JP2005189765A - Electrophotographic photoreceptor, process cartridge with the electrophotographic photoreceptor and electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which exhibits stable potential properties in repetitive use in any environment from low temperature and low humidity to high temperature and high humidity, can continuously form excellent images of an early date, and is excellent in production stability, and to provide a process cartridge with the electrophotographic photoreceptor and an electrophotographic apparatus. <P>SOLUTION: In the electrophotographic photoreceptor having on a conductive substrate at least a photosensitive layer containing a charge generating material and an electron transport high molecular compound in the same layer, an electron mobility of the electron transport high molecular compound is in a range of 1×10<SP>-8</SP>-1×10<SP>-5</SP>cm/V s. The process cartridge with the electrophotographic photoreceptor and the electrophotographic apparatus are also provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrophotographic photosensitive member and an electrophotographic apparatus provided with the electrophotographic photosensitive member, and more particularly, to an electrophotographic photosensitive member having a photosensitive layer having an electron transport ability and containing a high molecular compound having a specific structure. The present invention relates to a process cartridge containing an electrophotographic photosensitive member and an electrophotographic apparatus.

  The electrophotographic photoreceptor is 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. In addition, it is required to have an environment in which the characteristics are sufficiently exhibited even in repeated use over a long period of time and stability to repeated use.

  The electrophotographic photosensitive member is basically composed of a conductive support and a photosensitive layer having photoconductivity, and the photosensitive layer is a so-called laminated type that is a function-separated type including a charge generation layer and a charge transport layer. The electrophotographic photosensitive member is classified into a so-called single layer type electrophotographic photosensitive member having a charge generation function and a charge transport function in the same layer.

In the case of a multilayer electrophotographic photoreceptor, the charge generation layer is composed of a charge generation material having a charge generation function and a binder resin, and the charge transport layer is composed of a charge transport material having a charge transport function. In the electrophotographic process, charges generated in the charge generation layer by exposure, that is, holes and electrons, are ideally injected and moved to the charge transport layer and the conductive support according to an electric field, respectively. For example, in the process of negatively charging the photosensitive layer side, holes generated in the charge generation layer are injected and moved to the charge transport layer, and electrons generated in the charge generation layer are injected and moved to the conductive support. However, in reality, the charge generated in the charge generation layer cannot be completely injected and moved into the charge transport layer or the conductive support, and is trapped in the charge generation layer or at the interface between the charge generation layer and the charge transport layer or intermediate layer. And accumulated by repeated use. As a result, for example, electrical characteristics such as increase in residual potential, change in dark and bright potentials, increase in dark attenuation, and image quality such as ghost and fog are caused by repeated use. As a method for suppressing charge trapping in the charge generation layer, for example, Patent Document 1 and Patent Document 2 propose that the charge generation layer contains a charge transporting substance or an electron withdrawing substance, and the effect thereof is shown. Has been.
JP-A-6-180509 JP 2000-39730 A

  However, the photosensitive layer is composed of a charge generation material, an organic compound having a relatively low molecular weight as an electron transport material, and a binder resin. In this photosensitive layer, since the binder resin is present in the charge generation layer, there is a limit to the amount of the electron transport material that can be added. There is. In the case of a multilayer electrophotographic photosensitive member, when forming a charge transport layer on a charge generation layer, depending on the solvent of the charge transport layer solution, the molecular weight of the electron transport material is small, so that part of the electron transport material is an electron. It may elute into the transport layer, limiting the choice of solvent when forming the charge transport layer. In particular, in the case of dip coating, problems such as elution of the electron transport material into the charge transport layer solution occur.

  An object of the present invention is to provide an electrophotographic photosensitive member that exhibits stable potential characteristics and can continuously form excellent images at the time of repeated use in all environments from low temperature and low humidity to high temperature and high humidity. An object is to provide an electrophotographic photoreceptor excellent in production stability.

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

The present invention relates to an electrophotographic photosensitive member having a photosensitive layer containing a charge generating material and a polymer compound in at least the same layer on a conductive support, wherein the polymer compound has an electron transport ability and The electrophotographic photosensitive member is characterized in that the molecular compound has an electron mobility of 1 × 10 ^{−8 to} 1 × 10 ⁻⁵ cm / V · sec.

  The photosensitive layer is a laminated electrophotographic photoreceptor comprising a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material, wherein the charge generation layer contains an electron transporting polymer compound. An electrophotographic photoreceptor is preferred.

  The electron transporting polymer compound is preferably an electrophotographic photoreceptor having a repeating structural unit represented by the following formula (1).

(Wherein R ₁ represents a hydrogen atom or an alkyl group, X ₁ represents an alkylene group, an arylene group, an ether group, a thioether group, or a —CO—O— group, and A ₁ represents a structural unit having an electron transporting ability. , M is 0 or 1.)

  The electron transporting polymer compound is preferably an electrophotographic photoreceptor having a repeating structural unit represented by the following formula (2).

(Wherein X ₂ represents an alkylene group, an arylene group, an ether group, a thioether group, or a —CO—O— group, A ₂ represents a structural unit having an electron transporting ability, and n is 0 or 1. )

In addition, the structural unit A ₁ having the electron transporting ability in the formula (1) or the structural unit A ₂ having the electron transporting ability in the formula (2) is a structural unit represented by the following formula (3). A photographic photoreceptor is preferred.

(In the formula, Y represents an alkyl group, aryl group, aralkyl group or heterocyclic group which may have a substituent, and R _{2 to} R ₅ may each independently have a hydrogen atom or a substituent. A good alkyl group, aryl group, aralkyl group, heterocyclic group, halogen atom, nitro group, or cyano group.)

In addition, the structural unit A ₁ having the electron transporting ability in the formula (1) or the structural unit A ₂ having the electron transporting ability in the formula (2) is a structural unit represented by the following formula (4). A photographic photoreceptor is preferred.

(In the formula, R ₆ and R ₇ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group, an aralkyl group, a heterocyclic group, or a cyano group, and R ₈ and R ₉ Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a halogen atom, a nitro group, a cyano group, or an ester group, and a and b each represent 0, 1 or 2. )

In addition, the structural unit A ₁ having the electron transporting ability in the formula (1) or the structural unit A ₂ having the electron transporting ability in the formula (2) is a structural unit represented by the following formula (5). A photographic photoreceptor is preferred.

(Wherein, R ₈ and R ₉ are each independently a hydrogen atom, a substituent alkyl group which may have a an alkoxy group, a halogen atom, a nitro group, a cyano group or an ester group,, R ₁₀ is An alkyl group, an aryl group, an aralkyl group, a heterocyclic group, or a cyano group which may have a substituent, and c and d each represent 0, 1 or 2)

In addition, the structural unit A ₁ having the electron transporting ability in the formula (1) or the structural unit A ₂ having the electron transporting ability in the formula (2) is a structural unit represented by the following formula (6). A photographic photoreceptor is preferred.

(In the formula, Z represents an oxygen atom or a sulfur atom, and R ₈ and R ₉ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a halogen atom, a nitro group, a cyano group, Or an ester group, e and f each represents 0, 1 or 2)

In addition, the structural unit A ₁ having the electron transport ability in the formula (1) or the structural unit A ₂ having the electron transport ability in the formula (2) is a structural unit represented by the following formula (7). A photographic photoreceptor is preferred.

(In the formula, P represents an oxygen atom, a sulfur atom or a dicyanomethylene group, and R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a halogen atom or a nitro group. Or a cyano group, g and h each represent 0, 1 or 2)

  The electron transporting polymer compound is preferably an electrophotographic photoreceptor having a repeating structural unit represented by the following formula (8).

(In the formula, Q represents an alkylene group or an arylene group which may have a substituent, and R _{2 to} R ₅ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group, or an aralkyl group. A group, a heterocyclic group, a halogen atom, a nitro group, or a cyano group.)

  In addition, it is preferable that the charge generating material is an electrophotographic photoreceptor in which the oxytitanyl phthalocyanine pigment, hydroxygallium phthalocyanine pigment, or chlorogallium phthalocyanine pigment is used.

  The electrophotographic photoreceptor is preferably an electrophotographic photoreceptor in which the charge generation material is an azo pigment.

  Further, the present invention integrally supports the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, an image exposure means, a developing means, and a cleaning means, and is attached to and detached from the electrophotographic apparatus main body. It is a process cartridge characterized by being possible.

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

  In the electrophotographic photoreceptor of the present invention, since the electron transporting polymer compound in the charge generation layer also serves as the binder resin, there is no need for a separate binder resin, and the density of the electron transport material increases. Therefore, electrons generated in the charge generation layer are efficiently injected and moved to the conductive support side by the electron transporting polymer compound, so that electron traps in the charge generation layer and at the interface are reduced, and charge generated by repeated use is reduced. Accumulation also decreases.

  On the other hand, the holes generated in the charge generation layer are also freed from electrostatic binding due to less trapping and accumulation of electrons, and the injection and movement into the charge transport layer are promoted, resulting in the reduction and repetition of the residual potential. A great effect is seen in stabilization of electrophotographic characteristics such as suppression of potential fluctuation in use.

  In addition, since the electrophotographic photosensitive member of the present invention contains a polymer compound as an electron transport material in the charge generation layer, elution or dip coating on the charge transport layer when forming the charge transport layer on the charge generation layer. In this case, elution of the electron transport material into the charge transport layer solution is eliminated, and production stability is greatly improved.

  As described above, according to the present invention, in all environments from low temperature and low humidity to high temperature and high humidity, it has excellent potential characteristics and image characteristics with respect to environmental stability and stability due to repeated use, and production. An electrophotographic photoreceptor excellent in stability, a process cartridge and an electrophotographic apparatus having the electrophotographic photoreceptor can be provided.

  The photosensitive layer of the electrophotographic photoreceptor of the present invention includes a single layer type containing a charge generating material and a charge transporting material in the same layer, and a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material. Although it is divided roughly into the laminated type which has, any case may be sufficient.

  The electron transporting polymer compound containing the repeating structural unit represented by the above formula (1) contained in the photosensitive layer of the present invention is prepared by, for example, introducing an acrylic group, a vinyl group or the like into the electron transporting compound by a conventional method. These are synthesized by a thermal radical polymerization method using an initiator, but are not limited to this reaction.

  The electron transporting polymer compound containing the repeating structural unit represented by the above formula (2) contained in the photosensitive layer of the present invention is synthesized, for example, by the reaction of polyvinyl alcohol and an aldehyde compound represented by the following formula. The reaction is not limited to this.

  The degree of acetalization of the electron transporting polymer compound containing the repeating structural unit represented by the above formula (2) was measured according to the method described in Japanese Industrial Standard K6728 (Testing method for polyvinyl butyral). The degree of acetalization of the electron transporting polymer compound of the present invention is preferably 50 mol% or more, particularly preferably 70 to 90 mol%. Furthermore, the saponification degree of polyvinyl alcohol which is a raw material of the electron transporting polymer compound of the present invention is preferably 85% or more.

  The electron transporting polymer compound containing the repeating structural unit represented by the above formula (8) contained in the photosensitive layer of the present invention is, for example, opened in an organic polar solvent of tetracarboxylic dianhydride and diamine. It is synthesized by a cyclopolyaddition reaction or by a ring-opening polyaddition reaction between a tetracarboxylic dianhydride and a diamine that has been previously N-silylated. As another synthesis example, tetracarboxylic dianhydride may be esterified and chlorinated, and then synthesized by polymerization reaction with diamine in an organic polar solvent. Polyesteric acid and alcohol are particularly suitable for esterification. Can be synthesized by esterification in the presence of a simple catalyst. Examples of the organic polar solvent include amide solvents such as N, N-dimethylacetamide, N, N-dimethylformamide and N-methylpyrrolidone, phenol solvents such as cresol and chlorophenol, ether solvents such as diethylene glycol dimethyl ether, or these And the like. Further, in order to control the molecular weight of the resin, the reaction can be carried out by containing 5% or less of water as required. The reaction temperature is preferably 20 to 120 ° C, and particularly preferably 20 to 60 ° C.

  The electron transporting polymer compound of the present invention preferably has a weight average molecular weight in the range of 1,000 to 1,000,000, more preferably in the range of 5,000 to 1,000,000, particularly 10,000. It is preferably in the range of ~ 500,000.

  In addition, the binder resin in the charge generation layer can be mixed with an electron transporting polymer compound if necessary. Examples of the binder resin in the charge generation layer include polycarbonate, polyester, benzal resin, polyamide, phenol resin, polyimide, and polyamic acid.

The electron transporting polymer compound contained in the charge generation layer of the present invention has an electron transport ability, and its electron mobility is 1 × 10 ^{−8 to} 1 × 10 5 under an electric field condition of 100 V / μm. It is in the range of ⁻⁵ cm / V · sec, particularly preferably 1 × 10 ^{−6 to} 1 × 10 ⁻⁵ cm / V · sec.

  Specific examples of the electron transporting polymer compound of the present invention are listed in Tables 1 to 6. However, the electron transporting polymer compound of the present invention is not limited to the following exemplified compounds.

  Examples of charge generation materials include azo pigments such as monoazo, disazo and trisazo, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, indigo pigments such as indigo and thioindigo, and perylenes such as perylene anhydride and perylene imide. Pigments, polycyclic quinone pigments such as anthrone, pyrenequinone, squarylium dyes, pyrylium, thiopyrylium salts, triphenylmethane dyes, and the like, particularly oxyphthalocyanine pigments, hydroxygallium phthalocyanine pigments and chlorogallium phthalocyanine pigments Phthalocyanine pigments and azo pigments are preferred.

  Examples of the charge transport material include polycyclic aromatic compounds such as pyrene and anthracene, carbazole, indole, imidazole, oxazole, thiazole, oxadiazol, pyrazole, pyrazoline, thiadiazol , A heterocyclic compound such as triazol, a hydrazone compound such as p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, N, N-diphenylhydrazino-3-methylden-9-ethylcarbazole, α-phenyl-4 Styryl compounds such as' -N, N-diphenylaminostilbene, 5- [4- (di-p-tolylamino) benzylidene] -5H-dibenzo [a, d] dichloroheptene, benzidine compounds, triarylmethane compounds, Triphenylamine or a group consisting of these compounds as a main chain or side chain A polymer - (such as poly -N- vinylcarbazole - le, polyvinyl anthracene and the like).

  The charge generation layer is formed by dissolving a charge generation substance in a solvent together with the specific resin and applying it. The charge transport layer is formed by dissolving the charge transport material in a solvent together with the specific resin and coating it, and the film thickness is preferably 5 to 40 μm, particularly preferably 15 to 30 μm.

  As the conductive support, for example, aluminum, aluminum alloy, copper, zinc, stainless steel, titanium, nickel, indium, gold, platinum, or the like is used. Also, plastics (for example, polyethylene, polypropylene, polyvinyl chloride and polyethylene terephthalate, acrylic resin, etc.) or conductive particles (for example, carbon black, silver particles, etc.) in which the above metal or alloy is formed by vacuum deposition. And a support obtained by coating a plastic or metal support with a suitable binder resin, or a support obtained by impregnating plastic or paper with conductive particles.

  The electrophotographic photoreceptor of the present invention may have an intermediate layer as a barrier layer between the conductive support and the photosensitive layer, and examples of the intermediate layer include polymer compounds such as polyamide, polyester and phenol resin. Alternatively, a conductive intermediate layer in which a conductive material such as tin oxide, zinc oxide, or carbon black and a polymer compound are dispersed together may be used. Further, the intermediate layer in the present invention may be composed of only one layer or may be composed of a plurality of functionally separated layers.

  In the electrophotographic photoreceptor of the present invention, a resin layer or a resin layer containing conductive particles may be laminated as a protective layer on the photosensitive layer.

  The various layers described above can be applied by, for example, immersion coating, spray coating, spinner coating, bead coating, blade coating, and beam coating. It can carry out by arbitrary coating methods, such as.

  The electrophotographic photosensitive member of the present invention can be used not only for electrophotographic copying machines, but also for laser beam printers, CRT printers, LED printers, liquid crystal printers, laser plate making, facsimiles, etc. It can be widely used in electrophotographic application fields.

  The present invention also comprises an electrophotographic apparatus provided with the electrophotographic photosensitive member of the present invention.

  FIG. 1 shows a schematic configuration of an electrophotographic apparatus having 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 the direction of an arrow at a predetermined peripheral speed. In the rotating process, the electrophotographic photosensitive member 1 is charged uniformly (positive or negative) by a charging means (primary charging means) 3 on its peripheral surface, and then exposed to exposure means (such as slit exposure or laser beam scanning exposure). The exposure light 4 that is emphasized and modulated corresponding to the time-series electric digital image signal of the target image information output from the not-shown image 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 then developed with toner by the developing means 5 and is taken out from a paper feeding unit (not shown) between the electrophotographic photoreceptor 1 and the transfer means 6 in synchronism with the rotation of the electrophotographic photoreceptor 1. The toner image formed and supported on the surface of the electrophotographic photosensitive member 1 is sequentially transferred by the transfer means 6 onto the transferred transfer material 7.

  The transfer material 7 that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member, introduced into the image fixing means 8, and subjected to image fixing to be printed out as an image formed product (print or copy). .

  After the image transfer, the surface of the electrophotographic photosensitive member 1 is cleaned by removing the transfer residual toner by the cleaning unit 9, and is further subjected to charge removal processing by the pre-exposure light 10 from the pre-exposure unit (not shown). Used repeatedly for image formation.

  The charging unit 3 may be a scorotron charger or a corotron charger using corona discharge, or a contact type charger using a known form such as a roller shape, a blade shape, or a brush shape. As a material of the member of the contact charger, an elastic body imparted with conductivity is generally used. The voltage applied to the contact charging member may be only a DC voltage or an oscillating voltage obtained by superimposing an AC voltage on a DC voltage. The oscillating voltage referred to here is a voltage whose voltage value periodically changes with time, and the AC voltage has a peak-to-peak voltage that is at least twice the charging start voltage of the electrophotographic photosensitive member when only the DC voltage is applied. It is preferable.

  When the 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 constituent elements such as the electrophotographic photosensitive member 1, the charging means 3, the developing means 5, and the cleaning means 9 described above are housed in a container 11 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 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 detachable from the apparatus main body using a guide unit 12 such as a rail of the apparatus main body. Process cartridge.

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

(Example 1)
120 parts by weight of a powder composed of barium sulfate fine particles having a tin oxide coating layer (coverage: 50 wt%, powder specific resistance: 700 Ωcm) and resol type phenol resin (Pryofen J-325, manufactured by Dainippon Ink and Chemicals, solid A solution consisting of 70 parts by weight and 100 parts by weight of 2-methoxy-1-propanol was dispersed with a ball mill for about 15 hours. The average particle size of the filler contained in this dispersion was 0.25 μm.

  The dispersion was applied on an aluminum cylinder (outer diameter 30 mm × length 357.5 mm) by a dipping method, and heat-cured at 150 ° C. for 20 minutes to form a conductive intermediate layer having a thickness of 15 μm.

  Next, a solution obtained by dissolving 10 parts by weight of a copolymer nylon resin (Amilan CM8000, manufactured by Toray) in a mixed solution of 60 parts by weight of methanol, 30 parts by weight of butanol, and 10 parts by weight of benzyl alcohol is dip coated on the intermediate layer. And dried by heating at 100 ° C. for 10 minutes to form a barrier layer having a thickness of 0.8 μm.

  Next, a solution comprising 4 parts by weight of an oxytitanium phthalocyanine pigment, 2 parts by weight of the polymer compound of Exemplified Compound 1 and 34 parts by weight of cyclohexanone is dispersed for 5 hours in a sand mill, and then 60 parts by weight of tetrahydrofuran is added to form a charge generating layer. A dispersion was prepared. This dispersion was applied onto the barrier layer by dip coating and dried by heating at 70 ° C. for 10 minutes to form a charge generation layer. The film thickness of the charge generation layer was about 0.1 μm.

  Next, 40 parts by weight of a triarylamine compound represented by the following formula (9) and 60 parts by weight of a bisphenol Z-type polycarbonate resin (Iupilon, Z-200, manufactured by Mitsubishi Gas Chemical) are added to 400 parts by weight of monochlorobenzene. The solution dissolved in 1 was dip-coated on the charge generation layer and dried by heating in an atmosphere at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 24 μm, thereby producing an electrophotographic photosensitive member.

The obtained electrophotographic photosensitive member is mounted on a reversal development type copying machine having a charging-exposure-development-transfer-cleaning process (GP-40 remodeling machine manufactured by Canon; exposure amount adjusted to 0.28 μJ / cm ² ). The potential (dark part potential V _D , bright) under the low temperature and low humidity (15 ° C., 10% RH), normal temperature and normal humidity (25 ° C., 40% RH) and high temperature and high humidity (30 ° C., 85% RH) environment. Part potential V _L ) Evaluation and potential fluctuation amount (ΔV) before and after repeating charging and exposure for 3 hours in a low temperature and low humidity environment were obtained. The evaluation results are shown in Table 7 and Table 8.

(Examples 2 to 7)
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the electron transporting polymer compound of the present invention of Exemplified Compounds 2, 7, 9, 15, 18, and 22 was used in the charge generation layer. The electrophotographic characteristics were evaluated by the same method as in 1. The evaluation results are shown in Table 7 and Table 8.

(Example 8)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the charge generating material was changed from an oxytitanium phthalocyanine pigment to a hydroxygallium phthalocyanine pigment and the production conditions shown below were changed. Was used to evaluate the electrophotographic characteristics.

  A mixture of 6 parts by weight of a hydroxygallium phthalocyanine pigment, 3 parts by weight of the polymer compound of Exemplified Compound 1 and 40 parts by weight of cyclohexanone was dispersed in a sand mill for 10 hours, and then 60 parts by weight of tetrahydrofuran was added to the dispersion for the charge generation layer. Was dip-coated on the intermediate layer, and further dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.1 μm. The evaluation results are shown in Table 7 and Table 8.

(Examples 9 to 13)
An electrophotographic photosensitive member was prepared in the same manner as in Example 8 except that the electron transporting polymer compound of the present invention of Exemplified Compounds 7, 10, 14, 19, and 26 was used for the charge generation layer. The electrophotographic characteristics were evaluated by the same method. The evaluation results are shown in Table 7 and Table 8.

(Example 14)
6 parts by weight of a hydroxygallium phthalocyanine pigment, 2 parts by weight of the polymer compound of Exemplified Compound 1 and 1 part by weight of polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.), 40 parts by weight of cyclohexanone The resulting mixture is dispersed in a sand mill for 8 hours, and then 60 parts by weight of tetrahydrofuran is added to prepare a dispersion for the charge generation layer, dip-coated on the intermediate layer, and further dried at 70 ° C. for 10 minutes. An electrophotographic photosensitive member was produced in the same manner as in Example 8 except that a charge generation layer of about 0.1 μm was formed, and the electrophotographic characteristics were evaluated by the same method as in Example 1. The evaluation results are shown in Table 7 and Table 8.

(Comparative Examples 1 and 2)
Electrophotography in the same manner as in Example 1 and Example 8 except that the electron transporting polymer compound of the present invention was changed to polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.). A photoconductor was prepared and electrophotographic characteristics were evaluated by the same method as in Example 1.

(Comparative Example 3)
6 parts by weight of a hydroxygallium phthalocyanine pigment, 1 part by weight of a polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.), an electron transporting low molecular weight compound having a structure represented by the following formula (10) After a mixed solution composed of 2 parts by weight and 40 parts by weight of cyclohexanone was dispersed by a sand mill for 10 hours, 60 parts by weight of tetrahydrofuran was added to prepare a dispersion for a charge generation layer, and dip-coated on the intermediate layer. An electrophotographic photosensitive member was produced in the same manner as in Example 8 except that a charge generation layer having a film thickness of about 0.1 μm was formed by drying at 100 ° C. for 10 minutes, and electrophotographic characteristics were obtained in the same manner as in Example 1. Evaluated. The evaluation results are shown in Table 7 and Table 8.

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 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 (14)

In an electrophotographic photosensitive member having a photosensitive layer containing a charge generating material and an electron transporting polymer compound in at least the same layer on a conductive support, the electron mobility of the electron transporting polymer compound is 1 × 10 ^−8. 1 to 10 × ^{5 −5} cm / V · sec.   The photosensitive layer is a laminated electrophotographic photosensitive member comprising a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material, wherein the charge generation layer contains an electron transporting polymer compound. The electrophotographic photosensitive member according to claim 1. The electrophotographic photoreceptor according to claim 1 or 2, wherein the electron transporting polymer compound has a repeating structural unit represented by the following formula (1).

(Wherein R ₁ represents a hydrogen atom or an alkyl group, X ₁ represents an alkylene group, an arylene group, an ether group, a thioether group, or a —CO—O— group, and A ₁ represents a structural unit having an electron transporting ability. , M is 0 or 1.) The electrophotographic photosensitive member according to claim 1, wherein the electron transporting polymer compound has a repeating structural unit represented by the following formula (2).

(Wherein X ₂ represents an alkylene group, an arylene group, an ether group, a thioether group, or a —CO—O— group, A ₂ represents a structural unit having an electron transporting ability, and n is 0 or 1. ) Wherein the structural unit A ₂ having an electron transporting ability of the structural units A ₁ or the formula (2) having an electron transporting ability of the formula (1) is a structural unit represented by the following formula (3) The electrophotographic photosensitive member according to claim 3 or 4.

(In the formula, Y represents an alkyl group, aryl group, aralkyl group or heterocyclic group which may have a substituent, and R _{2 to} R ₅ may each independently have a hydrogen atom or a substituent. A good alkyl group, aryl group, aralkyl group, heterocyclic group, halogen atom, nitro group, or cyano group.) Wherein the structural unit A ₂ having an electron transporting ability of the structural units A ₁ or the formula (2) having an electron transporting ability of the formula (1) is a structural unit represented by the following formula (4) The electrophotographic photosensitive member according to claim 3 or 4.

(In the formula, R ₆ and R ₇ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group, an aralkyl group, a heterocyclic group, or a cyano group, and R ₈ and R ₉ Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a halogen atom, a nitro group, a cyano group, or an ester group, and a and b each represent 0, 1 or 2. ) Wherein the structural unit A ₂ having an electron transporting ability of the structural units A ₁ or the formula (2) having an electron transporting ability of the formula (1) is a structural unit represented by the following formula (5) The electrophotographic photosensitive member according to claim 3 or 4.

(Wherein, R ₈ and R ₉ are each independently a hydrogen atom, a substituent alkyl group which may have a an alkoxy group, a halogen atom, a nitro group, a cyano group or an ester group,, R ₁₀ is An alkyl group, an aryl group, an aralkyl group, a heterocyclic group, or a cyano group which may have a substituent, and c and d each represent 0, 1 or 2) Wherein the structural unit A ₂ having an electron transporting ability of the structural units A ₁ or the formula (2) having an electron transporting ability of the formula (1) is a structural unit represented by the following formula (6) The electrophotographic photosensitive member according to claim 3 or 4.

(In the formula, Z represents an oxygen atom or a sulfur atom, and R ₈ and R ₉ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a halogen atom, a nitro group, a cyano group, Or an ester group, e and f each represents 0, 1 or 2) Wherein the structural unit A ₂ having an electron transporting ability of the structural units A ₁ or the formula (2) having an electron transporting ability of the formula (1) is a structural unit represented by the following formula (7) The electrophotographic photosensitive member according to claim 3 or 4.

(In the formula, P represents an oxygen atom, a sulfur atom or a dicyanomethylene group, and R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a halogen atom or a nitro group. Or a cyano group, g and h each represent 0, 1 or 2) The electrophotographic photosensitive member according to claim 1, wherein the electron transporting polymer compound has a repeating structural unit represented by the following formula (8).

(In the formula, Q represents an alkylene group or an arylene group which may have a substituent, and R _{2 to} R ₅ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group, or an aralkyl group. A group, a heterocyclic group, a halogen atom, a nitro group, or a cyano group.)   11. The electrophotographic photosensitive member according to claim 1, wherein the charge generating substance is any one of an oxytitanyl phthalocyanine pigment, a hydroxygallium phthalocyanine pigment, and a chlorogallium phthalocyanine pigment.   The electrophotographic photosensitive member according to claim 1, wherein the charge generating substance is an azo pigment.   An electrophotographic photosensitive member according to any one of claims 1 to 12, and at least one means selected from the group consisting of a charging means, an image exposure means, a developing means, and a cleaning means, are integrally supported, and electrophotography A process cartridge which is detachable from an apparatus main body.   An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a transferring unit.

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