JP3314702B2 - Electrophotographic photoreceptor and 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, a method of manufacturing the same, and an electrophotographic image forming apparatus using the same.

[0002]

2. Description of the Related Art Conventionally, an electrophotographic apparatus such as a plain paper copier (PPC), a laser printer, an LED printer,
Liquid crystal printers, etc. charge the photoconductor such as a rotating drum type,
An image is formed by applying an image forming process of exposure and development, and is transferred and fixed on a transfer material to obtain a copy. As the photoreceptor used for these, inorganic photoreceptors such as selenium, arsenic-selenium, cadmium sulfide, zinc oxide, and a-Si are used. Research and development of OPCs have also been active. Among them, a so-called function-separated type photoreceptor in which a charge generation layer and a charge transport layer are laminated has been used in terms of electrophotographic characteristics such as sensitivity, chargeability and repetition stability. And various proposals have been made and put to practical use.

However, the durability required for electrophotographic photoreceptors has become severer year by year, and the wear and damage of the surface layer due to repeated use, especially the wear and tear of the surface layer which is remarkably increased by use under contact electrification. With respect to problems such as scratches and oxidative deterioration of the surface layer due to oxidizing gas such as ozone generated from a corona charger, studies on techniques necessary for improving durability are being continued.

[0004] Recently, copiers and printers using the contact charging system have been increasing for reasons such as reduction of generation of oxidizing gas and reduction of power supply cost. However, when an applied voltage having an AC component is used to stabilize the charging potential of the photoconductor, there has been a problem that abrasion of the photoconductor surface is increased. It is considered that the cause of this is that the binding of the binder resin on the surface of the photoreceptor is cut by the discharge generated between the surface of the photoreceptor and the contact charger, thereby reducing the molecular weight. It has been found that when the molecular weight of the binder resin on the photoreceptor surface is reduced, abrasion is significantly increased when mechanical cleaning such as a cleaning blade is performed.

As a method of reducing the wear of the photoreceptor, there is a method of applying a surface protective layer having high mechanical strength to the surface of the photoreceptor. A cross-linkable curable resin is excellent in terms of mechanical strength. However, if the cross-linkable resin alone is used, the surface protective layer becomes an insulating layer, and the photoelectric characteristics of the photoconductor are sacrificed. 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, a method has been reported in which a conductive metal oxide fine powder is dispersed in a surface protective layer as a resistance control material (Japanese Patent Laid-Open No. 57-12834).
No. 4). The decrease in the photoelectric characteristics of the photoreceptor by this method is small, and the above-mentioned problems are remarkably improved. But,
Generally, there is a problem that the resistance value of the metal oxide used as the conductive fine powder largely depends on the humidity of the environment. Therefore, there has been an essential problem that the surface resistance of the photoreceptor is reduced particularly under high temperature and high humidity, and the image quality is largely reduced due to blurring of the electrostatic latent image.

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 Laid-Open No. Hei 4 (1999)). -15659). In this method, the surface resistance of the photoreceptor did not depend on humidity, and there was no problem in image quality. However, the addition of a low-molecular-weight component such as a charge transporting substance inhibits the curing reaction and lowers the mechanical strength of the surface protective layer. Therefore, even when a cross-linking curable resin having high mechanical strength is used alone, the mechanical strength of the surface protective layer is greatly reduced by adding a low-molecular component such as a charge transport material essential for improving photoelectric properties. There was a problem.

From this point of view, 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,
JP-A-5-323630). According to this method,
Sufficient mechanical strength can be initially obtained without deteriorating the photoelectric characteristics of the photoconductor. However, these surface layer configurations have a problem that when used under contact charging for a long period of time, the mechanical strength sharply decreases. It is thought that this is due to strong external stress such as breaking of the bond of the thermoplastic binder resin due to the application of AC voltage in contact charging.If mechanical cleaning such as a cleaning blade is used, abrasion may occur. Greatly increases.

In addition to the problem of abrasion of the photoreceptor, resistance to oxidizing gas is required. That is, when the contact charging method is used, ozone and NO
_Although the amount of _x is much smaller, these oxidizing gases are generated whenever an applied voltage having an AC component is used. If an attempt is made to extend the life by improving the mechanical strength of the photoreceptor surface, the generated oxidizing gas will affect the photoreceptor for a long time, so that a higher resistance to the oxidizing gas than before is required.

Further, in addition to these problems, if the mechanical strength of the surface protective layer alone is merely increased, paper powder and toner tend to adhere to the surface of the photoreceptor, thereby deteriorating the image quality. There is also the problem of getting lost.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-quality, non-environment-dependent, high photoelectric characteristic, mechanical strength, resistance to oxidizing gases, and high resistance to deposits such as paper dust. To provide an electrophotographic photoreceptor having excellent printing durability and an image forming apparatus using the same.

[0012]

Means for Solving the Problems The present inventors can solve the above problems by including a compound represented by the following general formula (I), a fluorine atom-containing compound and an antioxidant in a photosensitive layer. Was found. In particular, when this photoreceptor is used in an electrophotographic image forming apparatus having a contact charging system and a mechanical cleaning means, the printing durability can be significantly improved.

[0013]

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[0014] (wherein, G represents an inorganic glassy network subgroup, D is -C _x H _2x - _(x is from 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), there substituted
Or unsubstituted divalent aryl group, -CH = N-, -O
-, At least one selected from the group consisting of -COO-
(Provided that -C _x H _2x- (x is an integer of 1 to 15)
One kind of a substituted or unsubstituted divalent aryl group,
And -C _x H _2x- (x is an integer of 1 to 15)
Or a combination with an unsubstituted divalent aryl group
Excluding) and directly bonded to a heteroatom
Represents a divalent group that does not contain a child, and F is a photoelectric property subunit.)

The compound represented by the general formula (I) is preferably a compound represented by the following general formula (II).

[0016]

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In the general formula (II), 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 ^{1 to} 4 of Ar ^{1 to} Ar ⁵ have a substituent represented by G—D—, and k is 0 or 1
Represents

In a preferred embodiment, the compound of the general formula (I) forms a crosslinked structure in the photosensitive layer, and the fluorine-containing compound is a compound of the general formula (I) The compound can be bonded via the inorganic glassy network subgroup represented by G, and the compound represented by the general formula (I) and the fluorine-containing compound form a crosslinked structure in the photosensitive layer. preferable.

Further, the layer containing the compound represented by the general formula (I), the fluorine-containing compound and the antioxidant is preferably a layer on the outermost surface of the photosensitive layer,
It is preferable that the antioxidant is also contained in a layer not containing the compound represented by the general formula (I).

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic photoreceptor of the present invention will be described in detail below. The electrophotographic photoreceptor of the present invention has at least a photosensitive layer on a conductive support and, if necessary, other layers such as an undercoat layer and a protective layer.

(Conductive Support) The conductive support that can be used in the present invention is not particularly limited as long as it is generally used as a conductive support of an electrophotographic photosensitive member. , Chromium, metals such as stainless steel, aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, plastic film provided with a thin film such as ITO, and applying or impregnating a conductivity imparting agent Paper and plastic film.

The conductive support may be subjected to various treatments and the like as necessary within a range that does not affect the image quality.
Examples of such treatment include anodic oxide coating treatment on the surface of the conductive support, thermal hydroxylation treatment, chemical treatment, coloring treatment, irregular reflection treatment such as graining, and the like.
The shape of the conductive support is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a drum shape, a sheet shape, and a plate shape.

(Undercoat layer) A photosensitive layer is provided on one surface of the conductive support. In the present invention, an undercoat layer is preferably provided between the conductive support and the photosensitive layer. Can be provided. When the undercoat layer is provided on the electrophotographic photoreceptor, the undercoat layer, at the time of charging the photosensitive layer, while preventing the injection of charge from the conductive support to the photosensitive layer, A function as an adhesive layer for adhering and holding the photosensitive layer integrally with the conductive support, or, in some cases, a function of preventing the conductive support from reflecting light. Is advantageous.

The undercoat layer can be formed of a material generally used for an undercoat layer of an electrophotographic photoreceptor. For example, the undercoat layer contains at least a binder resin, and further includes fine particles and the like, if necessary. Comprising. The binder resin is not particularly limited and may be appropriately selected depending on the intended purpose.For example, a polyamide resin, a vinyl chloride resin,
Vinyl acetate resin, phenol resin, polyurethane resin,
Melamine resin, benzoguanamine resin, polyimide resin, polyethylene resin, polypropylene resin, polycarbonate resin, acrylic resin, methacrylic resin, vinylidene chloride resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, Nitrocellulose, casein,
Gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compound, titanyl chelate compound, titanyl alkoxide compound, organic titanyl compound, silane coupling agent, and the like. These may be used alone or in combination of two or more. Examples of the fine particles include titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, barium titanate, and silicone resin. These may be used alone or in combination of two or more.

The coating method for forming the undercoat layer is not particularly limited, and examples thereof include a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, and an air knife coating method. And a normal coating method such as a curtain coating method. The thickness of the undercoat layer is usually 0.01 to 10 μm, and 0.05 to 2 μm.
μm is preferred.

(Photosensitive Layer) The electrophotographic photoreceptor of the present invention comprises a photosensitive layer provided on a conductive support, wherein the photosensitive layer comprises a compound represented by the following general formula (I) or a fluorine atom-containing compound. And an antioxidant. The photosensitive layer may be of a single-layer type or may be of a laminated type in which the functions are separated into a charge generation layer and a charge transport layer.

[0027]

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In the general formula (I), G represents an inorganic glassy network subgroup. The inorganic glassy network subgroup has a bond of a metal oxide, and is capable of forming an inorganic glassy network by repeating bonding with another inorganic glassy network subgroup by a terminal reactive group. . Specifically, it can be obtained from any inorganic substance that can undergo hydrolysis and condensation, such as alkoxides, acids, and chlorides, but is preferably Si, Al, Ti, Cu, Fe, As, Se, Te.
Such a compound can be introduced by using a compound having an alkoxide or aryloxide group having about 1 to 20 carbon atoms at an atom. The compound capable of binding via the inorganic vitreous network subgroup represented by G in the compound represented by the general formula (I) may be the same as or different from another binding compound. It may be selected from the compounds represented by (I),
Other compounds that can bind to the inorganic glassy network subgroup represented by G in the compound represented by the general formula (I) may be used. As other compounds that can be bonded here, known organic metal compounds can be used, and organic zirconium compounds such as zirconium chelate compounds, zirconium alkoxide compounds, and zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, and titanates Organic titanium compounds such as coupling agents, aluminum chelate compounds, organic aluminum compounds such as aluminum coupling agents, aluminum silicon alkoxides, aluminum titanium alkoxides, and the like. Further, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane,
Silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like can also be preferably used, and these are used to obtain desired characteristics of the photosensitive layer. It can be selected as appropriate.

Since the compounds represented by the general formula (I) form at least a part of the crosslinked structure in the photosensitive layer via the inorganic glassy network subgroup represented by G, Has increased binding energy, and resistance to strong stress such as electric discharge and mechanical contact increases. Furthermore, even if a part of the bond is broken by these stresses, the molecular weight is not immediately reduced due to the formation of the crosslinked structure, and thus the mechanical strength is not immediately lost.

In the general formula (I), D represents a flexible organic subunit. The flexible organic subunit is a connecting portion for bonding the inorganic vitreous network subgroup represented by G and the photoelectric characteristic subunit represented by F, which form a crosslinked structure, and specifically, , -C _x H _2x
- (x is 1 to 15 _{integer), - C x 'H 2} x' -2 - (x ' is from 2 to 15 _{integer), - C x "H 2x} " -4 - (x " is 2 to 15
Integer) of - COO -, - S -, - O -, - CH 2 -C
_{6 H 4 -, - CH =} N -, - (C 6 H 4) - (C
₆ H ₄ ) —, or a combination thereof, or a compound having a substituent introduced therein (provided that —C _x H _2x — (x is an integer of 1 to 15).
Number) is a substituted or unsubstituted divalent aryl group.
One type, and -C _x H _2x- (x is an integer of 1 to 15)
Combination with a substituted or unsubstituted divalent aryl group
Except in cases) .

In the general formula (I), F represents a photoelectric characteristic subunit. The photoelectric characteristic subunit is a unit having photocarrier transport characteristics as described above, and a structure conventionally known as a charge transport material can be used as it is. Specifically, triarylamine compounds,
Skeletal structures of compounds having a hole transporting property such as benzene compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, and quinone compounds, fluorenone compounds, and xanthones A skeleton of a compound having an electron transporting property such as a compound, a benzophenone-based compound, a cyanovinyl-based compound, an ethylene-based compound, or the like can be used. In the photoreceptor of the present invention, the compound represented by the general formula (I) has a photoelectric characteristic subunit represented by F, and this is preferably an inorganic glassy network subgroup represented by G , It is directly bonded to at least a part of the crosslinked structure, so that the photoelectric structure can be imparted without losing the mechanical strength characteristics of the crosslinked structure. That is, the layer containing the compound represented by the general formula (I) can be used not only as a surface protective layer on the surface of a photoreceptor due to its mechanical properties, but also as a charge transport layer of a laminated photoreceptor. Can be.

In the present invention, in addition to the properties of the compound represented by the general formula (I), the addition of an antioxidant can improve the oxidation resistance by the antioxidant effect of the antioxidant. . Also, by adding a fluorine-containing compound,
Due to the lubricity and low adhesion of the fluorine-containing compound, the adhesion resistance of the photoreceptor can be improved.

In the present invention, the “sub” of the inorganic vitreous network subgroup, the flexible organic subunit and the photoelectric characteristic subunit includes the group or unit constituting the compound represented by the general formula (I). It is used in the meaning.

In the present invention, the compound represented by the general formula (I) used in the photosensitive layer is preferably a compound represented by the following general formula (II).

[0035]

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In the general formula (II), Ar ^{1 to} Ar ⁵ each independently represent a substituted or unsubstituted aryl group;
Ar ⁵ represents a substituted or unsubstituted aryl group or an arylene group, and 1 to 4 of Ar ^{1 to} Ar ⁵
Has a substituent represented by G-D-, and k is
Represents 0 or 1.

In the general formula (II), Ar ^{1 to} Ar
⁴ independently represents a substituted or unsubstituted aryl group, and specific examples include the groups shown in the following structural group 1.

[0038]

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In the structural formula of the structural group 1, R ³ represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, Or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, R ⁴ represents hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or halogen; Represents 0 or 1, and t represents an integer of 1 to 3. Z ′ is selected from groups represented by the following structural group 2.

[0040]

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In the structural formula of the structural group 1, X is a substituent represented by GD-, and is preferably a substituent represented by the following general formula (III).

[0042]

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In the general formula (III), R ¹ represents a hydrogen, an alkyl group, a substituted or unsubstituted aryl group, R ² represents a hydrogen, an alkyl group, a trialkylsilyl group, and a is an integer of 1 to 3. And Y represents a divalent group not containing a hydrogen atom directly bonded to a hetero atom. Specific examples of Y include groups represented by the following structural group 3 (provided that -C
_x H _2x- (x is an integer of 1 to 15) is one kind, substituted or
Divalent aryl group unsubstituted is one, and -C _x H _2x -
(X is an integer of 1 to 15) and substituted or unsubstituted divalent
Except in combination with an aryl group).

[0044]

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In the structural formula of Structural Group 3, x represents an integer of 1 to 10, x 'and x "each represent an integer of 2 to 15, and y and z each represent an integer of 1 to 5.
A group represented by the following structural formula 4 is preferred.

[0046]

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In the general formula (II), Ar ⁵ represents a substituted or unsubstituted aryl group or an arylene group;
Specifically, when = 0, a group represented by the following structural formula 5 is exemplified.

[0048]

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In the general formula (II), specific examples of Ar ⁵ when k = 1 include the groups shown in the following structural group 6.

[0050]

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In the structural formulas of the structural groups 5 and 6, Ar is selected from the groups represented by the following structural formula 7.

[0052]

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Z is selected from the groups shown in the following structural group 8.

[0054]

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In the structural formula of the structural group 8, R ⁵ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
Selected from halogen. Also, q and r are each 1
An integer of 10 to 10, t 'represents an integer of 1 or 2, and W is selected from the groups shown in the following structural group 9.

[0056]

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In the structural formula of the structural group 9, s ′ represents an integer of 0 to 3.

In the following Tables 1 to 25, exemplified compounds of the general formula (I), "Compounds 1 to 256", are listed by showing specific functional groups in the general formula (I). Is not limited to these. In addition,
Compound examples 59-68, 79-83, 89-98, 143
~ 152, 194 ~ 203, 224 ~ 229 are reference
It is a compound example. )

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

[Table 4]

[0063]

[Table 5]

[0064]

[Table 6]

[0065]

[Table 7]

[0066]

[Table 8]

[0067]

[Table 9]

[0068]

[Table 10]

[0069]

[Table 11]

[0070]

[Table 12]

[0071]

[Table 13]

[0072]

[Table 14]

[0073]

[Table 15]

[0074]

[Table 16]

[0075]

[Table 17]

[0076]

[Table 18]

[0077]

[Table 19]

[0078]

[Table 20]

[0079]

[Table 21]

[0080]

[Table 22]

[0081]

[Table 23]

[0082]

[Table 24]

[0083]

[Table 25]

The general formula (I) used in the photosensitive layer of the present invention
The content of the represented compound can be used in the range of 1 to 100% by weight, preferably 10 to 90% by weight, more preferably 40 to 60% by weight.

In the present invention, the fluorine-containing compound used in the photosensitive layer has an effect of preventing toner and paper powder from adhering to the surface of the photoreceptor, and includes trifluoroethylene, tetrafluoroethylene, vinyl fluoride, and the like.
A fluorine-containing resin such as bunylidene fluoride or fine particles thereof can be used.

Among the fluorine-containing compounds used in the photosensitive layer of the present invention, particularly preferred are the inorganic vitreous compounds represented by G in the compound represented by the general formula (I) having an alkoxysilane group, a silanol group or the like. A compound capable of undergoing a cross-linking reaction via the network subgroup, or by using these, the fluorine-containing compound and the compound represented by the general formula (I) form at least a part of a cross-linked structure in the photosensitive layer. It is suitable because the decrease in mechanical strength due to the inclusion of a fluorine-containing compound is reduced. Examples of the fluorine-containing compound having an alkoxysilane group or a silanol group include (tridecafluoro-1,1,2,2-
(Tetrahydrooctyl) triethoxysilane, (3,
3,3-trifluoropropyl) trimethoxysilane,
3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H
-Perfluorodecyltriethoxysilane, 1H, 1
H, 2H, 2H-perfluorooctyltriethoxysilane, and the like.

The addition amount of the fluorine-containing compound used in the photosensitive layer of the present invention is desirably 15% by weight or less in the layer to which the fluorine-containing compound is added. However, the compound is crosslinkable with the compound represented by the general formula (I). In some cases, it is possible to add about 40% by weight.

In the present invention, the antioxidant used in the photosensitive layer is added for the purpose of preventing deterioration by an oxidizing gas such as ozone generated in the charger. If the mechanical strength of the photoreceptor surface is increased, the photoreceptor comes into contact with the oxidizing gas for a long time, so that a higher resistance than before is required.
Accordingly, in the electrophotographic photoreceptor of the present invention, in addition to using an oxidation-resistant structure for the photoelectric characteristic subunit represented by F in the compound represented by the general formula (I), an antioxidant Has high oxidation resistance. As the antioxidant, hindered phenol or hindered amine is preferable,
Known antioxidants such as organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, and benzimidazole antioxidants may be used. Hindered phenolic antioxidants include 2,6-di-t-butyl-4.
-Methylphenol, 2,5-di-t-butylhydroquinone, N, N'-hexamethylenebis (3,5-di-t
-Butyl-4-hydroxyhydrocinnamide, 3,5
-Di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 2,4-bis [(octylthio) methyl] -o-cresol, 2,6-di-t-
Butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,
2′-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-butylidenebis (3-methyl-6
-T-butylphenol), 2,5-di-t-amylhydroquinone, 2-t-butyl-6- (3-butyl-2-
(Hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 4,4′-butylidenebis (3-methyl-6-t-butylphenol), and the like.

In the most preferred embodiment, the antioxidant used in the photosensitive layer in the present invention is simultaneously contained in the surface protective layer containing the compound represented by formula (I) and the fluorine-containing compound. However, ozone and NO _x gas generated by the charging member is not only only the surface of the photoreceptor,
Although the amount is small, it penetrates into the lower photosensitive layer such as the charge generation layer and the charge transport layer, and causes oxidation deterioration. Therefore, in order to improve the oxidation resistance of the entire photoreceptor, it is preferable to add an antioxidant to a layer not containing the compound represented by the general formula (I).

The amount of the antioxidant used in the photosensitive layer of the present invention is preferably 15% by weight or less, more preferably 10% by weight or less, in any layer. If it exceeds 15% by weight, the mechanical strength decreases,
The adverse effects such as a decrease in the photoelectric characteristics occur.

When forming a crosslinked film containing a compound represented by the general formula (I), a fluorine-containing compound and an antioxidant, the compound represented by the general formula (I) is capable of undergoing a crosslinking reaction by itself, A film can be formed. But,
In order to improve the film properties such as surface properties and strength, other curable compounds that can be bonded via the inorganic glassy network subgroup represented by G in the compound represented by the general formula (I) are simultaneously used. It is desirable to use.

When a compound represented by the general formula (II) is selected as a specific example of the compound represented by the general formula (I), the curable compound used for forming a film may be a silicon hard coat. For example, a known curable siloxane resin can be used. Specifically, an organic siloxane resin having a plurality of silanol groups, an alkoxysilane, a silane coupling agent, a mixture thereof, or the like can be used.

In the present invention, in order to obtain desired characteristics in the photosensitive layer, if necessary, in addition to the above-mentioned essential components,
A known additive, for example, a leveling agent such as silicone oil may be contained in the photosensitive layer.

In the present invention, the compound represented by the general formula (I), the fluorine-containing compound and the antioxidant used in the photosensitive layer can be used to prevent deterioration of the surface of the photoreceptor due to scratches and abrasion, and to prevent toner or paper It is preferably contained in the layer on the outermost surface of the photosensitive layer from the viewpoint of preventing powder from adhering and preventing deterioration due to oxidizing gas such as ozone generated in the charging process of the photoreceptor surface. For example, in the case of a structure having a surface protective layer on the outermost surface of the photosensitive layer, it is preferable to include these compounds in the surface protective layer, and a conventionally known photosensitive layer can be used as the underlying photosensitive layer. . The layer structure of the photoreceptor having the photosensitive layer is arbitrary, and may be a stacked type in which a charge generation layer and a charge transport layer are stacked, or a single layer type containing a charge generation material. In the case where the photosensitive layer is of a laminated type, the charge transport layer is represented by the general formula (I) when the charge transport layer is the outermost surface layer, and when the charge generation layer is the outermost layer, the charge generation layer. Compound
It is preferable to include a fluorine-containing compound and an antioxidant. Furthermore, when the photosensitive layer is of a single layer type, a compound represented by the general formula (I), together with a charge generation material and the like,
It can be used by incorporating a fluorine-containing compound and an antioxidant.

In the present invention, when a surface protective layer is provided on the photosensitive layer, the compound represented by the general formula (I), the fluorine-containing compound and the antioxidant are preferably contained in the surface protective layer as described above. However, in order to form a surface protective layer, a curable siloxane resin which is a curable compound as described above, if necessary, together with a compound represented by the general formula (I), a fluorine-containing compound and an antioxidant. For example, it is preferable from the viewpoint of surface strength to prepare a coating liquid in which a solvent or the like is mixed as necessary, apply the coating liquid on the photosensitive layer, and then heat and crosslink and cure.

In the present invention, the solvent used for forming the surface protective layer is added for the purpose of adjusting the viscosity of the liquid and the like.
n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone,
Methyl ethyl ketone, cyclohexanone, methyl acetate,
Examples thereof include ordinary organic solvents such as n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, and chloroform, which can be used alone or in combination of two or more.

In the formation of the surface protective layer of the present invention, the cross-linking curing reaction may be carried out without a catalyst, or an appropriate catalyst may be used. As a catalyst, hydrochloric acid, sulfuric acid,
Acid catalysts such as formic acid, acetic acid, and trifluoroacetic acid; bases such as ammonia and triethylamine; organic tin compounds such as dibutyltin diacetate, dibutyltin dioctoate and stannous octoate; tetra-n-butyl titanate and tetraisopropyl titanate And the like, organic iron compounds of organic carboxylic acids, manganese salts, cobalt salts, zinc salts, zirconium salts and the like. Further, the temperature at the time of the curing reaction is not particularly limited, but is preferably set to a temperature from room temperature to 150 ° C.

In the present invention, the coating method of the surface protective layer containing the compound represented by the general formula (I), the fluorine-containing compound and the antioxidant includes a blade coating method, a Meyer bar coating method, a spray coating method, and the like. Conventional methods such as a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method can be used. The thickness of the surface protective layer is preferably about 1 to 10 μm.

In the present invention, when a layered photosensitive layer is employed, the charge generation layer constituting the layer contains a charge generation material and a binder resin.
Known additives such as a leveling agent (surface smoothing) and a coupling agent (adhesion improvement) may be added.

Examples of the charge generation material used in the charge generation layer of the present invention include amorphous selenium, crystalline selenium-tellurium alloy, selenium-arsenic alloy, selenium compounds and alloys such as selenium alloys, zinc oxide and titanium oxide Organic pigments and dyes such as a photoconductive material, a phthalocyanine-based, a squarylium-based, an anthrone-based, perylene-based, azo-based, anthraquinone-based, pyrene-based, pyrylium salt, and thiapyrylium salt are used. Among them, phthalocyanine compounds are particularly suitable because of their high photosensitivity, and metal-free phthalocyanines, oxytitanium phthalocyanines, gallium phthalocyanines, hydroxygallium phthalocyanines, and tin phthalocyanines are preferred.
In particular, the Bragg angle (2θ) in the X-ray diffraction spectrum
± 0.2 °) is 7.4 °, 16.6 °, 25.5
°, chlorogallium phthalocyanine having a specific crystal form with a strong diffraction peak at 28.3 °, or Bragg angle in X-ray diffraction spectrum (2θ ± 0.2 °)
Are 7.5 °, 9.9 °, 12.5 °, 16.3 °,
Hydroxygallium phthalocyanine having a specific crystal form having strong diffraction peaks at 18.6 °, 25.1 °, and 28.3 ° has high charge generation efficiency with respect to a wide range of light from visible light to near infrared light. Which is particularly preferred.

Examples of the binder resin used in the charge generation layer of the present invention include polyvinyl butyral resin, polyvinyl formal resin, partially modified polyvinyl acetal resin, polycarbonate resin, polyester resin, acrylic resin,
Examples thereof include, but are not limited to, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, silicone resin, phenol resin, poly-N-vinylcarbazole resin, and the like.
These binder resins can be used alone or in combination of two or more. The compounding ratio (weight ratio) of the charge generating material and the binder resin used in the charge generating layer of the present invention is 10:
A range of 1 to 1:10 is preferred.

Solvents used for coating the charge generation layer of the present invention include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, and acetate. Examples include ordinary organic solvents such as n-butyl, dioxane, tetrahydrofuran, methylene chloride, chloroform and the like, and these can be used alone or as a mixture of two or more. In the present invention, the thickness of the charge generation layer is generally from 0.1 to 5 μm, preferably from 0.2 to 2.0 μm.

In the present invention, the charge generating layer may be coated by a conventional method such as a blade coating method, a Meyer 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 used.

In the present invention, the charge transporting layer in the laminated photosensitive layer contains a charge transporting material and a binder resin, or contains a polymer charge transporting material.

Examples of the charge transport material used in the charge transport layer of the present invention include quinone compounds such as p-benzoquinone, chloranyl, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, and 2,4,7-trinitrofluorenone. Such as fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds,
Examples include electron withdrawing substances such as ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, and the like. These charge transport materials can be used alone or in combination of two or more. In particular, the benzidine-based compound represented by the following general formula (IV) and the triarylamine-based compound represented by the following general formula (V) have high charge (hole) transport ability and excellent stability. Therefore, it can be particularly preferably used. Examples of each compound are shown in the table. These can be used alone or in combination of two or more.

[0106]

Embedded image

In the general formula (IV), R ⁶ and R ^{6 ′} 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. And may be different. R ⁷ , R ^{7 ′} , R ⁸ and R ^{8 ′} are a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. Represents a substituted substituted amino group, which may be the same or different. m and n represent the integer of 0-2.

[0108]

Embedded image

In the general formula (V), R ⁹ represents a hydrogen atom or a methyl group, and n represents 1 or 2. Ar ⁶ and Ar ⁷ represent a substituted or unsubstituted aryl group, and the substituent may be a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, or 1 to 2 carbon atoms. Represents a substituted amino group substituted with an alkyl group.

The following Table 26 shows examples of the benzidine-based compounds represented by the general formula (IV): "IV-1 to IV-5".
"4" is shown by indicating a specific functional group in the general formula (IV), but the present invention is not limited thereto.

[0111]

[Table 26]

Tables 27 to 31 below show examples of the triarylamine-based compound represented by the general formula (V):
To V-62 "by showing specific functional groups in the general formula (V), but the present invention is not limited thereto.

[0113]

[Table 27]

[0114]

[Table 28]

[0115]

[Table 29]

[0116]

[Table 30]

[0117]

[Table 31]

The binder resin used in the charge transport layer of the present invention includes polycarbonate resin, polyester resin,
Methacrylic resin, acrylic resin, polyvinyl chloride resin,
Polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicon Resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-acrylic resin, styrene-alkyd resin, poly-
Known resins such as N-vinylcarbazole and polysilane can be used.

The polymer charge transporting material used in the charge transporting layer of the present invention includes poly-N-vinylcarbazole,
A known material having a charge transporting property such as polysilane can be used. In particular, polyester-based polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have high charge transport properties and are particularly preferable.

Solvents used for coating the charge transport layer of the present invention include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, methylene chloride, chloroform, and the like. Examples thereof include ordinary organic solvents such as halogenated aliphatic hydrocarbons such as ethylene chloride, and cyclic or linear ethers such as tetrahydrofuran, ethyl ether, and dioxane, which may be used alone or in combination of two or more. it can.

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

In the present invention, an antioxidant may be added to the charge generation layer and / or the charge transport layer for the purpose of preventing the charge generation layer from being deteriorated by an oxidizing gas such as ozone generated in the charger. Even if the surface protective layer is provided, the oxidizing gas may penetrate through the surface protective layer and penetrate into the charge generation layer and / or the charge transport layer, thereby preventing oxidative deterioration. . As the antioxidant, the same ones as described above can be used. The addition amount of the antioxidant is preferably 15% by weight or less of the charge generation layer and / or the charge transport layer, and more preferably 10% by weight or less.

In the present invention, the single-layer type photosensitive layer contains a charge generation material and a binder resin, and if necessary, a charge transport material. As a charge generation material,
The same material as the charge generation material used for the charge generation layer can be used. As the binder resin, the same resins as those used for the charge generation layer and the charge transport layer can be used. As the solvent, those similar to the solvents 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 of the present invention is about 10 to 85% by weight, preferably 20 to 5% by weight.
0% by weight.

In the present invention, a charge transporting material may be added to the single-layer type photosensitive layer, if necessary. As the charge transporting material, those similar to the charge transporting material used for the charge transporting layer can be used, but the amount of addition is preferably 5 to 50% by weight. Furthermore, in the single-layer type photosensitive layer,
If necessary, an antioxidant may be added for the same reason as in the case of the charge transport layer. As the antioxidant, those similar to the above-mentioned ones can be used, but the addition amount is preferably 15% by weight or less, more preferably 10% by weight or less.

As the method for coating the single-layer type photosensitive layer of the present invention, the same method as described for the charge generation layer and the charge transport layer can be used. The film thickness is about 5 to 50 μm, and more preferably 10 to 40 μm.

In the present invention, when a surface protective layer is not provided on the photosensitive layer, the compound represented by the general formula (I), the fluorine-containing compound and the antioxidant are present on the outermost surface of the above-mentioned laminated type and single-layer type. Preferably, it is contained in a layer. Specifically, in the case of the stacked type, the compound represented by the general formula (I), the fluorine-containing compound, It is preferable to include an inhibitor. In the case of a single layer type, a compound represented by the general formula (I), a fluorine-containing compound, and an antioxidant can be contained therein together with a charge generation material and the like. A compound represented by the general formula (I),
The method of applying each layer containing the fluorine-containing compound and the antioxidant is the same as the method of applying each layer described above. In any case, crosslinking and curing are preferable, and the crosslinking and curing reaction can be performed in the same manner as in the case of the protective layer.

(Image Forming Apparatus) In the present invention, the image forming apparatus is an electrophotographic image forming apparatus having at least the above-mentioned electrophotographic photosensitive member, its charging means and mechanical cleaning means. The means is a contact charging method. Exposure means such as a laser optical system or an LED array, developing means for forming an image using toner, transfer means for transferring a toner image onto a medium such as paper, fixing means for fixing a toner image on a medium such as paper, a photoconductor If necessary, a known method may also be used to remove static electricity from the electrostatic latent image remaining on the surface. 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, and a known means such as a blade, a brush or a roll can be used. .

FIG. 1 is a schematic diagram showing an example of the image forming apparatus of the present invention. The image forming apparatus of the present invention includes a photoconductor 1
0, a contact charger using a charging roll 12, a laser exposure optical system 14, a developing device 16 using powder toner, a transfer roll 18, a cleaning blade 20, and a fixing roll 22. “A light source 19 for static elimination is disposed between the transfer roller 18 and the cleaning blade 20.

In the image forming apparatus of the present invention, the contact charging system charges the photosensitive member surface by applying a voltage to a conductive member in contact with the photosensitive member surface.
The shape of the conductive member may be any of a brush shape, a blade shape, a pin electrode shape, a roller shape, and the like, but a roller-shaped member is particularly preferable. Usually, the roller-like member is composed of a resistance layer, an elastic layer supporting them and a core material from the outside. Further, a protective layer can be provided outside the resistance layer as needed.

In the conductive member of the present invention, 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 in which conductive particles and the like are dispersed can be used.

In the conductive member of the present invention, the elastic layer is made of a material having conductivity or semi-conductivity.
Generally, conductive particles or semiconductive particles are dispersed in a rubber material. Rubber materials include EPDM, polybutadiene, natural rubber, polyisobutylene, SBR, CR,
NBR, silicone rubber, urethane rubber, epichlorohydrin rubber, SBS, thermoplastic elastomer, norbornene rubber, fluorosilicone rubber, ethylene oxide rubber and the like are used.

In the conductive member of the present invention, as the conductive particles or semiconductive particles, metals such as carbon black, zinc, aluminum, copper, iron, nickel, chromium and titanium, ZnO-Al ₂ O ₃ , SnO ₂ -Sb _{2
O 3, In 2 O 3 -SnO} 2, ZnO-TiO 2, Mg
_{O-Al 2 O 3, FeO} -TiO 2, TiO 2, SnO
₂ , Sb ₂ O ₃ , In ₂ O ₃ , ZnO, MgO, and other metal oxides can be used, and these materials may be used alone or in combination of two or more.

[0134] In the conductive member of the present invention, the resistive layer and the conductive particles or semiconductive particles in a binder resin dispersed as the material of the protective layer, obtained by controlling the resistance 10 ³ as resistivity -10 ¹⁴ Ωcm, preferably 10 ⁵
〜１０10 ¹² Ωcm, more preferably 10 ⁷ 〜１０10 ¹² Ωc
m is good. The thickness is 0.01 to 1000 μm,
Preferably it is 0.1 to 500 μm, more preferably 0.1 μm.
5-100 μm is preferred. As the binder resin, acrylic resin, cellulose resin, polyamide resin, methoxymethylated nylon, ethoxymethylated nylon, polyurethane resin, polycarbonate resin, polyester resin, polyethylene resin, polyvinyl resin, polyarylate resin,
Polythiophene resin, polyolefin resin such as PFA, FEP, PET, etc., styrene butadiene resin and the like are used. As the conductive particles or semiconductive particles, the same carbon black, metal, and metal oxide as those of the elastic layer are used. If necessary, an antioxidant such as hindered phenol and hindered amine, a filler such as clay and kaolin, and a lubricant such as silicone oil can be added.

In the conductive member of the present invention, means for forming these layers include blade coating, Meyer bar coating, spray coating, dip coating, bead coating, air knife coating, curtain coating and the like. Can be used.

As a method for charging a photosensitive member using these conductive members, a voltage is applied to the conductive members.
The applied voltage is preferably a DC voltage or a voltage obtained by superimposing an AC voltage on a DC voltage. The DC voltage range is a positive or negative 50 voltage depending on the required photoconductor charging potential.
2,000 V is preferable, and 100 to 1500 V is particularly preferable. When the AC voltage is superimposed, the peak-to-peak voltage is 4
00-1800V, preferably 800-1600V, more preferably 1200-1600V. The frequency of the AC voltage is 50 to 20,000 Hz, preferably
100-5,000 Hz.

[0137]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “parts” means parts by weight.

(Example 1) -Formation of Subbing Layer- Honed aluminum pipe (outer diameter 30
mm) 10 parts of a zirconium compound (trade name: "Organotics ZC540", manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 1 part of a silane compound (trade name: "A1110", manufactured by Nippon Unicar), 40 parts of isopropanol and butanol 20 Part of the solution is applied by a dip coating method, and dried by heating at 150 ° C. for 10 minutes to a thickness of 0.1 μm.
m undercoat layer was formed.

-Formation of charge generation layer- Bragg angle (2θ ± 0.2) in X-ray diffraction spectrum
°) is 7.4 °, 16.6 °, 25.5 °, 28.3.
A part of chlorogallium phthalocyanine having a strong diffraction peak at ° is mixed with 1 part of polyvinyl butyral (trade name: "ESLEC BM-S", manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of n-butyl acetate, and painted with glass beads. After dispersing by treating with a shaker for 1 hour, the obtained coating solution was dip-coated on the undercoat layer,
The resultant was dried by heating for 0 minutes to form a charge generation layer having a thickness of about 0.15 μm.

-Formation of Charge Transport Layer- 2 parts of a benzidine compound of the exemplified compound (IV-27) and 3 parts of a polymer compound (viscosity average molecular weight of 39,000) represented by the following basic unit (VI) are added to 20 parts of chlorobenzene. The dissolved coating solution 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.

[0141]

Embedded image

-Formation of Surface Protective Layer- 10 parts of the exemplified compound (compound 145), 20 parts of a curable siloxane resin (Shin-Etsu Silicon, X-40-2239), 3 parts of phenyltriethoxysilane, a fluorine-containing silane coupling agent ( Brand name: “KBM-7803”, manufactured by Shin-Etsu Silicone Co., Ltd. 2 parts, hindered phenolic antioxidant (brand name: “MDP-S”, manufactured by Sumilizer Co.) 1 part,
A coating solution obtained by mixing 1 part of acetic acid was spray-coated on the charge transport layer, and after touch drying for 30 minutes, 120
A heat treatment was performed at 60 ° C. for 60 minutes to form a surface protective layer having a thickness of 5 μm. As described above, the electrophotographic photosensitive member of Example 1 was manufactured.

(Examples 2 to 7) In the surface protective layer of Example 1, (Compound 3), (Compound 13) and (Compound 3) were used instead of the exemplified compound (Compound 145).
1), (Compound 155), (Compound 178), and (Compound 255) were used to prepare electrophotographic photosensitive members in exactly the same manner as in Example 1, except that Examples 2, 3, 4, 5,
6 and 7.

Example 8 —Formation of Undercoat Layer— An undercoat layer was formed on an aluminum pipe (30 mm) in the same manner as in Example 1.

—Formation of Charge Generating Layer— Instead of chlorogallium phthalocyanine in Example 1, the Bragg angle (2θ
± 0.2 °) is 7.5 °, 9.9 °, 12.5 °, 1
A charge generation layer was formed in the same manner except that hydroxygallium phthalocyanine having a specific crystal form having strong diffraction peaks at 6.3 °, 18.6 °, 25.1 °, and 28.3 ° was used.

-Formation of Charge Transport Layer- 2 parts of Exemplified Compound (IV-27) and 2 parts of Exemplified Compound (V-2)
8) 1 part of a coating solution obtained by dissolving 3 parts of the polymer compound represented by the basic unit (VI) (viscosity average molecular weight: 39,000) in 24 parts of chlorobenzene is applied on the charge generating layer by dip coating. At 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

—Formation of Surface Protective Layer— A surface protective layer was formed in the same manner as in Example 1. As described above, the electrophotographic photosensitive member of Example 8 was produced.

(Examples 9 to 12) In the surface protective layer of Example 8, instead of the exemplified compound (Compound 145),
(Compound 9), (Compound 10), (Compound 149),
Electrophotographic photoreceptors were prepared in the same manner as in Example 8 except that (Compound 150) was used, and Examples 9 to 12 were respectively obtained.

Example 13 Formation of Undercoat Layer An undercoat layer was formed on an aluminum pipe (30 mm) in the same manner as in Example 1. —Formation of Charge Generation Layer— Instead of chlorogallium phthalocyanine in Example 1, a Bragg angle (2θ) in an X-ray diffraction spectrum was used.
± 0.2 °) is 7.5 °, 9.9 °, 12.5 °, 1
A charge generation layer was formed in the same manner except that hydroxygallium phthalocyanine having a specific crystal form having strong diffraction peaks at 6.3 °, 18.6 °, 25.1 °, and 28.3 ° was used.

-Formation of charge transport layer- Bindered phenolic antioxidant (trade name: "MDP
-S ", manufactured by Sumilizer Co., Ltd.) 0.3 part, Exemplified Compound (I
V-27) 2 parts, Exemplified Compound (V-28) 1 part, and a polymer compound (viscosity average molecular weight 39,000) represented by the basic unit (VI) 3 parts dissolved in chlorobenzene 24 parts are coated with a coating solution. It is applied on the charge generation layer by a dip coating method, and heated at 110 ° C. for 40 minutes to form a film having a thickness of 20 μm.
m of the charge transport layer was formed.

—Formation of Surface Protective Layer— A surface protective layer was formed in the same manner as in Example 1. The electrophotographic photosensitive member of Example 13 was produced as described above.

Example 14 An electrophotographic photoreceptor was prepared in the same manner as in Example 13 except that the compound (225) was used instead of the exemplified compound (Compound 145) in the surface protective layer of Example 13. Produced.

Comparative Example 1 An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that no antioxidant was added in forming the surface protective layer of the electrophotographic photosensitive member.

Comparative Example 2 An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that no fluorine-containing silane coupling agent was added in forming the surface protective layer of the electrophotographic photosensitive member.

Comparative Example 3 An undercoat layer, a charge generation layer and a charge transport layer were sequentially formed on an aluminum pipe in the same manner as in Example 1, and an electrophotographic photosensitive member was formed without forming a surface protective layer. Produced.

The electrophotographic photoreceptors obtained in Examples 1 to 14 and Comparative Examples 1 to 3 were obtained by using “La” manufactured by Fuji Xerox.
and a press life test was carried out. This "LaserPress 4
The “160 modified machine” has a charging roll for contact charging, a laser exposure optical system, a toner developing device, a transfer roll, a cleaning blade, and a fixing roll.

The printing durability was evaluated by evaluating the image quality before and after printing 50,000 sheets and evaluating the amount of reduction in the thickness of the photosensitive member due to abrasion. The continuous printing was performed using an acidic paper at normal temperature and normal humidity (about 20 ° C., 40% RH). Further, the image quality was evaluated not only at normal temperature and normal humidity but also at high temperature and high humidity (about 28 ° C., 85% RH). These are acceleration evaluation methods for facilitating detection of image quality deterioration due to adhesion of paper powder to the photoreceptor surface. The results are shown in Table 32.

[0158]

[Table 32]

As shown in Table 32, when the electrophotographic photosensitive members of Examples 1 to 14 were used, good print quality (resolution and gradation) was obtained in all tests. In the electrophotographic photoreceptor of Comparative Example 1, image density unevenness occurred in image quality evaluation at high temperature and high humidity after the test. This is presumably due to the fact that the surface protective layer has been degraded by slight ozone generated by the charging. When the electrophotographic photoreceptor of Comparative Example 2 was used, in image quality evaluation at high temperature and high humidity after the test, image defects such as image density unevenness, image flow, and image blur were observed. This is presumably because paper powder such as talc adhered to the surface of the photoreceptor, partially reducing the surface resistance and causing defects in the electrostatic latent image. In Comparative Example 3 having no protective layer, image defects occurred even after the test at room temperature and normal humidity, and it was found that printing durability was low.

[0160]

As described above, the present invention has no environmental dependence, and has high photoelectric characteristics, mechanical strength, resistance to oxidizing gas, and resistance to deposits such as paper powder, and high quality. An electrophotographic photoreceptor having excellent printing durability and an image forming apparatus using the same can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram illustrating one embodiment of an image forming apparatus incorporating a photoconductor of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Photoreceptor 12 Charging roll 14 Laser exposure optical system 16 Developing device 18 Transfer roll 20 Cleaning blade 22 Fixing roll

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI G03G 15/02 101 G03G 15/02 101 (56) References 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-10-301302 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) G03G 5/00 101

Claims (11)

(57) [Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula (I), a fluorine atom-containing compound and an antioxidant. An electrophotographic photosensitive member characterized by the following. Embedded image (Wherein, G is an inorganic glassy network subgroup
Represents, 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 2
Divalent aryl group, -CH = N-, -O-, -COO-
At least one selected from the group consisting of
C _x H _2x - _(x is 1 to 15 integer) is one, substituted walk
_Represents one kind of unsubstituted divalent aryl group, and -C _x H _2x
-(X is an integer of 1 to 15) and substituted or unsubstituted divalent
Excluding the case of a combination with an aryl group of
Not including a hydrogen atom directly bonded to a heteroatom, 2
And F represents a photoelectric characteristic subunit.) 2. The electrophotographic photoreceptor according to claim 1, wherein the compound of the general formula (I) forms a crosslinked structure in the photosensitive layer. 3. The compound represented by the general formula (I), wherein the fluorine-containing compound is capable of bonding to the compound represented by the general formula (I) through an inorganic glassy network subgroup represented by G. 3. The composition according to claim 1, wherein the fluorine-containing compound forms a crosslinked structure in the photosensitive layer.
2. The electrophotographic photoreceptor of claim 1. 4. A layer containing a compound represented by the general formula (I), a fluorine atom-containing compound and an antioxidant,
4. The photosensitive layer according to claim 1, wherein said photosensitive layer is located on the outermost surface.
8. The electrophotographic photosensitive member according to any one of the above. 5. The electrophotograph according to claim 1, wherein the antioxidant is contained in a layer not containing the compound represented by the general formula (I). Photoconductor. 6. The electrophotograph according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II). Photoconductor. 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;
One to four of r ^{1 to} Ar ⁵ have a substituent represented by G—D—, and k represents 0 or 1. ) 7. The compound according to claim 1, wherein GD- in the compound represented by the general formula (I) is represented by the following general formula (III). The electrophotographic photosensitive member according to the above. Embedded image (Wherein, R ¹ represents a hydrogen, an alkyl group, a substituted or unsubstituted aryl group, R ² represents a hydrogen, an alkyl group, a trialkylsilyl group, a represents an integer of 1 to 3,
Y is, -C _x H _2x - _(x an integer of 1~15), - 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 divalent
From an aryl group of -CH = N-, -O-, -COO-
At least one member selected from the group consisting of
_x H _2x- (x is an integer of 1 to 15) is one kind, substituted or
Divalent aryl group unsubstituted is one, and -C _x H _2x -
(X is an integer of 1 to 15) and substituted or unsubstituted divalent
Excluding the case of a combination with an aryl group).
And a divalent group not containing a hydrogen atom directly bonded to a hetero atom. ) 8. The photosensitive layer according to claim 1, wherein the photosensitive layer contains gallium phthalocyanine halide or at least one member selected from the group consisting of hydroxygallium phthalocyanine, oxytitanium phthalocyanine, and tin phthalocyanine halide. 8. The electrophotographic photosensitive member according to any one of 1 to 7 . 9. The method according to claim 1, wherein the photosensitive layer contains at least one selected from a benzidine compound represented by the following general formula (IV) and a triarylamine compound represented by the following general formula (V). The electrophotographic photoreceptor according to any one of claims 1 to 8 , wherein Embedded image (Wherein R ⁶ and R ^{6 ′} are a hydrogen atom, a halogen atom,
Represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, which may be the same or different. R ⁷ , R ^{7 ′} , R ⁸ and R ^{8 ′} are substituted by a hydrogen atom, 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. And may be the same or different. m and n represent the integer of 0-2. ) (In the formula, R ⁹ represents a hydrogen atom or a methyl group, n represents 1 or 2. Ar ⁶ and Ar ⁷ represent a substituted or unsubstituted aryl group, and the substituent includes a halogen atom, (It represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a substituted amino group substituted with an alkyl group having 1 to 2 carbon atoms.) 10. An electrophotographic image forming apparatus having at least an electrophotographic photoreceptor, a charging unit for the same, and a mechanical cleaning unit, wherein the electrophotographic photoreceptor is an electrophotographic photoreceptor according to any one of claims 1 to 9. An electrophotographic image forming apparatus, wherein the electrophotographic image forming apparatus is a photographic photoreceptor and the charging means is of a contact charging type. 11. An electrophotographic image forming apparatus according to claim 10 , wherein a charging voltage used in said contact charging system has an AC component.