JP4006461B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member containing a compound obtained by polymerizing or cross-linking a charge transporting compound having a chain polymerizable functional group and cured, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  Conventionally, inorganic electrophotographic photoreceptors using inorganic materials such as selenium, cadmium sulfide and zinc oxide have been mainly used as photoconductive materials used in electrophotographic photoreceptors. On the other hand, organic electrophotographic photoreceptors using organic materials have been actively researched and developed due to the advantages of high productivity and non-polluting properties, and many have photoconductive properties similar to those of inorganic electrophotographic photoreceptors. In recent years, it has been found to be used as a mainstay in place of inorganic electrophotographic photoreceptors.

  These electrophotographic photoreceptors are often used as function-separated electrophotographic photoreceptors in which a charge generation layer and a charge transport layer are laminated in order to satisfy both electrical and mechanical characteristics. At this time, the structure and purity of the charge transporting compound are extremely important in order to express stable and highly sensitive electrical characteristics even when used for a long time as well as in the initial stage. On the other hand, as a matter of course, in the electrophotographic photoreceptor to be used repeatedly, the surface of the electrophotographic photoreceptor has electric and mechanical external forces such as charging, image exposure, toner development, transfer to paper, and cleaning treatment. Since they are added directly, durability against them is required. Specifically, durability against surface wear and scratches due to rubbing, surface deterioration due to charging (eg, transfer efficiency and slipperiness decrease), and durability against electrical property deterioration such as sensitivity reduction and potential reduction. Is also required.

  In general, the surface of an electrophotographic photoreceptor is a thin resin layer, and the characteristics of the resin are very important. In recent years, acrylic resins and polycarbonate resins have been put to practical use as resins that satisfy the above-mentioned conditions to some extent, but not all of the above-mentioned characteristics are satisfied with these resins, and in particular, electrophotographic photoreceptors. Therefore, it is difficult to say that the film hardness of the resin is sufficiently high. Even when these resins are used as the resin for forming the surface layer, there is a problem that the surface layer is worn during repeated use, and further scratches are generated.

  Furthermore, due to the recent demand for higher sensitivity of organic electrophotographic photoreceptors, low molecular weight compounds such as charge transporting compounds are often added in relatively large amounts. In this case, these low molecular weight substances are plasticizers. The film strength is remarkably lowered by the action, and there is a problem that the surface layer is worn or scratched during repeated use. Further, when the electrophotographic photosensitive member is stored for a long period of time, the above-described charge transporting compound having a low molecular weight component is deposited, resulting in a problem of layer separation.

  As means for solving these problems, an attempt to use a curable resin as a resin for a charge transport layer has been proposed (for example, see Patent Document 1). Thus, the mechanical strength is increased by curing and crosslinking the charge transport layer using a curable resin as the charge transport layer resin, and the abrasion resistance and scratch resistance during repeated use are greatly improved. However, even when a curable resin is used, the low molecular weight component acts as a plasticizer in the binder resin to the last, so the problems of precipitation and layer separation as described above are not fundamental solutions. In addition, in the charge transport layer composed of the charge transport compound and the binder resin, the charge transport ability is highly dependent on the resin. For example, a curable resin having a sufficiently high hardness does not have sufficient charge transport ability and is repeated. The residual potential has been increased during use, and both have not been satisfied.

  In addition, a monomer having a carbon-carbon double bond is contained in the charge transport layer, and the carbon-carbon double bond of the charge transport compound is reacted by heat or light energy to form a cured film of the charge transport layer. An electrophotographic photosensitive member has been proposed (see, for example, Patent Documents 2 to 4). However, this is because, like the present invention, the charge transporting compound is immobilized in a pendant form on the polymer backbone, but the charge transporting material has only one polymerizable group and is blended with a commercially available polyfunctional monomer. Since a film is formed by curing, a charge transporting compound having one carbon-carbon double bond must be used at a certain concentration in order to obtain a sufficient charge transporting ability. Due to the compatibility with the monomer, it is difficult to arrange the charge transport material uniformly and optimally in the film, and it is actually impossible to ensure both mechanical strength and charge transport ability. is there. Furthermore, there is a concern about the influence of initiators required for polymerization on the electrophotographic characteristics, which actually raises the residual potential and affects the potential fluctuation during durability.

  As another solution, there has been proposed an electrophotographic photosensitive member in which a charge transport layer is formed by introducing a group having a charge transport capability into a thermoplastic polymer main chain (see, for example, Patent Document 5). However, this charge transport layer is more effective for precipitation and layer separation than conventional molecular dispersion type charge transport layers and improves the mechanical strength. It is a resin, and its mechanical strength is limited, and it is difficult to say that it is sufficient in terms of handling and productivity including the solubility of the resin.

As described above, the conventional systems have not achieved both high mechanical strength and charge transport ability. In view of such a situation, the present inventors have shown that the above problem can be greatly improved by crosslinking / curing a charge transporting compound having a chain polymerizable functional group by electron beam irradiation, ultraviolet ray or heat. Proposed in the literature (for example, see Patent Literature 6 to Patent Literature 11).
JP-A-2-127852 JP-A-5-216249 Japanese Patent Laid-Open No. 7-72640 JP 2004-302451 A JP-A-8-248649 Japanese Patent Laid-Open No. 11-265085 JP 2000-66424 A JP 2000-66425 A JP 2000-206715 A JP 2000-206716 A JP 2001-166519 A

  As described above, an electrophotographic photosensitive member using a film obtained by polymerizing or crosslinking a charge transporting compound having a chain polymerizable functional group by electron beam, ultraviolet irradiation or heat as the outermost surface layer has been used so far. Compared to, the mechanical properties were sufficiently improved and sufficient mechanical strength was achieved. However, there are still some aspects that are not fully satisfactory in terms of electrical characteristics. In particular, a charge transporting film obtained by polymerizing or crosslinking a charge transporting compound having two or more chain-polymerizable functional groups is not sufficient in charge mobility or is not uniform in charge transport. The hem cut was bad. As a result, it is difficult to obtain sufficient electrical characteristics when these films are used as thick films or when used at high process speeds, and there may be a large difference depending on the environment in which they are used. It was. Furthermore, inadequate charge transfer often affects various types of electrophotographic photoconductor memories, and in particular, it is easy to cause an electrophotographic photoconductor-induced memory phenomenon called ghost on an image. An electrophotographic photoreceptor using a charge transporting film obtained by polymerizing or crosslinking a charge transporting compound having two or more chain polymerizable functional groups as described above as the outermost surface layer still has insufficient electrical characteristics. At present, there is a need for improvement.

  The object of the present invention is to provide an electrophotographic photoreceptor containing a charge transporting compound having two or more chain-polymerizable functional groups in the surface layer. An object of the present invention is to provide an electrophotographic photosensitive member that can sufficiently satisfy electrical characteristics.

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

  As a result of intensive studies in view of the above problems, the present inventors have found the following and have reached the present invention. The above Patent Documents 6 to 11 and the like show that two or more chain-polymerizable functional groups are clearly shown in the compound examples and examples of the charge transporting compound having two or more chain-polymerizable functional groups. Almost all films formed by polymerizing or cross-linking and curing a charge transporting compound having an electron beam, ultraviolet irradiation or heat are such that the charge transporting material is directly incorporated into the main chain of the three-dimensional cross-linked structure film. Yes. When the charge transport material is a three-dimensional cross-linked structure film in which the charge transport material is incorporated in the main chain, it is difficult to arrange the charge transport material uniformly and in the same state in the film. In other words, charge transport materials are twisted when polymerized or cross-linked and cured, and they are fairly firmly fixed, and they do not have the same conformation in the film, so that each energy level is in the film. Different charge transport materials exist, which slows down the charge transfer rate and, in some cases, causes charge trapping, which makes charge transfer non-uniform throughout the film It was thought that the delay of the charge occurred partially, and as a result, the tail of the charge transfer became worse.

  In order to solve the problem, the chain transporting functional group is not directly incorporated into the charge transporting material as much as possible, and can move freely in the film to some extent even after being cured, so that a normal low molecular charge transporting material can be used. We thought that it was important to be able to take a stable conformation close to thermodynamics uniformly in the film. Among them, among the three aryl groups of a triarylamine compound having an excellent charge transport ability, at least two aryl groups do not contain a chain-polymerizable functional group, which greatly affects the charge transport ability. It is important that a charge transporting compound having two or more chain-polymerizable functional groups having a specific structure is very preferable in order to exhibit its effect while ensuring sufficient mechanical strength. And found the present invention.

  According to the present invention, in an electrophotographic photosensitive member having a conductive support and a photosensitive layer provided on the conductive support, the outermost surface layer of the electrophotographic photosensitive member has the following general formula (1-1) or ( There is provided an electrophotographic photoreceptor comprising at least one obtained by polymerizing or cross-linking and curing a charge transporting compound having a chain polymerizable functional group represented by 1-2).

In formula (1-1), Ar ₁₁ and Ar ₁₂ represent an aryl group which may have a substituent, and Ar ₁₃ represents a phenyl group which may have a substituent. The substituent for Ar ₁₁ and Ar ₁₂ is selected from an alkyl group, an alkoxy group, an aryloxy group, an aralkyl group, an aryl group or a halogen atom, and the substituent for Ar ₁₃ is an alkyl group, an alkoxy group or a halogen atom. Selected from any of the atoms. However, it has at least two chain polymerizable functional groups represented by the following general formulas (2) to (6) only on Ar ₁₃ directly or via an organic residue. Ar ₁₁ and Ar ₁₂ may be the same or different.
In formula (1-2), Ar ₂₁ , Ar ₂₂ and Ar ₂₄ represent an aryl group which may have a substituent, and Ar ₂₁ , Ar ₂₂ and Ar ₂₄ may be the same or different. The substituent for Ar ₂₁ , Ar ₂₂ and Ar ₂₄ is selected from any of an alkyl group, an alkoxy group, an aryloxy group, an aralkyl group, an aryl group and a halogen atom. Ar ₂₃ represents a phenylene group which may have a substituent, and the substituent is selected from an alkyl group, an alkoxy group, an aryl group, and a halogen atom. Z represents a divalent organic residue, and n represents 0 or 1. However, it has at least two chain-polymerizable functional groups represented by the following general formulas (2) to (6) only on Ar ₂₄ or directly through an organic residue.

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

  By using a specific charge transporting compound having two or more chain polymerizable functional groups of the present invention, the charge transporting function of a film obtained by polymerizing or cross-linking them can be greatly improved as compared with the conventional one. . As a result, the electrophotographic photosensitive member using the cured film as the outermost layer maintains the mechanical durability such as the conventional wear resistance and scratch resistance, and is repetitively used as well as the initial electrical characteristics. It is possible to demonstrate stable performance at times, and to suppress changes in environmental characteristics to a small extent, and to significantly improve memory such as ghosts, etc. An electrophotographic photoreceptor capable of providing a high-quality image could be provided. Furthermore, an electrophotographic photosensitive member with little dependency on process speed could be provided.

  The effect of the electrophotographic photosensitive member is naturally exhibited in the process cartridge and the electrophotographic apparatus having the electrophotographic photosensitive member as well, and the high image quality is maintained with high durability and high stability.

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

  The electrophotographic photosensitive member having a photosensitive layer provided on a conductive support of the present invention is represented by the following general formula (1-1) or (1-2) where the outermost surface layer has at least a specific structure. And at least a product obtained by polymerizing, crosslinking, or curing a charge transporting compound having a chain polymerizable functional group.

In formula (1-1), Ar ₁₁ and Ar ₁₂ represent an aryl group which may have a substituent, and Ar ₁₃ represents a phenyl group which may have a substituent. The aryl group of Ar ₁₁ and Ar ₁₂ includes phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, biphenyl group, fluorenyl group, carbazolyl group, benzofuryl group, benzothiophenyl group, dibenzofuryl group, and dibenzothiophenyl group. Groups and the like. Examples of the substituent that Ar ₁₁ and Ar ₁₂ may have include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. Alkyl groups, preferably alkyl groups having 1 to 8 carbon atoms, alkoxy groups such as methoxy group, ethoxy group and propoxy group, aryloxy groups such as phenoxy group and naphthoxy group, benzyl group, phenethyl group, naphthylmethyl group, furfuryl Group and an aralkyl group such as a thienyl group, an aryl group such as a phenyl group, a naphthyl group, an anthryl group and a pyrenyl group, or a halogen atom such as fluorine, chlorine, bromine and iodine. The substituent that Ar ₁₃ may have is selected from any of an alkyl group, an alkoxy group, and a halogen atom that Ar ₁₁ and Ar ₁₂ may have. Ar ₁₁ and Ar ₁₂ may be the same or different. However, Ar ₁₃ has two or more chain-polymerizable functional groups of the following general formulas (2) to (6) directly or via an organic residue.

In formula (1-2), Ar ₂₁ , Ar ₂₂ and Ar ₂₄ represent an aryl group which may have a substituent, and Ar ₂₁ , Ar ₂₂ and Ar ₂₄ may be the same or different. As the aryl group represented by Ar ₂₁ , Ar ₂₂ and Ar ₂₄ , phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, biphenyl group, fluorenyl group, carbazolyl group, benzofuryl group, benzothiophenyl group, dibenzofuryl group And a dibenzothiophenyl group.

Ar ₂₁ , Ar ₂₂ and Ar ₂₄ may be substituted with alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, n-hexyl and cyclohexyl. Groups, preferably alkyl groups having 1 to 8 carbon atoms, alkoxy groups such as methoxy group, ethoxy group and propoxy group, aryloxy groups such as phenoxy group and naphthoxy group, benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and It is selected from aralkyl groups such as thienyl group, aryl groups such as phenyl group, naphthyl group, anthryl group and pyrenyl group, or halogen atoms such as fluorine, chlorine, bromine and iodine.

Ar ₂₃ represents a phenylene group which may have a substituent, and examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. Group and an alkyl group such as a cyclohexyl group, preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group such as a methoxy group, an ethoxy group and a propoxy group, an aryl group such as a phenyl group, a naphthyl group, an anthryl group and a pyrenyl group, or It is selected from any of halogen atoms such as fluorine, chlorine, bromine and iodine.

Z represents a divalent organic residue, for example, an oxygen atom, a carbonyl group, a sulfur atom, —CH═CH—, —CH ₂ —CH ₂ — or any one of the following general formula (11), preferably — CH = CH _-, - a following general formula _{(11) - CH 2 -CH 2} . n represents 0 or 1.

R ₂₄ and R ₂₅ represent an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom, and R ₂₄ and R ₂₅ are It may be the same or different. The substituent is selected from any of an alkyl group, an aralkyl group, an aryl group, and a halogen atom.

However, it has at least two chain-polymerizable functional groups represented by the following general formulas (2) to (6) only on Ar ₂₄ or directly through an organic residue.

  Among the charge transporting compounds having a chain polymerizable functional group of the general formula (1-1) having the above specific structure, a compound represented by the following general formula (7) or (9) is particularly suitable for solving the above-mentioned problems. Is more preferable.

In the formula, Ar ₁₁ and Ar ₁₂ each represent an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group and a biphenyl group, which may have a substituent, and the substituent includes a methyl group, An alkyl group such as an ethyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group, n-hexyl group and cyclohexyl group, preferably an alkyl group having 1 to 8 carbon atoms, a methoxy group, Ar ₁₁ and Ar ₁₂ may be the same or different and selected from any of alkoxy groups such as ethoxy group and propoxy group, and aryl groups such as phenyl group, naphthyl group and anthryl group.

R _{11 to} R ₁₅ are alkyl groups such as hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group, n-hexyl group and cyclohexyl group, preferably It is selected from an alkyl group having 1 to 8 carbon atoms, an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, or the following general formula (8), and R _{11 to} R ₁₅ may be the same or different. However, two or more of R _{11 to} R ₁₅ are represented by the following general formula (8).

In the formula, X ₁₁ represents a divalent organic residue which may have a substituent, and the substituent is selected from an alkyl group, an aralkyl group, an aryl group or a halogen atom, and a is 0 or 1 Indicates. P ₁₁ represents a chain polymerizable functional group represented by the general formulas (2) to (6). The organic residue represented by X ₁₁ is more preferably an oxygen atom, —O—Z ₁₁ — (Z ₁₁ is a divalent alkylene group) or a divalent alkylene group.

In the formula, Ar ₁₁ and Ar ₁₂ have the same meaning as defined in the general formula (7), and X ₁₂ is a divalent alkylene group which may have a substituent, an oxygen atom or —O—Z ₁₂ — ( Z ₁₂ represents a divalent alkylene group), and b = 0 or 1. R _{16 to} R ₁₈ are phenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, pyrenyl groups, and biphenyl groups that may have a substituent, methyl groups that may have a substituent, ethyl groups, It has an alkyl group such as an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group and a cyclohexyl group, preferably an alkyl group having 1 to 8 carbon atoms and a substituent. Aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group, aryloxy groups such as phenoxy group and naphthoxy group which may have a substituent, hydrogen atom or the above general formula (8) indicates any one _of, R 16 _{to R 18} may be the same or different. The substituent that R _{16 to} R ₁₈ may have is selected from an alkyl group, an aralkyl group, an aryl group, a halogen atom, or the general formula (8). However, any of R _{16 to} R ₁₈ has at least two chain-polymerizable functional groups represented by the above general formulas (2) to (6). In the general formula (9), R ₁₆ and R ₁₇ are preferably the above general formula (8), and in the general formula (8), a = 1 and X ₁₁ may be an alkylene group. Further preferred.

Furthermore, Ar ₁₁ and Ar ₁₂ of the charge transporting compound having a chain polymerizable functional group represented by the general formula (1-1), (7) or (9) may have a substituent. In particular, the case of being either a biphenyl group which may have a substituent or a fluorenyl group which may have a substituent is particularly preferable. In this case, Ar ₁₁ and Ar ₁₂ may be the same or different, and the substituent of Ar ₁₁ and Ar ₁₂ is either an alkyl group or an alkoxy group.

  In addition, as a chain-polymerizable functional group, general formula (2) and (3) are especially preferable in terms of the curing speed and the compatibility between mechanical strength and electrical characteristics.

  On the other hand, in order to solve the above-mentioned problem among the charge transporting compounds having the chain polymerizable functional group of the general formula (1-2) having the specific structure, the following general formula (10) or (13) The compounds shown are more preferred.

In the formula, Ar ₂₁ and Ar ₂₂ have the same definitions as defined in the general formula (1-2). Z represents —CH═CH—, —CH ₂ —CH ₂ — or any one of the above general formula (11), and n represents 0 or 1. R _{21 to} R ₂₃ are each a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group, preferably carbon. An alkyl group of formulas 1 to 8, an alkoxy group such as a methoxy group, an ethoxy group and a propoxy group, or the following general formula (12) is shown, and R _{21 to} R ₂₃ may be the same or different. However, at least two of R _{21 to} R ₂₃ are represented by the following general formula (12). In general formula (11), R ₂₄ and R ₂₅ represent an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. , R ₂₄ and R ₂₅ may be the same or different. The substituent is selected from any of an alkyl group, an aralkyl group, an aryl group, and a halogen atom.

In the formula, X ₂₁ represents a divalent organic residue which may have a substituent, and the substituent is selected from an alkyl group, an aralkyl group, an aryl group or a halogen atom, and a is 0 or 1 Indicates. The organic residue represented by X ₂₁ is more preferably an oxygen atom, a divalent alkylene group, or —O—Z ₂₁ — (Z ₂₁ is a divalent alkylene group). P ₂₁ represents a chain polymerizable functional group represented by the general formulas (2) to (6).

In the formula, Z, Ar ₂₁ , Ar ₂₂ and n have the same meaning as defined in the general formula (1-2), X ₂₂ represents a divalent organic residue, and may have a substituent. A case where it is a divalent alkylene group, an oxygen atom, or —O—Z ₂₂ — (Z ₂₂ is a divalent alkylene group) is preferred, and b = 0 or 1. R _{26 to} R ₂₈ are phenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, pyrenyl groups, and biphenyl groups that may have a substituent, methyl groups that may have a substituent, ethyl groups, It has an alkyl group such as an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group and a cyclohexyl group, preferably an alkyl group having 1 to 8 carbon atoms and a substituent. Aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group, aryloxy groups such as phenoxy group and naphthoxy group which may have a substituent, hydrogen atom or the above general formula (12) indicates any one _of, R 26 _{to R 28} may be the same or different. The substituent for R _{26 to} R ₂₈ is selected from an alkyl group, an aralkyl group, an aryl group, a halogen atom, or the general formula (12). However, any one of R _{26 to} R ₂₈ has at least two chain-polymerizable functional groups represented by the general formulas (2) to (6). In addition, it is preferable that R ₂₆ and R ₂₇ represented by the general formula (13) are the general formula (12), and in the general formula (12), a = 1 and X ₂₁ is an alkylene group. The case is preferred.

Furthermore, Ar ₂₁ and Ar ₂₂ of the charge transporting compound having a chain polymerizable functional group represented by the general formula (1-2), (10) or (13) may have a substituent. A group, a biphenyl group which may have a substituent, or a fluorenyl group which may have a substituent is particularly preferable. In this case, Ar ₂₁ and Ar ₂₂ may be the same or different, and the substituent of Ar ₂₁ and Ar ₂₂ is either an alkyl group or an alkoxy group.

In addition, as a chain-polymerizable functional group, general formulas (2) and (3) are particularly preferable in terms of curing speed and compatibility of mechanical strength and electrical characteristics.
The outermost surface layer of the electrophotographic photosensitive member of the present invention is preferably cured by an electron beam.
The present invention relates to the electrophotographic photosensitive member described herein, a charging means for charging the electrophotographic photosensitive member, a developing means for developing the electrophotographic photosensitive member on which an electrostatic latent image is formed with toner, and an electrophotographic image after the transfer process. There is provided a process cartridge characterized in that it integrally supports at least one means selected from the group consisting of cleaning means for collecting toner remaining on the photoreceptor, and is detachable from the main body of the electrophotographic apparatus.
Furthermore, the present invention relates to an electrophotographic photosensitive member described herein, a charging means for charging the electrophotographic photosensitive member, an exposure means for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, and an electrostatic latent image. An electrophotographic apparatus comprising: a developing unit that develops toner on the electrophotographic photosensitive member formed with the toner; and a transfer unit that transfers a toner image on the electrophotographic photosensitive member onto a transfer material.

  Next, specific examples of the charge transporting compound represented by the formula (1-1) having a specific chain polymerizable functional group used in the present invention are shown in Table 1 below. However, the compounds are not limited to these, and the present invention is not limited.

  Next, specific examples of the charge transporting compound represented by the formula (1-2) having a specific chain polymerizable functional group used in the present invention are shown in Table 2 below. However, the compounds are not limited to these, and the present invention is not limited.

  A typical synthesis method of a charge transporting compound having a chain polymerizable functional group used in the present invention is shown below.

(Synthesis Example 1: Synthesis of Exemplified Compound No. 18)
According to the following route, Exemplified Compound No. 18 was synthesized.

To a mixed solution consisting of glacial acetic acid (480 parts by mass; the following), 62.5% sulfuric acid (24 parts), and water (20 parts), 1 (100 parts), 50% periodic acid dihydrate aqueous solution ( 50 parts) and iodine (55 parts) were added, and the mixture was heated to about 70 ° C. with sufficient stirring and reacted for 24 hours. After allowing to cool, the crystals deposited in ice water were collected by filtration, washed with water, and then the crude crystals were recrystallized from hexane to obtain 2 (100 parts). 2 (100 parts) was added to ethanol, a catalytic amount of dilute sulfuric acid was added, and esterification was carried out by a conventional method to obtain 3 (98 parts). Next, 3 (67 parts), 4 (39 parts), copper powder (23 parts) and anhydrous potassium carbonate (36 parts) were added to o-dichlorobenzene (60 parts), and the mixture was heated and stirred at 200 to 210 ° C. for 16 hours. Went. After cooling the reaction solution, toluene (50 parts) was added and stirred, and solids were removed by filtration. After removing the filtrate under reduced pressure, the residue was purified by a silica gel column (developing solvent: hexane / toluene mixed solvent) to obtain 5 (30 parts). The obtained 5 (30 parts) was dissolved in 300 parts of methyl t-butyl ether, LiAlH ₄ (4 parts) was slowly added at room temperature, and the reaction was carried out at 50 ° C. for 5 hours after the addition. After completion of the reaction, the reaction mixture was neutralized with 6N hydrochloric acid and extracted with ethyl acetate. The extracted organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. After adding 18 parts of THF to the residue and dissolving, 70 parts of hexane was added to precipitate crystals to obtain 6 (16 parts). Next, 6 (15 parts) and triethylamine (15 parts) were added to 150 parts of dry THF and cooled to 0 to 5 ° C., and then acryloyl chloride (10 parts) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into water, neutralized, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified with a silica gel column (developing solvent: toluene) to obtain 15 parts of target compound 7 (Exemplary Compound No. 18).

(Synthesis Example 2: Synthesis of Exemplary Compound No. 1)
According to the following route, Exemplified Compound No. 1 was synthesized.

1 (100 parts), 2 (380 parts), copper powder (150 parts) and anhydrous potassium carbonate (135 parts) were added to o-dichlorobenzene (100 parts), and the mixture was heated and stirred at 200 to 210 ° C. for 24 hours. . After cooling the reaction solution, toluene (100 parts) was added and stirred, and solids were removed by filtration. After removing the filtrate under reduced pressure, the residue was purified by a silica gel column (developing solvent: hexane / toluene mixed solvent) to obtain 3 (130 parts). Next, 3 (100 parts) and pyridinium chloride (640 parts) were mixed and heated and stirred at 200 to 210 ° C. for 4 hours. After cooling the reaction solution to about 145 ° C., 600 parts of water was slowly added and cooled, the reaction solution was acidified with 6N-hydrochloric acid and extracted with toluene. The extracted organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. The residue was purified with a silica gel column (developing solvent: toluene / THF mixed solvent) to obtain 4 (90 parts). Next, 4 (80 parts) and triethylamine (42 parts) were added to 400 parts of dry THF and cooled to 0 to 5 ° C., and then acryloyl chloride (60 parts) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into water, neutralized, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed. The residue was purified with a silica gel column to obtain 75 parts of the target compound 5 (Exemplary Compound No. 1).

(Synthesis Example 3: Synthesis of Exemplary Compound No. 41)
According to the following route, Exemplified Compound No. 41 was synthesized.

1 (100 parts) was added to a hydrochloric acid aqueous solution of concentrated hydrochloric acid (35%) (680 parts by mass; following parts) / water (210 parts), and then cooled with ice water so that the internal temperature became 5 ° C. or less. Thereto, a cooled solution of sodium nitrate (47 parts) / water (200 parts) was slowly dropped into the liquid so that the internal temperature did not exceed 5 ° C. After completion of the dropwise addition, the mixture was stirred as it was for 30 minutes, the reaction solution was filtered, and the filtrate was again cooled to 5 ° C. or lower with ice water. An aqueous solution of sodium tetrafluoroborate (106 parts) / water (180 parts) was added dropwise to the liquid. The mixture was stirred for 30 minutes as it was, and then suction filtered to obtain 142 parts of crude 2 . Further, crude 2 was dissolved in acetonitrile, and isopropyl ether was added thereto for reprecipitation purification to obtain 115 parts of 2 . To a solution obtained by adding 2 (100 parts) and 18-crown-6-ether (5.3 parts) to iodobenzene (9000 parts), potassium acetate (80 parts) was added at room temperature and stirred for 3 hours. Went. The reaction solution was filtered, the filtrate was washed with brine, and the organic layer was dried over anhydrous magnesium sulfate. Thereafter, iodobenzene was removed by distillation, methanol was added to the residue to precipitate crystals, and the crystals were collected by filtration. The obtained crystals were recrystallized with a methanol / acetone mixed solvent to obtain 46 parts of 3 . Next, 3 (40 parts), p-ditolylamine (30 parts), copper powder (22 parts) and anhydrous potassium carbonate (25 parts) obtained were added to o-dichlorobenzene (120 parts), and the mixture was heated at 200 to 210 ° C. Stirring was performed for 16 hours. After cooling the reaction solution, toluene (100 parts) was added and stirred, and solids were removed by filtration. After removing the filtrate under reduced pressure, the residue was purified by a silica gel column (developing solvent: toluene) to obtain 4 (130 parts). Next, 4 (30 parts) and pyridinium chloride (210 parts) were mixed, and heated and stirred at 200 to 210 ° C. for 4 hours. After cooling the reaction solution to about 145 ° C., 350 parts of water was slowly added and cooled, the reaction solution was acidified with 6N-hydrochloric acid and extracted with toluene. The extracted organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. The residue was purified with a silica gel column (developing solvent: toluene / THF mixed solvent) to obtain 5 (23 parts). Next, 5 (20 parts) and triethylamine (6.8 parts) were added to 100 parts of dry THF and cooled to 0 to 5 ° C., and then acryloyl chloride (9.7 parts) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into water, neutralized, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed. The residue was purified with a silica gel column to obtain 16 parts of the target compound 6 (Exemplary Compound No. 41).

(Synthesis Example 4: Synthesis of Exemplary Compound No. 72)
According to the following route, Exemplified Compound No. 72 was synthesized.

To a mixed solution consisting of glacial acetic acid (600 parts), 62.5% sulfuric acid (24 parts) and water (20 parts), 1 (140 parts), 50% periodic acid dihydrate aqueous solution (50 parts) and Iodine (55 parts) was added, and the mixture was heated to about 70 ° C. with sufficient stirring and reacted for 24 hours. After allowing to cool, the crystals deposited in ice water were collected by filtration, washed with water, and then the crude crystals were recrystallized with a hexane / acetone mixed solvent to obtain 2 (120 parts). 2 (100 parts) was added to ethanol, and a catalytic amount of dilute sulfuric acid was added to carry out esterification by a conventional method to obtain 3 (95 parts). Next, 3 (80 parts), 4 (46 parts), copper powder (13 parts) and anhydrous potassium carbonate (35 parts) are added to o-dichlorobenzene (100 parts), and the mixture is heated and stirred at 200 to 210 ° C. for 16 hours. Went. After cooling the reaction solution, toluene (80 parts) was added and stirred, and solids were removed by filtration. After removing the filtrate under reduced pressure, the residue was purified with a silica gel column (developing solvent: hexane / toluene mixed solvent) to obtain 5 (55 parts). The obtained 5 (50 parts) was dissolved in 500 parts of methyl t-butyl ether, LiAlH ₄ (7 parts) was slowly added at room temperature, and the reaction was carried out at 50 ° C. for 5 hours after the addition. After completion of the reaction, the reaction mixture was neutralized with 6N hydrochloric acid and extracted with ethyl acetate. The extracted organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. Crystals were precipitated using a residue acetone / n-hexane mixed solvent to obtain 6 (28 parts). Next, 6 (20 parts) and triethylamine (15 parts) were added to 150 parts of dry THF, and after cooling to 0 to 5 ° C., acryloyl chloride (8.3 parts) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into water, neutralized, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified with a silica gel column (developing solvent: toluene) to obtain 14 parts of the target compound 7 (Exemplary Compound No. 72).

  In the present invention, the compound having charge transporting ability in the photosensitive layer is obtained by polymerizing or crosslinking and curing a specific charge transporting compound having two or more chain polymerizable functional groups in the same molecule. It is incorporated into the three-dimensional crosslinked structure through a covalent bond with two or more crosslinking points. However, when the charge transport material of the present invention is three-dimensionally cured, unlike the conventional case where the charge transport material is incorporated in the main chain, the twist of the charge transport material is reduced and the charge transport material is a normal low molecular weight charge transport material. Can take a stable arrangement close to the thermodynamics that can be taken. As a result, this system has a sufficient charge transport ability compared to the conventional ones, and it is possible to greatly improve the mechanical durability while ensuring electrical characteristics.

  The charge transporting compound can be polymerized, crosslinked, cured, or mixed with a compound having another chain polymerizable group, and the kind / ratio thereof is arbitrary. As used herein, the compound having another chain polymerizable group includes any monomer or oligomer / polymer having a chain polymerizable group. When the functional group of the charge transporting compound and the functional group of the other chain polymerizable compound are the same group or a group that can be polymerized with each other, they may have a copolymerized three-dimensional crosslinked structure via a covalent bond. Is possible. When both functional groups are functional groups that do not polymerize with each other, the photosensitive layer is a mixture of two or more three-dimensional cured products, or other chain-polymerizable compound monomer or its component in a three-dimensional cured product as a main component. Although it is comprised as what contains hardened | cured material, it is also possible to form an IPN (Inter Penetrating Network), ie, an interpenetrating network structure, by controlling the compounding ratio / film forming method well.

  Further, a photosensitive layer may be formed from the charge transporting compound and a monomer or oligomer / polymer having no chain polymerizable group, a monomer or oligomer / polymer having a polymerizable group other than the chain polymerizable group, and the like. .

  Further, in some cases, it is possible to contain a charge transporting compound that is not chemically bonded to the three-dimensional crosslinked structure, that is, does not have a chain polymerizable functional group. Moreover, you may contain other various additives, other lubricants, etc.

  The electrophotographic photosensitive member of the present invention has a structure in which a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material are laminated in this order on a conductive support, or vice versa. It is possible to adopt any configuration including a single layer in which the charge generation material and the charge transport material are dispersed in the same layer. In the former stacked type, the charge transport layer may be composed of two or more layers. In the latter single layer type, the charge transport layer may be further formed on the photosensitive layer containing the same charge generating material and charge transport material. Further, a protective layer can be formed on the charge generation layer or the charge transport layer. In any of these cases, the photosensitive layer may contain a charge transporting compound having a chain polymerizable group and / or a polymerized and cured product of the above charge transporting compound. However, from the viewpoint of characteristics as an electrophotographic photosensitive member, particularly electrical characteristics such as residual potential and durability, a function-separated type electrophotographic photosensitive member structure in which a charge generation layer / charge transport layer are laminated in this order is preferable. The advantage of the invention is that the surface layer can be made highly durable without lowering the charge transport ability.

  Next, a method for producing an electrophotographic photoreceptor according to the present invention will be specifically described.

  The support of the electrophotographic photosensitive member may be any material having conductivity, for example, aluminum, copper, chromium, nickel, zinc, stainless steel or other metal or alloy formed into a drum or sheet, aluminum and copper Metal foils such as those laminated on plastic films, aluminum, indium oxide and tin oxide deposited on plastic films, metals with conductive layers applied alone or with binder resin, and plastic Examples include films and paper.

  In the present invention, an undercoat layer having a barrier function and an adhesive function can be provided on the conductive support. The undercoat layer is used for improving the adhesion of the photosensitive layer, improving the coatability, protecting the support, covering defects on the support, improving the charge injection from the support, and protecting the photosensitive layer from electrical breakdown. Formed for. Materials for the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, copolymer nylon, glue and gelatin Etc. These are dissolved in a solvent suitable for each and coated on a support. The film thickness at that time is preferably 0.1 to 2 μm.

  When the electrophotographic photoreceptor of the present invention is a function separation type, a charge generation layer and a charge transport layer are laminated. Examples of the charge generation material used for the charge generation layer include selenium-tellurium, pyrylium, thiapyrylium dyes, various central metals and crystal systems, specifically, crystal types such as α, β, γ, ε, and X types. Phthalocyanine compounds, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, trisazo pigments, disazo pigments, monoazo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments, quinocyanines and amorphous materials described in JP-A No. 54-143645 Silicon etc. are mentioned.

  In the case of a function-separated type electrophotographic photosensitive member, the charge generation layer is composed of the charge generation material 0.3 to 4 times the amount of binder resin and solvent, homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor and roll mill. The film is sufficiently dispersed by a method such as the above, and a dispersion is applied and dried, or is formed as a single composition film such as a vapor deposition film of the charge generation material. The film thickness is preferably 5 μm or less, and particularly preferably in the range of 0.1 to 2 μm.

  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, polycarbonate, Examples include polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin.

  In the present invention, the charge transporting compound having a chain polymerizable functional group is formed on the charge transport layer formed on the charge generation layer, or a charge transport layer made of a charge transport material and a binder resin on the charge generation layer. After forming, it can be used for a surface protective layer having a charge transport capability. In any case, the surface layer is generally formed by applying a solution containing the charge transporting compound and then carrying out a polymerization / curing reaction, but the solution containing the charge transporting compound is reacted in advance. It is also possible to form a surface layer by using a material obtained by dispersing the resin in a solvent and then dissolving it. As a method for applying these solutions, for example, a dip coating method, a spray coating method, a curtain coating method, a spin coating method, and the like are known. From the viewpoint of efficiency / productivity, the dip coating method is preferable. Moreover, vapor deposition, plasma, and other known film forming methods can be appropriately selected.

  In the present invention, the charge transporting compound having a chain polymerizable functional group is preferably polymerized and cured by radiation. The greatest advantage of radiation polymerization is that it does not require a polymerization initiator, which makes it possible to produce a very high-purity three-dimensional photosensitive layer matrix and ensure good electrophotographic properties. . In addition, because it is a short and efficient polymerization reaction, the productivity is also high, and furthermore, because of its good radiation transmission, it inhibits curing when a thick film or additives such as additives are present in the film. The influence of the is very small. However, depending on the type of the chain polymerizable group and the type of the central skeleton, the polymerization reaction may not easily proceed, and in this case, the polymerization initiator can be added within a range that does not affect the polymerization reaction. The radiation used at this time is an electron beam or γ-ray. In the case of electron beam irradiation, any type of accelerator such as a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type can be used.

In the case of irradiating an electron beam, the irradiation condition is very important in the electrophotographic photosensitive member of the present invention in order to develop electric characteristics and durability. In the present invention, the acceleration voltage is preferably 250 KV or less, and optimally 150 KV or less. The absorbed dose of the electron beam is preferably 1 × 10 ³ to 1 × 10 ⁶ Gy, and more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ Gy. If the absorbed dose is less than 1 × 10 ³ Gy, it is difficult to sufficiently cure the surface layer, and if it exceeds 1 × 10 ⁶ Gy, the characteristics of sensitivity and residual potential are liable to be deteriorated. FIG. 1 shows a schematic configuration diagram of an electron beam irradiation apparatus used for producing the electrophotographic photosensitive member of the present invention.

  As shown in FIG. 1, the electron beam irradiation apparatus used in this embodiment includes an electron beam generator 10, an irradiation chamber 20, and an irradiation window 30.

The electron beam generator 10 includes a terminal 12 that generates an electron beam and an acceleration tube 14 that accelerates the electron beam generated at the terminal 12 in a vacuum space (acceleration space). Further, the inside of the electron beam generator 10 is maintained at a vacuum of 10 ⁻⁴ to 10 ⁻⁶ Pa by a diffusion pump (not shown) in order to prevent electrons from colliding with gas molecules and losing energy.

  The terminal 12 includes a linear filament 12a that emits thermoelectrons, a gun structure 12b that supports the filament 12a, and a grid 12c that controls thermoelectrons generated in the filament 12a. If the length of the filament 12a and the grid 12c in the depth direction in the drawing is longer than the length in the cylindrical axis direction of the irradiated portion of the irradiated body, the cylindrical axis direction of the irradiated body is one electron. The whole can be irradiated by irradiation.

  The electron beam generator 10 also includes a heating power source (not shown) for heating the filament 12a to generate thermoelectrons, and a control power source (not shown) that applies a voltage between the filament 12a and the grid 12c. A DC power source and an acceleration DC power source for applying a voltage between the grid 12c and the window foil 32 provided on the irradiation window portion 30 are provided.

  The irradiation chamber 20 includes an irradiation space 22 for irradiating an electron beam onto the surface of the cylindrical irradiated object 1. When the surface layer of the electrophotographic photosensitive member is cured as in the examples described later, the interior of the irradiation chamber 20 is an inert gas atmosphere in order to stabilize the curing. Here, the inert gas is nitrogen gas, argon gas, helium gas, or the like. The cylindrical irradiated body 1 is transported in the direction of arrow A in the irradiation chamber 20 by transport means such as a conveyor.

  Further, at least within the time during which the cylindrical irradiated object 1 passes through the electron beam irradiation window 30 and is irradiated with the electron beam, the conductive support is rotated around the cylindrical axis to thereby rotate the irradiated object. The irradiating body 1 rotates about the cylindrical axis in the direction of arrow B. The periphery of the electron beam generator 10 and the irradiation chamber 20 is shielded from lead so that X-rays that are secondarily generated during electron beam irradiation do not leak to the outside.

  The irradiation window 30 includes a window foil 32 made of a metal foil, and a window frame structure 34 that cools the window foil 32 and supports the window foil 32. The window foil 32 partitions the vacuum atmosphere in the electron beam generator 10 and the air atmosphere in the irradiation chamber 20, and takes out an electron beam into the irradiation chamber 20 through the window foil 32.

  When the filament 12a is heated by the heating power source through current, the filament 12a emits thermoelectrons, and these thermoelectrons are attracted in all directions by the control voltage of the control DC power source applied between the filament 12a and the grid 12c. . Of these, only those passing through the grid 12c are effectively extracted as electron beams. The electron beam taken out from the grid 12c is accelerated in the acceleration space in the accelerating tube 14 by the acceleration voltage of the acceleration DC power supply applied between the grid 12c and the window foil 32, and then the window foil 32. The cylindrical irradiated object 1 conveyed through the irradiation chamber 20 below the irradiation window 30 is irradiated. Normally, the beam current can be adjusted by setting the heating power source and the acceleration DC power source to predetermined values and making the control DC power source variable.

  When the charge transporting compound having a chain polymerizable group is used as a charge transporting layer, the amount of the charge transporting compound is the above general formula (1) with respect to the total mass of the charge transporting layer film after polymerization and curing. The hydrogenated product excluding the chain polymerizable group of the charge transporting compound having a chain polymerizable functional group represented by is preferably 20% or more in terms of molecular weight, particularly preferably 40% or more. . If it is less than 20%, the charge transport ability is lowered, and problems such as a reduction in sensitivity and an increase in residual potential occur. In this case, the thickness of the charge transport layer is preferably 1 to 50 μm, and particularly preferably 3 to 30 μm.

  When the charge transporting compound is used as a surface protective layer on the charge generation layer / charge transport layer, the charge transport layer corresponding to the lower layer is formed of a suitable charge transport material such as poly-N-vinylcarbazole and polystyrylanthracene. Polymer compounds having a heterocyclic ring or condensed polycyclic aromatics, heterocyclic compounds such as pyrazoline, imidazole, oxazole, triazole and carbazole, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, A solution in which a low molecular weight compound such as a phenylenediamine derivative, an N-phenylcarbazole derivative, a stilbene derivative, or a hydrazone derivative is dispersed / dissolved in a solvent together with an appropriate binder resin (which can be selected from the aforementioned resin for charge generation layer) Apply and dry by the above-mentioned known method. It can be. In this case, the ratio of the charge transport material and the binder resin is appropriately selected in the range of 30 to 100, more preferably 50 to 100, when the total mass of both is 100. . When the amount of the charge transport material is less than that, the charge transport ability is lowered, and problems such as a decrease in sensitivity and an increase in residual potential occur. The film thickness of the charge transport layer is determined so that the total film thickness combined with the upper surface protective layer is preferably 1 to 50 μm, and more preferably adjusted in the range of 5 to 30 μm.

  In the present invention, in any of the above cases, the charge transport material can be contained in the photosensitive layer containing the cured product of the charge transport compound having the chain polymerizable group.

  In the case of a single-layer type photosensitive layer, a charge generating material is simultaneously contained in the solution containing the charge transporting compound, and this solution may be provided with an appropriate undercoat layer or intermediate layer. The charge transporting compound is formed on a single layer type photosensitive layer composed of a charge generating material and a charge transporting material provided on a conductive support, and when formed by polymerization or crosslinking and curing after coating Any of the cases of polymerizing or crosslinking and curing after application of the contained solution is possible.

  Various additives can be added to the photosensitive layer of the electrophotographic photoreceptor of the present invention. Examples of the additives include deterioration inhibitors such as antioxidants and ultraviolet absorbers, and lubricants such as tetrafluoroethylene resin particles and carbon fluoride.

  FIG. 2 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

  In FIG. 2, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate at a predetermined peripheral speed in the direction of an arrow about a shaft (not shown). In the rotating process, the electrophotographic photosensitive member 1 is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the primary charging unit 2, and then the exposure light L from the exposure unit 3 such as slit exposure or laser beam scanning exposure. Receive. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1. The formed electrostatic latent image is then developed with toner by the developing means 4, and the developed toner developed image is transferred between the electrophotographic photosensitive member 1 and the transfer means 5 from a paper supply unit (not shown). The transfer means 5 sequentially transfers the transfer material P taken out in synchronization with the rotation of 1 and fed. The transfer material P that has received the image transfer 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 a copy (copy). After the image is transferred, the surface of the electrophotographic photosensitive member 1 is cleaned by removing the transfer residual toner by the cleaning unit 6, and is further subjected to charge removal processing by the pre-exposure light 7 from the pre-exposure unit (not shown). Used repeatedly for image formation. When the primary charging unit 2 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 2, the developing unit 4 and the cleaning unit 6 described above are integrally coupled as a process cartridge. The electrophotographic apparatus main body such as a copying machine or a laser beam printer may be detachable. For example, at least one of the primary charging unit 2, the developing unit 4, and the cleaning unit 6 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 guide means such as the rail 110 of the apparatus main body. A flexible process cartridge 100 can be obtained.

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

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

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. Note that “parts” appearing below mean “parts by mass” unless otherwise specified.

(Example 1-1)
1 part of a polyamide resin (6-60-64-124 original nylon copolymer) and 3 parts of an 8-nylon resin (methoxymethylated nylon, methoxylation rate of about 30%) are dissolved in 50 parts of methanol / 40 parts of butanol. An intermediate layer paint was prepared. This paint was applied on a honed-treated φ30 mm aluminum cylinder by a dip coating method and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.5 μm.

  3 parts of a hydroxygallium phthalocyanine crystal having strong peaks at 7.4 ° and 28.2 ° of the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα, polyvinyl butyral (trade name: ESREC BM2, Sekisui) Chemical Co., Ltd. (1.0 part) and cyclohexanone (35 parts) were dispersed in a sand mill using a φ1 mm glass bead for 24 hours, and then 60 parts of ethyl acetate was added to prepare a charge generation layer coating material. This paint was applied onto the intermediate layer by a dip coating method and dried at 105 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.12 μm.

Next, 1.25 parts of fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) as a dispersant was added to 1,1,2,2,3,3,4-heptafluorocyclopentane ( Trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd. 37.5 parts and 1-propanol 37.5 parts, and then tetrafluoroethylene resin powder as lubricant (trade name: Lubron L-2, Daikin) 12.5 parts of Kogyo Kogyo Co., Ltd.) was added, and the mixture was uniformly dispersed by applying 3 treatments at a pressure of 600 kgf / cm ^{2 with} a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA). It was. This was subjected to pressure filtration with a 10 μm polytetrafluoroethylene (PTFE) membrane filter to prepare a lubricant dispersion. Next, Compound Example Nos. 36 parts of a charge transporting compound having 17 chain polymerizable functional groups, 16.2 parts of a lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating for a charge transport layer.

This charge transport layer coating was applied onto the charge generation layer by a dip coating method, dried at 40 ° C. for 10 minutes, and then irradiated with an electron beam using the electron beam irradiation apparatus shown in FIG. The sample was conveyed to the lower part of the electron beam irradiation window part by a belt conveyor, stopped at the irradiation part and irradiated while rotating the sample (drum temperature at the start of irradiation was about 25 ° C.). After the irradiation is completed, it is transported again and carried outside. At this time, the effective electron beam irradiation width in the electron beam irradiation portion (in the electron beam density distribution on the sample surface, 1 / e or more of the peak position) was 4 cm. The electron beam irradiation conditions are: absorbed dose rate 3 × 10 ⁵ Gy / sec (absorbed dose within the effective electron beam irradiation width / time during which an arbitrary point on the sample surface exists within the effective electron beam irradiation width), acceleration voltage The absorbed dose (total absorbed dose received by the sample in the electron beam irradiation process) was 3 × 10 ⁵ Gy. The time from the start to the end of electron beam irradiation was 1.5 seconds. By irradiating an electron beam under the above conditions to cure the compound, a charge transport layer having a film thickness of 18 μm was formed, and further heat-treated at 150 ° C. for 1 hour to obtain an electrophotographic photoreceptor.

  The electrophotographic photoreceptor thus obtained was evaluated in a low-temperature and low-humidity (15 ° C./10% RH) environment using a copying machine GP40 manufactured by Canon Inc. The potential characteristics of the electrophotographic photosensitive member were measured by removing the developing unit from the copying machine main body and fixing the potential measuring probe at the developing position instead. At that time, the transfer unit was not in contact with the electrophotographic photosensitive member, and the paper was not passed. Initial electrophotographic photoreceptor characteristics [dark portion potential Vd, sensitivity: dark portion potential −650 V light intensity necessary for light attenuation to 170 V (light portion potential Vl), residual potential Vsl: light amount necessary for light portion potential Vl The potential when irradiated with 3 times the amount of light] was measured. Furthermore, 200,000 sheets were tested for endurance, and the presence or absence of image defects was observed. The amount of shaving of the electrophotographic photosensitive member and the amount of fluctuation ΔVl in the initial portion and immediately after endurance were measured. An eddy current film thickness meter (manufactured by Karl Fischer) was used for measurement of the amount of scraping. In addition, the sheet passing durability is an intermittent mode in which the printing is stopped once for each print.

Further, the mobility of the charge transport layer of the electrophotographic photoreceptor produced in the same manner was measured by a xerographic TOF method using a drum tester CYNTHIA (manufactured by GENTEC). The charge mobility at an electric field strength of 5 × 10 ⁵ V / cm was measured. The results are shown in Table 3.

(Examples 1-2 to 1-18)
Compound Example No. used in the preparation of the charge transport layer coating material of Example 1-1 The charge transporting compounds having 17 chain polymerizable functional groups were respectively referred to as Compound Example Nos. 1, no. 3, no. 4, no. 5, no. 7, no. 8, no. 9, no. 12, no. 18, no. 19, no. 26, no. 27, no. 29, no. 30, no. 31, no. 33 and no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1-1 except that 34 was used. The results are shown in Table 3.

(Example 1-19)
Compound Example No. used in the preparation of the charge transport layer coating material of Example 1-1 36 parts of a charge transporting compound having 17 chain polymerizable functional groups were added to Compound Example No. 17 (18 parts) and no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1-1, except that 36 (18 parts) was used. The results are shown in Table 3.

(Example 1-20)
Compound Example No. used in the preparation of the charge transport layer coating material of Example 1-1 36 parts of a charge transporting compound having 17 chain polymerizable functional groups were added to Compound Example No. 17 (27 parts) and electrophotography in the same manner as in Example 1-1 except that 9 parts of Compound A-1 (trade name: Biscote # 540, manufactured by Osaka Organic Chemical Industry Co., Ltd.) shown below was used. A photoconductor was prepared and evaluated in the same manner. The results are shown in Table 3.

(Comparative Example 1-1)
Compound Example No. used in the preparation of the charge transport layer coating material of Example 1-1 Except having replaced the charge transportable compound which has 17 chain polymerizable functional groups with the charge transportable compound (H-1) which has a chain polymerizable functional group shown below, it carried out similarly to Example 1-1. An electrophotographic photosensitive member was produced and evaluated in the same manner. The results are shown in Table 4.

(Comparative Examples 1-2 to 1-9)
The charge transporting compound (H-1) having a chain polymerizable functional group used in the preparation of the charge transport layer coating material of Comparative Example 1-1 was replaced with the charge transporting compound (H) having a chain polymerizable functional group shown below. -2) to (H-9) except that the electrophotographic photosensitive member was produced in the same manner as Comparative Example 1-1, and the same evaluation was performed. The results are shown in Table 4.

(Comparative Example 1-10)
36 parts of the charge transporting compound (H-1) having a chain polymerizable functional group used in the preparation of the charge transport layer coating material of Comparative Example 1-1 was replaced with a charge transporting compound having a chain polymerizable functional group shown below ( An electrophotographic photosensitive member was produced and evaluated in the same manner as in Comparative Example 1-1 except that 18 parts of H-10) and 18 parts of the compound (A-1) were replaced. The results are shown in Table 4.

(Comparative Example 1-11)
Comparative Example 1-10 except that the ratio of 18 parts of Compound (H-10) and 18 parts of Compound (A-1) was changed to 27 parts of Compound (H-10) and 9 parts of Compound (A-1). An electrophotographic photoreceptor was prepared in the same manner as in Example 1-10, and the same evaluation was performed. The results are shown in Table 4.

  As apparent from Tables 3 and 4, the electrophotographic photosensitive member using the charge transporting compound having a chain polymerizable functional group of the present invention for the charge transporting layer has good initial electrophotographic photosensitive member properties, and It was found that the amount of shaving during durability was small, image defects due to scratches and the like were not generated, and the potential fluctuation during durability was small, showing extremely excellent durability performance. Furthermore, it has been found that the charge transport layer obtained by curing the charge transport compound having a chain polymerizable functional group of the present invention has very good charge mobility.

(Example 2-1)
1 part of a polyamide resin (6-60-64-124 original nylon copolymer) and 3 parts of an 8-nylon resin (methoxymethylated nylon, methoxylation rate of about 30%) are dissolved in 50 parts of methanol / 40 parts of butanol. An intermediate layer paint was prepared. This paint was applied on a honed-treated φ30 mm aluminum cylinder 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.

  2.5 parts of a hydroxygallium phthalocyanine crystal having strong peaks at 7.4 ° and 28.2 ° of the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα, polyvinyl butyral (trade name S-REC BM2, Sekisui Chemical Co., Ltd. (1.0 part) and cyclohexanone (35 parts) were dispersed for 24 hours in a sand mill using φ1 mm glass beads, and then 60 parts of ethyl acetate was added to prepare a charge generation layer coating material. This paint was applied onto the intermediate layer by a dip coating method and dried at 105 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.14 μm.

Next, 1.25 parts of fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) as a dispersant was added to 1,1,2,2,3,3,4-heptafluorocyclopentane ( Trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd. 37.5 parts and 1-propanol 37.5 parts, and then tetrafluoroethylene resin powder as lubricant (trade name: Lubron L-2, Daikin) 10 parts of Kogyo Co., Ltd.) were added, and the mixture was uniformly dispersed by applying three treatments at a pressure of 600 kgf / cm ² with a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA). This was subjected to pressure filtration with a 10 μm polytetrafluoroethylene (PTFE) membrane filter to prepare a lubricant dispersion. Next, Compound Example Nos. 36 parts of a charge transporting compound having 41 chain polymerizable functional groups, 16.2 parts of a lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating for a charge transport layer.

This charge transport layer coating was applied onto the charge generation layer by a dip coating method, dried at 40 ° C. for 10 minutes, and then irradiated with an electron beam using the electron beam irradiation apparatus shown in FIG. The sample was conveyed to the lower part of the electron beam irradiation window part by a belt conveyor, stopped at the irradiation part and irradiated while rotating the sample (drum temperature at the start of irradiation was about 25 ° C.). After the irradiation is completed, it is transported again and carried outside. At this time, the effective electron beam irradiation width in the electron beam irradiation portion (in the electron beam density distribution on the sample surface, 1 / e or more of the peak position) was 4 cm. The electron beam irradiation conditions are: absorbed dose rate 1.5 × 10 ⁵ Gy / sec (absorbed dose within the effective electron beam irradiation width / time during which an arbitrary point on the sample surface exists within the effective electron beam irradiation width), The acceleration voltage was 100 KV, and the absorbed dose (total absorbed dose received by the sample in the electron beam irradiation process) was 1.5 × 10 ⁵ Gy. The time from the start to the end of electron beam irradiation was 1.5 seconds. By irradiating an electron beam under the above conditions to cure the compound, a charge transport layer having a thickness of 20 μm was formed, and further heat-treated at 150 ° C. for 1 hour to obtain an electrophotographic photoreceptor.

  The electrophotographic photoreceptor thus obtained was evaluated in a normal temperature and low humidity (23 ° C./10% RH) environment using a copying machine GP40 manufactured by Canon Inc. The potential characteristics of the electrophotographic photosensitive member were measured by removing the developing unit from the copying machine main body and fixing the potential measuring probe at the developing position instead. At that time, the transfer unit was not in contact with the electrophotographic photosensitive member, and the paper was not passed. Initial electrophotographic photoreceptor characteristics [dark portion potential Vd, sensitivity: dark portion potential −650 V light intensity necessary for light attenuation to 170 V (light portion potential Vl), residual potential Vsl: light amount necessary for light portion potential Vl The potential when irradiated with 3 times the amount of light] was measured. Furthermore, 200,000 sheets were tested for endurance, and the presence or absence of image defects was observed, the amount of shaving of the electrophotographic photosensitive member, and the amount of fluctuation ΔVl in the initial portion and immediately after endurance of the bright portion potential were measured. An eddy current film thickness meter (manufactured by Karl Fischer) was used for measurement of the amount of scraping. In addition, the sheet passing durability is an intermittent mode in which the printing is stopped once for each print.

Further, the mobility of the charge transport layer of the electrophotographic photoreceptor produced in the same manner was measured by a xerographic TOF method using a drum tester CYNTHIA (manufactured by GENTEC). The charge mobility at an electric field strength of 5 × 10 ⁵ V / cm was measured. The results are shown in Table 5.

(Examples 2-2 to 2-32)
Compound No. used in preparation of the charge transport layer coating material of Example 2-1 The charge transporting compounds having 41 chain polymerizable functional groups were respectively referred to as Compound Example Nos. 42, no. 43, no. 44, no. 45, no. 46, no. 47, no. 48, no. 49, no. 50, no. 57, no. 58, no. 59, no. 60, no. 61, no. 64, no. 65, no. 66, no. 72, no. 73, no. 74, no. 75, no. 77, no. 78, no. 80, no. 81, no. 82, no. 83, no. 84, no. 85, no. 87 and no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 2-1, except that 89 was used. The results are shown in Table 5.

(Example 2-33)
Compound No. used in preparation of the charge transport layer coating material of Example 2-1 36 parts of a charge transporting compound having 41 chain polymerizable functional groups were added to Compound Example No. 41 (18 parts) and no. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-1, except that 72 (18 parts) was used. The results are shown in Table 5.

(Example 2-34)
Compound No. used in preparation of the charge transport layer coating material of Example 2-1 36 parts of a charge transporting compound having 41 chain polymerizable functional groups were added to Compound Example No. 41 (27 parts) and the following compound A-1 (trade name: Biscote # 540, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 9 parts, electrophotography similar to Example 2-1. A photoconductor was prepared and evaluated in the same manner. The results are shown in Table 5.

(Comparative Example 2-1)
Compound No. used in preparation of the charge transport layer coating material of Example 2-1 The charge transporting compound having 41 chain polymerizable functional groups was replaced with the charge transporting compound (H-13) having a chain polymerizable functional group shown below in the same manner as in Example 2-1. An electrophotographic photosensitive member was produced and evaluated in the same manner. The results are shown in Table 6.

(Comparative Examples 2-2 to 2-9)
The charge transporting compound (H-13) having a chain polymerizable functional group used in the preparation of the charge transport layer coating material of Comparative Example 2-1 was replaced with the charge transporting compound (H-13) having a chain polymerizable functional group shown below. -14) to (H-21), except that the electrophotographic photosensitive member was produced in the same manner as in Comparative Example 2-1, and the same evaluation was performed. The results are shown in Table 6.

(Comparative Example 2-10)
36 parts of the charge transportable compound (H-13) having a chain polymerizable functional group used in the preparation of the charge transport layer coating material of Comparative Example 2-1 was replaced with the charge transport compound having a chain polymerizable functional group shown below ( An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Comparative Example 2-1, except that 18 parts of H-22) and 18 parts of the previous compound (A-1) were used. The results are shown in Table 6.

(Comparative Example 2-11)
Comparative Example 2-10 except that the ratio of 18 parts of Compound (H-22) and 18 parts of Compound (A-1) was changed to 27 parts of Compound (H-22) and 9 parts of Compound (A-1). An electrophotographic photoreceptor was prepared in the same manner as in Example 2-10, and the same evaluation was performed. The results are shown in Table 6.

  As apparent from Tables 5 and 6, the electrophotographic photosensitive member using the charge transporting compound having a chain polymerizable functional group of the present invention for the charge transporting layer has good initial electrophotographic photosensitive member properties, and It was found that the amount of shaving during durability was small, image defects due to scratches and the like were not generated, and the potential fluctuation during durability was small, showing extremely excellent durability performance. Furthermore, it has been found that the charge transport layer obtained by curing the charge transport compound having a chain polymerizable functional group of the present invention has very good charge mobility.

(Example 1-21)
An intermediate layer and a charge generation layer were prepared in the same manner as in Example 1-1. Next, 4.0 parts of the compound (D-1) and 0.5 part of the compound (D-2) and 5.5 parts of a bisphenol Z-type polycarbonate (viscosity average molecular weight 45,000) shown below as charge transporting materials were used. Dissolved in 38 parts of monochlorobenzene to prepare a charge transport layer coating. This paint was applied onto the charge generation layer by a dip coating method and dried at 100 ° C. for 60 minutes to form a charge transport layer having a thickness of 12 μm.

Next, 1.25 parts of fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) as a dispersant was added to 1,1,2,2,3,3,4-heptafluorocyclopentane ( Trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd. 37.5 parts and 1-propanol 37.5 parts, and then tetrafluoroethylene resin powder as lubricant (trade name: Lubron L-2, Daikin) 25 parts of Kogyo Kogyo Co., Ltd. were added, and the mixture was uniformly dispersed by applying three treatments at a pressure of 600 kgf / cm ² with a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA). This was subjected to pressure filtration with a 10 μm PTFE membrane filter to prepare a lubricant dispersion. Next, Compound Example Nos. 36 parts of a charge transporting compound having 3 chain polymerizable functional groups, 16.2 parts of a lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane / 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a protective layer coating.

This protective layer coating material was applied onto the charge transport layer by a dip coating method, dried at 40 ° C. for 10 minutes, and then irradiated with an electron beam using the electron beam irradiation apparatus shown in FIG. The sample was conveyed to the lower part of the electron beam irradiation window part by a belt conveyor, stopped at the irradiation part and irradiated while rotating the sample (drum temperature at the start of irradiation was about 25 ° C.). After the irradiation is completed, it is transported again and carried outside. At this time, the effective electron beam irradiation width in the electron beam irradiation portion (in the electron beam density distribution on the sample surface, 1 / e or more of the peak position) was 4 cm. The electron beam irradiation conditions are: absorbed dose rate 2.5 × 10 ⁵ Gy / sec (absorbed dose within the effective electron beam irradiation width / time during which an arbitrary point on the sample surface exists within the effective electron beam irradiation width), The acceleration voltage was 150 KV, and the absorbed dose (total absorbed dose received by the sample in the electron beam irradiation process) was 1.5 × 10 ⁵ Gy. The time from the start to the end of electron beam irradiation was 1.5 seconds. By irradiating with an electron beam under the above conditions to cure the compound, a protective layer having a film thickness of 5 μm was formed, and further heat-treated at 150 ° C. for 1 hour to obtain an electrophotographic photoreceptor.

The electrophotographic photosensitive drum obtained above is mounted on a Hewlett-Packard Laser Jet 4300n remodeling machine (modified so that the DC component and light quantity of charging can be changed), and under normal temperature and normal humidity (23 ° C./50% RH) conditions. The charging is set so that the initial DC dark potential (Vd) becomes -650 (V) by changing the DC component and the light amount of the charging, and the laser beam having a wavelength of 780 (nm) is irradiated to this to -650 (V) The amount of light required to reduce the potential of -170 (V) (light portion potential Vl) was measured and used as sensitivity. Further, the initial characteristics were measured by setting the potential when the light amount of 20 (μJ / cm ² ) was irradiated as the residual potential (Vr). evaluated. The potential was measured by attaching a probe to the position of the developing device.

  Next, continuous 10,000 sheet passing durability was performed, and the amount of change (ΔVd, ΔVl) and scraping amount of the dark portion potential and the light portion potential immediately after the end and after the endurance were measured. The initial potential setting is the same as above, dark portion potential: -650 (V), bright portion potential: -170 (V), and the endurance pattern uses an image printed with lines of about 2 mm width every 7 mm vertically and horizontally. Paper endurance was performed.

  Furthermore, in accordance with the above durability, the ghost after the initial and after durability was also evaluated. The ghost is evaluated by arranging a 25 mm square square solid black image portion on the electrophotographic photosensitive member 1 rotation after the print image is written, and the entire halftone image (1 dot 1 space) after the second rotation of the electrophotographic photosensitive member. The image of the dot density was printed, and it was confirmed whether or not a ghost phenomenon occurred from the image sample. Image samples were each sampled at the machine development volume, F5 (center value) and F9 (thin density). The evaluation criteria are rank 1 if no ghost is visible in any mode, rank 2 if it is faint in F9, rank 3 if it is visible in any mode, and ghost is clearly visible in any mode Rank 4 was assigned. The results are shown in Table 7.

(Examples 1-22 to 1-31)
Compound Example No. used in the preparation of the charge transport layer coating material of Example 1-21 3, each of the charge transporting compounds having a chain polymerizable functional group is referred to as Compound Example No. 8, no. 9, no. 10, no. 11, no. 12, no. 17, no. 26, no. 29, no. 31 and no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1-21 except that 34 was used. The results are shown in Table 7.

(Example 1-32)
Compound Example No. used in the preparation of the protective layer coating material of Example 1-21 36 parts of a charge transporting compound having a chain polymerizable functional group of 3 is added to Compound Example No. 3 (24 parts) and Compound A-2 shown below (trade name: Kayarad TMPTA, manufactured by Nippon Kayaku Co., Ltd.) 12 parts, an electrophotographic photoreceptor in the same manner as in Example 1-21 The same evaluation was performed. The results are shown in Table 7.

(Comparative Example 1-12)
Compound Example No. used in the preparation of the protective layer coating material of Example 1-21 3 except that the charge transporting compound (3) having a chain polymerizable functional group (3) was replaced with the charge transporting compound (H-4) having a chain polymerizable functional group (1). A body was prepared and evaluated in the same manner. The results are shown in Table 8.

(Comparative Examples 1-13 to 1-18)
The charge transporting compound (H-4) having a chain polymerizable functional group used in the preparation of the protective layer coating material of Comparative Example 1-12 was replaced with the charge transporting compound (H-1) having a previous chain polymerizable functional group, Except for (H-2), (H-5), (H-7) and the charge transporting compounds (H-11) and (H-12) having the chain polymerizable functional group shown below, An electrophotographic photoreceptor was prepared in the same manner as in Comparative Example 1-12, and the same evaluation was performed. The results are shown in Table 8.

(Comparative Example 1-19)
36 parts of the charge transporting compound (H-4) having a chain polymerizable functional group used in the preparation of the protective layer coating material of Comparative Example 1-12 was replaced with the charge transporting compound (H-10) having the above chain polymerizable functional group. ) An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Comparative Example 1-12 except that 18 parts and 18 parts of the previous compound (A-2) were used. The results are shown in Table 8.

  As is apparent from Tables 7 and 8, the electrophotographic photosensitive member using the charge transporting compound having a chain polymerizable functional group of the present invention for the protective layer has, of course, good initial electrophotographic photosensitive member characteristics. It was found that the wear amount and the potential fluctuation in durability were small, the ghost was good including the initial and after durability, and extremely excellent durability performance was exhibited.

(Example 2-35)
An intermediate layer and a charge generation layer were produced in the same manner as in Example 2-1. Next, 4.5 parts of the compound (D-1) and 0.5 part of the compound (D-2) and 5.5 parts of a bisphenol Z-type polycarbonate (viscosity average molecular weight 45,000) shown below as charge transport materials Dissolved in 38 parts of monochlorobenzene to prepare a charge transport layer coating. This paint was applied onto the charge generation layer by a dip coating method and dried at 100 ° C. for 60 minutes to form a charge transport layer having a thickness of 10 μm.

Next, 1.25 parts of fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) as a dispersant was added to 1,1,2,2,3,3,4-heptafluorocyclopentane ( Trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd. 37.5 parts and 1-propanol 37.5 parts, and then tetrafluoroethylene resin powder as lubricant (trade name: Lubron L-2, Daikin) 25 parts of Kogyo Co., Ltd.) was added, and the mixture was uniformly dispersed by applying three treatments at a pressure of 600 kgf / cm ² with a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA). This was subjected to pressure filtration with a 10 μm PTFE membrane filter to prepare a lubricant dispersion. Next, Compound Example Nos. 36 parts of a charge transporting compound having 41 chain polymerizable functional groups, 16.2 parts of a lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a protective layer coating.

This protective layer coating was applied on the charge transport layer by a dip coating method, dried at 40 ° C. for 10 minutes, and then irradiated with an electron beam using the electron beam irradiation apparatus shown in FIG. The sample was conveyed to the lower part of the electron beam irradiation window part by a belt conveyor, stopped at the irradiation part and irradiated while rotating the sample (drum temperature at the start of irradiation was about 25 ° C.). After the irradiation is completed, it is transported again and carried outside. At this time, the effective electron beam irradiation width in the electron beam irradiation portion (in the electron beam density distribution on the sample surface, 1 / e or more of the peak position) was 4 cm. The electron beam irradiation conditions are: absorbed dose rate 2.5 × 10 ⁵ Gy / sec (absorbed dose within the effective electron beam irradiation width / time during which an arbitrary point on the sample surface exists within the effective electron beam irradiation width), The acceleration voltage was 150 KV, and the absorbed dose (total absorbed dose received by the sample in the electron beam irradiation process) was 2.5 × 10 ⁵ Gy. The time from the start to the end of electron beam irradiation was 1.5 seconds. By irradiating with an electron beam under the above conditions to cure the compound, a protective layer having a film thickness of 5 μm was formed and further heat-treated at 150 ° C. for 1 hour to obtain an electrophotographic photoreceptor.

The electrophotographic photosensitive drum obtained above is mounted on a Hewlett Packard Laser Jet 4300n remodeling machine (modified so that the DC component and light quantity of charging can be changed), and under normal temperature and normal humidity (23 ° C./50%) conditions, The charge is set so that the initial DC dark potential (Vd) becomes −650 (V) by changing the DC component and the amount of charge, and this is irradiated with laser light having a wavelength of 780 (nm) to −650 (V). The amount of light required to reduce the potential to -170 (V) (bright part potential Vl) was measured and used as sensitivity. Furthermore, the initial characteristics were measured and evaluated with the potential when irradiated with a light amount of 20 (μJ / cm ² ) as the residual potential (Vr). The potential was measured by attaching a probe to the position of the developing device.

  Next, continuous 10,000 sheet passing durability was performed, and the amount of change (ΔVd, ΔVl) and scraping amount of the dark portion potential and the light portion potential immediately after the end and after the endurance were measured. The initial potential setting is the same as before, dark portion potential: -650 (V), bright portion potential: -170 (V), and the endurance pattern uses an image printed with lines of about 2 mm width every 7 mm vertically and horizontally. Paper endurance was performed.

  Furthermore, in accordance with the above durability, the ghost after the initial and after durability was also evaluated. The ghost is evaluated by arranging a 25 mm square square solid black image portion on the electrophotographic photosensitive member 1 rotation after the print image is written, and the entire halftone image (1 dot 1 space) after the second rotation of the electrophotographic photosensitive member. The image of the dot density was printed, and it was confirmed whether or not a ghost phenomenon occurred from the image sample. Image samples were each sampled at the machine development volume, F5 (center value) and F9 (thin density). The evaluation criteria are rank 1 if no ghost is visible in any mode, rank 2 if it is faint in F9, rank 3 if it is visible in any mode, and ghost is clearly visible in any mode Rank 4 was assigned. The results are shown in Table 9.

(Examples 2-36 to 2-54)
Compound Example No. used in the preparation of the charge transport layer coating material of Example 2-35 The charge transporting compounds having 41 chain polymerizable functional groups were respectively referred to as Compound Example Nos. 43, no. 45, no. 50, no. 51, no. 53, no. 63, no. 68, no. 70, no. 72, no. 74, no. 83, no. 84, no. 88, no. 91, no. 92, no. 93, no. 94, no. 95 and No. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 2-35 except that 96 was used. The results are shown in Table 9.

(Example 2-55)
Compound No. used in the preparation of the protective layer coating material of Example 2-35 36 parts of a charge transporting compound having 41 chain polymerizable functional groups were added to Compound Example No. 43 (24 parts) and Compound A-2 (trade name: Kayalard TMPTA, manufactured by Nippon Kayaku Co., Ltd.) 12 parts shown below, and an electrophotographic photoreceptor in the same manner as in Example 2-35. The same evaluation was performed. The results are shown in Table 9.

(Example 2-56)
Compound No. used in the preparation of the protective layer coating material of Example 2-35 36 parts of a charge transporting compound having 41 chain polymerizable functional groups were added to Compound Example No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-35 except that 41 (24 parts) and the compound H-22 (12 parts) having a chain polymerizable functional group were used. It was. The results are shown in Table 9.

(Comparative Example 2-12)
Compound No. used in the preparation of the protective layer coating material of Example 2-35 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-35 except that the charge transporting compound having 41 chain polymerizable functional groups was replaced with the previous (H-15). . The results are shown in Table 10.

(Comparative Examples 2-13 to 2-18)
The charge transporting compound (H-15) having a chain polymerizable functional group used in the preparation of the protective layer coating material of Comparative Example 2-12 was used as the charge transporting compound (H-13) having the previous chain polymerizable functional group, Except for (H-14), (H-17), (H-20), and charge transporting compounds (H-23) and (H-24) having a chain polymerizable functional group shown below. In the same manner as in Comparative Example 2-12, an electrophotographic photosensitive member was produced and evaluated in the same manner. The results are shown in Table 10.

(Comparative Example 2-19)
36 parts of the charge transporting compound (H-13) having a chain polymerizable functional group used in the preparation of the protective layer coating material of Comparative Example 2-13 was replaced with the charge transporting compound (H-22) having the above chain polymerizable functional group. ) An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Comparative Example 2-12 except that 24 parts and 12 parts of the previous compound (A-2) were used. The results are shown in Table 10.

(Comparative Example 2-20)
Compound Example No. used in preparation of the protective layer coating material of Example 2-56 An electrophotographic photosensitive member was prepared in the same manner as in Example 2-56 except that 24 parts of the charge transporting compound having 41 chain polymerizable functional groups was replaced with the previous compound H-13 (24 parts). Evaluation was performed. The results are shown in Table 10.

  As is apparent from Tables 9 and 10, the electrophotographic photosensitive member using the charge transporting compound having a chain polymerizable functional group of the present invention for the protective layer has, of course, good initial electrophotographic photosensitive member characteristics. It was found that the wear amount and the potential fluctuation in durability were small, the ghost was good including the initial and after durability, and extremely excellent durability performance was exhibited.

(Example 1-33)
First, 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol and a silicone compound (polydimethylsiloxane polyoxyalkylene copolymer, (Average molecular weight 3000) 0.002 part, and prepared by dispersing for 2 hours in a sand mill using φ1 mm glass beads. This paint was applied on a φ30 mm aluminum cylinder 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, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare an intermediate layer coating material. This paint was applied onto the conductive layer by a dip coating method and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.5 μm.

  Next, 3 parts of an azo pigment represented by the following structural formula (P-1) and 2 parts of polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) are added to 80 parts of cyclohexanone, together with glass beads. The mixture was dispersed in a sand mill for 15 hours, and 80 parts of tetrahydrofuran was added thereto to prepare a charge generation layer coating material. This paint was applied onto the intermediate layer by a dip coating method and dried at 105 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.15 μm.

  Next, 4.5 parts of the above compound (D-1) and 5.5 parts of bisphenol Z-type polycarbonate (viscosity average molecular weight 45,000) are dissolved in 38 parts of monochlorobenzene as a charge transport material, and the charge transport layer coating material is obtained. Was prepared. This paint was applied onto the charge generation layer by a dip coating method and dried at 100 ° C. for 60 minutes to form a charge transport layer having a thickness of 15 μm.

  Subsequently, Compound Example No. 1 in Table 1 was used. After dissolving 36 parts of a charge transporting compound having 17 chain polymerizable functional groups in a mixed solvent of 24 parts of 1-propanol / 1,1,2,2,3,3,4-heptafluorocyclopentane, Pressure filtration was performed with a PTFE 0.2 μm membrane filter to prepare a protective layer coating.

This protective layer coating material was applied onto the charge transport layer by a dip coating method, dried at 40 ° C. for 10 minutes, and then irradiated with an electron beam using the electron beam irradiation apparatus shown in FIG. The sample was conveyed to the lower part of the electron beam irradiation window part by a belt conveyor, stopped at the irradiation part and irradiated while rotating the sample (drum temperature at the start of irradiation was about 25 ° C.). After the irradiation is completed, it is transported again and carried outside. At this time, the effective electron beam irradiation width in the electron beam irradiation portion (in the electron beam density distribution on the sample surface, 1 / e or more of the peak position) was 4 cm. The electron beam irradiation conditions are: absorbed dose rate 5 × 10 ⁵ Gy / sec (absorbed dose within the effective electron beam irradiation width / time during which an arbitrary point on the sample surface exists within the effective electron beam irradiation width), acceleration voltage The absorbed dose (total absorbed dose received by the sample in the electron beam irradiation process) was 5 × 10 ⁵ Gy. The time from the start to the end of electron beam irradiation was 1.5 seconds. By irradiating with an electron beam under the above conditions to cure the compound, a protective layer having a film thickness of 5 μm was formed and further heat-treated at 150 ° C. for 1 hour to obtain an electrophotographic photoreceptor.

  The obtained electrophotographic photoreceptor for electrophotography is electrophotographic characteristics in a low-temperature and low-humidity (15 ° C./10% RH) environment using a drum electrophotographic photoreceptor test apparatus (“Cynthia-59” manufactured by Gentec). Was measured.

In the measurement method, the drum electrophotographic photosensitive member was negatively charged by corona discharge while rotating at 60 rpm in the dark, and the primary current was controlled so that the potential V ₀ at the potential probe position was −700 V. Here, using a halogen lamp as a light source, it is irradiated with those monochromatic light (775 nm) with a filter, determine the amount of exposure until the surface potential is reduced to 1/2 of V _0, the half decay exposure amount E _{1 / 2} was the sensitivity. Further, after charging / exposure, a pre-exposure step for removing electricity by applying energy of 15 μJ / cm ² with a light emitting diode having a wavelength of 700 nm was performed, and the potential after this elimination was defined as a residual potential (Vr).

  Further, the above process was repeated 1000 times, and the same potential measurement was performed immediately thereafter to evaluate the stability repeatedly. Further, the same measurement was performed by changing the 60 rpm to 210 rpm. The results are shown in Table 11.

(Examples 1-34 to 1-37)
Compound Example No. used in the preparation of the charge transport layer coating material of Example 1-33 The charge transporting compounds having 17 chain polymerizable functional groups were respectively referred to as Compound Example Nos. 3, no. 26, no. 27 and no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1-33 except that 31 was used. The results are shown in Table 11.

(Comparative Examples 1-20 to 1-23)
Compound Example No. used in the preparation of the protective layer coating material of Example 1-33 The charge transporting compound having 17 chain polymerizable functional groups is converted into the charge transporting compounds (H-1), (H-2), (H-5) and (H-12) having the chain polymerizable functional group. The electrophotographic photosensitive member was produced in the same manner as in Example 1-33, except that the above evaluation was performed. The results are shown in Table 12.

  As is apparent from Tables 11 and 12, the electrophotographic photoreceptor using the charge transporting compound having a chain polymerizable functional group of the present invention for the protective layer is extremely stable and has excellent performance even when the process speed is changed. It turns out that it shows.

(Example 2-57)
First, 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol and a silicone compound (polydimethylsiloxane polyoxyalkylene copolymer, (Average molecular weight 3000) 0.002 part, and prepared by dispersing for 2 hours in a sand mill using φ1 mm glass beads. This paint was applied on a φ30 mm aluminum cylinder 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, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare an intermediate layer coating material. This paint was applied on the conductive layer by a dip coating method and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.5 μm.

  Next, 3 parts of an azo pigment represented by the following structural formula (P-1) and 2 parts of polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) are added to 80 parts of cyclohexanone, together with glass beads. The mixture was dispersed in a sand mill for 15 hours, and 80 parts of tetrahydrofuran was added thereto to prepare a charge generation layer coating material. This paint was applied onto the intermediate layer by a dip coating method and dried at 105 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.15 μm.

  Next, 4.5 parts of the above compound (D-1) and 5.5 parts of bisphenol Z-type polycarbonate (viscosity average molecular weight 45,000) are dissolved in 38 parts of monochlorobenzene as a charge transport material, and the charge transport layer coating material is obtained. Was prepared. This paint was applied onto the charge generation layer by a dip coating method and dried at 100 ° C. for 60 minutes to form a charge transport layer having a thickness of 15 μm.

  Subsequently, compound example No. of Table 2 was shown. After dissolving 36 parts of the charge transporting compound having 43 chain polymerizable functional groups in a mixed solvent of 24 parts of 1-propanol / 1,1,2,2,3,3,4-heptafluorocyclopentane, Pressure filtration was performed with a PTFE 0.2 μm membrane filter to prepare a protective layer coating.

This protective layer coating was applied on the charge transport layer by a dip coating method, dried at 40 ° C. for 10 minutes, and then irradiated with an electron beam using the electron beam irradiation apparatus shown in FIG. The sample was conveyed to the lower part of the electron beam irradiation window by a belt conveyor, stopped at the irradiation unit, and irradiated while rotating the sample (drum temperature at the start of irradiation was about 30 ° C.). After the irradiation is completed, it is transported again and carried outside. At this time, the effective electron beam irradiation width in the electron beam irradiation portion (in the electron beam density distribution on the sample surface, 1 / e or more of the peak position) was 4 cm. Electron beam irradiation conditions include absorbed dose of 2.0 × 10 ⁵ Gy / sec (absorbed dose within the effective electron beam irradiation width / time during which an arbitrary point on the sample surface exists within the effective electron beam irradiation width), acceleration The voltage was 150 KV, and the absorbed dose (total absorbed dose received by the sample in the electron beam irradiation process) was 2.0 × 10 ⁵ Gy. The time from the start to the end of electron beam irradiation was 1.5 seconds. By irradiating with an electron beam under the above conditions to cure the compound, a protective layer having a film thickness of 5 μm was formed and further heat-treated at 150 ° C. for 1 hour to obtain an electrophotographic photoreceptor.

  The obtained electrophotographic photoreceptor was measured for electrophotographic characteristics in a low-temperature and low-humidity (15 ° C./10% RH) environment using a drum electrophotographic photoreceptor testing apparatus (“Cynthia-59” manufactured by Gentec Corporation). .

In the measurement method, the drum electrophotographic photosensitive member was negatively charged by corona discharge while rotating at 60 rpm in the dark, and the primary current was controlled so that the potential V ₀ at the potential probe position was −700 V. Here, using a halogen lamp as a light source, it is irradiated with those monochromatic light (775 nm) with a filter, determine the amount of exposure until the surface potential is reduced to 1/2 of V _0, the half decay exposure amount E _{1 / 2} was the sensitivity. Further, after charging / exposure, a pre-exposure step for removing electricity by applying energy of 15 μJ / cm ² with a light emitting diode having a wavelength of 700 nm was performed, and the potential after this elimination was defined as a residual potential (Vr).

  Further, the above process was repeated 1000 times, and the same potential measurement was performed immediately thereafter to evaluate the stability repeatedly. Further, the same measurement was performed by changing the 60 rpm to 210 rpm. The results are shown in Table 13.

(Examples 2-58 to 2-61)
Compound Example No. used in the preparation of the charge transport layer coating material of Example 2-57 A charge transporting compound having a chain polymerizable functional group of 43 is respectively referred to as Compound Example No. 44, no. 45, no. 91 and no. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 2-57 except that 93 was used. The results are shown in Table 13.

(Comparative Examples 2-21 to 2-24)
Compound No. used in the preparation of the protective layer coating material of Example 2-57 The charge transporting compound having 43 chain polymerizable functional groups is converted into the charge transporting compounds (H-13), (H-14), (H-23) and (H-24) having the chain polymerizable functional group. The electrophotographic photosensitive member was produced in the same manner as in Example 2-57 except that it was replaced with (). The results are shown in Table 14.

  As is clear from Tables 13 and 14, the electrophotographic photosensitive member using the charge transporting compound having a chain polymerizable functional group of the present invention for the protective layer is extremely stable and excellent in performance even when the process speed is changed. It turns out that it shows.

It is a schematic block diagram which shows an example of the electron beam irradiation apparatus used in order to produce the electrophotographic photoreceptor of this invention. It is a schematic block diagram which shows an example of the electrophotographic apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Charging means 3 Exposure means 4 Developing means 5 Transfer means 6 Cleaning blade 7 Pre-exposure means 8 Fixing means 10 Electron beam generating part 12 Terminal 12a Filament 12b House 12c Grid 14 Accelerating tube 20 Irradiating part 22 Irradiation space 30 Irradiation window portion 32 Window foil 34 Window frame structure 100 Support member 110 Guide member L Exposure light P Transfer material

Claims (19)

In an electrophotographic photosensitive member having a conductive support and a photosensitive layer provided on the conductive support, the outermost surface layer of the electrophotographic photosensitive member has the following general formula (1-1) or (1-2): An electrophotographic photoreceptor comprising a cured product obtained by polymerizing or crosslinking a charge transporting compound having a chain polymerizable functional group represented by:

(In Formula (1-1), Ar ₁₁ and Ar ₁₂ represent an aryl group which may have a substituent, and Ar ₁₃ represents a phenyl group which may have a substituent. Ar ₁₁ and Ar ₁₂ The substituent is selected from any of an alkyl group, an alkoxy group, an aryloxy group, an aralkyl group, an aryl group or a halogen atom, and the substituent for Ar ₁₃ is selected from any of an alkyl group, an alkoxy group or a halogen atom However, at least two chain-polymerizable functional groups represented by the following general formulas (2) to (6) are present only on Ar ₁₃ or directly through an organic residue, and Ar ₁₁ and Ar ₁₂ may be the same. May be different.
In formula (1-2), Ar ₂₁ , Ar ₂₂ and Ar ₂₄ represent an aryl group which may have a substituent, and Ar ₂₁ , Ar ₂₂ and Ar ₂₄ may be the same or different. The substituent for Ar ₂₁ , Ar ₂₂ and Ar ₂₄ is selected from any of an alkyl group, an alkoxy group, an aryloxy group, an aralkyl group, an aryl group and a halogen atom. Ar ₂₃ represents a phenylene group which may have a substituent, and the substituent is selected from an alkyl group, an alkoxy group, an aryl group, and a halogen atom. Z represents a divalent organic residue, and n represents 0 or 1. However, Ar ₂₄ has at least two chain-polymerizable functional groups represented by the following general formulas (2) to (6) directly or via an organic residue.

The electrophotographic photosensitive member according to claim 1, wherein the charge transporting compound having a chain polymerizable functional group represented by the general formula (1-1) is represented by the following general formula (7):

(In the formula, Ar ₁₁ and Ar ₁₂ represent an aryl group which may have a substituent, and the substituent is selected from an alkyl group, an alkoxy group and an aryl group, and Ar ₁₁ and Ar ₁₂ may be the same. good _.R 11 _{to R 15} be different from a hydrogen atom, an alkyl group, selected from alkoxy groups or the following general formula _{(8), R} 11 _{~R 15} may be the same or different. _{However, R} 11 to R _At least two of ₁₅ are represented by the following general formula (8)).

(In the formula, X ₁₁ represents a divalent organic residue which may have a substituent, and the substituent is selected from an alkyl group, an aralkyl group, an aryl group or a halogen atom, and a is 0 or 1 represents P _11. P ₁₁ represents a chain polymerizable functional group represented by the general formulas (2) to (6). In the general formula _{(8), a = 1 X} 11 is an oxygen atom in the case _{of, -O-Z 11 - (Z} 11 is a divalent alkylene group) of claim 2 wherein the or a divalent alkylene group Electrophotographic photoreceptor. The electrophotographic photoreceptor according to claim 1, wherein the charge transporting compound having a chain polymerizable functional group represented by the general formula (1-1) is represented by the following general formula (9):

(In the formula, Ar ₁₁ and Ar ₁₂ represent an aryl group which may have a substituent, and the substituent is selected from an alkyl group, an alkoxy group and an aryl group, and Ar ₁₁ and Ar ₁₂ may be the same. X ₁₂ represents a divalent alkylene group which may have a substituent, an oxygen atom or —O—Z ₁₂ — (Z ₁₂ is a divalent alkylene group), and b = 0 or 1 R _{16 to} R ₁₈ are an aryl group which may have a substituent, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, and an aryl which may have a substituent. An oxy group, a hydrogen atom, or any one of the following general formula (8) is shown, and R _{16 to} R ₁₈ may be the same or different, and the substituents of R _{16 to} R ₁₈ include an alkyl group, an aralkyl group, and an aryl group. , Halogen atom or the following general formula (8 Selected from. _However, any of the above general formula R 16 _{to R 18} (2) ~ having at least two chain polymerizable functional group represented in (6))

(In the formula, X ₁₁ represents a divalent organic residue which may have a substituent, and the substituent is selected from an alkyl group, an aralkyl group, an aryl group or a halogen atom, and a is 0 or 1 represents P _11. P ₁₁ represents a chain polymerizable functional group represented by the general formulas (2) to (6). The electrophotographic photosensitive member according to claim 4, wherein R ₁₆ and R ₁₇ in the general formula (9) are the general formula (8). The electrophotographic photosensitive member according to claim 5, wherein in the general formula (8), a = 1 and X ₁₁ is an alkylene group. Ar ₁₁ and Ar ₁₂ of the charge transporting compound having a chain polymerizable functional group represented by the general formula (1-1), (7) or (9) may have a phenyl group which may have a substituent, Any one of a biphenyl group which may have a group or a fluorenyl group which may have a substituent, Ar ₁₁ and Ar ₁₂ may be the same or different, and a substituent for Ar ₁₁ and Ar ₁₂ is an alkyl group; The electrophotographic photosensitive member according to claim 1, which is either a group or an alkoxy group.   The electrophotographic photosensitive member according to claim 1, wherein the chain polymerizable functional group is any one of the general formulas (2) and (3). The electrophotographic photosensitive member according to claim 1, wherein the charge transport compound having a chain polymerizable functional group represented by the general formula (1-2) is represented by the following general formula (10):

(Wherein, _{Ar 21} and _{Ar 22} are the same meaning as defined in the general formula (1-2) .Z is -CH = CH _-, - either CH 2 -CH ₂ and the general formula (11) N represents 0 or 1. R _{21 to} R ₂₃ represent a hydrogen atom, an alkyl group, an alkoxy group or the following general formula (12), and R _{21 to} R ₂₃ may be the same or different. At least two of R _{21 to} R ₂₃ are represented by the following general formula (12): In general formula (11), R ₂₄ and R ₂₅ have an alkyl group which may have a substituent, and a substituent. R ₂₄ and R ₂₅ may be the same or different, and the substituent may be an alkyl group, an aralkyl group, an aryl group or a halogen atom. Selected from any of the above).

(In the formula, X ₂₁ represents a divalent organic residue which may have a substituent, and the substituent is selected from an alkyl group, an aralkyl group, an aryl group or a halogen atom, and a is 0 or 1 and P ₂₁ represents a chain polymerizable functional group represented by the general formulas (2) to (6). In the general formula _{(12), a = 1 X} 21 is an oxygen atom in the case of divalent alkylene group or _{-O-Z 21} - _(Z 21 is a divalent alkylene group) according to claim 9 which is Electrophotographic photoreceptor. The electrophotographic photosensitive member according to claim 1, wherein the charge transport compound having a chain polymerizable functional group represented by the general formula (1-2) is represented by the following general formula (13):

(Wherein, _{Ar 21} and _{Ar 22} are the same meaning as defined in the general formula (1-2) .Z is -CH = CH _-, - either CH 2 -CH ₂ and the following general formula (11) N represents 0 or 1. X ₂₂ represents a divalent organic residue, and b = 0 or 1. R _{26 to} R ₂₈ are aryl groups and substituents which may have a substituent. An alkyl group that may have a substituent, an aralkyl group that may have a substituent, an aryloxy group that may have a substituent, a hydrogen atom, or any one of the following general formula (12), R ₂₆ to R ₂₈ may be the same or different, and the substituent for R _{26 to} R ₂₈ is selected from an alkyl group, an aralkyl group, an aryl group, a halogen atom, or the following general formula (12), provided that R _{26 to} R ₂₈ Any of the chain polymerizable groups represented by the general formulas (2) to (6) Having at least two groups)

(Wherein, R ₂₄ and R ₂₅ optionally substituted alkyl group, an optionally substituted aralkyl group, an optionally substituted aryl group or a hydrogen atom, R ₂₄ And R ₂₅ may be the same or different, and the substituent is selected from an alkyl group, an aralkyl group, an aryl group, and a halogen atom)

(In the formula, X ₂₁ represents a divalent organic residue which may have a substituent, and the substituent is selected from an alkyl group, an aralkyl group, an aryl group or a halogen atom, and a is 0 or 1 and P ₂₁ represents a chain polymerizable functional group represented by the general formulas (2) to (6). In the general formula (13), when b = 1, X ₂₂ may have a divalent alkylene group, oxygen atom, or —O—Z ₂₂ — (Z ₂₂ is a divalent alkylene group). The electrophotographic photosensitive member according to claim 11. The electrophotographic photoreceptor according to claim 11, wherein R ₂₆ and R _{27 represented} by the general formula (13) are the general formula (12). The electrophotographic photosensitive member according to claim 13, wherein in the general formula (12), a = 1 and X ₂₁ is an alkylene group. Ar ₂₁ and Ar ₂₂ of the charge transporting compound having a chain polymerizable functional group represented by the general formula (1-2), (10) or (13) may be the same or different and have a substituent. Any of a phenyl group which may be substituted, a biphenyl group which may have a substituent or a fluorenyl group which may have a substituent, and the substituent of Ar ₂₁ and Ar ₂₂ is either an alkyl group or an alkoxy group The electrophotographic photosensitive member according to any one of claims 1 and 9 to 14.   The electrophotographic photosensitive member according to claim 1, wherein the chain-polymerizable functional group is any one of the general formulas (2) and (3).   The electrophotographic photosensitive member according to claim 1, wherein the outermost surface layer of the electrophotographic photosensitive member is cured by an electron beam.   18. The electrophotographic photosensitive member according to claim 1, charging means for charging the electrophotographic photosensitive member, developing means for developing the electrophotographic photosensitive member on which an electrostatic latent image is formed, and a transfer step A process cartridge characterized in that it integrally supports at least one means selected from the group consisting of cleaning means for collecting toner remaining on a later electrophotographic photosensitive member, and is detachable from the electrophotographic apparatus main body. . An electrophotographic photosensitive member according to any one of claims 1 to 17, a charging unit for charging the electrophotographic photosensitive member, an exposure unit for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, An electrophotographic apparatus comprising: a developing unit that develops toner on an electrophotographic photosensitive member on which a latent image is formed; and a transfer unit that transfers a toner image on the electrophotographic photosensitive member onto a transfer material.

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