JP2000187339A - Cleaning method of object to be cleaned and production of electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a manufacturing method of an electrophotographic photoreceptor by which uniform picture of high grade having no defect and density uneveness can be obtained. SOLUTION: In the manufacturing method of the electrophotographic photoreceptor which contains a process for forming a functional membrane on a substrate 101, especially on an aluminum substrate containing silicon, iron and copper, the surface of the substrate 101 is degreased and cleaned by water containing a surfactant before the process for forming the electrophotographic photoreceptor and then is cleaned by water containing at least one of the surfactant, carbon dioxide and a specific inhibitor. After forming a film on the surfacce of the substrate 101, consisting essentially of Al, Si and O, with the thickness of a range between 5Å and 150Å and a specific range of composition, the surface of the substrate 101 is subject to a shower water of pure water or carbon dioxide-dissolved water or inhibitor-containing water with shower water blowing pressure within a range of >=4.9×103 to <=9.8×104 Pa and with a shower water blowing flow rate within a range of >=1 l/to <=20 l/min.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for cleaning an object to be cleaned and a method for manufacturing an electrophotographic photosensitive member having a functional film.

[0002]

2. Description of the Related Art As a product utilizing a functional film, for example, an electrophotographic photosensitive member having a functional film formed on its surface can be cited, and as a substrate for forming a deposited film of the electrophotographic photosensitive member, Glass, heat-resistant synthetic resin, stainless steel, aluminum and the like have been proposed. Among them, practically, it is necessary to endure the electrophotographic process such as charging, exposure, development, transfer, and cleaning, and to keep the position accuracy high so as not to deteriorate the image quality. There are many. Among them, aluminum (Al) is one of the most suitable materials for the base of the electrophotographic photosensitive member because of its good workability, low cost and light weight.

Techniques relating to the material of a substrate of an electrophotographic photosensitive member are disclosed in JP-A-59-193463 and JP-A-60-2630.
No. 62936. JP-A-59-19
No. 3463 discloses that the iron (Fe) content of the support is 20%.
There is disclosed a technique for obtaining an amorphous silicon electrophotographic photoreceptor having good image quality by using an aluminum alloy of not more than 00 ppm.

Further, this publication discloses a procedure in which a cylindrical (cylindrical) substrate is cut by a lathe and mirror-finished, and then amorphous silicon is formed by glow discharge. JP-A-60-262936 discloses that magnesium (Mg) is 3.0 to 6.0 wt%.
Manganese (Mn) as an impurity
t% or less, chromium (Cr) less than 0.01 wt%, iron (Fe) 0.15 wt% or less, silicon (Si) 0.12 wt% or less, and the balance aluminum (A)
An extruded aluminum alloy excellent in vapor deposition property of amorphous silicon comprising 1) is disclosed.

[0005] These materials are subjected to a surface treatment of a substrate according to the use of the electrophotographic photosensitive member, and a light receiving portion layer is formed on the surface. The technology relating to the surface processing of the substrate is disclosed in
These are described in JP-A-1-231561 and JP-A-62-95545. As a technique for preventing corrosion in a water washing step when an aluminum alloy is used as a base, Japanese Patent Application Laid-Open No. 6-273955 proposes a technique for cleaning a base with water in which carbon dioxide is dissolved. There is no mention of defining a certain range of film thickness and composition ratio with water containing an inhibitor.

Further, Japanese Patent Application Laid-Open No. 63-31261, Japanese Patent Application Laid-Open No. 1-156758, and Japanese Patent Publication No. 7-3412
Patent Document 3 describes a technique for forming an oxide film on an Al substrate, but does not describe a method of forming a film by washing with water containing an inhibitor.

Various materials such as organic substances such as selenium, cadmium sulfide, zinc oxide, amorphous silicon, and phthalocyanine have been proposed as techniques for element members used for electrophotographic photosensitive members. Among them, non-single-crystal deposited films mainly containing silicon atoms typified by amorphous silicon, such as hydrogen and / or halogen (for example, fluorine,
Amorphous deposited films such as amorphous silicon compensated with chlorine or the like have been proposed as high-performance, high-durability, 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 film deposited film on a substrate, is a method for forming an amorphous silicon deposited film for electrophotography. It is optimal and is currently in very practical use. Among them, in recent years, a plasma CVD method using microwave glow discharge decomposition, that is, a microwave plasma CVD method has been attracting industrial attention as a deposition film forming method.

The microwave plasma CVD method has the advantages of a higher deposition rate and higher source gas utilization efficiency than other methods. One example of a microwave plasma CVD technique that takes advantage of these advantages is disclosed in US Pat.
No. 04,518. The technique described in this patent is to obtain a high-quality deposited film at a high deposition rate by a microwave plasma CVD method at a low pressure of 13.3 Pa or less.

Further, a technique for improving the utilization efficiency of raw material gas by microwave plasma CVD is disclosed in
No. 186849. The technology described in the publication generally provides an internal chamber (ie, a discharge space) by arranging a substrate so as to surround a means for introducing microwave energy, thereby greatly improving the efficiency of using a source gas. Things. Also, JP-A-61-
No. 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 a cylinder made of an aluminum alloy 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. Next, the surface-treated substrate is washed with triethane, and a deposited film mainly composed of amorphous silicon, which is a deposited film of a photoconductive member, is formed on the substrate by a glow discharge decomposition method.

However, when an electrophotographic photosensitive member is formed by using a conventionally reported electrophotographic manufacturing apparatus, or when an electrophotographic photosensitive member is formed by a conventionally reported electrophotographic manufacturing method, abnormal growth in a deposited film occurs. Parts may occur. The abnormally grown portion is a portion having a very small area and not having sufficient surface charge. This phenomenon is particularly remarkable in amorphous silicon formed by a plasma CVD method. Conventionally, as a method of reducing the portion where the surface potential does not multiply, optimization of the surface processing conditions, cleaning conditions and deposition conditions of the substrate has been performed.

However, as in recent years, 1) higher image quality of the electrophotographic apparatus has been required and the resolution of development has been improved, and 2) as the speed of the copying machine has increased and charging conditions have become more severe, A portion where the potential is not applied on the surface substantially has a large effect on the peripheral potential, and as a result, an image defect due to the abnormally grown portion has been pointed out.

Furthermore, the conventional electrophotographic apparatus is mainly used for copying characters, and is mainly used for originals of only printed characters (so-called line copy), so that image defects did not become a serious problem in practical use. However, recently, as the image quality of a copying machine has increased, many originals including halftones such as photographs have been copied, and an electrophotographic photoreceptor having a small abnormally growing portion has been required at present. In particular, in a color copier, which has been widely used recently, an electrophotographic photoreceptor having a small number of abnormally grown portions is required since the color copier becomes clearer.

Further, since the abnormally grown portion is very small, it is difficult to detect the presence of the abnormally grown portion by measuring the conductivity in the deposited film using an electrode. Further, when the electrophotographic photosensitive member is charged, exposed, and developed by an electrophotographic process, particularly when a uniform image is formed by halftone, a slight potential difference on the surface of the electrophotographic photosensitive member also causes an image defect. And appear as visually striking. In particular, in the case of an electrophotographic photosensitive member prepared by a microwave plasma CVD method, the above-mentioned problem appears more remarkably.

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

Also, in a device manufactured by the plasma CVD method, even if the position where the abnormally grown portion exists is concentrated at an arbitrary position on the substrate like a solar cell, a slight difference in the characteristics substantially causes the performance to be substantially different. The above-mentioned problem does not occur in a device that does not affect or a device that can be corrected by post-processing.

[0020]

In recent years, it has been difficult to use a chlorinated solvent such as trichloroethane in the washing step for environmental protection, so that aqueous washing has been replaced by washing with an organic solvent. However, when the aluminum is washed with water, the impurity forms a local battery with the surrounding normal aluminum portion in a portion where the impurity (Si or the like) which is partially exposed on the aluminum surface is large, and the corrosion of the substrate surface is caused. As a countermeasure, corrosion of the substrate surface is prevented by using an aqueous solution of carbon dioxide. However, in this case, the apparatus becomes complicated and the production cost increases. Therefore, it has become necessary to simplify the apparatus and take measures at low cost. Further, when the electrophotographic photosensitive member of a member elongated in the longitudinal direction is immersed in the cleaning solution contained in the cleaning tank and is pulled up from the cleaning tank, cleaning unevenness is likely to occur along the longitudinal direction of the electrophotographic photosensitive member. And so on.

An object of the present invention is to provide a method for cleaning an object to be cleaned. Another object of the present invention is to provide a method of manufacturing a high-performance electrophotographic photoreceptor that can be formed at high speed and has a small amount of abnormally grown portions at low cost and with high yield while preventing corrosion during processing of a substrate.

It is a further object of the present invention to solve the problem of the occurrence of image defects due to abnormally grown portions in an electrophotographic photoreceptor formed by a plasma CVD method, and to obtain an electrophotographic photoreceptor capable of obtaining a uniform high-quality image. An object of the present invention is to provide a method for manufacturing a photoconductor.

[0023]

In order to solve the above-mentioned problems, the present invention provides a method for reducing the pressure of shower water sprayed on a substrate.
Set to 9 × 10 ³ Pa or more and 9.8 × 10 ⁴ Pa or less,
In addition, the flow rate of the shower water is set to 1 liter / min or more and 20 liter / min or less, the surface of the base is showered with the shower water, and then a functional film is formed on the surface by a reduced pressure vapor deposition method. The present invention provides a method for producing an electrophotographic photoreceptor.

Further, according to the present invention, the pressure of the shower water sprayed on the object to be cleaned is set to 4.9 × 10 ³ Pa or more and 9.8 × 10 ⁴ P or more.
a, the flow rate of the shower water is set to 1 liter / min or more and 20 liters / min or less, and the surface of the object to be cleaned is showered with the shower water. .

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the embodiments of the present invention, aluminum will be described as an example of a substrate to be cleaned used in the present invention.

The cause of the abnormal growth of the aluminum substrate is as follows: (A) dust on the substrate, dirt from the washing water in the washing and drying steps adhere to the core, or (B) It can be broadly classified because surface defects are the core.

The adhesion described in (A) is prevented to some extent by strictly cleaning the inside of the furnace to clean the place where the substrate is handled, such as cutting and cleaning, and cleaning the surface of the substrate immediately before forming the deposited film. It became possible to do. Conventionally, this object has been achieved by washing with a chlorine-based solvent such as trichloroethane. However, in recent years, the use of such chlorinated solvents has been restricted for reasons such as destruction of the ozone layer, and it has become necessary to consider a washing method using water as a washing method using a chlorinated solvent. .

On the other hand, as a method for further reducing the surface defects described in (B), diligent studies have been made from the viewpoint of solving all of these problems by combining a specific component-containing aluminum with a specific cleaning method. As a result, the present invention was completed.

In the present invention, aluminum containing silicon is used. The reason is that it is usually preferable that the amount of impurities contained in aluminum is small, but when very high-purity aluminum is melt-processed into the shape of a base, an oxide is easily grown and many abnormally grown portions are generated. It has been clarified that it is effective to contain Si atoms with aluminum in order to prevent the abnormal growth portion, and the present invention uses an aqueous cleaning agent in which silicate or the like is dissolved as a corrosion inhibitor (inhibitor). To clean the aluminum containing Si atoms.

The reason for using the water-based detergent containing the inhibitor is that aluminum containing silicon (Si) atoms is easily corroded by water mainly in a portion where Si atoms are locally large, and the corrosion is prevented. . Or similar corrosion may occur not only in Si atoms but also in other parts where Fe atoms or Cu atoms are locally large, but it is possible to effectively prevent corrosion by using an inhibitor such as silicate. I can do it.

The corrosion is remarkable when the temperature of the washing water is high or when aluminum contains magnesium for the purpose of improving machinability together with Si, Fe and Cu atoms, and contains Si, Fe and Cu. It is preferable to add a corrosion inhibitor (inhibitor) for preventing corrosion of the aluminum substrate used as the substrate of the electrophotographic photosensitive member to the water detergent.

This inhibitor has A on the aluminum surface.
It is believed that an l-Si-O film can be formed to prevent corrosion of the aluminum substrate. When the Al—Si—O film is formed, there is no defect on the surface of the substrate, and as a result, it is possible to prevent the occurrence of abnormal growth during the formation of the functional film.

Further, by cleaning aluminum by using a water detergent containing a silicate as an inhibitor, not only the occurrence of abnormal growth is prevented but also the electrophotographic characteristics are improved.

The reason will be described in detail below. In the embodiment of the present invention, an amorphous silicon deposition film is formed on a substrate by a plasma CVD method. The plasma CVD method can be generally divided into three processes: a decomposition process of a raw material gas in a gas phase, a transport process of active species from a discharge space to a substrate surface, and a surface reaction process on the substrate surface. In particular, the surface reaction process plays a very important role in determining the structure of the completed deposited film. The surface reaction is affected by the temperature, the material, the shape, the adsorbed substance, and the like of the surface of the substrate, and is particularly greatly affected by the adsorbed substance.

In particular, water is easily adsorbed on the surface of a high purity aluminum substrate. For example, plasma CV on a substrate
When a deposited film made of amorphous silicon is formed by the method D using silicon or silicon containing hydrogen and fluorine, the substrate of the deposited film is formed by water adsorbed on the surface of the substrate.
There are portions where the composition and structure of the interface of the deposited film have changed.
As a result, when a substrate having a deposited film formed on its surface is used in an electrophotographic process as an electrophotographic photoreceptor, the portion has a different property from other portions of the substrate surface in terms of charge injecting property or surface potential. The image quality of the image obtained by the photographic process becomes uneven.

In the present invention, an Al-Si-O film is formed on the surface of a substrate with a silicate as an inhibitor before forming a functional film made of amorphous silicon by a plasma CVD method, and the surface of the substrate after the film is formed is showered. The pressure at the time of cleaning is reduced compared to the pressure set conventionally, and by increasing the shower flow rate, for example, the cleaning unevenness is eliminated for a member that is long in the longitudinal direction, such as a base of an electrophotographic photosensitive member, and formed. The deposited Al-Si-O film is made more uniform so that it does not peel off partly, a strong film can be formed, and an interface that allows good charge exchange when forming a deposited film is formed. Thus, a high-quality deposited film can be formed. For this reason, the obtained substrate has improved chargeability,
It is possible to improve electrophotographic characteristics such as light sensitivity.

In the present invention, before the film forming step of forming a deposited film on the cut substrate, a degreasing cleaning step of degreasing and cleaning the surface of the substrate, a rinsing step of rinsing the degreasing cleaned surface of the substrate, and Process in the order of drying process to dry,
In at least one of the three steps, a silicate film is formed on the aluminum substrate with water containing silicate.

Further, in the present invention, when the aluminum substrate on which the silicate film is formed is lifted in the rinsing step, the ratio of shower (shower water) pressure (low pressure) / shower (shower water) flow rate (high flow rate) is kept constant. By setting the rinsing rate within the range, it is possible to prevent the silicate film from flowing down by the blowing pressure of the shower (shower water) before the silicate film is firmly formed and to prevent the substrate surface from drying. Therefore, an aluminum substrate having a high-quality amorphous deposited film can be obtained.

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

The substrate accommodated in the substrate cleaning apparatus shown in FIG. 1 may be subjected to, for example, the following processing in advance. The processing is described in detail. Set a bite (trade name: Miracle bite, made by Tokyo Diamond) so as to obtain a rake angle of 5 ° with respect to the cylinder center angle.
The base was fixed to the rotating flange of the lathe by vacuum chucking, and spraying of white kerosene from the attached nozzle and suction of the swarf from the attached vacuum nozzle together with a peripheral speed of 100
Mirror cutting is performed so that the outer shape becomes 108 mm under the conditions of 0 m / min and a feed rate of 0.01 mm / R. The substrate used in the present invention does not necessarily need to have been subjected to the above-described treatment in advance.

The substrate after the cutting is transported to the cleaning device shown in FIG. FIG. 1 shows a cleaning apparatus for cleaning a substrate surface. The cleaning device includes a processing unit 102 and a substrate transport mechanism 103. The processing unit 102 includes the substrate loading table 11
1. Degreasing / washing tank 112, rinsing tank 113, drying tank 11
4. It is composed of a base carrier 115. Degreasing cleaning tank 11
2. The rinsing tank 113 and the drying tank 114 are provided with a temperature controller (not shown) for keeping the liquid temperature 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.

The substrate 101 placed on the loading table 111 is
The carrier is transported to the degreasing / cleaning tank 112 by the transport mechanism 103.
A water cleaning agent 12 containing a surfactant is contained in the degreasing cleaning tank 112.
2, the substrate 101 is subjected to ultrasonic cleaning to remove dust, oil, and the like adhering to the surface.

After the degreasing and cleaning step, the substrate 101 is transferred to the rinsing tank 11 by the transport mechanism 103 which is to be moved to the rinsing step.
It is carried to 3. The rinsing tank 113 contains a cleaning liquid 123 to which silicate has been added, and is further rinsed with pure water or the like kept at a temperature of 25 ° C. Thereafter, the base 101 is pulled up by a lifting mechanism (not shown), and at this time, the cleaning liquid 123 is showered on the base 101 by the shower nozzle 126. The purity of pure water or the like is constantly controlled by an industrial conductivity meter (trade name: α900R / C, manufactured by HORIBA, Ltd.). At this time, the shower nozzle 12
6 may be sprayed perpendicularly to the surface of the base 101, or at an angle so that the nozzle can spray water downward so that water does not flow out of the tank. May be set in the direction toward the inside of the tank.

The substrate after the rinsing step is then subjected to a drying step.
4 and is lifted and dried by a lifting device (not shown) using hot pure water or the like kept at a temperature of 60 ° C. The purity of hot pure water and the like is controlled to be constant by an industrial conductivity meter (trade name: α900R / C, manufactured by HORIBA, Ltd.).

Next, the substrate 101 after the drying step is carried to the carry-out table 115 by the carrying mechanism 103 and carried out of the cleaning device shown in FIG.

Next, a deposited film mainly composed of amorphous silicon is formed on the substrate by using a photoconductive member deposited film forming apparatus by the plasma CVD method shown in FIG.

In FIG. 2, a reaction vessel 202 comprises a base plate 205, a wall 203 also serving as a cathode electrode, and a top plate 204. Inside the reaction vessel 202, a substrate 20 on which an amorphous silicon deposition film is formed is formed.
Reference numeral 1 is provided at the center of the cathode electrode 203 and also serves as an anode electrode.

In order to form an amorphous silicon deposited film on the substrate 201 using this deposited film forming apparatus, first, the source gas inflow valve 211 is closed, and the exhaust valve 21 is closed.
4 is opened, and the reaction vessel 202 is evacuated. When the reading of the vacuum gauge (not shown) reaches about 6.65 × 10 ⁻⁴ Pa, the source gas inflow valve 211 is opened. The gas is supplied into the reaction vessel 202 through the source gas introduction pipes 209 and 210. The source gas introduction pipe has a plurality of openings. The openings are indicated by dotted lines in FIG. 2, but the portions not drawn correspond to the plurality of openings. The gas flow rate is adjusted to a predetermined flow rate in the mass flow controller 212. For example, a raw material gas such as SiH ₄ gas
2 Then, after confirming that the surface temperature of the base 201 is set to a predetermined temperature by the heater 208, a high frequency power supply (frequency: 13.56 MHz)
216 is set to a desired electric power to cause glow discharge in the reaction vessel 202.

During formation of the deposited film, the substrate 201 is rotated at a constant speed about a longitudinal direction by a motor (not shown) in order to make the deposited film uniform. In this way, an amorphous silicon deposition film is formed on the base 201.

In the present invention, the surface of the substrate is processed to have a flat surface, and the surface is mirror-finished as described above, or the surface is made non-mirror for the purpose of preventing interference fringes, or irregularities having a desired shape are provided. May be done.

In addition, since corrosion is easily promoted in a portion of the aluminum surface which is partially exposed to atoms such as Si, Fe, or Cu, the present invention provides a method of adding a silicate in the rinsing step to add a silicate. The formation of a film thereon is as described above. The reason is that it is necessary to form a film before the substrate comes into contact with pure water or the like. In the present invention, in addition to using the silicate in the liquid only in the rinse cleaning step, the silicate is converted into the liquid together with the cleaning step in at least one of the degreasing cleaning step and the drying step. It may be used in combination.

The inhibitors of the present invention include phosphates, silicates, borates and the like, and silicates are particularly preferred in the present invention.

Further, among silicates, any of potassium silicate, sodium silicate and the like may be used, but potassium silicate is particularly preferred in the present invention, and a stable film can be formed on the substrate.

The surfactant used in the present invention may be an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or a mixture thereof. Any thing is possible. Above all, when the liquid (water) is alkaline, use an anionic surfactant such as a carboxylate, a sulfonate, a sulfate or a phosphate, or a nonionic surfactant such as a fatty acid ester. Is preferred in the present invention.

It is desirable to use semiconductor grade pure water, particularly ultra LSI grade ultrapure water, which is used in the degreasing washing step, rinsing step or drying step of the present invention. Specifically, the lower limit is 1 MΩ as the resistivity at a water temperature of 25 ° C.
Cm or more, preferably 3 MΩcm or more, optimally 5
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.
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, if the temperature of the aqueous cleaning agent containing a surfactant is too high, spots due to liquid traces are generated on the surface of the substrate, and the deposited film is easily peeled off. If the temperature is too low, a sufficient degreasing effect cannot be obtained. The range of the temperature of the liquid used in the present invention is 10 ° C or higher and 60 ° C or lower, preferably 15 ° C or higher and 50 ° C or lower,
Optimally, it is in the range of 20 ° C. or more and 40 ° C. or less.

In the present invention, if the surfactant contained in water in a unit volume used in the degreasing and washing step has a weight percent concentration, if the concentration is too high, stains due to liquid traces are generated, and the deposited film is peeled off. Etc.

If it is too thin, the degreasing effect will be reduced. Liquid (water) in unit volume used in the present invention
The range of the concentration by weight of the surfactant contained in is 0.1 w
t% or more, 20 wt% or less, preferably 1 wt% or more,
The range is 10 wt% or less, optimally 2 wt% or more and 8 wt% or less.

In the present invention, if the pH of the aqueous detergent containing a surfactant is too high, stains due to liquid traces are generated, and the deposited film is easily peeled off. On the other hand, if it is too low, the degreasing effect is small, and the effect of the present invention cannot be sufficiently obtained. P of aqueous detergent containing surfactant used in the present invention
The range of the value of H is 8 or more and 12.5 or less, preferably 9 or more.
The range is not less than 12 and, optimally, not less than 10 and not more than 11.5.

In the present invention, if the concentration of the silicate contained in the water used for forming a film on the surface of the substrate is too high, spots due to liquid traces are generated and the deposited film is easily peeled off. Resulting in. On the other hand, if the thickness is too small, the effect of the film is small and the effect of the present invention cannot be sufficiently obtained. For this reason, the range of the concentration by weight of the silicate contained in the water per unit volume is as follows:
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%
The range is 1 wt% or less.

In the present invention, the effect is not exhibited if the thickness of the film formed on the aluminum substrate is too small. If the thickness is too large, the conductivity between the aluminum substrate and the deposited film formed thereon is reduced. Comes out. For this reason, the range of the thickness of the film is 5 ° to 150 °, preferably 1 °.
The range is from 0 ° to 130 °, optimally from 15 ° to 120 °.

In the present invention, the composition ratio of the Al—Si—O film formed on the aluminum substrate is set to Si or O.
If the content is small, the content of Al is large and the film is insufficient, and even if the content is large, the conductivity is lowered, which is not suitable. Al
Is set to 1, Si is 0.1 or more and 1.0 or less, preferably 0.15 or more and 0.8 or less, and most preferably 0.2 or more and 0.6 or less.
The following are suitable:

In the present invention, when shower cleaning is performed after rinsing cleaning, if the pressure of water is too high, the film is peeled off, and if the pressure is too weak, the rinsing effect does not appear. It is important to balance the pressure and flow rate of the water well, and the water pressure is 4.9 × 10 ³ (Pa)
Not less than 9.8 × 10 ⁴ (Pa), more preferably not more than 6.
9 × 10 ³ (Pa) or more and 7.8 × 10 ⁴ (Pa) or less is suitable for the present invention, and at the same time, the flow rate is 1 l / min or more and 20 l / min or less, more preferably 3 l / min.
As described above, 16 l / min or less is suitable for the present invention. At this time, for example, the control unit 180 such as a personal computer shown in FIG.
It is also preferable to control the pressure and flow rate of water because highly accurate cleaning can be performed in a short time. Alternatively, the control may be performed manually without using the control unit 180.

The use of ultrasonic waves in the degreasing and washing steps and the rinsing step of the present invention is effective in achieving the degreasing or rinsing effect of the present invention. The range of ultrasonic frequencies is
Preferably 100 Hz or more and 10 MHz or less, more preferably 1 kHz or more and 5 MHz or less, optimally 10 kHz
The range from z to 100 kHz is effective. The output of the ultrasonic wave is preferably 0.1 W / liter or more and 1 kW.
/ L or less, more preferably 1W / L or more,
100 W / liter or less is effective.

As described above, it is also preferable to form a film on the substrate by dissolving the silicate in water used in the rinsing step or the drying step. In the present invention, carbon dioxide may be dissolved in water used in the rinsing step or the drying step to improve the rinsing effect or the drying effect. At this time, the quality of the water is very important, and in a state before dissolving carbon dioxide, 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 optimally 5 MΩ · c.
m 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, and optimally 13 MΩ / cm.
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 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 amount of carbon dioxide dissolved in water can be any amount up to the saturation solubility, but the present invention is possible. However, if it is too large, bubbles are generated when the water temperature fluctuates and adhere to the surface of the substrate to form spots. Spots may occur. Furthermore,
If the amount of dissolved carbon dioxide is large, the pH will decrease,
The substrate may be damaged. On the other hand, if the amount of dissolved carbon dioxide is too small, the high rinsing effect or drying effect 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 not more than 60% of the saturation solubility, more preferably 4%.
The condition is 0%.

In the rinsing step of 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 μm.
S / cm or more, 40 μS / cm or less, more preferably 4 μS / cm or less
The range is preferably 3.8 or more and 6.0 or less, and more preferably 4.mu.S / cm or more, 30 .mu.S / cm or less, 6 .mu.S / cm or more, 25 .mu.S / cm or less and pH.
When the value is 0 or more and 5.0 or less, 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 temperature of water containing carbon dioxide is 5 ° C. or more,
90 ° 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 may be any of a method by bubbling and a method using a diaphragm.
Further, in the present invention, carbon dioxide is used as a solute, because the influence of a cation such as sodium ion on a substrate, which may occur when a carbonate such as sodium carbonate is used as a solute, is used. Can be prevented.

When the surface of the substrate is washed with water in which carbon dioxide is dissolved in this way, it is fundamental to immerse the substrate in a water tank into which water in which carbon dioxide is dissolved is introduced. The present invention will be more effective if sound waves are applied, a water stream is applied, or bubbling is performed with air or the like.

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.

In the drying step of 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 / c.
m or more and 40 μS / cm or less, more preferably 6 μS / cm
cm or more, 35 μS / cm or less, 8 μS / cm or more, 3
When the pH is controlled at 0 μS / cm or less, the preferable 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 purity of water for dissolving carbon dioxide and the dissolving method for dissolving carbon dioxide are the same as those in the rinsing step.

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 it is necessary to prevent unevenness due to drying.
00 mm / min or more, 2000 mm / min, more preferably 200 mm / min, optimally 300 mm / m
The range of not less than in and 1000 mm / min is suitable for the present invention.

If the time from the cleaning treatment with water in which carbon dioxide is dissolved to the introduction into the deposited film forming apparatus for forming the deposited film on the substrate is too long, the effect of the present invention is reduced, and the time is too short. And the process is not stable, so that it is 1 minute or more and 8 hours or less, preferably 2 minutes or more and 4 hours or less,
Optimally, the range of 3 minutes or more and 2 hours or less is suitable for the present invention.

In the present invention, any material can be used for the substrate as long as it has aluminum as a base material. The aluminum substrate contains at least 10 ppm of iron (Fe) and the aluminum substrate contains silicon (Si). It is suitable for the present invention that the aluminum base contains 10 ppm or more, and the aluminum base contains 10 ppm or more of copper (Cu) and the total content of Fe + Si + Cu exceeds 0.01 wt% and 1 wt% or less.

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, more preferably 0.2 wt% or more and 5 wt% or less.

Further, in the present invention, H, Li, Na, K, Be,
Ca, Ti, Cr, Mn, Co, Ni, Ag, Zn, C
d, Hg, B, Ca, In, C, Ge, Sn, N, P,
Elements such as As, O, S, Se, F, Cl, Br, and I may be contained 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 in the form of an endless belt or cylindrical as described above. Are the most suitable for the present invention. In the case of a cylindrical shape, the size of the substrate is not particularly limited, but practically, the outer diameter is 20 mm or more, 500 mm or less, the length is 10 mm or more,
1000 or less is preferred. 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, even 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, and an organic photoreceptor. In the case of a photoreceptor, the effect is remarkable.

When a non-single-crystal photoconductor containing silicon is prepared, silane (SiH ₄ ), disilane (Si ₂ H ₆ ), and silicon tetrafluoride (SiF ₄ ) are used as source gases for forming a deposited film. And an amorphous silicon forming material gas such as disilicon hexafluoride (Si ₂ F ₆ ) or a mixed gas thereof.

As the diluting gas, hydrogen (H ₂ ), argon (Ar), helium (He) and the like can be mentioned.

As a characteristic improving gas used to arbitrarily adjust the band gap width of the deposited film, nitrogen (N
₂ ), an element containing a nitrogen atom such as ammonia (NH ₃ ),
Oxygen (O ₂ ), nitric oxide (NO), nitrogen dioxide (NO
₂ ), dinitrogen oxide (N ₂ O), carbon monoxide (CO), carbon dioxide (CO ₂ ) and other elements containing oxygen atoms, methane (C
H ₄ ), ethane (C ₂ H ₆ ), ethylene (C ₂ H ₄ ),
Examples thereof include hydrocarbons such as acetylene (C ₂ H ₂ ) and propane (C ₃ H ₈ ), fluorine compounds such as germanium tetrafluoride (GeF ₄ ) and nitrogen fluoride (NF ₃ ), and a mixed gas thereof.

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

In the electrophotographic photoreceptor of the present invention, the total thickness of the deposited film deposited on the substrate may be any, but 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 observed in any region.
6 × 10 ^-2 Pa or more and 13.3 Pa or less, preferably 1
At 3.3 × 10 ^-2 Pa or more and 6.65 Pa 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, 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 any heating element of a vacuum specification, and more specifically, an electric resistance heating element such as a winding heater of a sheath-like heater, a plate-like heater, or a ceramics 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.

In the present invention, it is possible to use the above means alone or in combination.

In the present invention, the energy for generating the plasma may be DC, RF, microwave, VHF, or the like. In particular, the present invention is effective when microwaves are used, but this is because the present invention forms a uniform film without peeling off a film on a substrate, and as a result, a size that may cause unevenness in image quality. This is because it is possible to prevent the presence of moisture adsorbed on the substrate.
If the deposited film is formed using microwaves without removing the water, abnormal growth is likely to appear in the deposited film due to the water, and the absorbed water absorbs the microwave, The change in the interface tends to be more remarkable.

In the present invention, when microwaves are used for plasma generation, any microwave power may be used as long as discharge can be generated.
0 kW or less, preferably 500 W or more and 4 kW are 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.
It is preferable that an electric field is applied at least in a direction in which cations collide with the substrate. Note that the DC component voltage is 1 V or more and 5
It is desirable to apply a bias voltage of 00 V or less, preferably 5 V or more and 100 V or less during formation of the deposited film.

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 (registered trademark), polystyrene, and other materials with low microwave loss. 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.
mm or less is preferable. The number of substrates is not particularly limited as long as a discharge space can be formed in consideration of productivity, 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 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 produced 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 be widely used.

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

(Example 1) 0.05 wt% of Si, Fe
Is made of aluminum of 0.03 wt%, Cu is 0.01 wt%, diameter 108 mm, length 358 mm, wall thickness 5 m
The surface of the cylindrical substrate having a length of m was cut in the same procedure as in the above-described example of the procedure of the method for producing an electrophotographic photosensitive member according to the present invention. The abundance ratio of all the atoms present on the substrate shown in the present invention was determined by X-ray photoelectron spectroscopy (XPS) using an X-ray anode made of magnesium (Mg) at 15K.
v, 400 w, and the energy resolution is set to 0.
At 98 ev (Ag3d5 / 2), the degree of vacuum was 1.33 × 1
This is a value measured under the condition of 0 ⁻⁷ Pa or less.

The substrate was conveyed to the substrate surface cleaning apparatus of the present invention shown in FIG. 1 15 minutes after the completion of the cutting step, and was degreased, rinsed and dried with a detergent (nonionic surfactant) under the conditions shown in Table 1. The processing was given. Further, as shown in Table 3, an inhibition type electrophotographic photosensitive member was manufactured from the substrate obtained by changing the step of adding the inhibitor, and the obtained image was evaluated based on the evaluation of black spots and image defects described later. .

In this embodiment, the concentration of the surfactant contained in water per unit volume of the surfactant used for degreasing and washing is 3 wt%. The inhibitor used in this embodiment is potassium silicate, and the concentration of water per unit volume is 0.3 wt%.

The evaluation of the electrophotographic characteristics of the produced electrophotographic photosensitive member was performed as follows. That is, the process speed of the prepared electrophotographic photosensitive member is set to 200 to 8 in advance for the experiment.
Arbitrarily changed within the range of 00 mm sec.
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 photoreceptor by laser image exposure, and then modified so that an image could be formed on transfer paper by a normal copying process.
In P6650, image evaluation of black spots and image defects was performed. Table 3 shows the results.

Comparative Example 1 The procedure was the same as that of Example 1 except that no inhibitor was used. A blocking type electrophotographic photosensitive member was prepared in the same manner and evaluated in the same manner. The results are shown in Table 3 as in Example 1.

Evaluation of Black Spots and Image Defects The image process with the largest number of image defects among the image samples obtained when the entire halftone original and the character original were copied on the platen by changing the process speed was selected and evaluated. went. As an evaluation method, the image sample was observed with a magnifying glass, and evaluation was performed based on the state of white spots within the same area. The results of the evaluation are shown in the table using the following four symbols.

◎: Extremely good…: Good level with some small defects but no practical problem △: Level with slight defects on the entire surface but no practical problem ×: Large defect on the entire surface and problematic

[0109]

[Table 1]

[0110]

[Table 2]

[0111]

[Table 3]

As shown in the image evaluation results in Table 3, good results in image evaluation could be obtained by treating the substrate with water containing an inhibitor before contacting the substrate with pure water.

(Example 2) In Example 2 of the present invention, the same substrate as in Example 1 was used, and water used in the rinsing step shown in Table 1 was converted to pure water and carbon dioxide as shown in Table 4 through Table 4 below. 3
Varying combinations were used. Further, as shown in Table 5, in the rinsing step and the drying step, a blocking type electrophotographic photoreceptor was formed on a substrate in the same manner as in Example 1 except that the timing of adding an inhibitor was changed. Evaluation was performed in the same manner as in Example 1. Table 5 shows the results.

[0114]

[Table 4]

[0115]

[Table 5]

As shown in the image evaluation results shown in Table 5, good results in image evaluation can be obtained by treating the substrate with an aqueous solution of carbon dioxide or water containing an inhibitor before treating the substrate with pure water. Was.

Example 3 Using the same substrate as in Example 1, the treatment was carried out according to the method shown in Table 6, and the type of silicate to be introduced was changed as shown in Table 7. Further, a blocking type electrophotographic photosensitive member was formed on a substrate in the same manner as in Example 1 and evaluated in the same manner. Table 7 shows the results.

[0118]

[Table 6]

[0119]

[Table 7]

As is clear from Table 7, good results were obtained with any of the silicates, but the best overall evaluation was obtained especially when potassium silicate was used as the inhibitor.

(Example 4) Using the same substrate as in Example 1, washing was performed under the conditions shown in Table 6 in the same manner as in Example 3. At that time, the concentration of potassium silicate dissolved in water per unit volume was changed in ten ways as shown in Table 8, and the surface of the substrate after washing was observed based on a method for confirming the appearance (stain) described later. . Further, a blocking type electrophotographic photosensitive member was prepared in the same manner as in Example 1, and the evaluation was performed in the same manner as in Example 1. Table 8 shows the results.

Confirmation of Appearance (Stain) Light of strong exposure was reflected on the surface of the substrate after cleaning, and a stain on the substrate which could be visually confirmed was confirmed. The results are shown in Table 8 using the following three symbols. …: Good without any stains Δ: very thin and no problem at all ×: Spots are clearly recognized.

[0123]

[Table 8]

Table 8 shows that good results can be obtained when the concentration of potassium silicate dissolved in water per unit volume is in the range of 0.05 wt% to 2.0 wt%.

Example 5 Using the same substrate as in Example 1, cleaning was performed under the conditions shown in Table 9. At that time, using the water containing the inhibitor, the spraying pressure (shower pressure) and the flow rate at the time of showering in the rinsing bath were changed as shown in Tables 10 and 11, and the appearance state of the substrate surface after washing was visually observed. Observed. Thereafter, a blocking type electrophotographic photosensitive member was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. Table 10 shows the results of the appearance, and Table 11 shows the results of black spot image defects. still,
As the water used as the shower liquid, water in which an inhibitor was dissolved in pure water (10 MΩ · cm) used in the rinsing step was used.

[0126]

[Table 9]

(Evaluation of Appearance Observation) The condition of spots on the substrate and surface roughness of the substrate, which can be visually confirmed by reflecting strong exposure light on the surface of the substrate after cleaning, was comprehensively evaluated. The evaluation results are shown in the table with the following four symbols. ◎… very good ○… good △… No practical problem ×… Practical problem

[0128]

[Table 10]

As is apparent from Table 10, the appearance was such that the pressure of the shower was 4.9 × 10 ³ (Pa) to 9.8 × 10 ^4.
(Pa) and the flow rate of the shower is 1 (1 / m
good results were obtained in the range of (in) to 20 (1 / min).

[0130]

[Table 11]

As is clear from Table 11, even in the case of black spots and image defects, the shower pressure was 4.9 × 10 ³ (P
Good results were obtained in the range of a) to 9.8 × 10 ⁴ (Pa) and the flow rate of the shower was in the range of 1 (1 / min) to 20 (1 / min).

(Example 6) Using the same substrate as in Example 1, cleaning was performed by changing the processing temperature and time under the conditions shown in Table 12 to change the film thickness of the film. Thereafter, a blocking type electrophotographic photoreceptor equivalent to that of Example 1 was produced and subjected to the same evaluation. Table 13 shows the results. The overall evaluation method and criteria are the same as those described above.

[0133]

[Table 12]

[0134]

[Table 13]

According to the results shown in Table 13, the film thickness was 5 mm or more,
Good results were obtained in the range of 150 ° or less.

(Example 7) As shown in Table 15, nine types of Al substrates having different Si contents were used, and degreasing washing, rinsing and drying were performed under the conditions shown in Table 14. Thereafter, a blocking type electrophotographic photosensitive member was prepared using each substrate in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. Table 15 shows the results. The overall evaluation method is the same as described above.

[0137]

[Table 14]

[0138]

[Table 15]

As is clear from Table 15, the weight percentage of Si contained in the Al substrate was 0.001 wt% ≦ Si ≦ 1 wt
%, A good overall evaluation could be obtained even if the content varied.

(Example 8) A method similar to that of Example 7 was used, except that the content of Fe was changed. A blocking type electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 7.
Table 16 also shows the results.

[0141]

[Table 16]

As is clear from Table 16, the range of the weight percentage of Fe contained in the Al substrate was 0.001 wt% ≦ Fe.
Good overall evaluation could be obtained in the range of ≦ 1 wt%.

(Example 9) A method similar to that of Example 7 was adopted except that the content of Cu was changed. A blocking type electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 7. Table 17 also shows the results.

[0144]

[Table 17]

As is clear from Table 17, the range of the weight percentage of Cu contained in the Al substrate was 0.001 wt% ≦ Cu ≦
Good overall evaluation could be obtained in the range of 1.0 wt%.

(Example 10) Degreasing and washing, rinsing, and washing were performed in the same manner as in Example 7 using nine types of aluminum substrates in which the contents of Si, Fe, and Cu were changed as shown in Table 18.
Each drying process was performed. Thereafter, a blocking type electrophotographic photosensitive member was prepared in the same manner as in the example, and the same evaluation as in example 1 was performed. The results are also shown in Table 18.

[0147]

[Table 18]

As is clear from Table 18, Si, Fe,
When the total content of Cu is 0.01 wt% <Si + Fe + Cu ≦
It was found to be effective in the range of 1 wt%.

Example 11 Using the same substrate as in Example 1, the temperature of water used in the rinsing step and the time required for the rinsing step were changed under the conditions shown in Table 19, and
A film was formed under the following conditions. In addition, S contained in Al
The ratio between i and O was changed. Then, a blocking type electrophotographic photosensitive member equivalent to that of Example 1 was produced and comprehensively evaluated. The overall evaluation method and criteria are the same as described above. Table 20 shows Si
The content ratio of O was changed to 7 types, and the content ratio of O was changed to 6 types, showing the total evaluation results performed using a total of 42 types of substrates. The composition ratio at this time is a value measured by the XPS method shown in Example 1, and is a ratio of the number of each element when Al is set to 1.

[0150]

[Table 19]

[0151]

[Table 20]

As is clear from Table 20, good results were obtained when the composition ratio of Si was 0.1 or more and 0.5 or less and the composition ratio of O was 1 or more and 5 or less.

(Example 12) 0.03 wt% of Si, F
e, made of aluminum containing 0.05 wt% and 0.02 wt% of Cu, a diameter of 108 mm, a length of 358 mm,
A cylindrical substrate having a thickness of 5 mm was processed by the method for producing an electrophotographic photosensitive member of the present invention. The method for cutting the surface employed was the method described above. Note that the abundance ratio of all atoms present on the substrate shown in the present invention is determined by X-ray photoelectron spectroscopy (XPS).
Using magnesium (Mg) as the X-ray anode, the output conditions were 15 Kv, 400 w, the energy resolution was 0.98 ev (Ag3d5 / 2), and the degree of vacuum was 1.33 × 10 ⁻⁷ Pa or less. Value.

Fifteen minutes after the completion of the cutting step, degreasing, rinsing, and drying were performed with a detergent (nonionic surfactant) under the conditions shown in Table 21 using the substrate surface cleaning apparatus shown in FIG.

Thereafter, a deposited film was formed on the substrate under the conditions shown in Table 22 using the deposited film forming apparatus shown in FIG. FIG. 5A is a diagram schematically illustrating the layer configuration of the blocking type electrophotographic photosensitive member manufactured in this example. In this case, the composition ratio of each element of the Al—Si—O film was 1:
The thickness was 75 ° with a composition of 0.25: 3.

The electrophotographic photosensitive member thus produced was evaluated for electrophotographic characteristics as follows. The evaluation results are obtained from ten photoconductors manufactured under the same film forming conditions.

After the appearance of the electrophotographic photosensitive member thus produced was visually observed for film peeling and evaluated, the process speed was arbitrarily changed in the range of 200 to 800 mm / sec for experiments, and the charging device 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 23 shows the results of these evaluations.

The image evaluation was performed by the following method. or,
The base described in the present embodiment, that is, Si is 0.03
wt%, Fe 0.05%, Cu 0.02%
A method shown in Comparative Example 1 using the contained aluminum substrate as a comparative example, that is, a treatment using no inhibitor in any of the degreasing, rinsing, and drying treatments, followed by the same inhibition type electrophotography as in Example 12. A photoreceptor was prepared and evaluated in the same manner as in Example 12. Table 23 also shows the results.

Image Defect Evaluation The process speed was changed, and a halftone original and a text original were placed on an original platen, and an image sample having the most image defects among a plurality of image samples obtained when copying was selected and evaluated. Was done. As an evaluation method, the image sample was observed at an enlarged boundary, and evaluation was performed based on the state of white spots within the same area. The evaluation results are shown in the table with the following four symbols. ◎: Subtle white spots could hardly be confirmed, and an extremely good image could be obtained. 〇: A good image can be obtained although there are some small white spots. Δ: There is a slight white spot on the entire surface, but there is no problem in confirming the characters. X: Some characters are difficult to read due to many white spots.

An image was output so that the average density of an image obtained by placing the entire halftone original on a platen was 0.4 ± 0.1 while changing the process speed for evaluating black spots . Among the image samples obtained in this way, the most noticeable one was selected and evaluated. As a method of evaluation, these images were placed 40 cm from the eyes.
Observe at a distance to see if black spots are observed,
Evaluation was performed based on the following criteria. A: No black spot is observed on any copy. Very good images can be provided. 〇: Some black spots were observed. However, there is no problem because the image is small and a good image can be obtained. 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 properties 1 (electrophotographic properties 1 and
Hereinafter referred) to evaluate a relative value of the surface potential of the resulting photosensitive member in the developing position as chargeability when given the same charge voltage in the normal process speed. In addition, the charging ability of the electrophotographic photosensitive member obtained in Comparative Example 1 was evaluated as 100%.

Evaluation of electrophotographic characteristics (electrophotographic characteristics 2 and
Under referred) after giving the same charge voltage in the normal process speed,
The light amount obtained when the light is irradiated and dropped to a certain potential is evaluated as a sensitivity as a relative value. Note that the sensitivity of the electrophotographic photosensitive member obtained in Comparative Example 1 was evaluated as 100%.

[0163]

[Table 21]

[0164]

[Table 22]

[0165]

[Table 23]

As is clear from Table 23, image defects, black spots, and further improvement in electrophotographic characteristics were realized.

Table 2 shows the results of evaluation by another method.
It is shown in FIG.

Evaluation of Slipperiness An arbitrary load is applied to the blade installed in the modified Canon copier, NP6650, and a piezo element is used, and the blade pulling force before and after the start of rotation of the drum ( Friction force) was detected. 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. They were compared by relative values. (The lower the value, the better the slipperiness.) Evaluation of image unevenness A3 A 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 so that an image was obtained in a range from barely recognizing the line of the graph to the level at which the white portion started to be fogged, and ten copies having 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. The evaluation results are shown in the table with the following four symbols. A: No image unevenness is observed on any copy.
Very good condition. 〇: There is a copy in which image unevenness is recognized and a copy in which image unevenness is not recognized. However, each is in a good state without any problem at all. Δ: Image unevenness is observed on any copy. However, the image unevenness is slight on at least one copy, which does not hinder practical use. ×: Large image unevenness is observed on all copies.

Evaluation of fogging on white background An image sample obtained when a normal original consisting of whole characters was placed on a document table and copied on a white background was observed, and the fogging on the white background was evaluated. The evaluation results are shown in the table with the following four symbols. …: Very good with almost no fog on the white background. 〇: Some fogging is good, but good. Δ: There is a fog over the entire surface, but there is no problem in character recognition. ×: Some parts are difficult to read due to fog.

[0171]

[Table 24]

As is clear from Table 24, the sliding property and image characteristics could be further improved.

(Example 13) Using the same substrate as in Example 12, surface treatment was performed in the same manner as in Example 12, and the microstructure shown in FIGS. 3A and 3B was used. Table 2 using a deposition film forming device (μw PCVD) device that outputs waves
Table 26 shows the results of producing the blocking electrophotographic photosensitive member shown in FIG. 5-B under the conditions shown in FIG.

FIG. 3 is a side view for explaining a microwave CVD apparatus, wherein 302 is a chamber for accommodating the substrate 301, 305 is a motor for rotating the substrate 301 when a film is formed on the surface of the substrate 301, and 303 is a motor. A heater for heating the substrate 301 when forming a film, 304 is an exhaust path for exhausting the inside of the chamber 302, and a discharge space 306 is a space between the substrate 301 and the electrode 307. DC power is supplied to the electrode 307 by the power supply unit 308.
The electrode 307 also has a function of an introduction pipe for introducing gas into the chamber 302. 309 is a microwave introduction window for introducing microwaves transmitted through the introduction path 310 into the chamber 302, and FIG. 3B is a cross-sectional view taken along line XX of the microwave CVD apparatus shown in FIG. 3A. , And the same blocking type electrophotographic photosensitive member was prepared and evaluated by the same method. Note: 501 and 50 in FIG.
Reference numerals 2, 503-1, 503-2, and 504 denote an aluminum substrate, a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer, respectively.

[0175]

[Table 25]

[0176]

[Table 26]

As is clear from Table 26, the present invention is effective even if the apparatus and the layer structure are different.

Example 14 Using the same substrate as in Example 12, and performing the same surface treatment as in Example 12, FIG.
A blocking type electrophotographic photosensitive member having a layer configuration shown in FIG. 5-B was produced under the conditions shown in Table 27 using a PCVD apparatus 400 which outputs a VHF wave shown in FIG.
FIG. In FIG. 4, reference numeral 405 denotes a motor for rotating the base 401 when forming a film on the surface of the base 401;
Reference numeral 403 denotes a heater for heating the base 401 when forming a film, 404 denotes an exhaust path for exhausting the inside of the space, and discharge space 406 denotes a space between the base 401 and the electrode 408.
407 is a high-frequency matching box 407.

A source gas introduction pipe (not shown) and an electrode 408 are provided, and a high frequency matching box 407 is further connected to the electrode 408. The inside of the discharge space 406 is connected to a diffusion pump (not shown) through an exhaust pipe 404.

In this device, when the pressure is stabilized by evacuation, for example, a VHF power supply (not shown) having a frequency of 500 MHz is set to a desired power, and VHF power is introduced into the discharge space 406 through the high frequency matching box 407. Causes glow discharge. Thus, in the discharge space 406 surrounded by the base 401, the introduced source gas is excited by the discharge energy and dissociated, and a predetermined deposited film is formed on the base 401.

The apparatus shown in FIG. 4 is suitable for mass production because a plurality of photoconductors can be obtained by one-time production as in the apparatus shown in FIG.

[0182]

[Table 27]

[0183]

[Table 28]

As is clear from Table 26, the present invention is effective even if the apparatus and the layer structure are different.

[0185]

As described above, according to the present invention,
In a method of manufacturing an electrophotographic photoreceptor formed by depositing a functional film containing silicon atoms as a base material on the surface of an aluminum substrate that is long in the longitudinal direction by a reduced pressure vapor deposition method, the deposited film is formed. Before the process, water containing an inhibitor for protecting the aluminum substrate surface is used, and Al-Si
After forming the —O film on the surface of the substrate, the shower pressure was set to 4.9 × 10
^By setting the range of ³ ≦ P (Pa) ≦ 9.8 × 10 ⁴ and the flow rate of the shower within the range of 1 ≦ g (l / min) ≦ 2, it is possible to prevent the film from peeling off when spraying. In addition, the rinsing effect can be enhanced. As a result, a strong and uniform Al-Si-O film is formed on the substrate, so that it is possible to manufacture an electrophotographic photosensitive member that gives a uniform high-quality image with high productivity.

[Brief description of the drawings]

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

FIG. 2 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. 3A 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. 3B is a view in FIG. X-
It is X cross section.

FIG. 4 is a schematic longitudinal sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by a VHF plasma CVD method.

FIG. 5 is a cross-sectional view illustrating a layer configuration of the electrophotographic photosensitive member.

[Explanation of symbols]

 101, 201, 301 Substrate 102 Processing unit 103 Substrate transport mechanism 111 Substrate loading table 112 Degreasing / washing tank 113 Rinse tank 122, 123 Cleaning liquid 114 Drying tank 115 Substrate transport exit stand 126 Shower nozzle 161 Transport arm 162 Moving mechanism 163 Chucking mechanism 164 Air Cylinder 165 Transport rail 180 Control means 202, 302 Reaction vessel 203 Cathode electrode 204 Top plate 205 Base plate 206 Insulator 207 Base holder 208, 303, 403 Heater 209, 210 Source gas introduction pipe 211 Source gas inflow valve 212, 407 micro Controllers 213, 304, 404 Exhaust pipe 214 Exhaust valve 215 Vacuum exhaust device 216 High frequency power supply 301, 401 Base 302 Chamber 303, 403 Heater 304, 404 Exhaust passage 305, 406, 405 Motor 306, 406 Discharge space 307, 408 Electrode 308 Power supply means 407 High frequency matching box 309 Microwave introduction window 310 Waveguide 408 High frequency electrode 501 Aluminum substrate 502 Charge injection Blocking layer 503 Photoconductive layer 503-1 Charge transport layer 503-2 Charge generation layer 504 Surface layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 5/10 G03G 5/10 B (72) Inventor Hiroyuki Katagiri 3-30-2 Shimomaruko, Ota-ku, Tokyo Within Canon Inc. (72) Inventor Kazuhiko Takada 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term within Canon Inc. (reference) 2H068 AA42 CA33 CA34 DA24 DA62 DA64 DA72 EA05 EA24 3B201 AA18 AB24 BB02 BB23 BB82 BB83 BB90 BB92 BB93 BB94 CB01 CC01 CC11 CC21

Claims (27)

[Claims] 1. The pressure of shower water sprayed on a substrate is set to 4.9 × 10 ³ Pa or more and 9.8 × 10 ⁴ Pa or less, and the flow rate of the shower water is 1 liter / minute or more.
A method for producing an electrophotographic photoreceptor, wherein the surface is set to 0 liter / min or less, the surface of the substrate is showered with the shower water, and then a functional film is formed on the surface by a reduced pressure vapor deposition method. 2. The method according to claim 1, wherein the substrate is pulled up from the water before showering the substrate with the shower water. 3. The method according to claim 1, wherein the water contains an inhibitor, and the surface of the substrate made of aluminum (Al) is coated with a coating mainly composed of Al, silicon (Si) and oxygen (O) in a thickness of 5 Å to 150 Å. 3. The method of manufacturing an electrophotographic photoreceptor according to claim 2, wherein the composition ratio of Al, Si and O constituting the film satisfies the following formula (I). Al: Si: O = a: b: c, a
= 1, the range of b and c is 0.1 ≦ b ≦ 1.0 and 1 ≦ c ≦ 5 (I) 4. The method according to claim 2, wherein the water contains carbon dioxide. 5. The method according to claim 3, wherein the inhibitor is a silicate. 6. The method according to claim 5, wherein the silicate is a potassium silicate. 7. The electrophotograph according to claim 3, wherein the concentration of the inhibitor in the unit of water contained per unit volume of water containing the inhibitor is in the range of 0.05 wt% to 2 wt%. Manufacturing method of photoreceptor. 8. A plasma CV according to the reduced pressure vapor phase epitaxy.
3. The method according to claim 2, wherein an amorphous deposited film composed of silicon and at least one of hydrogen and fluorine is formed as the functional film on the substrate by Method D. 9. The method according to claim 2, wherein after the surface is showered, the substrate is immersed in warm water, pulled up and the surface is dried. 10. The method according to claim 9, wherein the hot water is hot pure water. 11. The hot water contains carbon dioxide.
The method for producing the electrophotographic photosensitive member according to the above. 12. The method according to claim 9, wherein the hot water contains an inhibitor. 13. The method according to claim 2, wherein the substrate is an aluminum substrate containing aluminum as a main component. 14. The method according to claim 1, wherein the aluminum substrate contains 10% Fe.
14. The method for producing an electrophotographic photoreceptor according to claim 13, wherein the aluminum substrate is contained in a range of not less than 1 ppm by weight and not more than 1 ppm. 15. The method according to claim 15, wherein the aluminum substrate comprises Si.
14. The method for producing an electrophotographic photoreceptor according to claim 13, wherein the aluminum substrate is contained in a range of not less than 1 ppm by weight and not more than 1 ppm. 16. The method according to claim 16, wherein the aluminum substrate is made of Cu.
14. The method for producing an electrophotographic photoreceptor according to claim 13, wherein the aluminum substrate is contained in a range of not less than 1 ppm by weight and not more than 1 ppm. 17. The method according to claim 17, wherein the aluminum substrate is Fe + Si.
+ Cu total content exceeds 0.01 wt% and 1 wt%
14. The method for producing an electrophotographic photoreceptor according to claim 13, wherein the aluminum substrate contains the following range. 18. A degreasing step for degreasing the base, a rinsing step for rinsing the base after the degreasing step, and a drying step for drying the base after the rinsing step, wherein the rinsing step 2. The method according to claim 1, wherein the shower water is showered. 19. The shower water contains an inhibitor, and a film mainly composed of Al, silicon (Si) and oxygen (O) is formed on the surface of the substrate made of aluminum (Al) in a range of 5 Å to 150 Å. Al and S which are formed in the range of
3. The method according to claim 2, wherein the composition ratio of i and O satisfies the following formula (I). Al: Si: O = a:
b: c, when a = 1, the range of b and c is 0.1 ≦ b ≦ 1.0 and 1 ≦ c ≦ 5 (I) 20. The method according to claim 2, wherein the shower water contains carbon dioxide. 21. The method according to claim 19, wherein the inhibitor is a silicate. 22. The method according to claim 21, wherein the silicate is a potassium silicate. 23. A weight% of the inhibitor contained in a unit volume of shower water containing the inhibitor.
20. The method according to claim 19, wherein the concentration ranges from 0.05 wt% to 2 wt%. 24. The method according to claim 2, wherein the water and the shower water have the same composition. 25. The pressure of shower water sprayed on the object to be cleaned is set at 4.9 × 10 ³ Pa or more and 9.8 × 10 ⁴ Pa or less, and the flow rate of the shower water is 1 liter / minute or more and 20 liters. / Min or less, and the surface of the object to be cleaned is showered with the shower water. 26. The cleaning method according to claim 25, wherein the object to be cleaned is a substrate for an electrophotographic photosensitive member. 27. An electrophotographic photosensitive member prepared by being cleaned and processed by the cleaning method according to claim 25.