JP2015225132A - Electrophotographic photosensitive member, method of producing the same, process cartridge, and electrophotographic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photosensitive member which is resistant to both abrasion and image deletion, and a method of producing the same.SOLUTION: A surface layer of the electrophotographic photosensitive member contains a polymerized product of a composition having a charge transport substance having two or more acryloyloxy groups and a charge transport substance having one methacryloyloxy group.

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. Therefore, an electrophotographic photosensitive member that is repeatedly used in an electrophotographic apparatus is required to have a surface layer having excellent wear resistance.

  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.

JP 2000-066425 A

  However, in order to further extend the life of the electrophotographic photosensitive member, it is necessary to improve scratches and image flow in addition to improving wear resistance.

  As a result of the study by the present inventors, in addition to a charge transport material having two or more acryloyloxy groups, polymerization of a composition further comprising a charge transport material having one acryloyloxy group in the surface layer of the electrophotographic photosensitive member It has been found that the image flow is improved by including the product. However, it has been found that a charge transport material having one acryloyloxy group needs to have improved scratch resistance in order to extend its life.

  An object of the present invention is to provide an electrophotographic photoreceptor excellent in both scratch resistance and image flow, 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.

The present invention is an electrophotographic photosensitive member having a support and a photosensitive layer formed on the support,
The surface layer of the electrophotographic photosensitive member contains a polymer obtained by polymerizing a composition containing a charge transport material having two or more acryloyloxy groups and a charge transport material having one methacryloyloxy group. An electrophotographic photoreceptor.

The present invention also provides a method for producing an electrophotographic photosensitive member for producing the electrophotographic photosensitive member, wherein the manufacturing method comprises:
Forming a coating film of a coating solution for a surface layer containing the composition, and
A method for producing an electrophotographic photoreceptor, comprising the step of forming the surface layer by polymerizing the composition contained in the coating film.

  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, it is possible to provide an electrophotographic photoreceptor excellent in both scratch resistance and image flow and a method for producing the same. Further, according to the present invention, a process cartridge and an electrophotographic apparatus having the 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.

  As described above, the electrophotographic photoreceptor of the present invention has a support and a photosensitive layer formed on the support. The surface layer of the electrophotographic photosensitive member contains a polymer (cured product) of a composition of a charge transport material having two or more acryloyloxy groups and a charge transport material having one methacryloyloxy group. And

  As described above, the electrophotographic photoreceptor of the present invention is excellent in scratch resistance and suppression of image flow. In particular, the inventors presume the reason why the scratch resistance is excellent as follows.

  First, the inventors presume the reason why the image flow is improved as follows. In addition to the charge transport material having two or more acryloyloxy groups, it is considered that the image flow is improved by using a charge transport material having one polymerizable functional group (acryloyloxy group, methacryloyloxy group). Yes. Compared to a charge transporting material having two polymerizable functional groups, a charge transporting material having one polymerizable functional group has a smaller twist (distortion) in the molecular structure during the polymerization reaction. An increase in oxidation potential due to (distortion) can be suppressed. It is presumed that the image flow is caused by a discharge product (NOx or the like) generated by charging altering the constituent material of the surface layer. Since this NOx preferentially acts on a structure having a low oxidation potential, it is considered that NOx preferentially acts on a charge transport material having one polymerizable functional group. From this, it is presumed that the image flow is improved by suppressing the influence of NOx acting on the polymer of the charge transport material having two or more acryloyloxy groups and deteriorating.

  Furthermore, it has been found that the scratch resistance is improved by changing the polymerizable functional group of the charge transport material having one polymerizable functional group to a methacryloyloxy group. The reason for this is estimated by the inventors as follows. Generally, when obtaining a copolymer of a composition of a monomer having an acryloyloxy group and a monomer having a methacryloyloxy group, it is known that the methacryloyloxy group tends to contribute to the polymerization reaction. Here, in the present invention, a composition in which a charge transport material having one methacryloyloxy group is further mixed with a charge transport material having two or more acryloyloxy groups is polymerized. Thereby, it is considered that the charge transport materials having one methacryloyloxy group that easily contributes to the polymerization reaction react preferentially. And it estimates that the surface layer obtained in this way exhibits the characteristic with favorable scratch resistance.

  It is a charge transport material having two acryloyloxy groups among charge transport materials having two or more acryloyloxy groups in that charge transport materials having one methacryloyloxy group are likely to react preferentially. preferable. Thereby, scratch resistance becomes better.

  From the viewpoint of improving scratch resistance, the mass ratio of the charge transport material having two or more acryloyloxy groups and the charge transport material having one methacryloyloxy group is preferably 100: 20 to 100: 1. More preferably, it is 100: 25-100: 1.

  Furthermore, the charge transport material having two or more acryloyloxy groups is preferably a triphenylamine compound represented by the following formula (1). In addition, the charge transport material having one methacryloyloxy group is also preferably a triphenylamine compound represented by the following formula (2).

From the viewpoint of image flow suppression, in the triphenylamine compound represented by the following formula (1) and the triphenylamine compound represented by the following formula (2), Ar1, Ar4 and Ar6 are the same group, and Ar ² , Ar ³ and Ar ⁵ are preferably the same group.

In the formula (1), Ar ¹ represents a substituted or unsubstituted aryl group. Ar ² and Ar ³ represent a substituted or unsubstituted arylene group. m and o each independently represent an integer of 1 or more.

In formula (2), Ar ⁴ and Ar ⁶ represent a substituted or unsubstituted aryl group. Ar ⁵ represents a substituted or unsubstituted arylene group. p represents an integer of 1 or more.

  Examples of the aryl group include a phenyl group, a biphenyl group, a fluorenyl group, and a dimethylfluorenyl group. Examples of the arylene group include a phenylene group, a biphenylene group, a fluorenylene group, and a dimethylfluorenylene group.

  Examples of the substituent of the substituted aryl group include an alkyl group such as a methyl group, an ethyl group, and an n-propyl group, an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, a halogen atom such as fluorine, chlorine, and bromine, and a dimethylamino group. , A cyano group, a nitro group, and the like. Among these, an alkyl group and a halogen atom are preferable.

  As the substituent of the substituted arylene group, an alkyl group such as a methyl group, an ethyl group or an n-propyl group, an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group, a halogen atom such as fluorine, chlorine or bromine, a dimethylamino group , A cyano group, a nitro group, and the like. Among these, an alkyl group and a halogen atom are preferable.

  The charge transport material having two or more acryloyloxy groups and the charge transport material having one methacryloyloxy group according to the present invention are described in, for example, Japanese Patent Application Laid-Open Nos. 2000-066425 and 2010-156835. It can be synthesized using a synthesis method.

  Specific examples (exemplary compounds) of charge transport materials having two acryloyloxy groups are listed below, but the present invention is not limited thereto.

  Specific examples (exemplary compounds) of charge transport materials having one methacryloyloxy group are listed below, but the present invention is not limited thereto.

  Various additives may be added to 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.

  Solvents used in the surface layer coating solution 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.

  Polymerization of a composition of a charge transport material having two or more acryloyloxy groups and a charge transport material having one methacryloyloxy group is performed using heat, light (such as ultraviolet rays), or radiation (such as electron beams). be able to. Among these, polymerization using radiation is preferable, and polymerization using an electron beam is more preferable among radiations.

  Polymerization using an electron beam is preferable because a very dense (high density) three-dimensional cross-linked structure is obtained and wear resistance is improved. 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.

  Moreover, when polymerizing the said composition using an electron beam, it is preferable to heat in an inert gas atmosphere after irradiating an electron beam in an inert gas atmosphere in order to suppress the polymerization inhibitory action by oxygen. Examples of the inert gas include nitrogen, argon, helium and the like.

  As described above, the electrophotographic photoreceptor of the present invention has a support and a photosensitive layer formed on the support. The photosensitive layer includes a single-layer type photosensitive layer containing both a charge generating substance and a charge transporting substance, and a laminated photosensitive layer separated into a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance. is there. Of these, a multilayer photosensitive layer having a charge generation layer and a charge transport layer formed on the charge generation layer is preferable. A protective layer may be formed on the photosensitive layer (charge transport layer).

  In the laminated photosensitive layer, when the charge transport layer is a surface layer, the charge transport layer contains the polymer. When a protective layer is formed on the photosensitive layer (charge transport layer) and the protective layer is a surface layer, the protective layer contains the polymer.

  FIGS. 1A and 1B are diagrams showing an example of the layer structure of the electrophotographic photosensitive member of the present invention. In FIGS. 1A and 1B, 101 is a support, 102 is a charge generation layer, 103 is a charge transport layer, and 104 is a protective layer. The surface layer of the electrophotographic photosensitive member is the charge transport layer 103 in FIG. 2A and the protective layer 104 in FIG.

  In the present invention, 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).

[Support]
As the support used in the electrophotographic photosensitive member, a conductive one (conductive support) is preferable. For example, a support made of metal such as aluminum, aluminum alloy, stainless steel, or alloy can be used. In the case of a support made of aluminum or an 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. A support in which a thin film of a conductive material such as aluminum, an aluminum alloy, or an indium oxide-tin oxide alloy is formed on a metal support or a resin support can also be used.

  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.

[Conductive layer]
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 may be formed by forming a coating film of a coating solution for a conductive layer obtained by dispersing conductive particles together with a binder resin and a solvent, and drying and / or curing the obtained coating film. it can.

  Examples of the conductive particles used in the conductive layer include metal particles such as carbon black, acetylene black, aluminum, nickel, iron, nichrome, copper, zinc, and silver, and metal oxide particles such as tin oxide and ITO. Can be mentioned. Further, the metal particles or metal oxide particles may have their surfaces treated with a surface treatment agent such as a silane coupling agent.

  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.

[Undercoat layer]
An undercoat layer may be provided between the support or the conductive layer and the photosensitive layer.

  The undercoat layer can be formed by forming a coating film of an undercoat layer coating solution containing a binder resin and drying or curing the obtained coating film.

  Examples of the binder 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 conductive particles, semiconductive particles, an electron transporting material, and an electron accepting material used in the above-described conductive layer.

  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.

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

  Examples of charge generating materials used in electrophotographic photoreceptors include pyrylium, thiapyrylium dyes, phthalocyanine compounds, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, azo pigments, indigo pigments, quinacridone pigments, and quinocyanine pigments. Can be mentioned. Among these, gallium phthalocyanine is preferable. Further, from the viewpoint of high sensitivity, hydroxygallium phthalocyanine is preferable, and among them, peaks are observed at 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° of the Bragg angle 2θ in CuKα characteristic X-ray diffraction. The hydroxygallium phthalocyanine crystal which has is preferable.

  Examples of the binder resin used for the charge generation layer include polycarbonate, polyester, butyral resin, polyvinyl acetal, acrylic resin, vinyl acetate resin, urea resin, and the like. 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 can be 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. 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, 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.

  When the photosensitive layer is a laminated photosensitive layer, a charge transport layer is formed on the charge generation layer. When the photosensitive layer is a laminated photosensitive layer, a charge transport layer is formed on the charge generation layer.

  When the charge transport layer is a surface layer as shown in FIG. 1 (a), the charge transport layer contains the above-mentioned polymer as described in the above-mentioned surface layer, and the charge transport layer is formed as follows. Form. That is, a coating film of a coating solution for a charge transport layer containing a composition containing a charge transport material having two or more acryloyloxy groups and a charge transport material having one methacryloyloxy group is formed, A charge transport layer can be formed by polymerizing the composition.

  When the protective layer is a surface layer, the charge transport layer forms a coating film of the charge transport layer coating solution obtained by dissolving the charge transport material and the binder resin in a solvent, and the obtained coating film is dried. Can be formed.

  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, triarylmethane compounds, and the like.

  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, polyvinylpyrrolidone and the like. 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.

[Protective layer]
A protective layer (surface layer) may be formed on the charge transport layer. The protective layer (surface layer) is as described above.

  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, a cylindrical (drum-shaped) electrophotographic photosensitive member 1 is rotationally driven around a shaft 2 in a direction indicated by 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.

  Among the components selected from the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, the transfer unit 6, and the cleaning unit 9, a plurality of components 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”.

<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 (trade name: ECT-62, manufactured by Titanium Industry Co., Ltd.) coated with tin oxide containing 10% antimony oxide, resol type phenol resin (trade name: Phenolite J-325, 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) A coating solution for a conductive layer was prepared by placing 0.002 part in a sand mill using glass beads having a diameter of 0.8 mm and dispersing the mixture for 2 hours. This conductive layer coating solution was dip-coated on a support to form a coating film, and this 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
7.5 parts of N-methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Nagase ChemteX)
An undercoat layer coating solution was prepared by dissolving in a mixed solvent of 100 parts of methanol and 90 parts of butanol. The 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 0.5 μm. did.

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

  Next, 10 parts of a charge transport material represented by the following formula (3) 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 this coating film was dried at 100 ° C. for 30 minutes to form a charge transport layer having a thickness of 18 μm.

  Next, 99.9 parts of exemplary compound (A-2) and 0.1 part of exemplary compound (M-2) were dissolved in 100 parts of n-propanol. To this solution, 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.) ) Made) A protective layer coating solution was prepared by adding 0.01 part. The protective layer coating solution was dip coated on the charge transport layer to form a coating film, and the 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 atmosphere, a heat treatment was performed for 12 minutes under the condition that the coating film became 115 ° C. to form a protective layer (surface layer) having a thickness of 5 μm.

  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 2>
In Example 1, electrophotography was carried out in the same manner as in Example 1, except that 99 parts of the exemplified compound (A-2) and 1 part of the exemplified compound (M-2) were changed to prepare a coating solution for a protective layer. A photoreceptor was manufactured.

<Example 3>
In Example 1, electrophotography was carried out in the same manner as in Example 1, except that the coating solution for protective layer was prepared by changing the exemplified compound (A-2) to 90 parts and the exemplified compound (M-2) to 10 parts. A photoreceptor was manufactured.

<Example 4>
In Example 1, electrophotography was carried out in the same manner as in Example 1 except that the coating solution for protective layer was prepared by changing the exemplified compound (A-2) to 80 parts and the exemplified compound (M-2) to 20 parts. A photoreceptor was manufactured.

<Example 5>
In Example 1, the same procedure as in Example 1 was carried out except that the protective compound coating solution was prepared by changing the exemplified compound (A-2) to 67 parts and the exemplified compound (M-2) to 33 parts. A photoreceptor was manufactured.

<Example 6>
In Example 3, an electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the protective layer was formed as follows.

The coating solution for protective layer used in Example 3 was dip-coated on the charge transport layer to form a coating film, and this 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 7>
In Example 1, electrophotography was carried out in the same manner as in Example 1, except that the coating solution for protective layer was prepared by changing the exemplified compound (A-9) to 90 parts and the exemplified compound (M-7) to 10 parts. A photoreceptor was manufactured.

<Example 8>
In Example 1, electrophotography was carried out in the same manner as in Example 1, except that 90 parts of the exemplified compound (A-2) and 10 parts of the exemplified compound (M-3) were prepared to prepare a coating solution for a protective layer. A photoreceptor was manufactured.

<Example 9>
In Example 1, electrophotography was carried out in the same manner as in Example 1, except that the coating solution for protective layer was prepared by changing the exemplified compound (A-6) to 90 parts and the exemplified compound (M-2) to 10 parts. A photoreceptor was manufactured.

<Example 10>
In Example 1, electrophotography was carried out in the same manner as in Example 1, except that the coating solution for protective layer was prepared by changing the exemplified compound (A-5) to 90 parts and the exemplified compound (M-2) to 10 parts. A photoreceptor was manufactured.

<Example 11>
In Example 1, electrophotography was carried out in the same manner as in Example 1, except that the coating solution for protective layer was prepared by changing the exemplified compound (A-2) to 90 parts and the exemplified compound (M-6) to 10 parts. A photoreceptor was manufactured.

<Comparative example 1>
In Example 1, the electrophotographic photosensitive member was prepared in the same manner as in Example 1, except that 100 parts of the exemplified compound (A-2) was used and a coating solution for protective layer was prepared without using the exemplified compound (M-2). Manufactured.

<Comparative example 2>
An electrophotographic photoreceptor in the same manner as in Example 1 except that in Example 1, the exemplified compound (M-2) was changed to a charge transport material represented by the following formula (4) to prepare a coating solution for a protective layer. Manufactured.

<Comparative Example 3>
In Example 1, the electrophotographic photoreceptor is prepared in the same manner as in Example 1 except that the coating compound for the protective layer is prepared by changing the exemplified compound (M-2) to the charge transporting material represented by the following formula (5). Manufactured.

(Evaluation)
About the evaluation method of the electrophotographic photoreceptor of Examples 1-10 and Comparative Examples 1-3, it is as follows.

(Evaluation of image flow)
As an evaluation apparatus, a modified machine of a copying machine GP-405 (trade name) manufactured by Canon Inc., which is an electrophotographic apparatus, was used. GP-405 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 discharge current amount is adjusted to be 300 μA by constant voltage control, and the initial dark portion potential (Vd) of the electrophotographic photosensitive member is about −900 V, and the initial bright portion potential (Vl) is about −200 V. The conditions of the direct current voltage applied to the charging roller and the exposure light quantity of the exposure apparatus were set. The cassette heater was always off.

  After the electrophotographic photosensitive member produced in each example is mounted on a process cartridge and mounted on the above-described evaluation apparatus, an image with an image ratio of 2% is printed on A4 vertical size paper in an environment of a temperature of 29 ° C. and a humidity of 75% RH. Output 1000 sheets. After 1000 images were output, the power supply to the evaluation device was stopped and suspended for 1 week. After one week of rest, power was supplied to the evaluation device again, and a character image (E character image) in which a halftone image and the letter E of the alphabet (font type: Times, font size 6 points) were repeated on A4 vertical size paper ) Was output.

About the obtained image, the effect which suppresses an image defect (image flow) was evaluated according to the following evaluation ranks. The larger the rank number, the better. Ranks 6, 5, 4 and 3 were judged to be levels at which the effects of the present invention were obtained. On the other hand, ranks 1 and 2 were judged as levels at which the effects of the present invention were not obtained.
Rank 6: No image defect is observed in both the halftone image and the E character image.
Rank 5: The density of the halftone image is slightly light, but there is no image defect of the E character image.
Rank 4: The halftone image is partially blank, but there is no image defect in the E character image.
Rank 3: The halftone image is partially blank and the E character image density is slightly light.
Rank 2: The halftone image is partially blank and the E character image density is partially blank.
Rank 1: The halftone image is mostly white and the E character image density is mostly white.

  The evaluation results are shown in Table 1.

(Evaluation of scratch resistance)
Using the electrophotographic photosensitive member for which the evaluation of the image flow was completed, another 200,000 sheets were repeatedly tested. The presence or absence of image defects (scratch images) due to generation of scratches on the surface of the electrophotographic photosensitive member was confirmed by visual inspection. The results are shown in Table 1. If no image defect (scratch image) is observed at 150,000 sheets 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 (10)

An electrophotographic photosensitive member having a support and a photosensitive layer formed on the support,
The surface layer of the electrophotographic photosensitive member contains a polymer of a composition containing a charge transport material having two or more acryloyloxy groups and a charge transport material having one methacryloyloxy group. Photoconductor.   The electrophotographic photoreceptor according to claim 1, wherein the charge transport material having two or more acryloyloxy groups is a charge transport material having two acryloyloxy groups.   The mass ratio of the charge transport material having two or more acryloyloxy groups and the charge transport material having one methacryloyloxy group in the composition is 100: 20 to 100: 1. Electrophotographic photoreceptor. The electrophotographic photoreceptor according to claim 1, wherein the charge transport material having two or more acryloyloxy groups is a triphenylamine compound represented by the following formula (1).

(In Formula (1), Ar ¹ represents a substituted or unsubstituted aryl group. Ar ² and Ar ³ represent a substituted or unsubstituted arylene group. M and o each independently represents one or more. Indicates an integer.) The electrophotographic photosensitive member according to any one of claims 1 to 4, wherein the charge transporting material having one methacryloyloxy group is a triphenylamine compound represented by the following formula (2).

(In formula (2), Ar ⁴ and Ar ⁶ represent a substituted or unsubstituted aryl group. Ar ⁵ represents a substituted or unsubstituted arylene group. P represents an integer of 1 or more.) In said Formula (1) and (2), Ar < ¹ >, Ar < ⁴ > and Ar < ⁶ > are the same groups, Ar < ² >, Ar < ³ > and Ar < ⁵ > are the same groups, The any one of Claims 1-5 The electrophotographic photoreceptor described in 1. An electrophotographic photoreceptor production method for producing the electrophotographic photoreceptor according to any one of claims 1 to 6, wherein the production method comprises:
Forming a coating film of a coating solution for a surface layer containing the composition, and
A method for producing an electrophotographic photoreceptor, comprising the step of forming the surface layer by polymerizing the composition contained in the coating film.   The method for producing an electrophotographic photosensitive member according to claim 7, 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 6 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 exposing unit, a developing unit, and a transfer unit.

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