JPH05142974A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To prevent the meandering of the seamless belt-like electrophotographic sensitive body without providing guide rails for preventing the meandering by providing sprocket holes on both sides of a base. CONSTITUTION:The metallic belt base is produced by previously forming the non-electrocast parts corresponding to the sprocket holes 9 of a nonconductive resin on a mandrel prior to the start of electrocasting and a photosensitive layer 2a is formed thereon to constitute the electrophotographic sensitive body 8. Namely, the photosensitive layer 2a formed by dispersing a charge generating material 3 into a binder 4 is provided. The material of the metallic belt-like base 1 includes metals, such as, for example, copper and nickel, or the alloys thereof. The charge generating material 3 includes, for example, azo pigments and inorg. materials, such as zinc sulfide. The photosensitive body is driven by using a driving roll 10 provided with the sprockets by which the photosensitive body is continuously transported without meandering.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor.

[0002]

2. Description of the Related Art In recent years, as electrophotographic copying machines and printers have become smaller and lighter, a method of using an electrophotographic photosensitive member as a flexible belt has attracted attention. Belt-shaped electrophotographic photoreceptors have traditionally required high-speed copiers and printers that required extremely large diameter metal drums, and color copiers that require multiple development processes, small and lightweight printers. Can be realized.

On the other hand, when the electrophotographic photoconductor is used in the form of a belt, the method of using the electrophotographic photoconductor in an endless form is advantageous in that the mechanism can be simplified. In order to realize such an endless belt-shaped electrophotographic photosensitive member, a method is known in which a sheet-shaped electrophotographic photosensitive member is cut and the end faces are joined. Further, in order to realize a seamless and seamless material, a method for producing a resinous seamless belt base material by a casting method or an inflation method, or a conductive base material using electroformed nickel has been proposed. ing.

[0004]

However, when the belt-shaped electrophotographic photosensitive member is mounted on a copying machine, a printer, etc., it is necessary to provide a meandering-preventing guide rail in order to prevent meandering when the belt is driven. Therefore, there is a problem that the production cost becomes high.

The problem to be solved by the present invention is to provide a method for preventing meandering of a belt-shaped electrophotographic photosensitive member, and to prevent meandering without a post-treatment for preventing meandering. An object is to provide a photoconductor for electrophotography.

[0006]

In order to solve the above-mentioned problems, the present invention provides a belt-shaped electrophotographic photosensitive member having a photosensitive layer formed on a support, having sprocket holes on both sides of the support. An electrophotographic photoreceptor is provided.

The electroformed metal belt is usually obtained by depositing a metal in the electrolyte solution on the surface of a conductive roll-shaped mandrel, and extracting the mandrel when the required thickness of deposition is obtained. However, the present invention, by the non-conductive resin on the mandrel before the start of electroforming, to form a non-electroformed portion corresponding to the sprocket hole, to produce a metallic belt support, on which the photosensitive layer To form a photoreceptor for electrophotography.

In the present invention, a photosensitive layer made of a photoconductive material is formed on a metal belt to be used as an electrophotographic photoreceptor, but the photosensitive layer can have various structures. Examples thereof are shown in FIGS.

The electrophotographic photoreceptor of FIG. 1 is provided with a photosensitive layer in which a charge generating material is dispersed in a binder. FIG. 2 shows a photosensitive layer formed by dispersing a charge generating material and a charge transporting material in a binder. 3 and 4 show a photosensitive layer in which a charge generating layer mainly composed of a charge generating material and a charge transporting layer mainly composed of a charge transporting material are laminated. The thickness of these photosensitive layers is 5 μm to 50 μm
Is preferred. If necessary, an intermediate layer may be provided between the metal belt and the photosensitive layer in order to improve the barrier property and the adhesive property.

Examples of the material for the metal belt-shaped support used in the electrophotographic photoreceptor of the present invention include copper, nickel, aluminum, zinc, iron, chromium, molybdenum,
Examples thereof include metals such as vanadium, indium, titanium, gold, silver and platinum, and alloys thereof, but copper and nickel are particularly preferable.

Examples of the charge generating material used in the photosensitive layer include azo pigments, quinone pigments, perylene pigments, indigo pigments, thioindigo pigments, bisbenzimidazole pigments, phthalocyanine pigments, quinacridone pigments, Quinoline pigments, lake pigments, azo lake pigments, anthraquinone pigments, oxazine pigments, dioxazine pigments, triphenylmethane pigments, azurenium dyes, squarium dyes, pyrylium dyes,
Various organic pigments and dyes such as triallylmethane dye, xanthene dye, thiazine dye, and cyanine dye, and further amorphous silicon, amorphous selenium, tellurium,
Inorganic materials such as selenium-tellurium alloy, cadmium sulfide, antimony sulfide, zinc oxide and zinc sulfide can be mentioned.

The charge generating substance is not limited to those listed here, and may be used alone or in combination of two or more when used.

The charge-transporting substance is generally classified into two types, a substance that transports electrons and a substance that transports holes, and both can be used in the electrophotographic photoreceptor of the present invention.

Examples of the electron transport substance include chloranil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone. , 9-dicyanomethylene-2,4,7-trinitrofluorenone, 9-dicyanomethylene-2,4,5,7
-Tetranitrofluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, tetranitrocarbazole chloranil, 2,3-
Dichloro-5,6-dicyanobenzoquinone, 2,4,7
-Trinitro-9,10-phenanthrenequinone, tetrachlorophthalic anhydride, organic compounds such as diphenoquinone derivatives, amorphous silicon, amorphous selenium, tellurium, selenium-tellurium alloy, cadmium sulfide, antimony sulfide, zinc oxide, zinc sulfide, etc. Inorganic materials may be mentioned.

As the hole-transporting substance, low molecular compounds such as pyrene, N-ethylcarbazole, N-isopropylcarbazole, N-phenylcarbazole,
Alternatively, N-methyl-2-phenylhydrazino-3-methylidene-9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, p-N, N-dimethylaminobenzaldehyde diphenylhydrazone, p Hydrazones such as -N, N-diethylaminobenzaldehyde diphenylhydrazone and p-N, N-diphenylaminobenzaldehyde diphenylhydrazone, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1- Phenyl-3- (p-diethylaminostyryl) -5- (p-
Pyrazolines such as diethylaminophenyl) pyrazoline, triphenylamine, N, N, N ', N'-tetraphenyl-1,1'-diphenyl-4,4'-diamine, N, N'-diphenyl-N, N Examples include'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine and the like. Examples of the polymer compound include poly-N-vinylcarbazole and halogenated poly-
Examples thereof include N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin, ethylcarbazole-formaldehyde resin, triphenylmethane polymer and polysilane.

These materials can be used in the photosensitive layer by being dispersed in a binder resin and applied, or formed into a film by a means such as vacuum deposition, sputtering, or CVD method.

The charge transport material is not limited to those listed here, and may be used alone or in combination of two or more when used.

As the binder resin, it is preferable to use a high molecular polymer which is hydrophobic and can form an electrically insulating film. Examples of such binder resin include polycarbonate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile polymer,
Vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, polyvinyl butyral, Examples thereof include, but are not limited to, polyvinyl formal and polysulfone. These binder resins may be used alone or in combination of two or more.

It is also possible to use additives such as a plasticizer, a sensitizer and a surface modifier together with these binder resins.

Examples of the plasticizer include biphenyl, biphenyl chloride, o-terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene and various fluorohydrocarbons. Etc.

Examples of the sensitizer include chloranil, tetracyanoethylene, methyl violet, rhodamine B, cyanine dye, merocyanine dye, pyrylium dye and thiapyrylium dye.

Examples of the surface modifier include silicone oil and fluororesin.

Further, in the present invention, in order to improve the adhesiveness between the metal belt-shaped support and the photosensitive layer and prevent the free charge from being injected from the support to the photosensitive layer, a metal belt-shaped support is used. If necessary, an adhesive layer or a barrier layer can be provided between the photosensitive layers. Examples of materials used for these layers include polymer compounds used for the binder resin, casein, gelatin, polyvinyl alcohol, ethyl cellulose, phenol resin, polyamide, carboxy-methyl cellulose, vinylidene chloride-based polymer latex, polyurethane, and aluminum oxide. , Silicon oxide, tin oxide, titanium oxide and the like.

When the laminated type electrophotographic photosensitive member is formed by coating, a paint prepared by dissolving the above charge generating agent or charge transporting substance in a binder or the like is dissolved in a solvent. It depends on the kind of the binder, but it is preferable to select from those which do not dissolve the lower layer. Specific examples of the organic solvent include alcohols such as methanol, ethanol and n-propanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; amides such as N, N-dimethylformamide and N, N-dimethylacetamide. Ethers such as tetrahydrofuran, dioxane and methyl cellosolve; Esters such as methyl acetate and ethyl acetate; Sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane; Aliphatic halogenated compounds such as methylene chloride, chloroform, carbon tetrachloride and trichloroethane Hydrocarbons; aromatics such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene and the like can be mentioned.

As the coating method, for example, dip coating method, spray coating method, spinner coating method, bead coating method, wire bar coating method, blade coating method, roller coating method,
A coating method such as a curtain coating method can be used.

[0026]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. In the examples, "part" means "part by weight".

(Example) A stainless steel was processed into a mandrel roll having a diameter of 120 mm and a length of 500 mm, which was used as an electroforming master. "OMR-83" (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used on both sides at a position 125 mm from the longitudinal center, and a resist film with a thickness of 2 μm and a width of 2 mm was used.
38 circular resist films having a film thickness of 2 .mu.m and a diameter .phi.3 mm corresponding to the sprocket hole were formed in the master-circumferential direction around the position of. This was immersed in an electrolyte solution in which 4 parts of nickel sulfamate, 0.3 part of nickel chloride and 0.4 part of boric acid were dissolved in 10 parts of pure water, and nickel was used as an anode at a liquid temperature of 50 ° C. to form a film. Nickel electroforming was performed at a speed of 100 angstrom / sec to prepare a nickel belt-shaped substrate having a sprocket hole with a thickness of 30 μm and a width of 250 mm.

Next, a solution prepared by dissolving 10 parts of modified polyamide resin (trade name "AQ-Nylon P-70" manufactured by Toray Co., Ltd.) in 50 parts of methanol and 50 parts of n-butanol was immersed on the obtained belt-shaped substrate. It was applied by the product method and dried to obtain a barrier layer having a thickness of 1 μm.

As the charge generating material, a material obtained by synthesizing titanyl phthalocyanine and recrystallizing it from a concentrated sulfuric acid solution was used. Next, the obtained crystals are 90 by an attritor mill.
5 parts pulverized at 90 ° C. for 90 minutes were mixed with 5 parts butyral resin (trade name “S-REC BL-1” manufactured by Sekisui Chemical Co., Ltd.) and 90 parts methylene chloride, and a dispersion for charge generation layer was prepared using a vibration mill. Obtained. Apply this paint on the above intermediate layer,
After drying, a charge generation layer having a film thickness of 0.4 μm was formed.

Next, as a hole transporting substance,

[0031]

[Chemical 1]

10 parts of a hydrazone compound represented by and a polycarbonate resin (trade name "Panlite L-1250"
W "Teijin Chemicals Co., Ltd.) 10 parts dissolved in 80 parts methylene chloride was applied by a dipping method and then dried to a thickness of 20.
A μm charge transport layer was formed.

(Electrical Characteristics) Next, with respect to the obtained belt-shaped electrophotographic photosensitive member, an electrostatic copying paper test apparatus "Mod" was used.
EL SP-428 "(manufactured by Kawaguchi Denki Seisakusho) was used to measure the electrical characteristics. The measuring method is as follows. An electrophotographic photosensitive member cut into a measurable size is attached to the apparatus, charged in a dark place by corona discharge with an applied voltage of -6 kV, and the surface potential immediately after this is set as an initial potential V ₀ in the electrophotography. It was used to evaluate the charging ability of the photoconductor. Next, the potential was measured after leaving it in the dark for 10 seconds, and was set to V ₁₀ . Here, the potential holding ability was evaluated by the ratio V ₀ / V ₁₀ . Then, monochromatic light having a wavelength of 780 nm was set so that the light intensity on the surface was 1 μW / cm ² , and the photosensitive layer was irradiated with light for 15 seconds to record the decay curve of the surface potential. Here, the surface potential after 15 seconds was measured and taken as the residual potential V _R. Further, the exposure amount until the surface potential was reduced to 1/2 of V ₁₀ by light irradiation was obtained, and the sensitivity was evaluated as the half exposure amount E _1/2 , and the results are shown in Table 1. As is clear from Table 1, this belt-shaped electrophotographic photosensitive member has sufficient practical performance.

[0034]

[Table 1]

(Durability test) In order to investigate the meandering prevention effect by the sprocket hole, a drive roll (diameter: φ20 mm, material: rubber) provided with a spirocket as shown in FIG.
Also, it is mounted on a driven roll (diameter: φ20 mm, material: aluminum), conveying speed 100 mm / sec, belt tension 3K.
When a durability test was conducted under the condition of g / full width, no abnormalities such as cracks occurred even during continuous 48-hour transportation without meandering.

[0036]

According to the present invention, in a belt-shaped electrophotographic photosensitive member having a photosensitive layer formed on a support, sprocket holes are provided on both sides of the support to provide guide rails for preventing meandering. It is possible to obtain a seamless belt-shaped electrophotographic photoreceptor that can be used without any practical use.

[Brief description of drawings]

FIG. 1 is an enlarged cross-sectional view showing an example of a layer structure of an electrophotographic photoreceptor of the present invention.

FIG. 2 is an enlarged cross-sectional view showing an example of the layer structure of the electrophotographic photoreceptor of the present invention.

FIG. 3 is an enlarged cross-sectional view showing an example of the layer structure of the electrophotographic photoreceptor of the present invention.

FIG. 4 is an enlarged cross-sectional view showing an example of the layer structure of the electrophotographic photosensitive member of the present invention.

FIG. 5 is a schematic view of an apparatus used for a durability test.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Metal belt-shaped support 2a Photosensitive layer 2b Photosensitive layer 2c Photosensitive layer 2d Photosensitive layer 3 Charge generating substance 4 Binder 5 Charge transporting substance 6 Charge generating layer 7 Charge transporting layer 8 Seamless belt-like electrophotographic photoconductor 9 Sprocket hole 10 Drive roll 11 Driven roll

Claims (2)

[Claims] 1. A belt-shaped electrophotographic photosensitive member having a photosensitive layer formed on a support, wherein the electrophotographic photosensitive member has sprocket holes on both sides of the support. 2. The electrophotographic photoconductor according to claim 1, wherein the support is a seamless belt produced by an electroforming method.