JPH0682216B2 - Photoconductive member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to a novel function-separated laminated electrophotographic photoreceptor,
In particular, it relates to a photoconductive member used for a photoconductor.

"Problems to be Solved by Conventional Techniques and Inventions" Generally, electrophotographic photoreceptors are roughly classified into a single layer body and a function-separated layered type. As a single layer type, Se series, Cd
S-based, ZnO-based, PVK / TNF-based, pyrylium salt-based, and more recently, amorphous silicon-based and the like. Since the single layer type has both functions of generating and transporting optical carriers in one layer, it is necessary that both functions are excellent, but such a material has not been easily found.

For this reason, in recent years, there have been 2
A function-separated multi-layer type photoconductor having three different functions has been developed. Examples of the charge generation layer include Se-based, chlorodian blue-based, squarerium-based, azo pigment-based, phthalocyanine-based, pyrylium salt-based, and the like, and the charge-transporting layer includes PVK, pyrazoline-based, hydrazone-based, cyclohexane-based, Etc.

Among the above materials, the low molecular weight organic semiconductor is usually used by dispersing it in an insulating resin.

Since the above-described charge generation layer is generally a micron-order thin layer, it has low mechanical strength and it is difficult to provide the charge generation layer on the surface. Therefore, it is general to provide a charge transport layer as an upper layer and a charge generation layer as a lower layer. Generally, holes control the conduction of the charge transport layer, so that the charge polarity of the laminated photoreceptor is negative.

However, if the photoreceptor is used with negative charging, problems such as ozone generation and charging instability during corona charging are likely to occur, which may be practically inconvenient.

In addition, any charge generation layer has low photocarrier generation efficiency (quantum efficiency), and thus has low photosensitivity. Further, any charge transport layer has a small transport efficiency (drift mobility) of photogenerated carriers.

An object of the present invention is to provide a photoconductive member that can obtain a good image when used as an electrophotographic photoreceptor.

"Means and Actions for Solving Problems" First Invention The first invention was made to improve the above-mentioned drawbacks of the prior art, and is a laminated electrophotographic photosensitive material that can be used in positive charging. A photoconductive member of the body is provided. Moreover, the charge transporting layer and the charge generating layer do not use the above-mentioned materials, and the charge transporting layer has about 10 to about 10% in the insulating resin.
A layer in which 75% by weight of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine was dispersed was used as a charge generation layer. Uses a layer in which amorphous silicon fine powder is dispersed in a resin binder.

Further, in the first invention, in order to prevent surface abrasion of the charge generation layer, a metal or metal oxide having an average particle size of 0.3 μm or less is dispersed in the intermediate layer or the transparent insulating resin on the laminated photoreceptor. It is preferable to stack a transparent protective layer.

The photoconductive member of the first invention is preferably a transparent protective layer,
A latent image is formed by positively charging the charge generation layer through the intermediate layer, the electrons photogenerated in the charge generation layer neutralize the surface charge, and holes escape from the charge transport layer to the support. Is.

Examples of the insulating resin used for the charge transport layer include polycarbonate, acrylic ester polymer, vinyl polymer,
Cellulose polymers, polyesters, polysiloxanes, polyamides, polyurethanes and epoxies as well as block, random, alternating or graft copolymers and the like can be mentioned. A preferred insulating resin is polycarbonate resin. The preferred molecular weight is about 20,000 to about 100,000, more preferably about 50,000 to about 100,000.

The most preferable substance as the insulating resin is poly (4,4′-) having a molecular weight of about 35,000 to about 40,000, which is commercially available as Lexan145 from General Electric Company.
Isopropylidene-diphenylene carbonate); Poly (4,4'-isopropylidene-diphenylene carbonate) having a molecular weight of about 40,000 to about 45,000, which is marketed as Lexan 141 by General Electric Company; , Company (Farben fabrlcke
n Bayer AG) as a polycarbonate resin with a molecular weight of about 50,000 to about 100,000 as MaKrolon and Mobay Chemical Co.
on), the molecular weight is about 20,000 to about 50,000.
Is a polycarbonate resin.

The formula of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine is as follows.

The support should preferably be any suitable electrical conductor. Suitable conductors include aluminum, copper, graphite,
It contains dispersed conductive salts, conductive polymers and the like. The support can be rigid or flexible and can be of any thickness. Typical supports include flexible belts or sleeves, sheets, webs, plates, cylinders, drums. The support is also a thin conductive coating layer contained on a paper base, a plastic coated with a thin conductive layer such as aluminum or copper iodide,
Alternatively it may consist of a composite structure such as glass coated with a thin conductive coating of chromium or tin oxide.

Recently, it has high photosensitivity, is rich in panchromatic properties, and is pollution-free.
Amorphous silicon electrophotographic photoreceptors having excellent heat resistance, abrasion resistance, and photoresponsiveness have been proposed.

However, thin film amorphous silicon has a slow film growth rate, and it is difficult to maintain the temperature of the support during film formation uniform over a long period of time.

On the other hand, powdery amorphous silicon can be mass-produced by a simple manufacturing apparatus and is applied in combination with a binder, so that a uniform and large-area electrophotographic photoreceptor can be mass-produced.

There are two methods for obtaining the amorphous silicon fine powder.

One is a method of obtaining powder from an amorphous silicon film.

The amorphous silicon film is formed by glow discharge method (RF, DC), sputtering method, ion plating method, or the like. Of the above methods, the glow discharge method is often used because the control for forming the amorphous silicon film having the desired characteristics is relatively easy. A method of obtaining fine powdery amorphous silicon by shaving a thin film formed by this method from a substrate and pulverizing the thin film is one method.

Other methods for producing amorphous silicon fine powder include SiH ₄ ,
Introduce silicon hydride gas such as Si ₂ H ₆ or its derivative gas into the chamber in vacuum state, and adjust the chamber internal pressure.
There is a method of depositing amorphous silicon fine powder by glow discharge decomposition by keeping the value of 0.1 to 10 Torr, applying an electric field of RF or DC or a combination of these, heating the source gas as necessary. The above-mentioned raw material gas may be diluted with H ₂ and Ar in an appropriate amount before use.

The amorphous silicon fine powder contains hydrogen atoms, and the content thereof is usually 10 to 40 atomic%, preferably 15 to 30 at.
omic% is good. At the time of the glow discharge, it is necessary to introduce a gas such as B ₂ H _{6 of} Group III of the periodic table, and the addition ratio to the silicon hydride gas is preferably 1 to 50 vppm.

The particle size of the amorphous silicon fine powder is preferably 0.01 to 1 μm.

The weight ratio of the resin binder and the amorphous silicon-based fine particles is usually 5 to 60% by weight, preferably 8 to 50% by weight, optimally 10
~ 40% by weight.

Among the resin binders, the insulating ones are as follows.

Phenol resin: Furan resin: Xylene resin: Formaldehyde resin: Urea resin: Melamine resin: Aniline resin: Sulfonamide resin: Alkyd resin: Unsaturated polyester resin: Epoxy resin: Triallyl sialate resin: Polyethylene: Polypropylene: Polystyrene: Polyacetic acid Vinyl: Polyacrylate: Polymethacrylate: Polyvinyl chloride: Polyvinylidene chloride: Polytetrafluoroethylene: Polychlorotrifluoroethylene:
Polyvinyl fluoride: Polyvinylidene fluoride: Tetrafluoroethylene: Hexafluoropropylene copolymer: Fluorocarbon resin such as chlorotrifluoroethylene: Vinylidene fluoride copolymer: Polyacrylonitrile: Polyvinyl ether: Polyvinyl ketone: Polyether: Polycarbonate: Polyester: Nylon 6, Nylon 66, Nylon
Polyamide such as 6/66: Polyurethane: Silicone cellulose acetate, ethyl cellulose, propion cellulose,
Cellulose derivatives such as: etc. Two or more of these may be mixed if necessary.

Among the resin binders, the photoconductive ones are as follows.

PVK, carbazole, N-ethylcarbazole, N-isopropylcarbazole, N-phenylcarbazole tetraphenylpyrene, 1-methylpyrene, perylene, chrysene, atracene, tetracene, tetraphene, 2-
Phenylnaphthalene, azapyrene, fluorene, fluorenone, 1-ethylpyrene, acetylpyrene, 2,3-benzoglycerin, 3,4-benzopyrene, 1,4-bromopyrene, phenylindole, polyvinylpyrene, polyvinyltetracene, polyvinylperylene, polyvinyltetraphene , Polyacrylonitrile, PVK: TNF (molar ratio 1: 1 in monomer), tetranitrofluorenone, dinitroanthracene, dinitroacridene, tetracyanophenylene, dinitroanthraquinone, etc.

These photoconductive resin binders may be used as a mixture of two or more kinds as required, or may be used as a mixture with the above-mentioned electrically insulating binder.

As a solvent for kneading and dispersing the amorphous silicon fine powder together with the resin binder, it adversely affects the combination of the a-Si powder particles and the binder depending on the kind of the binder used. Selected from none. As such a solvent,
Generally, many of the commercially available organic solvents can be effectively used. For example, methylene chloride, chloroform, ethane dichloride, 1,1,2 ethane trichloride, retylene trichloride, ethane tetrachloride, carbon tetrachloride, 1,2 propane, 1,1,1
Ethane trichloride, ethylene tetrachloride, ethyl acetate, butyl acetate, isoamyl acetate, cellosolve acenate, toluene, xylene, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, dimethylamide, N-methylpyrrolidone, methyl alcohol, ethyl alcohol,
Examples include alcohols such as isopropyl alcohol and butyl alcohol.

The photoconductive member according to the first aspect of the present invention comprises a support, a charge transport layer, an insulating resin such as a polycarbonate resin, and the like.
The layer in which the weight% of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine was dispersed was used as a non-charge generation layer. It is characterized in that layers in which crystalline silicon fine powder is dispersed in a resin binder are laminated.

The thickness of the charge transport layer should be about 5-100 μm, although thicknesses outside this range can be used. The thickness of the charge generation layer has been found to be satisfactory at about 0.005 to 20 μm, and good results are obtained at a thickness of about 0.2 to 5 μm. However, it must be thinner than the carrier range of holes, or it will cause a residual potential.

Since the photoconductive member of the first aspect of the present invention can be used with positive charging as compared with the prior art, various problems when using negative charging can be avoided. Further, since the layer in which the amorphous silicon-based fine powder is dispersed is used for the charge generation layer, it has high photosensitivity and is rich in panchromaticity. Further, as a low molecular weight organic semiconductor in the charge transport layer, N, N′-diphenyl-N, N′-bis (3
-Methylphenyl)-(1,1'-biphenyl) -4,4 '
-Because the diamine is used, the carrier (hole) transport efficiency is high and it is suitable for high-speed copying machines.

Furthermore, in a preferred aspect of the first aspect of the present invention, an average particle size is present in the intermediate layer and the transparent insulating resin on the photoconductive member.
By laminating a transparent protective layer in which a metal or metal oxide of 0.3 μm or less is dispersed, surface abrasion of the charge generation layer can be suppressed.

The intermediate layer has a function of preventing injection of holes from the transparent protective layer into the charge generation layer. Examples of the material for the intermediate layer include silane coupling agents, zirconium butoxide, nylon, and epoxy. Particularly, the zirconium butoxide-based intermediate layer can be dried at room temperature.
It has a high hole injection blocking ability. The film thickness is 0.01 to 0.1
μm is preferred.

The metal or metal oxide contained in the transparent protective layer has a volume resistivity of 10 ¹¹ Ωcm or less and an average particle size of 0.
Any metal or metal oxide powder can be used as long as it is 3 μm or less. Examples thereof include metals such as gold, silver, aluminum, iron, copper and nickel, and metal oxides such as zinc oxide, titanium oxide, tin oxide, bismuth oxide, indium oxide and antimony oxide. At this time, several kinds of metals and metal oxides may be mixed and used. Particularly preferred is a powder containing tin oxide and antimony oxide and having an average particle size of 0.15 μm or less.

As the transparent insulating resin, one that is practically transparent to visible light and is excellent in electrical insulation, mechanical strength, and adhesiveness is desirable. For example, polyester resin, polycarbonate resin, polyurethane resin, epoxy resin, acrylic resin,
A vinyl chloride-vinyl acetate copolymer, a silicone resin, an alkyd resin, a polyvinyl chloride resin, a cyclized butadiene rubber, a fluororesin or the like can be used. When the solvent resistance of the protective layer is required, it is desirable to use a curable resin.

The composition ratio of the metal or metal oxide in the resin of the protective layer is 5 to 500 parts by weight of metal or metal oxide with respect to 100 parts by weight of the resin.
It is used in parts by weight, preferably in the range of 5 to 100 parts by weight. The thickness of the protective layer can be set between 0.5 and 30 μm as required.

On the other hand, a carrier blocking layer or an adhesive layer may be provided between the support and the charge transport layer. The carrier blocking layer material includes a silane coupling agent, nylon, epoxy, aluminum oxide and the like, and the adhesive layer material includes an insulating resin binder such as polyester as described above. The thickness of both the carrier blocking layer and the adhesive layer is preferably 0.01 to 0.1 μm, and the support, the carrier blocking layer, the adhesive layer, and the charge transport layer are laminated in this order.

Second Invention The second invention was made in order to improve the above-mentioned drawbacks of the prior art, and neither the charge generation layer nor the charge transport layer used the above-mentioned materials at all. That is, a layer in which amorphous silicon fine powder is dispersed in a resin binder is used as the charge generation layer, and about 10 to 75% by weight of N, N'in the insulating resin is used as the charge transport layer. -Diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl)-
A layer in which 4,4'-diamine is dispersed is used.

Further, in the second invention, in order to prevent surface abrasion of the charge transport layer, a transparent protective layer in which a metal or metal oxide having an average particle size of 0.3 μm or less is dispersed in a transparent insulating resin may be laminated. preferable.

The photoconductive member of the second aspect of the present invention preferably charges a negative charge on the charge transport layer through the transparent protective layer and neutralizes the negative charge on the charge transport layer with holes photogenerated from the charge generation layer. ,
It forms a latent image.

In the description of the second invention, the description of the same components as those in the first invention will be omitted.

About 10-75 in the polycarbonate resin as the charge transport layer
A layer in which wt% of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine is dispersed is preferred. Although the charge transport layer is substantially non-absorbent to visible light, it allows the injection of holes generated from the charge generation layer and transports these holes through the active charge transport layer. It is "active" in that it can selectively dissipate surface charges on the surface of the layer.

The photoconductive member according to the second aspect of the present invention comprises a support, a layer of amorphous silicon fine powder dispersed in a resin binder as a charge generation layer, and an insulating resin such as a polycarbonate resin as a charge transport layer. About 10 to 75% by weight of N, N'-diphenyl-N, N'-
It is characterized in that layers in which bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine is dispersed are laminated.

It has been found that a thickness of the charge generation layer of about 0.05 to 20 μm is satisfactory, and good results are obtained at a thickness of about 0.2 to 5 μm. The thickness of the charge transport layer should be about 5-100 μm, although thicknesses outside this range can be used.

Since the photoconductive member of the second invention uses the amorphous silicon fine powder dispersion layer as the charge generation layer, it has high photosensitivity and rich panchromaticity as compared with the prior art. Further, N, N′-diphenyl-N, N ′ is used as a low-molecular organic semiconductor in the charge transport layer.
Since -bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine is used, it has a high carrier (hole) transport efficiency and is suitable for high-speed copying machines.

Furthermore, in a preferred embodiment of the second aspect of the present invention, a transparent protective layer in which a metal or metal oxide having an average particle diameter of 0.3 μm or less is dispersed in a transparent insulating resin is laminated on the photoconductive member. The surface abrasion of the charge transport layer can be suppressed.

[Example] First invention Next, about 10% of insulating resin was applied on the support for the photoconductive member.
Table 7 75% by weight of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine dispersed charge transport layer, resin A charge generation layer in which an amorphous silicon-based fine powder composed of silicon atoms, hydrogen atoms, and atoms of Group III of the periodic table is dispersed in a binder, and the charge generation layers are sequentially stacked. Examples of the photoconductive member of the first invention will be described. Further, on the photoconductive member, the average particle size in the intermediate layer and the transparent insulating resin is
An example in which a transparent protective layer having a metal or metal oxide of 0.3 μm or less dispersed therein is laminated will be described.

Example 1 N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine powder
5g and 5g of polycarbonate resin powder sold as Makrolon by Farben Fabryken Bayer AG
And were placed in a flask containing 50 g of methylene chloride, stirred with a magnetic stirrer and dissolved to form a homogeneous dispersion liquid. This dispersion was applied onto an aluminum vapor-deposited PET film having a thickness of 150 μm using an applicator and dried at 80 ° C./hr to form a charge transport layer having a thickness of 25 μm.

Then, in the capacitively coupled glow discharge apparatus, it sets up a Corning 7059 glass plate on one of the electrodes to raise the degree of vacuum by a diffusion pump to a vacuum degree of 10 ⁶ Torr. After that, set the temperature of the glass plate to 250 ℃, SiH ₄ 100sccm, H ₂ 89sccm, B ₂
H ₆ , 11sccm (However, since B ₂ H ₆ is diluted with H ₂ ,
B ₂ H ₆ gas was injected into the equipment at a flow rate of 10 vppm with respect to SiH ₄ , and glow discharge decomposition was carried out at 13.56 MHz RF. After discharge decomposition, fine amorphous silicon powder was obtained on a glass plate.

Since the particle size of the fine powder is preferably 0.01 to 1 μm, fine powder having an average particle size of 0.1 μm was collected this time.

Next, 1.5 g of amorphous silicon fine powder with an average particle size of 0.1 μm
And 3.5 g of poly-N vinylcarbazole powder manufactured by Basuf Co., together with 7.5 g of toluene and 17.5 g of tetrahydrofuran,
The mixture was placed in an attritor, stirred and dissolved to form a homogeneous dispersion.

The dispersion was applied onto the charge transport layer using an applicator and dried under the condition of 80 ° C. for 30 minutes to form a charge generation layer having a film thickness of 0.5 μm, which had a laminated structure.

Incidentally, FIG. 1 shows a photoconductive member according to Example 1, and in FIG. 1, 1 is a charge generation layer, 2 is a charge transport layer, 3 is a support, and 4 is a photoconductive member. is there.

The above electrophotographic photosensitive member is model SP428 electr manufactured by Kawaguchi Denki.
It was set on an ostatic paper amaglyger and the electrophotographic characteristics were evaluated. Then, with an applied voltage of +6 kv, the charging potential was 760 v, the residual potential was 10 v, and the sensitivity was about 11 uxsec at the half exposure amount. Further, after 1 k cycle, the charging potential was 770 v, the residual potential was 20 v, and the sensitivity was about 11 uxsec at the half exposure amount.

A copy test was performed using a commercially available copying machine. As expected from the above data, the first cycle, 1K
A clear and good image with no fog was obtained at every cycle.

Example 2 This Example 2 provides a photoconductive member in which an intermediate layer and a transparent protective layer are laminated in this order on the photoconductive member prepared in Example 1.

First, 4 g of zirconium butoxide solution sold as ZA-60 from Matsumoto Trading and 1 g of γ-methacryloxypropyltrimethoxysilane solution sold as KBM503 from Shin-Etsu Chemical were added to a flask containing 300 g of ethanol. And stirred with a magnetic starter to dissolve it into a homogeneous dispersion.

On the photoconductive member, the photoconductive member prepared in Example 1 which had been placed in the constant temperature tank (80 ° C. setting) in advance was taken out by the constant temperature tank, and the dispersion liquid was immediately poured on the photoconductive member. Then, an intermediate layer having a film thickness of 0.1 μm was formed.

Next, 14 g of tin oxide / antimony oxide fine powder with an average particle size of 0.1 μm manufactured by Mitsubishi Metals and Retan 4000 from Kansai Paint.
Polyacryl urethane resin powder sold as
0.9 g was put into a ball mill containing 44.1 g of methylene chloride, and the pole mill was rotated to be stirred and dissolved to form a homogeneous dispersion liquid.

After making a homogeneous dispersion, transferred to a flask, adding 5.1 g of a curing agent and 632 g of methylene chloride, which are sold as Desmodur TPL-5-2291 by Sumitomo Bayer Urethane Co., Ltd.,
It was stirred with a magnetic stirrer and dissolved to form a homogeneous dispersion.

This dispersion was applied onto the above intermediate layer using an applicator, and dried under the condition of 80 ° C. for 24 hours to prepare a transparent protective layer having a thickness of 1 μm, which had a laminated structure.

Note that FIG. 2 shows the photoconductive member according to Example 2, and in FIG. 2, 5 is an intermediate layer, and 6 is a surface protective layer.

The electrophotographic photoconductor is model SP428 electr manufactured by Kawaguchi Denki.
It was set on an ostatic paper amaglyger and the electrophotographic characteristics were evaluated.

Then, with an applied voltage of +6 kv, a charging potential of 780 v, a residual voltage of 20 v, and a sensitivity of about 11 uxsec at a half exposure amount were obtained. Furthermore, after 1k cycle, the charging potential is 810v, the residual potential is 30v,
The sensitivity was about 11uxsec at half exposure.

When a copy test was carried out using a commercially available copying machine, as expected from the above data, clear and good fog-free images were obtained in both the first cycle and the 1Kth cycle.

Example 3 In Example 3, as shown in FIG. 3, the carrier blocking layer 7 and the adhesive layer 8 were provided in the photoconductive member prepared in Example 2.

Second invention Next, an amorphous silicon fine powder composed of silicon atoms, hydrogen atoms and atoms of Group III of the periodic table is dispersed in a resin binder on a support for a photoconductive member. Charge generating layer, about 10 to 75% by weight of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4 'in the insulating resin Examples of a photoconductive member according to the second aspect of the invention will be described in which a charge transport layer having a diamine dispersed therein is sequentially laminated. Further, on the photoconductive member, the average particle size in the transparent insulating resin is 0.3μ.
An example in which a transparent protective layer in which a metal or metal oxide of m or less is dispersed is laminated is also described.

Example 4 A Corning 7059 glass plate was installed on one electrode in a capacitively coupled glow discharge device, and the vacuum level of the diffusion pump was raised to a vacuum level of 10 ^-6 Torr. After that, the temperature of the glass plate was set to 250 ° C, SiH ₄ 100sccm, H ₂ 89sccm, B ₂ H ₆ 11sc
cm (However, since B ₂ H ₆ is diluted with H ₂ , B ₂ H ₆ is
Inject gas at a flow rate of 10 vppm) with respect to H ₄ into the device, and
Glow discharge decomposition was performed at RF of 3.56MHz. After discharge decomposition, black fine powder was obtained on the glass plate and in the chamber.

Since the particle size of the fine powder is preferably 0.01 to 1 μm, fine particles having an average particle size of 0.1 μm were collected by fractionation.

Next, 1.5 g of amorphous silicon-based fine powder and Poly-N manufactured by BASF
3.5 g of vinylcarbazole powder and 7.5 g of toluene and 17.5 g of tetrahydrofuran were put in an attritor, stirred and dissolved to form a homogeneous dispersion liquid.

This dispersion was applied onto an aluminum vapor-deposited PET film having a thickness of 150 μm using an applicator and dried at 80 ° C. for 30 minutes to form a charge generation layer having a thickness of 2 μm.

Next, 5 g of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine powder and Huarben Huabriken Weil AG 5g of polycarbonate resin powder sold as Macrolon from, and placed in a flask containing 50g of methylene chloride,
It was stirred and dissolved with a magnetic stirrer to obtain a homogeneous dispersion liquid.

This dispersion was applied onto the charge transport layer using an applicator and dried under the conditions of 80 ° C. for 1 hour to give a film thickness of 25 μm.
The charge transport layer of was prepared to have a laminated structure.

Incidentally, FIG. 4 shows a photoconductive member according to Example 4, and in FIG. 4, 11 is a charge transport layer, 12 is a charge generation layer, 13 support, and 14 is a photoconductive member. .

When the electrophotographic characteristics of the above electrophotographic photosensitive member were evaluated with an applied voltage of 6 kv, the charging potential was −760 v, the residual potential was −10 v, and the sensitivity was about 11 uxsoc at a half-exposure amount. Furthermore, after 1k cycle, the charging potential was −770v and the residual potential was −
20v, sensitivity was about 11ux soc at half exposure.

Example 5 This example provides a photoconductive member in which a transparent protective layer is laminated on the photoconductive member prepared in Example 4.

Put 14g of tin oxide / antimony oxide derivative powder with an average particle size of 0.1μm made by Mitsubishi Metals and 20.9g of polyacryl urethane resin powder sold as Retan 4000 by Kansai Paint into a ball mill containing 44.1g of methylene chloride. The ball mill was rotated, stirred and dissolved to form a homogeneous dispersion liquid.

After making a homogeneous dispersion, transferred to a flask, adding 5.1 g of a curing agent and 632 g of methylene chloride, which are sold as Desmodur TPL-5-2291 by Sumitomo Bayer Urethane Co., Ltd.,
It was stirred with a magnetic stirrer and dissolved to form a homogeneous dispersion.

This dispersion liquid was applied onto the above-mentioned photoconductive member using an applicator and dried under the conditions of 80 ° C and 24 hr to give a film thickness of 2 μm.
A transparent protective layer of m was formed to have a laminated structure.

Incidentally, FIG. 5 shows a photoconductive member according to Example 5, and in FIG. 5, 17 is a transparent protective layer.

The electrophotographic photoconductor is model SP428 electr manufactured by Kawaguchi Denki.
It was set in an ostatic paper analyger and the electrophotographic characteristics were evaluated.

Then, with an applied voltage of −6 kv, a charging potential of −780 v, a residual voltage of 20 v, and a sensitivity of about 11 uxsec at a half exposure amount were obtained. Furthermore, after 1k cycle, the charging potential is -810v and the residual potential is -810v.
50v, sensitivity was about 11uxsec at half exposure.

Example 6 In Example 6, as shown in FIG. 6, a carrier blocking layer 15 and an adhesive layer 16 are provided in the photoconductive member produced in Example 4.

"Effects of the Invention" As described above, according to the present invention, a good image can be obtained when used as an electrophotographic photoreceptor.

[Brief description of drawings]

FIG. 1 is a structural explanatory view showing a photoconductive member according to Embodiment 1 of the first invention, FIG. 2 is a structural explanatory view showing a photoconductive member according to Embodiment 2 of the first invention, and FIG. FIG. 4 is a structural explanatory view showing a photoconductive member according to Embodiment 3, FIG. 4 is a structural explanatory view showing a photoconductive member according to Embodiment 4 of the second invention, and FIG. 5 is a photoconductive member according to Embodiment 5 of the second invention. 6 is a structural explanatory view showing a photoconductive member according to Example 6 of the second invention. 1 ... Charge generation layer, 2 ... Charge transport layer, 3 ... Support,
4 ... Photoconductive member, 5 ... Intermediate layer, 6 ... Surface protective layer,
7 ... Carrier blocking layer, 8 ... Adhesive layer, 11 ...
Charge transport layer, 12 ... Charge generation layer, 13 ... Support, 14 ...
Photoconductive member, 15 ... Carrier blocking layer, 16 ... Adhesive layer, 17 ... Transparent protective layer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masayuki Nishikawa 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture Fuji Zero Tsux Co., Ltd. Takematsu Plant (72) Inventor Masato Ono 1600 Takematsu, Minami Ashigara City, Kanagawa Prefecture Fuji Zero Tsux Corporation Takematsu Business In-house (56) Reference JP-A-56-60446 (JP, A) JP-A-56-35140 (JP, A) JP-A-55-79450 (JP, A) JP-A-53-27033 (JP, A)

Claims (4)

[Claims] 1. A support for a photoconductive member, comprising about 10 to 75% by weight of N, N'-diphenyl-in an insulating resin.
Charge transport layer in which N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine is dispersed, silicon atom, hydrogen atom and periodicity in resin binder Front
A photoconductive member comprising a charge generation layer in which fine particles of amorphous silicon based on group III atoms are dispersed, which are sequentially laminated. 2. The photoconductive member according to claim 1, wherein a metal or metal having an average particle size of 0.3 μm or less in the intermediate layer and the transparent insulating resin on the photoconductive member. A photoconductive member comprising a transparent protective layer in which an oxide is dispersed and which is laminated. 3. A resin binder containing silicon atoms, hydrogen atoms, and a periodic table on a support for a photoconductive member.
A charge generation layer in which fine particles of amorphous silicon composed of group III atoms are dispersed. About 10 to 75% by weight of N, N'-diphenyl-in an insulating resin.
A photoconductive member comprising a charge transport layer in which N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine is dispersed, which are sequentially laminated. . 4. The photoconductive member according to claim 3, wherein a metal or metal oxide having an average particle size of 0.3 μm or less is contained in the transparent insulating resin on the photoconductive member. A photoconductive member comprising a laminated transparent protective layer dispersed therein.