JPH11119458A - Electrophotographic photoreceptor and electrophotographic image forming device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor electrically and chemically stable and long in life and using an electron transferring compound soluble in a solvent at the time of coating but insoluble in the solvent after forming the film, and capable of forming a strong electron transferring film, and to provide an electrophotographic image forming device of a contact charger system by using this compound. SOLUTION: This electrophotographic photoreceptor is provided with an undercoat layer or a surface layer containing the compound represented by the formula in which L is a -CONH-,-CO2 -, -NH-, or -O- group; R1 is H atom or a 1-10C alkyl or optionally substituted aryl group; R2 is H atom or a 1-4C alkyl or 1-4C trialkylsilyl group; X is a =0 or =C(CN)2 or =C(CO2 C2 H5 )2 group; each of (a) and (c) is an integer of 1-10; (b) is 0 or 1; and (n) is 1, 2, or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photosensitive member, and more particularly, to an electrophotographic photosensitive member containing a specific electron transporting material.

[0002]

2. Description of the Related Art An electrophotographic photosensitive member is formed by providing a photosensitive layer on a conductive surface of a support, and after the photosensitive layer surface is charged, the surface potential is attenuated by light irradiation, and the latent image is electrostatically contrasted. On the surface of the photosensitive layer. On this occasion,
Since it is necessary to transport the generated electrons and holes to the opposite sides of the photosensitive layer, a charge transporting material is introduced into the photosensitive layer. That the charge transport material has a high charge transfer speed, that the charge is efficiently injected from the charge generation material,
There are many demands such as excellent chemical and electrical stability, and various electron-transporting materials and hole-transporting materials are being studied according to the purpose. Among them, examples of the electron transporting material include trinitrofluorenone described in JP-B-50-10496 and JP-A-61-14.
No. 3764, a dicyanomethylene fluorenone derivative described in JP-A-61-225151, and an anthraquinone derivative described in JP-A-61-225151.
Thiopyran derivatives described in JP-A-5-27
Fluorenone derivatives described in JP-A-9582, JP-A-7-233134, JP-A-7-258189 and the like; JP-A-8-245601;
Benzoxazole and benzothiazole derivatives described in JP-A-283249, JP-A-8-301858 and JP-A-8-286402, benzoquinone derivatives described in JP-A-8-15878, Journal of the Electrophotographic Society : Volume 30, Issue 3, 266 (19
91). The diphenoquinone derivative described in 91),
No. 25136, JP-A-5-25174, JP-A-5-117274, JP-A-5-125043, JP-A-5-132264, etc., imide compound derivatives, JP-A-52-12153 JP, JP-A-52-12154, and Macro
For example, an electron-transporting polymer in which an electron-transporting group described in Moleculars, 22, 2266 (1989) is introduced into a polymer is known. By the way, these materials focus on improvement of low solubility in an organic solvent or low compatibility with a binder polymer, which is an essential drawback of the electron transporting material.

On the other hand, an electrophotographic photoreceptor generally has improved adhesion between a photosensitive layer and a support, improvement in coating properties of the photosensitive layer, protection of the support surface, coating of defects on the support, A layer called an undercoat layer or an intermediate layer is interposed for protection from electric breakdown, improvement of carrier injection property of the photosensitive layer, and the like. In the case of a positive charge type electrophotographic photoreceptor, a charge generating material is generally used for the outermost surface layer, and in particular, a positive charge having a structure in which a charge generating layer is formed on a hole transporting charge transporting layer. In the case of a charge-type electrophotographic photosensitive member, an overcoat layer is formed to compensate for the low mechanical strength of the charge generation layer. For the undercoat layer or the overcoat layer, it is basically preferable to use an electron-transporting material. For example, Japanese Patent Publication No. 61-35551 and Japanese Patent Application Laid-Open No. 59-160147 disclose an undercoat layer. It is described that the layer contains an electron accepting substance. When an electron-transporting material is used for this purpose, for example, when used in an undercoat layer, it is dissolved in a coating solvent when forming the undercoat layer, and a photosensitive layer is further formed on the undercoat layer by coating. In this case, it is necessary that the coating solution used for forming the upper photosensitive layer is insoluble in a solvent. However, it is difficult to satisfy this requirement by using the above-mentioned materials, and the electron-transporting material dissolves at the time of formation by application of the upper layer, and the undercoat layer peels off, cracks or the like occur, and sufficient electrons are eluted by elution. There were problems such as inability to maintain transportability. When a charge-transporting material is used for the protective layer, it is preferable that the film be as thin as possible in order to maintain electrical characteristics. However, a material in which the above-described materials are dispersed in a binder resin is sufficient. Since high strength cannot be obtained and the film cannot be thinned, there are problems such as generation of residual potential and cycle-up of surface potential. In order to further improve this, Japanese Patent Publication No. 7-86694 discloses the use of a hydrolysis product of an alkoxysilane compound having an electron-accepting atom or an electron-withdrawing group for the protective layer. However, although the protective layer obtained by this method is excellent in strength, it has low electron transportability, and still has a problem that a residual potential is generated and a surface potential is cycled up. Patent No. 25
No. 75536 discloses that a material capable of forming an inorganic vitreous network having a photoresponsive subunit is used for an electrophotographic photoreceptor, and specific compounds are specifically disclosed. However, it is generally well known that the characteristics of an electrophotographic photoreceptor are largely influenced by the molecular structure such as the basic skeleton of the compound used and the polarity of the bonding chain, and the disclosed compounds are still insufficient. Was.

In a conventional electrophotographic photosensitive member,
In the surface layer configuration, there has been a problem that the mechanical strength sharply decreases when used for a long time under the contact charging or scorotron charging conditions. It is thought that this is due to strong external stress such as breaking of the bond of the thermoplastic binder resin by applying AC voltage in contact charging, or oxidation / decomposition of the charge transport material by ozone generated by scorotron charging. . As described above, when an AC voltage is applied in contact charging, a small amount of an oxidizing gas such as ozone is generated, which causes a problem of deterioration and wear of charging characteristics of the photoconductor. These problems can be solved by performing contact charging only with direct current without using alternating current, but it is difficult to obtain the required charging voltage.
There is a problem that the uniformity of charging is not very good.

[0005] As a method for solving the problem of contact charging only with direct current, a charge injection layer in which conductive fine powder such as tin oxide is dispersed in a binder resin is provided, and charging is performed by flowing a current directly from a contact charging member. A method has been proposed (Japanese Unexamined Patent Publication No.
-3921). However, this charge injection layer has exactly the same structure as a surface protective layer in which a metal oxide fine powder as a resistance control material is dispersed in a binder as typified by JP-A-57-128344. (Especially humidity).

As another method for improving the chargeability in contact charging with direct current only, a method in which a compound having a small reduction potential is added to the surface of a photoreceptor has been filed (JP-A-9-12).
No. 7763). However, in this method, since the film is not a film having a crosslinked structure, there is a problem that deterioration of the photoreceptor due to abrasion is increased in contact charging in which DC and AC are superimposed. In addition, when applied to a normal laminated photoreceptor, a low molecular weight compound having a small reduction potential is added to the hole transporting charge transporting layer, which becomes a hole trap site and has a disadvantage in photoelectric characteristics. In particular, there has been a problem that the residual potential tends to increase as the number of printed sheets increases.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, and has as its object to dissolve in a coating solvent at the time of coating and to form a film after forming the film. Is a material that does not dissolve in solvents and forms a strong electron-transporting film,
An object of the present invention is to provide a chemically stable and long-lived electrophotographic photosensitive member. Another object of the present invention is to provide an electrophotographic photoreceptor which is resistant to scratches and abrasion and has stable photoelectric characteristics and image quality even when used for large-volume printing. An electrophotographic photoreceptor which has a strong resistance to a photoreceptor having a large stress, such as contact charging, and which can easily obtain uniform charging even when used for DC only contact charging; and An object of the present invention is to provide an electrophotographic image forming apparatus using the same.

[0008]

Means for Solving the Problems The present inventors have made intensive studies in view of the above problems, and as a result, have solved the above problems by using a specific electron transporting compound having a curable alkoxysilyl group. They found what they could do and completed the invention.

The electrophotographic photoreceptor of the present invention is characterized in that the layer contains at least one compound represented by the following general formula (I). A- (CH ₂ ) _a- (L) _b- (CH ₂ ) _c -SiR _{1 (3-n)} (OR ₂ ) _n (I) wherein A represents the following general formula (A-1) A-8) represents a group having an electron transporting property represented by A-8),

Embedded image Wherein R ₃ and R ₄ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group or a cyano group; = O, = C (CN) ₂ , = C each independently
(CO ₂ R ₅ ) ₂ , ＝ N—CN or ＮN—Ar (where R ₅ represents an alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group; Represents an unsubstituted aryl group), and Y is -O-, -C
(= X ′) — or —SO ₂ — (where X ′ has the same meaning as described above), and r and p each independently represent 0, 1, 2 or 3. ] L is _{-CONH -, - CO 2 -,} - NH- or -O-
R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom.
Represents 4 to 3 trialkylsilyl groups, and a and c represent 1 to
Represents an integer of 10, b represents 0 or 1, n is 1
Means an integer of In the present invention, the compound represented by the general formula (I) is preferably contained in an undercoat layer. Further, it can be contained in the outermost surface layer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION First, the compound represented by the above general formula (I) will be described. The compound represented by the general formula (I) can be synthesized by various known methods. Here, the synthesis of compounds (A) and (B) represented by the following general formula will be described as an example. The compound (A) can be synthesized by the method of the synthesis route 1, and the compound (B) can be synthesized by either the method of the synthesis route 1 or the method of the synthesis route 2.

(Synthetic Route 1)

Embedded image First, the synthesis route 1 will be described. From the carboxylic acid derivative having the structure represented by (A-5), an acid halide is synthesized according to a conventional method as described in the 4th Edition, Jikken Kagaku Koza, Vol. 22, pages 115-127. As the halogenating reagent, thionyl chloride, phosphorus trichloride, phosphorus pentachloride,
Thionyl bromide, phosphorus pentabromide and the like can be used, and usually 1 to 3 equivalents, preferably 1 to 2 equivalents, are used based on the carboxylic acid derivative. The reaction can also be performed using a solvent such as benzene, toluene, dichloromethane, chloroform and the like. The amount of the solvent used is in the range of 1 to 50 parts by weight, preferably 1.5 to 30 parts by weight based on 1 part by weight of the carboxylic acid derivative. To further promote the reaction, dimethylformamide (DMF), pyridine, hexamethylphosphoric triamide (HMPA) or the like may be added. These amounts are optional, but 0.001 to 5 parts by weight, preferably 0.0% to 1 part by weight of the carboxylic acid derivative.
It is used in the range of 0.5 to 3 parts by weight. Reaction temperature is 0 ° C
To the boiling point of the solvent. Further, after the reaction is completed, it is preferable to remove excess halogenating reagent by distillation under reduced pressure or recrystallization.

Using the obtained acid halide, the compound (A) can be obtained by the method as described in the 4th edition of Jikken Kogaku Koza, Vol. 22, pages 144-146. In the reaction, first, an acid halide is added to a solvent such as benzene, toluene, dichloromethane, chloroform, and the like. toluene,
A solution dissolved in a solvent such as dichloromethane or chloroform is added dropwise slowly. At this time, if the reaction takes place vigorously, cooling is performed if necessary. In order to neutralize the hydrogen halide generated during the reaction, a base such as pyridine or sodium carbonate is added, or the amine compound represented by the general formula (II) is added in an amount of 2 equivalents or more based on the carboxylic acid derivative. May be neutralized by the amine compound itself. The obtained compound (A) is purified by column chromatography, recrystallization or the like, if necessary, and used for the next reaction.

The compound (B) is obtained by combining the compound (A) with malononitrile, for example, by encyclopedia of Reagents for Org.
anic Synthesis, vol.5, p.3214-3217 (John Wiley &
Sons, 1995). For example, 1 part by weight of compound (A) is
50 parts by weight, preferably 1.5 to 30 parts by weight, is dissolved in a solvent such as benzene, toluene, dichloromethane, chloroform, methanol, ethanol, and DMF, and 1 to 5 equivalents, preferably 1 to 5 equivalents to the compound (A) is added thereto. Is 1-3
An equivalent amount of malononitrile is added, and an optional amount of ammonium acetate, potassium acetate, sodium acetate, pyridine, piperidine, titanium tetrachloride or the like is added as a catalyst. The reaction temperature can be arbitrarily set between room temperature and the boiling point of the solvent. In particular, to prevent hydrolysis of the alkoxysilyl group, an alcohol having the same skeleton as R _2: it is preferable to use the R ₂ OH as a solvent. Further, as R ₂ , a branched alkyl group having 3 or more carbon atoms is preferable because hydrolyzability is suppressed. The obtained compound (B) is preferably purified by column chromatography, recrystallization and the like.

(Synthetic Route 2)

Embedded image Next, the synthesis route 2 will be described. First, (A-5)
A carboxylic acid derivative having the structure represented by and malononitrile, for example, Encyclopedia of Reagents for Organ
ic Synthesis, vol.5, p.3214-3217 (John Wiley & S
ons, 1995). 1 part by weight of a carboxylic acid derivative having a structure represented by (A-5) is 1 to 50 parts by weight, preferably,
1.5 to 30 parts by weight of benzene, toluene, dichloromethane, chloroform, methanol, ethanol, DMF
And 1 to 5 equivalents, preferably 1 to 3 equivalents of malononitrile with respect to the carboxylic acid derivative, and ammonium acetate, potassium acetate, sodium acetate, pyridine, piperidine, titanium tetrachloride as a catalyst. And the like are added in arbitrary amounts. The reaction temperature can be arbitrarily set between room temperature and the boiling point of the solvent. If desired, it is purified by column chromatography, recrystallization, etc. and used for the next reaction. Next, the 4th edition Jikken Chemistry Course, Volume 22, Volume 1
An acid halide is synthesized by a conventional method as described on pages 15 to 127. As the halogenating reagent, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, thionyl bromide, phosphorus pentabromide and the like can be used.
~ 3 equivalents, preferably 1-2 equivalents are used. The reaction can also be performed using a solvent such as benzene, toluene, dichloromethane, chloroform and the like. The amount of the solvent used is in the range of 1 to 50 parts by weight, preferably 1.5 to 30 parts by weight based on 1 part by weight of the carboxylic acid derivative. In order to further promote the reaction, DMF, pyridine, HMPA
Etc. may be added. These amounts are optional, but are used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, per 1 part by weight of the carboxylic acid derivative. The reaction temperature can be arbitrarily set between 0 ° C. and the boiling point of the solvent. Further, after the reaction is completed, it is preferable to remove excess halogenating reagent by distillation under reduced pressure or recrystallization.

Using the obtained acid halide, the compound (B) can be obtained by the method described in the 4th edition, Jikken Kagaku Koza, Vol. 22, pages 144-146. That is, in the reaction, first, an acid halide is added to a solvent such as benzene, toluene, dichloromethane, and chloroform.
In addition, one equivalent or more of the general formula (II) based on the acid halide
An amine compound represented by the following, if desired, benzene,
A solution dissolved in a solvent such as toluene, dichloromethane, chloroform or the like is added dropwise slowly. At this time, if the reaction takes place vigorously, cooling is performed if necessary. In order to neutralize the hydrogen halide generated during the reaction, a base such as pyridine or sodium carbonate is added, or an amine compound represented by the general formula (II) is added in an amount of 2 equivalents or more based on the carboxylic acid derivative. The amine compound may be neutralized by itself. The obtained compound (B) is preferably purified by column chromatography, recrystallization and the like.

In the case of synthesizing the compound (B), synthesis can be carried out by any of the synthesis routes 1 and 2, but the synthesis route 2 is particularly preferable. This is because the alkoxysilyl group is easily susceptible to hydrolysis, and the method using the synthesis route 1 requires an excess of malononitrile in the final step, which requires purification by column chromatography or the like, and lowers the yield. On the other hand, in the synthesis route 2, if the purification is sufficiently performed at the stage of an acid halide which is more stable than the alkoxysilyl group, the amidation in which the amine compound represented by the general formula (II) is reacted in the last step This is because, in addition to the quantitative progress of the reaction, by using the water-soluble amine compound represented by the general formula (II), the compound (B) having high purity can be obtained only by washing with water.

Further, by using an alcohol represented by the general formula (II ') instead of the amine compound represented by the general formula (II), esters represented by the compounds (A') and (B ') are also synthesized. be able to. The reaction formula is as follows.

[0018]

Embedded image The compound having the structure represented by (A-7) or (A-8) can be synthesized as follows.
That is, 1 equivalent or more, preferably 1.5 equivalent or more of the amine compound: H ₂ N based on the corresponding carboxylic anhydride.
_{- (CH 2) c -SiR 1} (3-n) (OR 2) n was added, obtained by heating in a solvent. At this time, as the solvent, benzene, toluene, dichloromethane, chloroform, DMF, dimethyl sulfoxide (DMSO) and the like can be used, but R ₂ OH is preferably used to prevent polymerization, and 1 part by weight of carboxylic anhydride is used. ~ 100
Parts, preferably 2 to 50 parts. Further, the obtained product may be purified by column chromatography or the like, if necessary.

Specific examples of the compound represented by the above general formula (I) are shown below. In the table, Me means a methyl group, and Bu means a butyl group.

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

[Table 4]

[0023]

[Table 5]

[0024]

[Table 6]

[0025]

[Table 7]

[0026]

[Table 8]

[0027]

[Table 9]

[0028]

[Table 10]

[0029]

[Table 11]

[0030]

[Table 12]

[0031]

[Table 13]

[0032]

[Table 14]

[0033]

[Table 15]

[0034]

[Table 16]

In the present invention, the compound represented by the general formula (I) is contained in at least one of the layers constituting the electrophotographic photosensitive member. Specifically, when it is contained in the undercoat layer, it is contained in the layer constituting the outermost surface, for example, the protective layer provided on the photosensitive layer, the charge transport layer or the charge generation layer constituting the surface layer of the photosensitive layer having a laminated structure. And a case where it is contained in a photosensitive layer having a single-layer structure.

Next, the details of the electrophotographic photosensitive member of the present invention will be described. FIG. 1 is a schematic diagram showing a cross section of the electrophotographic photosensitive member of the present invention. FIG. 1 shows a photosensitive layer having a laminated structure.
FIGS. 1A to 1C show a single-layer structure shown in FIGS. 1D and 1E. In FIG. 1A, an undercoat layer 1 is provided on a conductive support 4, and a charge generation layer 2 and a charge transport layer 3 are provided thereon. In FIG. The protective layer 5 is provided on the surface. In FIG. 1C, an undercoat layer 1 is provided on a conductive support 4, and a charge transport layer 3 and a charge generation layer 2 are provided thereon.
Is provided, and a protective layer 5 is further provided on the surface. In FIG. 1D, an undercoat layer 1 is provided on a conductive support 4 and a charge generation / charge transport layer 6 is provided thereon. Further, in FIG. , A protective layer 5 is provided on the surface.

Examples of the conductive support include metals such as aluminum, nickel, chromium, and stainless steel, and aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, and ITO.
And a plastic film provided with a thin film such as the above, or paper coated with or impregnated with a conductivity-imparting agent, and a plastic film. These conductive supports are used in an appropriate shape such as a drum shape, a sheet shape, and a plate shape, but are not limited thereto. Further, if necessary, the surface of the conductive support can be subjected to various treatments within a range that does not affect the image quality. For example, oxidation treatment, chemical treatment and coloring treatment of the surface, or irregular reflection treatment such as graining can be performed.

Next, the undercoat layer will be described. The undercoat layer mainly prevents unnecessary injection of carriers from the conductive support and improves image quality. It has an appropriate charge transport ability, does not accumulate charge even after long-term repeated use, and does not cause sensitivity fluctuation,
It has an appropriate withstand voltage against the charging voltage and does not cause image defects due to dielectric breakdown.
Alternatively, in some cases, it is provided for the purpose of exhibiting the effect of preventing light reflected from the support.

The undercoat layer may be constituted by using a known material for the undercoat layer shown below, but in the present invention, the compound represented by the general formula (I) may be formed alone or in a desired form. Is preferably mixed with other known materials. Other known materials used by mixing as desired include zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, and organic titanium compounds such as titanate coupling agents. , Aluminum chelate compounds, in addition to organic aluminum compounds such as aluminum coupling agents, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds,
Organic metal compounds such as indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds, aluminum zirconium alkoxide compounds, and the like, especially organic zirconium compounds, organic Titanyl compounds and organoaluminum compounds are preferably used because of their low residual potential and good electrophotographic properties. Also, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
Silanes such as -chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and β-3,4-epoxycyclohexyltrimethoxysilane A coupling agent can be contained and used. Furthermore, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester conventionally used for the undercoat layer Known resins such as phenol resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, polyacrylic acid and polyvinyl butyral can also be used. These mixing ratios can be appropriately set as necessary, but when the compound represented by the general formula (I) is used such that the ratio of the compound is 10% by weight or more, preferably 20% by weight or more. It is particularly preferable because it has excellent electrical characteristics.

In the undercoat layer of the present invention, an electron transporting pigment may be mixed or dispersed. Examples of the electron transporting pigment include perylene pigments described in JP-A-47-30330, bisbenzimidazole perylene pigments,
Organic pigments such as polycyclic quinone pigments, indigo pigments, and quinacridone pigments; organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as cyano, nitro, nitroso, and halogen atoms; zinc oxide And inorganic pigments such as titanium oxide. Among these pigments, perylene pigments, bisbenzimidazole perylene pigments and polycyclic quinone pigments are preferably used because of their high electron mobility.

In this case, the mixing and / or dispersion may be carried out by dispersing the electron transporting pigment in a solution of the compound represented by the general formula (I), A method of adding and mixing the compound shown in the formula, a dispersion of an electron transporting pigment dispersed in a resin,
A method of adding and mixing the compound represented by formula (I), a method of adding and mixing the compound represented by formula (I) to the resin solution, and then dispersing the electron transporting pigment; It is possible to adopt a method of adding and mixing the indicated compound and then dispersing it in a resin solution, but it is important that gelation or aggregation does not occur when mixed and / or dispersed. If the amount of the electron-transporting pigment is too large, the strength of the undercoat layer is reduced to cause a coating film defect. As a mixing and / or dispersion method, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. The mixing and / or dispersion is performed in an organic solvent. As the organic solvent, an organic metal compound or a resin is dissolved, and no gelation or aggregation occurs when the electron transporting pigment is mixed and / or dispersed. Anything can be used.
For example, methanol, ethanol, n-propanol,
n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate,
Known organic solvents such as dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene can be used alone or in combination of two or more.

The thickness of the undercoat layer in the present invention is as follows:
Generally, 0.1-20 μm, preferably 0.2-1
A range of 0 μm is appropriate. Further, as an application method used when providing the undercoat layer, a usual 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, a curtain coating method, or the like. Can be used. After application, the coating is dried to form an undercoat layer. Usually, drying is performed at a temperature at which a solvent can be evaporated and a film can be formed.

Next, the charge generation layer when the photosensitive layer has a laminated structure will be described. The charge generation layer is composed of a known charge generation material and a binder resin. As the charge generation material, any known materials can be used. Pigments are preferred. Among them, hydroxygallium phthalocyanine, chlorogallium phthalocyanine, dichlorotin phthalocyanine and titanyl phthalocyanine having specific crystals are particularly preferable. These phthalocyanine pigments are described, for example, in JP-B-44-14106, JP-A-4-189.
No. 837, Japanese Unexamined Patent Application Publication No. 5-66594, Japanese Unexamined Patent Application Publication No.
-98181, JP-A-5-140472-3, JP-A-5-263007, JP-A-5-279
No. 591 and the like, and can be used after being converted into a desired crystal form by a known method described in these publications.

The chlorogallium phthalocyanine crystal which can be used in the present invention is disclosed in JP-A-5-9818.
As disclosed in JP-A No. 1 (1993), a chlorogallium phthalocyanine crystal produced by a known method is used to prepare an automatic mortar, a planetary mill, a vibration mill, a CF mill, a roller mill, a sand mill,
It can be manufactured by mechanically dry pulverizing with a kneader or the like, or by performing wet pulverization using a ball mill, a mortar, a sand mill, a kneader or the like together with a solvent after the dry pulverization. Solvents used in the above treatment include aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.),
Aliphatic polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.),
Esters (acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, ethers (diethyl ether, tetrahydrofuran, etc.), furthermore, a mixture of several kinds, a mixture of water and these organic solvents, etc. It is. The solvent used is used in an amount of 1 to 200 parts, preferably 10 to 100 parts, based on chlorogallium phthalocyanine. The treatment temperature is in the range of 0 ° C. to the boiling point of the solvent or lower, preferably 10 to 60 ° C.
Further, at the time of pulverization, a grinding aid such as salt and sodium nitrate can be used. The grinding aid is used 0.5 to 20 times, preferably 1 to 10 times the pigment.

Dichlorotin phthalocyanine crystals are disclosed in JP-A-5-140472 and JP-A-5-14047.
As disclosed in Japanese Unexamined Patent Publication (Kokai) No. 3 (1994) -93, a dichlorotin phthalocyanine crystal produced by a known method can be obtained by pulverization and solvent treatment in the same manner as the above-mentioned chlorogallium phthalocyanine.

Hydroxygallium phthalocyanine crystals are disclosed in JP-A-5-263007 and JP-A-5-252.
As disclosed in JP-A-795991, chlorogallium phthalocyanine crystals produced by a known method are subjected to hydrolysis or acid pasting in an acid or alkaline solution to synthesize hydroxygallium phthalocyanine crystals, and a direct solvent Performing the treatment, or the hydroxygallium phthalocyanine crystals obtained by the synthesis with a solvent ball mill, mortar, sand mill, kneader, etc. It can be manufactured by processing. Solvents used in the above treatment include aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol,
Butanol), aliphatic polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.),
Aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, ethers (diethyl ether, tetrahydrofuran, etc.), and several types And a mixed system of water and these organic solvents. The solvent used is based on hydroxygallium phthalocyanine.
It is used in the range of 1 to 200 parts, preferably 10 to 100 parts. The processing temperature is 0 to 150 ° C., preferably room temperature to
It is performed in the range of 100 ° C. Further, at the time of pulverization, a grinding aid such as salt and sodium nitrate can be used. The grinding aid is used in the range of 0.5 to 20 times, preferably 1 to 10 times the pigment.

The titanyl phthalocyanine crystal is disclosed in
As disclosed in JP-A-189873 and JP-A-5-43813, oxytitanyl phthalocyanine crystals produced by a known method are subjected to acid pasting, or a ball mill, a mortar, a sand mill,
After salt milling with an inorganic salt using a kneader or the like to give a relatively low-crystalline titanyl phthalocyanine crystal having a peak at 27.2 ° in the X-ray diffraction spectrum, directly perform solvent treatment, or It can be produced by performing wet pulverization using a ball mill, a mortar, a sand mill, a kneader or the like together with a solvent. As the acid used for acid pasting, sulfuric acid is preferable, and the concentration is 70 to 100%, preferably 95 to 1%.
The dissolution is set in the range of -20 to 100 ° C, preferably 0 to 60 ° C. The amount of concentrated sulfuric acid is 1 to 1 with respect to the weight of the titanyl phthalocyanine crystal.
It is set in the range of 100 times, preferably 3 to 50 times.
As a solvent to be precipitated, water or a mixed solvent of water and an organic solvent is used in an arbitrary amount, and a mixture of water and an alcohol solvent such as methanol or ethanol, or a mixture of water and an aromatic solvent such as benzene or toluene. Solvents are particularly preferred. The temperature for the precipitation is not particularly limited, but is preferably cooled with ice or the like in order to prevent heat generation. The ratio between the titanyl phthalocyanine crystal and the inorganic salt is 1 by weight.
/0.1 to 1/20, preferably in the range of 1 / 0.5 to 1/5. Solvents used in the above solvent treatment include aromatics (toluene, chlorobenzene, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), and halogenated hydrocarbons (dichloromethane, chloroform,
Trichloroethane, etc.), several types of mixed systems, mixed systems of water and these organic solvents, and the like. The solvent used is 1 to 100 parts with respect to oxytitanyl phthalocyanine,
It is preferably used in the range of 5 to 50 parts. The treatment temperature is in the range of room temperature to 100 ° C, preferably 50 to 100 ° C. The grinding aid is 0.5 to 20 times the pigment,
Preferably, it is used in the range of 1 to 10 times.

The binder resin can be selected from a wide range of insulating resins, and can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene and polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate resin, Examples include, but are not limited to, insulating resins such as polyamide resins, acrylic resins, polyacrylamide resins, polyvinyl pyridine resins, cellulosic resins, urethane resins, epoxy resins, caseins, polyvinyl alcohol resins, and polyvinylpyrrolidone resins. In particular, a resin having a hydroxyl group that easily causes a reaction such as crosslinking with an organometallic compound is preferable. 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 is preferably in the range of 10: 1 to 1:10. In addition, as a method of dispersing the charge generating material, known methods such as a ball mill dispersion method, an attritor dispersion method, and a sand mill dispersion method can be used. You. Incidentally, it has been confirmed that the crystal form does not change before and after dispersion in any of the above-mentioned dispersion methods carried out in the present invention.
Further, at the time of this dispersion, it is effective that the particles have a particle size of 0.5 μm or less, preferably 0.3 μm or less, and more preferably 0.15 μm or less. Solvents used for these dispersions include methanol, ethanol, n
-Propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone,
Methyl ethyl ketone, cyclohexanone, methyl acetate,
Known organic solvents such as n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene can be used alone or in combination of two or more. The thickness of the charge generation layer in the present invention is generally 0.1 to 5 μm, preferably 0.2 to 5 μm.
It is set in the range of ２．０2.0 μm. In addition, as a coating method used when providing the charge generation layer, known methods 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.

The charge transporting layer in the electrophotographic photoreceptor of the present invention is formed by incorporating a known charge transporting material into a suitable binder or by using a charge transporting polymer alone.
Alternatively, it is formed by mixing a charge transporting polymer with a known charge transporting material and a binder. As the charge transport material, 2,5-bis (p-diethylaminophenyl)
Oxadiazole derivatives such as -1,3,4-oxadiazole, pyrazoline derivatives such as 1- [pyridyl- (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, Aromatic tertiary amino compounds such as triphenylamine and dibenzylaniline, N, N'-diphenyl-N. N'-bis- (3-methylphenyl)-[1,1'-biphenyl] -4,4 '
Aromatic tertiary diamino compounds such as -diamine; hydrazone derivatives such as 4-diethylaminobenzaldehyde-1,1'-diphenylhydrazone; α such as p- (2,2'-diphenylvinyl) -N, N-diphenylaniline −
A known charge transport material such as a stilbene derivative can be used. Further, semi-conductive polymers such as poly-N-vinylcarbazole and derivatives thereof, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9-biphenylanthracene, pyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin can also be used. However, the present invention is not limited to these. These charge transport materials can be used alone or in combination of two or more. However, in the present invention, the compound represented by the general formula (I) or
It is preferable to contain a benzidine compound represented by the following general formula (III) or an amine compound represented by the general formula (IV).

[0051]

Embedded image (Wherein, R ₆ and R ₆ 'may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 5 carbon atoms, 1 to 5 carbon atoms, R _7, R ₇ ′, R ₈ and R ₈ ′ may be the same or different and each represents 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 a C 1 to 2 Represents an amino group substituted with an alkyl group, and k and m represent an integer of 1 or 2.)

Embedded image (Wherein R ₉ represents a hydrogen atom or a methyl group;
₁ and Ar ₂ represent a substituted or unsubstituted aryl group, and the substituent includes a halogen atom, a carbon number of 1 to 5;
An alkyl group, an alkoxy group having 1 to 5 carbon atoms, or an amino group substituted with an alkyl group having 1 to 3 carbon atoms,
j means an integer of 1 or 2. )

Specific examples of the benzidine compound represented by the general formula (III) include those shown in Table 17 below.

[Table 17]

Specific examples of the amine compound represented by the general formula (IV) include those shown in Tables 18 to 21 below.

[Table 18]

[0054]

[Table 19]

[0055]

[Table 20]

[0056]

[Table 21]

Further, as the binder used for the charge transport layer, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, chloride Vinylidene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-
Known resins such as alkyd resins and poly-N-vinylcarbazole can be used, and further, zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents,
Titanium chelate compounds, titanium alkoxide compounds, organotitanium compounds such as titanate coupling agents, aluminum chelate compounds, other organic aluminum compounds such as aluminum coupling agents, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds,
Organic metal compounds such as manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds, and aluminum zirconium alkoxide compounds can be used.
In particular, organic zirconium compounds, organic titanyl compounds, and organic aluminum compounds are preferably used because of their low residual potential and good electrophotographic properties. Further, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane,
γ-ureidopropyltriethoxysilane, β-3,4
-A silane coupling agent such as epoxycyclohexyltrimethoxysilane, or a curable matrix such as a photocurable resin may be used, and a charge transport material curable with these may be used. These binder resins can be used alone or in combination of two or more.

The compounding ratio (weight ratio) of the charge transporting material to the binder resin is preferably in the range of 10: 1 to 1: 5. The thickness of the charge transport layer used in the present invention is generally in the range of 5 to 50 μm, preferably 10 to 30 μm. As a coating method, a known 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. Further, as a solvent used when forming the charge transport layer, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, ketones such as acetone and 2-butanone, and halogenated solvents such as methylene chloride, chloroform, and ethylene chloride. Known organic solvents such as aliphatic hydrocarbons, cyclic or linear ethers such as tetrahydrofuran and ethyl ether can be used alone or in combination of two or more.

For the purpose of preventing deterioration of the photoreceptor due to ozone or other oxidizing gas generated in the copying machine, or light or heat, an antioxidant, a light stabilizer,
Additives such as heat stabilizers can be added. For example,
Examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, organic phosphorus compounds and the like. Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine. Further, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, reducing fatigue when repeatedly used, and the like. Examples of the electron acceptor usable in the electrophotographic photoreceptor of the present invention include, for example, succinic anhydride,
Maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o
-Nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid, etc.
And the compound represented by the general formula (I). Among these, fluorenone-based, quinone-based, and benzene derivatives having an electron-withdrawing substituent such as Cl, CN, and NO ₂ are particularly preferable. When the compound represented by the general formula (I) is contained, the content is 10 parts by weight (weight ratio) of the binder resin and the compound represented by the general formula (I).
A range of 00: 1 to 20: 1 is preferred.

Further, if necessary, a protective layer may be provided on the charge transport layer. This protective layer is used to prevent the charge transport layer from being chemically altered during charging of the photosensitive layer having a laminated structure, and to improve the mechanical strength of the photosensitive layer. This protective layer is formed by including a conductive material in a suitable binder resin. As the conductive material, N,
Metallocene compounds such as N'-dimethylferrocene;
Aromatic amine compounds such as N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine, antimony oxide, tin oxide,
Materials such as metal oxides such as titanium oxide, indium oxide, and tin oxide-antimony oxide can be used, but are not limited thereto. Further, as the binder resin used for this protective layer, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinylketone resin, polystyrene resin, polyacrylamide resin, polyimide resin, polyamideimide resin, polyether A known resin such as an imide resin can be used. Further, a charge transport layer using the above-mentioned curable matrix can be used as a protective layer.

Further, the compound represented by the general formula (I) can be contained in the protective layer. In that case, zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds such as titanate coupling agents, aluminum chelate compounds, aluminum coupling agents, etc. In addition to the organoaluminum compound, antimony alkoxide compound, germanium alkoxide compound, indium alkoxide compound, indium chelate compound, manganese alkoxide compound, manganese chelate compound, tin alkoxide compound, tin chelate compound, aluminum silicon alkoxide compound, aluminum titanium alkoxide compound, aluminum Organic metal compounds such as zirconium alkoxide compounds It can be used as Nda, especially organic zirconium compound,
Organic titanyl compounds and organic aluminum compounds are preferably used because of their low residual potential and good electrophotographic properties. Also, vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris 2 methoxy ethoxy silane, vinyl triacetoxy silane, γ-glycidoxy propyl trimethoxy silane,
γ-methacryloxypropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxy It is more preferable to use a curable matrix such as a silane coupling agent such as cyclohexyltrimethoxysilane. When the compound represented by the general formula (I) is contained, the content is 1: 100 to 50:50 in a ratio (weight ratio) of the compound represented by the general formula (I) and the curable matrix material. Preferably it is in the range of 10:90 to 50:50.

The protective layer has an electric resistance of 10 ⁹ to 10 ^14.
It is preferable to configure so as to be Ω · cm. When the electric resistance is 10 ¹⁴ Ω · cm or more, the residual potential rises to produce a fogged copy, and when the electric resistance is 10 ⁹ Ω · cm or less, blurring of an image and reduction in resolution occur. Also,
The protective layer must be configured so as not to substantially impede the transmission of light used for image exposure. The thickness of the protective layer is 0.
A range of 5 to 20 μm, preferably 1 to 10 μm is appropriate. As a coating method for forming the protective layer, known methods 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 may be used. it can.

When the photosensitive layer has a single-layer structure, the charge generation material, the charge transport material, the binder resin and the compound represented by the formula (I) are mixed at a desired ratio, and the dispersion is performed in the same manner as described above. The photosensitive layer can be prepared by a coating method. At this time, the charge generating material is used in an amount of 5 to 50% by weight, preferably 5 to 30% by weight to maintain the mechanical strength. Further, the compound represented by the general formula (I) accounts for 5 to 50% by weight, preferably 5 to 30% by weight of the whole.
Content within the range.

The electrophotographic photoreceptor of the present invention exhibits excellent characteristics when a contact charging method is used in addition to a conventional corona discharge type charging member. In the contact charging method, the contact charging member is disposed so as to be in contact with the surface of the photoconductor, and applies a voltage directly and uniformly to the electrophotographic photoconductor,
The surface of the photoconductor is charged to a predetermined potential.

Next, an electrophotographic image forming apparatus of the present invention using a contact charging system will be described. An electrophotographic image forming apparatus according to the present invention includes at least the electrophotographic photoreceptor described above and a charging unit for charging the photoreceptor to a predetermined potential, an exposure unit for forming an electrostatic latent image, and an electrostatic latent image. , A transfer unit for transferring the developer on the photoreceptor to paper or the like, and a fixing unit for fixing the transferred image. The electrophotographic photoreceptor can be used in an image forming apparatus using a non-contact charger such as a scorotron charger as a charging unit, and has excellent photoelectric characteristics and durability. Further, when the present invention is applied to an image forming apparatus using a contact charger such as a charging roll as a charging unit, it exhibits extremely strong durability against abrasion of a photoreceptor which is conspicuously caused by contact charging.

FIG. 3 shows an example of the electrophotographic image forming apparatus of the present invention. Contact charger (charging roll) as charging means
11, a laser exposure optical system 12, a developing device 13 containing a magnetic one-component toner, a transfer corotron or transfer roll 14, a light elimination light source (LED) 15, a cleaning blade 16, and a fixing roll 17 are provided. Reference numeral 18 denotes a sheet.

As the contact charger, a conductive member is used, and the shape may be any shape such as a brush shape, a blade shape, a belt shape, a pin electrode shape or a roll shape. Is preferred. Usually, the roll-shaped member is composed of a resistance layer, an elastic layer supporting them and a core material from the outside. If necessary, a protective layer can be provided outside the resistance layer. The material of the core material is a material having 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 fine particles and the like are dispersed can be used.

The material of the elastic layer has conductivity or semi-conductivity. Generally, a material in which conductive fine particles or semi-conductive fine particles are dispersed in a rubber material is used. Rubber materials include EPDM, polybutadiene, natural rubber, polyisobutylene, SBR, CR, NBR, silicone rubber, urethane rubber, epichlorohydrin rubber, SBS,
Thermoplastic elastomer, norbornene rubber, acrylic rubber, fluorine rubber, fluorosilicone rubber, ethylene oxide rubber and the like are used. As the conductive fine particles and semiconductive fine particles, substances such as carbon black, copper iodide, silver iodide, zinc sulfide, silicon carbide, zinc, aluminum,
Metals such as copper, iron, nickel, chromium and titanium, Zn
_{O-Al 2 O 3, SnO} 2 -Sb 2 O 3, In 2 O 3 -
_{SnO 2, ZnO-TiO 2,} MgO-Al 2 O 3, F
_{eO-TiO 2, TiO 2,} SnO 2, Sb 2 O 3, I
Metal oxides such as n ₂ O ₃ , ZnO, MgO, and MoO ₃ can be used, and these materials may be used alone or in combination of two or more. Alternatively, a conductive polymer material such as polyacetylene, polypyrrole, or polythiophene can be used. In addition, a conductivity may be imparted by including a perchlorate in the elastomer material.

The material of the resistance layer and the protective layer is a material in which conductive fine particles or semiconductive fine particles are dispersed in a binder resin as required and the resistance thereof is controlled.
10 ³ to 10 ¹⁴ Ω · cm, preferably 10 ⁵ to 10 ¹² Ω
Cm, more preferably in the range of 10 ⁷ to 10 ¹² Ω · cm. Further, the film thickness is 0.01 to 10
It is set in the range of 00 μm, preferably 0.1 to 500 μm, more preferably 0.5 to 100 μm.

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, styrene- Butadiene resin or the like is used. Further, an emulsion resin-based material, for example, an acrylic resin emulsion, a polyester resin emulsion, or a polyurethane, particularly, an emulsion resin synthesized by soap-free emulsion polymerization can be used.
As the conductive fine particles or semiconductive fine particles, the same carbon black, metal and metal oxide as in 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. Further, in order to improve the film forming property when forming the coating layer, the emulsion resin may contain a leveling agent or a surfactant.

As means for forming these layers, 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, a curtain coating method and the like can be used.

As a method of charging an electrophotographic photosensitive member using these conductive members, a voltage is applied to the conductive members, and the applied voltage may be either DC only or DC superimposed with AC. . As the range of the applied voltage, the DC voltage is preferably a positive or negative range of 50 to 2000 V depending on the required photoconductor charging potential.
The range of 00 to 1500 V is preferred. When the AC voltage is superimposed, the peak-to-peak voltage is 400 to 1800 V, preferably 800 to 1600 V, more preferably 1200 to 1V.
It is set in the range of 600V. AC voltage frequency is 50
The frequency is set in the range of ２０20,000 Hz, preferably 100１００2000 Hz.

Any method can be used for contacting the conductive member with the electrophotographic photosensitive member. For example, when a roll-shaped charging member is used, the roll-shaped charging member is brought into contact with the electrophotographic photosensitive member. The rotation may be performed at the same relative speed, or the two may be different in relative speed.

Since the surface protective layer of the electrophotographic photosensitive member according to the present invention has a three-dimensional network structure, it has a sufficient resistance to a strong stress due to an AC voltage. Further, since it has an electron transporting property, a uniform negative charge can be obtained with good reproducibility even when only DC is charged.

[0075]

The present invention will be described below by way of examples. In addition, "part" means "part by weight". Example 1 A brominated dibromoanthanthrone (trade name: Monolight Red 2) represented by the following structural formula (1) was used on a honing-treated aluminum pipe as a support.
Y, I. C. I. 8 parts), 1 part of polyvinyl butyral resin (trade name: Esrec BM-S, manufactured by Sekisui Chemical Co., Ltd.)
After mixing and mixing 20 parts of cyclohexanone and treating with glass beads for 1 hour using a paint shaker and dispersing the mixture, the obtained coating solution was used as an electron transporting material for the above-mentioned exemplified compound 227.
Was added, and the mixture was dispersed by treating with a paint shaker for 10 minutes. The obtained coating solution was applied by a dip coating method and dried by heating at 170 ° C. for 10 minutes to form an undercoat layer having a thickness of 3.0 μm. Then, 0.1 part of a hydroxygallium phthalocyanine crystal showing the powder X-ray diffraction pattern shown in FIG. After mixing with 10 parts of n-butyl and dispersing by treating with glass beads for 1 hour using a paint shaker, 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. Thus, a charge generation layer having a thickness of about 0.15 μm was formed.

Next, 2 parts of a charge transporting material represented by the following structural formula (2) and 3 parts of a polycarbonate resin composed of a structural unit represented by the following structural formula (3) were mixed with monochlorobenzene 2
0 parts, and the obtained coating solution was applied on the aluminum substrate on which the charge generation layer was formed by dip coating, and dried by heating at 120 ° C. for 1 hour to form a film having a thickness of 20 μm.
m of the charge transport layer was formed.

Embedded image (In the formula, Me means a methyl group.)

The electrophotographic characteristics of the electrophotographic photoreceptor thus obtained were measured using a laser printer modified scanner (XP-15 modified machine, manufactured by Fuji Xerox Co., Ltd.).
(1) In a normal temperature and normal humidity (20 ° C., 40% RH) environment, the battery is charged with a scorotron charger with a grid application voltage of −800 V (A), and after 1 second, 10.0 erg / cm ² using a 780 nm semiconductor laser. (B) Red LED of 50.0 erg / cm ² after 1 second
The potential of each part was measured by the process of irradiating light to remove electricity (C). The higher the potential VH in (A), the higher the potential of the photoreceptor, so that the contrast can be increased. The lower the potential VL in (B), the higher the sensitivity, and the lower the potential of VRP in (C). The smaller the residual potential, the less the image memory and the less fogging. In addition, the charge of each part was repeated 10,000 times, and the potential of each part after the exposure was measured. Also, a drum-type photoreceptor was manufactured under the same conditions, and this electrophotographic photoreceptor was used as a printer for a personal computer (trade name: PR1000, manufactured by NEC Corporation).
At room temperature and humidity (20 ° C, 40% RH).
A printing durability test was performed on 10,000 sheets to evaluate the image. Image evaluation was performed on the occurrence of black spots and the occurrence of afterimages (ghosts) due to dielectric breakdown. 5 m as the charging member at this time
An elastic layer and a resin layer formed on the outer periphery of a 18.8 stainless steel shaft having a diameter of mφ were used. That is, an elastic layer made of a polyether-based polyurethane rubber having an elasticity by adding 0.5% of lithium perchlorate to the outer periphery of the shaft is formed so as to have a thickness of 15 mm,
A coating solution composed of an aqueous solution of a polyester-based polyurethane emulsion resin to which a 01% methylphenylsilicone leveling agent is added is applied by a dip coating method.
For 20 minutes, and a roll-type charging member obtained by forming a coating layer having a thickness of 20 μm was used. Table 22 shows the results.

Examples 2 to 25 Electrophotographic photosensitive members were prepared and evaluated in the same manner as in Example 1 except that the materials shown in Table 18 were used as the electron transporting material and the charge generating material. The results are shown in Table 22. Comparative Examples 1 to 5 Example 1 was repeated except that the electron transporting material was not used.
Electrophotographic photosensitive members were prepared and evaluated in the same manner as in 8, 13, 17 and 21. The results are shown in Table 22.

In the following table, metal-free phthalocyanine is “H ₂ PC”, chlorogallium phthalocyanine is “ClGaPC”, hydroxygallium phthalocyanine is “HOGaPC”, dichlorotin phthalocyanine is “Cl ₂ SnPC”, and titanyl phthalocyanine is "T
"iOPC".

[0080]

[Table 22]

Example 26 Polyvinyl butyral resin (trade name: Eslec BM-
S, manufactured by Sekisui Chemical Co., Ltd.) 1 part was mixed and dissolved in 20 parts of cyclohexanone.
One part of the exemplified compound 227 was added. The obtained coating solution was applied on an aluminum pipe by a dip coating method, and was heated and dried at 170 ° C. for 10 minutes.
An undercoat layer of 0 μm was formed. Next, brominated dibromoanthanthrone (DBA) (trade name: Monolight Red 2) represented by the structural formula (1) is used as a charge generation material.
Y, I. C. I. 0.9 parts of polyvinyl butyral resin (trade name: Esrec BM-S, manufactured by Sekisui Chemical Co., Ltd.)
0.1 part and 10 parts of n-butyl acetate were mixed and treated with glass beads for 1 hour with a paint shaker and dispersed. The resultant was dried by heating at 10 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.5 μm.

Next, 2 parts of the charge transporting material represented by the structural formula (2) and 3 parts of the polycarbonate resin composed of the structural unit represented by the structural formula (3) were mixed with monochlorobenzene 2
0 parts, and the obtained coating solution was applied on the aluminum substrate on which the charge generation layer was formed by dip coating, and dried by heating at 120 ° C. for 1 hour to form a film having a thickness of 20 μm.
m of the charge transport layer was formed. The obtained electrophotographic photoreceptor was set in a copying machine (2700 copying machine manufactured by Fuji Xerox Co., Ltd.), and 5,000 under normal temperature and normal humidity (20 ° C., 40% RH) environment.
A print durability test was performed on the sheets to evaluate the image. The results are shown in Table 23.

Examples 27 to 28 Benzimidazole perylene pigments (Bz) comprising a mixture of the following structural formulas (4) and (5) as the charge generating material
P), a bisazo pigment represented by the following structural formula (6) (AZ
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 26 except that O) was used. The results are shown in Table 23.

Embedded image

Comparative Examples 6 to 8 Except that no electron transport material was used, Examples 26 to 2 were used.
An electrophotographic photoreceptor was prepared in the same manner as in No. 8 and evaluated. The results are shown in Table 23.

[Table 23]

Example 29 An aluminum pipe was placed on a support, and 10 parts of a zirconium compound (trade name: Organix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 1 part of a silane compound (trade name: A1110, manufactured by Nippon Unicar), and isopropanol 40 Part and a solution consisting of 20 parts of butanol were applied by a dip coating method, and dried by heating at 150 ° C. for 10 minutes.
m was formed. Next, as a charge generation material, 0.3 part of hydroxygallium phthalocyanine crystal showing the powder X-ray diffraction pattern shown in FIG. 6 was mixed with 0.7 part of polyvinyl butyral resin (trade name: Esrec BM-S, manufactured by Sekisui Chemical Co., Ltd.) and acetic acid After mixing with 10 parts of n-butyl and dispersing by treating with glass beads for 1 hour using a paint shaker, 0.2 part of Exemplified Compound 234 and a compound represented by the following structural formula (7) are added to the obtained coating solution. 0.5
Coating was then applied on the undercoat layer by dip coating, and dried by heating at 100 ° C. for 10 minutes.
A 0 μm photosensitive layer was formed.

Embedded image (In the formula, Me means a methyl group.)

The electrophotographic characteristics of the thus obtained electrophotographic photosensitive member were measured using a laser printer modified scanner (XP-15 modified machine, manufactured by Fuji Xerox Co., Ltd.).
(1) In a normal temperature and normal humidity (20 ° C., 40% RH) environment, charged by a scorotron charger with a grid applied voltage of 700 V (A), and after 1 second, 10.0 erg / cm ² was applied using a 780 nm semiconductor laser. Discharge by irradiating light (B) After 1 second, 50.0 erg / cm ² red LED
The potential of each part was measured by the process of irradiating light to remove electricity (C). The higher the potential VH in (A), the higher the potential of the photoreceptor, so that the contrast can be increased. The lower the potential VL in (B), the higher the sensitivity, and the lower the potential of VRP in (C). The smaller the residual potential, the less the image memory and the less fogging. In addition, the charge of each part was repeated 10,000 times, and the potential of each part after the exposure was measured. Further, a drum-type photoreceptor was prepared under the same conditions, and mounted on an XP-15 modified machine.
In a 0% RH environment, a print durability test was performed on 5000 sheets to evaluate the image. Table 24 shows the results.

Examples 30 to 33 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 29 except that the materials shown in Table 24 were used as the electron transporting material and the charge generating material. The results are shown in Table 24. Comparative Examples 9 to 13 Except that the electron transport material was not used, Examples 29 to 3 were used.
An electrophotographic photoreceptor was prepared in the same manner as in No. 3 and evaluated. The results are shown in Table 24.

[0088]

[Table 24]

Example 34 An aluminum pipe was placed on a support, and 10 parts of a zirconium compound (trade name: Organix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 1 part of a silane compound (trade name: A1110, manufactured by Nippon Unicar), and isopropanol 40 Part and a solution consisting of 20 parts of butanol were applied by a dip coating method, and heated and dried at 150 ° C. for 10 minutes to obtain a solution containing 0.1 μm.
m was formed. Next, 2 parts of the charge transporting material represented by the structural formula (2) and 3 parts of a polycarbonate resin composed of the structural unit represented by the structural formula (3) are dissolved in 20 parts of monochlorobenzene. Is applied on the aluminum pipe on which the undercoat layer is formed by a dip coating method, and dried by heating at 120 ° C. for 1 hour.
A charge transport layer having a thickness of 20 μm was formed. Next, as a charge generation material, 0.1 part of hydroxygallium phthalocyanine crystal showing the powder X-ray diffraction pattern shown in FIG. 6 was added to a polyvinyl butyral resin (trade name: Eslec BM-
S, manufactured by Sekisui Chemical Co., Ltd.) and mixed with 0.1 part of n-butyl acetate and treated with glass beads for 1 hour using a paint shaker, and then dispersed. The resultant was applied by a coating method and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 1 μm.

Then, 0.4 parts of the above exemplified compound 220
And a silicon hard coat material (X-40-2239,
After mixing 0.5 part with Shin-Etsu Chemical Co., Ltd. and 3 parts of n-butyl ether, the obtained coating solution was applied on the charge generation layer by a dip coating method, and heated and dried at 100 ° C. for 10 minutes. A protective layer having a thickness of about 2 μm was formed. The obtained electrophotographic photoreceptor was mounted on an XP-15 modified machine, and a printing durability test of 5,000 sheets was performed in an environment of normal temperature and normal humidity (20 ° C., 40% RH) to evaluate an image. Table 25 shows the results.

Examples 35 to 38 Electrophotographic photosensitive members were produced and evaluated in the same manner as in Example 34 except that the materials shown in Table 25 were used as the electron transporting material and the charge generating material. The results are shown in Table 25. Comparative Examples 14 to 18 Electrophotographic photosensitive members were produced and evaluated in the same manner as in Examples 34 to 38 except that the protective layer was not formed. The results are shown in Table 25.

[0092]

[Table 25]

Example 39 An aluminum pipe having a honing treatment (outer diameter 30
mm) on a zirconium compound (Organotics ZC
540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts, silane compound (A
1110, manufactured by Nippon Unicar Co., Ltd.) and a solution composed of 40 parts of isopropanol and 20 parts of butanol were 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. . A part of chlorogallium phthalocyanine having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 ° and 28.3 ° in the X-ray diffraction spectrum was converted to polyvinyl butyral. (Eslec BM-S, manufactured by Sekisui Chemical Co., Ltd.) 1 part and n-butyl acetate 100 parts,
After treating and dispersing with a glass shaker for 1 hour using a paint shaker, the obtained coating solution was dip-coated on the undercoat layer, and heated and dried at 100 ° C. for 10 minutes to obtain a film thickness of about 0.1 μm.
A 15 μm charge generation layer was formed. The exemplified compound (II
I-27) A high molecular compound (viscosity average molecular weight: 39,000) comprising 2 parts of a structural unit represented by the structural formula (3)
A coating solution in which 3 parts were dissolved in 20 parts of a chlorobenzene compound was applied on 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. Then, 10 of Exemplified Compound 227
Parts, curable siloxane resin (X-40-2239, manufactured by Shin-Etsu Silicon Co., Ltd.), 20 parts, phenyltriethoxysilane 3
Parts of acetic acid and 1 part of acetic acid, spray-coated on the charge transport layer, and dried by touching for 30 minutes.
Heat treatment was performed at 20 ° C. for 60 minutes to form a surface protective layer having a thickness of 5 μm.

Comparative Example 19 An electrophotographic photosensitive member was obtained in the same manner as in Example 39 except that no surface protective layer was provided. Comparative Example 20 An electrophotographic photoreceptor was obtained in the same manner as in Example 39 except that methyltrimethoxysilane was used instead of Exemplified Compound 227 when forming the surface protective layer. This compound had neither an electron transporting property nor a hole transporting property, and only formed a siloxane-based crosslinked film.

(Evaluation) The electrophotographic photosensitive member obtained as described above was used in an electrophotographic image forming apparatus (Laser Pr).
(Ess 4160II modified machine, manufactured by Fuji Xerox Co., Ltd.), and a printing durability test was performed. This modified 4160II 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 connected to an external power supply. The applied voltage to the charging roll is -450 V unless otherwise specified.
And a DC voltage of 800 Hz / 1.7 kVpp was superimposed on the DC voltage. 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 film thickness of the electrophotographic photosensitive member due to abrasion. The image quality evaluation was performed using an 8-bit gradation pattern and a 400 dpi resolution pattern. The results are shown in Table 26 below. When the electrophotographic photosensitive member of Example 39 was used, no serious problem was found in the image quality evaluation at the initial stage and after printing 50,000 sheets. Comparative Example 19
In the case of using the electrophotographic photoreceptor of No. 1, streaky image defects frequently occurred in the printed image after printing 50,000 sheets. The surface of the photoreceptor has a large number of streaky scratches, which are considered to be caused by friction with the cleaning blade, and this is considered to be the cause of image defects. In the case of Comparative Example 20, the image density was low from the beginning.

[0096]

[Table 26]

Example 40 Instead of chlorogallium phthalocyanine in Example 39, the Bragg angle (2θ
± 0.2 °) 7.5 °, 9.9 °, 12.5 °, 16.
An electrophotographic photoreceptor was prepared in exactly the same manner except that hydroxygallium phthalocyanine having a specific crystal form having strong diffraction peaks at 3 °, 18.6 °, 25.1 °, and 28.3 ° was used. Examples 41 to 43 Instead of chlorogallium phthalocyanine in Example 39, except that X-type metal-free phthalocyanine, dichlorotin phthalocyanine and titanyl phthalocyanine were used,
An electrophotographic photosensitive member was produced in exactly the same manner.

Examples 44 to 46 In the same manner as in Example 39, an undercoat layer and a charge generation layer were formed on an aluminum pipe. Next, 2 parts of the exemplified compound (III-27) and 2 parts of the exemplified compound (IV-28)
Of a polymer compound (viscosity average molecular weight 39,000) consisting of 4 parts of a structural unit represented by the structural formula (3) in 20 parts of chlorobenzene was applied on the charge generating layer by a dip coating method. Then, heating was performed at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.
Next, in place of the exemplary compound 227 used for forming the surface protective layer in Example 39, the exemplary compounds 220 and 23 were used.
0 and 234 respectively to form a surface protective layer,
An electrophotographic photosensitive member was manufactured.

The electrophotographic photosensitive members obtained in Examples 40 to 46 were evaluated in the same manner as described above. The results are shown in Table 27 below.

[Table 27] As is clear from the results in Table 27 above, all the electrophotographic photosensitive members had good image quality characteristics before and after printing. In addition, even when the surface of the electrophotographic photosensitive member was observed, generation of a large scratch or the like was not required.

Comparative Example 21 An electrophotographic photoreceptor was prepared in the same manner as in Example 39 except that a compound represented by the following structural formula (8) was used instead of the compound 227 when forming the surface protective layer. Was prepared. This compound has a hole transporting property, not an electron transporting property.

[0101]

Embedded image (However, Me means a methyl group.)

Example 39, Examples 44 to 46, Comparative Example 1
The electrophotographic photoreceptors in Nos. 9 to 21 were mounted on an electrophotographic image forming apparatus (Laser Press 4160II modified machine, manufactured by Fuji Xerox Co., Ltd.), and evaluated in the same manner as described above. However, the voltage applied to the charging roll is DC-
450 V was used. The results are shown in Table 28 below.

[0103]

[Table 28] Since the electrophotographic photoreceptors of Examples 39 and 44 to 46 also correspond to contact charging (negative charging) using only DC, there was no problem in initial image evaluation. Further, there was no problem in the image evaluation after printing 50,000 sheets, and no significant damage was observed by the silent observation of the electrophotographic photosensitive member surface. On the other hand, Comparative Example 19
As for the initial image quality when the electrophotographic photosensitive members of Nos. 1 to 21 were used, image unevenness due to non-uniform charging was severe. Therefore, the subsequent printing test was not performed. The reason for this is that the surface protective layer in these electrophotographic photosensitive members does not support negative contact charging.

[0104]

According to the present invention, since the compound represented by the above general formula (I) is contained as an electron transporting material to form a layer, the compound is dissolved in a coating solvent at the time of coating and dissolved in a solvent after the film is formed. A strong electron-transporting film is formed. Therefore, the electrophotographic photoreceptor of the present invention has environmental stability, as is clear from the comparison between the above Examples and Comparative Examples.
Excellent long-term durability, no dielectric breakdown due to contact charging,
A ghost does not occur due to use in an erase-less machine, and an image with excellent image quality can be created for a long time.

Further, the electrophotographic photoreceptor of the present invention is provided with a surface protective layer having a cross-linking structure on the surface of the photoreceptor, and is resistant to scratches and abrasion when combined with an image forming apparatus using contact charging. Shows printing durability. Further, since the surface protective layer of the electrophotographic photoreceptor of the present invention has an electron transporting property, the charged negative charges do not directly ride on the photoreceptor surface, so that the deterioration of photoelectric characteristics and image characteristics does not easily occur. . Further, since the electrophotographic image forming apparatus of the present invention also supports contact charging (negative charging) using only DC, generation of ozone and the like is small.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of an electrophotographic photosensitive member of the present invention.

FIG. 2 is a view showing a powder X-ray diffraction pattern of a hydroxygallium phthalocyanine crystal used in Examples.

FIG. 3 is a schematic configuration diagram of an example of the electrophotographic image forming apparatus of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Undercoat layer, 2 ... Charge generation layer, 3 ... Charge transport layer, 4 ...
Conductive support, 5: protective layer, 6: charge generation / charge transport layer, 11: charging roll, 12: laser exposure optical system, 1
3 ... Developer, 14 ... Transfer roll, 15 ... Light source for static elimination,
16 cleaning blade, 17 fixing roll, 1
8 Paper.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03G 5/147 504 G03G 5/147 504

Claims (8)

[Claims] 1. An electrophotographic photoreceptor comprising a conductive support and a layer containing at least one compound represented by the following general formula (I) provided on the conductive support. A- (CH ₂ ) _a- (L) _b- (CH ₂ ) _c -SiR _{1 (3-n)} (OR ₂ ) _n (I) wherein A represents the following general formulas (A-1) to (A-1) A-8) a group having an electron transporting property represented by the formula: Wherein R ₃ and R ₄ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group or a cyano group; = O, = C (CN) ₂ , = C each independently
(CO ₂ R ₅ ) ₂ , ＝ N—CN or ＮN—Ar (where R ₅ represents an alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group; Represents an unsubstituted aryl group), and Y is -O-, -C
(= X ′) — or —SO ₂ — (where X ′ has the same meaning as described above), and r and p each independently represent 0, 1, 2 or 3. ] L is _{-CONH -, - CO 2 -,} - NH- or -O-
R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom.
Represents 4 to 3 trialkylsilyl groups, and a and c represent 1 to
Represents an integer of 10, b represents 0 or 1, n is 1
Means an integer of ｝ 2. The method according to claim 1, wherein the layer containing the compound represented by the general formula (I) is an undercoat layer provided between the conductive support and the photosensitive layer. 2. The electrophotographic photoreceptor of claim 1. 3. The electrophotographic photoreceptor according to claim 1, wherein the layer containing the compound represented by the general formula (I) is an outermost surface layer. 4. The method according to claim 1, wherein a layer containing an anthantrone pigment, a perylene pigment, an azo pigment or a phthalocyanine pigment is provided as the charge generating material. Electrophotographic photoreceptor. 5. The method according to claim 1, wherein the charge generation material is a metal-free phthalocyanine,
5. The electrophotographic photoreceptor according to claim 4, wherein the photoreceptor is chlorogallium phthalocyanine, hydroxygallium phthalocyanine, dichlorotin phthalocyanine, or titanyl phthalocyanine. 6. An electrophotographic image forming apparatus having an electrophotographic photoreceptor and a charging means of a contact charging type for initially charging the photoreceptor negatively, wherein the electrophotographic photoreceptor has a charge generation layer on a conductive support, It has a hole transporting charge transporting layer and a surface protective layer, and the surface protective layer is a crosslinked film containing an electron transporting compound or a crosslinked film containing a structural unit having an electron transporting property. Electrophotographic image forming apparatus. 7. An electrophotographic image forming apparatus according to claim 6, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1. 8. The electrophotographic image forming apparatus according to claim 6, wherein the charging means of the contact charging system is based on the application of a DC voltage.