JP6955333B2 - Electrophotographic photosensitive member, its manufacturing method, process cartridge and electrophotographic apparatus - Google Patents

Description

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

The electrophotographic photosensitive member mounted on the electrophotographic apparatus includes an organic electrophotographic photosensitive member containing an organic photoconductive substance (charge generating substance) (hereinafter referred to as “electrophotographic photosensitive member”), and a wide range of studies have been conducted so far. Has been done. In recent years, there has been a demand for improving the mechanical durability (wear resistance) of electrophotographic photosensitive members for the purpose of extending the life of electrophotographic photosensitive members and improving the image quality during repeated use, and many attempts have been made to date. Has been made.

As a method for improving abrasion resistance, for example, Patent Document 1 describes an electrophotographic photosensitive member having a surface layer cured by applying a solution containing a photocurable acrylic monomer. Further, Patent Document 2 describes an electrophotographic photosensitive member in which inorganic fine particles are dispersed in a surface layer.

Japanese Unexamined Patent Publication No. 5-40360 Japanese Unexamined Patent Publication No. 4-281461

Inorganic fine particles such as metal oxides are highly hydrophilic because many hydroxyl groups are present on the particle surface. Therefore, the electrophotographic photosensitive member in which inorganic fine particles are dispersed in the surface layer exhibits excellent wear resistance, but the surface becomes highly hydrophilic, resulting in image defects (image flow) that occur in a high humidity environment. ) Level deteriorates significantly.

An object of the present invention is to provide an electrophotographic photosensitive member which exhibits good wear resistance and good electrical characteristics and can suppress image defects such as image flow for a long period of time, and a method for producing the same. A further object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

（式（１）中、Ｒ ^１ は、炭素数１１以上の直鎖状あるいは分岐状のアルキル基であり、Ｐ ^１ は、前記連鎖重合性官能基Ａと重合可能な連鎖重合性官能基Ｂを有する１価の官能基である。） In the present invention, in an electrophotographic photosensitive member having a support and a photosensitive layer, the surface layer of the electrophotographic photosensitive member comprises a copolymer and a non-polymerizable hole-transporting compound having a triphenylamine skeleton. contained, the copolymerization product is a non-positive hole transport chain polymerizable compound having a chain polymerizable functional group a is selected from the group consisting of chain polymerizable functional groups two or more, represented by the following formula (1) and no fine particles that have a structure on the surface to be directed to the copolymer der electrophotographic photoreceptor according to claim Rukoto.

In the formula (1), R ¹ is a linear or branched alkyl group having 11 or more carbon atoms, and P ¹ is a chain-growth functional group B that can be polymerized with the chain-growth functional group A. It is a monovalent functional group having.)

The A chain polymerizable functional group, a monovalent chain-polymerizable functional group capable of containing a functional group represented by the following formula (P-1) ~ (P -7).

（式（５）中、Ｒ ^１ は、炭素数１１以上の直鎖状あるいは分岐状のアルキル基であり、Ｐ ^１ は、前記連鎖重合性官能基Ａと重合可能な連鎖重合性官能基Ｂを有する１価の官能基であり、Ｘ ^１ およびＸ ^２ は、それぞれ、アルコキシ基である。）
前記表面処理剤は単独で用いても複数で用いてもよく、該表面処理工程で表面処理された特定の無機微粒子は、炭素数１１以上の直鎖状あるいは分岐状のアルキル基および前記連鎖重合性官能基Ａと重合可能な連鎖重合性官能基Ｂを表面に有する。
また、前記連鎖重合性官能基とは、上記式（Ｐ−１）〜（Ｐ−７）で示される１価の官能基を含む連鎖重合が可能な官能基である。 Further, the present invention is a method for producing an electrophotographic photosensitive member having a support and a surface layer provided on the support, wherein the production method is an inorganic surface treatment agent represented by the following formula (5). a surface treatment step of the fine particles to surface treatment, the method comprising the steps of: preparing a front surface layer coating solution, to form a coating film of the surface layer coating solution, the surface of the electrophotographic photosensitive member by curing the coating film possess a step of forming a layer, in this order, the surface layer coating solution, the positive hole transport compound of non-polymerizable with the triphenylamine skeleton, two or more the chain polymerizable functional group a An electrophotographic feature containing a non-hole-transporting chain-polymerizable compound having a structure, and inorganic fine particles having a structure represented by the formula (1) on the surface, which has been surface-treated in the surface treatment step. The present invention relates to a method for producing a photoconductor.

In the formula (5), R ¹ is a linear or branched alkyl group having 11 or more carbon atoms, and P ¹ is a chain-growth functional group B that can be polymerized with the chain-growth functional group A. It is a monovalent functional group having, and X ¹ and X ² are each an alkoxy group.)
The surface treatment agent may be used alone or in combination of two, and the specific inorganic fine particles surface-treated in the surface treatment step include a linear or branched alkyl group having 11 or more carbon atoms and the chain polymerization. It has a chain-growth functional group B that can be polymerized with the sex functional group A on its surface.
Further, with the chain-polymerizable functional group, a monovalent chain-polymerizable functional group capable of containing a functional group represented by the formula (P-1) ~ (P -7).

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

The present invention also relates to the electrophotographic photosensitive member and an electrophotographic apparatus having charging means, exposure means, developing means and transfer means.

According to the present invention, it is possible to provide an electrophotographic photosensitive member which exhibits good wear resistance and good electrical characteristics and can suppress image defects such as image flow for a long period of time, and a method for producing the same. Further, according to the present invention, it is possible to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

It is a figure which shows an example of the schematic structure of the electrophotographic apparatus provided with the process cartridge which has the electrophotographic photosensitive member of this invention. It is a figure for demonstrating an example of the layer structure of the electrophotographic photosensitive member of this invention.

The electrophotographic photosensitive member of the present invention has a support and a photosensitive layer provided on the support. In the present invention, the electrophotographic photosensitive member, the above formula (P-1) ~ (P -7) chain polymerizable functional group selected from the group consisting of chain-polymerizable functional group containing a group represented by any one of non having a non-positive hole transport chain polymerizable compound having two or more a, and a copolymer of free fine particles of the structure that Yusuke on the surface of the above-described formula (1), a triphenylamine skeleton It is characterized by having a surface layer containing a polymerizable hole-transporting compound.

これらの中でも、連鎖重合性官能基Ａは上記式（Ｐ−１）または（Ｐ−２）のいずれかが特に好ましく、より良好な耐摩耗性を示す電子写真感光体を得ることができる。 Hereinafter, the structure of the surface layer according to the present invention will be described.
[Non-hole transporting chain-growth polymerizable compound]
Non hole transporting chain polymerizable compound according to the present invention, selected from the group consisting of groups represented by any one of the following formulas (P-1) ~ (P -7) from including chained polymerizable functional group It has two or more monovalent chain-growth functional groups A. Since this chain-growth polymerizable compound is polymerized and the surface layer of the electrophotographic photosensitive member has a dense crosslinked structure, an electrophotographic photosensitive member showing good wear resistance can be obtained.

Among these, the chain-growth functional group A is particularly preferably one of the above formulas (P-1) or (P-2), and an electrophotographic photosensitive member exhibiting better wear resistance can be obtained.

式（２）中、Ｒ^２１〜Ｒ^２４は、それぞれ、水素原子、炭素数１以上２以下のアルキル基、ヒドロキシ基、アクリロイルオキシ基、または、メタクリロイルオキシ基であり、式（２）で示される化合物中のアクリロイルオキシ基およびメタクリロイルオキシ基の総数は３または４である。

式（３）中、Ｒ^３１〜Ｒ^３６は、それぞれ、水素原子、炭素数１以上２以下のアルキル基、ヒドロキシ基、アクリロイルオキシ基、または、メタクリロイルオキシ基であり、式（３）で示される化合物中のアクリロイルオキシ基およびメタクリロイルオキシ基の総数は３以上６以下である。 Further, the non-hole transporting chain-growth polymerizable compound is preferably a compound represented by the following formula (2) or (3), and an electrophotographic photosensitive member showing better wear resistance can be obtained. ..

In the formula ^(2), R 21 ^{to R 24} are each a hydrogen atom, 1 to 2 alkyl groups carbon atoms, a hydroxyalkyl group, acryloyloxy group, or a methacryloyloxy group, represented by formula (2) acrylate total acryloyloxy group and methacryloyloxy group in the compound is 3 or 4.

In the formula ^(3), R 31 ^{to R 36} are each a hydrogen atom, 1 to 2 alkyl groups carbon atoms, a hydroxyalkyl group, acryloyloxy group, or a methacryloyloxy group, represented by the formula (3) acrylate total acryloyloxy group and methacryloyloxy group in a compound is 3 to 6.

Specific examples (A-1) to (A-12) of the non-hole transporting chain-growth compound are given below, but the present invention is not limited thereto.

[Specific inorganic fine particles]
The specific inorganic fine particles according to the present invention have a linear or branched alkyl group having 11 or more carbon atoms and a chain-growth functional group B which can be polymerized with the chain-growth functional group A on the surface.

By having a linear or branched alkyl group having 11 or more carbon atoms on the surface of the specific inorganic fine particles, it is possible to impart hydrophobicity to the inorganic fine particles which are originally highly hydrophilic. Therefore, the hydrophobicity of the surface of the electrophotographic photosensitive member is improved, and the effect of suppressing image defects such as image flow can be exhibited. Further, by having the chain-growth functional group A and the chain-growth functional group B that can be polymerized on the surface, it polymerizes with the non-hole-transporting chain-polymerizable compound, and in the surface layer of the above-mentioned electrophotographic photosensitive member. Specific inorganic fine particles can be incorporated into the dense crosslinked structure. Therefore, it is possible to show the effect of suppressing image defects such as image flow over a long period of time.

The chain-growth functional group B that can be polymerized with the chain-growth functional group A is preferably represented by the following formulas (P-1) to (P-3). Particularly preferably, the chain-growth functional group B has the following formula (P-3). Having these chain-growth functional groups on the surface allows certain inorganic microparticles to be properly incorporated into the dense crosslinked structure in the surface layer of the electrophotographic photosensitive member described above, thus providing better wear resistance and electrical properties. The electrophotographic photosensitive member shown can be obtained.

The linear or branched alkyl group preferably has 16 or more and 20 or less carbon atoms. When the number of carbon atoms is 16 or more, the surface layer of the electrophotographic photosensitive member has sufficient hydrophobicity, and it is possible to obtain a more excellent effect of suppressing image defects such as image flow. Further, when the number of carbon atoms is 20 or less, the surface layer has sufficient hardness, so that an electrophotographic photosensitive member exhibiting more excellent wear resistance can be obtained.

These specific inorganic fine particles can be obtained by surface-treating the inorganic fine particles (base material fine particles) with a surface treatment agent.
Examples of the base material fine particles include magnesium oxide, zinc oxide, lead oxide, aluminum oxide, silicon oxide, tantalum oxide, indium oxide, bismuth oxide, yttrium oxide, cobalt oxide, copper oxide, manganese oxide, selenium oxide, and iron oxide. Examples include metal oxides such as zirconium oxide, germanium oxide, tin oxide, titanium oxide, niobium oxide, molybdenum oxide, and vanadium oxide.
Among these, zinc oxide, tin oxide, and titanium oxide are particularly preferable, and an electrophotographic photosensitive member exhibiting good electrical characteristics can be obtained.

式（５）中、Ｒ^１は炭素数１１以上の直鎖状あるいは分岐状のアルキル基であり、Ｐ^１は前記連鎖重合性官能基Ａと重合可能な連鎖重合性官能基Ｂを有する１価の官能基であり、Ｘ¹およびＸ^２はそれぞれアルコキシ基である。 The surface treatment agent used for the surface treatment may be one or more.
When surface treatment is performed using a single surface treatment agent, specific inorganic fine particles according to the present invention can be obtained by using the surface treatment agent represented by the following formula (5).

In the formula (5), R ¹ is a linear or branched alkyl group having 11 or more carbon atoms, and P ¹ is a monovalent group having a chain-growth functional group A polymerizable with the chain-growth functional group A. X ¹ and X ² are alkoxy groups, respectively.

式（１）中、Ｒ^１は炭素数１１以上の直鎖状あるいは分岐状のアルキル基であり、Ｐ^１は前記連鎖重合性官能基Ａと重合可能な連鎖重合性官能基Ｂを有する１価の官能基である。 The specific inorganic fine particles surface-treated with the surface treatment agent represented by the following formula (5) have a structure represented by the above formula (1) on its surface.

In the formula (1), R ¹ is a linear or branched alkyl group having 11 or more carbon atoms, and P ¹ is a monovalent group having a chain-growth functional group A polymerizable with the chain-growth functional group A. Functional group.

Specific examples of the surface treatment agent represented by the formula (5) are given below, but the present invention is not limited thereto.

When surface treatment is performed using a plurality of surface treatment agents, specific inorganic fine particles according to the present invention can be obtained by using at least the following two types of surface treatment agents 6A and 6B, respectively.
Surface treatment agent 6A: A silane coupling agent having a linear or branched alkyl group having 11 or more carbon atoms Surface treatment agent 6B: 1 including the chain-growth functional group A and a polymerizable functional group B that can be polymerized. Silane coupling agent having a valence group

式（６Ａ）中、Ｒ^１は炭素数１１以上の直鎖状あるいは分岐状のアルキル基であり、Ｘ¹およびＸ^２はそれぞれアルコキシ基であり、Ｙ^１は炭素数１以上３以下のアルキル基、アルコキシ基、シロキシ基、アミノキシ基、フェノキシ基のいずれかである。

式（６Ｂ）中、Ｐ^１は前記連鎖重合性官能基Ａと重合可能な連鎖重合性官能基Ｂを有する１価の官能基であり、Ｘ¹およびＸ^２はそれぞれアルコキシ基であり、Ｙ^１は炭素数１以上３以下のアルキル基、アルコキシ基、シロキシ基、アミノキシ基、フェノキシ基のいずれかである。

The specific inorganic fine particles surface-treated with the surface treatment agents 6A and 6B, respectively, have the structures represented by the following formulas (6A) and (6B) on the surface, respectively.

In formula (6A), R ¹ is a linear or branched alkyl group having 11 or more carbon atoms, X ¹ and X ² are alkoxy groups, respectively, and Y ¹ is an alkyl group having 1 or more carbon atoms and 3 or less carbon atoms. , Alkoxy group, syroxy group, aminoxy group, phenoxy group.

In formula (6B), P ¹ is a monovalent functional group having the chain polymerizable functional group A and a polymerizable chain polymerizable functional group B, and X ¹ and X ² are alkoxy groups, respectively, and Y ¹ Is any of an alkyl group having 1 or more and 3 or less carbon atoms, an alkoxy group, a syroxy group, an aminoxy group, and a phenoxy group.

Hereinafter, specific examples of the surface treatment agents 6A and 6B include, but are not limited to, the exemplified compounds (6A-1) to (6B-6).

As a method for surface-treating the substrate fine particles, a wet method of mixing and stirring the substrate fine particles and the surface treatment agent in a solvent to remove the solvent can be used. It is preferable to use 0.1 to 200 parts of the surface treatment agent, more preferably 7 to 70 parts, and 50 to 5000 parts of the solvent with respect to 100 parts of the base material fine particles.

基材微粒子や表面処理剤をそれぞれ変更することで、本発明に係る特定の無機微粒子を任意に得ることができる。 An example of the surface treatment step of the specific inorganic fine particles according to the present invention is shown below.
(Manufacturing Example 1)
100 parts of tin oxide particles, 10 parts of the surface treatment agent represented by the above-exemplified compound (5-1), and 500 parts of toluene were stirred and mixed for 6 hours. Then, toluene was distilled off under reduced pressure, and the mixture was heated and dried at 130 ° C. for 2 hours to obtain specific inorganic fine particles (B-1) having a structure represented by the following formula (7) on the surface.

By changing the base material fine particles and the surface treatment agent, the specific inorganic fine particles according to the present invention can be arbitrarily obtained.

基材微粒子や表面処理剤６Ａおよび表面処理剤６Ｂをそれぞれ変更することで、本発明に係る特定の無機微粒子を任意に得ることができる。 (Manufacturing Example 2)
100 parts of tin oxide particles, 5 parts of the surface treatment agent represented by the above-mentioned exemplary compound (6A-1), 5 parts of the surface treatment agent shown by the above-mentioned example compound (6B-1), and 500 parts of toluene were stirred and mixed for 6 hours. Then, toluene is distilled off under reduced pressure, and the mixture is heated and dried at 130 ° C. for 2 hours to obtain specific inorganic fine particles (B-21) having the structures represented by the following formulas (8A) and (8B) on their surfaces. Got

By changing the base material fine particles, the surface treatment agent 6A, and the surface treatment agent 6B, respectively, the specific inorganic fine particles according to the present invention can be arbitrarily obtained.

Table 1 shows examples of specific inorganic fine particles obtained by the above surface treatment step. The specific inorganic fine particles according to the present invention are not limited to these.

式（４）中、Ｒ^４１〜Ｒ^４４はそれぞれ水素原子、炭素数１以上３以下のアルキル基、炭素数１以上３以下のアルコキシ基であり、ｎ^１〜ｎ^３は１以上５以下の整数、ｎ^４は１以上４以下の整数である。また、ｎ^１〜ｎ^４が２以上の整数である場合、これら複数の基は同一であっても、異なっていてもよい。 [Non-polymerizable hole-transporting compound]
The non-polymerizable hole-transporting compound according to the present invention has a triphenylamine skeleton. The triphenylamine skeleton is known to have excellent hole transport properties, and an electrophotographic photosensitive member showing good electrical properties can be obtained. The non-polymerizable hole-transporting compound is preferably a compound represented by the following formula (4), and since aggregation of the hole-transporting compound is suppressed, an electrophotographic photosensitive member exhibiting better electrical characteristics. Can be obtained.

In formula (4), R ^{41 to} R ⁴⁴ are hydrogen atoms, alkyl groups having 1 or more and 3 or less carbon atoms, and alkoxy groups having 1 or more carbon atoms and 3 or less carbon atoms, respectively, and n ^{1 to} n ³ are integers of 1 or more and 5 or less. , N ⁴ is an integer of 1 or more and 4 or less. Further, when n ^{1 to} n ⁴ are integers of 2 or more, these plurality of groups may be the same or different.

Hereinafter, specific examples of the non-polymerizable hole-transporting compound having a triphenylamine skeleton are exemplified compounds (C-1) to (C-8), but the present invention is not limited thereto. No.

The surface layer is a non-hole-transporting chain-polymerizable compound having two or more chain-polymerizable functional groups A selected from the chain-polymerizable functional group group, and a linear or branched alkyl group having 11 or more carbon atoms. And a coating for a surface layer containing specific inorganic fine particles having a chain-polymerizable functional group A and a polymerizable chain-polymerizable functional group B on the surface and a non-polymerizable hole-transporting compound having a triphenylamine skeleton. It can be formed by forming a liquid coating film and curing the coating film.

In addition, various additives can be added to the surface layer. As the additive, for example, a deterioration inhibitor such as an antioxidant or an ultraviolet absorber, or a lubricant such as polytetrafluoroethylene (PTFE) particles or carbon fluoride can be used. Further, a polymerization inhibitor such as a polymerization reaction initiator and a polymerization reaction terminator, a leveling agent such as a siloxane-modified acrylic compound and silicone oil, and a surfactant can also be used. The siloxane-modified acrylic compound is a compound in which siloxane is introduced as a side chain into an acrylic polymer, and is obtained, for example, by copolymerizing an acrylic monomer and a siloxane having an acrylic group.

When the surface layer is a protective layer, the film thickness is preferably 0.1 μm or more and 15 μm or less. Further, it is more preferably 0.5 μm or more and 10 μm or less.

As the solvent used for preparing the coating liquid for the surface layer, it is preferable to use a solvent that does not dissolve the layer provided under the surface layer. More preferably, it is an alcohol solvent such as methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 1-methoxy-2-propanol and the like.

As a means for curing the coating film of the coating liquid for the surface layer, a method of curing by heat, ultraviolet rays, or electron beam irradiation can be mentioned. In order to maintain the strength of the surface layer and the durability of the electrophotographic photosensitive member, it is preferable to cure using ultraviolet rays or electron beams.

Polymerization using an electron beam is preferable because a very dense (high density) cured product (three-dimensional crosslinked structure) can be obtained and a surface layer having higher durability can be obtained. When irradiating an electron beam, examples of the accelerator include a scanning type, an electrocurtain type, a broad beam type, a pulse type, and a laminar type.

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

Further, when the above composition is cured (polymerized) using an electron beam, it is possible to irradiate the composition with the electron beam in an inert gas atmosphere and then heat it in the inert gas atmosphere for the purpose of suppressing the polymerization inhibitory action by oxygen. preferable. Examples of the inert gas include nitrogen, argon and helium.

Further, it is preferable to heat the electrophotographic photosensitive member to 100 ° C. or higher and 170 ° C. or lower after irradiation with ultraviolet rays or electron beams. By doing so, a surface layer having higher durability and suppressing image defects can be obtained.

Next, the overall configuration and manufacturing method of the electrophotographic photosensitive member of the present invention will be described.
[Electrophotophotoreceptor]
The electrophotographic photosensitive member of the present invention has a support and a photosensitive layer. Examples of the photosensitive layer include a single-layer photosensitive layer containing both a charge generating substance and a charge transporting substance, and a laminated photosensitive layer separated into a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance. Can be mentioned. In the present invention, a laminated photosensitive layer is preferable.

FIG. 2 is a diagram showing an example of the layer structure of the electrophotographic photosensitive member. In FIG. 2, the electrophotographic photosensitive member has a support 21, an undercoat layer 22, a charge generation layer 23, a charge transport layer 24, and a protective layer 25. In this case, the charge generation layer 23 and the charge transport layer 24 form a photosensitive layer, and the protective layer 25 is a surface layer. When the protective layer is not provided, the charge transport layer 24 is the surface layer. In the present invention, it is preferable that the protective layer provided on the charge transport layer is used as the surface layer.

Hereinafter, the electrophotographic photosensitive member of the present invention will be further described by taking as an example an electrophotographic photosensitive member having a protective layer and the protective layer is a surface layer.
[Support]
As the support used for the electrophotographic photosensitive member, a support having conductivity (conductive support) is preferable. For example, supports made of metal or alloy such as iron, copper, gold, silver, aluminum, zinc, titanium, lead, nickel, tin, antimony, indium, chromium, aluminum alloy and stainless steel. Further, a metal support or a resin support having a coating film formed by vacuum vapor deposition of aluminum, an aluminum alloy, an indium tin oxide alloy, or the like can also be used. Further, a support formed by impregnating a resin with conductive particles such as carbon black, tin oxide particles, titanium oxide particles, and silver particles, and a support containing a conductive resin can also be used. Examples of the shape of the support include a cylindrical shape, a belt shape, a sheet shape, a plate shape, and the like, but in the present invention, the cylindrical shape is preferable.
The surface of the support may be subjected to cutting treatment, roughening treatment, alumite treatment or the like for the purpose of suppressing interference fringes due to scattering of laser light.

A conductive layer may be provided between the support and the photosensitive layer or the undercoat layer for the purpose of suppressing interference fringes due to scattering of a laser or the like and covering scratches on the support.
The conductive layer is formed by applying a coating liquid for a conductive layer obtained by dispersing conductive particles together with a binder resin and a solvent to form a coating film, and drying and / or curing the obtained coating film. can do.

Examples of the conductive particles used in the conductive layer include metal particles such as carbon black, acetylene black, aluminum, nickel, iron, dichrome, copper, zinc, and silver, zinc oxide, titanium oxide, tin oxide, and antimony oxide. , Indium oxide, bismuth oxide, particles of metal oxides such as ITO, and the like. Further, indium oxide doped with tin and tin oxide doped with antimony or tantalum may be used.

Examples of the solvent for the coating liquid for the conductive layer include ether solvents, alcohol solvents, ketone solvents, aromatic hydrocarbon solvents and the like. The film thickness of the conductive layer is preferably 0.1 μm or more and 50 μm or less, more preferably 0.5 μm or more and 40 μm or less, and further preferably 1 μm or more and 30 μm or less.

Examples of the binder resin used for the conductive layer include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, and trifluoroethylene, and polyvinyl alcohol. Examples thereof include resins, polyvinyl acetal resins, polycarbonate resins, polyester resins, polysulfone resins, polyphenylene oxide resins, polyurethane resins, cellulose resins, phenol resins, melamine resins, silicon resins, epoxy resins and isocyanate resins.

An undercoat layer (intermediate layer) may be provided between the support or the conductive layer and the charge generation layer.
The undercoat layer can be formed by applying a coating liquid for an undercoat layer obtained by dissolving a binder resin in a solvent to form a coating film, and drying the obtained coating film.

Examples of the binder resin used for the undercoat layer include polyvinyl alcohol resin, poly-N-vinylimidazole, polyethylene oxide resin, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide resin, and N-methoxymethylated 6 Examples thereof include nylon resin, copolymerized nylon resin, phenol resin, polyurethane resin, epoxy resin, acrylic resin, melamine resin, and polyester resin.

The undercoat layer may further contain metal oxide particles. For example, particles containing titanium oxide, zinc oxide, tin oxide, zirconium oxide, and aluminum oxide can be mentioned. Further, the metal oxide particles may be metal oxide particles in which the surface of the metal oxide particles is treated with a surface treatment agent such as a silane coupling agent.

As the solvent used for the coating liquid for the undercoat layer, organic solvents such as alcohol-based solvent, sulfoxide-based solvent, ketone-based solvent, ether-based solvent, ester-based solvent, aliphatic halogenated hydrocarbon-based solvent, and aromatic compound are used. Can be mentioned. The film thickness of the undercoat layer is preferably 0.05 μm or more and 30 μm or less, and more preferably 1 μm or more and 25 μm or less. The undercoat layer may further contain organic resin fine particles and a leveling agent.

[Photosensitive layer]
A photosensitive layer is provided on the support, the conductive layer, or the undercoat layer.

In the case of a laminated photosensitive layer, the charge generating layer is formed by mixing a charge generating substance and a binder resin with a solvent and applying a coating liquid for the charge generating layer obtained by dispersion treatment to form a coating film. It can be formed by drying the coating film. Further, the charge generation layer may be a vapor deposition film of a charge generation substance.

Examples of the charge generating substance used in the charge generating layer include azo pigments, phthalocyanine pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, squarylium pigments, pyrylium salts, thiapyrylium salts, triphenylmethane pigments, quinacridone pigments, and azulenium salts. Examples thereof include pigments, cyanine dyes, anthanthron pigments, pyranthron pigments, xanthene pigments, quinoneimine pigments, and styryl pigments. Only one kind of charge generating substance may be used, or two or more kinds may be used. Among the charge generating substances, phthalocyanine pigments and azo pigments are preferable from the viewpoint of sensitivity, and phthalocyanine pigments are more preferable.

Examples of the binder resin used for the charge generation layer include polymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, and trifluoroethylene, polyvinyl alcohol resin, and polyvinyl. Examples thereof include acetal resin, polycarbonate resin, polyester resin, polysulfone resin, polyphenylene oxide resin, polyurethane resin, cellulose resin, phenol resin, melamine resin, silicon resin and epoxy resin.

The mass ratio of the charge generating substance to the binding resin (charge generating substance: binding resin) is preferably in the range of 1: 0.3 to 1: 4.
Examples of the dispersion treatment method include a method using a homogenizer, ultrasonic dispersion, a ball mill, a vibrating ball mill, a sand mill, an attritor, and a roll mill.

Examples of the solvent used in the coating liquid for the charge generation layer include alcohol-based solvents, sulfoxide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, aliphatic halogenated hydrocarbon-based solvents, and aromatic compounds.

The film thickness of the charge generation layer is preferably 0.01 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 1 μm or less. Further, various sensitizers, antioxidants, ultraviolet absorbers, and plasticizers can be added to the charge generation layer, if necessary.

Next, the charge transport layer will be described. The charge transport layer is formed on the charge generation layer. The charge transport layer is formed by applying a coating liquid for a charge transport layer obtained by dissolving a charge transport substance and a binder resin in a solvent to form a coating film, and drying the obtained coating film. Can be done.

Examples of the binder resin used for the charge transport layer include polyvinyl butyral, polycarbonate resin, polyester resin, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyamide, polyvinylpyridine, cellulose resin, urethane resin, and epoxy resin. .. A polycarbonate resin is preferable.

Examples of the charge transporting substance used in the charge transporting layer include a triarylamine compound, a hydrazone compound, a stillben compound, a pyrazoline compound, an oxazole compound, a triarylmethane compound, and a thiazole compound. Only one type of charge transporting substance may be used, or two or more types may be used.

The ratio of the charge-transporting substance to the binder resin in the charge-transporting layer is preferably 0.3 parts by mass or more and 10 parts by mass or less of the charge-transporting substance with respect to 1 part by mass of the binder resin.
Further, from the viewpoint of suppressing cracks in the charge transport layer, the drying temperature is preferably 60 ° C. or higher and 150 ° C. or lower, and more preferably 80 ° C. or higher and 120 ° C. or lower. The drying time is preferably 10 minutes or more and 60 minutes or less.

Examples of the solvent used in the coating liquid for the charge transport layer include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbon solvents, aromatic hydrocarbon solvents and the like.
The film thickness of the charge transport layer is preferably 5 μm to 40 μm, and more preferably 10 μm to 35 μm.

Further, an antioxidant, an ultraviolet absorber, a plasticizer, metal oxide particles, and inorganic particles can be added to the charge transport layer as needed. Further, fluorine atom-containing resin particles, silicone-containing resin particles, and the like may be contained.

As described above, the protective layer, which is the surface layer, contains a non-hole-transporting chain-polymerizable compound having two or more chain-polymerizable functional groups A selected from the chain-polymerizable functional group group and 11 carbon atoms. Specific inorganic fine particles having the above linear or branched alkyl group and the chain polymerizable functional group B polymerizable with the chain polymerizable functional group A on the surface, and a non-polymerizable positive having a triphenylamine skeleton. It can be formed by forming a coating film of a coating liquid for a surface layer containing a pore-transporting compound and curing the coating film.

When applying the coating liquid for each layer, for example, a coating method such as a dip coating method, a spray coating method, a ring coating method, a spin coating method, a roller coating method, a Meyer bar coating method, or a blade coating can be used.

[Configuration of process cartridge and electrophotographic device]
Next, FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention.
In FIG. 1, the cylindrical electrophotographic photosensitive member 1 is rotationally driven around a shaft 2 in the direction of an arrow at a predetermined peripheral speed. The surface (peripheral surface) of the electrophotographic photosensitive member 1 is positively or negatively charged by the charging means (primary charging means) 3 in the rotation process. Next, the surface of the electrophotographic photosensitive member 1 is irradiated with exposure light (image exposure light) 4 output from the exposure means (image exposure means) (not shown). The exposure light 4 is intensity-modulated corresponding to the time-series electric digital image signal of the target image information. Examples of the exposure means include slit exposure and laser beam scanning exposure. In this way, an electrostatic latent image corresponding to the target image information is formed on the surface of the electrophotographic photosensitive member 1.

The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is then developed (regular development or reverse development) with the toner contained in the developing means 5 to form a toner image. 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. Here, when the transfer material 7 is paper, it is taken out from the paper feed unit (not shown) in synchronization with the rotation of the electrophotographic photosensitive member 1 and fed between the electrophotographic photosensitive member 1 and the transfer means 6. Will be done. Further, a bias voltage having a polarity opposite to the charge held by the toner is applied to the transfer means 6 from a bias power source (not shown). Further, the transfer means may be an intermediate transfer type transfer means having a primary transfer member, an intermediate transfer body and a secondary transfer member.
The transfer material 7 to which the toner image is transferred is separated from the surface of the electrophotographic photosensitive member 1, transported to the fixing means 8, and subjected to the fixing treatment of the toner image, so that the transfer material 7 is electron as an image forming product (print, copy). It is printed out of the photographic device.

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

Among the components such as the electrophotographic photosensitive member 1, the charging means 3, the developing means 5, the transferring means 6, and the cleaning means 9, a plurality of elements are selected, stored in a container, and integrally supported as a process cartridge. do. This process cartridge may be detachably configured with respect to the main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. In FIG. 1, the electrophotographic photosensitive member 1 and the charging means 3, the developing means 5, and the cleaning means 9 are integrally supported to form a cartridge. A process cartridge 11 that can be attached to and detached from the electrophotographic apparatus main body is formed by using a guiding means 12 such as a rail of the electrophotographic apparatus main body.

Hereinafter, the present invention will be described in more detail with reference to specific examples. In addition, "part" in an Example means "mass part".

(Example 1)
A conductive support was prepared by cutting the surface of a cylindrical aluminum support having a diameter of 60 mm to make the surface finely roughened.
Next, 1 part of polyamide resin (trade name: CM8000, manufactured by Toray Industries, Inc.), 3 parts of titanium oxide particles (trade name: SMT500SAS, manufactured by TAYCA Corporation), and 20 parts of methanol are mixed, and 10 parts are mixed using a sand mill. After time dispersion, a coating liquid for the undercoat layer was prepared.
The coating liquid for the undercoat layer was immersed and coated on the aluminum support to form a coating film, and the obtained coating film was heat-dried to form an undercoat layer having a film thickness of 20 μm.

Next, a titanyl phthalocyanine pigment having a strong peak at 27.3 ° at a Bragg angle of 2θ ± 0.2 ° for CuKα characteristic X-ray diffraction was prepared.
20 parts of this titanyl phthalocyanine pigment, 10 parts of polyvinyl butyral resin (trade name: # 6000-C, manufactured by Denki Kagaku Kogyo Co., Ltd.), 700 parts of t-butyl acetate, 300 parts of 4-methoxy-4-methyl-2-pentanone. Was mixed and dispersed for 10 hours using a sand mill to prepare a coating liquid for a charge generation layer.
The coating liquid for the charge generating layer was immersed and coated on the undercoat layer to form a coating film, and the obtained coating film was heated and dried to form a charge generating layer having a film thickness of 0.3 μm.

Next, 225 parts of the compound (charge transport substance) represented by the following formula (D), 300 parts of polycarbonate resin (trade name: Iupiron Z300, manufactured by Mitsubishi Engineering Plastics Co., Ltd.), antioxidant (trade name: Irganox1010, Mix 6 parts of Ciba Japan Co., Ltd., 1600 parts of tetrahydrofuran, 400 parts of toluene, and 1 part of silicone oil (trade name: KF-50, manufactured by Shin-Etsu Chemical Co., Ltd.) to prepare a coating liquid for the charge transport layer. Made.
The coating liquid for the charge transport layer was immersed and coated on the charge generation layer to form a coating film, and the obtained coating film was heat-dried to form a charge transport layer having a film thickness of 20 μm.

この表面層用塗布液を電荷輸送層上に浸漬塗布して塗膜を形成し、室温で１０分間乾燥させた。得られた塗膜にメタルハライドランプを用いて紫外線（照射強度：１５ｍＷ／ｃｍ^２）を１分間照射した。その後、塗膜を８０℃で１２０分乾燥させることにより、膜厚５μｍの表面層（保護層）を形成し、電子写真感光体を完成させた。 Next, 100 parts of the non-hole transporting chain-polymerizable compound represented by the above-exemplified compound (A-1), 50 parts of the specific inorganic fine particles (B-10) shown in Table 1, and the above-mentioned exemplary compound (C-). 15 parts of the non-polymerizable hole-transporting compound represented by 3), 10 parts of the polymerization initiator represented by the following formula (E), 320 parts of 2-butanol and 80 parts of tetrahydrofuran were mixed and dispersed using a sand mill. , A coating liquid 1 for a surface layer was prepared.

This coating liquid for the surface layer was immersed and coated on the charge transport layer to form a coating film, and dried at room temperature for 10 minutes. The obtained coating film was irradiated with ultraviolet rays (irradiation intensity: 15 mW / cm ² ) for 1 minute using a metal halide lamp. Then, the coating film was dried at 80 ° C. for 120 minutes to form a surface layer (protective layer) having a film thickness of 5 μm, and an electrophotographic photosensitive member was completed.

The obtained electrophotographic photosensitive member was mounted on a cyan station of a commercially available full-color multifunction device bizhub PRO C6500 manufactured by Konica Minolta Co., Ltd., and image evaluation was performed in a high temperature and high humidity environment (30 ° C., relative humidity 85% RH). rice field.

Image evaluation was performed as follows. 5000 consecutive images were formed using a test chart with an image ratio of 5%. After the image formation was completed, the power supply to the copying machine was stopped and left for 3 days. After leaving it for 3 days, the power supply to the copier was started again, and a grid image and a character image (Iroha image) in which the Hiragana Iroha was repeated were output on A4 horizontal size paper.

The image flow level of the obtained image of the entire surface of A4 was evaluated according to the following criteria. In the present invention, it was determined that ranks A to C sufficiently obtained the effect of suppressing image flow, and ranks D and E did not have the effect of suppressing image flow.
Rank A: No image defects are seen in both the lattice image and Iroha image Rank B: Part of the lattice image is hazy, but no image defects are seen in the Iroha image Rank C: The lattice image is partially hazy and Iroha Part of the image becomes lighter Rank D: The lattice image is partially lost and the Iroha image is completely thinned Rank E: The lattice image is completely lost and the Iroha image is completely thinned 100,000 It was also carried out after the formation of the images, and the image flow level was evaluated in the same manner.

In addition, the amount of wear (μm) of the electrophotographic photosensitive member after forming 100,000 images was also confirmed. In the present invention, it was determined that there is no problem in the wear resistance of the electrophotographic photosensitive member when the amount of wear is less than 2.0 μm.

Separately, 1000 images were continuously formed under the same conditions, and the potential fluctuation of the electrophotographic photosensitive member was examined. The value of "potential after 1000 images-initial potential" of the image exposure unit VL was calculated as ΔVL. In the present invention, it is determined that there is no problem in the electrical characteristics of the electrophotographic photosensitive member when ΔVL is less than 30V.

(Example 2)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the specific inorganic fine particles (B-10) were changed to the specific inorganic fine particles (B-14) shown in Table 1.

(Example 3)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the specific inorganic fine particles (B-10) were changed to the specific inorganic fine particles (B-16) shown in Table 1.

(Example 4)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the specific inorganic fine particles (B-10) were changed to the specific inorganic fine particles (B-11) shown in Table 1.

(Example 5)
Examples except that the above-mentioned exemplary compound (A-1), which is a non-hole-transporting chain-growth compound, was changed to the non-hole-transporting chain-polymerizable compound represented by the above-mentioned exemplary compound (A-4). An electrophotographic photosensitive member was produced and evaluated in the same manner as in 1.

(Example 6)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the specific inorganic fine particles (B-10) were changed to the specific inorganic fine particles (B-18) shown in Table 1.

(Example 7)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the specific inorganic fine particles (B-10) were changed to the specific inorganic fine particles (B-20) shown in Table 1.

(Example 8)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the specific inorganic fine particles (B-10) were changed to the specific inorganic fine particles (B-4) shown in Table 1.

(Example 9)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the specific inorganic fine particles (B-10) were changed to the specific inorganic fine particles (B-8) shown in Table 1.

(Example 10)
Electrophotograph in the same manner as in Example 9 except that the non-polymerizable hole-transporting compound (C-3) was changed to the non-polymerizable hole-transporting compound represented by the above-exemplified compound (C-8). Photoreceptors were manufactured and evaluated.

(Example 11)
Example 9 and Example 9 except that the above-mentioned exemplary compound (C-3), which is a non-polymerizable hole-transporting compound, was changed to the non-polymerizable hole-transporting compound represented by the above-mentioned exemplary compound (C-6). An electrophotographic photosensitive member was produced in the same manner and evaluated.

(Example 12)
Examples except that the above-mentioned exemplary compound (A-1), which is a non-hole-transporting chain-growth compound, was changed to the non-hole-transporting chain-polymerizable compound represented by the above-mentioned exemplary compound (A-6). An electrophotographic photosensitive member was produced in the same manner as in No. 10 and evaluated.

(Example 13)
The same as in Example 10 except that the non-hole transporting chain-growth polymerizable compound (A-1) was changed to the non-hole transporting chain-growth polymerizable compound represented by the above-exemplified compound (A-8). An electrophotographic photosensitive member was manufactured and evaluated.

(Example 14)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 10 except that the specific inorganic fine particles (B-8) were changed to the specific inorganic fine particles (B-3) shown in Table 1.

(Example 15)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 10 except that the specific inorganic fine particles (B-8) were changed to the specific inorganic fine particles (B-7) shown in Table 1.

(Example 16)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 10 except that the specific inorganic fine particles (B-8) were changed to the specific inorganic fine particles (B-5) shown in Table 1.

(Example 17)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 10 except that the specific inorganic fine particles (B-8) were changed to the specific inorganic fine particles (B-1) shown in Table 1.

(Example 18)
Examples except that the above-mentioned exemplary compound (A-1), which is a non-hole-transporting chain-growth compound, was changed to the non-hole-transporting chain-polymerizable compound represented by the above-mentioned exemplary compound (A-3). An electrophotographic photosensitive member was produced and evaluated in the same manner as in 17.

(Example 19)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 18 except that the specific inorganic fine particles (B-1) were changed to the specific inorganic fine particles (B-21) shown in Table 1.

(Example 20)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that a curing method using an electron beam was used as a curing method for the coating film of the surface layer coating liquid.

The curing method using an electron beam was carried out by the following method.
After the surface layer coating liquid is immersed and coated on the charge transport layer to form a coating film, the support (irradiated body) is applied at a speed of 200 rpm under the conditions of an acceleration voltage of 70 kV and a beam current of 5.0 mA under a nitrogen atmosphere. The coating film was irradiated with an electron beam for 1.6 seconds while rotating at. Then, in a nitrogen atmosphere, the temperature of the coating film was raised from 25 ° C. to 140 ° C. over 15 seconds to heat the coating film. Next, in the atmosphere, the coating film is naturally cooled to 25 ° C., and then heat-treated at 105 ° C. for 15 minutes to form a surface layer (protective layer) having a film thickness of 3 μm. Was completed.

(Example 21)
The specific inorganic fine particles (B-10) are changed to the specific inorganic fine particles (B-8) shown in Table 1, and the non-polymerizable hole transporting compound (C-3) is replaced with the above-mentioned exemplary compound (C-8). ) Was changed to a non-polymerizable hole-transporting compound, and an electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 20.

(Comparative Example 1)
Except that the specific inorganic fine particles (B-10) were changed to the inorganic fine particles (F-1) in which the tin oxide particles were surface-treated using only the surface treatment agent shown in the above-exemplified compound (6A-2). , An electrophotographic photosensitive member was produced in the same manner as in Example 1 and evaluated.

(Comparative Example 2)
Examples except that the specific inorganic fine particles (B-10) were changed to the inorganic fine particles (F-2) in which the tin oxide particles were surface-treated using only the surface treatment agent represented by the following formula (G). An electrophotographic photosensitive member was produced in the same manner as in No. 1 and evaluated.

(Comparative Example 3)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the specific inorganic fine particles (B-10) were changed to tin oxide particles (F-3) which had not been surface-treated. ..

(Comparative Example 4)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that specific inorganic fine particles (B-10) were not used.

(Comparative Example 5)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the non-polymerizable hole transporting compound (C-3) was not used.

(Comparative Example 6)
The electrophotograph was carried out in the same manner as in Example 1 except that the non-hole transporting chain polymerizable compound (A-1) was changed to the non-hole transporting chain polymerizable compound represented by the following formula (H). Photoreceptors were manufactured and evaluated.

Table 2 shows the evaluation results of each Example and each Comparative Example.

As a result of the evaluation, in the examples, the effect of suppressing the image flow was sufficiently obtained even after the formation of 5000 images and the formation of 100,000 images, and there were no problems in wear resistance and electrical characteristics.

In Comparative Examples 1 and 2, the image flow suppressing effect was not obtained especially after the formation of 100,000 images. In Comparative Example 3, the image flow suppressing effect was not obtained both after the formation of 5000 images and after the formation of 100,000 images. In Comparative Example 4, the image flow suppression effect was not obtained, and the abrasion resistance deteriorated. In Comparative Example 5, the electrical characteristics deteriorated. In Comparative Example 6, the surface layer was not sufficiently cured and could not be used for evaluation.

1 Electrophotographic photosensitive member 2 axes 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means 21 Support 22 Undercoat layer 23 Charge generation layer 24 Charge transport layer 25 Surface layer

Claims (12)

In an electrophotographic photosensitive member having a support and a photosensitive layer,
The surface layer of the electrophotographic photosensitive member is
With the copolymer,
Non-polymerizable hole-transporting compounds with a triphenylamine skeleton,
Contains,
The copolymer
Formula (P-1) ~ (P -7) non hole transporting having a chain polymerizable functional group A is selected from the group consisting of chain polymerizable functional groups two or more, including a group represented by any With chain-growth compounds
And no fine particles that have a structure on the surface represented by the following formula (1),
An electrophotographic photosensitive member , which is a copolymer of.

In the formula (1), R ¹ is a linear or branched alkyl group having 11 or more carbon atoms, and P ¹ is a chain-growth functional group B that can be polymerized with the chain-growth functional group A. It is a monovalent functional group having.) The chain-polymerizable functional group A is an electrophotographic photosensitive member according to claim 1 containing a group represented by any one of the following formulas (P-1) and (P-2).

Before Killen chain polymerizable functional group B is represented by the following formula (P-1), (P -2) and electrons according to claim 1 or 2 (P-3) is a group represented by any one of Photophotoreceptor.

The linear or branched alkyl group having 11 or more carbons, electrophotography according to any one of claims 1 to 3 is a linear or branched alkyl group having 16 to 20 carbon atoms Photoreceptor. Before Kihi hole transporting chain polymerizable compound, an electrophotographic photosensitive member according to any one of claims 1-4 which is a compound represented by any one of the following formulas (2) and (3).

(In the formula ^(2), R 21 ^{to R 24} are each a hydrogen atom, 1 to 2 alkyl groups carbon atoms, a hydroxyalkyl group, acryloyloxy group, or a methacryloyloxy group, represented by formula (2) acrylate total acryloyloxy groups and methacryloyloxy groups in compounds of is 3 or 4.)

(In the formula ^(3), R 31 ^{to R 36} are each a hydrogen atom, 1 to 2 alkyl groups carbon atoms, a hydroxyalkyl group, acryloyloxy group, or a methacryloyloxy group, represented by the formula (3) acrylate total acryloyloxy groups and methacryloyloxy groups in compounds of is 3 or more and 6 or less.) The electrophotographic photosensitive member according to any one of claims 1 to 5 , wherein the non-polymerizable hole-transporting compound having a triphenylamine skeleton is a compound represented by the following formula (4).

(In the formula (4), R ^{41 to} R ⁴⁴ are hydrogen atoms, alkyl groups having 1 or more and 3 or less carbon atoms , or alkoxy groups having 1 or more carbon atoms and 3 or less carbon atoms, respectively, ^{and n 1 to} n ³ are . is 1 to 5 integer, n ⁴ is 1 to 4 which is an integer. in addition, when n ¹ ~n ⁴ is an integer of 2 or more, even the plurality of groups are identical, different May be. ) Before Killen chain polymerizable functional group B is The electrophotographic photosensitive member according to any one of claims 1 to 6 is a group represented by the following formula (P-3).

Before Kina fine particles has a base particles therein, the base particle is tin oxide, electrophotography according to any one of claims 1 to 7 is particulate titanium oxide or zinc oxide Photoreceptor. A method for producing an electrophotographic photosensitive member according to any one of claims 1 to 8, wherein the electrophotographic photosensitive member is produced.
The manufacturing method is
A surface treatment step of surface-treating inorganic fine particles with a surface treatment agent represented by the following formula (5), and
The process of preparing the coating liquid for the surface layer and
A step of forming a coating film of the coating liquid for the surface layer and curing the coating film to form a surface layer of the electrophotographic photosensitive member .
Have a in this order,
The coating liquid for the surface layer
The non-polymerizable hole-transporting compound having a triphenylamine skeleton and
A non-hole transportable chain-growth compound having two or more chain-growth functional groups A,
Inorganic fine particles having a structure represented by the formula (1) on the surface, which has been surface-treated in the surface treatment step,
A method for producing an electrophotographic photosensitive member, which comprises.

In the formula (5), R ¹ is a linear or branched alkyl group having 11 or more carbon atoms, and P ¹ is a chain-growth functional group B that can be polymerized with the chain-growth functional group A. It is a monovalent functional group having, and X ¹ and X ² are each an alkoxy group.) The method for producing an electrophotographic photosensitive member according to claim 9 , wherein the method for curing the coating film is a method for irradiating the coating film with an electron beam. An electrophotographic photosensitive member according to any one of claims 1-8, charging means, developing means, and at least one means selected from the group consisting of the transfer means and cleaning means, integrally supported and electronic A process cartridge that is removable from the main body of the photographic device. An electrophotographic apparatus having the electrophotographic photosensitive member according to any one of claims 1 to 8 and a charging means, an exposure means, a developing means, and a transfer means.

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