JPH03245156A - Electrophotographic sensitive body and substrate for the same - Google Patents

Abstract

PURPOSE:To obtain superior characteristics of the photosensitive body without requiring mechanical grinding by laminating on a cylindrical substrate made of a glass selected from a group composed of soda lime glasses, lime glasses and borosilicic acid glasses and formed by the mechanical tube drawing method, a conductive layer and a photosensitive layer. CONSTITUTION:The conductive layer 31 and the photosensitive layer 32 are laminated on the cylindrical glass substrate 30 in this order. The glass substrate 30 is made of a soda lime glass, a lead glass, or a borosilicic acid glass and formed by the mechanical tube drawing method has superior surface characteristics, such as linearity, parallelism, circularity, and cylindricality, and there is no need to apply grinding work and no fear of being stained by oil. The conductive layer 31 serves not only as a conductive electrode, but also as an undercoat layer for enhancing electric characteristics and adhesion between the layer 32 and the substrate 30 and promoting reparation of the defects of the substrate, thus permitting photosensitivity characteristics to be enhanced and the obtained photosensitive body to be reduced in heat deformation and enhanced in precision.

Description

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

(Prior Art) An electrophotographic photoreceptor basically consists of a support and a photosensitive layer. Conventionally, aluminum has been mainly used as a support for photoreceptors. This is because aluminum was the most suitable in terms of required properties such as mechanical strength, workability such as Q-mirror machinability and high dimensional accuracy, and surface conductivity.

On the other hand, an electrophotographic photoreceptor using glass as a support material other than aluminum has been disclosed ("Electrophotography" P.
62-68, Hide Inoue-translator, Kyoritsu Shuppan). These photoreceptor supports have indium oxide (In20
．． A transparent conductive electrode such as i) is provided.

(Problems to be Solved by the Invention) However, aluminum contains trace amounts of impurities such as iron and yj<element. Therefore, when processed by mechanical grinding, minute gates W and defects are generated on the surface. Also,
In order to coat aluminum well with a photosensitive layer, it is usually subjected to degreasing treatment by washing. This degreasing treatment is intended to wash away the cutting oil used during machining, and is often insufficient. If the degreasing treatment is insufficient and oil remains on the aluminum surface, a photosensitive layer cannot be satisfactorily formed on the aluminum, causing poor characteristics and image defects in the resulting electrophotographic photoreceptor. moreover,
An aluminum support with a mirror-finished surface generates interference fringes and causes image defects when monochromatic light such as a laser is used as an exposure means.

As described above, it is difficult to obtain sufficient strength characteristics with a support made only of aluminum.

In the electrophotographic photoreceptor actually used, an undercoat consisting of casein, polyvinyl alcohol, ethyl cellulose, polyamide, polyurethane, alcohol-soluble nylon, or vinyl chloride-vinyl acetate copolymer is provided between the support and the photosensitive layer. There are layers. Generally, by providing an undercoat layer, it is possible to improve the electrical properties of the electrophotographic photoreceptor, improve the adhesion between the photosensitive layer and the support, or protect the support from defects. However, the manufacturing process of an electrophotographic photoreceptor having an undercoat layer is complicated, and since aluminum itself is expensive, the manufacturing cost is inevitably high. In addition, aluminum has a low surface hardness, so
It may be damaged during the manufacturing process after mirror polishing. For this reason, special consideration was required in handling it.

On the other hand, those in which transparent conductive electrodes such as indium oxide are provided on the glass surface are very expensive because they require heat treatment at high temperatures. In addition, this method is intended to be used for special purposes such as a simultaneous exposure method, and is technically difficult to put into practical use. Therefore, with respect to glass support photoreceptors for use in general-purpose electrophotographic devices such as electrophotographic copying machines and printers, no substantial studies have been conducted on technical improvements or cost reduction measures. For this reason, few concrete configuration means that can withstand practical use have been disclosed, and the present situation is that they have not been put into practical use.

The present invention has been made in view of these points, and is an electronic device that does not require mechanical grinding, prevents contamination by cutting oil used during cutting, exhibits excellent photoreceptor characteristics, and is inexpensive. The purpose is to provide a photographic photoreceptor.

[Structure of the Invention] (Means for Solving the Problems) The electrophotographic photoreceptor of the present invention is made of glass selected from the group consisting of soda coal glass, lead glass, and borosilicate glass, and is made of glass selected from the group consisting of soda coal glass, lead glass, and borosilicate glass, and It is characterized by comprising a molded cylindrical glass support, a conductive layer provided on the glass support, and a photosensitive layer provided on the conductive layer.

(Function) Since the electrophotographic photoreceptor of the present invention uses cylindrical glass formed by a mechanical drawing method as a support, it has excellent surface properties such as straightness, parallelism, roundness, and cylindricity. has. Furthermore, since the support is made of glass, there is no need for cutting, and contamination due to oil during cutting is prevented. Therefore, a conductive layer and a photosensitive layer can be formed satisfactorily on a glass support.

The conductive layer functions not only as a conductive electrode but also as an undercoat layer for improving electrical properties, adhesion between the photosensitive layer and the support, and defect protection of the support.

Furthermore, the soda coal glass, lead glass, and borosilicate glass used for the support of the electrophotographic photoreceptor of the present invention are
For example, since it is a raw material for mass-produced products such as raw tubes for fluorescent lamps,
The support can be manufactured as a by-product of such mass-produced products. Therefore, it can be manufactured at low cost and with high productivity.

(Embodiments) Hereinafter, embodiments of the present invention will be specifically described with reference to the accompanying drawings.

The manufacturing process of the electrophotographic photoreceptor will be explained in the order of manufacturing the glass support, forming the conductive layer, and forming the photosensitive layer.

1. Manufacture of the glass support The requirements that the photoreceptor support as mentioned above, especially the commonly used cylindrical support (hereinafter referred to as the base tube), should have include mechanical dimensional accuracy, Examples include surface roughness (specularity) and low price.

Such glass tubes have mechanical dimensional accuracy such as straightness, parallelism, roundness, and cylindricity, which are required as cylindrical supports for electrophotographic photoreceptors, and roughness of the surface of the raw tube (specularity). In order to improve the surface properties of the pipes, they are manufactured using mechanical pipe drawing methods such as the flattened up-draw, down-draw, and tongue-type methods.

Further, as the material of the glass tube constituting the support of the electrophotographic photoreceptor, for example, soda lime glass, lead glass, or borosilicate glass having a composition as shown in Table 1 below is used.

This is because this raw tube is manufactured as a by-product of a raw fluorescent lamp tube, so it is desirable that it has the same composition as other mass-produced products manufactured in a glass furnace.

Table Hv: Vickers hardness (kgl 2) The following methods are used to create and manufacture high-precision glass tubes that can meet these requirements.

An example of how to manufacture the glass support for the electrophotographic photoreceptor of the present invention will be shown below.

First, an automatic glass tube drawing process is performed using the Danchy method. The continuous glass tank furnace and Gunnar equipment used in this process meet the following management points.

・Generation of homogeneous glass by controlling glass raw materials, blending, and melting. ・Increasing the amount of glass tube drawn (1 to 2 t/hr)
- Chemotization, ・Appropriateness and stabilization of glass temperature and dancer molding atmosphere temperature, ・Stabilization and zero speed of incidental equipment such as sleeve blow cheating machines and drawing machines, ・Temperature, outer diameter, wall thickness, and bending Optimization of measurement and control mechanisms such as: Optimization of pipe bend straightening mechanism Figure 1 is a schematic explanatory diagram showing a continuous glass tank furnace and damper equipment. In the figure, 10 is a trough. A flow port 11 is provided at the bottom of the trough 10 to allow the glass to flow down. The trough IO is placed in a trough 14, in which glass 13 in a molten state is stored. A sleeve 14 is installed below the trough 10 within the pine full 12. Here, in order to stabilize the temperature and force of the glass 13 flowing down onto the sleeve 14, the temperature distribution and temperature fluctuations across the trough 1 (1) and the matsuru 12 are minimized. Therefore, a unique combustion method and high-precision temperature control mechanism are adopted for these areas, and the sleeve 14 is placed in a sealed matsufuru 12 to be isolated from the influence of outside air. . In addition, the shape of sleeve] 4 (diameter size,
The design of the outer surface is determined in consideration of dimensional accuracy, penetration resistance, etc., which are critical factors in improving the dimensional accuracy of the resulting glass tube. In addition, the sleeve 14 is adjusted to the optimum height and position from the trough [0], inclination angle, and rotation speed.
Set so that the tip of the sleeve does not shake.

The sleeve 14 is supported by a sleeve shaft 15 made of stainless steel that passes through its center, and its negative end is fixed to a sleeve low cheating machine 16 installed outside the matsufuru 12. The sleeve blow cheating machine 16 has an air outlet 1 for blowing air into a hole passing through the center of the sleeve shaft 15.
7 is provided and communicates with an air blower (not shown). Further, a guide roller 19 is installed below the tip 18 at the end of the sleeve 12.

Guide roller 19 is covered by an annealing chamber 20. The guide roller unit 9 is connected to a drawing machine 21 installed downstream thereof. Furthermore, a cutting machine 23 for cutting the obtained glass tube 22 is placed further downstream of the drawing machine 21.

In an apparatus with such a configuration, a tank furnace (not shown)
Glass beams melted in a finer furnace, forehearth (
The trough 10 is reached through a passageway (none of which is shown). A stirrer is installed in the forehearth to homogenize the glass material and glass temperature. A ribbon-shaped glass 13 is caused to flow down from the tip of the trough 10 onto a rotating sleeve 14. The glass flow rate is adjusted by a fine vertical movement device (not shown) of the gate fitted in the trough 10.

The glass 13 flows over the sleeve 14, leaves the tip 18, passes through the guide rollers 19 and passes through the drawing machine 21.
passed through. At this time, blow air is blown from the air outlet 17 through a hole passing through the center of the sleeve shaft 15. The glass is drawn into a glass tube 22 by a drawing machine 21. The angle of the upper and lower rubber belts that pull the glass tube 22 of the drawing machine 21 can be adjusted with respect to the direction in which the tube travels, thereby correcting the bending of the glass tube 22.

The outer diameter and wall thickness of the resulting glass tube 22 are determined based on the relationship between the amount of glass flowing down, the tube drawing speed, and the blow air pressure. The outer diameter and wall thickness are continuously measured using a laser beam without contact. In addition, we have adopted an automatic control system that adjusts the blow air pressure for the outer diameter and the tube drawing speed for the wall thickness, and has also adopted an automatic sorting mechanism to deal with cases where each of them is out of the control level. There is.

In addition, this device automates the cutting of glass tubes, and there is no negative effect on productivity even if complex types of glass tubes with different lengths are manufactured at the same time.This device allows glass for multiple uses. It is possible to efficiently produce raw pipes.

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

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

If both ends of the obtained glass tube 22 are left cut, they are susceptible to shocks such as impact and stiffening, and are easily damaged. In addition, there are cases where both ends are processed into a shape that makes it easy to attach flanges, or where the imaginary axis and the flange are made coaxial with respect to the surface of the imaging section.

In case 2, it is necessary to process both ends into the shape shown in FIGS. 2(A) to 2(C). This process is performed on both ends of the glass tube using the surface of the imaging section as a reference plane.
Burning (glazing or mouth-burning), heating press,
Alternatively, heat treatment such as heating and squeezing may be performed.

In the above method, for example, diameter 29.81111% length 349
Next, a glass raw tube with a wall thickness of 1.0 mm was prepared, five tubes were extracted, and the straightness, roundness, and cylindricity of the outer shape were determined. As a result, the average value of the five pieces was 13.2 μ
m, roundness is 16.6μm, and cylindricity is 42.5μm.
It was m. Each value is judged to be as accurate as conventional aluminum tubes. From the above results, it was confirmed that the glass tube produced by the Danchy method satisfies the accuracy required for electrophotographic photoreceptors. Furthermore, as shown in Table 1, the glass hardness of the second glass tube is considerably higher than about 20 to 40 (Brinell hardness) of aluminum, and the surface is less likely to be scratched. Furthermore, this glass tube has a coefficient of thermal expansion that is much smaller than that of aluminum, and is effective in preventing deformation due to heat during the production of an amorphous silicon photoreceptor, which will be described later.

2. Formation of conductive layer Next, a conductive layer is formed on the outer surface of the manufactured glass tube. As a means for forming the conductive layer, vacuum evaporation, ion sputtering, ion blating, chemical vapor deposition (C
(VD), coating with a metal film by electroless plating, coating with a composite conductive resin in which a conductive filler such as metal powder, carbon powder, graphite, metal oxide, etc. is dispersed in a resin, and the like.

When depositing metal thin films, the required conductivity is usually 1
Since the resistance is 07 to 104Ω or less, most metal vapor deposited films can be used, but in particular, aluminum, nickel, gold, silver, chromium, In2O, etc. can be used relatively easily.

In addition, when coating a conductive resin, mix and disperse mass, metal powder, carbon powder, etc. in a binder resin such as epoxy resin, urethane resin, acrylic resin, ABS resin, modified polyopine, etc. A conductive resin is obtained by using a solvent to obtain an appropriate viscosity and resistance. In addition, a sand mill, a ball mill, a roll mill, a paint shaker, etc. are used for dispersion. Next, the obtained conductive resin is applied to the glass tube that has been immersed in alcohol and cleaned with steam. Methods for applying the conductive resin include a dipping method, a spray method, a roll method, a blade method, etc., and dipping or spraying is suitable for a cylindrical support. Regardless of the coating method used, uniformity of film thickness and stability of electrical resistance are important, and it is also necessary to prevent contamination by dust and the like. Such conductive resin coating is
A conductive resin coating layer is preferable because it improves adhesion to the photoreceptor layer and functions as a charge barrier layer.

Furthermore, in order to improve the adhesion between these metal films or conductive resin layers and the photosensitive layer or protective layer, a resin layer of 0.05 to 1.0 μm may be provided as an intermediate layer as necessary. Also good. Examples of such resins include nitrocellulose and polyamide. In addition, in the case of a metal film, the thickness of the conductive layer should be about 0.1 t1 m or more to the extent that defects such as pinholes do not occur, and in the case of a conductive resin layer, it is necessary to have a thickness of about 0.1 t1 m or more, so that defects such as pinholes do not occur. Since defects are likely to occur, a range of 0.5 to 30 μm is preferable. In either case, the optimal thickness varies depending on the coating method and material.

3. Formation of photosensitive layer The photoreceptor used in the electrophotographic photoreceptor of the present invention includes:
Known organic or inorganic materials can be used.

The organic photoreceptor includes: ■ one consisting of a photoconductive polymer alone such as Ho-IJ-N-vinylcarbazole, and ■ one consisting of an electron-donating polymer such as poly-N-vinylcarbazole and 2.4.7-Dolini 10-9. -A charge transfer complex consisting of an electron-accepting low-molecular compound such as a full primary nonone, ■A charge-transfer complex consisting of an electron-accepting polymer and an electron-donating low-molecular substance, ■A eutectic of polycarbonates and thiapyrylium, etc. Complexes, ■ Low-molecular charge-generating materials such as phthalocyanine that have a photocharge-generating function, low-molecular charge-transporting materials that have a hole-transporting ability such as hydrazone, and electron-transporting materials such as 2,4,7-dolinitro-9-fluorenone. Examples include so-called dispersed organic photoreceptors in which a low-molecular charge-transporting material is dispersed in a resin serving as a binder. In recent years, dispersed organic photoreceptors that utilize the diversity of organic materials have become mainstream.

Here, the layer structure of the dispersed organic photoreceptor includes: (1) a so-called single-layer type in which a layer consisting of a substance containing a charge generating material and a charge transporting material in a binder is provided on a substrate; (2) a charge generating material; A so-called functionally separated type, in which a charge generating layer (CGL) consisting of a charge transporting material and a binder as required, and a charge transporting layer (CTL) consisting of a charge transporting material and a binder are sequentially provided on a substrate.Charge transporting material and binder A so-called functionally separated type in which a charge transport layer consisting of and a charge generating layer consisting of a charge generating material and a binder are sequentially provided on a substrate. ■In the functionally separated type, a protective layer or insulating layer is placed on the top layer for the purpose of improving mechanical strength or weather resistance against ozone, etc. One example is the one provided above. In addition, 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 functionally separated type has become mainstream, as it can provide a photosensitive layer with high photosensitivity and high printing durability.

Charge generating materials include biryllium, thiazoles, azulenium dyes, phthalocyanine dyes, anthorone dyes, dibenzpyrenequinone dyes, vilanthrone dyes, trisazo dyes, disazo dyes, azo dyes, indigo dyes, quinacridone dyes, and asymmetrical dyes. Examples include quinocyanine dyes, perylene dyes, polycyclic quinone dyes, quinocyanine dyes, squarylium dyes, and mixtures thereof.

Examples of the electron transport material include electron-accepting substances such as chloranil, broranil, tetracyanoquinodimethane, and 2,4.7-)linitro-9-fluorenone, and polymerized versions of these substances. In addition, as hole transport materials, various carbazoles, hydrazones, pyrazolones, oxadeazoles, oxazoles, thiazoles, triarylmethanes, polyarylalkanes, polyarylalkenes, triarylamines, Conceivable examples include fused polycyclic hydrocarbons, mixtures thereof, and the like.

Examples of the binder for the charge generating material include butyral resin, phenoxy resin, polycarbonate, polyester, acrylic resin, styrene resin, etc., and it can also be used as a thermosetting type by adding an appropriate curing agent to the thermoplastic resin. good. In addition, binders for charge transport materials include polyarylate resins, polysulfone resins, polyamide resins, acrylic resins, acrylonitrile resins, methacrylic resins, vinyl chloride resins, vinyl acetate resins, phenol resins, epoxy resins, polyester resins, alkyd resins, and polycarbonates. , polyurethane, etc.

The solvent used for coating the photoreceptor made of the above materials must be selected in consideration of the dispersibility of the charge generating material or compatibility with the charge transporting material, as well as the drying speed of the solvent. As such, various ketones, amides, sulfoxides, ethers, esters, aliphatic halogenated hydrocarbons, aromatic hydrocarbons, etc. can be used. Note that in consideration of solvent balance, two or more of these solvents may be used in combination.

In addition, the blending ratio of the charge generating material to the binder is 0.5
-2.0, preferably 0.5-1.5, and the blending ratio of the charge transport material to the binder is in the range of 0.5-3.0, preferably 0.5-2.0.

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

A glass tube is coated with the obtained coating solution. First, the glass tube is immersed in an alcohol-based solvent and cleaned with steam. If there is a risk of fingerprints or other oils being attached due to handling, etc., degrease cleaning with a 10-gen solvent, steam cleaning, and further UV/ozone cleaning if necessary. Thereafter, a multilayer film is formed by repeating vapor deposition, dip coating, and spray coating. The preferred thickness of the conductive layer is 0.15 to 30 μm, preferably 11 μm.
5-20ti, intermediate layer 0.05-1.0!1m.

Preferably (1.3 to 0.7 μm, charge generation layer or 0.1
~1.0 μm1 preferably 0.2-0.6 μm5 charge transport layer 10-30 μm, preferably 15-25 μm1 and protective layer 0.5-30 μm1 preferably 0.5-1
．． It is 5 μm. In the case of deep coating, in consideration of productivity, when forming a relatively thick charge transport layer,
The pulling speed of the substrate must be kept to about 12 to 15 min/min at maximum. When forming the conductive layer, charge generation layer, and protective layer, which are relatively WiH, the substrate pulling speed must be set to 30 to 40 cm/min.

The method for forming the charge transport layer or charge generation layer is as follows:
In addition to dip coating, spray coating,
Examples include roll coating and blade coating. When the object to be coated is a cylindrical substrate, dip coating or spraying is preferred. In order to obtain a layer of a predetermined thickness by these methods, it is necessary to adjust the degree of non-volatile content of coating melting, viscosity, coating speed, etc.

In particular, when using spray coating, the distance between the spray nozzle and the cylindrical substrate, the ejection 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 Adjustments such as synchronization with scanning are required. In order to ensure electrical continuity with the conductive layer and improve cleaning performance, after coating with the solution, if necessary, a coating is applied to at least one end of the cylindrical substrate corresponding to the non-image forming area of the cylindrical substrate. i'IJM,
The coating is removed from the inner wall or end face. This peeling/removal is performed using a good solvent for the film or a wiping member impregnated with the same.

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

After coating, the coating layer is air-dried for a predetermined period of time, 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 minutes, preferably 10 to 30 minutes.

Functional separation type photoreceptors require multilayer coating, so after that,
Cool and apply the next coating if necessary. At this time, it is necessary to prevent the lower layer coating or coloring material from eluting when coating the upper layer, and this is taken into consideration when selecting the solvent and setting the drying time. After the final coating and drying, icing is performed to increase sensitivity through morphological changes in the coating. This aging is performed at room temperature to 100℃ for half a day to 1 day.
This is done by processing over a period of weeks.

Examples of the inorganic photoreceptor include those based on selenium, a-3i, and selenium-arsenic. CVD for a-5i series
For some, a vacuum deposition method is used.

When using an inorganic photoreceptor, if a resin coating layer is used as the conductive layer, gas generation etc. will have an adverse effect.
It is preferable to use metal as the conductive layer.

The shape of the end surface of the photoreceptor is as shown in Fig. 3(A) to Fig. 3(
Examples include the shape shown in C). The electrophotographic photoreceptor shown in FIG.
iJ) conductive layer 31 provided on the glass tube 30
A photosensitive layer 32 is provided so that the photosensitive layer 32 is exposed, and a conductive flange 33 made of metal such as aluminum, conductive plastic, rubber, or a composite structure of these is fitted in the direction of the arrow. It is designed so that it can be electrically connected to the rotating shaft in the same way as the body. In the electrophotographic photoreceptor shown in FIG. 3(B), a conductive layer 31 is also coated on the inside of the end portion of the glass tube 30, so that electrical conduction can be achieved with the flange 34 fitted to this portion. There is. Figure 3 (C
In the electrophotographic photoreceptor shown in ), the end of the glass tube 30 is drawn, and the drawn part 35 at at least one end of the conductive layer 31 is exposed without being covered with the photosensitive layer 32. 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. Note that if there is a risk of cracking due to the application of large stress during fitting, the fitting should be made light and the gap filled with conductive adhesive. Alternatively, a conductive elastic body (rubber) may be provided at the fitting portion between the flange and the glass tube to reduce distortion during fitting and ensure reliable attachment.

Test examples conducted to clarify the effects of the present invention are shown below.

Test Example 1 First, the diameter was 60 mm and the length was 18011 m using the Danchi method.
A glass tube (hereinafter abbreviated as glass tube) made of soda lime glass and having a wall thickness of 1.1 mm was prepared. The obtained glass tube was immersed in alcohol and cleaned with steam.

Next, aluminum was vapor-deposited onto the glass tube to a thickness of 1 μm.
m conductive layers were formed.

This glass raw tube was installed in the apparatus shown in FIG. Fourth
In the figure, 40 is a reaction container. A base rotating shaft 41 is inserted into the bottom of the reaction vessel 40 .

A support 42 is attached to the base rotating shaft 41, and a heater 43 is installed on the support 42. Note that the base rotating shaft 41 is connected to a rotating device (not shown). The glass tube 44 is inserted into the heater 43.
is installed. Further, an electrode 45 is attached to the side wall of the reaction vessel 40. A high frequency power source 46 is installed 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 a pressure gauge 48 and four regulating valves are attached to each cylinder 47.

Also, piping 5 from each cylinder 47 to the mixer 50 is provided.
1 is extended. Further, a piping 52 is connected from the mixer 50 to the reaction vessel 40, and a regulating valve 53 is installed in the middle of the piping 52 to adjust the flow rate of the mixed gas. An exhaust port 54 is provided at the bottom of the reaction container 40 to reduce the pressure inside the container, and a regulating valve 56 is attached to a pipe 55 extending from the exhaust port 54 to adjust the degree of vacuum inside the container. .

In this apparatus, the inside of the reaction vessel 40 is heated to about 10-5 Torr.
It was evacuated to a vacuum degree of r. At the same time, the temperature of the heater 41 is
The temperature was set at 50° C., and the substrate rotating shaft 4] was rotated at 10 rpI11. When the surface temperature of the substrate became constant, the SiH4 gas, B, H6 gas, and CH4 gas in the bomb 47 were mixed in the mixer 50, and the mixed gas was introduced into the reaction vessel 40. The flow rate ratio is SiH4:B2H6:CH4
-1: 10-'+0.5. Next, the reaction container 40
The internal pressure was adjusted to 0.5 Torr. 1'3.
A 56 MHz high frequency power of 150 W was applied to generate plasma, and the mixed gas was reacted to form a p-type a-5iC:H barrier layer with a thickness of 0.5 μm.

Next, the gas flow rate ratio in the reaction vessel 40 is set to S iH4:
B2 Hb: CH4-1+ 10-': 0,
The pressure inside the reaction vessel was set at 0.7 Torrl: A.

A 300 W high frequency power of 13.56 MHz was applied to form an i-type a-5i:H photoconductive layer with a thickness of 30 μm.

Then, the gas flow ratio in the reaction vessel was set to 5xH4:CH4-
1, +10. The pressure inside the reaction vessel was set to 0 and 7 T.
orr, and set the 13.56 MHz high frequency power to 150 MHz.
W was applied to form a 0.1 μm thick a-5iC:8 surface layer. p-type a-5iC:H barrier layer, i-type a-5i:H
The photoconductive layer and the a-5iC:8 surface layer constituted the photosensitive layer.

In this way, an electrophotographic photoreceptor of the present invention was obtained.

The roundness of the obtained electrophotographic photoreceptor was measured.

The results are shown in Table 2 below. Note that the roundness was determined using the following formula.

Roundness - (Maximum diameter - Minimum diameter)/2 At this time, no abnormality was observed on the end surface of the electrophotographic photoreceptor.

In addition, the obtained electrophotographic photoreceptor was used in a Toshiba copier BD-3.
It was installed on the 810 to produce halftone images, solid black images, and character images. As a result, no image density unevenness occurred. This is probably because the thermal expansion coefficients of a-5i and glass are almost the same.

Furthermore, no image defects such as white spots were observed. this is,
This is probably because the glass surface is homogeneous.

Moreover, even after continuous use for 200 times, images as clear as the initial image were obtained.

Comparative Example 1 Aluminum (equivalent to J153003) was added to a blank tube with a diameter of 60 mm, a length of 280 mtx, and a wall thickness of 2II11. The surface of this tube was mirror polished. Next, the aluminum tube was immersed in 1.1.2-trichloroethane,
Ultrasonic cleaning was performed to remove cutting waste, and steam cleaning was used to remove cutting oil.

This aluminum tube was subjected to the same treatment as in Test Example 1 to form an a-5i photosensitive layer to obtain an electrophotographic photoreceptor.

The roundness of the obtained electrophotographic photoreceptor was measured in the same manner as in Test Example 1. The results are also listed in Table 2 below.

Table 2 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. Also, aluminum 1. In the electrophotographic photoreceptor using a blank tube (comparative example), there was considerable distortion at one end phase as shown in FIG. The amount of distortion W at this time was about 0.1 degrees. This distortion is thought to be caused by the difference in thermal expansion coefficient between a-5i and aluminum during cooling of the substrate.

Furthermore, halftone images, solid black images, and character images were produced using the obtained electrophotographic photoreceptor in the same manner as in Sample S Example 1. As a result, density unevenness in the circumferential direction was observed in halftone and solid black images due to low circularity, and white spots were observed in solid black and halftone images.

This tendency further increased with continuous use. When this white spot was observed using a SEM, it was found to be a pinhole-shaped hole that reached the substrate. This is thought to be a trace of a-Si abnormally growing on the protruding precipitates on the aluminum surface and peeling off during film formation. It is thought that the particles that cannot be peeled off during film formation are also scraped off by the blade in the copying machine, resulting in an increase in white spots.

Test example 2 Diameter 78 mm, length 324 mm, thickness 1 by Danchi method
．． A glass tube made of 1 mm lead glass was prepared. In the same manner as in Test Example 1, a conductive layer and a photosensitive layer were formed on a glass tube to obtain an electrophotographic photoreceptor of the present invention. The obtained electrophotographic photoreceptor was transferred to a copying machine B D-8560, B
When mounted on D-9110 and BD9230, and outputting halftone images, 7 black, and character images in the same manner as in Test Example 1, clear images were obtained.

Test Example 3 In place of the a-5iCH surface layer, N2 gas was used at a flow rate of 2. OSU, pressure 2, OTorr, 25
An electrophotographic photoreceptor of the present invention was obtained in the same manner as in Test Example 1, except that an a-5iNH surface layer having a thickness Q of 0511 m was formed by applying a power of 0 W. The obtained electrophotographic photoreceptor was mounted on a car-transfer copying machine B D-3810.
When a ＼-tone image, solid black, and character image were produced in the same manner as in Test Example 1, clear images were obtained.

Test Example 4 a-5iC: 5IH4 gas 50S instead of 8 surface layer
CCM, CH4 gas 4 [10SCCM, N2 gas 1
n OOSCCM was introduced into the reaction vessel and the pressure was increased to 1To.
rr, and the thickness obtained by applying a power of 200 W is 0.
An electrophotographic photoreceptor of the present invention was obtained in the same manner as in Test Example 1 except that a 1 μm a-5i (C,N):8 surface layer was formed. The obtained electrophotographic photoreceptor is transferred to a copying machine BD.
-3810 was installed, and halftone images, solid black images, and character images were produced in the same manner as in Test Example 1, and clear images were obtained.

Test Example 5 A glass tube with a length of 262 mm was used, and PH3 gas was used instead of B and H6 gas when forming the barrier layer.
The flow rate ratio is SiHa + P H31: 5x10-
As Example 5, an electrophotographic photoreceptor of the present invention was obtained in the same manner as in Test Example 1 except that an n-type a-5iC:H barrier layer was formed. The obtained electrophotographic photoreceptor was transferred to a copying machine BD-2.
810 was installed in the same manner as in Test Example 1. When a flat-tone image, a solid black image, and a character image were produced, clear images were obtained.

Test Example 6 A glass tube made of lead glass having a diameter of 30 mm, a length of 324,111%, and a wall thickness of 1.1 mm was prepared by the Danchy method. A negatively charged type a-5i photoreceptor was formed in the same manner as in Test Example 5 to obtain an electrophotographic photoreceptor of the present invention. The obtained electrophotographic photoreceptor was mounted on a laser beam printer TN-7200 manufactured by Jyuhashi Corporation, and halftone images, solid black images, and character images were produced in the same manner as in the test flll, and clear images were obtained.

Test Example 7 P-type a-SiC+H without vapor depositing an aluminum conductive layer
An electrophotographic photoreceptor of the present invention was obtained in the same manner as in Test Example 1 except that the layer thickness was 5 μm. The obtained electrophotographic photoreceptor was installed in a car-transfer copying machine BD~3810, and
When halftone images, solid black images, and character images were produced in the same manner as above, clear images were obtained.

By forming an a-Si photosensitive layer on a glass tube as described above, it is not necessary to use an organic solvent for cleaning, and it is possible to obtain an electrophotographic photoreceptor that has less distortion and does not cause image defects. .

Test Example 8 Diameter 60 m + *, length 240 mm, by Danchi method
A glass tube made of borosilicate glass with a wall thickness of 1.1+sm was produced. The obtained glass tube was immersed in alcohol and cleaned with steam.

Next, polyvinyl alcohol containing tin oxide powder (particle size of 1 μm or less) was applied onto the surface of the glass tube to a thickness of 5 μm to form a conductive layer. Next, alcohol-soluble nylon is deposited on the conductive layer to a thickness of 0. It was applied at a thickness of 5 μm. Next, metal-free phthalocyanine as a charge generating material and 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 form a charge generation layer with a thickness of 0.2 μm.

Next, a hydrazone derivative (structural formula ■
) and a butadiene derivative (structural formula ■) (mixing ratio 5:5), polycarbonate (structural formula ■) is used as the binder resin, and the mixing ratio is charge transport material: resin -〇, S: 1. A charge transport solution was prepared. A glass tube provided with a charge generation layer was immersed in this solution to a thickness of 19 μm.
A charge transport layer was provided.

(Structural formula ■) H3 (Structural formula ■) The above steps were performed continuously to produce 100 electrophotographic photoreceptors for laser beam printers.

The obtained electrophotographic photoreceptor was mounted on a laser beam printer, a one-dot pattern image 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 placed into a blank tube with a diameter of 60 mm and a length of 240 mm. The surface of this tube was mirror polished. Next, the aluminum tube was immersed in 1.1.1-h dichloroethane, subjected to ultrasonic cleaning to remove cutting debris, and steam cleaned to remove cutting oil.

Next, alcohol-soluble nylon was applied to a thickness of 0.5 μm on the cleaned aluminum tube.

A charge generation layer and a charge transport layer were sequentially formed thereon in the same manner as in Test Example 8, thereby producing 100 electrophotographic photoreceptors.

The obtained electrophotographic photoreceptor 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 also listed in Table 3 below.

Table 3 As is clear from Table 3, the electrophotographic photoreceptor using the glass tube had fewer white spots in the image. This is because the surface roughness of the glass tube is very small, 50A. In addition, clear normal images were also obtained. On the other hand, electrophotographic photoreceptors using aluminum tubes had many white spots in the images. this is,
This is probably because a charge generation layer and a charge transport layer were not formed due to protruding precipitates on the aluminum surface. Furthermore, when aluminum tubes are used, the coating liquid deteriorates after repeated use due to the high reactivity of aluminum and organic solvents. The characteristics of the electrophotographic photoreceptor coated with the deteriorated coating liquid were deteriorated. Furthermore, in an electrophotographic photoreceptor using an aluminum tube, wood grain-like interference fringes were generated by the laser beam. In addition, the above-mentioned problems were not observed in those using glass tubes, and the characteristics were stable.

Test Example 9 An electrophotographic photoreceptor of the present invention was produced in the same manner as Test Example 8 except that copper phthalocyanine (Structural Formula V) was used as the charge generating material. Regarding the obtained electrophotographic photoreceptor, the number of white spots was examined in the same manner as in Test Example 8, and almost no white spots were found.

Test Example 10 Using a hydrazone type material (structural formula ■) as a charge transport material,
An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Test Example 8, except that polyacrylate (Structural Formula 2) was used as the binder resin at a mixing ratio of 1:1. Regarding the obtained electrophotographic photoreceptor, the number of white spots was examined in the same manner as in Test Example 8, and almost no white spots were found.

2H5 (Structural Formula ■) Test Example 11 An electrophotographic photoreceptor of the present invention was produced in the same manner as Test Example 8, except that the conductive layer was a vapor-deposited aluminum film with a thickness of 2 μm. When an image was produced on the obtained electrophotographic photoreceptor 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 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 produced on the obtained electrophotographic photoreceptor 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 Test Example 8, except that the conductive layer was formed of polycarbonate resin in which carbon black was dispersed to a thickness of 2 μm. When an image was produced using the obtained electrophotographic photoreceptor in the same manner as in Test Example 8, a clear image was obtained, and no interference fringes were observed.

Test Example 14 Diameter 60 mm, length 262 IIm by Danchi method
A glass tube made of soda lime glass with a wall thickness of 1.1 mm was produced. The obtained glass tube was immersed in alcohol and cleaned with steam.

Next, polyvinyl alcohol containing carbon black was applied onto the surface of the glass tube to a thickness of 5 μm to form a conductive layer. Alcohol-soluble nylon was then applied onto the conductive layer to a thickness of 0.5 μm.

Next, a bisazo pigment (structural formula (2)) as a charge generating material and a phenoxy resin as a binder resin were dispersed in 1,12-trichloroethane at a mixing ratio of charge generating material:resin-1=1. A glass tube was immersed in this solution to form a charge generation layer with a thickness of 0.5 μm.

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

The above steps were performed continuously to produce 100 electrophotographic photoreceptors for copying machines.

The obtained electrophotographic photoreceptor was transferred to a copying machine BD-2810.
It was installed in the system and produced halftone images, solid rings, and character images. As a result, a clear image was obtained, although image density unevenness occurred.

Comparative Example 3 Aluminum was processed into a raw tube with a diameter of 60++n and a length of 26211 m. The surface of this tube was mirror polished. Next, the aluminum tube was immersed in 1.1.1-trichloroethane, subjected to ultrasonic cleaning to remove cutting waste, and steam cleaned to remove cutting oil.

Next, alcohol-soluble nylon was applied to a thickness of 0.5 μm on the cleaned aluminum tube.

A charge generation layer and a charge transport layer were sequentially formed thereon in the same manner as in Sample M Example U 4 to produce 100 electrophotographic photoreceptors.

The obtained electrophotographic photoreceptor was mounted on a BD2810 copying machine, and a halftone image, a solid ring, and a character image were produced. As a result, there were white spots 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 Test Example 14, except that a glass tube having a diameter of 78 m+* and a length of 326 m was used.

When the obtained electrophotographic photoreceptor was mounted on an M/C (30 CPM), which is a negatively charged copying machine (BD7610), a clear image was obtained. Also, even after 80 consecutive copies, 17 images remain the same as the initial one.
It was done.

Test Example 16 In Test Example 12, two types of roughness (0.07s and 0.55) were prepared by subjecting the surface of the glass tube to hydrofluoric acid treatment or sandblasting, and a charge generation layer was formed on the surface. The film thickness of 0.1.0. i2,0.15,0
．． A total of 12 electrophotographic photoreceptors with diameters of 18, 0, 20, and 25 μm were produced. A one-dot line pattern image was produced for these electrophotographic photoreceptors. The results of density unevenness are shown in Table 4 below.

Table 4 As is clear from Table 4, density unevenness tends to occur when the thickness of the charge generation layer is small, but by roughening the surface of the glass tube, density unevenness can be prevented even if the thickness of the charge generation layer is small. Buffered.

Test Example 17 Se and Te powders with a purity of 99.99% or more were mixed in a weight ratio of 8=2, and this mixed powder was sealed in a quartz ampoule at a vacuum level of about 10-3 Torr. The ampoule was then heated at approximately 750° C. for 10 hours to melt the contents. Next, this ampoule was put into water and rapidly cooled to obtain a glassy 5e-Te alloy.

Next, a diameter of 60111% was produced by the Dunchy method.
A conductive layer was formed by covering an aluminum film to a thickness of approximately 2 μm on a glass tube made of lead glass having a length of 280 m1. Thereafter, the above-mentioned glassy alloy was vacuum-deposited on this glass tube to form a photosensitive layer having a thickness of 55 μm, thereby obtaining an electrophotographic photoreceptor of the present invention.

In addition, vacuum evaporation is performed at a vacuum degree of 10-' to 10-5+*m H
g, s Substrate temperature is 60-65℃, evaporation source temperature is 300℃
It was carried out in

The obtained electrophotographic photoreceptor was transferred to a copying machine BD-3810.
When the camera was mounted on a camera and images were taken, clear images were obtained.

Test Example] 8 A mixed powder of Se and Te powders with a purity of 99.99% or higher in a weight ratio of 8:2 and a Te powder were each mixed in a quartz ampoule with approximately 10- 3 Tor
The ampoule of mixed powder was then heated at about 750°C for 10 hours, and the ampoule of Te powder was heated at about 60°C.
Heated at 0°C for 10 hours to melt the contents. Next, these were put into water and rapidly cooled to obtain a glassy alloy of 5e-Te and Te.

Next, a glass tube made of borosilicate glass with a diameter of 60 m and a length of 280 mm prepared by the Dunchy method was immersed in alcohol and then steam-cleaned. This glass tube was coated with an aluminum film having a thickness of about 5 μm to form a conductive layer.

Thereafter, the above-mentioned glassy alloy of 5e-Te was vacuum-deposited on this glass tube to form a photosensitive layer having a thickness of 50 μm. In addition, vacuum evaporation is performed at a vacuum degree of 104 to 10-'111 m)Ig
The substrate temperature was 70 to 75°C, and the deposition source temperature was 350°C. Next, the Te board was gradually heated 17 until the temperature of the vapor deposition source reached 350° C., and then the temperature was lowered to perform vapor deposition at a high concentration of Te near the surface of the substrate.

In this way, a Te richs type electrophotographic photoreceptor was obtained.

Note that the total thickness of the photosensitive layer was 60 μm.

When the obtained electrophotographic photoreceptor was mounted on a copying machine BD3810, and an image was produced, a clear image was obtained.

Test Example 1 A 5e-Te electrophotographic photoreceptor was obtained in the same manner as in Test Example 18, except that a glass tube with a diameter of 78 mm and a length of 324 mm was used. However, the concentration of Dine near the surface was increased by increasing the temperature of the deposition source.

The obtained electrophotographic photoreceptor was transferred to a copying machine BD-8510.
When the camera was mounted on a camera and images were taken, clear images were obtained.

Test Example 20 Next, a glass blank tube made of soda lime glass with a diameter of 78 mm and a length of 324 m+i produced by the Dunchy method was immersed in alcohol and then steam cleaned.

This glass tube was coated with an aluminum film having a thickness of about 2 μm to form a conductive layer. After that, add A to this glass tube.
A photosensitive layer having a thickness of 55 μm was formed by vacuum evaporation of s2Se3 to obtain an electrophotographic photoreceptor of the present invention. Ta. For vacuum evaporation, the degree of vacuum is 10-5 Torr, and the temperature of the evaporation source is 400°C.
It was carried out in

The obtained electrophotographic photoreceptor was transferred to a copying machine BD-3810 manufactured by Jushiho Co., Ltd.
When the camera was mounted on a camera and images were taken, clear images were obtained.

[Effects of the Invention] As explained above, the electrophotographic photoreceptor of the present invention exhibits excellent photosensitive characteristics and is highly accurate with little thermal deformation. Furthermore, it is highly compatible with various photoreceptor manufacturing conditions. Further, since glass has a lower specific gravity than aluminum, it is possible to reduce the weight of the photoreceptor. 72. Glass has a high surface hardness, so it is less prone to scratches. Furthermore, in the case of glass tubes, a mirror surface can be obtained by surface polishing, and there are fewer surface defects, so surface treatment, which is essential for aluminum tubes, can be omitted. In addition, when a metal filler resin dispersion layer is used, it serves both the functions of a conductive layer and an undercoat layer, and also has the effect of absorbing or diffusing (scattering) monochromatic light such as laser light. Interference effects due to reflections from the support are prevented,
It is possible to prevent image defects such as uneven shading.

In addition, by treating the surface of the glass tube to an appropriate level of roughness, it becomes easier to uniformly apply the charge generation layer, and
Even if metal is used as the conductive layer, interference fringes can be prevented from occurring.

Note that the equipment for manufacturing glass tubes using the mechanical tube drawing method used in the above examples has extremely high productivity and can produce a large amount of glass tubes with high precision in a short period of time, making it possible to produce photoreceptors at extremely low cost. I can do it.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of an apparatus for manufacturing a glass tube for the electrophotographic photoreceptor of the present invention, and FIGS. 2(A) to 2(C) are the ends of the glass tube for the electrophotographic photoreceptor of the present invention. FIG. 3(A) to FIG. 3(C) are explanatory diagrams showing the end portion of the electrophotographic photoreceptor of the present invention, and FIG. 4 is a schematic diagram of the apparatus used in forming the photosensitive layer. 5 are explanatory diagrams showing the distortion of the aluminum tube of a conventional electrophotographic photoreceptor. DESCRIPTION OF SYMBOLS 10...Trough, 12...Matsuful, 14...Sleeve, 15...Sleeve shaft, 16...Sleeve low cheating machine, 17...Air outlet, 19...Guide roller 20 ...Aniling Champer 21...Drawing Machine, 22...
Glass tube, 23...Cutting machine, 30.44
... Glass tube, 31 ... Conductive layer, 32 ... Photosensitive layer, 33, 34. 36 ... Flange, 35 ... Squeezed part, 40 ... Reaction container, 41 ... Substrate Rotating axis, 4
2... Support body, 43... Heater, 45... Electrode,
46...High frequency power supply, 47...Cylinder, 48...
Pressure gauge, 49.53.56...Adjusting valve, 50...Mixer, 51.52.55...Piping, 54...Exhaust port. Figure 4 556

Claims (2)

[Claims] (1) A cylindrical support made of glass selected from the group consisting of soda lime glass, lead glass, and borosilicate glass and formed by a mechanical tube drawing method, and a conductive layer provided on the support. , and a photosensitive layer provided on the conductive layer. (2) A support for an electrophotographic photoreceptor, which is formed by a mechanical tube drawing method and is made of glass selected from the group consisting of soda lime glass, lead glass, and borosilicate glass.