JP6420693B2 - 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 recent years, electrophotographic apparatuses are required to produce a large amount of printed matter with high print quality. Thus, an electrophotographic photoreceptor that is repeatedly used in an electrophotographic apparatus is required to have wear resistance and excellent electrical characteristics.

  Patent Document 1 discloses that the surface layer of an electrophotographic photosensitive member contains a polymer obtained by polymerizing a charge transport material having two or more chain polymerizable functional groups, thereby improving the abrasion resistance of the electrophotographic photosensitive member. Techniques for improving are disclosed.

  Patent Document 1 discloses a charge transport material having two or more chain polymerizable functional groups on the surface layer of the electrophotographic photosensitive member and a material having no charge transport performance having two or more chain polymerizable functional groups. And a technique for containing a polymer obtained by polymerizing the composition.

JP 2000-066425 A

  Even the surface layer disclosed in Patent Document 1 may not be fully satisfactory depending on the electrophotographic process. As a result of intensive studies, the present inventors have found that the surface layer of an electrophotographic photosensitive member has a charge transporting performance having two or more specific chain polymerizable functional groups different from the compound disclosed in Patent Document 1. A polymer obtained by polymerizing was added. As a result, it has been found that potential fluctuations during repeated use of the electrophotographic photosensitive member are further suppressed, and good electrical characteristics can be obtained.

  An object of the present invention is to provide an electrophotographic photoreceptor excellent in both wear resistance and electrical characteristics, and a method for producing the same.

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

式（１）中、Ｒ^１は、水素原子もしくはメチル基を示し、式（２）中、ｎは２以上の整数を示し、Ｍは式（１）で定義される１価の基を示し、Ｒ^２は、（７×（ｎ−１））以上の炭素原子からなる直鎖構造もしくは分岐構造もしくは単環構造のいずれかの構造を有するｎ価の飽和炭化水素基を示す。 The present invention relates to a support and an electrophotographic photoreceptor having a photosensitive layer on the support, wherein the surface layer of the photosensitive layer has two or more monovalent groups represented by the formula (1). An electrophotographic photoreceptor characterized in that it is a surface layer containing a compound and a polymer of a composition with the compound represented by formula (2).

In formula (1), R ¹ represents a hydrogen atom or a methyl group, in formula (2), n represents an integer of 2 or more, M represents a monovalent group defined by formula (1), R ² represents an n-valent saturated hydrocarbon group having a linear structure consisting of (7 × (n−1)) or more carbon atoms, a branched structure, or a monocyclic structure.

  The present invention is also a method for producing an electrophotographic photosensitive member for producing the electrophotographic photosensitive member, wherein the production method forms a coating film using a surface layer coating solution containing the composition. And a method for producing an electrophotographic photoreceptor, comprising a step of forming a surface layer by polymerizing the composition contained in the coating film.

  Furthermore, 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.

  Furthermore, the present invention is an electrophotographic apparatus comprising the electrophotographic photosensitive member, a charging unit, an exposure unit, a developing unit, and a transfer unit.

  According to the present invention, in an electrophotographic photosensitive member having a support and a photosensitive layer on the support, electrophotography having excellent electrical characteristics such as high abrasion resistance and good potential fluctuation during repeated use. A photoreceptor and a method for manufacturing the same can be provided. In addition, according to the present invention, a process cartridge and an electrophotographic apparatus having such an electrophotographic photosensitive member can be provided.

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

  As described above, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a support and a photosensitive layer on the support. The electrophotographic photoreceptor contains a charge transporting compound having two or more monovalent groups represented by the formula (1) and a polymer of a composition with the compound represented by the formula (2). It has a layer.

In formula (1), R ¹ is a hydrogen atom or a methyl group.

  The charge transporting compound is a small skeleton in which the site exhibiting a charge transporting function easily aggregates, and it is considered that the electrical properties of the electrophotographic photosensitive member are impaired by the aggregation. Therefore, the charge transporting compound having two or more monovalent groups represented by the formula (1) may be any compound as long as it does not easily aggregate due to the constitution of the present invention. Two or more monovalent groups represented by the formula (1) of the charge transporting compound may be the same or different.

  The charge transporting compound having two monovalent groups represented by the formula (1) is preferably a triphenylamine compound having two monovalent groups represented by the formula (1). In the triphenylamine compound, the monovalent group represented by the formula (1) may be directly bonded to the triphenylamine compound or may be bonded via a divalent alkylene group such as ethylene or propylene. . Two or more monovalent groups represented by the formula (1) may be substituted with the same phenyl group or may be substituted with different phenyl groups. Furthermore, the triphenylamine compound may have other substituents.

  In formula (2), n is an integer of 2 or more. N is preferably 2 in that the electrophotographic photoreceptor of the present invention exhibits excellent electrical characteristics.

  In formula (2), M is a monovalent group represented by formula (1), and may be the same as or different from the monovalent group represented by formula (1) in the charge transporting compound. Good.

In the formula (2), R ² is an n-valent saturated hydrocarbon group having a linear structure or a branched structure or a monocyclic structure consisting of (7 × (n−1)) or more carbon atoms. is there. In view of the effects of the present invention, R ² preferably has a branched structure.

  As described above, the electrophotographic photoreceptor of the present invention has high wear resistance and good potential fluctuation during repeated use. In particular, the present inventors speculate as follows why the potential fluctuation during repeated use is good.

  Patent Document 1 discloses an electrophotographic photosensitive member having a surface layer formed by crosslinking a charge transporting compound having two or more monovalent groups represented by the formula (1) alone. However, the electrophotographic photosensitive member is likely to aggregate because the portions exhibiting the charge transport function in the charge transport compound are close to each other, and as a result, the electrophotographic photoreceptor may have been a cause of impairing electrical characteristics. They thought. Therefore, as a result of intensive studies, the present inventors have found that electrical characteristics are improved by allowing a low-polarity alkyl compound represented by formula (2) to coexist in the surface layer. This is because the compatibility between the site exhibiting the charge transport function in the charge transporting compound and the alkyl site in the alkyl compound is good, so that a cross-linked film in which the site exhibiting the charge transport function in the charge transporting compound is difficult to aggregate is formed. I think it is because it was formed on the surface layer.

  However, at the same time, even if the present inventors are alkyl compounds, it is difficult to obtain the effects of the present invention with an alkyl compound having no monovalent group represented by formula (1) or having only one. I also found. Since the alkyl compound does not become a constituent of the crosslinked film, it is considered that it is difficult to sufficiently suppress the aggregation of the sites exhibiting the charge transport function in the charge transport compound.

  Furthermore, even in the case of the alkyl compound represented by the formula (2) having two or more monovalent groups represented by the formula (1), if the number of carbon atoms constituting the alkyl moiety is not sufficiently large, electrophotography The present inventors have found that it is difficult to improve the electrical characteristics of the photoreceptor. Specifically, when the alkyl compound represented by the formula (2) has two monovalent groups represented by the formula (1), the number of carbon atoms constituting the alkyl group is at least 7 or more. Furthermore, every time one monovalent group represented by the formula (1) increases, the number of carbon atoms constituting the alkyl group needs to be 7 or more. This is because the total number of atoms other than hydrogen atoms in the monovalent group represented by the formula (1) is 5 or 6, so that it is necessary to give more carbon atoms than this. thinking.

  If there are too many monovalent groups represented by the formula (1) in the alkyl compound represented by the formula (2), the in-film stress at the time of curing increases, and as a result, the charge transport function in the charge transport compound is increased. It is easy to promote aggregation between the indicated sites. Therefore, it is preferable that the number of monovalent groups represented by the formula (1) is two in that the electrophotographic photosensitive member of the present invention exhibits excellent electrical characteristics.

  In addition, the alkyl compound represented by the formula (2) has 9 or more carbon atoms constituting the alkyl group in view of the effect that the electrophotographic photosensitive member of the present invention exhibits high wear properties and excellent electrical characteristics. It is more preferable that the number of carbon atoms constituting the alkyl group is 30 or less in that the electrical characteristics are not easily impaired.

  Furthermore, the electrophotographic photoreceptor of the present invention has a structure in which the alkyl group is branched in that the alkyl group can effectively act on a site exhibiting a charge transport function in the charge transport compound even when crosslinked. This is preferable in that it exhibits excellent electrical characteristics.

  From the above, the alkyl group of the alkyl compound represented by the formula (2) is most preferably a divalent branched saturated hydrocarbon group consisting of only a hydrogen atom and 9 to 30 carbon atoms.

In view of the effect that the electrophotographic photoreceptor of the present invention exhibits high wear properties and excellent electrical properties, the compound represented by the following formula (3), the compound represented by the formula (4), or the formula (5) It is preferable that it is a surface layer containing the polymer of the composition which added the compound shown by this. The surface layer may be a polymer of a composition obtained by adding a compound represented by the formula (3), a compound represented by the formula (4), or a compound represented by the formula (5) alone, or a plurality thereof. The polymer of the composition which added the compound shown by Formula (3), the compound shown by Formula (4), and the compound shown by Formula (5) may be sufficient.

In formulas (3) to (5), D ¹¹ and D ¹² , D ^{21 to} D ²⁶ , D ^{31 to} D ³⁶ are each independently a substituted or unsubstituted benzyl group or an unsubstituted alkyl group, At least one of D ¹¹ and D ¹² and at least one of D ^{21 to} D ²⁶ is a substituted or unsubstituted benzyl group. Examples of the substituent that the benzyl group may have include an alkyl group, a halogen atom-substituted alkyl group, an alkoxy group, an amino group, an alkyl-substituted amino group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and a halogen atom. It is done.

In formulas (3) to (5), Ar ¹¹ and Ar ¹² , Ar ²¹ , Ar ²⁴ , Ar ³¹ , Ar ³² are substituted or unsubstituted aryl groups. Examples of the substituent that the aryl group may have include an alkyl group, a halogen atom-substituted alkyl group, an alkoxy group, an amino group, an alkyl-substituted amino group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and a halogen atom. It is done.

In the formula (4), Ar ²² and Ar ²³ are a substituted or unsubstituted arylene group. Examples of the substituent that the arylene group may have include an alkyl group, a halogen atom-substituted alkyl group, an alkoxy group, an amino group, an alkyl-substituted amino group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and a halogen atom. It is done.

In the formulas (3) to (5), at least one of Ar ¹¹ and Ar ¹² , at least one of Ar ^{21 to} Ar ²⁴ , and at least one of Ar ³¹ and Ar ³² is a group represented by the formula (6) is there.
In Formula (6), R ³ is a hydrogen atom or a methyl group, and m is an integer of 0 or more.

In formula (5), E is a group represented by formula (7).

In formulas (4) to (5), m ² and m ³ are each an integer of 0 or more. When m ² and m ³ are integers of 2 or more, the structures shown in parentheses may be the same or different.

  Specific examples (example compounds (A-1) to (A-18) and (M-1) to (M-18)) of the compound represented by the formula (2) of the present invention are listed below. Is not limited to these.

  The electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a support and a photosensitive layer formed on the support.

  FIG. 1 is a view showing an example of the layer structure of the electrophotographic photosensitive member of the present invention. In FIG. 1, 101 is a support, 102 is a charge generation layer, 103 is a charge transport layer, 104 is a surface layer, and 105 is a photosensitive layer.

  In the present invention, if necessary, a conductive layer and an undercoat layer described later may be provided between the support and the photosensitive layer (charge generation layer, charge transport layer, surface layer).

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

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

The conductive layer can be formed by applying a conductive layer coating solution obtained by dispersing conductive particles together with a binder resin and a solvent, and drying and / or curing the obtained coating film.
Examples of the conductive particles used in the conductive layer include carbon black, acetylene black, metal particles such as aluminum, nickel, iron, nichrome, copper, zinc, silver, tin oxide, zinc oxide, titanium oxide, Examples thereof include particles of metal oxides such as ITO.
Examples of the resin used for the conductive layer include acrylic resin, alkyd resin, epoxy resin, phenol resin, butyral resin, acetal resin, urethane resin, melamine resin, polyester, and polycarbonate.
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 photosensitive layer.
The undercoat layer can be formed by applying a coating solution for an undercoat layer containing a resin, 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 undercoat layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents.
The thickness of the undercoat layer is preferably 0.05 μm or more and 40 μm or less, and more preferably 0.1 μm or more and 20 μm or less.

  A photosensitive layer (a charge generation layer, a charge transport layer, a surface layer) is formed on the support, the conductive layer, or the undercoat layer.

  The charge generation layer in the electrophotographic photosensitive member of the present invention 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, and drying the obtained coating film. can do. The charge generation layer may be a vapor generation film of a charge generation material.

  Examples of the charge generation material used in the charge generation layer include pyrylium dyes, thiapyrylium dyes, phthalocyanine compounds, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, azo pigments, indigo pigments, quinacridone pigments, and quinocyanine pigments. Can be mentioned. Among these, phthalocyanine compounds are preferable, and gallium phthalocyanine is particularly 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 butyral resin, acrylic resin, urea resin, polycarbonate, polyester, polyvinyl acetal, and polyvinyl acetate. Among these, a butyral resin is preferable. These resin may use only 1 type and may use 2 or more types together as a mixture or a copolymer.

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

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

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

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

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

  The charge transport layer in the electrophotographic photoreceptor of the present invention is formed by applying a charge transport layer coating solution obtained by dissolving a charge transport material and a binder resin in a solvent, and drying the obtained coating film. can do.

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

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

  The ratio of the charge transporting compound is preferably 30% by mass or more and 70% by mass or less based on the total mass of the charge transporting 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.

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

The surface layer in the electrophotographic photosensitive member of the present invention can be formed as follows. First, a coating solution for a surface layer is obtained by dissolving a composition comprising a charge transporting compound having two or more monovalent groups represented by the formula (1) and a compound represented by the formula (2) in a solvent. . Subsequently, using the surface layer coating solution, a coating film is formed on a support of an electrophotographic photosensitive member, and the composition is polymerized to obtain a three-dimensional crosslinked product, thereby forming the surface layer. be able to.
The proportion of the compound represented by formula (2) in the composition is preferably 1% by mass or more and 50% by mass or less of the compound represented by formula (2) with respect to the total mass of the composition.

  Solvents used in the surface layer coating solution include alcohol solvents such as methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol and 1-methoxy-2-propanol, and ketones such as acetone, methyl ethyl ketone and cyclohexanone. Solvents, ester solvents such as ethyl acetate and butyl acetate, ether solvents such as tetrahydrofuran and dioxane, halogen solvents such as 1,1,2,2,3,3,4-heptafluorocyclopentane, dichloromethane, dichloroethane, chlorobenzene Solvents, aromatic solvents such as benzene, toluene and xylene, and cellosolve solvents such as methyl cellosolve and ethyl cellosolve can be mentioned. These solvents may be used alone or in combination of two or more.

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

  Various additives can be added to the coating solution for the surface layer. Examples of additives include degradation inhibitors such as antioxidants and ultraviolet absorbers, lubricants such as polytetrafluoroethylene (PTFE) particles and carbon fluoride, polymerization control such as polymerization reaction initiators and polymerization reaction stoppers. Agents, leveling agents such as silicone oil, and surfactants.

  In the present invention, the polymerization of the composition contained in the coating film can be performed using heat, light (such as ultraviolet rays), or radiation (such as an electron beam). Among these, polymerization using radiation is preferable, and polymerization using an electron beam is more preferable among radiations.

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

  When polymerized using an electron beam, a very dense (high density) three-dimensional crosslinked structure is obtained, and a surface layer having high durability is obtained. Further, since the polymerization reaction is efficient in a short time, productivity is also increased. When irradiating an electron beam, 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 surface layer coating solution is preferably 5 kGy or more and 50 kGy or less, and more preferably 1 kGy or more and 10 kGy or less.

  In addition, when the composition contained in the coating film is polymerized using an electron beam, after irradiation with an electron beam in an inert gas atmosphere for the purpose of suppressing the polymerization inhibition action by oxygen, the inert gas atmosphere is used. It is preferable to heat. Examples of the inert gas include nitrogen, argon, helium and the like.

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

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

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

  The electrostatic latent image formed on the surface of the electrophotographic 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 photosensitive member 1 and at least one means selected from the group consisting of the charging means 3, the developing means 5, the transfer means 6 and the cleaning means 9 are integrally supported to form a cartridge, and the main body of the electrophotographic apparatus The process cartridge 11 can be detachably attached to the main body of the electrophotographic apparatus using the guide means 12 such as a rail.

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

<Example 1>
An aluminum cylinder having a diameter of 30 mm, a length of 357.5 mm, and a 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) as a metal oxide are stirred and mixed with 500 parts of toluene, and a silane coupling agent (compound) Name: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.8 part 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 butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 15 parts of blocked isocyanate (trade name: Sumijoule 3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.) as a polyol resin and methyl ethyl ketone 73. It was dissolved in a mixed solution of 5 parts and 73.5 parts of 1-butanol. To this solution, 80.64 parts of the surface-treated zinc oxide particles and 0.8 part of a compound represented by the structural formula (A) (manufactured by Tokyo Chemical Industry Co., Ltd.) are added, 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), crosslinked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER SSX-103, manufactured by Sekisui Plastics Co., Ltd.) 5.6 parts of an average primary particle size of 3.1 μm) was added and stirred to prepare an undercoat layer coating solution.
This coating solution for undercoat layer was dip-coated on the support to form a coating film, and this coating film was dried by heating at 145 ° C. for 40 minutes to form an undercoat layer having a thickness of 18 μm.

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

（式（Ｅ）中、０．９５および０．０５は２つの構造単位のモル比（共重合比）である。） Next, 2 parts of the charge transporting compound represented by the structural formula (B), 7 parts of the charge transporting compound represented by the structural formula (C), 1 part of the charge transporting compound represented by the structural formula (D), polycarbonate ( Product name: 10 parts of Iupilon Z400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 0.002 part of a polycarbonate having a structural unit represented by the structural formula (E) (viscosity average molecular weight Mv: 20000), 70 parts of monochlorobenzene and A charge transport layer coating solution was prepared by dissolving in a mixed solvent of 30 parts of dimethoxymethane. The charge transport layer coating solution was dip-coated on the charge generation layer, 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.

(In formula (E), 0.95 and 0.05 are the molar ratio (copolymerization ratio) of the two structural units.)

Next, 90 parts of a charge transporting compound having two monovalent groups represented by the formula (1) represented by the structural formula (F), an exemplary compound (A-1) corresponding to the compound represented by the formula (2) ) 10 parts, 30 parts of polytetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd.), a resin having a repeating structural unit represented by the formulas (G1) and (G2) (weight average molecular weight 130,000) , (G1) / (G2) = 1/1) 1.5 parts is added to 100 parts of n-propanol, and 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora) H, 100 parts of Nippon Zeon Co., Ltd.), 0.01 parts of 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) are added, and this is dispersed with an ultra-high pressure disperser to obtain a coating solution for the surface layer Was prepared. This surface layer coating solution was dip coated on the charge transport layer, 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 surface 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 surface layer was produced.

<Example 2>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the exemplified compound (A-1) was changed to the exemplified compound (A-17) to prepare a surface layer coating solution.

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

<Example 4>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the exemplified compound (A-1) was changed to the exemplified compound (A-8) to prepare a surface layer coating solution.

<Example 5>
In Example 1, an electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the exemplified compound (A-1) was changed to the exemplified compound (A-18) to prepare a surface layer coating solution.

<Example 6>
In Example 1, a charge transporting compound having two monovalent groups represented by the formula (1) represented by the structural formula (F) is represented by the formula (1) represented by the structural formula (H). An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution was prepared by changing the charge transporting compound having four valent groups.

<Example 7>
In Example 1, 90 parts of a charge transporting compound having two monovalent groups represented by formula (1) represented by structural formula (F), 10 parts of exemplary compound (A-8), structural formula (I) 10 parts of a compound represented by the formula, 30 parts of polytetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Corporation), a resin having a repeating structural unit represented by the formula (G1) and the formula (G2) (weight average molecular weight) 130,000, 1.5 parts of (G1) / (G2) = 1/1) are added to 100 parts of n-propanol, and 1,1,2,2,3,3,4-heptafluorocyclopentane (product) Name: 100 parts of Zeolora H, manufactured by Nippon Zeon Co., Ltd., 0.01 parts of 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), and dispersed by an ultra-high pressure disperser to obtain a surface layer. Except for preparing coating solution It was prepared an electrophotographic photosensitive member in the same manner as in Example 1.

<Example 8>
In Example 7, an electrophotographic photosensitive member was produced in the same manner as in Example 7, except that the exemplified compound (A-8) was changed to the exemplified compound (M-8) to prepare a coating solution for the surface layer.

<Example 9>
In Example 7, 90 parts of a charge transporting compound having two monovalent groups represented by the formula (1) represented by the structural formula (F), 10 parts of the exemplary compound (A-8), the structural formula (I) 10 parts of a compound represented by the formula: 1 part of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by BASF), 30 parts of polytetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd.) , 1.5 parts of a resin having a repeating structural unit represented by formula (G1) and formula (G2) (weight average molecular weight 130,000, (G1) / (G2) = 1/1) in 100 parts of n-propanol In addition, 100 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.), 4-methoxyphenol (Tokyo Chemical Industry Co., Ltd.) Ltd.) 0.01 part was added, which by dispersion treatment with ultra-high pressure dispersion machine was changed to that prepared a coating liquid for a surface layer. Further, this surface layer coating solution is dip-coated on the charge transport layer, and the resulting coating film is heat-treated at 50 ° C. for 5 minutes, and then using a metal halide lamp, irradiation intensity: 500 mW / cm ² . Under the conditions, the coating film was irradiated with ultraviolet rays for 20 seconds, and heat-treated for 30 minutes under the condition that the coating film reached 140 ° C., thereby forming a protective layer having a thickness of 5 μm. An electrophotographic photoreceptor was produced in the same manner as in Example 7 except for these.

<Comparative example 1>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution was prepared without using the exemplary compound (A-1).

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

<Comparative Example 3>
In Example 1, the electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface compound coating solution was prepared by changing the exemplified compound (A-1) to the compound represented by the structural formula (K). did.

<Comparative example 4>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the surface layer coating solution was prepared by changing the exemplified compound (A-1) to the compound represented by the structural formula (L). did.

<Comparative Example 5>
In Example 1, an electrophotographic photoreceptor is produced in the same manner as in Example 1 except that the surface compound coating solution is prepared by changing the exemplified compound (A-1) to the compound represented by the structural formula (M). did.

<Comparative Example 6>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the surface layer coating solution was prepared by changing the exemplified compound (A-1) to the compound represented by the structural formula (N). did.

<Comparative Example 7>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the surface layer coating solution was prepared by changing the exemplified compound (A-1) to the compound represented by the structural formula (O). did.

<Comparative Example 8>
In Example 1, the electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface compound coating solution was prepared by changing the exemplified compound (A-1) to the compound represented by the structural formula (P). did.

<Comparative Example 9>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the surface layer coating solution was prepared by changing the exemplified compound (A-1) to the compound represented by the structural formula (Q). did.

<Comparative Example 10>
In Example 1, a charge transporting compound having two monovalent groups represented by the formula (1) represented by the structural formula (F) is represented by the formula (1) represented by the structural formula (R). An electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the surface layer coating solution was prepared by changing to a charge transporting compound having one valent group.

<Comparative Example 11>
In Comparative Example 10, an electrophotographic photosensitive member was produced in the same manner as Comparative Example 10 except that Example Compound (A-1) was not used.

(Evaluation)
(Evaluation of potential fluctuation)
About the evaluation method of the electrophotographic photoreceptor manufactured in Examples 1-9 and Comparative Examples 1-11, it is as follows.
IR AVD C5051 (trade name) was used as an evaluation machine. First, the electrophotographic photosensitive member was left together with an evaluation machine in a normal temperature and humidity environment of a temperature of 23 ° C./humidity of 50% 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 -250V. The pre-exposure was adjusted so that the charge amount of −700 V was 3 times the amount of LED light that attenuated to −250 V. Thereafter, repeated charging, exposure, and pre-exposure cycles (VL endurance test, full-screen black image mode) are continuously performed without changing the above-described charging settings, image exposure amount, pre-exposure amount, and process speed settings. I went a thousand revolutions. A series of evaluations were all performed in a room temperature and humidity environment. The light portion potential (VL) at the 3000th rotation was measured, and the VL difference (potential fluctuation amount) between the initial rotation and the 3000th rotation was calculated as ΔVL.

  The evaluation results are shown in Table 1.

  When the potential fluctuation amount is 25 V or less, it can be determined that the electrophotographic photosensitive member of the present invention has excellent electrical characteristics.

(Evaluation of wear)
About the evaluation method of the electrophotographic photosensitive member manufactured in Example 1 and Comparative Example 1, it is as follows.
An iR AVD C5051 (trade name) remodeling machine was used as an evaluation apparatus. iR AVD C5051 has a charging roller as charging means. The modification was made so that power could be supplied to the charging roller from outside the copier.
A high voltage power supply control system (Model 615-3, manufactured by Trek) was used as a power source for supplying power for the charging roller from the outside of the copying machine. Then, the peak-to-peak voltage and frequency of the AC component applied to the charging roller were set so that the discharge current amount was 150 μA by constant voltage control. Further, the voltage of the DC component applied to the charging roller is set so that the initial dark portion potential (Vd) of the electrophotographic photosensitive member is about −700 [V] and the initial bright portion potential (Vl) is about −250 [V]. The exposure light quantity conditions of the exposure apparatus were set.
The electrophotographic photosensitive member was left together with an evaluation machine in a normal temperature and humidity environment of 23 ° C./50% RH for 1 day. Thereafter, the pre-exposure was adjusted so that the charge potential of −700 V was 3 times the amount of LED light that attenuated to −250 V. Thereafter, 100,000 images with an image ratio of 5% were output on A4 vertical size paper without changing the above-described charging settings, image exposure amount, pre-exposure amount, and process speed settings. The amount of change in the thickness of the photosensitive layer before and after outputting 100,000 images was evaluated as the amount of wear.

  The evaluation results are shown in Table 1.

  When the wear amount is 1.0 μm or less, it can be determined that the wear resistance is good. As shown in Table 1, it can be determined that the electrophotographic photosensitive member of the present invention has excellent wear resistance as in the conventional product.

DESCRIPTION OF SYMBOLS 101 Support body 102 Charge generation layer 103 Charge transport layer 104 Surface layer 105 Photosensitive layer 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 guide means

Claims (11)

In the electrophotographic photosensitive member having a support and a photosensitive layer on the support, the surface layer of the photosensitive layer has a charge transporting compound having two or more monovalent groups represented by the formula (1), and a formula An electrophotographic photoreceptor, which is a surface layer containing a polymer of a composition with the compound represented by (2).

(In formula (1), R ¹ represents a hydrogen atom or a methyl group, in formula (2), n represents an integer of 2 or more, M represents a monovalent group represented by formula (1), R ² represents a saturated hydrocarbon group having a linear structure consisting of (7 × (n−1)) or more carbon atoms, a branched structure, or a monocyclic structure.)   2. The electrophotographic photosensitive member according to claim 1, wherein n is 2 in the formula (2). 3. The electrophotographic photosensitive member according to claim 2, wherein, in the formula (2), R ² is a divalent linear or branched saturated hydrocarbon group composed of only a hydrogen atom and 9 or more carbon atoms. . 4. The electrophotographic photosensitive member according to claim 3, wherein in the formula (2), R ² is a divalent branched saturated hydrocarbon group composed of only a hydrogen atom and 9 or more carbon atoms. 5. The electrophotographic photosensitive member according to claim 4, wherein, in the formula (2), R ² is a divalent branched saturated hydrocarbon group composed of only a hydrogen atom and 9 to 30 carbon atoms.   In Claim 1, the charge transporting compound having two or more monovalent groups represented by the formula (1) is a triphenylamine compound having two monovalent groups represented by the formula (1). The electrophotographic photosensitive member according to claim 1, wherein: 2. The charge transporting compound according to claim 1, wherein the surface layer has two or more monovalent groups represented by the formula (1), the compound represented by the formula (2), and the following formula (3): It is a surface layer containing the polymer of a composition with the compound shown, the compound shown by Formula (4), or the compound shown by Formula (5), The any one of Claims 1-6 characterized by the above-mentioned. The electrophotographic photosensitive member according to Item.

(In formulas (3) to (5), D ¹¹ and D ¹² , D ^{21 to} D ²⁶ , and D ^{31 to} D ³⁶ each independently represent a substituted or unsubstituted benzyl group or an unsubstituted alkyl group. At least one of D ¹¹ and D ¹² and at least one of D ^{21 to} D ²⁶ is a substituted or unsubstituted benzyl group Ar ¹¹ and Ar ¹² , Ar ²¹ , Ar ²⁴ , Ar ³¹ , Ar ³² are A substituted or unsubstituted aryl group, Ar ²² and Ar ²³ represent a substituted or unsubstituted arylene group, at least one of Ar ¹¹ and Ar ¹² , at least one of Ar ^{21 to} Ar ²⁴ , Ar ³¹ and At least one of Ar ³² has a group represented by the formula (6), E represents a group represented by the formula (7), and m ² and m ³ are each 0 or more. When an integer is shown and m ² and m ³ are integers of 2 or more, the structures shown in parentheses may be the same or different.)

(In Formula (6), R ³ represents a hydrogen atom or a methyl group, and m represents an integer of 0 or more.)

  It is a manufacturing method of the electrophotographic photoreceptor which manufactures the electrophotographic photoreceptor of any one of Claims 1-7, Comprising: This manufacturing method uses the coating liquid for surface layers containing the said composition. A method for producing an electrophotographic photosensitive member, comprising: a step of forming a coating film; and a step of forming a surface layer by polymerizing the composition contained in the coating film.   The method for producing an electrophotographic photosensitive member according to claim 8, wherein the composition is polymerized by irradiating the coating film with an electron beam.   An electrophotographic photosensitive member according to any one of claims 1 to 7, 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 which is detachable from the apparatus main body.   An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, and a charging unit, an exposure unit, a developing unit, and a transfer unit.

Images