JP2000147814A - Electrophotographic sensitive body, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic sensitive body which has excellent effects on a wear resistance and a scratch resistance and is extremely good in the electrophotographic characteristics such as sensitivity and residual potential and which is able to exhibit stable performance even when it is repeatedly used. SOLUTION: The electrophotographic sensitive body has a photosensitive layer on an electroconductive supporting material, and a charge generating material contained in the photosensitive layer is a phthalocyanine compound. The electrophotographic sensitive body contains one or both of a positive hole transporting compound containing at least two chain polymerizable functions in the same molecule and a cured material obtained by polymerizing or cross- linking the positive hole transporting compound by heat or UV-rays.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photoreceptor,
More specifically, the present invention relates to an electrophotographic photosensitive member having a surface layer containing a specific resin, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as selenium, cadmium sulfide and zinc oxide have been known as photoconductive materials used for electrophotographic photosensitive members. On the other hand, organic materials such as polyvinyl carbazole, phthalocyanine, and azo pigments are noted for their advantages such as high productivity and no pollution, and they tend to be inferior in terms of photoconductive properties and durability as compared with inorganic materials. , Has become widely used.

[0003] These electrophotographic photosensitive members are often used as function-separated type photosensitive members 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, optical characteristics, and durability characteristics according to the electrophotographic process to be applied.

In recent years, digitalization of copying machines has been rapidly developed, and high-speed, high-definition, and high durability have been developed in the field of laser beam printers. Have been. At present, digitization has become the mainstream, and although electrophotographic devices using a semiconductor laser as a light source are generally used, their oscillation wavelength is 790 ± 20 nm, which is in the infrared region. Phthalocyanine compounds have been widely used as one of the charge generation materials having the following.

There are many types, and they are classified into metal-free phthalocyanines and metal phthalocyanines. Among the metal phthalocyanines, copper phthalocyanine as disclosed in JP-A-50-38543, JP-A-61-21705, and JP-A-61-239248, JP-A-64-1
Oxytitanium phthalocyanines described in, for example, JP-A-7066 and JP-A-3-128973 are well known. Furthermore, in recent years, Japanese Patent Application Laid-Open Nos. 1-222159, 5-98181, 7-20717
Chlorogallium phthalocyanine disclosed in JP-A-5-236007 and JP-A-7-538.
No. 92, phthalocyanine compounds having a central metal, such as hydroxygallium phthalocyanine, are disclosed. In addition, the existence of various crystal forms has been reported for each of the above phthalocyanine compounds.

[0006] When these phthalocyanine compounds are used as a charge generation material, a combination of charge transport materials is very important in order to exhibit sufficient sensitivity and electrophotographic characteristics. Generally, the photoconductivity of an electrophotographic photoreceptor is
For example, taking as an example the current mainstream photoreceptor having a stacked function, light is first absorbed by the charge generation material to generate photocarriers, which are injected into the charge transport layer and transported. It is thought to be expressed by Here, it has been reported that the charge transporting material has a very large contribution not only to the charge transporting ability but also to the generation and injection of charges in the charge generating material, and the phthalocyanine compound is no exception.

In general, the charge transport layer is formed by mixing a low molecular weight charge transport material in an inert linear polymer.
As described above, it is desirable that the concentration of the charge transporting material is sufficiently high in order to sufficiently exhibit the charge generation / injection efficiency and the charge transporting ability. On the other hand, however, increasing the content of such a low-molecular-weight material lowers the film-forming property and causes the occurrence of precipitation, cracks, and the like. Further, when the mechanical strength of the film itself is reduced, the film is liable to be scraped or damaged when repeatedly used in an electrophotographic process, and sufficient durability cannot be secured.

As a means for solving these problems, an attempt to use a curable resin as a resin for the charge transport layer has been made.
For example, it is disclosed in JP-A-2-127652 or the like, but also in this case, the low molecular weight component acts as a plasticizer in the binder resin to the last,
It does not fundamentally solve the problems of precipitation and cracks as described above.

[0009] In addition, although a curable resin is used, a large amount of a low-molecular component, which contributes to sufficient photosensitivity, has a large plastic effect, and it is difficult to obtain sufficient mechanical strength. Also, JP-A-5-216249, JP-A-7-7264
In the publication No. 0, etc., the charge transport layer contains a monomer having a carbon-carbon double bond, and reacts with the carbon-carbon double bond of the charge transport material by heat or light energy to form a cured film of the charge transport layer. Although the formed electrophotographic photoreceptor is disclosed, the charge transporting material is merely fixed in a pendant manner to the polymer main skeleton, and the plastic action cannot be sufficiently eliminated, so that the mechanical strength is sufficient. is not.
In addition, when the concentration of the charge transporting material is increased to improve the charge transporting ability, the crosslink density becomes low and sufficient mechanical strength cannot be secured. Furthermore, there is a concern that the initiators required for polymerization may affect the electrophotographic properties.

Another solution is disclosed in Japanese Patent Application Laid-Open No.
JP-A-248649 discloses an electrophotographic photoreceptor having a charge transport layer formed by introducing a group having charge transport ability into a thermoplastic polymer main chain. It has an effect on precipitation etc. compared to the transport layer and improves mechanical strength, but it is a thermoplastic resin only, its mechanical strength is limited, handling including resin solubility etc. And productivity is not enough. As described above, the conventional systems have not achieved both high mechanical strength and excellent photosensitivity, and at present it is strongly desired to improve them.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide excellent light sensitivity and excellent abrasion resistance when used repeatedly.
It is still another object of the present invention to provide an electrophotographic photoreceptor which exhibits very little change or deterioration in photoreceptor characteristics such as an increase in residual potential during repeated use and can exhibit stable performance even after repeated use.

Another object of the present invention is to improve the abrasion resistance and scratch resistance of the surface layer of a photoreceptor, to provide a long-life, high-quality electrophotographic photoreceptor, a process cartridge having the electrophotographic photoreceptor, and an electrophotographic apparatus. Is to provide.

[0013]

According to the present invention, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the charge generation material in the photosensitive layer is a phthalocyanine compound,
Electrons containing one or both of a hole transporting compound having two or more chain polymerizable functional groups in the same molecule of the electrophotographic photoreceptor, and those obtained by polymerizing or crosslinking and curing the hole transporting compound by heat or ultraviolet rays. A photographic photosensitive member, a process cartridge having an electrophotographic photosensitive member, and an electrophotographic apparatus are provided.

[0014]

Embodiments of the present invention will be described below in detail.

First, the chain polymerizable functional group in the present invention will be described. The term chain polymerization in the present invention refers to the former type of polymerization reaction when the formation reaction of a polymer is largely divided into chain polymerization and sequential polymerization.For example, for example, Gihodo Shuppan Tadahiro Miwa's `` Basic synthetic resin chemistry '' (New edition) 1
July 25, 995 (1st edition, 8th press) As described in 24, the form mainly refers to unsaturated polymerization, ring-opening polymerization, isomerization polymerization and the like in which the reaction proceeds mainly through intermediates such as radicals or ions.

The chain-polymerizable functional group P in the general formula (1) means a functional group capable of performing the above-mentioned reaction mode. Here, unsaturated polymer or ring-opening polymer which occupies most of the functional group and has a wide application range. Specific examples of the functional group are shown below.

Unsaturated polymerization refers to an unsaturated group such as C ＝ C, C≡C, C ＝ O, C ＝
This is a reaction in which N, C 重合 N, and the like are polymerized, and most of the cases mainly involve CＣC. Specific examples of the unsaturated polymerizable functional group are shown in Table 1, but are not limited thereto.

[0018]

[Table 1]

In the table, R represents an alkyl group such as a methyl group, an ethyl group, or a propyl group which may have a substituent; an aralkyl group such as a benzyl group or a phenethyl group which may have a substituent; And an aryl group such as a phenyl group, a naphthyl group, and an anthryl group or a hydrogen atom which may be present.

Ring-opening polymerization is a process in which an unstable cyclic structure having a strain, such as a carbon ring, an oxo ring, or a nitrogen heterocycle, is activated by the action of a catalyst, and the polymerization is repeated at the same time as the ring is opened. Is generated, but 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.

[0021]

[Table 2]

In the table, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group which may have a substituent; an aralkyl group such as a benzyl group or a phenethyl group which may have a substituent; And an aryl group such as a phenyl group, a naphthyl group, and an anthryl group or a hydrogen atom which may be present.

Among the chain polymerizable functional groups according to the present invention as described above, the following general formulas (11) to (1)
Those shown in 3) are preferred.

[0024]

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In the formula, E is a hydrogen atom, fluorine, chlorine, bromine
A halogen atom, a methyl group which may have a substituent,
Alkyl groups and substituents such as tyl, propyl and butyl groups
A benzyl group, a phenethyl group, a naphthyl
Aralkyl groups such as tyl group, furfuryl group and thienyl group;
Optionally substituted phenyl, naphthyl, ans
Acrylic, pyrenyl, thiophenyl, furyl, etc.
Reel group, CN group, nitro group, methoxy group, ethoxy
Group, alkoxy group such as propoxy group, -COOR ²⁶Or
-CONR²⁷R²⁸Is shown.

W is an arylene group such as a divalent phenylene group, a naphthylene group or an anthracenylene group which may have a substituent, a methylene group which may have a substituent, an ethylene group,
Divalent alkylene group such as butylene group, -COO-, -O
-, - OO -, - represented by - S- or -CONR ^29.

Here, R ^{26 to} R ^{29 each} have a hydrogen atom, a halogen atom such as fluorine, chlorine or bromine, an alkyl group such as a methyl group, an ethyl group or a propyl group which may have a substituent, or a substituent. A benzyl group, an aralkyl group such as a phenethyl group or a phenyl group which may have a substituent, a naphthyl group,
It represents an aryl group such as an anthryl group, and R ²⁸ and R ²⁹ may be the same or different. F is 0 or 1
Is shown.

Examples of the substituent which may be present in E and W include a halogen atom such as fluorine, chlorine, bromine and iodine, a nitro group or a cyano group, a hydroxyl group, a methyl group, an ethyl group, a propyl group and a butyl group. An alkyl group or a methoxy group, an ethoxy group, an alkoxy group such as a propoxy group, or an aroxy group such as an aryloxy group such as a phenoxy group, a naphthoxy group, or a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, or a thienyl group; or a phenyl group. , Naphthyl group, anthryl group, aryl group such as pyrenyl group and the like.

[0029]

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In the formula, R ³⁰ and R ³¹ represent a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group or an butyl group which may have a substituent; a benzyl group which may have a substituent;
It represents an aralkyl group such as a phenethyl group or an aryl group such as a phenyl group or a naphthyl group which may have a substituent, and n represents an integer of 1 to 10 or less.

[0031]

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In the formula, R ³² and R ³³ are a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group which may have a substituent; a benzyl group which may have a substituent;
It represents an aralkyl group such as a phenethyl group or an aryl group such as a phenyl group or a naphthyl group which may have a substituent, and n represents 0 or an integer of 1 to 10 or less.

The above general formulas (12) and (1)
Examples of the substituent which R ^{30 to} R ^{33 of} 3) may have include a halogen atom such as fluorine, chlorine, bromine and iodine, or an alkyl group such as methyl group, ethyl group, propyl group and butyl group, or a methoxy group. Alkoxy groups such as ethoxy group, propoxy group or phenoxy group, aryloxy groups such as naphthoxy group, or aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group or phenyl group, naphthyl group, anthryl group And an aryl group such as a pyrenyl group.

Further, among the above general formulas (11) to (13), more particularly preferred chain polymerizable functional groups include those represented by the following general formulas (14) to (20).

[0035]

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In the present invention, "a hole-transporting compound having a chain-polymerizable functional group" means that the above-described chain-polymerizable group is chemically bonded to the above-described hole-transporting compound by two or more functional groups. Are shown. In this case, all of the chain polymerizable functional groups may be the same or different. The hole transporting compound having two or more chain polymerizable functional groups is preferably a compound represented by the following general formula (1).

[0037]

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In the formula, P ¹ and P ² represent a chain polymerizable functional group, and P ¹ and P ² may be the same or different. Z represents an organic residue which may have a substituent, and Y represents a hydrogen atom.
a, b and d each represent 0 or an integer of 1 or more. Where a
If b = 0, b + d is an integer of 3 or more; if b or d is 0, a is an integer of 2 or more; otherwise, a + b + d is 3
The following integers are shown. When a is 2 or more, P ¹ may be the same or different. When d is 2 or more, P ² may be the same or different. When b is 2 or more, Z may be the same or different. .

Here, "when a is 2 or more, P ¹ may be the same or different" means that n different kinds of chain polymerizable functional groups are respectively P ¹¹ , P ¹² , P ¹³ , P ¹⁴ , P ¹⁵ ··
··· When P ¹ⁿ is shown, for example, when a = 3, the chain polymerizable functional groups P ¹ directly bonded to the hole transporting compound A are the same, but two are the same and one is different ( For example,
P ¹¹ Toka and P ¹¹ and P ¹²⁾ But three different from even respectively (for example, if it is intended to mean that may be Toka P ¹² and P ¹⁵ and P ¹⁷⁾ ( "d is 2 or P ^"2 may be the same or different" and "when b is 2 or more, Z may be the same or different" mean the same.)

A in the general formula (1) represents a hole-transporting group, and any one having a hole-transporting property may be used. The bonding site with P ¹ or Z is replaced by a hydrogen atom. As a hydrogenation compound (hole transport compound), for example,
Oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triarylamine derivatives such as triphenylamine, 9- (P-diethylaminostyryl) anthracene, 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, Styryl pyrazoline, phenylhydrazone, thiazole derivative, triazole derivative, phenazine derivative, acridine derivative, benzofuran derivative, benzimidazole derivative,
Thiophene derivatives, N-phenylcarbazole derivatives,
Optionally substituted naphthalene, anthracene, phenanthrene, pyrene, fluorene, fluorancene, azulene, indene, perylene, chrysene, condensed ring hydrocarbons such as coronene, or optionally substituted benzofuran, indole, carbazole , Benzcarbazole,
Condensed complex rings such as acridine, phenothiazine and quinoline;

Further, among the above hole transport compounds, those represented by the following formulas (2), (3), (4), (5) and (7) are preferable.

[0042]

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In the formula, R ¹ , R ² and R ³ each have an optionally substituted C ₁ -C ₁₀ alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; Benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, aralkyl group such as thienyl group or phenyl group optionally having a substituent, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl And aryl groups such as a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, and a dibenzothiophenyl group.

[0044] provided that at least two of R ^1, R ² and R ³ represents an aryl group, R ^1, R ² and R ³ may each be the same or different. Further, among them, those in which all of R ¹ , R ² and R ³ are aryl groups are particularly preferred. Any two of R ¹ or R ² or R ^{3 in} the general formula (2) may be bonded directly or via a bonding group, and the bonding group includes a methylene group, an ethylene group, Examples include an alkylene group such as a propylene group, a hetero atom such as an oxygen and sulfur atom, and a CH = CH group.

[0045]

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In the formula, R ⁴ , R ⁵ , R ⁸ and R ⁹ are a C ₁ -C ₁₀ alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group which may have a substituent; May have a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, an aralkyl group such as a thienyl group or an optionally substituted phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl Group, furyl group,
An aryl group such as a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, a dibenzothiophenyl group, and R ⁴ , R ⁵ , R ⁸ and R ⁹ May be the same or different. R ⁶ and R ⁷ are a methylene group which may have a substituent, an ethylene group,
A C ₁ -C ₁₀ alkylene group such as a propylene group or an optionally substituted arylene group (benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran From benzothiophene, dibenzofuran, dibenzothiophene, etc.
Arylene groups from which hydrogen has been removed), R ⁶ and R ⁷
May be the same or different. Q represents an organic residue which may have a substituent.

Further, among them, R in the above general formula (3)
It is preferable that two or more of ⁴ , R ⁵ , R ⁸ and R ⁹ are an aryl group which may have a substituent, and R ⁶ and R ⁷ are an arylene group which may have a substituent. , And R ⁴ ,
It is particularly preferred that all of R ⁵ , R ⁸ and R ⁹ are aryl groups which may have a substituent. Any two of R ^4, R ^5, or R ⁶ of the general formula (3) or any two of R ^7, R ^8, or R ⁹ may be bonded directly or via a bonding group, respectively. Examples of the bonding group include an alkylene group such as a methylene group, an ethylene group and a propylene group, a hetero atom such as an oxygen atom and a sulfur atom, and CH ＝ C.
H group and the like.

[0048]

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In the formula, m represents 0 or 1, and R ^{10 to} R ¹³ are a C _{1 to} C ₁₀ alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group which may have a substituent; Optionally substituted benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, aralkyl group such as thienyl group or optionally substituted phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group , a thiophenyl group, a furyl group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, an aryl group such as a dibenzothiophenyl group, R ¹⁰ to R
¹³ may be the same or different.

Ar ¹ is an optionally substituted arylene group (benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine,
An arylene group obtained by removing two hydrogen atoms from benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, or the like), and when m ² is 0, a phenyl group, a naphthyl group, an anthryl group, which may have a substituent, Represents an aryl group such as a phenanthryl group, a pyrenyl group, a thiophenyl group, a furyl group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, and a dibenzothiophenyl group. , M = 1 represents the same arylene group as Ar ¹ described above. When m = 1, Ar ¹ and Ar ² may be the same or different.

Further, among them, R in the above general formula (4)
^TenAnd R¹¹Is an aryl group which may have a substituent
Is preferred, and R^Ten~ R¹³Have all four substituents
Particularly preferred is an aryl group which may be substituted. Also,
R of the above general formula (4)^TenAnd R ¹¹Or R¹²And R¹³Or Ar
¹And Ar^TwoAre linked directly or via a linking group, respectively
And the bonding group may be a methylene group,
Alkylene groups such as oxygen and propylene groups, oxygen and sulfur atoms
And the like, a CH ＝ CH group and the like.

[0052]

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In the formula, at least one of Ar ³ , Ar ⁴ and R ¹⁴ has at least one substituent represented by the following general formula (6).

[0054]

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In the above general formulas (5) and (6), Ar ³ ,
Ar ⁴ and Ar ⁵ are a phenyl group which may have a substituent,
Naphthyl, anthryl, phenanthryl, pyrenyl, thiophenyl, furyl, pyridyl, quinolyl, benzoquinolyl, carbazolyl, phenothiazinyl, benzofuryl, benzothiophenyl, dibenzofuryl, dibenzothiophenyl And R ¹⁴ , R ¹⁵ and R ¹⁶ each represent a C ₁ to C ₅ group such as a methyl group, an ethyl group, a propyl group, or a butyl group which may have a substituent.
A C ₁₀ alkyl group, a benzyl group which may have a substituent,
Phenethyl group, naphthylmethyl group, furfuryl group, aralkyl group such as thienyl group, phenyl group which may have a substituent, naphthyl group, anthryl group, phenanthryl group,
Pyrenyl group, thiophenyl group, furyl group, pyridyl group,
Represents an aryl group such as a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, a dibenzothiophenyl group, or a hydrogen atom (however, when R ¹⁴ is a hydrogen atom, except). Note that Ar ³ and Ar ⁴ and R ¹⁵ and R
¹⁶ may be the same or different.

Further, among them, it is particularly preferred that R ¹⁴ and R ¹⁶ are aryl groups. Further, any two of R ¹⁴ or Ar ³ or Ar ⁴ , or Ar ⁵ and R ¹⁶ may be bonded directly or via a bonding group, and the bonding group includes a methylene group, an ethylene group, Alkylene group such as propylene group, hetero atom such as oxygen and sulfur atom, C
H = CH group and the like. n ¹ is an integer of 0 or 1.

[0057]

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However, the general formula (7), the condensed ring hydrocarbon and the condensed complex ring have at least one substituent represented by the following general formula (8).

[0059]

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In the above general formulas (7) and (8), Ar⁶Passing
And Ar⁷Is a phenyl group which may have a substituent, naphthyl
Group, anthryl group, phenanthryl group, pyrenyl group,
Ophenyl, furyl, pyridyl, quinolyl,
Nzoquinolyl group, carbazolyl group, phenothiazinyl
Group, benzofuryl group, benzothiophenyl group, dibenzo
Represents an aryl group such as a furyl group or dibenzothiophenyl group
Then R¹⁷, R¹⁸, R¹⁹And R²⁰May have a substituent
C such as methyl group, ethyl group, propyl group and butyl group ₁~
C_TenAn alkyl group, a benzyl group which may have a substituent,
Phenethyl, naphthylmethyl, furfuryl, thie
Aralkyl groups such as an enyl group, and phenyl which may have a substituent;
Group, naphthyl group, anthryl group, phenanthryl group,
Pyrenyl group, thiophenyl group, furyl group, pyridyl group,
Quinolyl, benzoquinolyl, carbazolyl,
Notiazinyl, benzofuryl, benzothiophenyl
Groups, dibenzofuryl groups, dibenzothiophenyl groups, etc.
Represents a reel group or a hydrogen atom (provided that R¹⁷And R¹⁸Is hydrogen
Excluding atoms). Note that R¹⁷And R¹⁸And R¹⁹When
R²⁰May be the same or different.

Among them, it is preferable that R ²⁰ is an aryl group, and it is particularly preferable that the hole transporting group is represented by the general formula (2) and R ¹⁷ and R ¹⁸ are aryl groups. Further, any two of R ¹⁷ or R ¹⁸ or Ar ⁶ , or A
r ⁷ and R ²⁰ may be bonded directly or via a bonding group. Examples of the bonding group include a methylene group, an ethylene group, an alkylene group such as a propylene group, a hetero atom such as oxygen and a sulfur atom, and CH = CH group and the like. n ²
Represents 0 or an integer of 1 to 2.

Z in the above general formula (1) or Q in the above general formula (3) represents an alkylene group which may have a substituent, an arylene group which may have a substituent, CR ²¹ = CR
²² (R ²¹ and R ²² represent an alkyl group, an aryl group or a hydrogen atom, and R ²¹ and R ²² may be the same or different),
C = O, S = O, SO ₂ , an organic residue which is one or arbitrarily combined from an oxygen atom or a sulfur atom. Among them, a compound represented by the following general formula (9) is preferable, and a compound represented by the following general formula (10) is particularly preferable.

[0063]

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[0064]

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In the above general formula (9), X ^{1 to} X ³ are a C _{1 to} C ₂₀ alkylene group such as a methylene group, an ethylene group or a propylene group which may have a substituent, and (CR ²³ = CR ²⁴ ) M ¹ ,
C = O, S = O, SO ₂ , an oxygen atom or a sulfur atom, and Ar ⁸ and Ar ⁹ are optionally substituted arylene groups (benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine , Quinoline, benzoquinoline, carbazole, phenothiazine,
An arylene group obtained by removing two hydrogen atoms from benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, or the like. R ²³ and R ²⁴ each may have an alkyl group such as a methyl group, an ethyl group, or a propyl group;
An aryl group or a hydrogen atom such as a phenyl group, a naphthyl group, and a thiophenyl group which may have a substituent, and R ²³ and R ²⁴ may be the same or different. m ¹ is an integer of ¹ to 5,
pt indicates 0 or an integer of 1 to 10 (however, pt is not simultaneously 0).

In the general formula (10), X ⁴ and X ⁵ represent (C
H ₂ ) _g , (CH ＝ CR ²⁵ ) _h , C ＝ O, or an oxygen atom, and Ar ¹⁰ is an optionally substituted arylene group (benzene, naphthalene, anthracene, phenanthrene,
An arylene group in which two hydrogen atoms have been removed from pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, or the like. R ²⁵ represents an alkyl group such as a methyl group, an ethyl group or a propyl group which may have a substituent, an aryl group such as a phenyl group, a naphthyl group or a thiophenyl group which may have a substituent, or a hydrogen atom. g represents an integer of 1 to 10, h represents an integer of 1 to 5, and u to w represents an integer of 0 or 1 to 10 (especially 0 or an integer of 1 to 5 is preferable.
w cannot be 0 at the same time).

It should be noted that R in the above general formulas (1) to (10)
Substituents that each of ^{1 to} R ²⁵ , Ar ^{1 to} Ar ¹⁰ , X ^{1 to} X ⁵ , Z and Q may have are fluorine, chlorine, bromine,
A halogen atom such as iodine or a nitro group or a cyano group or a hydroxyl group or an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, or an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group, or a phenoxy group or a naphthoxy group; Aryloxy or benzyl group, phenethyl group,
Naphthylmethyl group, furfuryl group, aralkyl group such as thienyl group or phenyl group, naphthyl group, anthryl group,
An aryl group such as a pyrenyl group or a substituted amino group such as a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, a di (p-tolyl) amino group; an arylvinyl group such as a styryl group or a naphthylvinyl group; No.

In the present invention, the hole transporting compound having two or more chain polymerizable functional groups in the same molecule 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 preferably have an oxidation potential of 1.2 (V) or less. , 0.4 to 1.2 (V).
That is, if the oxidation potential exceeds 1.2 (V), injection of charges (holes) from the charge generating material is difficult to occur, causing problems such as an increase in residual potential, deterioration in sensitivity, and a large potential fluctuation during repeated use. If the voltage is less than 0.4 (V), the compound itself is easily oxidized and deteriorates easily in addition to problems such as a decrease in charging ability, resulting in deterioration of sensitivity, image blur and potential fluctuation during repeated use. This is because a problem such as an increase in size occurs.

The oxidation potential described here is measured by the following method.

(Method of Measuring Oxidation Potential) A saturated calomel electrode was used as a reference electrode, and 0.1 N (n-Bu) ₄ N ⁺ ClO ₄ was used as an electrolyte.
^- using the acetonitrile solution, sweeping the potential applied to the working electrode (platinum) by the potential sweeper,
The potential when the obtained current-potential curve showed a peak was defined as the oxidation potential. Specifically, the sample is set to 0.1N (n-B
^{_{u) 4 N + ClO 4 -}} 5~10mmo in acetonitrile solution
Dissolve to a concentration of about 1%. Then, a voltage is applied to this sample solution by a 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 when the current value showed a peak (the first peak when there were a plurality of peaks) was defined as the oxidation potential.

Further, the hole transporting compound having a chain polymerizable functional group has a hole transporting ability of 1 × 10 ⁻⁷ (cm ^2).
/ V. sec) or more having a drift mobility of at least (provided electric field: 5 × 10 ⁴ V / cm). 1x
If it is less than 10 ^-7 (cm ² /V.sec), there is a problem that, as an electrophotographic photoreceptor, holes cannot move sufficiently before development after exposure, so that the sensitivity apparently decreases and the residual potential increases. There are cases.

The following are typical examples of the hole transporting compound having a chain polymerizable functional group according to the present invention, but the invention is not limited thereto.

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In the present invention, a typical method for synthesizing a hole transporting compound having a chain polymerizable functional group is shown below.

(Synthesis Example 1: Synthesis of Compound No. 6) The compound was synthesized according to the following route.

[0164]

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1 (50 g: 0.47 mol), 2 (406
g: 1.4 mol), anhydrous potassium carbonate (193 g) and copper powder (445 g) in 1.2 kg of 1,2-dichlorobenzene.
At 180 to 190 ° C. for 15 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.

3 (120 g: 0.28 mol) was added to 1.5 kg of methylcellosolve, and sodium methylate (150 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 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 by a silica gel column to give 78 g of 4.

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 to 5 ° C., and acryloyl chloride (55 g: 0.6 mol) was slowly added dropwise. did. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into water, neutralized, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was subjected to column purification using a silica gel column to obtain 42 g of 5 (compound No. 6) (oxidation potential: 0.83 V).

(Synthesis Example 2: Synthesis of Compound No. 71) 4 (10 g: 29 mmol) obtained in the above Synthesis Example 1 was added to 50 ml of dry THF, cooled to 0 to 5 ° C., and then oily sodium hydride (about 60% 3.5 g was added slowly.
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 obtained.
Was slowly added dropwise. After the completion of the dropwise addition, the mixture was stirred for 1 hour, 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 with a silica gel column to purify the target compound (Compound No. 7).
5.6 g of 1) was obtained (oxidation potential: 0.81 V).

Synthesis Example 3: Synthesis of Compound No. 55 3.0 g of Compound No. 71 obtained in Synthesis Example 2 was dissolved in 20 ml of dichloromethane, cooled to 0 to 5 ° C., and m-chloroperbenzoic acid was added. (-70%) 5.2 g was slowly added, and the mixture was stirred for 1 hour, then returned to room temperature and stirred for 12 hours. The reaction solution was poured into water and extracted with dichloromethane. After 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 desired compound (Compound No. 55) (oxidation potential: 0.81 V).

(Synthesis Example 4: Synthesis of Compound No. 152)
Synthesized according to the following route.

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1 (70 g: 0.35 mol), 2 (98
g: 0.42 mol), anhydrous potassium carbonate (73 g) and copper powder (111 g) in 600 g of 1,2-dichlorobenzene.
At 180 to 190 ° C. for 10 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 86.2 g of 3.

3 (80 g: 0.26 mol) was added to 300 g of N, N-dimethylformamide (DMF), and ethanethiol sodium salt (about 90%:
62g) was added slowly. 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 was poured into water, made weakly acidic with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer was further extracted with a 1.2 N aqueous sodium hydroxide solution, the aqueous layer was 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 with a silica gel column to give 64 g of 4.

4 (60 g: 0.21 mol) was converted to N, N-
Caustic soda (8.3 g) was slowly added to 300 g of dimethylformamide 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 stirring for 30 minutes after completion of dropping, the mixture was 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 purified with a silica gel column to give 49.1 g of 5.

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 the completion of dropping, 5 (4
(2.2 g: 0.07 mol) / 102 g of DMF was slowly added dropwise. After completion of the dropping, the mixture was stirred for 30 minutes, 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 an aqueous solution of about 15% sodium acetate and stirred for 12 hours. After neutralizing it, extraction was performed with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified by column using a silica gel column to obtain 23 g of 6.

0.89 g of lithium aluminum hydride was added to 100 ml of dry THF, and the mixture was stirred at room temperature. 6 (15 g: 0.023 mol) / 100 m of dry THF
1 solution was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours, and 200 ml of a 5% hydrochloric acid aqueous solution was slowly added dropwise. After completion of the dropwise addition, the mixture was 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 13.6 g of 7.

7 (10 g: 0.015 mol) and triethylamine (6.1 g: 0.06 mol) were added to dry THF 1
After adding 20 ml and cooling to 0-5 ° C, 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 the mixture was 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 by column using a silica gel column to obtain 6.4 g of 8 (Compound No. 152) (oxidation potential:
0.78V).

(Synthesis Example 5: Synthesis of Compound No. 263)
Synthesized according to the following route.

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1 (50 g: 0.123 mol), 2 (6
2.4 g: 0.369 mol), anhydrous potassium carbonate (25.
5 g) and copper powder (32 g) were heated and stirred at 180 to 190 ° C. for 18 hours together with 200 g of 1,2-dichlorobenzene. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was recrystallized twice with a mixed solvent of toluene / methanol to obtain 60.2 g of 3.

After cooling 242 g of DMF to 0 to 5 ° C., phosphorus oxychloride (84.8 g: 553.2 mmol) was added at 10 ° C.
Was slowly dropped so as not to exceed. After stirring for 15 minutes after the completion of the dropwise addition, 3 (45.0 g: 92.2 mmol) / D
A 135 g solution of MF was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 30 minutes, returned to room temperature, stirred for 2 hours, and
The mixture was heated to 85 ° C. and stirred for 8 hours. About 15%
And then stirred for 12 hours. After neutralization, 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 40.5.
g was obtained.

0.89 g of lithium aluminum hydride was added to 100 ml of dry THF, and the mixture was stirred at room temperature. 4 (37 g: 68 mmol) / 600 ml of dry THF
The solution was slowly dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours, and then 500 ml of a 5% hydrochloric acid aqueous solution was slowly added dropwise. After completion of the dropwise addition, the mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was purified by a silica gel column to give 26.3 g of 5.

5 (20 g: 36 mmol) and triethylamine (12.8 g: 126 mol) were added to dry THF 1
After adding 30 ml and cooling to 0-5 ° C, 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 the mixture was 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 with a silica gel column to give 11.2 g of 6 (Compound No. 263) (oxidation potential:
0.80V).

(Synthesis Example 6: Synthesis of Compound No. 320)
Synthesized according to the following route.

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1 (50 g: 0.173 mol), 2 (8.
0 g: 86 mmol), anhydrous potassium carbonate (47.8 g)
And copper powder (55 g) in 1,2-dichlorobenzene 200
The mixture was heated and stirred at 180 to 190 ° C. for 13 hours together with the g. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was recrystallized twice with an acetone / methanol mixed solvent to obtain 51 g of 3.

After cooling 35 g of DMF to 0 to 5 ° C., phosphorus oxychloride (18.4 g: 0.12 mol) was slowly added dropwise so as not to exceed 10 ° C. After completion of the dropwise addition, the mixture was stirred for 15 minutes, and then 3 (50.0 g: 0.12 mol) / DMF50
g solution was slowly added dropwise. After completion of the dropping, the mixture was stirred for 30 minutes, returned to room temperature, stirred for 1 hour, further heated to 80 to 85 ° C., and stirred for 5 hours. The reaction solution was poured into about 15% aqueous sodium acetate solution (800 g) and stirred for 12 hours. After neutralization of the residue, the residue 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 37.8 g of 4.

4 (30 g: 67 mmol) and 1,1-diphenylmethyldiethyl phosphate (20.5 g: 6
7 mmol) was dissolved in 200 ml of dry THF, and oily sodium hydride (about 60%: 2.97 g: about 74 mmol) was slowly added thereto at room temperature. After completion of the addition, the mixture was stirred at room temperature for 30 minutes and then heated and stirred for 3 hours. After cooling, the reaction solution was poured into water and extracted with toluene. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed. The residue was purified by a silica gel column to give 21.1 g of 5.

5 (20 g: 33.6 mmol) was added to 200 g of methylcellosolve, and sodium methylate (7.0 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 then further heated at 70-80 ° C for 1 hour.
Heating and stirring were performed for 2 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 with a silica gel column to give 15.1 g of 6.

6 (15 g: 29.3 mmol) and triethylamine (8.88 g: 87.9 mmol) were added to 100 ml of dry THF, cooled to 0-5 ° C., and acryloyl chloride (8.0 g: 88.4 mmol) was slowly added. It was dropped. After the completion of dropping, slowly return to room temperature, and leave at room temperature for 6 hours.
Stirring was performed for hours. The reaction solution was poured into water, neutralized, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified with a silica gel column to give 9.8 g of 7 (Compound No. 320) (oxidation potential: 0.76 V).

(Synthesis Example 7: Synthesis of Compound No. 410)
Synthesized according to the following route.

[0192]

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1 (50 g: 0.173 mol), 2 (7.
5 g: 81 mmol), anhydrous potassium carbonate (47.8 g)
And copper powder (55 g) in 1,2-dichlorobenzene 200
The resulting mixture was heated and stirred at 180 to 190 ° C. for 10 hours together with g. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was purified using a silica gel column to obtain 58 g of 3.

After cooling 35 g of DMF to 0 to 5 ° C., phosphorus oxychloride (18.4 g: 0.12 mol) was slowly added dropwise so as not to exceed 10 ° C. After completion of the dropwise addition, the mixture was stirred for 15 minutes, and then 3 (50.0 g: 0.12 mol) / DMF50
g solution was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 30 minutes, returned to room temperature, stirred for 1 hour, further heated to 80 to 85 ° C., and stirred for 5 hours. The reaction solution was poured into about 15% aqueous sodium acetate solution (800 g) and stirred for 12 hours.
After neutralization of the residue, the residue 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 37.8 g of 4.

4 (25 g: 56 mmol) was added to 200 ml of ethanol, and 1,1-diphenylhydrazine hydrochloride (35 g: 159 mmol) was added thereto. After completion of the addition, the mixture was stirred at room temperature for 1 hour and then stirred at 50 ° C. for 2 hours. After cooling, the reaction solution was poured into water and extracted with toluene. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed. The residue was purified by a silica gel column to give 24.5 g of 5.

5 (20 g: 33 mmol) was added to 200 g of methylcellosolve, and sodium methylate (12.0 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 stirred at 40 to 50 ° C for 8 hours.
Heating and stirring were performed for 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 with a silica gel column to give 7.1 g of 6.

6 (7.0 g: 11 mmol) and triethylamine (3.5 g: 35 mmol) were added to dry THF 10
After adding 0 ml and cooling to 0 to 5 ° C, acryloyl chloride (2.5 g: 28 mmol) was slowly added dropwise. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into water, neutralized, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified with a silica gel column to give 2.8 g of 7 (Compound No. 410) (oxidation potential: 0.69).
V).

In the present invention, the compound having a hole transporting property in the photosensitive layer is obtained by polymerizing and crosslinking a hole transporting compound having two or more chain polymerizable functional groups in the same molecule. Is incorporated into a three-dimensional crosslinked structure via a covalent bond with two or more crosslink points. The hole transporting compound can be polymerized / crosslinked alone or mixed with a compound having another chain polymerizable group, and the type / ratio thereof is all arbitrary. The compound having another chain polymerizable group as referred to herein means a monomer or oligomer having a chain polymerizable group.
Any of the polymers are included.

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 which can be polymerized with each other, both of them have a copolymerized three-dimensional crosslinked structure via a covalent bond. It is possible to take When the two functional groups are functional groups that do not polymerize with each other, the photosensitive layer may be a mixture of two or more three-dimensional cured products or a three-dimensional cured product of the main component in which another chain-polymerizable compound monomer or its monomer is present. Although it is configured as containing a cured product, its compounding ratio /
By properly controlling the film forming method, IPN (I
internet Penetrating Network)
That is, it is possible to form a mutual intrusion network structure.

Further, a photosensitive layer is formed from the above-mentioned hole transporting compound and a monomer or oligomer / polymer having no chain polymerizable group or a monomer or oligomer / polymer having a polymerizable group other than chain polymerizable group. May be.

Further, in some cases, it is possible to contain a hole transporting compound which is not chemically incorporated into the three-dimensional crosslinked structure, that is, has no chain polymerizable functional group. Further, other various additives, lubricants such as fine particles of fluorine atom-containing resin and the like may be contained.

The photoreceptor of the present invention may have a structure in which a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material are laminated in this order on a conductive support, or vice versa. It is possible to adopt any of the above-described configurations and a configuration including a single layer in which the charge generation material and the charge transport material are dispersed in the same layer. In the former laminated type, the charge transport layer may have two or more layers, and in the latter single layer type, a charge transport layer may be further formed on the photosensitive layer containing the same charge generation material and charge transport material. Further, a protective layer can be formed on the charge generation layer or the charge transport layer.

In any of these cases, if the photosensitive layer contains one or both of the above-described hole transporting compound having a chain polymerizable group and the one obtained by polymerizing or crosslinking the preceding hole transporting compound and curing the compound. Good. However, in view of the characteristics as an electrophotographic photoreceptor, in particular, electrical characteristics such as residual potential and durability, a function-separated type photoreceptor having a charge generation layer / charge transport layer laminated in this order is preferable. The advantage is also charge generation
/ It is possible to increase the durability of the surface layer without lowering the injection efficiency and the charge transport ability.

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

The support of the electrophotographic photosensitive member may be any conductive material, for example, aluminum,
A metal or alloy such as copper, chromium, nickel, zinc and stainless steel formed into a drum or sheet, a metal foil such as aluminum and copper laminated on a plastic film, a plastic film made of aluminum, indium oxide and tin oxide And a metal provided with a conductive layer by applying a conductive material alone or together with a binder resin, and a plastic film and paper.

In the present invention, an undercoat layer having a barrier function and an adhesive function can be provided on the conductive support. The undercoat layer is used for improving the adhesiveness of the photosensitive layer, improving the coating property, protecting the support, covering defects on the support, improving the charge injection property from the support, and protecting the photosensitive layer against electrical breakdown. Formed.

As materials for the undercoat layer, polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, copolymer nylon, Glue and gelatin are known. These are dissolved in a suitable solvent and applied on a support. At this time, the film thickness is set to 0.
1-2 μm is preferred.

When the photoreceptor of the present invention is a function-separated type photoreceptor, a charge generation layer and a charge transport layer are laminated. The charge generation layer contains a metal-free or metal phthalocyanine compound, and if necessary, is composed of such a charge generation material and a suitable binder resin. Here, the central metal can take any form of a metal element alone or a metal compound such as an oxide, a halide such as chlorine or fluorine, or a hydroxide. Further, a polymer having a dimer or more multimeric structure or a substituent may be used.

Among these, among the metal-free phthalocyanines and metal phthalocyanines, oxytitanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are preferred because they exhibit particularly good photoreceptor characteristics. Further, these phthalocyanines have crystal forms such as α, β, γ, ε and X type,
The choice is arbitrary. It is also possible to use a mixture of two or more of various phthalosinin compounds. Further, as other charge generating materials, inorganic materials such as selenium and silicon, anthantrone pigments, dibenzopyrene quinone pigments, pyranthrone pigments, trisazo pigments, disazo pigments, monoazo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments It is also possible to mix organic materials such as quinocyanine and the like.

In the case of the function-separated type photoreceptor, the charge generation layer is formed by mixing the charge generation material with a binder resin and a solvent in an amount of 0.3 to 4 times the amount of a homogenizer, ultrasonic dispersion, ball mill,
It is well dispersed by a method such as a vibrating ball mill, a sand mill, an attritor, and a roll mill, coated with a dispersion, and dried, or formed as a film having a single composition such as a vapor-deposited film of the charge generation material. The thickness is preferably 5 μm or less, particularly preferably in the range of 0.1 to 2 μm.

When a binder resin is used, for example, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylate, methacrylate, vinylidene fluoride and trifluoroethylene, polyvinyl alcohol, polyvinyl alcohol Acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin,
Phenol resins, melamine resins, silicon resins, epoxy resins, and the like.

The hole transporting compound having a chain polymerizable functional group according to the present invention may be a charge transporting layer comprising a charge transporting material and a binder resin on the charge generating layer or on the charge generating layer. Can be used as a surface protective layer having a hole transporting ability. In any case, the method of forming the surface layer is generally that a solution containing the hole transporting compound is applied, followed by polymerization or cross-linking to cause a curing reaction, but the hole transporting compound is contained in advance. After reacting the solution to obtain a cured product,
It is also possible to form the surface layer using a material that is dispersed or dissolved again in a solvent.

[0213] The method of applying these solutions is, for example, as follows.
A dip coating method, a spray coating method, a curtain coating method, a spin coating method and the like are known, but a dip coating method is preferred from the viewpoint of efficiency and productivity. In addition, vapor deposition, plasma, and other known film forming methods can be appropriately selected.

In the present invention, the polymerization / crosslinking reaction of the chain polymerizable group can use either heat or light. When the polymerization reaction is carried out by heat, the polymerization reaction proceeds only with heat energy and a polymerization initiator may be required.However, in order to promote the reaction efficiently at a lower temperature, the addition of the initiator is required. Is desirable.

The polymerization initiator used in this case may be any one having a half-life at room temperature or higher. Specific examples thereof include ammonium persulfate, dicumyl peroxide,
Examples thereof include peroxides such as benzoyl peroxide, cyclohexane peroxide, t-butyl hydroperoxide and di-t-butyl peroxide, and azo compounds such as azobisbutyronitrile. The addition amount is 0.01 to 1 part by weight based on 100 parts by weight of the total weight of the compound having a chain polymerizable group.
It is about 0 parts by weight, and the temperature of the reaction system can be appropriately selected from room temperature to 200 ° C. depending on the initiator.

In the case of polymerization and crosslinking using light in the present invention, it is extremely rare that the reaction proceeds only by light energy, and a photopolymerization initiator is generally used in combination.
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, but specific examples thereof include:
Radical polymerization initiators such as acetophenone, benzoin, benzophenone, and thioxanthone, diazonium compounds, sulfonium compounds, iodonium compounds,
And ionic polymerization initiators such as metal complex compounds.

In recent years, however, a polymerization initiator which absorbs light in the infrared / visible region at a wavelength of 400 nm or more and generates the above-mentioned active species has been disclosed, and their use is also possible. The amount of the initiator to be added is 1 to the total weight of the compound having a chain polymerizable group.
It is about 0.01 to 50 parts by weight with respect to 00 parts by weight.
In the present invention, the above-mentioned heat and photopolymerization initiators can be used in combination.

When the hole transporting compound having a chain polymerizable group is used as the charge transporting layer, the amount of the hole transporting compound is based on the total weight of the charge transporting layer film after curing. The hydrogenated product of the hole transporting group A having a chain polymerizable functional group represented by the general formula (1) is 20% in terms of molecular weight.
More preferably, it is desirable to contain 40% or more. If it is less than that, the charge transporting ability decreases, and problems such as a decrease in sensitivity and an increase in residual potential occur. In this case, the film thickness of the charge transport layer is preferably from 1 to 50 μm, and particularly preferably from 3 to 30 μm.

When the above-mentioned hole transporting compound is used as a surface protective layer on the charge generating layer / charge transporting layer, the underlying charge transporting layer may be made of a suitable charge transporting material such as poly-N
-A polymer compound having a heterocyclic or condensed polycyclic aromatic such as vinylcarbazole, polystyrylanthracene, or pyrazoline, imidazole, oxazole, triazole,
Suitable are heterocyclic compounds such as carbazole, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, low molecular weight compounds such as phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, and hydrazone derivatives. A solution obtained by dispersing / dissolving in a solvent together with a suitable binder resin (which can be selected from the above-described resins for the charge generation layer) can be applied and dried by the above-described known method.

In this case, the ratio of the charge transporting material to the binder resin is desirably 30 to 100, preferably 50, when the total weight of both is 100.
It is appropriately selected in the range of ~ 100. If the amount of the charge transporting material is less than that, the charge transporting ability is reduced, causing problems such as a decrease in sensitivity and an increase in residual potential. The total thickness of the charge transport layer, including the upper surface protective layer, is 1 to 50 μm.
Is determined so as to be preferably adjusted in the range of 5 to 30 μm.

In the present invention, in any of the cases described above, the charge transporting material can be contained in the photosensitive layer containing the cured product of the hole transporting compound.
In the case of a single-layer type photosensitive layer, the charge-generating material is simultaneously contained in the solution containing the hole-transporting compound, and the solution may be provided with an appropriate undercoat layer or an intermediate layer.
The case where the polymer is formed by polymerization and crosslinking after coating on the conductive support, and the case where the hole transport is performed on the single-layer photosensitive layer composed of the charge generation material and the charge transport material provided on the conductive support. Any of the methods of polymerizing and cross-linking after applying the solution containing the acidic compound is possible.

Various additives can be added to the photosensitive layer in the present invention. The additive is a deterioration inhibitor such as an antioxidant and an ultraviolet absorber, a lubricant such as fine particles of a fluorine atom-containing resin, and the like.

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 driven to rotate around a shaft 2 at a predetermined peripheral speed in a direction indicated by an arrow. The photoreceptor 1 rotates during the rotation process.
The peripheral surface thereof is uniformly charged at a predetermined positive or negative potential by the primary charging means 3, and then image exposure light 4 from an image exposure means (not shown) such as slit exposure or laser beam scanning exposure.
Receive. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.

[0225] The formed electrostatic latent image is then
The toner-developed image is developed by the image forming apparatus, and the developed toner-developed image is taken out from a paper feeding unit (not shown) between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1 and fed.
Are sequentially transferred by the transfer means 6.

The transfer material 7 which has undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing, thereby being printed out of the apparatus as a copy.

After the transfer of the image, the surface of the photoreceptor 1 is cleaned by removing the untransferred toner by the cleaning means 9, and the pre-exposure light 10 from the pre-exposure means (not shown).
Is used for image formation repeatedly after the charge removal processing. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure is not necessarily required.

In the present invention, a plurality of components such as the above-described electrophotographic photosensitive member 1, primary charging means 3, developing means 5, and cleaning means 9 are integrally connected as a process cartridge. The process cartridge may be configured to be detachable from a main body of an electrophotographic apparatus 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 photoreceptor 1 to form a cartridge, which can be attached to and detached from the apparatus main body using a guide unit such as a rail 12 of the apparatus main body. Process cartridge 1
It can be 1.

When the electrophotographic apparatus is a copier or a printer, the image exposure light 4 is reflected light or transmitted light from the original, or the original is read by a sensor, converted into a signal, and a laser beam is emitted in accordance with the signal. Beam scanning,
Light emitted by driving the LED array, driving the liquid crystal shutter array, and the like.

The electrophotographic photosensitive member of the present invention can be used not only for an electrophotographic copying machine but also for a laser beam printer,
It can be widely used in electrophotographic applications such as CRT printers, LED printers, liquid crystal printers, and laser plate making.

[0231]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. In addition, "part" shows a weight part.

Example 1 First, a paint for a conductive layer was prepared in the following procedure. 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of phenolic resin, 20 parts of methyl cellosolve, 5 parts of methanol, and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average (Molecular weight 3000)
It was prepared by dispersing 0.002 parts in a sand mill using 1 mmφ glass beads for 2 hours. 30mm of this paint
It was applied on a φ 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.

Next, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare a coating for an intermediate layer. This paint was applied on the conductive layer by a dip coating method and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.6 μm.

Next, the CuKα characteristic X-ray diffraction Bragg angles (2θ ± 0.2 °) of 9.0 °, 14.2 °, 23.9 °
3 parts of oxytitanium phthalocyanine having strong peaks at 2 ° and 27.1 °, polyvinyl butyral resin 2
And 35 parts of cyclohexanone were dispersed for 2 hours by a sand mill using 1 mmφ glass beads, and then 60 parts of ethyl acetate was added to obtain a paint for a charge generation layer. This paint was applied on the above-mentioned 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.

Next, Compound Example No. 6, a photopolymerization initiator of the following structural formula (21):
6 parts of monochlorobenzene 30 parts / dichloromethane 30
Of the mixed solvent to prepare a coating material for the charge transport layer. This paint is coated on the charge generation layer,
By curing with a light intensity of 500 mW / cm ² for 30 seconds using a metal halide lamp, a charge transport layer having a thickness of 15 μm was formed, and an electrophotographic photosensitive member was obtained.

[0236]

Embedded image

With respect to the produced electrophotographic photosensitive member, the photosensitive member was mounted on LBP-SX manufactured by Canon Inc., and the electrophotographic characteristics and durability were evaluated. Initial photoconductor characteristics [dark section potential Vd, light attenuation sensitivity (dark section potential -1 at 700 V setting)
And the residual potential Vsl (potential when irradiating a light amount three times the light attenuation sensitivity light amount)], and further conducts a 10,000-sheet paper endurance test and visually observes it. Of the occurrence of image defects, the amount of scraping of the photoreceptor, and the characteristics of the photoreceptor after the endurance were measured. The amount of change in Vl when the light amount was irradiated after the durability test) and ΔVsl were determined.

The results are shown in Table 3. The photoreceptor of the present invention has very good initial photoreceptor characteristics, a small amount of abrasion at endurance, and almost no change in photoreceptor characteristics at endurance. It shows very stable and good characteristics, such as not being able to be performed.

(Example 2) In Example 1, oxytitanium phthalocyanine was used in place of the Bragg angle (2θ ± 0.2) of CuKα characteristic X-ray diffraction described in JP-A-5-98181.
2 °) 7.4 °, 16.6 °, 25.5 °, and 2
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the crystalline chlorogallium phthalocyanine having a strong peak at 8.3 ° was replaced. Table 3 shows the results.

(Example 3) In Example 1, oxytitanium phthalocyanine was subjected to the Bragg angle (2θ ± 2) of CuKα characteristic X-ray diffraction described in JP-A-5-263007.
0.2 °) 7.4 °, 9.9 °, 25.0 °, 26.
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the crystalline form of hydroxygallium phthalocyanine having strong peaks at 2 ° and 28.2 ° was replaced. Table 3 shows the results.

Example 4 In Example 1, except that oxytitanium phthalocyanine was replaced with a τ-type nonmetallic phthalocyanine described in JP-A-58-182639.
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1.
Table 3 shows the results.

(Examples 5 to 10) In Example 1, the hole transporting compound No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that Table 6 was replaced with Table 4. Table 3 shows the results.

(Example 11) An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 3, except that the hole transporting compound No. 263 was used instead of the hole transporting compound No. 6. Table 3 shows the results.

Example 12 The procedure of Example 7 was repeated except that the amount of the hole-transporting compound No. 263 was changed to 48 parts, and that 12 parts of an acrylic monomer having the structure of the following structural formula (22) was added. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1. Table 3 shows the results.

[0245]

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Example 13 After forming a charge generation layer in Example 7, 20 parts of a styryl compound of the following structural formula (23) and 10 parts of a polycarbonate resin having a repeating unit of the following structural formula (24) were combined with monochlorobenzene. 50
A charge transport layer was formed on the charge generation layer using a charge transport layer coating solution prepared by dissolving in a mixed solvent of 20 parts by weight / 20 parts of dichloromethane. At this time, the thickness of the charge transport layer is 10
μm.

[0247]

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[0248]

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Next, the hole transporting compound No. 263
60 parts and 0.6 parts of the photopolymerization initiator of the structural formula (21) were dissolved in a mixed solvent of 50 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating for a surface protective layer. This paint is applied on the charge transporting layer by a spray coating method, and 500 mW / c using a metal halide lamp.
Curing for 30 seconds at a light intensity of m ² gives a film thickness of 5
A μm surface protective layer was formed to obtain an electrophotographic photosensitive member. This photoreceptor was evaluated in the same manner as in Example 1. Table 3 shows the results.
Shown in

Example 14 In Example 1, the hole transporting compound No. 6 was replaced with No. 55, and the photopolymerization initiator of the structural formula (21) was replaced with a photopolymerization initiator of the following structural formula (25). An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that
evaluated. Table 3 shows the results.

[0251]

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(Example 15) An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the hole transporting compound No. 55 was used in place of the hole transporting compound No. 55 in Example 14. Table 3 shows the results.

Example 16 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the hole transporting compound No. 295 was used in place of the hole transporting compound No. 55. Table 3 shows the results.

(Example 17) In Example 1, the hole transporting compound No. 6 was replaced with No. 71, and the photopolymerization initiator of the structural formula (21) was changed to a thermal polymerization initiator of the following structural formula (26). , Thermal curing reaction instead of ultraviolet curing
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except for the time. Table 3 shows the results.

[0255]

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(Example 18) An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 17, except that the hole transporting compound No. 71 was used in place of the hole transporting compound No. 71. Table 3 shows the results.

[0257]

[Table 3]

[0258]

[Table 4]

(Comparative Example 1) After forming a charge generation layer in Example 1, 15 parts of a styryl compound of the structural formula (23) and 15 parts of a polymethyl methacrylate resin having a repeating unit of the following structural formula (27) were added to a monolayer. Chlorobenzene 5
A charge transport layer was formed on the charge generation layer using a charge transport layer paint prepared by dissolving in a mixed solvent of 0 parts / dichloromethane 20 parts. At this time, the thickness of the charge transport layer is 1
It was 5 μm. The electrophotographic photoreceptor was evaluated in the same manner as in Example 1. As a result, the initial electrophotographic properties were good, but the amount of surface layer shaved during durability was large, and image defects such as fogging and scratches occurred. I have. Further, after 8000 sheets, the thickness of the charge transport layer was reduced due to scraping, and poor charging occurred, making image formation impossible. Table 5 shows the results.

[0260]

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(Comparative Example 2) In Comparative Example 1, the structural formula (2
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Comparative Example 1 except that the polycarbonate resin represented by the structural formula (24) was used instead of the polymethyl methacrylate resin represented by 7). Although the durability slightly improved compared to the case of, it is not enough,
Image defects after durability also occurred. Table 5 shows the results.

(Comparative Example 3) In Comparative Example 2, the structural formula (2
10 parts of a styryl compound represented by 3), structural formula (24)
, Except that 15 parts of the polycarbonate resin represented by
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Comparative Example 2. As a result, although the durability was improved as compared with Comparative Example 2, the charge transporting ability was reduced due to the increase in the distance between the charge transporting materials, and the sensitivity was reduced. A decrease and an increase in the residual potential were observed. As a result, a ghost was observed in the image. Table 5 shows the results.

(Comparative Example 4) In Comparative Example 2, the structural formula (2
15 parts of a styryl compound represented by 3), structural formula (24)
Except that 10 parts of the polycarbonate resin represented by
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Comparative Example 2, and as a result, the sensitivity increased and the residual potential decreased as compared with Comparative Example 2,
Although good photoreceptor characteristics were obtained, the film strength was significantly reduced due to the plastic effect of the charge transport material, and the durability was significantly reduced. Table 5 shows the results.

Comparative Example 5 A compound having the following structural formula (28) disclosed in JP-A-5-216249 was used in place of the hole-transporting compound No. 6 in Example 1, except that An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1. As a result, the electrophotographic characteristics in the initial stage were good, but the durability was significantly lower than that of Example 1. Table 5 shows the results.

[0265]

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(Comparative Example 6) After the charge generation layer was formed in Example 1, P10 of JP-A-8-248649 was used.
And charge transporting on the charge generating layer using a charge transporting layer coating prepared by dissolving 20 parts of a polycarbonate resin represented by the following structural formula (29) in 80 parts of tetrahydrofuran, which was synthesized according to the production method described in any one of (1) to (11). A layer was formed.
At this time, the thickness of the charge transport layer was 15 μm. The electrophotographic photoreceptor was evaluated in the same manner as in Example 1. As a result, although the mechanical strength was improved as compared with Comparative Examples 1 and 2, sufficient durability could not be secured. Table 5 shows the results.

[0267]

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[0268]

[Table 5]

[0269]

The electrophotographic photoreceptor of the present invention has excellent effects on abrasion resistance and scratch resistance. Further, the electrophotographic characteristics such as sensitivity and residual potential are very good, and stable performance can be exhibited even when repeatedly used. Also,
The effect of the electrophotographic photosensitive member is naturally exerted also in a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member, and high image quality is maintained for a long time.

[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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 16/12 C08F 16/12 20/10 20/10 C08K 5/3472 C08K 5/3472 C08L 25/00 C08L 25/00 29/10 29/10 33/14 33/14 G03G 5/07 101 G03G 5/07 101 (72) Inventor Akio Maruyama 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72 Inventor Shoji Amemiya 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Michiyo Sekiya 3-30-2 Shimomaruko 3-chome, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Tanaka Hiroyuki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kazunari Nakamura 3-30-2 Shimomaruko, Ota-ku, Tokyo F-ter in Canon Inc. (Ref.) BC48P BC49P BC52P BC54P BC79P BC83P CA01 CA04 JA43

Claims (30)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the charge-generating material in the photosensitive layer is a phthalocyanine compound, and the electrophotographic photoreceptor has two or more compounds in the same molecule. An electrophotographic photoreceptor comprising: a hole transporting compound having a chain polymerizable functional group; and one or both of the hole transporting compound polymerized or crosslinked and cured by heat or ultraviolet light. 2. The electrophotographic photoreceptor according to claim 1, wherein the hole transporting compound having a chain polymerizable functional group is represented by the following general formula (1). Embedded image (Where 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 may have a substituent A represents a good organic residue, Y represents a hydrogen atom; a, b, and d each represent 0 or an integer of 1 or more; provided that when a = 0, b + d is an integer of 3 or more; A is an integer greater than or equal to 2;
+ B + d represents an integer of 3 or more; and when a is 2 or more, P ¹ may be the same or different, and when d is 2 or more, P ²
May be the same or different, and when b is 2 or more, Z
May be the same or different) 3. The hole-transporting compound of the above formula (1) wherein the bonding site of A to P ¹ and Z is replaced by a hydrogen atom, represented by the following formula (2): The electrophotographic photosensitive member according to the above. Embedded image (Wherein, 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; At least two of them represent an aryl group; and R ¹ , R ² and R
³ may be the same or different) 4. The hole-transporting compound in which the bonding site of A to P ¹ and Z in the general formula (1) is replaced by a hydrogen atom is represented by the following general formula (3). The electrophotographic photosensitive member according to the above. Embedded image (Wherein, R ⁴ , R ⁵ , R ⁸ and R ⁹ 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. , R ⁶ and R ⁷ represent an alkylene group which may have a substituent or an arylene group which may have a substituent; R ⁴ , R ⁵ , R ⁸ and R ⁹ and R
⁶ and R ⁷ may each be the same or different;
Represents an organic residue which may have a substituent) 5. The hole-transporting compound of the above general formula (1) wherein the bonding site of A to P ¹ and Z is replaced by a hydrogen atom, represented by the following general formula (4): The electrophotographic photosensitive member according to the above. Embedded image (Wherein, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ 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. ;Also,
R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different; Ar ¹ and Ar ² each represent an arylene group which may have a substituent, and may be the same or different; ; M represents 0 or 1) 6. The hole-transporting compound of the above general formula (1) wherein the bonding site of A to P ¹ and Z is replaced by a hydrogen atom, represented by the following general formula (5): The electrophotographic photosensitive member according to the above. Embedded image (Wherein, Ar ³ and Ar ⁴ represents an aryl group which may have a substituent, Ar ³ and Ar ⁴ may be the same or different; R ¹⁴ represents an alkyl group which may have a substituent, Represents an aralkyl group which may have a substituent or an aryl group which may have a substituent; provided that at least one of Ar ³ , Ar ⁴ and R ¹⁴ is a substituent represented by the following general formula (6) Having at least one) (Wherein, R ¹⁵ and R ¹⁶ are an optionally substituted alkyl group, an optionally substituted aralkyl group, an optionally substituted aryl group 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; n ¹ represents 0 or an integer of 1 to 2) 7. In the above general formula (1), the hole transporting compound in which the bonding site of A to P ¹ and Z is replaced by a hydrogen atom is a fused ring hydrocarbon, a fused complex ring or the following general formula (7) )
The electrophotographic photoreceptor according to claim 1 or 2, wherein Embedded image (Wherein, 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; Ar ⁶ represents an aryl group which may have a substituent; provided that the condensed ring hydrocarbon, condensed complex ring and general formula (7) are represented by the following general formula (8) Having one or more substituents) (Wherein, R ¹⁹ and R ²⁰ optionally substituted alkyl group, an optionally substituted aralkyl group, an optionally substituted aryl group 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; n ² represents 0 or an integer of 1 to 2) 8. Z of the above general formula (1) or general formula (3)
Q is an alkylene group which may have a substituent, an arylene group which may have a substituent, CR ²¹ ＣＲCR ²² (where R ²¹ and R ²² are an alkyl group which may have a substituent, An aryl group or a hydrogen atom which may have a group, R ²¹ and R ²²
May be the same or different), C = O, S = O, S
O _2, electrophotographic photosensitive member according to claim 1, an organic residues combined in one or optionally more oxygen atom or a sulfur atom. 9. Z of the above general formula (1) or general formula (3)
Q is represented by the following general formula (9).
An electrophotographic photosensitive member according to any one of the above. Embedded image(Where X¹~ X^ThreeIs an alkylene which may have a substituent
Group, (CR^{twenty three}= CR^{twenty four}) M ¹, C = O, S = O, SO_Two,
Represents an oxygen atom or a sulfur atom;⁸And Ar⁹Is a substituent
R represents an arylene group optionally having^{twenty three}And R^{twenty four}Is
Alkyl group which may have a substituent, may have a substituent
R represents an aryl group or a hydrogen atom;^{twenty three}And R ^{twenty four}Are the same
May also be different; m¹Is an integer of 1 to 5, p to t is 0 or
Represents an integer of 1 to 10, provided that p to t are simultaneously 0
Never) 10. The method according to claim 1, wherein Z in the general formula (1) or Q in the general formula (3) is represented by the following general formula (10).
9. The electrophotographic photosensitive member according to any one of items 1 to 8. Embedded image (Wherein, Ar ¹⁰ represents an arylene group which may have a substituent; X ⁴ and X ⁵ represent (CH ₂ ) _g , (CH ＝ CR ²⁵ ) _h ,
C = represents O or an oxygen atom; R ²⁵ represents an alkyl group which may have a substituent group, an optionally substituted aryl group or a hydrogen atom, g is an integer of from 1 to 10, h is 1 Integers from 5 to 5, u to w each represent 0 or an integer from 1 to 10;
Are never 0 at the same time) 11. R ¹ , R ² and R ^{3 in the} general formula (2)
Is an aryl group which may have a substituent,
The electrophotographic photosensitive member according to any one of 3, 8, 9 and 10. 12. At least two of R ⁴ , R ⁵ , R ⁸ and R ^{9 in} the general formula (3) are an aryl group which may have a substituent, and R ⁶ and R ⁷ are a substituent. The electrophotographic photoreceptor according to any one of claims 1, 4, 8, 9 and 10, which is an arylene group which may have 13. R ⁴ , R ⁵ , R ⁸ and R ^{9 in the} general formula (3) are an aryl group which may have a substituent, and R ⁶ and R ⁷ have a substituent. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is an arylene group. 14. The method according to claim 1, wherein R ¹⁰ and R ^{11 in} the general formula (4) are an aryl group which may have a substituent.
The electrophotographic photosensitive member according to any one of 8, 9 and 10. 15. The method according to claim 1, wherein R ^{10 to} R ^{13 in} the general formula (4) are an aryl group which may have a substituent.
The electrophotographic photosensitive member according to any one of 9 and 10, wherein 16. The electrophotographic photosensitive member according to claim 1, wherein R ^{14 in the} general formula (5) is an aryl group which may have a substituent. 17. The electrophotographic photosensitive member according to claim 1, wherein R ^{16 in the} general formula (6) is an aryl group which may have a substituent. 18. The method according to claim 1, wherein R ¹⁷ and R ^{18 in} the general formula (7) are an aryl group which may have a substituent.
The electrophotographic photosensitive member according to any one of 8, 9 and 10. 19. The electrophotographic photosensitive member according to claim 1, wherein R ^{20 in the} general formula (8) is an aryl group which may have a substituent. 20. The electrophotographic photosensitive material according to claim 1, wherein one or both of the chain polymerizable groups P ¹ and P ² is an unsaturated polymerizable functional group represented by the following general formula (11). body. Embedded image (Wherein E is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, a cyano group, a nitro group, an alkoxy group, -COOR ²⁶
{R ²⁶ is 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} or -CONR ²⁷ R
²⁸ ｛R ²⁷ and R ^{28 each} 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; Represents the same or different｝, and W represents a divalent aryl group optionally having a substituent, a divalent alkylene group optionally having a substituent, -COO-, -O −, −
OO—, —S— or —CONR ²⁹ — ｛R ²⁹ is 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; f represents 0 or 1) 21. The electrophotographic photosensitive member according to claim 1, wherein one or both of the chain polymerizable groups P ¹ and P ² is a cyclic ether group represented by the following general formula (12). Embedded image (Wherein, R ³⁰ and R ³¹ represent a hydrogen 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, and n is 1 to 10
Indicate the following integer) 22. The electrophotographic photoreceptor according to claim 1, wherein one or both of the chain polymerizable groups P ¹ and P ² is an alicyclic epoxy group represented by the following general formula (13). . Embedded image (Wherein, R ³² and R ³³ represent a hydrogen 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, and n is 0 or 1
Represents an integer of 10 to 10) 23. The electrophotographic photosensitive member according to claim 1, wherein one or both of the chain polymerizable groups P ¹ and P ² are any of the following formulas (14) to (20). Embedded image 24. The compound according to claim 1, wherein the oxidation potential of the hole transporting compound having two or more chain-polymerizable functional groups in the same molecule is from 0.4 to 1.2 (V). An electrophotographic photoreceptor as described in Crab. 25. The electrophotographic photosensitive member according to claim 1, wherein the phthalocyanine compound is oxytitanium phthalocyanine. 26. The electrophotographic photosensitive member according to claim 1, wherein the phthalocyanine compound is chlorogallium phthalocyanine. 27. The electrophotographic photosensitive member according to claim 1, wherein the phthalocyanine compound is hydroxygallium phthalocyanine. 28. The electrophotographic photoconductor according to claim 1, wherein the phthalocyanine compound is a metal-free phthalocyanine. 29. The electrophotographic photosensitive member according to claim 1, wherein a charging means for charging the electrophotographic photosensitive member, and the electrophotographic photosensitive member on which an electrostatic latent image is formed are developed with toner. Developing means, and at least one means selected from the group consisting of a cleaning means for recovering toner remaining on the photoreceptor after the transfer step, are integrally supported together, and are detachable from the main body of the electrophotographic apparatus. Process cartridge. 30. An electrophotographic photosensitive member according to claim 1, a charging means for charging the electrophotographic photosensitive member, and image exposure of the charged electrophotographic photosensitive member to form an electrostatic latent image. An electrophotographic apparatus comprising: an image exposing unit for developing an electrophotographic photosensitive member having an electrostatic latent image formed thereon with toner; and a transfer unit for heating and transferring a toner image on a transfer material.