JP4971764B2 - Electrophotographic photosensitive member, method for manufacturing electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

The present invention relates to an electrophotographic photosensitive member, a method for producing an electrophotographic photosensitive member, a process cartridge, and an electrophotographic apparatus, and more specifically, an electrophotographic photosensitive member containing a specific charge transport material, a method for producing the electrophotographic photosensitive member, The present invention relates to a process cartridge and an electrophotographic apparatus including the electrophotographic photosensitive member.

  Electrophotographic photoreceptors are required to have high image quality without sensitivity, electrical characteristics, optical characteristics and image defects according to the applied electrophotographic process, and in any environment from low temperature and low humidity to high temperature and high humidity. It is required to have environmental stability so that the characteristics are sufficiently exhibited.

  Typical image defects include image streaks, black spots on white portions, white spots on black portions, ground fog on white portions, and the like. Furthermore, when exposure is performed using a laser diode such as a digital copying machine or a laser beam printer as a light source, there are interference fringes generated due to factors such as the surface shape of the support and the film thickness unevenness of the electrophotographic photosensitive member.

  An intermediate layer is used as necessary as a method for preventing the image defects. The intermediate layer is required to have an electrical blocking function so that charge injection does not occur from the support when a voltage is applied to the electrophotographic photosensitive member. If there is charge injection from the support, the chargeability, image contrast, and reversal development method cause black spots and fogging on a white background, resulting in a significant decrease in image quality.

  On the other hand, if the electrical resistance of the intermediate layer is too high, the charge generated in the photosensitive layer stays inside the photosensitive layer, resulting in an increase in residual potential and potential fluctuation due to repeated use. Therefore, in addition to the electrical blocking function, it is necessary to reduce the electrical resistance value of the intermediate layer to some extent, and the blocking function and electrical resistance characteristics change greatly in any environment from low temperature to low humidity to high temperature and high humidity. Must not.

  As an intermediate layer having a blocking function and an appropriate range of electric resistance characteristics, for example, as an intermediate layer made of an organic polymer, Patent Document 1 and Patent Document 2, and metal oxides and metal nitrides in an organic polymer are used. Patent Documents 3 and 4 have been proposed as intermediate layers dispersed in the above.

  An electrophotographic photosensitive member using the above-described material as an intermediate layer has an electric potential that is stable in all environments from low temperature and low humidity to high temperature and high humidity because the electric resistance of the intermediate layer easily changes according to changes in temperature and humidity. It has been difficult to produce an electrophotographic photosensitive member having characteristics and capable of forming an excellent image.

  Further, as an intermediate layer for improving the carrier injecting property from the photosensitive layer to the conductive support, for example, Patent Documents 5 to 9 describe that the undercoat layer contains an electron transport material.

  However, the development of today's electrophotographic technology is remarkable, and very advanced technology is required for the characteristics required for electrophotographic photoreceptors. For example, process speeds are increasing year by year, and charging characteristics, sensitivity, durability stability, and the like have been demanded. In particular, in recent years, high-quality images have been screamed as typified by colorization, and black-and-white images that have been character-centered have become more and more halftone images and solid images typified by photographs. Yes. In particular, image quality with respect to changes in halftone density and solid image density when used continuously is increasing year by year, and it has been desired to suppress these image changes under low temperature and low humidity.

With the recent improvement in image quality and durability, in order to provide a superior electrophotographic photoreceptor, it is necessary to maintain the electrical blocking function and solve the potential fluctuation problem under low temperature and low humidity. It was.
JP-A-46-47344 JP 52-100240 A Japanese Patent Laid-Open No. 54-151843 JP-A-1-118848 JP-A-5-27469 JP-A-9-319128 JP 2000-321805 A JP-A-4-353858 Japanese Patent Laid-Open No. 2004-307809

An object of the present invention is to provide an electrophotographic photosensitive member capable of suppressing potential fluctuation under low temperature and low humidity and continuously forming excellent images, and a method for producing the electrophotographic photosensitive member .

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

According to the present invention, in an electrophotographic photoreceptor having a conductive support, an intermediate layer formed on the conductive support, and a photosensitive layer formed on the intermediate layer, the intermediate layer has the following structural formula: An electrophotographic photoreceptor comprising a polymer of an electron transport material having a structure represented by any one of (1) to (3) is provided.

In the structural formulas (1) to (3), Z ₁₁ , Z ₁₂ , Z ₂₁ , Z ₂₂ , Z ₃₁ and Z ₃₂ are each independently an oxygen atom , C (CN) ₂ , N—R, C ( CN) COR, C (CN) COOR, C (CN) R, or, C _(COOR) 2 (R represents a.) which represents an aryl group or an alkyl group optionally having a substituent. At least one of X ₁₁ to _{X 16,} at least one of _{X 21} to _{X 28,} and at least one of _{X 31} to _{X 36} each represent a polymerizable functional group, other than the polymerizable functional group are each independently Represents a hydrogen atom, a halogen atom, a nitro group, a trifluoroalkyl group, an alkoxy group which may have a substituent , or an alkyl group which may have a substituent.

  Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

  Further, according to the present invention, a process cartridge and an electrophotographic apparatus provided with the electrophotographic photosensitive member are provided.

  The electrophotographic photoreceptor of the present invention can suppress potential fluctuations under low temperature and low humidity, and can continuously form excellent images.

  In addition, the effect of the electrophotographic photosensitive member is naturally exhibited in a process cartridge and an electrophotographic apparatus including the electrophotographic photosensitive member.

  The electron transport material having the structure represented by any one of the structural formulas (1) to (3) of the present invention will be described.

  The polymerizable functional group in the present invention is, for example, an alkoxysilyl group, a hydroxyl group, an amino group, a carboxyl group, an aldehyde group or the like, a functional group capable of condensation reaction, a group having a carbon-carbon double bond, or carbon-carbon. Examples include a group having a triple bond, an epoxy group, and a functional group capable of chain reaction.

  Among these, a group selected from the group consisting of a hydroxyl group, a carboxyl group, and an aldehyde group, and a group having a carbon-carbon double bond are preferable. In particular, among groups having a carbon-carbon double bond, a group selected from the group consisting of an acryloyl group, a methacryloyl group, and a styryl group is more preferable.

  Representative examples of the electron transport material having the structure represented by any one of the structural formulas (1) to (3) are listed in Tables 1 to 3, but are not limited thereto.

  The present invention is effective by polymerizing an electron transport material having a structure represented by any one of structural formulas (1) to (3). Particularly in the intermediate layer.

  According to the present invention, a solution containing at least one polymerizable functional group of the electron transport material is applied and reacted with heat of room temperature drying or heat drying, radiation, electromagnetic waves, or the like. In this case, it is sufficient that at least one polymerizable functional group in the structure represented by any one of structural formulas (1) to (3) has reacted.

  The electrophotographic photoreceptor of the present invention may have two or more of the above electron transport materials. Moreover, you may mix the compound which has a functional group which can react with the said electron transport substance as needed. When the polymerizable functional group capable of undergoing the condensation reaction is one electron transport material, it is preferable to mix a compound having a polymerizable functional group capable of reacting with it.

  Examples of the compound having a polymerizable functional group capable of reacting include a polyfunctional isocyanate compound, a polyfunctional epoxy compound, a polyfunctional carbon-carbon double bond compound, and an alkoxysilane compound.

  For example, for an electron transport material having an alkoxysilyl group, an alkoxysilane compound is used for an electron transport material having a hydroxyl group, a carboxyl group or an aldehyde group, and a polyfunctional isocyanate, polyfunctional ketene, or polyfunctional carbodiamide is used. And the like, for an electron transport material having a carbon-carbon double bond, a polyfunctional carbon-carbon double bond compound and the like can be mentioned as a combination.

  An initiator may be used when polymerizing an electron transport material having a carbon-carbon double bond. Examples thereof include benzoyl peroxide, acetyl peroxide, lauroyl peroxide, dicumyl peroxide and azobisisobutyronitrile.

  Further, other known materials may be mixed and used. Examples thereof include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, copolymer nylon, polycarbonate, and polyvinyl acetal. Resin.

  When the electron transport material according to the present invention is reacted, the electron transport material is not necessarily a main chain, and can be reacted with a polymer having a reactive substituent such as a hydroxyl group (pendant type).

The content of the electron-transporting material having a structure represented by any one of the previous SL structure of the intermediate layer coating liquid (1) to (3), 30 mass relative to the total solid content of the intermediate layer coating solution % To 100% by mass, more preferably 50% to 100% by mass. When the content of the electron transport material is 30% by mass or more and 100% by mass or less, the mobility of carriers can be increased even under low temperature and low humidity, which is effective in suppressing potential fluctuation. The thickness of the intermediate layer is preferably in the range of 0.1 μm to 15 μm, more preferably 0.4 μm to 10 μm.

  The photosensitive layer of the electrophotographic photosensitive member of the present invention has a structure in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated, and the charge generation material and the charge transport material are the same layer. It is possible to take any configuration consisting of a single layer dispersed therein. Among these structures, a laminated photosensitive layer having a structure in which a charge generation layer and a charge transport layer are laminated in this order is preferable in terms of electrophotographic characteristics.

  In the present invention, the reason why the image under low temperature and low humidity is suppressed by using an intermediate layer containing a polymer of a specific electron transport material has not yet been elucidated. I am thinking. In general, an electron transport material has a lower solubility in a solvent or a binder resin and a lower mobility than a hole transport material. The electron transport material according to the present invention has relatively high solubility, can achieve a high electron transport material concentration, and has sufficient mobility at low temperature and low humidity even when the process speed is high. It is.

  Next, the electrophotographic photoreceptor of the present invention will be described in detail.

  As an electroconductive support body used for this invention, what consists of metals or alloys, such as aluminum, nickel, copper, gold | metal | money, and iron. In addition, a thin film of conductive material such as metal such as aluminum, silver and gold or indium oxide or tin oxide on an insulating support such as polyester, polycarbonate, polyimide and glass, carbon or conductive filler Examples thereof include those dispersed therein and imparted with conductivity. The surface of these supports is a support that has been subjected to electrochemical treatment such as anodization to improve electrical characteristics or adhesion, and the surface of the conductive support is alkali phosphate, phosphoric acid or tannic acid. It is also possible to use a solution obtained by chemical treatment with a solution obtained by dissolving a metal salt compound or a fluorine compound metal salt in an acidic aqueous solution containing as a main component.

  In addition, when the electrophotographic photosensitive member is used in a printer using a single wavelength laser beam or the like, the surface of the conductive support needs to be appropriately roughened in order to suppress interference fringes. is there. Specifically, a support having a surface treated with honing, blasting, cutting, electropolishing, or the like, or a support having a conductive film made of a conductive metal oxide and a binder resin on aluminum and an aluminum alloy. Must be used.

  As the honing treatment, there are dry and wet treatment methods, and any of them may be used. The wet honing process is a method in which a powdered abrasive is suspended in a liquid such as water and sprayed onto the surface of the support at a high speed to roughen the surface. The surface roughness is the spray pressure, speed, and amount of abrasive. It can be controlled by the type, shape, size, hardness, specific gravity, suspension temperature and the like. Similarly, the dry honing process is a method in which an abrasive is sprayed onto the surface of the conductive support with air at a high speed to roughen the surface, and the surface roughness can be controlled in the same manner as the wet honing process. Examples of the abrasive used for the wet or dry honing treatment include particles such as silicon carbide, alumina, iron, and glass beads.

  A conductive layer may be provided between the support and the photosensitive layer or intermediate layer for the purpose of preventing interference fringes due to scattering of laser light or the like, and covering the scratches on the support. The conductive layer can be formed by dispersing conductive particles such as carbon black, metal particles, and metal oxide particles in a binder resin. Suitable metal oxide particles include zinc oxide and titanium oxide particles. Also, barium sulfate particles can be used as the conductive particles. A conductive layer may be provided on the conductive particles.

  Examples of the binder resin used for the conductive layer include a phenol resin, a polyurethane resin, and a polyamide resin. These have good adhesion to the support, improve the dispersibility of the conductive particles, and have good solvent resistance after film formation. Among these, a phenol resin, a polyurethane resin, and a polyamide resin are preferable.

  In addition, the conductive layer may contain fluorine or antimony as necessary, and a leveling agent may be added to improve the surface properties of the conductive layer.

As the charge generation material used in the present invention,
(1) Azo pigments such as monoazo, disazo and trisazo (2) Phthalocyanine pigments such as metal phthalocyanine and non-metal phthalocyanine (3) Indigo pigments such as indigo and thioindigo (4) Perylene acid anhydride and perylene imide Perylene pigments (5) polycyclic quinone pigments such as anthraquinone and pyrenequinone (6) squarylium dyes (7) pyrylium salts, thiapyrylium salts (8) triphenylmethane dyes (9) selenium, selenium-tellurium and amorphous silicon Inorganic substances such as (10) quinacridone pigment (11) azurenium salt pigment (12) cyanine dye (13) xanthene dye (14) quinoneimine dye (15) styryl dye (16) cadmium sulfide (17) zinc oxide and the like.

  In particular, metal phthalocyanine pigments are preferable, and among them, oxytitanium phthalocyanine crystal, chlorogallium phthalocyanine crystal, dichlorotin phthalocyanine crystal and hydroxygallium phthalocyanine pigment are preferable. In particular, a hydroxygallium phthalocyanine pigment is more preferable.

  The oxytitanium phthalocyanine crystal has a Bragg angle (2θ ± 0.2 °) of 9.0 °, 14.2 °, 23.9 ° and 27.1 ° in the characteristic X-ray diffraction using CuKα as a radiation source. Oxytitanium phthalocyanine crystals with strong peaks, Bragg angles (2θ ± 0.2 °) of 9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° and Oxytitanium phthalocyanine crystals having a strong peak at 27.3 ° are preferred.

  As a chlorogallium phthalocyanine crystal, in characteristic X-ray diffraction using CuKα as a radiation source, it is strong at 7.4 °, 16.6 °, 25.5, and 28.2 ° of the Bragg angle (2θ ± 0.2 °). Chlorogallium phthalocyanine crystals having peaks, chlorogallium phthalocyanine crystals having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 6.8 °, 17.3 °, 23.6 ° and 26.9 °, and Chlorogallium phthalocyanine crystals having strong peaks at Bragg angles (2θ ± 0.2 °) of 8.7 ° to 9.2 °, 17.6 °, 24.0 °, 27.4 ° and 28.8 ° preferable.

  As a dichlorotin phthalocyanine crystal, in characteristic X-ray diffraction using CuKα as a radiation source, Bragg angles (2θ ± 0.2 °) of 8.3 °, 12.2 °, 13.7 °, 15.9 °, Dichlorotin phthalocyanine crystals with strong peaks at 18.9 ° and 28.2 °, Bragg angles (2θ ± 0.2 °) of 8.5 °, 11.2 °, 14.5 ° and 27.2 ° A dichlorotin phthalocyanine crystal having a strong peak, Bragg angle (2θ ± 0.2 °) of 8.7 °, 9.9 °, 10.9 °, 13.1 °, 15.2 °, 16.3 °, Dichlorotin phthalocyanine crystals with strong diffraction peaks at 17.4 °, 21.9 ° and 25.5 °, and 9.2 °, 12.2 °, 13.4 with Bragg angles (2θ ± 0.2 °) Dicks with strong diffraction peaks at °, 14.6 °, 17.0 ° and 25.3 ° Loroszphthalocyanine crystals are preferred.

  As the hydroxygallium phthalocyanine crystal, in characteristic X-ray diffraction using CuKα as a radiation source, hydroxy having strong peaks at Bragg angles (2θ ± 0.2 °) of 7.3 °, 24.9 °, and 28.1 °. Gallium phthalocyanine crystals, Bragg angles (2θ ± 0.2 °) of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° A hydroxygallium phthalocyanine crystal having a strong peak is preferred.

  As binder resins, butyral resin, polyester resin, polycarbonate resin, polyarylate resin, polystyrene resin, polyvinyl methacrylate resin, polyvinyl acrylate resin, polyvinyl acetate resin, polyvinyl chloride resin, polyamide resin, polyurethane resin, silicone resin, alkyd Resins, epoxy resins, cellulose resins, melamine resins and the like can be mentioned, but are not limited thereto. In particular, a butyral resin is preferred.

  The dispersed particle diameter of the charge generation material in the charge generation layer is preferably 0.5 μm or less, more preferably 0.3 μm or less, and more preferably 0.01 μm or more and 0.2 μm or less. The film thickness of the charge generation layer is preferably from 0.01 μm to 2 μm, more preferably from 0.05 μm to 0.3 μm.

  The charge transport layer is formed of a suitable charge transport material, for example, a heterocyclic ring such as poly-N-vinylcarbazole and polystyrylanthracene, a polymer compound having a condensed polycyclic aromatic ring, a heterocyclic ring such as pyrazoline, imidazole, oxazole, triazole and carbazole. Compounds, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, low molecular weight compounds such as phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, hydrazone derivatives, etc. A solution dispersed / dissolved in a solvent together with the resin for charge generation layer) can be applied by the above-mentioned known method and dried. In this case, the ratio of the charge transporting material to the binder resin is preferably 20 or more and 100 or less, more preferably 30 or more and 100 or less, when the total mass of both is 100. If the amount of the charge transport material is smaller than that, the charge transport ability is lowered, and problems such as a decrease in sensitivity and an increase in residual potential are likely to occur. In this case, the thickness of the charge transport layer is preferably adjusted in the range of 1 μm to 50 μm, more preferably 3 μm to 30 μm.

  Furthermore, a surface protective layer may be formed on the charge transport layer. The surface protective layer may be a resin alone, or may be added with a charge transport material as described above or a conductive material such as conductive powder for the purpose of reducing the residual potential. Conductive powders include metal powders such as aluminum, copper, nickel and silver, flaky metal powders, short metal fibers, conductive metal oxides such as antimony oxide, indium oxide and tin oxide, polypyrrole, and polyaniline. And a polymer conductive agent such as a polymer electrolyte, carbon black, carbon fiber, graphite powder, an organic or inorganic electrolyte, and a conductive powder whose surface is coated with these conductive substances.

  FIG. 1 shows a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

  In FIG. 1, a drum-shaped electrophotographic photosensitive member 1 of the present invention is rotationally driven with a predetermined peripheral speed (process speed) in the direction of an arrow about a shaft 2. In the rotation process, the electrophotographic photosensitive member 1 is subjected to uniform charging at a predetermined positive or negative potential on its peripheral surface by the primary charging unit 3, and then, for example, slit exposure or laser beam scanning exposure that is reflected light from the original. The exposure light 4 intensity-modulated in response to the time-series electric digital image signal of the target image information output from the exposure means (not shown) is received. In this way, electrostatic latent images corresponding to the target image information are sequentially formed on the peripheral surface of the electrophotographic photoreceptor 1.

  The formed electrostatic latent image is visualized as a transferable particle image (toner image) by regular development or reversal development with charged particles (toner) in the developing means 5 and is electrophotographic from a paper supply unit (not shown). A toner image formed and carried on the surface of the electrophotographic photosensitive member 1 is transferred to the transfer material 7 which is taken out and fed between the photosensitive member 1 and the transfer unit 6 in synchronization with the rotation of the electrophotographic photosensitive member 1. The images are sequentially transferred 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 means from a bias power source (not shown).

  The transfer material 7 (in the case of a final transfer material (such as paper or film)) that has received the transfer of the toner image is separated from the electrophotographic photosensitive member surface, conveyed to the image fixing means 8, and subjected to a toner image fixing process. Printed out of the apparatus as an image formed product (print, copy). When the transfer material 7 is a primary transfer material (intermediate transfer material or the like), it is printed out after a fixing process after a plurality of transfer processes.

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

  In the present invention, a plurality of components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9 described above are housed in a container and integrally combined as a process cartridge. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary 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, and is attached to and detached from the apparatus main body using the guide unit 12 such as a rail of the apparatus main body. A flexible process cartridge 11 can be obtained.

  Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected or transmitted light from the original, or the original is read by a sensor and converted into a signal, and a laser beam scanning performed according to this signal is performed. The light emitted by driving the LED array or the liquid crystal shutter array.

  The electrophotographic photosensitive member of the present invention can be applied not only to electrophotographic copying machines but also to general electrophotographic apparatuses such as laser beam printers, LED printers, FAX, liquid crystal shutter printers, etc. It can be widely applied to apparatuses such as applied displays, recording, light printing, plate making and facsimile.

<Synthesis example>
Examples of the electron transport material having the structure represented by any one of the structural formulas (1) to (3) of the present invention include boronic acid derivatives and halides having a polymerizable functional group such as a hydroxyl group, an aldehyde group, and a carboxyl group. And a general functional group conversion reaction.

  A typical synthesis example of an electron transport material having the structure represented by any one of the structural formulas (1) to (3) of the present invention is shown below.

(Exemplary Compound No. 1-7)
In 500 parts by weight of tetrahydrofuran (THF), 3.63 parts by mass of B- (6-hydroxyhexyl) -9-borabicyclo [3,3,1] nonane, B- (2- (4-hydroxyphenyl) methyl) -9 -To 3.33 parts by mass of borabicyclo [3,3,1] nonane, 3.40 parts by mass of 4,7-dibromo-acenaphthylene-1,2-dione was added in a nitrogen atmosphere, and 300% by mass of 20% aqueous sodium carbonate solution A portion was dropped. Thereafter, tetrakis (triphenylphosphine) palladium (0) (Pd _{(PPh 3) 4)} a was added 5.00 parts by weight, the mixture was refluxed for 2 hours. After the reaction, the organic phase was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, 9.02 parts by mass of a brown viscous body was obtained.

  After this viscous body and 5.00 parts by mass of acrylic acid and 0.04 part of 2-methoxyphenol were dissolved in 26 parts by mass of toluene, 0.10 parts by mass of p-toluenesulfonic acid monohydrate was added and heated to 110 ° C. The dehydration reaction was performed for 6 hours. After cooling, it was poured into a 10% aqueous sodium hydroxide solution and extracted with ethyl acetate. The organic layer was further washed with water and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel chromatography. As a result, 1.05 parts by mass of 1-7 was obtained.

When the molecular weight was measured (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C ₆₀ ), peak top As a result, 456 was obtained. It was confirmed that it was the same as 1-7.

(Exemplary Compound No. 2-2)
To 100 parts by mass of toluene and 50 parts by mass of ethanol, 1.17 parts by mass of 3,6-dibromo-9,10-phenanthrene rangeone was added to 0.97 parts by mass of 3- (hydroxymethyl) phenylboronic acid under a nitrogen atmosphere. 100 parts by mass of 20% aqueous sodium carbonate solution was added dropwise. Thereafter, tetrakis (triphenylphosphine) palladium (0) (Pd _{(PPh 3) 4)} was added 0.55 parts by weight, and the mixture was refluxed for 2 hours. After the reaction, the organic phase was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel chromatography. 1.33 mass parts of 2-2 were obtained.

When the molecular weight was measured (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C ₆₀ ), peak top As a result, 421 was obtained. It was confirmed that it was the same as 2-2.

(Exemplary Compound No. 2-7)
To 100 parts by mass of toluene and 50 parts by mass of ethanol, 0.55 parts by mass of 2-bromo-9,10-phenanthrene dione was added to 0.91 part by mass of 4-hydroxyphenylboronic acid under a nitrogen atmosphere, and 20% sodium carbonate. 100 parts by mass of an aqueous solution was added dropwise. Thereafter, 0.28 parts by mass of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) was added, followed by refluxing for 2 hours. After the reaction, the organic phase was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel chromatography to obtain 0.45 parts by mass of pale yellow crystals.

  In 50 parts by mass of methanol and 50 parts by mass of THF, 3 drops (10 μl) of this crystal, 0.2 parts by mass of malononitrile and piperidine were added and refluxed for 12 hours.

  After the reaction, the solvent was removed, washed with water, extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel chromatography to obtain 0.20 parts by mass of Exemplary Compound 2-7.

When the molecular weight was measured (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C ₆₀ ), peak top As a result, 348 was obtained, which was confirmed to be the same as that of Exemplified Compound 2-7.

(Exemplary Compound No. 2-16)
To 100 parts by mass of toluene and 50 parts by mass of ethanol, 1.16 parts by mass of 3,6-dibromo-9,10-phenanthrene dione was added to 2.12 parts by mass of 4-carboxyphenylboronic acid under a nitrogen atmosphere, and 20% 100 mass parts of sodium carbonate aqueous solution was dripped. Thereafter, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) was added in an amount of 0.55 parts by mass, and the mixture was refluxed for 2 hours. After the reaction, the organic phase was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel chromatography. As a result, 0.57 parts by mass of 2-16 was obtained.

When the molecular weight was measured (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C ₆₀ ), peak top 448 was obtained as the value, and Exemplified Compound No. It was confirmed that it was the same as 2-16.

(Exemplary Compound No. 3-10)
To 100 parts by mass of toluene and 50 parts by mass of ethanol, to 1.64 parts by mass of 3-formylphenylboronic acid, 1.16 parts by mass of 3,6-dibromo-9,10-phenanthrene rangeone was added in a nitrogen atmosphere, and 20% 100 mass parts of sodium carbonate aqueous solution was dripped. Thereafter, tetrakis (triphenylphosphine) palladium (0) (Pd _{(PPh 3) 4)} was added 0.55 parts by weight, and the mixture was refluxed for 2 hours. After the reaction, the organic phase was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel chromatography. 0.48 mass parts of 3-10 was obtained.

When the molecular weight was measured (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C ₆₀ ), peak top As a result, 418 was obtained. It was confirmed that it was the same as 3-10.

(Exemplary Compound No. 3-13)
In 100 parts by mass of toluene and 50 parts by mass of ethanol, 1.17 parts by mass of 3,6-dibromo-9,10-phenanthrene dione is added to 0.88 parts by mass of 4-hydroxyphenylboronic acid under a nitrogen atmosphere, and 20% 100 mass parts of sodium carbonate aqueous solution was dripped. Thereafter, tetrakis (triphenylphosphine) palladium (0) (Pd _{(PPh 3) 4)} was added 0.55 parts by weight, and the mixture was refluxed for 2 hours. After the reaction, the organic phase was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel chromatography. As a result, 1.04 parts by mass of 3-13 was obtained.

When the molecular weight was measured (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C ₆₀ ), peak top As a result, 394 was obtained. It was confirmed to be the same as 3-13.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, embodiments of the present invention are not limited to these. In the examples, “part” means “part by mass”.

Example 1
An aluminum cylinder having a diameter of 30 mm was subjected to a honing treatment and subjected to ultrasonic water cleaning to obtain a conductive support.

  Next, Exemplified Compound Nos. 6 parts of 1-7, 4 parts of a compound represented by the following structural formula (4), 0.1 part of 2,2-azobisisobutyronitrile (AIBN) are dissolved in 190 parts of tetrahydrofuran (THF), A layer coating solution was prepared. This coating solution was applied onto the conductive support by a dip coating method, heated and dried at 160 ° C. for 30 minutes, and reacted to form an intermediate layer having a thickness of 0.8 μm.

  Next, as the coating solution for the charge generation layer, the Bragg angle (2θ ± 0.2 °) of CuKα characteristic X-ray diffraction is 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25. 10 parts of crystalline hydroxygallium phthalocyanine having strong peaks at 1 ° and 28.3 °, and 5 parts of polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) are added to 250 parts of cyclohexanone. The mixture was dispersed in a sand mill using glass beads having a diameter of 1 mm for 4 hours, and 250 parts of ethyl acetate was added thereto for dilution. This was coated on the intermediate layer and then dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.18 μm.

  Next, 10 parts of a styryl compound represented by the following structural formula (5)

And 10 parts of a polyarylate resin having a repeating unit represented by the following structural formula (6)

Was dissolved in a mixed solvent of 50 parts of monochlorobenzene and 30 parts of dichloromethane to prepare a charge transport layer coating solution. This coating solution was applied onto the charge generation layer by a dip coating method and dried at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 17 μm.

  The electrophotographic photoreceptor thus prepared was subjected to potential evaluation under a low temperature and low humidity (15 ° C./10% RH) environment, and subjected to potential fluctuation and image evaluation under a high temperature and high humidity (30 ° C./80% RH) environment. went.

  For potential evaluation and image evaluation, LBP “Color Laser Jet 4600” (process speed 94.2 mm / sec, DC contact charging) manufactured by Hewlett-Packard was installed in a device modified to process speed 190.0 mm / sec and variable exposure light quantity. I went.

  The potential fluctuation is performed in a state where the apparatus and the drum cartridge are left for 48 hours in an environment of 15 ° C./10% RH. The surface potential of the electrophotographic photosensitive member was measured by removing the developing cartridge from the evaluator and inserting a potential measuring device there. The potential measuring apparatus is configured by arranging a potential measuring probe at the developing position of the developing cartridge, and the position of the potential measuring probe with respect to the electrophotographic photosensitive member is set at the center in the drum axis direction.

  The amount of light was set so that the dark portion potential (Vd) was −700V and the light portion potential (Vl) was −150V. A continuous 1000-sheet durability test was performed at the exposure amount set in that state (state where the potential probe is in the developing unit). Table 4 shows Vd and Vl after endurance.

  Evaluation under high temperature and high humidity is performed in a state where the apparatus and the drum cartridge are left for 48 hours in an environment of 30 ° C./80% RH.

The image evaluation under high temperature and high humidity was performed by charging the dark part potential (Vd) to −700 V and evaluating a solid white image. The solid white image was evaluated using a REFECTMETER MODELTC-6DS manufactured by Tokyo Denshoku. The fog evaluation was calculated from the following formula with an average of 10 solid white images;
Fog (reflectance) (%) = reflectance on non-image area (%) − reflectance of solid white image area (%)
If the fog on paper is 1.0% or less, a good image is obtained.

  The potential evaluation under high temperature and high humidity was evaluated in the same manner as the potential evaluation under low temperature and low humidity. The results are shown in Table 4.

(Examples 2 to 7)
In Example 1, Exemplified Compound No. No. 1-7 1-10, No. 1 2-4, No. 2 2-8, no. 2-9, no. 3-6, no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that 3-12 was used. The results are shown in Table 4.

(Examples 8 to 10)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the intermediate layer of Example 1 was produced as follows. The results are shown in Table 4.

"Production of intermediate layer"
In each Example, Exemplified Compound No. 1-9, No. 1 2-16, no. The coating solution for intermediate layer which consists of 5 parts in order of 3-10, 5 parts of melamine resin (trade name: Yuban 20HS, manufactured by Mitsui Chemicals) and 190 parts of THF was prepared. This coating solution was applied on a conductive support by a dip coating method so that the film thickness after drying was 0.8 μm, and was heated and dried at 150 ° C. for 60 minutes to form an intermediate layer.

(Examples 11 and 12)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the intermediate layer of Example 1 was produced as follows. The results are shown in Table 4.

"Production of intermediate layer"
In each Example, Exemplified Compound No. 1-8, No. 1 The coating solution for intermediate layer was prepared by adding 6 parts of phenol resin (trade name: Plyofen J325, manufactured by Dainippon Ink & Chemicals) and 190 parts of THF in order of 3 parts in the order of 3-13. This coating solution was applied on a conductive support by a dip coating method so that the film thickness after drying was 1.2 μm, and was heated and dried at 150 ° C. for 60 minutes to form an intermediate layer.

(Examples 13 to 16)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the intermediate layer of Example 1 was produced as follows. The results are shown in Table 4.

"Production of intermediate layer"
In each Example, Exemplified Compound No. 1-15, No. 1 2-2, No. 3-1. The coating solution for intermediate layer was prepared in the order of 2-13, 6 parts each, and 4 parts of hexamethylene diisocyanate and 190 parts of THF. This coating solution was applied on the conductive support by a dip coating method so that the film thickness after drying was 1.0 μm, and was heated and dried at 160 ° C. for 30 minutes to form an intermediate layer.

(Example 17)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the intermediate layer of Example 1 was produced as follows. The results are shown in Table 4.

"Production of intermediate layer"
Exemplified compound No. 1 in Table 1 1-14 10 parts was melt | dissolved in THF 190 parts, and the coating liquid for intermediate | middle layers was prepared. This coating solution was applied on a conductive support by a dip coating method, and reacted by irradiating with an electron beam under the conditions of an acceleration voltage of 150 kV and an irradiation dose of 20 Mrad to form an intermediate layer having a thickness of 1.0 μm.

(Examples 18 to 20)
In Example 17, Exemplified Compound No. 1-14 to No.1. 2-14, no. 3-2, no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 17 except that it was replaced with 1-4. The results are shown in Table 4.

(Examples 21 to 25)
In the intermediate layer of Example 2, the electron transport material No. The addition amount of 1-10 is 10 parts, 8 parts, 5 parts, 3 parts, 2.5 parts, and the addition amount of structural formula (4) is 0 parts, 2 parts, 5 parts, 7 parts, 7.5 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2 except that the parts were changed. The results are shown in Table 4.

(Examples 26 to 29)
In the intermediate layer of Example 9, the electron transport material No. The addition amount of 2-16 is 8 parts, 6 parts, 3 parts, 2.5 parts, and the addition amount of melamine resin (trade name: Uban 20HS, manufactured by Mitsui Chemicals) is 2, 4 parts, 7 parts, 7. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 9 except that the amount was changed to 5 parts. The results are shown in Table 4.

(Example 30)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the intermediate layer of Example 1 was produced as follows. The results are shown in Table 4.

"Production of intermediate layer"
4 parts of polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) was added to 250 parts of cyclohexanone, and the exemplified compound No. An intermediate layer coating solution comprising 4 parts of 2-7, 3 parts of hexamethylene diisocyanate and 190 parts of THF was prepared. This coating solution was applied on the conductive support by a dip coating method so that the film thickness after drying was 1.0 μm, and was heated and dried at 160 ° C. for 30 minutes to form an intermediate layer.

(Examples 31 and 32)
In Example 30, Exemplified Compound No. 2-7. 1-16, No. 1 An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 30 except that 3-9 was used. The results are shown in Table 4.

(Example 33)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the intermediate layer of Example 1 was produced as follows. The results are shown in Table 4.

"Production of intermediate layer"
Exemplified Compound No. 4-8, No. 3-8. 4 parts of 3-12, 2 parts of the above structural formula (4) and 0.1 part of AIBN were dissolved in 190 parts of THF to prepare a coating solution for an intermediate layer. This coating solution was applied onto a conductive support by a dip coating method, heated and dried at 160 ° C. for 30 minutes, and reacted to form an intermediate layer having a thickness of 0.9 μm.

(Example 34)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the intermediate layer of Example 1 was produced as follows. The results are shown in Table 4.

"Production of intermediate layer"
Exemplified Compound No. 4-15, No. 2-15. 3 parts of 2-16 and 3 parts of hexamethylene diisocyanate were dissolved in 190 parts of THF to prepare a coating solution for an intermediate layer. This coating solution was applied onto a conductive support by a dip coating method, heated and dried at 160 ° C. for 30 minutes, and reacted to form an intermediate layer having a thickness of 0.9 μm.

(Example 35)
In Example 6, the charge generating substance hydroxygallium phthalocyanine crystal was subjected to Bragg angles (2θ ± 0.2 °) of 9.0 °, 14.2 °, 23.9 °, and 27.1 in the characteristic X-ray diffraction of CuKα. An electrophotographic photosensitive member was prepared in the same manner as in Example 6 except that the crystalline oxytitanium phthalocyanine having a strong peak at 0 ° was used, and the same evaluation was performed. The results are shown in Table 4.

(Example 36)
In Example 6, an electrophotographic photosensitive member was prepared in the same manner as in Example 6 except that the charge generating substance hydroxygallium phthalocyanine crystal was replaced with an azo pigment represented by the following structural formula (7). went. The results are shown in Table 4.

(Example 37)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 14 except that the charge generation layer of Example 14 was prepared as follows. The results are shown in Table 4.

"Production of charge generation layer"
Strong peaks at 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction 10 parts of crystalline hydroxygallium phthalocyanine and 5 parts of polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) are added to 250 parts of cyclohexanone, and 4 by a sand mill using glass beads having a diameter of 1 mm. This was dispersed over time, and this was followed by the exemplified compound No. 0.5 parts of 2-2, 0.5 parts of hexamethylene diisocyanate and 250 parts of ethyl acetate were added to prepare a coating solution for a charge generation layer. After coating this on the intermediate layer, it was reacted by heating and drying at 140 ° C. for 30 minutes to form a charge generation layer having a thickness of 0.18 μm.

(Examples 38 to 42)
50 parts of titanium oxide powder coated with tin oxide containing 10% by mass of antimony oxide, 25 parts of resol type phenol resin, 30 parts of methoxypropanol, 30 parts of methanol and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, weight) 0.002 part of average molecular weight 3000) was dispersed in a sand mill device for 2 hours using 1 mmφ glass beads to prepare a coating solution for a conductive layer. This coating solution was applied onto an aluminum cylinder having a diameter of 30 mm by a dip coating method and heated at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

  An electrophotographic photosensitive member was prepared and evaluated in the same manner except that the intermediate layer, charge generation layer, and charge transport layer of Examples 3, 6, 8, 11, and 14 were formed on this conductive layer. The results are shown in Table 4.

(Comparative Example 1)
An aluminum cylinder having a diameter of 30 mm was subjected to a honing treatment and subjected to ultrasonic water cleaning to obtain a conductive support.

  Next, 5 parts of N-methoxymethylated 6 nylon was dissolved in 95 parts of methanol to prepare an intermediate layer coating solution. This coating solution was applied onto the conductive support by a dip coating method and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.6 μm.

  An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the charge generation layer and charge transport layer of Example 1 were formed thereon. The results are shown in Table 5.

(Comparative Example 2)
In Example 1, an electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the intermediate layer was not provided. The results are shown in Table 5.

(Comparative Example 3)
In the intermediate layer of Example 1, the electron transport material No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that 1-7 was not added and the addition amount of the structural formula (4) was changed to 10 parts. The results are shown in Table 5.

(Comparative Example 4)
In the intermediate layer of Example 8, the electron transport material No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 8 except that the addition amount of melamine resin (trade name: Yuban 20HS, manufactured by Mitsui Chemicals) was changed to 10 parts without adding 1-9. did. The results are shown in Table 5.

(Comparative Example 5)
In the intermediate layer of Example 11, the electron transport material No. An electrophotographic photosensitive member was prepared in the same manner as in Example 11 except that 1-8 was not added and the addition amount of the phenol resin (trade name: Plyofen J325, manufactured by Dainippon Ink & Chemicals) was changed to 10 parts. Prepared and evaluated. The results are shown in Table 5.

(Comparative Example 6)
An aluminum cylinder having a diameter of 30 mm was subjected to a honing treatment and subjected to ultrasonic water cleaning to obtain a conductive support.

  Next, 5 parts of an alcohol-soluble polyamide resin (trade name: Amilan CM8000: manufactured by Toray Industries, Inc.) and 2 parts of a compound represented by the following structural formula (8) are dissolved in 50 parts of methanol and 50 parts of benzyl alcohol. A coating solution was prepared. This coating solution was applied onto the conductive support by a dip coating method and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.6 μm.

  An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the charge generation layer and charge transport layer of Example 1 were formed thereon. The results are shown in Table 5.

(Comparative Example 7)
In Comparative Example 6, an electrophotographic photosensitive member was produced in the same manner as in Comparative Example 6, except that the compound represented by Structural Formula (8) in the intermediate layer was replaced with the compound represented by Structural Formula (9) below. Evaluation was performed. The results are shown in Table 5.

(Comparative Example 8)
In Example 13, Exemplified Compound No. 2 in the intermediate layer was used. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 13 except that 1-8 was replaced with the compound represented by the following structural formula (10). The results are shown in Table 5.

  As shown in Table 5, since Comparative Example 2 had no intermediate layer, the potential fluctuation under low temperature and low humidity was small, but the potential fluctuation under high temperature and high humidity was large, and a fogged image was generated in the solid white image. In Comparative Examples 1, 3, 4, 5, 6, 7, and 8, since the electron transport material of the present invention is not contained in the intermediate layer, the potential fluctuation under low temperature and low humidity is large. Produced a solid white image even under high temperature and high humidity, and further suppressed potential fluctuation under low temperature and low humidity.

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.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photosensitive member 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means

Claims (9)

In an electrophotographic photosensitive member having a conductive support, an intermediate layer formed on the conductive support, and a photosensitive layer formed on the intermediate layer, the intermediate layer has the following structural formula (1) to An electrophotographic photoreceptor comprising a polymer of an electron transport material having a structure represented by any one of (3).
(In the structural formulas (1) to (3), Z ₁₁ , Z ₁₂ , Z ₂₁ , Z ₂₂ , Z ₃₁ , and Z ₃₂ are each independently an oxygen atom, C (CN) ₂ , N—R, C (CN) COR, C (CN) COOR, C (CN) R, or C (COOR) ₂ (R represents an aryl group or an alkyl group which may have a substituent.) X ₁₁ or at least one of _{X 16,} at least one of _{X 21} to _{X 28,} and at _least one of _{X 31} to _{X 36} each represent a polymerizable functional group, other than the polymerizable functional group are each independently, A hydrogen atom, a halogen atom, a nitro group, a trifluoroalkyl group, an alkoxy group that may have a substituent, or an alkyl group that may have a substituent.   The electrophotographic photosensitive member according to claim 1, wherein the polymerizable functional group is a group having a carbon-carbon double bond.   The electrophotographic photosensitive member according to claim 2, wherein the group having a carbon-carbon double bond is a group selected from the group consisting of an acryloyl group, a methacryloyl group, and a styryl group.   The electrophotographic photoreceptor according to claim 1, wherein the polymerizable functional group is a group selected from the group consisting of a hydroxyl group, a carboxyl group, and an aldehyde group. A method for producing the electrophotographic photosensitive member according to claim 1 ,
After coating the intermediate layer coating solution containing the electron transport material on the conductive support, the polymerizable functional group of the electron transport material in the coated intermediate layer coating solution is applied by heat or radiation. A method for producing an electrophotographic photosensitive member comprising a step of reacting and polymerizing the electron transport material to form the intermediate layer. The electrophotographic photosensitive member according to claim 5 , wherein the content of the electron transport material in the intermediate layer coating solution is 30% by mass or more and 100% by mass or less based on the total solid content in the intermediate layer coating solution. Body manufacturing method. 6. The electrophotographic photosensitive member according to claim 5 , wherein the content of the electron transport material in the intermediate layer coating solution is 50% by mass or more and 100% by mass or less based on the total solid content in the intermediate layer coating solution. Body manufacturing method. In the electrophotographic photosensitive member according to any one of claims 1 to 4, charging means for charging the surface of the electrophotographic photosensitive member, an electrostatic latent image formed on the surface of the electrophotographic photoconductor toner It integrally supports at least one means selected from the group consisting of developing means for developing and cleaning means for removing the transfer residual toner on the surface of the electrophotographic photosensitive member, and is detachably attached to the main body of the electrophotographic apparatus. A process cartridge characterized by being. The electrophotographic photosensitive member according to any one of claims 1 to 4 , a charging means for charging the surface of the electrophotographic photosensitive member, and exposing the charged surface of the electrophotographic photosensitive member. Exposure means for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member, developing means for developing the electrostatic latent image formed on the surface of the electrophotographic photosensitive member with toner, and the electrophotographic photosensitive member An electrophotographic apparatus comprising transfer means for transferring a toner image formed on the surface of the toner image onto a transfer material.