JP6218507B2 - Electrophotographic photosensitive member, method for manufacturing electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

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

  In an electrophotographic apparatus, an electrophotographic photosensitive member that is repeatedly used is required to have high wear resistance and good potential fluctuation characteristics.

  Patent Document 1 and Patent Document 2 contain a cured product obtained by curing a charge transporting monomer having a polymerizable functional group in the surface layer of an electrophotographic photosensitive member to improve the abrasion resistance of the electrophotographic photosensitive member. Techniques to improve are described.

JP 2000-066425 A JP 2010-156835 A

  An object of the present invention is to provide an electrophotographic photosensitive member having excellent protection against potential fluctuations caused by repeated use in an electrophotographic photosensitive member having a protective layer containing a cured product of a composition containing a charge transporting monomer, and a method for producing the same. There is.

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

The present invention comprises a support, a charge generation layer formed on the support, the charge generation layer a charge transport layer formed on, and an electrophotographic photosensitive having a protective layer formed on the charge transport layer Body,
The charge transport layer contains a charge transport material;
The electrophotographic photoreceptor, wherein the protective layer contains a cured product of a composition containing a charge transporting monomer represented by the following formula (5) .

(In the formula (5), r is 0 or 1. Ar ²¹ , Ar ²² , Ar when r is 0 ²³ (When r is 0, -Ar ²⁴ Not Ar ²³ Is a monovalent group. ) And Ar ²⁴ Each independently represents a group represented by the following formula (6), a group represented by the following formula (7), or a substituted or unsubstituted aryl group. Ar ²¹ ~ Ar ²² , Ar when r is 0 ²³ And Ar ²⁴ Among these, at least one is a group represented by the following formula (6), and at least one is a group represented by the following formula (7). Ar when r is 1 ²³ (When r is 1, Ar ²³ Is a divalent group. ) Represents a group represented by the following formula (8), a group represented by the following formula (9), or a substituted or unsubstituted arylene group. However, Ar ²¹ ~ Ar ²⁴ Among them, at least one is a group represented by the following formula (6) or a group represented by the following formula (8), and at least one is a group represented by the following formula (7), or And a group represented by the following formula (9). )

(In the formulas (6) and (7), Ar ³¹ And Ar ³² Each independently represents a substituted or unsubstituted arylene group. In formulas (8) and (9), Ar ³³ And Ar ³⁴ Each independently represents a substituted or unsubstituted trivalent aromatic group. R ¹ Represents a substituted or unsubstituted alkylene group. X ³ ~ X ⁶ , Y ³ ~ Y ⁶ And Z ³ ~ Z ⁶ Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group. )

Further, the present invention comprises a support, a charge generation layer formed on the support, the charge generation layer to form the charge transport layer, and electrons having a protective layer formed on the charge transport layer A method of manufacturing a photoconductor,
The manufacturing method comprises:
Preparing a protective layer coating liquid containing a composition comprising a charge transporting monomer represented by the following formula (5) and,
To form a coating film having a-holding Mamoruso coating liquid, comprising the step of forming the protective layer by curing the composition in the coating film,
The method for producing an electrophotographic photoreceptor , wherein the charge transport layer contains a charge transport material.

(In the formula (5), r is 0 or 1. Ar ²¹ , Ar ²² , Ar when r is 0 ²³ (When r is 0, -Ar ²⁴ Not Ar ²³ Is a monovalent group. ) And Ar ²⁴ Each independently represents a group represented by the following formula (6), a group represented by the following formula (7), or a substituted or unsubstituted aryl group. Ar ²¹ ~ Ar ²² , Ar when r is 0 ²³ And Ar ²⁴ Among these, at least one is a group represented by the following formula (6), and at least one is a group represented by the following formula (7). Ar when r is 1 ²³ (When r is 1, Ar ²³ Is a divalent group. ) Represents a group represented by the following formula (8), a group represented by the following formula (9), or a substituted or unsubstituted arylene group. However, Ar ²¹ ~ Ar ²⁴ Among them, at least one is a group represented by the following formula (6) or a group represented by the following formula (8), and at least one is a group represented by the following formula (7), or And a group represented by the following formula (9). )

(In the formulas (6) and (7), Ar ³¹ And Ar ³² Each independently represents a substituted or unsubstituted arylene group. In formulas (8) and (9), Ar ³³ And Ar ³⁴ Each independently represents a substituted or unsubstituted trivalent aromatic group. R ¹ Represents a substituted or unsubstituted alkylene group. X ³ ~ X ⁶ , Y ³ ~ Y ⁶ And Z ³ ~ Z ⁶ Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group. )

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

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

  According to the present invention, there are provided an electrophotographic photosensitive member having a protective layer containing a cured product of a composition containing a charge transporting monomer and excellent in suppressing potential fluctuations caused by repeated use, and a method for producing the same. be able to. In addition, according to the present invention, a process cartridge and an electrophotographic apparatus having such an electrophotographic photosensitive member can be provided.

It is a figure which shows an example of the layer structure of an electrophotographic photoreceptor. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member.

  The electrophotographic photoreceptor of the present invention is characterized in that the protective layer of the electrophotographic photoreceptor contains a cured product of the following (i) or (ii).

  (I) A cured product (polymer) having a charge transporting monomer having at least one group represented by the following formula (1) and having at least one group represented by the following formula (2): .

  (Ii) a charge transport material having one polymerizable functional group, one or more groups represented by the following formula (1), one or more groups represented by the following formula (2), and Hardened | cured material of the composition containing the monomer which does not have a charge transport structure.

In Formula (1) and Formula (2), R ¹ represents a substituted or unsubstituted alkylene group. X ¹ , X ² , Y ¹ , Y ² , Z ¹ and Z ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group. Indicates.

  As described above, the electrophotographic photosensitive member of the present invention is excellent in suppressing potential fluctuation due to repeated use. The inventors presume the reason as follows.

  The charge transporting monomer forms a cured product by polymerizing the polymerizable functional group of the charge transporting monomer. When the polymerization reaction of the charge transporting monomer proceeds to some extent, the degree of freedom of the charge transporting structure tends to decrease. When a polymerizable functional group that has not reacted yet undergoes a polymerization reaction, the charge transport structure may be twisted due to a decrease in the degree of freedom of the charge transport skeleton, and charge trapping may easily occur. As a result, it is assumed that potential fluctuations are likely to occur due to repeated use.

On the other hand, when the charge transporting monomer having at least one group represented by the formula (1) and one group represented by the formula (2) proceeds to some extent, the group represented by the formula (2) is polymerized. However, it is considered that the group represented by the formula (1) exists in an unreacted state. It is believed that this suppresses a decrease in the degree of freedom of the charge transport structure. The group represented by the formula (1) has a site represented by —O—CH ₂ —CH ₂ — as compared with the group represented by the formula (2), and has an ether structure that is easily bent. It is considered that the decrease in the degree of freedom of the charge transporting structure is suppressed. And when the group shown by Formula (1) which has not reacted yet undergoes a polymerization reaction, it is considered that the polymerization reaction is suppressed by twisting the charge transporting structure. As a result, it is estimated that the potential fluctuation suppressing effect by repeated use is improved.

  Further, the monomer having one or more groups represented by the formula (1) and one represented by the formula (2) and having no charge transporting structure is the same as the charge transporting monomer. Therefore, it is presumed that it is excellent in suppressing potential fluctuation by repeated use. That is, when this monomer has a group represented by the formula (1), it undergoes a polymerization reaction so as to twist the charge transporting structure when polymerizing with a charge transporting material having one polymerizable functional group. I think that it is suppressed.

In the formula (1) and the above formula (2), R ¹ represents a substituted or unsubstituted alkylene group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonanylene group, and a decylene group. Examples of the substituent that the substituted alkylene group may have include a methyl group, an ethyl group, a propyl group, a trimethylsilyl group, a trifluoromethyl group, and a fluorine atom. From the viewpoint of exhibiting a specific structure of the moiety represented by —O—CH ₂ —CH ₂ — in the above formula (1), R ¹ is an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group. Preferably there is.

In the formula (1) and the above formula (2), X ¹ , X ² , Y ¹ , Y ² , Z ¹ and Z ² are as described above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonanyl group, and a decyl group. Examples of the substituent that the substituted alkyl group may have include a methyl group, an ethyl group, a propyl group, and a phenyl group. Examples of the aryl group include a phenyl group, a biphenyl group, a fluorenyl group, a 9,9′-dimethylfluorenyl group, and a naphthyl group. Examples of the substituent that the substituted aryl group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a nitro group, and a cyano group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. From the viewpoint of the effect of the present invention, it is preferable that all of X ¹ , X ² , Y ¹ , Y ² , Z ¹ and Z ² are hydrogen atoms.

  Specifically, the charge transporting monomer is preferably a monomer represented by the following formula (5).

In the formula (5), r is 0 or 1. Ar ^{21 to} Ar ²² , Ar ²³ when r is 0 (when r is 0, there is no —Ar ²⁴ and Ar ²³ is a monovalent group), and Ar ²⁴ are each independently represented by the following formulae: A group represented by (6), a group represented by the following formula (7), or a substituted or unsubstituted aryl group; Of Ar ^{21 to} Ar ²² , Ar ²³ when r is 0, and Ar ²⁴ , at least one is a group represented by the following formula (6), and at least one is represented by the following formula (7) Group. Ar ²³ when r is 1 (when r is 1, Ar ²³ is a divalent group) is a group represented by the following formula (8), a group represented by the following formula (9), a substituted or An unsubstituted arylene group is shown. However, at least one of Ar ^{21 to} Ar ²² , Ar ²³ , and Ar ²⁴ is a group represented by the following formula (6) or a group represented by the following formula (8), and at least one is It is a group represented by the following formula (7) or a group represented by the following formula (9).

In formulas (6) and (7), Ar ³¹ and Ar ³² represent a substituted or unsubstituted arylene group. In formulas (8) and (9), Ar ³³ and Ar ³⁴ each independently represent a substituted or unsubstituted trivalent aromatic group. R ¹ represents a substituted or unsubstituted alkylene group. X ^{3 to} X ⁶ , Y ^{3 to} Y ⁶ and Z ^{3 to} Z ⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group. Indicates.

  Examples of the aryl group include a phenyl group, a biphenylyl group, a fluorenyl group, a 9,9'-dimethylfluorenyl group, and a naphthyl group. Examples of the substituent of the substituted aryl group include a methyl group, for example, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a nitro group, and a cyano group. Examples of the arylene group include a phenylene group, a biphenylylene group, a fluorenylene group, a 9,9'-dimethylfluorenylene group, and a naphthylene group. Examples of the substituent for the substituted arylene group include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a nitro group, and a cyano group. Examples of the trivalent aromatic group include groups represented by the following formulas (10) to (13). Examples of the substituent of the substituted trivalent aromatic group include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a nitro group, and a cyano group.

  The charge transporting monomer is preferably contained in an amount of 1% by mass to 100% by mass with respect to the total mass of the composition. More preferably, they are 5 mass% or more and 100 mass% or less. In addition to the charge transporting monomer, the charge transporting monomer used in combination is not particularly limited. From the viewpoint of good electrophotographic characteristics and compatibility, a charge transporting monomer having no group represented by the formula (1) and having two or more groups represented by the formula (2) is preferable.

  Regarding the charge transport material having a polymerizable functional group (ii) above, the polymerizable functional group is preferably a group represented by the formula (1). Moreover, it is preferable that it is a charge transport material which has one polymeric functional group. Examples of the charge transporting structure of the charge transporting material include a triarylamine structure, a hydrazone structure, and a stilbene structure.

  In (ii), a monomer having one or more groups represented by the formula (1), one or more groups represented by the formula (2), and having no charge transporting structure is represented by the formula ( Those having one group represented by 1) and two groups represented by formula (2) are preferred.

  In (ii), a monomer having one or more groups represented by the formula (1), one or more groups represented by the formula (2), and having no charge transporting structure is a composition. It is preferable to make it contain in 1 mass% or more and 50 mass% or less with respect to the total mass of. In addition to this monomer, the composition further comprises a monomer that does not have a group represented by the formula (1), has two or more groups represented by the formula (2), and does not have a charge transporting structure. You may make it contain.

  A protective layer can be formed by forming the coating film of the coating liquid for protective layers containing the above-mentioned composition, and hardening the composition in a coating film.

  The charge transporting monomer having at least one group represented by the above formula (1) and one group represented by the above formula (2) can be synthesized as follows. For example, in the synthesis method described in JP2000-066425A and JP2010-156835A, it is possible to synthesize using an appropriate carboxylic acid and 2-hydroxyethyl carboxylate. A monomer having one or more groups represented by the following formula (1), one or more groups represented by the following formula (2), and having no charge transporting structure is as follows. It can be synthesized. For example, it can be synthesized using a compound having one or more hydroxy groups and an appropriate carboxylic acid and 2-hydroxyethyl carboxylate.

  Specific examples (exemplary compounds) of charge transporting monomers having at least one group represented by the formula (1) and at least one group represented by the formula (2) will be given below.

  Specific examples of the monomer having one or more groups represented by the formula (1), one or more groups represented by the formula (2), and having no charge transporting structure (exemplary compounds) ).

  Among these, exemplary compound (A-15) is preferable.

  Specific examples of the charge transporting monomer having no group represented by the formula (1) and having two or more groups represented by the formula (2) are shown below.

  The electrophotographic photosensitive member of the present invention comprises a support, a charge generation layer formed on the support, a charge transport layer formed on the charge generation layer, and a protective layer formed on the charge transport layer. Have.

  FIG. 1 is a diagram illustrating an example of a layer structure of an electrophotographic photosensitive member. In FIG. 1, the electrophotographic photosensitive member includes a support 101, a charge generation layer 102, a charge transport layer 103, and a protective layer 104. If necessary, a conductive layer or undercoat layer described later may be provided between the support and the photosensitive layer (charge generation layer, charge transport layer).

  As the support used in the electrophotographic photosensitive member, a conductive one (conductive support) is preferable. For example, a support made of a metal such as aluminum, an aluminum alloy, or stainless steel or an alloy can be used. In the case of a support made of aluminum or aluminum alloy, an ED tube, an EI tube, or a support obtained by cutting, electrolytic composite polishing, wet or dry honing treatment of these can also be used. Alternatively, a thin film of a conductive material such as aluminum, an aluminum alloy, or an indium oxide-tin oxide alloy may be formed on a metal support or resin support, and used as a support.

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

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

  A conductive layer containing conductive particles and a binder resin may be provided between the support and the charge generation layer or the undercoat layer described below.

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

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

  Examples of the resin used for the conductive layer include acrylic resin, alkyd resin, epoxy resin, phenol resin, butyral resin, polyacetal, polyurethane, polyester, polycarbonate, and melamine resin.

  Examples of the solvent used in the conductive layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents.

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

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

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

  Examples of the resin used for the undercoat layer include polyacrylic acid, methylcellulose, ethylcellulose, polyamide, polyimide, polyamideimide, polyamic acid, melamine resin, epoxy resin, and polyurethane.

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

  Examples of the solvent used in the coating solution for the undercoat layer include ether solvents, alcohol solvents, ketone solvents, aromatic hydrocarbon solvents, and the like.

  The thickness of the undercoat layer is preferably 0.05 μm or more and 40 μm or less, and more preferably 0.4 μm or more and 20 μm or less.

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

  Examples of the charge generating material used in the electrophotographic photosensitive member include pyrylium, thiapyrylium dyes, phthalocyanine compounds, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, azo pigments, indigo pigments, quinacridone pigments, and quinocyanine pigments. It is done. Among these, gallium phthalocyanine is preferable. Furthermore, from the viewpoint of high sensitivity, hydroxygallium phthalocyanine is preferable, and among them, strong peaks at the Bragg angle 2θ of 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° in CuKα characteristic X-ray diffraction Hydroxygallium phthalocyanine crystals having the following are preferred.

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

  The charge generation layer is formed by applying a charge generation layer coating solution obtained by dispersing a charge generation material together with a binder resin and a solvent to form a coating film, and then drying the obtained coating film. Can do. The charge generation layer may be a vapor generation film of a charge generation material.

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

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

  Examples of the solvent used in the charge generation layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

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

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

  The charge transport layer is formed by applying a charge transport layer coating solution obtained by dissolving a charge transport material and a binder resin in a solvent to form a coating film, and then drying the obtained coating film. Can do.

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

  Among the charge transport materials, stilbene compounds represented by the following formula (3) are preferable. Although this stilbene compound has excellent mobility, since the deviation of the ionization potential from the conventional protective layer is large, when the protective layer is provided, sufficient potential fluctuation characteristics may not be obtained. However, when a protective layer containing a cured product of the above composition is provided and a charge transport layer containing this stilbene compound is used in combination, the deviation in ionization potential is reduced, and a good potential fluctuation suppressing effect is exhibited.

In formula (3), Ar ^{1 to} Ar ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted aryl group. Examples of the aryl group include a phenyl group, a biphenyl group, a fluorenyl group, a 9,9′-dimethylfluorenyl group, and a naphthyl group. Examples of the substituent of the substituted aryl group include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a nitro group, and a cyano group. Ar ¹¹ represents a substituted or unsubstituted arylene group. Examples of the arylene group include a phenylene group, a biphenylene group, a fluorenylene group, a 9,9′-dimethylfluorenylene group, and a naphthylene group. Examples of the substituent of the substituted arylene group include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a nitro group, and a cyano group. R ² and R ³ each independently represent a single bond or an ethylene group. More preferably, it is a compound shown by following formula (4).

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

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

  Examples of the solvent used in the charge transport layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents. The thickness of the charge transport layer is preferably 5 μm or more and 40 μm or less.

  The protective layer of the electrophotographic photosensitive member in the present invention contains the above-described cured product.

  Various additives can be added to the protective layer. Examples of the additive include deterioration preventing agents such as antioxidants and ultraviolet absorbers, and lubricants such as polytetrafluoroethylene (PTFE) particles and carbon fluoride. Further, polymerization control agents such as polymerization reaction initiators and polymerization reaction terminators, leveling agents such as silicone oil, surfactants, and the like are also included.

Solvents used in the coating solution for the protective layer include alcohol solvents such as methanol, ethanol and propanol, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, tetrahydrofuran, dioxane and the like. Ether solvents, 1,1,2,2,3,3,4-heptafluorocyclopentane, halogen solvents such as dichloromethane, dichloroethane, chlorobenzene, aromatic solvents such as benzene, toluene, xylene, methyl cellosolve, ethyl Examples include cellosolve solvents such as cellosolve. These solvents may be used alone or in combination of two or more.
The thickness of the protective layer is preferably 2 μm or more and 20 μm or less.

  When applying the coating solution for each layer, for example, a coating method such as a dip coating method (dipping method), a spray coating method, a spinner coating method, a bead coating method, a blade coating method, or a beam coating method can be used.

  The effect of the composition can be achieved using heat, light (such as ultraviolet rays), or radiation (such as electron beams). Among these, polymerization using radiation is preferable, and polymerization using an electron beam is more preferable among radiations.

  When polymerized using an electron beam, a very dense (high density) cured product (three-dimensional cross-linked structure) is obtained, and a protective layer having high durability is obtained. Further, since the polymerization reaction is efficient in a short time, productivity is also increased. When irradiating an electron beam, examples of the accelerator include a scanning type, an electro curtain 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 material property deterioration 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 protective layer coating solution is preferably 5 kGy or more and 50 kGy or less, and more preferably 1 kGy or more and 10 kGy or less.

  In addition, when the above composition is cured (polymerized) using an electron beam, it may be heated in an inert gas atmosphere after being irradiated with an electron beam in an 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.

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

  In FIG. 2, a cylindrical electrophotographic photosensitive member 1 is driven to rotate at a predetermined peripheral speed (process speed) in the direction of an arrow about an axis 2. The surface (circumferential surface) of the electrophotographic photosensitive member 1 is positively or negatively charged by a charging unit (primary charging unit) 3 during the rotation process. Next, the surface of the electrophotographic photoreceptor 1 is irradiated with exposure light (image exposure light) 4 output from an exposure means (image exposure means) (not shown). The exposure light 4 is intensity-modulated corresponding to the time-series electric digital image signal of the target image information. Examples of exposure means include slit exposure and laser beam scanning exposure. Thus, an electrostatic latent image corresponding to the target image information is formed on the surface of the electrophotographic photoreceptor 1.

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

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

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

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

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

(Synthesis Example: Synthesis of Exemplary Compound (A-1)))
In a 1 L flask, 80 parts of a compound represented by the following formula (A), 30 parts of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10 parts of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), p -5 parts of toluenesulfonic acid and 200 ml of toluene were added and stirred at room temperature for 24 hours. After completion of the reaction, the resulting oil was purified by silica gel column chromatography to obtain 5 g of exemplary compound (A-1). When the HPLC purity was confirmed by LC-MS (Agilent Technology Co., Ltd., Agilent 6130), it was 99.0%.

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

  Next, 50 parts of titanium oxide particles coated with tin oxide containing 10% antimony oxide (trade name: ECT-62, manufactured by Titanium Industry Co., Ltd.), resol type phenol resin (trade name: phenolite) J-325, manufactured by Dainippon Ink & Chemicals, Inc., solid content: 70% by mass.) 25 parts, methyl cellosolve 20 parts, methanol 5 parts, and silicone oil (polydimethylsiloxane / polyoxyalkylene copolymer, (Average molecular weight: 3000.) 0.002 part was placed in a sand mill using glass beads having a diameter of 0.8 mm and dispersed for 2 hours to prepare a coating solution for a conductive layer. This conductive layer coating solution was dip-coated on a support to form a coating film, and the resulting coating film was dried and cured at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

  Next, 2.5 parts of nylon 6-66-610-12 quaternary copolymer (trade name: CM8000, manufactured by Toray Industries, Inc.) and N-methoxymethylated 6 nylon resin (trade name: Toresin EF) -30T, manufactured by Nagase ChemteX.) A coating solution for an undercoat layer was prepared by dissolving 7.5 parts in a mixed solvent of 100 parts of methanol and 90 parts of butanol. This undercoat layer coating solution is dip-coated on the conductive layer to form a coating film, and the resulting coating film is dried at 100 ° C. for 10 minutes to form an undercoat layer having a thickness of 1.2 μm. did.

  Next, 11 parts of a hydroxygallium phthalocyanine crystal (having strong peaks at 7.4 ° and 28.2 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction) as a charge generating substance, polyvinyl 5 parts of butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 130 parts of cyclohexanone were mixed. 500 parts of glass beads having a diameter of 1 mm were added thereto, and the mixture was dispersed for 2 hours under the condition of 1800 rpm while being cooled with cooling water at 18 ° C. After the dispersion treatment, 300 parts of ethyl acetate and 160 parts of cyclohexanone were added and diluted to prepare a charge generation layer coating solution. This coating solution for charge generation layer is dip coated on the undercoat layer to form a coating film, and the resulting coating film is dried at 110 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.16 μm. Formed.

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

  Next, 10 parts of the charge transport material represented by the above formula (4) and 10 parts of polycarbonate (trade name: Iupilon Z400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) are mixed with 70 parts of monochlorobenzene and 30 parts of dimethoxymethane. A coating solution for a charge transport layer was prepared by dissolving in a solvent. The charge transport layer coating solution was dip coated on the charge generation layer to form a coating film, and the resulting coating film was dried at 100 ° C. for 30 minutes to form a charge transport layer having a thickness of 18 μm. .

  Next, 100 parts of exemplary compound (A-3) is dissolved in 100 parts of n-propanol, and 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, Japan). A protective layer coating solution was prepared by adding 100 parts of Zeon Co., Ltd.) and 0.01 part of 4-methoxyphenol (Tokyo Chemical Industry Co., Ltd.). This protective layer coating solution was dip coated on the charge transport layer to form a coating film, and the resulting coating film was heat treated at 50 ° C. for 5 minutes. Thereafter, the coating film was irradiated with an electron beam for 1.6 seconds under the conditions of an acceleration voltage of 70 kV and an absorbed dose of 50000 Gy in a nitrogen atmosphere. Then, it heat-processed for 25 second on the conditions which a coating film becomes 130 degreeC in nitrogen atmosphere. The oxygen concentration from the electron beam irradiation to the heat treatment for 25 seconds was 18 ppm. Next, in the air, a protective layer having a thickness of 5 μm was formed by heat treatment for 12 minutes under the condition that the coating film became 115 ° C.

  Thus, an electrophotographic photosensitive member having a support, a conductive layer, an undercoat layer, a charge generation layer, a charge transport layer and a protective layer was produced.

<Examples 2 to 15>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the exemplified compound (A-3) was changed to the exemplified compounds shown in Table 1 to prepare a coating solution for protective layer.

<Example 16>
In Example 1, 100 parts of the exemplified compound (A-3) was changed to 50 parts of the exemplified compound (B-1) and 50 parts of the charge transport material represented by the following formula (14) to prepare a coating solution for a protective layer. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that.

<Example 17>
In Example 1, 100 parts of the exemplified compound (A-3) was changed to 50 parts of the exemplified compound (B-4) and 50 parts of the charge transport material represented by the above formula (14) to prepare a coating solution for a protective layer. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that.
<Example 18>
In Example 1, as the charge transport material, 1 part of the charge transport material represented by the above formula (4), 6 parts of the charge transport material represented by the following formula (15), and the charge transport material 3 represented by the following formula (16) The coating solution for charge transport layer was prepared using the part. Otherwise, an electrophotographic photoreceptor was produced in the same manner as in Example 1.

<Example 19>
In Example 1, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that a charge transport layer coating solution was prepared using 10 parts of the charge transport material represented by the following formula (17) as the charge transport material. Manufactured.

<Example 20>
In Example 1, an electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that a charge transport layer coating solution was prepared using 10 parts of the charge transport material represented by the following formula (18) as the charge transport material. Manufactured.

<Example 21>
In Example 1, except that 100 parts of the exemplified compound (A-3) was changed to 20 parts of the exemplified compound (A-3) and 80 parts of the exemplified compound (19) to prepare a protective layer coating solution. An electrophotographic photoreceptor was produced in the same manner as in Example 1.

<Example 22>
In Example 1, except that 100 parts of the exemplified compound (A-3) was changed to 5 parts of the exemplified compound (A-3) and 95 parts of the exemplified compound (19) to prepare a protective layer coating solution. An electrophotographic photoreceptor was produced in the same manner as in Example 1.

<Example 23>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the exemplified compound (A-3) was changed to the exemplified compound (A-32) to prepare a protective layer coating solution.

<Example 24>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that a protective layer was formed as follows.
100 parts of exemplary compound (A-1) and 1 part of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) are dissolved in 100 parts of n-propanol, and 1,1 , 2, 2, 3, 3, 4-heptafluorocyclopentane and 0.01 part of 4-methoxyphenol were added to prepare a protective layer coating solution. This coating solution for protective layer was dip coated on the charge transport layer to form a coating film, and the resulting coating film was heat-treated at 50 ° C. for 5 minutes. Then, using a metal halide lamp, the coating film was irradiated with ultraviolet rays for 20 seconds under the condition of irradiation intensity: 500 mW / cm ² , and the film thickness was 5 μm by heat treatment for 30 minutes under the condition that the coating film reached 130 ° C. A protective layer was formed.

<Example 25>
An aluminum cylinder having a diameter of 30 mm, a length of 357.5 mm, and a wall thickness of 1 mm was used as a support (conductive support).

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

  Next, 15 parts of a butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 15 parts of a blocked isocyanate (trade name: Sumidur 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.) are used as the methyl resin. It was dissolved in a mixed solution of 73.5 parts and 73.5 parts of 1-butanol. 80.8 parts of the surface-treated zinc oxide particles and 0.4 part of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to this solution, and this is added to glass beads having a diameter of 0.8 mm. Was dispersed in an atmosphere of 23 ± 3 ° C. for 3 hours. After dispersion, 0.01 parts of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone), cross-linked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER SSX-102, manufactured by Sekisui Plastics Co., Ltd.) 5.6 parts of an average primary particle size of 2.5 μm) was added and stirred to prepare an undercoat layer coating solution.

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

  Next, a charge generation layer and a charge transport layer were formed in the same manner as in Example 1.

  Next, 5 parts of the exemplified compound (A-12) and 95 parts of the exemplified compound (20) are dissolved in 100 parts of n-propanol, and further 1,1,2,2,3,3,4-heptafluorocyclo A protective layer coating solution was prepared by adding 100 parts of pentane and 0.01 part of 4-methoxyphenol. This protective layer coating solution was dip coated on the charge transport layer to form a coating film, and the resulting coating film was heat treated at 50 ° C. for 5 minutes. Thereafter, the coating film was irradiated with an electron beam for 1.6 seconds under the conditions of an acceleration voltage of 70 kV and an absorbed dose of 50000 Gy in a nitrogen atmosphere. Then, it heat-processed for 25 second on the conditions which a coating film becomes 130 degreeC in nitrogen atmosphere. The oxygen concentration from the electron beam irradiation to the heat treatment for 25 seconds was 18 ppm. Next, in the air, a protective layer having a thickness of 5 μm was formed by heat treatment for 12 minutes under the condition that the coating film became 115 ° C.

  Thus, an electrophotographic photosensitive member having a support, a conductive layer, an undercoat layer, a charge generation layer, a charge transport layer and a protective layer was produced.

<Example 26>
In Example 25, 5 parts of the exemplified compound (A-12) and 95 parts of the exemplified compound (20) were changed to 5 parts of the exemplified compound (A-13) and 95 parts of the exemplified compound (21), and applied for protective layer. An electrophotographic photosensitive member was produced in the same manner as in Example 25 except that the solution was prepared.

<Example 27>
In Example 25, 5 parts of Exemplified Compound (A-12) and 95 parts of Exemplified Compound (20) were changed to 5 parts of Illustrated Compound (A-11) and 95 parts of Illustrated Compound (22), and a protective layer coating was applied. An electrophotographic photosensitive member was produced in the same manner as in Example 25 except that the solution was prepared.

<Example 28>
In Example 25, 5 parts of the exemplified compound (A-12) and 95 parts of the above formula (20) were changed to 5 parts of the exemplified compound (A-15) and 95 parts of the exemplified compound (23), and the coating for protective layer was applied. An electrophotographic photosensitive member was produced in the same manner as in Example 25 except that the solution was prepared.

<Comparative example 1>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the coating compound for the protective layer was prepared by changing the exemplified compound (A-3) to the compound represented by the following formula (24). did.

<Comparative example 2>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the coating compound for the protective layer was prepared by changing the exemplified compound (A-3) to the compound represented by the following formula (25). did.

<Comparative Example 3>
In Example 1, an electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the protective compound coating solution was prepared by changing the exemplified compound (A-3) to the following formula (26).

(Evaluation)
About the evaluation method of the electrophotographic photoreceptor of Examples 1-28 and Comparative Examples 1-3, it is as follows. As an evaluation apparatus, a Canon Co., Ltd. copier (trade name: GP405) was used. The process speed is modified to 320 mm / sec. The charging means applies a voltage obtained by superimposing an AC voltage on a DC voltage to a roller-type contact charging member (charging roller). The exposure means is a laser image exposure system (wavelength). 780 nm) was used. Further, the developing means used was a one-component magnetic negative toner non-contact developing system, the transfer means used was a roller-type contact transfer system, the cleaning means used a blade cleaning system, and the pre-exposure means used a fuse lamp.

(Evaluation of potential fluctuation)
First, the electrophotographic photosensitive member was left together with an evaluation apparatus in a normal temperature and low humidity environment at a temperature of 23 ° C. and a humidity of 15% RH for one day. Thereafter, under the same environment, the charging potential (VD) was adjusted to -700V, and the light portion potential (VL) was adjusted to -150V. Thereafter, the cycle of charging, exposure, and pre-exposure was repeated continuously (full screen black image mode) for 3000 revolutions. A series of evaluations were all performed in a room temperature and low humidity environment. The light portion potential (VL) at the 3000th rotation was measured, and the difference (light portion potential fluctuation amount) between the initial VL and the VL at the 3000th rotation was calculated as ΔVL.

  The evaluation results are shown in Table 2. Note that when the potential fluctuation amount (ΔVL) is 40 V or less, it can be determined that the effect of the present invention can be obtained.

DESCRIPTION OF SYMBOLS 101 Support body 102 Charge generation layer 103 Charge transport layer 104 Protective layer 1 Electrophotographic photosensitive member 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means

Claims (11)

Support, a charge generation layer formed on the support, the charge generation layer a charge transport layer formed on, and a electrophotographic photosensitive member having a protective layer formed on the charge transport layer ,
The charge transport layer contains a charge transport material;
The electrophotographic photoreceptor, wherein the protective layer contains a cured product of a composition containing a charge transporting monomer represented by the following formula (5) .

(In the formula (5), r is 0 or 1. Ar ²¹ , Ar ²² , Ar ²³ when r is 0 (when r is 0, there is no —Ar ²⁴ , and Ar ²³ is a monovalent group) in a.), and, ^{Ar 24} are each independently a group represented by the following formula (6), a group represented by the following formula (7), or, ^{.Ar 21} ~ of a substituted or unsubstituted aryl group Ar ²² , Ar ²³ when r is 0 , and Ar ²⁴ , at least one is a group represented by the following formula (6), and at least one is represented by the following formula (7) Ar ²³ when r is 1 ( when r is 1, Ar ²³ is a divalent group) is a group represented by the following formula (8) and represented by the following formula (9). group, or a substituted or unsubstituted arylene group. ^However, Ar 21 ^{to Ar 24} That is, at least one is a group represented by the following formula (6), or a group represented by the following formula (8), and at least one is a group represented by the following formula (7), or (It is a group represented by the following formula (9).)

(In the formulas (6) and (7), Ar ³¹ and Ar ³² each independently represent a substituted or unsubstituted arylene group. In the formulas (8) and (9), Ar ³³ and Ar ³⁴ are respectively independently, .R ¹ showing a substituted or unsubstituted trivalent aromatic group is ^.X 3 ^{to X 6,} Y 3 to Y ⁶ and ^Z 3 to Z ⁶ showing a substituted or unsubstituted alkylene group, Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group.) The electrophotographic photosensitive member according to claim 1, wherein the charge transport material is a compound represented by the following formula (3).

(In the formula ^(3), Ar 1 ~Ar ⁴ each independently represent a hydrogen atom or,, ^{.Ar 11} showing a substituted or unsubstituted aryl group, .R ² and represents a substituted or unsubstituted arylene group R ³ each independently represents a single bond or an ethylene group.) The electrophotographic photoreceptor according to claim 2, wherein the charge transport material is a compound represented by the following formula (4).

The substituted or unsubstituted alkylene group, an ethylene group, a propylene group, butylene group, pentylene group, or electrophotographic photosensitive member according to any one of claims 1 to 3 which is a hexylene group. Support, a charge generation layer formed on the support, the charge generation layer a charge transport layer formed on, and method for producing an electrophotographic photosensitive member having a protective layer formed on the charge transport layer Because
The manufacturing method comprises:
Preparing a protective layer coating liquid containing a composition comprising a charge transporting monomer represented by the following formula (5) and,
To form a coating film having a-holding Mamoruso coating liquid, comprising the step of forming the protective layer by curing the composition in the coating film,
The method for producing an electrophotographic photoreceptor , wherein the charge transport layer contains a charge transport material.

(In the formula (5), r is 0 or 1. Ar ²¹ , Ar ²² , Ar ²³ when r is 0 (when r is 0, there is no —Ar ²⁴ , and Ar ²³ is a monovalent group) in a.), and, ^{Ar 24} are each independently a group represented by the following formula (6), a group represented by the following formula (7), or, ^{.Ar 21} ~ of a substituted or unsubstituted aryl group Ar ²² , Ar ²³ when r is 0 , and Ar ²⁴ , at least one is a group represented by the following formula (6), and at least one is represented by the following formula (7) Ar ²³ when r is 1 ( when r is 1, Ar ²³ is a divalent group) is a group represented by the following formula (8) and represented by the following formula (9). group, or a substituted or unsubstituted arylene group. ^However, Ar 21 ^{to Ar 24} That is, at least one is a group represented by the following formula (6), or a group represented by the following formula (8), and at least one is a group represented by the following formula (7), or (It is a group represented by the following formula (9).)

(In the formulas (6) and (7), Ar ³¹ and Ar ³² each independently represent a substituted or unsubstituted arylene group. In the formulas (8) and (9), Ar ³³ and Ar ³⁴ are respectively independently, .R ¹ showing a substituted or unsubstituted trivalent aromatic group is ^.X 3 ^{to X 6,} Y 3 to Y ⁶ and ^Z 3 to Z ⁶ showing a substituted or unsubstituted alkylene group, Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, a nitro group, or a cyano group.) The method for producing an electrophotographic photosensitive member according to claim 5 , wherein the charge transport material is a compound represented by the following formula (3).

(In the formula ^(3), Ar 1 ~Ar ⁴ each independently represent a hydrogen atom or,, ^{.Ar 11} showing a substituted or unsubstituted aryl group, .R ² and represents a substituted or unsubstituted arylene group R ³ each independently represents a single bond or an ethylene group.) The method for producing an electrophotographic photosensitive member according to claim 6 , wherein the charge transport material is a compound represented by the following formula (4).

The method for producing an electrophotographic photosensitive member according to claim 5, wherein the substituted or unsubstituted alkylene group is an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group. It said step of forming a protective layer, according to any one of the coating film according to claim 5-8 step Ru der of forming the protective layer by curing the composition by irradiating an electron beam A method for producing an electrophotographic photoreceptor. An electrophotographic photosensitive member according to any one of claims 1 to 4 , and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means, are integrally supported, and electrophotographic A process cartridge that is detachable from the main unit. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to any one of claims 1 to 4 , and a charging unit, an exposing unit, a developing unit, and a transfer unit.

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