JPH11194515A - Manufacture of electrophotographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of an electrophotographic sensitive material, by which a uniform and high-quality picture having no picture defects and no uneven picture concentration can be obtained. SOLUTION: The subject manufacturing method has a process in which a functional membrane, which is composed of an amorphous material having silicon atoms as a parent material, is formed on the surface of an aluminium substrate by a vacuum gas-phase growth method. In this case, before a process in which an electrophotographic sensitive material is formed, the method has a process in which such a film, that a film thickness is in the range over 5 Åand below 150 Å and that its main components are aluminium, silicon and oxygen with an undermentioned composition ratio, is formed by using water containing an inhibitor. aluminium:silicon:oxygen = a:b:c, where, if a=1, then 0.1<=b<=1.0, 1<=c<=5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art As a substrate for forming a deposited film of an electrophotographic photosensitive member, glass, heat-resistant synthetic resin, stainless steel, aluminum (Al) and the like have been proposed. However, in practice, metal is often used to withstand electrophotographic processes such as charging, exposure, development, transfer, and cleaning, and to always maintain high positional accuracy so as not to deteriorate image quality. Among them, aluminum is one of the most suitable materials for the base of the electrophotographic photoreceptor 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%.
By making the aluminum alloy not more than 00 ppm,
A technique for obtaining an amorphous silicon electrophotographic photosensitive member having good image quality has been disclosed. Further, the 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-60-262
No. 936 discloses that magnesium (Mg) is 3.0 to 3.0.
Manganese (M) as an impurity.
n) is not more than 0.3 wt% and chromium (Cr0) is not more than 0.01%.
wt%, Fe is 0.15 wt% or less, silicon (S
An extruded aluminum alloy which suppresses i) to 0.12% by weight or less and has excellent vapor deposition properties of amorphous silicon composed of the remaining Al is disclosed.

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

Also, JP-A-63-31261, JP-A-1-156758, and JP-B-7-341223.
The publications each disclose a technique for forming an oxide film on an Al substrate, but do not describe forming a film by washing with water containing an inhibitor of a specific component.

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

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

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

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

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

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

When 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 substrate subjected to the surface treatment 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. Then, an electrophotographic photoreceptor is manufactured using the thus obtained deposited film.

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

However, as in recent years, 1) higher image quality of the electrophotographic apparatus has been required and the resolution of development has been improved with it. 2) As the speed of the copying machine has increased and the charging conditions have become more severe, the surface In this case, a portion where no potential is applied substantially has a great influence on a peripheral potential, and as a result, image defects due to the portion have been pointed out.

Further, the conventional electrophotographic apparatus is mainly used for copying characters, and therefore 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, as the image quality of copying machines has recently increased, many originals including halftones such as photographs have been copied (at present, an electrophotoreceptor having a smaller abnormally growing portion is required). In a popular color copying machine, an electrophotoreceptor having less abnormally grown portions is required at present. Since image defects become more visually apparent, an electrophotographic photoreceptor having fewer abnormally grown portions is required. In addition, since the abnormally grown portion is very small, it is difficult to detect the presence 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 causes an image defect. Appears as visually striking. In particular, in the case of an electrophotographic photosensitive member prepared by a microwave plasma CVD method, the above-mentioned problem appears more remarkably.

On the other hand, such 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.

Further, even in a device manufactured by the plasma CVD method, 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 a device which can be corrected by post-processing, has the above problem. Does not occur.

In the prior art, the step of cleaning the substrate is
Although trichlorethane was used, it did not cause any problem. However, due to environmental problems in recent years, these chlorinated solvents cannot be easily used, and have been changed to aqueous cleaning. However, when cleaning aluminum with water,
Impurities partially exposed on the aluminum surface (Si, etc.)
However, there is a problem in that the high-concentration portion forms a local battery with the surrounding normal aluminum portion, and promotes corrosion of the substrate surface.

[0020]

SUMMARY OF THE INVENTION The present invention provides a high-performance electrophotographic photoreceptor with a small number of abnormally grown portions, which can prevent corrosion during processing of a substrate, can be formed stably at low cost and with good yield, and has a high yield. It is to provide a manufacturing method for manufacturing with.

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

[0022]

The above object is achieved by the following means.

That is, the present invention provides a method for manufacturing an electrophotographic photoreceptor having a step of forming a functional film made of an amorphous material containing silicon atoms as a base material on the surface of an aluminum substrate by a low pressure vapor phase epitaxy method. Prior to the step of forming an electrophotographic photoreceptor, a film containing aluminum, silicon and oxygen as main components having a film thickness in the range of 5 ° to 150 ° and a composition ratio represented by the following formula: And a method of manufacturing an electrophotographic photoreceptor characterized by having a step of forming aluminum: silicon: oxygen = a: b: c. The range is 0.1 ≦ b ≦ 1.0 1 ≦ c ≦
5

The said inhibitor is silicate, said silicate is potassium silicate, the molar concentration of the inhibitor contained in the water is 10 ⁰ to 10 ^-6 mol / l
Wherein the step of forming the functional film on the aluminum substrate includes forming an amorphous deposited film composed of silicon atoms and at least one of a hydrogen atom and a fluorine atom by the plasma CVD method. A step of forming on a substrate, the water contains one of a surfactant and carbon dioxide, and the water contains 2 kg · f
Cleaning the substrate at a pressure of / cm ^{2 to} 300 kg · f / cm ² , pulling up the substrate from hot water and drying, the hot water is hot pure water, hot water in which carbon dioxide is dissolved, and the inhibitor. The aluminum base is an aluminum base containing 10 ppm or more and 1 wt% or less of iron; and the aluminum base is an aluminum base containing 10 ppm or more and 1 wt% or less of silicon. The aluminum substrate contains 10 ppm or more and 1 wt% or less of copper; and the total content of iron, silicon and copper in the aluminum substrate exceeds 0.01 wt% and 1 wt%. % Or less.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The causes of image defects that cause abnormal growth of an aluminum substrate are as follows: (A) Dust on the substrate, dirt of cleaning water in the cleaning and drying processes, and the like become the core. (B) A surface defect of the substrate becomes a nucleus. Roughly divided into

(A) Adhering of dust and the like is to clean the place where the substrate is handled such as cutting and cleaning, and to strictly clean the inside of the film forming furnace and to clean the surface of the substrate immediately before forming the deposited film. Has made it possible to prevent it to some extent. Conventionally, this object has been achieved by washing with a chlorine-based solvent such as trichloroethane. However, in recent years, the use of such chlorine-based solvents has been restricted for reasons such as destruction of the ozone layer, and it is necessary to consider a washing method using water as an alternative to a washing method using a chlorine-based solvent. is there.

On the other hand, as a method for reducing the defect (B), it is necessary to consider a specific cleaning method for aluminum containing a specific component.

Further, there are locally high hardness portions in the aluminum, and as a pre-process prior to the formation of a deposited film, these high hardness portions are cut off by a blade of a processing machine during surface processing such as cutting. It became clear that surface defects on the substrate were the cause of (B).

In order to prevent these phenomena, the present invention uses aluminum containing silicon. The reason for this is that it is preferable that the amount of impurities contained in aluminum is small. However, when extremely high-purity aluminum is melt-processed into the shape of a base, an oxide is easily generated and many abnormally grown portions are generated. On the other hand, the inclusion of Si atoms in aluminum can suppress the generation of oxides.

In the present invention, an aqueous detergent in which silicate or the like is dissolved as a corrosion inhibitor (inhibitor) is used because aluminum containing silicon (Si) atoms is
Inhibitors are used for the purpose of preventing the corrosion, which may be corroded by water, mainly in a portion where atoms are locally large. In addition to Si atoms, other Fe atoms, Cu
Although similar corrosion may occur in a portion where atoms are locally large, corrosion can be effectively prevented by using an inhibitor such as a silicate.

Corrosion is remarkable when the temperature of washing water is high, or when aluminum contains magnesium for the purpose of improving machinability together with Si, Fe and Cu atoms, and electrons containing Si, Fe and Cu are contained. It is preferable to add a corrosion inhibitor for preventing corrosion of the aluminum substrate used as the substrate of the photoreceptor to the aqueous detergent.

The inventor of the present invention carried out a process of adding a certain corrosion inhibitor to a surfactant used for cleaning in a substrate processing step before depositing a functional film on the substrate, so that the subsequent functional film was not affected. As a result of intensive research focusing on the possibility of forming a coating that does not affect the above and suppressing the occurrence of the above-mentioned defects, the present invention has been completed.

S partially exposed on the aluminum surface
It is considered that the portion containing many i, Fe, and Cu atoms forms a local battery with the surrounding normal aluminum portion, and the corrosion is promoted under water.

The reason why the inhibitor can be used to prevent corrosion and protect the surface of the substrate is considered to be because an Al—Si—O film can be formed on the aluminum surface. 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 abnormal growth during the formation of the functional film.

In addition, not only the occurrence of abnormal growth is prevented, but also by washing with an aqueous detergent containing silicate,
The electrophotographic properties are improved.

In the embodiment of the present invention, the plasma CV
An amorphous silicon deposition film is formed on a substrate by the D method. The reaction at this time is the decomposition process of the source gas in the gas phase, the transport process of the active species from the discharge space to the substrate surface,
The surface reaction process on the substrate surface can be divided into three. 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 surface of the substrate.

In particular, water is non-uniformly adsorbed on the surface of a high-purity aluminum substrate.

Therefore, when silicon for forming an amorphous silicon film or a deposited film containing hydrogen and fluorine is formed on a substrate by, for example, a plasma CVD method, the reaction on the surface is caused by water on the surface of the substrate. Then, the composition and structure of the interface between the substrate and the deposited film of the deposited film partially changes. As a result, during the electrophotographic process, the charge injection property of that portion changes, and a difference in surface potential appears.

In the present invention, before the formation of the functional film made of amorphous silicon by the plasma CVD method, the surface of the aluminum substrate is Al-S-coated with a silicate as an inhibitor.
By forming the i-O film, it is possible to form an interface through which good charges can be exchanged when forming a deposited film. For this reason, the obtained substrate is improved in chargeability and can achieve improvement in electrophotographic characteristics such as photosensitivity.

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 substrate surface of the substrate, a rinsing step of rinsing the substrate surface, and a drying step of drying the substrate surface Process in order. In the degreasing cleaning step, residues such as oils and fats and halides on the substrate are removed by incorporating a water-based detergent having a surfactant, and further, a silicate is added to the aluminum substrate surface to prevent corrosion. To obtain an aluminum substrate having a high quality amorphous deposited film.

An example of a procedure for actually forming an electrophotographic photosensitive member (substrate) by the method of manufacturing an electrophotographic photosensitive member of the present invention using a cylinder made of an aluminum alloy as a substrate is shown in FIG. This will be described below using the deposited film forming apparatus shown in FIG. The substrate transported to the cleaning step is a mirror-cut substrate. Lathe with air damper for precision cutting (PNEUMO PRECLESION IN
C. ), A diamond bite (trade name: Miracle bite, manufactured by Tokyo Diamond) is set so as to obtain a rake angle of 5 ° with respect to the cylinder center angle. Next, the substrate was vacuum-chucked to the rotating flange of the lathe, and white kerosene was sprayed from the attached nozzle, and the chip was sucked from the attached vacuum nozzle.
Mirror cutting is performed so that the outer shape becomes 108 mm under the conditions of m / min and a feed rate of 0.01 mm / R.

The substrate after the cutting is conveyed to the cleaning device. FIG. 1 shows a cleaning apparatus for cleaning a substrate surface.

The cleaning apparatus comprises a processing section 102 and a substrate transport mechanism 103. The processing unit 102 includes the substrate loading table 1
11, substrate cleaning tank 121, rinsing tank 131, drying tank 14
1. It is composed of a substrate discharge table 151. Substrate cleaning tank 12
1. Both the rinsing tank 131 and the drying layer 141 have a temperature control device (not shown) for keeping the temperature of the liquid constant.
The transfer mechanism 103 includes a transfer rail 165 and a transfer arm 16.
The transport arm 161 includes a moving mechanism 162 that moves on the rail 165, a chucking mechanism 163 that holds the base 101, and an air cylinder 164 that moves the chucking mechanism 163 up and down.

The substrate 101 placed on the loading table 111 is
The wafer is transported to the cleaning tank 121 by the transport mechanism 103. The cleaning tank 121 contains a water-based cleaning agent containing a surfactant or a water-based cleaning agent 122 containing a surfactant to which a silicate is added. Clean dust, grease, etc.

The substrate 101 that has been subjected to the degreasing and cleaning step is then subjected to a rinsing step. Rinse tank 1 by transport mechanism 103
It is transported to 31 and further rinsed with pure water or the like kept at a temperature of 25 ° C. The purity of pure water or the like is constantly controlled by an industrial conductivity meter (trade name: α900R / C, manufactured by HORIBA, Ltd.). Substrate 1 after rinsing step
01 then goes to the drying step. The substrate 101 is moved by a transport mechanism 103 to a drying tank 141 of hot pure water or the like,
Lifting and drying is performed by a lifting device (not shown) using hot pure water maintained at a temperature of 60 ° C. The precision of the hot pure water or the like is constantly controlled by an industrial conductivity meter (trade name: α900R / C, manufactured by HORIBA, Ltd.).

The substrate 101 after the drying step is carried to the carry-out table 151 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 a plasma CVD method shown in FIG.

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

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

During the formation of the deposited film, the substrate 306 is rotated at a constant speed by a motor (not shown) in order to equalize the formation of the deposited film. Thus, an amorphous silicon deposition film is formed on the base 306.

In the present invention, the substrate is made by treating the surface irregularities of the substrate to be flat and making it a mirror surface, or a non-mirror surface for the purpose of preventing interference fringes, or a substrate provided with irregularities of a desired shape. But it is good.

Further, since corrosion is promoted in a portion where Si, Fe and Cu atoms are partially exposed on the aluminum surface, the present invention is used in at least one of the degreasing and washing steps, the rinsing step and the drying step. The silicate is added to the water to form a film. It is more preferable that the film is formed before the substrate comes into contact with pure water or the like. Since the film of the present invention is formed at a relatively early stage, pure water can be used in the rinsing step and the drying step once the film has been formed on the substrate. Specific examples include a method in which silicate is contained only in an aqueous cleaning agent containing a surfactant in a substrate cleaning tank for a degreasing cleaning step after cutting, and a method in which silicate is rinsed without using a degreasing cleaning step. There is a method using a silicate only in the process, a method using the silicate in the rinsing step and the drying step without using the degreasing and washing step, or a method using the silicate in all the steps, all of which are suitable for the present invention. .

Phosphate as an inhibitor of the present invention,
Silicates, borates and the like can be mentioned, and silicates are particularly preferred in the present invention.

Among the silicates, potassium silicate, sodium silicate and the like may be used, and any of them may be used, but potassium silicate is particularly preferred in the present invention.

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. But it is possible. Among them,
In the present invention, it is particularly preferable to use an anionic surfactant such as a carboxylate, a sulfonate, a sulfate ester salt or a phosphate ester salt, or a nonionic surfactant such as a fatty acid ester.

The water used in the degreasing and washing step, the rinsing step and the drying step of the present invention is preferably semiconductor grade pure water, especially ultra LSI grade ultra pure water. Specifically, the lower limit is 1M as the resistivity at a water temperature of 25 ° C.
Ω · cm or more, preferably 3 MΩ · cm or more, optimally 5 MΩ · 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 it is 17 MΩ · cm from the viewpoint of cost and productivity.
Or less, preferably 15 MΩ · cm or less, optimally 13 MΩ
Ω · 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 detergent containing a surfactant containing a silicate is too high, stains due to liquid traces are generated on the surface of the substrate, 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 a sufficient film cannot be obtained. As a result, it is difficult to obtain a high-quality deposited film. For this reason, the temperature is 10 ° C. or more,
A temperature of 60 ° C or lower, preferably 15 ° C or higher and 50 ° C or lower, optimally 20 ° C or higher and 40 ° C or lower is suitable for the present invention.

In the present invention, if the concentration of the aqueous cleaning agent containing a surfactant is too high, stains due to the traces of the liquid are generated, which causes printing of a 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 percent concentration of the silicate-containing surfactant in the aqueous detergent is 0.1 w
t. % Or more, 20% wt. Or less, preferably 1% wt.
As described above, 10 wt. %, Optimally 2 wt. % Or more, 8
wt. % Or less is suitable for the present invention.

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

For this reason, p of aqueous detergent containing a surfactant
H is 8 or more and 12.5 or less, preferably 9 or more and 12
Below, optimally 10 or more and 11.5 or less are suitable for the present invention.

In the present invention, when the concentration of the silicate contained in the water during the cleaning is too high, spots due to the traces of the liquid are generated, which causes peeling of the deposited film. On the other hand, if it is too thin, the degreasing effect and the film effect are small, and the effect of the present invention cannot be sufficiently obtained. Therefore, the scope of the molar concentration of silicate in the water is 10 ^-6 to 10 ⁰ within preferably 10 ^-5
〜１０10 ^−1, optimally 10 ⁻² 〜１０10 ^-4 are suitable for the present invention.

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

In the present invention, as the composition ratio of the Al—Si—O film formed on the aluminum substrate, if the content of Si or O is small, the content of Al is large and the film is insufficient. Not suitable for it. When Al is 1, Si is 0.1 or more and 1.0 or less, preferably 0.1 to 1.0.
15 or more and 0.8 or less, optimally 0.2 or more and 0.6 or less 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 optimally 2 or more and 3 or less.
5 or less is suitable.

The use of ultrasonic waves in the cleaning of the present invention is effective in achieving the effects of the present invention. The ultrasonic frequency 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 frequency range from z to 100 kHz is effective. The output of the ultrasonic wave is preferably 0.1 W / L or more and 1 kW / L or less, more preferably 1 W / L or more and 100 W / L or more.
W / liter or less is effective.

In the present invention, shower cleaning and warm air drying after the cleaning step is effective in producing a high-performance aluminum substrate, but cleaning using a cleaning apparatus is particularly effective. is there.

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, in the rinsing step or the drying step, carbon dioxide may be dissolved in water used to improve the rinsing effect or the drying effect. The quality of the water used at this time is
It is very important, and in a state before dissolving carbon dioxide, pure water of semiconductor grade, particularly ultra-pure water of ultra LSI grade is desirable. Specifically, as the resistivity at a water temperature of 25 ° C., the lower limit is 1 MΩ · cm or more, preferably 3 MΩ · cm or more,
Optimally, 5 MΩ · cm or more is suitable for the present invention. The upper limit of the resistance value can be any value up to the theoretical resistance value (18.25 MΩ · cm), but from the viewpoint of cost and productivity, 17 MΩ · cm or less, preferably 15 MΩ · cm or less.
Optimally, 13 MΩ · cm or less is suitable for the present invention.
Regarding the amount of fine particles, 0.2 μm or more is preferably 10,000 or less, preferably 1000 or less, and optimally 100 or less per milliliter in the present invention. As for the amount of microorganisms, the total viable count is 100 or less per milliliter,
Preferably 10 or less, optimally 1 or less are suitable for the present invention. The amount of organic matter (TOC) is 1 per liter
9 mg or less, preferably 1 mg or less, optimally 0.2 m
g or less is suitable for the present invention.

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

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

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

In general, the preferred amount of carbon dioxide dissolved according to the present invention is 60% or less of the saturation solubility, more preferably 4%.
The condition is 0%.

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

The method of dissolving carbon dioxide in water may be any of a method by bubbling, a method using a diaphragm, and the like. Further, in the present invention, the use of water in which carbon dioxide is dissolved to prevent the effect of cations such as sodium ions on the substrate, which may occur when a carbonate such as sodium carbonate is used to obtain carbonate ions. Can be.

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 washing by dipping, it is fundamental that the substrate is 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 air is introduced. The present invention is more effective when bubbling is performed in combination.

In the case of spraying, if the water pressure is too weak, the effect of the present invention is small, and if it is too strong, a pear-skin pattern is formed on the obtained electrophotographic photoreceptor image, particularly on a halftone image. Will occur. For this reason, the pressure of water is 2 kg · f / cm 2 or more and 300 kg · f / cm
2 or less, preferably 10 kg · f / cm 2 or more, 200
kg · f / cm2 or less, optimally 20 kg · f / cm2
As described above, 150 kg · f / cm 2 or less is suitable for the present invention. However, the pressure unit in the present invention is kg · f / cm2.
Means gravity kilograms per square centimeter and 1
kg · f / cm 2 is equal to 98066.5 Pa.

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

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

The processing 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 seconds 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 / cm or more and 40 μS or less. / Cm or less, more preferably 6 μS / cm or more, 35 μS / cm or less, 8 μS / c
When the pH is controlled at m or more and 30 μS / cm or less and the pH is controlled, 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 purity of water for dissolving carbon dioxide and the method for dissolving and 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 more and 80 ° C. or less, and most preferably 40 ° C. or less.
A temperature between 70 ° C. and 70 ° 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, 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 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 it is too short, it is not stable. Time or less, preferably 2 minutes or more,
4 hours or less, optimally 3 minutes or more and 2 hours or less are suitable for the present invention.

In the present invention, a silicate may be added to at least one of the rinsing step and the drying step. If the concentration of the silicate-containing water is too high, stains due to the traces of the liquid may occur, causing the deposited film to peel off. 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 scope of the molar concentration of silicate in the water is 10 ⁰ to 10 ^-6 within preferably 10 ^-1 to 10 ^-5
Optimally 10 ^-2 to 10 ^{- 4} are suitable for the present invention.

In the present invention, when cleaning after surface processing is performed, if the pH of water containing silicate is too high, spots due to liquid traces are generated, which causes peeling of the deposited film. 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 range of the silicate molar concentration contained in water is from 8 to 12.5, preferably from 9 to 12, and most preferably from 10 to 11.5. Is suitable.

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

In the present invention, it is effective to include magnesium in order to improve the workability of the substrate. The preferable magnesium content is in the range of 0.1 wt% or more and 10 wt% or less, and more preferably in the range of 0.2 wt% or more and 5 wt% or less.

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

In the present invention, the shape of the substrate is determined as desired. For example, when the substrate is used for electrophotography, in the case of a continuous high-speed copying machine, it is in the form of an endless belt or a cylindrical shape as described above. Those 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 preferably 20 mm or more and 500 mm or less, 10 mm or more and 1000 mm or less in diameter. The thickness of the support is appropriately determined so that a desired photoconductive member is formed. However, when the possibility of the photoconductive member is required, the thickness is within a range where the function as the support is sufficiently exhibited. If possible, make it as thin as possible. However, in such a case,
The thickness is usually 10 μm or more from the viewpoints of the production and handling of the support and the mechanical strength.

The photoreceptor used in the present invention may be any of an amorphous silicon photoreceptor, a selenium photoreceptor, a cadmium sulfide photoreceptor, and an organic photoreceptor. In the case of the body, the effect is remarkable.

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

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

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

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

In the electrophotographic photoreceptor of the present invention, the total thickness of the deposited film deposited on the substrate may be any, but is preferably 5 μm to 100 μm, more preferably 10 μm to 7 μm.
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.
At a pressure of 5 mtorr or more and 100 mtorr or less, preferably 1 mtorr or more and 50 mtorr or less, particularly good results were obtained with good reproducibility in terms of discharge stability and uniformity of the deposited film.

In the present invention, the substrate temperature at the time of depositing the deposited film is effective in the range of 100 ° C. or more and 500 ° C. or less, 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 winding heater of a sheath heater, a plate heater, a ceramic heater, or a halogen. Examples of the heating element include a heat radiation lamp heating element such as a lamp and an infrared lamp, and a heating element using a liquid or a gas as a heating medium and a heat exchange unit.
As the surface material of the heating means, metals such as stainless steel, nickel, aluminum, and copper, ceramics, heat-resistant polymer resins, and the like can be used. In addition, other methods such as providing a dedicated heating vessel separately from the reaction vessel, heating, and then transporting the substrate into the reaction vessel in a vacuum can be used. It is possible in the present invention to use the above means alone or in combination.

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

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

In the present invention, it is effective to apply a voltage (bias voltage) to the discharge space during the formation of the deposited film.
It is preferable that an electric field is applied at least in a direction in which cations collide with the substrate. 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 reaction vessel using a dielectric window, the dielectric window may be made of alumina (Al ₂ O ₃ ), aluminum nitride (Al ₂ O ₃ ).
N), boron nitride (BN), silicon nitride (SiN), silicon carbide (SiC), silicon oxide (SiO ₂ ), beryllium oxide (BeO), Teflon, polystyrene, and other materials with low microwave loss are usually used. .

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

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

Hereinafter, experimental examples of the present invention will be described, but the present invention is not limited thereto. <Experimental Example 1> 0.05 wt% of Si and 0.03 w of Fe
A cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a thickness of 5 mm made of aluminum having t% and Cu of 0.01 wt% is subjected to the same procedure as the above-described example of the procedure of the method of manufacturing an electrophotographic photosensitive member according to the present invention. Surface cutting was performed. The abundance ratio of all atoms present on the substrate shown in the present invention was determined by X-ray photoelectron spectroscopy (XPS) using an X-ray anode of Mg,
Energy resolution of 0.98 at 15KV, 400W
eV (Ag3d5 / 2) to reduce the degree of vacuum to 1 × 10 ⁻⁹ Torr
It was measured under the following conditions.

Fifteen minutes after the end of cutting, degreasing, rinsing, and drying were performed with a detergent (nonionic surfactant) under the conditions shown in Table 1 using the surface treatment apparatus of the present invention shown in FIG.
At that time, the tank in which the inhibitor was placed was changed as shown in Table 3. (Note: Inhibitor is A manufactured by Nippon Chemical Industry Co., Ltd.
Potassium silicate (trade name) was used. A potassium silicate is 1
400 g of potassium silicate (K ₂ O.3SiO ₂ ) in Kg
Is a dissolved solution. ) The pH value of the water in which potassium silicate A was dissolved was 11.0. At that time, for each surface-treated substrate, surface defects (streak-like flaws, etc.) occurring in the surface treatment were inspected visually and with a metallographic microscope. The results are also shown in Table 3.

Next, an amorphous silicon deposited film was formed on the substrate subjected to the surface treatment under the conditions shown in Table 2 using the deposited film forming apparatus shown in FIG. A blocking type electrophotographic photosensitive member having the above configuration was produced. In FIG. 6, reference numerals 601, 602, 603 and 604 indicate an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer, respectively.

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

The process speed of the electrophotographic photosensitive member thus prepared was arbitrarily changed in advance within the range of 200 to 800 mmsec for experiments, a voltage of 6 to 7 kV was applied to the charger, corona charging was performed, and laser image exposure at 788 nm was performed. After a latent image was formed on the surface of the electrophotographic photoreceptor, a copy machine manufactured by Canon Inc., which was modified so that an image could be formed on transfer paper by a normal copying process, was placed in NP6650, black spots, image defects, electrophotography Comprehensive evaluation of characteristics (sensitivity) and evaluation of environmental properties were performed. Table 3 also shows the results. <Evaluation of black spots and image defects> Select and evaluate the image sample with the most image defects among the image samples obtained when the process speed was changed and the full-halftone original and character original were copied on the platen. Was. As an evaluation method, the image sample was observed with a magnifying glass, and the evaluation was performed based on the state of the own point within the same area.

A: Good.

・ ・ ・: Some minor defects but no problem.

Δ: There are slight defects on the entire surface, but there is no problem in practical use.

×: There is a problem with a large defect on the entire surface. <Evaluation of environmental properties> ○ ・ ・ ・ Do not use substances related to ozone layer destruction in the pretreatment process.

×: A substance relating to destruction of the ozone layer is used in the pretreatment.

[0119]

[Table 1]

[0120]

[Table 2]

[0121]

[Table 3] From Table 3, good results were obtained by adding the inhibitor in the surfactant or immediately after the surfactant. <Comparative Experimental Example 1> Washing was carried out in the same manner as in Experimental Example 1 except that no inhibitor was used in the washing step. Thereafter, a blocking type electrophotographic photosensitive member was prepared and evaluated in the same manner. . The results are also shown in Table 3 as a comparative experiment gradient. <Conventional Example 1> After the surface was cut using the same aluminum cylindrical substrate as in Experimental Example 1, degreasing and cleaning were performed under the conditions shown in Table 4 using the conventional substrate surface cleaning apparatus shown in FIG. Was. The substrate cleaning apparatus shown in FIG.
And a substrate transport mechanism 203. Processing tank 202
Comprises a substrate loading table 211, a substrate cleaning tank 221, and a substrate discharging table 251. The cleaning tank 221 is provided with a temperature controller (not shown) for keeping the temperature of the liquid constant.
The transfer mechanism 203 includes a transfer rail 265 and a transfer arm 26.
The transfer arm 261 includes a moving mechanism 262 that moves on the rail 265, a chucking mechanism 263 that holds the base 201, and an air cylinder 264 that moves the chucking mechanism 263 up and down.

[0122]

[Table 4] After cutting, the substrate 201 placed on the loading table 211 is transported to the cleaning tank 221 by the transport mechanism 203. Cleaning tank 22
Washing is performed to remove cutting oil and chips adhering to the surface from trichloroethane (trade name: Eterna VG, manufactured by Asahi Kasei Corporation) 221 in 1.

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

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

Table 3 shows the results of evaluation of the electrophotographic photosensitive member thus produced in the same manner as in Experimental Example 2 as Conventional Example 1. As described above, when the inhibitor (silicate) is contained in at least one of the degreasing and washing step and the rinsing step, the result that the performance of the electrophotographic photoreceptor is good has appeared. <Experimental Example 2> A blocking type electrophotographic photoreceptor was prepared on a substrate in the same manner as in Experimental Example 1 except that the rinsing and drying steps shown in Table 1 of Experimental Example 1 were used, and water was used. Thereafter, evaluation was performed in the same manner as in Experimental Example 1. Table 6 shows the results.
Shown in As described above, when the inhibitor (silicate) is contained in at least one of the degreasing and washing step and the rinsing step, the result that the performance of the electrophotographic photoreceptor is good has appeared.

[0126]

[Table 5]

[0127]

[Table 6] <Experimental Example 3> Using the same substrate as in Experimental Example 1, as shown in Table 7, in each of the degreasing and washing steps, the rinsing step, and the drying step, use of a surfactant, water temperature, treatment time, and presence or absence of ultrasonic treatment When the treatment was carried out with the addition of the silicate as an inhibitor, the type of silicate to be introduced was changed as shown in Table 8. Thereafter, a blocking type electrophotographic photosensitive member was formed on the substrate in the same manner as in Experimental Example 1, and the measurement was performed in the same manner. Table 8 also shows the results.

[0128]

[Table 7]

[0129]

[Table 8] As is clear from Table 8, good results were obtained using any of the silicates, but the best results were obtained especially with potassium silicate. <Experimental Example 4> The same substrate as in Experimental Example 1 was used, and the treatment was performed under the conditions shown in Table 7 as in Experimental Example 3. The molar concentration of potassium silicate introduced at that time was changed as shown in Table 9, and the stained state was observed with the naked eye on the substrate surface after washing.
Thereafter, a blocking type electrophotographic photoreceptor was produced in the same manner as in Experimental Example 1 and evaluated in the same manner as in Experimental Example 1.
Table 9 also shows the results. <Confirmation of Appearance (Stain)> Light of strong exposure was reflected on the surface of the substrate after washing, and a stain on the substrate that could be visually confirmed was confirmed.

・ ・ ・: Good without any stains Δ: very thin, no problem at all

×: Spots are clearly observed.

[0132]

[Table 9] From the results in Table 9, good results were obtained when the molar concentration of potassium silicate dissolved in water was in the range of 10 @ -2 to 10 @ -4. <Experimental example 5> Table 10 shows the content of Si contained in the Al base.
The degreasing and washing were performed in the same manner as in Experimental Example 1 using aluminum changed as shown in FIG. Thereafter, a blocking type electrophotographic photosensitive member equivalent to that of Experimental Example 1 was manufactured.
The same evaluation was performed. Table 10 also shows the results.

[0133]

[Table 10] As is evident from Table 10, the present invention is effective even when the content of Si in the Al substrate changes by 0.001 wt% ≦ Si ≦ 1 wt%. <Experimental Example 6> A blocking type electrophotographic photosensitive member was manufactured in the same manner as in Experimental Example 5 except that the content of Fe contained in the Al substrate was changed, and the same evaluation was performed. Table 11 also shows the results.

[0134]

[Table 11] As is clear from Table 11, good results were shown when the weight percent concentration of Fe contained in the Al substrate was in the range of 0.001 wt% ≦ Fe ≦ 1 wt%. <Experimental Example 7> A blocking type electrophotographic photosensitive member was prepared in the same manner as in Experimental Example 5 except that the content of Cu contained in the Al substrate was changed, and the same evaluation was performed. Table 12 also shows the results.

[0135]

[Table 12] As is clear from Table 12, each weight percent concentration of Cu contained in the Al substrate is 0.001 wt% ≦ Cu ≦ 1.0 w
Good results were shown in the range of t%. <Experimental Example 8> Degreasing and washing were performed in the same manner as in Experimental Example 1 using aluminum in which the contents of Si, Fe, and Cu contained in the Al substrate were changed as shown in Table 10. Thereafter, a blocking type electrophotographic photosensitive member equivalent to that of Experimental Example 1 was manufactured, and the same evaluation as in Experimental Example 1 was performed. Table 13 also shows the results.

[0136]

[Table 13] As is clear from Table 13, Si, F contained in the Al substrate
e, the total weight percent concentration of Cu is 0.01 wt%, <
The present invention is more effective in the range of Si + Fe + Cu ≦ 1 wt%. <Experimental Example 9> Using the same substrate as in Experimental Example 1, changing the processing temperature and time under the conditions shown in Table 14 to change the film thickness of the film, and thereafter, a blocking type electrophotographic photosensitive member equivalent to Experimental Example 1 And the same evaluation was performed. Table 15 shows the results.

[0137]

[Table 14]

[0138]

[Table 15] <Experimental example 10> Using the same substrate as in Experimental example 1, the treatment temperature and time were changed under the conditions shown in Table 16, and a film was formed under the conditions shown in Table 16. Was changed. Thereafter, a blocking type electrophotographic photosensitive member equivalent to that of Experimental Example 1 was prepared and evaluated.
Table 17 shows the results. The composition ratio at that time is experimental example 1.
Is a value measured by the XPS method shown in FIG.

[0139]

[Table 16]

[0140]

[Table 17] Good results were obtained when Si was 0.1 or more and 1.0 or less and O was 1 or more and 5 or less. <Experimental example 11> Using the same substrate as in Experimental example 1, degreased cleaning was performed under the conditions shown in Table 18, and the spraying pressure was changed in the subsequent cleaning (rinsing). Thereafter, a blocking type electrophotographic photosensitive member equivalent to that of Experimental Example 1 was prepared and evaluated. Table 19 shows the results. <Evaluation of Appearance Observation> Comprehensively evaluated the condition of spots on the substrate and surface roughness of the substrate which can be visually confirmed by reflecting light of strong exposure on the substrate surface after washing.

A: Very good B: Good B: No problem in practical use.

[0142]

[Table 18]

[0143]

[Table 19] 2kg ・ f / cm2 ~ 300k
g · f / cm 2, especially 20 kg · f / cm 2 to 1
A pressure range of 50 kg · f / cm 2 gave very good results.

[0144]

<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 was cut in the same procedure as in the example of the above-described method of manufacturing the electrophotographic photoreceptor according to the present invention, and after 15 minutes from the end of cutting, the substrate surface was degreased, rinsed and dried under the conditions shown in Table 20. Was. afterwards,
Using a deposition film forming apparatus shown in FIG. 3, a blocking type electrophotographic photosensitive member having a layer constitution shown in FIG. In this case, the Al—Si—O film had a composition of 1: 0.25: 3 and a film thickness of 75A.

The electrophotographic characteristics of the electrophotographic photosensitive member thus prepared were evaluated as follows. However,
The same evaluation was performed for each of 10 photoconductors manufactured under the same film forming conditions.

The appearance of the produced electrophotographic photosensitive member was visually observed and the film peeling was observed and evaluated. After that, 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.

[0147]

[Table 20]

[0148]

[Table 21]

[0149]

[Table 22] The following four methods were used for image evaluation. Table 22 shows the results. [Evaluation of Image Defects] An image sample having the largest number of image defects among image samples obtained when the process speed was changed and the entire halftone original and the text original were placed on the original plate and copied was evaluated. As an evaluation method, the image sample was observed with a magnifying glass, and evaluation was performed based on the state of white spots within the same area.

A: Good.

・ ・ ・: There are some minute white spots.

Δ: There are minute white spots on the entire surface, but there is no problem in character recognition.

C: Some characters are difficult to read due to many white spots. [Evaluation of black spots] The average density of an image obtained by changing the process speed and placing a halftone original on the entire surface on a platen is 0.
Images were output to be 4 ± 0.1. Among the image samples obtained in this way, the most noticeable one was selected and evaluated. As a method of evaluation, these images were observed at a distance of 40 cm from the eyes to check whether black spots were observed, and evaluated according to the following criteria.

A: No black spot is observed on any copy.

・ ・ ・: Some black spots were observed.

However, there was no problem at all.

Δ: Black spots are observed on all copies.

However, it is slight and does not hinder practical use.

C: Large black spots are observed on all copies. [Evaluation of Electrophotographic Characteristics 1] The surface potential of the photoconductor obtained at the developing position when the same charging voltage is applied at a normal process speed is evaluated as a relative value as a charging ability. However, the charging ability of the electrophotographic photosensitive member obtained in Conventional Example 1 was 10
0%. [Evaluation of Electrophotographic Characteristics 2] After applying the same charging voltage at a normal process speed, light is irradiated and the amount of light obtained when the potential drops to a certain potential is evaluated as a relative value as sensitivity. However, the charging ability of the electrophotographic photosensitive member obtained in Conventional Example 1 is set to 100%. [Evaluation of cost] ・ ・ ・: Can be manufactured inexpensively. 同等: Same as before. ・ ・ ・: Increase in cost. <Example 2> Using the same base as in Example 1, and using the same method as in Example 1. Table 23 shows the results of evaluating the inhibition type electrophotographic photosensitive member produced in the above method 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 photosensitive member was produced. The following three methods were used for image evaluation. Table 23 shows the results.

[0160]

[Table 23] [Evaluation of slipperiness] An arbitrary load is applied to the blade, and a piezo element is used to detect the frictional force, ie, 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 with relative values (lower value indicates better slipperiness) [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. Thus, the exposure amount of the original 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.

[0161] 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 was observed on any of the coby.

・ ・ ・: There is a copy in which image unevenness is recognized and a copy in which image unevenness is not recognized.

However, all of them are minor and have no problem at all.

Δ: Image unevenness is observed on any copy.

However, on at least one copy, the image unevenness is slight and does not hinder practical use.

C: Large image unevenness is observed on all copies. [Evaluation of fogging on white background] An image sample obtained when a normal original composed of characters on a white background was copied on a platen was observed, and the fogging of the white background was evaluated.

A: Good.

・ ・ ・: Some fog was found.

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

×: There are portions where characters are difficult to read due to fog. <Example 3> Using the same substrate as in Example 1 and performing a surface treatment in the same manner as in Example 1, FIG.
The microwave CVD device (μwPCV) shown in FIG.
D) under the conditions shown in Table 24 to produce a blocking type electrophotographic photosensitive member shown in FIG. In the image evaluation, the above-described image defect, black spot, image photograph characteristic 1 and image photograph characteristic 2 were performed. The results are shown in Table 25. As Comparative Example 3, after processing by the method shown in Conventional Example 1, a similar blocking type electrophotographic photoreceptor was produced and evaluated by the same method. Note: 601, 602, 6 in FIG.
03-2, 603-2 and 604 represent an aluminum substrate, a charge injection blocking layer, a charge transport layer, a charge generation layer,
And a surface layer.

[0172]

[Table 24]

[0173]

[Table 25] As is clear from Table 25, the present invention is effective even if the device and the layer configuration are different. <Embodiment 4> Using the same substrate as in Embodiment 1 and performing the same surface treatment as in Embodiment 1, VHF PCV shown in FIG.
A blocking type electrophotographic photoreceptor having the layer configuration shown in FIG. 6-B was prepared using the D apparatus under the conditions shown in Table 26, and evaluated by the same method. As a result, the same good results as in Example 1 were obtained.

[0174]

[Table 26]

[0175]

As described above, according to the present invention, in a method for manufacturing a photoreceptor for forming a functional film on an aluminum substrate, the surface of the substrate is formed before the functional film is formed. Is applied to the surface of the composition substrate in the range of 5 to 150 ° in water containing an inhibitor.
l: Si: O = a: b: c, and when a = 1, 0.1 ≦ b
≦ 0.5, 1 ≦ c ≦ 5 and the film thickness is Al-Si
By forming the —O film, it is possible to manufacture an electrophotographic photoreceptor that gives uniform high-quality images at low cost and with high yield.

[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 sectional view of a cleaning apparatus for cleaning a substrate by a conventional method.

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

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

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

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

[Explanation of symbols]

 101, 201, 306, 406, 526 Substrate 102, 202 Processing unit 103, 203 Substrate transport mechanism 111, 211 Substrate loading table 131 Rinse tank 122, 142 Water-based cleaning agent 141 Drying tank 151, 251 Substrate discharge table 161, 261 Transport arm 162, 262 Moving mechanism 163, 263 Chucking mechanism 164, 264 Air cylinder 165, 265 Transfer rail 301 Reaction vessel 302 Cathode electrode 303 Top plate 304 Base plate 305 Insulator 307 Base holder 308, 403, 523 Heating heater 309 Source gas introduction pipe 311 Source gas inflow valve 312, 528 Micro controller 313, 404, 524 Exhaust pipe 314 Exhaust valve 315 Vacuum exhaust device 316 High frequency power supply 402, 522 529 Rotation motor 407 Discharge space 408 Source gas introduction tube and DC application electrode 409 DC power supply 410 Microwave introduction window 411 Waveguide 601 Aluminum substrate 602 Charge injection blocking layer 603-1 Charge transport layer 603-1 Charge generation layer 604 Surface layer

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

Claims (13)

[Claims] 1. A method for producing an electrophotographic photoreceptor comprising a step of forming a functional film made of an amorphous material containing silicon atoms as a base material on a surface of an aluminum substrate by a low pressure vapor phase epitaxy method. Prior to the step of forming a photoreceptor, a film containing aluminum, silicon, and oxygen as main components and having a film thickness in the range of 5 ° to 150 ° and a composition ratio represented by the following formula is formed using water containing an inhibitor. A method for producing an electrophotographic photoreceptor, comprising the steps of: Aluminum: silicon: oxygen = a: b: c, a =
When it is set to 1, the range of b and c is 0.1 ≦ b ≦ 1.0
1 ≦ c ≦ 5. 2. The method according to claim 1, wherein the inhibitor is a silicate. 3. The method according to claim 2, wherein the silicate is potassium silicate. Claim 1 is in the range of ⁶ mol / l ^- wherein the molar concentration of the inhibitor contained in the water is 10 ⁰ to 10
3. The method for producing an electrophotographic photoreceptor according to item 1. 5. The step of forming the functional film on the aluminum substrate includes the step of forming an amorphous deposited film comprising at least one of hydrogen atoms and fluorine atoms and silicon atoms by plasma CVD on the aluminum substrate. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the method is a step of forming the photoreceptor thereon. 6. The method according to claim 1, wherein the water contains one of a surfactant and carbon dioxide. 7. The method according to claim 1, wherein the water is 2 kg · f / cm ^{2 to} 300 kg / f ^2.
The method according to claim 1, wherein the substrate is washed at a pressure of kg · f / cm ² . 8. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the substrate is taken out of hot water and dried. 9. The method according to claim 1, wherein the hot water is at least one of hot pure water, hot water in which carbon dioxide is dissolved, and hot water containing the inhibitor. 10. The method according to claim 1, wherein the aluminum base is made of iron.
2. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the substrate is an aluminum substrate containing not less than pm and not more than 1 wt%. 11. The method according to claim 1, wherein the aluminum substrate is a substrate containing aluminum containing 10 ppm or more and 1 wt% or less of silicon. 12. The method according to claim 1, wherein the aluminum substrate is made of
2. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the substrate is an aluminum substrate containing not less than pm and not more than 1 wt%. 13. The total content of iron, silicon and copper in the aluminum base is more than 0.01 wt% and 1 wt%.
The method for producing an electrophotographic photosensitive member according to claim 1, wherein: