JPH07181704A - Electrophotographic photoreceptor and its production - Google Patents

Abstract

PURPOSE:To easily form a transparent conductive layer by forming an electrophotographic photoreceptor out of an insulating transparent substrate, a specified transparent conductive layer formed on the insulating transparent substrate, and a photosensitive layer laminated on the transparent conductive layer. CONSTITUTION:The electrophotographic photoreceptor has an insulating transparent substrate, a transparent conductive layer comprising polyarylene vinylene expressed by formula I, polythienylene vinylene expressed by formula II or polyfurylene vinylene expressed by formula III on the insulating transparent substrate, and a photosensitive layer on the transparent conductive layer. The intermediates of polyarylene vinylene, polythienylene vinylene, and polyfurylene vinylene are soluble in a solvent, so that the intermediates are diluted with a solvent, applied on the insulating transparent substrate, dried and heat treated to form the layer comprising polyarylene vinylene, polythienylene vinylene, polyfurylene vinylene expressed by formula I to III. After the layer is formed, the layer is treated by doping to decrease the resistance. Thus, the transparent conductive layer is formed, or the film thickness of the transparent conductive layer is specified to obtain a layer having both of transparency and conductivity. Then, the photosensitive layer is formed on the transparent conductive layer to obtain the electrophotographic photoreceptor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member used in a process in which a transparent conductive layer is provided on an insulating transparent substrate, a photosensitive layer is laminated on the transparent conductive layer, and exposure is performed from the back surface of the photosensitive member. It relates to a manufacturing method. Current copier or high speed
A high-print quality printer generally uses an electrophotographic recording system. This system is a Carlson process in which a photoreceptor is used as a recording medium and recording is performed in seven steps of uniform charging, image exposure, development, transfer, fixing, charge removal, and cleaning. In charging, a positive or negative uniform electrostatic charge is applied to the surface of a photoconductor having photoconductivity, and in the subsequent exposure process, the surface charge of a specific portion is erased by irradiating a laser beam or the like to erase a specific part of the surface charge. Then, an electrostatic latent image corresponding to the image information is formed. Next, the latent image is electrostatically developed with toner to form a visible image with the toner on the photoconductor, and finally, the toner image is electrostatically transferred onto a recording paper to generate heat, Printing is obtained by fusing with light, pressure, or the like. However, in the conventional recording apparatus using the Carlson process, means used for each step are arranged around the photoconductor, and as the apparatus is miniaturized, the means for each step are closely connected around the photoconductor. As a result, there are drawbacks in that there is a limit to downsizing and that the developer is scattered from the developing device to stain the optical system used for the image exposing means, which adversely affects printing.

[0002]

2. Description of the Related Art Recently, in view of the above problems, an apparatus has been devised in which an image exposure source is installed inside a photoconductor in the image exposure process and light is irradiated from the backside of the photoconductor (for example, Japanese Patent Laid-Open Publication No. Sho. 63-174072). When the image exposure source is installed inside the photoconductor, it contributes to downsizing of the apparatus and elimination of dirt on the optical system due to scattering of the developer.
As the image exposing means, an LED array optical system, a laser optical system, an EL optical system, a liquid crystal shutter optical system, etc. can be used. In order to realize the above-mentioned apparatus, a photoreceptor for backside exposure which has the same printing characteristics as in the case where the exposure is performed from the outside is required even when the backside of the photoreceptor is exposed. A conventional photoconductor is one in which a conductive layer connected to a ground and a photoconductive layer are sequentially laminated on an insulating support, but a photoconductor for backside exposure has a support and a conductive layer for exposing light irradiated from the backside. It must penetrate and reach the photosensitive layer. For that purpose, a photoreceptor is required in which a layer having both transparency and conductivity is laminated on a support of an insulating transparent substrate.

[0003]

In a conventional backside exposure photoreceptor, when a transparent conductive layer is formed, indium tin oxide (I) having both high transparency and conductivity is formed.
TO) is used. As the forming technique, vacuum deposition or sputtering is used. However, this technique requires a long time of several tens of minutes to 1 hour to form a film with a film thickness of 100 Å, and has a further time and complicated process for putting the substrate in and out of the vacuum system. There were drawbacks such as difficulty in mass production.

[0004]

In order to solve the above problems, the present inventors have paid attention to an organic conductive layer that can be easily and inexpensively formed on an insulative transparent substrate, and an organic material suitable for this purpose. The present invention has been completed by developing or selecting a conductive material and improving the poor adhesion that occurs when forming such an organic conductive layer on an insulating substrate.

That is, according to the first aspect of the present invention, an insulative transparent substrate, and polyarylene vinylene of the following structural formula 1 and polythienylene of the following structural formula 2 laminated on the insulative transparent substrate. Provided is an electrophotographic photoreceptor including a transparent conductive layer made of vinylene or polyphenylene vinylene of Structural Formula 3 and a photosensitive layer laminated on the transparent conductive layer.

[0006]

[Chemical 8]

The polyarylene vinylene may be a substituted arylene vinylene, and is typically poly-p-phenylene vinylene of the following structural formula 4 or polydimethoxyphenylene vinylene of the following structural formula 5.

[0008]

[Chemical 9]

The intermediates of polyarylene vinylene, polythienylene vinylene and polyphenylene vinylene are soluble in a solvent. A solution prepared by diluting this intermediate with a solvent is applied on an insulating transparent substrate, dried and then heat treated. Then, a layer made of polyarylene vinylene, polythienylene vinylene, or polyphenylene vinylene of structural formulas 1 to 3 is formed. After the formation, a doping process is performed to reduce the resistance to form a transparent conductive layer. Further, by setting the film thickness of the transparent conductive layer within a specific range, a layer having both transparency and conductivity can be formed. After that, a photosensitive layer was formed on the transparent conductive layer to prepare a photosensitive body, and a photosensitive body applicable to a process of exposing from the back surface of the photosensitive body could be found.

The steps for producing the photoconductor will be described below. The production method of polyarylene vinylene, polythienylene vinylene, polyphenylene vinylene is known,
And since these polymers can be formed via a soluble intermediate, the soluble intermediate is converted into a suitable solvent, for example,
Pure water, an aqueous solution of sodium hydroxide, dimethylformamide, a solution of a general-purpose solvent such as pyridine dissolved in a single solvent or a mixed solvent is coated on an insulating substrate, and then converted into the above polymer by heat treatment or another method. Can be formed into a film of polymer.

For example, a method for producing poly-p-phenylene vinylene is described in M. Kanbe, Mokamura, J .; P
olym. Sci. Part A, 6, 1058 (196
According to the method described in 8), a sulfonium salt that is a soluble intermediate monomer was prepared, and the obtained sulfonium salt monomer was treated with F.I. E. Karast, J .; D. Capist
ran, D.I. R. Gangron and R.G. W. L
enz, Mol. Cryst. Liq. Cryst. The soluble intermediate and poly-p-phenylene vinylene can be synthesized by the method described in (1).

A method for synthesizing a polythienylene vinylene film is described in "Synthesis of Poly (2,5-thienylene vinylene) Film" by Murata et al.
11, No. 2, 187-193 (September 1989))
Has been reported to. After polymerizing 2,5-bis (methylenedimethylsulfonium chloride) thiophene (monomer) to obtain a sulfonium salt polymer electrolyte solution, an intermediate is obtained by substituting a methanol group for the sulfonium base bonded to the linear methylene group. Obtain the polymer. This intermediate is TH
It is soluble in F, and after casting to form a film, the methoxy group is thermally released to obtain a polythienylene vinylene film.

The transparent substrate is transparent such as glass and plastic. A known method such as a dip coating method, a spray coating method, a wire bar code method or a doctor blade coating method is used as a coating method on the transparent substrate. Further, as will be described later, in consideration of wettability with the transparent substrate, adhesiveness, etc., injection of additives or the like, or surface treatment with a silane coupling agent may be performed. Then, the solvent is dried and then subjected to a specific heat treatment to form a layer of polyarylene vinylene or the like on the transparent substrate.

After formation, a doping process is performed to reduce the resistance of the layer to form a transparent conductive layer. As the dopant used for the doping treatment, known ones such as concentrated sulfuric acid, iodine, sulfur trioxide, and arsenic pentafluoride can be used alone or in combination. The method of doping treatment is to use the diffusion from the liquid phase to the film by immersing it in a solution containing the dopant, or to expose the soluble conductive polymer layer to the gas phase and use the diffusion from the gas phase to the film. A known method such as a method of performing is used.

The thickness of the layer made of poly (p-phenylene vinylene) is preferably 0.01 μm to 5.0 μm. The thickness of the layer made of poly (dimethoxyphenylene vinylene) is 2.0 nm to 4.5 μm.
It is preferably m. The thickness of the layer made of poly (2,5-thienylene vinylene) is 1.0 nm to 4.
It is preferably 0 μm.

The thickness of the layer made of poly (2,5-thienylenevinylene) is preferably 2.0 nm to 4.3 μm. Next, as the photosensitive layer formed on the transparent conductive layer, known layers such as an inorganic photosensitive layer such as a so-called a-Se photosensitive layer and an a-Si photosensitive layer or an organic photosensitive layer can be used. Hereinafter, the organic photosensitive layer will be described in detail as an example, but the present invention is not limited thereto.

As the organic photosensitive layer, it is possible to use a single layer type or a laminated type organic photosensitive layer in which a charge generation layer-charge transport layer or a charge transport layer-charge generation layer are laminated in this order. Is preferably a layer in which a charge generation layer and a charge transport layer are laminated in this order. Each of these layers is usually obtained by binding a charge generating substance or a charge transporting substance with a binder resin, and is applied and formed by a known method such as dip coating, spray coating, doctor blade coating. When a sublimable substance such as a phthalocyanine pigment is used, the charge generator may be formed by a vapor deposition method. The charge generation layer preferably has a thickness of about 0.1 to 5 μm, particularly 1 μm or less, and the charge transport layer has a thickness of about 5 to 30 μm.

As the charge generating substance, known dyes and pigments such as phthalocyanine type, azo type, squarylium type and perylene type can be used alone or in combination, and selected in consideration of spectral sensitivity characteristics. As the charge transport material, compounds capable of transporting either holes or electrons among the photocarriers generated in the charge generation layer are used alone or in combination. Hole-transporting charge-transporting substances such as hydrazone, triarylamine, trinitrofluorenone and the like are known. Further, a photoconductive polymer having a charge transporting ability by itself such as polyvinyl carbazole or polysilane may be used, and in this case, the binder resin may be omitted.

As the binder resin, known resins such as polyester, epoxy, silicone, polyvinyl acetal, polycarbonate, acryl and aretane can be used alone or in combination. Further, as a solvent for forming each layer by coating using the above method, various organic solvents such as alcohol, tetrahydrofuran, chloroform, methylsorosolve, toluene and dichloromethane can be used alone or in combination.

An intermediate layer made of a resin such as cellulose, pullulan, casein or PVA may be provided between the transparent conductive layer and the photosensitive layer. The preferable thickness of the intermediate layer is 0.1.
˜5 μm, more preferably 1 to 2 μm, and can be formed by coating in the same manner as the photosensitive layer by a known method. In this aspect of the present invention, the conductive polymer polyarylene vinylene or the like is formed in the transparent conductive layer formed on the transparent substrate as described above by using a soluble intermediate such as polyarylene vinylene. The transparent conductive layer is formed from this intermediate by applying and drying a solution obtained by diluting the intermediate with a solvent, and performing heat treatment,
By performing the doping process and adjusting the film thickness to a specific value, it is possible to form a transparent conductive layer having both transparency and conductivity that can be applied to the process of exposing from the transparent conductive layer side of the photoconductor. For this reason, it is possible to simplify the transparent conductive layer by a conventional technique, for example, to form the transparent conductive layer by vapor deposition, sputtering, or the like, to fabricate the transparent conductive layer in a short time, and to mass-produce it.

According to the second aspect of the present invention, in an electrophotographic photoreceptor in which an organic conductive layer is formed on an insulating substrate and a photosensitive layer is laminated thereon, the organic conductive layer is bonded to the insulating substrate. There is provided an electrophotographic photosensitive member characterized by comprising an adhesive material contained in an organic conductive layer or an insulating base material, or formed as an adhesive layer on an insulating base material.

As described above, the light back exposure method requires a transparent conductive substrate and a transparent conductive layer. Conventionally, indium tin oxide having high transparency and conductivity is used for such a conductive layer. As the forming technique, vacuum deposition or sputtering is used. But,
With this technology, it takes several tens of minutes to 1 to make a film with a film thickness of 100Å.
Since it takes a long time and the substrate is put in and taken out from the vacuum system, it has a drawback that it has more time and complicated steps and is difficult to mass-produce.

When the film-forming area is large like a photoconductor, it is considered that the film can be formed most efficiently by the dip coating method similar to the conventional organic photoconductor. In order to form a transparent conductive film using the dip coating method, a solvent-soluble conductive material is required. As a soluble conductive material, a soluble conductive polymer or a metal oxide dispersed resin (Japanese Patent Application No. 05-0590) is used.
57) and the like have been considered, and a conductive layer having both transparency and conductivity can be obtained by controlling the film thickness of the conductive film. The organic conductive material disclosed in the first aspect of the present invention is also developed from such a viewpoint.

However, the adhesiveness between an organic conductive material in general, and an organic conductive material in particular, and an inorganic material is extremely low. Therefore, it is very difficult to put the photoconductor into practical use by using such a conductive material. Therefore, the inventors have studied to solve such problems and found that the problems can be solved by the second aspect of the present invention. By using this photoconductor, it is possible to establish an image forming method applicable to the optical backside process.

The steps for producing the photoconductor will be described below. First, engineered plastic for the insulating substrate,
A known insulating material such as glass can be used. As the conductive layer adhesive material, a material that can improve the adhesiveness between the organic conductive material and the inorganic insulating material is used. Typically, the organic silane compound of Structural Formula 6 and the both-end reactive organic silicone compound of Structural Formula 7 are used. A compound having two or more functional units in one molecule, which is a one-end reactive organosilicone compound of structural formula 8, an organic titanate compound of structural formula 9, an organoaluminum compound, and an organic zircoaluminate compound, and There is an oxazoline-based reactive polymer of structural formula 10.

[0026]

[Chemical 10]

[0027]

[Chemical 11]

Specific examples of the organic silane compound include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, β- (3,4epoxycyclohexyl) ethyltrimethoxysilane, γ. -Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-metacryloxypropyltrimethoxysilane, γ- Methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-
Aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane,
Known organic silane compounds represented by Structural Formula 6 such as γ-mercaptopropyltrimethoxysilane can be used alone or in combination.

As the both-end reactive organosilicone compound, an organosilicone compound represented by the structural formula 7, for example, known organic silicone compounds represented by the structural formulas 15 to 20 can be used alone or in combination.

[0030]

[Chemical 12]

As the one-end reactive organosilicone compound, an organosilicone compound represented by Structural Formula 3, for example, known organic silicone compounds represented by Structural Formulas 21 to 23 can be used alone or in combination.

[0032]

[Chemical 13]

Examples of the organic titanate compound include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra ( 2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl Titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tridodecylbenzene sulfonyl Taneto, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, etc. known organic titanate compound represented by the structural formula 9 can be used alone or as a mixture.

As the organic aluminum compound, known organic aluminum compounds such as acetoalkoxyaluminum diisopropylate can be used alone or in combination. An organic zircoaluminate compound means at least one Zr atom and at least one Al in the molecule.
A compound having at least one functional unit having an atom and capable of reacting with a conductive material. As the organic zircoaluminate compound, a commercially available one (for example, CAVCO MOD (trade name) manufactured by CAVEDON CHEMICAL CO. INK. In the US) can be used as it is. Specifically, for example, CAVCO MOD
-A (Amino group-containing compound, CAVEDONCHEMI
CALCA), CAVCO MOD-C (carboxyl group-containing compound) CAVEDON MOD-C-1
(Compound containing carboxyl group), CAVCO MOD-
F (fatty acid-containing compound), CAVCO MOD-M (methacryloxy group-containing compound), CAVCO MOD-
M-1 (methacryloxy group-containing fatty acid reaction product), CA
VCO MOD-S (mercaptan group-containing compound), C
AVCO MOD-APG (Amino group-containing compound), C
AVCO MOD-CPG (carboxyl group-containing compound), CAVCO MOD-CPM (carboxyl group-containing compound), CAVCO MOD-FP (fatty acid-containing compound), CAVCOMOD-MPG (methacryloxy group-containing compound), CAVCO MOD-MPM (methacryloxy) Known compounds such as group-containing compounds) can be used alone or in combination.

As the oxazoline-based reactive polymer,
As the compound represented by Structural Formula 10, a commercially available compound (for example, K-1000 series or RPS / RAS series (trade name) manufactured by Nippon Shokubai) can be used as it is. Specifically, K-1010E (manufactured by Nippon Shokubai), K-1020E, K-1030E, RPS-10
Known oxazoline compounds such as 01, RPS-1005 and RAS-1005 can be used alone or in combination.

As a treatment method, there is a method of mixing a conductive layer adhesive material with a conductive layer or an insulating substrate, and forming an adhesive layer on the surface of the insulating substrate. When the adhesive material is mixed with the conductive layer, the mixing ratio is 0.01 to 50 wt%,
More preferably, it is 0.1 to 10 wt%. When the amount of the adhesive material is small, the effect of improving the adhesiveness is insufficient, while when the amount of the adhesive material is too large, there is a disadvantage that the conductivity decreases.

When the adhesive material is mixed with the insulating substrate, the mixing ratio is preferably 0.01 to 50 wt%, more preferably 0.1 to 10 wt%. When the adhesive material is formed as an adhesive layer on the surface of the insulating substrate, the adhesive layer has an effect of improving the adhesiveness, so the thickness of the adhesive layer may be thin, but preferably 1Å to 50 μm, more preferably 100Å to 5
μm.

As a method for forming the adhesive layer, known methods such as a dry method, a wet method and a spray coating method can be used. As the treatment solvent, known solvents such as water, ethanol, methanol, toluene, acetone, chloroform, dichloromethane and tetrahydrofuran can be used alone or in combination. Further, the conductive layer adhesive material is the above-mentioned organic silane compound, organic silicone compound,
Organic titanate compounds, organic aluminum compounds, organic zircoaluminate compounds, and oxazoline-based polymers can be used alone or in combination.

The conductive material used for the conductive layer is not particularly limited, but polyaniline or polypyrrole derivative having structural formula 11 and structural formula 12 as repeating units (structural formula 1
3), polythiophene derivative (structural formula 14), poly (p
-Phenylene vinylene) (structural formula 4) and poly (2,5)
-Thienylenevinylene) (structural formula 5) and the like poly (arylenevinylene) (structural formula 1), poly (2,5-furinylenevinylene) (structural formula 2), poly (dimethoxyphenylenevinylene) (structural formula 3) ), Or a resin in which a metal oxide is dispersed can be used alone or as a mixture.

[0040]

[Chemical 14]

[0041]

[Chemical 15]

In the structural formulas 13 and 14, R is mainly a linear substituent and is preferably an alkyl group, an alkoxy group, an allyl group or a combination of these groups, and further, a sulfonate group, an ester group, an amide group. Etc. may be combined or combined. It suffices that the property of the soluble conductive polymer is not lost. As the metal oxide, known ones such as indium tin oxide and SnO ₂ can be used alone or in combination. The resin to be dispersed is polyester, epoxy, silicone,
Polyvinyl acetal, polycarbonate, acrylic,
Known resins such as urethane can be used alone or in combination.

As a method for forming the conductive layer, known methods such as a dip coating method, a spray coating method, a wire bar code method and a doctor blade coating method are used. Also,
As the solvent for forming the conductive layer using these methods, known solvents such as water, dichloromethane, chloroform, tetrahydrofuran, trichloroethane, N-methyl-2-pyrrolidone, toluene, cyclohexane and xylene can be used.

If necessary, the above conductive material can be subjected to a doping treatment. As the dopant used for the doping treatment, known ones such as sulfuric acid, iodine, sulfur trioxide, arsenic pentafluoride, p-toluenesulfonic acid, naphthalenesulfonic acid, alkylbenzenesulfonic acid and camphorsulfonic acid can be used alone or in combination. . The method of doping treatment includes a method of utilizing the diffusion from the liquid phase to the film by immersing it in a solution containing a dopant, a method of exposing the conductive layer to the gas phase and utilizing the diffusion from the gas phase to the film, or the above-mentioned method. A known method such as a method of mixing a dopant with a solution of a conductive material is used.

As the photosensitive layer formed on the conductive layer, a known layer such as an inorganic photosensitive layer such as a so-called a-Se photosensitive layer or an a-Si photosensitive layer or an organic photosensitive layer can be used.
Hereinafter, the organic photosensitive layer will be described in detail as an example, but the present invention is not limited thereto. The organic photosensitive layer may be a single layer type or a laminated organic photosensitive layer in which a charge generating layer-charge transport layer or a charge transport layer-charge generating layer are stacked in this order. It is preferable that the layers and the charge transport layer are laminated in this order. Each of these layers is usually obtained by binding a charge generating substance or a charge transporting substance with a binder resin, and is applied and formed by a known method such as dip coating, spray coating, doctor blade coating. When a sublimable substance such as a phthalocyanine pigment is used, the charge generation layer may be formed by vapor deposition. The charge generation layer preferably has a thickness of about 0.1 to 5 μm, particularly 1 μm or less, and the charge transport layer has a thickness of about 5 to 30 μm.

As the charge generating substance, known dyes and pigments such as phthalocyanine type, azo type, squarylium type and perylene type can be used alone or in combination, and selected in consideration of the spectral sensitivity characteristic. As the charge transport material, compounds capable of transporting either holes or electrons among the photocarriers generated in the charge generation layer are used alone or in combination. Hole-transporting charge-transporting substances such as hydrazone, triarylamine, trinitrofluorenone, and butadiene derivatives are known. Further, a photoconductive polymer having a charge transporting ability by itself such as polyvinyl carbazole or polysilane may be used, and in this case, the binder resin may be omitted.

As the binder resin, known resins such as polyester, epoxy, silicone, polyvinyl acetal, polycarbonate, acryl and urethane can be used alone or in combination. Further, as a solvent for forming each layer by coating using the above method, various organic solvents such as alcohol, tetrahydrofuran, chloroform, methylsorosolve, toluene and dichloromethane can be used alone or in combination.

An intermediate layer made of a resin such as cellulose, pullulan, casein or PVA may be provided between the conductive layer and the photosensitive layer. The preferred thickness of the intermediate layer is 0.1 to
The thickness is 5 μm, more preferably 1 to 2 μm, and can be formed by coating by a known method similarly to the photosensitive layer. Second of the present invention
On the side surface of, an electrophotographic photosensitive member having a conductive layer formed on an insulating substrate, and a photosensitive layer further laminated thereon, wherein the conductive layer or the insulating substrate has the conductive layer adhesive material.
Alternatively, an adhesive layer may be provided between the insulating substrate and the conductive layer, and the adhesive layer may have a conductive layer adhesive material to remarkably improve the adhesion between the insulating substrate and the conductive layer. A photographic photoreceptor was found.

[0049]

EXAMPLES The present invention will be described below in detail based on examples, but the invention is not limited thereto. Example 1 p-xylylene bis (diethylsulfonium bromide)
And a sodium hydroxide aqueous solution were mixed and reacted to obtain a soluble intermediate of poly (p-phenylene vinylene) having a sulfonium salt represented by the following structural formula 24 in the side chain.

[0050]

[Chemical 16]

The reaction solution was dialyzed against water for 1 week using a dialysis membrane (cellophore, molecular weight fraction 3500). A transparent substrate of the photoconductor is dip-coated in this aqueous solution, dried under reduced pressure, and treated at 300 ° C. for 2 hours in a nitrogen atmosphere to give poly (p-phenylene vinylene) of structural formula 4 on the transparent substrate. Layers were formed. This was dipped in a concentrated sulfuric acid solution and subjected to a doping treatment to form a transparent conductive layer having a film thickness of 0.5 μm. Next, 1 part of cyanoethylated pullulan was added to 10 parts of acetone (parts by weight).
Was dissolved in, and was coated on the conductive layer by dip coating, and dried at 100 ° C. for 1 hour to form an intermediate layer having a film thickness of 1 μm. next,
α-type oxo tital phthalocyanine 1 part, polyester 1
Parts, 1,2,2-trichloroethane 20 parts were dispersed and mixed for 24 hours using a hard glass ball and a hard glass pot, and the mixture was coated on the intermediate layer and dried at 100 ° C. for 1 hour to obtain a film thickness. A charge generation layer of about 0.3 μm was formed. A coating solution was prepared by dissolving 1 part of a butadiene derivative and 1 part of polycarbonate in 17 parts of dichloromethane. This was applied onto the above charge generation layer by dip coating and dried at 90 ° C. for 1 hour to form a charge transport layer having a film thickness of about 15 μm to form a photosensitive layer. The photoconductor of Example 1 was obtained.

[0052]

[Chemical 17]

Example 2 In Example 1, a soluble intermediate of poly (2,5-thienylenevinylene) represented by the following structural formula 25 was used to prepare the transparent conductive layer, and poly (2,5) represented by the following structural formula 3 was used. A photoconductor of Example 2 was obtained in exactly the same manner as in Example 1 except that a transparent conductive layer made of thienylenevinylene) was used.

[0054]

[Chemical 18]

Example 3 In Example 1, a soluble intermediate of poly (2,5-phenylenevinylene) represented by the following structural formula 26 was used to prepare the transparent conductive layer, and poly (2,5) represented by the following structural formula 3 was used. A photoconductor of Example 3 was obtained in exactly the same manner as in Example 1 except that a transparent conductive layer made of (phenylene vinylene) was used.

[0056]

[Chemical 19]

Example 4 In Example 1, a soluble intermediate of poly (dimethoxyphenylenevinylene) represented by the following structural formula 27 was used to prepare a transparent conductive layer, and a transparent transparent poly (dimethoxyphenylenevinylene) of the following structural formula 5 was used. A photoconductor of Example 4 was obtained in exactly the same manner as in Example 1 except that a conductive layer was used.

[0058]

[Chemical 20]

Example 5 A photoconductor of Example 5 was obtained in exactly the same manner as in Example 1 except that the thickness of the transparent conductive layer was 5.0 μm. Example 6 A photoreceptor of Example 6 was obtained in exactly the same manner as in Example 2 except that the film thickness of the transparent conductive layer was 4.0 μm. Example 7 A photoconductor of Example 7 was obtained in exactly the same manner as in Example 3 except that the thickness of the transparent conductive layer was 4.3 μm. Example 8 A photoreceptor of Example 8 was obtained in exactly the same manner as in Example 4 except that the thickness of the transparent conductive layer was 4.5 μm. Example 9 A photoreceptor of Example 9 was obtained in exactly the same manner as in Example 1 except that the thickness of the transparent conductive layer was 0.01 μm. Example 10 A photoreceptor of Example 10 was obtained in exactly the same manner as in Example 2 except that the thickness of the transparent conductive layer was 1.0 nm.

Example 11 A photoreceptor of Example 11 was obtained in exactly the same manner as in Example 3 except that the thickness of the transparent conductive layer was 2.0 nm.

Example 12 A photoreceptor of Example 12 was obtained in exactly the same manner as in Example 4 except that the thickness of the transparent conductive layer was 2.0 nm.

Comparative Example 1 A photoreceptor of Example 5 was obtained in exactly the same manner as in Example 1 except that the film thickness of the transparent conductive layer was 6.0 μm.

Comparative Example 2 A photoconductor of Example 6 was obtained in exactly the same manner as in Example 2 except that the thickness of the transparent conductive layer was 4.5 μm.

Comparative Example 3 A photoreceptor of Example 7 was obtained in exactly the same manner as in Example 3 except that the thickness of the transparent conductive layer was 5.0 μm.

Comparative Example 4 A photoconductor of Example 8 was obtained in exactly the same manner as in Example 4 except that the thickness of the transparent conductive layer was 5.0 μm.

Comparative Example 5 A photoconductor of Example 9 was obtained in exactly the same manner as in Example 1 except that the thickness of the transparent conductive layer was 1.0 nm.

Comparative Example 6 A photoconductor of Example 10 was obtained in exactly the same manner as in Example 2 except that the thickness of the transparent conductive layer was 0.5 nm.

Comparative Example 7 A photoconductor of Example 11 was obtained in exactly the same manner as in Example 3 except that the thickness of the transparent conductive layer was 1.0 nm.

Comparative Example 8 A photoconductor of Example 12 was obtained in exactly the same manner as in Example 4 except that the thickness of the transparent conductive layer was 1.0 nm. The photoconductor characteristics of the photoconductors manufactured in Examples and Comparative Examples were examined and a printing test was conducted. When the photoconductor characteristics were examined, the exposure was performed from the outside of the photoconductor. Regarding the characteristics of the photoconductor, the half exposure amount, the residual potential and the charge retention rate were measured. In the measurement, light having a wavelength of 660 nm was used for exposure. This is light of the same wavelength as the optical system used for the print test. Tables 1 and 2 show the measurement results of the photoreceptor characteristics. The photoconductor characteristics of the photoconductors of Examples 1 to 12 and Comparative Examples 1 to 4 could be measured, but the photoconductors of Comparative Examples 5 to 8 showed no attenuation of the potential even when irradiated with light, and the half exposure amount The residual potential could not be measured.

Further, FIG. 1 shows a printing apparatus used for a printing test, and FIG. 2 shows an image forming process. 1 and 2,
The photoreceptor 2 having the optical system 1 accommodated therein is composed of the transparent substrate 3, the above-mentioned conductive layer 4 and the photosensitive layer 5, and the transparent conductive layer 4 is grounded. The developer 7 in the developing unit 6 is a magnetic two-component developer, and the toner 8 and the carrier 9 are magnetic. In the developing roller 10, a conductive sleeve 12 is provided on a magnet roller 11, and the developer 7 is attracted to the developing roller 10 by a magnetic force and is carried to the photoconductor 2 while being attached to the conductive sleeve 12.

The optical system 1 is arranged on the back side of the photoconductor 2 at a position facing the developing device 6. The optical system 1 includes an LED array 1A that emits light according to an image signal and a SELFOC lens array 1 that collects the image light of the LED array 1A.
B, and a glass plate 1C that fixes the LED array 1A so that the focal position of the image light does not shift. In addition, a negative bias voltage is applied to the conductive sleeve 12 from the DC power supply 16.

In this process, the surface of the photoreceptor is first shown in FIG.
As in (a), the developer 7 is uniformly charged.
Next, as shown in FIG. 2B, the charged photoreceptor 2 is image-exposed as indicated by an arrow A from the transparent substrate side (inside), and
A latent image is formed as shown in (c). In the latent image forming portion, the electric adhesive force B of the toner 8 to the photoconductor 2 is the developing roller 10.
Is developed due to the magnetic force of the developing roller 10 and the carrier 9 and the electric repulsive force between the photosensitive member surface and the toner 8 in the background portion other than the latent image forming portion. Is not attached to the developing device 6 and is collected by the developing device 6. The developed toner is transferred to the recording medium 13, that is, paper or a plastic plate through the transfer roller 14, and the print is obtained through the fixing device 15.

Tables 1 and 2 show the evaluation results of the printing test. With the photoreceptors of Examples 1 to 12, good printing could be obtained. However, good printing could not be obtained with the photoreceptors of Comparative Examples 1-8. In the photoconductors of Comparative Examples 1 to 4, the print density was lower than that of the photoconductors of Examples, and
In No. 8, it was not possible to form a powder image with toner on the photoconductor.

From the above, 0.01 μm to 5.0 μm for poly (p-phenylene vinylene), 1.0 nm to 4.3 μm for poly (parachenylene vinylene), and poly (2,5-phenylene vinylene) Then 2.0 nm to 4.3
It was found that, in the case of poly (dimethoxyphenylene vinylene), the range of 2.0 nm to 4.5 μm can be applied to the process of exposing from the back surface of the photoreceptor.

[0075]

[Table 1]

[0076]

[Table 2]

Example 13 1 part (part by weight) of soluble polyaniline containing structural formulas 11 and 12 as repeating units and 0.1 part of γ-glydoxypropyltrimethoxysilane in 99 parts of n-methyl-2-pyrrolidone Apply the dissolved solution by dip coating, and after coating 15
It was heated and dried at 0 ° C. for 30 minutes to form a 0.5 μm polyaniline film on glass. 1 mol of the polyaniline film
immersing in 1 p-toluenesulfonic acid aqueous solution for 1 hour,
A doping process was performed to form a conductive layer.

Next, 1 part of cyanoethylated pullulan is dissolved in 10 parts of acetone, and this is applied onto the conductive layer by dip coating.
It was heated and dried at 00 ° C. for 1 hour to form an intermediate layer having a film thickness of about 1 μm. 1 part of α-type oxo tital phthalocyanine, 1 part of polyester, and 20 parts of 1,1,2-trichloroethane dispersed and mixed for 24 hours using a hard glass ball and a hard glass pot are applied on the above-mentioned intermediate layer, 100 ° C
And dried for 1 hour to form a charge generation layer having a thickness of about 0.3 μm.

A coating solution was prepared by dissolving 1 part of a butadiene derivative and 1 part of polycarbonate in 17 parts of dichloromethane. This was applied onto the above charge generation layer by dip coating and dried at 90 ° C. for 1 hour to form a charge transport layer having a film thickness of about 15 μm, and a photosensitive layer was formed to obtain a photoreceptor of Example 13.

Example 14 A photoconductor of Example 14 was obtained in the same manner as in Example 13, except that γ-glydoxypropyltrimethoxysilane in Example 13 was replaced with a silicone compound having an epoxy group at both terminals of Structural Formula 20.

Example 15 A photoconductor of Example 15 was obtained in the same manner as in Example 13, except that γ-glydoxypropyltrimethoxysilane in Example 13 was replaced with a silicone compound having an epoxy group at one terminal of Structural Formula 22.

Example 16 A photoconductor of Example 16 was obtained in exactly the same manner as Example 13 except that γ-glydoxypropyltrimethoxysilane was replaced with isopropyltri (N-aminoethyl-aminoethyl) titanate.

Example 17 A photoconductor of Example 17 was obtained in exactly the same manner as in Example 13, except that γ-glydoxypropyltrimethoxysilane was changed to acetoalkoxyaluminum diisopropylate.

Example 18 γ-Glydoxypropyltrimethoxysilane used in Example 13 was replaced with a mercaptan group-containing organic zircoaluminate compound (CACVO MOD-S, CAVEDON C).
A photoreceptor of Example 18 was obtained in exactly the same manner except that it was manufactured by HEMICAL.

Example 19 An example was carried out in the same manner as in Example 13, except that the γ-glydoxypropyltrimethoxysilane in Example 13 was replaced by an oxazoline-based reactive polymer (RPS-1001, manufactured by Nippon Shokubai) whose main chain was polystyrene. 19 photoconductors were obtained.

Example 20 Glass was dipped in a solution prepared by dissolving 1 part of γ-glydoxypropyltrimethoxysilane in 9 parts of pure water for 15 minutes, dipped and dried at 105 ° C. to form an adhesive layer on the glass surface. Formed. Next, a solution of 1 part of soluble polyaniline having Structural Formulas 11 and 12 as repeating units dissolved in 99 parts of n-methyl-2-pyrrolidone was applied by dip coating to form a 0.5 μm polyaniline film on glass. . The polyaniline film was dipped in a 1 mol / l p-toluenesulfonic acid aqueous solution for 1 hour and subjected to a doping treatment to form a conductive layer. Except for the above, the conductive layer and the upper layer were the same as in Example 1 to obtain a photoconductor of Example 20.

Example 21 A photoconductor of Example 21 was obtained in exactly the same manner as in Example 20, except that γ-glydoxypropyltrimethoxysilane was replaced with a silicone compound having an epoxy group at both terminals of Structural Formula 20.

Example 22 A photoconductor of Example 22 was obtained in the same manner as in Example 20, except that γ-glydoxypropyltrimethoxysilane was replaced by a silicone compound having an epoxy group at one terminal of Structural Formula 22.

Example 23 A photoconductor of Example 23 was obtained in exactly the same manner as in Example 21, except that γ-glydoxypropyltrimethoxysilane was replaced with isopropyltri (N-aminoethyl-aminoethyl) titanate.

Example 24 A photoconductor of Example 23 was obtained in exactly the same manner as in Example 21, except that γ-glydoxypropyltrimethoxysilane was changed to acetoalkoxyaluminum diisopropylate.

Example 25 γ-Glydoxypropyltrimethoxysilane used in Example 8 was replaced with a mercaptan group-containing organic zircoaluminate compound (CACVO MOD-S, CAVEDON CH).
A photoconductor of Example 25 was obtained in exactly the same manner except that it was manufactured by EMICAL.

Example 26 An example was carried out in the same manner as in Example 8 except that γ-glydoxypropyltrimethoxysilane was replaced by an oxazoline-based reactive polymer (RPS-1001, manufactured by Nippon Shokubai) whose main chain was polystyrene. 26 photoconductors were obtained.

Example 27 On a insulating substrate prepared by mixing 100 parts of polycarbonate with 1 part of γ-glydoxypropyltrimethoxysilane, 1 part of soluble polyaniline having structural formulas 11 and 12 as repeating units was added. -Methyl-2-pyrrolidone 99
The dissolved solution was applied by dip coating, and after coating, it was heated and dried at 150 ° C. for 30 minutes to form a 0.5 μm polyaniline film on the glass. The polyaniline film was immersed in a 1 mol / l p-toluenesulfonic acid aqueous solution for 1 hour to perform a doping treatment to form a conductive layer. A photoreceptor of Example 27 was obtained in the same manner as in Example 13, except for the above, from the conductive layer to the upper layer.

Example 28 A photoconductor of Example 28 was obtained in exactly the same manner as in Example 27 except that γ-glydoxypropyltrimethoxysilane was replaced by a silicone compound having a structural formula 20 having epoxy groups at both ends.

Example 29 A photoconductor of Example 29 was obtained in exactly the same manner as in Example 27 except that γ-glydoxypropyltrimethoxysilane was replaced by a silicone compound having an epoxy group at one terminal of structural formula 22.

Example 30 A photoreceptor of Example 30 was obtained in exactly the same manner as in Example 27 except that γ-glydoxypropyltrimethoxysilane was replaced with isopropyltri (N-aminoethyl-aminoethyl) titanate.

Example 31 A photoconductor of Example 31 was obtained in exactly the same manner as in Example 27 except that γ-glydoxypropyltrimethoxysilane was changed to acetoalkoxyaluminum diisopropylate.

Example 32 The γ-glydoxypropyltrimethoxysilane used in Example 27 was replaced with a mercaptan group-containing organic zircoaluminate compound (CACVO MOD-S, CAVEDON C).
A photoreceptor of Example 32 was obtained in exactly the same manner except that it was manufactured by HEMICAL.

Example 33 A photoreceptor of Example 33 was prepared in the same manner as in Example 27 except that γ-glydoxypropyltrimethoxysilane was replaced by an oxazoline-based reactive polymer (RPS-1001) whose main chain was polystyrene. Obtained.

Example 34 Glass was dipped in a solution prepared by dissolving 1 part of N-β (aminoethyl) γ-aminopropyltrimethoxysilane in 9 parts of pure water for 15 minutes, dipped at 105 ° C. and dried to obtain glass. An adhesive layer was formed on the surface. Next, a solution prepared by diluting 1 part of the polypyrrole derivative of structural formula 24 with 50 parts of tetrahydrofuran was applied by dip coating. After the application, it was heated and dried at 100 ° C. for 30 minutes to prepare a polypyrrole derivative film having a film thickness of 0.3 μm. The film was doped with bromine ions to prepare a conductive layer. Except for the above, the conductive layer and the upper layer were the same as in Example 13 to obtain a photoconductor of Example 22.

[0101]

[Chemical 21]

Example 35 Glass was immersed in a solution prepared by dissolving 1 part of γ-glydoxypropyltrimethoxysilane in 9 parts of pure water for 15 minutes, and after the immersion, dried at 105 ° C. to form an adhesive layer on the glass surface. Formed. Next, a solution prepared by diluting 1 part of the polythiophene derivative represented by Structural Formula 25 with 50 parts of tetrahydrofuran was applied by dip coating. After coating, the coating is dried by heating at 100 ° C. for 30 minutes to give a film thickness of 0.
A 3 μm polypyrrole derivative film was prepared. The film was doped with bromine ions to prepare a conductive layer. Other than the above
A photoreceptor of Example 35 was obtained in the same manner as in Example 13 except for the conductive layer and the upper layer.

[0103]

[Chemical formula 22]

Example 36 Glass was immersed in a solution prepared by dissolving 1 part of vinyltrimethoxysilane in 9 parts of pure water for 15 minutes, and after the immersion, it was dried at 105 ° C. to form an adhesive layer on the glass surface. Next, p-
Xylylene bis (diethyl sulfonium bromide) and sodium hydroxide aqueous solution were mixed and reacted to obtain a soluble intermediate of poly (p-phenylene vinylene) having a sulfonium salt as a side chain. The reaction solution was dialyzed against water for one week using a dialysis membrane (cellophore, molecular weight fraction 3500). The aqueous solution was applied onto the adhesive layer by dip coating, dried under reduced pressure, and treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a poly (p-phenylene vinylene) layer of structural formula 4. This is soaked in a sulfuric acid solution and subjected to a doping treatment to obtain a film thickness of 0.5.
A μm conductive layer was formed. Except for the above, the conductive layer and the upper layer were the same as in Example 13 to obtain a photoconductor of Example 36.

Example 37 In Example 24, a soluble intermediate of poly (2,5-chenylenevinylene) was used to prepare the conductive layer, and a conductive layer made of poly (2,5-chenylenevinylene) of Structural Formula 2 was used. A photoconductor of Example 37 was obtained in exactly the same manner as in Example 36 except that was used.

Example 38 A conductive layer made of poly (2,5-phenylenevinylene) having the structural formula 3 using a soluble intermediate of poly (2,5-phenylenevinylene) in the production of the conductive layer in Example 24. A photoconductor of Example 38 was obtained in the same manner as in Example 36 except that was used.

Example 39 Example 36 was the same as Example 36 except that a soluble intermediate of poly (dimethoxyphenylene vinylene) was used for the production of the conductive layer and a conductive layer made of poly (dimethoxyphenylene vinylene) of Structural Formula 5 was used. A photoconductor of Example 27 was obtained in exactly the same manner.

Example 40 A slide glass was immersed in a solution prepared by dissolving 1 part of N-β (aminoethyl) γ-aminopropyltrimethoxysilane in 9 parts of pure water for 15 minutes, and after drying, it was dried at 105 ° C.
An adhesive layer was formed on the glass surface. Next, a tin oxide resin dispersion solution (ELCOM-P3002, manufactured by Catalyst Kasei) was applied by dip coating. After coating, it was heated and dried at 120 ° C. for 30 minutes to form a conductive layer having a film thickness of 2 μm. A photoreceptor of Example 40 was obtained in the same manner as in Example 13, except for the above, from the conductive layer to the upper layer.

Comparative Example 9 A solution prepared by dissolving 1 part of soluble polyaniline having Structural Formula 11 and Structural Formula 12 as a repeating unit in 99 parts of n-methyl-2-pyrrolidone was applied by dip coating, and dried by heating at 150 ° C. for 30 minutes. A 0.5 μm polyaniline film was formed on the glass. The polyaniline film was immersed in a 1 mol / l p-toluenesulfonic acid aqueous solution for 1 hour to perform a doping treatment to form a conductive layer. A photoreceptor of Comparative Example 9 was obtained in the same manner as in Example 13, except for the above, from the conductive layer to the upper layer.

Comparative Example 10 A photoreceptor of Comparative Example 10 was obtained in exactly the same manner as Comparative Example 9 except that the glass used in Comparative Example 1 was polycarbonate. Using the photoconductors produced in Examples 13 to 40 and Comparative Examples 9 to 10, the adhesiveness between the insulating substrate and the photosensitive layer was examined. The cross-cut test was used as the adhesion evaluation method.
In the cross-cut test, a 2 mm square cross-cut was made on the surface of the photoreceptor, and then cellophane adhesive tape (cellophane, Nichiban Co., Ltd.)
JIS-Z1522 standard product) made a peel test in the direction of 180 degrees, 5th grade: No peeling, 4th grade: 25% peeling, 3
Grade: 50% peeling, 2nd grade: 75% peeling, 1st grade: Whole face peeling,
The grade was evaluated as.

Further, Examples 13 to 40 and Comparative Examples 9 to
The photoconductor characteristics of the photoconductor prepared in No. 10 were examined and a printing test was conducted. In examining the photoreceptor properties, the exposure was applied from outside the photoreceptor. Regarding the characteristics of the photoconductor, the half exposure amount, the residual potential and the charge retention rate were measured. Half decay exposure, the time required for the start of exposure of the photosensitive member surface potential is attenuated to half t _1/2
The product of (S) and incident light intensity per unit time (μJ / cm ² ) was used. The residual potential was the surface potential when 10 × t _{1/2 had} elapsed from the start of exposure. The charge retention rate is the decay rate of the surface potential for 1 second. At the time of measurement, light having a wavelength of 660 nm was used for exposure. This is light of the same wavelength as the optical system used for the print test. The process unit structure of the printing apparatus used for the print test is shown in FIG. 1 and the image forming process is shown in FIG.

The evaluation method of the printing test was carried out by using a Sakura densitometer (PDA-65, manufactured by Konica), and the optical parts of the printed image and the background part of the printed matter obtained by the printing test.
Density (OD) was measured to evaluate print density and background fog. The print density of the print area is 0. D. The value and background part fog are background part O. D. Value and O. D. Difference from the value of 0.12 ΔO. D. Value.

The evaluation results are shown in Tables 3 and 4. Example 13
.About.40 and Comparative Examples 9 to 10 produced good results in terms of both photoconductor characteristics and printing characteristics, but the photoconductors of Comparative Examples 9 to 10 were obtained by continuous printing. The film has peeled off. Further, in the cross-cut test, the photoconductors of Comparative Examples 9 to 10 were completely peeled off.
On the other hand, none of the photoconductors of Examples 13 to 40 peeled off and were excellent in durability in the continuous printing test.

From the above results, it was found that the use of the conductive layer adhesive material significantly improves the adhesion between the insulating substrate and the conductive layer without impairing the characteristics of the conventional photoreceptor. As a result, it was possible to find an electrophotographic photoreceptor applicable to the optical backside process.

[0115]

[Table 3]

[0116]

[Table 4]

[0117]

As described above, the first aspect of the present invention
According to the aspect of the invention, in forming the transparent conductive layer on the surface of the insulating support of the electrophotographic photosensitive member, by using a specific intermediate soluble in a solvent, it is possible to easily form the transparent conductive layer. This makes it possible to obtain a transparent conductive layer more easily and cheaply than using conventional materials, and to downsize the optical printer device.
It greatly contributes to cost reduction.

Further, according to the second aspect of the present invention, in an electrophotographic photoreceptor in which a conductive layer is formed on an insulating substrate and a photosensitive layer is laminated thereon, a conductive layer is formed on the insulating substrate or the conductive layer. Adhesive layer having an adhesive material or provided between the insulating substrate and the conductive layer and using a conductive layer adhesive material for the adhesive layer significantly improves the adhesiveness between the insulating substrate and the conductive layer, and improves the optical back surface. It is possible to find an electrophotographic photosensitive member applicable to the process, and it largely contributes to downsizing and cost reduction of the optical printer device.

[Brief description of drawings]

FIG. 1 is a diagram showing a printing apparatus used in a print test.

FIG. 2 is a diagram showing an image forming process of a printing apparatus.

[Explanation of symbols]

 1: Optical System 1A: LED Array 1B: Selfoc Lens 1C: Glass Plate 2: Photosensitive Body 3: Transparent Substrate 4: Transparent Conductive Layer 5: Photosensitive Layer 6: Developing Device 7: Developer 8: Toner 9: Carrier 10: Developing roller 11: Magnet roller 12: Conductive sleeve 13: Recording medium 14: Transfer roller 15: Fixing device 16: DC power supply

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsuneo Watanuki 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Fujitsu Limited (72) Inventor Norio Saruwatari, 1015, Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Fujitsu Limited

Claims (8)

[Claims] 1. An insulating transparent substrate, and a polyarylene vinylene of the following structural formula 1 laminated on the insulating transparent substrate,
An electrophotographic photoreceptor comprising a transparent conductive layer made of polythienylene vinylene of structural formula 2 or polyphenylene vinylene of structural formula 3, and a photosensitive layer laminated on the transparent conductive layer. [Chemical 1] 2. The electrophotographic photosensitive member according to claim 1, wherein the polyarylene vinylene is poly-p-phenylene vinylene of the following structural formula 4 or polydimethoxyphenylene vinylene of the following structural formula 5. [Chemical 2] 3. A polyarylene vinylene of the following structural formula 1, a polythienylene vinylene of the following structural formula 2, or a structural formula 3 below.
Polyphenylenevinylene, polythienylenevinylene, or polyphenylenevinylene, which has conductivity after being coated with a solution prepared by diluting the soluble intermediate of polyphenylenevinylene with a solvent and drying it on an insulating transparent substrate. A method of manufacturing an electrophotographic photosensitive member, comprising forming a layer made of, and performing a doping treatment after the formation to form a transparent conductive layer having a low resistance. [Chemical 3] 4. An organic conductive layer is formed on an insulating substrate,
In an electrophotographic photoreceptor having a photosensitive layer laminated thereon, an adhesive material for adhering an organic conductive layer to an insulating substrate is contained in the organic conductive layer or an insulating base material, or an adhesive layer is formed on the insulating base material. An electrophotographic photosensitive member characterized by being formed as. 5. The organic silane compound of structural formula 6, a both-end reactive organosilicone compound of structural formula 7, a single-end reactive organosilicone compound of structural formula 8, as the adhesive material.
The electrophotographic photosensitive member according to claim 4, comprising at least one of the organic titanate compound of structural formula 9, the organic aluminum compound, the organic zircoaluminate compound, and the oxazoline-based reactive polymer of structural formula 10. [Chemical 4] [Chemical 5] 6. The organic conductive layer comprises polyaniline having repeating units of structural formulas 11 and 12, and structural formula 13
6. The electron according to claim 5, comprising at least one of the polypyrrole derivative of, the polythiophene derivative of structural formula 14, the polyarylene vinylene of structural formula 1, the polythienylene vinylene of structural formula 2, and the polyphenylene vinylene of structural formula 3. Photoreceptor. [Chemical 6] [Chemical 7] 7. The electrophotographic photosensitive member according to claim 5, wherein the organic conductive layer is a layer in which a conductive metal oxide is dispersed in a resin. 8. An electrophotographic photosensitive member is obtained by laminating a conductive layer on an insulating substrate and a photosensitive layer on the conductive layer, and using a developing device having a conductive sleeve arranged in proximity to the photosensitive member,
The developer is conveyed by the sleeve, the developer is brought into contact with the photoconductor, a voltage is applied between the sleeve of the developing device and the conductive layer to charge the photoconductor, and the developing is performed from the insulating substrate side. A method for forming an image by performing image exposure on a portion in contact with an agent, wherein
An image forming method comprising using the electrophotographic photosensitive member according to any one of items 2, 4 to 7.