JP2017227723A - Electrophotographic photoreceptor, method for manufacturing the same, process cartridge, and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor excellent in potential variation suppressing effect when images are repeatedly formed in a high-temperature and high-humidity environment, and a method for manufacturing the same.SOLUTION: An electrophotographic photoreceptor comprises a substrate, an intermediate layer formed on the substrate, and a photosensitive layer formed on the intermediate layer; the intermediate layer contains a metal oxide and a compound represented by the formula (1). (In the formula (1), Ris a hydroxy group or a carboxy group, and Rto Rare each independently a hydrogen atom, alkyl group, hydroxy group, carboxy group, amino group, and alkoxy group. One of the carbon atoms in a principal chain of the alkyl group may be substituted by O or N, and the alkyl group and the alkoxy group may be substituted by an alkyl group, aryl group, halogen atom, or carbonyl group.SELECTED DRAWING: None

Description

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

  In recent years, with the demand for higher definition and higher resolution, the electrophotographic photosensitive member mounted in the process cartridge and the electrophotographic apparatus has sensitivity, electrical characteristics, optical characteristics and image defects corresponding to the applied electrophotographic process. No high quality image quality is required.

  As an electrophotographic photoreceptor, an electrophotographic photoreceptor having an intermediate layer on a support and a photosensitive layer containing an organic charge generating material and a charge transport material formed on the intermediate layer is often used. The intermediate layer has a function of blocking charges, and has a function of suppressing the occurrence of image defects such as black spots by suppressing charge injection from the support to the photosensitive layer side.

  On the other hand, if the electrical resistance of the intermediate layer is made too high for the purpose of suppressing image defects, the charge generated in the photosensitive layer tends to stay inside the photosensitive layer. As a result, there is a problem that a residual potential increases and a ghost is likely to occur. Specifically, in the output image, there is a phenomenon called so-called positive ghost in which the density is increased only in a portion irradiated with light during the previous rotation, or a so-called negative ghost in which the concentration is decreased only in a portion irradiated with light during the previous rotation. Likely to happen.

  As a technique for suppressing such charge retention, Patent Document 1 discloses a technique for suppressing generation of ghosts by including a compound having a metal oxide and an anthraquinone structure in an intermediate layer. Patent Document 2 discloses a technique for suppressing ghost generation in a low temperature and low humidity environment by using an intermediate layer having phenanthrenequinone, phenanthroline quinone, and acenaphthenequinone.

JP 2006-221094 A JP 2006-251328 A

However, in recent years, there has been a demand for higher process speed and longer life, and it is necessary to improve charge retention more than ever. In such a case, there is room for further improvement of the techniques disclosed in Patent Documents 1 and 2 against image degradation due to the ghost phenomenon.
Further, when the energy level of the compound contained in the intermediate layer has an energy gap that absorbs the exposure wavelength, the sensitivity of the electrophotographic photosensitive member is deteriorated.

The present invention has been made in view of the above circumstances, and an object thereof is to provide an electrophotographic photosensitive member in which image deterioration due to a ghost phenomenon is suppressed while maintaining good sensitivity.
Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.
Another object of the present invention is to provide a method for producing the electrophotographic photosensitive member.

（式（１）中、Ｒ^１はヒドロキシ基またはカルボキシ基であり、Ｒ^２〜Ｒ^６はそれぞれ独立に水素原子、アルキル基、ヒドロキシ基、カルボキシ基、アミノ基、アルコキシ基である。該アルキル基の主鎖中の炭素原子の１つは、ＯまたはＮに置き換わってもよく、該アルキル基および該アルコキシ基は、アルキル基、アリール基、ハロゲン原子、またはカルボニル基で置換されていてもよい。） The present invention is an electrophotographic photosensitive member having a support, an intermediate layer formed on the support, and a photosensitive layer formed on the intermediate layer in this order,
An electrophotographic photoreceptor, wherein the intermediate layer contains a metal oxide and a compound represented by the following formula (1).

(In Formula (1), R ¹ is a hydroxy group or a carboxy group, and R ^{2 to} R ⁶ are each independently a hydrogen atom, an alkyl group, a hydroxy group, a carboxy group, an amino group, or an alkoxy group. The alkyl group One of the carbon atoms in the main chain may be replaced with O or N, and the alkyl group and the alkoxy group may be substituted with an alkyl group, an aryl group, a halogen atom, or a carbonyl group. )

  In the present invention, the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means, and a cleaning means are integrally supported and detachable from the main body of the electrophotographic apparatus. Is a process cartridge.

  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.

As described above, according to the present invention, it is possible to provide an electrophotographic photosensitive member in which image deterioration due to a ghost phenomenon is suppressed while maintaining good sensitivity.
In addition, according to the present invention, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member can be provided.
Another object of the present invention is to provide a method for producing the electrophotographic photosensitive member.

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. It is a figure explaining an example of a layer structure of an electrophotographic photosensitive member. It is a figure for demonstrating the printing for ghost evaluation used in the case of ghost image evaluation.

（式（１）中、Ｒ^１はヒドロキシ基またはカルボキシ基であり、Ｒ^２〜Ｒ^６はそれぞれ独立に水素原子、アルキル基、ヒドロキシ基、カルボキシ基、アミノ基、およびアルコキシ基である。該アルキル基の主鎖中の炭素原子の１つは、ＯまたはＮに置き換わってもよく、該アルキル基および該アルコキシ基は、アルキル基、アリール基、ハロゲン原子、またはカルボニル基で置換されていてもよい。） The present invention is characterized in that the intermediate layer of the electrophotographic photoreceptor contains a metal oxide and a compound represented by the following formula (1).

(In Formula (1), R ¹ is a hydroxy group or a carboxy group, and R ^{2 to} R ⁶ are each independently a hydrogen atom, an alkyl group, a hydroxy group, a carboxy group, an amino group, and an alkoxy group. One of the carbon atoms in the main chain of the group may be replaced with O or N, and the alkyl group and the alkoxy group may be substituted with an alkyl group, an aryl group, a halogen atom, or a carbonyl group. .)

The present inventors speculate as follows why the electrophotographic photosensitive member having the intermediate layer having the above-described structure is excellent in the effect of suppressing potential fluctuation when repeatedly used in a high-temperature and high-humidity environment.
The compound represented by the formula (1) has a structure having high polarity, wide conjugation, and difficulty in stacking the compounds. In particular, it is a structure having a large dipole moment derived from a five-membered ring structure and a carbonyl group bonded to the five-membered ring. And it is known from the structure that the compound shown by Formula (1) has the property that an electric charge does not stay easily in a compound. Therefore, by using the compound represented by the formula (1) in the intermediate layer, the flow of electrons from the photosensitive layer to the intermediate layer becomes smooth, and the retention of charge in the photosensitive layer, which is the cause of ghost generation, is suppressed. Can do. In addition, the carbonyl group in the 5-membered ring of the compound represented by the formula (1) and the hydroxy group or carbonyl group of R ¹ coordinate the compound represented by the formula (1) to the metal oxide, A charge transfer complex is formed by the interaction. As a result of the formation of the charge transfer complex, the compound represented by the formula (1) hinders the coordination of water molecules to the metal oxide, resulting in a smooth flow of electrons from the photosensitive layer to the intermediate layer, which causes ghosting. Charge retention in the photosensitive layer can be suppressed.

[Electrophotographic photoconductor]
The electrophotographic photoreceptor of the present invention has at least a support, an intermediate layer, and a photosensitive layer in this order.
Examples of the method for producing an electrophotographic photoreceptor include a method in which a coating solution for each layer described later is prepared, applied in the order of desired layers, and dried. At this time, examples of the application method of the coating liquid include a dip coating method (dip coating method), a spray coating method, a curtain coating method, and a spin coating method. Among these, the dip coating method is preferable from the viewpoints of efficiency and productivity.
Hereinafter, each layer will be described.

(Support)
In the present invention, the electrophotographic photosensitive member has a support. The support is preferably a conductive support. Examples of the conductive support include a support formed of a metal such as aluminum, iron, nickel, copper, and gold, or an alloy thereof, or an insulating support such as a polyester resin, a polycarbonate resin, a polyimide resin, or glass. In addition, a thin film of metal such as aluminum, chromium, silver, gold, etc .; a thin film formed by vacuum deposition of a conductive material such as indium oxide, tin oxide, zinc oxide; a thin film of conductive ink with silver nanowires added The support can be used. Also, use a support in which conductive particles such as carbon black, tin oxide particles, titanium oxide particles and silver particles are impregnated with plastic or paper together with a binder resin, or a plastic support having a conductive binder resin. You can also. Examples of the shape of the support include a cylindrical shape, a belt shape, and a film shape, and a cylindrical shape is preferable.
In addition, the surface of the support is subjected to electrochemical treatment such as anodization, wet honing treatment, blast treatment, cutting treatment, roughening for the purpose of improving electrical characteristics and suppressing interference fringes due to laser light scattering. Surface treatment or alumite treatment may be performed.

(Conductive layer)
In the present invention, a conductive layer may be provided between the support and an intermediate layer described later for the purpose of suppressing interference fringes due to scattering of laser light, covering scratches on the support, and the like.
The average film thickness of the conductive layer is preferably 5 μm or more and 40 μm or less, and more preferably 10 μm or more and 30 μm or less.

  The conductive layer can be formed by applying a coating liquid for conductive layer obtained by dispersing carbon black and conductive particles together with a binder resin and a solvent, followed by drying by heating (thermosetting). Examples of the conductive particles include zinc oxide, lead white, aluminum oxide, indium oxide, silicon oxide, zirconium oxide, tin oxide, titanium oxide, magnesium oxide, antimony oxide, bismuth oxide, tin-doped indium oxide, antimony, Examples thereof include metal oxide particles such as tin oxide and zirconium oxide doped with tantalum. Among these, metal oxide particles containing zinc oxide, titanium oxide, and tin oxide are preferable. Further, in order to improve the dispersibility of the metal oxide particles, the surface of the metal oxide particles may be treated with a silane coupling agent or the like. Furthermore, in order to control the resistance of the conductive layer, the metal oxide particles may be doped with another metal or metal oxide.

  Examples of the binder resin used for the conductive layer include polyester, polycarbonate, polyvinyl butyral, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, alkyd resin, and the like.

  Examples of the solvent for the conductive layer coating solution include ether solvents, alcohol solvents, sulfoxide solvents, ketone solvents, ester solvents, and aromatic hydrocarbon solvents. Examples of the dispersion method for dispersing the metal oxide particles in the conductive layer coating liquid include a method using a paint shaker, a sand mill, a ball mill, and a liquid collision type high-speed disperser.

(Middle layer)
In this invention, it has an intermediate | middle layer containing the compound shown by Formula (1) on a support body or a conductive layer.
The average film thickness of the intermediate layer is preferably 0.5 μm or more and 40 μm or less, and more preferably 1 μm or more and 30 μm or less.

  The intermediate layer of the present invention contains a metal oxide. The metal oxide is not particularly limited as long as it is used for the purpose of imparting conductivity to the intermediate layer. Among these, metal oxides such as zinc oxide, titanium oxide, tin oxide, zirconium oxide, and aluminum oxide are preferable from the viewpoint of imparting appropriate conductivity. Of these, zinc oxide, titanium oxide, and tin oxide are particularly preferable.

  In the present invention, it is preferable to use metal oxide particles as the metal oxide. The average primary particle size of the metal oxide particles is preferably from 50 nm to 500 nm, more preferably from 50 nm to 300 nm. The average primary particle size of the metal oxide particles can be obtained by observing the cross section with a scanning electron microscope (SEM) or the like, measuring the particle size of 100 arbitrary particles, and determining the average value.

  The surface of the metal oxide particles may be treated with a surface treatment agent to improve dispersibility. The surface treatment method may be any known method, and a dry method or a wet method is used.

  Examples of the surface treatment material include organic compounds such as silane coupling agents, titanate coupling agents, aluminum coupling agents, and surfactants. Among these, a silane coupling agent is preferable, and a silane coupling agent having an amino group is particularly preferable.

  Specific examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane, N-2- (aminoethyl) -3-aminoisobutylmethyldimethoxysilane, N-ethylaminoisobutylmethyldiethoxysilane, N-methylaminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropylmethyldiethoxysilane, (phenylaminomethyl) trimethoxysilane, N-2- (aminoethyl) -3-aminoisobutyltrimethoxysilane, N-ethylaminoisobutyltriethoxysilane, N-methyl Aminopropy Such as trimethoxysilane. However, the present invention is not limited to these. Moreover, you may use 2 or more types in mixture.

  When surface treatment is performed by the dry method, the surface treatment agent dissolved in an organic solvent is dropped or sprayed with dry air or nitrogen gas while stirring the metal oxide particles with a mixer having a large shearing force. To be processed. The addition or spraying is preferably performed at a temperature below the boiling point of the solvent. After addition or spraying, baking may be performed at 100 ° C. or higher. The baking temperature and time are carried out in an arbitrary range.

  As a wet method, metal oxide particles are stirred in a solvent, dispersed using an ultrasonic wave, a sand mill, an attritor, a ball mill, etc., added with a surface treatment agent, stirred or dispersed, and then treated by removing the solvent. The The solvent removal method is distilled off by filtration or distillation. After removing the solvent, baking may be performed at 100 ° C. or higher. The baking is not particularly limited as long as it is a temperature and time for obtaining electrophotographic characteristics.

The content of the surface treatment agent in the intermediate layer is preferably 0.5% by mass or more and 20% by mass or less based on the metal oxide particles from the viewpoint of electrophotographic characteristics.
In addition, two or more kinds of metal oxide particles having different metal oxide species, different surface treatments, or different particle diameters may be used.

  Further, the metal oxide particles may be particles coated with at least one of alumina and silica. By coating at least one of alumina and silica, the compatibility with the binder resin of the intermediate layer can be improved and the effect of suppressing black spots can be enhanced.

式（１）中、Ｒ^１はヒドロキシ基またはカルボキシ基である。Ｒ^２〜Ｒ^６はそれぞれ独立に水素原子、置換若しくは無置換のアルキル基、ヒドロキシ基、カルボキシ基、アミノ基、およびアルコキシ基を示す。該アルキル基の主鎖中の炭素原子の１つは、ＯまたはＮに置き換わっても良い。該アルキル基および該アルコキシ基は、アルキル基、アリール基、ハロゲン原子、またはカルボニル基で置換されていてもよい。 The intermediate layer contains an acenaphthenequinone compound represented by the following formula (1).

In formula (1), R ¹ is a hydroxy group or a carboxy group. R ^{2 to} R ⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a hydroxy group, a carboxy group, an amino group, and an alkoxy group. One of the carbon atoms in the main chain of the alkyl group may be replaced with O or N. The alkyl group and the alkoxy group may be substituted with an alkyl group, an aryl group, a halogen atom, or a carbonyl group.

The alkyl group as R ^{2 to} R ⁶ may be any alkyl group as long as the electrophotographic photoreceptor having the intermediate layer having the compound represented by the formula (1) can exhibit the effects of the present invention. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, and an isobutyl group. One of the carbon atoms in the main chain of these alkyl groups may be replaced with O or N. Such groups include methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, N-methylaminomethyl group, N-ethylaminomethyl group, 1- (N-methylamino) ethyl. Group, 2- (N-methylamino) ethyl group, N, N-dimethylaminomethyl group and the like.

The alkoxy group as R ^{2 to} R ⁶ may be any alkoxy group as long as the electrophotographic photoreceptor having the intermediate layer having the compound represented by the formula (1) can exhibit the effects of the present invention. Examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, a t-butoxy group, and an isobutoxy group.

  Examples of the substituent for the alkyl group and the alkoxy group include the alkyl groups described above, aryl groups such as phenyl group and naphthyl group, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and carbonyl group. It is done. The alkyl group and alkoxy group having a carbonyl group as a substituent are groups in which one or more carbon atoms of the alkyl group and the alkoxy group are carbonyl groups (C═O). Here, the alkyl group as a substituent may be substituted with an aryl group or a halogen atom as a substituent, and the aryl group as a substituent is substituted with an alkyl group or a halogen atom as a substituent. Also good.

Although the compounds (1-1) to (1-12) are shown as specific examples of the compound represented by the formula (1) below, the compound represented by the formula (1) is not limited to these.

  The content of the compound represented by the formula (1) is preferably 0.025% by mass or more and 10% by mass or less, particularly 0.05% by mass or more and 5% by mass or less with respect to the metal oxide. Is preferred. When the content of the compound represented by the formula (1) is in the above range with respect to the metal oxide, the interaction with the metal oxide works efficiently, and the potential fluctuation suppressing effect is higher. Compatibility between the ghost suppression effect and sensitivity is further enhanced.

  In the intermediate layer of the present invention, the compound represented by the formula (1) and the metal oxide preferably form a complex. By forming the complex, the rigidity of the site contributing to the complex formation in the compound represented by the formula (1) is increased, so that the energy when the compound represented by the formula (1) is oxidized is reduced. As a result, it is considered that charges are less likely to stay in the compound. Moreover, since the metal oxide and the compound represented by the formula (1) are closer to each other by forming a complex, it is possible to smoothly receive electrons from the photosensitive layer and exchange electrons between the metal oxides. It is considered that charge retention in the photosensitive layer can be suppressed. From the above mechanism, the ghost suppression effect is further enhanced by using a metal oxide in combination.

  Whether the compound represented by the formula (1) forms a complex with the metal oxide can be confirmed by the following method. For example, when the compound represented by the formula (1) forms a complex with the metal oxide, the UV spectrum of the compound represented by the formula (1) shifts to the higher wavelength side due to the deep color effect. Therefore, it can be determined from the presence or absence of the deep color effect whether the compound represented by the formula (1) forms a complex with the metal oxide.

  In the present invention, the intermediate layer may contain a binder resin. As the binder resin, any resin can be used as long as it is a known resin. However, a curable resin is preferable from the viewpoint of elution to the upper layer during formation of the photosensitive layer and small resistance fluctuation.

  As the curable resin, for example, phenol resin, urethane resin, epoxy resin, acrylic resin, melamine resin or polyester is preferable. Among these, it is preferable to use a urethane resin, and a urethane resin made of a cured product of an isocyanate compound and a polyol is more preferable.

  Examples of the isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, hexamethylene diisocyanate (HDI), HDI-trimethylolpropane adduct, HDI-isocyanate. Examples thereof include nurate bodies, HDI-biuret bodies and the like blocked with oximes. Examples of the oxime include formaldehyde oxime, acetoaldoxime, methyl ethyl ketoxime, and cyclohexanone oxime. The isocyanate compound may be a blocked isocyanate compound in which an isocyanate group is blocked.

  Examples of the polyol include polyether polyol, polyester polyol, acrylic polyol, epoxy polyol, and fluorine-based polyol.

  The content of the binder resin in the intermediate layer is preferably 10% by mass or more and 50% by mass or less with respect to the content of the metal oxide. By setting it as such a range, the uniformity of the intermediate layer is improved.

  Further, the intermediate layer may further contain an additive. Examples of the additive include hydrophobic organic resin particles such as silicone particles, hydrophilic organic resin particles such as cross-linked polymethacrylate resin (PMMA) particles, and leveling agents. In particular, the use of PMMA particles is preferable because the surface roughness of the intermediate layer can be adjusted to an appropriate range and the film can be made uniform.

  In the present invention, the intermediate layer is a step of preparing an intermediate layer coating solution containing a metal oxide, a compound represented by the formula (1), and a binder resin, and a step of forming a coating film of the intermediate layer coating solution. And a step of drying the coating film to form an intermediate layer. What is necessary is just to prepare the coating liquid for intermediate | middle layers according to the structural component of an intermediate | middle layer.

  The intermediate layer coating solution may be an intermediate layer coating solution obtained by dispersion treatment together with the metal oxide particles, the compound represented by the formula (1), the binder resin, and the solvent. Alternatively, an intermediate layer obtained by adding a liquid in which a binder resin is dissolved to a dispersion obtained by dispersing the above-described metal oxide particles and the compound represented by formula (1) together with a solvent, and further dispersing the resin. It may be used as a coating solution. Examples of the dispersion method include a method using a homogenizer, an ultrasonic disperser, a ball mill, a sand mill, a roll mill, a vibration mill, an attritor, a liquid collision type high-speed disperser, and the like.

  Examples of the method for applying the intermediate layer include dip coating methods, spray coating methods, spinner coating methods, bead coating methods, blade coating methods, and beam coating methods.

  The intermediate layer is formed by first forming a coating film of the intermediate layer coating solution prepared by the above method. The intermediate layer can be formed by drying the coating film.

  As a drying method, heat drying or blow drying is used, and can be arbitrarily set within a range where desired characteristics of the electrophotographic photosensitive member can be obtained in consideration of the curing temperature and curing time of the resin.

  Examples of the solvent used in the intermediate layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbon solvents, aromatic solvents, and the like. It is done. For example, methylal, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, butyl alcohol, methyl cellosolve, methoxypropanol, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, dioxane, tetrahydrofuran and the like are appropriately used. Moreover, the solvent used for these intermediate | middle layer coating liquids can be used individually or in mixture of 2 or more types.

  FIG. 2 shows an example of the layer structure of the electrophotographic photosensitive member of the present invention. In FIG. 2A, 101 is a support, 102 is an intermediate layer, and 103 is a single-layer type photosensitive layer. In FIG. 2B, 101 is a support, 102 is an intermediate layer, 104 is a charge generation layer, 105 is a charge transport layer, and the charge generation layer 104 and the charge transport layer 105 are A laminated photosensitive layer 106 is formed.

(Photosensitive layer)
In the electrophotographic photoreceptor of the present invention, the photosensitive layer includes a single-layer type photosensitive layer 103 containing a charge generation material and a charge transport material in a single layer, as shown in FIG. And a laminated photosensitive layer 106 in which a charge generation layer 104 containing a charge generation material and a charge transport layer 105 containing a charge transport material are laminated. The laminated photosensitive layer 106 is preferable.

(1) Multilayer Photosensitive Layer The multilayer photosensitive layer 106 includes a charge generation layer 104 and a charge transport layer 105.

(1-1) Charge Generation Layer The average film thickness of the charge generation layer 104 is preferably 0.01 μm or more and 5.00 μm or less, and more preferably 0.10 μm or more and 2.00 μm or less.

  The charge generation layer 104 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 to form a coating film and drying the coating film. The charge generation layer 104 may be a vapor deposition film of a charge generation material.

  Examples of charge generating substances include azo pigments, phthalocyanine pigments, indigo derivatives, perylene pigments, anthraquinone derivatives, dibenzpyrenequinone derivatives, squarylium dyes, pyrylium salts, thiapyrylium salts, triphenylmethane dyes, quinacridone pigments, and azurenium salt pigments. , Cyanine dyes, anthanthrone derivatives, pyranthrone derivatives, violanthrone derivatives, isoviolanthrone derivatives, indigo derivatives, thioindigo derivatives, bisbenzimidazole derivatives, xanthene dyes, quinoneimine dyes, styryl dyes. These charge generation materials may be used alone or in combination of two or more.

  Among these charge generation materials, phthalocyanine pigments and azo pigments are preferable, and phthalocyanine pigments are more preferable. Among phthalocyanine pigments, oxytitanium phthalocyanine, chlorogallium phthalocyanine, or hydroxygallium phthalocyanine is particularly preferable because of its excellent charge generation efficiency.

  Furthermore, among the hydroxygallium phthalocyanines, crystals having peaks at Bragg angles 2θ of 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° in CuKα characteristic X-ray diffraction from the viewpoint of sensitivity and potential characteristics. A form of hydroxygallium phthalocyanine crystal is more preferred.

  Examples of the binder resin used for the charge generation layer 104 include ethylene, butadiene, propylene, styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, trifluoroethylene, styrene-butadiene copolymer, and vinyl chloride. -Polymers and copolymers of vinyl compounds such as vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, acrylic resin, allyl resin, alkyd resin, epoxy resin, diallyl phthalate resin, butyral resin Benzal resin, polyacetal, polyamideimide, polyamide, polyallyl ether, polyarylate, polyimide, polyurethane, urea resin, etc.Among these, a polyester resin, a polycarbonate resin, and a polyvinyl acetal resin are preferable, and a polyvinyl acetal resin is more preferable. In particular, a butyral resin is preferred. These can be used individually or in mixture of 2 or more types.

The charge generation layer 104 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 to form a coating film, and then drying the coating film. . Examples of the solvent used in the charge generation layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbons, and aromatic compounds. Examples of a method for dispersing the charge generating substance, the binder resin, and the solvent include a method using a homogenizer, an ultrasonic disperser, a ball mill, a sand mill, a roll mill, a vibration mill, an attritor, a liquid collision type high-speed disperser, and the like. The mass ratio of the charge generation material to the binder resin (charge generation material / binder resin) is preferably in the range of 0.3 to 10.
In addition, various sensitizers, antioxidants, ultraviolet absorbers, and plasticizers can be added to the charge generation layer 104 as necessary.

(1-2) Charge Transport Layer The average film thickness of the charge transport layer 105 is preferably 5 μm or more and 40 μm or less, and more preferably 8 μm or more and 30 μm or less. When the charge transport layer 105 has a laminated structure, the average thickness of the charge transport layer on the support side is preferably 5 μm or more and 30 μm or less, and the average thickness of the charge transport layer on the surface side is 0.5 μm or more and 10 μm. The following is preferable.

  Examples of the charge transport material include polycyclic aromatic compounds, heterocyclic compounds, triarylamine compounds such as triphenylamine, hydrazone compounds, styryl compounds, stilbene compounds, enamine compounds, benzidine compounds, and butadiene compounds. In addition, examples of the charge transport material include polymers having groups derived from these compounds in the main chain or side chain. Among these, a triarylamine compound and a benzidine compound are preferable from the viewpoint of high charge mobility and potential stability during repeated use. Moreover, the charge transport material may contain a plurality of types.

  Examples of the binder resin used for the charge transport layer 105 include polyester, acrylic resin, phenoxy resin, polycarbonate, polystyrene, polyvinyl acetate, polysulfone, polyarylate, acrylonitrile resin, allyl resin, alkyd resin, epoxy resin, silicone resin, and phenol resin. , Polyacrylamide, polyamideimide, polyamide, polyallyl ether, polyimide, polyurethane, polyethylene, polyphenylene oxide, polybutadiene, polypropylene, methacrylic resin, polyvinylidene chloride, acrylonitrile copolymer and the like. In particular, polyarylate and polycarbonate are preferable. These can be used individually or in mixture of 2 or more types.

  In the charge transport layer 105, the mass ratio of the charge transport material to the binder resin (charge transport material / binder resin) is preferably in the range of 0.3 to 10.

  The charge transport layer 105 can be formed by forming a coating film of a coating solution for a charge transport layer prepared by dissolving a charge transport material and a binder resin in a solvent, and drying the coating film. Examples of the solvent used in the coating solution for the charge transport layer include alcohol solvents (particularly alcohols having 3 or more carbon atoms), sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents. And alicyclic hydrocarbon solvents. From the viewpoint of suppressing cracks, the drying temperature is preferably 60 ° C. or higher and 150 ° C. or lower, and more preferably 80 ° C. or higher and 120 ° C. or lower. The drying time is preferably 10 minutes or more and 60 minutes or less.

When the charge transport layer 105 has a laminated structure, the charge transport layer 105 is formed by applying a charge transport layer coating solution obtained by dissolving a charge transport material and a binder resin in a solvent, It can be formed by drying the coating film. The charge transport layer on the surface side of the electrophotographic photoreceptor is cured by polymerizing and / or crosslinking a charge transport material having a chain polymerizable functional group in order to increase the mechanical strength of the electrophotographic photoreceptor. A layer is preferred. Examples of the chain polymerizable functional group include an acryloyloxy group, a methacryloyloxy group, an alkoxysilyl group, and an epoxy group. In order to polymerize and / or crosslink a charge transport material having a chain polymerizable functional group, heat, light, radiation (electron beam or the like) can be used.
In addition, an antioxidant, an ultraviolet absorber, a plasticizer, or the like can be added to the charge transport layer 105 as necessary.

(2) Single-layer type photosensitive layer The single-layer type photosensitive layer 103 forms a coating film of a coating solution for a photosensitive layer prepared by mixing a charge generating substance, a charge transporting substance and a binder resin in a solvent. It can be formed by drying the film. The charge transporting substance and the binder resin are the same as those exemplified in the above-mentioned “(1) Multilayer type photosensitive layer”.

(Protective layer)
In the present invention, a protective layer may be provided on the single-layer type photosensitive layer 103 or the charge transport layer 105. The average thickness of the protective layer is preferably from 0.5 μm to 10.0 μm, and more preferably from 1.0 μm to 7.0 μm.

  The protective layer preferably contains conductive particles or a charge transport material and a binder resin. Furthermore, the protective layer may contain an additive such as a lubricant. Further, the binder resin itself of the protective layer may have conductivity and charge transport properties. In that case, the protective layer may not contain conductive particles or a charge transport material. The binder resin of the protective layer may be a thermoplastic resin or a curable resin that is cured by heat, light, or radiation (such as an electron beam).

  Further, the outermost layer (surface layer) of the electrophotographic photosensitive member may contain a lubricant such as silicone oil, wax, polytetrafluoroethylene particles, silica particles, alumina particles, and boron nitride.

  When applying the coating liquid for each of the above layers, for example, a coating method such as a dip coating method (dip coating method), a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method, a blade coating method, or the like should be used. Can do.

[Process cartridge, electrophotographic equipment]
The process cartridge of the present invention integrally supports the electrophotographic photosensitive member described so far and at least one means selected from the group consisting of a charging means, a developing means, and a cleaning means. It is detachable.

  The electrophotographic apparatus of the present invention includes the electrophotographic photosensitive member, the charging unit, the exposure unit, the developing unit, and the transfer unit described so far.

  FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge 9 having an electrophotographic photosensitive member 1.

  In FIG. 1, a cylindrical electrophotographic photosensitive member 1 is rotationally driven in a direction of an arrow about a shaft 2 at a predetermined peripheral speed. The peripheral surface of the electrophotographic photosensitive member 1 is uniformly charged to a predetermined positive or negative potential by a charging means (charging roller or the like) 3 during the rotation process. Next, the charged surface of the electrophotographic photosensitive member 1 is converted into a time-series electric digital image signal of target image information output from exposure means (image exposure means, not shown) such as slit exposure or laser beam scanning exposure. Corresponding intensity-modulated exposure light (image exposure light) 4 is received. In this way, electrostatic latent images corresponding to the target image are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1. The voltage applied to the charging unit 3 may be only a DC voltage or a DC voltage on which an AC voltage is superimposed.

  The electrostatic latent image formed on the peripheral surface of the electrophotographic photoreceptor 1 is developed (regular development or reversal development) with the toner of the developing unit 5, and a toner image is formed on the surface of the electrophotographic photoreceptor 1. Next, the toner image formed on the peripheral surface of the electrophotographic photosensitive member 1 is transferred to a transfer material (such as paper) P by a transfer bias from a transfer unit (such as a transfer roller) 6. The transfer material P is fed from a transfer material supply means (not shown) between the electrophotographic photoreceptor 1 and the transfer means 6 (contact portion) in synchronization with the rotation of the electrophotographic photoreceptor 1.

  The transfer material P that has received the transfer of the toner image from the electrophotographic photosensitive member 1 is separated from the peripheral surface of the electrophotographic photosensitive member 1 and is introduced into the fixing means 8 to undergo image fixing, thereby forming an image formed product (print, copy). ) Is printed out of the apparatus.

  The peripheral surface of the electrophotographic photosensitive member 1 after the toner image is transferred to the transfer material P is subjected to removal of adhering matters such as toner (transfer residual toner) by a cleaning means (cleaning blade or the like) 7. In recent years, a cleanerless system has also been developed, and the transfer residual toner can be directly removed by the developing means 5 or the like. Further, after being subjected to charge removal processing by pre-exposure light 11 from a pre-exposure means (not shown), it is repeatedly used for image formation. When the charging unit 3 is a contact charging unit, pre-exposure 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 7 and the like described above are selected and placed in a container. Alternatively, the process cartridge 9 may be integrally coupled. The process cartridge 9 may be configured to be detachable from the main body of the electrophotographic apparatus. In FIG. 1, an electrophotographic photosensitive member 1, a charging unit 3, a developing unit 5 and a cleaning unit 7 are integrally supported to form a cartridge, and an electrophotographic apparatus is provided using a guide unit 10 such as a rail of the electrophotographic apparatus main body. The process cartridge 9 is detachable from the main body.

  Furthermore, the exposure light 4 may be reflected light or transmitted light from the original when the electrophotographic apparatus is a copying machine or a printer. Alternatively, it may be light emitted by reading a document with a sensor, converting it into a signal, scanning a laser beam performed according to this signal, driving an LED array, driving a liquid crystal shutter array, or the like.

  The electrophotographic photoreceptor 1 of the present invention can be widely applied to electrophotographic application fields such as laser beam printers, CRT printers, LED printers, FAX, liquid crystal printers, and laser plate making.

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited thereto. In the examples, “%” and “part” mean “% by mass” and “part by mass”, respectively.

[Example 1]
An aluminum cylinder (JIS-A3003, aluminum alloy, length 357.5 mm) having a diameter of 30 mm was used as a support (conductive support).

Next, 100 parts of zinc oxide particles (number average primary particle diameter: 50 nm, specific surface area (hereinafter, BET value): 19 m ² / g, powder resistance: 3.7 × 10 ⁷ Ω · cm) and 500 parts of toluene After stirring and mixing, 0.75 part of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred for 2 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 3 hours to obtain surface-treated zinc oxide particles M1.

Next, 14 parts of polyvinyl acetal resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 32 parts of blocked isocyanate (trade name: TPA-B80E, 80% solution, manufactured by Asahi Kasei Co., Ltd.) And dissolved in a mixed solvent of 77 parts of methyl ethyl ketone and 77 parts of 1-butanol. 100 parts of the surface-treated zinc oxide particles M1 and 2 parts of the compound (1-1) were added to this liquid, and this was added in a 23 ± 3 ° C. atmosphere in a sand mill apparatus using glass beads having a diameter of 0.9 mm. Dispersed for 3 hours. After dispersion, 7 parts of cross-linked polymethyl methacrylate particles (Sekisui Plastics Co., Ltd., SSX-103) and 0.01 parts of silicone oil SH28PA (Toray Dow Corning Silicone) are added as resin particles and stirred. Layer coating solution 1 was prepared.
The obtained intermediate layer coating solution 1 was dip coated on the support to form a coating film, and the coating film was dried at 160 ° C. for 20 minutes to form an intermediate layer having an average film thickness of 25 μm.

この電荷発生層用塗布液を、中間層上に浸漬塗布して塗膜を形成し、塗膜を１０分間１００℃で乾燥させることによって、平均膜厚が０．１５μｍの電荷発生層を形成した。 Next, Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and A crystalline hydroxygallium phthalocyanine crystal (charge generation material) having a peak at 28.3 ° was prepared. 10 parts of this hydroxygallium phthalocyanine crystal, 0.1 part of a compound represented by the following formula (A), 5 parts of polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 250 parts of cyclohexanone The mixture was placed in a sand mill using 0.8 mm glass beads and dispersed for 1.5 hours. Next, 250 parts of ethyl acetate was added thereto to prepare a charge generation layer coating solution.

The charge generation layer coating solution was dip coated on the intermediate layer to form a coating film, and the coating film was dried at 100 ° C. for 10 minutes to form a charge generation layer having an average film thickness of 0.15 μm. .

このようにして、支持体、中間層、電荷発生層、電荷輸送層を有する電子写真感光体を製造した。 Next, 4 parts each of a compound represented by the following formula (B) (charge transporting substance) and a compound represented by the following formula (C) (charge transporting substance), and a bisphenol Z-type polycarbonate (trade name: Z400, A charge transport layer coating solution was prepared by dissolving 10 parts of Mitsubishi Gas Chemical Co., Ltd. in a mixed solvent of 40 parts of dimethoxymethane and 60 parts of chlorobenzene. The charge transport layer coating solution was dip coated on the charge generation layer to form a coating film, and the coating film was dried at 120 ° C. for 40 minutes to form a charge transport layer having an average film thickness of 15 μm.

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

(Ghost evaluation)
The manufactured electrophotographic photosensitive member for evaluation was mounted on a modified machine of a laser beam printer (trade name: LBP-2510) manufactured by Canon Inc. for evaluation. Details are as follows.
As a remodeling point, the pre-exposure was not turned on, and the charging condition and laser exposure amount were changed. In addition, the manufactured electrophotographic photosensitive member was attached to a cyan process cartridge and attached to a cyan process cartridge station.
Under an environment of a temperature of 32.5 ° C. and a humidity of 80% RH, the drum surface potential was set such that the initial dark portion potential was −550 V and the bright portion potential was −150 V. To measure the surface potential when setting the potential, the cartridge was remodeled, and a potential probe (trade name: model6000B-8, manufactured by Trek Japan Co., Ltd.) was attached to the development position. Product name: model 344, manufactured by Trek Japan Co., Ltd.).

  For the ghost image evaluation, a ghost evaluation image as shown in FIG. 3 (a square solid image was produced in a white background (white image) at the head of the image and then a 1-dot Keima pattern image was produced) was used. In FIG. 3, a portion described as “ghost” is a ghost portion for evaluating the presence or absence of the appearance of a ghost due to the solid image. When a ghost appears, it appears in a portion described as “ghost” in FIG. 3. The evaluation order of ghosts was evaluated by outputting a white image as the first image and then outputting five consecutive ghost evaluation images. Evaluation of the image for ghost evaluation is performed by measuring the density difference between the image density of the 1-dot Keima pattern image and the image density of the ghost portion with a spectral densitometer (trade name: X-Rite 504/508, manufactured by X-Rite Co., Ltd.). Five points were measured with one ghost evaluation image, and the average of these five points was taken as one result, and all the above-mentioned five ghost evaluation images were measured in the same manner, and their average values were obtained. . The results are shown in Table 1. This density difference means that the smaller the value, the better the ghost suppression. When the value of the density difference was 0.05 or more, it was determined that the ghost was not sufficiently suppressed and the level of the effect of the present invention was not obtained. A density difference value of 0.025 or less means that ghost suppression is extremely excellent.

(Sensitivity evaluation)
The manufactured electrophotographic photosensitive member for evaluation was mounted on a modified laser beam printer (trade name: LBP-2510) manufactured by Canon Inc., which was modified in the same manner as the ghost evaluation, and evaluated. Details are as follows.
The drum surface potential was set such that the initial dark portion potential was −550 V under an environment of a temperature of 32.5 ° C. and a humidity of 80% RH. To measure the surface potential when setting the potential, the cartridge was remodeled, and a potential probe (trade name: model6000B-8, manufactured by Trek Japan Co., Ltd.) was attached to the development position. Product name: model 344, manufactured by Trek Japan Co., Ltd.).
The sensitivity evaluation was performed by measuring the drum surface potential when a solid image was printed using an exposure light amount of 0.30 μJ / cm ² . The results are shown in Table 1. The smaller the absolute value of this value, the better the sensitivity of the electrophotographic photosensitive member.

(Complex formation evaluation)
The intermediate layer coating solution 1 was diluted 100 times with a mixed solvent of methyl ethyl ketone and 1-butanol in a mass ratio of 1: 1 to obtain a complex formation evaluation sample 1. Moreover, the compound (1-1) was diluted with the mixed solvent, and a complex formation comparative sample 1 having the same concentration as the compound (1-1) in the complex formation evaluation sample 1 was obtained. When the UV spectra of both samples were measured using an ultraviolet-visible spectrometer (device name: UV-2700, manufactured by Shimadzu Corporation), the peak derived from the compound (1-1) in the complex formation evaluation sample 1 was It appeared on the longer wavelength side than the peak derived from the compound (1-1) in the complex formation comparative sample 1. From this, in the coating liquid 1 for intermediate | middle layers, it confirmed that the compound (1-1) and the zinc oxide had formed the complex.

  Next, an intermediate layer was formed from the intermediate layer coating solution 1 in the same manner as in Example 1, and a film having a width of 1 cm, a height of 3 cm, and a thickness of 0.3 μm was cut out from the intermediate layer to obtain a complex formation evaluation sample 2. . When the UV spectrum of the complex formation evaluation sample 2 and the compound (1-1) was measured using an ultraviolet-visible spectrometer (device name: UV-2700, manufactured by Shimadzu Corporation), the compound in the complex formation evaluation sample 2 The peak derived from (1-1) appeared on the longer wavelength side than the peak derived from the compound (1-1). From this, in the intermediate layer formed from the intermediate layer coating solution 1, it was confirmed that the compound (1-1) and zinc oxide formed a complex.

[Example 2]
100 parts of rutile-type titanium oxide particles (trade name: TTO55N, manufactured by Ishihara Sangyo Co., Ltd., average primary particle size 40 nm) are stirred and mixed with 500 parts of toluene, and N-2- is a silane coupling agent (surface treatment agent). 1.5 parts of (aminoethyl) -3-aminopropyltrimethoxysilane (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed with stirring for 6 hours. Thereafter, toluene was distilled off under reduced pressure and dried at 140 ° C. for 6 hours to obtain titanium oxide particles N1 surface-treated with a silane coupling agent.
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the zinc oxide particles M1 of Example 1 were changed to the titanium oxide particles N1 to prepare a coating solution for intermediate layer.

[Example 3]
Rutile-type titanium oxide particles (trade name: TTO55N, manufactured by Ishihara Sangyo Co., Ltd., average primary particle size 40 nm) and 3% methyldimethoxysilane (Momentive Performance Materials Japan GK (formerly) : “TSL8117” manufactured by Toshiba Silicone Co., Ltd.) was introduced into a high-speed fluid mixing kneader (“SMG300” manufactured by Kawata Co., Ltd.), and the surface obtained by high-speed mixing at a rotational peripheral speed of 34.5 m / sec. The treated titanium oxide particles were dispersed by a ball mill in a mixed solvent of methanol / 1-propanol to obtain a dispersion slurry of hydrophobized treated titanium oxide particles.

In addition, methanol, 1-propanol, toluene, and N-methoxymethylated nylon (manufactured by Nagase Chemitex Co., Ltd., trade name: Toresin F-30K, degree of methoxymethylation: about 30) %) Powder and the above compound (1-1) are added, stirred and mixed while warming, the nylon powder is dissolved, and then ultrasonic dispersion treatment is performed, so that methanol / 1-propanol is finally obtained. The solid content is: the mass ratio of / toluene is 7/1/2 and the hydrophobized titanium oxide / N-methoxymethylated nylon / compound (1-1) is contained at a mass ratio of 3/1 / 0.06 A dispersion having a concentration of 18% was prepared and used as an intermediate layer coating solution 2.
The obtained coating solution 2 for intermediate layer was dip-coated on the support to form a coating film, and the coating film was dried at 160 ° C. for 20 minutes to form an intermediate layer having an average film thickness of 2 μm.

[Example 4]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (1-1) was changed to the compound (1-2) to prepare an intermediate layer coating solution.

[Example 5]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (1-1) was changed to the compound (1-3) to prepare a coating solution for intermediate layer.

[Example 6]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (1-1) was changed to the compound (1-4) to prepare an intermediate layer coating solution.

[Example 7]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (1-1) was changed to the compound (1-5) to prepare an intermediate layer coating solution.

[Example 8]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (1-1) was changed to the compound (1-7) to prepare an intermediate layer coating solution.

[Example 9]
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 1 except that the compound (1-1) was changed to the compound (1-8) to prepare a coating solution for intermediate layer.

[Example 10]
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 1 except that the compound (1-1) was changed to the compound (1-9) to prepare a coating solution for intermediate layer.

[Example 11]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (1-1) was changed to the compound (1-10) to prepare a coating solution for intermediate layer.

[Example 12]
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 1 except that the compound (1-1) was changed to the compound (1-11) to prepare a coating solution for intermediate layer.

[Example 13]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 7 except that the intermediate layer coating solution was prepared by changing the compound (1-5) to 0.025 part.

[Example 14]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 7 except that the compound (1-5) was changed to 0.05 part to prepare an intermediate layer coating solution.

[Example 15]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 7 except that the compound (1-5) was changed to 0.25 part to prepare an intermediate layer coating solution.

[Example 16]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 7 except that the intermediate layer coating solution was prepared by changing the compound (1-5) to 2.5 parts.

[Example 17]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 7 except that the compound (1-5) was changed to 5 parts to prepare an intermediate layer coating solution.

[Example 18]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 7 except that the compound (1-5) was changed to 10 parts to prepare an intermediate layer coating solution.

[Example 19]
100 parts of rutile-type titanium oxide particles (trade name: JR-405, manufactured by Teika, average primary particle size 210 nm) are stirred and mixed with 500 parts of toluene, and N- (silane coupling agent (surface treatment agent) is added thereto. 2-Aminoethyl) -3-aminopropylmethyldimethoxysilane (trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) (1.5 parts) was added and mixed with stirring for 6 hours. Thereafter, toluene was distilled off under reduced pressure and dried at 140 ° C. for 6 hours to obtain titanium oxide particles N2 surface-treated with a silane coupling agent.
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the zinc oxide particles M1 of Example 1 were changed to the titanium oxide particles N2 to prepare the intermediate layer coating solution.

[Example 20]
Except for changing the butyral resin and the isocyanate compound to a phenolic resin (trade name: Praiofen J-325, DIC Corporation (former: Dainippon Ink & Chemicals)) and adjusting the coating solution for the intermediate layer In the same manner as in Example 1, an electrophotographic photosensitive member was produced and evaluated.

[Comparative Example 1]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 2 except that the intermediate layer coating solution was prepared without using the compound (1-1). The evaluation results are shown in Table 2.

[Comparative Example 2]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 2 except that the compound (1-1) was changed to the following compound (2-1) to prepare an intermediate layer coating solution. The evaluation results are shown in Table 2.

[Comparative Example 3]
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 2 except that the compound (1-1) was changed to the following compound (2-2) to prepare an intermediate layer coating solution. The evaluation results are shown in Table 2.

[Comparative Example 4]
14 parts of polyvinyl acetal resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 32 parts of blocked isocyanate (trade name: TPA-B80E, 80% solution, manufactured by Asahi Kasei Co., Ltd.) And 77 parts of 1-butanol were dissolved in a mixed solvent. Two parts of the above compound (1-1) was added to this liquid, and this was dispersed at 23 ± 3 ° C. for 3 hours by a sand mill apparatus using glass beads having a diameter of 0.9 mm. After dispersion, 7 parts of cross-linked polymethyl methacrylate particles (Sekisui Plastics Co., Ltd., SSX-103) and 0.01 parts of silicone oil SH28PA (Toray Dow Corning Silicone) are added as resin particles and stirred. A layer coating solution was prepared. The obtained coating solution for the intermediate layer was dip-coated on the above support to form a coating film, and the coating film was dried at 160 ° C. for 20 minutes, so that an intermediate layer having an average film thickness of 15 μm was formed. In the same manner as in Example 1, an electrophotographic photoreceptor was produced and evaluated. The evaluation results are shown in Table 2.

[Comparative Example 5]
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 2 except that the intermediate layer coating solution was prepared by changing the compound (1-1) to 2,3-dihydroxyanthraquinone. The evaluation results are shown in Table 2.

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Cleaning means 8 Fixing means 9 Process cartridge 10 Guide means P Transfer material 101 Support body 102 Intermediate layer 103 Single layer type photosensitive layer 104 Charge generation layer 105 Charge transport layer 106 Multilayer type photosensitive layer

Claims (9)

In an electrophotographic photosensitive member having a support, an intermediate layer formed on the support, and a photosensitive layer formed on the intermediate layer in this order,
The electrophotographic photoreceptor, wherein the intermediate layer contains a metal oxide and a compound represented by the formula (1).

(In Formula (1), R ¹ is a hydroxy group or a carboxy group, and R ^{2 to} R ⁶ are each independently a hydrogen atom, an alkyl group, a hydroxy group, a carboxy group, an amino group, and an alkoxy group. One of the carbon atoms in the main chain of the group may be replaced with O or N, and the alkyl group and the alkoxy group may be substituted with an alkyl group, an aryl group, a halogen atom, or a carbonyl group. .)   2. The electrophotographic photosensitive member according to claim 1, wherein the content of the compound represented by the formula (1) is 0.05% by mass or more and 5% by mass or less with respect to the metal oxide. 3. The electrophotographic photoreceptor according to claim 1, wherein in the compound represented by the formula (1), R ^{2 to} R ⁶ are each independently a hydrogen atom, a hydroxy group, or a carboxy group.   The electrophotographic photosensitive member according to any one of claims 1 to 3, wherein the metal oxide is particles containing zinc oxide, titanium oxide, or tin oxide. In an electrophotographic photosensitive member having a support, an intermediate layer formed on the support, and a photosensitive layer formed on the intermediate layer,
The electrophotographic photoreceptor, wherein the intermediate layer contains a complex containing a metal oxide and a compound represented by the formula (1).

(In Formula (1), R ¹ is a hydroxy group or a carboxy group, and R ^{2 to} R ⁶ are each independently a hydrogen atom, an alkyl group, a hydroxy group, a carboxy group, an amino group, and an alkoxy group. One of the carbon atoms in the main chain of the group may be replaced with O or N, and the alkyl group and the alkoxy group may be substituted with an alkyl group, an aryl group, a halogen atom, or a carbonyl group. .)   6. The electrophotographic photosensitive member according to claim 5, wherein the metal oxide is particles containing zinc oxide, titanium oxide, or tin oxide. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the production method comprises:
Preparing a coating solution for an intermediate layer containing the metal oxide and the compound represented by the formula (1), forming a coating film of the coating solution for the intermediate layer, and drying and curing the coating film A method of producing an electrophotographic photosensitive member, comprising the step of forming the intermediate layer.   An electrophotographic apparatus main body integrally supporting the 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, and a cleaning means. A process cartridge that is detachable.   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.

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