JP3314732B2 - Electrophotographic photoreceptor and electrophotographic image forming apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member applicable to a wide range of fields such as a copying machine, a printer and a facsimile, and an electrophotographic image forming apparatus using the same. More specifically, the present invention relates to an electrophotographic photosensitive member called an organic photosensitive member (OPC) having a photosensitive layer formed on a conductive support, and an electrophotographic image forming apparatus using the same. It is intended to improve the mechanical strength, oxidation gas resistance, and contamination adhesion resistance.

[0002]

2. Description of the Related Art Conventionally, electrophotographic apparatuses, such as plain paper copiers (PPC), laser printers, LED printers, liquid crystal printers, etc., have a rotating drum type electrophotographic photoconductor (hereinafter simply referred to as "photoconductor"). Is formed through an image forming process of charging, exposing, and developing,
The obtained image is transferred to a transfer material and fixed to obtain a copy. As a photoreceptor, conventionally, selenium, arsenic-selenium, cadmium sulfide, zinc oxide, a
-Inorganic photoreceptors such as Si have been used, but in recent years, research and development of organic photoreceptors (OPC) which are inexpensive and excellent in terms of manufacturability and disposability have been actively conducted. A so-called function-separated type laminated photoreceptor laminated with a charge transport layer has excellent electrophotographic properties such as sensitivity, chargeability, and stability when such properties are repeatedly used, and various proposals have been made. Has been

However, the level of durability required for an electrophotographic photoreceptor has become stricter year by year, and technologies required for improving the durability have been studied. Specific durability problems include wear and scratches on the surface layer due to repeated use, and oxidative deterioration of the surface layer due to oxidizing gas such as ozone generated from the corona charger. In particular, when using a contact charging type charging means,
The problem of surface layer wear and scratches is greatly increased.

[0004] Recently, copiers and printers using contact charging type charging means have been increasing for reasons such as generation of oxidizing gas is reduced and power supply cost is suppressed. At this time, when an applied voltage having an AC component is applied to the electrophotographic photosensitive member in order to stabilize the charging potential of the photosensitive member, there has been a problem that abrasion of the surface of the photosensitive member increases. It is considered that the cause of this is that a discharge generated between the surface of the photoreceptor and the charging means breaks the binding of the binder resin on the surface of the photoreceptor to reduce the molecular weight. It has been found that when the binder resin on the surface of the photoreceptor has a low molecular weight, when the surface of the photoreceptor is cleaned by a mechanical cleaning means such as a cleaning blade, the abrasion on the surface of the photoreceptor is significantly increased.

[0005] As a method for preventing the wear of the photoreceptor surface,
In general, studies on polymerization of a charge transport material constituting a surface layer of a photoreceptor have been actively conducted. For example, U.S. Pat. No. 4,806,443 discloses a polycarbonate obtained by polymerization of a specific dihydroxyarylamine and bischloroformate, and U.S. Pat. No. 4,806,444 discloses a polycarbonate. Polycarbonates by polymerization of certain dihydroxyarylamines with phosgene are disclosed. Also, U.S. Pat.
No. 01,517 discloses a polycarbonate obtained by polymerizing a bishydroxyalkylarylamine with bischloroformate or phosgene, and is disclosed in U.S. Pat. No. 4,937,165 and U.S. Pat. No. 288 discloses a polycarbonate obtained by polymerization of a specific dihydroxyarylamine or bishydroxyalkylarylamine with bischloroformate, or a polyester obtained by polymerization of a bisacyl halide.

Further, US Pat. No. 5,034,296 discloses a polycarbonate or polyester of an arylamine having a specific fluorene skeleton.
U.S. Pat. No. 4,983,482 discloses a polyurethane. Furthermore, Tokubiko Sho 59
Japanese Patent No. 28903 discloses a polyester having a specific bisstyrylbisarylamine as a main chain. Further, Japanese Patent Application Laid-Open No. 61-20953,
JP-A-134456, JP-A-1-134457,
JP-A-1-134462, JP-A-4-13306
No. 5, JP-A-4-133066 and the like also propose a polymer in which a charge transporting substituent such as hydrazone or triarylamine is pendant, and a photoreceptor using the same. However, the above-mentioned polymer charge transporting materials are not sufficient in sensitivity, residual potential, and the like, and also have insufficient durability as a photoreceptor.

Further, a method has been proposed in which a low-molecular charge transporting material is dispersed in a binder resin or a precursor thereof, and then the binder resin or a precursor thereof is reacted and cured. As such a proposal, for example, JP-A-56-48637 and JP-B-56-42863 disclose an example of using an acrylic polymer.
JP-A-22347 and JP-B-7-120051 disclose examples of using a silicone-based polymer or a polymer precursor. However, in order to obtain sufficient characteristics as an electrophotographic photoreceptor, it is necessary to increase the concentration of the low-molecular charge transport material to 30 to 50%, so that the curing reaction of the binder resin does not proceed sufficiently. In some cases, the low-molecular-weight charge transporting material may escape from between the resin deposits and eventually be worn away, and the problem has not yet been sufficiently solved.

Another method for reducing the wear of the photoreceptor is to apply a surface protective layer having high mechanical strength to the surface of the photoreceptor. From the viewpoint of mechanical strength, a cross-linking curable resin is excellent, but if the surface protective layer is composed of only this resin, the surface protective layer becomes an insulating layer, and the photoelectric characteristics of the photoconductor are sacrificed. Would. Specifically, the problem that the development potential margin is narrowed due to an increase in the light portion potential at the time of exposure, and the residual potential after static elimination is increased, especially when long-term repeated printing is performed, image density is reduced. There was a problem of lowering.

As a method for imparting photoelectric properties to the surface protective layer, a method has been reported in which a conductive metal oxide fine powder is dispersed in the surface protective layer as a resistance control material (Japanese Patent Application Laid-Open No. 57-15757).
-128344). According to this method, the decrease in the photoelectric characteristics of the photoconductor is small, and the above-described problem is remarkably improved. However, there is a problem that the resistance value of the metal oxide generally used as the conductive fine powder largely depends on the humidity of the environment in which it is used. Therefore, there is an essential problem that the surface resistance of the photoreceptor is reduced particularly under high temperature and high humidity, the electrostatic latent image is blurred, and the image quality is greatly reduced.

As another method for improving the photoelectric characteristics, there has been reported a method in which a charge transporting substance is dispersed in a binder resin, and then the binder resin is cured to form a surface protective layer (Japanese Patent Application Laid-Open No. Hei 4 (1999)). -15659). In this method, the surface resistance of the photoreceptor does not show humidity dependency, and there is no problem in image quality. However, the addition of a low-molecular-weight component such as a charge-transporting substance inhibits a curing reaction at the time of forming the surface protective layer, and lowers the mechanical strength of the surface protective layer. Therefore,
Even when a cross-linking curable resin with high mechanical strength is used alone, the mechanical strength of the surface protective layer is greatly reduced by adding a low molecular weight component called a charge transport material essential for improving photoelectric properties. There was a problem.

From such a viewpoint, it has been reported that the mechanical strength of the surface layer is improved by using a charge transport material having a functional group and reacting it with a thermoplastic binder resin ( JP-A-6-202354 and JP-A-5-323630). According to this method, a sufficient mechanical strength can be initially obtained without lowering the photoelectric characteristics of the photoconductor. However, such a structure of the surface protective layer has a problem that when used for a long period of time by using a charging means of a contact charging system, a sharp decrease in mechanical strength occurs. The cause is considered to be due to strong external stress such as disconnection of the thermoplastic binder resin due to the application of an AC voltage in the charging means.If a mechanical cleaning means such as a cleaning blade is employed, the surface protection layer may be damaged. Wear is greatly increased.

The photoreceptor is required to have resistance to an oxidizing gas in addition to a reduction in the abrasion of the surface. The amount of ozone and NO _X generated by the charging means the contact charging method, although much less than the charging means scorotron discharge type, in the case of using an applied voltage having an AC component, always these occur . In order to extend the life of the photoconductor by improving the mechanical strength of the photoconductor surface, the photoconductor is exposed to the generated oxidizing gas for a longer period of time. Can be

Further, in addition to these problems, when the mechanical strength of the surface protective layer is to be increased,
Since it is not refreshed due to abrasion, paper dust, toner, discharge products, and the like accumulate, and these adhesion stains become apparent, resulting in a problem that image quality is reduced.

[0014]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an electrophotographic photosensitive member which has solved these problems and an image forming apparatus using the same. That is, an object of the present invention is to provide a high mechanical strength of the surface, therefore high abrasion resistance, high resistance to oxidizing gas, stable photoelectric characteristics, paper powder, toner and discharge products by continuous use. It is an object of the present invention to provide an electrophotographic photoreceptor which is less likely to cause adhesion stains (having high anti-contaminant adhesion) and an image forming apparatus using the same.

[0015]

Means for Solving the Problems The present inventors have proposed a surface protective layer or a photosensitive layer as a surface layer of an electrophotographic photosensitive member (hereinafter, these may be collectively referred to as "outermost surface layer"). Was found to be able to solve the above problem by adopting the following configuration of the first invention or the configuration of the second invention.

A first aspect of the present invention comprises at least a compound represented by the following general formula (Ia), silicon-containing fine particles, and a crosslinked cured film formed from a crosslinkable compound.

[0017] G-D-F general formula (Ia) (wherein, G represents a Si-containing glassy network subunit, D is -C _x H _2x - _(x is 1 to 15 integer),
_{-C x 'H 2x'-2 -} (x' is from 2 to 15 integer), - C _x "H
_{2x "-4-} (x" is an integer of 2 to 15), substituted or unsubstituted
Replacement divalent aryl group, -CH = N-, -O-, -CO
At least one selected from the group consisting of O-
And -C _x H _2x- (x is an integer of 1 to 15) is substituted.
Or one kind of unsubstituted divalent aryl group, and -C
_x H _2x - _(x is an integer from 1 to 15) and a substituted or unsubstituted
Excluding the case of combination with a divalent aryl group).
And does not include hydrogen atoms directly bonded to heteroatoms.
Represents a divalent group, and F represents a photoelectric characteristic subunit. )

Second invention The present invention relates to a crosslinked cured film formed from at least a compound represented by the following general formula (Ib) and a crosslinkable compound having two or more substituents represented by the following general formula (IV) Configuration.

GDF General Formula (Ib) (where D is -C _x H _2x- (x is an integer of 1 to 15),-
_{C x 'H 2x'-2 -} (x' is from 2 to 15 integer), - C _x "H
_{2x "-4-} (x" is an integer of 2 to 15), substituted or unsubstituted
Replacement divalent aryl group, -CH = N-, -O-, -CO
At least one selected from the group consisting of O-
And -C _x H _2x- (x is an integer of 1 to 15) is substituted.
Or one kind of unsubstituted divalent aryl group, and -C
_x H _2x - _(x is an integer from 1 to 15) and a substituted or unsubstituted
Excluding the case of combination with a divalent aryl group).
And does not include hydrogen atoms directly bonded to heteroatoms.
There, represents a divalent group, F is a photoelectric characteristics subunit Table
And G represents —Si (R ¹ ) _(3-a) (OR ² ) _a ;
¹ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, R ² represents a hydrogen, an alkyl group, or a trialkylsilyl group, and a represents an integer of 1 to 3. )

—Si (R ³ ) _(3-b) (OR ⁴ ) _b general formula (IV) wherein R ³ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, and R ⁴ represents hydrogen , An alkyl group or a trialkylsilyl group, and b represents an integer of 1 to 3.)

The electrophotographic photoreceptor having the outermost surface layer having any one of the above constitutions is contacted with a contact charging type charging means, and / or
Alternatively, when used in an electrophotographic image forming apparatus having a mechanical cleaning means, the printing durability can be dramatically improved.

When the G-portion of the compound represented by the general formula (Ia) or (Ib) is subjected to a cross-linking polymerization reaction with the cross-linkable compound to form a matrix-like outermost surface layer, the mechanical strength is improved. I do. Therefore, when such an electrophotographic photosensitive member is used in an electrophotographic image forming apparatus having a contact charging type charging unit and / or a mechanical cleaning unit, the effect of improving the printing durability is particularly great. This is presumably because the cross-linking structure increases the total binding energy per unit volume and increases the resistance to strong stress such as electric discharge and mechanical contact. Even if some of the bonds in the outermost surface layer are cut by these stresses, a three-dimensional crosslinked structure is formed, so that the molecular weight is not immediately reduced, and high mechanical strength is obtained. continue.

Although the outermost surface layer having the crosslinked structure as described above has a high hardness of itself, the first invention of the present invention further comprises silicon-containing fine particles to provide not only mechanical strength but also contamination resistance. Adhesion and lubricity can be improved and maintained over a long period of time.

The silicon-containing fine particles are represented by the general formula (I)
It is preferable to use colloidal silica having a large number of silanol groups on its surface that can react with the G- moiety in the compound represented by a). It is also preferable to use silicone microparticles as silicon-containing microparticles. In addition to mechanical strength, surface lubricity, abrasion resistance, and water repellency are improved, and adhesion to hydrophilic contaminants such as discharge products is improved. The contamination is improved and they can be maintained for a long period of time.

The outermost surface layer having the structure of the second aspect of the present invention is formed by a cross-linking reaction of both Si-containing groups in the compound represented by the general formula (Ib) and in the cross-linkable compound. Three-dimensional -Si-O-Si- bond (glass bond)
Is a crosslinked cured film of an organic-inorganic composite film in which the photoelectric characteristic subunit (organic component) represented by F in the general formula (Ib) is incorporated into the inorganic matrix based on the bond. The film can be said to be a kind of sol-gel cured film because of the method for forming a -Si-O-Si- bond. Since the outermost surface layer of this crosslinked cured film has an excellent surface mechanical strength unique to an inorganic matrix, even if it is used in an electrophotographic image forming apparatus that uses contact charging with high stress on the photoreceptor, it can be used as a conventional photosensitive material. It shows extremely high printing durability compared to the body.

In the electrophotographic photoreceptor of the present invention (hereinafter, simply referred to as “the present invention” means both “the first present invention” and “the second present invention”), Due to the photoelectric characteristic subunit represented by F in the compound represented by the general formula (Ia) or (Ib), the outermost surface layer has a charge transporting property. Since the photoelectric property subunit represented by F, which is responsible for the charge transport property, is directly bonded to the crosslinked structure constituting the outermost surface layer, the electrophotographic photosensitive member of the present invention can be obtained without losing the mechanical properties of the crosslinked structure. It is possible to impart photoelectric properties to the body. Therefore, the outermost layer having the above structure is not only applicable as a surface protective layer on the surface of the photoreceptor due to its mechanical properties, but also a photosensitive layer in a single-layer type photoreceptor, a charge transport layer in a multilayer type photoreceptor, It can function as it is even as a generating layer.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to embodiments. According to a first aspect of the present invention, an outermost surface layer of an electrophotographic photoreceptor comprises at least a compound represented by the following general formula (Ia), silicon-containing fine particles, and a crosslinked cured film formed from a crosslinkable compound. Features.

GDF general formula (Ia) (wherein G represents a Si-containing vitreous network subunit, D represents -C _x H _2x- (x is an integer of 1 to 15),
_{-C x 'H 2x'-2 -} (x' is from 2 to 15 integer), - C _x "H
_{2x "-4-} (x" is an integer of 2 to 15), substituted or unsubstituted
Replacement divalent aryl group, -CH = N-, -O-, -CO
At least one selected from the group consisting of O-
And -C _x H _2x- (x is an integer of 1 to 15) is substituted.
Or one kind of unsubstituted divalent aryl group, and -C
_x H _2x - _(x is an integer from 1 to 15) and a substituted or unsubstituted
Excluding the case of combination with a divalent aryl group).
And does not include hydrogen atoms directly bonded to heteroatoms.
Represents a divalent group, and F represents a photoelectric characteristic subunit. )

In the second aspect of the present invention, the outermost surface layer of the electrophotographic photoreceptor comprises at least a compound represented by the following formula (Ib) and a substituent represented by the following formula (IV): A structure comprising a crosslinked cured film formed from two or more crosslinkable compounds.

GDF General Formula (Ib) (where D is -C _x H _2x- (x is an integer of 1 to 15),-
_{C x 'H 2x'-2 -} (x' is from 2 to 15 integer), - C _x "H
_{2x "-4-} (x" is an integer of 2 to 15), substituted or unsubstituted
Replacement divalent aryl group, -CH = N-, -O-, -CO
At least one selected from the group consisting of O-
And -C _x H _2x- (x is an integer of 1 to 15) is substituted.
Or one kind of unsubstituted divalent aryl group, and -C
_x H _2x - _(x is an integer from 1 to 15) and a substituted or unsubstituted
Excluding the case of combination with a divalent aryl group).
And does not include hydrogen atoms directly bonded to heteroatoms.
There, represents a divalent group, F is a photoelectric characteristics subunit Table
And G represents —Si (R ¹ ) _(3-a) (OR ² ) _a ;
¹ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, R ² represents a hydrogen, an alkyl group, or a trialkylsilyl group, and a represents an integer of 1 to 3. )

—Si (R ³ ) _(3-b) (OR ⁴ ) _b Formula (IV) (wherein R ³ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, and R ⁴ represents hydrogen , An alkyl group or a trialkylsilyl group, and b represents an integer of 1 to 3.)

If the outermost surface layer of the electrophotographic photosensitive member has one of the constitution of the first present invention and the constitution of the second present invention, the above object of the present invention is achieved.
It is of course possible to have both configurations. Hereinafter, the first and second aspects of the present invention will be described in detail separately for each component.

[Compound represented by the general formula (Ia) or (Ib)] The compound represented by the general formula (Ia) or (Ib) is a compound represented by each of the subunits represented by G, D and F as described above. Consists of G is a Si-containing glassy network subunit, which can be obtained from any of a number of inorganic substances that can undergo hydrolysis and condensation, such as alkoxides, acids, halides and oxalates. The Si-containing vitreous network subunit represented by G is a portion that forms a strong crosslinked structure by performing a crosslink polymerization reaction with a crosslinkable compound described below during formation of the outermost surface layer.

In the second aspect of the present invention, the structure of G is -Si
_{^{(R 1) (3-a}} ) (OR 2) a [ wherein, R ¹ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, R ²
Represents hydrogen, an alkyl group, or a trialkylsilyl group. ]
Need to be With such a structure, the G portions cause a cross-linking reaction with each other or a cross-linkable compound described below, thereby forming a three-dimensional Si—O—Si bond, that is, an inorganic glassy network.

F is a photoelectric characteristic subunit, which is a part having charge transport properties. The photoelectric property subunit represented by F can be obtained from a precursor having a charge transporting property, and examples of the precursor include pyrazoline, oxadiazole, hydrazone, triphenylamine, benzidine, a triphenylmethane derivative, (Nitroxyl fluorenylidene) malononitrile such as trinitrofluorenone (TNF) and butoxycarbonylfluorenylidene malononitrile (BCFM).

Further, as the structure of F, a structure conventionally known as a charge transport material can be used as it is. Specifically, a compound skeleton having a hole transporting property such as a triarylamine compound, a benzidine compound, an arylalkane compound, an aryl-substituted ethylene compound, a stilbene compound, an anthracene compound, a hydrazone compound, and the like, and Compound skeletons having charge transport properties such as quinone compounds, fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, and ethylene compounds can be given.

D is a flexible organic subunit, which functions as a linking group for the subunits represented by G and F. Such a flexible organic subunit represented by D can be obtained from a polymer precursor having two or more reactive groups and having flexibility. A strong and stable bond cannot be directly obtained between the subunits represented by G and F, and a certain degree of flexibility is imparted to the compound, so that the cross-linked structure can be flexibly and densely formed during film formation. If it can be formed, and if the obtained film is not flexible, the film itself becomes brittle and the mechanical strength is rather reduced. Through subunits, G and F
Are connected.

[0038] D is -C _x H _2x - _(x is 1 to 15 _{integer), - C x 'H 2x'} -2 - (x' is from 2 to 15 integer), -
_{C x "H 2x" -4 -} (x " integer 2 to 15), a substituted or unsubstituted divalent aryl group, -CH = N -, - O- ,
At least one selected from the group consisting of -COO-
(However, -C _x H _2x- (x is an integer of 1 to 15) is 1
One or more substituted or unsubstituted divalent aryl groups,
And -C _x H _2x- (x is an integer of 1 to 15) or
Except when combined with an unsubstituted divalent aryl group.
A) and a hydrogen atom directly bonded to a hetero atom
And a divalent group containing no substituents , and further having a substituent introduced.

The compound represented by formula (Ia) or (Ib) can be obtained, for example, by a sol-gel method described in JP-A-2-333495. The substituent represented by GD- in the general formula (Ia) or (Ib) is preferably a structure represented by the following general formula (II).

—Y—Si (R ¹ ) _(3-a) (OR ² ) _a Formula (II) In the formula, R ¹ represents a hydrogen, an alkyl group, a substituted or unsubstituted aryl group, and R ² represents Represents a hydrogen, an alkyl group, or a trialkylsilyl group, and a represents an integer of 1 to 3.

In the general formula (II), -Si (R ¹ )
_(3-a) (OR ² ) _a undergoes a cross-linking reaction with each other or with a cross-linkable compound described below to form a three-dimensional Si—O—S
It forms an i-bond, ie, an inorganic vitreous network.

Y represents a divalent group which does not contain a hydrogen atom directly bonded to a hetero atom, and specifically has a general formula (I
In the substituent represented by I) -Y- is, -C _x H _2x - _(x
Is an integer of _{1~15), - C x 'H} 2x'-2 - (x' is 2 to 1
5 _{integer), - C x "H 2x} " -4 - (x " integer 2 to 15), a substituted or unsubstituted divalent aryl group, -CH
= N -, - O -, - at least one selected from the group consisting of COO- (However, -C _x H _2x - _(x is 1 to 1
5) is a substituted or unsubstituted divalent aryl
Le group one, and -C _x H _2x - _(x is an integer from 1 to 15
Number) and a substituted or unsubstituted divalent aryl group
(Excluding the case of combining) .
When Y contains a hydrogen atom directly bonded to a hetero atom, a problem arises that environmental fluctuation of charge transport characteristics becomes large, and particularly in a high-temperature and high-humidity environment, image characteristics such as a decrease in resolution are deteriorated. Of course, the present invention is not limited to these. As Y, No. 1 shown below
To 11 are exemplified.

[0043]

Embedded image

Here, R ⁴ is selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and halogen. x is an integer of 1 to 10, x 'and x "are each an integer of 2 to 15, y and z are each an integer of 1 to 5, and t is an integer of 1 to 3. Among the above structures, No. The structures shown in 1 to 7 are preferred.

As the compound represented by the general formula (Ia), a compound represented by the following general formula (IIIa) is particularly desirable in terms of charge transport properties and oxidation resistance. General formula (IIIa)

[0046]

Embedded image

(Wherein, Ar ^{1 to} Ar ⁴ each independently represent a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or an arylene group, and among Ar ^{1 to} Ar ⁵ , 1-4 are substituents represented by G-D-, and k represents 0 or 1.)

Similarly, as the compound represented by the general formula (Ib), a compound represented by the following general formula (IIIb) is particularly desirable in terms of charge transport properties and oxidation resistance. General formula (IIIb)

[0049]

Embedded image

(Wherein, Ar ^{1 to} Ar ⁴ each independently represent a substituted or unsubstituted aryl group; Ar ⁵ represents a substituted or unsubstituted aryl group or an arylene group; and among Ar ^{1 to} Ar ⁵ , 1-4 are represented by the general formula (I
a substituent represented by G-D- in b), and k is 0
Or 1 is indicated. )

In the general formulas (IIIa) and (IIIb),
Ar ^{1 to} Ar ⁴ each independently represent a substituted or unsubstituted aryl group, and specific examples include the following structures.

[0052]

Embedded image

Here, R ³ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, It is selected from aralkyl groups having 7 to 10 carbon atoms. R ⁴ is selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and halogen. m and s represent 0 or 1, t represents an integer of 1 to 3, and Ar is selected from the following.

[0054]

Embedded image

Here, R ⁸ is selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and halogen. T represents an integer of 0 to 3.

Further, Z ′ is selected from the following structures.

[0057]

Embedded image

X represents a substituent represented by GD-, and preferably has a structure represented by the general formula (II) as described above.

On the other hand, the general formulas (IIIa) and (IIIb)
In the above, Ar ⁵ represents a substituted or unsubstituted aryl group or an arylene group, and specific examples thereof include the following structures.

K in the general formulas (IIIa) and (IIIb)
When Ar is 0, specific examples of Ar ⁵ include:

[0061]

Embedded image

In formulas (IIIa) and (IIIb), k
Specific examples of Ar ⁵ when is 1 include:

[0063]

Embedded image

Here, R ³ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, It is selected from aralkyl groups having 7 to 10 carbon atoms. R ⁴ is selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and halogen. s represents 0 or 1, and t represents an integer of 1 to 3. Ar is selected from the structures shown below.

[0065]

Embedded image

Here, R ⁴ is selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and halogen. T represents an integer of 1 to 3. Further, Z is selected from the structures shown below.

[0067]

Embedded image

Here, R ₅ is selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and halogen. Further, q and r each represent an integer of 1 to 10, t 'represents an integer of 1 or 2, and W is selected from the following groups.

[0069]

Embedded image

Here, s' represents an integer of 0 to 3.

Specific examples of the compound represented by the general formula (IIIa) or (IIIb) are shown together with the reference compound examples in the following table by specifying each substituent. Of course, the present invention is not limited to the following compounds. In addition,
A symbol in which "III-" is added to a compound number in the following table is used as a symbol of an exemplary compound in the present specification (for example,
The compound having the compound number “27” is referred to as “exemplary compound (III-
27))). (In addition, 1 to 10, 69 of the compound examples
~ 73, 89 ~ 98, 143 ~ 152, 194 ~ 20
3, 224 to 229 are reference compound examples. )

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

[0077]

[Table 6]

[0078]

[Table 7]

[0079]

[Table 8]

[0080]

[Table 9]

[0081]

[Table 10]

[0082]

[Table 11]

[0083]

[Table 12]

[0084]

[Table 13]

[0085]

[Table 14]

[0086]

[Table 15]

[0087]

[Table 16]

[0088]

[Table 17]

[0089]

[Table 18]

[0090]

[Table 19]

[0091]

[Table 20]

[0092]

[Table 21]

[0093]

[Table 22]

[0094]

[Table 23]

[0095]

[Table 24]

[0096]

[Table 25]

[0097]

[Table 26]

[0098]

[Table 27]

[0099]

[Table 28]

[0100]

[Table 29]

[0101]

[Table 30]

[0102]

[Table 31]

[0103]

[Table 32]

[0104]

[Table 33]

[0105]

[Table 34]

[0106]

[Table 35]

[0107]

[Table 36]

[0108]

[Table 37]

[0109]

[Table 38]

[0110]

[Table 39]

[0111]

[Table 40]

[0112]

[Table 41]

[0113]

[Table 42]

[0114]

[Table 43]

[0115]

[Table 44]

[0116]

[Table 45]

[0117]

[Table 46]

[0118]

[Table 47]

[0119]

[Table 48]

[0120]

[Table 49]

[0121]

[Table 50]

[0122]

[Table 51]

[0123]

[Table 52]

In the electrophotographic photosensitive member of the present invention, the content of the compound represented by the formula (Ia) or (Ib) in the outermost surface layer is 5 to 50% by weight based on the total solid content of the outermost surface layer. The range is preferably 10 to 40% by weight.

[Crosslinkable Compound] The crosslinkable compound used in the present invention is a curable compound capable of bonding to the Si-containing glassy subunit represented by G in the above general formula (Ia) or (Ib). Is a compound of It is also possible to crosslink and cure only the compound represented by the general formula (Ia) or (Ib) and silicon-containing fine particles described below to form an outermost surface layer having both a certain mechanical strength and a charge transporting property. However, it is essential to use such a crosslinkable compound in order to further improve film properties such as surface properties and strength.

As such a crosslinking compound, a known reactive silicone compound can be used. Specifically, commercially available coating agents such as silicone hard coating agents, organic siloxane compounds having a plurality of functional groups, alkoxysilane compounds, silane coupling agents,
And mixtures thereof.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxysilane. Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethylsilane Methoxysilane, dimethyldimethoxysilane and the like can be mentioned.

Commercially available hard coat agents include KP-8
5, CR-39, X-12-2208, X-40-97
40, X-41-1007, KNS-5300, X-4
0-2239 (all manufactured by Shin-Etsu Silicone Co., Ltd.) and A
Y42-440, AY42-441, AY49-208
(Both manufactured by Toray Dow Corning).

In the second invention, the crosslinkable compound is
It is essential to use a compound having at least two substituents represented by the following general formula (IV). —Si (R ³ ) _(3-b) (OR ⁴ ) _b general formula (IV) (wherein R ³ represents a hydrogen, an alkyl group, a substituted or unsubstituted aryl group, and R ⁴ represents a hydrogen, an alkyl group , A trialkylsilyl group, and b represents an integer of 1 to 3.)

In the second invention, since a crosslinkable compound having such a structure is used, the portion of the general formula (IV) contained in the crosslinkable compound is a compound represented by the general formula (Ib):
Alternatively, it reacts with the crosslinkable compound itself to form Si-O-Si
It becomes a bond to form a three-dimensional crosslinked cured film.

The compound represented by the general formula (Ib) also has a portion similar to the structure represented by the general formula (IV).
Although it is possible to form a cured film only with the compound represented by the general formula (Ib) itself, since the crosslinkable compound having the above structure has two or more moieties of the general formula (IV), By using the crosslinkable compound, the crosslinked structure of the cured film becomes 3
This is considered to be dimensional and has higher mechanical strength, which is a preferable embodiment. Further, the crosslinkable compound also has a role of imparting appropriate flexibility to the crosslinked cured film, similarly to the flexible organic subunit represented by D in the compound represented by the general formula (Ib).

It is essential that the number of the substituents represented by the general formula (IV) in the crosslinkable compound is two or more. However, a more dense crosslinked structure is obtained, In order to increase the strength, it is preferably three or more.

The compound having two or more substituents represented by the general formula (IV) is preferably a compound represented by the following general formula (V). General formula (V)

[0134]

Embedded image

(Wherein A represents a substituent represented by the general formula (IV), and B represents a divalent or higher valent hydrocarbon group which may contain a branch, a divalent or higher valent aryl group, —NH—, At least one or a combination thereof, and n represents an integer of 2 or more.) In particular, the compound represented by the general formula (V) is a compound represented by any of the following general formulas It is desirable.

[0136]

Embedded image

(Wherein T ₁ and T ₂ represent a divalent or trivalent hydrocarbon group which may be branched, A represents a substituent represented by the general formula (IV), and h, i , J is an integer of 1 to 3, and is selected such that the number of A in the molecule is 2 or more.)

The following table shows specific examples of the compound represented by formula (V). The symbol in which "V-" is added to the compound number in the following table is used as the symbol of the exemplified compound in the present specification (for example, the compound number "7" means "exemplified compound (V-7)"). Becomes).

[0139]

[Table 53]

The content of the crosslinking compound in the outermost surface layer of the electrophotographic photoreceptor of the present invention is in the range of 20 to 80% by weight, preferably 30 to 70% by weight, based on the total solid content of the outermost surface layer.
% By weight.

[Silicon-Containing Fine Particle] The silicon-containing fine particle, which is an essential component in the first invention, is a fine particle containing silicon as a constituent element, and specific examples thereof include colloidal silica and silicone fine particles. . Colloidal silica and silicone fine particles may be used alone or in combination.

The colloidal silica used as the silicon-containing fine particles in the present invention has an average particle diameter of 1 to 100 n.
m, preferably 10 to 30 nm, selected from acidic or alkaline aqueous dispersions or those dispersed in organic solvents such as alcohols, ketones and esters, and generally commercially available ones can be used.

By adding colloidal silica,
The surface properties of the electrophotographic photoreceptor can be improved without inhibiting the crosslinked structure between the compound represented by the general formula (Ia) and the crosslinkable compound. That is, the contamination resistance and lubricity of the electrophotographic photoreceptor surface are improved, and the colloidal silica is a portion of the Si-containing glassy subunit represented by G in the above general formula (Ia) or crosslinked. Since it is held on the outermost surface layer of the electrophotographic photoreceptor surface in a state of being bonded to the hydrophilic compound, it is possible to maintain good stain resistance and lubricity over a long period of time.

The solid content of colloidal silica in the outermost surface layer of the electrophotographic photosensitive member of the present invention is in the range of 1 to 50% by weight, preferably 5 to 30% by weight, based on the total solid content of the outermost surface layer. % By weight.

The silicone fine particles used as the silicon-containing fine particles in the present invention are spherical and have an average particle diameter of 1 to 3.
500 nm, preferably 10 to 100 nm, selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, commercially available ones can be used.

Silicone microparticles are chemically inert,
Since the particles are small-diameter particles excellent in dispersibility in a resin and the content required for obtaining more sufficient properties is low, a crosslinking reaction between the compound represented by the general formula (Ia) and the crosslinkable compound is performed. The surface properties of the electrophotographic photoreceptor can be improved without obstructing the image quality. In other words, it is possible to improve the lubricity and water repellency of the electrophotographic photoreceptor surface and maintain good abrasion resistance and contamination resistance over a long period of time while being uniformly incorporated in the strong crosslinked structure. it can.

In the electrophotographic photoreceptor of the present invention, the content of the silicone fine particles in the outermost surface layer is in the range of 0.1 to 10% by weight based on the total solid content of the outermost surface layer, and preferably 0.1 to 10% by weight.
It is in the range of 5-5% by weight.

[Other components that can be added to the outermost surface layer] The crosslinked cured film constituting the outermost surface layer is made up of the above-mentioned components, but may be further added with various other components according to the purpose. Is also good.

To further enhance the effect of preventing toner and paper powder from adhering to the surface of the photoreceptor, a fluorine-containing compound may be added. Specific examples of the fluorine-containing compound include (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, and 3- (hepta Fluoroisopropoxy) propyltriethoxysilane, 1H,
Examples include 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane.

The fluorine-containing compound has the general formula (Ia)
Alternatively, it is more desirable to have an alkoxysilyl group or a silanol group capable of undergoing a cross-linking polymerization reaction with the compound represented by (Ib), since the addition of the fluorine-containing compound does not cause a decrease in the mechanical strength of the outermost surface layer, and is more desirable.

The amount of the fluorine-containing compound to be added is preferably 20% by weight or less, and more preferably 15% by weight, based on the total solid content of the outermost surface layer, since a problem may occur in the film formability of the crosslinked cured film. It is more preferable that the content be as follows, but in the case of a fluorine-containing compound capable of undergoing a cross-linking polymerization reaction with the compound represented by the general formula (Ia) or (Ib), it is possible to add about 40% by weight. .

Further, an antioxidant may be added for the purpose of more effectively preventing deterioration due to oxidizing gas such as ozone generated by the charging means. If the mechanical strength of the photoreceptor surface is increased, the photoreceptor comes into contact with the oxidizing gas for a long time. The outermost surface layer is provided with sufficient oxidation resistance by adding an antioxidant. However, in the electrophotographic photoreceptor of the present invention, F in the compound represented by the general formula (Ia) or (Ib) is used. By adopting a structure having resistance to oxidation as a structure of the subunit represented by, a structure having higher oxidation resistance is obtained.

The antioxidant is preferably a hindered phenol-based or hindered amine-based antioxidant, such as an organic sulfur-based antioxidant, a phosphite-based antioxidant,
Known antioxidants such as dithiocarbamate-based antioxidants, thiourea-based antioxidants, and benzimidazole-based antioxidants may be used. The addition amount of these antioxidants is preferably 15% by weight or less based on the total solid content of the outermost surface layer, and more preferably 10% by weight or less.

[Conductive Support of Electrophotographic Photoreceptor] The conductive support used in the electrophotographic photosensitive member of the present invention includes:
Any material conventionally used as a conductive support of an electrophotographic photosensitive member can be used, and opaque or substantially transparent materials can be used. For example, aluminum, nickel, chromium, metals such as stainless steel, aluminum, titanium, zirconium, nickel,
Plastic film provided with a thin film of chromium, stainless steel, gold, platinum, silver oxide, indium oxide, ITO, etc.
Examples include glass and ceramics, or paper or plastic film coated with or impregnated with a conductivity-imparting agent, glass and ceramics, and the like. The shape of the conductive substrate can be appropriately selected depending on the purpose of use, such as a drum shape, a sheet shape, and a plate shape.

The surface of the conductive support can be subjected to various treatments as needed and within a range that does not affect the image quality. For example, surface oxidation treatment (anodizing treatment or the like), chemical treatment, liquid honing, graining treatment by graining, other chemical treatment, coloring treatment, or the like can be performed. Oxidation treatment and surface roughening treatment of the conductive support surface
In addition to roughening the surface of the conductive support, the surface of the layer applied thereon is also roughened, causing a problem when using a coherent light source such as a laser as a light source for exposure. An effect of preventing the occurrence of interference fringes due to regular reflection at the surface of the support and / or at the interface of the laminated film can be exerted.

[Layer Configuration of Electrophotographic Photoreceptor] Regarding the electrophotographic photoreceptor of the present invention, regardless of the layer configuration, as described above, the outermost surface layer has the configuration according to the first aspect of the present invention or the second aspect. The composition of the present invention (hereinafter, may be collectively referred to as a “layer constituting the composition of the present invention”), and the layer composition includes the following.

A layer structure in which a laminated photosensitive layer comprising a charge transport layer and a charge generation layer is provided on a conductive support, and a surface protective layer is further provided thereon. In this case, the stacking order of the charge transport layer and the charge generation layer is as follows:
Either one may be an upper layer, and each may have a laminated structure. Then, the surface protective layer, which is the uppermost layer, is a layer constituting the configuration of the present invention.

A layer structure in which a laminated photosensitive layer comprising a charge transport layer and a charge generation layer is provided on a conductive support. In this case, as the stacking order of the charge transport layer and the charge generation layer, any one may be an upper layer, and a configuration in which each is further stacked may be used. When the charge transport layer is an upper layer, the charge transport layer (when the charge transport layer is laminated, the uppermost charge transport layer among them) is used when the charge generation layer is an upper layer. In this case, the charge generation layer (the uppermost charge generation layer in the case where the charge generation layers are laminated) is a layer constituting the structure of the present invention.

A layer structure in which a single-layer type photosensitive layer having both a charge transport function and a charge generation function is provided on a conductive support, and a surface protective layer is further provided thereon. In this case, the surface protective layer, which is the uppermost layer, is a layer constituting the configuration of the present invention.

A layer structure in which only a single-layer photosensitive layer having both a charge transport function and a charge generation function is provided on a conductive support. In this case, the photosensitive layer is a layer constituting the configuration of the present invention.

In the electrophotographic photoreceptor of the present invention, in the above-mentioned layer constitution, it is essential that at least the outermost layer is a layer constituting the constitution of the present invention, but other layers constitute the constitution of the present invention. The layer may be a layer, and it can be said that it is a rather preferable mode for improving the mechanical strength of the entire layer on the surface of the electrophotographic photosensitive member.

An undercoat layer may be provided between the conductive support and the photosensitive layer, if necessary. The undercoat layer is effective for preventing unnecessary charge injection from the conductive support, and has an effect of improving the chargeability of the photoconductor. Further, it has an effect of improving the adhesiveness between the photosensitive layer and the conductive support.

The binder resin used for the undercoat layer is polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, Vinylidene resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose, casein, gelatin,
Known materials such as polyglutamic acid, starch, starthiacetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compounds, titanyl chelate compounds, titanyl alkoxide compounds, organic titanyl compounds, and silane coupling agents can be used. Can be used alone or in combination of two or more.

Further, fine particles such as titanium oxide, silicon oxide, zirconium oxide, barium titanate, and silicone resin can be blended in the undercoat layer. The dry film thickness of the undercoat layer is suitably in the range of 0.01 to 10 μm, and more preferably in the range of 0.05 to 2 μm.

As a method for applying the undercoat layer, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method may be used. it can.

[Surface Protective Layer] The surface protective layer constituting the constitution of the present invention may further comprise, if necessary,
A coating solution prepared by mixing a fluorine-containing compound, an antioxidant, a solvent, and the like is prepared, and the coating solution is coated on a photosensitive layer formed on a conductive support, and then heated and cross-linked and cured. can do. The formation of the photosensitive layer will be described later.

Solvents to be used when preparing a coating solution, if necessary, for adjusting the viscosity of the solution, include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, and cyclohexanone. Ordinary organic solvents such as methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride and chloroform can be used alone or in combination of two or more.

As a coating method, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method can be employed. The dry thickness of the surface protective layer is preferably about 1 to 10 μm.

The cross-linking curing reaction may be carried out without a catalyst, but an appropriate catalyst may be used. As a catalyst,
Acid catalysts such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, phosphoric acid and trifluoroacetic acid; bases such as ammonia and triethylamine; organic tin compounds such as dibutyltin diacetate, dibutyltin dioctoate and stannous octoate; tetra-n- Examples thereof include organic titanium compounds such as butyl titanate and tetraisopropyl titanate, iron salts, manganese salts, cobalt salts, zinc salts, and zirconium salts of organic carboxylic acids. Also,
The temperature at the time of the crosslinking and curing reaction is not particularly limited, but is preferably set in the range of room temperature to 150 ° C.

[Photosensitive layer provided with surface protective layer] When the surface protective layer having the constitution of the present invention is provided, the photosensitive layer formed thereunder may be the photosensitive layer of any conventionally known photosensitive member. It can be employed, and may be a laminated photosensitive layer in which a charge generation layer and a charge transport layer are laminated, or may be a single-layer photosensitive member containing a charge generation material. Hereinafter, the laminated type and the single-layer type will be described separately.

[0171] 1. Laminated photosensitive layer The charge generating layer in the laminated photosensitive layer is formed of at least a charge generating material and a binder resin.

Examples of charge generation materials include amorphous selenium, crystalline selenium-tellurium alloy, selenium-arsenic alloy, other selenium compounds and inorganic photoconductive materials such as selenium alloys, zinc oxide and titanium oxide, and phthalocyanine compounds. And organic pigments or dyes such as squarylium compounds, anthantrone compounds, perylene compounds, azo compounds, anthraquinone compounds, pyrene compounds, pyrylium salts, and thiapyrylium salts. Of these, phthalocyanine-based compounds are preferred because of their high photosensitivity. Specifically, metal-free phthalocyanines, oxytitanium phthalocyanines, gallium phthalocyanines, hydroxygallium phthalocyanines, and tin phthalocyanines are preferred.

In particular, in the X-ray diffraction spectrum, the Bragg angles (2q ± 0.2 °) of 7.4 °, 16.6 °, 2
Chlorogallium phthalocyanine having a specific crystal form having a strong diffraction peak at 5.5 ° or 28.3 °, or a Bragg angle (2q ±
0.2 °) 7.5 °, 9.9 °, 12.5 °, 16.
Hydroxygallium phthalocyanine having a specific crystal form having strong diffraction peaks at 3 °, 18.6 °, 25.1 °, and 28.3 ° is high with respect to light in a wide range from visible light to near infrared light. It has a charge generation efficiency and is particularly preferable.

Examples of the binder resin for the charge generation layer include polyvinyl butyral resin, polyvinyl formal resin, partially modified polyvinyl acetal resin, polycarbonate resin,
Examples include, but are not limited to, polyester resins, acrylic resins, polyvinyl chloride resins, polystyrene resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymers, silicone resins, phenolic resins, poly-N-vinylcarbazole resins, and the like. Not something. These binder resins can be used alone or in combination of two or more.

The mixing ratio (weight ratio) of the charge generating material to the binder resin is preferably in the range of 10: 1 to 1:10. The charge generation layer was prepared by dissolving and dispersing a charge generation material and a binder resin in an appropriate solvent to prepare a coating solution, and forming the coating solution on a conductive support or a conductive support described later. Can be formed by applying the composition on the charge transport layer and drying by heating.

Solvents used for preparing the coating solution include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, and tetrahydrofuran. , Methylene chloride, chloroform and the like can be used alone or in combination of two or more.

As a coating method, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method and the like can be adopted. The dry film thickness of the charge generation layer is generally suitably from 0.1 to 5 μm, and more preferably from 0.2 to 2.0 μm.

The charge transport layer in the laminated photosensitive layer is formed of at least a charge transport material and a binder resin, or is composed of a polymer charge transport material. Examples of the charge transport material include quinone compounds such as p-benzoquinone, chloranil, bromanyl, and anthraquinone; tetracyanoquinodimethane compounds; fluorenone compounds such as 2,4,7-trinitrofluorenone; xanthone compounds; and benzophenone compounds. , Cyanovinyl compounds,
Examples thereof include an electron-withdrawing substance such as an ethylene compound, a triarylamine compound, a benzidine compound, an arylalkane compound, an aryl-substituted ethylene compound, a stilbene compound, an anthracene compound, and a hydrazone compound. These charge transport materials can be used alone or in combination of two or more.

In particular, benzidine compounds represented by the following general formula (VI) and triphenylamine compounds represented by the following general formula (VII) have high charge (hole) transport ability and excellent stability. Therefore, it can be particularly preferably used. General formula (VI)

[0180]

Embedded image

In the above formula, R ⁶ and R ⁶ ′ may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. . R ⁷ , R ⁷ ′, R ⁸ and R ⁸ ′ may be the same or different and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, Represents an amino group substituted by an alkyl group of Formulas 1 and 2, and m and n represent integers of 0 to 2. General formula (VII)

[0182]

Embedded image

In the above formula, R ⁹ represents a hydrogen atom or a methyl group, and n represents 1 or 2. Ar ⁶ Ar ⁷ represents a substituted or unsubstituted aryl group, and examples of the substituent include a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an alkyl group having 1 to 2 carbon atoms. Represents an amino group substituted with

The compound example of the benzidine-based compound represented by the above general formula (VI) can be obtained by specifying each substituent.
The following table summarizes them. In addition, the symbol which added "VI-" to the compound number in the following table | surface is used as the symbol of the exemplary compound in this specification (For example, the thing of the compound number of "27" is "the exemplary compound (VI-27)." Becomes).

[0185]

[Table 54]

[0186]

[Table 55]

Examples of the triphenylamine-based compound represented by the general formula (VII) are shown in the following table by specifying each substituent. In addition, the symbol of the compound number in the following table with "VII-" added thereto is referred to as the symbol of the exemplified compound in the present specification (for example, the compound having the compound number of "27" is referred to as "exemplified compound (VII-27)").
Becomes).

[0188]

[Table 56]

[0189]

[Table 57]

[0190]

[Table 58]

These charge transporting materials can be used alone or in combination of two or more.

Examples of the binder resin for the charge transport layer include a polycarbonate resin, a polyester resin, a methacrylic resin, an acrylic resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polystyrene resin, a polyvinyl acetate resin,
Styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, Known resins such as styrene-acrylic resin, styrene-alkyd resin, poly-N-vinylcarbazole, and polysilane can be used.

On the other hand, as the polymer charge transporting material, a known charge transporting material such as poly-N-vinylcarbazole and polysilane can be used. For example,
Polyester polymer charge transport materials disclosed in U.S. Pat. No. 4,801,517 and the like have high charge transport properties and are preferred. An antioxidant may be added to the charge transport layer for the purpose of preventing deterioration due to an oxidizing gas such as ozone generated in the charging device. Even if there is a surface protective layer, an oxidizing gas may permeate the surface protective layer and penetrate into the charge transport layer, and it is preferable to add an antioxidant in order to prevent oxidative deterioration due to this. As the antioxidant, those similar to those used for the surface protective layer can be used. The addition amount of the antioxidant is preferably 15% by weight or less of the total solids of the charge transport layer, more preferably 10% by weight or less.

The compounding ratio (weight ratio) of the charge transporting material to the binder resin is preferably in the range of 1: 9 to 7: 3. The charge transport layer is prepared by dissolving a charge transport material and a binder resin and, if necessary, an antioxidant in an appropriate solvent and dispersing the same, and preparing the coating solution on a conductive support, or It can be formed by coating on the charge generation layer formed on the conductive support and then drying by heating.

Solvents used in preparing the coating solution include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenated aliphatics such as methylene chloride, chloroform and ethylene chloride. Common organic solvents such as hydrocarbons, cyclic or linear ethers such as tetrahydrofuran, ethyl ether and dioxane can be used alone or in combination of two or more.

As the method for applying the charge transport layer, the same known methods as those described for the surface protective layer and the charge generation layer can be employed. The dry thickness of the charge transport layer is 5 to 50 μm, preferably 10 to 40 μm.

[0197] 2. Single-layer type photosensitive layer In the case of a single-layer type photosensitive layer, it is formed by containing the above-mentioned charge generating material and a binder resin. As the binder resin, the same resins as those used for the charge generation layer and the charge transport layer can be used. The content of the charge generating material in the single-layer type photosensitive layer is about 10 to 85% by weight, preferably 20 to 50% by weight of the total solids of the photosensitive layer.

A charge transport material may be added to the single-layer type photosensitive layer as needed. The addition amount is preferably 5 to 50% by weight of the total solids of the photosensitive layer. Further, if necessary, an antioxidant may be added to the single-layer type photosensitive layer for the same reason as in the case of the charge transport layer. The addition amount is preferably 15% by weight or less, more preferably 10% by weight or less of the total solids of the photosensitive layer.

The single-layer type photosensitive layer is prepared by dissolving and dispersing a charge generating material, a binder resin, and, if necessary, a charge transporting material and an antioxidant in an appropriate solvent, and preparing the coating solution. It can be formed by applying a liquid on a conductive support and then drying by heating. The same solvent and the same coating method as those described for the charge generation layer and the charge transport layer can be used. The thickness of the single-layer type photosensitive layer is about 5 to 50 μm, and more preferably 10 to 40 μm.

[Photosensitive layer without surface protective layer] When the surface protective layer is not provided, as described above, the outermost surface layer of the photosensitive layer formed on the surface of the conductive support is constituted by the constitution of the present invention. Layer. As the photosensitive layer, there are two types, a lamination type and a single layer type.

In the case of a laminate type photosensitive layer, the charge transport layer is the layer constituting the structure of the present invention if the charge transport layer is on the surface, and the charge generation layer if the charge generation layer is on the surface. In this case, in the outermost layer, instead of the charge transport layer or the charge generation layer described above as the [photosensitive layer in the case where a surface protective layer is provided], a layer configuration that constitutes the configuration of the present invention is adopted, As the other layers, the structure described above as the “photosensitive layer provided with the surface protective layer” is employed as it is.

However, when the charge generation layer is a layer constituting the constitution of the present invention, it is necessary to add a charge generation material to the layer. As the charge generating material, the same materials as in the case of the charge generating layer described in the above [Photosensitive layer in the case where a surface protective layer is provided] can be used. 10-60% by weight
And more preferably 20 to 50% by weight.

In the case where the charge transport layer is a layer constituting the constitution of the present invention, the above-mentioned general formula (Ia) or (Ib)
Since the photoelectric characteristic subunit represented by F in the compound represented by the formula (1) has a charge transporting property, it is not essential to add a charge transporting material to the layer. Of course, it is also possible to add a charge transport material. When adding a charge transport material, the same materials as in the case of the charge transport layer described in the above [Photosensitive layer in the case where a surface protective layer is provided] can be used,
The addition amount thereof is 5 to 50% of the total solid content of the charge transport layer.
% By weight, more preferably from 10 to 40% by weight
It is.

On the other hand, in the case of a single-layer type photosensitive layer, the photosensitive layer itself is a layer constituting the constitution of the present invention. However, it is necessary to add a charge generating material to the single-layer type photosensitive layer. As the charge generation material, the same materials as in the case of the charge generation layer described in the above [Photosensitive layer in the case where a surface protective layer is provided] can be used. It is preferably from 10 to 60% by weight, more preferably from 20 to 50% by weight.

In order to form the outermost surface layer of the photosensitive layer without the surface protective layer, a charge generating material, a charge transporting material, a fluorine-containing compound, It can be formed by preparing a coating solution in which an antioxidant, a solvent and the like are mixed, applying the coating solution on a photosensitive layer formed on a conductive support, and then heating and crosslinking and curing. .

Solvents to be used when preparing the coating solution as necessary for adjusting the viscosity of the solution include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, and cyclohexanone. Ordinary organic solvents such as methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride and chloroform can be used alone or in combination of two or more.

As a coating method, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method and the like can be adopted.

When the cross-linking curing reaction is carried out, it may be carried out without a catalyst, but an appropriate catalyst may be used. As a catalyst,
Acid catalysts such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, phosphoric acid and trifluoroacetic acid; bases such as ammonia and triethylamine; organic tin compounds such as dibutyltin diacetate, dibutyltin dioctoate and stannous octoate; tetra-n- Examples thereof include organic titanium compounds such as butyl titanate and tetraisopropyl titanate, iron salts, manganese salts, cobalt salts, zinc salts, and zirconium salts of organic carboxylic acids. Also,
The temperature at the time of the crosslinking and curing reaction is not particularly limited, but is preferably set in the range of room temperature to 150 ° C.

[Electrophotographic Image Forming Apparatus] The electrophotographic photosensitive member of the present invention as described above can be applied to any conventionally known electrophotographic image forming apparatus. In particular, the electrophotographic photoreceptor of the present invention has a high resistance to an oxidizing gas generated by a charging unit, and also has a photosensitive layer having high mechanical strength even when it has a mechanical cleaning unit. Even when used under these severe conditions, good photoreceptor characteristics can be maintained for a long period of time.

An example of a specific electrophotographic image forming apparatus is an electrophotographic image forming apparatus having at least the electrophotographic photosensitive member of the present invention, a charging unit, and a mechanical cleaning unit. Is a contact charging system. In addition, an exposure unit such as a laser optical system or an LED array, a developing unit that forms an image using toner or the like, a transfer unit that copies a toner image onto a medium such as paper, a fixing unit that fixes a toner image on a medium such as paper, If necessary, a known method may be used to remove static electricity remaining on the surface of the photoreceptor.

FIG. 1 is a schematic diagram showing an example of an electrophotographic image forming apparatus to which the electrophotographic photosensitive member of the present invention is applied. A photoreceptor 10 which is an electrophotographic photoreceptor of the present invention; a charging roll 12 which is a contact charging type charging means; a laser exposure optical system 14; a developing device 16 using powder toner; a transfer roll 18; It has a cleaning blade 20 and a fixing roll 22 as mechanical cleaning means.

The mechanical cleaning means is a means for directly contacting the surface of the photoreceptor and removing toner, paper dust, dust and the like adhering to the surface. In addition, a known type such as a brush and a roll can be applied.

[0213] The charging means of the contact charging type is a photoconductor 10
The surface of the photosensitive member is charged by applying a voltage to the conductive member brought into contact with the surface of the photosensitive member. The shape of the conductive member is not limited to a roll shape such as the charging roll 12 in FIG. Any of a brush shape, a blade shape, a pin electrode shape, and the like may be used, but a roll-shaped conductive member is particularly preferable. Usually, the roll-shaped conductive member is formed by forming an elastic layer on the roll surface as a core material, and further forming a resistance layer thereon. Further, if necessary, a protective layer can be provided outside the resistance layer.

The material of the core material has conductivity, and generally, iron, copper, brass, stainless steel, aluminum, nickel or the like is used. In addition, a resin molded product or the like in which conductive particles or the like are dispersed can also be used. The material of the elastic layer is an elastic material having conductivity or semi-conductivity, and is generally a material in which conductive particles or semi-conductive particles are dispersed in a rubber material.

As rubber materials, EPDM, polybutadiene, natural rubber, polyisobutylene, SBR, CR, NB
R, silicone rubber, urethane rubber, epichlorohydrin rubber, SBS, thermoplastic elastomer, norbornene rubber, fluorosilicone rubber, ethylene oxide rubber and the like are used.

Examples of the conductive particles or semiconductive particles include carbon black, zinc, aluminum, copper, iron, and the like.
Metals such as nickel, chromium, and titanium, ZnO-Al
₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO
_{-TiO 2, MgO-Al 2 O} 3, FeO-TiO 2, Ti
Metal oxides such as O ₂ , SnO ₂ , Sb ₂ O ₃ , In ₂ O ₃ , ZnO, and MgO can be used, and these materials may be used alone or as a mixture of two or more.

The resistive layer and the protective layer are made of a conductive resin
Disperse particles or semiconductive particles and control their resistance
Acrylic resin, cellulosic binder resin
Resin, polyamide resin, methoxymethylated nylon
, Ethoxymethylated nylon, polyurethane resin,
Recarbonate resin, polyester resin, polyethylene
Resin, polyvinyl resin, polyarylate resin, polythio
Polyolefin such as phen resin, PFA, FEP, PET
Resin, styrene butadiene resin and the like are used. Conductive
As the conductive particles or semiconductive particles, the same as the elastic layer
Carbon black, metal, and metal oxide are used. Usually
The resistivity of the resistive layer and the protective layer is 10 ^Three-10¹⁴Ω
cm, preferably 10^Five-10¹²Ωcm, more preferred
H10⁷-10¹²Ωcm is good. Also, a resistance layer and
The thickness of the protective layer is preferably 0.01 to 1,000 μm.
Preferably 0.1 to 500 µm, more preferably 0.5
１００100 μm is preferred. Also, if necessary, hindered
Antioxidants such as knol, hindered amine, clay,
Add a filler such as Olin or a lubricant such as silicone oil.
Can be added.

A method for forming these layers can be performed by dissolving and dispersing each of the above-mentioned materials in an appropriate solvent to prepare a coating solution, and applying this to an object to be coated. As a means for applying, conventionally known means such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method can be employed.

In order to charge the photosensitive member by the conductive member of the charging means, it is necessary to apply a voltage to the conductive member. The applied voltage is a DC voltage or a DC voltage with an AC voltage superimposed thereon. It is particularly preferable to superimpose an AC voltage on a DC voltage in terms of uniform charging and stabilizing the environment.

As for the magnitude of the voltage, the DC voltage is a positive or negative 50 to 2.0, depending on the required photosensitive member charging potential.
00V is preferable, and 100 to 1,500V is particularly preferable. When the AC voltage is superimposed, the peak-to-peak voltage is 400
To 3,000 V, more preferably 800 to 2,500 V, and still more preferably 1,200 to
2,500V. The frequency of the AC voltage is 50
２０20,000 Hz, preferably 100５，5,000
Hz.

[0221]

(Example 1) 10 parts of a zirconium compound (trade name: Organotics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and a silane compound (applied on the outer peripheral surface of a honing-treated aluminum pipe (length: 340 mm, outer diameter: 30 mm)) Product name: A1110, manufactured by Nippon Unicar Co., Ltd.) A solution consisting of 1 part, 40 parts of isopropanol and 20 parts of butanol was applied by a dip coating method, and heated and dried at 150 ° C. for 10 minutes to form a 0.1 μm-thick undercoat layer. Formed.

The Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum were 7.4 °, 16.6 °, 25.
1 part of chlorogallium phthalocyanine having a strong diffraction peak at 5 ° and 28.3 ° is mixed with 1 part of polyvinyl butyral (Eslec BM-S, Sekisui Chemical) and 100 parts of n-butyl acetate, and the mixture is mixed with glass beads and a paint shaker. For 1 hour to prepare a coating solution by dispersing. The obtained coating solution is applied on the undercoat layer by a dip coating method, and heated and dried at 100 ° C. for 10 minutes to form a film having a thickness of about 0.15 μm. A charge generation layer was formed.

A coating solution was prepared by dissolving 2 parts of the triphenylamine compound of the exemplified compound (VII-28) and 3 parts of a polymer compound (viscosity average molecular weight 39,000) represented by the following basic unit (VIII) in 20 parts of chlorobenzene. Was prepared, and the obtained coating solution was applied onto the charge generation layer by a dip coating method, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm. Basic unit (VIII)

[0224]

Embedded image

Exemplified compound (III-249) (6 parts), isopropanol-dispersed colloidal silica (manufactured by Nissan Chemical Industries, IPA
-ST, 10% solid content 30%, silicone hard coat coating agent (Shin-Etsu Silicon, X-40-)
2239) 10 parts were mixed to prepare a coating solution, and the obtained coating solution was stored at 20 ° C. for 2 days, aged, and then applied on the charge transport layer by a spray coating method. After leaving to stand for 30 minutes and drying by touch, heat treatment was performed at 120 ° C. for 60 minutes to form a surface protective layer having a thickness of 3 μm, thereby obtaining an electrophotographic photosensitive member of the present invention.

Example 2 A charge transport layer was formed in the same manner as in Example 1. Exemplified compound (III-270) 35
Parts, silicone-treated silica fine particles (KP-X-100,
1 part spherical, average particle diameter 100 nm, manufactured by Shin-Etsu Chemical Co., Ltd., 1 part, silicone hard coat coating agent (Shin-Etsu Silicon, X-40-2239) 50 parts, dibutyl ether 8
0 parts were mixed and dispersed with a glass shaker for 1 hour using a paint shaker to prepare a coating solution. After adding 6 parts of 2% sulfuric acid aqueous solution to the obtained coating solution, spray coating was performed on the charge transport layer. Was applied. After leaving it to dry for 30 minutes, heat-treat it at 120 ° C. for 60 minutes to give a film thickness of 3 μm.
m of the surface protective layer was formed to obtain an electrophotographic photosensitive member of the present invention.

(Comparative Example 1) The thickness of the charge transport layer was 23 μm
The electrophotographic photoreceptor of Comparative Example 1 was obtained in the same manner as in Example 1 except that the surface protective layer was not formed.

(Comparative Example 2) In forming the surface protective layer,
An electrophotographic photoreceptor of Comparative Example 2 was obtained in the same manner as in Example 1, except that no isopropanol-dispersed colloidal silica was added.

(Comparative Example 3) In forming the surface protective layer,
An electrophotographic photoreceptor of Comparative Example 3 was obtained in the same manner as in Example 2, except that the silicone-treated silica fine particles were not added.

(Comparative Example 4) In forming the surface protective layer,
An electrophotographic photosensitive member of Comparative Example 4 was obtained in the same manner as in Example 1, except that the exemplified compound (III-249) was not added.

(Comparative Example 5) In forming the surface protective layer,
An electrophotographic photosensitive member of Comparative Example 5 was obtained in the same manner as in Example 2, except that the exemplified compound (III-270) was not added.

<Print Durability Test> Each of the electrophotographic photoreceptors of Examples 1 and 2 and Comparative Examples 1 to 5 obtained as described above was used with LaserPress 4160 manufactured by Fuji Xerox.
Remodeled machine (only the photoconductor can be replaced with each electrophotographic photoconductor of Examples 1 and 2 and Comparative Examples 1 to 5)
And a printing durability test was performed in a high temperature and high humidity environment (28 ° C., 85% RH). This LaserPress
The modified 4160 machine has a charging roll as a contact-type charging unit, a laser exposure optical system, a toner developing unit, a transfer roll, a cleaning blade as a mechanical cleaning unit, and a fixing roll.

The printing durability was evaluated by printing 50,000 test patterns for evaluating tone reproducibility and resolution reproducibility, evaluating the image quality before and after printing, visually observing the surface of the photoreceptor, and abrading the surface layer of the photoreceptor. This was done by measuring the amount. Note that acidic paper was used as the paper. This is to make it easier to detect image quality deterioration due to the adhesion of paper powder to the photoreceptor surface. The results are shown in Table 59 below.

[0234]

[Table 59]

With the electrophotographic photosensitive members of Examples 1 and 2,
The amount of wear of the surface layer of the photoreceptor after printing 50,000 sheets was small, and no change was observed in the surface condition of the photoreceptor. Further, the image quality in both the initial stage and after printing 50,000 sheets was good in both gradation and resolution.

In the electrophotographic photosensitive member of Comparative Example 1, a decrease in image density was observed. This is presumed to be because the photoreceptor had a large amount of abrasion after printing 50,000 sheets, so that the photoelectric characteristics changed, and the surface potential did not sufficiently decrease even when exposed by the laser exposure optical system. Further, a large number of streak-like and dot-like scratches, which are considered to be caused by contact with a developer, transfer paper, and the like, are generated on the surface of the photoreceptor, and this causes image defects.

With the electrophotographic photosensitive members of Comparative Examples 2 and 3,
A brown deposit was observed on the surface of the photoreceptor after printing 50,000 sheets, and in the image quality evaluation under a high-temperature and high-humidity environment, image blur was generated in the resolution pattern, and reduction in resolution was confirmed. This is presumed to be because hydrophilic discharge products generated from the contact charging roll at the time of charging adhere to the surface of the photoreceptor, and the adhered substances absorb moisture in a high humidity environment to lower the surface resistance.

In Comparative Examples 4 and 5, although the abrasion loss of the surface layer of the photoreceptor after printing 50,000 sheets was small, the image density decreased after printing 10,000 sheets, and almost no No image was obtained. This is presumably because the surface protective layer did not have the charge transporting property, so that the bright portion potential increased and the photoelectric property decreased.

Example 3 10 parts of a zirconium compound (trade name: Organotics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and a silane compound (trade name) were placed on the outer peripheral surface of a honing-treated aluminum pipe (length: 340 mm, outer diameter: 30 mm). Name: A1110, manufactured by Nippon Unicar Co., Ltd.) A solution comprising 1 part, 40 parts of isopropanol and 20 parts of butanol is applied by a dip coating method, and heated and dried at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.1 μm. did.

In the X-ray diffraction spectrum, the Bragg angles (2θ ± 0.2 °) were 7.5 °, 9.9 °, 12.5 °
°, 16.3 °, 18.6 °, 25.1 °, 28.3 °
1 part of hydroxygallium phthalocyanine having a strong diffraction peak is mixed with 1 part of vinyl chloride-vinyl acetate copolymer resin (manufactured by Union Carbide Co., Ltd., vinylite VMCH) and 100 parts of chlorobenzene, and treated with glass beads for 1 hour with a paint shaker. A coating solution was prepared by dispersion, and the obtained coating solution was applied on the undercoat layer by a dip coating method, and was heated and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm. .

A coating liquid was prepared by dissolving 2 parts of a benzidine compound of the exemplified compound (VI-27) and 3 parts of a polymer compound (viscosity average molecular weight 39,000) represented by the following basic unit (VIII) in 20 parts of chlorobenzene. Then, the obtained coating solution was applied on the charge generation layer by a dip coating method,
Heating was performed at 0 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

[0242]

Embedded image

6 parts of the exemplified compound (III-255), colloidal silica dispersed with methyl isobutyl ketone (manufactured by Nissan Chemical Industries, Ltd.)
MIBK-ST, solid content 30%) 10 parts, silicone hard coat coating agent (Shin-Etsu Silicon, X
-40-2239) 10 parts and 10 parts of dibutyl ether were mixed to prepare a coating solution, and the obtained coating solution was stored at 20 ° C. for 2 days, aged, and then applied on the charge transport layer by a spray coating method. did. Let dry for 30 minutes,
Heat treatment was performed at 120 ° C. for 60 minutes to form a surface protective layer having a thickness of 3 μm, thereby obtaining an electrophotographic photosensitive member of the present invention.

(Examples 4 to 7) In the formation of the surface protective layer, Example 4 was replaced with Example Compound (III-249).
(III-3), (III-31) in Example 5, (III-145) in Example 6, and (III-17) in Example 7.
An electrophotographic photoreceptor of the present invention was obtained in the same manner as in Example 1 except that each of 8) was used.

Example 8 A charge transport layer was formed in the same manner as in Example 1. 6 parts of exemplary compound (III-249),
Isopropanol dispersed colloidal silica (Nissan Chemical,
10 parts of IPA-ST, solid content concentration 30%), 9 parts of methyltrimethoxysilane, and 1 part of dimethylpolysiloxane (molecular weight: 1500) were mixed to prepare a coating solution, and the obtained coating solution was mixed at 20 ° C. After storage and aging for days, it was applied on the charge transport layer by a spray coating method. After leaving to stand for 30 minutes and drying by touch, heat treatment was performed at 120 ° C. for 60 minutes to form a surface protective layer having a thickness of 3 μm, thereby obtaining an electrophotographic photosensitive member of the present invention.

Example 9 A charge transport layer was formed in the same manner as in Example 3. Exemplified compound (III-255) 25
Part, silicone-treated silica fine particles (KP-X-50, spherical, average particle diameter 50 nm, manufactured by Shin-Etsu Chemical Co., Ltd.), 1 part, silicone hard coat coating agent (Shin-Etsu Silicone, X
-40-2239) 50 parts and 80 parts of dibutyl ether are mixed and mixed with glass beads using a paint shaker.
A coating solution is prepared by performing dispersion treatment for one hour, and 1
After adding 3 parts of N hydrochloric acid aqueous solution, it was applied on the charge transport layer by a spray coating method. After leaving to stand for 30 minutes and drying by touch, heat treatment was performed at 120 ° C. for 60 minutes to form a surface protective layer having a thickness of 3 μm, thereby obtaining an electrophotographic photosensitive member of the present invention.

(Examples 10 to 13) In forming the surface protective layer, (III-3) in Example 10 and (III-3) in Example 11 instead of the exemplified compound (III-270).
1) The electrophotographic photoreceptor of the present invention was obtained in the same manner as in Example 2 except that (III-145) was used in Example 12 and (III-178) was used in Example 13 respectively.

Example 14 A charge transport layer was formed in the same manner as in Example 1. Exemplified compound (III-270) 35
Part, spherical silicone-treated silica fine particles (KP-X-10
0, an average particle diameter of 100 nm, 1 part of Shin-Etsu Chemical Co., Ltd., 45 parts of methyltrimethoxysilane, 5 parts of dimethylpolysiloxane (molecular weight: 1500), and 50 parts of isopropanol were mixed, and mixed with glass beads using a paint shaker.
A time-dispersion treatment is performed to prepare a coating solution, and 2
After adding 6 parts of an aqueous sulfuric acid solution, the mixture was applied onto the charge transport layer by a spray coating method. After leaving to stand for 30 minutes and drying by touch, heat treatment was performed at 120 ° C. for 60 minutes to form a surface protective layer having a thickness of 3 μm, thereby obtaining an electrophotographic photosensitive member of the present invention.

<Print Durability Test> The electrophotographic photosensitive members of Examples 3 to 14 thus obtained were subjected to a print durability test in the same manner as in Example 1 described above. The results are shown in Table 60 below.

[0250]

[Table 60]

In the electrophotographic photosensitive members of Examples 3 to 14, 5
The wear amount of the surface layer of the photoreceptor after printing thousands of sheets is small, the photoelectric characteristics are stable, and streak and dot-like scratches, which are thought to be due to the contact with the developer, transfer paper, etc., and discharge generation There was no occurrence of image blur or a decrease in resolution, which is considered to be caused by the adhesion of an object. Therefore, the image quality after printing 50,000 sheets was good in both gradation and resolution.

Example 15 A charge generation layer was formed in the same manner as in Example 1. A coating solution obtained by dissolving 2 parts of a benzidine compound of the exemplified compound (VI-27) and 3 parts of a high molecular compound represented by the following basic unit (viscosity average molecular weight 39,000) in 20 parts of chlorobenzene is immersed on the charge generation layer. The composition was applied by a coating method and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

Exemplified compound (III-3) 10 parts, Exemplified compound (V-1) 5.5 parts, silicone hard coat coating agent (X-40-2239, manufactured by Shin-Etsu Silicone)
A coating solution obtained by mixing 8 parts, 7 parts of acetic acid, and 0.001 part of 1N hydrochloric acid was dip-coated on the charge transport layer, left to dry for 30 minutes at 120 ° C. for 2 hours. Heat treatment was performed to form a surface protective layer having a thickness of about 5 μm, thereby obtaining an electrophotographic photosensitive member of the present invention.

(Comparative Example 6) An electrophotographic photosensitive member of Comparative Example 6 was obtained in the same manner as in Example 15, except that the surface protective layer was not formed.

(Comparative Example 7) In forming the surface protective layer,
Except that the exemplified compound (III-3) was not added,
In the same manner as in Example 15, an electrophotographic photosensitive member of Comparative Example 7 was obtained.

(Comparative Example 8) An electrophotographic photosensitive member of Comparative Example 8 was obtained in the same manner as in Example 15 except that phenyltrimethoxysilane was used instead of Exemplified Compound (III-1). . In addition, phenyltrimethoxysilane is
It is a compound having only one substituent represented by the general formula (IV).

<Printing Durability Test> Each of the electrophotographic photoreceptors of Example 15 and Comparative Examples 6 to 8 obtained as described above was subjected to Laser Press 4160 manufactured by Fuji Xerox.
Modified machine (only the photoreceptor was used in Example 15 and Comparative Example 6)
To 8 each of which can be replaced by an electrophotographic photoreceptor), and a printing durability test was performed in an environment of 20 ° C. and 40% RH. This modified LaserPress 4160 has a charging roll as a contact type charging unit, a laser exposure optical system, a toner developing unit, a transfer roll, a cleaning blade as a mechanical cleaning unit, and a fixing roll.

The printing durability was evaluated by printing 100,000 sheets of test patterns for evaluation of gradation reproducibility and resolution reproducibility.
The evaluation was performed by evaluating the image quality after printing 50,000 sheets and 100,000 sheets, visually observing the surface of the photoconductor, and measuring the abrasion amount of the surface layer of the photoconductor. In addition, Fuji Xerox PPC paper (L, A4) was used as the paper. The results are shown in Table 61 below.

[0259]

[Table 61]

With the electrophotographic photosensitive member of Example 15, the 256 gradation pattern and 400
Both the dpi resolution pattern was good, the amount of wear was small, and no large streak-like scratches were found on the surface of the photoreceptor, indicating that the photoreceptor had sufficient mechanical strength.

In the electrophotographic photosensitive member of Comparative Example 6, although the initial image quality was good, after printing 50,000 sheets, many streaky and dot-like scratches occurred on the surface of the photosensitive member, which caused image defects. Was to occur. In addition, a decrease in image density, which is considered to be caused by a decrease in film thickness, has occurred. Therefore, no further printing test was performed.

In the electrophotographic photoreceptor of Comparative Example 7, since the surface protective layer did not have photoelectric characteristics, that is, it did not have carrier transport performance, although several initial sheets could be printed, more than ten prints could be printed. , The surface potential does not attenuate and printing becomes impossible. The value of the abrasion amount in the table is obtained by performing printing processing of 50,000 sheets in a state where no image appears.

In the electrophotographic photosensitive member of Comparative Example 8, there was no problem in image characteristics after printing 50,000 sheets. However, at this stage, all the surface protective layers were worn out, and after printing 100,000 sheets, Image defects due to scratches on the body surface and a decrease in image density due to a decrease in film thickness were observed.

(Examples 16 to 21) In forming a surface protective layer, Example 1 was replaced with Example 1 (III-3).
In Example 6, (III-13), and in Example 17, (III-3)
1), Example 18 (III-32) and Example 19 (II
I-145), the electrophotographic photoreceptor of the present invention was obtained in the same manner as in Example 15 except that (III-178) was used in Example 20, and (III-255) was used in Example 21. Each of the electrophotographic photoreceptors of Examples 16 to 21 thus obtained was subjected to a printing durability test in the same manner as in Example 15 (however, a durability test up to 50,000 sheets). The results are shown in Table 62 below.

[0265]

[Table 62]

Example 22 A charge generation layer was formed in the same manner as in Example 1. 2 parts of Exemplified Compound (VI-27), 1 part of Exemplified Compound (VII-28), and 3 parts of the same high molecular compound (viscosity average molecular weight 39,000) used in Example 15 for forming the charge transport layer were chlorobenzene. The coating solution dissolved in 24 parts was applied on the charge generation layer by dip coating, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

Exemplified compound (III-270) 10 parts, Exemplified compound (V-1) 5.5 parts, silicone hard coat
Coating agent (Shin-Etsu Silicon, X-40-223
9) A coating solution obtained by mixing 18 parts, 7 parts of acetic acid, and 0.001 part of 1N hydrochloric acid was applied onto the charge transport layer by dip coating.
After leaving to stand for 30 minutes and drying by touch, heat treatment was performed at 120 ° C. for 2 hours to form a surface protective layer having a thickness of about 5 μm, thereby obtaining an electrophotographic photosensitive member of the present invention.

Example 23 A charge transport layer was formed in the same manner as in Example 22. Exemplified compound (III-270) 1
0 parts, 5.5 parts of exemplified compound (V-1), silicone hard coat / coating agent (X-40, manufactured by Shin-Etsu Silicon Co., Ltd.)
18 parts, fluorine-containing silane coupling agent (Shin-Etsu Silicon, KBM-7803) 2 parts, hindered phenolic antioxidant (Sumilyzer, MDP-S)
One part, 7 parts of acetic acid, and 0.001 part of 1N hydrochloric acid were mixed, and the coating solution was applied onto the charge transport layer by dip coating. Heat treatment for a time to form a surface protective layer having a thickness of about 5 μm,
An electrophotographic photosensitive member of the present invention was obtained.

(Example 24) Instead of chlorogallium phthalocyanine used in forming the charge generation layer in Example 22, the Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum were 7.5 ° and 9 °. .9 °, 12.5
°, 16.3 °, 18.6 °, 25.1 °, 28.3 °
A charge generation layer was formed in the same manner as in Example 22 except that hydroxygallium phthalocyanine having a specific crystal form having a strong diffraction peak was used, to thereby obtain an electrophotographic photosensitive member of the present invention.

(Example 25) Instead of chlorogallium phthalocyanine used in forming the charge generation layer in Example 23, the Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum were 7.5 ° and 9 °. .9 °, 12.5
°, 16.3 °, 18.6 °, 25.1 °, 28.3 °
A charge generation layer was formed in the same manner as in Example 23, except that hydroxygallium phthalocyanine having a specific crystal form having a strong diffraction peak was used, to thereby obtain an electrophotographic photosensitive member of the present invention.

(Examples 26 to 28) In the formation of the surface protective layer, Example 26 was used instead of Exemplified Compound (V-1).
(V-3), Example 27 (V-5), Example 2
8 except that (V-7) was used.
In the same manner as in Example 2, an electrophotographic photosensitive member of the present invention was obtained. In addition,
Exemplary compound (V-7) in Example 28 includes 1
A mixture of -substitution and 3-substitution was used.

Examples 22 to 28 thus obtained
For each of the electrophotographic photoreceptors, a printing durability test was performed in the same manner as in Example 15 (however, a durability test was performed up to 50,000 sheets). The results are shown in Table 63 below.

[0273]

[Table 63]

[0274]

According to the first aspect of the present invention, the electrophotographic photoreceptor of the present invention contains silicon-containing fine particles together with the compound represented by the formula (Ia) in the outermost surface layer, so that the surface strength is high and the photoelectric characteristics are stable. At the same time, it is highly resistant to adhesion contamination of toner, paper powder, discharge products and the like in continuous use.

On the other hand, the electrophotographic photoreceptor of the second aspect of the present invention
Since the outermost surface layer is formed of a siloxane-based crosslinked cured film composed of a compound represented by the general formula (Ib) and a crosslinkable compound having two or more substituents represented by the general formula (IV), High mechanical strength is achieved while having photoelectric characteristics. Therefore, when used as an electrophotographic image forming apparatus, it has high durability, and has an effect of suppressing the printing running cost.

The electrophotographic photoreceptor of the present invention is particularly suitable for use in an electrophotographic image forming apparatus having a charging means employing a contact charging method, especially a contact charging method having an AC component, or a mechanical cleaning means. The effect is remarkable.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram illustrating an example of an electrophotographic image forming apparatus to which an electrophotographic photosensitive member of the present invention is applied.

[Explanation of symbols]

 10: Photoreceptor 12: Charging roll (charging means) 14: Laser exposure optical system 16: Developing device 18: Transfer roll 19: Static eliminator 20: Cleaning blade (Cleaning means)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03G 5/06 372 G03G 5/06 372 5/147 502 5/147 502 503 503 15/02 101 15/02 101 (56) Reference Document JP-A-9-190004 (JP, A) JP-A-3-191358 (JP, A) JP-A-10-301318 (JP, A) JP-A-10-301305 (JP, A) JP-A 10-301 301302 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03G 5/00 101

Claims (16)

(57) [Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is formed of at least a compound represented by the following general formula (Ia), silicon-containing fine particles, and a crosslinkable compound. An electrophotographic photoreceptor comprising a crosslinked and cured film. GDF general formula (Ia) (wherein G represents a Si-containing vitreous network subunit, D represents -C _x H _2x- (x is an integer of 1 to 15),
_{-C x 'H 2x'-2 -} (x' is from 2 to 15 integer), - C _x "H
_{2x "-4-} (x" is an integer of 2 to 15), substituted or unsubstituted
Replacement divalent aryl group, -CH = N-, -O-, -CO
At least one selected from the group consisting of O-
And -C _x H _2x- (x is an integer of 1 to 15) is substituted.
Or one kind of unsubstituted divalent aryl group, and -C
_x H _2x - _(x is an integer from 1 to 15) and a substituted or unsubstituted
Excluding the case of combination with a divalent aryl group).
And does not include hydrogen atoms directly bonded to heteroatoms.
Represents a divalent group, and F represents a photoelectric characteristic subunit. ) 2. An electrophotographic photosensitive member having a photosensitive layer in which at least a charge generating layer and a charge transporting layer are laminated on a conductive support, wherein the charge transporting layer is the outermost surface or the charge generating layer is the outermost surface. Has at least the following general formula (I
An electrophotographic photoreceptor comprising a compound represented by a), silicon-containing fine particles, and a crosslinked cured film formed from a crosslinkable compound. GDF general formula (Ia) (wherein G represents a Si-containing vitreous network subunit, D represents -C _x H _2x- (x is an integer of 1 to 15),
_{-C x 'H 2x'-2 -} (x' is from 2 to 15 integer), - C _x "H
_{2x "-4-} (x" is an integer of 2 to 15), substituted or unsubstituted
Replacement divalent aryl group, -CH = N-, -O-, -CO
At least one selected from the group consisting of O-
And -C _x H _2x- (x is an integer of 1 to 15) is substituted.
Or one kind of unsubstituted divalent aryl group, and -C
_x H _2x - _(x is an integer from 1 to 15) and a substituted or unsubstituted
Excluding the case of combination with a divalent aryl group).
And does not include hydrogen atoms directly bonded to heteroatoms.
Represents a divalent group, and F represents a photoelectric characteristic subunit. ) 3. An electrophotographic photosensitive member in which at least a photosensitive layer and a surface protective layer are sequentially laminated on a conductive support, wherein at least the surface protective layer, which is the outermost surface, is a compound represented by the following general formula (Ia): An electrophotographic photoreceptor comprising: a crosslinked cured film formed from a silicon-containing fine particle and a crosslinkable compound. GDF general formula (Ia) (wherein G represents a Si-containing vitreous network subunit, D represents -C _x H _2x- (x is an integer of 1 to 15),
_{-C x 'H 2x'-2 -} (x' is from 2 to 15 integer), - C _x "H
_{2x "-4-} (x" is an integer of 2 to 15), substituted or unsubstituted
Replacement divalent aryl group, -CH = N-, -O-, -CO
At least one selected from the group consisting of O-
And -C _x H _2x- (x is an integer of 1 to 15) is substituted.
Or one kind of unsubstituted divalent aryl group, and -C
_x H _2x - _(x is an integer from 1 to 15) and a substituted or unsubstituted
Excluding the case of combination with a divalent aryl group).
And does not include hydrogen atoms directly bonded to heteroatoms.
Represents a divalent group, and F represents a photoelectric characteristic subunit. ) 4. The electrophotographic photosensitive member according to claim 1, wherein the silicon-containing fine particles are colloidal silica and / or silicone fine particles. 5. A compound represented by the general formula (Ia) is an electrophotographic photosensitive according to any one of claims 1-4, characterized in that a compound represented by the following general formula (IIIa) body. General formula (IIIa) (Wherein, Ar ¹ to Ar ⁴ each independently represent a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or arylene group, and Ar ¹
1 to 4 of Ar ⁵ to Ar ⁵ represent G in the general formula (Ia).
It has a substituent represented by -D-, and k represents 0 or 1. 6. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer comprises at least a compound represented by the following general formula (Ib) and a compound represented by the following general formula (IV)
An electrophotographic photoreceptor comprising a crosslinked cured film formed from a crosslinkable compound having two or more substituents represented by the following formula: GDF general formula (Ib) (where D is -C _x H _2x- (x is an integer of 1 to 15),-
_{C x 'H 2x'-2 -} (x' is from 2 to 15 integer), - C _x "H
_{2x "-4-} (x" is an integer of 2 to 15), substituted or unsubstituted
Replacement divalent aryl group, -CH = N-, -O-, -CO
At least one selected from the group consisting of O-
And -C _x H _2x- (x is an integer of 1 to 15) is substituted.
Or one kind of unsubstituted divalent aryl group, and -C
_x H _2x - _(x is an integer from 1 to 15) and a substituted or unsubstituted
Excluding the case of combination with a divalent aryl group).
And does not include hydrogen atoms directly bonded to heteroatoms.
There, represents a divalent group, F is a photoelectric characteristics subunit Table
And G represents —Si (R ¹ ) _(3-a) (OR ² ) _a ;
¹ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, R ² represents a hydrogen, an alkyl group, or a trialkylsilyl group, and a represents an integer of 1 to 3. ) —Si (R ³ ) _(3-b) (OR ⁴ ) _b general formula (IV) (wherein R ³ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, and R ⁴ represents hydrogen, alkyl Represents a group or a trialkylsilyl group, and b represents an integer of 1 to 3.) 7. An electrophotographic photosensitive member having a photosensitive layer in which at least a charge generating layer and a charge transporting layer are laminated on a conductive support, wherein the charge transporting layer is the outermost surface, or the charge generating layer is the outermost surface. Has at least the following general formula (I
An electrophotographic photosensitive member comprising: a compound represented by b); and a crosslinked cured film formed from a crosslinkable compound having two or more substituents represented by the following general formula (IV). GDF general formula (Ib) (where D is -C _x H _2x- (x is an integer of 1 to 15),-
_{C x 'H 2x'-2 -} (x' is from 2 to 15 integer), - C _x "H
_{2x "-4-} (x" is an integer of 2 to 15), substituted or unsubstituted
Replacement divalent aryl group, -CH = N-, -O-, -CO
At least one selected from the group consisting of O-
And -C _x H _2x- (x is an integer of 1 to 15) is substituted.
Or one kind of unsubstituted divalent aryl group, and -C
_x H _2x - _(x is an integer from 1 to 15) and a substituted or unsubstituted
Excluding the case of combination with a divalent aryl group).
And does not include hydrogen atoms directly bonded to heteroatoms.
There, represents a divalent group, F is a photoelectric characteristics subunit Table
And G represents —Si (R ¹ ) _(3-a) (OR ² ) _a ;
¹ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, R ² represents a hydrogen, an alkyl group, or a trialkylsilyl group, and a represents an integer of 1 to 3. ) —Si (R ³ ) _(3-b) (OR ⁴ ) _b general formula (IV) (wherein R ³ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, and R ⁴ represents hydrogen, alkyl Represents a group or a trialkylsilyl group, and b represents an integer of 1 to 3.) 8. An electrophotographic photoreceptor in which at least a photosensitive layer and a surface protective layer are sequentially laminated on a conductive support, wherein the outermost surface protective layer is at least a compound represented by the following general formula (Ib): And the following general formula (IV)
An electrophotographic photoreceptor comprising a crosslinked cured film formed from a crosslinkable compound having two or more substituents represented by the following formula: GDF general formula (Ib) (where D is -C _x H _2x- (x is an integer of 1 to 15),-
_{C x 'H 2x'-2 -} (x' is from 2 to 15 integer), - C _x "H
_{2x "-4-} (x" is an integer of 2 to 15), substituted or unsubstituted
Replacement divalent aryl group, -CH = N-, -O-, -CO
At least one selected from the group consisting of O-
And -C _x H _2x- (x is an integer of 1 to 15) is substituted.
Or one kind of unsubstituted divalent aryl group, and -C
_x H _2x - _(x is an integer from 1 to 15) and a substituted or unsubstituted
Excluding the case of combination with a divalent aryl group).
And does not include hydrogen atoms directly bonded to heteroatoms.
There, represents a divalent group, F is a photoelectric characteristics subunit Table
And G represents —Si (R ¹ ) _(3-a) (OR ² ) _a ;
¹ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, R ² represents a hydrogen, an alkyl group, or a trialkylsilyl group, and a represents an integer of 1 to 3. ) —Si (R ³ ) _(3-b) (OR ⁴ ) _b general formula (IV) (wherein R ³ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, and R ⁴ represents hydrogen, alkyl Represents a group or a trialkylsilyl group, and b represents an integer of 1 to 3.) 9. The electrophotographic photoreceptor according to claim 6 , wherein the crosslinkable compound is a compound represented by the following general formula (V). General formula (V) (Wherein A represents a substituent represented by the general formula (IV),
Is composed of at least one of a divalent or higher valent hydrocarbon group which may contain a branch, a divalent or higher valent aryl group, -NH-, or a combination thereof, and n represents an integer of 2 or more. ) 10. The electrophotographic photosensitive member according to claim 9 , wherein the compound represented by the general formula (V) is a compound represented by any of the following general formulas. Embedded image (Wherein T ₁ and T ₂ each represent a divalent or trivalent hydrocarbon group which may be branched, A represents a substituent represented by the general formula (IV), and h, i, and j represent An integer from 1 to 3,
In addition, the number of A in the molecule is selected to be 2 or more. ) 11. A compound represented by the general formula (Ib):
The electrophotographic photosensitive member according to any one of claims 6 to 10 , which is a compound represented by the following general formula (IIIb). General formula (IIIb) (Wherein, Ar ¹ to Ar ⁴ each independently represent a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or arylene group, and Ar ¹
1 to 4 of Ar ⁵ to Ar ⁵ represent G in the general formula (Ib)
It has a substituent represented by -D-, and k represents 0 or 1. 12. A cross-linked cured film, a fluorine-containing compound and / or electrophotographic photosensitive member according to any one of claims 1 to 11, characterized by containing an antioxidant. 13. A photosensitive layer comprising at least one charge generation material selected from the group consisting of gallium phthalocyanine halide, hydroxygallium phthalocyanine, oxytitanium phthalocyanine, and tin phthalocyanine halide. Item 13. The electrophotographic photosensitive member according to any one of Items 1 to 12 . 14. A benzidine compound represented by the following general formula (VI) and / or a general formula (VI)
The electrophotographic photoreceptor according to any one of claims 1 to 13 , further comprising a triphenylamine compound represented by the formula (I). General formula (VI) (Wherein, R ⁶ and R ⁶ ′ may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ⁷ ,
R ⁷ ′, R ⁸ and R ⁸ ′ may be the same or different and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, 2
Represents an amino group substituted with an alkyl group of m and n
Represents an integer of 0 to 2. ) General formula (VII) (Wherein, R ⁹ represents a hydrogen atom or a methyl group, and n represents 1 or 2. Ar ⁶ , Ar ⁷ represents a substituted or unsubstituted aryl group, and the substituent includes a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms,
Represents an amino group substituted with an alkyl group having 1 to 2 carbon atoms. ) 15. At least the electrophotographic photosensitive member, charging means, and an electrophotographic image forming apparatus having a mechanical cleaning means, wherein the electrophotographic photoreceptor claim 1-1
4. The electrophotographic photoreceptor according to any one of 4 ), and
An electrophotographic image forming apparatus, wherein the charging means is a contact charging type charging means. 16. The electrophotographic image forming apparatus according to claim 15 , wherein the charging means is means for applying an applied voltage obtained by superimposing an AC voltage on a DC voltage to the electrophotographic photosensitive member.