JP3001666B2 - Manufacturing method of electrophotographic photoreceptor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an electrophotographic photoreceptor, and more particularly, to a method for forming a photoconductive layer on a substrate provided with an anodic oxide film, and mainly used in a reversal development system. The present invention relates to a method for manufacturing an electrophotographic photoreceptor, which is improved so that a good image can be obtained, and which is industrially advantageous.

[0002]

2. Description of the Related Art Conventionally, an image forming system using an electrophotographic system has been widely applied in the field of copying. Recently, digital signal data processing systems have become widespread, and there has been a demand for improved functions of printers for printing and outputting such data. The use of electrophotographic printing systems in this field has been studied and put into practical use. ing.

The above-mentioned system converts the data of an electric signal into an optical signal by means of a laser scanner, an LED array, a liquid crystal shutter, etc., irradiates the photoconductor, forms an electrostatic latent image on the photoconductor, and forms a toner. Visualized by development,
It is a system that obtains images and is also called an optical printer. This system has been rapidly spreading because it has a very high printing speed and no noise as compared with the conventional impact system, and can perform high-quality printing.

[0004] As a photoreceptor used in an optical printer,
Se, CdS, As inorganic photoconductor such as ₂ Se _3, although an organic photosensitive material such as a charge transfer complex of polyvinyl carbazole and trinitrofluorenone, etc. have been used,
Organic photoconductors that are relatively easy to select in the photosensitive wavelength range, and that are relatively easy to provide sensitivity in the near infrared, which is the output wavelength range of the semiconductor laser, are extremely suitable, and various materials have been developed. .

[0005] Among the organic photoconductors, in particular, a stacked photoconductor comprising a charge generation layer and a charge transfer layer can make full use of the variety of organic compounds, and has already achieved high sensitivity and high durability. This is extremely useful in that a photoreceptor for printing can be obtained, and a non-polluting material can be selected in terms of safety.

On the other hand, as an image forming method in an optical printer, a so-called reversal developing method of forming an image by adhering toner to a portion irradiated with light is often adopted for the purpose of effectively utilizing light or increasing resolution. However, in the reversal development method, the dark potential portion becomes a white background,
The bright potential portion becomes a black background portion (image portion), but if there is a local charging failure due to a defect or the like on the photoreceptor, black spots are generated on a white background, and subsequently, a background fog development is caused by a large number of black spots. As a result, a remarkable image defect appears.

[0007] Even if the above-mentioned local charging failure is at a level that does not cause any problem when used in regular development, it is likely to cause an image failure in reversal development. However, it turned out that there was a problem with sunspots and ground fogging phenomena to varying degrees. Although various causes can be considered for the local charging failure, it is considered that charge injection occurs locally between the conductive support, which is an electrode, and the photoconductive layer, and the charging potential does not increase. .

[0008] Conventionally, as a method of solving a local charging failure,
A method of providing a blocking layer between a conductive support and a photoconductive layer is known. As the blocking layer, an inorganic layer such as aluminum oxide and aluminum hydroxide, polyvinyl alcohol, casein, sodium caseinate, polyvinyl pyrrolidone, and poly Organic resin layers such as acrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, and polyamide are used.

However, when a photoreceptor having a blocking layer is used in a reversal development system, black spots still occur, and ground fogging becomes remarkable particularly under high humidity environmental conditions. When used repeatedly under low humidity,
The black background potential rises to such an extent that it cannot be practically used.

[0010] Among the conventionally known blocking layers, those having an aluminum oxide substrate provided with a sealed anodic oxide coating have relatively small environmental dependence of electrical characteristics and have good characteristics. However, when used in the reversal development system, image defects such as spots or flowing patterns appear remarkably, especially under high temperature and high humidity.

The present applicant has previously proposed a method of manufacturing an electrophotographic photosensitive member which has solved the above-mentioned problems by manufacturing an electrophotographic photosensitive member having a photoconductive layer provided on an aluminum substrate having an anodized film. A method for producing an electrophotographic photoreceptor, characterized in that, after forming an anodized film on an aluminum substrate, the surface of the film is physically rubbed and washed (Japanese Patent Laid-Open No. 5068/1990). .

The invention described above has been completed based on the finding that black spots and ground fogging are caused by foreign substances adhering to the surface of the anodic oxide film, and physically contact the surface of the anodic oxide film. By rubbing, foreign substances adhering to the anodic oxide film surface are removed. And, specifically, using a brush-like, foam-like, cloth-like rubbing material, when water containing a high concentration of water vapor is sprayed on the surface after the contact rubbing cleaning treatment, the water droplet film is substantially uniformly formed. The foreign matter is removed by rubbing and cleaning to the extent of formation.

[0013]

However, the above-mentioned manufacturing method is a method of physically rubbing the surface of the anodic oxide coating, and is not suitable for an industrial method in which a large amount and continuous operation is performed. In addition, there is a new problem that the removal of the foreign matter is not constant at a sufficient level because the foreign matter which should have been removed sometimes adheres again.

[0014]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned new problems of the above-mentioned manufacturing method. The gist of the present invention is to form an anodic oxide film on an aluminum cylindrical substrate. And sealing the anodic oxide film if necessary, and then cleaning the anodic oxide film surface of the aluminum cylindrical substrate, and then providing a photoconductive layer thereon. As a method of cleaning the coating surface, a driving means for moving the aluminum cylindrical base up and down while rotating it without contacting the outer surface thereof is provided on an upper part, and a centralized chip connected to an ultrasonic vibrator is provided inside. Is used and a cleaning tank containing a cleaning liquid is used, and by the above-described driving means, the aluminum cylindrical substrate is placed so that its side faces the centralized chip in the cleaning tank. It is lower movement, and resides in the method for producing a photoreceptor, characterized by using the cleaning method of performing at least one of the moving operation by rotating the aluminum cylindrical substrate ultrasonic cleaning.

Hereinafter, the present invention will be described in detail. In the present invention, it is preferable that the aluminum cylindrical substrate is subjected to a degreasing treatment by various degreasing methods such as an acid, an alkali, an organic solvent, a surfactant, an emulsion and electrolysis before the anodizing treatment is performed.

The anodic oxide film is usually formed by anodizing in an acidic bath such as chromic acid, sulfuric acid, oxalic acid, boric acid, and sulfamic acid. Gives good results. In the case of anodic oxidation in sulfuric acid, the sulfuric acid concentration is 100 to 300 g / l, the dissolved aluminum concentration is 2 to 15 g / l, and the liquid temperature is 15 to 30.
° C, electrolysis voltage is 5-20V, current density is 0.5-3A /
It is better to set it in the range of dm ² . The average thickness of the anodic oxide coating is usually 20 μm or less, particularly preferably 7 μm or less.

The anodic oxide coating on the aluminum cylindrical substrate can be used as it is. However, since it is porous, it has poor weather resistance and is liable to cause corrosion and the like. It is preferable to use it after performing a sealing treatment.

The sealing treatment can be carried out by treatment with pressurized steam or boiling water, but it is efficient and preferable to use a sealing agent. As the sealing treatment using a sealing agent, for example, low-temperature sealing treatment using an aqueous solution containing nickel fluoride as a main component, for example, high-temperature sealing using an aqueous solution containing nickel acetate as a main component Processing.

In the case of the low-temperature sealing treatment, the concentration of the nickel fluoride aqueous solution can be appropriately selected, but the most effective concentration is in the range of 3 to 6 g / l. The pH of the nickel fluoride aqueous solution is
The range is from 4.5 to 6.5, preferably from 5.5 to 6.0. As the pH adjuster, oxalic acid, boric acid, formic acid, acetic acid, sodium hydroxide, sodium acetate, aqueous ammonia and the like can be used.

The processing temperature in the low-temperature sealing processing is as follows:
In order to smoothly carry out the sealing treatment, the temperature of the nickel fluoride aqueous solution is in the range of 25 to 40 ° C, preferably 30 to 35 ° C.
H is in the range of 4.5 to 6.5, preferably 5.5 to 6.0. The processing time is from 1 to 1 μm in average film thickness.
A range within 3 minutes is preferred. In addition, nickel fluoride, cobalt acetate, nickel sulfate, a surfactant and the like may be added to the nickel fluoride aqueous solution in order to improve the film properties.

In the case of high-temperature sealing, an aqueous solution of a metal salt such as cobalt acetate, lead acetate, nickel-cobalt acetate, or barium nitrate can be used in addition to an aqueous solution of nickel acetate, but nickel acetate is particularly preferable. . The concentration of the aqueous nickel acetate solution is preferably in the range of 3 to 20 g / l. The pH of the aqueous nickel acetate solution is preferably in the range of 5.0 to 6.0. Ammonia water, sodium acetate and the like can be used as the pH adjuster.

The processing temperature in the high-temperature sealing processing is as follows:
The range is 65 to 100 ° C, preferably 80 to 98 ° C. Also in this case, sodium acetate, an organic carboxylate, an anionic or nonionic surfactant or the like may be added to the aqueous nickel acetate solution in order to improve the physical properties of the film.

The sealing agent preferably used for the low-temperature sealing treatment and the high-temperature sealing treatment includes Hard Wall-3 manufactured by Nikka Chemical Co., Ltd. and Alumite Sealer manufactured by Nippon Chemical Industry Co., Ltd. And Topseal DX manufactured by Okuno Manufacturing Co., Ltd.

In the present invention, the aluminum cylindrical substrate having the anodic oxide film or the anodic oxide film subjected to the sealing treatment as described above is washed in a washing tank.
Foreign matter adhering to the anodic oxide film surface is removed.

A feature of the present invention is that, as a method for cleaning the surface of the anodic oxide film, a driving means for vertically moving the aluminum cylindrical substrate while rotating it without contacting the outer surface is provided at the upper portion. A centralized chip connected to an ultrasonic vibrator is arranged and a cleaning tank containing a cleaning liquid is used, and the side face of the cleaning tank is opposed to the centralized chip in the cleaning tank by the driving means. Thus, a cleaning method is used in which the aluminum cylindrical base is moved up and down so as to perform ultrasonic cleaning by rotating the aluminum cylindrical base during at least one of the moving operations.

FIG. 1 is an explanatory view conceptually showing an example of a cleaning tank used in the production method of the present invention, and shows a state in which an aluminum cylindrical substrate is being cleaned.

Inside the cleaning tank (30), a centralized chip (32) connected to an ultrasonic vibrator (31) is arranged. And as a preferable aspect, the washing tank (30)
Is of the overflow type, and the cleaning liquid overflowing from the overflow port (33) passes through the pump (34), the cooler (35) and the filter (36), and then flows into the cleaning tank (3).
0). Therefore, the cleaning liquid is constantly flowing as a circulating flow, and the accumulation of foreign matter removed from the anodic oxide film surface in the cleaning tank (30) is prevented. Of course, instead of the overflow type, a batch exchange method of the cleaning liquid can be adopted.

In FIG. 1, only one cleaning tank (30) is shown. However, industrially, a large number of cleaning tanks are arranged in parallel, or ultrasonic vibration is applied to one long cleaning tank. Advantageously, a number of centralized chips (32) connected to the child (31) are arranged, while simultaneously cleaning a plurality of aluminum cylindrical substrates (4). In FIG. 1,
(1) and (17) are a hollow shaft and a triangular plate of a chuck device used for driving the aluminum cylindrical substrate (4), respectively, and the chuck device will be described later.

Although the washing liquid is not particularly limited, in order to more effectively remove foreign substances adhering to the surface of the anodic oxide film, the applicant of the present invention has filed Japanese Patent Application No. Hei 2-19705.
It is preferable to use a cleaning liquid containing alcohol or ketone according to the method of manufacturing an electrophotographic photoreceptor already proposed as No. 1.

That is, the pore-sealing agent used for the pore-sealing treatment contains a trace amount of a surfactant or an organic carboxylate in addition to the metal salt. The foreign substances adhering to the surface of the anodic oxide film are considered to be organic compounds derived from a surfactant or the like having incorporated inorganic compounds. Further, even when the sealing agent is not used, the organic compound (such as a polymer lubricant) mixed in the air or from the apparatus adheres to the anodic oxide film surface. The above-mentioned foreign substances made of such organic compounds are much more easily removed by a cleaning liquid containing alcohol or ketone than pure water.

As the alcohol or ketone, those having a relatively low molecular weight are used, and specific examples include methanol, ethanol, isopropanol, n-propanol or acetone, and methyl ethyl ketone. And
The concentration of alcohol or ketone in the washing liquid is not particularly limited, but generally, in any case, it is preferable to use an aqueous solution of 4 to 50% by weight.

A driving means is provided at the upper part of the above-mentioned washing tank for vertically moving the aluminum cylindrical substrate (4) while rotating it without contacting the outer surface thereof. And
By this driving means, the aluminum cylindrical base (4) is
The side surface is moved up and down so as to face the centralized chip (32) in the cleaning tank, and the ultrasonic cleaning of the anodic oxide coating surface is performed during at least one of the moving operations.

Although the driving means is not particularly limited, it is easy to handle, and always keeps the distance between the side surface of the aluminum cylindrical base (4) and the centralized chip (32) constant. In addition, it is preferable to use a driving means capable of vertically moving the aluminum cylindrical base (4) in a state where there is no backlash in rotation.

FIGS. 2 to 4 are explanatory views showing an essential part of an example of a driving means suitably used in the above-mentioned cleaning tank (30). FIG. FIG. 3 is a partial cross-sectional view taken along the line AA 'of FIG. 2, illustrating a holding mechanism of the device, and FIG. FIG. 3 is a partial plan view, taken along the line BB ′ of FIG. 2, for explaining a piece member of the apparatus.

The above-mentioned chuck device comprises a hollow shaft (1) relatively inserted into an aluminum cylindrical base (4) from an open end of one end thereof, and a mandrel inserted into the hollow shaft and movable vertically. (7) a restraining mechanism (11) that contracts and expands in a radial direction of the aluminum cylindrical base at one end of the hollow shaft by vertical movement of the mandrel, and is formed at equal intervals or integrally around the hollow shaft. Further, a piece member (15) having an inclined portion inserted into the aluminum cylindrical base and abutting on the inner surface of the cylindrical base is provided.

In the chuck device described above, the bridge member (15) having the inclined portion is inserted into the inside of the aluminum cylindrical base (4) to abut on the inner surface of the cylindrical base, and then the aluminum cylindrical base (4). ) Is guided by the inclined portion of the bridge member (15) as it rises, and moves so that its center coincides with the center of the hollow shaft (1). As a result, the above-mentioned chuck device has a feature that it can be easily inserted into the aluminum cylindrical substrate (4) with a simple structure, and can easily perform centripetal alignment with the cylindrical substrate.

The hollow shaft (1) is rotatably supported by a fixed frame (3) via a bearing (2) arranged around the base. The hollow shaft (1) is moved up and down by the aluminum cylindrical base (4) or the fixed frame (3).
The aluminum cylindrical base (4) is relatively inserted into one end opening part of the base.

Further, the hollow shaft (1) has three notched grooves (5) formed along the axial direction at equal intervals in the circumferential direction at the tip end side thereof. Has a spring chamber (6) formed with an enlarged inner diameter.

The mandrel (7) is inserted into the hollow shaft (1) and arranged so as to be able to move up and down. And mandrel (7)
Has three fixed crotch fixing members (8) at its distal end and a stopper (9) fixed at its base side. The base of the mandrel (7) protrudes from the hollow shaft (1), and the stopper (9) of the mandrel receives the repulsive force of the spring (10) housed in the spring chamber (6) of the hollow shaft. .

The retaining mechanism (11) is composed of three sets of two rod-like members (12) and (13) constituting a link mechanism, and each of the end parts of one of the rod-like members (12) is a hollow shaft. And the other end of the other bar-shaped member (13) is fixed to one of three crotch fixing members (8).
Pinned in the crotch. In FIG. 2, (14) indicates a pin.

The restraining mechanism (11) includes a mandrel (7)
Causes the aluminum cylindrical base (4) to contract and expand in the radial direction at one end of the hollow shaft (1). That is, when the mandrel (7) is pulled down by the lowering of the piston rod (20) of the air cylinder (19), which will be described later, the rod-like member (1) constituting the restraining mechanism (11) is formed.
Each of the three sets (2) and (13) extends in a straight line and is accommodated in the corresponding notch groove (5). And
For example, the aluminum cylindrical base (4) is raised, the hollow shaft (1) is inserted from one end opening portion, the piston rod (20) is raised, and the mandrel (7) is pulled up by the repulsive force of the spring (10). When the rod-shaped member (1
2) and (13) project from each notch groove (5) by the link mechanism, and form an aluminum cylindrical base (4).
It expands in the radial direction and is held at three points.

The bridge member (15) is composed of a slider (16) fitted to the hollow shaft (1) and four triangular plates (17) having inclined portions diverging toward the base of the hollow shaft (1). The triangular plates are configured and fixed at equal intervals around the slider (16). And the piece member (15)
Moves along the hollow shaft (1), is inserted into the aluminum cylindrical base (4), and abuts the inclined portion on the inner surface of the cylindrical base. The slider (16) is a piece member (1
5) is provided as a preferred embodiment so as to be movable along the hollow shaft (1). According to such a configuration, various aluminum cylindrical substrates having different lengths can be held. .

In addition to the above-mentioned structure, the bridge member (15) may be composed of a slider (16) and an inverted triangular pyramid (not shown) integrally formed therearound. The inclined portion of each triangular plate (17) constituting the piece member (15) has a vertical portion formed at a position where it can be tightly fitted to various aluminum cylindrical substrates (4) having different inner dimensions. It is preferably a multi-stage. When the above-mentioned inverted triangular pyramid is used, this multi-stage shape is formed in the same central circle shape.

A single protrusion (not shown) is formed on the surface of the hollow shaft (1) along the axial direction, and a groove (18) fitted to the protrusion is formed on the inner surface of the slider (16). )
(See FIG. 4). According to such a configuration, the slider (16) can smoothly move along the hollow shaft (1) without rotating.

An air cylinder (19) is arranged on the fixed frame (3), and its piston rod (20) is
The mandrel (7) is arranged to abut the protruding end. A motor (21) is disposed on the fixed frame (3), and the tip of the drive shaft (22) is provided around the protrusion of the mandrel (7) via a power transmission mechanism (23). Connected to the rotation drive unit (24).

In the above-described chuck device, when the hollow shaft (1) is inserted from the one end opening portion of the aluminum cylindrical base (4), the inclined portion of the triangular plate (17) constituting the bridge member is formed by the aluminum cylindrical base (4). 4) Contact the inner surface. Then, the aluminum cylindrical base (4) is guided by the inclined portion of the triangular plate (17) as it rises, and moves so that its center coincides with the center of the hollow shaft (1). As a result, even when the hollow shaft (1) is large enough to be easily inserted into the aluminum cylindrical base (4), centripetal alignment with the aluminum cylindrical base (4) can be easily achieved.

When the triangular plate (17) has a multi-staged inclined portion, the multi-staged vertical portion immediately fits into the inner diameter of the aluminum cylindrical base (4) to be restrained. Centripetal alignment is easier. Also,
In the vertical portion of the multi-stage inclined portion, the aluminum cylindrical base (4) is fitted in a relatively tight state, so that the motor (21) is driven and the aluminum cylindrical base (4) is driven.
When it is held in the rotating state, rattling between the hollow shaft (1) and the aluminum cylindrical base (4) can be effectively prevented.

In FIG. 2, only one chuck device is shown in the fixed frame (3). However, industrially, the number of radix chips corresponding to the plurality of centralized chips (32) arranged in the cleaning tank is increased. Chuck device (usually two to one fixed frame
10), and simultaneously, the plurality of aluminum cylindrical substrates (4) are cleaned. In this case, the motor (21)
Is located at the end of the fixed frame (3) and comprises a plurality of mandrels (7).
Each of the rotation drive units (24) has a plurality of power transmission mechanisms (2).
Are interconnected by 3).

Although not shown, the fixed frame (3) is usually configured to move up and down by, for example, a speed control motor, and a rail on which the fixed frame (3) runs is placed above the washing tank. The fixing frame (3) may be configured to be able to reciprocate between the disposition position of the aluminum cylindrical substrate (4) that has been horizontally laid and anodized or sealed and the cleaning tank (30). .

In the present invention, the cleaning of the anodic oxide film on the aluminum cylindrical substrate (4) is performed, for example, as follows using the driving means having the chuck device configured as described above.

First, for example, the fixing frame (3) is moved to a position where the aluminum cylindrical substrate (4) that has been subjected to anodizing or sealing treatment is placed, and the aluminum cylindrical substrate (4) is held by the chuck device. The fixed frame (3) is moved to the upper part of the washing tank (30). Next, the fixed frame (3) is moved downward by a speed control motor (not shown) to immerse the aluminum cylindrical substrate (4) in the cleaning liquid, and then the aluminum cylindrical substrate (4) is removed by the motor (21). While rotating, the fixed frame (3) is moved upward by, for example, a speed control motor and the ultrasonic vibrator (31) is driven.

By the above operation, the entire side surface of the aluminum cylindrical substrate (4) faces the centralized chip (32) in the cleaning tank, and the ultrasonic cleaning of the anodic oxide coating surface is performed. The ultrasonic energy applied to the ultrasonic vibrator (31) is usually 30 to 9 to obtain a sufficient cleaning effect by one-way movement of the aluminum cylindrical base (4).
0w / cm ² range to the well, also the distance between the end surface of the side with the centralized chip aluminum cylindrical substrate (4) (32) is 1 to 50 mm, preferably in the range of 5 to 30 mm, the aluminum cylindrical substrate For example, when the centralized tip (32) having a diameter of 32 mm is used, the amount of movement per rotation of (4) is 〜 to 1/4 (2.5
mm to 8 mm), and in this case,
The moving speed and the rotating speed of the aluminum cylindrical substrate (4) are in the range of 2.5 to 40 mm / sec, 75 to 3 mm, respectively.
The range is 00 rpm.

In the present invention, a photoconductive layer is provided on the anodic oxide film subjected to the ultrasonic cleaning as described above, and a blocking layer made of an organic resin is provided between the anodic oxide film and the photoconductive layer. Other processing may be performed.

As the photoconductive layer, for example, various inorganic and organic photoconductive layers can be applied according to the following modes. In the present invention, the following laminated photoconductive layer is preferably used. preferable. (1) A stacked photoconductive layer comprising a charge generation layer containing a photoconductive substance as a main component and a charge transfer layer containing a charge transfer material. (2) A dispersed photoconductive layer in which photoconductive particles are dispersed in a binder composed of a charge transfer material and a binder resin.

In the case of the above-mentioned laminated photoconductive layer, the photoconductor used for the charge generation layer is Se and its alloys, arsenic-selenium, cadmium sulfide, other inorganic photoconductors, phthalocyanine, azo dye, Organic pigments such as quinacridone and polycyclic quinone can be used. Above all, metal-free phthalocyanine; copper, indium chloride, gallium chloride, tin,
Metals such as oxytitanium, zinc, and vanadium or oxides thereof, and phthalocyanines in which chlorides are coordinated; azo pigments such as monoazo, bisazo, trisazo, and polyazo are preferable.

The charge generation layer is formed as a uniform layer of a photoconductive substance or in a state where the photoconductive substance is dispersed in a binder resin. Examples of the binder resin used here include phenoxy, epoxy, polyester, acryl, polyvinyl butyral, and polycarbonate resin. The film thickness is usually 0.1 to 1 μm, preferably 0.15 to 0.6 μm. The content of these photoconductors is usually in the range of 20 to 300 parts, preferably 30 to 150 parts with respect to 100 parts by weight (hereinafter abbreviated as "parts") of the binder resin.

As the charge transfer material in the charge transfer layer, high molecular compounds such as polyvinyl carbazole, polyvinyl pyrene and polyacenaphthylene, or low molecular compounds such as various pyrazoline derivatives, oxazole derivatives, hydrazone derivatives and stilbene derivatives are used. it can.

[0058] A binder resin is blended with the above-mentioned charge transfer material as needed. Preferred binder resins include polymethyl methacrylate, polystyrene,
Vinyl polymers such as polyvinyl chloride, and copolymers thereof,
Examples thereof include polycarbonate, polyester, phenoxy, epoxy, and silicone resin, and partially crosslinked and cured products thereof.

The content of the charge transfer material in the charge transfer layer is usually 30 parts with respect to 100 parts of the binder resin.
To 200 parts, preferably 50 to 150 parts. In addition, an antioxidant, if necessary,
Various additives such as a sensitizer may be included. The thickness of the charge transfer layer is 10 to 40 μm, preferably 10 to 30 μm.

In the case of a dispersion type photoconductive layer, the above photoconductor and a charge transfer material are used in combination, and 20 to 200 parts, preferably 40 to 1, based on 100 parts of the binder resin.
A blend of about 50 parts is used.

[0061]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 30 g of a degreaser, NG- # 30 (manufactured by Kizai Co., Ltd.) was applied to a 1 mm-thick aluminum cylindrical substrate having a mirror-finished surface.
Degreasing washing was performed at 60 ° C. for 5 minutes in a 1 / l aqueous solution. Subsequently, it was immersed in 7% nitric acid at 25 ° C. for 1 minute. Further, after washing with water, anodic oxidation was performed at a current density of 1.2 A / dm ^{2 in} a 180 g / l sulfuric acid electrolyte (dissolved aluminum concentration: 7 g / l) to form an anodic oxide film having an average film thickness of 6 μm.
Then, after washing with water, a high-temperature sealing agent top seal DX-500 containing nickel acetate as a main component (manufactured by Okuno Pharmaceutical Co., Ltd.)
After immersion in a 10 g / l aqueous solution of 95 ° C. for 30 minutes,
The high-temperature sealing agent cooled to almost room temperature was lifted up while sprinkling on the aluminum cylindrical substrate to perform a sealing treatment.

Subsequently, after washing with water, a washing tank shown in FIG. 1 having a driving means provided with a chuck device shown in FIGS. 2 and 3 (Nippon Seiki Seisakusho Co., Ltd. Ultrasonic Homogenizer US-6
00) is filled with an aqueous solution of 10% by weight of ethyl alcohol as a washing liquid, and while overflowing, the aluminum cylindrical base is moved downward to be immersed in the washing liquid, then moved upward while rotating at 240 rpm and concentrated. The anodic oxide film surface was subjected to ultrasonic cleaning by driving a type ultrasonic device. In addition, the centralized ultrasonic device
The aluminum cylinder was mounted at a position where the distance between the side surface of the aluminum cylindrical substrate and the end face of the centralized chip was 10 mm. The moving speed of the aluminum cylindrical substrate was 10 mm / sec, and the effective output of the centralized ultrasonic device was about 40 w / cm ² .

Next, using a washing tank having the same driving means as above at the upper part, the aluminum cylindrical
The anodic oxide film surface was ultrasonically cleaned with pure water to which directional high-frequency ultrasonic waves were applied while being moved up and down one reciprocation at a moving speed of 10 mm / sec while rotating at pm. The ultrasonic cleaning was performed using a jet horn type directional high-frequency ultrasonic device (Pulse Jet W-357P manufactured by Honda Electronics Co., Ltd.) arranged on the upper part of the cleaning tank. And finally,
90 ° C. in a washing tank having the same driving means as above
Was immersed in ultrapure water for 1 minute, pulled up at a rising speed of 10 mm / sec, and dried.

On the other hand, oxytitanium phthalocyanine 1
0 parts by weight, polyvinyl butyral (Sekisui Chemical Co., Ltd.)
Manufactured by Esrec BH-3) was added to 500 parts by weight of 1,2-dimethoxyethane, and pulverized and dispersed by a sand grind mill. The aluminum cylinder substrate provided with the previously formed anodic oxide coating was dip-coated on this dispersion, and the charge generation layer was provided so that the film thickness after drying was 0.4 μm.

Next, 56 parts by weight of a hydrazone compound represented by the following chemical formula [Chemical Formula 1]
14 parts by weight of the hydrazone compound shown in [Chemical Formula 2], [Chemical Formula 3]
1.5 parts by weight of a cyano compound and a polycarbonate resin (NOVAREX (registered trademark) 70, manufactured by Mitsubishi Kasei Corporation)
30A) 100 parts by weight of 1,4-dioxane 1000
Dip-coated in a solution dissolved in parts by weight and dried to a film thickness of 1
The charge transfer layer was provided to have a thickness of 7 μm. The drum thus obtained is referred to as a photoconductor A.

[0067]

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[0068]

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[0069]

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For comparison, an electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that ultrasonic cleaning was performed, and instead of ultrasonic cleaning, three reciprocal rub cleanings were performed with a polyester sponge, followed by water washing. Was manufactured. The drum thus obtained is referred to as a photoconductor B.

Next, each photoreceptor was mounted on a commercially available reversal developing type laser printer, and the image characteristics under each environment were evaluated. As a result, in the photoconductor A of the embodiment,
5 ° C / 10% (RH), 25 ° C / 60% (RH), 35
Under both environmental conditions of ° C / 85% (RH), good images were obtained for both white and black background images.
In particular, streak-like image defects considered to be caused by poor rubbing and cleaning appeared on the white background image, and the ratio of obtaining good images was small. From the above results, it can be determined that the electrophotographic photoreceptor produced by the production method of the present invention has extremely excellent performance.

[0072]

When the electrophotographic photoreceptor obtained by the present invention is used in an electrophotographic system including a process of a reversal development system, it is free from fogging and the like under a wide range of environmental conditions including high humidity. Give a nice picture.

[Brief description of the drawings]

FIG. 1 is an explanatory view conceptually showing an example of a cleaning tank used in a production method of the present invention.

FIG. 2 is a side sectional view illustrating an example of a chuck device used for driving the aluminum cylindrical base in the cleaning tank shown in FIG. 1;

FIG. 3 is a partial plan view, taken along the line AA 'of FIG. 2, for explaining a holding mechanism of the chuck device shown in FIG. 2;

FIG. 4 illustrates a piece member of the chuck device shown in FIG. 2;
FIG. 3 is a partial plan view taken along line BB ′ of FIG. 2.

[Description of Signs] (1): Hollow shaft (4): Aluminum cylindrical base (5): Notched groove (7): Mandrel (11): Holding mechanism (15): Piece member (16): Slider (17) : Triangular plate (30): Cleaning tank (31): Ultrasonic vibrator (32): Centralized chip

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 5/00 101 B08B 3/12

Claims (1)

(57) [Claims] 1. An anodic oxide film is formed on an aluminum cylindrical substrate, the anodic oxide film is sealed if necessary, and then the surface of the anodic oxide film of the aluminum cylindrical substrate is washed, and then a photoconductive film is formed thereon. In the method for producing an electrophotographic photoreceptor provided with a layer, as a method for cleaning the anodic oxide film surface,
The upper part is provided with a driving means for moving the aluminum cylinder base up and down while rotating it without contacting the outer surface of the aluminum cylinder base. Inside, a centralized chip connected to the ultrasonic vibrator is arranged and the cleaning liquid is provided. Is used, and the above driving means moves the aluminum cylindrical base up and down so that the side faces the centralized chip in the cleaning tank, and during at least one of the moving operations A method for producing an electrophotographic photosensitive member, characterized by using a cleaning method of performing ultrasonic cleaning by rotating an aluminum cylindrical substrate.