JP4411231B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

The present invention relates to an electrophotographic photoreceptor, relates to a process cartridge and an electrophotographic apparatus, particularly, an intermediate layer between the electrophotographic photosensitive member or the conductive support and the photosensitive layer containing a compound photosensitive layer having a specific structure The present invention relates to an electrophotographic photosensitive member containing a compound having a specific structure, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

  Conventionally, as electrophotographic photoreceptors, inorganic electrophotographic photoreceptors mainly composed of inorganic photoconductive compounds such as selenium, zinc oxide and cadmium sulfide have been widely used. In recent years, various proposals have been made regarding a laminated organic electrophotographic photoreceptor having two functionally separated layers, a charge transport layer in which an organic photoconductive material is bound with a resin or the like, and a charge generation layer. (For example, Patent Documents 1 to 5).

  In particular, an electrophotographic photosensitive member having a layer structure in which a charge transport layer is provided on a charge generation layer is excellent in durability and is currently mainstream. For example, an electrophotographic photoreceptor having a charge transfer layer containing triallyl pyrazoline (for example, Patent Document 6), a charge generation layer made of a derivative of perylene pigment, and a charge transfer layer made of a condensate of 3-propylene and formaldehyde. An electrophotographic photosensitive member (for example, Patent Document 7) is disclosed. Further, there are electrophotographic photoreceptors (for example, Patent Documents 8 and 9) using a disazo pigment or a trisazo pigment as a charge generation material. Further, the organic photoconductive compound can freely select the photosensitive wavelength region of the electrophotographic photosensitive member depending on the compound. For example, azo-based organic pigments that exhibit high sensitivity in the visible region (for example, Patent Documents 10 and 11) are disclosed, and those that have sensitivity in the infrared region (for example, Patent Document 12). 13).

  Of these materials, materials having sensitivity in the red or infrared region are used in laser beam printers, LED printers, and the like that have made remarkable progress in recent years, and the frequency of demand thereof is increasing. Conventionally, copper phthalocyanine (for example, Patent Document 14), metal-free phthalocyanine, and the like are listed as materials having sensitivity in the infrared region. However, these materials are insufficient for high sensitivity today. Furthermore, in a multilayer organic electrophotographic photoreceptor, it has been proposed to increase the sensitivity by adding an organic acceptor to the charge generation layer (for example, Patent Document 15), but this is not sufficient. Oxytitanium phthalocyanine pigments (for example, Patent Documents 16 and 17), gallium phthalocyanine pigments (for example, Patent Documents 18 and 19), chlorogallium phthalocyanine pigments (for example, Patent Documents 20 and 21), etc. The electrophotographic photosensitive member using them realizes high quantum efficiency.

  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, the process speed is 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 avoided as represented by colorization, and black-and-white images that have been character-centered have become more and more halftone images and solid images represented by photographs. Their image quality is increasing year by year. In particular, a phenomenon in which the light-irradiated portion of one image is darkened only in the light-irradiated portion in the halftone image at the next rotation, a so-called positive ghost image, on the contrary, the density of the portion is lightened. The permissible range for so-called negative ghosts and the like has become much stricter than the permissible range for black and white printers and black and white copiers. These ghost images use a highly sensitive charge generation material, because the number of carriers is large, and electrons after holes are injected into the charge transport layer are likely to remain in the charge generation layer, resulting in a memory. This phenomenon is considered to be a particularly remarkable phenomenon in recent high-sensitivity charge generation materials.

  For example, it has been disclosed that a charge generation layer using oxytitanium phthalocyanine contains an acceptor compound to reduce residual potential and ghost (Patent Document 22), but the electrophotographic photosensitive member is charged to + 500V. After standing for 5 hours in a state and making the phenomenon noticeable, a ghost evaluation is performed, which shows a ghost effect by a positively charged memory, which is different from a normal ghost. In addition, the addition of an electron transporting material, an electron acceptor or an electron withdrawing substance to the charge generation layer (for example, Patent Documents 23 to 30) is disclosed, but is effective for the severe ghost level as described above. It wasn't. Further, although a method for producing a phthalocyanine pigment produced by adding an electron transporting material during the phthalocyanine pigmentation step is disclosed (for example, Patent Document 31), the electron transporting material is located near the charge generation material. Although it is disclosed that achieving high sensitivity is important, this is also not effective for the severe ghost level as described above.

In addition, since the electrophotographic apparatus has entered the market that has conventionally been a printing area such as offset printing and screen printing, an increase in printing speed is required. Along with this, the process speed is increasing year by year, and the potential stability is more demanded.
JP-A-57-54942 JP 60-59355 A JP-A-61-203461 JP-A 62-47054 JP-A 62-67094 U.S. Pat. No. 3,378,851 U.S. Pat. No. 3,871,882 JP 60-29108 A JP 56-46237 A JP 60-272754 A JP 56-167759 A JP-A-57-195767 Japanese Patent Laid-Open No. 61-228453 Japanese Patent Laid-Open No. 50-38543 JP-A-61-2157 JP-A-63-366 JP-A-1-319934 JP-A-5-249716 Japanese Patent Laid-Open No. 5-263007 JP-A-5-188615 JP-A-5-194523 JP 7-104495 A Japanese Patent Laid-Open No. 2-136860 JP-A-2-136661 Japanese Patent Laid-Open No. 2-146048 Japanese Patent Laid-Open No. 2-146049 JP-A-2-146050 JP-A-5-150498 JP-A-6-313974 JP 2000-39730 A JP 2001-40237 A

  An object of the present invention is to provide an electrophotographic photosensitive member having good potential characteristics and capable of outputting a good image, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by including a compound having a specific structure in the electrophotographic photosensitive member.

According to the invention, it has a conductive support and the conductive support a photosensitive layer formed on the support, and meet electrophotographic photoreceptor containing a compound represented by formula (2), under following formula ( electrophotographic photoreceptor compounds represented by 2), characterized that you have been contained in the photosensitive layer.

Further, according to the present invention has a conductive support and a photosensitive layer formed on the conductive support member, and meet electrophotographic photosensitive member having containing a compound represented by the following formula (2), the electronic further comprising photoreceptor an intermediate layer between the conductive support and the photosensitive layer, the electrophotographic photosensitive characterized by Rukoto compound represented by the following formula (2) is not contained in the layer between the intermediate The body is provided.

  Furthermore, according to the present invention, there are provided a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

In the formula ( 2 ), X ₃ and X ₄ are C (CN) COR, C (CN) COOR, C (CN) R, C (COOR) ₂ (R is a substituted or unsubstituted aryl group, an unsubstituted alkyl group.), or an oxygen atom (wherein, X ₃ and X ₄ are never simultaneously oxygen atom.). Y _{9 to} Y _{14 each} represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a nitro group, a cyano group, a halogen atom, or a hydrogen atom.

In the formula ( 2 ), examples of the substituent that R and Y ₉ to Y ₁₄ have include a nitro group, a cyano group, a halogen atom, an ester group, a carbonyl group, an amide group, an ether group, an aryl group, and an alkyl group. It is done.

In the formula ( 2 ), examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the alkyl group include a methyl group, an ethyl group, and the like. A propyl group etc. are mentioned.

As described above, the present invention, by containing a compound photosensitive layer having a specific structure, or an intermediate layer between the electroconductive support and the photosensitive layer by containing a compound having a specific structure, It has become possible to provide an electrophotographic photosensitive member having good potential characteristics and capable of outputting a good image, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

  Hereinafter, embodiments of the present invention will be described in more detail.

  First, the configuration of the electrophotographic photosensitive member of the present invention will be described.

  Examples of the conductive support used in the present invention include metals or alloys such as aluminum, nickel, copper, gold and iron, and metals such as aluminum, silver and gold on an insulating support such as polyester, polycarbonate, polyimide and glass. Or what formed the thin film of electrically conductive materials, such as an indium oxide and a tin oxide, what disperse | distributed carbon and a conductive filler in resin, and provided the electroconductivity etc. can be illustrated. The surface of these supports is a support that has been subjected to an electrochemical treatment such as anodization to improve electrical properties or adhesion, and the surface of a conductive support is alkali phosphate, phosphoric acid or tannin. 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 an acid 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 the surface of the support subjected to 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 is provided. It is necessary to use it.

  As the honing treatment, there are dry and wet treatment methods, and any of them may be used. The wet honing treatment is a method of suspending a powdery abrasive in a liquid such as water and spraying the surface of the substrate at a high speed to roughen the surface. The surface roughness is the spray pressure, speed, 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 a conductive substrate 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 in these wet or dry honing processes include particles such as silicon carbide, alumina, iron, and glass beads.

  In a method in which a conductive film made of a conductive metal oxide and a binder resin is applied to a support of aluminum or aluminum alloy to form a conductive support, a powder made of conductive fine particles is used as a filler in the conductive film. Containing. In this method, the fine particles are dispersed in the film, so that the laser beam is diffusely reflected to prevent interference fringes and to conceal the scratches and protrusions of the support before coating. Barium sulfate, titanium oxide, or the like is used for the fine particles, and if necessary, a conductive coating layer is provided on the fine particles with tin oxide or the like to obtain a specific resistance suitable as a filler. The specific resistance of the conductive fine particle powder is preferably 0.1 to 1000 Ω · cm, more preferably 1 to 1000 Ω · cm. The content of the filler is preferably 1.0 to 90% by mass, and more preferably 5.0 to 80% by mass with respect to the conductive film layer. The coating layer may contain fluorine or antimony as necessary.

  As the binder resin used for the conductive film, for example, phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, epoxy resin, acrylic resin, melamine resin, and polyester are preferable. These resins may be used alone or in combination of two or more. These resins have good adhesion to the support, improve the dispersibility of the filler, and have good solvent resistance after film formation. Among the above resins, phenol resin, polyurethane and polyamic acid are particularly preferable.

The conductive film can be formed, for example, by dipping or solvent application with a Meyer bar or the like. The thickness of the conductive film is preferably from 0.1 to 30 μm, more preferably from 0.5 to 20 μm. The volume resistivity of the conductive film is preferably 10 ¹³ Ω · cm or less, more preferably 10 ¹² Ω · cm or less and 10 ⁵ Ω · cm or more. In addition to the powder made of fine particles such as barium sulfate having a coating layer, the conductive film may contain a filler made of powder such as zinc oxide or titanium oxide. Furthermore, a leveling agent may be added to enhance the surface property.

A photosensitive layer is formed on the conductive support. The photosensitive layer of the present invention comprises a single layer type containing both a charge generation material and a charge transport material in the same layer, a charge generation layer containing a charge generation material, and a charge transport layer containing a charge transport material. And the laminated type. As a stacked type structure, there are a normal layer type in which a charge generation layer and a charge transport layer are stacked in this order on a substrate, and a reverse layer type in which a charge transport layer and a charge generation layer are stacked in this order. The compound represented by the formula (2) may be contained in any photosensitive layer.

Hereinafter, although the compound example shown by Formula (2) with Table 1-Table 3 with another compound example is shown, it is not necessarily limited to these. Hereinafter, the compound represented by the formula (2) is referred to as a quinone compound.

  In the case of the laminated type, the charge used varies depending on the charge polarity, and therefore the materials used are different. The charge transport layer of the forward layer type used for negative charge and the reverse layer type used for positive charge contains a hole transport material, and the forward layer type used for positive charge and the reverse layer type charge transport layer used for negative charge Contains an electron transport material.

  In an electrophotographic process using an organic electrophotographic photosensitive member, it is generally used with a negative charge, and a normal layer type is generally used from the viewpoint of durability.

  Hereinafter, an electrophotographic photosensitive member having a laminated (normal layer) photosensitive layer used for negative charging will be described.

  Examples of the charge generating material used in the present invention include (1) azo pigments such as monoazo, disazo and trisazo, (2) phthalocyanine pigments such as metal phthalocyanine and nonmetal phthalocyanine, and (3) indigo materials such as indigo and thioindigo. Pigments, (4) perylene pigments such as perylene anhydride and perylene imide, (5) polycyclic quinone pigments such as anthraquinone and pyrenequinone, (6) squarylium dyes, (7) pyrylium salts and thiapyrylium salts, ( 8) Triphenylmethane dyes, (9) inorganic substances such as selenium, selenium-tellurium, amorphous silicon, (10) quinacridone pigments, (11) azulenium salt pigments, (12) cyanine dyes, (13) xanthene dyes, 14) quinoneimine dye, (15) styryl dye, (16) cadmium sulfide and (17) zinc oxide.

  In particular, metal phthalocyanine pigments are preferable. Among them, oxytitanium phthalocyanine crystals, chlorogallium phthalocyanine crystals, dichlorotin phthalocyanine crystals and hydroxygallium phthalocyanine pigments are preferable, and hydroxygallium phthalocyanine pigments are particularly preferable.

  The oxytitanium phthalocyanine pigment 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 pigment with strong peaks, Bragg angles (2θ ± 0.2 °) of 9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° and Oxytitanium phthalocyanine pigments having a strong peak at 27.3 ° are preferred.

  The chlorogallium phthalocyanine crystal has a Bragg angle (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 ° and 28.2 ° in the characteristic X-ray diffraction using CuKα as a radiation source. Chlorogallium phthalocyanine crystals having strong peaks, chlorogallium phthalocyanine crystals having strong 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 having strong peaks at 17.4 °, 21.9 ° and 25.5 ° and Bragg angles (2θ ± 0.2 °) of 9.2 °, 12.2 °, 13.4 ° , Dichlorotin phthalos having strong peaks at 14.6 °, 17.0 ° and 25.3 ° Anine 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.

  Examples of the binder resin include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride and trifluoroethylene, polyvinyl alcohol, polyvinyl acetal, and polycarbonate. , Polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, epoxy resin, and the like, but are not limited thereto. Among these, polyester, vinyl acetate, and polyvinyl acetal are preferable, and polyvinyl acetal is more preferable. The molecular weight is preferably Mw = 60,000 to 150,000.

  The film thickness of the charge generation layer is preferably from 0.01 to 2 μm, and more preferably from 0.05 to 0.5 μm. The mass ratio between the charge generation material and the binder resin in the charge generation layer is preferably 0.5 / 1 to 4/1, and more preferably 1/1 to 1/3.

  And it is preferable to have the said quinone compound. Although there is no restriction | limiting in the addition amount of a quinone compound, it is preferable that it is 1-100% (mass conversion) of a charge generation material, and 10-50% is more preferable. The quinone compound may be used alone or in combination. Moreover, you may contain an additive for the purpose of improving an electrical property, film formability, etc.

  The charge generation layer is formed by dispersing the pigmented charge generation material together with a binder resin and other compounds by a solvent and a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor and roll mill, and then coating and drying. To be formed. The quinone compound and the binder resin may be added after dispersion.

  The charge transport layer contains a hole transport material in a molecular dispersion state and a binder resin, and a solution in which a binder resin having a film forming property and a hole transport material as described below are dissolved is applied, Formed by drying.

  Examples of the hole transport material include polycyclic aromatic compounds such as pyrene and anthracene, heterocyclic compounds such as carbazole, indole, imidazole, oxazole, thiazole, oxadiazole, pyrazole, pyrazoline, thiadiazole and triazole, p-diethylaminobenzaldehyde Hydrazone compounds such as N, N-diphenylhydrazone and N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, α-phenyl-4′-N, N-diaminostilbene and 5- [4- (di -P-tolylamino) benzylidene] -5H-dibenzo [a, d] dicycloheptene and other styryl compounds, benzidine compounds, triarylamine compounds, triphenylamine or a group consisting of these compounds in the main chain or side chain Having poly Chromatography (e.g., poly -N- vinylcarbazole and polyvinyl anthracene, etc.) are mentioned, it is not limited thereto.

  Examples of the resin having a film forming property include, but are not limited to, polyester, polycarbonate, polymethacrylic acid ester, polyarylate, polysulfone, and polystyrene. In particular, polycarbonate and polyarylate having a carbonate bond are preferable.

  The mass ratio between the hole transport material and the binder resin is preferably 10/2 to 2/10, and more preferably 10/6 to 6/10.

  Furthermore, a surface protective layer may be formed on the charge transport layer. The surface protective layer contains conductive particles or a hole transport material in a binder resin. You may contain additives, such as a lubrication agent. The binder resin itself may have conductivity and charge transport properties. In that case, it is not necessary to include conductive particles / hole transport materials and the like in addition to the resin. The resin may be a curable resin curable by heat / light / radiation or the like, or a non-curable known thermoplastic resin.

  In the electrophotographic photoreceptor of the present invention, an intermediate layer can be provided between the photosensitive layer and the conductive support. Examples of these materials include polyvinyl alcohol, polyvinyl acetal, polyethylene oxide, ethyl cellulose, methyl cellulose, polyamide, polyamic acid, polyurethane, polyimide, melamine, various metal chelate compounds such as titanium and zirconium, and various metal alkoxides. It is not necessarily limited to. In addition, it is preferable to have a quinone compound. The quinone compound may be used alone or in combination. Moreover, you may contain an additive for the purpose of improving an electrical property, film formability, etc. The thickness of the intermediate layer is preferably from 0.1 to 5 μm, more preferably from 0.3 to 3 μm.

  As a method for applying the coating solution for producing these electrophotographic photoreceptors, for example, a dip coating method, a spray coating method, a curtain coating method, a spin coating method, and the like are known, but from the viewpoint of efficiency / productivity. Is preferably a dip coating method.

  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, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in a direction indicated by an arrow with a predetermined peripheral speed (process speed). 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, among the above-described components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9, a plurality of components 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.

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

( Reference Example 1)
[Production of electrophotographic photoreceptor]
First, the coating material for the conductive layer was prepared according to the following procedure. 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% by weight of antimony oxide, 25 parts of resol type phenolic resin (trade name: Pryofen J-325, manufactured by Dainippon Ink & Chemicals), methyl cellosolve 20 Parts, 5 parts of methanol, 0.002 part of a silicone compound (polydimethylsiloxane polyoxyalkylene copolymer), and dispersion was adjusted for 2 hours with a sand mill using φ1 mm glass beads. This paint was applied on an aluminum cylinder having a diameter of 30 mm and a length of 260 mm by a dip coating method, and dried at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 15 μm.

  Next, 15 parts of an alcohol-soluble polyamide resin (trade name: Amilan CM8000: manufactured by Toray) is dissolved in 200 parts of methanol / 150 parts of benzyl alcohol, and this solution is applied onto the conductive layer by a dip coating method. Drying was performed at a temperature of 10 ° C. for 10 minutes to form an intermediate layer having a thickness of 0.6 μm.

  Next, 5 parts of a hydroxygallium phthalocyanine (HOGaPc) pigment having strong peaks at 7.3 °, 24.9 ° and 28.1 ° of the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα, Polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) 2.5 parts, tetrahydrofuran 25 parts and cyclohexanone 10 parts, dispersed in a sand mill apparatus using φ1 mm glass beads for 3 hours, and then tetrahydrofuran 200 Part, 100 parts of cyclohexanone and 2.5 parts of compound E26 shown in Table 1 were added to prepare a charge generation layer coating material having an average particle size of 0.17 μm (measured by centrifugal sedimentation method with CAPA700 manufactured by Horiba, Ltd.). This paint was applied onto the intermediate layer by a dip coating method and dried at 95 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.18 μm.

Next, polyarylate resin 60 parts {average molecular weight Mw = 100,000 with a repeating structural unit represented by ant over triethanolamine compound 50 parts and formula represented by the following formula as a hole transport material (4) (5) ( Measured with gel permeation chromatography “HLC-8120” manufactured by Tosoh Corporation and calculated in terms of polystyrene, developing solvent: THF, 0.1% by mass solution, column: “TSKgel SuperHM-N” manufactured by Tosoh Corporation Detector: RI, column temperature: 40 ° C., injection amount: 20 μl, flow rate: 1.0 ml / min)} is dissolved in 250 parts of monochlorobenzene / 200 parts of tetrahydrofuran, and this solution is dip-coated on the charge generation layer. And dried at 105 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm to obtain an electrophotographic photosensitive member.

[Evaluation]
The evaluation was made by Canon color laser printer LBP 2510 (primary charging: roller contact DC charging, one-component contact development, process speed 94.2 mm / second, remodeling to variable charging conditions, using Trek's high voltage power supply Model 610. Charging conditions: DC applied so that the surface potential of the electrophotographic photosensitive member becomes −600 V. The laser exposure amount can be changed, and the electrophotographic photosensitive member obtained above is mounted on a cyan process cartridge. The cartridge was remodeled, a potential probe (model 6000B-8: manufactured by Trek) was attached to the developing position, and a surface potential meter (model 344: manufactured by Trek) was used. After setting the amount of light so that the post-exposure potential is -150 V in an environment of 20 ° C./15% RH, the initial dark portion potential Vd and bright portion potential Vl are measured, and 5000 images with an image density of 10% are obtained. After the endurance, the dark portion potential Vd and the bright portion potential Vl were measured again, and potential changes ΔVd and ΔVl due to the endurance were obtained. ΔVd was −5 (V) and ΔVl was −25 (V).

After setting the pre-exposure potential / post-exposure potential to −600 V / −150 V again, the ghost image was evaluated in a state where the pre-exposure was turned off. As for the ghost image, as shown in FIG. 2, a solid and square image was produced at the head of the image, and then a halftone image of 1 dot and 1 space was produced. The order of image production is to take a solid white image as the first image, then take five consecutive ghost images, then take one solid black image and then take five ghost images again for a total of ten images. Evaluation was performed using a ghost image. The evaluation of the ghost image is performed by measuring the density difference between the 1-dot 1-space image density and the image density of the ghost portion with a spectral densitometer X-Rite 504/508 (manufactured by X-Rite Co., Ltd.). The ten points were averaged, and the average of these ten points was taken as one result, and all the above-mentioned ten ghost images were measured in the same manner. Their average value was determined. The density difference was 0.024 . This density difference means that the smaller the value, the better the ghost.

(Examples 7 to 10)
Electrons were produced in the same manner as in Reference Example 1 except that the quinone compounds listed in Table 4 were used in place of Compound E26 and the electrophotographic photoreceptor processing method listed in Table 4 was used in the preparation of the charge generation layer coating. Photoconductors were prepared and evaluated. The results are shown in Table 4.

(Example 15 )
An oxytitanium phthalocyanine having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 1 except that the electrophotographic photosensitive member processing method shown in Table 4 was used instead of the (TioPc) pigment. The results are shown in Table 4.

(Examples 18 to 19 )
An electrophotographic photosensitive member was prepared in the same manner as in Reference Example 1 except that the quinone compound shown in Table 4 was added during the preparation of the intermediate layer coating solution and the electrophotographic photosensitive member processing method shown in Table 4 was used. And evaluated. The results are shown in Table 4.

(Comparative Example 1)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 1 except that the fluorene compound represented by the following formula (7) was added to the charge generation layer and the electrophotographic photosensitive member processing method shown in Table 4 was used. Went. The results are shown in Table 4.

(Comparative Example 2)
In the same manner as in Reference Example 1, except that the fluorene compound represented by the above formula (7) was added and the electrophotographic photoreceptor processing method shown in Table 4 was used when the intermediate layer coating solution was prepared. A body was prepared and evaluated. The results are shown in Table 4.

(Comparative Example 3)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 1 except that the compound E26 was not used and the electrophotographic photosensitive member processing method shown in Table 4 was used. The results are shown in Table 4.

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. The ghost evaluation print used for ghost image evaluation in the embodiment will be described.

Explanation of symbols

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

Claims (8)

Have a conductive support and the conductive support a photosensitive layer formed on the support, and meet electrophotographic photoreceptor containing a compound represented by the following formula (2),
Electrophotographic photoreceptor compound represented by the following following formula (2) is characterized that you have been contained in the photosensitive layer:

{In Formula ( 2 ), X ₃ and X ₄ are C (CN) COR, C (CN) COOR, C (CN) R, C (COOR) ₂ (R is a substituted or unsubstituted aryl group or substituted or an unsubstituted alkyl group.), or an oxygen atom (wherein, X ₃ and X ₄ are never simultaneously oxygen atom.). Y _{9 to} Y _{14 each} represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a nitro group, a cyano group, a halogen atom, or a hydrogen atom. }. The photosensitive layer is a laminated photosensitive layer in which a charge generation layer and a charge transport layer are laminated in this order from the conductive support side, and the charge generation layer contains a compound represented by the formula (2) , The electrophotographic photosensitive member according to claim 1, wherein the charge transport layer contains a hole transport material. The electrophotographic photoreceptor according to claim 1 or 2, wherein the compound represented by the formula (2) is a compound represented by the following formula (E29), (E33), (E37) or (E40).
Electrically conductive support and a photosensitive layer formed on the conductive support member, and meet electrophotographic photosensitive member having containing a compound represented by the following formula (2),
Electrons electrophotographic photoreceptor further comprises an intermediate layer between the conductive support and the photosensitive layer, characterized that you have been contained in the intermediate layer is a compound represented by the following formula (2) Photoconductor:

{In Formula ( 2 ), X ₃ and X ₄ are C (CN) COR, C (CN) COOR, C (CN) R, C (COOR) ₂ (R is a substituted or unsubstituted aryl group or substituted or is an unsubstituted alkyl group.), or an oxygen atom (wherein, X ₃ and X ₄ are never simultaneously oxygen atom.). Y _{9 to} Y _{14 each} represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a nitro group, a cyano group, a halogen atom, or a hydrogen atom. }. 5. The photosensitive layer according to claim 4 , wherein the photosensitive layer is a laminated photosensitive layer in which a charge generation layer and a charge transport layer are laminated in this order from the conductive support side, and the charge transport layer contains a hole transport material. Electrophotographic photoreceptor. The electrophotographic photoreceptor according to claim 4 or 5, wherein the compound represented by the formula (2) is a compound represented by the following formula (E38) or (E42).
An electrophotographic photosensitive member according to any one of claims 1 to 6 charging means for charging the electrophotographic photoreceptor, the electrophotographic developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner It comprises developing means for forming a toner image on a photographic photosensitive member and cleaning means for removing toner remaining on the electrophotographic photosensitive member after the toner image formed on the electrophotographic photosensitive member is transferred onto a transfer material. A process cartridge which integrally supports at least one means selected from a group and is detachable from a main body of an electrophotographic apparatus. The electrophotographic photosensitive member according to any one of claims 1 to 6 charging means for charging the electrophotographic photoreceptor, an electrostatic on the electrophotographic photosensitive member is subjected to exposure with respect to the charged electrophotographic photosensitive member Exposure means for forming a latent image, developing means for developing an electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image on the electrophotographic photosensitive member, and on the electrophotographic photosensitive member An electrophotographic apparatus comprising transfer means for transferring a formed toner image onto a transfer material.