JP2016145876A - Electrophotographic photoreceptor, process cartridge, and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor that suppresses ghost even in a low-temperature and low-humidity environment, and a process cartridge and an electrophotographic device which include the electrophotographic photoreceptor.SOLUTION: The electrophotographic photoreceptor includes a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer and containing a charge generating material and a hole transport material. The undercoat layer contains a specific urea compound.SELECTED DRAWING: Figure 1

Description

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

  In recent years, electrophotographic apparatuses such as copying machines and laser beam printers have an electrophotographic photosensitive member (organic electrophotographic photosensitive member) having a photosensitive layer containing a charge generating material and a hole transporting material (charge transporting material) which are organic compounds. ) Is widely used.

  Among charge generation materials, phthalocyanine pigments and azo pigments are known as charge generation materials having high sensitivity.

  However, electrophotographic photoreceptors using phthalocyanine pigments or azo pigments generate a large amount of photocarriers (holes and electrons), so that electrons as pairs of holes transferred by the hole transport material are transferred to the photosensitive layer (charges). It tends to stay in the generation layer). For this reason, electrophotographic photoreceptors using phthalocyanine pigments or azo pigments have a problem that a phenomenon called ghost is likely to occur. Specifically, in the output image, a positive ghost in which the density is increased only in a portion irradiated with light during the previous rotation, or a negative ghost in which the density is decreased only in a portion irradiated with light during the previous rotation.

  Patent Document 1 discloses a technique for reducing an environmental change in exposure potential and residual potential by including an electron transport material and a polyamide resin in an undercoat layer provided between a conductive support and a photosensitive layer. Has been.

  Patent Document 2 discloses a technique for suppressing a ghost by containing an electron transport material in a charge generation layer and an undercoat layer.

  Patent Document 3 discloses a technique in which a white metal oxide or metal fluoride and a thiourea derivative are contained in an undercoat layer to suppress an increase in residual potential after repeated use with high sensitivity.

JP 2002-091044 A JP 2007-148293 A Japanese Patent Laid-Open No. 7-140693

  Currently, it is desired to suppress ghosts in various environments. Among various environments, ghosts are particularly likely to occur in a low-temperature and low-humidity environment, but the above-described conventional technology has not been sufficiently effective in suppressing ghosts in a low-temperature and low-humidity environment.

  An object of the present invention is to provide an electrophotographic photosensitive member in which ghosts are suppressed even in a low temperature and low humidity environment, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

The present invention is an electrophotographic photoreceptor having a support, an undercoat layer formed on the support, and a photosensitive layer containing a charge generation material and a hole transport material formed on the undercoat layer. And
The undercoat layer contains a urea compound;
The urea compound has one or more and three or less urea moieties having a carbonyl group and two nitrogen atoms,
At each of the urea sites, at least one of the two nitrogen atoms is
An electrophotographic photoreceptor having at least one substituent selected from the group consisting of an unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted arylene group.

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

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

  According to the present invention, it is possible to provide an electrophotographic photosensitive member in which ghosts are suppressed even in a low temperature and low humidity environment, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

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. 2 is a powder X-ray diffraction pattern of a hydroxygallium phthalocyanine crystal obtained in Example 1. FIG. 6 is a powder X-ray diffraction pattern of hydroxygallium phthalocyanine crystal obtained in Example 8. FIG. It is a figure which shows the image for ghost evaluation.

The electrophotographic photosensitive member of the present invention includes a support, an undercoat layer formed on the support, and a photosensitive layer containing a charge generation material and a hole transport material formed on the undercoat layer. It is a photoreceptor. In the present invention, the undercoat layer contains a urea compound,
The urea compound has one or more and three or less urea moieties having a carbonyl group and two nitrogen atoms,
At each of the urea sites, at least one of the two nitrogen atoms is
It has at least one substituent selected from the group consisting of an unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted arylene group.

  The present inventors infer the reason why the electrophotographic photosensitive member of the present invention is excellent in the ghost suppression effect as follows.

  That is, by extracting electrons from the charge generation material by the strong polarity of the urea compound contained in the undercoat layer of the electrophotographic photoreceptor of the present invention and the electron withdrawing property of the carbonyl group, Make the flow better. In addition to this, the inclusion of the urea compound and the symmetrical arrangement of nitrogen atoms with respect to the carbonyl group eliminates the formation of trap sites that retain electrons in the undercoat layer. The uneven distribution of physical characteristics. By these, it is considered that the stagnation of electrons and the decrease in mobility in the electrophotographic photosensitive member are suppressed, and the ghost which is the density difference between the exposed portion and the non-exposed portion is improved.

  Among the urea compounds, at least one urea compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2) is preferable.

式（１）、式（２）中、Ｒ^１１、Ｒ^１２、Ｒ^２１〜Ｒ^２４は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基を示す。Ａｒ^１１、Ａｒ^１２、Ａｒ^２１、Ａｒ^２３は、それぞれ独立に、水素原子、置換もしくは無置換のアリール基を示す。Ａｒ^２２は置換もしくは無置換のアリーレン基を示す。ただし、Ａｒ^１１、Ａｒ^１２のうち少なくとも１つは置換もしくは無置換のアリール基であり、Ａｒ^２１、Ａｒ^２３のうち少なくとも１つは置換もしくは無置換のアリール基である。該置換アルキル基の置換基としては，シアノ基、ジアルキルアミノ基、水酸基、アルコキシ基、アルコキシ置換アルコキシ基、ハロゲン置換アルコキシ基、ニトロ基、または、ハロゲン原子である。該置換アリール基の置換基としては、シアノ基、ジアルキルアミノ基、水酸基、アルキル基、ヒドロキシアルキル基、アルコキシ置換アルキル基、ハロゲン置換アルキル基、アルコキシ基、アルコキシ置換アルコキシ基、ハロゲン置換アルコキシ基、ニトロ基、または、ハロゲン原子である。該置換アリーレン基の置換基としては、アルキル基、ヒドロキシアルキル基、アルコキシ置換アルキル基、ハロゲン置換アルキル基、アルコキシ基、アルコキシ置換アルコキシ基、ハロゲン置換アルコキシ基、または、ハロゲン原子である。

In formula (1) and formula (2), R ¹¹ , R ¹² and R ^{21 to} R ²⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. Ar ¹¹ , Ar ¹² , Ar ²¹ and Ar ²³ each independently represent a hydrogen atom or a substituted or unsubstituted aryl group. Ar ²² represents a substituted or unsubstituted arylene group. However, at least one of Ar ¹¹ and Ar ¹² is a substituted or unsubstituted aryl group, and at least one of Ar ²¹ and Ar ²³ is a substituted or unsubstituted aryl group. The substituent of the substituted alkyl group is a cyano group, a dialkylamino group, a hydroxyl group, an alkoxy group, an alkoxy-substituted alkoxy group, a halogen-substituted alkoxy group, a nitro group, or a halogen atom. Examples of the substituent for the substituted aryl group include cyano group, dialkylamino group, hydroxyl group, alkyl group, hydroxyalkyl group, alkoxy-substituted alkyl group, halogen-substituted alkyl group, alkoxy group, alkoxy-substituted alkoxy group, halogen-substituted alkoxy group, nitro A group or a halogen atom. The substituent of the substituted arylene group is an alkyl group, a hydroxyalkyl group, an alkoxy-substituted alkyl group, a halogen-substituted alkyl group, an alkoxy group, an alkoxy-substituted alkoxy group, a halogen-substituted alkoxy group, or a halogen atom.

  The aryl group possessed by the nitrogen atom of the urea compound represented by the above formulas (1) and (2) functions as a conductive path that moves electrons in the undercoat layer, and is thus presumed to further improve the ghost suppression ability. .

Of the urea compounds represented by the formula (2), Ar ²² is preferably a phenylene group.

In the formulas (1) and (2), R ¹¹ , R ¹² and R ^{21 to} R ²⁴ are each independently a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, or a substituted or unsubstituted group. A substituted propyl group is preferred.

Furthermore, at least one of R ¹¹ , R ¹² and R ^{21 to} R ^{24 in} the formulas (1) and (2) is preferably a hydroxyalkyl group. It is surmised that the hydrogen bonding property of the hydroxyalkyl group works more effectively to eliminate the formation of trap sites in the undercoat layer.

In the formulas (1) and (2), Ar ¹¹ , Ar ¹² , Ar ²¹ and Ar ²³ are each independently a substituted or unsubstituted phenyl group (provided that the substituent of the substituted phenyl group is a hydroxyl group) And a group selected from the group consisting of an alkyl group, a hydroxyalkyl group, an alkoxy group, a dialkylamino group and a halogen atom. When the phenyl group is symmetrically arranged with respect to the carbonyl group of the urea compound, the phenyl group has a structure in which the phenyl groups face each other, and the distance between the phenyl groups is shortened so that the two phenyl groups have an anisotropic conductive path. This is presumed to be due to the fact that it acts and improves the ghost suppression ability by improving the flow of electrons.

Furthermore, it is preferable that at least one of Ar ¹¹ , Ar ¹² , Ar ²¹ and Ar ^{23 in} the formulas (1) and (2) is a hydroxyl group-substituted phenyl group or a hydroxyalkyl group-substituted phenyl group. It is presumed that the hydrogen bonding property of the hydroxyl group or hydroxyalkyl group works more effectively to eliminate the formation of trap sites in the undercoat layer.

  Moreover, it is preferable that content of the said urea compound in the said undercoat layer is 0.05 to 15 mass% with respect to the total mass of the said undercoat layer. This is because if the content of the urea compound in the undercoat layer is too small, the ghost suppressing ability is not sufficient, and if the content is too large, the urea compound tends to precipitate. More preferably, it is 0.1 mass% or more and 10 mass% or less.

  The undercoat layer preferably contains metal oxide particles. This is because the electronic conduction mechanism using metal oxide particles is less subject to variations in electrical characteristics due to repeated use and environmental fluctuations than the ion conduction mechanism. Examples of the metal oxide particles include zinc oxide particles and titanium oxide particles.

  Furthermore, the content of the urea compound in the undercoat layer is preferably 0.1% by mass or more and 10% by mass or less with respect to the total mass of the metal oxide particles. If it is this range, an electrical property fluctuation | variation will fully be suppressed and generation | occurrence | production of a crack will be suppressed.

  The photosensitive layer preferably includes a charge generation layer containing the charge generation material and a hole transport layer containing the hole transport material formed on the charge generation layer.

  Furthermore, the charge generation layer preferably contains the charge generation material and the urea compound. It is assumed that the exchange of electrons at the interface between the charge generation layer and the undercoat layer becomes better by containing the urea compound in both the charge generation layer and the undercoat layer.

  Furthermore, it is preferable that the urea compound contained in the undercoat layer and the urea compound contained in the charge generation layer are urea compounds having the same structure. It is assumed that the exchange of electrons at the interface between the charge generation layer and the undercoat layer is further improved when the urea compound contained in the charge generation layer and the undercoat layer is the same.

  The charge generation material is preferably a gallium phthalocyanine crystal.

  Further, the gallium phthalocyanine crystal is a crystalline gallium phthalocyanine crystal having peaks at 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° of the Bragg angle 2θ in the X-ray diffraction of CuKα ray. It is preferable. This is because the use of a hydroxygallium phthalocyanine crystal as a charge generation material improves the stability of electrical characteristics against environmental fluctuations, and the present invention works more effectively.

  Furthermore, the gallium phthalocyanine crystal is preferably a gallium phthalocyanine crystal containing the urea compound in the crystal. By containing the urea compound in the crystal, the flow of electrons from the gallium phthalocyanine crystal becomes good, and the electrons stay from the electron generation part (gallium phthalocyanine crystal) through the charge generation layer to the undercoat layer. It is inferred that it will flow without any problems.

  Furthermore, the content of the urea compound in the gallium phthalocyanine crystal is preferably 0.02% by mass or more and 2% by mass or less. If the content of the urea compound in the gallium phthalocyanine crystal is too small, the ghost suppressing ability is not sufficient, and if the content is too large, the urea compound may impair the dispersibility of the gallium phthalocyanine crystal. is there.

  Specific examples (exemplary compounds) of the urea compound of the present invention are shown below, but the present invention is not limited thereto.

  As described above, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer.

  FIG. 1 is a diagram showing an example of the layer structure of the electrophotographic photosensitive member according to the present invention. In FIG. 1, 101 is a support, 102 is an undercoat layer, 103 is a charge generation layer, 104 is a hole transport layer, and 105 is a photosensitive layer (laminated photosensitive layer).

  As a support body, what has electroconductivity (conductive support body) is preferable. For example, a support made of metal (alloy) such as aluminum, stainless steel, or nickel, or a support made of metal, plastic, or paper having a conductive film on the surface can be used. Examples of the shape of the support include a cylindrical shape and a film shape. Among these, a cylindrical aluminum support is excellent in terms of mechanical strength, electrophotographic characteristics, and cost. The raw tube may be used as a support, but the surface of the raw tube is supported by physical treatment such as cutting or honing, anodizing treatment, chemical treatment using acid, etc. It may be used as a body. By performing physical processing such as cutting and honing on the raw tube, the support processed to a surface roughness of 0.8 μm or more with a 10-point average roughness Rzjis value defined in JIS B0601: 2001 is excellent. Has interference fringe suppression function.

  A conductive layer may be provided between the support and the undercoat layer as necessary. By forming the conductive layer, an interference fringe suppression function can be imparted.

  The conductive layer can be formed by applying the conductive layer coating liquid onto the support and then drying the obtained coating film. The coating liquid for the conductive layer can be prepared by dispersing the conductive particles, the binder resin, and the solvent. Examples of the conductive particles include tin oxide particles, indium oxide particles, titanium oxide particles, barium sulfate particles, and carbon black. Examples of the binder resin include phenol resin. Moreover, you may add a rough particle to the coating liquid for conductive layers as needed.

  The film thickness of the conductive layer is preferably 5 to 40 μm, and more preferably 10 to 30 μm, from the viewpoints of interference fringe suppression function, concealment (coating) of defects on the support, and the like.

  An undercoat layer is provided on the support or the conductive layer.

  For the undercoat layer, the urea compound of the present invention and the coating solution for the undercoat layer prepared by dissolving the resin in a solvent are applied onto the support or the conductive layer, and the resulting coating film is dried. Can be formed.

  Examples of the resin used for the undercoat layer include acrylic resin, allyl resin, alkyd resin, ethyl cellulose resin, ethylene-acrylic acid copolymer, epoxy resin, casein resin, silicone resin, gelatin resin, phenol resin, butyral resin, polyacrylate. Resin, polyacetal resin, polyamideimide resin, polyamide resin, polyallyl ether resin, polyimide resin, polyurethane resin, polyester resin, polyethylene resin, polycarbonate resin, polystyrene resin, polysulfone resin, polyvinyl alcohol resin, polybutadiene resin, polypropylene resin, urea resin , Agarose resin, cellulose resin and the like. Among these, a polyurethane resin and a polyamide resin are preferable.

  Examples of the solvent used in the coating solution for the undercoat layer include benzene, toluene, xylene, tetralin, chlorobenzene, dichloromethane, chloroform, trichloroethylene, tetrachloroethylene, carbon tetrachloride, methyl acetate, ethyl acetate, propyl acetate, methyl formate, and formic acid. Ethyl, acetone, methyl ethyl ketone, cyclohexanone, diethyl ether, dipropyl ether, propylene glycol monomethyl ether, dioxane, methylal, tetrahydrofuran, water, methanol, ethanol, n-propanol, isopropanol, butanol, methyl cellosolve, methoxypropanol, dimethylformamide, dimethyl Examples include acetamide and dimethyl sulfoxide.

  The thickness of the undercoat layer is preferably 0.1 to 30.0 μm.

  The urea compound of the present invention contained in the undercoat layer may be amorphous or crystalline. Also, two or more urea compounds of the present invention can be used in combination.

  A photosensitive layer containing a charge generation material and a hole transport material is provided on the undercoat layer.

  As the charge generation material, a phthalocyanine pigment or an azo pigment is preferable in terms of high sensitivity, and among these, a phthalocyanine pigment is more preferable.

  Examples of the phthalocyanine pigment include metal-free phthalocyanine and metal phthalocyanine, which may have an axial ligand or a substituent. Among the phthalocyanine pigments, oxytitanium phthalocyanine and gallium phthalocyanine are preferable because they have high sensitivity and easily generate ghosts, so that the present invention works effectively.

  When the photosensitive layer is a laminated photosensitive layer, examples of the binder resin for the charge generation layer include polyvinyl butyral, polyarylate, polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyvinyl pyridine, and cellulose. And resins (insulating resins) such as resin, urethane resin, epoxy resin, agarose resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. Moreover, organic photoconductive polymers, such as poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene, can also be used.

  Examples of the solvent used in the charge generation layer coating solution include toluene, xylene, tetralin, chlorobenzene, dichloromethane, chloroform, trichloroethylene, tetrachloroethylene, carbon tetrachloride, methyl acetate, ethyl acetate, propyl acetate, methyl formate, ethyl formate, Acetone, methyl ethyl ketone, cyclohexanone, diethyl ether, dipropyl ether, propylene glycol monomethyl ether, dioxane, methylal, tetrahydrofuran, water, methanol, ethanol, n-propanol, isopropanol, butanol, methyl cellosolve, methoxypropanol, dimethylformamide, dimethylacetamide, Examples thereof include dimethyl sulfoxide.

  The charge generation layer can be formed by applying a charge generation layer coating solution containing a charge generation material and, if necessary, a binder resin, and drying the obtained coating film.

  The coating solution for the charge generation layer may be prepared by adding only the charge generation material to the solvent and then dispersing and then adding the binder resin. Alternatively, the charge generation material and the binder resin may be added to the solvent together and dispersed. May be prepared.

  The thickness of the charge generation layer is preferably 0.05 μm or more and 5 μm or less.

  The content of the charge generation material in the charge generation layer is preferably 30% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 80% by mass or less with respect to the total mass of the charge generation layer.

  Examples of the hole transport material include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, triallylmethane compounds, and the like.

  When the photosensitive layer is a laminated photosensitive layer, examples of the binder resin for the hole transport layer include polyvinyl butyral, polyarylate, polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide resin, and polyamide resin. , Polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, agarose resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone, and other resins (insulating resin). Moreover, organic photoconductive polymers, such as poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene, can also be used.

  Examples of the solvent used for the coating solution for the hole transport layer include toluene, xylene, tetralin, monochlorobenzene, dichloromethane, chloroform, trichloroethylene, tetrachloroethylene, carbon tetrachloride, methyl acetate, ethyl acetate, propyl acetate, methyl formate, formic acid. Ethyl, acetone, methyl ethyl ketone, cyclohexanone, diethyl ether, dipropyl ether, propylene glycol monomethyl ether, dioxane, methylal, tetrahydrofuran, water, methanol, ethanol, n-propanol, isopropanol, butanol, methyl cellosolve, methoxypropanol, dimethylformamide, dimethyl Examples include acetamide and dimethyl sulfoxide.

  The hole transport layer is formed by applying a hole transport material and, if necessary, a coating solution for a hole transport layer obtained by dissolving a binder resin in a solvent, and drying the obtained coating film. be able to.

  The thickness of the hole transport layer is preferably 5 μm or more and 40 μm or less.

  The content of the hole transport material is preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 60% by mass or less with respect to the total mass of the hole transport layer.

  The urea compound of the present invention contained in the charge generation layer in the multilayer photosensitive layer may be either amorphous or crystalline. Also, two or more urea compounds of the present invention can be used in combination.

A protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer.
The protective layer dissolves resins such as polyvinyl butyral, polyester, polycarbonate (such as polycarbonate Z and modified polycarbonate), nylon, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-acrylic acid copolymer, styrene-acrylonitrile copolymer in a solvent. It can form by apply | coating the coating liquid for protective layers prepared by making it apply | coat on a photosensitive layer, and drying / curing the obtained coating film. When the coating film is cured, heating, electron beam, or ultraviolet light can be used.
The thickness of the protective layer is preferably 0.05 to 20 μm.

  Further, the protective layer may contain lubricating particles such as conductive particles, an ultraviolet absorber, and fluorine atom-containing resin particles. Examples of the conductive particles include metal oxide particles such as tin oxide particles.

  Examples of the coating method for the coating solution for each layer include a dip coating method (dipping method), a spray coating method, a spinner coating method, a bead coating method, a blade coating method, and a beam coating method.

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

  Reference numeral 1 denotes a cylindrical (drum-shaped) electrophotographic photosensitive member, which is rotationally driven around a shaft 2 at a predetermined peripheral speed (process speed) in the direction of an arrow.

  The surface of the electrophotographic photosensitive member 1 is charged to a predetermined positive or negative potential by the charging unit 3 during the rotation process. Next, the surface of the electrophotographic photosensitive member 1 is irradiated with image exposure light 4 from an image exposure unit (not shown), and an electrostatic latent image corresponding to target image information is formed. The image exposure light 4 is light whose intensity is modulated corresponding to the time-series electric digital image signal of the target image information, and is output from image exposure means such as slit exposure or laser beam scanning exposure.

  The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed (regular development or reversal development) with toner contained in the developing unit 5, and a toner image is formed on the surface of the electrophotographic photosensitive member 1. The The toner image formed on the surface of the electrophotographic photoreceptor 1 is transferred to the transfer material 7 by the transfer means 6. At this time, a bias voltage having a polarity opposite to the charge held in the toner is applied to the transfer unit 6 from a bias power source (not shown). When the transfer material 7 is paper, the transfer material 7 is taken out from a paper feed unit (not shown) and is synchronized with the rotation of the electrophotographic photosensitive member 1 between the electrophotographic photosensitive member 1 and the transfer means 6. Are sent.

  The transfer material 7 onto which the toner image has been transferred from the electrophotographic photosensitive member 1 is separated from the surface of the electrophotographic photosensitive member 1, conveyed to the image fixing means 8, and subjected to a toner image fixing process, thereby forming an image. Printed out as an object (print, copy) out of the electrophotographic apparatus.

  The surface of the electrophotographic photosensitive member 1 after the toner image is transferred to the transfer material 7 is cleaned by the cleaning means 9 after removal of deposits such as toner (transfer residual toner). In recent years, a cleanerless system has also been developed. If it is adopted, the transfer residual toner can be directly removed by a developing device or the like. Further, the surface of the electrophotographic photosensitive member 1 is subjected to charge removal treatment with pre-exposure light 10 from a pre-exposure unit (not shown), and then repeatedly used for image formation. When the charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure unit is not always necessary.

  In the present invention, among the components selected from the above-described electrophotographic photosensitive member 1, charging unit 3, developing unit 5, transfer unit 6 and cleaning unit 9, a plurality of components are housed in a container and integrally supported. Thus, a process cartridge can be formed and can be configured to be detachable from the electrophotographic apparatus main body. For example, the configuration is as follows. At least one selected from the charging unit 3, the developing unit 5 and the cleaning unit 9 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge. This can be a process cartridge 11 that is detachable from the main body of the electrophotographic apparatus using guide means 12 such as a rail of the main body of the electrophotographic apparatus.

  The image exposure light 4 may be reflected light or transmitted light from an 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 photosensitive member 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 in more detail with reference to specific examples. However, the present invention is not limited to these. In addition, the film thickness of each layer of the electrophotographic photoconductors of Examples and Comparative Examples was determined by specific gravity conversion from an eddy current film thickness meter (Fischerscope, manufactured by Fischer Instrument Co.) or mass per unit area. In the examples, “part” means “part by mass”.

Example 1
An aluminum cylinder having a diameter of 24 mm and a length of 257 mm was used as a support (cylindrical support).

Next, 60 parts of barium sulfate particles (trade name: Pastoran PC1, manufactured by Mitsui Mining & Smelting Co., Ltd.) coated with tin oxide,
15 parts of titanium oxide particles (trade name: TITANIX JR, manufactured by Teika)
43 parts of a resol type phenolic resin (trade name: Phenolite J-325, manufactured by DIC Corporation, solid content 70% by mass),
0.015 part of silicone oil (trade name: SH28PA, manufactured by Toray Silicone Co., Ltd.)
3.6 parts of silicone resin particles (trade name: Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.)
A conductive layer coating solution was prepared by placing 50 parts of 2-methoxy-1-propanol and 50 parts of methanol in a ball mill and dispersing the mixture for 20 hours.
This conductive layer coating solution was dip-coated on a support, and the resulting coating film was heated at 140 ° C. for 1 hour to cure the coating film, thereby forming a conductive layer having a thickness of 20 μm.

Next, 36 parts of alkyd resin (trade name: Beckolite M6401-50-S (solid content 50%), manufactured by DIC Corporation),
20 parts of melamine resin (trade name: Super Becamine L-121-60 (solid content 60%), manufactured by DIC Corporation),
Surface untreated rutile type titanium oxide particles (trade name: CR-EL, average particle size 0.25 μm, manufactured by Ishihara Sangyo Co., Ltd.) 120 parts,
0.88 parts of exemplary compound (39), and
Undercoat layer coating solution was prepared by mixing 280 parts of 2-butanone.
The undercoat layer coating solution was applied onto the conductive layer by dip coating, and the resulting coating film was dried at 130 ° C. for 45 minutes to form an undercoat layer having a thickness of 3 μm.

Next, hydroxygallium phthalocyanine obtained by processing in the same manner as in Example 1-1 following (Synthesis Example 1) described in JP2011-94101A was prepared. Hereinafter, this hydroxygallium phthalocyanine is referred to as hydroxygallium phthalocyanine A. Milling treatment of 0.5 parts of hydroxygallium phthalocyanine A, 0.5 parts of the exemplified compound (39) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature (23 C.) for 52 hours. Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.45 part of a hydroxygallium phthalocyanine crystal. A powder X-ray diffraction pattern of the obtained crystals is shown in FIG.
It was confirmed by NMR measurement that 0.05 mass% of the exemplified compound (39) was contained in the phthalocyanine crystal in terms of the proton ratio.

ポリビニルブチラール（商品名：ＢＸ−１、積水化学工業（株）製）１０部、および、シクロヘキサノン５１９部を、直径１ｍｍのガラスビーズを用いたサンドミルに入れ、４時間分散処理した。その後、酢酸エチル７６４部を加えることによって、電荷発生層用塗布液を調製した。
この電荷発生層用塗布液を下引き層上に浸漬塗布し、得られた塗膜を１００℃で１０分間乾燥させることによって、膜厚が０．１８μｍの電荷発生層を形成した。 Next, 20 parts of the obtained hydroxygallium phthalocyanine crystal (charge generating substance), 0.2 part of a calixarene compound represented by the following formula (3),

10 parts of polyvinyl butyral (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 519 parts of cyclohexanone were placed in a sand mill using glass beads having a diameter of 1 mm and dispersed for 4 hours. Thereafter, 764 parts of ethyl acetate was added to prepare a coating solution for charge generation layer.
This charge generation layer coating solution was dip-coated on the undercoat layer, and the resulting coating film was dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.18 μm.

下記式（５）で示されるトリアリールアミン化合物（正孔輸送物質）１０部、

ポリカーボネート樹脂（商品名：ユーピロンＺ−２００、三菱エンジニアリングプラスチックス（株）製）１００部を、モノクロロベンゼン６３０部に溶解させることによって、正孔輸送層用塗布液を調製した。
この正孔輸送層用塗布液を電荷発生層上に浸漬塗布し、得られた塗膜を１２０℃で１時間乾燥させることによって、膜厚が１９μｍの正孔輸送層を形成した。 Next, 70 parts of a triarylamine compound (hole transport material) represented by the following formula (4),

10 parts of a triarylamine compound (hole transport material) represented by the following formula (5),

A coating solution for a hole transport layer was prepared by dissolving 100 parts of polycarbonate resin (trade name: Iupilon Z-200, manufactured by Mitsubishi Engineering Plastics) in 630 parts of monochlorobenzene.
This hole transport layer coating solution was dip coated on the charge generation layer, and the resulting coating film was dried at 120 ° C. for 1 hour to form a hole transport layer having a thickness of 19 μm.

The coating films of the conductive layer, undercoat layer, charge generation layer and hole transport layer were dried using an oven set at each temperature. The same applies hereinafter.
As described above, a cylindrical (drum-shaped) electrophotographic photosensitive member 1 was manufactured.

[Example 2]
In Example 1, the usage-amount of exemplary compound (39) used when preparing the coating liquid for undercoat layers was changed from 0.88 part to 0.018 part. Otherwise, the electrophotographic photosensitive member 2 was produced in the same manner as in Example 1.

Example 3
In Example 1, the usage-amount of exemplary compound (39) used when preparing the coating liquid for undercoat layers was changed from 0.88 part to 0.18 part. Other than that was carried out similarly to Example 1, and manufactured the electrophotographic photoreceptor 3. FIG.

Example 4
In Example 1, the usage-amount of exemplary compound (39) used when preparing the coating liquid for undercoat layers was changed from 0.88 part to 3.52 parts. Other than that was carried out similarly to Example 1, and manufactured the electrophotographic photoreceptor 4. FIG.

Example 5
In Example 1, the usage-amount of exemplary compound (39) used when preparing the coating liquid for undercoat layers was changed from 0.88 part to 17.6 parts. Other than that was carried out similarly to Example 1, and manufactured the electrophotographic photoreceptor 5. FIG.

Example 6
In Example 1, the usage-amount of exemplary compound (39) used when preparing the coating liquid for undercoat layers was changed from 0.88 part to 35.2 parts. Otherwise, the electrophotographic photosensitive member 6 was produced in the same manner as in Example 1.

Example 7
In Example 1, the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Other than that was carried out similarly to Example 1, and manufactured the electrophotographic photoreceptor 7. FIG.
Milling treatment of 0.5 parts of the above hydroxygallium phthalocyanine A, 2.0 parts of the exemplified compound (39) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.46 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 0.18% by mass of the exemplified compound (39) was contained in the phthalocyanine crystal in terms of the proton ratio.

Example 8
In Example 1, the dispersion and filtration of the hydroxygallium phthalocyanine crystal and the preparation of the coating solution for the charge generation layer were changed as follows. Other than that was carried out similarly to Example 1, and manufactured the electrophotographic photoreceptor 8. FIG.

  Milling of 0.5 parts of the hydroxygallium phthalocyanine A and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm was performed at room temperature (23 ° C.) for 52 hours. Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.44 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals is shown in FIG.

Next, 20 parts of the obtained hydroxygallium phthalocyanine crystal (charge generation material),
0.2 part of a calixarene compound represented by the above formula (3),
1 part of exemplary compound (39),
10 parts of polyvinyl butyral (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.)
519 parts of cyclohexanone was placed in a sand mill using glass beads having a diameter of 1 mm and dispersed for 4 hours. Thereafter, 764 parts of ethyl acetate was added to prepare a coating solution for charge generation layer.

Example 9
In Example 1, the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photosensitive member 9 was produced in the same manner as in Example 1.
Milling treatment of 0.5 parts of the above hydroxygallium phthalocyanine A, 0.5 parts of the exemplified compound (29) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.43 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 0.09% by mass of the exemplified compound (29) was contained in the phthalocyanine crystal in terms of the proton ratio.

Example 10
In Example 8, the exemplary compound (39) was not used when preparing the coating solution for charge generation layer. Otherwise, the electrophotographic photoreceptor 10 was manufactured in the same manner as in Example 8.

Example 11
An aluminum cylinder having a diameter of 24 mm and a length of 257 mm was used as a support (cylindrical support).
Next, 56 parts of butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.)
56 parts of blocked isocyanate (trade name: Sumidur 3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
300 parts of zinc oxide fine particles (Silane coupling agent: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.)) 300 parts,
2.2 parts of exemplary compound (39), and
596 parts of a mixed solution of 2-butanone / n-butanol = 1/1 were mixed and dispersed in a sand mill using glass beads having a diameter of 1 mm for 3.3 hours. Thereafter, 0.04 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.) and polymethyl methacrylate resin particles (PMMA, manufactured by Sekisui Plastics Co., Ltd., SSX-102, average particle size 2) 0.5 μm) was added to prepare an undercoat layer coating solution.
This undercoat layer coating solution was dip-coated on a support, and the resulting coating film was dried at 160 ° C. for 30 minutes to form an undercoat layer having a thickness of 16 μm.
Next, a charge generation layer and a hole transport layer were formed in the same manner as in Example 1 to produce an electrophotographic photoreceptor 11.

Example 12
An aluminum cylinder having a diameter of 24 mm and a length of 257 mm was used as a support (cylindrical support).
Next, 25 parts of N-methoxymethylated nylon 6 (trade name: Toresin EF-30T, manufactured by Nagase ChemteX Corporation) was dissolved in 225 parts of a mixed solvent of n-butanol (dissolved by heating at 65 ° C.). The resulting solution was cooled. Thereafter, the solution was filtered through a membrane filter (trade name: FP-022, pore size: 0.22 μm, manufactured by Sumitomo Electric Industries, Ltd.). Next, 56 parts of rutile acid titania sol containing tin atoms was added to the filtrate, and the mixture was placed in a sand mill apparatus using 500 parts of glass beads having an average diameter of 0.8 mm and dispersed at 800 rpm for 30 minutes. After the dispersion treatment, the glass beads were separated by mesh filtration. The separated liquid was diluted with methanol and n-butanol so that the solid content was 3.0% by mass and the solvent ratio was methanol: n-butanol = 2: 1. An undercoat layer coating solution was prepared by adding 0.08 part of Exemplified Compound (39) to 500 parts of this diluted solution. The content of the titanium oxide crystal particles contained in the undercoat layer coating solution was 25% by mass with respect to the total mass of the dry solid content in the undercoat layer coating solution.
The undercoat layer coating solution was dip-coated on a support, and the resulting coating film was dried at 100 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.45 μm.
Next, a charge generation layer and a hole transport layer were formed in the same manner as in Example 1 to produce an electrophotographic photoreceptor 12.

Example 13
An aluminum cylinder having a diameter of 24 mm and a length of 257 mm was used as a support (cylindrical support).
Next, a solution prepared by dissolving 25 parts of N-methoxymethylated nylon 6 (trade name: Toresin EF-30T) in a mixed solvent of 320 parts of methanol / 160 parts of n-butanol (heating and dissolving at 65 ° C.) is cooled. did. Thereafter, the solution was filtered through a membrane filter (trade name: FP-022), and 0.13 part of the exemplified compound (39) was added to the filtrate to prepare an undercoat layer coating solution.
The undercoat layer coating solution was dip-coated on a support, and the resulting coating film was dried at 100 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.45 μm.
Next, a charge generation layer and a hole transport layer were formed in the same manner as in Example 1 to produce an electrophotographic photoreceptor 13.

Example 14
In Example 1, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (26), and the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photosensitive member 14 was produced in the same manner as in Example 1.
Milling treatment of 0.5 parts of the above hydroxygallium phthalocyanine A, 1.0 part of the exemplified compound (26) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.46 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 1.6 mass% of the exemplified compound (26) was contained in the phthalocyanine crystal in terms of the proton ratio.

Example 15
In Example 14, the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photoreceptor 15 was manufactured in the same manner as in Example 14.
Milling treatment of 0.5 parts of the hydroxygallium phthalocyanine A, 0.2 parts of the exemplified compound (26) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.45 part of a hydroxygallium phthalocyanine crystal. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 0.37 mass% of the exemplified compound (26) was contained in the phthalocyanine crystal in terms of the proton ratio.

Example 16
In Example 14, the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photosensitive member 16 was produced in the same manner as in Example 14.
Milling treatment of 0.5 parts of the hydroxygallium phthalocyanine A, 2.0 parts of the exemplified compound (26) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.46 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 2.9 mass% of the exemplified compound (26) was contained in the phthalocyanine crystal in terms of the proton ratio.

Example 17
In Example 10, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (26). Otherwise, the electrophotographic photosensitive member 17 was produced in the same manner as in Example 10.

Example 18
In Example 14, the preparation of the coating solution for the undercoat layer was changed as follows. Otherwise, the electrophotographic photosensitive member 18 was manufactured in the same manner as in Example 14.
A solution prepared by dissolving 25 parts of N-methoxymethylated nylon 6 (trade name: Toresin EF-30T) in a mixed solvent of 320 parts of methanol / 160 parts of n-butanol (heating and dissolving at 65 ° C.) was cooled. Thereafter, the solution was filtered through a membrane filter (trade name: FP-022), and 0.13 part of the exemplified compound (26) was added to the filtrate to prepare an undercoat layer coating solution.

Example 19
In Example 17, the preparation of the coating solution for the undercoat layer was changed as follows. Otherwise, the electrophotographic photosensitive member 19 was produced in the same manner as in Example 17.
A solution prepared by dissolving 25 parts of N-methoxymethylated nylon 6 (trade name: Toresin EF-30T) in a mixed solvent of 320 parts of methanol / 160 parts of n-butanol (heating and dissolving at 65 ° C.) was cooled. Thereafter, the solution was filtered through a membrane filter (trade name: FP-022), and 0.13 part of the exemplified compound (26) was added to the filtrate to prepare an undercoat layer coating solution.

Example 20
In Example 11, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (40), and the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photoreceptor 20 was manufactured in the same manner as in Example 11.
Milling of 0.5 parts of the hydroxygallium phthalocyanine A and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm was performed at room temperature (23 ° C.) for 52 hours. Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.44 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.

Example 21
In Example 12, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (47), and the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photosensitive member 21 was produced in the same manner as in Example 12.
Milling of 0.5 parts of the hydroxygallium phthalocyanine A and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm was performed at room temperature (23 ° C.) for 52 hours. Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.44 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.

[Example 22]
In Example 21, the usage-amount of exemplary compound (47) used when preparing the coating liquid for undercoat layers was changed from 0.08 part to 0.005 part. Otherwise, the electrophotographic photosensitive member 22 was manufactured in the same manner as in Example 21.

Example 23
In Example 21, the usage-amount of exemplary compound (47) used when preparing the coating liquid for undercoat layers was changed from 0.08 part to 0.02 part. Otherwise, the electrophotographic photosensitive member 23 was manufactured in the same manner as in Example 21.

Example 24
In Example 21, the usage-amount of exemplary compound (47) used when preparing the coating liquid for undercoat layers was changed from 0.08 part to 0.23 part. Otherwise, the electrophotographic photosensitive member 24 was produced in the same manner as in Example 21.

Example 25
In Example 21, the usage-amount of exemplary compound (47) used when preparing the coating liquid for undercoat layers was changed from 0.08 part to 0.75 part. Otherwise, the electrophotographic photosensitive member 25 was produced in the same manner as in Example 21.

Example 26
In Example 10, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (5). Otherwise, the electrophotographic photosensitive member 26 was manufactured in the same manner as in Example 10.

Example 27
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (5). Otherwise, the electrophotographic photosensitive member 27 was manufactured in the same manner as in Example 19.

Example 28
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (10). Otherwise, the electrophotographic photosensitive member 28 was manufactured in the same manner as in Example 19.

Example 29
In Example 13, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (13), and dispersion and filtration of hydroxygallium phthalocyanine crystals and preparation of the coating solution for the charge generation layer were performed. Was changed as follows. Otherwise, the electrophotographic photosensitive member 29 was produced in the same manner as in Example 13.
Milling treatment of 0.5 parts of the hydroxygallium phthalocyanine A, 2.0 parts of the exemplified compound (13) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.49 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 3.5 mass% of the exemplified compound (13) was contained in the phthalocyanine crystal in terms of the proton ratio.

  Next, 20 parts of the obtained hydroxygallium phthalocyanine crystal (charge generating substance), 0.2 part of calixarene compound represented by the above formula (3), 1 part of exemplary compound (13), polyvinyl butyral (trade name: BX- 1) 10 parts) and 519 parts of cyclohexanone were placed in a sand mill using glass beads having a diameter of 1 mm and dispersed for 4 hours. Thereafter, 764 parts of ethyl acetate was added to prepare a coating solution for charge generation layer.

Example 30
In Example 11, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (13), and the dispersion and filtration of hydroxygallium phthalocyanine crystals were carried out in the same manner as in Example 29. It was. Otherwise, the electrophotographic photoreceptor 30 was manufactured in the same manner as in Example 11.

Example 31
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (15). Otherwise, the electrophotographic photosensitive member 31 was manufactured in the same manner as in Example 19.

[Example 32]
In Example 13, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (18), and the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photosensitive member 32 was produced in the same manner as in Example 13.
Milling treatment of 0.5 parts of the above hydroxygallium phthalocyanine A, 1.0 part of the exemplified compound (18) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.46 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 0.9 mass% of the exemplified compound (18) was contained in the phthalocyanine crystal in terms of the proton ratio.

Example 33
In Example 12, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (18), and the dispersion and filtration of the hydroxygallium phthalocyanine crystals were carried out in the same manner as in Example 32. It was. Otherwise, the electrophotographic photosensitive member 33 was produced in the same manner as in Example 12.

Example 34
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (20). Otherwise, the electrophotographic photosensitive member 34 was manufactured in the same manner as in Example 19.

Example 35
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (25). Otherwise, the electrophotographic photosensitive member 35 was manufactured in the same manner as in Example 19.

Example 36
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (28). Otherwise, the electrophotographic photosensitive member 36 was manufactured in the same manner as in Example 19.

Example 37
In Example 8, the undercoat layer coating solution was prepared in the same manner as in Example 36, and the exemplified compound (39) used in the preparation of the charge generation layer coating solution was changed to the exemplified compound (28). . Otherwise, the electrophotographic photosensitive member 37 was manufactured in the same manner as in Example 8.

Example 38
In Example 36, the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photosensitive member 38 was produced in the same manner as in Example 36.
Milling treatment of 0.5 parts of the above hydroxygallium phthalocyanine A, 0.5 parts of the exemplary compound (28) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.48 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 1.48% by mass of the exemplified compound (28) was converted from the proton ratio in the phthalocyanine crystal.

Example 39
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (29). Otherwise, the electrophotographic photosensitive member 39 was manufactured in the same manner as in Example 19.

Example 40
In Example 39, the usage-amount of exemplary compound (29) used when preparing the coating liquid for undercoat layers was changed from 0.13 part to 0.005 part. Otherwise, the electrophotographic photosensitive member 40 was manufactured in the same manner as in Example 39.

Example 41
In Example 39, the usage-amount of exemplary compound (29) used when preparing the coating liquid for undercoat layers was changed from 0.13 parts to 1.25 parts. Otherwise, the electrophotographic photosensitive member 41 was produced in the same manner as in Example 39.

Example 42
In Example 39, the usage-amount of exemplary compound (29) used when preparing the coating liquid for undercoat layers was changed from 0.13 parts to 5 parts. Otherwise, the electrophotographic photosensitive member 42 was manufactured in the same manner as in Example 39.

Example 43
In Example 8, the undercoat layer coating solution was prepared in the same manner as in Example 39, and the exemplified compound (39) used in the preparation of the charge generation layer coating solution was changed to the exemplified compound (29). . Otherwise, the electrophotographic photosensitive member 43 was produced in the same manner as in Example 8.

Example 44
In Example 39, the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photosensitive member 44 was produced in the same manner as in Example 39.
Milling treatment of 0.5 parts of the above hydroxygallium phthalocyanine A, 0.5 parts of the exemplified compound (29) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.43 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 0.09% by mass of the exemplified compound (29) was contained in the phthalocyanine crystal in terms of the proton ratio.

Example 45
In Example 44, the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photosensitive member 45 was produced in the same manner as in Example 44.
Milling treatment of 0.5 parts of the hydroxygallium phthalocyanine A, 1.0 part of the exemplary compound (29) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.46 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 0.18% by mass of the exemplified compound (29) was contained in the phthalocyanine crystal in terms of the proton ratio.

Example 46
In Example 1, the exemplified compound (39) used in preparing the undercoat layer coating solution was changed to the exemplified compound (29). Otherwise, the electrophotographic photosensitive member 46 was manufactured in the same manner as in Example 1.

Example 47
In Example 10, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (29). Otherwise, the electrophotographic photosensitive member 47 was produced in the same manner as in Example 10.

Example 48
In Example 20, the exemplified compound (40) used in preparing the undercoat layer coating solution was changed to the exemplified compound (29). Otherwise, the electrophotographic photosensitive member 48 was produced in the same manner as in Example 20.

Example 49
In Example 21, the exemplified compound (47) used in preparing the undercoat layer coating solution was changed to the exemplified compound (29). Otherwise, the electrophotographic photosensitive member 49 was produced in the same manner as in Example 21.

Example 50
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (30). Otherwise, the electrophotographic photoreceptor 50 was manufactured in the same manner as in Example 19.

Example 51
In Example 50, the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photosensitive member 51 was produced in the same manner as in Example 50.
Milling treatment of 0.5 parts of the above hydroxygallium phthalocyanine A, 0.5 parts of the exemplified compound (30) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.49 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 0.04% by mass of the exemplified compound (30) was contained in the phthalocyanine crystal in terms of the proton ratio.

Example 52
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (33). Otherwise, the electrophotographic photosensitive member 52 was produced in the same manner as in Example 19.

Example 53
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (34). Otherwise, the electrophotographic photosensitive member 53 was produced in the same manner as in Example 19.

Example 54
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (37). Otherwise, the electrophotographic photosensitive member 54 was manufactured in the same manner as in Example 19.

Example 55
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (42). Otherwise, the electrophotographic photosensitive member 55 was manufactured in the same manner as in Example 19.

Example 56
In Example 1, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (42), and the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photosensitive member 56 was manufactured in the same manner as in Example 1.
Milling treatment of 0.5 parts of the hydroxygallium phthalocyanine, 0.2 part of the exemplified compound (42) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.45 part of a hydroxygallium phthalocyanine crystal. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 0.05 mass% of the exemplified compound (42) was contained in the phthalocyanine crystal in terms of the proton ratio.

Example 57
In Example 11, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (42), and dispersion and filtration of hydroxygallium phthalocyanine crystals were carried out in the same manner as in Example 56. It was. Otherwise, the electrophotographic photosensitive member 57 was manufactured in the same manner as in Example 11.

Example 58
In Example 12, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (42), and dispersion and filtration of hydroxygallium phthalocyanine crystals were carried out in the same manner as in Example 56. It was. Otherwise, the electrophotographic photosensitive member 58 was manufactured in the same manner as in Example 12.

Example 59
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (43). Otherwise, the electrophotographic photosensitive member 59 was manufactured in the same manner as in Example 19.

Example 60
In Example 19, the exemplified compound (26) used in preparing the undercoat layer coating solution was changed to the exemplified compound (45). Otherwise, the electrophotographic photosensitive member 60 was manufactured in the same manner as in Example 19.

Example 61
In Example 1, the exemplified compound (39) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (45), and the dispersion and filtration of hydroxygallium phthalocyanine crystals were changed as follows. Otherwise, the electrophotographic photoreceptor 61 was manufactured in the same manner as in Example 1.
Milling treatment of 0.5 parts of the hydroxygallium phthalocyanine A, 0.2 parts of the exemplified compound (45) and 9.5 parts of N, N-dimethylformamide together with 15 parts of glass beads having a diameter of 0.8 mm at room temperature ( 23 hours). Gallium phthalocyanine crystals were taken out of this dispersion using N, N-dimethylformamide, filtered, and the filter was thoroughly washed with N, N-dimethylformamide and then thoroughly washed with tetrahydrofuran. The filtered product was vacuum-dried to obtain 0.48 parts of hydroxygallium phthalocyanine crystals. The powder X-ray diffraction pattern of the obtained crystals was the same as FIG.
It was confirmed by NMR measurement that 0.20% by mass of the exemplified compound (45) was converted from the proton ratio in the phthalocyanine crystal.

Example 62
In Example 56, the exemplified compound (42) used in preparing the coating solution for the undercoat layer was changed to the exemplified compound (45). Otherwise, the electrophotographic photosensitive member 62 was manufactured in the same manner as in Example 56.

Example 63
In Example 1, the charge generation layer was changed as follows. Otherwise, the electrophotographic photosensitive member 63 was manufactured in the same manner as in Example 1.
A chlorogallium phthalocyanine pigment (charge generation material) obtained by the method described in (Synthesis Example 1) described in JP2011-94101A was prepared. 20 parts of this chlorogallium phthalocyanine pigment, 10 parts of polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 519 parts of cyclohexanone are placed in a sand mill using glass beads having a diameter of 1 mm. Time distributed processing. Thereafter, 764 parts of ethyl acetate was added to prepare a coating solution for charge generation layer. This charge generation layer coating solution was dip-coated on the undercoat layer, and the resulting coating film was dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.27 μm.

[Example 64]
In Example 1, the charge generation layer was changed as follows. Otherwise, the electrophotographic photosensitive member 64 was manufactured in the same manner as in Example 1.
Characteristic X-ray diffraction of CuKα ray Crystalline oxytitanium phthalocyanine crystals having peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° with a Bragg angle 2θ ± 0.2 ° (charge generation) Substance). 20 parts of this oxytitanium phthalocyanine crystal, 10 parts of polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 519 parts of cyclohexanone are placed in a sand mill using glass beads having a diameter of 1 mm. Time distributed processing. Thereafter, 764 parts of ethyl acetate was added to prepare a coating solution for charge generation layer. This charge generation layer coating solution was dip-coated on the undercoat layer, and the resulting coating film was dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.18 μm.

[Comparative Example 1]
In Example 1, the exemplified compound (39) was not used when preparing the coating solution for the undercoat layer and dispersing and filtering the hydroxygallium phthalocyanine crystals. Otherwise, the comparative electrophotographic photosensitive member 1 was produced in the same manner as in Example 1.

[Comparative Example 2]
In Example 20, the exemplified compound (40) used in preparing the coating solution for the undercoat layer was changed to a urea compound represented by the following formula (6). Otherwise, the comparative electrophotographic photosensitive member 2 was produced in the same manner as in Example 20.

[Comparative Example 3]
In Example 21, the exemplified compound (47) used in preparing the coating solution for the undercoat layer was changed to a urea compound represented by the following formula (7). Otherwise, the comparative electrophotographic photosensitive member 3 was produced in the same manner as in Example 21.

[Comparative Example 4]
In Example 19, the exemplified compound (26) used in preparing the coating solution for the undercoat layer was changed to a urea compound represented by the following formula (8). Otherwise, the comparative electrophotographic photosensitive member 4 was produced in the same manner as in Example 19.

[Comparative Example 5]
In Example 19, the exemplified compound (26) used in preparing the coating solution for the undercoat layer was changed to a urea compound represented by the following formula (9). Otherwise, the comparative electrophotographic photosensitive member 5 was manufactured in the same manner as in Example 19.

[Evaluation of Examples 1 to 64 and Comparative Examples 1 to 5]
For the electrophotographic photoreceptors produced in Examples 1 to 64 and Comparative Examples 1 to 5, the ghost was used in a normal temperature and humidity environment at a temperature of 23 ° C./humidity of 50% RH and in a low temperature and low humidity environment of a temperature of 15 ° C./humidity of 10% RH. Was evaluated.

  As examples of the electrophotographic apparatus for evaluation, lasers manufactured by Hewlett-Packard Company were used for Examples 1 to 10, 12 to 19, 21 to 29, 31 to 47, 49 to 56, 58 to 64 and Comparative Examples 1 and 3 to 5. A modified machine of a beam printer (trade name: Color Laser Jet CP3525dn) was used. As a remodeling point, the pre-exposure was not turned on, and the charging conditions and laser exposure were variable. In addition, the manufactured electrophotographic photosensitive member is mounted on a cyan process cartridge, mounted on a cyan process cartridge station, and operates without mounting a process cartridge for another color on the laser beam printer body. I made it.

  On the other hand, in Examples 11, 20, 30, 48, 57 and Comparative Example 2, a modified machine of a copying machine (trade name: imageRUNNER iR-ADV C5051) manufactured by Canon Inc. was used. As a remodeling point, the charging condition and the laser exposure amount can be changed. In addition, the manufactured electrophotographic photosensitive member is mounted on a cyan color process cartridge and mounted on a cyan process cartridge station so that it operates without mounting a process cartridge for another color on the copying machine main body. did.

  When outputting the image, only the cyan process cartridge was attached to the laser beam printer main body or the copying machine main body, and a monochromatic image only with cyan toner was output.

  As for the surface potential of the electrophotographic photosensitive member, the initial dark portion potential was-for Examples 1 to 10, 12 to 19, 21 to 29, 31 to 47, 49 to 56, 58 to 64 and Comparative Examples 1 and 3 to 5. The voltage was set to 500 V and the bright part potential to be −120 V. On the other hand, in Examples 11, 20, 30, 48, 57 and Comparative Example 2, the initial dark part potential was set to −600 V and the bright part potential was set to −220 V. For the measurement of the surface potential of the electrophotographic photosensitive member at the time of potential setting, an electrophotographic sensor using a potential probe (trade name: model6000B-8, manufactured by Trek Japan Co., Ltd.) mounted at the development position of the process cartridge is used. The potential at the center in the longitudinal direction of the photoreceptor was measured using a surface electrometer (trade name: model 344, manufactured by Trek Japan Co., Ltd.).

  First, a ghost was evaluated in a normal temperature and humidity environment with a temperature of 23 ° C./humidity of 50% RH. Thereafter, 1,000 paper passing durability tests were performed under the same environment, and ghosts were evaluated immediately after the durability testing. Table 1 shows the evaluation results in a room temperature and normal humidity environment.

Next, the electrophotographic photoreceptor was allowed to stand for 3 days in a low-temperature and low-humidity environment at a temperature of 15 ° C./humidity of 10% RH together with an electrophotographic apparatus for evaluation, and ghost was evaluated. Then, 1,000 paper passing durability tests were performed under the same environment, and ghosts were evaluated immediately after the durability testing. Table 1 shows the evaluation results in a low temperature and low humidity environment.
During the paper passing durability test, an E character image with a printing rate of 1% was formed on A4 size plain paper in a single cyan color.

The criteria for evaluation are as follows.
As shown in FIG. 5, the ghost evaluation image is obtained by outputting a square image of solid black 301 in solid white 302 at the head of the image and then outputting a halftone image 304 having a 1-dot Keima pattern. Formed by. First, a solid white image is output to the first sheet, and then five ghost evaluation images are output in succession. Next, after one solid black image is output, five ghost evaluation images are again output. Images were output in the order of output, and evaluation was performed using a total of 10 ghost evaluation images.

  The evaluation of the ghost is performed by measuring the density difference between the 1-dot Keima pattern image density and the image density of the ghost portion (the portion 303 where the ghost caused by the solid black 301 can be generated) by a spectral densitometer (trade name: X-Rite 504/508 X-Rite Co., Ltd.). Ten points were measured on one ghost evaluation image, and the average of these ten points was taken as one result. And after measuring all the 10 images for ghost evaluation similarly, those average values were calculated | required and it was set as the density | concentration difference of each example. This density difference means that the smaller the value, the smaller the degree of ghost and the better. The results are shown in Table 1. In Table 1, “Initial” means a density difference before a 1,000 sheet passing durability test is performed under a normal temperature and normal humidity environment or a low temperature and low humidity environment. “After endurance” means a density difference after a 1,000 sheet passing durability test in a normal temperature and normal humidity environment or a low temperature and low humidity environment.

DESCRIPTION OF SYMBOLS 101 Support body 102 Subbing layer 103 Charge generation layer 104 Hole transport layer 105 Photosensitive layer 1 Electrophotographic photosensitive member 2 Axis 3 Charging means 4 Image exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Image fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means

Claims (19)

An electrophotographic photosensitive member having a support, an undercoat layer formed on the support, and a photosensitive layer containing a charge generating material and a hole transport material formed on the undercoat layer,
The undercoat layer contains a urea compound;
The urea compound has one or more and three or less urea moieties having a carbonyl group and two nitrogen atoms,
At each of the urea sites, at least one of the two nitrogen atoms is
An electrophotographic photosensitive member having at least one substituent selected from the group consisting of an unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted arylene group. 2. The electrophotographic photoreceptor according to claim 1, wherein the urea compound is at least one urea compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2).

(In Formula (1) and Formula (2), R ¹¹ , R ¹² , R ^{21 to} R ²⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. Ar ¹¹ , Ar ¹² , Ar ²¹ , Ar ²³ each independently represents a hydrogen atom or a substituted or unsubstituted aryl group, Ar ²² represents a substituted or unsubstituted arylene group, provided that at least one of Ar ¹¹ and Ar ¹² is substituted or An unsubstituted aryl group, and at least one of Ar ²¹ and Ar ²³ is a substituted or unsubstituted aryl group, and examples of the substituent of the substituted alkyl group include a cyano group, a dialkylamino group, a hydroxyl group, and an alkoxy group. , An alkoxy-substituted alkoxy group, a halogen-substituted alkoxy group, a nitro group, or a halogen atom. A cyano group, a dialkylamino group, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an alkoxy-substituted alkyl group, a halogen-substituted alkyl group, an alkoxy group, an alkoxy-substituted alkoxy group, a halogen-substituted alkoxy group, a nitro group, or a halogen atom. The substituent for the substituted arylene group is an alkyl group, a hydroxyalkyl group, an alkoxy-substituted alkyl group, a halogen-substituted alkyl group, an alkoxy group, an alkoxy-substituted alkoxy group, a halogen-substituted alkoxy group, or a halogen atom. The electrophotographic photosensitive member according to claim 2, wherein Ar ²² in the formula (2) is a phenylene group. R ¹¹ , R ¹² , R ^{21 to} R ^{24 in the} formulas (1) and (2) are each independently a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, or a substituted or unsubstituted group. The electrophotographic photosensitive member according to claim 2, which is a propyl group. 5. The electrophotographic photosensitive member according to claim 2, wherein at least one of R ¹¹ , R ¹² , and R ^{21 to} R ^{24 in} the formulas (1) and (2) is a hydroxyalkyl group. . Ar ¹¹ , Ar ¹² , Ar ²¹ , Ar ^{23 in the} formulas (1) and (2) are each independently a substituted or unsubstituted phenyl group (provided that the substituent of the substituted phenyl group is a hydroxyl group, an alkyl group, The electrophotographic photosensitive member according to claim 2, which is a group, a hydroxyalkyl group, an alkoxy group, a dialkylamino group, or a halogen atom. Any one of Ar ¹¹ , Ar ¹² , Ar ²¹ , Ar ^{23 in} the formulas (1) and (2) is a hydroxyl group-substituted phenyl group or a hydroxyalkyl group-substituted phenyl group. The electrophotographic photosensitive member according to Item.   The electrophotography according to any one of claims 1 to 7, wherein a content of the urea compound in the undercoat layer is 0.05% by mass or more and 15% by mass or less with respect to a total mass of the undercoat layer. Photoconductor.   The electrophotographic photosensitive member according to claim 1, wherein the undercoat layer contains metal oxide particles.   The electrophotographic photosensitive member according to claim 9, wherein the content of the urea compound in the undercoat layer is 0.1% by mass or more and 10% by mass or less with respect to the total mass of the metal oxide particles.   11. The photosensitive layer according to claim 1, further comprising a charge generation layer containing the charge generation material and a hole transport layer containing the hole transport material formed on the charge generation layer. The electrophotographic photosensitive member according to Item.   The electrophotographic photosensitive member according to claim 11, wherein the charge generation layer contains the charge generation material and the urea compound.   The electrophotographic photosensitive member according to claim 12, wherein the urea compound contained in the undercoat layer and the urea compound contained in the charge generation layer are urea compounds having the same structure.   The electrophotographic photosensitive member according to claim 1, wherein the charge generation material is a gallium phthalocyanine crystal.   The gallium phthalocyanine crystal is a hydroxygallium phthalocyanine crystal having crystal forms having peaks at 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° of Bragg angle 2θ in X-ray diffraction of CuKα ray. 14. The electrophotographic photosensitive member according to 14.   The electrophotographic photosensitive member according to claim 14 or 15, wherein the gallium phthalocyanine crystal is a gallium phthalocyanine crystal containing the urea compound in the crystal.   The electrophotographic photosensitive member according to claim 16, wherein the content of the urea compound in the gallium phthalocyanine crystal is 0.02 mass% or more and 2 mass% or less.   An electrophotographic photosensitive member according to any one of claims 1 to 17, 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 image exposing unit, a developing unit, and a transferring unit.

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