KR20040090669A - Organic photoconductor for use in electrophotograph - Google Patents

Abstract

PURPOSE: An electrophotographic organic photoreceptor is provided, to improve photosensitivity, to prevent the deterioration of electrostatic properties and to reduce the abrasion of layers by enhancing mechanical durability. CONSTITUTION: The electrophotographic organic photoreceptor comprises a conductive substrate, an intermediate layer on the substrate, a charge generation layer on the intermediate layer and a charge transfer layer on the charge generation layer, wherein the charge transfer layer comprises a fluoride resin, a charge transfer material, a binder resin and a solvent. Also the electrophotographic organic photoreceptor comprises a conductive substrate, an intermediate layer on the substrate, a charge generation layer on the intermediate layer, a charge transfer layer on the charge generation layer and a surface protective layer on the charge transfer layer, wherein the surface protective layer comprises a fluoride resin, a charge transfer material, a binder resin and a solvent. The fluoride resin is at least one represented by the formula 1 or 2; the charge transfer material is a mixture of hydrazone-based and butadiene-based materials in the ratio of 50:50 to 0:100 by weight; and the ratio of the binder resin and the charge transfer material is 60:40 to 40:60 by weight, wherein R1, R2, R3 and R4 are independently H or an alkyl or cycloalkyl group of C2-C10, X is a halogen atom and n is an integer of 1=50.

Description

Organophotoreceptor for Electrophotography {ORGANIC PHOTOCONDUCTOR FOR USE IN ELECTROPHOTOGRAPH}

The present invention relates to an electrophotographic organophotoreceptor used in an electrophotographic printer or copier, and more particularly, a fluoride resin is added to a charge transport layer or a protective layer above the charge transport layer, and a butadiene-based and / or a main charge transfer material. Alternatively, the present invention relates to an electrophotographic organophotoreceptor in which mechanical durability including film abrasion and crack marks according to long-term use is improved and light sensitivity and electrostatic properties are improved by using a hydrazone-based compound in a predetermined ratio.

The electrophotographic method introduced by Carlson in US Pat. No. 2,297,691 has been widely applied to copiers and printers, and in particular, in recent years, the electrophotographic method using semiconductor lasers or LEDs suitable for digital processing as a light source due to the advancement and speed of information processing. Laser printers and digital copiers are widely available. Since the semiconductor laser has a light emission wavelength of approximately 790 nm long wavelength region, there is an urgent need for an electrophotographic photosensitive member having sufficient sensitivity to such long wavelength light.

Currently, the electrophotographic organophotoreceptor has a stacked type in which a charge transport layer is formed on the charge generation layer, which generates charges by light irradiation, to transfer charges generated from the charge generation layer to the drum surface. In general, a charge transport layer, in particular, a low molecular dispersion charge transport layer forms a surface layer. Such a low molecular dispersion charge transport layer is satisfactory in terms of electrical characteristics. However, since the low molecular weight charge transport material is used by dispersing it in a binder resin, the inherent mechanical performance of the binder resin is degraded, and as a result, there is a problem in that it is vulnerable to abrasion. Therefore, for the purpose of improving the abrasion resistance of the low molecular dispersion type charge transport layer, a method using an additive which lowers surface energy such as hard fine particles or silicone oil, or as described in Japanese Patent Application Laid-open No. Hei 6-282092, is separately provided on the charge transport layer. A method of forming a protective layer has been proposed. However, although the wear resistance can be improved by forming the protective layer, it is difficult to control the electrical properties of the photoconductor due to the high insulation of the material itself used for the protective layer, and in particular, it is pointed out that there is a problem in the stability of the photoconductor against environmental changes. It became.

For this reason, for example, as described in US Pat. No. 4,801,517 or the like, a charge transport layer is formed using a charge transport polymer, or an existing low molecular dispersion charge transport layer is heat treated as described in Japanese Patent Application Laid-open No. Hei 6-250423. A method of reinforcing the wear resistance of the charge transport layer itself by curing by means of a new has been newly proposed. In particular, the method of US Pat. No. 517 does not need to disperse a low molecular weight charge transport material in a binder resin as long as it can secure a charge transport polymer having sufficient performance, thereby greatly improving the mechanical performance of the finished charge transport layer. It has the advantage that it can be improved and that the conventional organophotoreceptor manufacturing equipment can be used as it is. However, the performance of known charge transport polymers is insufficient to provide a viable organophotoreceptor.

In addition, the electrophotographic organophotoreceptor developed so far has a disadvantage in that the performance is deteriorated due to the effects of electrical stress or environmental change caused by long-term use, and as a measure for improvement, at present, generally between the conductive substrate and the photosensitive layer. A method of interposing a layer called an underlayer or an intermediate layer is performed. As a material usable for forming such an intermediate layer, for example, Japanese Patent Application Laid-Open No. 62-284362 and the like include polyurethane, polyamide, polyvinyl alcohol, epoxy ethylene acrylic acid copolymer, ethylene vinyl acetate copolymer, casein, methyl cellulose Nitro cellulose, phenolic resin, organometallic compound, etc. have been proposed, but in the photosensitive member to which the intermediate layer of these materials is applied, the moisture contained in these materials is mainly responsible for transport of charge, so the performance of the photosensitive member is sensitive to humidity. There is a flaw done. Correspondingly, an electron donating material is introduced into the intermediate layer as a means for preventing changes in the characteristics of the photoconductor due to humidity (see, for example, Japanese Patent Laid-Open Nos. 61-35551 and 60-218655), or Various methods are proposed, such as introducing an n-type pigment or a pigment into an intermediate layer or a method of introducing an electron-movable pigment (see, for example, Japanese Patent Laid-Open Nos. 58-209751 and 63-210848). Has been.

As such, in the field of electrophotography, sensitivity, acceptance potential, potential retention, potential stability, residual potential, spectroscopic properties, mechanical durability such as abrasion resistance, chemical stability against moisture, heat, light and discharge products, and dielectric breakdown The organic photoconductor, which is satisfactory in all respects, has not been provided.

The present invention is to solve the problems of the prior art as described above, adding a fluorine resin of a specific structure to any one of the charge transport layer or the protective layer of the layered organic photosensitive member, and the butadiene-based and / or hydrazone-based compound as a charge transfer material By using at a predetermined ratio, an object of the present invention is to provide an electrophotographic organophotoreceptor having low mechanical degradation and excellent mechanical durability due to electrical stress or environmental change caused by long-term use.

That is, one aspect of the present invention is an electrophotographic organophotoreceptor in which an intermediate layer, a charge generating layer, and a charge transport layer are sequentially stacked on a conductive substrate, wherein the charge transport layer includes a fluorine resin, a charge transfer material, a binder resin, and a solvent. , Wherein the fluorine resin is at least one resin having a structure of Formulas 1 and / or 2 below, wherein the charge transfer material is a hydrazone-based butadiene-based compound: 50: 50-0: 100 (w / w) It includes, and provides an organophotoreceptor, characterized in that the ratio of the binder resin and the mixed charge transfer material is 60:40 ~ 40:60 (w / w):

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or an alkyl or cycloalkyl having 2 to 10 carbon atoms, X is a halogen group and n is an integer of 1 to 50.

Another aspect of the present invention is an electrophotographic organophotoreceptor in which an intermediate layer, a charge generating layer, a charge transport layer, and a surface protective layer are sequentially stacked on a conductive substrate, wherein the surface protective layer is a fluorine resin, a charge transfer material, a binder resin, and a solvent. Including, wherein the fluorine resin is at least one resin having a structure of Formula 1 and / or 2, the charge transfer material is a hydrazone-based: butadiene-based = 50: 50 ~ 0: 100 (w / w) mixed It includes a charge transfer material, and provides an organophotoreceptor, characterized in that the ratio of the binder resin and the mixed charge transfer material is 60:40 ~ 40:60 (w / w).

1 is a graph showing a comparison of film reduction rates of photosensitive drums according to Examples 1 to 3 and Comparative Examples; And

2A to 2C are enlarged photographs 30 times showing the crevices of the photosensitive drums according to Examples 1 to 2 and Comparative Examples.

The inventors of the present invention have been seeking ways to extend the life of the photoconductor by improving wear resistance while improving electrical properties deterioration due to long-term use or environmental change of the electrophotographic organophotoreceptor, and the surface of the charge transport layer or the upper surface of the charge transport layer. By adding a fluorine resin with a specific structure to the protective layer and using butadiene-based compounds and hydrazone-based compounds as a main charge transfer material in a predetermined ratio, an organophotoreceptor having greatly improved electrical performance stability, photosensitivity and durability can be manufactured. The present invention has been made.

Hereinafter, the present invention will be described in more detail.

In the present invention, as the conductive substrate, a metal such as aluminum, an aluminum alloy, nickel or stainless steel, or a conductive treatment on glass or a resin film is used in various shapes such as a plate shape, a cylindrical shape, and a film shape.

On the surface of these substrates, an intermediate layer is formed for the purpose of insulating. In the present invention, an 'intermediate layer' is a layer located between the conductive substrate and the photosensitive layer, and includes an insulating layer, an anodized layer, and an undercoat layer. Used to encompass (Undercoat Layer). The insulating layer is mainly a metal oxide film or resin film having a uniform surface and good adhesion to a substrate. Typically, the material of such a resin film is insulating material such as casein, polyvinyl alcohol, polyamide, polyimide, melamine, cellulose, or the like. A mixture obtained by adding a metal oxide powder or the like to a polymer or a conductive polymer such as polythiophene, polypyrrole or polyaniline is used.

On the other hand, in the organophotoreceptor of the present invention, the charge generating layer is composed of a charge generating material, a binder resin, a solvent, and other additives. As the charge generating material, metal phthalocyanine and its derivatives may be used alone or in combination of two or more, or metal phthalocyanine and its derivatives in which the metal is substituted at the center of the phthalocyanine may be used alone or in combination of two or more. The type of metal phthalocyanine that can be used in the present invention is not particularly limited as long as the object of the present invention is not impaired, and representative examples thereof include copper phthalocyanine, aluminum chloride phthalocyanine, and titanyl phthalocyanine. Vanadium oxide Phthalocyanine, Indium chloride Phthalocyanine, Hydroxygallium Phthalocyanine, Tin oxide Phthalocyanine, Tin phthalocyanine derivatives, and Tin Phthalocyanine derivatives thereof do. It is also possible to use a combination of a metal-free phthalocyanine or a derivative thereof and a metal-substituted phthalocyanine or a derivative thereof.

Binder resins used in the charge generating layer include vinyl acetate, vinylpyrrolidine, acrylic, polyurethane, polycarbonate, polyester, polyamide, epoxy, polyvinyl butyral, polyvinyl acetal, phenoxy resin, silicone resin, Vinyl chloride resin, vinylidene chloride resin, formal resin, cellulose resin, and copolymerized resins thereof may be used alone or in combination of two or more thereof. In this case, each resin may be used in the form of a halide or cyanoethyl compound. It may be.

Solvents used in the charge generating layer include methyl isopropyl ketone, methyl isobutyl ketone, 4-methoxy-4-methyl-2-pentanone, isopropyl acetate, isobutyl acetate, tertiary butyl acetate, isopropyl alcohol, Isobutyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloro Ethylene, tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 1-methoxy-2-propanol, ethyl acetate, butyl acetate, dimethyl sulfoxide , Methyl cellosolve, butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N'-dimethylformamide, benzene, toluene, xylene, methylbenzene, ethylbenzene, cyclohexane, etc. Alone or two or more It can be used in combination.

As an additive used for the charge generating layer, a conventional dispersant, an antifoaming agent, a surfactant, etc. used for an electrophotographic organophotoreceptor are suitably used as needed.

In the organophotoreceptor of the present invention, the charge transport layer is composed of one or more fluorine resins, charge transfer materials, binder resins, solvents, and other additives having the structures of the following Chemical Formulas 1 and / or 2.

Where

R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or alkyl or cycloalkyl having 2 to 10 carbon atoms, X is a halogen group and n is an integer of 1 to 50.

Where

R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or an alkyl or cycloalkyl having 2 to 10 carbon atoms, X is a halogen group and n is an integer of 1 to 50.

The fluorine resin serves to reduce the film wear rate by reducing surface friction.

In the present invention, a hydrazone-based charge transfer material and a butadiene-based charge transfer material are used as the main charge transfer material, but the mixing ratio is limited to 50:50 to 0: 100 (w / w). What is important to the characteristics of the present invention is a combination of a hydrazone-based charge transfer material and a butadiene-based charge transfer material, only when the two materials are mixed in the above ratio to improve the photosensitivity of the photoconductor aimed in the present invention, the residual potential decreases And reduction of frictional scars can be achieved.

In addition, the ratio of the binder resin and the hydrazone / butadiene mixed charge transfer material described later in the charge transport layer of the present invention is preferably 60:40 to 40:60 (w / w). If the ratio of the hydrazone-based butadiene-based mixed charge transfer material is low, there is a disadvantage that a crevice occurs, while vice versa, a problem of increasing the film reduction rate occurs.

Examples of preferred hydrazone-based charge transfer materials include N-ethyl-3-carbozolylaldehyde-N, N'-diphenylhydrazone, N, N-diethylaminobenzaldehydediphenyl-hydrazone, N, N-dimethylamino Benzaldehyde diphenyl-hydrazone, 4-dibenzylamino-2-methylbenzaldehydediphenylhydrazone, 4-dimethylamino-benzaldehyde-N, N-diphenylhydrazone, 9-ethylcarbazole-3-aldehyde-N- Methyl-N-phenylhydrazone, 4-diethylamino-benzaldehyde-N, N-diphenylhydrazone, 9-ethylcarbazole-3-aldehyde-N, N-diphenylhydrazone, 4-diphenylamino- Benzaldehyde-N, N-diphenylhydrazone, 4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone, 4-dibenzylamino-3-methylbenzaldehyde-N, N-diphenylhydrazone and the like. .

Examples of preferred butadiene-based charge transfer materials include 1,1-bis- (para-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene, (4,4-diphenyl-1, 3-butadiene) and the like.

In the present invention, in addition to the hydrazone-based and butadiene-based compounds, other compounds known to be able to transfer the charges generated in the charge generating layer to the drum surface may be further used. Representative charge transfer materials useful in the present invention include, for example, N, N'-bis (Olso, para-dimethylphenyl) -N, N'-diphenylbenzidine, 3,3'-dimethyl-N, N, N ' N'-tetrakis-4-methylphenyl- (1,1'-biphenyl) -4,4'-diamine, 4- (N, N-bis (para-toluyl) amino) -betaphenylstilbene, N , N, N ', N'-tetrakis (3-methylphenyl) -1,3-diaminobenzene, 2,5-bis (4-aminophenyl)-[1,3,4] oxadiazole, (2 -Phenylbenzo [5,6-b] -4H-thiopyran-4-ylidene) -propanedinitrile-1,1-dioxide, 4-bromo-triphenylamine, 4,4 '-(1,2 -Ethanediylidene) -bis (2,6-dimethyl-2,5-cyclohexadien-1-one), 3,4,5-triphenyl-1,2,4-triazole, 2- (4 -Methylphenyl) -6-phenyl-4H-thiopyran-4-ylidene] -propanedinitrile-1,1-dioxide, 5- (2-chlorophenyl) 3- [2- (2-chlorophenyl) ethenyl ] -1-phenyl-4,5-dihydro-1H-pyrazole, N-biphenylyl-N-phenyl-N- (3-methylphenyl) amine, 3,5-bis (4-tert-butylphenyl) 4-phenyltriazole, 3- (4-biphenylyl) -4-phenyl -5-tert-butylphenyl-1,2,4-triazole, 5- (4-diethylaminophenyl) -3- [2- (4-diethylaminophenyl) -ethenyl] -1-phenyl- 4,5-dihydro-1-pyrazole, N, N'-di (4-methylphenyl) -N, N'-diphenyl-1,4-phenylenediamine, 4,4'-bis (carbazole- 9-yl) biphenyl, N, N, N ', N'-tetraphenylbenzidine, N, N'-bis (4-methylphenyl) -N, N'-bis (phenyl) -benzidine, N, N'- Bis (3-methylphenyl) -N, N'-bis (phenyl) benzidine, N, N, N ', N'-tetrakis (4-methylphenyl) benzidine, N, N, N', N'-tetrakis ( 3-methylphenyl) benzidine, di (4-dibenzylaminophenyl) ether, N, N'-di (naphthalen-2-yl) -N, N'-diphenylbenzidine, N, N'-di (naphthalene-1 -Yl) -N, N'-diphenylbenzidine, 1,3-bis (4 (4-diphenylamino) phenyl-1,3,4-oxadiazol-2-yl) benzene, N, N'- Di (naphthalen-2-yl) N, N'-di (3-methylphenyl) benzidine, N, N'-di (naphthalen-1-yl) -N, N'-di (4-methylphenyl) benzidine, N, N'-di (naphthalen-2-yl) -N, N'-di (3-methylphenyl) benzidine, 1,1-bis (4-bis (4-methylphenyl) aminophenyl) cyclohexane , 4,4 ', 4 "-tris (carbazol-9-yl) -triphenylamine, 4,4', 4" -tris (N, N-diphenylamino) -triphenylamine, N, N ' -Bis (biphenyl-1-yl) -N, N'-bis (naphth-1-yl) benzidine, 4,4 ', 4 "-tris (N-3-methylphenyl-N-phenylamino) triphenyl Amine, N, N, N ', N'-tetrakis (biphenyl-4-yl) benzidine, 4,4', 4 "-tris (N- (1-naphthyl) -N-phenylamino) triphenyl Amine, 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) triphenylamine, etc., These can be used individually or in combination of 2 or more types.

As the binder resin used in the charge transport layer, polyvinyl butyral resin, polyvinyl alcohol resin, polyamide resin, polyvinylacetate resin, polyvinyl chloride resin, polyacrylic resin, polyurethane resin, polycarbonate resin, polymethacryl resin , Polyvinylidene chloride resin, polystyrene resin, styrene-butadiene copolymer resin, styrene-methyl methacrylate resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinylacetate copolymer resin, vinyl chloride-vinylacetate Maleic anhydride copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-vinylacetate copolymer resin, methylcellulose, nitrocellulose, polysilicon resin, silicone-alkyd resin, phenol-formaldehyde resin, cresol-formaldehyde resin, styrene Alkyd Resin, Poly-N-Vinyl Bazol resin, polyvinylformal resin, polyhydroxystyrene resin, polynovonyl resin, polycycloolefin resin, polyvinylpyrrolidone resin, poly (2-ethyl-oxazoline) resin, melamine resin, urea resin, amino Resin, isocyanate resin, epoxy resin, etc. can be used individually or in combination of 2 or more types.

As a solvent used in the charge transport layer, the same solvent as that used in the charge generating layer may be used. Specific examples thereof include methyl isopropyl ketone, methyl isobutyl ketone, and 4-methoxy-4-methyl-2-pentanone. , Isopropyl acetate, isobutyl acetate, tertiary butyl acetate, isopropyl alcohol, isobutyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, 1,2-dichloroethane, 1,2-dichloropropane, 1,1, 2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 1-methoxy-2-propanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve, butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N'-dimethylform amides , Benzene, toluene, xylene, methylbenzene, ethylbenzene, cyclohexane and the like can be used alone or in combination of two or more thereof.

As the additive used in the charge transport layer, an antioxidant, an antifoaming agent, an oil, etc. which are commonly used are appropriately selected and used as necessary.

Finally, the organophotoreceptor of the present invention may further include a surface protective layer on the charge transport layer, wherein the protective layer is one or more fluorine resins, charge transfer materials, and binder resins having the structures of Formulas 1 and / or 2. And a solvent and other additives, wherein the charge transfer material essentially includes the same hydrazone / butadiene mixed charge transfer material as used in the charge transport layer, and the ratio of the binder resin and the mixed charge transfer material is also The same as in the example of the charge transport layer.

As the binder resin used for the protective layer, polycarbonate, polyvinyl butyral resin, polyvinyl alcohol resin, polyamide resin, polyvinylacetate resin, polyvinyl chloride resin, polyacrylic resin, polyurethane resin, polycarbonate resin, poly Methacryl resin, polyvinylidene chloride resin, polystyrene resin, styrene-butadiene copolymer resin, styrene-methyl methacrylate resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinylacetate copolymer resin, vinyl chloride -Vinyl acetate-maleic anhydride copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-vinylacetate copolymer resin, methyl cellulose, nitrocellulose, polysilicon resin, silicone-alkyd resin, phenol-formaldehyde resin, cresol-formaldehyde Resin, styrene-alkyd resin, Poly-N-vinylcarbazole resin, polyvinylformal resin, polyhydroxystyrene resin, polynovonyl resin, polycycloolefin resin, polyvinylpyrrolidone resin, poly (2-ethyl-oxazoline) resin, melamine Resin, urea resin, amino resin, isocyanate resin, epoxy resin, etc. can be used individually or in combination of 2 or more types.

The solvent used for the protective layer is methyl isopropyl ketone, methyl isobutyl ketone, 4-methoxy-4-methyl-2-pentanone, isopropyl acetate, isobutyl acetate, tertiary butyl acetate, isopropyl alcohol, iso Butyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene , Tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 1-methoxy-2-propanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, Methyl cellosolve, butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N'-dimethylformamide, benzene, toluene, xylene, methylbenzene, ethylbenzene, cyclohexane and the like alone Or combinations of two or more Can be used.

As an additive used for a protective layer, the metal oxide, antioxidant, antifoamer, oil, etc. which are normally used are selected suitably as needed.

When the organophotoreceptor of the present invention is provided with such a protective layer, the charge transport layer does not include a fluorine resin separately.

In the organophotoreceptor of the present invention, the content of the fluorine resin contained in the charge transport layer or the protective layer is preferably 0.01 to 0.1% by weight. If the content of the fluorine resin is less than 0.01% by weight, the object of the present invention can not be achieved, while if the content of the fluorine resin exceeds 0.1% by weight, a problem occurs that the electrostatic property is lowered.

The organophotoreceptor of the present invention does not require a special manufacturing apparatus or method, and can be produced according to a conventional method for producing a laminated organophotoreceptor.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example 1

4.6 parts by weight of the charge generating material (Syntec 10 / 10.2), 3.1 parts by weight of polyvinyl butyral resin (# 6000C, DENKI), and 81.6 parts by weight of tetrahydrofuran, together with glass beads (1 mm), using a paint shaker and a ball mill. By dispersing, a dispersion having an average particle size of about 250 nm was prepared. The dispersion was diluted with 3.8-fold volume tetrahydrofuran, and ultrasonic waves were injected for 30 minutes to prepare a coating solution for forming a stable charge generating layer. The coating solution was uniformly coated on the first anodized aluminum drum using the sedimentation coating method, and then dried at 120 ° C. for 30 minutes.

Subsequently, 4.2 parts by weight of 4-dibenzylamino-2-methylbenzaldehydediphenylhydrazone (CTC-191, ANAN CORPORATION), 1,1-bis- (para-diethylaminophenyl) -4,4-diphenyl- 4.2 parts by weight of 1,3-butadiene (T-405, ANAN CORPORATION), 11 parts by weight of polycarbonate (TS2050, ANAN CORPORATION), 0.4 parts by weight of dibutylhydroxytoluene as antioxidant, 0.04 parts by weight of silicone oil, fluorine resin (LF710, Lumifron) 0.4 parts by weight, 55.7 parts by weight of tetrahydrofuran, and 24 parts by weight of toluene were stirred together to completely dissolve the solid components to prepare a coating solution for forming a charge transport layer. The drum on which the charge generating layer was formed was precipitated again with this coating solution, and then dried at 120 ° C. for 30 minutes to form a charge transport layer on the charge generating layer.

Example 2

3.16 parts by weight of 4-dibenzylamino-2-methylbenzaldehydediphenylhydrazone (CTC-191, ANAN CORPORATION) and 1,1-bis- (para-diethylaminophenyl) -4 as charge transfer materials in the formation of the charge transport layer A photosensitive drum was manufactured in the same manner as in Example 1, except that 5.88 parts by weight of 4-4-diphenyl-1,3-butadiene (T-405, ANAN CORPORATION) was used.

Example 3

3.03 parts by weight of 4-dibenzylamino-2-methylbenzaldehydediphenylhydrazone (CTC-191, ANAN CORPORATION) and 1,1-bis- (para-diethylaminophenyl) -4 as charge transfer materials in the formation of the charge transport layer A photoconductive drum was manufactured in the same manner as in Example 1, except that 7.11 parts by weight of 4-4-phenyl-1,3-butadiene (T-405, ANAN CORPORATION) was used.

Comparative example

A photosensitive drum was manufactured in the same manner as in Example 1, except that no fluorine resin was used in forming the charge transport layer.

The photosensitive drums prepared in Examples 1 to 3 and Comparative Examples were evaluated for electrostatic properties, photosensitivity, and durability by the method described below, and the results are shown in Tables 1 to 3 and FIGS. 1 to 2.

[Assessment Methods]

(1) blackout evaluation

Each photoconductor drum was charged with a -6KV to -7KV corona using an electrostatic charge tester (PDA-2000LA; QEA Inc., USA), and after 1.0 seconds irradiated with 780nm light with energy of 1.0μJ / cm2 for 1.0 seconds. After repeating the electrophotographic circulation process 1000 times after eliminating the potential of the drum surface with a red LED light source for 1.0 second, the initial charge potential V ₀ (-V) formed on the drum surface, The potential Ve and the potential Vr of the drum surface after 1.0 second of the erasing operation were respectively measured (see Table 1).

In addition, the exposure energy E _1/2 (μJ / cm 2) per unit area until the surface potential immediately before the exposure was reduced to half when the drum was irradiated with light of 780 nm and the surface potential immediately before the exposure became -100V. The exposure energy E ₁₀₀ (μJ / cm 2) per unit area was measured, and the surface potential retentions DD ₁ (%) and DD ₅ (%) were measured after being left for 1 second and 5 seconds in the dark state after charging (see Table: One).

(2) Burn test and film thickness reduction evaluation

Each photosensitive drum was mounted in an electrophotographic device that outputs images in an electrophotographic manner, and then 30,000 sheets of A3 paper were printed using a Hewlett Packard LaserJet HP8000 printer, and the image quality was visually evaluated (see Table 2). The film thickness of the photoconductor before printing and after printing 30000 sheets was measured, respectively, to calculate the thickness variation (see Fig. 1 and Table 3). At this time, the thickness change amount was set to 20 points on each photosensitive drum surface, the thickness change amount at each site was measured, and the average value was set.

(3) Evaluation of Friction Wounds on Membrane Surface

Each photosensitive drum was fixed on one axis and subjected to external friction by rotating for 12 hours at a constant speed, and then the surface wound was confirmed by a 30 times magnification (see FIG. 2).

division Electrostatic characteristics Vr E _1/2 E ₁₀₀ DD ₁ DD ₅ VL Example 1 7 0.130 0.330 98.2% 93.7% -210V Example 2 7 0.129 0.321 98.7% 95.1% -130V Example 3 7 0.126 0.312 98.6% 94.5% -90V Comparative example 9 0.131 0.355 98.9% 96.0% -220V

¹⁾ VL (-V): Surface potential when toner adheres to the drum surface

burn Liquid stability Early After 30000 sheets ○ Example 1 ○ ○ ○ Example 2 ○ ○ ○ Example 3 ○ ○ ○ Comparative Example 1 ○ ○ ○

¹⁾ ○: good, X: bad

²⁾ ○: no change, X: crystallization, phase separation or gelation within 1 month when left at room temperature

Example 1 Example 2 Example 3 Comparative Example 1 Early 22.5 μm 21.9㎛ 22.4 μm 22.5 μm After 30000 17.7㎛ 18.2 μm 20.9 ㎛ 16.3㎛ Change -4.8㎛ -3.7㎛ -1.5㎛ -6.2 μm

As described in detail above, the organophotoreceptor of the present invention is very useful as an electrophotographic photosensitive member, even when it is used for a long time, the electrostatic characteristic is not degraded, the image characteristic and the sensitivity are excellent, and the film finish is low.

Claims (4)

An electrophotographic organophotoreceptor in which an intermediate layer, a charge generating layer, and a charge transport layer are sequentially stacked on a conductive substrate, wherein the charge transport layer includes a fluorine resin, a charge transfer material, a binder resin, and a solvent, wherein the fluorine resin is represented by Formula 1 below. And / or at least one resin having a structure of 2, wherein the charge transfer material comprises a mixed charge transfer material of hydrazone: butadiene = 50: 50 to 0: 100 (w / w), and the binder resin An organophotoreceptor, characterized in that the ratio of the mixed charge transfer material is 60:40 ~ 40:60 (w / w): [Formula 1] ; [Formula 2] In Chemical Formulas 1 and 2, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or an alkyl or cycloalkyl having 2 to 10 carbon atoms, X is a halogen group and n is an integer of 1 to 50. An electrophotographic organophotoreceptor in which an intermediate layer, a charge generating layer, a charge transport layer, and a surface protective layer are sequentially stacked on a conductive substrate, wherein the surface protective layer includes a fluorine resin, a charge transfer material, a binder resin, and a solvent. Resin is at least one resin having the structure of Formula 1 and / or 2, the charge transfer material comprises a hydrazone system: butadiene system = 50: 50 ~ 0: 100 (w / w) mixed charge transfer material And the ratio of the binder resin and the mixed charge transfer material is 60:40 to 40:60 (w / w). [Formula 1] ; [Formula 2] In Chemical Formulas 1 and 2, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or an alkyl or cycloalkyl having 2 to 10 carbon atoms, X is a halogen group and n is an integer of 1 to 50. The method of claim 1 or 2, wherein the charge transfer material is N, N'-bis (Olso, para-dimethylphenyl) -N, N'-diphenylbenzidine, 3,3'-dimethyl-N, N, N'N'- tetrakis-4-methylphenyl- (1,1'-biphenyl) -4,4'-diamine, 4- (N, N-bis (para-toluyl) amino) -betaphenylstilbene , N, N, N ', N'-tetrakis (3-methylphenyl) -1,3-diaminobenzene, 2,5-bis (4-aminophenyl)-[1,3,4] oxadiazole, (2-phenylbenzo [5,6-b] -4H-thiopyran-4-ylidene) -propanedinitrile-1,1-dioxide, 4-bromo-triphenylamine, 4,4 '-(1 , 2-ethanediylidene) -bis (2,6-dimethyl-2,5-cyclohexadien-1-one), 3,4,5-triphenyl-1,2,4-triazole, 2- (4-methylphenyl) -6-phenyl-4H-thiopyran-4-ylidene] -propanedinitrile-1,1-dioxide, 5- (2-chlorophenyl) 3- [2- (2-chlorophenyl) Ethenyl] -1-phenyl-4,5-dihydro-1H-pyrazole, N-biphenylyl-N-phenyl-N- (3-methylphenyl) amine, 3,5-bis (4-tert-butyl Phenyl) 4-phenyltriazole, 3- (4-biphenylyl) -4-phenyl-5-tert -Butylphenyl-1,2,4-triazole, 5- (4-diethylaminophenyl) -3- [2- (4-diethylaminophenyl) -ethenyl] -1-phenyl-4,5- Dihydro-1-pyrazole, N, N'-di (4-methylphenyl) -N, N'-diphenyl-1,4-phenylenediamine, 4,4'-bis (carbazol-9-yl) Biphenyl, N, N, N ', N'-tetraphenylbenzidine, N, N'-bis (4-methylphenyl) -N, N'-bis (phenyl) -benzidine, N, N'-bis (3- Methylphenyl) -N, N'-bis (phenyl) benzidine, N, N, N ', N'-tetrakis (4-methylphenyl) benzidine, N, N, N', N'-tetrakis (3-methylphenyl) Benzidine, di (4-dibenzylaminophenyl) ether, N, N'-di (naphthalen-2-yl) -N, N'-diphenylbenzidine, N, N'-di (naphthalen-1-yl)- N, N'-diphenylbenzidine, 1,3-bis (4 (4-diphenylamino) phenyl-1,3,4-oxadiazol-2-yl) benzene, N, N'-di (naphthalene- 2-yl) N, N'-di (3-methylphenyl) benzidine, N, N'-di (naphthalen-1-yl) -N, N'-di (4-methylphenyl) benzidine, N, N'-di (Naphthalen-2-yl) -N, N'-di (3-methylphenyl) benzidine, 1,1-bis (4-bis (4-methylphenyl) aminophenyl) cyclohexane, 4,4 ', 4 "-tris (carbazol-9-yl) -triphenylamine, 4,4 ', 4" -tris (N, N-diphenylamino) -triphenylamine, N, N'-bis (biphenyl- 1-yl) -N, N'-bis (naphth-1-yl) benzidine, 4,4 ', 4 "-tris (N-3-methylphenyl-N-phenylamino) triphenylamine, N, N, N ', N'- tetrakis (biphenyl-4-yl) benzidine, 4,4', 4 "-tris (N- (1-naphthyl) -N-phenylamino) triphenylamine, and 4,4 An organophotoreceptor further comprising at least one member selected from the group consisting of ', 4'-tris (N- (2-naphthyl) -N-phenylamino) triphenylamine. The organophotoreceptor of claim 1 or 2 wherein the fluorine resin content of the charge transport layer or the protective layer is 0.01 to 0.1% by weight.