JPH05142790A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the seamless belt electrophotographic sensitive body without providing guide rails for preventing meandering. CONSTITUTION:This photosensitive body is constituted by forming a photosensitive layer on a base obtd. by forming a resist film for which a photosensitive resin is used on the parts on electrocasting masters corresponding to the edges on both sides of the base, then executing electrocasting.

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. As a method of realizing such an endless belt-shaped electrophotographic photosensitive member, a method of cutting a sheet-shaped electrophotographic photosensitive member and joining the end faces is known. In addition, in order to achieve seamless and seamless, casting method and inflation-type
There has been proposed a method for producing a resin-made seamless belt base material by an application method or the like.

A conductive substrate using electroformed nickel has also been proposed. Making a metal belt by electroforming,
Usually, it is obtained by depositing a metal in the electrolyte solution on the surface of a conductive roll-shaped mandrel and extracting the mandrel at the time when the required thickness of deposition is obtained. Because it is different, the length of the electroformed master is made longer than the required belt width, and it is cut into the required belt width after electroforming, or the belt width is set in advance in the central portion of the electroformed master. It is conceivable to attach a non-conductive tape or the like correspondingly to obtain an electroformed belt having a uniform film thickness.

However, in any case, when the belt electrophotographic photosensitive member is mounted on a copying machine, a printer or the like, the belt is prevented from meandering when it is driven, or cracks in the support due to the meandering are prevented. Therefore, it is necessary to provide a guide rail for preventing meandering, which causes a problem of high production cost.

[0006]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is to provide a practical electroless photoreceptor for a seamless belt without a meandering prevention treatment.

[0007]

In order to solve the above-mentioned problems, the present invention provides an electrophotographic photoreceptor comprising a support and a photosensitive layer formed on the support by electroforming. Provided is an electrophotographic photoreceptor, which is formed on a master by electroforming after forming a resist film using a photosensitive resin on portions corresponding to both side edge portions of a support.

By using the resist film, the precision at both ends of the support is improved and the durability is increased, whereby the guide rail for preventing meandering is successfully made unnecessary.

In the present invention, a photosensitive layer made of a photoconductive material is formed on a metal belt and used as an electrophotographic photoreceptor, but the structure of the photosensitive layer can take various forms. 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. The electrophotographic photoreceptor of FIG. 2 has a photosensitive layer formed by dispersing a charge generating material and a charge transporting material in a binder. The electrophotographic photoreceptors of FIGS. 3 and 4 are provided with 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 film thickness of these photosensitive layers is preferably in the range of 5 to 50 μm.

Further, if necessary, an intermediate layer may be formed between the metal belt and the photosensitive layer in order to improve the barrier property and the adhesive property.

Examples of the material of 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.

As the charge generating material used in the photosensitive layer, for example, 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 substances are generally classified into two types: substances that transport electrons and substances that transport holes.
Both of them can be used in the electrophotographic photoreceptor of the present invention.

Examples of the electron transport material 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
Organic compounds such as -trinitro-9,10-phenanthrenequinone, tetrachlorophthalic anhydride, diphenoquinone derivatives; inorganic materials such as amorphous silicon, amorphous selenium, tellurium, selenium-tellurium alloy, cadmium sulfide, antimony sulfide, zinc oxide, zinc sulfide. Can be mentioned.

As the hole-transporting substance, low molecular weight 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) pyrazolin; 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, halogenated poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin, ethylcarbazole- Formaldehyde resin, triphenylmethane polymer, polysilane, etc. may be mentioned.

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

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, it is preferable to use a high molecular polymer which is hydrophobic and is capable of forming an electrically insulating film.
Examples of such high molecular weight polymers include polycarbonate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile polymer, and chloride. Vinyl-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-
Alkyd resin, phenol-formaldehyde resin,
Examples thereof include styrene-alkyd resin, poly-N-vinylcarbazole, polyvinyl butyral, polyvinyl formal, and polysulfone, but are not limited thereto. These binders 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 binders.

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. As materials used for these layers, other than the polymer compound used for the binder, casein, gelatin, polyvinyl alcohol, ethyl cellulose, phenol resin, polyamide, carboxy-methyl cellulose, vinylidene chloride-based polymer latex, polyurethane, aluminum oxide, Examples thereof include silicon oxide, tin oxide and titanium oxide.

When the laminated type electrophotographic photoreceptor is formed by coating, a paint prepared by dissolving the above-mentioned 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 organic solvents 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 halogenation such as methylene chloride, chloroform, carbon tetrachloride and trichloroethane hydrocarbon;
Benzene, toluene, xylene, monochlorobenzene,
Examples thereof include aromatics such as dichlorobenzene.

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.

[0029]

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, "parts" means "parts by weight".

Example 1 Stainless steel was processed to prepare a mandrel roll having a diameter of 120 mm and a length of 500 mm, which was used as an electroformed master. "OMR-83" (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used on both sides 125 mm from the center in the longitudinal direction to form a resist film having a thickness of 2 μm and a width of 2 mm in the master-circumferential direction. 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 angstroms / second, and the thickness was 30 μm and the width was 250.
A nickel belt-shaped substrate of mm was prepared. The edges of both ends of this support were completed with extremely high precision.

Next, a modified polyamide resin (trade name "AQ-Nylon P-70" manufactured by Toray Industries, Inc.) 1 was formed on the belt-shaped substrate.
0 part was applied by a dipping method with a solution prepared by dissolving 50 parts of methanol and 50 parts of n-butanol, and the film thickness after drying was 1 μm.
A barrier layer was obtained.

As the charge generating material, a material obtained by synthesizing titanyl phthalocyanine and recrystallizing it from a concentrated sulfuric acid solution was used. 5 parts of the obtained crystal of titanyl phthalocyanine was crushed with an attritor mill at 90 ° C. for 90 minutes.
5 parts of butyral resin (trade name "ESREC BL-1" manufactured by Sekisui Chemical Co., Ltd.) and 90 parts of methylene chloride were mixed and a coating for a charge generation layer was obtained using a vibration mill. This paint was applied on the above intermediate layer, and after drying, a charge generation layer having a film thickness of 0.4 μm was formed.

Next, the formula of the hole transport material

[0034]

[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.

(Example 2) In Example 1, "OMR
-83 "instead of" CIR707 "(Nippon Synthetic Rubber
A belt-shaped substrate made of nickel was prepared in exactly the same manner as in Example 1 except that the belt-shaped substrate was used. The edges of both ends of this support were also finished with extremely high precision.

Then, a photosensitive layer was formed on this substrate in the same manner as in Example 1 to obtain a belt-shaped electrophotographic photosensitive member.

(Comparative Example) In Example 1, "OMR-8"
A nickel belt-shaped substrate was prepared in exactly the same manner as in Example 1 except that the Teflon tape was used to regulate the belt width instead of forming the resist film using "3". Many small notches were formed at the edges of both ends of this support, and it was not possible to finish it accurately.

Then, a photosensitive layer was formed on this substrate in the same manner as in Example 1 to obtain a belt-shaped electrophotographic photosensitive member.

(Electrical Characteristics) In order to compare the electrical characteristics of the belt-shaped electrophotographic photoconductors, the characteristics are measured by using an electrostatic copying paper test apparatus “Model SP-428” (manufactured by Kawaguchi Electric Co., Ltd.). It was measured. The measuring method is to mount the electrophotographic photosensitive member cut into a measurable size on the device,
Charged by corona discharge with an applied voltage of -6 kV in the dark,
Immediately after this, the surface potential was used as the initial potential V ₀ for evaluation of the charging ability of the electrophotographic photoreceptor. Next, the potential after leaving it in the dark for 10 seconds was measured and set to V ₁₀ . Where the ratio V ₀
The potential holding ability was evaluated by / V ₁₀ . Then wavelength 78
The intensity of 0 nm monochromatic light on the surface is 1 μW / cm.
^Then , the photosensitive layer was irradiated with light for 15 seconds, and the decay curve of the surface potential was recorded. 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 .
The results are shown in Table 1. As is clear from the table, it is understood that there is no difference in electrophotographic characteristic between the example and the comparative example.

[0041]

[Table 1]

(Durability Test) In order to check whether or not the meandering prevention treatment is required, as shown in FIG. 5, a driving roll (diameter: φ20 mm, material: rubber) provided with a flange and a driven roll are used. -Attached to the ruler (diameter: φ20 mm, material: aluminum),
A durability test was conducted under the conditions of a conveying speed of 100 mm / sec and a belt tension of 3 kg / full width.
Edge cracks begin to form within hours and 5 to 24 hours later
While several 10 mm cracks were generated, Examples 1 and 2
No crack was generated on the edge even after being continuously conveyed for 48 hours.

[0043]

According to the present invention, in an electrophotographic photoreceptor having a metal belt as a support by an electroforming method, both side edge portions of the support are coated with a photosensitive resin on an electroforming master. By making the plate by photolithography, it is possible to obtain a practical electroless photoreceptor for a seamless belt without providing a guide rail for preventing meandering.

[Brief description of drawings]

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

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

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

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

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

[Explanation of symbols]

 1 Metal Belt Support 2a Photosensitive Layer 2b Photosensitive Layer 2c Photosensitive Layer 2d Photosensitive Layer 3 Charge Generating Material 4 Binder 5 Charge Transporting Material 6 Charge Generating Layer 7 Charge Transporting Layer 8 Driving Roll 9 Driven Roll 10 Shearing Mures Belt Electrophotographic photoconductor

Claims (1)

[Claims] 1. An electrophotographic photosensitive member comprising a support and a photosensitive layer formed on the support by electroforming, wherein the support is on an electroforming master and corresponds to both side edge portions of the support. An electrophotographic photoreceptor, which is electroformed after a resist film is formed on a portion of the photosensitive resin.