JPH11143103A - Production of electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a producing method of an electrophotographic photoreceptor by which corrosion during processing a base body is prevented and an image of high quality without image defects and irregular image density can be obtd. SOLUTION: An aluminum base body is subjected to reduced pressure vapor growth method to form a functional film of an amorphous material on the surface of the base body. In this producing method of an electrophotographic photoreceptor, before the electrophotographic photoreceptor is formed, the surface of the base body is cleaned with a water containing an inhibitor of a specified component. The specified inhibitor used in the cleaning process is a silicate or potassium silicate, and the concn. of the inhibitor of the specified component in the water containing the inhibitor is adjusted to >=0.05% and <=2%.

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, practically, metal is often used to withstand photographic 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 has good workability, low cost,
It is one of the most suitable materials for a substrate of an electrophotographic photosensitive member because of its 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. Japanese Patent Application Laid-Open No. 61-231561 describes a method in which a rigid true sphere is naturally dropped and irregularities are formed on the surface of a metal support by the trace dents. Japanese Unexamined Patent Publication (Kokai) No. 61-95545 describes a method for forming irregularities using a liquid obtained by mixing polybutene and triethane (trichloroethane: C ₂ H ₃ Cl ₃ ). It is described that these techniques are effective in generating interference fringes on an image.

Japanese Patent Application Laid-Open No. 61-171798 discloses a method of processing a substrate before surface unevenness is disclosed in Japanese Unexamined Patent Publication (Kokai) No. 61-171798. A technique for obtaining an electrophotographic photoreceptor has been disclosed. After cutting in the publication, triethane (trichloroethane: C ₂ H ₃ Cl ₃ )
However, there is no mention of washing with water containing a specific inhibitor.

Further, 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 the base with water in which carbon dioxide is dissolved. However, there is no mention of washing with water containing a particular inhibitor.

Japanese Patent Application Laid-Open No. 61-273551 discloses S
When e is deposited on an aluminum substrate to produce an electrophotographic photoreceptor, pretreatment of the substrate includes alkali cleaning, trichlene cleaning, and UV irradiation cleaning with a mercury lamp. As a treatment, liquid degreasing cleaning, steam degreasing cleaning and pure water cleaning are performed to remove oils and fats adhering to the surface of the cylindrical aluminum substrate. Japanese Patent Application Laid-Open No. 63-264774 discloses that the surface of the substrate is water jetted. However, there is no description about washing with water containing a specific inhibitor.

Japanese Patent Application Laid-Open No. 1-130159 discloses a technique for cleaning an electrophotographic photosensitive member support with a water jet. In this publication, amorphous silicon is listed as an example of a photoconductor together with Se and an organic photoconductor, but there is no mention of a problem peculiar to the plasma CVD method.

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,
Amorphous deposited films such as amorphous silicon compensated with chlorine or the like have been proposed as high-performance, high-durability, pollution-free photoconductors, and some of them have been put to practical use. Japanese Patent Application Laid-Open No. 54-86341 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 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 a raw material gas by a microwave plasma CVD method is disclosed in Japanese Patent Application Laid-Open No. Sho 60/1985.
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. Sho 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 a 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 triethane. In some cases,
In order to prevent interference, the surface is finished to have a predetermined or arbitrary shape.

FIG. 8 shows a method of forming the uneven shape.
Are used to form a spherical trace depression as follows. For example, as shown in FIG. 8, the spherical trace depression 4 is formed by dropping the rigid true sphere 3 naturally from the position of the surface 2 and colliding with the surface 2. Further, if necessary, the hardness and the depression between the rigid true sphere and the surface of the metal body can be formed at a predetermined density.

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. No problems had occurred.

However, as in recent years, 1) high image quality of the electrophotographic apparatus has been demanded, and the resolving power of development has been improved accordingly. 2) As the speed of the copying machine has been increased and the charging conditions have become more severe, the portion on the surface where no potential is applied has substantially affected the peripheral potential.

In such a situation, a minute portion on which the electric charge is not applied, which has not been a problem in the past, has been pointed out as an image defect.

Further, in the past, copying was mainly used for originals consisting only of characters (so-called line copies), so that these image defects did not cause 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 an electrophotographic photosensitive member is charged, exposed, and developed by an electrophotographic process, particularly when a uniform image is formed in halftone, a slight potential difference on the surface of the electrophotographic photosensitive member also causes an image defect. And appear visually striking. In particular, microwave plasma CV
In the case of the electrophotographic photosensitive member prepared by the method D, the above-mentioned problem appears more remarkably.

On the other hand, such an image defect is more likely to be caused by an electrophotographic photosensitive member produced by plasma CVD than an Se electrophotographic photosensitive member produced by vacuum evaporation or an OPC electrophotographic photosensitive member produced by a blade coating method or a dipping method. It is particularly noticeable in the body.

Also, in a device manufactured by the plasma CVD method, a delicate difference in characteristics depending on a position on a substrate does not affect the performance as in a solar cell. In a device that can be repaired by post-processing, the above-described problem does not occur.

In the prior art, the step of cleaning the substrate is
The use of triethane did not pose a problem, but due to recent environmental problems, these chlorinated solvents cannot be used easily and have been replaced by aqueous cleaning. However, when the aluminum is washed with water, a portion of the aluminum surface partially exposed to impurities (such as Si) forms a local battery with the surrounding normal aluminum portion, thereby accelerating corrosion of the substrate surface. There was a problem of doing.

[0026]

SUMMARY OF THE INVENTION It is an object of the present invention to prevent corrosion at the time of processing a substrate in order to overcome the above-mentioned various problems in the conventional method of manufacturing an electrophotographic photosensitive member, and to provide a stable and inexpensive product with a good yield. An object of the present invention is to provide a method of manufacturing an electrophotographic photosensitive member which can be formed at high speed and is easy to use.

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

[0028]

The above object is achieved by the following means.

That is, the present invention provides an electrophotography in which an aluminum substrate is mounted on a substrate holder and a functional film made of an amorphous material containing silicon atoms as a base material is formed on the surface of the substrate by a reduced pressure vapor deposition method. In the method for producing a photoreceptor, a method for producing an electrophotographic photoreceptor, which comprises washing the surface of a substrate using water containing an inhibitor of a specific component before the step of forming an electrophotographic photoreceptor. It is proposed, said, that the specific inhibitor silicate used in the cleaning step, the specific inhibitor used in the cleaning step is potassium silicate, the specific component used in the cleaning step The concentration of the inhibitor of a specific component contained in the water containing the inhibitor is 0.05% or more and 2% or less, Forming a non-single-crystal deposited film containing one or both of hydrogen atoms and fluorine atoms and silicon atoms on an aluminum substrate by a plasma CVD method, wherein the aluminum substrate comprises: Fe + Si + Cu is an aluminum substrate containing more than 0.01 wt% and 1 wt% or less, and the aluminum substrate contains 10 ppm or more and 1 wt% of Fe.
%, An aluminum substrate containing 10 ppm or more and 1 wt% or less of Si, and an aluminum substrate containing 10 ppm or more and 1 wt% or less of Cu. Including.

According to the present invention, there is provided an electrophotographic photoreceptor in which an aluminum substrate is mounted on a substrate holder and a functional film made of an amorphous material containing silicon atoms as a base material is formed on the surface of the substrate by a reduced pressure vapor deposition method. In the method for producing a body, prior to the step of forming an electrophotographic photoreceptor, using water containing an inhibitor of a specific component, degreasing the surface of the substrate and forming irregularities due to a plurality of spherical trace depressions. The present invention proposes a method for manufacturing an electrophotographic photoreceptor, in which the irregularities are formed by depressions having substantially the same curvature and width, and the curvature R and the width D of the depressions are 0.035 ≦ D / A value satisfying R ≦ 0.5, and the width of the depression is 4 μ
00 μm or less, the inhibitor used in the step of forming unevenness is a silicate, the inhibitor used in the step of forming unevenness is potassium silicate, and a plurality of spherical traces on the surface of the base. After forming the irregularities due to the depressions, the surface of the substrate, a surfactant, pure water, water dissolved carbon dioxide, any of water containing an inhibitor of a specific component, or a combination of two or more, Washing the substrate, in a drying step in washing after forming irregularities due to a plurality of spherical trace depressions on the substrate surface, the surface of the substrate, hot pure water, hot pure water in which carbon dioxide is dissolved, an inhibitor of a specific component Any one of the hot pure water containing, or a combination of two or more kinds, pulls up and dries, and forms a functional film on the aluminum substrate. Step, the non-single-crystal deposited films containing either one or both silicon atoms of hydrogen atoms and fluorine atoms, including the step of forming on an aluminum substrate by a plasma CVD method, the aluminum substrate, F
e + Si + Cu is an aluminum substrate containing more than 0.01 wt% and 1 wt% or less; the aluminum substrate is an aluminum substrate containing 10 ppm or more and 1 wt% or less of Fe; and the aluminum substrate is 10 ppm or more of Si. An aluminum substrate containing not more than 1 wt%, wherein the aluminum substrate is C
This includes an aluminum substrate containing 10 ppm or more and 1 wt% or less of u.

[0031]

DETAILED DESCRIPTION OF THE INVENTION According to the study of the present inventors, the causes of image defects that occur when an aluminum substrate is used are: (A) dust on the substrate, dirt from the washing water in the washing and drying steps, and the like. That is the core. (B) The surface defects of the substrate become nuclei. Can be roughly divided into

(A) Adhering of dust and the like is to clean the place where the substrate is handled such as cutting and cleaning, and to strictly clean the inside of the film forming furnace and to clean the surface of the substrate immediately before forming the deposited film. Has made it possible to prevent it 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 present inventor has sought to solve all of these problems by combining a specific component-containing aluminum with a specific cleaning method and combining a specific component-containing aluminum with a specific surface unevenness processing method. As a result of intensive studies from the viewpoint, the present invention was completed.

According to the study of the present inventor, 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 became clear that the cause of (B) was that a part was cut off and a surface defect was formed on the aluminum substrate.

In order to prevent these phenomena, it is generally preferable that the amount of impurities contained in aluminum is small. But,
In the case of very high-purity aluminum, an oxide that is inevitably generated during melting for processing aluminum as a raw material into a substrate shape grows, and causes the above-described defects. In order to prevent this, it has been found that it is effective to include 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 cutting the surface of the substrate, the occurrence of image defects due to the surface properties of the substrate can be sufficiently prevented only by the above.

However, in recent years, these chlorine-based solvents cannot be used easily due to environmental problems, and the present inventors have also studied cleaning and surface unevenness processing. 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. It was also found that corrosion occurred not only in Si atoms but also in portions where Fe atoms and Cu atoms were locally large.

This phenomenon is more remarkable when the temperature of the water is higher, and is more remarkable when aluminum contains Si, Fe, and Cu atoms and 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 if a defect is slightly generated on a large-area substrate, a problem may occur. The use of the conventional corrosion inhibitor is limited because the corrosion inhibitor may adversely affect the formation of a functional film after cleaning and after surface unevenness processing.

However, in the substrate processing step before depositing the functional film on the substrate, the present inventor added some corrosion inhibitor to the water used for washing, and affected the subsequent functional film. As a result of intensive research focusing on the formation of a coating that does not affect the formation of the coating and the suppression of the occurrence of the above-mentioned defects, 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, potassium silicate added to water at the time of cleaning or potassium silicate added to the surface roughening treatment solution causes Al—
Since the Si—O film is formed, a local battery is not formed and the action of accelerating the corrosion is not performed, so that the corrosion is effectively prevented. In addition, by providing the Al—Si—O film, there is no defect on the surface of the substrate, so that the occurrence of abnormal growth from those 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 is performed in a process of decomposing a source gas in a gas phase, a process of transporting active species from a discharge space to a surface of the substrate, and a reaction in a surface of the substrate. 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 high-purity aluminum substrate is in a state where it is simply cleaned with a non-aqueous solvent such as trichloroethane after cutting, or in a state where only surface unevenness processing is performed with a non-aqueous solvent, or other cleaning after cutting. In the state where the cleaning with pure water is merely performed without performing the above, the 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, the reaction on the surface is as follows.
It is particularly strongly affected by the amount of water molecules left on the substrate surface. Due to this, depending on the amount of water adsorbed at the position of the substrate,
The composition and structure of the interface of the deposited film changes, and as a result, the charge injectability from the substrate in that portion changes during the electrophotographic process, and a difference in surface potential appears.

According to the present invention, before forming a functional film by the plasma CVD method, a uniform silicate is applied to the surface of the substrate with a silicate.
By forming an l-Si-O film, an interface through which good charge exchange can be performed when forming a deposited film can be formed. For this reason, it has become possible to improve the electrophotographic characteristics such as improvement of charging and reduction of photosensitivity.

In the present invention, a surfactant removes fats and oils and halogen-based residues which hinder the effect of the present invention completely during cleaning or surface roughening, and furthermore, a silicate prevents corrosion of the substrate surface. The above-mentioned effect is achieved by a method which has not heretofore been applied in which a film is formed.

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

Lathe with air damper for precision cutting (PNE)
UMO PRECLESION INC. Is set so that a rake angle of 5 ° with respect to the cylinder center angle is obtained. Next, the base was vacuum-chucked to the rotary flange of the lathe, and white kerosene was sprayed from the attached nozzle, and swarf was also sucked from the attached vacuum nozzle, with a peripheral speed of 1000 m / min and a feed speed of 0.1 m / min.
Mirror cutting is performed so that the outer shape becomes 108 mm under the condition of 01 mm / R.

The cut substrate is cleaned using the cleaning apparatus shown in FIG. The substrate cleaning apparatus includes a processing unit 102 and a substrate transport mechanism 103. The processing unit 102 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. Each of the pre-cleaning tank 121, the rinsing tank 131, and the drying layer 141 has 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. It consists of a cylinder 164.

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 in the surfactant 122 containing a surfactant or a silicate in the pre-cleaning tank 121 removes dusts and oils adhered to the surface.

Next, the substrate 101 is transferred to the rinsing tank 131 by the transfer mechanism 103, and further rinsed with pure water or the like maintained at a temperature of 25 ° C. Pure water and the like are constantly controlled by an industrial conductivity meter (trade name: α900R / C, manufactured by Horiba, Ltd.). Next, the base 101 is
03 to the drying tank 141 with hot pure water or the like,
Lifting and drying is performed by a lifting device (not shown) using hot pure water or the like maintained at a temperature of 0 ° C. The hot pure water and the like are controlled to be constant by an industrial conductivity meter (trade name: α900R / C, manufactured by HORIBA, Ltd.).

The substrate 101 after the drying step is carried by the carrying mechanism 103 to the carry-out stand 151. In some cases, the washed substrate may be processed to have an irregular surface of a predetermined shape or an arbitrary shape in order to prevent interference fringes.

Next, a deposited film mainly composed of amorphous silicon is formed on the cleaned substrate by the apparatus for forming a photoconductive member deposited film by the plasma CVD method shown in FIG. In FIG. 7, a reaction vessel 301 is composed of a base plate 304, a wall 302 also serving as a cathode electrode, and a top plate 303.
The base 306 on which the amorphous silicon deposition film is formed is provided at the center of the cathode electrode 302, and also serves as the anode electrode.

In order to form an amorphous silicon deposited film on the substrate 306 using this deposited film forming apparatus, first, the raw material gas inflow bubble 311 is closed, and the exhaust valve 31 is closed.
4 is opened, and the reaction vessel 301 is evacuated. Opening the raw material gas inlet valve 311 at the time the readings became about 5 × 10- ⁶ torr of vacuum gauge (not shown). The gas inflow is adjusted to a predetermined flow rate in the mass flow controller 312. For example, a source gas such as a SiH ₄ gas is caused to flow into the reaction vessel 301. Then, after confirming that the surface temperature of the base 306 is set to a predetermined temperature by the heater 308, a high frequency power supply (frequency: 13.56 MHz) 316
Is set to a desired power to cause glow discharge in the reaction vessel 301.

During the 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 first aspect of the present invention, the part of the aluminum surface partially exposed to Si, Fe, and Cu atoms forms a local battery with the surrounding ordinary aluminum part, and particularly in pure water or the like. Since corrosion is promoted, when a film is formed by adding a silicate, the film must be formed before the substrate comes into contact with pure water or the like. Since it is formed at an early stage, it is effective in the present invention even if a film is formed during washing with pure water or the like. That is, there are a method in which a silicate is contained in a surfactant of a substrate cleaning tank for degreasing cleaning after cutting, and a method in which a silicate is contained in pure water or the like of a rinse tank. Suitable for Further, when the film is formed as described above, the cleaning in the rinsing tank immediately after the film is formed or the cleaning in the drying tank may be performed using any of pure water, water in which carbon dioxide is dissolved, and water containing silicate. Alternatively, washing with a combination of two or more types is effective in the present invention.

Next, an example of a procedure for actually forming an electrophotographic photosensitive member by an electrophotographic photosensitive member manufacturing method according to the second invention of the present invention using an aluminum alloy cylinder as a base will be described with reference to FIG. This will be described below using the substrate surface unevenness processing device 3.

Lathe with air damper for precision cutting (PNE)
UMO PRECLESION INC. Is set so that a rake angle of 5 ° with respect to the cylinder center angle is obtained. Next, the base was vacuum-chucked to the rotary flange of the lathe, and white kerosene was sprayed from the attached nozzle, and swarf was also sucked from the attached vacuum nozzle, with a peripheral speed of 1000 m / min and a feed speed of 0.1 m / min.
Mirror cutting is performed so that the outer shape becomes 108 mm under the condition of 01 mm / R.

After the substrate has been cut, the surface of the substrate is treated by a substrate surface unevenness processing apparatus (FIG. 7). The substrate surface unevenness processing apparatus shown in FIG. 7 includes a liquid tank 76, a metal net barrel 72, a rigid true sphere 73, a processing liquid injection nozzle 74, and a shower nozzle 75.

After the cutting, the base 7 put into the barrel 72
1 is rotated together with the barrel 72 at a speed of about 30 rpm by a motor (not shown). At this time, the rigid true sphere 73 is lifted upward in the rotation direction by a plate provided in the barrel 72. Raised rigid true sphere 73
Is about 1 k from the natural drop and the processing liquid injection nozzle 74
The processing liquid having a pressure of g / cm ² is blown toward the substrate 71. The blown rigid true sphere 73 collides with the base 71 and forms irregularities on the base 71. The size, depth, and the like of the irregularities can be arbitrarily set according to the rotation speed, the processing liquid ejection pressure, the size of the rigid true sphere, the distance to the substrate, and the like.

The substrate 71 subjected to the surface unevenness treatment is washed with pure water or the like jetted from a shower nozzle 75. After that, it may be dried by a warm air mechanism (not shown),
As the cleaning method after the surface unevenness processing of the present invention, it is preferable to use the cleaning apparatus of FIG.

Since the mechanism of the cleaning device is the same as that of the first invention,
Description is omitted.

After the cutting, the same as the first invention, the loading table 111
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, the substrate 101 is transported to the rinsing tank 131 by the transport mechanism 103, and further rinsed with pure water or the like maintained at a temperature of 25 ° C. Pure water and the like are constantly controlled by an industrial conductivity meter (trade name: α900R / C, manufactured by Horiba, Ltd.). Next, the base 101 is
03 to the drying tank 141 with hot pure water or the like,
Lifting and drying is performed by a lifting device (not shown) using hot pure water or the like maintained at a temperature of 0 ° C. The hot pure water and the like are controlled to be constant 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 table 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 pretreatment by a photoconductive member deposited film forming apparatus by a plasma CVD method shown in FIG. Since the formation of the deposited film is the same as that of the first invention, the description is omitted.

In the second invention of the present invention, the surface of the substrate is
According to the present invention, the surface is treated to be mirror-finished, non-mirror-finished for the purpose of preventing interference fringes, etc., or irregularities of a desired shape are provided. For example, if the surface of the substrate is made non-mirror, or if the surface is roughened by providing irregularities, irregularities also occur on the surface of the photosensitive layer together with the irregularities on the surface of the substrate. A phase difference is generated in the reflected light, and interference fringes due to senior ring interference are generated, or black spots or streaks are generated during reversal development to cause image defects. Such a phenomenon is particularly noticeable when laser beam exposure, which is coherent light, is performed.

In the present invention, such interference fringes can be prevented by adjusting the curvature R and the width D of the spherical trace depression formed on the substrate surface. That is, when the surface-treated metal body of the present invention is used as a substrate, D / R is 0.03.
When the number is 5 or more, 0.5 or more nutrings due to the interference of the senior ring are present in each trace depression, and when the D / R is 0.055 or more, such a nutring is 1
Since there are more than one, the interference fringes of the entire photoconductive member can be dispersed in each of the trace depressions, and interference fringes can be prevented. Also, the width D of the trace depression is preferably 4 μm or more and 500 μm or less in the present invention, and it is desirable that the width D is equal to or less than the diameter of the light irradiation spot. Is desirable.

In the second aspect of the present invention, performing shower cleaning and hot-air drying after the surface unevenness processing is effective in achieving the effects of the present invention. In particular, cleaning using a cleaning apparatus is more effective. It is valid. The cleaning liquid and water used for these cleaning means may be cleaned by using any one of surfactant, pure water, water in which carbon dioxide is dissolved, water containing silicate, or a combination of two or more kinds. Suitable for

As a drying means in the case of using a washing apparatus, the present invention may employ hot pure water, warm pure water in which carbon dioxide is dissolved, warm pure water containing a specific inhibitor, or a combination of two or more kinds of the pull-up and drying methods. Suitable for

Inhibitors used in the washing step in the first invention of the present invention and the unevenness forming step in the second invention include phosphates, silicates, borates and the like, and any of them can be used. Is suitable. Among the silicates, potassium silicate, sodium silicate and the like can be mentioned, and any of them is possible. However, potassium silicate is suitable for the present invention.

The surfactant used in the washing step of the first invention of the present invention and the surfactant used in the washing step of the second invention include an anionic surfactant, a cationic surfactant and a nonionic surfactant. Any of surfactants, amphoteric surfactants, and mixtures thereof can be used. Among them, anionic surfactants such as carboxylate, sulfonate, sulfate ester salt and phosphate ester salt, and nonionic surfactants such as fatty acid ester are particularly effective in the present invention.

In the present invention, in the case of performing cleaning or surface unevenness processing, an aqueous method using a surfactant or a surfactant containing a silicate is preferred. In that case, the water quality before dissolving the surfactant and the silicate,
Either is possible, especially semiconductor grade pure water,
In particular, ultra LSI grade ultrapure water is desirable. Specifically, the lower limit of the resistivity at a water temperature of 25 ° C. is 1 MΩ−
cm or more, preferably 3MΩ-cm or more, optimally 5M
Ω-cm or more is suitable for the present invention. The upper limit 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, 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, the total viable count is 100 or less per milliliter, preferably 10
No more than one, optimally no more than one is suitable for the present invention. An amount of organic matter (TOC) of 10 mg or less per liter, preferably 1 mg or less, optimally 0.2 mg 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.

In the present invention, in the case of performing cleaning or surface unevenness processing, if the concentration of the silicate contained in the water containing the surfactant is too high, stains due to liquid traces may occur. This may cause 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. For this reason, the concentration of the silicate contained in the water containing the surfactant is 0.05% or more and 2% or less, preferably 0.1% or more and 1.5% or less, and most preferably 0.2% or less.
% Or more and 1% or less are suitable for the present invention.

The surfactant or surfactant in the cleaning of the first invention
If the temperature of the water of the surfactant containing the silicate is too high, spots due to the traces of the liquid are generated, which causes peeling of the deposited film and the like. 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 temperature of water is 10 ° C. or more and 90 ° C. or less, preferably 15 ° C.
Above, 70 ° C. or less, optimally 20 ° C. or more and 60 ° C. or less are suitable for the present invention.

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

If the pH of the silicate-containing surfactant is too high in the case of performing the cleaning of the first invention or in the case of performing the surface unevenness processing of the second invention, spots due to liquid traces are generated, This may cause 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 surfactant containing silicate
Is 8 or more and 12.5 or less, preferably 9 or more and 12 or less, optimally 10 or more and 11.5 or less.

The use of ultrasonic waves in the cleaning step of the first invention and in the cleaning step after the surface unevenness processing of the second invention is effective in achieving the effects of the present invention. The ultrasonic frequency is preferably 100 Hz or more and 10 MH or less, more preferably 1 kHz or more and 5 MHz or less, and most preferably 10 kHz or more and 100 kHz or less. The output of the ultrasound
Preferably 0.1 W / liter or more and 1 kW / liter or less, more preferably 1 W / liter or more and 100 W liter or less are effective.

In the washing step of the first invention of the present invention or the washing step after the surface treatment of the second invention, the quality of water used when using water in which carbon dioxide is dissolved is very important. Before the dissolution of carbon dioxide, semiconductor grade pure water, particularly ultra LSI grade ultrapure water, is desirable. Specifically, the lower limit is 1 MΩ as the resistivity at a water temperature of 25 ° C.
-Cm or more, preferably 3 MΩ-cm or more, optimally 5 MΩ-cm or more.
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).
-Cm or less, preferably 15 MΩ-cm or less, optimally 13 MΩ-cm or less is suitable for the present invention. As the amount of fine particles, 0.2 μm or more is 100 μm per milliliter.
00 or less, preferably 1000 or less, optimally 10
Zero or less are suitable for the present invention. As the amount of microorganisms,
A total viable count of 100 or less, preferably 10 or less, and optimally 1 or less per milliliter is suitable for the present invention. An amount of organic matter (TOC) of 10 mg or less per liter, preferably 1 mg or less, optimally 0.2 mg or less is 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, an ultraviolet sterilization method, and the like. It is desirable to increase the water quality to be used.

The present invention can be carried out 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.

Considering the quality and the like 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 carbon dioxide dissolved according to the present invention is 60% or less of the saturation solubility, more preferably 4%.
The condition is 0%.

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 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 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 surface of the substrate is washed with water obtained by dissolving carbon dioxide thus obtained, there are a method of washing by dipping and a method of spraying by applying water pressure.

In the case of cleaning by dipping, it is fundamental that the substrate is immersed in a water tank into which water in which carbon dioxide is dissolved is applied. At this time, an ultrasonic wave is 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 case of spraying, if the water pressure is too weak, the effect of the present invention is small, and if the water pressure is too strong, a pear-skin pattern is formed on the obtained image of the electrophotographic photosensitive member, particularly on a halftone image. Will occur. For this reason, the pressure of water is 2 kg · f / cm 2 or more and 300 kg · f / cm
2 or less, preferably 10 kg · f / cm 2 or more, 200
kg · f / cm2 or less, optimally 20 kg · f / cm2
As described above, 150 kg · f / cm 2 or less is suitable for the present invention. However, the pressure unit in the present invention is kg · f / cm2.
Means gravity kilograms per square centimeter and 1
kg · f / cm 2 is equal to 98066.5 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 in front of a 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 carbon 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.

The quality of water used when silicate-dissolved water is used in the cleaning step of the first invention of the present invention or the cleaning step after the surface unevenness processing of the second invention or in the shower of the surface unevenness processing pair Is very important, and in a state before dissolving the silicate, 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 or more, and most preferably 5 MΩ-cm or more. The upper limit of the resistance value is the theoretical resistance value (1
Any value up to 8.25 MΩ-cm) is possible, but from the viewpoint 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. I have. The amount of fine particles is 0.2
10,000 or less, preferably 1000 or less, and optimally 100 or less in 1 milliliter 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 (T
OC) is 10 mg or less, preferably 1 mg / liter.
mg or less, optimally 0.2 mg or less is 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. Temperature of water in which silicate is dissolved is 5 ° C or more, 90 ° C
Or less, preferably 10 ° C or more and 55 ° C or less, and most preferably 1 ° C or less.
5 ° C or more and 40 ° C or less are suitable for the present invention.

In the first invention of the present invention, when the cleaning is performed, or when the cleaning is performed after the surface unevenness processing according to the second invention, the concentration of the silicate-containing water is too high to cause the liquid trace. This causes stains, which may cause 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. For this reason, the concentration of water containing silicate is 0.05% or more and 2% or less, preferably 0.1% or more and 1.5% or less, and most preferably 0.2% or more.
Less than 1% is suitable for the present invention.

In the present invention, if the pH of the silicate-containing surfactant during cleaning is too high, spots due to liquid traces are generated, which causes peeling of the deposited film and the like. . 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, the pH of water containing silicate
Is 8 or more and 12.5 or less, preferably 9 or more and 12 or less, optimally 10 or more and 11.5 or less. When the substrate surface is washed with water obtained by dissolving the silicate thus obtained, the same method and time as in the case of dissolving the carbon dioxide are preferable. Second embodiment of the present invention
In the present invention, when performing a shower at the time of surface unevenness processing, when a surfactant containing a silicate is used for the unevenness treatment, the water contains pure water, water in which carbon dioxide is dissolved, and silicate. Any of water is possible, but in the case of a surfactant that does not contain silicate, the film is formed by using silicate-containing water for the shower.

In the cleaning step of the first invention of the present invention or the cleaning step after the surface unevenness processing of the second invention, the water quality when using pure water is very important.
In particular, ultra LSI grade ultrapure water is desirable. Specifically, the lower limit of the resistivity at a water temperature of 25 ° C. is 1 MΩ−
cm or more, preferably 3MΩ-cm or more, optimally 5M
Ω-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, it is 17 MΩ-c.
m or less, preferably 15 MΩ-cm or less, optimally 13 MΩ-cm or less.
MΩ-cm or less is suitable for the present invention. As for the amount of fine particles, 0.2 μm or more
No more than 1,000, preferably no more than 1,000, optimally no more than 100 are suitable for the present invention. As the amount of microorganisms, the total viable count is 100 or less per milliliter, preferably 1
0 or less, optimally 1 or less are suitable for the present invention.
The amount of organic matter (TOC) is 10 mg or less per liter,
Preferably 1 mg or less, optimally 0.2 mg 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 5 ° C or higher and 90 ° C or lower, preferably 10 ° C or higher and 55 ° C or lower, optimally 15 ° C or higher and 40 ° C or lower.
C. or less is suitable for the present invention.

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

In the drying step of the first invention of the present invention or the hot water drying of the second invention, the quality of water used when using water in which carbon dioxide is dissolved is very important. Before the dissolution of carbon dioxide, semiconductor grade pure water, particularly ultra LSI grade ultrapure water, is desirable. Specifically, the lower limit is 1 MΩ as the resistivity at a water temperature of 25 ° C.
-Cm or more, preferably 3 MΩ-cm or more, optimally 5 MΩ-cm or more.
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 1 MΩ-cm or less.
3 MΩ-cm or less is suitable for the present invention. As for the amount of fine particles, 0.2 μm or more
0 or less, preferably 1000 or less, optimally 100
No more than one is 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. An amount of organic matter (TOC) of 10 mg or less per liter, preferably 1 mg or less, optimally 0.2 mg 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 amount of carbon dioxide dissolved in water can be any amount up to the saturation solubility, but the present invention is possible. However, if the amount is too large, bubbles are generated when the water temperature fluctuates and adhere to the surface of the substrate, thereby causing a spot on the substrate. 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 and the like 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 carbon dioxide dissolved according to the present invention is 60% or less of the saturation solubility, more preferably 4%.
The condition is 0%.

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 / or less, more preferably. Is 6 μS / cm or more, 35 μS / cm or less, 8 μS / cm or more, 30 μS
/ Cm or less, the preferred range is 3.
8 or more and 6.0 or less, more preferably 4.0 or more and 5.
When the value is 0 or less, the effect is remarkable. Conductivity is measured by a conductivity meter or the like.
Use the value converted to.

The method of dissolving carbon dioxide in water may be any of a method using 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 at the time of pulling and drying is very important, and the preferable range is 100 mm / min or more, 2000 mm / min, more preferably 200 mm / min.
/ Min, optimally 300 mm / min or more, 1000
mm / min is suitable for the present invention.

If the time from the cleaning treatment with the water in which carbon dioxide is dissolved to the introduction into the deposited film forming apparatus is too long, the effect of the present invention is reduced, and if the time is too short, the process is not stable. 8 hours or less, preferably 2 minutes or more and 4 hours or less, optimally 3 minutes or more and 2 hours or less are suitable for the present invention.

In the drying step of the first invention of the present invention or the drying step after the surface unevenness processing of the second invention, the quality of water used when water containing a silicate is used is very important. Semiconductor-grade pure water before salt dissolution,
In particular, ultra LSI grade ultrapure water is desirable. Specifically, the lower limit of the resistivity at a water temperature of 25 ° C. is 1 MΩ−
cm or more, preferably 3MΩ-cm or more, optimally 5M
Ω-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, it is 17 MΩ-c.
m or less, preferably 15 MΩ-cm or less, optimally 13 MΩ-cm or less.
MΩ-cm or less is suitable for the present invention. As for the amount of fine particles, 0.2 μm or more
No more than 1,000, preferably no more than 1,000, optimally no more than 100 are suitable for the present invention. As the amount of microorganisms, the total viable count is 100 or less per milliliter, preferably 1
0 or less, optimally 1 or less are suitable for the present invention.
The amount of organic matter (TOC) is 10 mg or less per liter,
Preferably 1 mg or less, optimally 0.2 mg or less is suitable for the present invention.

Examples of the method for obtaining water of 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 the cleaning after the surface unevenness processing is performed, if the concentration of the silicate-containing water is too high, stains due to the traces of the liquid are generated, and the deposition of the deposited film or the like may occur. Cause. 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 water containing silicate is 0.05% or more and 2% or less, preferably 0.1% or more and 1.5% or less, and most preferably 0.2% or more.
More than 1% is suitable for the present invention.

In the present invention, if the pH of the silicate-containing water is too high when washing is performed after the surface unevenness processing, spots due to the traces of the liquid are generated, and the deposited film may be peeled off. Cause. 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, the pH of the water containing silicate is 8 or more and 12.5 or less, preferably 9 or more,
12 or less, optimally 10 or more and 11.5 or less are suitable for the present invention. When the substrate surface is washed with water obtained by dissolving the silicate thus obtained, the same method and time as in the case of dissolving the carbon dioxide are preferable.

In the drying step of the first invention of the present invention or the drying step after the surface unevenness processing of the second invention, the water quality when using pure water is very important, and pure water of semiconductor grade, especially ultra LSI Grade ultrapure water is preferred. Specifically, the lower limit is 1 MΩ as the resistivity at a water temperature of 25 ° C.
-Cm or more, preferably 3 MΩ-cm or more, optimally 5 MΩ-cm or more.
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 1 MΩ-cm or less.
3 MΩ-cm or less is suitable for the present invention. As for the amount of fine particles, 0.2 μm or more
0 or less, preferably 1000 or less, optimally 100
No more than one is 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. An amount of organic matter (TOC) of 10 mg or less per liter, preferably 1 mg or less, optimally 0.2 mg or less is suitable for the present invention.

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

The temperature of pure water is 30 ° C. or more, 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, the same method and time as in the case of dissolving the carbon dioxide are preferable. In the first invention and the second invention of the present invention, any material can be used as the material of the base as long as the base material is aluminum.
The aluminum base contains less than 10ppm of Si and 1wt%
The aluminum base contains less than 10ppm of Cu and 1wt%
Fe + Si + Cu exceeding 0.01 wt% and 1 w
Those containing t% or less are suitable for the present invention.

In the present invention, it is effective to include 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, in the present invention, H, Li, Na, K, B
e, Ca, Ti, Cr, Mn, Fe, Co, Ni, C
u, Ag, Zn, Cd, Hg, B, Ca, In, C, S
i, Ge, Sn, N, P, As, O, S, Se, F, C
It is effective to include any substance such as l, Br, I in aluminum.

In the present invention, the shape of the substrate is determined as desired. For example, when used for electrophotography, in the case of a continuous high-speed copying machine, an endless belt or a cylindrical shape as described above is used. 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 the body, the effect is remarkable.

In the case of a non-single-crystal photosensitive member containing silicon, silane (SiH
₄ ), disilane (Si ₂ H ₆ ), silicon tetrafluoride (SiF
₄ ), amorphous silicon forming raw material gas such as disilicon hexafluoride (Si ₂ F ₆ ), or a mixed gas thereof.

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

Further, the band gap width of the deposited film was changed.
Nitrogen (N_Two ),ammonia
(NH_Three ) And other elements containing a nitrogen atom, oxygen (O_Two ),one
Nitrogen oxide (NO), nitrogen dioxide (NO_Two ), Nitrous oxide
(N_Two O), carbon monoxide (CO), carbon dioxide (CO
_Two ) Such as methane (CH)_Four ), Ethane
(C_Two H₆ ), Ethylene (C_Two H_Four ), Acetylene (C
_Two H_Two ), Propane (C _Three H₈ ) And other hydrocarbons, tetrafluoride
Germanium (GeF_Four ), Nitrogen fluoride (NF_Three )
An elemental compound is a mixed gas of these.

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

In the present invention, the effect of the pressure in the discharge space during the deposition of the deposited film was recognized 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 wound heater of a sheath heater, a plate 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 the plasma can be any of DC, RF, microwave, etc. In particular, when the microwave is used for the energy for generating the plasma, abnormal growth due to surface defects of the substrate is caused. Appears remarkably, and the absorbed moisture absorbs the microphone mouth wave,
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, but the 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 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 reactor using a dielectric window, the dielectric window may be made of alumina (Al ₂ O ₃ ), aluminum nitride (AI).
N), boron nitride (BN), silicon nitride (SiN), silicon carbide (SiC), silicon oxide (Si 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 discharge space is surrounded by a plurality of substrates, 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 base is provided so as to surround a discharge space, and a microwave is introduced from at least one end of the base 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.

Hereinafter, the effects of the present invention will be specifically described with reference to experimental examples, but the present invention is not limited thereto.

Si is 0.05 wt% and Fe is 0.03 w
A cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a thickness of 5 mm made of aluminum having t% and Cu of 0.01 wt% is subjected to a procedure similar to the above-described example of the procedure of the method of manufacturing an electrophotographic photosensitive member according to the present invention. Surface cutting was performed. Fifteen minutes after the end of the cutting process, the detergent (nonionic surfactant) was used under the conditions shown in Table 1 by the surface treatment apparatus of the present invention shown in FIG.
, Rinsing and drying. At that time, the tank in which the inhibitor was placed was changed as shown in Table 3. (still:
As an inhibitor, potassium silicate was used, and 3 g / l was added to an aqueous surfactant solution to adjust the pH to 11.0. )

Next, an amorphous silicon deposited film was formed on the substrate subjected to the surface treatment under the conditions shown in Table 2 using the deposited film forming apparatus shown in FIG. A blocking type electrophotographic photosensitive member having the above configuration was produced. Figure 6
In A, 601, 602, 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 thus produced electrophotographic photosensitive member were evaluated as follows. The process speed of the prepared electrophotographic photoreceptor was set to 2 in advance for experiments.
A Canon copier, NP6060, which has been improved so that it can be arbitrarily changed within the range of 00 to 800 mm / sec, performs corona charging by applying a voltage of 6 to 7 kV to the charger, and performs a normal copying process. An image was prepared on a transfer paper, and a comprehensive evaluation of black spots and image defects and an environmental evaluation were performed. Table 3 also shows the results.

<Evaluation of Black Spots and Image Defects> An image sample having the most image defects among image samples obtained when the process speed is changed and the full-length halftone original and the character original are copied on the original platen is selected. An evaluation was performed. 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.

A: Good.・ ・ ・: There are some small defects but no problem at all. Δ: There are minute defects on the entire 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> ・ ・ ・: No substance relating to destruction of the ozone layer is used in the pretreatment step. ×: A substance related to destruction of the ozone layer is used in the pretreatment step.

[0146]

[Table 1]

[0147]

[Table 2]

[0148]

[Table 3] Note) ● indicates that the inhibitor was added, and-indicates that the inhibitor was not added. From Table 3, good results were obtained by adding the inhibitor in the surfactant or immediately after the surfactant.

<Comparative Experimental Example 1> Washing was performed in the same manner as in Experimental Example 1 except that the inhibitor was not used in the washing step. Thereafter, an inhibition type electrophotographic photosensitive member was manufactured in the same manner and the same evaluation was performed. Was performed. The results are shown in Comparative Experimental Example 1.
Are also shown in Table 3.

Conventional Example 1 A conventional substrate surface cleaning apparatus shown in FIG. 2 was prepared using the same substrate as in Experimental Example 1 and using a solution in which polybutene was dissolved in 1-1-1 trichloroethane under the conditions shown in Table 4. Table 4
Under the conditions described above, degreasing and washing were performed.

[0151]

[Table 4] The substrate cleaning apparatus shown in FIG. 2 includes a processing tank 202 and a substrate transport mechanism 203. The processing tank 202 includes a substrate loading table 211, a substrate cleaning tank 221, and a substrate unloading table 251. The cleaning tank 221 is provided with a temperature controller (not shown) for keeping the temperature of the liquid constant. Transport mechanism 203
Comprises a transfer rail 265 and a transfer arm 261. The transfer arm 261 has a moving mechanism 262 that moves on the rail 265 and a chucking mechanism 26 that holds the base 201.
3 and an air cylinder 264 for moving the chucking mechanism 263 up and down.

After cutting, the substrate 20 placed on the loading table 211
1 is transported to the cleaning tank 221 by the transport mechanism 203. Trichlorethane (trade name: Eterna VG, manufactured by Asahi Kasei Kogyo Co., Ltd.) 222 in the cleaning tank 221 performs cleaning for removing cutting oil and chips adhering to the surface.

After the cleaning, the substrate 201 is carried to the carry-out table 251 by the carrying mechanism 203.

Thereafter, an electrophotographic photosensitive member was manufactured in the same manner as in Experimental Example 1.

Table 3 shows the results of evaluation of the electrophotographic photosensitive member thus produced in the same manner as in Experimental Example 1 as Conventional Example 1.

Experimental Example 2 A blocking type electrophotographic photosensitive member was prepared on a substrate in the same manner as in Experimental Example 1, except that the rinsing and drying steps shown in Table 1 of Experimental Example 1 were used. Then, evaluation was performed in the same manner as in Experimental Example 1. Table 6 shows the results.

[0157]

[Table 5]

[0158]

[Table 6] As is clear from Table 6, good results can be obtained by adding an inhibitor in the surfactant or immediately after the surfactant using a combination of an aqueous solution of carbon dioxide and pure water in the washing (rinsing) step and the drying step. Was done.

Experimental Example 3 Using the same substrate as in Experimental Example 1, the type of silicate was changed as shown in Table 8 to be introduced when cleaning was performed by the method shown in Table 7. 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. Table 8 also shows the results.

[0160]

[Table 7]

[0161]

[Table 8] As is clear from Table 8, good results were obtained with any of the silicates, but the best results were obtained especially with potassium silicate.

Experimental Example 4 Using the same substrate as in Experimental Example 1, cleaning was performed under the same conditions as in Experimental Example 3 shown in Table 7. The concentration of the potassium silicate introduced at that time was changed as shown in Table 9, and the stained state was observed with the naked eye on the substrate surface after washing. Thereafter, a blocking type electrophotographic photoreceptor was manufactured in the same manner as in Experimental Example 1, and Experimental Example 1
Evaluation was performed in the same manner as described above. Table 9 also shows the results.

Appearance (stain) The light of strong exposure was reflected on the surface of the washed substrate, and stains on the substrate which could be visually confirmed were confirmed.

・ ・ ・: Good without any Δ: Very thin and no problem at all. X: clearly recognized.

[0165]

[Table 9] From the results in Table 9, the concentration of potassium silicate is 0.05% or more,
Good results were obtained in the range of 2.0 or less.

Experimental Example 5 Degreasing and washing were performed in the same manner as in Experimental Example 3 using aluminum in which the contents of Si, Fe and Cu were changed as shown in Table 10. Thereafter, a blocking type electrophotographic photosensitive member equivalent to that of Experimental Example 1 was manufactured, and the same evaluation as in Experimental Example 1 was performed. Table 10 also shows the results.

[0167]

[Table 10] As is clear from Table 10, 0.01 wt% <Si + Fe +
The present invention is effective even if the content of Cu, ≦ 1 wt% changes.

Experimental Example 6 An inhibition type was prepared in the same manner as in Experimental Example 4 except that Fe was fixed at 0.003 wt% and Cu was fixed at 0.006 wt%, and the content of Si was changed as shown in Table 11. An electrophotographic photoreceptor was prepared and evaluated in the same manner. Table 1 also shows the results.
It is shown in FIG.

[0169]

[Table 11] As is clear from Table 11, good results were obtained in the range of 0.001 ≦ Si ≦ 1.0.

Experimental Example 7 Inhibition type electrons were produced in the same manner as in Experimental Example 5 except that Si was fixed at 0.005 wt% and Cu was fixed at 0.004 wt%, and the Fe content was changed as shown in Table 12. A photographic photoreceptor was prepared and evaluated in the same manner. Table 12 also shows the results.

[0171]

[Table 12] As is clear from Table 12, good results were obtained in the range of 0.001 ≦ Fe ≦ 1.0.

Experimental Example 8 An inhibition type was performed in the same manner as in Experimental Example 4 except that the content of Cu was changed as shown in Table 13 while fixing Si at 0.006 wt% and Fe at 0.003 wt%. An electrophotographic photoreceptor was prepared and evaluated in the same manner. Table 1 also shows the results.
3 is shown.

[0173]

[Table 13] As is clear from Table 13, good results were obtained in the range of 0.001 ≦ Cu ≦ 1.0.

Experimental Example 9 A rigid sphere made of SUS stainless steel having a diameter of 2 mm was used, and an aluminum substrate (diameter of 108) was formed by using the apparatus of the present invention shown in FIG.
(mm, length 358 mm) was treated to form irregularities.

When the relationship between the diameter R 'of the true sphere, the drop height h, the curvature R of the trace dent, and the width D was examined, the curvature R of the trace dent and the width D were determined.
Has been confirmed to be determined by conditions such as the diameter R 'of the true sphere and the drop height h. In addition, it was confirmed that the pitch of the trace dents (density of the trace dents and the pitch of the irregularities) can be adjusted to a desired pitch by controlling the rotation speed of the cylinder, the rotational dispersion, or the amount of fall of the rigid true sphere. Was done.

Experimental Example 10 A diameter of 108 m made of aluminum containing 0.05 wt% of Si, 0.03 wt% of Fe, and 0.01 wt% of Cu.
The surface of a cylindrical substrate having a length of 358 mm, a length of 358 mm, and a thickness of 5 mm was cut in the same manner as in the above-described example of the method of manufacturing the electrophotographic photosensitive member according to the present invention.

Fifteen minutes after the completion of the cutting step, degreasing was performed with a detergent (nonionic surfactant) containing an inhibitor under the conditions shown in Table 14 by the surface treatment apparatus of the present invention shown in FIG. Was changed to form irregularities. Thereafter, washing with an aqueous system was performed. Note that D in the support of the light-receiving member was 500 μm, and the inhibitor used for degreasing and forming irregularities was 3 g / l in an aqueous surfactant solution, and the pH was 11.0.

At that time, for each surface-treated substrate, surface defects (streak-like flaws, etc.) occurring in the surface treatment were inspected visually and by a metallographic microscope. Table 16 shows the results.

Next, an amorphous silicon deposited film was formed on the substrate subjected to the surface treatment under the conditions shown in Table 15 using the deposited film forming apparatus shown in FIG.
A blocking type electrophotographic photosensitive member having the layer configuration shown in (A) was prepared. In FIG. 6A, 601, 602, 603 and 6
04 is an aluminum substrate, a charge injection blocking layer,
3 shows a photoconductive layer and a surface layer.

The electrophotographic characteristics of the thus produced electrophotographic photosensitive member were evaluated as follows. The process speed of the prepared electrophotographic photoreceptor was set to 2 in advance 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 photosensitive member by laser image exposure at 788 nm, a Canon copier, NP6650, which was modified so as to be able to produce an image on transfer paper by a normal copying process, was inserted into an interference fringe. Comprehensive evaluation of black spots and image defects and evaluation of environmental properties were performed.

<Evaluation of Interference Fringes, Black Spots, and Image Defects> An image in which most image defects appear in image samples obtained when the process speed is changed and an entire halftone original and a character original are copied on a platen. A sample was selected and evaluated. 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.

A: Good.・ ・ ・: There are some small defects but no problem at all. Δ: There are minute defects on the entire 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> ・ ・ ・: No substance relating to destruction of the ozone layer is used in the pretreatment step. X: A substance related to destruction of the ozone layer is used in the pretreatment step.

[0184]

[Table 14]

[0185]

[Table 15]

[0186]

[Table 16] Good results were obtained in the range of 0.035 ≦ D / R ≦ 0.5.

Conventional Example 2 The unevenness forming step was performed by changing polybutene to 1-
Using a solution dissolved in 1-1 trichloroethane, irregularities were formed on the D / R in the same manner as in Experimental Example 10. Thereafter, the substrate was degreased and cleaned by the conventional substrate surface cleaning apparatus shown in FIG. 2 under the conditions shown in Table 17. The substrate cleaning apparatus shown in FIG. 2 includes a processing tank 202 and a substrate transport mechanism 203. The processing tank 202 includes a substrate loading table 211, a substrate cleaning tank 221, and a substrate unloading table 251. Cleaning tank 2
21 has a temperature controller (not shown) for keeping the temperature of the liquid constant. The transport mechanism 203 is a transport rail 2
65 and the transfer arm 261.
Is a moving mechanism 262 that moves on the rail 265,
01, and an air cylinder 264 for moving the chucking mechanism 263 up and down.

After cutting, the substrate 20 placed on the loading table 211
1 is transported to the cleaning tank 221 by the transport mechanism 203. Trichlorethane (trade name: Eterna VG, manufactured by Asahi Kasei Kogyo Co., Ltd.) 222 in the cleaning tank 221 performs cleaning for removing cutting oil and chips adhering to the surface.

After the cleaning, the substrate 201 is carried to the carry-out table 251 by the carrying mechanism 203.

Thereafter, an electrophotographic photosensitive member was manufactured in the same manner as in Experimental Example 10.

Table 16 shows the results of evaluation of the electrophotographic photosensitive member thus produced in the same manner as in Experimental Example 10 as Conventional Example 2.

[0192]

[Table 17] * A treatment solution in which 5% of polybutene was dissolved.

Experimental Example 11 The same substrate as in Experimental Example 10 was used.
As shown in Table 18, the width D of the spherical trace depression
Was changed. Thereafter, a blocking type electrophotographic photosensitive member was formed on a substrate in the same manner as in Experimental Example 10 and evaluated in the same manner. Table 18 also shows the results.

[0194]

[Table 18] As is clear from Table 18, good results were obtained in the range of 4 μm ≦ D ≦ 500 μm.

Experimental Example 12 The same substrate as in Experimental Example 10 was used, and when D / R = 0.056 in the degreasing and unevenness forming steps equivalent to those in Experimental Example 10, the inhibitor used was changed. Experimental example 1
A blocking type electrophotographic photosensitive member similar to that of Comparative Example No. 0 was produced, and the same evaluation was performed. Table 19 shows the results. In addition, the inhibitor was adjusted to 3 g / l with respect to the surface active aqueous solution, and the pH was set to 10.5 in each case.

[0196]

[Table 19] As is clear from Table 19, good results were obtained with any of the silicates, but the best results were obtained especially with potassium silicate.

EXPERIMENTAL EXAMPLE 13 Using the same substrate as in Experimental Example 10, the area containing potassium silicate was changed as shown in Table 20 in the step of combining cleaning (rinsing) in the same apparatus as degreasing and forming irregularities. Was.

Thereafter, a water-based washing was performed to form a blocking type electrophotographic photosensitive member equivalent to that of Experimental Example 10, and the same evaluation was performed. Table 20 shows the results. However, the surfactant in the table indicates a nonionic surfactant, and as an inhibitor, potassium silicate was introduced at a rate of 3 g / l to the treatment solution and the pH was adjusted to 1
0.8. D / R = 0.056.

[0199]

[Table 20] Comparative Experimental Example 2 On a substrate equivalent to that of Experimental Example 13, a detergent (surfactant) containing no potassium silicate was used in the degreasing and unevenness forming steps, and then 10 μS carbon dioxide was used in the cleaning (rinsing) step in the same apparatus. A blocking type electrophotographic photosensitive member was formed in the same manner as in Experimental Example 13 except that an aqueous solution was used, and the same evaluation was performed. The results are similarly shown in Table 20 as Comparative Experimental Example 2.

Comparative Experimental Example 3 On a substrate equivalent to that of Experimental Example 13, a detergent (surfactant) containing no potassium silicate was used in the degreasing and unevenness forming steps, and then 10 MΩ was used in the cleaning (rinsing) step in the same apparatus. -C
A blocking type electrophotographic photosensitive member was formed in the same manner as in Experimental Example 13 except that m of pure water was used, and the same evaluation was performed. The results are similarly shown in Table 20 as Comparative Example 3.

As described above, it has been found that the present invention is effective when potassium silicate is used in any of the steps of degreasing and forming unevenness, or washing (rinsing) in the same apparatus as forming unevenness.

Experimental Example 14 Using the same substrate as in Experimental Example 10, under the conditions shown in Table 21, degreasing, forming unevenness, and washing (rinsing) were performed. Thereafter, cleaning (rinsing / drying) was performed using the cleaning apparatus shown in FIG. 1 under the conditions shown in Table 22 to form a blocking type electrophotographic photosensitive member in the same manner as in Experimental Example 10, and the same evaluation was performed. . The results are also shown in Table 22. Note that D / R = 0.
053, the inhibitor in Table 22 was set to 3 g / l with respect to the treatment solution, and the pH was set to 11.

[0203]

[Table 21]

[0204]

[Table 22] As is clear from Table 22, the subsequent cleaning (rinsing and drying) is performed by using potassium silicate in the degreasing and unevenness forming steps.
The present invention is effective under any conditions in the process.

Experimental Example 15 Degreasing and forming of irregularities were performed in the same manner as in Experimental Example 14. Thereafter, a step of performing ultrasonic treatment using a surfactant was provided before the step of performing cleaning (rinsing / drying) under the conditions shown in Table 22 of Experimental Example 14 to perform cleaning. As a result, an effect equivalent to that of Experimental Example 14 was obtained under any conditions.

EXPERIMENTAL EXAMPLE 16 Using aluminum in which the contents of Si, Fe and Cu were changed as shown in Table 25, degreasing, forming unevenness and washing (rinsing) were performed under the conditions shown in Table 23. The cleaning was performed under the conditions shown in Table 24. Thereafter, a blocking type electrophotographic photosensitive member equivalent to that of Experimental Example 10 was manufactured, and the same evaluation as that of Experimental Example 10 was performed. Incidentally, the pH of the treatment liquid into which the inhibitor was introduced was set to 11. The results are also shown in Table 25.

[0207]

[Table 23]

[0208]

[Table 24]

[0209]

[Table 25] As is clear from Table 25, 0.01 wt% <Si + Fe +
The present invention is effective even if the content of Cu ≦ 1 wt% changes.

Experimental Example 17 A blocking electron was produced in the same manner as in Experimental Example 16 except that the content of Si was changed to 0.005 wt% of Fe and 0.004 wt% of Cu as shown by the fixed index 25. A photographic photoreceptor was prepared and evaluated in the same manner. The results are also shown in Table 26.

[0211]

[Table 26] As is clear from Table 26, good results were obtained in the range of 0.001 ≦ Si ≦ 1.0.

Experimental Example 18 A blocking electron was produced in the same manner as in Experimental Example 16 except that the content of Fe was changed as shown in Table 27 while fixing Si at 0.004 wt% and Cu at 0.005 wt%. A photographic photoreceptor was prepared and evaluated in the same manner. Table 27 also shows the results.
Shown in

[0213]

[Table 27] As is clear from Table 27, good results were shown in the range of 0.001 ≦ Fe ≦ 1.0.

Experimental Example 19 An inhibition type was prepared in the same manner as in Experimental Example 16 except that the content of Cu was changed as shown in Table 28 while fixing Si at 0.004 wt% and Fe at 0.005 wt%. An electrophotographic photoreceptor was prepared and evaluated in the same manner. The results are also shown in Table 28.

[0215]

[Table 28] As is clear from Table 28, good results were shown in the range of 0.001 ≦ Cu ≦ 1.0.

[0216]

<Example 1> A cylindrical substrate made of aluminum containing 0.06 wt% of Si, 0.02 wt% of Fe, and 0.02 wt% of Cu, having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, The surface is cut by the same procedure as the above-described example of the method of manufacturing the electrophotographic photoreceptor according to the present invention, and after 15 minutes from the end of the cutting step, the cleaning apparatus shown in FIG. After doing
Using the deposited film forming apparatus shown in FIG. 3, a blocking type electrophotographic photosensitive member having the layer configuration shown in FIG.

The evaluation of the electrophotographic characteristics of the electrophotographic photosensitive member thus prepared was performed as follows. However,
Ten photoconductors each manufactured under the same film forming conditions were evaluated.

[0218]

[Table 29]

[0219]

[Table 30] 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;
The copying machine NP6060 manufactured by Canon Inc. was placed in a copying machine modified for experiment, and an image was formed on transfer paper by a normal copying process, and the image quality was evaluated. Table 31 shows the results of these evaluations. Image evaluation was performed by the following method. Further, as a comparative example 1, after processing by the method shown 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.
It is shown in FIG.

[Evaluation of Image Defects] An image sample having the most image defects among image samples obtained when the process speed is changed and a halftone original and a character original are placed on an original plate and copied is evaluated. Was. 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.

A: Good.・ ・ ・: There are some minute white spots. Δ: There are minute white spots on the entire surface, but there is no problem in character recognition. X: Some characters are difficult to read due to many white spots.

[Evaluation of Black Spots] The process speed was changed and an image was output such that the average density of the image obtained by placing the entire halftone original on the platen was 0.4 ± 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 to check whether black spots were observed, and 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 photoconductor obtained at the developing position when the same charging voltage is applied at a normal process speed is evaluated as a charging ability by a relative value. However, the charging ability of the electrophotographic photosensitive member obtained in Conventional Example 1 is set to 100%.

[Evaluation of Electrophotographic Characteristics 2] After applying the same charging voltage at a normal process speed, irradiating light and lowering the potential, a light amount obtained 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%.

[0226]

[Table 31] As is clear from Table 31, very good results were obtained, and an unexpected effect of improving the electrophotographic properties was obtained.

Example 2 Table 32 shows the results of evaluation of the inhibition type electrophotographic photosensitive member produced by the same method as in Example 1 using the same substrate as in Example 1 by the following method. Further, as a comparative example 2, after processing by the method shown in the conventional example 1, a blocking type electrophotographic photoreceptor was prepared and evaluated by the same method as in the example 1, and the result is shown in Table 32.

[Evaluation of Image Unevenness] A3 grid paper (manufactured by KOKUYO Co., Ltd.) was placed on a platen of a copying machine, and the exposure of the document was changed by changing the aperture of the copying machine. Was changed to obtain an image in a range up to the point at which fogging starts, and ten copies with different densities were output. These images were observed at a distance of 40 cm from the eyes to see if there was any difference in density, and evaluated according to the following criteria.

A: No image unevenness is observed on any copy.・ ・ ・: There is a copy in which image unevenness is recognized and a copy in which 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. X: Large black spots are observed on all copies.

[Evaluation of fog on white background] An image sample obtained when a normal original composed of characters on a white background was copied on a platen was observed, and the fog on the white background was evaluated.

A: 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 fog.

[0232]

[Table 32] As is clear from Table 32, good results were obtained.

Example 3 Using the same substrate as in Example 1 and performing a surface treatment in the same manner as in Example 1,
A blocking type electrophotographic photosensitive member shown in FIG. 6-B was prepared using the μw PCVD apparatus shown in FIGS. 4A and 4B under the conditions shown in Table 33, and evaluated by the same method as in Example 1. The results are shown in Table 34. 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.
Note that in FIG. 6- (B), 601, 602, 603-1,
Reference numerals 603-2 and 604 denote an aluminum substrate, a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer, respectively.

[0234]

[Table 33]

[0235]

[Table 34] As apparent from Table 34, the present invention is effective even if the device and the layer configuration are different.

<Example 4> Using the same substrate as in Example 1 and performing the same surface treatment as in Example 1, the VHFPCVD apparatus shown in FIG. 5 was used and the layers shown in FIG. A blocking type electrophotographic photosensitive member having the above configuration was prepared and evaluated by the same method. As a result, the same good results as in Example 1 were obtained.

[0237]

[Table 35]

Example 5 Si was 0.05 wt%, Fe
Of a cylindrical substrate made of aluminum containing 0.03 wt% of Cu and 0.02 wt% of Cu, having a diameter of 108 mm, a length of 358 mm, and a thickness of 5 mm, and an example of the procedure of the above-described method of manufacturing an electrophotographic photosensitive member according to the present invention. The surface was cut in the same manner, and 15 minutes after the end of the cutting step, the surface of the base was degreased, formed with irregularities, and washed (rinse) with the conditions shown in Table 36 using the unevenness forming apparatus shown in FIG. Then, after performing a cleaning process under the conditions shown in Table 37, the blocking type electron-emitting device having the layer configuration shown in FIG. A photoreceptor was prepared.

The evaluation of the electrophotographic characteristics of the electrophotographic photosensitive member thus prepared was performed as follows. However,
Ten photoconductors each manufactured under the same film forming conditions were evaluated.

[0240]

[Table 36]

[0241]

[Table 37]

[0242]

[Table 38] 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 39 shows the results of these evaluations. Image evaluation was performed by the following method. Also, as a comparative example 4, after processing by the method shown in the conventional example 2, a blocking type electrophotographic photosensitive member equivalent to that of the example 5 was produced and evaluated by the same method as in the example 5, and the results are shown in Table 39. .

[Evaluation of Image Defects] An image sample having the most image defects among image samples obtained when the process speed is changed and a full-tone halftone document and a character document are placed on a platen and copied is evaluated. Was. 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.

A: Good.・ ・ ・: There are some minute white spots. Δ: There are minute white spots on the entire surface, but there is no problem in character recognition. X: Some characters are difficult to read due to many white spots.

[Evaluation of Black Spots] The process speed was changed and an image was output such that the average density of the image obtained by placing the full-face halftone original on the platen was 0.4 ± 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 to check whether black spots were observed, and 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 a charging ability. However, the charging ability of the electrophotographic photosensitive member obtained in Conventional Example 2 is set to 100%.

[Evaluation of Electrophotographic Characteristics 2] After applying the same charging voltage at a normal process speed, the light quantity obtained when the light is applied and the potential drops to a certain level 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] A: It can be manufactured at low cost.・ ・ ・: Same as before. ×: Cost increases.

[0250]

[Table 39] As is clear from Table 39, very good results were obtained, and an unexpected effect of improving electrophotographic properties was obtained.

Example 6 Using the same substrate as in Example 5, a blocking type electrophotographic photosensitive member manufactured by the same method as in Example 5 was evaluated by the following method. Show. Further, as a comparative example 5, after processing by the method shown in the conventional example 2, a blocking type electrophotographic photosensitive member was prepared and evaluated by the same method as in the example 5, and the results are shown in Table 40.

[Evaluation of slipperiness] An arbitrary load is applied to the plate, and a piezo element is used to detect the force of pulling the blade before and after the rotation of the drum = frictional force. From the load and the “maximum static friction force” immediately before the start of rotation, the “maximum static friction coefficient” is similarly calculated as “dynamic friction force” during steady rotation.
100% compared to Conventional Example 2 when the “dynamic friction coefficient” was calculated from
(The lower the value, the better the slipperiness)

[Evaluation of Image Unevenness] A3 grid paper (manufactured by KOKUYO Co., Ltd.) was placed on a platen of a copier, and the aperture of the copier was changed. Was changed to obtain an image in the range up to the point where fogging starts, and ten copies with different densities were output. These images were observed at a distance of 40 cm from the eyes to see if there was any difference in density, and evaluated according to the following criteria.

A: Image unevenness is not recognized 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. X: Large black spots are observed on all copies.

[Evaluation of Fog on White Background] An image sample obtained when a normal original consisting of characters on the entire surface was placed on a platen and copied on a white background was observed, and the fog on the white background was evaluated.

A: 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 fog.

[0257]

[Table 40] As is clear from Table 40, good results were obtained.

<Example 7> Using the same substrate as in Example 5 and performing a surface treatment in the same manner as in Example 5,
Using the μw PCVD apparatus shown in FIGS. 4A and 4B, the blocking type electrophotographic photosensitive member shown in FIG. 6B was produced under the conditions shown in Table 41, and evaluated by the same method as in Example 5. The results obtained are shown in Table 42. Also, as a comparative example 6, after processing by the method shown in the conventional example 2, the same blocking type electrophotographic photoreceptor was produced and evaluated by the same method. Note that in FIG. 6B, 601, 602, 603-
Reference numerals 1, 603-2, and 604 respectively indicate an aluminum substrate, a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer.

[0259]

[Table 41]

[0260]

[Table 42] As is clear from Table 42, the present invention is effective even if the device and the layer configuration are different.

<Embodiment 8> Using the same substrate as in Embodiment 5 and performing the same surface treatment as in Embodiment 5, using the VHFPCVD apparatus shown in FIG.
A blocking type electrophotographic photosensitive member having the layer constitution shown in (A) was prepared and evaluated by the same method. As a result, the same good results as in Example 5 were obtained.

[0262]

[Table 43]

[0263]

As described above, according to the first aspect of the present invention, there is provided an electrophotographic photosensitive member manufacturing method including a step of forming a functional film on an aluminum substrate by a plasma CVD method. Before the step of forming the deposited film, the surface of the substrate is washed with water containing a specific inhibitor, so that the surface of the substrate is cleaned, thereby making it possible to reduce the cost of the electrophotographic photoreceptor that provides a uniform high-quality image. It can be manufactured stably.

According to a second aspect of the present invention, there is provided an electrophotographic photoreceptor manufacturing method including a step of forming a functional film on an aluminum substrate by a plasma CVD method, the method comprising the steps of: Electrophotography that provides a uniform high-quality image by degreasing the surface of the substrate and forming irregularities due to multiple spherical trace depressions using water containing a surfactant and a specific inhibitor on the surface of the substrate The photosensitive member can be stably manufactured at low cost.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a cleaning apparatus used to implement an electrophotographic photosensitive member of the present invention.

FIG. 2 is a schematic longitudinal sectional view of a cleaning apparatus for cleaning a substrate in 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 vertical 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 sectional view of FIG. ) X
It is -X cross-sectional view.

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. 6A is a cross-sectional view illustrating an example of a layer configuration of the electrophotographic photoreceptor, and FIG. 6B is a cross-sectional view illustrating another example of the layer configuration of the electrophotographic photoreceptor.

FIG. 7 is a schematic view of a concavo-convex forming apparatus used for carrying out the method of manufacturing an electrophotographic photoreceptor of the present invention.

FIG. 8 is a schematic diagram for explaining the shape of irregularities on the surface of a metal body according to the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Surface treatment metal body 2 Surface 3 Rigid true sphere 4 Spherical trace recess 71,101,201,306,406,526 Base 72 Barrel 73 Rigid true sphere 74 Nozzle 75 Shower nozzle 76 Liquid tank 102,202 Processing part 103,203 Base Transport mechanism 111, 211 Substrate loading table 121, 221 Cleaning layer 131 Rinse layer 122, 132, 142 Cleaning liquid 141 Dry layer 151, 251 Substrate discharge table 161, 261 Transport arm 162, 262 Moving mechanism 163, 263 Chucking mechanism 164, 264 Air cylinder 165, 265 Transfer rail 301 Reaction vessel 302 Cathode electrode 303 Top plate 304 Base plate 305 Insulation insulator 307 Base holder 308, 403, 523 Heater 309, 310 Source gas introduction pipe 3 1 Source gas inflow valve 312, 528 Maslow controller 313, 404, 524 Exhaust pipe 314 Exhaust valve 315 Vacuum exhaust device 316 High frequency power supply 402, 522, 529 Rotation motor 407 Discharge space 408 Source gas introduction pipe 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 603-1 Charge transport layer 603-2 Charge generation layer 604 Surface layer

Claims (18)

[Claims] 1. Production of an electrophotographic photoreceptor in which an aluminum substrate is mounted on a substrate holder and a functional film made of an amorphous material having silicon atoms as a base material is formed on the surface of the substrate by a reduced pressure vapor deposition method. In the method, prior to the step of forming the electrophotographic photoreceptor, the surface of the substrate is washed using water containing an inhibitor of a specific component. 2. The method according to claim 1, wherein the specific inhibitor used in the washing step is a silicate. 3. The method according to claim 2, wherein the specific inhibitor used in the washing step is potassium silicate. 4. The method according to claim 1, wherein the concentration of the inhibitor of the specific component contained in the water containing the inhibitor of the specific component used in the washing step is 0.05% or more and 2% or less. The method for producing the electrophotographic photosensitive member according to the above. 5. The step of forming a functional film on an aluminum substrate includes the step of: depositing a non-single-crystal deposited film containing one or both of hydrogen atoms and fluorine atoms and silicon atoms on an aluminum substrate by a plasma CVD method. The method for producing an electrophotographic photosensitive member according to claim 1, further comprising a step of forming the photosensitive member. 6. Production of an electrophotographic photoreceptor in which an aluminum substrate is mounted on a substrate holder and a functional film made of an amorphous material containing silicon atoms as a base material is formed on the surface of the substrate by a reduced pressure vapor deposition method. In the method, prior to the step of forming an electrophotographic photoreceptor, water containing an inhibitor of a specific component is used to degrease the surface of the substrate and form irregularities due to a plurality of spherical trace depressions. How to make the body. 7. The method according to claim 6, wherein the irregularities are formed by depressions having substantially the same curvature and width. 8. The method for producing an electrophotographic photoreceptor according to claim 6, wherein the curvature R and the width D of the depressions and depressions have values satisfying 0.035 ≦ D / R ≦ 0.5. 9. The method of manufacturing an electrophotographic photosensitive member according to claim 6, wherein the width of the depression is 4 μm or more and 500 μm or less. 10. The method of manufacturing an electrophotographic photoreceptor according to claim 6, wherein the inhibitor used in the step of forming irregularities is a silicate. 11. The method according to claim 10, wherein the inhibitor used in the step of forming irregularities is potassium silicate. 12. After forming irregularities due to a plurality of spherical trace depressions on the surface of the substrate, the surface of the substrate is treated with water containing a surfactant, pure water, carbon dioxide, and water containing an inhibitor of a specific component. The method for producing an electrophotographic photoreceptor according to claim 6, wherein the substrate is washed by any one of the above or a combination of two or more kinds. 13. A drying step in washing after forming irregularities due to a plurality of spherical trace depressions on the surface of the substrate, wherein the surface of the substrate contains hot pure water, hot pure water in which carbon dioxide is dissolved, and an inhibitor of a specific component. The method for producing an electrophotographic photoreceptor according to claim 12, wherein the electrophotographic photoreceptor is pulled up and dried by using one of warm pure water or a combination of two or more kinds. 14. The step of forming a functional film on the aluminum substrate includes the step of: depositing a non-single-crystal deposited film containing one or both of hydrogen atoms and fluorine atoms and silicon atoms on an aluminum substrate by a plasma CVD method. 14. The method of manufacturing an electrophotographic photoreceptor according to claim 6, further comprising the step of: 15. The method according to claim 15, wherein the aluminum substrate is Fe + Si.
The method for producing an electrophotographic photoreceptor according to any one of claims 1, 2, 4 to 5, 6 to 10, and 12 to 13, wherein the aluminum substrate contains more than 0.01 wt% and not more than 1 wt% of + Cu. . 16. The method according to claim 16, wherein the aluminum substrate contains 10% Fe.
16. The method for producing an electrophotographic photoreceptor according to claim 15, wherein the aluminum substrate contains at least 1 ppm by weight and not more than 1 ppm. 17. The method according to claim 17, wherein the aluminum substrate contains 10% of Si.
16. The method for producing an electrophotographic photoreceptor according to claim 15, wherein the aluminum substrate contains at least 1 ppm by weight and not more than 1 ppm. 18. The method according to claim 18, wherein the aluminum substrate comprises Cu
16. The method for producing an electrophotographic photoreceptor according to claim 15, wherein the aluminum substrate contains at least 1 ppm by weight and not more than 1 ppm.