JP2928572B2 - Electrophotographic photoreceptor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to an electrophotographic photosensitive member using a support made of glass.

(Prior Art) An electrophotographic photosensitive member is basically composed of a support and a photosensitive layer. Conventionally, a support for a photoreceptor mainly uses aluminum. This is because aluminum was most suitable for required properties such as mechanical strength, workability such as good mirror surface machinability and high dimensional accuracy, and surface conductivity.

On the other hand, an electrophotographic photoreceptor using glass as a support material other than aluminum is disclosed (“electrophotography”).
P62-68, translated by Eiichi Inoue, Kyoritsu Shuppan). These photoreceptor supports have a hard glass surface provided with a transparent conductive electrode such as indium oxide (In ₂ O ₃ ).

(Problems to be Solved by the Invention) However, aluminum contains trace amounts of impurities such as iron and hydrogen. For this reason, when processing by mechanical grinding, minute irregularities and defects are generated on the surface. Also, in order to coat the photosensitive layer on aluminum well,
Degreasing by washing is performed. This degreasing treatment is mainly for cleaning the cutting oil used at the time of cutting, but is often insufficient. If the degreasing treatment is insufficient and the oil remains on the aluminum surface, a photosensitive layer cannot be formed on the aluminum well, resulting in poor characteristics and image defects of the obtained electrophotographic photosensitive member. Furthermore, an aluminum support having a mirror-finished surface causes interference artifacts when monochromatic light such as a laser is used as exposure means, resulting in image defects. As described above, it is difficult to obtain sufficient properties from a support made of only aluminum.

The electrophotographic photoreceptor actually used is an undercoat made of casein, polyvinyl alcohol, ethyl cellulose, polyamide, polyurethane, alcohol-soluble nylon, or a vinyl chloride-vinyl acetate copolymer between the support and the photosensitive layer. Layers are provided. In general, by providing an undercoat layer, it is possible to improve the electrical characteristics of the electrophotographic photosensitive member, improve the adhesion between the photosensitive layer and the support, or protect the support against defects. However, an electrophotographic photoreceptor having an undercoat layer requires a complicated manufacturing process, and the cost of aluminum itself is high, so that the manufacturing cost is inevitably high. Also, aluminum has a low surface hardness and may be damaged during the manufacturing process after mirror polishing. For this reason, special consideration was required for handling.

On the other hand, those provided with a transparent conductive electrode such as indium oxide on a glass surface are very expensive because they require heat treatment at a high temperature. Further, they are intended to be used for special applications such as a simultaneous exposure and development system, and are technically difficult and have not been put to practical use. Therefore, no substantial study has been made on the technical improvement or cost reduction of the glass support photoreceptor for use in a general electrophotographic apparatus such as an electrophotographic copying machine or a printer. For this reason, practically no concrete configuration means capable of withstanding practical use has been disclosed, and at present it has not been put to practical use.

The present invention has been made in view of the above circumstances, does not require mechanical grinding, prevents contamination by cutting oil or the like used during cutting, exhibits excellent photoreceptor characteristics, and is inexpensive. It is intended to provide a photoreceptor.

[Constitution of the Invention] (Means for Solving the Problems) The electrophotographic photoreceptor of the present invention is made of glass, and is provided on a cylindrical glass support formed by a mechanical drawing method, and provided on the glass support. And a photosensitive layer provided on the conductive layer.

(Function) Since the electrophotographic photoreceptor of the present invention uses a cylindrical glass formed by a mechanical drawing method as a support, excellent surface characteristics such as straightness, parallelism, roundness, and cylindricity are excellent. Having. Further, since the support is made of glass, it is not necessary to perform a cutting process, thereby preventing contamination by oil during the cutting process. Therefore, the conductive layer and the photosensitive layer can be favorably formed on the glass support.

In addition to functioning as a conductive electrode, the conductive layer functions as an undercoat layer for improving electrical characteristics, adhesion between the photosensitive layer and the support, and defect protection of the support.

Furthermore, since the glass used for the support of the electrophotographic photoreceptor of the present invention is a raw material of a mass-produced product such as a fluorescent lamp tube, the support can be manufactured as a by-product of such a mass-produced product. . Therefore, it can be manufactured at low cost and with good productivity.

(Example) Hereinafter, an example of the present invention will be specifically described with reference to the accompanying drawings.

The steps of manufacturing the electrophotographic photosensitive member will be described in the order of manufacturing the glass support, forming the conductive layer, and forming the photosensitive layer.

1. Manufacture of glass support The requirements for the support of the photoreceptor as described above, especially the generally used cylindrical support (hereinafter referred to as a base tube), include mechanical dimensional accuracy and base tube. Surface roughness (specularity) and low cost.

Such a glass tube is required as a cylindrical support of an electrophotographic photosensitive member, and has mechanical dimensional accuracy such as straightness, parallelism, roundness, and cylindricity, and roughness (mirrorness) of a rough tube surface. In order to improve the surface characteristics of the device, it is manufactured by a mechanical drawing method such as a dunner, updraw, downdraw, bellows method.

Further, as the material of the glass tube constituting the support of the electrophotographic photosensitive member, for example, soda-lime glass, lead glass, and borosilicate glass having the composition shown in Table 1 below are used. This is because this tube is manufactured as a by-product of a fluorescent lamp tube, and therefore it is desirable to have the same composition as other mass-produced products manufactured in a glass furnace.

The following method is used as a composition and a manufacturing method of a high-precision glass tube capable of meeting such demands.

Hereinafter, an example of the method for producing the glass support of the electrophotographic photosensitive member of the present invention will be described.

First, an automatic glass tube drawing step by the Danner method is performed. The continuous glass tank furnace and the dunnner equipment used in this process satisfy the following management points.

・ Generation of homogeneous glass by controlling glass raw materials, blending and melting, ・ Large amount of glass tube drawn (1-2t / hr) and stabilization, ・ Aptitude of glass temperature, temperature of Danner molding atmosphere ・ Stabilization, ・Stabilization and speed-up of auxiliary equipment such as sleeve rotating machine and drawing machine, ・ Optimization of measurement and control mechanism such as temperature, outer diameter, wall thickness, bending, etc. ・ Optimization of pipe straightening mechanism, 1 The figure is a schematic explanatory view showing a continuous glass tank furnace and a dunnner equipment. In the figure, reference numeral 10 denotes a trough. trough
A flow-down port 11 for flowing down the glass is provided at the bottom of 10. The trough 10 is placed in a muffle 12, in which a glass 13 in a molten state is stored. A sleeve 14 is provided below the trough 10 in the muffle 12. Here, in order to stabilize the temperature of the glass 13 flowing down on the sleeve 14 and the distribution state of the glass 13, it is necessary to reduce the temperature distribution and the temperature fluctuation over the trough 10 and the muffle 12. A unique combustion method and a high-precision temperature control mechanism are adopted in the area, and the sleeve 14 is placed in the sealed muffle 12 so as to be shielded from the influence of the outside air. The shape (the size of the diameter and the design of the outer surface) of the sleeve 14 is determined in consideration of the dimensional accuracy of the surface, the erosion resistance, and the like, which are important factors in improving the dimensional accuracy of the obtained glass tube. Also, sleeve 14 is trough 10
Optimum adjustment of head and position, tilt angle, and rotation speed from, and set so that the tip of the sleeve (tip) does not run out.

The sleeve 14 is supported by a stainless steel sleeve shaft 15 penetrating the center thereof, and one end of the sleeve 14 is fixed to a sleeve rotating machine 16 installed outside the muffle 12. The sleeve rotating machine 16 is provided with an air blow port 17 for blowing blow air through a hole passing through the center of the sleeve shaft 15, and communicates with an air blower (not shown). A guide roller 19 is provided below the tip 18 at the end of the sleeve 12. The guide roller 19 is covered by an annealing chamber 20. guide roller
19 is a drawing machine 21 installed downstream
It is connected to. Further, a cutting machine 23 for cutting the obtained glass tube 22 is mounted further downstream of the drawing machine 21.

In the apparatus having such a configuration, glass melted in a tank furnace (not shown) reaches the trough 10 via a refiner furnace and a forehearth (neither is shown). A stirrer is installed in the forehearth to homogenize the glass material and glass temperature. The ribbon-shaped glass 13 flows down onto the rotating sleeve 14 from the tip of the trough 10. The glass flow rate is adjusted by a fine-movement vertical drive device (not shown) of the gate fitted to the trough 10.

The glass 13 flows over the sleeve 14 and leaves the tip 18,
It passes through a drawing machine 21 via a guide roller 19. At this time, blow air is blown from the air blow port 17 through a hole penetrating through the center of the sleeve shaft 15. The glass is pulled by a drawing machine 21 to form a glass tube 22. Glass tube 22 of drawing machine 21
The upper and lower rubber belts that pull the glass can be adjusted in angle with respect to the traveling direction of the tube, thereby correcting the bending of the glass tube 22.

The outer diameter and wall thickness of the obtained glass tube 22 are determined based on the relationship between the glass flow rate, the drawing speed, and the blow air pressure. The outer diameter and thickness are measured by non-contact continuous measurement using a laser beam. In addition, the outer diameter adopts an automatic control method that controls while adjusting the blow air pressure and the wall thickness while adjusting the pipe drawing speed, and furthermore, adopts an automatic sorting mechanism to respond to each case when it goes outside the management level I have.

In this device, the cutting of the glass tube is automated, and the simultaneous production of complicated types of glass tubes with different lengths has no adverse effect on the productivity. It is possible to produce a raw tube efficiently.

The obtained glass tube 22 is cut by a cutting machine 23.

 Next, both ends of the glass tube 22 are processed.

When both ends of the obtained glass tube 22 are cut, they are easily damaged by shocks such as impacts and squeezing. Further, there are cases where the flanges are machined into a shape that allows easy attachment of the flanges to both ends, and cases where the virtual axis and the flanges are coaxial with the surface of the imaging unit. In such a case, FIG.
It is necessary to process both ends into a shape as shown in FIG. 2 (C). This processing is performed on both ends of the glass tube using the surface of the imaging unit as a reference surface by a heat treatment such as baking (glazing or burning), a heating press, or a heating draw.

In the above method, for example, diameter 29.8 mm, length 349 mm, wall thickness 1.0
A 5 mm glass tube was prepared, and five tubes were extracted. The straightness, roundness and cylindricity of the outer shape were measured. As a result, 5
The average value of the book is straightness 13.2 μm, roundness 16.6 μm,
And the cylindricity was 42.5 μm. Each value is judged to be the same level as the accuracy of the conventional aluminum pipe. From the above results, it was confirmed that the glass tube manufactured by the Danner method satisfies the accuracy required for the electrophotographic photosensitive member. Also, this glass tube is the first
As shown in the table, the hardness of each of the glasses is considerably higher than about 20 to 40 (Brinell hardness) of aluminum, and the surface is hardly scratched. Further, the glass tube has a coefficient of thermal expansion much smaller than that of aluminum, and is effective in preventing deformation due to heat at the time of manufacturing an amorphous silicon photoreceptor described later.

2. Formation of conductive layer Next, a conductive layer is formed on the outer surface of the prepared glass tube. Means for forming the conductive layer include metal film coating by vacuum evaporation, ion sputtering, ion plating, chemical vapor deposition (CVD), and electroless plating, and metal powder, carbon powder, graphite, and metal oxide in resin. Coating of a composite material conductive resin in which a conductive filler such as the above is dispersed.

When depositing thin metal films, the required conductivity is usually
Since it is 10 ⁷ to 10 ⁴ Ωcm or less, most metal deposited films can be used, but in particular, aluminum, nickel,
Gold, silver, chromium, In ₂ O _{3 and the} like can be used relatively easily.

When coating the conductive resin, first, metal powder,
Carbon powder, etc. is mixed and dispersed in a binder resin such as epoxy resin, urethane resin, acrylic resin, ABS resin, modified polyolefin, and the like. Get. Note that a sand mill, a ball mill, a roll mill, a paint shaker, or the like is used for dispersion. Next, the obtained conductive resin is applied to a glass tube immersed in alcohol and washed with steam. The method of applying the conductive resin includes a dipping method, a spray method, a roll method, a blade method, and the like.
Dipping or spraying is suitable for cylindrical supports. Whichever coating method is used, uniformity of the film thickness and stability of electric resistance are important, and it is necessary to prevent dust and the like from being mixed. Such a conductive resin coating is preferable because the conductive resin coating layer improves the adhesiveness to the photoconductor layer and functions as a charge barrier layer.

Further, a resin layer having a thickness of 0.05 to 1.0 μm may be provided as an intermediate layer, if necessary, to improve the adhesiveness between the metal film or the conductive resin layer and the photosensitive layer or the protective layer. Examples of such a resin include nitrocellulose and polyamide. In the case of a metal film, the thickness of the conductive layer need only be about 0.1 μm or more as long as a defect such as a pinhole does not occur. Is preferably in the range of 0.5 to 30 μm. In any case, the optimum thickness depends on the application method and the material.

3. Formation of Photosensitive Layer As the photoconductor used for the electrophotographic photoconductor of the present invention, a known organic or inorganic photoconductor can be used.

Organic photoreceptors include photoconductive polymers such as poly-N-vinyl carbazole alone, electron-donating polymers such as poly-N-vinyl carbazole, and 2,4,7-trinitro-9-fluorenone. A charge transfer complex composed of an electron-accepting low-molecular compound, a charge transfer complex composed of an electron-accepting polymer and an electron-donating low-molecular substance, a eutectic complex of polycarbonates with thiapyrylium, etc. A low molecular charge generating material such as phthalocyanine, for example, a low molecular charge transporting material having hole transport capability such as hydrazone or a low molecular charge transporting material having electron transporting capability such as 2,4,7-trinitro-9-fluorenone. And so-called dispersed organic photoreceptors dispersed in a resin serving as a binder. In recent years, dispersed organic photoreceptors utilizing the diversity of organic substances have become mainstream.

Here, the layer structure of the dispersion type organic photoreceptor is a so-called single layer type in which a layer made of a substance in which a charge generating material and a charge transporting material are contained in a binder is provided on a substrate. A charge generation layer (CGL) composed of a binder and a charge transport layer (CTL) composed of a charge transport material and a binder, which are sequentially provided on a substrate, a so-called function-separated type comprising a charge transport material and a binder. In a so-called function-separated type or function-separated type in which a charge transport layer and a charge generation layer composed of a charge generation material and a binder are sequentially provided on a substrate, injection of charges is prevented, adhesion to the substrate is improved, and the like. A resin layer interposed directly above the substrate for the purpose of (1), a function-separated type in which a protective layer or insulating layer is provided on the uppermost layer for the purpose of improving mechanical strength or improving weather resistance to ozone, etc. , etc Conceivable. In each of these layers, various additives may be contained in the binder within a qualitative and quantitative range that does not adversely affect the properties. In recent years, a function-separated type capable of obtaining a photosensitive layer having high photosensitivity and high printing durability has been mainly used.

Examples of the charge generating material include pyrylium, thiapyrilm, azulhenium dye, phthalocyanine dye, anthantrone dye, dibenzapyrene quinone dye, pyranthrone dye, trisazo dye, disazo dye, azo dye, indigo dye, quinacridone dye, and asymmetric quinocyanine. Dyes, perylene dyes, polycyclic quinone dyes, quinocyanine dyes, squarylium dyes, and mixtures thereof.

Examples of the electron transporting material include electron accepting substances such as chloranil, brolanyl, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, and those obtained by polymerizing these substances. Examples of the hole transport material include various carbazoles, hydrazones, pyrazolones, oxadiazoles, oxazoles, thiazoles, triarylmethanes, polyarylalkanes, polyarylalkenes, triarylamines, and condensed polyamines. Ring hydrocarbons, and mixtures thereof, and the like are conceivable.

As a binder for the charge generation material, butyral resin,
Examples thereof include phenoxy resins, polycarbonates, polyesters, acrylic resins, and styrene resins, and a thermosetting resin may be used by adding an appropriate curing agent to a thermoplastic resin. Further, as a binder of the charge transport material, polyarylate resin, polysulfone resin, polyamide resin, acrylic resin, acrylonitrile resin, methacrylic resin,
Examples thereof include vinyl chloride resin, vinyl acetate resin, phenol resin, epoxy resin, polyester resin, alkyd resin, polycarbonate, and polyurethane.

It is necessary to select a solvent used when applying the photoreceptor composed of the above in consideration of the dispersibility of the charge generating material, the compatibility with the charge transporting material, the drying speed of the solvent, and the like. As such, various ketones, amides, sulfoxides, ethers, esters, aliphatic halogenated hydrocarbons, aromatic hydrocarbons and the like can be used. Note that two or more of these solvents may be used in combination in consideration of the solvent balance.

Further, the compounding ratio of the charge generating material to the binder is 0.5
To 2.0, preferably 0.5 to 1.5, and the compounding ratio of the charge transport material to the binder is 0.5 to 3.0, preferably 0.5 to 2.0.
Range.

For dispersion, first, a predetermined amount of a binder, which is a vehicle prepared in advance, and a charge generating material or an electric charge transporting material are mixed. This mixing is performed using a sand mill, a ball mill, a roll mill, a paint shaker, an attritor, a high-speed grind mill, a pebble mill, etc., and let-down as necessary. Thereafter, the obtained mixture is prepared into a coating solution by the above-mentioned solvent.

The obtained coating solution is coated on a glass tube. First, the glass tube is immersed and cleaned with an alcohol-based solvent. If oils such as fingerprints may adhere during handling or the like, degrease and wash with a halogen-based solvent and steam, and if necessary, further wash with ultraviolet light / ozone. Thereafter, a multilayer film is formed by repeating the vapor deposition method, dip coating and spray coating. The preferred film thickness is 0.5 to 30 μm, preferably 15 to 20 μm for the conductive layer.
m, the intermediate layer is 0.05 to 1.0 μm, preferably 0.3 to 0.7 μm
m, the charge generation layer is 0.1 to 1.0 μm, preferably 0.2 to 0.6 μm
m, the charge transport layer is 10 to 30 μm, preferably 15 to 25 μm,
And the protective layer is 0.5 to 30 μm, preferably 0.5 to 1.5 μm
It is. In the case of dip coating, the pulling speed of the substrate must be suppressed to a maximum of about 12 to 15 cm / min when forming a relatively thick charge transport layer in consideration of productivity. When forming a relatively thin conductive layer, charge generation layer and protective layer, the substrate pulling speed needs to be set so as to be 30 to 40 cm / min.

Examples of a method for forming the charge transport layer or the charge generation layer include, in addition to dip coating, spray coating, roll coating, blade coating, and the like. When the object to be coated is a cylindrical substrate, dip coating or spraying is preferred. In order to obtain a layer having a predetermined film thickness by these methods, it is necessary to adjust the non-volatile content concentration, viscosity, coating speed, and the like of the coating solution. In particular, when spray coating is used, the distance between the spray nozzle and the cylindrical substrate, the discharge pressure of the coating liquid droplets, the shape of the spray nozzle, the rotation of the cylindrical substrate, and the longitudinal direction of the cylindrical substrate of the spray. Adjustment such as synchronization with scanning is required. After the solution coating, if necessary, at least one end of the cylindrical substrate corresponding to the non-image forming area of the cylindrical substrate to secure electrical conduction with the conductive layer and improve cleaning performance. Of the coating and removal of the coating from the inner wall or the end face. This peeling / removing is performed by using a good solvent for the coating or using a wiping member impregnated with the solvent.

Further, the binderless charge generation layer can be formed by vapor deposition. In the vapor deposition method, the crystal form of the charge generation material and the film thickness of the charge generation layer are controlled by the degree of vacuum, the temperature of the deposition substrate, the substrate temperature, the deposition time, the rotation speed of the cylindrical substrate, the setting elevation angle of the cylindrical substrate, and the like. .

After coating, the coating layer is air-dried in a predetermined manner, and then dried at a drying temperature of 50 to 140 ° C, preferably 80 to 120 ° C, for a drying time of 5 to 60 ° C.
Minutes, preferably 10 to 30 minutes. In the case of the function-separated type photoreceptor, multi-layer coating is performed. Thereafter, if necessary, cooling is performed to perform the next coating. At this time, it is necessary not to elute the lower layer coating or coloring material when coating the upper layer,
The selection of the solvent and the setting of the drying time are performed in consideration of these.
After the final coating and drying, aging is performed to increase the sensitivity by morphological change of the coating. This aging is performed by treating at room temperature to 100 ° C. for half a day to one week.

Examples of the inorganic photoreceptor include selenium, a-Si, and selenium-arsenic. In the a-Si system, a CVD method is used, and in others, a vacuum evaporation method is used. In the case of using an inorganic photoreceptor, if a resin coating layer is used as the conductive layer, the generation of gas or the like adversely affects the conductive layer. Therefore, it is preferable to use a metal as the conductive layer.

Examples of the shape of the end surface of the photoreceptor include shapes as shown in FIGS. 3 (A) to 3 (C). The electrophotographic photoreceptor shown in FIG. 3 (A) is provided with a photosensitive layer 32 at the end of the photoreceptor (either one end is acceptable) so that the conductive layer 31 provided on the glass tube 30 is exposed. By fitting a conductive flange 33 made of a metal such as aluminum, conductive plastic, rubber, or a composite structure thereof as shown by an arrow to the portion, conduction with the rotating shaft can be achieved in the same manner as a general photoconductor. It has become. In the electrophotographic photoreceptor shown in FIG. 3 (B), the conductive layer 31 is also coated on the inside of the end of the glass tube 30, so that it can be electrically connected to the flange 34 fitted to this portion. I have. In the electrophotographic photosensitive member shown in FIG. 3 (C), the end of the glass tube 30 is drawn, and at least one end 35 of the conductive layer 31 is exposed without being covered by the photosensitive layer 32. ing. By fitting the flange 36 so as to cover this portion, consideration is given to withstand even if some stress is applied to both ends. If there is a possibility that a large stress may be applied during the fitting to cause a crack, the gap is filled with a conductive adhesive in a lightly fitted state. Alternatively, a conductive elastic body (rubber) may be provided at the fitting portion between the flange and the glass tube to reduce distortion at the time of fitting and to perform secure mounting.

Hereinafter, test examples performed to clarify the effects of the present invention will be described.

Test Example 1 First, the diameter was 60 mm, the length was 180 mm, and the wall thickness was by the Danner method.
A 1.1 mm glass tube (hereinafter abbreviated as a glass tube) was produced. The obtained glass tube was immersed in alcohol and washed with steam.

Next, aluminum was deposited on the glass tube to a thickness of 1 mm.
A μm conductive layer was formed.

The glass tube was mounted in the apparatus shown in FIG. In FIG. 4, reference numeral 40 denotes a reaction vessel. A substrate rotating shaft 41 is inserted into the bottom of the reaction vessel 40. The support is on the substrate rotating shaft 41
A heater 42 is provided on the support 42. The base rotating shaft 41 is connected to a rotating device (not shown). The glass tube 44 is mounted so that the heater 43 is inserted. An electrode 45 is attached to a side wall of the reaction vessel 40. A high-frequency power supply 46 is provided outside the reaction vessel 40, and is connected to the reaction vessel 40 to generate plasma.

On the other hand, four cylinders 47 are placed outside the reaction vessel 40, and each cylinder 47 has a pressure gauge 48 and a regulating valve 49.
Is attached. A pipe 51 extends from each cylinder 47 to the mixer 50. In addition, the mixer
A pipe 52 is communicated from 50 to the reaction vessel 40, and the pipe 52
An adjusting valve 53 for adjusting the flow rate of the mixed gas is mounted in the middle of the process. An exhaust port 54 for depressurizing the inside of the vessel is provided at the bottom of the reaction vessel 40, and a piping 55 extending from the exhaust port 54 is provided with an adjustment valve 56 for adjusting the degree of vacuum in the vessel. .

In this apparatus, the inside of the reaction vessel 40 was evacuated to a degree of vacuum of about 10 ^-5 Torr. At the same time, the temperature of the heater 41 was set to 250 ° C., and the substrate rotating shaft 41 was rotated at 10 rpm. When the surface temperature of the substrate became constant, SiH ₄ gas and B ₂ H ₆ in cylinder 47
The gas and CH ₄ gas were mixed in the mixer 50, and the mixed gas was introduced into the reaction vessel 40. The flow ratio is SiH ₄ : B ₂ H ₆ : CH ₄
= 1: 10 ^-3 : 0.5. Next, the pressure in the reaction vessel 40 is set to 0.5 T
Adjusted to orr. 13.56MHz high frequency power of 150W is applied to generate plasma, and the mixed gas reacts to a thickness of 0.5μ.
An m-type a-SiC: H barrier layer was formed.

Next, the gas flow ratio in the reaction vessel 40 was changed to SiH ₄ : B ₂ H ₆ : CH ₄
= 1: 10 ⁻⁶ : 0, and the pressure in the reaction vessel was adjusted to 0.7 Torr. An i-type a-Si: H photoconductive layer having a thickness of 30 μm was formed by applying 300 W of 13.56 MHz high frequency power.

Next, the gas flow ratio in the reaction vessel was set to SiH ₄ : CH ₄ = 1: 10. The pressure in the reaction vessel was set to 0.7 Torr, and a high frequency power of 13.56 MHz was applied at 150 W to form an a-SiC: H surface layer having a thickness of 0.1 μm. A photosensitive layer was composed of a p-type a-SiC: H barrier layer, an i-type a-Si: H photoconductive layer, and an a-SiC: H surface layer.

 Thus, the electrophotographic photosensitive member of the present invention was obtained.

The roundness of the obtained electrophotographic photosensitive member was measured. The results are shown in Table 2 below. The roundness was determined by the following equation.

Roundness = (maximum diameter−minimum diameter) / 2 At this time, no abnormality was recognized on the end face of the electrophotographic photosensitive member.

The obtained electrophotographic photoreceptor was copied to a copier BD-38 manufactured by Toshiba.
A halftone image, solid black, and a character image were output by mounting on the 10. As a result, no image density unevenness occurred. This is probably because the thermal expansion coefficients of a-Si and glass are almost the same. Further, no image defects such as white spots occurred. This is probably because the surface of the glass is homogeneous. Even after continuous use of 200k times, a clear image equivalent to the initial one was obtained.

Comparative Example 1 Aluminum (equivalent to JIS3003) was used with a diameter of 60 mm and a length of 280
It was processed into a 2 mm thick tube. The surface of the tube was mirror-polished. Next, the aluminum tube was immersed in 1,1,2-trichloroethane, subjected to ultrasonic cleaning to remove cutting chips, and degreased cutting oil by steam cleaning.

The aluminum tube was treated in the same manner as in Test Example 1 to form an a-Si photosensitive layer to obtain an electrophotographic photosensitive member.

The roundness of the obtained electrophotographic photosensitive member was measured in the same manner as in Test Example 1. The results are shown in Table 2 below.

As is clear from Table 2, the glass tube of the electrophotographic photoreceptor according to the present invention exhibited higher roundness than the conventional aluminum tube. Further, in the electrophotographic photosensitive member using the aluminum tube (comparative example), the end face was distorted as shown in FIG. The distortion amount W at this time was about 0.1 mm. This strain is considered to be a strain at the time of cooling the substrate due to a difference in thermal expansion coefficient between a-Si and aluminum.

The obtained electrophotographic photoreceptor produced a halftone image, a solid black image, and a character image in the same manner as in Test Example 1. As a result, since the roundness was low, density unevenness in the circumferential direction was observed in halftone and solid black, and white spots were observed in solid black and halftone images. This tendency was further increased by continuous use. When this white spot was observed by SEM, it was found to be a horn-shaped hole and reached the substrate. This is because a-Si abnormally grows on protruding precipitates on the aluminum surface,
It is considered to be a trace that peeled off during the film formation. It is thought that the material that does not come off during the film formation is scraped off by the blade in the copying machine and the white spot increases.

Test Example 2 A glass tube having a diameter of 78 mm, a length of 324 mm, and a thickness of 1.1 mm was produced by a Danner method. A conductive layer and a photosensitive layer were formed on a glass tube in the same manner as in Test Example 1 to obtain an electrophotographic photosensitive member of the present invention. The obtained electrophotographic photoreceptor was mounted on each of Toshiba BD-8560, BD-9110, and BD-9230 copiers, and halftone images, solid black, and character images were obtained in the same manner as in Test Example 1. Image was obtained.

Instead of Test Example 3 a-SiCH surface layer, the flow rate by using the N ₂ gas 2.
The electrophotographic photosensitive member of the present invention was prepared in the same manner as in Test Example 1 except that an a-SiNH surface layer having a thickness of 0.05 μm obtained by applying 0 SLM and a pressure of 2.0 Torr and applying a power of 250 W was used. Obtained. The obtained electrophotographic photosensitive member was mounted on a copying machine BD-3810 manufactured by Toshiba, and a halftone image, a solid black and a character image were produced in the same manner as in Test Example 1. As a result, a clear image was obtained.

Test Example 4 Instead of the a-SiC: H surface layer, 50 SCCM of SiH ₄ gas, 400 SCCM of CH ₄ gas, and 1000 SCCM of N ₂ gas were introduced into the reaction vessel to obtain a pressure of 1 Torr, and a power of 20 W was applied. Thickness 0.1
An electrophotographic photoreceptor of the present invention was obtained in the same manner as in Test Example 1 except that a μm a-Si (C, N): H surface layer was formed.
The obtained electrophotographic photosensitive member was mounted on a copying machine BD-3810 manufactured by Toshiba, and a halftone image, a solid black and a character image were produced in the same manner as in Test Example 1. As a result, a clear image was obtained.

Test Example 5 A glass tube having a length of 262 mm was used, a PH ₃ gas was used instead of a B ₂ H ₆ gas when forming a barrier layer, and a flow rate ratio was SiH.
_The electrophotographic photoreceptor of the present invention was obtained in the same manner as in Test Example 1 except that an n-type a-SiC: H barrier layer was formed at a ratio of ₄ : PH ₃ 1: 5 × 10 ⁻⁵ . The obtained electrophotographic photoreceptor was copied by Toshiba copier.
A halftone image, a solid black image, and a character image were provided in the same manner as in Test Example 1 with the BD-2810 mounted thereon, and a clear image was obtained.

Test Example 6 A glass tube having a diameter of 30 mm, a length of 324 mm, and a wall thickness of 1.1 mm was produced by a Danner method. A negatively charged a-Si photosensitive layer was formed in the same manner as in Test Example 5 to obtain an electrophotographic photosensitive member of the present invention. The obtained electrophotographic photosensitive member was mounted on a laser beam printer TN-7200 manufactured by Toshiba, and a halftone image, a solid black image and a character image were produced in the same manner as in Test Example 1. As a result, a clear image was obtained.

Test Example 7 An electrophotographic photoreceptor of the present invention was obtained in the same manner as in Test Example 1, except that the thickness of the p-type a-SiC: H layer was changed to 5 μm without depositing an aluminum conductive layer. The obtained electrophotographic photosensitive member was mounted on a copying machine BD-3810 manufactured by Toshiba, and a halftone image, a solid black and a character image were produced in the same manner as in Test Example 1. As a result, a clear image was obtained.

By forming an a-Si photosensitive layer on a glass tube as described above, it is not necessary to use an organic solvent in cleaning, and it is possible to obtain an electrophotographic photosensitive member having less distortion and no image defects. .

Test Example 8 A glass tube having a diameter of 60 mm, a length of 240 mm, and a wall thickness of 1.1 mm was produced by a Danner method. The obtained glass tube was immersed in alcohol and washed with steam.

Next, polyvinyl alcohol containing tin oxide powder (particle diameter of 1 μm or less) was applied to the surface of the glass tube at a thickness of 5 μm to form a conductive layer. Next, alcohol-soluble nylon was applied on the conductive layer to a thickness of 0.5 μm. Next, a metal-free phthalocyanine as a charge generating material and a phenoxy resin (structural formula I) as a binder resin were mixed at a mixing ratio of charge generating material: resin = 1: 1. A glass tube was immersed in this solution to provide a 0.2 μm thick charge generation layer.

Next, a hydrazone derivative (structural formula
II) and a butadiene derivative (structural formula III) in a mixture (mixing ratio of 5: 5) and a binder resin of polycarbonate (structural formula IV) and a charge ratio of charge transport material: resin = 0.8: 1. A transport solution was prepared. A glass tube provided with a charge generation layer was immersed in this solution to provide a charge transport layer with a thickness of 19 μm.

The above steps were continuously performed to produce 100 electrophotographic photosensitive members for a laser beam printer.

The obtained electrophotographic photosensitive member was mounted on a laser beam printer, and an image of one dot pattern was printed, and the number of white spots in the image was examined. The results are shown in Table 3 below.

Comparative Example 2 Aluminum was processed into a base tube having a diameter of 60 mm and a length of 240 mm. The surface of the tube was mirror-polished. Next, the aluminum tube was immersed in 1,1,1-trichloroethane, subjected to ultrasonic cleaning to remove cutting debris, and degreased cutting oil by steam cleaning.

Next, alcohol-soluble nylon was applied with a thickness of 0.5 μm on the washed aluminum tube. A charge generation layer and a charge transport layer were sequentially formed thereon in the same manner as in Test Example 8 to produce 100 electrophotographic photosensitive members.

The obtained electrophotographic photosensitive member was mounted on a laser beam printer, and the number of white spots in the image was examined in the same manner as in Test Example 8. The results are shown in Table 3 below.

As is clear from Table 3, the electrophotographic photoreceptor using the glass tube had few white spots in the image.
This is because the surface roughness of the glass tube is very small at 50A. Also, clear images were obtained for ordinary images. On the other hand, the electrophotographic photosensitive member using the aluminum tube had many white spots in the image. This is presumably because the charge generation layer and the charge transport layer were not formed due to the protruding precipitates on the aluminum surface. In addition, when an aluminum tube is used, the coating liquid is deteriorated by repeated use because of high reactivity between aluminum and the organic solvent. The characteristics of the electrophotographic photoreceptor coated with the deteriorated coating solution were deteriorated. Further, in the electrophotographic photosensitive member using the aluminum tube, grain-shaped interference fringes due to the laser beam were generated. In the case of using a glass tube, the above problems were not observed, and the characteristics were stable.

Test Example 9 An electrophotographic photoreceptor of the present invention was produced in the same manner as in Test Example 8, except that copper phthalocyanine (structural formula V) was used as the charge generating material. About the obtained electrophotographic photoreceptor,
When the number of vitiligo was examined in the same manner as in Test Example 8, almost no vitiligo occurred.

Test Example 10 Using a hydrazone-based charge-transporting material (structural formula VI) and a polyacrylate (structural formula VII) as the binder resin
The electrophotographic photoreceptor of the present invention was produced in the same manner as in Test Example 8 except that the mixing ratio was set to 1: 1. The obtained electrophotographic photoreceptor was examined for the number of white spots in the same manner as in Test Example 8, and almost no white spots occurred.

Test Example 11 An electrophotographic photoreceptor of the present invention was produced in the same manner as in Test Example 8, except that the conductive layer was a 2 μm-thick aluminum vapor-deposited film. When an image was formed on the obtained electrophotographic photosensitive member in the same manner as in Test Example 8, a clear image was obtained.

Test Example 12 An electrophotographic photoreceptor of the present invention was produced in the same manner as in Test Example 8, except that a glass tube having a diameter of 30 mm, a length of 326 mm and a wall thickness of 1.1 mm was used. When an image was formed on the obtained electrophotographic photosensitive member in the same manner as in Test Example 8, a clear image was obtained.

Test Example 13 An electrophotographic photoreceptor of the present invention was produced in the same manner as in Test Example 8, except that a polycarbonate resin in which carbon black was dispersed was formed to a thickness of 2 μm as the conductive layer.
When an image was formed on the obtained electrophotographic photosensitive member in the same manner as in Test Example 8, a clear image was obtained, and no generation of interference fringes was observed.

Test Example 14 A glass tube having a diameter of 60 mm, a length of 262 mm and a wall thickness of 1.1 mm was produced by a Danner method. The obtained glass tube was immersed in alcohol and washed with steam.

Next, polyvinyl alcohol containing carbon black was applied on the surface of the glass tube at a thickness of 5 μm to form a conductive layer. Next, alcohol-soluble nylon was applied on the conductive layer to a thickness of 0.5 μm. Next, a bisazo pigment (structural formula VIII) as a charge generating material and a phenoxy resin as a binder resin were mixed at a charge generating material: resin = 1: 1 ratio.
Dispersed in 1,1,2-trichloroethane. A glass tube was immersed in this solution to provide a charge generating layer having a thickness of 0.5 μm.

Next, a charge transport layer was provided on the charge generation layer in the same manner as in Test Example 8.

The above steps were continuously performed to produce 100 electrophotographic photosensitive members for a copying machine.

The obtained electrophotographic photosensitive member was mounted on a copying machine BD-2810 manufactured by Toshiba to produce a halftone image, a solid black image, and a character image. As a result, no image density unevenness occurred, and a clear image was obtained.

Comparative Example 3 Aluminum was processed into a base tube having a diameter of 60 mm and a length of 262 mm. The surface of the tube was mirror-polished. Next, the aluminum tube was immersed in 1,1,1-trichloroethane, subjected to ultrasonic cleaning to remove cutting debris, and degreased cutting oil by steam cleaning.

Next, alcohol-soluble nylon was applied with a thickness of 0.5 μm on the washed aluminum tube. A charge generating layer and a charge transporting layer were sequentially formed thereon in the same manner as in Test Example 14 to produce 100 electrophotographic photosensitive members.

The obtained electrophotographic photosensitive member was mounted on a copying machine BD-2810 manufactured by Toshiba to produce a halftone image, a solid black image, and a character image. As a result, there was a white spot in the image, and a clear image could not be obtained.

Test Example 15 An electrophotographic photoreceptor of the present invention was produced in the same manner as in Test Example 14, except that a glass tube having a diameter of 78 mm and a length of 326 mm was used.

The obtained electrophotographic photoreceptor was mounted on an M / C (30 CPM) in which a copying machine BD-7610 manufactured by Toshiba was converted to a negative charging type and an image was produced. A clear image was obtained. In addition, an image that was the same as the initial image was obtained even after continuous copying of 80k times.

Test Example 16 In Test Example 12, the surface of the glass tube was subjected to hydrofluoric acid treatment or sandblasting treatment to produce two types of roughness (0.07 s and 0.5 s), and the charge generation layer film was formed on the surface. A total of 12 electrophotographic photosensitive members having a thickness of 0.1, 0.12, 0.15, 0.18, 0.2 and 0.25 μm were produced. For these electrophotographic photosensitive members, a pattern image of one dot line was produced. The results of the density unevenness are shown in Table 4 below.

As is evident from Table 4, when the thickness of the charge generation layer is small, density unevenness tends to occur. However, even when the thickness of the charge generation layer is small, the density unevenness is buffered by roughening the surface of the glass tube. .

Test Example 17 Each powder of Se and Te having a purity of 99.99% or more was blended at a weight ratio of 8: 2, and this mixed powder was mixed in a quartz ampoule for about 10 ^-3 To
Sealed at a vacuum of rr. Next, this ampoule is heated to about 750 ° C.
For 10 hours to melt the contents. Next, this ampoule was put into water and quenched to obtain a glassy alloy of Se-Te.

Next, the diameter 60 mm, length produced by the Danner method
Aluminum film about 2μm thick on 280mm glass tube
To form a conductive layer. Thereafter, the above glassy alloy was vacuum-deposited on the glass tube to form a 55 μm-thick photosensitive layer to obtain an electrophotographic photosensitive member of the present invention. The vacuum deposition was performed at a degree of vacuum of 10 ^-4 to 10 ^-5 mmHg, the substrate temperature was 60 to 65 ° C,
The deposition was performed at a temperature of 300 ° C.

The obtained electrophotographic photoreceptor was mounted on a copying machine BD-3810 manufactured by Toshiba to produce an image, and a clear image was obtained.

Test Example 18 Two kinds of powders of a powder mixture of Se and Te having a purity of 99.99% or more in a weight ratio of 8: 2 and a Te powder were mixed in a quartz ampoule at about 10 ^-3 Torr. Sealed in a vacuum,
Next, the ampoule of the mixed powder was heated at about 750 ° C. for 10 hours, and the ampoule of the Te powder was heated at 600 ° C. for 10 hours to melt the contents. Next, they are put into water and quenched to
-A glassy alloy of Te and Te was obtained.

Next, the diameter 60 mm, length produced by the Danner method
After a glass tube of 280 mm was immersed in alcohol, steam cleaning was performed. An aluminum film was coated on the glass tube to a thickness of about 5 μm to form a conductive layer. Thereafter, the glassy alloy of Se-Te was vacuum-deposited on the glass tube to form a photosensitive layer having a thickness of 50 μm. The vacuum evaporation was performed at a degree of vacuum of 10 ⁻⁴ to 10 ⁻⁵ mmHg, a substrate temperature of 70 to 75 ° C., and an evaporation source temperature of 350 ° C. Next, the evaporation source temperature is 350 ° C
, The Te board was gradually heated, and then the temperature was lowered to increase the concentration of Te near the surface of the substrate, and vapor deposition was performed. Thus, a Te rich Se electrophotographic photosensitive member was obtained. The total thickness of the photosensitive layer was 60 μm.

The obtained electrophotographic photoreceptor was mounted on a copying machine BD-3810 manufactured by Toshiba to produce an image, and a clear image was obtained.

Test Example 19 An Se-Te-based electrophotographic photoreceptor was obtained in the same manner as in Test Example 18, except that a glass tube having a diameter of 78 mm and a length of 324 mm was used. However, the concentration of Te near the surface was increased by increasing the temperature of the evaporation source.

When the obtained electrophotographic photosensitive member was mounted on a copying machine BD-8510 manufactured by Toshiba and an image was output, a clear image was obtained.

Test Example 20 Next, a diameter of 78 mm and a length produced by the Danner method
After immersing the 324 mm glass tube in alcohol, steam cleaning was performed. An aluminum film was coated on the glass tube at a thickness of about 2 μm to form a conductive layer. Thereafter, the As ₂ Se ₃ to form a photosensitive layer having a thickness of 55μm by vacuum evaporation to give an electrophotographic photoreceptor of the present invention to the glass mother tube. The vacuum deposition was performed at a degree of vacuum of 10 ⁻⁵ Torr and the temperature of the deposition source was 400 ° C.

The obtained electrophotographic photoreceptor was mounted on a copying machine BD-3810 manufactured by Toshiba to produce an image, and a clear image was obtained.

[Effects of the Invention] As described above, the electrophotographic photoreceptor of the present invention exhibits excellent photosensitive characteristics and is highly accurate with little thermal deformation. In addition, it has good compatibility with various photoconductor production conditions. Further, since the specific gravity of glass is smaller than that of aluminum, the weight of the photoconductor can be reduced. Further, since the glass has a high surface hardness, scratches are unlikely to occur. Furthermore, in the case of a glass tube, a mirror surface can be obtained without surface polishing and the number of surface defects is small, so that surface treatment which is indispensable for an aluminum tube can be omitted. In addition, when a resin dispersion layer of a metal filler is used, the function of the conductive layer and the function of the undercoat layer are also used, and the effect of absorbing or diffusing (scattering) monochromatic light such as laser light is also obtained. Interference due to reflection from the support is prevented, and image defects such as uneven shading can be prevented.

In addition, by treating the surface of the glass tube with an appropriate roughness, uniform application of the charge generation layer is facilitated, and interference fringes can be prevented even when metal is used as the conductive layer. it can.

The production equipment for the glass tube by the mechanical tube drawing method used in the above embodiment has extremely high productivity, and can produce a large amount of glass tube with high accuracy in a short time. Can be.

[Brief description of the drawings]

FIG. 1 is an explanatory view of an apparatus for producing a glass tube of an electrophotographic photoreceptor of the present invention, and FIGS. 2A to 2C are end portions of the glass tube of the electrophotographic photoreceptor of the present invention. Explanatory diagram showing the third
3A to 3C are explanatory views of an end portion of the electrophotographic photosensitive member of the present invention, FIG. 4 is a schematic diagram of an apparatus used for forming a photosensitive layer, and FIG. FIG. 4 is an explanatory diagram illustrating distortion of an aluminum tube of the electrophotographic photosensitive member. 10 ... trough, 12 ... muffle, 14 ... sleeve, 15 ...
... Sleeve shaft, 16 ... Sleeve rotating machine, 17 ... Air blower, 19 ... Guide roller,
20: Annealing chamber, 21: Drawing machine, 22: Glass tube, 23: Cutting machine, 3
0,44: Glass tube, 31: Conductive layer, 32: Photosensitive layer, 3
3, 34, 36 ... flange, 35 ... throttle part, 40 ... reaction vessel, 41 ... substrate rotating shaft, 42 ... support, 43 ... heater,
45 ... electrode, 46 ... high frequency power supply, 47 ... cylinder, 48 ...
Pressure gauge, 49,53,56 …… Regulatory valve, 50 …… Mixer, 51,52,55
…… Piping, 54 …… Exhaust port.

──────────────────────────────────────────────────続 き Continued on the front page (72) Haruhiko Ishida, Inventor 70, Yanagicho, Yuki-ku, Kawasaki, Kanagawa Prefecture Inside the Toshiba Yanagicho Plant (72) Inventor Eiichi Kaga 70, Yanagicho, Yuki-ku, Kawasaki, Kanagawa Prefecture Co., Ltd. Inside the Toshiba Yanagimachi Plant (72) Inventor Yoshitoshi Yoshida, Kanagawa Prefecture, Kawasaki City, 70 Yanagicho, Toshiba Corporation Inside the Toshiba Yanagimachi Plant Co., Ltd. (72) Inventor Minoru Inada 8 Shingsugitacho, Isogo-ku, Yokohama-shi, Kanagawa Prefecture Inside the Toshiba Yokohama Office (72) Inventor Naoyuki Oguni 1-1-1 Shibaura, Minato-ku, Tokyo Inside the Toshiba head office (72 ) Inventor Masaaki Yoshida 5358 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture 5 Toshiba Glass Co., Ltd. (56) References JP-A-59-29143 (JP) A) JP-A-59-48770 (JP, A) JP-A-1-102583 (JP, A) "Glass Handbook", September 30, 1975, first edition, Asakura Shoten A. Sakuhana, Teruo Sakaino, Katsuaki Takahashi Page 441 §4.5-3 "Glass tube forming machine" (58) Fields investigated (Int. Cl. ⁶ , DB name) G03G 5/00-5/16 C03B 17/04 C

Claims (1)

(57) [Claims] 1. A cylindrical support made of glass, formed by a mechanical drawing method and having both ends strengthened by heat treatment, a conductive layer provided on the support, and An electrophotographic photoreceptor comprising: a photosensitive layer provided.