JP4115055B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.
[0002]
[Prior art]
Conventionally, inorganic materials such as selenium, cadmium sulfide and zinc oxide have been known as photoconductive materials used for electrophotographic photoreceptors. On the other hand, polyvinylcarbazole, phthalocyanine, and azo pigments, which are organic materials, are attracting attention for advantages such as high productivity and non-pollution, and tend to be inferior in terms of photoconductive properties and durability compared to inorganic materials. , Has come to be widely used. These electrophotographic photoreceptors are often used as function-separated photoreceptors in which a charge generation layer and a charge transport layer are laminated in order to satisfy both electrical and mechanical properties. On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process. In particular, in the case of a photoreceptor to be used repeatedly, the surface of the photoreceptor is directly subjected to electrical and mechanical external forces such as charging, image exposure, toner development, transfer to paper, and cleaning treatment, so that the durability against them is increased. Sex is required. Specifically, durability against surface wear and scratches caused by rubbing, surface deterioration due to charging (for example, transfer efficiency and slipperiness decrease), durability against deterioration of electrical characteristics such as sensitivity reduction and potential reduction. Is also required.
[0003]
In general, the surface of the 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, high durability of the photoreceptor. It is difficult to say that the coating film hardness of the resin is sufficiently high in order to measure the conversion. 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 transport materials are often added in relatively large amounts. In this case, due to the plasticizer action of these low molecular weight materials. The film strength is remarkably lowered, and the surface layer is worn and scratched during repeated use. Further, when the electrophotographic photosensitive member is stored for a long period of time, the above-mentioned low molecular weight component is precipitated, resulting in a problem of layer separation.
[0004]
As means for solving these problems, an attempt to use a curable resin as a resin for a charge transport layer is disclosed in, for example, JP-A-2-127852. 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 if 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, the charge transport layer composed of an organic charge transport material and a binder resin has a large dependence on the charge transport ability of the resin. For example, a curable resin with sufficiently high hardness does not have sufficient charge transport ability and is used repeatedly. At the same time, the residual potential has been increased, and both have not been satisfied. In JP-A-5-216249 and JP-A-7-72640, etc., the charge transfer layer contains a monomer having a carbon-carbon double bond, and the carbon-carbon double bond of the charge transfer material and heat or light. An electrophotographic photosensitive member in which a charge transfer layer cured film is formed by reacting with the energy of the above is disclosed, but the charge transport material is only immobilized in a pendant form on the polymer main skeleton, The mechanical strength is not sufficient because the action cannot be sufficiently eliminated. Further, if the concentration of the charge transport material is increased to improve the charge transport capability, the crosslink density is decreased and sufficient mechanical strength cannot be ensured. Furthermore, there is a concern about the influence of initiators required during polymerization on the electrophotographic characteristics.
[0005]
As another solution, for example, JP-A-8-248649 discloses an electrophotographic photoreceptor in which a charge transporting layer is formed by introducing a group having a charge transporting ability into a thermoplastic polymer main chain. Compared with the conventional molecular dispersion type charge transport layer, it is effective for precipitation and layer separation and improves mechanical strength, but it is a thermoplastic resin, and its mechanical strength is limited. It is difficult to say that it is sufficient in terms of handling and productivity including the solubility of the resin.
[0006]
As described above, the conventional systems have not achieved both high mechanical strength and charge transport ability.
[0007]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member that has high film strength to improve wear resistance and scratch resistance and that has good precipitation resistance.
[0008]
Another object of the present invention is to provide stable and excellent potential characteristics regardless of repeated use and environmental fluctuations, to provide good image quality without image defects such as fogging, and for transfer memories and photo memories. An extremely small and excellent electrophotographic photosensitive member, and a process cartridge and an electrophotographic apparatus using the same are provided.
[0009]
[Means for Solving the Problems]
  The present invention relates to a conductive support.And the conductive supportaboveProvidedIn an electrophotographic photoreceptor having a photosensitive layer,
TheElectronic photographyThe outermost surface layer of the photoconductor heats a hole transporting compound having two or more chain polymerizable functional groups in the same molecule.orContains compounds polymerized by ultraviolet light,
TheThe amount of heat generated by differential scanning calorimetry of the outermost layer is,60 mJ / mg or less
An electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0011]
First, the chain polymerizable functional group in the present invention will be described. The chain polymerization in the present invention refers to the former polymerization reaction mode when the polymer compound formation reaction is largely divided into chain polymerization and sequential polymerization. For details, see, for example, “Chemical Chemistry of Basic Synthetic Resins” by Giho Tadahiro Miho. (New Edition) ”July 25, 1995 (1 edition, 8 prints) As described in FIG. 24, the form mainly refers to unsaturated polymerization, ring-opening polymerization, isomerization polymerization, etc. in which the reaction proceeds via an intermediate such as a radical or ion. Chain-polymerizable functional group P in the general formula (1)¹ And P² Means a functional group capable of the above-described reaction form, and here, a specific example of an unsaturated polymerization or ring-opening polymerizable functional group that occupies most of the functional group and has a wide application range.
[0012]
Unsaturated polymerization is a reaction in which unsaturated groups such as C═C, C≡C, C═O, C═N, and C≡N are polymerized by radicals, ions, etc., but mainly C═C. It is. Specific examples of the unsaturated polymerizable functional group are shown in Table 1, but are not limited thereto.
[0013]
[Table 1]
[0014]
Ring-opening polymerization means that unstable cyclic structures with distortions such as carbocycles, oxo rings, and nitrogen heterocycles are activated by the action of a catalyst, and at the same time, the polymerization is repeated to produce a chain polymer. In this case, most of the reactions basically have ions acting as active species. Specific examples of the ring-opening polymerizable functional group are shown in Table 2, but are not limited thereto.
[0015]
[Table 2]
[0016]
In the table, R represents an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent, an aralkyl group such as a benzyl group, a phenethyl group and a naphthylmethyl group which may have a substituent. Represents an aryl group such as a phenyl group, a naphthyl group, an anthryl group and a pyrenyl group which may have a substituent, or a hydrogen atom.
[0017]
Among the chain polymerizable functional groups according to the present invention as described above, those represented by the following general formulas (11) to (13) are preferable.
[0018]
Embedded image
(In the formula, E has a hydrogen atom, a fluorine atom, a halogen atom such as a chlorine atom and a bromine atom, an optionally substituted alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, and a substituent. Aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group, phenyl group, naphthyl group, anthryl group, pyrenyl group, thiophenyl group and furyl group which may have a substituent Aryl groups, CN groups, nitro groups, methoxy groups, ethoxy groups, propoxy groups and other alkoxy groups, -COOR²⁶Or CONR²⁷R²⁸Indicates.
[0019]
W is an alkylene group such as methylene, ethylene and butylene which may have a substituent, an arylene group such as phenylene, naphthylene and anthracenylene which may have a substituent, -COO-, -CH₂ -, -O-, -OO-, -S- or -CONR²⁹-Is shown.
[0020]
R²⁶~ R²⁹Is a hydrogen atom, a fluorine atom, a halogen atom such as a chlorine atom and a bromine atom, an alkyl group such as an optionally substituted methyl group, an ethyl group and a propyl group, an optionally substituted benzyl group and An aralkyl group such as a phenethyl group or an aryl group such as a phenyl group, a naphthyl group and an anthryl group which may have a substituent;²⁷And R²⁸May be the same or different. F represents 0 or 1. )
The substituents that may be present in E and W include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group; cyano group; hydroxyl group; methyl group, ethyl group, propyl group and butyl group Alkyl groups such as methoxy groups, ethoxy groups and propoxy groups; aryloxy groups such as phenoxy groups and naphthoxy groups; aralkyl groups such as benzyl groups, phenethyl groups, naphthylmethyl groups, furfuryl groups and thienyl groups; and Examples thereof include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group.
[0021]
Embedded image
(Wherein R³⁰And R³¹Has a hydrogen atom, an alkyl group such as an optionally substituted methyl group, an ethyl group, a propyl group and a butyl group, an aralkyl group such as an optionally substituted benzyl group and a phenethyl group, or a substituent. And an aryl group such as a phenyl group and a naphthyl group, and n represents an integer of 1 to 10. )
[0022]
Embedded image
(Wherein R³²And R³³Has a hydrogen atom, an alkyl group such as an optionally substituted methyl group, an ethyl group, a propyl group and a butyl group, an aralkyl group such as an optionally substituted benzyl group and a phenethyl group, or a substituent. And an aryl group such as a phenyl group and a naphthyl group, and n represents 0 or an integer of 1 to 10. )
In the general formulas (12) and (13), R³⁰~ R³³The substituent that may have a halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl group such as methyl group, ethyl group, propyl group and butyl group; methoxy group, ethoxy group and propoxy group Alkoxy groups such as phenoxy and naphthoxy groups; aralkyl groups such as benzyl, phenethyl, naphthylmethyl, furfuryl and thienyl; and phenyl, naphthyl, anthryl and pyrenyl An aryl group etc. are mentioned.
[0023]
Among general formulas (11) to (13), particularly preferred chain polymerizable functional groups include those represented by the following structural formulas (14) to (20).
[0024]
Embedded image
[0025]
Furthermore, among the structural formulas (14) to (20), the acryloyloxy group (14) and the methacryloyloxy group (15) are particularly preferable from the viewpoint of polymerization characteristics and the like.
[0026]
Next, the hole transporting substance in the present invention will be described.
[0027]
In the present invention, “a hole transporting compound having a chain polymerizable functional group” means that the chain polymerizable group described above is preferably chemically bonded as a functional group to the hole transporting compound described below as a functional group. Compound. In this case, all the chain polymerizable functional groups may be the same or different.
[0028]
The hole transporting compound having at least two of these chain polymerizable functional groups is preferably the following general formula (1).
[0029]
Embedded image
(In the formula, A represents a hole transporting group; P¹ And P² Represents a chain polymerizable functional group; P¹ And P² May be the same or different; Z represents an organic group which may have a substituent; a, b and d represent 0 or an integer of 1 or more, and a + b × d represents an integer of 2 or more; , A is 2 or more P¹ May be the same or different, and when d is 2 or more, P² May be the same or different, and when b is 2 or more, Z and P² May be the same or different. )
[0030]
In general formula (1), “when a is 2 or more P¹ May be the same or different ”means that n different types of chain-polymerizable functional groups are different from each other.¹¹, P¹², P¹³, P¹⁴, P¹⁵.... P¹ⁿFor example, when a = 3, the polymerizable functional group P directly bonded to the hole transporting group A¹ Are the same for all three, but the same for two but one for different (eg P¹¹And P¹¹And P¹²However, each of the three is different (for example, P¹²And P¹⁵And P¹⁷Or the like) (If “d is 2 or more, P² May be the same or different ”because“ when b is 2 or more, Z and P² "May be the same or different" means the same thing).
[0031]
A in the general formula (1) represents a hole transporting group, and any group may be used as long as it exhibits hole transportability.¹ And a hydrogenation compound (hole transporting compound) in which the bonding site to Z is replaced with a hydrogen atom, for example, triarylamine derivatives such as oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine, 9- (P-diethylaminostyryl) anthracene, 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, Examples thereof include benzimidazole derivatives, thiophene derivatives, and N-phenylcarbazole derivatives.
[0032]
Furthermore, among the above hole transport compounds, the compounds represented by the following general formulas (2), (3), (4), (5) and (7), and the condensation having a group represented by the following general formula (8) A condensed heterocyclic ring having a ring hydrocarbon and a group represented by the following general formula (8) is preferred. Among these, the compounds represented by the following general formulas (2), (3) and (4) are particularly preferable.
[0033]
Embedded image
In general formula (2), R¹ ~ R^Three Is an alkyl group having 10 or less carbon atoms such as an optionally substituted methyl group, ethyl group, propyl group and butyl group, an optionally substituted benzyl group, phenethyl group, naphthylmethyl group, furfuryl group. And a phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenol group, which may have an aralkyl group or a substituent such as thienyl group An aryl group such as a thiazinyl group, a benzofuryl group and a benzothiophenyl group is shown.
[0034]
However, R¹ ~ R^Three At least two of them represent an aryl group, and R¹ ~ R^Three May be the same or different.
[0035]
Furthermore, among them, R¹ ~ R^Three Those in which all are aryl groups are particularly preferred.
[0036]
In addition, R in the general formula (2)¹ ~ R^Three Any two of them may be bonded directly or via a bonding group, such as an alkylene group such as methylene, ethylene and propylene, a hetero atom such as an oxygen atom and a sulfur atom, and CH═CH. Groups and the like.
[0037]
Embedded image
In general formula (3), R^Four , R^Five , R⁸ And R⁹ Is an alkyl group having 10 or less carbon atoms such as an optionally substituted methyl group, ethyl group, propyl group and butyl group, an optionally substituted benzyl group, phenethyl group, naphthylmethyl group, furfuryl group. And a phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenol group, which may have an aralkyl group or a substituent such as thienyl group An aryl group such as a thiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, and a dibenzothiophenyl group;^Four , R^Five , R⁸ And R⁹ May be the same or different. R⁶ And R⁷ Is an alkylene group having 10 or less carbon atoms such as an optionally substituted methylene group, an ethylene group and a propylene group, or an arylene group which may have a substituent (benzene, naphthalene, anthracene, phenanthrene, pyrene group, A group obtained by removing two hydrogen atoms from thiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran and dibenzothiophene)⁶ And R⁷ May be the same or different. Q represents an organic group which may have a substituent.
[0038]
Furthermore, among them, R^Four , R^Five , R⁸ And R⁹ Two or more of them are optionally substituted aryl groups, and R⁶ And R⁷ Is preferably an arylene group which may have a substituent, and further R^Four , R^Five , R⁸ And R⁹ It is particularly preferred that all four are aryl groups which may have a substituent. R^Four , R^Five And R⁶ Any two of R or R⁷ , R⁸ And R⁹ Any two of them may be bonded directly or via a bonding group, such as alkylene groups such as methylene, ethylene and propylene, heteroatoms such as oxygen and sulfur atoms, and CH═CH groups. Etc.
[0039]
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In general formula (4), m¹ Represents 0 or 1, m¹ = 1, preferably R^Ten~ R¹³Is an alkyl group having 10 or less carbon atoms such as an optionally substituted methyl group, ethyl group, propyl group and butyl group, an optionally substituted benzyl group, phenethyl group, naphthylmethyl group, furfuryl group. And a phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenol group, which may have an aralkyl group or a substituent such as thienyl group An aryl group such as a thiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, and a dibenzothiophenyl group;^Ten~ R¹³May be the same or different.
[0040]
Ar¹ May be substituted arylene groups (from benzene, naphthalene, anthracene, phenanthrene, pyrene group, thiophene, furan, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. A group in which one hydrogen atom has been removed), Ar² Is m¹ In the case of = 0, phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenothiazinyl group, which may have a substituent, An aryl group such as a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group and a dibenzothiophenyl group;¹ = 1 for Ar¹ And the same arylene group. M¹ = 1 if Ar¹ And Ar² May be the same or different.
[0041]
Furthermore, among them, R^TenAnd R¹¹Is preferably an aryl group which may have a substituent, R^Ten~ R¹³It is particularly preferred that all four are aryl groups. R^TenAnd R¹¹, R¹²And R¹³And Ar¹ And Ar² May be bonded directly or via a bonding group, and examples of the bonding group include alkylene groups such as methylene, ethylene and propylene, heteroatoms such as oxygen and sulfur atoms, and CH═CH groups.
[0042]
Embedded image
[0043]
However, in the general formula (5), Ar^Three , Ar^Four And R¹⁴At least one of them has one or more substituents of the following general formula (6).
[0044]
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[0045]
In the general formulas (5) and (6), Ar^Three ~ Ar^Five May have a phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenothiazinyl group, benzofuryl group, benzo An aryl group such as a thiophenyl group, a dibenzofuryl group, and a dibenzothiophenyl group, and R¹⁴~ R¹⁶Is an alkyl group having 10 or less carbon atoms such as an optionally substituted methyl group, ethyl group, propyl group and butyl group, an optionally substituted benzyl group, phenethyl group, naphthylmethyl group, furfuryl group. And an aralkyl group such as a thienyl group, an optionally substituted phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenol An aryl group such as a thiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group and a dibenzothiophenyl group, or a hydrogen atom (provided that R¹⁴Except when is a hydrogen atom). Ar^Three And Ar^Four And R¹⁵And R¹⁶May be the same or different.
[0046]
Furthermore, among them, R¹⁴And R¹⁶Is particularly preferably an aryl group.
[0047]
R¹⁴, Ar^Three And Ar^Four Any two of them, or Ar^Five And R¹⁶May be bonded directly or via a bonding group, and examples of the bonding group include alkylene groups such as methylene, ethylene and propylene, heteroatoms such as oxygen and sulfur atoms, and CH═CH groups. n¹ Represents an integer of 0 or 1-2.
[0048]
Embedded image
[0049]
However, in the general formula (7), Ar⁶ , R¹⁷And R¹⁸At least one of them has one or more substituents of the following general formula (8).
[0050]
Embedded image
[0051]
In the general formulas (7) and (8), Ar⁶ And Ar⁷ May have a phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenothiazinyl group, benzofuryl group, benzo An aryl group such as a thiophenyl group, a dibenzofuryl group, and a dibenzothiophenyl group, and R¹⁷~ R²⁰Is an alkyl group having 10 or less carbon atoms such as an optionally substituted methyl group, ethyl group, propyl group and butyl group, an optionally substituted benzyl group, phenethyl group, naphthylmethyl group, furfuryl group. And an aralkyl group such as a thienyl group, an optionally substituted phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenol An aryl group such as a thiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group and a dibenzothiophenyl group, or a hydrogen atom (provided that R¹⁷And R¹⁸Except when is a hydrogen atom). R¹⁷And R¹⁸And R¹⁹And R²⁰May be the same or different.
[0052]
Among them, R²⁰Is preferably an aryl group, and further R¹⁷And R¹⁸Is particularly preferably an aryl group.
[0053]
R¹⁷, R¹⁸And Ar⁶ Any two of them, or Ar⁷ And R²⁰May be bonded directly or via a bonding group, and examples of the bonding group include alkylene groups such as methylene, ethylene and propylene, heteroatoms such as oxygen and sulfur atoms, and CH═CH groups. n² Represents an integer of 0 or 1-2. Further, the compound having the group represented by the general formula (8) may have a substituent, such as naphthalene, anthracene, phenanthrene, perene, fluorene, fluoranthene, azulene, indene, perylene, chrysene, coronene, etc. And condensed heterocyclic rings such as benzofuran, indole, carbazole, benzcarbazole, acridine, phenothiazine and quinoline, each of which may have a substituent.
[0054]
Z in the general formula (1) and Q in the general formula (3) are an alkylene group which may have a substituent, an arylene group which may have a substituent, CR^{twenty one}= CR^{twenty two}(R^{twenty one}And R^{twenty two}Represents an alkyl group, an aryl group or a hydrogen atom, R^{twenty one}And R^{twenty two}May be the same or different), C = O, S = O, SO₂ And an organic group in which one or any combination of oxygen and sulfur atoms is present. Among them, those represented by the following general formula (9) are preferable, and those represented by the following general formula (10) are particularly preferable.
[0055]
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[0056]
In the general formula (9), X¹ ~ X^Three Is an alkylene group having 20 or less carbon atoms such as methylene group, ethylene group and propylene group which may have a substituent, (CR^{twenty three}= CR^{twenty four}) M² , C = O, S = O, SO₂ Represents an oxygen atom or a sulfur atom, Ar⁸ And Ar⁹ Is an arylene group which may have a substituent (from benzene, naphthalene, anthracene, phenanthrene, pyrene group, thiophene, pyridine, furan, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. Group from which a single hydrogen atom has been removed). R^{twenty three}And R^{twenty four}Represents an alkyl group such as an optionally substituted methyl group, ethyl group or propyl group, an aryl group such as an optionally substituted phenyl group, naphthyl group or thiophenyl group, or a hydrogen atom; R^{twenty three}And R^{twenty four}May be the same or different. m² Represents an integer of 1 to 5, and pt represents 0 or an integer of 1 to 10 (provided that pt is not simultaneously 0).
[0057]
In the general formula (10), X^Four And X^Five Is (CH₂ ) M^Three , (CH = CR^{twenty five}) M^Four , C = O or an oxygen atom, Ar^TenIs an arylene group which may have a substituent (2 from benzene, naphthalene, anthracene, phenanthrene, pyrene group, thiophene, furan, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. Group from which a single hydrogen atom has been removed). R^{twenty five}Represents an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aryl group such as a phenyl group, a naphthyl group and a thiophenyl group which may have a substituent, or a hydrogen atom. m^Three Is an integer from 1 to 10, m^Four Represents an integer of 1 to 5, and u to w represent 0 or an integer of 1 to 10 (in particular, 0 or an integer of 1 to 5 is preferred, provided that u to w are not 0 at the same time).
[0058]
In the above general formulas (3) to (13), R^Four ~ R³³, Ar¹ ~ Ar^Ten, X¹ ~ X^Five , Z and Q each may have a halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group; cyano group; hydroxyl group; methyl group, ethyl group, propyl group and butyl group Alkyl groups such as methoxy groups, ethoxy groups and propoxy groups; aryloxy groups such as phenoxy groups and naphthoxy groups; aralkyl groups such as benzyl groups, phenethyl groups, naphthylmethyl groups, furfuryl groups and thienyl groups; phenyl And aryl groups such as a group, a naphthyl group, an anthryl group and a pyrenyl group. Further, R in the general formula (2)¹ ~ R^Three Examples of the substituent which may have include the above-mentioned substituents excluding an aryl group and diarylamino groups such as a diphenylamino group and a di (p-tolyl) amino group.
[0059]
The hole transporting compound having two or more chain polymerizable functional groups in the same molecule in the present invention preferably has an oxidation potential of 1.2 (v) or less. That is, the hole transporting compound having a chain polymerizable functional group represented by the general formula (1) and the hydrogenated product of the hole transporting group A may have an oxidation potential of 1.2 (v) or less. It is particularly preferable that it is 0.4 to 1.2 (v). The problem is that when the oxidation potential exceeds 1.2 (v), injection of charges (holes) from the charge generating material is difficult to occur, the residual potential is increased, the sensitivity is lowered, and the potential fluctuation during repeated use increases. In addition to problems such as a decrease in charging ability, if the compound is less than 0.4 (v), the compound itself is easily oxidized and easily deteriorates, resulting in reduced sensitivity, image blur and repeated use. This is because a problem such as a large potential fluctuation occurs.
[0060]
The oxidation potential described here is measured by the following method.
[0061]
(Measurement method of oxidation potential)
Saturated calomel electrode as reference electrode and 0.1N (n-Bu) as electrolyte_Four N⁺ ClO_Four ^-Using an acetonitrile solution, the potential applied to the working electrode (platinum) was swept by a potential sweeper, and the potential when the obtained current-potential curve showed a peak was defined as an oxidation potential. Specifically, the sample is 0.1N (n-Bu)_Four N⁺ ClO_Four ^-Dissolve in acetonitrile solution to a concentration of about 5-10 mmol%. Then, a voltage is applied to the sample solution by the working electrode, and a current change when the voltage is linearly changed from a low potential (0 v) to a high potential (+1.5 v) is measured to obtain a current-potential curve. In this current-potential curve, the potential at the peak top position when the current value showed a peak (or the first peak when there are a plurality of peaks) was defined as the oxidation potential.
[0062]
Furthermore, the hole transporting compound having the chain polymerizable functional group has a hole transporting ability of 1 × 10^-7(Cm² / V · sec) or more is preferable (provided that the applied electric field: 5 × 10^Four v / cm). 1 × 10^-7(Cm² If it is less than / v · sec), holes may not move sufficiently between the post-exposure development and the electrophotographic photosensitive member, so that the apparent sensitivity may be reduced and the residual potential may be increased.
[0063]
Hereinafter, typical examples of the hole transporting compound having a chain polymerizable functional group according to the present invention are shown in Table 3, but the invention is not limited thereto.
[0064]
Table 3: Specific examples of hole transporting compounds having a chain polymerizable functional group
[0065]
[Table 3]
[0066]
[Table 4]
[0067]
[Table 5]
[0068]
[Table 6]
[0069]
[Table 7]
[0070]
[Table 8]
[0071]
[Table 9]
[0072]
[Table 10]
[0073]
[Table 11]
[0074]
[Table 12]
[0075]
[Table 13]
[0076]
[Table 14]
[0077]
[Table 15]
[0078]
[Table 16]
[0079]
[Table 17]
[0080]
[Table 18]
[0081]
[Table 19]
[0082]
[Table 20]
[0083]
[Table 21]
[0084]
[Table 22]
[0085]
[Table 23]
[0086]
[Table 24]
[0087]
[Table 25]
[0088]
[Table 26]
[0089]
[Table 27]
[0090]
[Table 28]
[0091]
[Table 29]
[0092]
[Table 30]
[0093]
[Table 31]
[0094]
[Table 32]
[0095]
[Table 33]
[0096]
[Table 34]
[0097]
[Table 35]
[0098]
[Table 36]
[0099]
[Table 37]
[0100]
[Table 38]
[0101]
[Table 39]
[0102]
[Table 40]
[0103]
[Table 41]
[0104]
[Table 42]
[0105]
[Table 43]
[0106]
[Table 44]
[0107]
[Table 45]
[0108]
[Table 46]
[0109]
[Table 47]
[0110]
[Table 48]
[0111]
[Table 49]
[0112]
[Table 50]
[0113]
[Table 51]
[0114]
[Table 52]
[0115]
[Table 53]
[0116]
[Table 54]
[0117]
[Table 55]
[0118]
[Table 56]
[0119]
[Table 57]
[0120]
[Table 58]
[0121]
[Table 59]
[0122]
[Table 60]
[0123]
[Table 61]
[0124]
[Table 62]
[0125]
[Table 63]
[0126]
[Table 64]
[0127]
[Table 65]
[0128]
[Table 66]
[0129]
[Table 67]
[0130]
[Table 68]
[0131]
[Table 69]
[0132]
[Table 70]
[0133]
[Table 71]
[0134]
[Table 72]
[0135]
[Table 73]
[0136]
[Table 74]
[0137]
[Table 75]
[0138]
[Table 76]
[0139]
[Table 77]
[0140]
[Table 78]
[0141]
[Table 79]
[0142]
[Table 80]
[0143]
[Table 81]
[0144]
[Table 82]
[0145]
[Table 83]
[0146]
[Table 84]
[0147]
[Table 85]
[0148]
[Table 86]
[0149]
[Table 87]
[0150]
[Table 88]
[0151]
[Table 89]
[0152]
[Table 90]
[0153]
[Table 91]
[0154]
A typical method for synthesizing a hole transporting compound having a chain polymerizable functional group in the present invention is shown below.
[0155]
(Synthesis Example 1: Synthesis of Compound No. 6)
Synthesized according to the following route.
[0156]
Embedded image
[0157]
1 (50 g: 0.47 mol), 2 (406 g: 1.4 mol), anhydrous potassium carbonate (193 g) and copper powder (445 g) were heated and stirred at 180-190 ° C. with 1.2 kg of 1,2-dichlorobenzene. Went for hours. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was subjected to column purification using a silica gel column to obtain 132 g of 3.
[0158]
3 (120 g: 0.28 mol) was added to 1.5 kg of methyl cellosolve, and sodium methylate (150 g) was slowly added with stirring at room temperature. After completion of the addition, the mixture was stirred as it was at room temperature for 1 hour, and further heated and stirred at 70 to 80 ° C. for 10 hours. The reaction solution was poured into water, neutralized with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified using a silica gel column to obtain 78 g of 4.
[0159]
4 (70 g: 0.2 mol) and triethylamine (40 g: 0.4 mol) were added to 400 ml of dry THF and cooled to 0-5 ° C., and then acryloyl chloride (55 g: 0.6 mol) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature and 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 using a silica gel column to obtain 42 g of 5 (Compound No. 6).
[0160]
(Synthesis Example 2: Synthesis of Compound No. 71)
4 (10 g: 29 mmol) obtained in Synthesis Example 1 was added to 50 ml of dry THF, and after cooling to 0 to 5 ° C., 3.5 g of oily sodium hydride (about 60%) was slowly added. After completion of the addition, the mixture was returned to room temperature, stirred for 1 hour, cooled again to 0 to 5 ° C., and allyl bromide (17.5 g: 145 mmol) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour and then returned to room temperature and further stirred for 5 hours. The reaction solution was poured into water, neutralized, extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was subjected to column purification using a silica gel column to obtain 5.6 g of the target compound (Compound No. 71).
[0161]
(Synthesis Example 3: Synthesis of Compound No. 55)
Compound No. obtained in Synthesis Example 2 above. 7 13.0 g was dissolved in 20 ml of dichloromethane and then cooled to 0 to 5 ° C., 5.2 g of m-chloroperbenzoic acid (˜70%) was slowly added and stirred as it was for 1 hour, then returned to room temperature and stirred for 12 hours. . The reaction solution was poured into water and extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was subjected to column purification using a silica gel column to obtain 2.1 g of the target compound (Compound No. 55).
[0162]
(Synthesis Example 4: Synthesis of Compound No. 152)
Synthesized according to the following route.
[0163]
Embedded image
[0164]
1 (70 g: 0.35 mol),2(98 g: 0.42 mol), anhydrous potassium carbonate (73 g) and copper powder (111 g) were heated and stirred at 180 to 190 ° C. for 10 hours together with 600 g of 1,2-dichlorobenzene. After the reaction solution was filtered, the solvent was removed under reduced pressure, and the residue was subjected to column purification using a silica gel column to obtain 86.2 g of 3.
[0165]
3 (80 g: 0.26 mol) was added to 300 g of N, N-dimethylformamide, and ethanethiol sodium salt (about 90%: 62 g) was slowly added with stirring at room temperature. After completion of the addition, the mixture was stirred at room temperature for 1 hour, and further heated and stirred under reflux for 3 hours. After cooling, the reaction solution is poured into water, made weakly acidic with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer is further extracted with 1.2M aqueous sodium hydroxide solution, the aqueous layer is made acidic with dilute hydrochloric acid, and extracted with ethyl acetate. After drying with sodium sulfate, the solvent was removed under reduced pressure. The residue was purified using a silica gel column to obtain 64 g of 4.
[0166]
4 (60 g: 0.21 mol) was added to 300 g of N, N-dimethylformamide, and caustic soda (8.3 g) was slowly added while stirring at room temperature. After completion of the addition, the mixture was stirred at room temperature for 30 minutes, and 1,2-diiodoethane (31.7 g: 0.1 mol) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 30 minutes, and further heated and stirred at 70 ° C. for 5 hours. The reaction solution was poured into water and extracted with toluene. The organic layer was further washed with water and dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified using a silica gel column to obtain 49.1 g of 5.
[0167]
After cooling 182 g of DMF to 0 to 5 ° C., 63.6 g of phosphorus oxychloride was slowly added dropwise so as not to exceed 10 ° C. After stirring for 15 minutes after completion of dropping,5(42.2 g: 0.07 mol) / 102 g of DMF was slowly added dropwise. After completion of dropping, the mixture was stirred as it was for 30 minutes, then returned to room temperature, stirred for 2 hours, further heated to 80 to 85 ° C. and stirred for 15 hours. The reaction solution was poured into 1.5 kg of about 15% aqueous sodium acetate solution and stirred for 12 hours. After neutralization, extraction was performed using toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was subjected to column purification using a silica gel column to obtain 23 g of 6.
[0168]
To a place where 0.89 g of lithium aluminum hydride was added to 100 ml of dry THF and stirred at room temperature, a solution of 6 (15 g: 0.023 mol) / 100 ml of dry THF was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 4 hours, and 200 ml of 5% hydrochloric acid aqueous solution was slowly added dropwise. After completion of dropping, the mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was purified using a silica gel column to obtain 13.6 g of 7.
[0169]
7 (10 g: 0.015 mol) and triethylamine (6.1 g: 0.06 mol) were added to 120 ml of dry THF and cooled to 0-5 ° C., and then acryloyl chloride (4.1 g: 0.045 mol) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature and stirred at room temperature for 6 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 subjected to column purification using a silica gel column to obtain 6.4 g of 8 (Compound No. 152) (oxidation potential: 0.88 v).
[0170]
(Synthesis Example 5: Synthesis of Compound No. 263)
Synthesized according to the following route.
[0171]
Embedded image
[0172]
1 (50 g: 0.123 mol), 2 (62.4 g: 0.369 mol), anhydrous potassium carbonate (25.5 g) and copper powder (32 g) with 200 g of 1,2-dichlorobenzene heated and stirred at 180 to 190 ° C. For 18 hours. After the reaction solution was filtered, the solvent was removed under reduced pressure, and the residue was recrystallized twice with a toluene / methanol mixed solvent to obtain 60.2 g of 3.
[0173]
After cooling 242 g of DMF to 0 to 5 ° C., phosphorus oxychloride (84.8 g: 553.2 mmol) was slowly added dropwise so as not to exceed 10 ° C. After stirring for 15 minutes after completion of the dropwise addition, a 3 (45.0 g: 92.2 mmol) / 135 g DMF solution was slowly added dropwise. After completion of dropping, the mixture was stirred as it was for 30 minutes, then returned to room temperature, stirred for 2 hours, further heated to 80 to 85 ° C. and stirred for 8 hours. The reaction solution was poured into 2.5 kg of about 15% sodium acetate aqueous solution and stirred for 12 hours. After neutralization, extraction was performed using toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was subjected to column purification using a silica gel column to obtain 40.5 g of 4.
[0174]
To a place where 0.89 g of lithium aluminum hydride was added to 100 ml of dry THF and stirred at room temperature, a solution of 4 (37 g: 68 mmol) / 600 ml of dry THF was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 4 hours, and 500 ml of 5% hydrochloric acid aqueous solution was slowly added dropwise. After completion of dropping, the mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was subjected to column purification using a silica gel column to obtain 26.3 g of 5.
[0175]
5 (20 g: 36 mmol) and triethylamine (12.8 g: 126 mol) were added to 130 ml of dry THF and cooled to 0-5 ° C., and then acryloyl chloride (9.8 g: 108 mmol) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature and stirred at room temperature for 6 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 using a silica gel column to obtain 11.2 g of 6 (Compound No. 263) (oxidation potential: 0.80 v).
[0176]
In the present invention, by polymerizing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule, at least two or more compounds having a hole transporting ability are contained in the photosensitive layer. Are incorporated into a three-dimensional crosslinked structure via a covalent bond. The hole transporting compound can be polymerized / crosslinked only, or can be 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 hole 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 both have a three-dimensional cross-linked copolymer structure via a covalent bond. Is possible. When the functional groups of the two are functional groups that do not polymerize with each other, the photosensitive layer is a mixture of at least two or more three-dimensional cured products or other chain polymerizable compound monomers in the three-dimensional cured product of the main component. Although it is comprised as what contains the hardened | cured material, it is also possible to form IPN (Inter Penetrating Network), ie, an interpenetrating network structure, by controlling the compounding ratio / film forming method well.
[0177]
The photosensitive layer may be formed from a monomer or oligomer / polymer having a polymerizable group other than the chain polymerizable functional group of the hole transporting compound.
[0178]
Further, in some cases, it is possible to contain a hole transporting compound that is not chemically bonded to the three-dimensional crosslinked structure, that is, does not have a chain polymerizable functional group.
[0179]
Further, other various additives and a lubricant such as fluorine atom-containing resin fine particles may be contained.
[0180]
The structure of the photoreceptor of the present invention is a structure in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated in this order as a photosensitive layer on a conductive support.
[0181]
The charge transport layer contains a compound obtained by polymerizing and curing the hole transport compound having the chain polymerizable functional group, and the thickness of the charge transport layer is preferably 1 to 50 μm, preferably 5 to 30 μm. In particular, when used as a second charge transport layer described later, the thickness of the protective layer is preferably 1 to 20 μm, particularly preferably 1 to 6 μm.
[0182]
Next, a method for producing an electrophotographic photoreceptor according to the present invention will be specifically described.
[0183]
The electrophotographic photosensitive member may be any support as long as it has conductivity. For example, aluminum, copper, chromium, nickel, zinc, stainless steel, or a metal or alloy formed into a drum or sheet, aluminum, copper, etc. Metal foil laminated with plastic film, aluminum, indium oxide and tin oxide deposited on plastic film, metal with conductive layer applied alone or with binder resin, and plastic film And paper.
[0184]
In the present invention, an undercoat layer having a barrier function and an adhesive function can be provided on the conductive support.
[0185]
The undercoat layer is used to improve the adhesion of the photosensitive layer, improve the coatability, protect the support, cover defects on the support, improve the charge injection from the support, and protect against electrical breakdown of the photosensitive layer. Formed. 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, gelatin, etc. Is mentioned. 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.
[0186]
The photoreceptor of the present invention is a function separation type photoreceptor in which a charge generation layer and a charge transport layer are laminated. Examples of the charge generation material used in 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, plantron pigments, trisazo pigments, disazo pigments, monoazo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments, quinocyanines, and JP-A No. 54-143645 Examples thereof include amorphous silicone.
[0187]
The charge generation layer is well dispersed by a method such as homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor and roll mill together with the above-mentioned charge generation material 0.3 to 4 times the amount of binder resin and solvent. The dispersion is applied and dried, or formed as a single composition film such as a vapor-deposited film of the charge generating material. The film thickness is preferably 5 μm or less, and particularly preferably 0.1 to 2 μm.
[0188]
Examples of using binder resins are polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, trifluoroethylene, polyvinyl alcohol, polyvinyl Examples include acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin.
[0189]
The compound obtained by polymerizing the hole-transporting compound having the chain-polymerizable functional group in the present invention has a chain-polymerizable functional group as a charge-transporting material for the charge-transporting layer on the charge-generating layer or on the charge-generating layer. It can be used as the second charge transport layer after forming a charge transport layer composed of a charge transport material and a binder resin which are not present. In either case, the surface layer is generally formed by applying a solution containing the hole transporting compound and then polymerizing the surface layer, but by reacting a solution containing the hole transporting compound in advance. It is also possible to form a surface layer using a material obtained by dispersing or dissolving in a solvent after obtaining a cured product. 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.
[0190]
In the present invention, the hole transporting compound having a chain polymerizable group can be polymerized by heat or light. Therefore, the formation of the photosensitive layer in the present invention includes forming the hole-transporting compound having the chain polymerizable group and, if necessary, the polymerization initiator into the coating solution for the photosensitive layer, and using the coating solution. The hole transporting compound having the chain polymerizable group is polymerized by irradiating the coated film with heat or light.
[0191]
When performing the polymerization reaction with heat, the polymerization reaction may proceed only with thermal energy or a polymerization initiator may be required, but in order to proceed the reaction efficiently at a lower temperature, the polymerization start It is preferable to add an agent.
[0192]
The polymerization initiator used in this case is not particularly limited as long as it has a half-life at room temperature or higher. Specifically, ammonium persulfate, dicumyl peroxide, benzoyl peroxide, cyclohexane peroxide, t-butyl hydroperoxide. Examples thereof include peroxides such as oxide and di-t-butyl peroxide, and azo compounds such as azobisbutyronitrile. The addition amount is about 0.01 to 10 parts by mass with respect to 100 parts by mass of the compound having a chain polymerizable group, and the temperature of the reaction system can be appropriately selected between room temperature and 200 ° C. depending on the initiator.
[0193]
When performing the polymerization reaction with light, it is preferable to use ultraviolet rays as the light. In addition, when light is used, it is very rare that the reaction proceeds with only light energy, and a photopolymerization initiator is generally used in combination.
[0194]
In this case, the polymerization initiator mainly refers to those that absorb ultraviolet rays having a wavelength of 400 nm or less to generate active species such as radicals and ions and initiate polymerization, and specific examples thereof include acetophenone, benzoin, Radical polymerization initiators such as benzophenone and thioxanthone, and ion polymerization initiators such as diazonium compounds, sulfonium compounds, iodonium compounds and metal complex compounds. In recent years, however, polymerization initiators that absorb light in the infrared / visible region at wavelengths of 400 nm or more to generate the above active species have been announced, and their use is also possible. The addition amount of the initiator is about 0.01 to 50 parts by mass with respect to 100 parts by mass of the compound having a chain polymerizable group.
[0195]
In the present invention, the aforementioned heat and photopolymerization initiators can be used in combination.
[0196]
The amount of the hole transporting compound when the hole transporting compound having a chain polymerizable group is used in the charge transporting layer is the above general formula (1) with respect to the total mass of the charge transporting layer film after polymerization. The hydrogen adduct of the hole transporting group A having a chain polymerizable functional group represented by () is preferably 20% or more, more preferably 40% or more in terms of molecular weight. 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.
[0197]
When the hole transporting compound is used as the second charge transport 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 polystyryl. Heterocycles such as anthracene and polymer compounds having condensed polycyclic aromatics, heterocyclic compounds such as pyrazoline, imidazole, oxazole, triazole and carbazole, triarylalkane derivatives such as triphenylmethane, and triaryls such as triphenylamine Low molecular weight compounds such as amine derivatives, phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives and hydrazone derivatives are dispersed / dissolved in a solvent together with an appropriate binder resin (which can be selected from the aforementioned resin for charge generation layer). Apply the solution by the above-mentioned known method and dry it. It is possible to form Te. In this case, the ratio of the charge transport material to the binder resin is preferably 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 30, the charge transport ability is lowered, and problems such as a decrease in sensitivity and an increase in residual potential occur.
[0198]
As described above, a charge transport layer obtained by polymerizing and curing a hole transport compound having a chain polymerizable functional group has a calorific value of 60 mJ / mg or less when differential thermal analysis is performed by the following method. Is particularly preferable, and it is preferably 40 mJ / mg or less. This exotherm is presumed to be mainly due to the reaction of unreacted chain polymerizable groups in the charge transport layer, but this calorific value is not only the wear resistance of the photoreceptor, but also the potential due to repeated use and environmental changes. It has been found that there is a significant correlation between fluctuations and various memories such as transfer memory and photo memory, and that the above values exhibit very good characteristics.
[0199]
(Differential scanning calorimetry measurement method)
The charge transport layer of the photoconductor drum was evenly scraped from the outermost surface without biasing to a specific depth component, and this was ground with a mortar or the like to obtain small uniform particles. Samples were taken from arbitrary three locations on the photosensitive drum, measured by the following method, and the average of the three points was taken as the calorific value of the present invention.
[0200]
In differential scanning calorimetry, several mg of the sample collected as described above was uniformly placed in the bottom of an aluminum container, and the lid was crimped to prepare a measurement sample. Similarly, a reference was made by crimping a lid on an aluminum container containing nothing. These were set in a differential scanning calorimeter, heated at 10 ° C. per minute, and heated at 500 ° C. for 50 minutes. (To control the atmosphere around the sample, 50 ml of nitrogen gas was used during the measurement. / Min). The exothermic peak appearing at this time was measured, and the calorific value was determined from the exothermic peak area.
[0201]
Various additives can be added to the photosensitive layer in the present invention. Examples of the additive include deterioration inhibitors such as antioxidants and ultraviolet absorbers, and lubricants such as fluorine atom-containing resin fine particles.
[0202]
FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention. In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven in the direction of an arrow at a predetermined peripheral speed without stopping the shaft 2. In the rotating process, the photosensitive member 1 is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the primary charging unit 3, and then an image from an image exposure unit (not shown) such as slit exposure or laser beam scanning exposure. Exposure light 4 is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the photoreceptor 1. The formed electrostatic latent image is then developed with toner by the developing unit 5, and the developed toner developed image is rotated between the photosensitive member 1 and the transfer unit 6 from a sheet feeding unit (not shown). The image is sequentially transferred by the transfer means 6 to the transfer material 7 that is synchronously taken out and fed. The transfer material 7 that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means 8, and subjected to image fixing, thereby being printed out as a copy (copy). After the image transfer, the surface of the photoreceptor 1 is cleaned by removing the transfer residual toner by the cleaning unit 9 and further subjected to charge removal processing by the pre-exposure light 10 from the pre-exposure unit (not shown), and then repeatedly. Used for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary. In the present invention, a plurality of components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9 described above are integrally coupled as a process cartridge. May be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photosensitive member 1 to form a cartridge, and can be attached to and detached from the apparatus main body using guide means such as a rail 12 of the apparatus main body. The process cartridge 11 can be obtained. In addition, when the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 is a reflected light or transmitted light from a document, or a signal is read by a sensor and converted into a signal, and laser beam scanning performed according to this signal is performed. Light emitted by driving the LED array, driving the liquid crystal shutter array, or the like.
[0203]
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.
[0204]
【Example】
Hereinafter, the present invention will be described with reference to examples. In the examples, “part” means part by mass.
[0205]
Example 1
First, the coating material for conductive layers was prepared by the following procedure. 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 silicone compound (polydimethylsiloxane polyoxyalkylene copolymer, average 0.002 part of molecular weight 3000) was prepared by dispersing for 2 hours in a sand mill using φ1 mm glass beads. This paint was applied on a 30φ aluminum cylinder by a dip coating method and dried at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 18 μm.
[0206]
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.
[0207]
3 parts of oxytitanium phthalocyanine having strong peaks at 9.0 degrees, 14.2, 23.9 degrees, and 27.1 degrees of black angle 2θ ± 0.2 degrees in X-ray diffraction of CuKα, polyvinyl butyral Disperse 4.0 parts of name S REC BM2, manufactured by Sekisui Chemical Co., Ltd. and 35 parts of cyclohexanone for 15 hours in a sand mill using φ1 mm glass beads, and then add 60 parts of ethyl acetate to form a coating for the charge generation layer Was prepared. This paint was applied onto the intermediate layer by a dip coating method and dried at 90 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.2 μm.
[0208]
Next, Compound Example Nos. 60 parts of the hole transporting compound 6 and the following structural formula (A)
[0209]
Embedded image
A photopolymerization initiator (0.6 part) was dissolved in a mixed solvent of 30 parts of monochlorobenzene and 30 parts of dichloromethane to prepare a coating material for a charge transport layer. This paint is applied on the charge generation layer by a dip coating method, and 300 mW / cm using a metal halide lamp.² Was cured for 30 seconds at a light intensity of 1 to form a charge transport layer having a film thickness of 17 μm to obtain an electrophotographic photosensitive member.
[0210]
This photoconductor is mounted on a modified machine of a laser beam printer (Laser Writer 16 / 600PS: manufactured by Apple), and the initial dark potential (Vd) at normal temperature and humidity (23 ° C., 55% RH) (N / N). Is set to be −700 (V), and the amount of light necessary to irradiate the laser beam with a wavelength of 780 (nm) to lower the potential of −700 (V) to −200 (V) ( EΔ₅₀₀ ) Was measured as sensitivity. Furthermore, 20 (μJ / cm² The initial characteristics were measured by setting the potential when the light amount of) was irradiated as the residual potential (Vr). The other conditions were as follows: transfer current: +5.5 μA, process speed: 96 mm / sec.
[0211]
Thereafter, the environment was changed to high temperature and high humidity (32 ° C., 85% RH) (H / H), and the amount of fluctuation (ΔVl) of the initial bright part potential (Vl) from normal temperature and normal humidity was measured.
[0212]
Next, an electrophotographic photosensitive member newly produced by the same method as described above is mounted on a remodeling machine similar to the above, and continuous 5000 sheets are obtained under normal temperature and low humidity (23 ° C., 10% RH) (N / L). A paper passing durability test was performed, and the amount of variation ΔVd between the dark part potential and the light part potential immediately after the end and the durability¹ And ΔVl¹ Was measured. Further, the amount of abrasion of the photoconductor was measured using an eddy current film thickness measuring instrument (Permascope Type E111, manufactured by FISCHER).
[0213]
Furthermore, the transfer memory and photo memory were measured as follows.
[0214]
The transfer memory is measured by mounting a newly prepared electrophotographic photosensitive member in the same manner as described above on a remodeling machine similar to the above, and using N / N, the primary charging potential when the transfer current is OFF is Vd.² The primary charging potential when the transfer current is ON is Vd^Three As | Vd² -Vd^Three | Was measured.
[0215]
Furthermore, as a photo memory measurement for white light, an electrophotographic photosensitive member newly produced by the same method as described above is mounted on a remodeling machine similar to the above, and the initial dark portion potential (Vd) / initial bright portion is N / N. The charge and image exposure light quantity are set so that the potential (Vl) is -700 (V) /-200 (V), and then the electrophotographic photosensitive member is masked so that dark portions and bright portions are formed, and fluorescent light is emitted. After irradiating light at 3000 Lux under a lamp for 20 minutes, the sample was left for 5 minutes, and the potential was measured in the same manner, and the absolute value (ΔVd^Four ) Was measured as a photo memory.
[0216]
Further, the charge transport layer portion of the electrophotographic photosensitive member produced in the same manner as described above was sampled by the method described above, and differential scanning calorimetry was performed.
[0217]
Each result is shown in Table 4-1.
[0218]
(Examples 2-17, Comparative Examples 1-11)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the hole-transporting compound of Example 1 and the light intensity of ultraviolet rays were changed as shown in Tables 4-1 and 4-2. The results are shown in Tables 4-1 and 4-2.
[0219]
(Examples 18 to 34, Comparative Examples 12 to 22)
The photopolymerization initiator (A) in Example 1 is represented by the following structural formula (B)
[0220]
Embedded image
Example 1 except that the thermal polymerization initiator was a thermosetting at 140 ° C. for 1 hour instead of UV curing, and the hole transporting compound and the curing temperature were changed as shown in Tables 4-1 and 4-2. An electrophotographic photoreceptor was prepared and evaluated in the same manner as described above. The results are shown in Tables 4-1 and 4-2.
[0221]
(Comparative Example 23)
After forming up to the charge generation layer in Example 1, the triarylamine compound (C) having the following structural formula
[0222]
Embedded image
Charge is formed on the charge generation layer using a coating for a charge transport layer prepared by dissolving 20 parts and 10 parts of polycarbonate resin Z type (average molecular weight 20,000) in a mixed solvent of 50 parts of monochlorobenzene and 20 parts of dichloromethane. A transport layer was formed to obtain a photoreceptor. At this time, the thickness of the charge transport layer was 18 μm. This photoreceptor was evaluated in the same manner as in Example 1, and the results are shown in Table 4-2.
[0223]
(Comparative Example 24)
The following styryl compound (D) was used as the charge transport compound of Comparative Example 21.
[0224]
Embedded image
A photoconductor was prepared in the same manner as in Comparative Example 21 except that it was changed to, and the same evaluation was performed. The results are shown in Table 4-2.
[0225]
(Comparative Example 25)
After forming up to the charge generation layer in Example 1, polycarbonate resin (E) having the following structural formula synthesized according to the production method described on pages 10 to 11 of JP-A-8-248649
[0226]
Embedded image
A charge transport layer was formed on the charge generation layer using a charge transport layer coating prepared by dissolving 20 parts in 80 parts of tetrahydrofuran. At this time, the thickness of the charge transport layer was 18 μm. This electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 4-2.
[0227]
As is apparent from Tables 4-1 and 4-2, the photoconductor of the present invention has high sensitivity and low residual potential, has very little potential fluctuation in various environments, and has stable characteristics. Further, it is clear that transfer memory, photo memory, and the like are extremely small and exhibit excellent characteristics. These characteristics are correlated with the calorific value of the differential scanning calorimetry of the charge transport layer, and it is clear that the calorific value is good when it is 60 mJ / mg or less, and particularly good when it is 40 mJ / mg or less. It is.
[0228]
(Example 35)
First, the coating material for conductive layers was prepared by the following procedure. 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 silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average 0.002 part of molecular weight 3000) was prepared by dispersing for 2 hours in a sand mill using φ1 mm glass beads. This paint was applied on a 30φ aluminum cylinder by a dip coating method and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.
[0229]
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 0.65 μm.
[0230]
Next, the following bisazo pigment
[0231]
Embedded image
5 parts, 2 parts of polyvinyl butyral resin and 60 parts of dichlorohexanone were dispersed for 24 hours in a sand mill using φ1 mm glass beads, and 60 parts of tetrahydrofuran was further 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 100 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.25 μm.
[0232]
Next, Compound Example Nos. A charge transport layer coating material was prepared by dissolving 60 parts of the H.263 hole transporting compound in a mixed solvent of 50 parts of monochlorobenzene and 30 parts of dichloromethane, and this paint was applied on the charge generation layer by the dip coating method. 400 mW / cm using a metal halide lamp² Was cured for 30 seconds at a light intensity of 1 to form a charge transport layer having a thickness of 13 μm to obtain an electrophotographic photosensitive member.
[0233]
The electrophotographic photoreceptor thus prepared was mounted on a Canon printer LBP-2000 equipped with a pulse modulation device, and the following image evaluation was performed.
[0234]
(Evaluation of dot and character reproducibility)
A dark part potential Vd = −650 V and a bright part potential Vl = −200 V were set, and a 1-dot 1-space image and a character (5-point) image were output.
[0235]
(Ghost evaluation)
At normal temperature and humidity (23 ° C, 55% RH) (N / N), an appropriate character pattern was printed for one round of the drum in the initial stage, and then a halftone image was taken on the entire surface to check whether a ghost phenomenon occurred. . Next, the following endurance pattern was continuously printed on 2000 sheets, and after the endurance test, an entire halftone image was taken to confirm whether or not a ghost phenomenon occurred.
[0236]
The durable pattern was printed with a line having a width of about 2 mm every 7 mm. The image sample was an entire black image and an image having a dot density of one dot and one space, and was sampled with a development volume of the machine, F5 (center value) and F9 (thin density), respectively.
[0237]
Evaluation criteria are rank 5 when ghost is not visible, rank 4 when visible with 1 dot 1 space F9, rank 3 when visible with 1 dot 1 space F5, rank 2 when visible with full black F9, rank 2 with full black F5 The ones that can be seen are ranked 1.
[0238]
Further, the differential transport calorific value was measured by sampling the charge transport layer portion of the electrophotographic photosensitive member prepared in the same manner as described above.
[0239]
The results are shown in Table 5 below.
[0240]
(Examples 36 to 42, Comparative Examples 26 to 30)
An electrophotographic photoreceptor was prepared in the same manner as in Example 35 except that the irradiation doses of the hole transporting compound and ultraviolet rays in Example 35 were changed as shown in Table 5, and evaluated in the same manner. The results are shown in Table 5.
[0241]
(Comparative Example 31)
After forming up to the charge generation layer in Example 35, a charge transport layer was formed in exactly the same formulation as in Comparative Example 23 (however, the film thickness was 13 μm) to produce an electrophotographic photosensitive member. Evaluated. The results are shown in Table 5.
[0242]
(Comparative Example 32)
After forming up to the charge generation layer in Example 35, a charge transport layer was formed in exactly the same formulation as in Comparative Example 25 (however, the film thickness was 13 μm) to produce an electrophotographic photosensitive member. Evaluated. The results are shown in Table 5.
[0243]
(Examples 43 to 50, Comparative Examples 33 to 37)
The photopolymerization initiator (A) in Example 35 was replaced with the thermal polymerization initiator of the structural formula (B), and heat curing was performed at 140 ° C. for 1 hour instead of UV curing, and the hole transporting compound and the curing temperature were expressed. An electrophotographic photosensitive member was produced in the same manner as in Example 35 except that the amount was changed as in 5, and evaluated in the same manner. The results are shown in Table 5.
[0244]
[Table 92]
[0245]
[Table 93]
[0246]
[Table 94]
[0247]
[Table 95]
[0248]
[Table 96]
[0249]
From these results, it can be seen that the photoconductor of the present invention is excellent in dot reproducibility and character reproducibility and can provide a high-resolution output image. Moreover, a clear image having no defects was stably obtained. These results correlate with the calorific value of differential scanning calorimetry of the charge transport layer, and it is clear that the calorific value is good when it is 60 mJ / mg or less, and particularly good when it is 40 mJ / mg or less. .
[0250]
【The invention's effect】
The electrophotographic photosensitive member of the present invention, and the process cartridge and the electrophotographic apparatus having the electrophotographic photosensitive member are not only excellent in abrasion resistance, but also stably excellent regardless of repeated use and environmental fluctuations. It shows potential characteristics, and the memory such as transfer memory and photo memory is small, and it is possible to give good image quality without image defects such as fog.
[Brief description of the drawings]
FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.

Claims (26)

In an electrophotographic photosensitive member having a conductive support and a photosensitive layer provided on the conductive support ,
The outermost layer of the electrophotographic photosensitive member, a hole-transporting compound having two or more chain polymerizable functional groups in the same molecule heat also contains a compound polymerized by ultraviolet radiation,
An electrophotographic photosensitive member the amount of heat generated by the differential scanning calorimetry of the outermost surface layer, characterized in that it is 60 mJ / mg or less. The electrophotographic photosensitive member according to claim 1 , wherein a calorific value of the outermost surface layer in differential scanning calorimetry is 40 mJ / mg or less. The chain-polymerizable hole transporting compound having a functional group, an electrophotographic photosensitive member according to 2 claim 1 or a compound represented by the following general formula (1).
(In general formula (1) , A represents a hole transporting group . P ¹ and P ² represent a chain polymerizable functional group . P ¹ and P ² may be the same or different . Z represents a substituent . . a, b and d also showing a good organic group having 0 or is an integer of 1 or more, a + b × d represents an integer of 2 or more. in addition, P ¹ when a is 2 or more in the same And may be different. When d is 2 or more, P ² may be the same or different. When b is 2 or more, Z and P ² may be the same or different. Of A in the general formula (1), a hole transporting compound binding sites was replaced by a hydrogen atom of the binding site and A and Z of the A and P ¹ is a compound represented by the following general formula (2) A compound represented by the following general formula (3), a compound represented by the following general formula (4), a compound represented by the following general formula (5), a compound represented by the following general formula (7), a condensed ring hydrocarbon, And a condensed heterocyclic ring (provided that the compound represented by the following general formula (7), the condensed ring hydrocarbon, and the condensed heterocyclic ring have one or more substituents of the following general formula (8)). The electrophotographic photosensitive member according to claim 3 , which is at least one selected from the group consisting of:
(Shown in the general formula (2), R ¹ ~R ³ is an alkyl group which may have a substituent, also aralkyl group which may have a substituent an aryl group which may have a substituent. ^However, it shows at least two of the aryl group of R 1 to R ^3. in ^addition, R 1 to R ³ may be the be the same or different.)
(In General Formula (3), R ⁴ , R ⁵ , R ⁸ and R ⁹ may have an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Represents an aryl group, and R ⁴ , R ⁵ , R ⁸ and R ⁹ may be the same or different, and R ⁶ and R ⁷ have an alkylene group or a substituent which may have a substituent. R ⁶ and R ⁷ may be the same or different, and Q represents an organic group which may have a substituent.
(In General Formula (4), R ^{10 to} R ¹³ represent an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or an aryl group that may have a substituent, and R ¹⁰ to R ¹³ is .Ar ¹ and Ar ² may be different even in the same represents an arylene group which may have a substituent, Ar ¹ and Ar ² be different even in the same Good, m ¹ represents 0 or 1.)
(In General Formula (5), Ar ³ and Ar ⁴ represent an aryl group which may have a substituent, and Ar ³ and Ar ⁴ may be the same or different. R ¹⁴ represents a substituent. An alkyl group that may have, an aralkyl group that may have a substituent, or an aryl group that may have a substituent, provided that at least one of Ar ³ , Ar ^4, and R ¹⁴ is It has a substituent represented by general formula (6).
(In general formula (6), Ar ⁵ represents an aryl group which may have a substituent. R ¹⁵ and R ¹⁶ represent an alkyl group which may have a substituent, and an aralkyl which may have a substituent. A group, an aryl group which may have a substituent, or a hydrogen atom, R ¹⁵ and R ¹⁶ may be the same or different, and n ¹ represents an integer of 0 to 2. )
(In General Formula (7), Ar ⁶ represents an aryl group which may have a substituent. R ¹⁷ and R ¹⁸ represent an alkyl group which may have a substituent, and an aralkyl which may have a substituent. An aryl group which may have a group or a substituent, and R ¹⁷ and R ¹⁸ may be the same or different.)
(In the general formula (8), Ar ⁷ represents an aryl group which may have a substituent. R ¹⁹ and R ²⁰ represent an alkyl group which may have a substituent and an aralkyl which may have a substituent. A group, an aryl group which may have a substituent, or a hydrogen atom, R ¹⁹ and R ²⁰ may be the same or different, and n ² represents an integer of 0 to 2. ) Formula (1) Z or Formula in (3) Q in is an optionally substituted alkylene group, an arylene group which may have a substituent ^{group, CR} 21 ⁼ CR 22 (R and R ²² represents an alkyl group which may have a substituent group, an optionally substituted aryl group or also represents a hydrogen atom, R ²¹ and R ²² may be different even in the same. ), C = O, S = O, SO 2, according to claim 3 or 4 of one selected from the group consisting of an oxygen atom and a sulfur atom, or two or more are combined to become an organic group Electrophotographic photoreceptor. Formula (1) Z or Formula in (3) Q in the electrophotographic photosensitive member according to any one of claims 3-5 is a group represented by the following general formula (9).
(In the general formula (9) , Ar ⁸ and Ar ⁹ represent an arylene which may have a substituent, and X ^{1 to} X ³ represent an alkylene group which may have a substituent, (CR ²³ = CR ²⁴ ). _{m2, C = O, S =} O, SO 2, oxygen atom or represents a sulfur atom ^{.R 23} and ^{R 24} represents an alkyl group which may have a substituent group, an optionally substituted aryl group or Represents a hydrogen atom, and R ²³ and R ²⁴ may be the same or different, m2 represents an integer of 1 to 5, and p , q, r, s, and t represent an integer of 0 to 10. , P , q, r, s, and t are not 0 at the same time.) Formula (1) Z or Formula in (3) Q in the electrophotographic photosensitive member according to any one of claims 3-5 is a group represented by the following general formula (10).
(In the general formula (10), ^{Ar 10} is .X ⁴ and ^{X 5} represents an arylene group which may have a substituent ^{_{(CH 2) m3, (CH}} = CR 25) m4, C = O or oxygen .R ²⁵ indicating the atom alkyl group which may have a substituent group, an optionally substituted aryl group or also represents a hydrogen atom .u, v and w is an integer of 0-10. However , U , v, and w are not 0 at the same time.) The electrophotographic photosensitive member according to claim 4, wherein R ^{1 to} R ³ in the general formula (2) are aryl groups which may have a substituent. Are two or more optionally substituted aryl group of ^{R 4,} R 5, ^{R 8} and ^{R 9} in the general formula (3), ^{R 6} and ^{R 7} have a substituent The electrophotographic photosensitive member according to claim 4 , which may be an arylene group. ^{R 4,} R 5, ^{R 8} and electrophotographic photosensitive member according to claim 9 ^{R 9} are both an aryl group which may have a substituent in the general formula (3). The electrophotographic photosensitive member according to claim 4 , wherein R ¹⁰ and R ¹¹ in the general formula (4) are aryl groups which may have a substituent. The electrophotographic photoreceptor according to claim 11, wherein m ¹ in the general formula (4) is 1, and R ^{10 to} R ¹³ are aryl groups which may have a substituent. The electrophotographic photoreceptor according to claim 4 , wherein R ¹⁴ in the general formula (5) is an aryl group which may have a substituent. The electrophotographic photosensitive member according to claim 13, wherein R ¹⁶ in the general formula (6) is an aryl group which may have a substituent. The electrophotographic photosensitive member according to claim 4 , wherein R ¹⁷ and R ¹⁸ in the general formula (7) are aryl groups which may have a substituent. The electrophotographic photoreceptor according to claim 15, wherein R ²⁰ in the general formula (8) is an aryl group which may have a substituent. Both one or of the chain polymerizable functional groups P ¹ and P ^2, the electrophotographic photosensitive member according to any one of claims 3-16 which is an unsaturated polymerizable functional group represented by the following general formula (11) .
(In the general formula (11), E is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, a cyano group, a nitro group, an alkoxy group, -COOR ²⁶ (R ²⁶ is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aralkyl group or also denotes an aryl group which may have a substituent.) or - CONR ²⁷ R ²⁸ (R ²⁷ and R ²⁸ are a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or an aryl group that may have a substituent. R ²⁷ and R ²⁸ may be the same or different . ) And W represents an alkylene group which may have a substituent, an arylene group which may have a substituent, —COO— _{, -CH 2 -, - O -} , - OO -, - S - or -CONR 29 - ^{(R 29} is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, also aralkyl group which may have a substituent an aryl group which may have a substituent show .f that shows.) is 0 or represents 1.) Both said one or chain polymerizable functional groups P ¹ and P ^2, the electrophotographic photosensitive member according to any one of claims 3-16 which is a cyclic ether group represented by the following general formula (12).
(In the general formula (12), R ³⁰ and R ³¹ are a hydrogen atom, an optionally substituted alkyl group, the aralkyl group or may have a substituent an optionally substituted aryl group And n represents an integer of 1 to 10.) Both said one or chain polymerizable functional groups P ¹ and P ^2, the electrophotographic photosensitive member according to any one of claims 3-16 which is an alicyclic epoxy group represented by the following general formula (13).
(In the general formula (13), R ³² and R ³³ are a hydrogen atom, an optionally substituted alkyl group, also aralkyl group which may have a substituent an optionally substituted aryl group And n represents an integer of 0 to 10.) Both one or of the chain polymerizable functional groups ^{P 1} and ^{P 2,} electrophotography according to any one of claims 3-16 is a group represented by any one of the following structural formulas (14) - (20) Photoconductor.
Electrophotographic according to any of the claims 3-20 oxidation potential of the hole transporting compound is 0.4 to 1.2 (V) having two or more chain polymerizable functional groups in the same molecule Photoconductor. The electrophotographic photosensitive member according to any one of claims 1 to 21 , wherein the temperature of the heat is 50C to 250C. The electrophotographic photosensitive member according to any one of claims 1 to 21 light intensity of the ultraviolet rays is 1000 mW / cm ² or less. The electrophotographic photosensitive member according to any one of claims 1 to 21 and 23 the irradiation time of the ultraviolet rays is not more than 120 seconds. An electrophotographic photosensitive member according to any one of claims 1 to 24 charging unit, and at least one means selected from the group consisting of the developing means and cleaning means integrally supported, detachably attached to an electrophotographic apparatus main body Process cartridge characterized by being. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to any one of claims 1 to 24 , a charging unit, an exposure unit, a developing unit, and a transfer unit.