples unless the gist is exceeded. In the following description of the examples, "parts" are by mass unless otherwise specified.

<Production of electrophotographic photosensitive member>
<Support>
A cylindrical aluminum cylinder having a diameter of 29.9 mm, a length of 357.5 mm and a thickness of 0.7 mm was used as a support.

<Subbing layer>
100 parts by mass of zinc oxide particles (specific surface area: 19 m ² / g, powder resistance: 4.7 × 10 ⁶ Ω · cm) as metal oxides were stirred and mixed with 500 parts by mass of toluene. To this, 0.8 parts by mass of N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a silane coupling agent and stirred for 6 hours. Thereafter, toluene was distilled off under reduced pressure, and the residue was heated and dried at 140 ° C. for 6 hours to obtain surface-treated zinc oxide particles.

  Next, 15 parts by mass of polyvinyl butyral (trade name: S-LEC (registered trademark) B BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 15 parts by mass of blocked isocyanate (trade name: SUMIDUR 3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.) Was dissolved in the mixed solution. The mixed solution is a mixed solution of 73.5 parts by mass of methyl ethyl ketone and 73.5 parts by mass of 1-butanol.

  80.8 parts by mass of the surface-treated zinc oxide particles prepared above and 0.4 parts by mass of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added to this solution, and these were added with a diameter of 0. It disperse | distributed for 3 hours in 23 degreeC atmosphere using the sand mill apparatus using a glass bead of 8 mm. After dispersion, 0.01 parts by mass of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning), crosslinked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER (registered trademark) SSX-103, Sekisui Chemical Co., Ltd. stock 5.6 parts by mass of an average primary particle size of 3.1 μm, manufactured by a company, was added and stirred to prepare a coating solution for undercoat layer.

  The undercoat layer coating solution was dip-coated on the above support, and the obtained coating film was dried at 160 ° C. for 40 minutes to form an undercoat layer having a thickness of 18 μm.

<Charge generation layer>
The following four materials were placed in a sand mill using glass beads with a diameter of 1 mm, dispersed for 4 hours, and then 700 parts by mass of ethyl acetate were added to prepare a coating solution for charge generation layer.
-Hydroxygallium phthalocyanine crystal (charge generating material) having a strong peak at Bragg angles 2θ ± 0.2 ° at 7.4 ° and 28.2 ° in CuKα characteristic X-ray diffraction: 20 parts by mass-polyvinyl butyral ( Brand name: S-LEC (registered trademark) B BX-1, manufactured by Sekisui Chemical Co., Ltd.): 10 parts by mass · Compound represented by the following structural formula (A): 0.2 parts by mass cyclohexanone: 600 parts by mass The layer coating solution was dip-coated on the undercoat layer, and the obtained coated film was dried at 80 ° C. for 15 minutes to form a charge generation layer having a film thickness of 0.18 μm.

<Charge transport layer>
The following four materials were dissolved in a mixed solvent of 600 parts by mass of xylene and 200 parts by mass of dimethoxymethane to prepare a coating liquid for charge transport layer.
Compound represented by the following structural formula (B) (charge transporting substance): 30 parts by mass Compound represented by the following structural formula (C) (charge transporting substance): 60 parts by mass represented by the following structural formula (D) Compound (charge transporting substance): 10 parts by mass Polycarbonate (trade name: Iupilon (registered trademark) Z400, manufactured by Mitsubishi Engineering Plastics Co., Ltd., bisphenol Z type polycarbonate): 100 parts by mass
The coating solution for charge transport layer was dip-coated on the charge generation layer, and the obtained coated film was dried at 110 ° C. for 30 minutes to form a charge transport layer having a thickness of 18 μm.

<Protective layer>
Next, coating liquids 1 to 48 for protective layer were prepared.
A group of particles (particles a-1, 2, 3, 4, 5, 6, particles P) corresponding to the following acrylic resin particles in 100 parts by mass of 1-propanol, a group of melamine resin particles (particle d-1, particles 2, 3, 4, 5), a group of compounds corresponding to compound b (compounds b-4, 5, 6, 10, 11, compound Q, TMPTA), a group of compounds corresponding to compound c (compound c-3 Materials selected from 1, 5, 6, 7, 9, 10, 11 (compounds of structural formula (D)) are mixed and stirred in the types and parts by mass described in Tables 1 and 2 and coating liquid for protective layer 1 to 45, 47 and 48 were obtained.
The mass described in Table 2 for melamine resin particles (d-3), compounds (compound b-9) other than hole transporting compounds, and hole transporting compounds (compound c-5) in 100 parts by mass of 1-butanol The solution was mixed and stirred in a part to obtain a coating solution 46 for protective layer.

  In the coating solutions 1 to 25 for the protective layer, the ratio B / A of the mass B of the compound b to the mass A of the acrylic resin particles, and the mass B of the compound b in the coating solution for forming the surface layer of the mass A of the acrylic particles, The values of the ratio A / (A + B + C) of the mass A of the acrylic resin particles to the sum of the mass C of the compound c and the mass A of the acrylic resin particles are described in Table 1.

  In the coating solutions 26 to 48 for the protective layer, the ratio B / D of the mass B of the compound b to the mass D of the melamine resin particles, and the mass B of the compound b in the coating solution for forming the surface layer of the mass D of the melamine particles, The value of the ratio D / (D + B + C) of the mass D of the melamine resin particles to the sum of the mass C of the compound c and the mass D of the melamine resin particles is described in Table 2.

[Group of particles corresponding to acrylic resin particles]
Particles a-1 manufactured by Sekisui Plastics Co., Ltd. XX-159AP
(Poly (methyl methacrylate) particles, particle size 0.1 μm)
Particles a-2 manufactured by Sekisui Plastics Co., Ltd. XX-160AP
(Poly (methyl methacrylate) particles, particle size 0.1 μm)
Particles a-3 manufactured by Sekisui Plastics Co., Ltd. SSX-102
(Poly methyl methacrylate particles, particle size 2.0 μm)
Particles a-4 Nippon Paint Industrial Coatings Co., Ltd. MG-451
(Polystyrene acrylic particles, particle size 0.1 μm)
Particles a-5 Nippon Paint Industrial Coatings Co., Ltd. FS-201
(Polystyrene acrylic particles, particle size 0.5 μm)
Particles a-6 Nippon Paint Industrial Coatings Co., Ltd. FS-301
(Polystyrene acrylic particles, particle size 1.0 μm)
Particle P made by Shin-Etsu Chemical Co., Ltd. QSG-170
(Silica particles, particle size 0.17 μm)

[Group of particles corresponding to melamine resin particles]
Particle d-1 Nippon Shokuhin Co., Ltd. EPOSTER SS
(Melamine / formaldehyde particles, particle size 0.1 μm)
Particle d-2 Nippon Shokuhin Co., Ltd. EPOSTER S
(Melamine / formaldehyde particles, particle size 0.2 μm)
Particle d-3 Nippon Shokuhin Co., Ltd. EPOSTER S6
(Melamine / formaldehyde particles, particle size 0.4 μm)
Particle d-4 Nippon Shokuhin Co., Ltd. EPOSTER S12
(Melamine / formaldehyde particles, particle size 1.2 μm)
Particles d-5 manufactured by Nippon Shokubai Co., Ltd.
(Melamine / formaldehyde particles, particle size 2.0 μm)

[Group of Compounds Corresponding to Compound b]
Tricelol propane triacrylate (TMPTA) manufactured by Daicel-Cytec Co., Ltd.

[Group of compounds corresponding to compound c]

  These protective layer coating solutions were dip coated on the charge transport layer. Next, the obtained coating film was dried at 40 ° C. for 6 minutes. Then, the electron beam was irradiated to the coating film in nitrogen for 1.6 seconds, rotating a support body (irradiated body) at 200 rpm. The conditions of the electron beam were set so that the absorbed dose was 8000 Gy at an acceleration voltage of 70 kV. Subsequently, the film was heated from 25 ° C. to 120 ° C. in 30 seconds in nitrogen to heat the coating. The oxygen concentration in the atmosphere at the time of electron beam irradiation and subsequent heating was 15 ppm. Next, heat treatment was performed at 100 ° C. for 30 minutes in the air to form a protective layer with a thickness of 5 μm.

As described above, as shown in Table 3, using the protective layer coating liquids 1 to 48, electrophotographic photosensitive members 1 to 48 were formed.
The following evaluation was performed using the coating liquids 1 to 48 for a protective layer and the electrophotographic photosensitive members 1 to 48.

[Evaluation]
<Evaluation of Aging of Coating Liquid for Protective Layer>
The coating solution for protective layer was put in a glass bottle, sealed, and allowed to stand in a cold dark place for 1 week, and then the added particles were visually observed to see if it had settled. The results are shown in Tables 1 and 2. More specifically, in the protective layer coating liquids 10, 25, 44 and 45, the particles were sedimented. It was confirmed that these glass bottles were shaken by hand and dispersed again, although the protective layer coating solution 25 was not dispersed, the protective layer coating solutions 10, 44 and 45 were dispersed again. Therefore, the coating solution for forming a surface layer formed by the production method of the present invention has a long pot life and is preferable from the viewpoint of productivity.

<Evaluation of Function of Electrophotographic Photoreceptor>
It was evaluated whether the produced electrophotographic photosensitive member had no problem in the function of the basic electrophotographic photosensitive member such as electrical characteristics and developability. Image electrophotographic photosensitive members 1, 8, 11, 13, 19, 26, 32, 34, 39, 40, 42 are mounted on an image RUNNER (registered trademark) -ADV 4545 (manufactured by Canon Inc.), and problems with images are caused. Was confirmed. When 10,000 A4 images having a printing ratio of 5% were output in an environment of 23 ° C. and 50% RH, no abnormality occurred in the images of any of the electrophotographic photosensitive members. Therefore, the electrophotographic photosensitive member produced by the production method of the present invention sufficiently satisfies the function as an electrophotographic photosensitive member.

<Evaluation of lubricity>
The dynamic friction coefficient was measured with a rotating Haydon. The rotary Haydon has a mechanism that supports and rotates the electrophotographic photosensitive member, a mechanism that abuts and supports the cleaning blade on the surface of the electrophotographic photosensitive member with a desired angle and penetration amount, and a mechanism that abuts and supports the cleaning blade And detecting means for detecting As the cleaning blade, a urethane rubber blade having a wall hardness (the value of method M of the IRHD hardness test method) of 77 degrees and a rebound resilience of 20% was used. A blade having a width of 10 mm, a thickness of 2 mm and a free length of 8 mm was rotated at a set angle of 25 °, an intrusion amount of 1.4 mm, and a rotational speed of 168 rpm. Reading the tangential load of the electrophotographic photosensitive member at the blade contact portion obtained by the detection means and the normal load one minute after the start of rotation and dividing the tangential load by the normal load Dynamic friction coefficient was calculated by The results are shown in Table 2. In the electrophotographic photosensitive members 21, 24, 25, and 47, the blade was twisted during measurement, and the dynamic friction coefficient could not be measured.

<Evaluation of wear resistance>
Using the Heidon: Type 14 manufactured by Shinto Scientific Co., Ltd., the method of surface scratch hardness JIS K5600 was simulated to evaluate the ease with which the surface layer was scratched. The electrophotographic photosensitive member was brought into contact with a conical scratching needle (diamond needle) with a tip radius of 0.03 mm, and a vertical load of 30 g was applied with a weight. The depth of the scratch formed in the circumferential direction of the electrophotographic photosensitive member was evaluated by the mechanism of rotatably supporting the electrophotographic photosensitive member separately prepared from Heidon: Type 14 at a speed of 1 rpm. The depth is measured using a surface roughness measuring machine Surfcoder SE3500 manufactured by Kosaka Laboratory Ltd., and the maximum height Rmax according to JIS B 0601 (1982) in the generatrix direction of the electrophotographic photosensitive member (in the direction crossing the scratch). It was measured. The results are shown in Table 3.

  According to the production method of the present invention, at least one of the acrylic resin particles and the melamine resin particles is contained in the surface layer only by mixing and stirring at least one of the acrylic resin particles and the melamine resin particles in the coating solution. An electrophotographic photosensitive member having excellent abrasion resistance and lubricity can be produced.

DESCRIPTION OF SYMBOLS 1 electrophotographic photosensitive member 2 axis 3 Charging means 4 Exposure light 5 Development means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means

Claims (15)

Organic resin particles of at least one of acrylic resin particles and melamine resin particles,
A compound having a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule,
A hole transporting compound having a polymerizable functional group,
A method of producing an electrophotographic photosensitive member, comprising: applying a coating solution for forming a surface layer containing the above; and curing the formed coating film to form a surface layer.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the organic resin particles are acrylic resin particles.   The ratio B / A of the mass B of the compound having the monovalent hydrocarbon group having 7 or more carbon atoms and the polymerizable functional group in the same molecule to the mass A of the acrylic resin particles is 8 mass% or more The method for producing an electrophotographic photosensitive member according to claim 2 characterized by the above.   The mass A of the acrylic resin particles, the mass B of the compound having the monovalent hydrocarbon group having 7 or more carbon atoms and the polymerizable functional group in the same molecule, and the hole transporting compound having the polymerizable functional group 4. The electrophotographic photosensitive member according to claim 2, wherein a ratio A / (A + B + C) of the mass A of the acrylic resin particles to the total mass C of the particles is 10% by mass to 25% by mass. Manufacturing method. The method for producing an electrophotographic photosensitive member according to any one of claims 2 to 4, wherein the acrylic resin particles are particles containing a styrene acrylic resin.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the organic resin particles are melamine resin particles.   A ratio B / D of mass B of a compound having a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule to mass D of the melamine resin particle is 10 mass% or more. A method of manufacturing an electrophotographic photosensitive member according to claim 6.   Hole transportable compound having the mass D of the melamine resin particle, the mass B of the compound having the monovalent hydrocarbon group having 7 or more carbon atoms and the polymerizable functional group in the same molecule, and the polymerizable functional group 8. The electrophotographic photosensitive member according to claim 6, wherein a ratio D / (D + B + C) of the mass D of the melamine resin particles to the total mass C of the particles is 13% by mass or more and 32% by mass or less. Manufacturing method.   The method for producing an electrophotographic photosensitive member according to any one of claims 5 to 8, wherein the melamine resin particles are particles containing a melamine / formaldehyde resin. 10. The compound according to any one of claims 1 to 9, wherein the compound having the monovalent hydrocarbon group having 7 or more carbon atoms and the polymerizable functional group in the same molecule is a compound represented by the following formula (1). A method for producing an electrophotographic photosensitive member according to item 1.
(In formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is a linear or branched alkyl group having 7 or more carbon atoms. X is —OCO— (oxy A carbonyl group) or -COO- (carbonyloxy group))   The hole transportable compound having a polymerizable functional group is a hole transportable compound having an acryloyloxy group or a hole transportable compound having a methacryloyloxy group. A method for producing an electrophotographic photosensitive member according to item 1. The method for producing an electrophotographic photosensitive member according to any one of claims 1 to 10, wherein the hole transporting compound having a polymerizable functional group is a compound represented by the following formula (2). .
(In the formula (2), P ¹ is a polymerizable functional group, a monovalent group represented by the following formula (3), a monovalent group represented by the following formula (4), a formula (5) below, Or a is a group represented by the following formula (6), a is an integer of 1 or more and 4 or less, and when a is 2 or more, a pieces of P 1 may be the same or different. The hydrogen adduct in which P ¹ in the above formula (2) is replaced by a hydrogen atom is a compound represented by the following formula (7) or the following formula (8).
In the formula (7), R ₃₁ is a phenyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, or biphenyl which may have an alkyl group having 1 to 3 carbon atoms as a substituent Indicates a group. R ³² and R ³³ each represent a phenyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent. R ³¹ , R ³² and R ³³ may be identical to or different from each other.
In formula (8), R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ each represent a phenyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent.
R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ may be identical to or different from each other.
R ³⁸ and R ^{39 each} represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
R ³⁸ and R ³⁹ may be identical to or different from each other. )   The method for producing an electrophotographic photosensitive member according to any one of claims 1 to 12, wherein a particle diameter of the organic resin particles is 1.0 μm or less.   The method for producing an electrophotographic photosensitive member according to any one of claims 1 to 13, wherein the coating solution for forming the surface layer contains an alcohol having 3 or less carbon atoms.   In an electrophotographic photosensitive member having a support and a photosensitive layer formed on the support, the surface layer of the electrophotographic photosensitive member has a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule. An electrophotographic photosensitive member comprising: a compound contained therein; a hole transporting compound having a polymerizable functional group; and at least one of an acrylic resin particle and a melamine resin particle.