JPH11212287A - Production of electrophotographic photoreceptor and apparatus therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to obtain a high-grade image which is uniform and is free of image defects and uneven image densities. SOLUTION: This process for production consists in mounting an aluminum substrate on a substrate holder and forming a functional film consisting of an amorphous material contg. silicon atoms as its base material on the surface of this substrate by a reduced pressure vapor phase growth method. In such a case, the substrate surface is degreased and washed by using a surfactant and an inhibitor in the washing stage for washing the substrate surface before the stage for forming the electrophotographic photoreceptor and thereafter, the substrate is inverted 180 deg. in a vertical direction and is transported. The surface is then washed by any of pure water, water dissolved with carbon dioxide and more particularly water contg. a specific inhibitor or a combination of >=2 kinds thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for manufacturing an electrophotographic photosensitive member having a functional film.

[0002]

2. Description of the Related Art As a substrate for forming a deposited film of an electrophotographic photoreceptor, glass, heat-resistant synthetic resin, stainless steel,
Aluminum and the like have been proposed. However, practically, metal is often used to withstand electrophotographic processes such as charging, exposure, development, transfer, and cleaning, and to always maintain high positional accuracy so as not to deteriorate image quality. Among them, aluminum is one of the most suitable materials for the base of the electrophotographic photoreceptor because of its good workability, low cost and light weight. These materials are subjected to a surface treatment of a substrate according to the use of the electrophotographic photoreceptor, and a light receiving layer is formed on the surface. Techniques relating to surface treatment of the substrate are described in JP-A-61-231561 and JP-A-62-65545. As a technique for preventing unevenness and spots in a water washing process when an aluminum alloy is used as a substrate, there is no description of a method of transporting the substrate.
Japanese Patent Application Laid-Open No. HEI 6-273955 proposes a technique for cleaning a substrate with water in which carbon dioxide is dissolved. No mention is made of washing with water containing. Also, JP-A-63-311
No. 261 and JP-A-1-156758 and JP-B-7-34123 each describe a technique for forming an oxide film on an Al substrate, but they are washed with water containing an inhibitor of a specific component. There is no mention of forming a film by doing so. On the other hand, JP-A-6-163
Japanese Patent Publication No. 493 proposes a technique for cleaning by reversing an object to be processed, but for cleaning different surfaces, a technique for reversing a cylindrical substrate in a vertical direction, or a specific component. No mention is made of washing with water containing.

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

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

The plasma CVD method, that is, a method in which a raw material gas is decomposed by direct current, high frequency or microwave glow discharge to form a thin film deposition film on a substrate, is a method for forming an amorphous silicon deposition film for electrophotography. It is optimal and is currently in very practical use.

[0006] 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 the 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 described in JP-A-60-186849. 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. In addition, JP
Japanese Patent Publication No. 1-283116 discloses an improved microwave technology for manufacturing a semiconductor member. That is, in this publication, an electrode (bias electrode) is provided as a plasma potential control in a discharge space, and a desired voltage (bias voltage) is applied to the bias electrode to control the ion bombardment of the deposited film to perform film deposition. A technique for improving the characteristics of a deposited film in such a manner is disclosed.

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

If necessary, the workpiece is machined to a flatness within a predetermined range by diamond cutting using a lathe, a milling machine, or the like, and then washed with triethane. Next, the substrate subjected to these surface treatments is subjected to triethane cleaning (not shown),
A deposited film mainly composed of amorphous silicon is formed on a base by a deposited film forming apparatus for a photoconductive member by a glow discharge decomposition method shown in FIG.

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 is not superimposed can be minimized by optimizing the surface processing conditions, cleaning conditions and deposition conditions of the substrate, and conventionally, the resolution of development is lower than or less than that. Therefore, there was no practical problem.

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 of the surface where no potential is applied has substantially affected the peripheral potential substantially.

Under these circumstances, these minute portions on which electric charges do not exist, which have not been a problem in the past, have been pointed out as image defects.

[0013] 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 pose 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 by halftone, a slight potential difference on the surface of the electrophotographic photosensitive member also causes an image defect. Appears as visually striking. Particularly, in the case of an electrophotographic photoreceptor produced by a microwave plasma CVD method, 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 formed by a plasma CVD method than a Se electrophotographic photosensitive member formed by vacuum evaporation or an OPC electrophotographic photosensitive member formed by a blade coating method or a dipping method. It is particularly noticeable in the body. Also, plasma CV
Even in a device manufactured by the method D, such a problem does not occur in a device such as a solar cell in which a delicate difference in characteristics depending on a position on a substrate does not affect its performance or can be corrected by post-processing. In the prior art, the substrate cleaning step did not pose a problem because triethane was used, but these chlorine-based solvents can be easily used due to recent environmental problems. Because there is not, it is changing to water-based 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.

[0016]

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 problems in the conventional method of manufacturing an electrophotographic photoreceptor, and to prevent the degreasing and cleaning of the substrate. An object of the present invention is to provide an easy-to-use method for manufacturing an electrophotographic photoreceptor capable of suppressing unevenness and spots, inexpensively and stably forming a high yield at a high yield.

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

[0018]

The above objects are 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 of manufacturing a photoreceptor, before the step of forming an electrophotographic photoreceptor, by using water containing a specific inhibitor, the substrate is turned upside down by 180 ° when transported to a rinsing tank. A method of manufacturing an electrophotographic photoreceptor characterized by suppressing a shift in a cleaning time of the substrate in the generatrix direction, wherein a film of Al, Si and O formed on an aluminum substrate has a thickness of 5 angstroms. As described above, at a film thickness of 150 angstroms or less, a composition of 0.1 ≦ b ≦ 0.5 and 1 ≦ c ≦ 5 in a relation of Al: Si: O = a: b: c (when a = 1). What is expressed, the washing process Inhibitors of particular components used it is silicate, wherein, that inhibitors of certain components used in the washing step is potassium silicate, the,
The weight percent 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 wt% or more and 2 wt% or less;
The step of forming the functional film on the aluminum substrate includes the step of forming an amorphous crystal deposition film containing one or both of hydrogen atoms and fluorine atoms and silicon atoms on an aluminum substrate by a plasma CVD method. Including.

[0020]

DETAILED DESCRIPTION OF THE INVENTION According to the study of the present inventor, the causes of image defects that occur when an aluminum substrate is used are: (A) dust on the substrate, dirt from washing water in the washing and drying steps, and the like. That is the core.

(B) The surface defects of the substrate serve as nuclei.

(C) Surface defects caused by a change in temperature of the substrate itself generated during cleaning of the substrate become nuclei.

It can be roughly classified into:

The adhesion of dust and the like in (A) 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 much more difficult to reduce the defects (B) and (C). The present inventor has completed the present invention as a result of earnestly studying from the viewpoint that all these problems can be solved by combining a specific component-containing aluminum with a specific cleaning method and a conveying method. .

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 has been clarified that (B) is caused by the fact that a part is cut off and a surface defect is 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.

However, very high-purity aluminum grows as an oxide which is inevitably generated during melting for processing aluminum as a raw material into the shape of a substrate, and causes the above-mentioned defects. In order to prevent this, it has been found that the inclusion of Si atoms is effective. Further, from the viewpoint of the cost of the substrate, the high-purity material is expensive, so that there is sufficient room for study.

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

However, in recent years, these chlorinated solvents cannot be used easily due to environmental problems, and the present inventors have conducted intensive studies. As a result, it was discovered that aluminum is corroded by water, and in particular, aluminum containing these silicon atoms, when immersed in water during cleaning, is significantly corroded by water, mainly in areas where Si atoms are locally large. did. It was found that corrosion occurred not only in Si atoms but also in portions where Fe atoms and Cu atoms were locally large.

This phenomenon became more pronounced as the temperature of the water was higher. In order to prevent aluminum corrosion, various corrosion inhibitors have been proposed. However, in the case where the present invention is used for a substrate of an electrophotographic photosensitive member as in the present invention, even a defect which occurs slightly on a substrate having a large area poses a problem. Therefore, the effect is insufficient and the use of conventional corrosion inhibitors is limited. The inventors of the present invention have conducted intensive studies focusing on the transport process in addition to the cleaning process. As a result, the time from the degreasing of the substrate surface to the transport to the cleaning (rinsing) process and the cleaning was shifted in the generatrix direction of the substrate. As a result, the cleaning unevenness in the generatrix direction became remarkable, and it became clear that this was the cause of (C). This phenomenon becomes more conspicuous as the transport time becomes longer. In order to prevent the cleaning unevenness, a method of reducing the time lag in the generatrix direction of the substrate has been considered, but the effect was insufficient.

The present inventor pays attention to the point that it is possible to reduce the transport time by changing the structure of the substrate transport device as shown in FIG. 1 and to suppress the above-mentioned uneven cleaning. As a result of intensive research, 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. In the cleaning step, the substrate is cleaned in a degreasing tank, and when the substrate is transferred to a rinsing tank, the substrate is turned upside down by 180 °, so that a difference in cleaning time in the generatrix direction of the substrate can be suppressed. As a result, it was possible to eliminate the cleaning unevenness which causes a defect on the surface of the base.

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 highly pure aluminum substrate is in a state where it is washed with a non-aqueous solvent such as trichloroethane after cutting, or in a state where it is washed with pure water without any other washing after cutting. In this case, the state of adsorption of water on the substrate surface is partially different. When a deposited film containing silicon atoms, such as an amorphous silicon film, and hydrogen atoms and / or fluorine atoms is formed on a substrate having such a surface state by, for example, a plasma CVD method, a reaction on the surface is caused by the surface of the substrate. It is particularly strongly affected by the amount of water molecules remaining on top. Due to this, 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, unevenness in cleaning is suppressed by suppressing the difference in cleaning time in the generatrix direction of the base by inverting the base vertically by 180 ° before forming the functional film by the plasma CVD method. Al with uniform silicate on the substrate surface
_- Si - _O film By forming was able to form an interface that can exchange good charge during formation of the deposited film. For this reason, it has become possible to improve the electrophotographic properties such as improvement of charging and reduction of photosensitivity.

In the present invention, during the cleaning, a surfactant is used to completely remove oils and fats and halogen-based residues which hinder the effects of the present invention. The above-described effect is achieved by an unconventional method of suppressing uneven cleaning by suppressing the difference in the cleaning time of the substrate in the generatrix direction in the process.

One example of a procedure for actually forming an electrophotographic photosensitive member by an electrophotographic photosensitive member manufacturing method of the present invention using an aluminum alloy cylinder as a substrate is shown in FIG. 1 and a substrate cleaning apparatus according to the present invention, and FIG. This will be described below using the deposited film forming apparatus shown in FIG. Lathe with air damper for precision cutting (PNEUMO PRECLESION INC.)
Then, insert a diamond bite (trade name: Miracle bite, manufactured by Tokyo Diamond) at 5 ° to the cylinder center angle.
Set to get the rake angle of the corner. Next, the base was vacuum-chucked onto the rotating flange of the lathe, and white kerosene was sprayed from the attached nozzle, and the suction speed of the cutting powder was also used from the attached vacuum nozzle.
Mirror cutting is performed so that the outer shape becomes 108 mm at a feed rate of 0.01 mm / R.

After the cutting is completed, the surface of the substrate is degreased and cleaned using the cleaning apparatus of the present invention shown in FIG. The substrate cleaning apparatus includes a processing unit 102, a substrate transport mechanism 103, and a reversing automatic hand 104. The processing unit 102 includes a substrate loading table 111, a degreasing and cleaning tank 112, a rinsing tank 113, a drying tank 114, a substrate unloading table 115, an elevator 135, and an air cylinder 131. Degreasing cleaning tank 11
2. Both the rinsing tank 113 and the drying layer 114 are provided with a temperature controller (not shown) for keeping the temperature of the liquid constant. The transfer mechanism 103 includes a transfer rail 165 and a transfer arm 161.
The transport arm 161 includes a moving mechanism 162 that moves on the rail 165, a chucking mechanism 132 that holds the base 101, and an air cylinder 130 that moves the chucking mechanism 132 up and down. 180 °
The reversing auto hand mechanism 104 is an auto hand 1 in which a chucking mechanism 132 for holding the base 101 is integrated.
33 and a reversing mechanism 134 for reversing the auto hand 133 by 180 °.

After cutting, the substrate 1 placed on the loading table 111
01 is transported to the degreasing / cleaning tank 112 by the transport mechanism 103. By performing ultrasonic treatment in a surfactant or a surfactant to which silicate is added in the degreasing cleaning tank 112, dust and oils and fats adhering to the surface are decleaned.

Next, the substrate 101 is provided with the chucking mechanism 13.
2, it is raised by the air cylinder 130, turned upside down by 180 ° by the reversing mechanism 134, transported to the elevator 135, lowered by the air cylinder 130, and placed on the elevator 135. Next, the elevator 135 is connected to the air cylinder 13
Then, the substrate 101 is placed in the rinsing bath 113, and further rinsed with pure water or the like maintained at a temperature of 25 ° C. Pure water is an industrial conductivity meter (product name: α9
00R / C, manufactured by Horiba, Ltd.).
Next, the substrate 101 is transported by a transport mechanism 103 to a drying tank 114 made of hot pure water or the like, and is pulled up and dried by a lifting device (not shown) using hot pure water or the like maintained at a temperature of 60 ° C. Pure hot water is an industrial conductivity meter (trade name: α90
ORR / C, manufactured by Horiba, Ltd.).

The substrate 101 after the drying step is carried to the carry-out stand 115 by the carrying mechanism 103. Next, a deposited film mainly composed of amorphous silicon is formed on the substrate having been subjected to the cutting and the pre-treatment by the apparatus for forming a deposited photoconductive member by the plasma CVD method shown in FIG.

Referring to FIG. 3, a reaction vessel 302 includes a base plate 305, a wall 303 also serving as a cathode electrode, and a top plate 304. Inside the reaction vessel 302, a substrate 3 on which an amorphous silicon deposition film is formed is formed.
Reference numeral 01 is provided at the center of the cathode electrode 303 and also serves as an anode electrode.

Using this deposited film forming apparatus,
In order to form a silicon deposition film on the substrate 301,
First, the raw gas inflow valve 311 is closed and the exhaust valve 31 is closed.
4 is opened, and the reaction vessel 302 is evacuated. Vacuum gauge (shown
Reading) is about 6.65 × 10 ^-FourAt the time when it becomes Pa
The charge gas inflow valve 311 is opened. Gas flow rate is
-Adjusted to a predetermined flow rate in the controller 312. An example
For example, SiH_FourSource gas such as gas flows into the reaction vessel 302.
To enter. And the surface temperature of the substrate 301 is a heater
Confirmed that the temperature was set to the predetermined value by 308
Then, a high frequency power supply (frequency: 13.56 MHz) 316
Glow discharge is set in the reaction vessel 302 by setting the desired power.
Raise it. Also, while the deposition film is being formed,
In order to make the formation uniform, the base 301 is moved by a motor (not shown).
) To rotate at a constant speed. Thus, the base 3
01 to form an amorphous silicon deposition film
it can. In the invention of the present invention, a silicate is added to form a film.
When forming, the film is formed before the substrate comes into contact with pure water, etc.
Must be formed. In addition, the film of the present invention
Because it is formed at an early stage, it can be used during cleaning with pure water, etc.
Even if it is formed, it is effective in the present invention. That is,
Silicate in surfactant of degreasing base for degreasing cleaning after cutting
Method for containing acid salt, pure water in rinse tank and drying tank, etc.
And a method of incorporating a silicate into the mixture.
Suitable for

In the present invention, the inhibitors used in the washing step include phosphates, silicates, borates and the like, and any of them can be used, and silicates are suitable for the present invention.
Among the silicates, potassium silicate, sodium silicate and the like can be mentioned, and any of them is possible, but potassium silicate is suitable for the present invention.

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

In the present invention, when cleaning the surface of the aluminum substrate, an aqueous method using a surfactant containing a silicate is preferred. In that case, the water quality of the water before dissolving the surfactant and the silicate can be any,
Particularly, semiconductor grade pure water, particularly ultra LSI grade ultra pure water is desirable. Specifically, as the resistivity at a temperature 25 ° C., the lower limit 1 M.OMEGA _- cm or more, preferably 3 milliohms _-
cm or more, optimally 5 MQ _- cm or more is suitable for the present invention. The upper limit is the theoretical resistance (18.25 MΩ _- cm)
Although any of the above values is possible, 17 MΩ _- cm or less, preferably 15 MΩ _- cm or less, and optimally 13 MΩ _- cm or less is suitable for the present invention in terms of cost and productivity. The amount of the fine particles is 0.2 μm or more, 10,000 or less, preferably 1,000 or less, and optimally 100 or less per milliliter in the milliliter. As the amount of microorganisms, the total viable count was 100 per milliliter.
No more than 10, preferably no more than 10, optimally no more than 1 are 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 water of the above-mentioned water quality, there are 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 to.

In the present invention, if the temperature of the water of the surfactant containing the silicate is too high, spots due to the liquid traces are generated, which causes peeling of the deposited film. On the other hand, if it is too low, the degreasing effect and the film effect are small, and the effect of the present invention cannot be sufficiently obtained. For this reason, the water temperature should be 10 ° C. or higher and 60 ° C.
C. or lower, preferably 15 ° C. or higher and 50 ° C. or lower, optimally 20 ° C. or higher and 40 ° C. or lower are suitable for the present invention.

In the present invention, if the concentration by weight of the surfactant used in the cleaning step is too high, stains due to the liquid traces are generated, which causes peeling of the deposited film. On the other hand, if it is too thin, the degreasing effect and the film effect are small, and the effect of the present invention cannot be sufficiently obtained. Therefore, the weight% concentration of the surfactant containing the silicate is 0.1 wt% or more and 20 wt% or less, preferably 1 wt% or more and 10 wt% or less, and optimally 2 w%.
At least t% and at most 8 wt% are suitable for the present invention.
If H is too high, stains due to liquid traces occur, which causes peeling of the deposited film. Also, if too thin, the degreasing effect,
The film effect is small, and the effect of the present invention cannot be sufficiently obtained. For this reason, the pH of the surfactant is 8 or more and 12.5 or less, preferably 9 or more and 12 or less, and most preferably 10 or more and 11.
Five or less is suitable for the present invention.

In the present invention, when cleaning is performed, if the concentration of the silicate contained in the water containing the surfactant is too high, stains due to the liquid traces are generated, and the deposited film is peeled off. 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. For this reason, the weight% concentration of the silicate contained in the water containing the surfactant is:
0.05 wt% or more and 2 wt% or less, preferably 0.1 wt%
wt% or more, 1.5 wt% or less, optimally 0.2 wt%
Above, 1 wt% or less is suitable for the present invention. In the present invention, if the thickness of the film formed on the aluminum substrate is too small, no effect is exhibited. If the thickness is too large, the conductivity with the aluminum substrate is reduced, and adverse effects are caused. For this reason, the film thickness of the film is preferably from 5 Å to 150 Å, preferably from 10 Å to 130 Å, and most preferably from 15 Å to 120 Å.

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

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

In the present invention, it is effective to carry out shower cleaning and hot air drying after the surface processing in order to bring out the effects of the present invention, but it is particularly more effective to carry out cleaning using a cleaning apparatus. The washing liquid and water used in these washing means should be washed with any of surfactant, pure water, water in which carbon dioxide is dissolved, water containing an inhibitor of a specific component, or a combination of two or more kinds. Are suitable for the present invention.

As a drying means in the case of using a washing apparatus, it is possible to pull up and dry with any of warm pure water, warm pure water in which carbon dioxide is dissolved, warm pure water containing an inhibitor of a specific component, or a combination of two or more kinds. Suitable for the present invention.

In the washing step of the present invention, the quality of water used when using water in which carbon dioxide is dissolved is very important. Before the carbon dioxide dissolution, the quality of the water is very important. LSI grade ultrapure water is desirable.
Specifically, as the resistivity at a temperature 25 ° C., the lower limit 1 M.OMEGA _- cm or more, preferably 3 milliohms _- cm or more, and optimally 5 M [Omega _- cm or more it is suitable for the present invention. The upper limit of the resistance value can be any value up to the theoretical resistance value (18.25 MΩ _- cm).
Ω _- cm or less, preferably 15 MΩ _- cm or less, optimally 13 MΩ _- cm or less is suitable for the present invention. The amount of fine particles was 0.2 μm,
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.

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 leaching method, a reverse osmosis method, an ultraviolet sterilization method, and the like. It is desirable to increase the required water quality. The present invention is possible with any amount of carbon dioxide dissolved in water up to the saturation solubility.However, if the amount is too large, bubbles are generated when the water temperature fluctuates, and spots are generated on the spot by adhering to the substrate surface. May be. Further, 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 effect of the present invention cannot be obtained, so it is necessary to optimize the amount of dissolved carbon dioxide according to the situation while considering the quality required for the substrate. There is. Generally, the preferred amount of dissolved carbon dioxide according to the present invention is 60% or less, more preferably 40% of the saturated solubility.

In the present invention, it is practical to control the dissolved amount of carbon dioxide by the conductivity or pH of water, but when controlled by the conductivity, the preferable range is 2 μS / cm or more and 40 μS / cm. Below, more 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. Water temperature is 5 ℃ or more, 9
0 ° C. or lower, preferably 10 ° C. or higher and 55 ° C. or lower, optimally 15 ° C. or higher and 40 ° C. or lower are suitable for the present invention. The method of dissolving carbon dioxide in water is by bubbling,
Any method such as a method using a diaphragm may be used. In the present invention, it is important to use water in which carbon dioxide is dissolved,
When a carbonate such as sodium carbonate is used to obtain a carbonate ion, a cation such as a sodium ion inhibits the effect of the present invention. When the substrate surface 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 basically immersed in a water tank into which water in which carbon dioxide is dissolved is introduced. At this time, ultrasonic waves are applied, a water flow is given, and bubbling is carried out by introducing air or the like. The present invention will be more effective when used together. In the case of spraying, if the pressure of water is too weak, the effect of the present invention is small, and if it is too strong, a pear-skin pattern occurs on the obtained electrophotographic photoreceptor image, particularly on a halftone image. I will. For this reason, the pressure of water is 2.0 × 10 ⁵
(Pa) or more and 2.9 × 10 ⁷ (Pa) or less, preferably 9.8 × 10 ⁵ (Pa) or more and 2.0 × 10 ⁷ (Pa)
Below, optimally 2.0 × 10 ⁶ (Pa) or more, 1.5 × 1
0 ⁷ (Pa) or less is suitable for the present invention. 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. As the flow rate of water, the effect of the invention and
From economics, 1 liter / min or more per substrate, 2
00 liter / min or less, preferably 2 liter / m
In the range from in to 100 l / min, optimally from 5 l / min to 50 l / min is suitable for the present invention.

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

In the cleaning step after the surface processing of the present invention,
The water quality when using pure water is very important, and pure water of a semiconductor grade, particularly ultrapure water of an ultra LSI grade is desirable. Specifically, as the resistivity at a temperature 25 ° C., the lower limit 1 M.OMEGA _- cm or more, preferably 3 milliohms _- cm or more,
Optimally, 5 MΩ _- cm or more is suitable for the present invention. The upper limit is the theoretical resistance value of the resistance value (18.25MΩ _- cm) are possible at any value up to, cost, productivity 17MΩ terms of _- cm or less, preferably 15MΩ _- cm or less, and optimally 13Emuomega _- cm or less is suitable for the present invention. Regarding the amount of fine particles, 0.2 μm or more is preferably 10,000 or less, preferably 1000 or less, and optimally 100 or less per milliliter in the present invention. As the amount of microorganisms, a total viable cell count of 100 or less, preferably 10 or less, and optimally 1 or less per milliliter is suitable for the present invention. The amount of organic matter (TOC) is 10 per liter.
mg or less, preferably 1 mg or less, optimally 0.2 mg
The following are suitable for the present invention. As a method for obtaining water of the above-mentioned water quality, there are 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 to. The temperature of pure water is 5 ℃ or more, 90
C. or lower, preferably 10 to 55.degree. C., optimally 15 to 40.degree. C. is suitable for the present invention. When the substrate surface is washed with the pure water thus obtained, a method and a time similar to those in the case of dissolving carbon dioxide are preferable.

In the present invention, when hot water drying is performed using water in which carbon dioxide is dissolved, the quality of the water used is very important. LSI grade ultrapure water is desirable. Specifically, as the resistivity at a temperature 25 ° C., the lower limit 1 M.OMEGA _- cm or more, preferably 3 milliohms _- cm or more, and optimally 5 M [Omega _- cm or more it is suitable for the present invention. The upper limit of the resistance value can be any value up to the theoretical resistance value (18.25 MΩ _- cm).
7 MΩ _- cm or less, preferably 15 MΩ _- cm or less, optimally 13 MΩ _- cm or less is suitable for the present invention. As for the amount of fine particles, 0.2 μm or more
0000 or less, preferably 1000 or less, optimally 100 or less are suitable for the present invention. As the amount of microorganisms, a total viable cell count of 100 or less, preferably 10 or less, and optimally 1 or less per milliliter is suitable for the present invention. Organic matter (TOC) is 10m / l
g or less, preferably 1 mg or less, optimally 0.2 mg or less are suitable for the present invention. As a method for obtaining water of the above-mentioned water quality, there are 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 to. The present invention is possible with any amount of carbon dioxide dissolved in water up to the saturation solubility.However, if the amount is too large, bubbles are generated when the water temperature fluctuates, and spots are generated on the spot by adhering to the substrate surface. May be. Further, 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 effect of the present invention cannot be obtained. It is necessary to optimize the dissolved amount of carbon dioxide according to the situation, taking into account the quality required for the substrate. Generally, the preferred amount of dissolved carbon dioxide according to the present invention is 60% or less, more preferably 40% of the saturated solubility.

In the present invention, it is practical to control the dissolved amount of carbon dioxide by the conductivity or pH of water, but when controlled by the conductivity, the preferable range is 5 μS / cm or more.
0 μS / cm or less, more preferably 6 μS / cm or more,
35 μS / cm or less, 8 μS / cm or more, 30 μS / c
When the pH is controlled at m or less, the preferred range is 3.8 or more and 6.0 or less, more preferably 4.0 or more and 5.0 or less, and the effect of the present invention is remarkable. The conductivity is measured by a conductivity meter or the like, and a value converted to 25 ° C. by temperature correction is used. 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 exert the effects of the present invention. Will hinder you. The temperature of the hot water is
30 ° C or more and 90 ° C or less, preferably 35 ° C or more and 80 ° C or less.
C. or less, optimally from 40.degree. C. to 70.degree. C. is 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, and 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 oxygen 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. 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 after the surface treatment of the present invention, the quality of water used when using water in which silicate is dissolved is very important, and in the state before silicate dissolution, semiconductor grade pure water, particularly Super L
SI grade ultrapure water is desirable. Specifically, water temperature 2
As the resistivity at 5 ° C., the lower limit is 1 MΩ _- cm or more,
Preferably 3 milliohms _- cm or more, and optimally 5 M [Omega _- cm or more is suitable for the present invention. The upper limit is the theoretical resistance value of the resistance value (18.25MΩ _- cm) are possible at any value up to, cost, productivity l7MΩ terms of _- cm or less, preferably 15MΩ _- cm or less, and optimally 13Emuomega _- cm or less is suitable for the present invention. The amount of fine particles is 0.2
1 μm, 1 μm or less, preferably 1000 or less, and optimally 100 or less in 1 ml are suitable for the present invention. As the amount of microorganisms, the total viable count is 100 or less per milliliter, preferably 10 or less,
Optimally, no more than one is suitable for the present invention. An organic matter foot (TOC) of less than 10 mg per liter, preferably less than 1 mg, optimally less than 0.2 mg is suitable for the present invention. As a method for obtaining water of the above-mentioned water quality, there are 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 to. The temperature of the water in which the silicate is dissolved is 30 ° C or more and 90 ° C
Or less, preferably 35 ° C or more and 80 ° C or less, optimally 4 ° C or less.
A temperature between 0 ° C. and 70 ° C. is suitable for the present invention.

In the present invention, when cleaning after surface processing is performed, if the concentration of silicate-containing water is too high, spots due to the traces of the liquid may occur, causing the deposited film to peel off. Becomes Also, if it is too thin, the degreasing effect and film effect are small,
The effect of the present invention cannot be sufficiently obtained. For this reason, the concentration of water containing silicate is 0.1% or more and 20% or less, preferably 1% or more and 10% or less, and optimally 2% or more and 8% or less is suitable for the present invention. I have. In the present invention, when cleaning after surface processing, the pH of water containing silicate is:
If it is too high, stains due to the liquid traces will occur, causing the deposited film to peel off. 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. For this reason, the pH of the water containing silicate is 8 or more and 12.5 or less, preferably 9 or more and 12 or less, and most preferably 10 or more and 11.5 or less. When the surface of the substrate is washed with the water obtained by dissolving the silicate thus obtained, the same method and time as those in the case of dissolving carbon dioxide are preferable.

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

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

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

In the present invention, it is effective to include magnesium in order to improve the workability of the substrate. The preferable content of magnesium 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, Be, Ca, Ti, Cr, Mn, F
e, CO, Ni, Cu, Ag, Zn, Cd, Hg, B,
Ca, In, C, Si, Ge, Sn, N, P, As,
It is effective to include any substance such as ○, S, Se, F, Cl, Br and I in aluminum.

In the present invention, the shape of the substrate is determined as desired. For example, if the substrate is to be used for electrophotography, in the case of a continuous high-speed copying machine, it is an endless belt or a cylinder as described above. Shapes are best suited for the present invention. In the case of a cylindrical shape, the size of the substrate is not particularly limited, but is practically 20 mm or more in diameter, 500 mm or less, and 10 mm in length.
Above, 1000 mm or less is preferable. The thickness of the support is
It is appropriately determined so that a desired photoconductive member is formed, but when the possibility as a photoconductive member is required, as long as it is within a range in which the function as a support is sufficiently exhibited, Thinned. However, in such a case,
The thickness is usually 10 μm or more from the viewpoints of production and handling of the support, mechanical strength and the like. The photoreceptor used in the present invention may be any of an amorphous silicon photoreceptor, a selenium photoreceptor, a cadmium sulfide photoreceptor, an organic photoreceptor, and the like. The effect is remarkable.

In the case of a non-single-crystal photosensitive member containing silicon, the deposited film type
The raw material gas used during the formation is silane (Si
H_Four), Disilane (Si_TwoH₆), Silicon tetrafluoride (Si
F_Four), Disilicon hexafluoride (Si_TwoF₆)
Recon forming raw material gas or their mixed gas
You. Hydrogen (H_Two), Argon (A
r), helium (He) and the like. In addition,
As a gas for improving characteristics such as changing the band gap width
And nitrogen (N _Two), Ammonia (NH_Three) Etc.
Containing element, oxygen (0_Two), Nitric oxide (NO), dioxide
Nitrogen (NO_Two), Nitrous oxide (N_Two0), carbon monoxide (C
O), carbon dioxide (CO_Two) Elements containing oxygen atoms,
Tan (CH_Four), Ethane (C_TwoH₆), Ethylene (C
_TwoH_Four), Acetylene (C_TwoH_Two), Propane (C_ThreeH₈)etc
Hydrocarbons, germanium tetrafluoride (GeF_Four), Nitrogen fluoride
Elementary (NF_Three) Or a mixed gas of these compounds
No. Also, in the present invention, the purpose of doping is
Diborane (B_TwoH₆), Boron fluoride (BF_Three), E
Sufin (PH_Three) And other dopant gases are discharged simultaneously.
The present invention is equally effective if introduced in between. The present invention
In a photoconductor, the total thickness of the deposited film deposited on the substrate is
Any of them may be used, but 5 μm or more, 100 μm or less,
Preferably 10 μm or more and 70 μm or less, optimally l
In the range of 5 μm or more and 50 μm or less,
As a result, particularly good images could be obtained.

In the present invention, the effect of the pressure in the discharge space during the deposition of the deposited film was observed in any region.
6 × 10 ⁻² (Pa) or more and 13.3 (Pa) or less, preferably 13.3 × 10 ⁻² (Pa) or more and 6.65 (P)
a) In the following, 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, but is particularly 150 ° C. or more and 450 ° C. or less, preferably 20 ° 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, or a ceramic heater. , Halogen lamps, infrared lamps and other heat radiation lamp heating elements, heating elements using liquids, gases, etc. as a heating medium and heat exchange means.
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. Alternatively, a method may be used in which a heating-only container is provided separately from the reaction container, and after heating, the substrate is transferred into the reaction container in a vacuum. 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 may be any of DC, RF, microwave, etc., and particularly when the microwave is used as the energy for generating the plasma, the energy may be caused by surface defects of the substrate. Abnormal growth appears remarkably and microwaves are absorbed by the adsorbed moisture,
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 may be used as long as discharge can be generated.
A power of 0 kW or less, preferably 500 W or more and 4 kW or less is suitable for practicing the present invention.

In the present invention, it is effective to apply a voltage (bias voltage) to the discharge space during formation of the deposited film, and 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.
V or more and 500 V or less, preferably 5 V or more and 100 V
It is desirable to apply the following bias voltage 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 (Al
N), boron nitride (BN), silicon nitride (SiN), silicon carbide (SiC), silicon oxide (SiO ₂ ), beryllium oxide (BeO), Teflon, polystyrene, and other materials with low microwave loss are usually used. . In a deposition film forming method in which a plurality of substrates surround a discharge space, the distance between the substrates is preferably 1 mm or more and 50 mm or less. 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 electrophotographic photosensitive member manufacturing method. In particular, a base is provided so as to surround a discharge space, and microwaves are 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 photoreceptor 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. It can also be used widely. Hereinafter, the effects of the present invention will be specifically described using experimental examples, but the present invention is not limited thereto. (Experimental example 1) Diameter 108 mm, length 358 mm, wall thickness 5
The surface of a cylindrical substrate having a thickness of 2 mm was cut in the same manner as in the above-described example of the procedure of the method for producing an electrophotographic photosensitive member according to the present invention.

Fifteen minutes after the completion of the cutting step, the substrate was washed under the conditions shown in Table 1 using an auto-hand having a 180 ° reversibility in the vertical direction according to the present invention shown in FIG.
At this time, Table 2 shows the results of visually inspecting the surface defects (unevenness, stains, flaws) generated on the surface of the substrate at both ends in the generatrix direction of the substrate and the results of comprehensive evaluation of the cleaning unevenness of the substrate. . In addition, the time to be transported to the degreasing step is the same as the time when the conventional apparatus shown in FIG. 2 is used. Evaluation of spots Light after strong exposure was reflected on the substrate surface after washing, and spots on the substrate that could be visually confirmed were confirmed.

◎: good without any

・ ・ ・: Good.

Δ: Very thin, no problem at all.

×: clearly recognized. Evaluation of Scratches The surface of the substrate after cleaning was reflected with strong exposure light and scratches on the substrate that could be visually confirmed were confirmed.

◎: good without any

・ ・ ・: Good.

Δ: Very thin, no problem at all.

×: clearly recognized. Evaluation of Unevenness Light of strong exposure was reflected on the surface of the washed substrate to confirm unevenness on the substrate which could be visually confirmed.

A: Good without any.

・ ・ ・: Good. Δ: Very thin and no problem at all.

×: clearly recognized. (Conventional Example 1) Fifteen minutes after the end of the cutting step, the substrate was washed in the same manner as in Experimental Example 1 using a conventional auto-hand having no 180 ° reversibility in the vertical direction shown in FIG. The same evaluation as in Example 1 was performed. Table 2 also shows the results.

[0090]

[Table 1]

[0091]

[Table 2] As is clear from Table 2, it was found that the occurrence of spots and unevenness in the generatrix direction of the substrate was improved by inverting the substrate by 180 ° and washing. (Experimental Example 2) The substrate was washed in the same manner as in Experimental Example 1 except that the transfer time when shifting from the degreasing step to the rinsing step was changed as shown in Table 3, and thereafter, the synthesis shown in Experimental Example 1 was performed. Evaluation "cleaning unevenness" was performed. Note) The transfer time of the conventional device shown in FIG. 2 is assumed to be 100%.

[0092]

[Table 3] As is clear from Table 3, it was confirmed that the same effect was exhibited even when the transport time was shortened by using the apparatus of the present invention. (Experimental Example 3) The substrate was washed by changing the transport time in the same manner as in Experimental Example 2. Thereafter, an amorphous silicon deposited film was formed on the substrate having been subjected to the surface treatment using the deposited film forming apparatus shown in FIG. 3 under the conditions shown in Table 4, and a blocking type electrophotograph having the layer configuration shown in FIG. A photoreceptor was produced. In FIG. 6, 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 photoreceptor thus produced was evaluated for electrophotographic characteristics as follows. The wrestling speed of the prepared electrophotographic photoreceptor was set to 200 to 80 in advance for the experiment.
Change it arbitrarily within the range of 0 mmsec.
A voltage of V was applied to perform corona charging, a latent image was formed on the surface of the electrophotographic photosensitive member by laser image exposure at 788 nm, and then a modification was made so that an image could be formed on transfer paper by a normal copying process. Canon copier, NP66
50, and evaluated for halftone image density unevenness. Table 5 shows the results.

Evaluation of Image Unevenness A3 paper (prepared by KOKUYO) was placed on a platen of a copying machine.
By changing the aperture of the copier, the exposure of the original is changed so that an image can be obtained in the range from barely recognizing the line of the graph to fogging of the white background, and outputting 10 copies with different densities did. These images were observed at a distance of 20 cm from the eyes to see if a difference in density was observed, and evaluated according to the following criteria.

A: No image unevenness is observed on any copy.

・ ・ ・: Image unevenness is observed, but all are slight and there is no problem at all. Δ: Image unevenness is observed on any copy. However, the image unevenness is slight on at least one copy, and there is no practical problem.

×: clearly recognized.

[0098]

[Table 4]

[0099]

[Table 5] As is apparent from Table 5, an unexpected effect of improving the image unevenness by shortening the transport time was obtained. (Experimental example 4) Experimental example 1 using the apparatus of the present invention shown in FIG.
Using the same substrate as described above, degreasing, rinsing, and drying were performed by washing (nonionic surfactant) under the conditions shown in Table 6.
At that time, the tank in which the inhibitor was placed was changed as shown in Table 7 (note that the inhibitor was potassium silicate, and 3 g / 1 was added to the surfactant aqueous solution, and the pH was set to 11.0).
A blocking type electrophotographic photoreceptor was formed on a substrate in the same manner as in Experimental Example 3 except for the above.

The electrophotographic characteristics of the electrophotographic photosensitive member produced as described above were evaluated as follows. The process speed of the prepared electrophotographic photoreceptor was set to 200 beforehand for experiments.
Arbitrarily changed within the range of ~ 800 mmsec,
A voltage of ~ 7 kv is applied to perform corona charging, and 788 n
m, a latent image was formed on the surface of the electrophotographic photosensitive member by laser image exposure, and then modified so that an image could be formed on transfer paper by a normal copying process.
6650 and evaluated for black spots and image defects. The results are also shown in Table 7. (Evaluation of black spots and image defects) Select an image sample with the most image defects among the image samples obtained when the process speed is changed and a full-halftone original and a character original are copied on the platen. 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.

×: There is a large defect on the entire surface, and there is a problem.

[0105]

[Table 6]

[0106]

[Table 7] From Table 7, good results were obtained by adding the inhibitor in the surfactant or immediately after the surfactant. (Experimental example 5) Experimental example 3 except that the same substrate as in Experimental example 1 was used, and the rinsing step and the drying step shown in Table 6 were changed using a combination of pure water and carbon dioxide as shown in Table 8 and the inhibitor was changed. A blocking type electrophotographic photoreceptor was formed on a substrate in the same manner as described above, and then evaluated in the same manner as in Experimental Example 4. Table 9 shows the results.

[0107]

[Table 8]

[0108]

[Table 9] As shown in Table 9, good results were obtained by adding an inhibitor in the surfactant or immediately after the surfactant even when a combination of an aqueous carbon dioxide solution and pure water was used in the rinsing and drying steps. (Experimental example 6) When cleaning was performed by the method shown in Table 10 using the same substrate as in Experimental example 1 and the cleaning apparatus of the present invention shown in FIG. Was changed. Thereafter, a blocking type electrophotographic photosensitive member was formed on the substrate in the same manner as in Experimental Example 4, and the measurement was performed in the same manner as in Experimental Example 3. Table 11 shows the results.

[0109]

[Table 10]

[0110]

[Table 11] As is clear from Table 11, good results were obtained with any of the silicates, but the best results were obtained especially with potassium silicate. (Experimental example 7) Using the same substrate as in Experimental example 1, cleaning was performed under the same conditions as in Experimental example 3 shown in Table 10.

The inhibitor to be introduced at that time was potassium silicate, and the concentration by weight of potassium silicate was changed as shown in Table 12, and the surface of the substrate after washing was visually observed for stains. Thereafter, a blocking type electrophotographic photosensitive member was formed on the substrate in the same manner as in Experimental Example 3, and the evaluation was performed in the same manner as in Experimental Example 3. Table 12 shows the results. Appearance spots High-exposure light was reflected on the surface of the substrate after cleaning, and spots on the substrate that could be visually confirmed were confirmed.

◎: good without any・ ・ ・: Good.

Δ: Very thin, no problem at all.

×: clearly recognized.

[0115]

[Table 12] From the results shown in Table 12, good results were obtained when the concentration of potassium silicate was in the range of 0.05% or more and 2.0%. (Experimental Example 8) Using the same substrate as in Experimental Example 1 and the cleaning apparatus of the present invention shown in FIG. 1, the treatment temperature and time were changed under the conditions shown in Table 13 to change the film thickness. Thereafter, a blocking type electrophotographic photosensitive member was formed on the substrate by the same method as in the experimental example, and evaluated by the same method as in experimental example 4. Table 14 shows the results.

[0116]

[Table 13]

[0117]

[Table 14] According to the results shown in Table 14, good results were obtained when the film thickness was in the range of 5 Å to 150 Å. (Experimental Example 9) Using the same substrate as in Experimental Example 1, the treatment temperature and time were changed under the conditions shown in Table 15, and a film was formed under the conditions shown in Table 15; The ratio was changed.

Thereafter, a blocking type electrophotographic photosensitive member was formed on a substrate in the same manner as in Experimental Example 4, and evaluated in the same manner as in Experimental Example 4. Table 16 shows the results.

[0119]

[Table 15]

[0120]

[Table 16] As is evident from Table 16, good results were shown when Si was 0.1 or more and 0.5 or less and O was 1 or more and 5 or less.

[0121]

(Example 1) A cylindrical substrate made of aluminum containing 0.03 wt% of Si, 0.05 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 was used. The surface is cut in the same procedure as one example of the above-described method of manufacturing the electrophotographic photosensitive member according to the present invention, and the surface of the substrate is degreased and cleaned (rinse) 15 minutes after the completion of the cutting step under the conditions shown in Table 17. Was. Thereafter, using the deposition film forming apparatus shown in FIG. 3, a blocking type electrophotographic photosensitive member having the layer configuration shown in FIG. The Al _— Si _— O film at this time had a composition of 1: 0.25: 3 and a thickness of 75 Å.

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

After the appearance of the electrophotographic photosensitive member thus produced was visually observed and evaluated for film peeling, the process speed was arbitrarily changed in the range of 200 to 800 mm / sec for experiments, and the charger was charged with 6 to 7 kv. A voltage was applied to perform corona charging, a latent image was formed on the surface of the electrophotographic photosensitive member by laser image exposure at 788 nm, and then modified so that an image could be formed on transfer paper by a normal copying process. It was placed in a copying machine, NP6650, and evaluated for image quality. Table 19 shows the results of these evaluations.

The image evaluation was performed by the following method. Further, as a comparative example 1, after processing by the method 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. .

[0125]

[Table 17]

[0126]

[Table 18] Evaluation of black spots The image was output so that the average density of the image obtained by placing the full-face halftone original on the platen while changing the process speed was 0.1 ± 0.1. Among the image samples obtained in this way, the one with the most noticeable stain was selected and evaluated. As for the method of evaluation, these images were
Inspection was performed at a distance of 1 cm to check whether black spots were observed, and the evaluation was performed according to the following criteria.

A: No black spot is observed on any copy.

・ ・ ・: Some black stains were slightly observed, but slight, and no problem was observed.

Δ: Black spots are observed on all copies,
However, there was no problem at all.

X: Large black spots are observed on all copies. Evaluation of Electrophotographic Characteristics 1 The surface potential of the photoreceptor 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,
The light quantity obtained when the light is irradiated and the potential drops to a certain level is evaluated as a sensitivity 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 3 After applying the same charging voltage at a normal process speed,
The change in the surface potential of the electrophotographic photosensitive member obtained at the developing position when the surface temperature of the electrophotographic photosensitive member is changed from room temperature to 45 ° C. is evaluated by a relative value as a temperature characteristic. However, the charging ability of the electrophotographic photosensitive member obtained in Conventional Example 1 is set to 100%.

[0131]

[Table 19] As is clear from Table 19, very good results were obtained, and an unexpected effect of improving electrophotographic properties was obtained. (Example 2) Table 20 shows the results of evaluation of the inhibition type electrophotographic photosensitive member manufactured by the same method as in Example 1 using the same substrate as in Example 1 by the following method. 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. Evaluation of image unevenness Place A3 grid paper (manufactured by KOKUYO Co., Ltd.) on the platen of the copier, and change the aperture of the copier to adjust the exposure of the original. The image was changed so as to obtain an image in a range up to the start, 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 is not a problem for practical use.

×: Large image unevenness is observed on all copies. Evaluation of slipperiness An arbitrary load is applied to the plate, and a piezo element is used to detect the frictional force, which is the force of the blade being pulled by the drum before and after the start of rotation of the drum. When the “maximum static friction coefficient” was calculated from the load and the “maximum static friction force” immediately before the start of rotation, and similarly, the “dynamic friction coefficient” was calculated from the “dynamic friction force” during steady rotation. Comparison by relative value (lower value indicates better slipperiness) Evaluation of fog on white background Observation of an image sample obtained when placing a normal original consisting of characters on a white background on a platen and copying And the fog on the white background was evaluated.

A: Good.

・ ・ ・: Some fog was observed.

Δ: There is fogging over the entire surface, but there is no problem in character recognition.

X: There are portions where characters are difficult to read due to fog.

[0141]

[Table 20] As is clear from Table 20, the sliding property and the image characteristics were further improved. . Using the same base (Example 3) Example 1 was subjected to surface treatment in the same manner as in Example 1, FIG. 4 _- (A),
Figure 4 _- under the conditions shown in Table 21 using the μwPCVD device shown in (B) the results were evaluated by elimination electrophotographic photosensitive member was prepared the same way as in Example 1 shown in FIG. 6-B Table 22 Show. Also, as a comparative example 3, after processing by the method shown in the conventional example 1, a similar blocking type electrophotographic photoreceptor was prepared and evaluated by the same method. In FIG. 6B, 601, 602, 603, 604 and 605 indicate an aluminum substrate, a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer, respectively.

[0142]

[Table 21]

[0143]

[Table 22] As is clear from Table 22, the present invention is effective even if the device and the layer configuration are different. (Example 4) After using the same substrate as in Example 1 and performing the same surface treatment as in Example 1, the VHFPCV shown in FIG.
A blocking type electrophotographic photoreceptor having a layer constitution shown in FIG. 6 _- B was prepared using the apparatus D under the conditions shown in Table 23, and evaluated by the same method. Table 24 shows the results.

[0144]

[Table 23]

[0145]

[Table 24] As is clear from Table 24, the present invention is effective even if the device and the layer configuration are different.

[0146]

As described above, according to the present invention, in the method of manufacturing an electrophotographic photoreceptor, the method includes the step of forming a functional film on an aluminum substrate by a plasma CVD method. In the cleaning step before the cleaning step, when moving from the degreasing step to the cleaning (rinsing) step, the substrate is conveyed while being turned upside down by 180 °, thereby suppressing the difference in the cleaning time in the generatrix direction of the substrate. As a result, the occurrence of spots and unevenness could be suppressed. In addition, by using water containing a specific inhibitor and forming an Al _- Si _- O film, it is possible to stably manufacture an electrophotographic photoreceptor that gives a uniform high-quality image at low cost. It is.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of an automatic hand device having a 180 ° reversal function used for implementing an electrophotographic photosensitive member of the present invention.

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

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

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

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

FIGS. 6A and 6B are cross-sectional views illustrating a layer configuration of an electrophotographic photosensitive member.

[Explanation of symbols]

101, 201, 301, 401, 501
Substrates 102, 202
Processing unit 103, 203
Substrate transport mechanism 104 180 ° reversing automatic hand mechanism 111, 211
Substrate loading table 112, 212
Degreasing cleaning tank 113
Rinse tank 122, 123, 124, 222, 223, 224
Cleaning liquid 114, 214
Drying tank 115, 215
Substrate delivery table 130, 131
Air cylinder 132
Chucking mechanism 133
Auto hand 134
Reversing mechanism 135
Elevators 161 and 261
Transfer arm 162,262
Moving mechanism 163, 263
Chucking mechanism 164,264
Air cylinder 165,265
Transport rails 302, 402, 502
Reaction vessel 303
Cathode electrode 304
Top plate 305
Base plate 306
Insulator 307
Base holder 308, 403, 503
Heater 309, 310
Source gas inlet pipe 311
Source gas inflow valve 312,507 Micro controller 313,404,504
Exhaust piping 314
Exhaust valve 315
Evacuation device 316
High frequency power supply 405, 505
Rotation motor 406, 506
Discharge space 407,508 Source gas introduction tube and DC application electrode 408
DC power supply 409
Microwave introduction window 410
Waveguide 601
Aluminum substrate 602
Charge injection blocking layer 603
Photoconductive layer 604
Surface layer

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor ▲ Taka ▼ Yasuyoshi I 3-3-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc.

Claims (12)

[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, in a washing step of washing the surface of the substrate before the step of forming an electrophotographic photoreceptor, the surface of the substrate is degreased and washed using a surfactant and an inhibitor, and then the substrate is vertically moved. An electrophotograph wherein the substrate surface is washed with any one of pure water, water in which carbon dioxide is dissolved, water containing a specific inhibitor, or a combination of two or more kinds after transporting by 180 ° inversion. Manufacturing method of photoreceptor. 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 a potassium silicate salt. 4. The electronic device according to claim 1, wherein the weight percent concentration of the inhibitor contained in the water containing the inhibitor of the specific component used in the washing step is 0.05 wt% or more and 2 wt% or less. Manufacturing method of photoreceptor. 5. The composition ratio is represented by the following formula when the thickness of the coating mainly composed of Al, Si and O formed on the substrate surface by the specific inhibitor is in the range of 5 Å to 150 Å. The method for producing an electrophotographic photosensitive member according to claim 1. A
l: Si: O = a: b: c, and when a = 1, the range of b and c is 0.1 ≦ b ≦ 0.5 1 ≦ c ≦ 5 6. The step of forming a functional film on the aluminum substrate includes forming an amorphous deposited film containing one or both of hydrogen atoms and fluorine atoms and silicon atoms on the aluminum substrate by a plasma CVD method. The method for producing an electrophotographic photoreceptor according to claim 1, further comprising a step of forming. 7. 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 apparatus, before the step of forming an electrophotographic photoreceptor, the surface of the substrate is degreased and washed using a surfactant and an inhibitor, and then the substrate is transported by turning the substrate upside down by 180 °, pure water, Water containing dissolved carbon dioxide, water containing a specific inhibitor,
Alternatively, an apparatus for manufacturing an electrophotographic photosensitive member, further comprising a substrate cleaning device for cleaning the substrate surface by a combination of two or more types. 8. The apparatus according to claim 7, wherein the specific inhibitor used in the washing step is a silicate. 9. The apparatus according to claim 8, wherein the specific inhibitor used in the washing step is a potassium silicate salt. 10. The method according to claim 7, wherein the weight percent concentration of the inhibitor contained in the water containing the inhibitor of the specific component used in the washing step is 0.05 wt% or more and 2 wt% or less. Item 2. An apparatus for producing an electrophotographic photosensitive member according to item 1. 11. The composition ratio is represented by the following formula when the thickness of the coating mainly composed of Al, Si and O formed on the substrate surface by the specific inhibitor is in the range of 5 Å to 150 Å. Claims 7 to 10
The apparatus for manufacturing an electrophotographic photoreceptor according to any one of the above. Al: Si: O = a: b: c, and when a = 1, the range of b and c is 0.1 ≦ b ≦ 0.5 1 ≦ c ≦ 5 12. The step of forming a functional film on the aluminum substrate includes the steps of: depositing an amorphous deposited film containing at least one of hydrogen atoms and fluorine atoms or silicon atoms with a plasma C;
The apparatus for manufacturing an electrophotographic photosensitive member according to any one of claims 7 to 11, further comprising a step of forming on an aluminum substrate by a VD method.