JP3336846B2 - Electrophotographic photoreceptor - 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 having high sensitivity and high reliability. More specifically, the present invention relates to an electrophotographic photosensitive member having a cured film formed using an organometallic compound and an electron-accepting compound as an undercoat layer.

[0002]

2. Description of the Related Art An electrophotographic apparatus has high speed and high printing quality, and is used in fields such as a copying machine and a laser beam printer. As a photoconductor used in an electrophotographic apparatus, an organic photoconductor (OPC) using an organic photoconductive material has been developed and widely used. In addition, the structure of the photoconductor is changed from a single-layer photoconductor in which a charge transfer complex structure or a charge generation material is dispersed in a binder resin to a function separation type photoconductor in which a charge generation layer and a charge transport layer are separated. And changed,
Performance has improved. In this function separation type photoreceptor,
At present, a structure in which an undercoat layer is formed on an aluminum substrate first, and then a charge generation layer and a charge transport layer are formed is mainly used. With the progress of electrophotographic apparatuses, higher quality image quality has been demanded for the performance of photoconductors. For improvement of photoreceptor repetition stability and environmental stability, the charge generation layer, charge transport layer, and undercoat layer are all important for each of electrophotographic characteristics such as sensitivity, image quality, and repetition stability. Have an effect.

Conventionally, formation of an undercoat layer or an intermediate layer using a curable compound which undergoes polycondensation by hydrolysis of an organometallic compound has been disclosed in, for example, JP-A-59-224.
No. 38, No. 61-94057, JP-A No. 2-5
Nos. 9767, 3-18858 and 4-12
No. 4674, No. 4-145416, No. 4-1
It is described in, for example, JP-A-62047, and is known.

[0004]

Among the carriers generated in the charge generation layer, holes move in the charge transport layer and recombine with the charges on the surface, but electrons move in the undercoat layer and move on the substrate. Need to recombine with the induced charge. However, when the electron transport property in the undercoat layer is low, the electrons remain localized in the undercoat layer or at the interface with the charge generation layer, and when the photoconductor is used repeatedly, the residual potential increases. And image quality defects occur. Therefore, it is necessary to impart high electron transportability to the undercoat layer. However, when an undercoat layer is formed using a coating liquid for forming an undercoat layer in which a low-molecular-weight electron-transporting material such as trinitrofluorenone or a diphenoquinone-based compound is dissolved in a polymer binder resin, charge generation in the upper layer is generated. Low molecular weight components elute during the formation of the layer and the charge transport layer,
It often mixes with the upper layer to cause secondary obstacles in electrical characteristics or to impair the uniformity of the coating film. Also,
In the case of an electrophotographic photoreceptor having an undercoat layer formed using the above-mentioned curable compound, the electrophotographic photoreceptor was not sufficiently satisfactory in electrical characteristics.

[0005] The present invention has been made to solve the above-mentioned problems in the prior art. Therefore, an object of the present invention is to provide an electrophotographic photoreceptor having an improved undercoat layer and having excellent sensitivity, image quality and repetition stability.

[0006]

Means for Solving the Problems In view of the above points, the present inventor has studied an undercoat layer having higher sensitivity, image quality and repetition stability, and as a result, it has a specific electron accepting compound. The inventors have found that the above object can be achieved by using a cured film containing an organometallic compound as an undercoat layer, and have completed the present invention. That is, the electrophotographic photoreceptor of the present invention is obtained by sequentially laminating a charge generation layer and a charge transport layer on a conductive support, wherein an organometallic compound and a charge generating layer are provided between the conductive support and the charge generation layer. One or both of a silane coupling agent and a benzoquinone,
Fluorenones, diphenoquinones and 4- (butoki)
From (carbonyl) -9-dicyanomethylenefluorene
It has a cured film formed of the selected electron-accepting compound and a binder resin as an undercoat layer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a laminated electrophotographic photosensitive member of the present invention will be described in detail. As the conductive support, in addition to metals such as copper, aluminum, nickel, and iron, plastic or paper that has been subjected to a conductive treatment by evaporating a metal on the surface or forming a coating film in which a conductive powder is dispersed is used. The formed tubular, belt-like, and sheet-like substrates can be used. In order to prevent interference fringes, the surface of the conductive support can be subjected to a surface roughening treatment using a method such as etching, anodic oxidation, wet blasting, sand blasting, rough cutting, and centerless grinding. .

[0008] An undercoat layer is formed on the surface of the conductive support for the purpose of stabilizing electrical characteristics, preventing image quality defects, improving chargeability and improving adhesion. The pulling layer is a cured film formed of one or both of an organometallic compound and a silane coupling agent, an electron-accepting compound, and a binder resin. In the undercoat layer,
By performing the curing treatment using an organometallic compound or a silane coupling agent, the low-molecular-weight electron-accepting compound is prevented from being eluted at the time of coating the upper layer, and a more stable and excellent electrophotographic photoreceptor can be formed. . In addition, when an organometallic compound or a silane coupling agent is used, excellent electrophotographic properties that cannot be obtained without using them in combination can be obtained. In addition, excellent electrophotographic characteristics such as high light attenuation and low residual potential in the electrophotographic photoreceptor of the present invention cannot be obtained by using other curable resins.

The following compounds can be used as the electron-accepting compound for use in the undercoat layer of the present invention. Sand <br/> I Chi, o - benzoquinone, p- benzoquinone, methoxy benzoquinone, 2,3-dimethoxy-5-methyl-1,
Benzoquinones such as 4-benzoquinone, 2,3-dichloro-5,6-dicyano-p-benzoquinone, quinhydrone
And 3,3 ', 5,5'-tetra-tert-butyl-
4,4'-diphenoquinone, 3,5'-di-tert-
Butyl-3 ', 5-diphenyl-4,4'-diphenoquinone, 3,5-dimethyl-3', 5'-di-tert-
Butyl-4,4'-diphenoquinone, 3,5'-diphenyl-3 ', 5-di-tert-butyl-4,4'-diphenoquinone, 3,5-dimethoxy-3', 5'-di-
tert-butyl-4,4'-diphenoquinone, 3,
3 ', 5,5'-tetra-t-butyl-4,4'-diphenoquinone, 3,5'-bis (α, α, γ, γ-tetramethylbutyl) -3', 5-di (α- Methylpropyl)
-4,4'-diphenoquinone, 3,5-bis (α, α,
γ, γ-tetramethylbutyl) -3 ′, 5′-di (α-
Methylpropyl) -4,4'-diphenoquinone, 3,
5'-bis (α, α, γ, γ-tetramethylbutyl)-
3 ', 5-diphenyl-4,4'-diphenoquinone,
3,5'-bis (α, γ-dimethylbutyl) -3 ', 5
-Diphenyl-4,4'-diphenoquinone, 3,5'-
Bis (α-dimethylbenzyl) -3 ′, 5-di (α-methylpropyl) -4,4′-diphenoquinone, 3,5-
Bis (α-dimethylbenzyl) -3 ′, 5′-di (α-
Methylpropyl) -4,4'-diphenoquinone, 3,
5'-bis (α-dimethylbenzyl) -3 ', 5-dimethyl-4,4'-diphenoquinone, 3,5-bis (α-
Dimethylbenzyl) -3 ', 5'-dimethyl-4,4'
-Diphenoquinone, 3,5-dimethoxy-3 ', 5'-
Di-tert-butyl-4,4'-diphenoquinone,
3,3'-dimethoxy-5,5'-di-tert-butyl-4,4'-diphenoquinone, 3,5-diethoxy-
3 ', 5'-di-tert-butyl-4,4'-diphenoquinone, 3,3'-diethoxy-5,5'-di-te
diphenoquinones such as rt-butyl-4,4'-diphenoquinone; 2,4,7-trinitro-9-fluorenone (TNF), 2,4,5,7-tetranitro-9-fluorenone, 2,4,7- Trinitro-9-dicyanomethylene fluorenone, 2- (1,1-dimethoxybutyl)
Fluorenones such as -4,5,7-trinitro-9-fluorenone, 2-hydroxy-9-fluorenone ;
(Butoxycarbonyl) -9-dicyanomethylene fluoride <br/> les emissions; can have use of.

[0010] When the structure has one or more hydrolytic polymerizable substituents, a coating film having more curability is formed. As the hydrolyzable polymerizable group,
Methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, t-butoxy group, an alkoxyl group such as hexyl group, and a hydroxyl Ru mentioned.

In the undercoat layer of the present invention, one or both of an organometallic compound and a silane coupling agent are used in combination with the above-mentioned electron accepting compound. These compounds can be used alone or as a mixture or a polycondensate of a plurality of compounds. Among them, zirconium-containing organic compounds or silane coupling agents are excellent in performance, such as having high film-forming properties, low residual potential, small potential change due to environment, and small potential change due to repeated use.

The organometallic compound which can be used in the present invention includes an organometallic compound containing zirconium, titanium, aluminum, manganese and the like. The following are illustrated as specific examples thereof.
Examples of organic zirconium compounds include zirconium butoxide, ethyl zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl zirconium butoxide acetoacetate, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, Examples include zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, zirconium butoxide methacrylate, zirconium butoxide stearate, zirconium butoxide isostearate, and the like.

Examples of the organic titanium compound include tetraisopropyl titanate, tetra-normal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium Lactate, titanium lactate ammonium salt, titanium lactate ethyl ester, titanium triethanol aminate, polyhydroxytitanium stearate and the like can be mentioned.

Examples of the organoaluminum compound include aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, diethylacetoacetate, aluminum diisopropylate, aluminum tris (ethylacetoacetate) and the like.

The organometallic compounds containing zirconium, titanium, aluminum and silicon shown herein are compounds having a hydrolytic condensation property, and a cured coating film is obtained by humidifying treatment in the curing step. Can be

Examples of the silane coupling agent include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-β- (methoxyethoxysilane),
γ-methacryloxypropyltrimethoxysilane, γ
-Methacryloxypropyl-tris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β
-Aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane,
N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Chloropropyltrimethoxysilane and the like can be mentioned. Among these, a silane compound that is particularly preferably used is
Vinyltriethoxysilane, vinyltris-β- (methoxyethoxysilane), γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ -Aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane,
N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Chloropropyltrimethoxysilane and the like.

The amount of the electron accepting compound is from 0.1 to 98% by weight, preferably from 5 to 90% by weight, based on the total amount of the electron accepting compound, the organometallic compound and the silane coupling agent.

As the binder resin used for the undercoat layer,
Acetal resin such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride High molecular compounds such as strong acid resin, silicone resin, silicone alkyd resin, phenol formaldehyde resin, and melamine resin can be used. The binder resin is 1 to 9 with respect to the total solid content of the undercoat layer.
It can be used in a range of 5% by weight, preferably 5 to 90% by weight.

In the undercoat layer, various organic or inorganic fine powders can be mixed for the purpose of preventing interference fringes and improving electrical characteristics. In particular, white pigments such as titanium oxide, zinc oxide, zinc white, zinc sulfide, lead white, and lithopone; extender pigments such as alumina, calcium carbonate, and barium sulfate; or Teflon resin particles, benzoguanamine resin particles, and styrene resin particles are effective. It is. When blending the fine powder, it can be blended in a range of up to 90% by weight. The particle size of the fine powder to be added is 0.01 μm to 2 μm
Are preferred. If the particle size is too large, the undercoat layer will have severe irregularities and electrical non-uniformity will be large, and image quality defects will easily occur. If the particle diameter is too small, a sufficient light scattering effect cannot be obtained.

In general, when the thickness of the undercoat layer is increased, the concealing property of the unevenness of the base material is enhanced, so that the image quality defect tends to decrease, but the electrical repetition stability also deteriorates. Therefore, the thickness of the undercoat layer is preferably in the range of 0.1 to 5 μm. The undercoat layer in the present invention becomes a hard cured film that does not dissolve when the upper layer is formed with the coating liquid by undergoing a drying and curing treatment after the application. Usually, the curing treatment by drying the undercoat layer is performed at a temperature in the range of 40 ° C. to 200 ° C. for 3 minutes to 8 hours. By performing the reaction of the hydrolyzable reactive group used in the present invention more strongly, better electrical stability and image quality can be obtained, but in order to more reliably advance the hydrolysis reaction,
Humidification treatment may be added during the drying step. The humidification treatment is performed by applying wet hot air to the coating film surface. It is desirable that the temperature of the hot humid air used at that time is between 30 and 180 ° C.

The charge generation layer provided on the undercoat layer is
The charge generation material is formed by vacuum evaporation or by dispersing and applying the charge generation material together with an organic solvent and a binder resin. As the charge generation material, amorphous selenium, crystalline selenium, selenium-tellurium alloy, selenium-arsenic alloy, other selenium compounds and selenium alloys, zinc oxide, inorganic photoconductors such as titanium oxide, metal-free phthalocyanine, Various organic pigments and dyes such as titanyl phthalocyanine, copper phthalocyanine, tin phthalocyanine, various phthalocyanine pigments such as gallium phthalocyanine, squarium-based, anthrone-based, perylene-based, azo-based, anthraquinone-based, pyrene-based, pyrylium-salt, and thiapyrylium-salt. Used. In addition, these organic pigments generally have several types of crystal forms, and particularly in the case of phthalocyanine pigments, α
Various crystal types are known, including a type, a β type, etc., and any of these crystal types can be used as long as the pigment can obtain the sensitivity according to the purpose. In the charge generation layer, a silane coupling agent or an organometallic alkoxide can be used for various purposes such as preventing aggregation of the charge generation material, improving dispersibility, and improving electrical characteristics. When these are added, the surface of the charge generating material may be treated in advance with these, and then the dispersion treatment may be performed, or a silane coupling agent or an organometallic alkoxide may be added to the coating solution.

The following can be exemplified as the binder resin in the charge generation layer. For example, polycarbonate resin such as bisphenol A type or bisphenol Z type, polyester resin, methacrylic resin,
Acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, silicone resin, silicone -Alkyd resins, phenol-formaldehyde resins, styrene-alkyd resins, poly-N-vinylcarbazole and the like. These binder resins can be used alone or in combination of two or more. The mixing ratio (weight ratio) of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10. Further, the thickness of the charge generation layer is generally 0.0
It is set in the range of 1 to 5 μm, preferably 0.05 to 2.0 μm.

As a method for dispersing the charge generating material in the resin, a method using a roll mill, a ball mill, a vibration mill, an attritor, a sand mill, a colloid mill or the like can be adopted. The solvent used at that time is methanol. ,
Alcohols such as ethanol, propanol and n-butyl alcohol, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane, etc. can give.

The charge transport layer is provided on the charge generation layer. The charge transport layer is composed of a charge transport material and, if desired, a binder resin. Examples of the charge transporting material used for the charge transporting layer include the following. 2,5-
Oxadiazole derivatives such as bis (p-diethylaminophenyl) -1,3,4-oxadiazole;
5-triphenyl-pyrazoline, 1- [pyridyl-
(2)]-3- (p-Diethylaminostyryl) -5-
Pyrazoline derivatives such as (p-diethylaminostyryl) pyrazoline, aromatic compounds such as triphenylamine, tri (p-methylphenyl) amine, N, N-bis (3,4-dimethylphenyl) biphenyl-4-amine and dibenzylaniline Group tertiary amino compounds, N, N'-diphenyl-
Aromatic tertiary diamino compounds such as N, N'-bis (3-methylphenyl)-[1,1-biphenyl] -4,4'-diamine; 3- (4'-dimethylaminophenyl)-
5,6-di (4'-methoxyphenyl) -1,2,4-
1,2,4-triazine derivatives such as triazine, hydrazone derivatives such as 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, quinazoline derivatives such as 2-phenyl-4-styryl-quinazoline, 6-hydroxy-2,3- Benzofuran derivatives such as di (p-methoxyphenyl) -benzofuran, α-stilbene derivatives such as p- (2,2-diphenylvinyl) -N, N-diphenylaniline, enamine derivatives, carbazole derivatives such as N-ethylcarbazole, Hole transport substances such as poly-N-vinylcarbazole and its derivatives. Chloranil,
Quinone compounds such as bromoanil and anthraquinone, tetracyanoquinodimethane compounds, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitro-9
-Electron transport substances such as fluorenone compounds such as fluorenone, xanthone compounds, thiophene compounds and diphenoquinone compounds. Further, a polymer or the like having a group consisting of the above-described compound in the main chain or side chain can also be used.
The above charge transport materials can be used alone or in combination of two or more.

Examples of the binder resin used for the charge transport layer include acrylic resin, polyarylate, polyester resin, bisphenol A type and bisphenol Z.
Polycarbonate resin, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-
Examples thereof include insulating resins such as butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone, polyacrylamide, polyamide, and chlorine rubber, and organic photoconductive polymers such as polyvinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene.

The charge transport layer can be formed by applying and drying a solution in which the above-described charge transport material and binder resin are dissolved in a suitable solvent. As the solvent used for forming the charge transport layer, for example, benzene, toluene, aromatic hydrocarbons such as chlorobenzene,
Ketones such as acetone and 2-butanone, methylene chloride,
Halogenated aliphatic hydrocarbons such as chloroform and ethylene chloride, cyclic or straight-chain ethers such as tetrahydrofuran, dioxane, ethylene glycol and diethyl ether, or a mixed solvent thereof can be used. The compounding ratio of the charge transport material and the binder resin is 10: 1.
１ ： 1: 5 is preferred.

An antioxidant, a light stabilizer, a heat stabilizer and the like are added to the charge transport layer for the purpose of preventing deterioration of the photoreceptor due to ozone or oxidizing gas generated in the electrophotographic apparatus, or light or heat. Agents 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, an electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue when repeatedly used. Examples of the electron-accepting substance that can be used in the electrophotographic photoreceptor of the present invention include, for example, succinic anhydride, maleic anhydride,
Dibromo maleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoate Acid, p
-Nitrobenzoic acid, phthalic acid and the like.
Among them, fluorenone type, quinone type, Cl, C
A benzene derivative having an electron-withdrawing substituent such as N or NO ₂ can be particularly preferably used.

The coating can be performed by using a coating method such as a dip coating method, a spray coating method, a bead coating method, a blade coating method, and a roller coating method. Heat drying is 30 ° C ~
It is desirable to carry out at a temperature of 200 ° C. for a time ranging from 5 minutes to 2 hours. The thickness of the charge transport layer is generally 5 to 50 μm.
m, preferably in the range of 10 to 40 μm.

On the charge transport layer, a surface protective layer can be formed if necessary. As the surface protective layer, there is an insulating resin protective layer or a low resistance protective layer in which a resistance adjusting agent is added to the insulating resin. In the case of a low resistance protective layer,
For example, there is a layer in which conductive fine particles are dispersed in an insulating resin. As the conductive fine particles, the electric resistance is 10 ⁹ Ω ·
cm or less and fine particles having an average particle size of 0.3 μm or less, preferably 0.1 μm or less, exhibiting white, gray or bluish white are preferably used. For example, molybdenum oxide, tungsten oxide, antimony oxide, tin oxide, titanium oxide, indium oxide, a solid solution of tin oxide and antimony or antimony oxide, or a mixture thereof, or a mixture of these metal oxides in a single particle And coated ones. Among them, tin oxide, a solid solution of tin oxide and antimony or antimony oxide,
It is preferably used because the electric resistance can be appropriately adjusted and the protective layer can be made substantially transparent (JP-A-57-30847, JP-A-57-128344). Reference). Examples of the insulating resin include condensation resins such as polyamide, polyurethane, polyester, epoxy resin, polyketone, and polycarbonate, and vinyl polymers such as polyvinylketone, polystyrene, and polyacrylamide.

The electrophotographic photoreceptor of the present invention is used in electrophotographic devices such as light lens type copiers, laser beam printers emitting near infrared light or visible light, digital copiers, LED printers, and laser facsimile machines. be able to. Further, the electrophotographic photoreceptor of the present invention can be applied to a system using either a one-component or two-component regular developer or a reversal developer. In addition, the electrophotographic photoreceptor of the present invention has good characteristics with little current leakage even when a contact charging method using a charging roller, a charging brush or the like is applied.

[0032]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Example 1 3 parts by weight of a polyvinyl butyral resin (Eslec BM-S manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 10 parts by weight of toluene, and further 3,3 ', 5,5'-tetra-t-butyl-4,
5 parts by weight of 4'-diphenoquinone was dissolved. To this solution, 40 parts by weight of a 50% by weight solution of an organic zirconium compound (zirconium tetrabutyrate) in toluene was added dropwise, stirred and mixed, and filtered to obtain a coating liquid for forming an undercoat layer. This coating liquid was treated with a liquid
Ring coating is performed on an aluminum substrate having a diameter of mmφ, and is air-dried at room temperature for 5 minutes.
After drying and curing for 0 minutes, an undercoat layer having a thickness of 1 μm was formed.

A mixture comprising 15 parts by weight of gallium chloride phthalocyanine as a charge generation material, 10 parts by weight of a vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nippon Unicar), and 300 parts by weight of n-butyl alcohol was subjected to a sand mill. Time dispersed. The obtained dispersion was dip-coated on the undercoat layer and dried to form a 0.2 μm-thick charge generation layer. Next, N, N'-diphenyl-N,
4 parts by weight of N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine and 6 parts by weight of a bisphenol Z polycarbonate resin (molecular weight of 40,000) are mixed with 80 parts by weight of chlorobenzene. In addition, it dissolved. The resulting solution was applied and dried to form a 20 μm-thick charge transport layer, thereby producing a three-layer electrophotographic photosensitive member. The obtained electrophotographic photosensitive member was charged at -700 V using an electrical property evaluation device, and then exposed at a predetermined light amount to measure the potential. Table 1 shows the results.

Comparative Example 1 3 parts by weight of a polyvinyl butyral resin was dissolved in 10 parts by weight of toluene, and 43 parts by weight of a 50% by weight solution of an organic zirconium compound (zirconium tetrabutyrate) in toluene was added dropwise, stirred, mixed, and filtered. Thus, a coating liquid for forming an undercoat layer was obtained. An electrophotographic photoreceptor comprising an undercoat layer, a charge generation layer and a charge transport layer was prepared by the method shown in Example 1 using this coating solution. Table 1 shows the results of the electrical characteristics evaluated using the obtained electrophotographic photosensitive member.

Comparative Example 2 3 parts by weight of polyvinyl butyral resin was dissolved in 10 parts by weight of toluene, and 3,3 ', 5,5'-tetra-t was further dissolved.
5 parts by weight of -butyl-4,4'-diphenoquinone was dissolved and filtered to obtain a coating liquid for forming an undercoat layer. Using this coating solution, an electrophotographic photoreceptor comprising an undercoat layer, a charge generation layer and a charge transport layer was prepared by the method shown in Example 1. Table 1 shows the results of the electrical characteristics evaluated using the obtained electrophotographic photosensitive member.

Comparative Example 3 The binder resin was changed to 3 parts by weight of a resole phenol resin (Plyofen J-325, manufactured by Dainippon Ink and Chemicals, Inc.) and dissolved in 10 parts by weight of n-butyl alcohol.
Without using an organic metal compound, 5 parts by weight of 3,3 ', 5,5'-tetra-t-butyl-4,4'-diphenoquinone was dissolved and filtered to obtain a coating liquid for forming an undercoat layer. . An electrophotographic photoreceptor comprising an undercoat layer, a charge generation layer and a charge transport layer was prepared by the method shown in Example 1 using this coating solution. Table 1 shows the results of the electrical characteristics evaluated using the obtained electrophotographic photosensitive member.

[0037]

[Table 1]

Example 2 10 parts by weight of cyclohexanone was dissolved in 3 parts by weight of a polyvinyl butyral resin (ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.), and 2,3-dimethoxy-5-methyl-1,2
5 parts by weight of 4-benzoquinone was dissolved. To the resulting solution, an organic zirconium compound (A cetyl acetone zirconium butyrate) and 50 wt% toluene solution 42 parts by weight of the mixture was dissolved by stirring to obtain a coating liquid for forming an undercoat layer was filtered. The coating liquid onto the Aluminum bromide substrate 30 mm?, Thickness after drying was coated so that 1 [mu] m, 1
After drying and curing at 70 ° C. for 10 minutes, an undercoat layer was formed. 15 parts by weight of titanyl phthalocyanine, which is a charge generation material, and polyvinyl butyral resin (S-lec BM-
S, manufactured by Sekisui Chemical Co., Ltd.) and a mixture comprising 10 parts by weight of n-butyl alcohol and 300 parts by weight of n-butyl alcohol was subjected to dispersion treatment in a sand mill for 4 hours. The resulting dispersion was applied on the undercoat layer and dried to form a 0.2 μm-thick charge generation layer. Next, a charge transport material tri (p- methylphenyl) amine 90 parts by weight, Porika Bo sulphonate resin (C-1
400, 100 parts by weight of Teijin Chemicals Ltd.), 0.002 parts by weight of silicone oil (KF-54, manufactured by Shin-Etsu Chemical Co., Ltd.), and 870 parts by weight of tetrahydrofuran to prepare a coating solution for a charge transport layer. The resultant was applied and dried to form a charge transport layer having a thickness of 24 μm, thereby producing an electrophotographic photosensitive member having three layers. The obtained electrophotographic photosensitive member was charged at -700 V using an electrical property evaluation device, and then exposed at a predetermined light amount to measure the potential. Table 2 shows the results.

Examples 3 to 9 In Example 2, 2,3-dimethoxy-5-methyl-
An electrophotographic photoreceptor was prepared in the same manner as in Example 2 except that the mixture shown in Table 2 was used instead of 1,4-benzoquinone, and evaluation was performed in the same manner. Table 2 shows the obtained results.

Comparative Example 4 In Example 2, an undercoat layer having a film thickness of 1 μm was obtained by using a coating solution obtained by dissolving 1 part by weight of polyvinyl butyral resin in 10 parts by weight of toluene as a coating solution for forming an undercoat layer. The charge generation layer and the charge transport layer were formed under the same conditions as in Example 2 except that the electrophotographic photosensitive member was formed. This electrophotographic photosensitive member was similarly evaluated. Table 2 shows the obtained results.

[0041]

[Table 2]

Examples 10 to 18 In Example 2, acetylacetone zirconium butyrate and 2,3-dimethoxy-5-methyl-1,4
An electrophotographic photoreceptor was prepared in the same manner as in Example 2 except that the compounds shown in Table 3 were used instead of -benzoquinone, and the evaluation was performed in the same manner. Table 3 shows the obtained results.

[0043]

[Table 3]

Example 19 To 10 parts by weight of tetrahydrofuran was added 3,3 ', 5,5'
5 parts by weight of tetra-t-butyl-4,4'-diphenoquinone, 40 parts by weight of a 50% by weight solution of an organic zirconium compound (acetylacetone zirconium butyrate) in toluene and 20 parts by weight of γ-aminopropyltrimethoxysilane 20
Parts by weight were added, mixed, stirred and filtered to obtain a coating liquid for forming an undercoat layer. This coating solution is applied on a 30 mmφ aluminum substrate roughened by liquid honing treatment by ring coating, air-dried at room temperature for 5 minutes, and then dried and cured at 170 ° C. for 10 minutes. 0.2
An undercoat layer of μm was formed. 15 parts by weight of hydroxygallium phthalocyanine as a charge generating material, vinyl chloride-
A mixture comprising 10 parts by weight of a vinyl acetate copolymer resin (VMCH, manufactured by Nippon Unicar) and 300 parts by weight of n-butyl alcohol was subjected to dispersion treatment in a sand mill for 4 hours. The resulting dispersion is dip-coated on the undercoat layer,
After drying, a charge generation layer having a thickness of 0.2 μm was formed. Next, N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-
A charge transport layer having a film thickness of 20 μm was formed by applying and drying a solution obtained by adding and dissolving 4 parts by weight of diamine and 6 parts by weight of bisphenol Z polycarbonate resin (molecular weight: 40,000) to 80 parts by weight of chlorobenzene. Thus, an electrophotographic photosensitive member having three layers was prepared. The obtained electrophotographic photosensitive member was charged at -700 V using an electrical property evaluation device, and then exposed at a predetermined light amount to measure the potential. Table 4 shows the results.

[0045]

[Table 4]

[0046]

According to the electrophotographic photoreceptor of the present invention, in a photoreceptor in which a charge generation layer and a charge transport layer are sequentially laminated on a conductive support, at least an organic material is interposed between the conductive support and the charge generation layer. One or both of a metal compound and a silane coupling agent, a benzoquinone, a fluorenone,
Phenoquinones and 4- (butoxycarbonyl) -9
-An electron-accepting compound selected from dicyanomethylene fluorene , and a cured film formed from a binder resin as an undercoat layer, so that the undercoat layer does not elute during application of the upper layer, and has stable electric properties. Things. In addition, with organometallic compounds or silane coupling agents
By using in combination with the above-mentioned electron accepting compound, it has excellent electrophotographic properties, such as high light attenuating property and low residual potential, as compared with the case of using them alone, sensitivity, image quality and repetition stability. Is an excellent one.

Claims (1)

(57) [Claims] 1. An electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are sequentially laminated on a conductive support, wherein an organometallic compound and a silane coupling agent are interposed between the conductive support and the charge generation layer. either one or both and Benzoki of
Nonones, fluorenones, diphenoquinones and 4-
(Butoxycarbonyl) -9-dicyanomethylenefluoro
An electrophotographic photoreceptor comprising, as an undercoat layer, a cured film formed from an electron-accepting compound selected from len and a binder resin.