JPH06175375A - Production of electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enable producing an electrophotographic sensitive body having high quality at which cleaning of the cylindrical substrate surface can be attained to extremely high degree, a photosensitive layer can be uniformly formed with excellent adhesion thereon and thus excellent picture images with less generation of picture defects, such as void, picture concentration unevenness, fogging and black spot are formed. CONSTITUTION:In the method for producing the electrophotographic sensitive body, members for cleaning are made to come into contact with the cylindrical substrate surface while rotating the cylindrical substrate around an axis of the substrate and spraying the surface with a cleaning liquid, the substrate is washed by the sprayed cleaning liquid on which an ultrasonic wave is superposed, the substrate is dried and then the photosensitive layer is formed on the substrate surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electrophotographic photosensitive member having a photosensitive layer formed on a cylindrical substrate, and more particularly to a method for cleaning the surface of the cylindrical substrate before forming the photosensitive layer.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors have a substrate structure in which a photosensitive layer is formed on a conductive substrate. Conventionally, selenium is generally used as the photosensitive layer, and other inorganic photoconductive substances are used. Cadmium sulfide, zinc oxide, etc. are known. However, in recent years, electrophotographic photoreceptors using organic photoconductive materials have good film-forming properties and can be produced by coating, have extremely high productivity and are inexpensive, and sensitizers for the organic pigments used. It has the advantage that the color sensitivity can be controlled freely, and has been extensively studied. In particular, with the development of a function-separated type photoreceptor in which an organic photoconductive pigment is used as a charge generation layer and a charge transport layer made of a photoconductive polymer or a low molecular weight organic photoconductive substance is laminated, the range of material selection is greatly expanded. The sensitivity and durability, which have been regarded as the drawbacks of the organic electrophotographic photoconductor of (1), were remarkably improved.

An electrophotographic photosensitive member using such an organic photoconductive material is subjected to cleaning such as ultrasonic cleaning of a machined conductive cylindrical substrate in an organic cleaning agent such as trichlene. It is manufactured by forming a photosensitive layer containing an organic photoconductive material on the surface of this substrate.

[0004]

However, the conductive cylindrical substrate that has been subjected to cutting or the like has adhesion of oil and the like during machining and fine particles of cutting and the like. Therefore, cleaning is performed by the method as described above. It is difficult to completely remove minute foreign matter and dirt, and when such a substrate is used for PPC,
There are problems such as a white blank defect in a black solid part, uneven image density in a halftone part having an intermediate image density, and a black stain defect or fog in a white solid part.

Also, the surface of a substrate coated with an anodic oxide film has the same problem of detergency, and it is difficult to completely remove minute inorganic substances and stains even with precision cleaning. When the photoconductor used was used for an optical printer of the reversal phenomenon type, there was a problem that a white spot defect was generated in a black solid portion and a black spot was generated in the white solid portion.

[0006]

The present invention has been made to solve the above-mentioned problems, and its gist is to provide a surface of a cylindrical substrate while rotating the cylindrical substrate about the axis of the substrate. While spraying the cleaning liquid to the cleaning member, contact the cleaning member, and sprinkle with a cleaning liquid superposed with ultrasonic waves to clean, then dry,
A method for producing an electrophotographic photosensitive member is characterized in that a photosensitive layer is formed on the surface of the substrate.

The present invention will be described in detail below. The cylindrical substrate in the present invention includes an aluminum-based substrate,
That is, a base body made of aluminum or an aluminum alloy, or a base body made of aluminum or an aluminum alloy and having its surface subjected to alumite treatment is used. Also, a conductive substrate such as copper, nickel, stainless steel, etc. can be used. The cleaning member in the present invention is preferably a brush or sponge-like member.
The shape of the cleaning member may be any as long as it can contact the cylindrical substrate and scrape off the dirt, but for example, a part of the periphery of the cylindrical substrate surface contacts,
A shape that is in contact with almost the entire substrate in the axial direction is preferable.

Further, the cleaning member may be movable or fixed depending on its shape, but it is preferable that the cleaning member reciprocates in the axial direction of the substrate. As the cleaning liquid to be sprayed, a liquid containing water as a main component can be applied, and deionized water is particularly preferably used.
The cleaning liquid may be sprayed on the surface of the substrate so as to constantly wet the surface of the rotating substrate. For example, the cleaning liquid is sprayed from one or two or more spray nozzles arranged at a position higher than the holding position of the substrate. It may be sprayed on the surface of the substrate in the state. It is preferable that the spraying of the cleaning liquid starts before the cleaning member comes into contact with the rotating cylindrical substrate and ends after the cleaning member stops contacting.

As a method of spraying with a cleaning liquid superposed with ultrasonic waves, for example, the method described in JP-A-3-4968 can be used. As the cleaning liquid on which ultrasonic waves are superposed, any cleaning liquid such as a water-soluble cleaning agent, deionized water, an emulsion type cleaning agent, an organic cleaning agent, etc. can be used, but an aqueous solution of a water-soluble cleaning agent or deionized water is particularly preferable.

As the water-soluble cleaning agent, for example, a non-etching type weak alkaline cleaning agent (for example, trade name NG-30,
Okuno Pharmaceutical Co., Ltd.) can be used. As the cleaning liquid on which ultrasonic waves are superposed, any cleaning liquid may be sprinkled on the surface of the substrate from an ultrasonic horn nozzle having a vibrator coupled to an ultrasonic oscillator to remove stains and / or wash away. The area where the cleaning liquid sprinkled on the substrate from the ultrasonic horn nozzle hits the substrate is usually 3 to 300 mm ^2.
It is preferable that the nozzle is movable relative to the surface of the substrate, and it can be sprinkled over the entire surface of the substrate by moving in the axial direction of the substrate.

The number of ultrasonic horn nozzles may be one or two or more and can be arbitrarily selected in consideration of the time required for cleaning and the like. In this case, it is preferable that the cleaning liquid on which the ultrasonic waves are superposed is sprinkled on the surface of the cylindrical substrate close to the position where the cleaning member is in contact. When viewed from the axial direction of the cylindrical substrate, the contact of the cleaning member is made. The position is preferably within 90 ° from the position, more preferably within 45 °.

As shown in FIG. 1-a, two ultrasonic horn nozzles are arranged on both sides of the cleaning member, and both sides of the cleaning member contacting the cylindrical substrate are substantially the same on the substrate. It is particularly preferable to sprinkle the cleaning liquid on which ultrasonic waves are superposed on the circumference at the same time. First of all, the cleaning liquid on which ultrasonic waves are superposed on the substrate is used to mainly remove the dirt,
A very remarkable cleaning effect can be obtained by scraping off with a cleaning member and then mainly rinsing with a cleaning liquid superposed with ultrasonic waves to be sprinkled.

As is apparent from the above description, the present invention is characterized in that the cylindrical substrate is rotated about the axis of the substrate,
An electrophotographic photosensitive member characterized in that a cleaning member is brought into contact with the surface of the cylindrical substrate while being sprayed with the cleaning liquid, and a cleaning liquid on which ultrasonic waves are superposed is sprinkled on the surface of the cylindrical substrate to be dried, thereby forming a photosensitive layer on the surface of the substrate. In addition to the method for producing a body, the method includes any of the following features. 1) Manufacture of an electrophotographic photosensitive member characterized in that the cleaning member is in partial contact with the circumference of the surface of the cylindrical substrate, and is in contact with almost the entire substrate in the axial direction. Method. 2) An electrophotographic photosensitive member characterized in that a cleaning liquid on which ultrasonic waves are superposed is sprinkled on both sides of the cleaning member that is in contact with the surface of the cylindrical substrate and in the axial direction on almost the entire substrate. Manufacturing method. 3) Sprinkle a cleaning liquid on which ultrasonic waves are superposed on two positions on both sides of the cleaning member that are in contact with the surface of the cylindrical substrate at substantially the same circumference on the surface of the substrate at the same time. A method for manufacturing an electrophotographic photosensitive member, comprising: moving a cleaning liquid discharge nozzle superposed with a sound wave along an axial direction of a substrate.

An example of the washing operation in the present invention will be shown below.
FIG. 1 is a schematic view of a cleaning device used in Examples and Comparative Examples. The cylindrical substrate (7) is held on the drum chuck (1) using a drum lifter (8), and the drum rotary motor (3) rotates the cylindrical substrate (7) to 10 to 2000 rpm. p. m. Preferably 1
20-1200 r. p. m. While spraying deionized water on the cylindrical substrate from the spray nozzle (2) in a sprayed state while rotating the shaft of the substrate as a center, the cleaning member (4) is contacted and reciprocated in the axial direction of the substrate. The cleaning liquid on which ultrasonic waves are superposed is sprayed from one ultrasonic horn nozzle (5) at a rate of 1 to 10 liters / minute, preferably 2 to 5 liters / minute. The ultrasonic horn motor (6) drives the ultrasonic horn nozzle at 1 to 200 mm / sec, preferably 2 to 10 mm.
After moving at 0 mm / sec to clean the surface of the cylindrical substrate, the injection of the cleaning liquid superposed with ultrasonic waves is stopped, the cleaning member is separated from the substrate, and the reciprocating motion is stopped. After washing the surface of the cylindrical substrate by spraying deionized water from the spray nozzle, the spraying of deionized water is stopped and the rotation of the cylindrical substrate is stopped. By taking out the washed cylindrical substrate with a drum lifter and drying it, it can be used as a cylindrical substrate for an electrophotographic photoreceptor having a photosensitive layer formed on the surface of the substrate.

[0015]

According to the method of the present invention, the degree of cleaning of the surface of a machined cylindrical substrate or the surface of a cylindrical substrate coated with an anodized film can be extremely increased.
It is possible to form a photosensitive layer on it uniformly with good adhesion, and it is possible to produce a high-quality electrophotographic photosensitive member that is a good image with few image defects such as white spots, image density unevenness, and fog black spots. .

[0016]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 A degreasing agent fine cleaner 3 was used to remove an aluminum pipe, which is a cylindrical substrate made of JIS6063 alloy whose surface is mirror-finished, from a degreasing agent.
After degreasing in 15 (manufactured by Nippon Parker Rising Co., Ltd.) 40 g / l aqueous solution at 65 ° C. for 10 minutes and washing with water, 25 ° C.
It was immersed in 7% nitric acid for 1 minute. After washing with water, 180g / l
1.0 in sulfuric acid electrolyte (dissolved aluminum concentration 7 g / l)
Anodic oxidation was performed at a current density of A / dm ² , and an average film thickness of 7
A μm anodic oxide coating was formed. After further washing with water, it was immersed in a 10 g / l aqueous solution of alumite sealer (manufactured by Nippon Kagaku Sangyo Co., Ltd.) containing nickel acetate as a main component at 94 ° C. for 30 minutes and then pulled up. The cylindrical substrate was rotated at a rotation speed of 435 r. p. While rotating at m, spraying deionized water from the spray nozzle in a sprayed state, contacting the urethane sponge as a cleaning member with the cylindrical substrate and reciprocating in the axial direction, from the ultrasonic horn nozzle 1 Deionized water superposed with ultrasonic waves of 1 MHz was sprayed onto the cylindrical substrate at a rate of 3 l / min while spraying. The ultrasonic horn motor was caused to travel horizontally at 33 mm / sec, and the cylindrical substrate was washed, rinsed with the deionized water, and dried by a drying device.

Thus, an anodized film is formed on the surface,
The sealed aluminum pipe was added to 10 parts by weight of oxytitanium phthalocyanine and 5 parts by weight of polyvinyl butyral (Eslec BH-3 manufactured by Sekisui Chemical Co., Ltd.).
1,500 parts by weight of 1,2-dimethoxyethane was added, and the mixture was pulverized with a sand grind mill and subjected to a dispersion treatment, and then dip-coated, and a charge generation layer was provided so that the film thickness after drying was 0.4 μm.

Next, 56 parts by weight of the hydrazone compound represented by the structural formula (1), 14 parts by weight of the hydrazone compound represented by the structural formula (2), and the cyan compound represented by the structural formula (3) were used for the aluminum pipe. 1.5 parts by weight and

[0020]

[Chemical 1]

[0021]

[Chemical 2]

[0022]

[Chemical 3]

And 100 parts by weight of a polycarbonate resin (Novarex 7030A manufactured by Mitsubishi Kasei Co., Ltd.)
The solution was dissolved in 1,000 parts by weight of 4-dioxane, was applied by dip coating, and a charge transfer layer was provided so that the film thickness after drying was 17 μm. The drum type electrophotographic photosensitive member thus obtained was mounted on a commercially available copying machine which was modified for reversal development, and the image characteristics were evaluated. As a result, large white spots and small white spots of 1 mm or less were found in the solid black portion. In addition, no large black spots were observed in the solid white portion, and a good image was obtained without fog.

Example 2 An anodized film was formed in the same manner as in Example 1 except that a JIS 3003 alloy aluminum pipe was used as the cylindrical substrate instead of the JIS 6063 alloy aluminum pipe. After further washing with water, it was immersed in a 5 g / l aqueous solution of a metal salt-sealing agent Hard Wall-3 (manufactured by Nikka Kagaku Co., Ltd.) containing nickel fluoride as a main component at 33 ° C. for 10 minutes and then pulled up. And the cylindrical substrate is rotated at a rotation speed of 580 r. p. While spraying deionized water from the spray nozzle in a sprayed state while rotating at m, the nylon brush, which is a cleaning member, is in contact with the cylindrical substrate and reciprocates in the axial direction. Deionized water superposed with ultrasonic waves of 1 MHz was sprayed onto the cylindrical substrate at 3 liters / minute while sprinkling the ultrasonic horn horizontally with an ultrasonic horn motor at 45 mm / sec to remove the cylindrical substrate after cleaning. After rinsing with ionized water, it was dried with a dryer. After that, a photosensitive layer was provided by the same method as in Example 1 to prepare an electrophotographic photosensitive member, and the same evaluation as in Example 1 was performed. As a result, in the solid black portion, a large white gap and a small white area of 1 mm or less were obtained. There were no blanks, no large black spots were found in the white solid area, and a good image was obtained without fog.

Comparative Example-1 An electrophotographic photosensitive member was manufactured and image characteristics were evaluated in the same manner as in Example-1, except that the urethane sponge as the cleaning member was not used during the cleaning conditions in Example-1. As a result, in the black solid part, white spots with a size of about several mm are seen,
Black dots of about 1 mm were generated on the white solid part.

COMPARATIVE EXAMPLE-2 Example-2 except that ultrasonic waves from an ultrasonic horn were not superposed and deionized water was sprinkled under the cleaning conditions of Example-1.
As a result of manufacturing an electrophotographic photosensitive member and evaluating the image characteristics in exactly the same manner as in Example 1, small white spots were observed in the black solid portion, and fog was observed in the white solid portion.

Example 3 JIS606 whose surface is mirror-finished as a cylindrical substrate
3 aluminum alloy pipe was set in the manufacturing apparatus shown in FIG. 1, and the cylindrical substrate was rotated at a rotation speed of 435 rpm. p. While rotating at m, spray deionized water from the spray nozzle in a sprayed state, contact the urethane sponge, which is the cleaning member, with the cylindrical substrate, and reciprocate in the axial direction. A 40 g / l aqueous solution of a weak alkaline detergent (NG-30 Okuno Seiyaku Co., Ltd.) at a temperature of 30 to 50 ° C. superposed with an ultrasonic wave of 1.1 MHz was sprayed onto the cylindrical substrate at 3 liters / minute, and sprinkled on the substrate. The sonic horn nozzle was horizontally moved by an ultrasonic horn motor at 33 mm / sec, the cylindrical substrate was washed, rinsed with the deionized water, and dried.

The substrate thus washed is then represented by its structural formula (4). 10 parts by weight of bisazo-based pigment and polyvinyl butyral resin (S-REC BH- manufactured by Sekisui Chemical Co., Ltd.)
3) 500 parts by weight of 1,2-dimethoxyethane was added to 5 parts by weight of phenol resin and 5 parts by weight of phenol resin, and the mixture was pulverized and dispersed by a sand grind mill and dispersed by dip coating. The charge generation layer was provided so as to have a thickness of 6 μm.

[0029]

[Chemical 4]

Next, 56 parts by weight of the hydrazone compound represented by the structural formula (1), 14 parts by weight of the hydrazone compound represented by the structural formula (2), and the cyan compound represented by the structural formula (3) were used for the aluminum pipe. 1.5 parts by weight and polycarbonate resin (Novarex 7030 manufactured by Mitsubishi Kasei Co., Ltd.)
A) 100 parts by weight of a solution of 1,000 parts by weight of 1,4-dioxane was applied by dip coating, and the film thickness after drying was 21 μm.
The charge transfer layer was provided so as to have m. The drum type electrophotographic photosensitive member thus obtained was mounted on a commercially available copying machine which was modified for reversal development, and the image characteristics were evaluated.As a result, white clear was not seen in the black solid part and in the halftone part. A good image was obtained with no image density unevenness and no fog on the white solid part.

Comparative Example 3 An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the urethane type sponge as a cleaning member was not used during the cleaning conditions in Example 3, and the image characteristics were evaluated. A relatively large amount of white spots was observed in the area, and uneven image density occurred in the halftone area.

Comparative Example 4 Electrophotographic sensitization was carried out in the same manner as in Example 3 except that 40 g / l of a weak alkaline detergent water solvent was sprinkled without superimposing ultrasonic waves from an ultrasonic horn under the washing conditions of Example 3. As a result of manufacturing the body and evaluating the image characteristics, small white spots were found in the black solid part and fog was found in the white solid part.

[Brief description of drawings]

FIG. 1 is a schematic view of a cleaning apparatus, FIG. 1-a is a schematic plan view, and FIG. 1-b is a schematic vertical view.

[Explanation of symbols]

 1 Drum chuck 2 Spray nozzle 3 Drum rotation motor 4 Cleaning member 5 Ultrasonic horn nozzle 6 Ultrasonic horn motor 7 Cylindrical substrate 8 Drum lifter

Claims (1)

[Claims] 1. A cylindrical substrate is rotated around an axis of the substrate, a cleaning member is brought into contact with the surface of the cylindrical substrate while spraying a cleaning liquid, and a cleaning liquid on which ultrasonic waves are superposed is sprinkled on the cylindrical member to clean the surface. A method for producing an electrophotographic photosensitive member, which comprises drying and forming a photosensitive layer on the surface of the substrate.