JPH11119447A - Production of electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing an electrophotographic photoreceptor which realizes uniform and high-grade images free of image defects and image density unevenness. SOLUTION: In the process for producing an electrophotographic photoreceptor by subjecting a substrate 101 to a degreasing treatment, washing treatment and drying treatment, then forming a functional film consisting of an amorphous material consisting of silicone atoms as a base material on the surface of this substrate 101; the substrate 101 is subjected to a spraying treatment by a spraying treatment mechanism 166 while the substrate 101 is transported from a degreasing tank 121 for executing the degreasing treatment to a washing tank 131 for executing the washing treatment. Any treatment among the spraying treatment, the degreasing treatment, the washing treatment and the drying treatment is executed by using a water contg. an inhibitor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a method for manufacturing an electrophotographic photosensitive member having a functional film formed thereon.

[0002]

2. Description of the Related Art Glass, heat-resistant synthetic resin, stainless steel, aluminum and the like have been proposed as a substrate for forming a deposited film of an electrophotographic photosensitive member. However, in practice, metal is often used to withstand electrophotographic processes such as charging, exposure, development, transfer, and cleaning, and to always maintain high positional accuracy so as not to deteriorate image quality. Among them, aluminum is one of the most suitable materials for a base of an electrophotographic photosensitive member because of its good workability, low cost and light weight.

Techniques relating to the material of a substrate of an electrophotographic photosensitive member are disclosed in JP-A-59-193463 and JP-A-60-2630.
No. 62936. JP-A-59-19
No. 3463 discloses that the support has a Fe content of 2000 p.
A technique for obtaining an amorphous silicon electrophotographic photoreceptor having good image quality by using an aluminum alloy having a particle size of pm or less is disclosed. Further, in this publication, after a cylindrical (cylindrical) substrate is cut by a lathe and mirror-finished,
A procedure up to forming amorphous silicon by glow discharge is disclosed. Japanese Patent Application Laid-Open No. Sho 60-262936 discloses that Mg is contained in an amount of 3.0 to 6.0 wt%, and as impurities, Mn is 0.3 wt% or less and Cr is 0.01 wt%.
t%, Fe is 0.15 wt% or less, Si is 0.12 wt%
An extruded aluminum alloy is disclosed which is suppressed to not more than wt% and has excellent vapor deposition properties of amorphous silicon composed of the remainder Al.

[0004] These materials are subjected to a surface treatment of a base according to the use of the electrophotographic photosensitive member, and a light receiving portion layer is formed on the surface. The technology relating to the surface processing of the substrate is disclosed in
These are described in JP-A-1-231561 and JP-A-62-95545. As a technique for preventing corrosion in a water washing step when an aluminum alloy is used as a base, Japanese Patent Application Laid-Open No. 6-273955 proposes a technique for cleaning a base with water in which carbon dioxide is dissolved. There is no mention of defining a certain range of film thickness and composition ratio with water containing a particular inhibitor.

JP-A-63-31261, JP-A-1
No. 156758 and Japanese Patent Publication No. 7-34123 each describe a technique for forming an oxide film on an Al substrate, but the film is formed by washing with water containing an inhibitor of a specific component. There is no mention of what to do.

JP-A-8-44090 discloses that an electrophotographic photoreceptor is formed on a substrate surface-treated with a silicate solution, but is vaporized during transportation from a spray device attached to the transportation. No technique is described for spraying the resulting liquid or for washing with water containing a specific inhibitor.

Various materials such as organic substances such as selenium, cadmium sulfide, zinc oxide, amorphous silicon, and phthalocyanine have been proposed as techniques for element members used for electrophotographic photosensitive members. Among them, non-single-crystal deposited films mainly containing silicon atoms typified by amorphous silicon, such as hydrogen and / or halogen (for example, fluorine,
Amorphous deposited films such as amorphous silicon compensated with chlorine or the like have been proposed as high-performance, high-durability, and non-polluting photosensitive members, some of which have been put to practical use. JP 5
Japanese Patent Application Laid-Open No. 4-86341 discloses an electrophotographic photosensitive member technology in which a photoconductive layer is mainly formed of amorphous silicon.

Conventionally, as a method of forming such a non-single-crystal deposited film containing silicon atoms as a main component, a sputtering method,
A method of decomposing a source gas by heat (thermal CVD method), a method of decomposing a source gas by light (photo CVD method), and a method of decomposing a source gas by plasma (plasma CVD method)
And many other methods are known.

The plasma CVD method, that is, a method in which a raw material gas is decomposed by direct current, high frequency or microwave glow discharge to form a thin film deposited film on a substrate, is a method for forming an amorphous silicon deposited film for electrophotography. It is optimal and is currently in very practical use. Among them, in recent years, a plasma CVD method using microwave glow discharge decomposition, that is, a microwave plasma CVD method has been attracting industrial attention as a deposition film forming method.

The microwave plasma CVD method has the advantages of a higher deposition rate and higher source gas utilization efficiency than other methods. One example of a microwave plasma CVD technique that takes advantage of these advantages is disclosed in US Pat.
No. 04,518. The technique described in this patent is to obtain a high-quality deposited film at a high deposition rate by a microwave plasma CVD method at a low pressure of 0.1 torr or less.

Further, a technique for improving the utilization efficiency of raw material gas by microwave plasma CVD is disclosed in
No. 186849. The technology described in the publication generally provides an internal chamber (ie, a discharge space) by arranging a substrate so as to surround a means for introducing microwave energy, thereby greatly improving the efficiency of using a source gas. Things.

Japanese Patent Application Laid-Open No. 61-283116 discloses an improved microwave technology for manufacturing semiconductor members. That is, in this publication, an electrode (bias electrode) is provided as a plasma potential control in a discharge space, and a desired voltage (bias voltage) is applied to the bias electrode to control the ion bombardment of the deposited film to perform film deposition. A technique for improving the characteristics of a deposited film in such a manner is disclosed.

When an aluminum alloy cylinder is used as the substrate, the method for producing an electrophotographic photosensitive member according to these conventional techniques is specifically carried out as follows.

If necessary, the workpiece is machined to a flatness within a predetermined range by diamond cutting using a lathe, a milling machine, or the like, and then washed with trichloroethane. Next, the substrate subjected to the surface treatment is washed with trichloroethane (FIG. 2), and is deposited on the substrate by a glow discharge decomposition method shown in FIG. Form a film.

However, in the prior art electrophotographic photosensitive member,
There is a portion of the deposited film that is abnormally grown, and that portion is a portion where a surface charge of a small area is not applied. These phenomena are particularly remarkable in the case of an electrophotographic photosensitive member having a deposited film formed by a plasma CVD method such as amorphous silicon.
However, those portions where the surface potential does not multiply can be minimized by optimizing the surface processing conditions, cleaning conditions and deposition conditions of the substrate. Conventionally, the resolution was less than or equal to the resolution of development. However, there was no practical problem.

However, in recent years, 1) high image quality of the electrophotographic apparatus has been demanded and the resolution of development has been improved, and 2) as the speed of the copying machine has increased and the charging conditions have become severe, the potential on the surface has increased. The non-existent part has substantially had a great influence on the peripheral potential. Under these circumstances, these minute portions on which electric charges do not have a problem have been pointed out as image defects.

Further, conventionally, the use of copying has mainly been a manuscript (so-called line copy) of only Kyushu, so that these image defects have not become a serious problem in practical use. However, recently, as the image quality of a copying machine has increased, a large number of originals including halftones such as photographs have been copied, which has become a problem. In particular, in color copiers that have recently become widespread, these defects have become a serious problem since they become more visually apparent.

Since these changes are very small, they cannot be detected even if an electrode is provided on the upper portion and the conductivity is measured.
However, when the electrophotographic photosensitive member is charged, exposed, and developed by an electrophotographic process, particularly when a uniform image is formed by halftone, a slight difference in potential on the surface of the electrophotographic photosensitive member also causes an image defect. Appears as visually striking. In particular, in the case of an electrophotographic photosensitive member prepared by a microwave plasma CVD method, the above-mentioned problem appears more remarkably.

On the other hand, such image defects are more likely to be caused by an electrophotographic photosensitive member prepared by plasma deposition than by a Se electrophotographic photosensitive member prepared by vacuum evaporation or an OPC electrophotographic photosensitive member prepared by a blade coating method or a diving method. This is particularly noticeable in the photoreceptor.

Also, in the case of a device manufactured by the plasma CVD method, a delicate difference in characteristics depending on the position on the substrate does not affect the performance of the device, such as a solar cell, or the device can be corrected by post-processing. Does not occur.

In the prior art, the step of cleaning the substrate is as follows.
Although trichlorethane was used, it did not cause any problem. However, due to environmental problems in recent years, these chlorinated solvents cannot be easily used, and have been changed to aqueous cleaning. However, when cleaning aluminum with water,
Parts that are partially stained during cleaning or have a large amount of impurities (Si, etc.) partially exposed on the aluminum surface form a local battery with surrounding normal aluminum parts to prevent corrosion of the substrate surface. There was a problem of promoting.

[0022]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the conventional method of manufacturing an electrophotographic photosensitive member by preventing corrosion during processing of a substrate, eliminating stains during cleaning, and reducing costs. Another object of the present invention is to provide an easy-to-use method for manufacturing an electrophotographic photoreceptor which can be formed stably at a high yield with a high yield.

It is a further object of the present invention to provide a method of manufacturing an electrophotographic photosensitive member capable of obtaining a uniform and high-quality image by solving the problem of occurrence of particularly remarkable image defects in a plasma CVD method. It is in.

[0024]

According to the present invention for solving the above-mentioned problems, a step of degreasing a substrate, a step of cleaning the substrate, a step of drying the substrate, and a surface of the substrate Forming a functional film made of an amorphous material having silicon atoms as a base material by a reduced pressure vapor deposition method, wherein the degreasing process and the cleaning process are performed. A process of spraying a spray processing liquid toward the substrate so as to prevent the surface of the substrate from drying, and performing a spraying process.

A step of degreasing the substrate, a step of cleaning the substrate, a step of drying the substrate,
Forming a functional film made of an amorphous material containing silicon atoms as a base material on the surface of the substrate by a reduced pressure vapor phase epitaxy method. Manufacturing the electrophotographic photoreceptor, wherein a spray processing liquid is sprayed on the substrate so that the surface of the substrate is not dried while the substrate is transported to a place where the cleaning process is performed; A method is provided. Here, the spraying process is performed by, for example, a spraying device provided in a mechanism for transporting the substrate.

The spraying treatment liquid is preferably sprayed in a vaporized state. For example, the liquid may be in a state of being vaporized by ultrasonic waves.

In the present invention, the spraying treatment, the washing treatment, and the drying treatment are preferably performed using pure water, water containing carbon dioxide, or water containing an inhibitor.

It is preferable that at least one of spraying, degreasing, washing and drying is performed using water containing an inhibitor.

The inhibitor is preferably a silicate, and particularly preferably a potassium silicate. The inhibitor concentration of the water containing the inhibitor is preferably 0.05% or more and 2% or less.

In the method of manufacturing an electrophotographic photoreceptor of the present invention, at least after the completion of the drying treatment, the surface of the substrate contains Al, Si, and O as main components and the composition ratio is
Al: Si: O = 1: a: b (0.1 ≦ a ≦ 1.0,
1 ≦ b ≦ 5), and a film having a thickness of 5 ° to 150 ° is preferably formed.

The functional film of the present invention contains hydrogen and / or fluorine and silicon, and is formed by plasma CVD.
It is preferably formed by a method.

The aluminum substrate according to the present invention comprises:
Preferably, Fe is contained in an amount of 0.001 wt% or more and 1 wt% or less. In addition, the content of Si is 0.001 wt% or more and 1 wt%.
% Is preferably contained. In addition, Cu is 0.00
It is preferable to contain 1 wt% or more and 1 wt% or less. Further, it contains any two or more of Fe, Si and Cu,
It is preferable that the total of the contents is 0.01 wt% or more and 1 wt% or less.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION Cleaning spots on an aluminum substrate are caused by thirst during cleaning. According to the study of the present inventors, the causes of image defects generated when an aluminum substrate is used are as follows: (A) Dust on the substrate, dirt of cleaning water in the cleaning and drying processes adhere to the core, and Becomes (B) The surface defects of the substrate become nuclei. Can be roughly divided into

In the above (A), the adhesion of dust and the like is to clean the place where the substrate is handled, such as cutting and cleaning, to clean the inside of the film forming furnace strictly and to clean the surface of the substrate immediately before forming the deposited film. To some extent. Conventionally, this object has been achieved by washing with a chlorine-based solvent such as trichloroethane. However, in recent years, the use of such a chlorine-based solvent has been restricted due to the destruction of the ozone layer and the like, and it has become necessary to newly examine this problem. On the other hand, it has been very difficult to reduce the defect (B).

The inventors of the present invention have conducted intensive studies from the viewpoint of solving all of these problems by combining a specific component-containing aluminum with a specific cleaning method, and have completed the present invention. .

According to the present invention, there are locally high-hardness portions in aluminum, and these high-hardness portions are applied to the blade of a processing machine at the time of surface processing such as cutting as pre-processing prior to formation of a deposited film. It has been found that surface defects on the aluminum substrate can be a cause of (B).

In order to prevent such a phenomenon, it is usually preferable that the amount of impurities contained in aluminum is small. However, extremely high-purity aluminum grows as an oxide that is inevitably generated during melting for processing aluminum as a raw material into the shape of a base, and causes the above-mentioned defects.
In order to prevent this, it became clear that it is effective to contain Si atoms. Further, from the viewpoint of the cost of the substrate, the high-purity material is expensive, so there is sufficient room for study.

When cleaning is performed using a chlorine-based solvent such as trichloroethane after the cutting of the surface of the substrate, the occurrence of image defects due to the surface properties of the substrate can be sufficiently prevented by only the above.

However, in recent years, these chlorinated solvents cannot be used easily due to environmental problems, and the present inventors have conducted intensive studies. As a result, it was discovered that aluminum is corroded by water, and in particular, aluminum containing these silicon atoms is more likely to be corroded by water, especially in areas where Si atoms are locally high, when applied to water during cleaning. did. Corrosion not only affects Si atoms,
It was found that Fe and Cu atoms also occurred locally.

This phenomenon is more remarkable when the temperature of water is higher, and is more remarkable when aluminum contains Si, Fe and Cu atoms together with magnesium for the purpose of improving machinability. Various corrosion inhibitors have been proposed to prevent the corrosion of aluminum.
When an aluminum substrate containing i, Fe, and Cu is used as a substrate for an electrophotographic photoreceptor, even a slight defect occurring on a large-sized substrate may cause a problem. The use of agents is restricted.

However, in the substrate processing step before depositing the functional film on the substrate, the present inventors
Using a mechanism to prevent thirst of the substrate, add a certain corrosion inhibitor to the cleaning solution to form a film that does not affect the subsequent functional film, and suppress the occurrence of cleaning stains and defects as described above. As a result of intensive research focusing on whether or not it is possible, the present invention has been completed.

Although the mechanism of the present invention has not yet been elucidated in many respects, the present inventor currently thinks as follows.

S partially exposed on the aluminum surface
The portion containing many i, Fe, and Cu atoms forms a local battery with the surrounding ordinary aluminum portion, and accelerates corrosion under water.

On the other hand, when the substrate washed at a high temperature is conveyed, the substrate is pulled up into the atmosphere from the cleaning liquid, and the longer the time of exposure to the atmosphere, the more the substrate becomes dry and the more stains occur. During the period from the time when it is raised to the time when it is transported to the next tank, thirst is prevented by spraying a vaporized liquid from the spray mechanism attached to the transport mechanism onto the substrate surface, and at the same time, potassium silicate added to the cleaning liquid is Since the Al-Si-O film is formed on the aluminum surface during the cleaning, a local battery is not formed and the action of accelerating the corrosion is not performed, so that the corrosion is effectively prevented. Al-
By forming the Si—O film, as a result, there is no defect on the surface of the base, so that the occurrence of abnormal growth from these portions during the formation of the functional film is prevented.

Further, as an unexpected effect of the present invention, improvement in electrophotographic characteristics was observed.

When, for example, an amorphous silicon deposition film is formed on a substrate by a plasma CVD method, the reaction may be a decomposition process of a raw material gas in a gas phase, a transport process of active species from a discharge space to a substrate surface, or a reaction on a substrate surface. Of the surface reaction process can be considered. In particular, the surface reaction process plays a very important role in determining the structure of the completed deposited film. These surface reactions are greatly affected by the temperature, material, shape, adsorbed substance, etc. of the substrate surface.

Particularly, a highly pure aluminum substrate is in a state where it is washed with a non-aqueous solvent such as trichloroethane after cutting or in a state where it is washed with pure water without any other washing after cutting. In this case, the state of adsorption of water on the substrate surface is partially different. When a deposited film containing silicon atoms, such as an amorphous silicon film, and hydrogen atoms and / or fluorine atoms is formed on a substrate having such a surface state by, for example, a plasma CVD method, a reaction on the surface is caused by the surface of the substrate. It is particularly strongly affected by the amount of water molecules remaining on top. As a result, the composition and structure of the interface of the deposited film changes depending on the amount of water adsorbed at the position of the substrate, and as a result, the charge injectability from the substrate in that portion changes during the electrophotographic process, and A potential difference appears.

In the present invention, before the functional film is formed by the plasma CVD method, thirst on the substrate surface is prevented by a spray mechanism attached to the transport mechanism, and the substrate surface is made of silicate to make the substrate surface more uniform. By forming an O film,
When forming a deposited film, an interface through which good charges can be exchanged can be formed. For this reason, it has become possible to improve the electrophotographic characteristics such as improvement of charging and reduction of photosensitivity.

One example of a procedure for actually forming an electrophotographic photosensitive member by the method of manufacturing an electrophotographic photosensitive member of the present invention using a cylinder made of an aluminum alloy as a substrate is shown in FIG. This will be described below using the spray mechanism according to the present invention and the deposited film forming apparatus shown in FIG.

Lathe with air damper for precision cutting (PNE)
UMOPRECLIONINC. ), A diamond bite (trade name: Miracle bite, manufactured by Tokyo Diamond) is set so as to obtain a rake angle of 5 ° with respect to the cylinder center angle. Next, the base was vacuum-chucked to the rotating flange of the lathe, and a peripheral speed of 1000 m / min and a feed speed of 0.0 m were also used while simultaneously spraying white kerosene from the attached nozzle and sucking chips from the attached vacuum nozzle.
Mirror polishing is performed so that the outer shape becomes 108 mm under the condition of 1 mm / R.

After the cutting is completed, the surface of the substrate is degreased and cleaned using the cleaning apparatus shown in FIG. The substrate cleaning apparatus includes a processing unit 102 and a substrate transport mechanism 103. Processing unit 1
Reference numeral 02 includes a substrate loading table 111, a substrate cleaning tank 121, a rinsing tank 131, a drying tank 141, and a substrate unloading table 151. Both the substrate cleaning tank 121 and the drying layer 141 have a temperature controller (not shown) for keeping the temperature of the liquid constant. The transport mechanism 103 includes a transport rail 165 and a transport arm 161. The transport arm 161 is a moving mechanism 162 that moves on the rail 165, a chucking mechanism 163 that holds the base 101, and air for moving the chucking mechanism 163 up and down. The cylinder 164 includes a spray mechanism 166 for spraying the vaporized liquid.

After cutting, the substrate 1 placed on the loading table 111
01 is transported to the cleaning tank 121 by the transport mechanism 103. Ultrasonic treatment is performed in a surfactant 122 or a surfactant 122 to which silicate is added in the substrate cleaning tank 121 to remove dusts and oils and fats adhered to the surface.

Next, when the substrate 101 is transported to the rinsing tank 131 by the transport mechanism 103, the substrate 101 is sprayed by the spray mechanism 166 until it is immersed in the rinsing tank 131. An outline of the spray mechanism will be described with reference to FIG. The spray processing liquid 702 supplied into the spray device 700 is supplied to the vaporizing liquid generating mechanism 7.
07. The vaporized spray processing liquid is sprayed by the air supplied from the air introduction hole 701 to the spray pipe 704.
And sprayed from the spray nozzle 707 toward the substrate 706.

Next, the substrate 101 is moved to a drying tank 141 of hot pure water or the like by the transport mechanism 103, and the substrate 101 is immersed in hot pure water or the like maintained at a temperature of 60 ° C. to sufficiently raise the temperature of the substrate 101. Later, lifting device (not shown)
And drying is performed. The quality of hot pure water or the like is constantly controlled by an industrial conductivity meter (trade name: α900R / C, manufactured by Horiba, Ltd.). The substrate 101 after the drying step is carried to the carry-out stand 151 by the carrying mechanism 103. Next, a deposited film mainly composed of amorphous silicon is formed on the substrate having been subjected to the cutting and the pre-treatment by the apparatus for forming a deposited photoconductive member by the plasma CVD method shown in FIG.

Referring to FIG. 3, a reaction vessel 301 includes a base plate 304, a wall 302 also serving as a cathode electrode, and a top plate 303. Inside the reaction vessel 301, a substrate 30 on which an amorphous silicon deposition film is formed is formed.
Reference numeral 6 is provided at the center of the cathode electrode 302 and also serves as an anode electrode.

In order to form an amorphous silicon deposited film on the substrate 306 using this deposited film forming apparatus, first, the source gas inflow valve 311 is closed, and the exhaust valve 31 is closed.
4 is opened, and the reaction vessel 301 is evacuated. When the reading of the vacuum gauge (not shown) becomes about 5 × 10 ⁻⁶ torr, the source gas inflow valve 311 is opened. The gas flow rate is adjusted to a predetermined flow rate in the mass flow controller 312. For example, a raw material gas such as SiH ₄ gas is supplied to the raw material gas introduction pipe 30.
9 into the reaction vessel 301. After confirming that the surface temperature of the base 306 is set to a predetermined temperature by the heater 308, the high-frequency power source (frequency: 13.56 MHz) 316 is set to a desired electric power, and the glow is placed in the reaction vessel 301. Causes discharge.

During formation of the deposited film, the substrate 306 is rotated at a constant speed by a motor (not shown) in order to make the deposited film uniform. In this way, an amorphous silicon deposition film can be formed on the base 306.

In the present invention, the surface of the substrate may be subjected to an uneven surface treatment to make it a mirror surface, or a non-mirror surface for the purpose of preventing interference fringes, or a substrate provided with irregularities of a desired shape. It is valid.

In the invention of the present invention, since corrosion is promoted in a portion where Si, Fe and Cu atoms are partially exposed on the aluminum surface, when a film is formed by adding a silicate, the substrate must be pure. A film needs to be formed before contact with water or the like. Further, since the film of the present invention is formed at a relatively early stage, it is effective in the present invention to form the film during washing with pure water or the like. That is, there is a method of including a silicate in a surfactant of a substrate cleaning tank for degreasing cleaning after cutting, and a method of including a silicate in pure water of a rinsing tank and a drying tank. Are also suitable for the present invention.

In the present invention, the inhibitors used in the washing step include phosphates, silicates, borates and the like, and any of them can be used, and silicates are suitable for the present invention.

As the silicate, potassium silicate, sodium silicate and the like can be mentioned, and any of them can be used. Potassium silicate is suitable for the present invention.

The surfactant used in the degreasing step in the present invention may be any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a mixture thereof. Is also possible. Among them, carboxylate, sulfonate, sulfate,
Anionic surfactants such as phosphate ester salts and nonionic surfactants such as fatty acid esters are particularly effective in the present invention.

In the present invention, when the surface of the aluminum substrate is degreased, an aqueous method using a surfactant containing a silicate is preferred. In this case, the water quality of the water before dissolving the surfactant and the silicate can be any, but pure water of a semiconductor grade, particularly ultrapure water of an ultra LSI grade is desirable. Specifically, the lower limit of the resistivity at a water temperature of 25 ° C. is 1 MΩ · cm or more, preferably 3 MΩ · cm.
cm or more, optimally 5 MΩ · cm or more is suitable for the present invention. The upper limit is the theoretical resistance value (18.25 MΩ · cm)
Any of the above values is possible, but from the viewpoints of cost and productivity, 17 MΩ · cm or less, preferably 15 MΩ · cm or less, and optimally 13 MΩ · cm or less is suitable for the present invention.

As for the amount of fine particles, 0.2 μm or more is 10,000 or less per milliliter, preferably 1000 μm or less.
No more than 100, optimally no more than 100 are suitable for the present invention. As the amount of microorganisms, a total viable cell count of 100 or less, preferably 10 or less, and optimally 1 or less per milliliter is suitable for the present invention. The amount of organic matter (TOC) is 1
Less than 10 mg per liter, preferably less than 1 mg, optimally less than 0.2 mg per liter is suitable for the present invention.

As a method for obtaining the water having the above-mentioned water quality, there are an activated carbon method, a distillation method, an ion exchange method, a filter filtration method, a reverse osmosis method, an ultraviolet sterilization method, and the like. It is desirable to increase the water quality to be used.

In the present invention, if the temperature of the water of the silicate-containing surfactant is too high, spots due to the liquid traces are generated, which causes peeling of the deposited film. On the other hand, if it is too low, the degreasing effect and the film effect are small, and the effect of the present invention cannot be sufficiently obtained. For this reason, the water temperature should be 10 ° C.
0 ° C or less, preferably 15 ° C or more and 50 ° C or less, optimally 20 ° C or more and 40 ° C or less are suitable for the present invention.

In the present invention, if the concentration of the surfactant used in the degreasing step is too high, stains due to liquid traces are generated, which causes peeling of the deposited film. On the other hand, if it is too thin, the degreasing effect and the film effect are small, and the effect of the present invention cannot be sufficiently obtained. Therefore, the concentration of the surfactant containing the silicate is 0.1% or more, 20% or less, preferably 1% or more,
10% or less, optimally 2% or more and 8% or less are suitable for the present invention.

In the present invention, if the pH of the surfactant used in the degreasing step is too high, stains due to traces of the liquid are generated, which causes peeling of the deposited film. On the other hand, if it is too thin, the degreasing effect and the film effect are small, and the effect of the present invention cannot be sufficiently obtained.

Therefore, the pH of the surfactant should be 8 or more,
2.5 or less, preferably 9 or more, 12 or less, optimally 1
0 or more and 11.5 or less are suitable for the present invention.

In the present invention, when the degreasing is performed, if the concentration of the silicate contained in the water containing the surfactant is too high, stains due to the traces of the liquid are generated, which may cause the peeling of the deposited film or the like. Becomes On the other hand, if it is too thin, the degreasing effect and the film effect are small, and the effect of the present invention cannot be sufficiently obtained. For this reason, the concentration of the silicate contained in the water containing the surfactant is 0.1.
05% or more and 2% or less, preferably 0.1% or more;
5% or less, optimally 0.2% or more and 1% or less are suitable for the present invention.

In the present invention, if the thickness of the film formed on the aluminum substrate is too small, no effect is exhibited. If the thickness is too large, the conductivity with the aluminum substrate is reduced, causing a problem. Therefore, the thickness of the film is 5 ° to 150 °, preferably 10 ° to 130 °, and most preferably 15 ° to 130 °.
It is suitable that the angle is not less than {120}.

In the present invention, the composition ratio of the Al—Si—O film formed on the aluminum substrate is insufficient if the content of Al or Al is large if the content of Si or O is small.
At most, it is not suitable because the conductivity is lowered. Al 1
Si is 0.1 or more and 0.5 or less, preferably 0.15 or more and 0.4 or less, and most preferably 0.2 or more and 0.35 or less.
The following are suitable: When Al is 1, O is 1 or more and 5 or less, preferably 1.5 or more and 4 or less, and most preferably 2 or more and 3.5 or less.

The use of ultrasonic waves in the degreasing step of the present invention is effective in achieving the effects of the present invention. The frequency of the ultrasonic wave is preferably 100 Hz or more and 10 MHz or less, more preferably 1 kHz or more and 5 MHz or less, and most preferably 10 kHz or more.
A frequency between kHz and 100 kHz is effective. The output of the ultrasonic wave is preferably 0.1 W / liter or more and 1 kW / liter.
1 liter or less, more preferably 1 W / liter or more, 1
Less than 00 W / liter is effective.

In the present invention, the cleaning liquid and water used for the cleaning means after surface processing may be any of a surfactant, pure water, water in which carbon dioxide is dissolved, water containing an inhibitor of a specific component, or Washing with a combination of two or more is suitable for the present invention.

When the washing apparatus is used, dry operation means may be any of warm pure water, warm pure water in which carbon dioxide is dissolved, warm pure water containing an inhibitor of a specific component, or
It is suitable for the present invention to further pull up and dry by a combination of more than one kind.

In the cleaning step of the present invention, the quality of the water used when using water in which carbon dioxide is dissolved is very important. LSI grade ultrapure water is desirable. Specifically, the lower limit is 1 as the resistivity at a water temperature of 25 ° C.
MΩ · cm or more, preferably 3 MΩ · cm or more, optimally 5 MΩ · cm or more is suitable for the present invention. The upper limit of the resistance value can be any value up to the theoretical resistance value (18.25 MΩ · cm).
Ω · cm or less, preferably 15 MΩ · cm or less, and optimally 13 MΩ · cm or less is suitable for the present invention. As for the amount of fine particles, 0.2 μm or more
000 or less, preferably 1000 or less, optimally 1
No more than 00 are suitable for the present invention. As the amount of microorganisms, a total viable cell count of 100 or less, preferably 10 or less, and optimally 1 or less per milliliter is suitable for the present invention. Organic matter (TOC) is 10m / l
g or less, preferably 1 mg or less, optimally 0.2 mg or less are suitable for the present invention.

Examples of the method for obtaining the water having the above-mentioned water quality include an activated carbon method, a distillation method, an ion exchange method, a filter filtration method, a reverse osmosis method, and an ultraviolet sterilization method. It is desirable to increase the water quality to be used.

The present invention is possible with any amount of carbon dioxide dissolved in water up to the saturation solubility. However, if the amount of carbon dioxide is too large, bubbles are generated when the water temperature fluctuates and adhere to the surface of the substrate due to the formation of bubbles. Spots may occur. Furthermore, if the amount of dissolved carbon dioxide is large, the pH may be reduced, which may damage the substrate. on the other hand,
If the amount of dissolved carbon dioxide is too small, the effects of the present invention cannot be obtained.

Considering the quality required for the substrate,
It is necessary to optimize the amount of dissolved carbon dioxide according to the situation.

In general, the preferred amount of dissolved carbon dioxide according to the present invention is from 5% to 60%, more preferably from 10% to 40% of the saturation solubility.

In the present invention, it is practical to control the dissolved amount of carbon dioxide by the conductivity or pH of water, but when controlled by the conductivity, the preferable range is 2 μS / cm or more and 40 μS / cm or less. Preferably 4 μS / cm
30 μS / cm or less, 6 μS / cm or more, 25 μS
When controlled at S / cm or lower and pH, the preferable range is 3.8 or higher, 6.0 or lower, more preferably 4.0 or higher,
When the value is 5.0 or less, the effect of the present invention is remarkable. Conductivity is measured by a conductivity meter or the like, and the value is 2
Use the value converted to 5 ° C.

The temperature of the water is 5 ° C. or more and 90 ° C. or less, preferably 10 ° C. or more and 55 ° C. or less, optimally 15 ° C. or more,
40 ° C. or lower is suitable for the present invention.

The method of dissolving carbon dioxide in water may be any of a method by bubbling, a method using a diaphragm, and the like. In the present invention, it is important to use water in which carbon dioxide is dissolved, and when a carbonate such as sodium carbonate is used to obtain carbonate ions, cations such as sodium ions inhibit the effects of the present invention. Would.

When the substrate is cleaned by dipping in the cleaning step (rinsing step), it is basically immersed in the water tank. At that time, ultrasonic waves are applied, a water flow is given, and air or the like is introduced. The present invention is more effective when bubbling is performed in combination.

In the present invention, it is effective to use a high-pressure shower in the rinsing step. However, when spraying a high-pressure shower, the effect of the present invention is small if the jet pressure of water is too weak, and if it is too strong. A pear-skinned pattern is generated on the obtained image of the electrophotographic photosensitive member, particularly on a halftone image. For this reason, the water pressure is 5 kg · f /
cm ² or more, 50 kg · f / cm ² or less, preferably 8 k
g · f / cm ² or more and 40 kg · f / cm ² or less, optimally 10 kg · f / cm ² or more and 30 kg · f / cm ² or less are suitable for the present invention. However, the pressure unit kg · f / cm ² in the present invention means the gravity kilogram per square centimeter, and 1 kg · f / cm ² is 98066.5.
It is equal to Pa.

As a method of spraying water, there is a method of spraying water pressurized by a pump from a nozzle, a method of mixing water pumped by a pump with high-pressure air just before the nozzle, and spraying the mixture by the pressure of air. .

The flow rate of water is preferably 1 liter / min or more and 200 liter / min or less, preferably 2 liter / min or more and 100 liter / min or less per substrate from the viewpoint of the effect of the invention and economy. 5 liters / min or more and 50 liters / min or less are suitable for the present invention.

The treatment time of the washing treatment with water in which oxygen dioxide is dissolved is 10 seconds or more and 30 minutes or less, preferably 20 minutes or less.
A time period of not less than seconds and not more than 20 minutes, optimally not less than 30 seconds and not more than 10 minutes is suitable for the present invention.

In the cleaning step after the surface treatment of the present invention, the quality of water when using pure water is very important, and pure water of semiconductor grade, particularly ultra-pure water of ultra LSI grade is desirable. Specifically, as the resistivity at a water temperature of 25 ° C., the lower limit is 1 MΩ · cm or more, preferably 3 MΩ · cm or more,
Optimally, 5 MΩ · cm or more is suitable for the present invention. The upper limit of the resistance value can be any value up to the theoretical resistance value (18.25 MΩ · cm), but from the viewpoint of cost and productivity, 17 MΩ · cm or less, preferably 15 MΩ · cm or less.
Optimally, 13 MΩ · cm or less is suitable for the present invention.
Regarding the amount of fine particles, 0.2 μm or more is preferably 10,000 or less, preferably 1000 or less, and optimally 100 or less per milliliter in the present invention. As for the amount of microorganisms, the total viable count is 100 or less per milliliter,
Preferably 10 or less, optimally 1 or less are suitable for the present invention. The amount of organic matter (TOC) is 1 per liter
0 mg or less, preferably 1 mg or less, optimally 0.2 m
g or less is suitable for the present invention.

As a method for obtaining the water having the above-mentioned water quality, there are an activated carbon method, a distillation method, an ion exchange method, a filter filtration method, a reverse osmosis method, an ultraviolet sterilization method, and the like. It is desirable to increase the water quality to be used.

The temperature of pure water is 5 ° C. or more and 90 ° C. or less, preferably 10 ° C. or more and 55 ° C. or less, and most preferably 15 ° C. or more and 40 ° C. or less is suitable for the present invention.

When the surface of the substrate is washed with the pure water thus obtained, the same method and time as those in the case of dissolving carbon dioxide are preferable.

In the present invention, when hot water drying is performed using water in which carbon dioxide is dissolved, the quality of the water used is very important. LSI grade ultrapure water is desirable.
Specifically, as the resistivity at a water temperature of 25 ° C., the lower limit is 1 MΩ · cm or more, preferably 3 MΩ · cm or more, and most preferably 5 MΩ · cm or more. The upper limit of the resistance value can be any value up to the theoretical resistance value (18.25 MΩ · cm).
MΩ · cm or less, preferably 15 MΩ · cm or less, optimally 13 MΩ · cm or less is suitable for the present invention. As for the amount of fine particles, 0.2 μm or more
0000 or less, preferably 1000 or less, optimally 100 or less are suitable for the present invention. As the amount of microorganisms, a total viable cell count of 100 or less, preferably 10 or less, and optimally 1 or less per milliliter is suitable for the present invention. Organic matter (TOC) is 10m / l
g or less, preferably 1 mg or less, optimally 0.2 mg or less are suitable for the present invention.

Examples of the method for obtaining the water having the above-mentioned quality include an activated carbon method, a distillation method, an ion exchange method, a filter passing method, a reverse osmosis method, an ultraviolet sterilization method, and the like. It is desirable to increase to the required water quality.

The present invention is possible with any amount of carbon dioxide dissolved in water up to the saturation solubility. However, if the amount is too large, bubbles are generated when the water temperature fluctuates and adhere to the surface of the substrate, so that the amount of carbon dioxide on the substrate is reduced. Spots may occur. Furthermore, if the amount of dissolved carbon dioxide is large, the pH may be reduced, which may damage the substrate. on the other hand,
If the amount of dissolved carbon dioxide is too small, the effects of the present invention cannot be obtained. It is necessary to optimize the dissolved amount of carbon dioxide according to the situation, taking into account the quality required for the substrate. In general, the preferred amount of dissolved carbon dioxide according to the present invention is from 5% to 60%, more preferably from 10% to 40% of the saturation solubility.

In the present invention, it is practical to control the amount of dissolved carbon dioxide by the conductivity or pH of water, but when controlled by the conductivity, the preferred range is 5 μS / cm or more and 40 μS / cm or less. Preferably 6 μS / cm
Above, 35 μS / cm or less, 8 μS / cm or more, 30 μ
When controlled at S / cm or lower and pH, the preferable range is 3.8 or higher, 6.0 or lower, more preferably 4.0 or higher,
When the value is 5.0 or less, the effect of the present invention is remarkable. Conductivity is measured by a conductivity meter or the like, and the value is 2
Use the value converted to 5 ° C.

The method of dissolving carbon dioxide in water may be any of a method by bubbling, a method using a diaphragm, and the like. In the present invention, it is important to use water in which carbon dioxide is dissolved, and when a carbonate such as sodium carbonate is used to obtain carbonate ions, cations such as sodium ions inhibit the effects of the present invention. Would.

The temperature of the hot water is 30 ° C. or more and 90 ° C. or less,
Preferably 35 ° C. or higher and 80 ° C. or lower, optimally 40 ° C. or higher and 70 ° C. or lower are suitable for the present invention.

The pulling speed in pulling and drying is important, and the preferable range is 100 mm / min or more,
00 mm / min, more preferably 200 mm / mi
n, optimally at least 300 mm / min, 1000 mm / min.
min is suitable for the present invention.

If the time from the cleaning treatment with water in which oxygen dioxide is dissolved to the introduction into the deposited film forming apparatus is too long, the effect of the present invention is diminished. If the time is too short, the process is not stable. Time or less, preferably 2 minutes or more, 4
Less than an hour, optimally from 3 minutes to 2 hours, is suitable for the present invention.

In the drying step after the surface treatment of the present invention, the quality of the water used when using water in which silicate is dissolved is very important. Water, especially ultra-pure water of ultra LSI grade is desirable. Specifically, as the resistivity at a water temperature of 25 ° C., the lower limit is 1 MΩ · cm or more, preferably 3 MΩ · cm or more,
Optimally, 5 MΩ · cm or more is suitable for the present invention. The upper limit of the resistance value can be any value up to the theoretical resistance value (18.25 MΩ · cm).
7 MΩ · cm or less, preferably 15 MΩ · cm or less, and optimally 13 MΩ · cm or less is suitable for the present invention. Regarding the amount of fine particles, 0.2 μm or more is preferably 10,000 or less, preferably 1000 or less, and optimally 100 or less per milliliter in the present invention. As the amount of microorganisms, a total viable cell count of 100 or less, preferably 10 or less, and optimally 1 or less per milliliter is suitable for the present invention. The amount of organic matter (TOC) is 10 per liter.
mg or less, preferably 1 mg or less, optimally 0.2 mg
The following are suitable for the present invention.

Examples of the method for obtaining the water having the above-mentioned quality include an activated carbon method, a distillation method, an ion exchange method, a filter filtration method, a reverse osmosis method, an ultraviolet sterilization method, and the like. It is desirable to increase the water quality to be used.

The temperature of the water in which the silicate is dissolved is from 30 ° C. to 90 ° C., preferably from 35 ° C. to 80 ° C.
Optimally, 40 ° C. or more and 70 ° C. or less are suitable for the present invention.

In the present invention, when cleaning after surface processing is performed, if the concentration of water containing silicate is too high, spots due to liquid traces are generated, which may cause peeling of the deposited film. Becomes Also, if it is too thin, the degreasing effect and film effect are small,
The effect of the present invention cannot be sufficiently obtained. For this reason, the concentration of water containing silicate is 0.1% or more and 20% or less, preferably 1% or more and 10% or less, and optimally 2% or more and 8% or less is suitable for the present invention. I have.

In the present invention, if the pH of the silicate-containing water is too high when cleaning is performed after the surface processing, spots due to the traces of the liquid may occur, causing the deposited film to peel off. Becomes On the other hand, if it is too thin, the effect of the film is small and the effect of the present invention cannot be sufficiently obtained. Therefore, water containing silicate
H is 8 or more and 12.5 or less, preferably 9 or more and 12
Below, optimally 10 or more and 11.5 or less are suitable for the present invention.

When the surface of the substrate is washed with water obtained by dissolving the silicate thus obtained, a method and a time similar to those in the case of dissolving carbon dioxide are preferable.

In the drying step after the surface processing of the present invention, the quality of the water when using pure water is very important, and pure water of a semiconductor grade, particularly ultrapure water of an ultra LSI grade is desirable. Specifically, as the resistivity at a water temperature of 25 ° C., the lower limit is 1 MΩ · cm or more, preferably 3 MΩ · cm or more,
Optimally, 5 MΩ · cm or more is suitable for the present invention. The upper limit of the resistance value can be any value up to the theoretical resistance value (18.25 MΩ · cm), but from the viewpoint of cost and productivity, 17 MΩ · cm or less, preferably 15 MΩ · cm or less.
Optimally, 13 MΩ · cm or less is suitable for the present invention.
Regarding the amount of fine particles, 0.2 μm or more is preferably 10,000 or less, preferably 1000 or less, and optimally 100 or less per milliliter in the present invention. As for the amount of microorganisms, the total viable count is 100 or less per milliliter,
Preferably 10 or less, optimally 1 or less are suitable for the present invention. The amount of organic matter (TOC) is 1 per liter
0 mg or less, preferably 1 mg or less, optimally 0.2 m
g or less is suitable for the present invention.

As a method for obtaining the water having the above-mentioned water quality, there are an activated carbon method, a distillation method, an ion exchange method, a filter filtration method, a reverse osmosis method, an ultraviolet sterilization method and the like. It is desirable to increase the water quality to be used.

The temperature of the pure water is 30 ° C. or more and 90 ° C. or less,
Preferably 35 ° C. or higher and 80 ° C. or lower, optimally 40 ° C. or higher and 70 ° C. or lower are suitable for the present invention. When the substrate surface is washed with the pure water thus obtained, a method and a time similar to those in the case of dissolving carbon dioxide are preferable.

In the present invention, any of pure water, water in which carbon dioxide is dissolved, and water containing a specific inhibitor is effective as the liquid supplied into the spray mechanism.

In the present invention, the pressure of the liquid to be sprayed is determined by the pressure of the supplied air. However, if the pressure is too low, the effect is small. If the pressure is too high, adverse effects are caused by winding up dust of the washing machine. , The preferred range is 0.2 kgf
/ Cm ² or more 3.0 kgf / cm ² or less, and more preferably 0.5 gf / cm ² or more 2.5 / cm ² or less, optimally is 1.0 kgf / cm ² or more 2.0 kgf / cm ² suitable .

In the present invention, the amount of the liquid to be sprayed is determined by the pressure and the diameter of the nozzle.
0 ml or more and 300 ml or less, optimally 50 ml or more and 20
0 ml or less is suitable.

In the present invention, the time of spraying is determined by the balance with the washing tact, but if it is too short, the effect is small, and if it is too long, it affects the tact. Therefore, it is preferably 1 sec to 40 sec, optimally 3 sec to 30 sec. The following are suitable:

As a means for vaporizing the liquid supplied to the spray in the present invention, a method of vaporizing by ultrasonic waves is effective in the present invention.

In the present invention, any material can be used as the base material as long as the base material is aluminum. The aluminum base is preferably an aluminum base containing 10 ppm or more of Fe, and the aluminum base is preferably an aluminum base containing 10 ppm or more of Si. Those containing 10 ppm or more of Cu and having a total content of Fe + Si + Cu of more than 0.01 wt% and 1 wt% or less are suitable for the present invention.

In the present invention, it is effective to contain magnesium in order to improve the workability of the substrate. The preferable magnesium content is in the range of 0.1 wt% or more and 10 wt% or less, and more preferably in the range of 0.2 wt% or more and 5 wt% or less. Further, H, Li, N
a, K, Be, Ca, Ti, Cr, Mn, Fe, CO,
Ni, Cu, Ag ヽ Zn, Cd, Hg, B, Ca, I
n, C, Si, Ge, Sn, N, P, AS, 0, S, S
Substances such as e, F, Cl, Br and I may be contained in the aluminum substrate.

In the present invention, the shape of the substrate is determined as desired. For example, if it is used for electrophotography, in the case of a continuous high-speed copying machine, it is an endless belt or a cylindrical one as described above. Are most suitable for the present invention. In the case of a cylindrical shape, the size of the substrate is not particularly limited, but is practically preferably 20 mm or more and 500 mm or less, 10 mm or more and 1000 mm or less in diameter. The thickness of the support is appropriately determined so that a desired photoconductive member is formed. However, when the possibility of the photoconductive member is required, the thickness is within a range where the function as the support is sufficiently exhibited. If possible, make it as thin as possible. However, in such a case,
The thickness is usually 10 μm or more from the viewpoints of the production and handling of the support and the mechanical strength.

The photoreceptor used in the present invention may be any of an amorphous silicon photoreceptor, a selenium photoreceptor, a cadmium sulfide photoreceptor, and an organic photoreceptor. In the case of a photoreceptor, the effect is remarkable. In the case of a non-single-crystal photoreceptor containing silicon, as a source gas used for forming a deposited film, silane (SiH ₄ ), disilane (Si ₂ H ₆ ), silicon tetrafluoride (SiF ₄ ), A material gas for forming amorphous silicon such as silicon (Si ₂ F ₆ ) or a mixed gas thereof may be used.

Examples of the diluting gas include hydrogen (H ₂ ), argon (Ar), helium (He) and the like.

Further, as a characteristic improving gas for changing the band gap width of the deposited film, an element containing a nitrogen atom such as nitrogen (N2) and ammonia (NH ₃ ), oxygen (O ₂ ), and nitrogen monoxide (NO) ), Nitrogen dioxide (NO ₂ ), nitrous oxide (N ₂₀ ), carbon monoxide (CO), carbon dioxide (CO ₂ )
Elements containing isooxygen, methane (CH ₄ ), ethane (C ₂
H ₆ ), ethylene (C ₂ H ₄ ), acetylene (C ₂ H ₂ ),
Examples thereof include hydrocarbons such as propane (C ₃ H ₈ ), fluorine compounds such as germanium tetrafluoride (GeF ₄ ) and nitrogen fluoride (NF ₃ ), and a mixed gas thereof.

In the present invention, diborane (B ₂ H ₆ ), boron fluoride (BF ₃ ),
The present invention is similarly effective when a dopant gas such as phosphine (PH ₃ ) is simultaneously introduced into the discharge space.

In the electrophotographic photosensitive member of the present invention, the total thickness of the deposited film deposited on the substrate may be any, but it is preferably 5 μm or more and 100 μm or less, more preferably 10 μm or more and 7 μm or more.
At a thickness of 0 μm or less, optimally 15 μm or more and 50 μm or less, a particularly good image as an electrophotographic photosensitive member could be obtained.

In the present invention, the effect of the pressure in the discharge space during the deposition of the deposited film was observed in any region.
At a pressure of 5 mtorr or more and 100 mtorr or less, preferably 1 mtorr or more and 50 mtorr or less, particularly good results were obtained with good reproducibility in terms of discharge stability and uniformity of the deposited film.

In the present invention, the substrate temperature at the time of depositing the deposited film is effective in the range of 100 ° C. or more and 500 ° C. or less.
0 ° C to 400 ° C, optimally 250 ° C to 35 ° C
A remarkable effect was confirmed below 0 ° C.

In the present invention, the heating means for the substrate may be a heating element of a vacuum specification, and more specifically, an electric resistance heating element such as a winding heater of a sheath-shaped heater, a plate-shaped heater, a ceramic heater, or a halogen. Examples of the heating element include a heat radiation lamp heating element such as a lamp and an infrared lamp, and a heating element using a liquid or a gas as a heating medium and a heat exchange unit.
As the surface material of the heating means, metals such as stainless steel, nickel, aluminum, and copper, ceramics, heat-resistant polymer resins, and the like can be used. In addition, other methods such as providing a dedicated heating vessel separately from the reaction vessel, heating, and then transporting the substrate into the reaction vessel in a vacuum can be used. It is possible in the present invention to use the above means alone or in combination.

In the present invention, the energy for generating plasma can be any of DC, RF, microwave, etc. In particular, when microwave is used as the energy for generating plasma, abnormal growth due to surface defects of the substrate Appears remarkably, and the absorbed moisture absorbs the microwave,
Since the change in the interface becomes more remarkable, the effect of the present invention becomes more remarkable.

In the present invention, when microwaves are used to generate plasma, any microwave power can be used as long as discharge can be generated. However, microwave power is preferably 100 W or more and 10 kW or less, preferably 500 W or more and 4 kW or less. Appropriate for practicing the invention.

In the present invention, it is effective to apply a voltage (bias voltage) to the discharge space during the formation of the deposited film.
It is preferable that an electric field is applied at least in a direction in which cations collide with the substrate. If no bias is applied, the effect of the present invention is significantly reduced, so that the DC component voltage is 1 V or more and 500 V or less, preferably 5 V or more and 10 V or more.
It is desirable to apply a bias voltage of 0 V or less during formation of the deposited film in order to obtain the effects of the present invention.

In the present invention, when microwaves are introduced into the reaction vessel using a dielectric window, the dielectric window may be made of alumina (Al ₂ O ₃ ), aluminum nitride (Al ₂ O ₃ ).
N), boron nitride (BN), silicon nitride (SiN), silicon carbide (SiC), silicon oxide (SiO ₂ ), beryllium oxide (BeO), Teflon, polystyrene, and other materials with low microwave loss are usually used. .

In the method of forming a deposited film in which a plurality of substrates surround the discharge space, the distance between the substrates is 1 mm or more and 50 mm or more.
mm or less is preferable. The number of substrates is not particularly limited as long as a discharge space can be formed, but is preferably 3 or more, more preferably 4 or more.

The present invention can be applied to any method for producing an electrophotographic photosensitive member. In particular, a substrate is provided so as to surround a discharge space, and a microwave is introduced from at least one end of the substrate by a waveguide. When a deposited film is formed by such a configuration, there is a great effect.

The electrophotographic photosensitive member manufactured by the method of the present invention is used not only for electrophotographic copying machines but also for electrophotographic applications such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making machines. Can also be widely used.

[0133]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. (Experimental example 1) 0.05 wt% of Si and 0.03 w of Fe
A cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm made of aluminum containing 0.1% by weight of Cu and 0.01% by weight of Cu was used in the procedure of the method of manufacturing an electrophotographic photosensitive member described in the embodiment of the invention. The surface was cut in the same procedure as in one example.

Fifteen minutes after the completion of the cutting step, degreasing, washing (rinsing), and drying were performed with a detergent (nonionic surfactant) under the conditions shown in Table 1 using the surface treatment apparatus of the present invention shown in FIG. At that time, the spray amount was changed using the spray device of the present invention shown in FIG. In addition, spraying was performed at the point of shifting from degreasing cleaning to rinsing cleaning. At that time, the appearance of the surface of the substrate was observed and evaluated. Table 3 shows the results. Next, an amorphous silicon deposited film was formed on the substrate subjected to the surface treatment using the deposited film forming apparatus shown in FIG. 3 under the conditions shown in Table 2 to prevent the layer structure shown in FIG. A type electrophotographic photosensitive member was prepared. In FIG. 6, 601, 602,
Reference numerals 603 and 604 indicate an aluminum substrate, a charge injection blocking layer, a photoconductive layer, and a surface layer, respectively.

The electrophotographic characteristics of the electrophotographic photosensitive member thus prepared were evaluated as follows.

The process speed of the electrophotographic photosensitive member thus prepared was arbitrarily changed in the range of 200 to 800 mmsec for experiments, and a voltage of 6 to 7 kV was applied to the charger to perform corona charging. After forming a latent image on the surface of the electrophotographic photoreceptor and modifying it so that an image can be formed on a transfer paper by a normal copying process, a Canon copier NP6650 was used to evaluate the density unevenness of the halftone image. I did it. Table 3 also shows the results. (Evaluation of appearance observation) The light of strong exposure was reflected on the surface of the substrate after washing, and the condition of the stain on the substrate and the surface roughness of the substrate surface, which can be visually confirmed, was comprehensively evaluated. ◎: very good ○: good △: no problem in practical use (Evaluation of image unevenness) A3 grid paper (manufactured by KOKUYO Co., Ltd.) was placed on the platen of a copying machine, and the exposure of the document was changed by changing the aperture of the copying machine. The image was changed so as to obtain an image in a range up to the start of fogging, and ten copies having different densities were output.

These images were observed at a distance of 40 cm from the eyes, and evaluation was made according to the following criteria to determine whether a difference in density was observed. A: No image unevenness is observed on any copy.・ ・ ・: There are copies where image unevenness is recognized and copies where image unevenness is not recognized. However, all are minor and have no problem at all. Δ: Image unevenness is observed on any copy.
However, image unevenness is slight on at least one copy, which does not hinder practical use. ×: Large image unevenness is observed on all copies.

[0138]

[Table 1]

[0139]

[Table 2]

[0140]

[Table 3] As is clear from Table 3, good results were shown in the range of 50 ml or more and 200 ml or less. (Experimental Example 2) A blocking type electrophotographic photosensitive member was formed on a substrate in the same manner as in Experimental Example 1 except that the spray time was changed.
Thereafter, the same evaluation as in Experimental Example 1 was performed, and the results are also shown in Table 4.

[0141]

[Table 4] As is clear from Table 4, good results were obtained in the range of 3 seconds to 30 seconds. (Experimental Example 3) A blocking type electrophotographic photosensitive member was formed on a substrate in the same manner as in Experimental Example 1 except that the treating agent sprayed was changed as shown in Table 5, and then the same as in Experimental Example 1 was conducted. Table 5 also shows the results of the evaluation. (However, potassium silicate was used for the inhibitor)

[0142]

[Table 5] As is clear from Table 5, good results were obtained using any of pure water, an aqueous solution of carbon dioxide, and water containing an inhibitor as the liquid to be vaporized. (Experimental example 4) Degreasing, washing (rinsing), and drying were performed by washing (nonionic surfactant) under the conditions shown in Table 6 using the same substrate as in Experimental example 1. At that time, the tank in which the inhibitor was placed was changed as shown in Table 7 (note that the inhibitor was made of potassium silicate and put in a surfactant aqueous solution at 3 g / l, and the pH was set to 11.0). Thereafter, an electrophotographic photoreceptor was prepared in the same manner as in Experimental Example 1, and an image was formed in the same manner as above, and comprehensive evaluation of black spots, image defects, and electrophotographic characteristics (sensitivity) and evaluation of environmental properties Was done. Table 7 also shows the results. (Evaluation of black spots and image defects) Change the process speed and select the image sample with the most image defects among the image samples obtained when copying the whole halftone document and the manuscript document on the platen. went. As an evaluation method, the image sample was observed with a magnifying glass, and evaluation was performed based on the state of white spots within the same area.・ ・ ・: Good.・ ・ ・: There are some minor defects but no problem. Δ: There are slight defects on the whole surface, but there is no problem in practical use. X: There is a problem with a large defect on the entire surface. (Evaluation of environmental properties) ○ ・ ・ ・ Do not use substances related to ozone layer destruction in the pretreatment process. X: A substance related to destruction of the ozone layer is used in the pretreatment step.

[0143]

[Table 6]

[0144]

[Table 7] Note) ● indicates that the inhibitor was added, and-indicates that the inhibitor was not added. From Table 7, good results were obtained by adding the inhibitor in the surfactant or immediately after the surfactant. (Comparative Experimental Example 1) Cleaning was performed in the same manner as in Experimental Example 4 except that no inhibitor was used in the cleaning step, and thereafter, a blocking type electrophotographic photosensitive member was prepared and evaluated in the same manner. . The results are also shown in Table 7 as Comparative Experimental Example 1. (Conventional Example 1) After the surface was cut using the same aluminum cylindrical substrate as in Experimental Example 1, degreasing and cleaning were performed using the conventional substrate surface cleaning apparatus shown in FIG. Was. The substrate cleaning apparatus shown in FIG.
And a substrate transport mechanism 203. Processing tank 202
Comprises a substrate loading table 211, a substrate cleaning tank 221, and a substrate discharging table 251. The cleaning tank 221 is provided with a temperature controller (not shown) for keeping the temperature of the liquid constant.
The transfer mechanism 203 includes a transfer rail 265 and a transfer arm 26.
The transfer arm 261 includes a moving mechanism 262 that moves on the rail 265, a chucking mechanism 263 that holds the base 201, and an air cylinder 264 that moves the chucking mechanism 263 up and down.

After the cutting, the substrate 2 placed on the loading table 211
01 is transported from the transport mechanism 203 to the cleaning tank 221. Washing is performed to remove cutting oil and chips adhering to the surface from trichloroethane (trade name = Eterna VG Asahi Kasei Kogyo Co., Ltd.) 221 in the washing tank 221. After the cleaning, the base 201 is carried to the carry-out table 251 by the transfer mechanism 203. Thereafter, an electrophotographic photosensitive member was produced in the same manner as in Experimental Example 1. The results of evaluating the electrophotographic photoreceptor thus prepared in the same manner as in Experimental Example 4 are shown in Table 7 as Conventional Example 1.

[0146]

[Table 8] (Experimental Example 5) A blocking type electrophotographic photoreceptor was formed on a substrate in the same manner as in Experimental Example 1 except that water shown in Table 9 was used in the rinsing and drying steps shown in the table of Experimental Example 4. Evaluation was performed in the same manner as in Experimental Example 4. Table 10 shows the results.
Shown in

[0147]

[Table 9]

[0148]

[Table 10] Note) ● indicates that the inhibitor was added, and 1 indicates that the inhibitor was not added. (Experimental Example 6) Using the same substrate as in Experimental Example 1, when cleaning was performed by the method shown in Table 11, the type of silicate to be introduced was changed as shown in Table 12. Thereafter, a blocking type electrophotographic photosensitive member was formed on the substrate in the same manner as in Experimental Example 1, and the measurement was performed in the same manner as in Experimental Example 4. Table 12 also shows the results.

[0149]

[Table 11] Note) ● indicates that an inhibitor has been added.

[0150]

[Table 12] As is clear from Table 12, good results were obtained with any of the silicates, but the best results were obtained especially with potassium silicate. (Experimental example 7) Using the same substrate as in Experimental example 1, cleaning was performed under the same conditions as in Experimental example 6 shown in Table 11. The concentration of potassium silicate introduced at that time was changed as shown in Table 13, and the surface of the substrate after washing was visually observed for stains.
Thereafter, a blocking type electrophotographic photoreceptor was produced in the same manner as in Experimental Example 1 and evaluated in the same manner as in Experimental Example 4.
Table 13 also shows the results. (Appearance (stain)) The surface of the substrate after cleaning was reflected with strong exposure light on the surface of the substrate, and a stain on the substrate that could be visually confirmed was confirmed.・ ・ ・: Good without any spots. Δ: The stain is very thin and has no problem at all. × ... is recognized as sticking.

[0151]

[Table 13] From the results in Table 13, good results were obtained when the concentration of potassium silicate was 0.05% or more and 2.0 or less. (Experimental Example 8) Degreasing and washing were performed in the same manner as in Experimental Example 4 using aluminum in which the content of Si was changed as shown in Table 14. Thereafter, a blocking type electrophotographic photosensitive member equivalent to that of Experimental Example 1 was manufactured, and the same evaluation as that of Experimental Example 4 was performed. The results are also shown in Table 14.

[0152]

[Table 14] As is clear from Table 14, 0.001wt% ≦ Si ≦ 1w
The present invention is effective even if the content changes at t%. (Experimental Example 9) A blocking type electrophotographic photoreceptor was produced in the same manner as in Experimental Example 1 except that the Fe content was changed as shown in Table 15, and the same evaluation as in Experimental Example 4 was performed. Done. The results are also shown in Table 15.

[0153]

[Table 15] As is clear from Table 15, 0.001wt% ≦ Fe ≦ 1w
Good results were shown in the range of t%. (Experimental Example 10) A blocking type electrophotographic photosensitive member was produced in the same manner as in Experimental Example 1 except that the content of Cu was changed as shown in Table 16, and then the same evaluation as in Experimental Example 4 was performed. Was. Table 16 also shows the results.

[0154]

[Table 16] As is clear from Table 16, 0.001 wt% ≦ Cu ≦ 1.
Good results were shown in the range of 0 wt%. (Experimental Example 11) Degreasing and washing were performed in the same manner as in Experimental Example 1 using aluminum in which the contents of Si, Fe, and Cu were changed as shown in Table 17. Then, Experimental Example 1
A blocking type electrophotographic photoreceptor equivalent to the above was produced, and the same evaluation as in Experimental Example 4 was performed. Table 17 also shows the results.

[0155]

[Table 17] As is clear from Table 17, the present invention is more effective in the range of 0.01 wt% <Si + Fe10Cu ≦ 1 wt%. (Experimental Example 12) Using a substrate equivalent to that of Experimental Example 1, changing the processing temperature and time under the conditions shown in Table 18 to change the film thickness of the coating. And the same evaluation was performed. Table 19 shows the results.

[0156]

[Table 18]

[0157]

[Table 19] (Experimental Example 13) Using the same substrate as in Experimental Example 1, changing the treatment temperature and time under the conditions shown in Table 20, forming a film under the conditions shown in Table 21, and the ratio of Al-Si-O at that time Was changed. Thereafter, a blocking type electrophotographic photosensitive member equivalent to that of Experimental Example 1 was prepared and evaluated. Table 2 also shows the results.
It is shown in FIG.

[0158]

[Table 20]

[0159]

[Table 21] As is clear from Table 21, good results were shown when Si was 0.1 or more and 0.5 or less and O was 1 or more and 5 or less. (Example 1) 0.03 wt% of Si and 0.05 w of Fe
The same procedure as an example of the procedure of the above-described method of manufacturing an electrophotographic photoreceptor according to the present invention is applied to a cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a thickness of 5 mm made of aluminum containing t% and 0.02 wt% of Cu. The surface of the substrate was degreased and cleaned (rinsed) under the conditions shown in Table 22 15 minutes after the completion of the cutting step. Then, using the deposited film forming apparatus shown in FIG.
A blocking type electrophotographic photosensitive member having a layer configuration shown in FIG. The Al—Si—O film at this time was 1: 0.2
The composition was 5: 3 and the film thickness was 75 °.

The electrophotographic characteristics of the electrophotographic photoreceptor thus prepared were evaluated as follows. However,
Ten photoconductors each manufactured under the same film forming conditions were evaluated.

[0161]

[Table 22]

[0162]

[Table 23] After observing and evaluating the appearance of the electrophotographic photoreceptor by visual inspection for film peeling, the process speed was set to 2 beforehand for experiments.
Arbitrarily changed in the range of 00 to 800 mm / sec, and a voltage of 6 to 7 kV is applied to the charger to perform corona charging;
After forming a latent image on the surface of the electrophotographic photoreceptor by laser image exposure at 788 nm, the image was transferred to a Canon copier NP6650, which was modified so that an image could be formed on transfer paper by a normal copying process. An evaluation was performed. Table 24 shows the results of these evaluations.

The image evaluation was performed by the following method. Further, as a comparative example 1, after processing by the method described in the conventional example 1, a blocking type electrophotographic photosensitive member equivalent to that of the example 1 was produced and evaluated by the same method as in the example 1, and the results are also shown in Table 24. . (Evaluation of black spots) The average density of an image obtained by changing the process speed and placing a full-length halftone original on a platen is 0.
Images were output to be 4 ± 0.1. Among the image samples obtained in this way, the most noticeable one was selected and evaluated. As a method of evaluation, these images were observed at a distance of 40 Cm from the eyes, and whether or not black spots were observed was evaluated according to the following criteria. A: No black spot is observed on any copy.・ ・ ・: Some black spots were observed. However, there was no problem at all. Δ: Black spots are observed on all copies. However, it is slight and does not hinder practical use. X: Large black spots are observed on all copies. (Evaluation of Electrophotographic Characteristics 1) The surface potential of the photosensitive member obtained at the developing position when the same charging voltage is applied at a normal process speed is evaluated as a relative value as charging ability. However, the charging ability of the electrophotographic photosensitive member obtained in Conventional Example 1 was 10
0%. (Evaluation of Electrophotographic Characteristics 2) After applying the same charging voltage at a normal process speed, light is irradiated and the light amount obtained when the potential drops to a certain potential is evaluated as a relative value as sensitivity. However, the charging ability of the electrophotographic photosensitive member obtained in Conventional Example 1 is set to 100%. (Evaluation of cost) ◎ ・ ・ ・ Can be manufactured inexpensively ○ ・ ・ ・ Same as conventional × ・ ・ ・ Increase in cost

[0164]

[Table 24] As is clear from Table 24, very good results were obtained, and an unexpected effect of improving electrophotographic properties was obtained. (Example 2) Table 25 shows the results of evaluation of a blocking type electrophotographic photosensitive member manufactured by the same method as in Example 1 using the same substrate as in Example 1 by the following method. Also, as a comparative example 2, after processing by the method shown in the conventional example 1, a blocking type electrophotographic photosensitive member was prepared and evaluated by the same method as in the example 1, and the results are shown in Table 25. (Image unevenness) The same method as in Experimental Example 1 (Evaluation of slip property) Using a piezo element by applying an arbitrary load to the plate, the force (= frictional force) by which the blade is pulled by the drum before and after the start of rotation of the drum is used. To detect. When the "maximum static friction coefficient" is calculated from the load and the maximum static friction force immediately before the start of rotation, and the "kinetic friction coefficient" is similarly calculated from the dynamic friction force during steady rotation, the values are compared with the relative value when Conventional Example 1 is set to 100%. (The lower the value, the better the slipperiness.) (Evaluation of white background fogging) Observation of an image sample obtained when a normal original consisting of a whole paper on a white background was copied on a platen, The fog on the white background was evaluated.・ ・ ・: Good.・ ・ ・: There is some fog. Δ: There is fogging over the entire surface, but there is no problem in character recognition. ×: Some parts are difficult to read due to fogging.

[0165]

[Table 25] As is clear from Table 25, good results were shown. (Example 3) Using the same substrate as in Example 1 and performing a surface treatment in the same manner as in Example 1, FIG.
The blocking type electrophotographic photosensitive member shown in FIG. 6-B was produced using the microwave plasma CVD apparatus shown in FIG. 4- (B) under the conditions shown in Table 26, and the results evaluated by the same method as in Example 1 were obtained. It is shown in Table 27. Further, as a comparative example 3, after processing by the method shown in the conventional example 1, a similar blocking type electrophotographic photoreceptor was produced and evaluated by the same method.
In FIG. 6B, 601, 602, 603, 604 and 605 indicate an aluminum substrate, a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer, respectively.

[0166]

[Table 26]

[0167]

[Table 27] As is clear from Table 27, the present invention is effective even if the device and the layer configuration are different. (Embodiment 4) After using the same substrate as in Embodiment 1 and performing the same surface treatment as in Embodiment 1, VHFPCVD shown in FIG.
A blocking type electrophotographic photosensitive member having a layer constitution shown in FIG. 6-B was prepared using the apparatus under the conditions shown in Table 28, and evaluated by the same method. As a result, the same good results as in Example 1 were obtained.

[0168]

[Table 28]

[0169]

As described above, according to the present invention, in the method of manufacturing an electrophotographic photoreceptor, the method includes the step of forming a functional film on an aluminum substrate by a plasma CVD method. In the process of cleaning the surface of the previous substrate, the liquid vaporized by the spray generator attached to the transporter at the time of transport is sprayed on the substrate to prevent thirst of the substrate, so that uniform high quality without cleaning stains It is possible to stably manufacture an electrophotographic photosensitive member that gives an image at low cost.

[Brief description of the drawings]

FIG. 1 is a schematic view illustrating an example of a cleaning apparatus used in a method of manufacturing an electrophotographic photosensitive member according to the present invention.

FIG. 2 is a schematic sectional view of a cleaning apparatus for cleaning a substrate by a conventional method.

FIG. 3 is a schematic longitudinal sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by an RF plasma CVD method. .

FIG. 4A is a schematic longitudinal sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by a microwave plasma CVD method, and FIG. 4B is a view in FIG. X-
It is X cross section.

FIG. 5 is a schematic vertical sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by a VHF plasma CVD method.

FIG. 6 is a cross-sectional view illustrating a layer configuration of an electrophotographic photosensitive member.

FIG. 7 is a schematic view showing a mechanism of the spray device.

[Explanation of symbols]

101, 201, 306, 406, 526, 601, 7
06 Substrate 102, 202 Processing unit 103, 203 Substrate transport mechanism 111, 211 Substrate loading table 121 Degreasing tank 131 Rinse tank 122, 132, 142 Cleaning liquid 141 Drying tank 151, 251 Substrate discharge table 161, 261 Transfer arm 162, 262 Movement Mechanism 163, 263 Chucking mechanism 164, 264 Air cylinder 165, 265 Transport rail 166 Spray mechanism 301, 401 Reaction vessel 302 Cathode electrode 303 Top plate 304 Base plate 305 Insulator 307 Base holder 308, 403, 523 Heater 309, 310 Raw material Gas introduction pipe 311 Source gas inflow valve 312, 528 Micro controller 313, 404, 524 Exhaust pipe 314 Exhaust valve 315 Vacuum exhaust device 316 High frequency power supply 402, 522, 529 Rotating motor 407 Discharge space 408 Source gas introduction tube and DC application electrode 409 DC power supply 410 Microwave introduction window 411 Waveguide 601 Aluminum substrate 602 Charge injection blocking layer 603 Photoconductive layer 604 Surface layer 701 Air supply Pipe 702 Spray treatment liquid 704 Spray liquid supply pipe 705 Spray nozzle 708 Vaporized liquid

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideaki Matsuoka 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc.

Claims (18)

[Claims] 1. A step of degreasing a substrate, a step of cleaning the substrate, a step of drying the substrate, and a function comprising an amorphous material having silicon atoms as a base material on the surface of the substrate. Forming a conductive film by a reduced pressure vapor phase epitaxy method, wherein between the degreasing step and the cleaning step, the surface of the substrate is not dried so as not to dry. A method for producing an electrophotographic photoreceptor, comprising a step of spraying a spray processing solution onto a substrate to perform a spray process. 2. A step of degreasing a substrate, a step of cleaning the substrate, a step of drying the substrate, and a function comprising an amorphous material containing silicon atoms as a base material on the surface of the substrate. Forming a conductive film by a reduced pressure vapor phase epitaxy method, wherein the surface of the substrate is transported while transporting the substrate from a location where the degreasing process is performed to a location where the cleaning process is performed. A method for producing an electrophotographic photoreceptor, comprising spraying a spray processing liquid onto the substrate so that the substrate does not dry. 3. The method according to claim 2, wherein the spraying process is performed by a spraying device provided in a mechanism for transporting the substrate. 4. The method according to claim 1, wherein the spray processing liquid is sprayed in a vaporized state. 5. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the spray processing liquid is sprayed in a state of being vaporized by ultrasonic waves. 6. The method according to claim 1, wherein the spray processing liquid is pure water, water containing carbon dioxide, or water containing an inhibitor. 7. The method for manufacturing an electrophotographic photoreceptor according to claim 1, wherein the cleaning treatment is performed using pure water, water containing carbon dioxide, or water containing an inhibitor. 8. The method according to claim 1, wherein the drying treatment is performed using pure water, water containing carbon dioxide, or water containing an inhibitor. 9. The method according to claim 1, wherein at least one of the degreasing treatment, the spraying treatment, the cleaning treatment, and the drying treatment is performed using water containing an inhibitor.
The method for producing the electrophotographic photosensitive member according to any one of the above. 10. The method for producing an electrophotographic photosensitive member according to claim 6, wherein said inhibitor is a silicate. 11. The method according to claim 10, wherein the silicate is a potassium silicate. 12. The method according to claim 6, wherein an inhibitor concentration of the water containing the inhibitor is 0.05% or more and 2% or less. 13. After the completion of the drying treatment, the surface of the base is made of Al, Si, and O as main components, and has a composition ratio of:
Al: Si: O = 1: a: b (0.1 ≦ a ≦ 1.0,1
≦ b ≦ 5), and a film having a thickness of 5 ° to 150 ° is formed. 14. The method according to claim 1, wherein the functional film contains hydrogen and / or fluorine and silicon and is formed by a plasma CVD method. 15. The method according to claim 15, wherein the base contains 0.001 wt% of Fe.
The method for producing an electrophotographic photoreceptor according to any one of claims 1 to 14, wherein the aluminum substrate contains at least 1 wt% or less. 16. The substrate according to claim 1, wherein said substrate contains 0.001 wt% of Si.
The method for producing an electrophotographic photoreceptor according to any one of claims 1 to 15, wherein the substrate is an aluminum substrate containing at least 1 wt% or less. 17. The method according to claim 1, wherein the base contains 0.001 wt% of Cu.
17. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the substrate is an aluminum substrate containing at least 1 wt% or less. 18. The substrate contains at least two of Fe, Si and Cu, and the total content thereof is 0.01
The method for producing an electrophotographic photoreceptor according to any one of claims 1 to 17, wherein the substrate is an aluminum substrate having a content of 1 wt% or more and 1 wt% or less.