JP4136238B2 - 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, a process cartridge, and an electrophotographic apparatus, and more particularly, to an electrophotographic photosensitive member having a specific hole transport compound in a photosensitive layer, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.
[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.
[0003]
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. 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.
[0004]
In particular, in an electrophotographic photosensitive member that is repeatedly used, electrical and mechanical external forces such as charging, image exposure, toner development, transfer to paper, and cleaning are directly applied to the surface of the electrophotographic photosensitive member. Therefore, durability against them is required. Specifically, durability against surface wear and scratches caused by rubbing, surface deterioration due to charging (for example, transfer efficiency and slipperiness drop), durability against deterioration of electrical characteristics such as sensitivity reduction and potential drop. Is also required.
[0005]
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. However, not all of the above-mentioned characteristics are satisfied with these resins, and in particular, electrophotographic photosensitive resins. It is difficult to say that the coating film hardness of the resin is sufficiently high in order to increase the durability of the body. 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.
[0006]
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 a relatively large amount. 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 damaged when repeatedly used. 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.
[0007]
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, Japanese Patent Application Laid-Open No. 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, since the low molecular weight component acts as a plasticizer in the binder resin, it is not a fundamental solution to the problems of precipitation and layer separation as described above.
[0008]
In addition, in the charge transport layer composed of the organic charge transport material 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 JP-A-5-216249, JP-A-7-72640 and the like, a monomer having a carbon-carbon double bond is contained in the charge transfer layer, and the carbon-carbon double bond and heat of the charge transfer material are added. Alternatively, an electrophotographic photosensitive member in which a charge transfer layer cured film is formed by reacting with light energy is disclosed, but the charge transport material is simply fixed in a pendant form on the polymer main skeleton, and the above-mentioned plastic The mechanical strength is not sufficient because the mechanical action cannot be sufficiently eliminated. In addition, if the concentration of the charge transport material is increased to improve the charge transport capability, the crosslink density is lowered and sufficient mechanical strength cannot be ensured. Furthermore, there is a concern about the influence of the initiators required during polymerization on the electrophotographic characteristics.
[0009]
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. However, compared with conventional molecular dispersion type charge transport layer, it is effective for precipitation and layer separation, and mechanical strength is improved, 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 resin solubility.
[0010]
As described above, the conventional systems have not achieved both high mechanical strength and charge transport ability.
[0011]
[Problems to be solved by the invention]
An object of the present invention is to solve the problems of an electrophotographic photoreceptor using a conventional resin as a surface layer, to improve the wear resistance and scratch resistance by increasing the film strength, and An object of the present invention is to provide an electrophotographic photosensitive member having good precipitation properties.
[0012]
Another object of the present invention is that it stably exhibits excellent potential characteristics regardless of repeated use and environmental fluctuations, gives good image quality without image defects such as fog, and is extremely small in transfer memory and photo memory. The object is to provide an excellent electrophotographic photoreceptor.
[0013]
Still another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.
[0014]
[Means for Solving the Problems]
  In accordance with the present invention, a conductive supportAnd the conductive supportaboveProvidedIn an electrophotographic photoreceptor having a photosensitive layer,
  The outermost surface layer of the electrophotographic photoreceptor is in the same molecule.2Containing a compound obtained by polymerizing a hole transporting compound having two or more chain polymerizable functional groups,
TheOutermost layerofThe calorific value in differential scanning calorimetry is,60mJ/ Mg or less
An electrophotographic photosensitive member is provided.
[0015]
In addition, according to the present invention, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member are provided.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The embodiment of the present invention will be described in detail below.
[0017]
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 formation reaction is largely divided into chain polymerization and sequential polymerization. For details, see, for example, “Basic Chemistry Resin Chemistry” by Tadahiro Miwa. (New Edition) "As described on July 25, 1995 (1st edition, 8th printing), page 24, unsaturated polymerization in which the reaction proceeds mainly via an intermediate such as a radical or ion, This refers to ring-opening polymerization and isomerization polymerization.
[0018]
Chain-polymerizable functional group P in the general formula (1)¹And P²Means 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.
[0019]
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.
[0020]
[Table 1]
[0021]
In the table, R is an optionally substituted alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an optionally substituted benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, and An aryl group such as a thienyl group, an aryl group such as a phenyl group, a naphthyl group and an anthryl group which may have a substituent, or a hydrogen atom.
[0022]
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 ions basically act as active species. Specific examples of the ring-opening polymerizable functional group are shown in Table 2, but are not limited thereto.
[0023]
[Table 2]
[0024]
In the table, R is an optionally substituted alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an optionally substituted benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, and An aryl group such as a thienyl group, an aryl group such as a phenyl group, a naphthyl group and an anthryl group which may have a substituent, or a hydrogen atom.
[0025]
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.
[0026]
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[0027]
In the formula, E may have a hydrogen atom, a halogen atom such as fluorine, chlorine and bromine, an optionally substituted alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, or a substituent. Aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group, optionally substituted phenyl group, naphthyl group, anthryl group, pyrenyl group, thiophenyl group and furyl group, aryl groups such as CN group, nitro group, methoxy group, alkoxy group such as ethoxy group and propoxy group, -COOR²⁶Or -CONR²⁷R²⁸Indicates.
[0028]
W is an arylene group such as an optionally substituted phenylene group, naphthylene group and anthracenylene group, an optionally substituted methylene group, an alkylene group such as an ethylene group and a butylene group, -COO-, -CH₂-, -O-, -OO-, -S- or -CONR²⁹Indicated by −.
[0029]
R²⁶~ R²⁹Is a hydrogen atom, a halogen atom such as fluorine, chlorine and bromine, an optionally substituted methyl group such as an ethyl group and an propyl group, an optionally substituted benzyl group and a phenethyl group An aryl group such as an aralkyl group or an optionally substituted phenyl group, naphthyl group and anthryl group;²⁷And R²⁸May be the same or different. F represents 0 or 1.
[0030]
Substituents that may be present in E and W include halogen atoms such as fluorine, chlorine, bromine and iodine; nitro groups, cyano groups, hydroxyl groups; alkyl groups such as methyl groups, ethyl groups, propyl groups and butyl groups Alkoxy groups such as methoxy group, ethoxy group and propoxy group; aryloxy groups such as phenoxy group and naphthoxy group; aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group; or phenyl group, naphthyl group; And aryl groups such as a group, anthryl group and pyrenyl group.
[0031]
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[0032]
Where R³⁰And R³¹Has a hydrogen atom, an alkyl group such as a methyl group which may have a substituent, an ethyl group propyl group or a butyl group, an aralkyl group such as a benzyl group or a phenethyl group which may have a substituent, 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.
[0033]
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[0034]
Where R³²And R³³Is a hydrogen atom, 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 and a phenethyl group which may have a substituent, or a substituent. An aryl group such as a phenyl group and a naphthyl group which may be present, and n represents an integer of 0 to 10.
[0035]
In the above general formulas (12) and (13), R³⁰~ R³³Substituents that may have are halogen atoms such as fluorine, chlorine, bromine and iodine; alkyl groups such as methyl, ethyl, propyl and butyl groups; alkoxy groups such as methoxy, ethoxy and propoxy Aryloxy groups such as phenoxy group and naphthoxy group; aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group; or aryl groups such as phenyl group, naphthyl group, anthryl group and pyrenyl group; Can be mentioned.
[0036]
Among the general formulas (11) to (13), more particularly preferable chain polymerizable functional groups include those represented by the following general formulas (14) to (20).
[0037]
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[0038]
Furthermore, among the general formulas (14) to (20), the acryloyloxy group of the general formula (14) and the methacryloyloxy group of the general formula (15) are particularly preferable from the viewpoint of polymerization characteristics and the like.
[0039]
In the present invention, the “hole transportable compound having a chain polymerizable functional group” means that the chain polymerizable functional group described above is chemically bonded to the hole transportable compound described above as a functional group. Compound. In this case, all of those chain polymerizable functional groups may be the same or different.
[0040]
The hole transporting compound having two or more of those chain polymerizable functional groups is preferably the following general formula (1).
[0041]
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[0042]
In the formula, A represents a hole transporting group. P¹And P²Represents a chain polymerizable functional group, P¹And P²May 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. If a is 2 or more, P¹May be the same or different, and if d is 2 or more, P²May be the same or different, and when b is 2 or more, Z and P²May be the same or different.
[0043]
Here, “If a is 2 or more, P¹May be the same or different ”means that n different types of chain polymerizable functional groups are represented by P¹¹, P¹², P¹³, P¹⁴, P¹⁵.... P¹ⁿFor example, when a = 3, the polymerizable functional group P directly bonded to the hole transporting compound A¹Is the same for all three, but two are the same and one is different (for example, P¹¹And P¹¹And P¹²However, each of the three is different (for example, P¹²And P¹⁵And P¹⁷Or the like) ("P if d is 2 or more P²May be the same or different. ”If b is 2 or more, Z and P²"May be the same or different" means the same thing).
[0044]
A in the general formula (1) represents a hole transporting group, and any group may be used as long as it exhibits hole transportability.¹As a hydrogenation compound (hole transport compound) in which the bonding site with Z or Z is replaced with a hydrogen atom, for example, triarylamine derivatives such as oxazole derivatives, oxadiazole derivatives, imidazole derivatives and 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.
[0045]
Further, among the above hole transport compounds, compounds represented by the general formula selected from the following general formulas (2), (3), (4), (5) and (7), or the following general formula (8) A condensed ring hydrocarbon having the group shown or a condensed heterocyclic ring having a group represented by the following general formula (8) is preferable. Among these, the case where it is a compound shown by General formula (2), (3) and (4) is especially preferable.
[0046]
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[0047]
In the general formula (2), R¹, R²And R^ThreeIs an alkyl group having 10 or less carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent, a benzyl group, a phenethyl group, a naphthylmethyl group and a furfuryl group which may have a substituent. And phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, thiophenyl, furyl, pyridyl, quinolyl, benzoquinolyl, carbazolyl, phenol, which may have an aralkyl group such as thienyl group or a substituent An aryl group such as a thiazinyl group, a benzofuryl group and a benzothiophenyl group is shown.
[0048]
However, R¹, R²And R^ThreeAt least two of them represent an aryl group, and R¹, R²And R^ThreeMay be the same or different. Furthermore, among them, R¹, R²And R^ThreeThose in which all are aryl groups are particularly preferred. In addition, R in the general formula (2)¹Or R²Or R^ThreeAny two of them may be bonded directly or via a linking group, such as a methylene group, an alkylene group such as an ethylene group and a propylene group, a hetero atom such as an oxygen and sulfur atom, or CH. ═CH group and the like.
[0049]
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[0050]
In the general formula (3), R^Four, R^Five, R⁸And R⁹Is an alkyl group having 10 or less carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent, a benzyl group, a phenethyl group, a naphthylmethyl group and a furfuryl group which may have a substituent. And phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, thiophenyl, furyl, pyridyl, quinolyl, benzoquinolyl, carbazolyl, phenol, which may have an aralkyl group such as thienyl group or a substituent An aryl group such as a thiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, and a dibenzothiophenyl group;^Four, R^Five, R⁸And R⁹May be the same or different. R⁶And R⁷Is an alkylene group having 10 or less carbon atoms such as methylene group, ethylene group and propylene group which may have a substituent, or an arylene group which may have a substituent (benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene) , A group obtained by removing two hydrogens from furan, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc.) and R⁶And R⁷May be the same or different. Q represents an organic group which may have a substituent.
[0051]
Among them, R in the above general formula (3)^Four, R^Five, R⁸And R⁹At least two of them are optionally substituted aryl groups, and R⁶And R⁷Is preferably an arylene group which may have a substituent, and further R^Four, R^Five, R⁸And R⁹It is particularly preferred that all four are aryl groups. In addition, R in the above general formula (3)^FourOr R^FiveOr R⁶Any two of R or R⁷Or R⁸Or R⁹Any two of them may be bonded directly or via a linking group, such as a methylene group, an alkylene group such as an ethylene group and a propylene group, a hetero atom such as an oxygen and sulfur atom, or CH. ═CH group and the like.
[0052]
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[0053]
In the general formula (4), m¹Represents 0 or 1, m¹= 1, preferably R^Ten~ R¹³Is an alkyl group having 10 or less carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent, a benzyl group, a phenethyl group, a naphthylmethyl group and a furfuryl group which may have a substituent. And phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, thiophenyl, furyl, pyridyl, quinolyl, benzoquinolyl, carbazolyl, phenol, which may have an aralkyl group such as thienyl group or a substituent 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.
[0054]
Ar¹Is an arylene group which may have a substituent (two from benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, furan, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. Group from which hydrogen was removed) and Ar²Is m¹In 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 Ar¹And the same arylene group. M¹If = 1, Ar¹And Ar²May be the same or different.
[0055]
Among them, R in the above general formula (4)^TenAnd R¹¹Is preferably an aryl group which may have a substituent, R^Ten~ R¹³It is particularly preferred that all four are aryl groups. In addition, R in the general formula (4)^TenAnd R¹¹Or R¹²And R¹³Or Ar¹And Ar²May be bonded directly or via a bonding group, such as an alkylene group such as a methylene group, an ethylene group and a propylene group, a heteroatom such as a carbonyl group, an oxygen and a sulfur atom, or a CH═CH group. Etc.
[0056]
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[0057]
  However, in the general formula (5), Ar³, Ar⁴And R¹⁴At least1Is a group represented by the following general formula (6):HaveTo do.
[0058]
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[0059]
In the general formulas (5) and (6), Ar^Three, Ar^FourAnd Ar^FiveIs optionally substituted phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, thiophenyl, furyl, pyridyl, quinolyl, benzoquinolyl, carbazolyl, phenothiazinyl, benzofuryl, benzo An aryl group such as a thiophenyl group, a dibenzofuryl group, and a dibenzothiophenyl group, and R¹⁴, R¹⁵And R¹⁶Is an alkyl group having 10 or less carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent, a benzyl group, a phenethyl group, a naphthylmethyl group and a furfuryl group which may have a substituent. 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;¹⁵And R¹⁶Represents a hydrogen atom in addition to these alkyl group, aralkyl group and aryl group. Ar^ThreeAnd Ar^FourAnd R¹⁵And R¹⁶May be the same or different.
[0060]
Among them, R¹⁴And R¹⁶Is particularly preferably an aryl group. R¹⁴Or Ar^ThreeOr Ar^FourAny two of them, or Ar^FiveAnd R¹⁶May be bonded directly or via a bonding group, and examples of the bonding group include alkylene groups such as methylene group, ethylene group and propylene group, heteroatoms such as oxygen and sulfur atoms, or CH═CH group. It is done. n¹Represents an integer of 0-2.
[0061]
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[0062]
However, the general formula (7) has at least one group represented by the following general formula (8).
[0063]
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[0064]
In the general formulas (7) and (8), Ar⁶And Ar⁷Is optionally substituted phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, thiophenyl, furyl, pyridyl, quinolyl, benzoquinolyl, carbazolyl, phenothiazinyl, benzofuryl, benzo An aryl group such as a thiophenyl group, a dibenzofuryl group, and a dibenzothiophenyl group, and R¹⁷, R¹⁸, R¹⁹And R²⁰Is an alkyl group having 10 or less carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent, a benzyl group, a phenethyl group, a naphthylmethyl group and a furfuryl group which may have a substituent. 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;¹⁹And R²⁰Represents a hydrogen atom in addition to these alkyl group, aralkyl group and aryl group. R¹⁷And R¹⁸And R¹⁹And R²⁰May be the same or different.
[0065]
Among them, R²⁰Is preferably an aryl group, and further R¹⁷And R¹⁸Is particularly preferably an aryl group. R¹⁷Or R¹⁸Or Ar⁶Any two of them, or Ar⁷And R²⁰May be bonded directly or via a bonding group, and examples of the bonding group include alkylene groups such as methylene group, ethylene group and propylene group, heteroatoms such as oxygen and sulfur atoms, or CH═CH group. It is done. n²Represents an integer of 0-2.
[0066]
Further, the compound having the group represented by the general formula (8) may have a substituent, naphthalene group, anthracene group, phenanthrene group, perene group, fluorene group, fluoranthene group, azulene group, indene group. Condensed ring hydrocarbons such as perylene group, chrysene group and coronene group or condensed heterocyclic rings such as benzofuran group, indole group, carbazole group, benzcarbazole group, acridine group, phenothiazine group and quinoline group which may have a substituent Is mentioned.
[0067]
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, SO₂Represents an organic group in which one or an arbitrary combination of an oxygen atom or a sulfur atom. Among them, those represented by the following general formula (9) are preferable, and those represented by the following general formula (10) are particularly preferable.
[0068]
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[0069]
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[0070]
  In the general formula (9), X¹~ X³Is an alkylene group having 20 or less carbon atoms such as methylene group, ethylene group and propylene group which may have a substituent, (CR²³= CR²⁴)_m2, C = O, S = O, SO₂Represents an oxygen atom or a sulfur atom, Ar⁸And Ar⁹Is an arylene group which may have a substituent (two from benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, furan, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. Group from which a hydrogen atom has been removed. R²³And R²⁴Represents 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;²³And R²⁴May be the same or different. m2Is an integer from 1 to 5, p, Q, r, s andt represents an integer of 0 to 10 (provided that p, Q, r, s andt cannot be 0 at the same time).
[0071]
  In the general formula (10), X⁴And X⁵Is (CH₂)_m3, (CH = CR²⁵)_m4, C = O, or an oxygen atom, Ar¹⁰Is an arylene group which may have a substituent (two from benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, furan, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. Group from which a hydrogen atom has been removed. R²⁵Represents 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. m3Is an integer from 1 to 10, m4Is an integer from 1 to 5, u, V andw represents an integer of 0 to 10 (particularly preferably 0 or an integer of 1 to 5; provided that u, V andw is not 0 at the same time).
[0072]
In the above general formulas (3) to (10), R^Four~ R^{twenty five}, Ar¹~ Ar^Ten, X¹~ X^Five, Z and Q each may have a halogen atom such as fluorine, chlorine, bromine and iodine; a nitro group, a cyano group, a hydroxyl group; an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group Alkoxy groups such as methoxy group, ethoxy group and propoxy group; aryloxy groups such as phenoxy group and naphthoxy group; aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group; phenyl group, naphthyl group; , Aryl groups such as anthryl group and pyrenyl group. Further, R in the general formula (2)¹~ R^FiveExamples of the substituent which may have include the above-mentioned substituents excluding the aryl group and diarylamino groups such as a diphenylamino group and a di (p-tolyl) amino group.
[0073]
In addition, 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, particularly 0.4 to 1. .2 (V) is preferred. That is, when the oxidation potential exceeds 1.2 (V), injection of charges (holes) from the charge generating material is difficult to occur, resulting in problems such as increase in residual potential, deterioration in sensitivity, and increase in potential fluctuation during repeated use. If it is less than 0.4 (V), in addition to problems such as a decrease in charging ability, the compound itself is easily oxidized and easily deteriorates, resulting in deterioration in sensitivity, image blurring, and potential during repeated use. This is because problems such as large fluctuations are likely to occur.
[0074]
The oxidation potential described here is measured by the following method.
[0075]
(Measurement method of oxidation potential)
Saturated calomel electrode as reference electrode and 0.1N (n-Bu) as electrolyte_FourN⁺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)_FourN⁺ClO_Four ^-Dissolve in acetonitrile solution to a concentration of about 5-10 mmol%. Then, a voltage is applied to the sample solution with 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.
[0076]
Furthermore, the hole transporting compound having the chain polymerizable functional group has a hole transporting ability of 1 × 10^-7(Cm²/ V. sec) or higher drift mobility is preferable (however, the applied electric field: 5 × 10^FourV / cm). 1 × 10^-7(Cm²/ V. If it is less than (sec), holes may not move sufficiently from the post-exposure development to the electrophotographic photosensitive member, so that the apparent sensitivity may be reduced and the residual potential may be increased.
[0077]
Although the typical example of the hole transportable compound which has a chain polymerizable functional group concerning this invention below is given, it is not limited to these.
[0078]
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[0134]
[Chemical Formula 86]
[0135]
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[0163]
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[0164]
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[0165]
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[0166]
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[0167]
In the present invention, a typical synthesis method of a hole transporting compound having a chain polymerizable functional group is shown below.
[0168]
(Synthesis Example 1: Synthesis of Compound Example No. 6)
Synthesized according to the following route.
[0169]
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[0170]
1 (50 g: 0.47 mol), 2 (406 g: 1.4 mol), anhydrous potassium carbonate (193 g) and copper powder (445 g) together with 1,2-dichlorobenzene 1200 g at 180-190 ° C. with heating and stirring for 15 hours. It was. 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.
[0171]
3 (120 g: 0.28 mol) was added to 1500 g of methyl cellosolve, and sodium methylate (150 g) was slowly added while 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.
[0172]
4 (70 g: 0.2 mol) and triethylamine (40 g: 0.4 mol) were added to 400 ml of dry tetrahydrofuran (THF), 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 Example No. 6).
[0173]
(Synthesis Example 2: Synthesis of Compound Example 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 purified using a silica gel column to obtain 5.6 g of the target compound (Compound Example No. 71).
[0174]
(Synthesis Example 3: Synthesis of Compound Example No. 55)
Compound No. obtained in Synthesis Example 2 above. 71 3.0 g dissolved in 20 ml dichloromethane, cooled to 0-5 ° C., slowly added 5.2 g m-chloroperbenzoic acid (˜70%), stirred as it was for 1 hour, then returned to room temperature and stirred for 12 hours. It was. 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 objective compound (Compound Example No. 55).
(Synthesis Example 4: Synthesis of Compound Example No. 152)
Synthesized according to the following route.
[0175]
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[0176]
1 (70 g: 0.35 mol), 2 (98 g: 0.42 mol), anhydrous potassium carbonate (73 g) and copper powder (111 g) together with 600 g of 1,2-dichlorobenzene at 180-190 ° C. with heating and stirring for 10 hours went. 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.
[0177]
3 (80 g: 0.26 mol) was added to 300 g of N, N-dimethylformamide (DMF), and ethaneol sodium salt (about 90%: 62 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 under reflux for 3 hours. After cooling, the reaction solution is poured into water and made weakly acidic with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer is further extracted with 1.2 mol / l sodium hydroxide aqueous solution, and the aqueous layer is made acidic with dilute hydrochloric acid and extracted with ethyl acetate. After drying over anhydrous sodium sulfate, the solvent was removed under reduced pressure. The residue was purified using a silica gel column to obtain 64 g of 4.
[0178]
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 dropping, 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, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was subjected to column purification using a silica gel column to obtain 49.1 g of 5.
[0179]
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 completion of the dropping, the mixture was stirred as it was for 15 minutes, and then a 5 (42.2 g: 0.07 mol) / 102 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 15 hours. The reaction solution was poured into 1500 g of an about 15% by mass 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.
[0180]
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 the dropping, the mixture was stirred at room temperature for 4 hours, and 200 ml of a 5% by mass 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 13.6 g of 7.
[0181]
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 purified using a silica gel column to obtain 6.4 g of 8 (Compound Example No. 152) (oxidation potential: 0.88 V).
(Synthesis Example 5: Synthesis of Compound Example No. 263)
Synthesized according to the following route.
[0182]
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[0183]
1 (50 g: 0.123 mol), 2 (62.4 g: 0.369 mol), anhydrous potassium carbonate (25.5 g) and copper powder (32 g) together with 200 g of 1,2-dichlorobenzene at 180 to 190 ° C. Heating and stirring were performed 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.
[0184]
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 completion of the dropwise addition, the mixture was stirred as it was for 15 minutes, and then a 3 (45.0 g: 92.2 mmol) / DMF 135 g 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 2500 g of about 15% by mass 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.
[0185]
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 the dropping, the mixture was stirred at room temperature for 4 hours, and 500 ml of 5% by mass 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 26.3 g of 5.
[0186]
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 Example No. 263) (oxidation potential: 0.80 V).
[0187]
In the present invention, by polymerizing a hole transporting compound having two or more chain-polymerizable functional groups in the same molecule, the compound having a hole transporting ability is crosslinked in the photosensitive layer. A three-dimensional crosslinked structure is formed with points. The hole transporting compound can be either polymerized alone or mixed with a compound having another chain polymerizable functional group, and the kind / ratio is arbitrary. The compound having another chain polymerizable functional group mentioned here includes any monomer or oligomer / polymer having a chain polymerizable functional group.
[0188]
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 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 IPN (Inter Penetrating Network), ie, an interpenetrating network structure, by controlling the compounding ratio / film forming method well.
[0189]
Further, a photosensitive layer is formed from the hole transporting compound and a monomer or oligomer / polymer having no chain polymerizable functional group or a monomer or oligomer / polymer having a polymerizable functional group other than the chain polymerization functional group. May be.
[0190]
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. Further, other various additives, a lubricant such as fluorine atom-containing resin fine particles, and the like may be contained.
[0191]
The electrophotographic photosensitive member of the present invention has a structure in which a charge generating layer containing at least a charge generating material and a charge transporting layer containing at least a charge transporting material are laminated in this order as a photosensitive layer on a conductive support. .
[0192]
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 μm to 50 μm, particularly preferably 5 When it is used as a second charge transport layer described later, the film thickness is preferably 1 to 20 μm, particularly preferably 1 to 6 μm.
[0193]
Next, a method for producing an electrophotographic photoreceptor according to the present invention will be specifically described.
[0194]
The support for the electrophotographic photosensitive member may have any 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, tin oxide, etc. deposited on plastic films, metals with conductive layers applied alone or with binder resin, plastic films And paper.
[0195]
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.
[0196]
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. are known. 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.
[0197]
The electrophotographic photoreceptor of the present invention is a function-separated type electrophotographic photoreceptor in which 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.
[0198]
The charge generation layer is well dispersed by a method such as a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor and roll mill together with 0.3 to 4 times the amount of binder resin and solvent. The 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.
[0199]
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.
[0200]
The compound obtained by polymerizing the hole-transporting compound having a chain-polymerizable functional group in the present invention is a charge that does not have a chain-polymerizable functional group on the charge-generating layer as a charge-transporting layer or on the charge-generating layer. After forming a charge transport layer made of a transport material and a binder resin, it can be used as the second charge transport layer. 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.
[0201]
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.
[0202]
In the present invention, the hole transporting compound having a chain polymerizable functional group can be polymerized by heat, light such as visible light or ultraviolet light, and further an electron beam. Therefore, the formation of the photosensitive layer in the present invention is performed using a coating solution containing a hole transporting compound having the chain polymerizable functional group and, if necessary, a polymerization initiator in the coating solution for the photosensitive layer. The hole transporting compound having a chain polymerizable functional group is polymerized by irradiating the coated film with heat, light or electron beam. In the present invention, it is preferable to polymerize a hole transporting compound having a chain polymerizable functional group by an electron beam. The greatest advantage of polymerization by electron beam is that a polymerization initiator is not required, which makes it possible to produce a very high-purity three-dimensional photosensitive layer and to ensure good electrophotographic characteristics. . Also, because it is a short and efficient polymerization reaction, the productivity is also high, and further, because of the good permeability of the electron beam, curing when a thick film or a shielding material such as an additive is present in the film. For example, the influence of inhibition is very small. However, depending on the type of the chain polymerizable functional group and the type of the central skeleton, the polymerization reaction may not easily proceed, and in this case, it is possible to add a polymerization initiator within a range that does not affect the polymerization reaction.
[0203]
  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 with 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 250.kV or less is preferred, optimally 150kV or less. The dose is preferably in the range of 1 Mrad to 100 Mrad, more preferably in the range of 3 Mrad to 50 Mrad. Acceleration voltage is 250kIf it exceeds V, the electron beam irradiation damage to the electrophotographic photosensitive member characteristics tends to increase. In addition, it is necessary to be careful because the curing tends to be insufficient when the dose is less than 1 Mrad, and the characteristics of the electrophotographic photosensitive member are likely to deteriorate when the dose exceeds 100 Mrad.
[0204]
The amount of the hole transporting compound when the hole transporting compound having the chain polymerizable functional group is used as a charge transporting layer is the above general formula with respect to the total mass of the charge transporting layer film after polymerization and curing. The hydrogenated product of the hole transporting group A having a chain polymerizable functional group represented by (1) is preferably 20% by mass or more, and particularly preferably 40% by mass or more. If it is less than 20% by mass, the charge transport ability is lowered, and problems such as a reduction in sensitivity and an increase in residual potential are likely to occur.
[0205]
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, poly Polymer compounds having a heterocyclic ring or condensed polycyclic aromatics such as styryl anthracene, heterocyclic compounds such as pyrazoline, imidazole, oxazole, triazole, carbazole, triarylalkane derivatives such as triphenylmethane, and triarylamines such as triphenylamine A low molecular weight compound such as a reelamine derivative, a phenylenediamine derivative, an N-phenylcarbazole derivative, a stilbene derivative, or a hydrazone derivative is dispersed in a solvent together with an appropriate binder resin (which can be selected from the aforementioned resin for charge generation layer). The dissolved solution is applied and dried by the known method described above. 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 are likely to occur.
[0206]
  As described above, when the charge transport layer obtained by polymerizing and curing the hole transport compound having a chain polymerizable functional group is subjected to a suggested thermal analysis by the following method, the calorific value is 60 m.J/ Mg or lessAnd goodPreferably 40mJ/ Mg or less. This exotherm is presumed to be mainly due to the reaction of the unreacted chain polymerizable functional group in the charge transport layer, but the value of this exotherm is not only the wear resistance of the electrophotographic photosensitive member, but also can be used repeatedly. It was found that the potential fluctuations due to environmental fluctuations and also various memories such as transfer memories and photo memories are extremely correlated, and that the above values exhibit very good characteristics.
[0207]
(Differential scanning calorimetry)
The charge transport layer of the electrophotographic photosensitive 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 three arbitrary locations of the electrophotographic photosensitive drum, measured by the following method, and the average of the three points was taken as the calorific value of the present invention.
[0208]
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.
[0209]
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.
[0210]
FIG. 1 shows a schematic configuration of an electrophotographic apparatus using a process cartridge having the electrophotographic photosensitive member of the present invention.
[0211]
In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotated about a shaft 2 in the direction of an arrow at a predetermined peripheral speed. In the rotating process, the electrophotographic photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the primary charging unit 3, and then from an exposure unit (not shown) such as slit exposure or laser beam scanning exposure. The exposure light 4 that is enhanced and modulated corresponding to the time-series electric digital image signal of the target image information to be output is received. In this way, electrostatic latent images corresponding to the target image information are sequentially formed on the peripheral surface of the electrophotographic photoreceptor 1.
[0212]
The formed electrostatic latent image is then developed with toner by the developing means 5 and is taken out from a paper feeding unit (not shown) between the electrophotographic photoreceptor 1 and the transfer means 6 in synchronism with the rotation of the electrophotographic photoreceptor 1. The toner image formed and supported on the surface of the electrophotographic photosensitive member 1 is sequentially transferred by the transfer means 6 onto the transferred transfer material 7.
[0213]
The transfer material 7 that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member, introduced into the image fixing means 8, and subjected to image fixing to be printed out as an image formed product (print, copy). .
[0214]
After the image transfer, the surface of the electrophotographic photosensitive member 1 is cleaned by removing the transfer residual toner by the cleaning unit 9, and is further subjected to charge removal processing by the pre-exposure light 10 from the pre-exposure unit (not shown). Used repeatedly for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.
[0215]
In the present invention, among the above-described components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9, a plurality of components are housed in a container 11 and integrally combined as a process cartridge. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge, and is attached to and detached from the apparatus main body using a guide unit 12 such as a rail of the apparatus main body. A flexible process cartridge can be obtained.
[0216]
Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected or transmitted light from the original, or the original is read by a sensor and converted into a signal, and a laser beam scanning performed according to this signal is performed. Light emitted by driving the LED array, driving the liquid crystal shutter array, or the like.
[0217]
The electrophotographic photoreceptor 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, FAX, liquid crystal printers, and laser plate making. .
[0218]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, "part" in an Example shows a mass part.
[0219]
Example 1
First, a coating material for the conductive layer was prepared by the following procedure. 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% by weight of antimony oxide, 25 parts of phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol and a silicone compound (polydimethylsiloxane polyoxyalkylene copolymer, 0.002 parts of an average molecular weight of 3000) was prepared by dispersing for 2 hours in a sand mill using φ1 mm glass beads. This paint was applied on an aluminum cylinder having a diameter of 30 mm by a dip coating method and dried at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 18 μm.
[0220]
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.
[0221]
Next, oxytitanium phthalocyanine having strong peaks at Bragg angles (2θ ± 0.2 degrees) of 9.0, 14.2, 23.9, and 27.1 degrees in characteristic X-ray diffraction of CuKα 3 parts of polyvinyl butyral (trade name: ESREC BM2, manufactured by Sekisui Chemical Co., Ltd.) and 35 parts of cyclohexanone are dispersed for 2 hours in a sand mill using φ1 mm glass beads. 60 parts of ethyl acetate was added to prepare a charge generation layer coating material. The 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.
[0222]
  Compound Example No. 6 parts of the hole transporting compound 6 are dissolved in a mixed solvent of 50 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating for the charge transport layer.Madedid.This paint is coated on the charge generation layer, and an acceleration voltage of 150 is applied.kBy irradiating an electron beam under the conditions of V and a dose of 7 Mrad to cure the resin, a charge transport layer having a film thickness of 15 μm was formed, and an electrophotographic photosensitive member was obtained.
[0223]
The electrophotographic photosensitive member is mounted on a modified machine of a laser beam printer (Laser Writer 16 / 600PS: manufactured by Apple), and is subjected to an initial dark potential (Vd) at room temperature and normal humidity (23 ° C./55% RH) (N / N). ) Is set to −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 and used as sensitivity. Furthermore, 20 (μJ / cm²The 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. Thereafter, the environment was changed to high temperature and high humidity (32 ° C./85% RH) (H / H), and the amount of fluctuation (ΔVl) of Vl from room temperature and normal humidity was measured.
[0224]
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 continuously 5000 sheets at room temperature and low humidity (23 ° C./10% RH) (N / L). The amount of fluctuation in the dark part potential and the bright part potential immediately after the end and after the endurance is expressed as ΔVd.¹And ΔVl¹Was measured. Further, the amount of abrasion of the electrophotographic photosensitive member was measured with a ket.
[0225]
Furthermore, the transfer memory and photo memory were measured as follows. To measure the transfer memory, 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 primary charging potential when the transfer current is OFF is set to Vd.²The primary charging potential when the transfer current is ON is Vd^Three│Vd²-Vd^Three│ was measured. 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 (N / N in a low temperature and low humidity environment), and the initial dark part potential ( Vd) / initial light portion potential (Vl) is set to −700 (V) / − 200 (V) so that the charge and exposure light amount are set, and then the electrophotographic photosensitive member is formed with dark portions and bright portions. The sample is masked with 3000 lux, irradiated with light for 20 minutes under a fluorescent lamp, and then allowed to stand for 5 minutes.^Four) Was measured as a photo memory.
[0226]
Further, the differential transport calorific value was measured by sampling the charge transport layer portion of the electrophotographic photosensitive drum produced in the same manner as described above. The respective results are shown in Table 3.
[0227]
(Examples 2-34 and Comparative Examples 1-20)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the hole transporting compound and the electron beam irradiation dose were changed as shown in Tables 3 and 4. The results are shown in Tables 3 and 4.
[0228]
(Comparative Example 21)
After forming the charge generation layer in Example 1, 20 parts of a triarylamine compound (A) having the following structural formula and 10 parts of a polycarbonate resin Z type (average molecular weight 20,000) are mixed with 50 parts of monochlorobenzene and 20 parts of dichloromethane. A charge transport layer was formed on the charge generation layer using a charge transport layer coating prepared by dissolving in a solvent to obtain an electrophotographic photoreceptor. At this time, the thickness of the charge transport layer was 18 μm. This electrophotographic photosensitive member was evaluated in the same manner as in Example 1, and the results are shown in Table 4.
[0229]
Embedded image
[0230]
(Comparative Example 22)
An electrophotographic photoreceptor was prepared in the same manner as in Comparative Example 21, except that the charge transport compound in Comparative Example 21 was replaced with the following styryl compound (B), and the same evaluation was performed. The results are shown in Table 4.
[0231]
Embedded image
[0232]
(Comparative Example 23)
In Example 1, up to the charge generation layer, 20 parts of a polycarbonate resin (C) having the following structural formula synthesized according to the production method described on pages 10 to 11 of JP-A-8-248649 was added to 80 parts of tetrahydrofuran. A charge transport layer was formed on the charge generation layer using a paint for a charge transport layer prepared by dissolving in a solution. 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.
[0233]
Embedded image
[0234]
  As is apparent from Tables 3 and 4, the electrophotographic photosensitive member 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 the calorific value is 60 m.J/ M or less is good, 40mJIt is clear that the case of / mg or less is particularly good.
[0235]
(Example 35)
First, a coating material for the conductive layer 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 φ30 mm 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.
[0236]
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.
[0237]
Next, 5 parts of the following bisazo pigment, 2 parts of polyvinyl butyral resin and 60 parts of cyclohexanone were dispersed for 24 hours in a sand mill apparatus using φ1 mm glass beads, and 60 parts of tetrahydrofuran was further added to obtain a coating material for a charge generation layer. 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.
[0238]
Embedded image
[0239]
  Compound Example No. 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 / 30 parts of dichloromethane..This paint is coated on the charge generation layer, and an acceleration voltage of 150 is applied.kBy irradiating an electron beam under the conditions of V and a dose of 30 Mrad to cure the resin, a charge transport layer having a film thickness of 13 μm was formed to obtain an electrophotographic photosensitive member.
[0240]
The electrophotographic photosensitive member produced in this way was mounted on a Canon printer LBP-2000 equipped with a pulse modulation device, and the following image evaluation was performed.
[0241]
(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.
[0242]
(Ghost evaluation)
Under normal temperature and humidity (23 ° C / 55% RH) (N / N), an appropriate character pattern was printed for the entire circumference of the drum in the initial stage, and then the entire halftone image was taken to check whether the ghost phenomenon had occurred. . Next, 2000 endurance patterns were printed continuously, half-tone images were taken after the endurance, and it was confirmed whether the ghost phenomenon after endurance had occurred. 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. 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.
[0243]
Further, the differential transport calorific value was measured by sampling the charge transport layer portion of the electrophotographic photosensitive drum produced in the same manner as described above. The results are shown in Table 5 below.
[0244]
(Examples 36 to 42 and Comparative Examples 24 to 28)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 35 except that the irradiation dose of the hole transporting compound and the electron beam was changed as shown in Table 5. The results are shown in Table 5.
[0245]
(Comparative Example 29)
After forming up to the charge generation layer in Example 35, a charge transport layer was prepared in exactly the same formulation as in Comparative Example 21 (however, the film thickness was 13 μm), and an electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 35. did. The results are shown in Table 5.
[0246]
(Comparative Example 30)
After the formation of the charge generation layer in Example 35, a charge transport layer was prepared in exactly the same formulation as in Comparative Example 23 (however, the film thickness was 13 μm), and an electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 35. did. The results are shown in Table 5.
[0247]
  From these results, it can be seen that the electrophotographic photosensitive member 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 the differential scanning calorimetry of the charge transport layer, and the calorific value is 60 m.J/ M or less is good, 40mJIt is clear that the case of / mg or less is particularly good.
[0248]
[Table 3]
[0249]
[Table 4]
[0250]
[Table 5]
[0251]
[Table 6]
[0252]
【The invention's effect】
  According to the present invention, ResistantNot only is the wearability extremely good, it shows stable and excellent potential characteristics regardless of repeated use and environmental changes, and the transfer memory, photo memory and other memories are small, and there is no image defect such as fog. Image quality can be given.
[Brief description of the drawings]
FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus using a process cartridge having an electrophotographic photosensitive member of the present invention.
[Explanation of symbols]
1 Electrophotographic photoreceptor
2 axis
3 Charging means
4 exposure light
5 Development means
6 Transfer means
7 Transfer material
8 Fixing means
9 Cleaning means
10 Pre-exposure light
11 Process cartridge container
12 Guide means

Claims (26)

In an electrophotographic photosensitive member having a conductive support and a photosensitive layer provided on the conductive support ,
Outermost surface layer of the electrophotographic photosensitive member contains a compound of the hole transporting compound was polymerized with two or more chain polymerizable functional groups in the same molecule,
The amount of heat generated by the differential scanning calorimetry of the outermost surface layer, the electrophotographic photosensitive member, characterized in that it is 60 m J / mg or less. The amount of heat generated by the differential scanning calorimetry of the outermost surface layer, the electrophotographic photosensitive member according to claim 1 is 40 m J / mg or less. The chain-polymerizable hole transporting compound having a functional group, an electrophotographic photosensitive member according to claim 1 or 2 which is a compound represented by the following general formula (1).
(In the 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 are 0 or an integer of 1 or more, a + b × d is an integer of 2 or more, and when a is 2 or more, P ¹ is the same or different P ² may be the same or different when d is 2 or more, and Z and P ² may be the same or different when b is 2 or more . The compound represented by the following general formula (2) is a hole transporting compound in which the bonding site of A and P ¹ and the bonding site of A and Z in A in the general formula (1) are replaced by hydrogen atoms. 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 represented by the following general formula (8)). The electrophotographic photosensitive member according to claim 3 , which is at least one member selected from the group consisting of:
(In the general formula (2), R ¹ , R ² and R ³ represent an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent. (However, at least two of them are aryl groups, and R ¹ , R ² and R ³ may 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. R ⁴ , R ⁵ , R ⁸ and R ⁹ may be the same or different, and R ⁶ and R ⁷ each 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 , R ¹¹ , R ¹² and R ¹³ may have an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different, Ar ¹ and Ar ² represent an arylene group which may have a substituent, Each may be the same or different. M ¹ represents 0 or 1.)
{(In the 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 has a substituent. An alkyl group, an aralkyl group which may have a substituent, or an aryl group which may have a substituent.) However, at least one of Ar ³ , Ar ⁴ and R ¹⁴ has the following general formula It has group shown by (6).
(In General Formula (6), R ¹⁵ and R ¹⁶ 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 ¹⁵ and R ¹⁶ may be the same or different, Ar ⁵ represents an aryl group which may have a substituent, and n ¹ represents an integer of 0 to 2.)}
(In the general formula (7), R ¹⁷ and R ¹⁸ represent an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, and R ¹⁷ and R ¹⁸ may be the same or different, and Ar ⁶ represents an aryl group which may have a substituent.
(In the general formula (8), R ¹⁹ and R ²⁰ 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 ¹⁹ and R ²⁰ may be the same or different, Ar ⁷ represents an aryl group which may have a substituent, and n ² represents an integer of 0 to 2. Before following general 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 ²¹ and R ²² are an optionally substituted alkyl group, which may have a substituent an aryl group or a hydrogen atom, R ²¹ and R ²² may be the same or different. ), C = O, S = O, SO 2, according to claim 3 or 4 is one, or two or more are combined to become an organic group selected from the group consisting of oxygen atom or a sulfur atom Electrophotographic photoreceptor. Before following general formula (1) Z or formula in (3) Q in the electrophotographic photosensitive member according to any one of claims 3 to 5 is a group represented by the following general formula (9).
(In the general formula (9) , X ^{1 to} X ³ are alkylene groups which may have a substituent, (CR ²³ = CR ²⁴ ) _m2 , C═O, S═O, SO ₂ , oxygen atom or sulfur atom. Ar ⁸ and Ar ⁹ represent an arylene group which may have a substituent, and R ²³ and R ²⁴ represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or represents a hydrogen ^{atom, R 23} and ^{R 24} may be different even in the same .m 2 is an integer of from 1 to 5, p, q, r, s and t is an integer of 0-10. However , P , q, r, s, and t are not 0 at the same time . Before following general formula (1) Z or formula in (3) Q in the electrophotographic photosensitive member according to any one of claims 3 to 5 is a group represented by the following general formula (10).
(In the general formula (10) , Ar ¹⁰ represents an arylene group which may have a substituent. X ⁴ and X ⁵ are (CH ₂ ) _m3 , ( _CH═CR ²⁵ ) _m4 , C═O or an oxygen atom. R ²⁵ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom, m 3 is an integer of 1 to 10, and m 4 is an integer of 1 to 5. , U 1 , v, and w represent an integer of 0 to 10, provided that u 1 , v, and w are not 0 at the same time . Before following general formula ⁽²⁾ R ^1, R 2 and R ³ is an electrophotographic photosensitive member according to any one of claims 4 to 7 is an aryl group which may have a substituent in. A pre-Symbol least two of an optionally substituted aryl group of ^{R 4,} R 5, ^{R 8} and ^{R 9} in the general formula (3) in, ^{R 6} and ^{R 7} have a substituent The electrophotographic photosensitive member according to claim 4, which is a good arylene group. ^{R 4,} R 5, electrophotographic photosensitive member according to claim 9 ^{R 8} and ^{R 9} are optionally substituted aryl groups before following general formula (3). Before following general formula (4) The electrophotographic photosensitive member according to any one of claims 4 to 7 R ¹⁰ and R ¹¹ is an aryl group which may have a substituent in. Before Symbol ^{m 1} in the general formula (4) is ^{1, R 10, R 11,} R 12 and electrophotographic photosensitive member according to claim 11 ^{R 13} is an aryl group which may have a substituent . Before following general formula (5) The electrophotographic photosensitive member according to any one of claims 4 to 7 R ¹⁴ is an aryl group which may have a substituent in. The electrophotographic photosensitive member according to claim 13 R ¹⁶ before following general formula (6) in is an aryl group which may have a substituent. Before following general formula (7) the electrophotographic photosensitive member of R ¹⁷ and R ¹⁸ is according to any one of claims 4 to 7 is an aryl group which may have a substituent in. The electrophotographic photosensitive member according to claim 15 before Symbol R ²⁰ in the general formula (8) is an aryl group which may have a substituent. Wherein one or both of the chain polymerizable functional groups P ¹ and P ^2, the electrophotographic photosensitive member according to any one of claims 3 to 16 which is an unsaturated polymerizable functional group represented by the following general formula (11).
(In the general formula (11) , E represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cyano group, a nitro group, an alkoxy group, —COOR ^26. {R ²⁶ represents 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 . } Or —CONR ²⁷ R ²⁸ {R ²⁷ and R ²⁸ represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent or an aryl group which may have a substituent, shows the each other the same or different} W is arylene group which may have a substituent, which may have a substituent alkylene group, -COO -.., - CH 2 -, -O-, -OO-, -S- or -CO R ^{29 -} {. R ²⁹ is hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a substituted or unsubstituted aralkyl group or a substituent shown also aryl group} and F represents 0 or 1 ) Wherein one or both of the chain polymerizable functional groups P ¹ and P ^2, the electrophotographic photosensitive member according to any one of claims 3 to 16, which is a cyclic ether group represented by the following general formula (12).
(In General Formula (12) , R ³⁰ and R ³¹ represent a hydrogen 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. shown to. n is an integer of 1 to 10.) Said chain one or both of the polymerizable functional groups P ¹ and P ^2, the electrophotographic photosensitive member according to any one of claims 3 to 16 which is an alicyclic epoxy group represented by the following general formula (13).
(In General Formula (13) , R ³² and R ³³ represent a hydrogen 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. shown to. n is an integer of 0.) One or both of the chain polymerizable functional groups ^{P 1} and P ^2, electrons according to any one of claims 3 to 16 is a group represented by either the following structural formula (14) to (20) Photoconductor.
Oxidation potential of the hole transporting compound having two or more chain polymerizable functional groups in the same molecule, electron according to any one of claims 1 to 20 is 0.4 to 1.2 (V) Photoconductor. The polymerization is, electrophotographic photosensitive member according to any one of claims 1 to 21 which is a polymerization carried out by the electron beam. The accelerating voltage of the electron beam, an electrophotographic photosensitive member according to claim 22 is 250 k V or less. Dose of the electron beam, an electrophotographic photosensitive member according to claim 22 or 23 is 1～100Mrad. An electrophotographic photosensitive member according to any one of claims 1 to 24, charging means for charging the electrophotographic photoreceptor, developing means for developing an electrophotographic photoreceptor formed of an electrostatic latent image with toner, and, and wherein the transfer and at least one means that is selected from the group consisting of cleaning means for recovering the toner remaining on the electrophotographic photosensitive member both integrally supports after step, it is detachable to the main body of the electrophotographic apparatus To process cartridge. The electrophotographic photosensitive member according to any one of claims 1 to 24, electrophotography charging means for the photosensitive member is charged, the charged electrostatic latent on the electrophotographic photosensitive member subjected to exposure to the electrophotographic photosensitive member exposing means for forming an image, developing means for developing the electrostatic latent image formed on the electric element photoreceptor with a toner, and, transfer means for transferring onto the transfer material the toner image on the electrophotographic photoreceptor An electrophotographic apparatus comprising: