JP3173940B2 - Manufacturing method of electrophotographic photoreceptor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electrophotographic photosensitive member having a functional film formed on an aluminum substrate.
In particular, the present invention relates to a method for manufacturing an electrophotographic photoreceptor in which a non-single crystal deposited film containing silicon atoms and hydrogen atoms is formed as a functional film on a silicon atom-containing aluminum substrate by a plasma CVD method.

[0002]

2. Description of the Related Art Glass, heat-resistant synthetic resin, stainless steel, aluminum and the like have been proposed as a substrate for forming a deposited film of an electrophotographic photosensitive member. However, in practice, metal is used to provide durability to electrophotographic processes such as charging, exposure, development, transfer, and cleaning, and to always maintain high positional accuracy so that image quality does not deteriorate. Often do. 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 support has a Fe content of 2000 p.
A technique for obtaining an amorphous silicon electrophotographic photoreceptor having good image quality by using an aluminum alloy of pm or less is 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-60-2629
No. 36 contains 3.0 to 6.0 wt% of Mg,
Mn is 0.3 wt% or less and Cr is 0.01 as impurities.
wt%, Fe is 0.15 wt% or less, Si is 0.1
An extruded aluminum alloy which is suppressed to 2 wt% or less and the balance is made of Al and which is excellent in vapor deposition of amorphous silicon is disclosed. However, these publications do not describe a washing method using water containing a specific component.

A technique relating to a method of processing a substrate of an electrophotographic photosensitive member is described in JP-A-61-171798. This publication discloses a technique for obtaining a good quality electrophotographic photosensitive member such as amorphous silicon by cutting a substrate using a cutting oil containing a specific component. The publication also describes that after cutting, the substrate is washed with triethane (trichloroethane: C ₂ H ₃ Cl ₃ ).

Techniques relating to the surface treatment of a substrate of an electrophotographic photosensitive member are described in JP-A-58-14841, JP-A-61-273551, and JP-A-63-264774.
And Japanese Patent Application Laid-Open No. 1-130159.

JP-A-58-14841 discloses a technique for removing a native oxide film on the surface of an aluminum support and then immersing the film in water at a temperature of 60 ° C. or higher to obtain a uniform oxide film. I have.

Japanese Patent Application Laid-Open No. 61-273551 discloses S
When e is deposited on an aluminum substrate to produce an electrophotographic photoreceptor, pretreatment of the substrate includes alkali cleaning, trichlene cleaning, and UV irradiation cleaning with a mercury lamp. It is described that liquid degreasing, steam degreasing and pure water cleaning are performed to remove oils and fats adhering to the surface of the cylindrical aluminum substrate as the treatment.

[0008] Japanese Patent Application Laid-Open No. 63-264764 discloses a technique for roughening the surface of a substrate with a water jet.

JP-A-1-130159 discloses a technique for cleaning an electrophotographic photosensitive member support with a water jet. In this publication, Se,
Amorphous silicon is mentioned at the same time as the organic photoconductor, but no problem specific to the plasma CVD method is mentioned at all.

On the other hand, as a pretreatment method for a substrate other than an electrophotographic photosensitive member, Japanese Unexamined Patent Publication No. 60-876 discloses a method in which carbon dioxide gas is added to ultrapure water to prevent discharge breakdown due to static electricity on a wafer surface. A blowing technique is disclosed. But,
This technique is a measure against static electricity generated on a high-resistance substrate such as a wafer, and does not mention a conductive substrate such as aluminum.

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 containing silicon atoms typified by amorphous silicon as a main component, 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.

As a method for forming such a non-single-crystal deposited film containing silicon atoms as a main component, there have conventionally been known 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), a method of decomposing a source gas by plasma (plasma CVD)
Numerous 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 most suitable for forming an amorphous silicon deposited film for electrophotography. At present, practical application is progressing considerably. 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 U.S. Pat.
No.18. The technology described in that patent is
Microwave plasma CVD at low pressure of 0.1 Torr or less
This is to obtain a high-quality deposited film at a high deposition rate by the method.

Further, a technique for improving the utilization efficiency of a source gas by microwave plasma CVD is disclosed in
0-186849. The technique described in that publication is such that a substrate is arranged so as to surround a means for introducing microwave energy to form an internal chamber (that is, a discharge space), thereby greatly improving the raw material gas use efficiency. is there.

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

When a cylinder made of an aluminum alloy is used as a substrate, the method for producing an electrophotographic photosensitive member according to the prior art is specifically carried out as follows.

Lathe with air damper for precision cutting (PNEUMO
PRECLUSION INC.), Set a diamond 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. Next, the base was vacuum-chucked to the rotating flange of the lathe, and a peripheral speed of 1000 m / min and a feed speed of 0.01 mm / were simultaneously used while spraying white kerosene from the attached nozzle and sucking chips from the attached vacuum nozzle. Mirror cutting is performed so that the outer shape becomes 108 mm under the condition of R.

Next, the cut substrate is washed with trichloroethane, and the cutting oil and chips adhering to the surface are washed.

Next, a deposited film mainly composed of amorphous silicon is formed on the mirror-finished and cleaned substrates by the apparatus for forming a deposited film of a photoconductive member by the glow discharge decomposition method shown in FIG.

Referring to FIG. 3, a reaction vessel 301 comprises a base plate 302, walls 303 and a top plate 304.
The substrate 306 on which the amorphous silicon deposited film is formed is provided at the center of the cathode electrode 305, and also serves as an anode electrode.

Using this deposited film forming apparatus,
To form a silicon deposition film on the substrate 306, first,
The source gas inflow valve 307 and the leak valve 308
Close, provide an exhaust valve 309, and exhaust the reaction vessel 301
I do. Reading of vacuum gauge 310 is about 5 × 10^-6Torr
When the source gas inflow valve 307 is opened,
-The source adjusted to a predetermined mixing ratio in the controller 311
Gas such as SiH _FourGas flows into the reaction vessel 301
To enter. And the surface temperature of the base 306 is a heater
Check that the temperature is set to the specified value by 312
After that, the high-frequency power supply 313 is set to a desired power and the reaction volume is set.
A glow discharge is generated in the vessel 301.

During the formation of the deposited film, the base 306 is moved to the motor 3 in order to make the deposited film uniform.
14 to rotate at a constant speed. Thus, an amorphous silicon deposition film can be formed on the base 306.

[0024]

However, these conventional methods for manufacturing an electrophotographic photoreceptor satisfy the requirements for uniform film quality and optical and electrical characteristics, particularly in a region where the deposition rate of the deposited film is high. In addition, it is difficult to obtain a deposited film having high image quality constantly and stably at a high yield (high yield) during image formation by an electrophotographic process.

That is, in the electrophotographic photosensitive member manufactured by the conventional method, there is a portion having a very small area where abnormal growth has occurred in the deposited film, and this portion is a portion where the surface charge is not applied.
Such a phenomenon is particularly remarkable in the case of an electrophotographic photosensitive member having a deposited film formed by a plasma CVD method like amorphous silicon. However, the portion where the surface potential does not multiply can be suppressed considerably by optimizing the surface processing conditions and deposition conditions of the substrate. Conventionally, the resolution was small enough to be at or below the resolving power of development. No problems had occurred.

However, in recent years, 1) higher image quality of the electrophotographic apparatus has been required, and accordingly, the resolution of development has been improved. 2) As the speed of the copying machine has increased and the charging conditions have become more severe, the surface of the electrophotographic apparatus has become more severe. The portion where the potential is not applied substantially has a great influence on the peripheral potential.

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

Further, since image copying has been mainly used for originals of only print (so-called line copy), such image defects have not been a serious problem in practical use, but recently, high image quality is provided. As copiers have been developed, many documents including halftones such as photographs have been copied, which has become a problem. In particular, in color copiers that have recently become widespread, these defects have become a serious problem because they become more visually apparent.

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

On the other hand, the electrophotographic photosensitive member manufactured by the plasma CV method has such a structure as compared with the Se electrophotographic photosensitive member manufactured by vacuum deposition, the OPC electrophotographic photosensitive member manufactured by the blade coating method or the dipping method, and the like. Image defects are particularly pronounced.

Also, in a device manufactured by the plasma CVD method, the above problem is not solved in a device such as a solar cell in which a delicate difference in characteristics depending on a position on a substrate does not affect its performance or can be repaired by post-processing. Does not occur.

An object of the present invention is to overcome the above-mentioned problems in the conventional method for manufacturing an electrophotographic photosensitive member, and to provide a method of manufacturing an electrophotographic photosensitive member which is easy to use and which can be formed stably at low cost and with good yield. Is to provide.

The present invention also provides a method of manufacturing an electrophotographic photosensitive member capable of solving the problem of occurrence of particularly remarkable image defects in the plasma CVD method and obtaining a uniform high-quality image. With that purpose.

[0034]

According to the present invention, there is provided an electrophotographic photoreceptor manufacturing method including a step of forming a functional film on an aluminum substrate. Washing with water in which carbon is introduced to dissolve carbon dioxide (hereinafter referred to as CO ₂ water) and warm water in which carbon dioxide is introduced to dissolve carbon dioxide (hereinafter referred to as CO ₂ water)
₂ ) The substrate is immersed in hot water.
The present invention provides a method for producing an electrophotographic photoreceptor, which comprises performing lifting and drying performed by lifting the body.

According to the studies conducted by the present inventors, the causes of image defects that occur when an aluminum substrate is used are as follows.
It can be roughly divided into the following two. (A) Dust or the like adheres to the substrate, which becomes a core. (B) The surface defects of the substrate become nuclei.

The adhesion of dust and the like in (A) is to clean the place where the substrate is handled, such as cutting and cleaning, and to clean the inside of the film forming furnace strictly, and furthermore, immediately before the formation of the deposited film, Could be prevented by washing. 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 thus it has become necessary to newly examine this problem.

On the other hand, reducing the defect of (B)
Conventionally, it has been extremely difficult.

By combining aluminum containing a specific component and a specific cleaning method, the present inventors
As a result of intensive studies from the viewpoint of solving all of these problems, the present invention has been completed.

According to the study of the present inventors, there are locally high hardness portions in aluminum, and when performing surface processing such as cutting as pre-processing prior to formation of a deposited film, these high hardness portions are processed. What can be excavated by the blade of the machine,
It became clear that this was the cause of the surface defect on the aluminum substrate of (B).

Further, in order to prevent such a phenomenon,
Generally, it is better that the amount of impurities contained in aluminum is small. However, with very high purity aluminum,
When the raw material aluminum is melted for processing according to the shape of the base, the generation and growth of oxides is inevitable,
That causes the above-mentioned defect. In order to prevent this, it has been found that containing silicon atoms is effective.

When cleaning with a chlorine-based solvent such as trichloroethane is performed after machining of the substrate surface, it is not sufficient to prevent the occurrence of image defects due to the surface properties of the substrate only by making such improvements. It is possible.

However, as described above, in recent years, chlorine-based solvents cannot be easily used due to environmental problems.
The present inventors also studied cleaning. As a result, it was found that aluminum corrodes due to water, and especially for aluminum containing silicon atoms, when it comes into contact with water at the time of cleaning, the corrosion due to water becomes remarkable mainly in a portion where silicon atoms are locally large. .

This phenomenon is more remarkable when the temperature of water is higher, and is more remarkable when magnesium is contained in aluminum together with silicon atoms to improve machinability. Various corrosion inhibitors have been proposed for the purpose of preventing corrosion of aluminum. However, when an aluminum substrate containing silicon is used as a substrate for an electrophotographic photosensitive member as in the present invention, a slight amount of Even if the defect is generated, the effect is insufficient because it causes a problem. Further, since a small amount of such a corrosion inhibitor remains on the surface of the substrate even after cleaning, the electrophotographic characteristics after the formation of the deposited film are adversely affected. That is, when a non-volatile component that does not volatilize immediately with water adheres to the surface of the aluminum substrate, an adverse effect such as blotting on an image occurs when an electrophotographic photosensitive member is manufactured. Therefore, the use of conventional corrosion inhibitors is limited.

The inventors of the present invention wondered if the above-mentioned defects could be suppressed by making some improvement to the water used in the cleaning step for removing the deposits such as dust prior to the formation of the deposited film. As a result of intensive thought and research, the present invention has been completed. As in the method of the present invention, CO 2
_{2 The} reason why good results can be obtained by using water (mechanism) has not yet been elucidated in many respects,
The present inventors currently consider as follows.

The portion of the aluminum substrate surface that is largely exposed to silicon atoms forms a local battery with the surrounding normal aluminum portion to promote corrosion.

On the other hand, carbon dioxide dissolved in water turns into carbonate ions in the water, and is attracted to these local battery parts to cover the surroundings, thereby preventing access of oxygen and the like in the water and effectively preventing corrosion. Further, the carbonate ions cause some alteration on the surface of the portion containing a large amount of silicon atoms, thereby preventing abnormal growth from occurring in this portion during the formation of the deposited film.

Further, as unexpected effects of the method of the present invention, reduction of image unevenness and improvement of electrophotographic characteristics were recognized.

When, for example, an amorphous silicon deposition film is formed on a substrate by the plasma CVD method, the reaction is 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 on the substrate surface. The reaction process can be divided into three parts. In particular, the surface reaction process plays a very important role in determining the structure of the completed deposited film. The surface reaction is greatly affected by the temperature, the material, the shape, the adsorbed substance and the like of the substrate surface.

Particularly, a high-purity aluminum substrate is obtained by simply washing with a non-aqueous solvent such as trichloroethane after cutting, or simply performing jet cleaning treatment with pure water without performing other washing after cutting. In the state, the adsorption of water on the substrate surface is partially different. When a deposited film containing silicon atoms and hydrogen atoms and / or fluorine atoms, such as an amorphous silicon film, is formed on a substrate having such a surface state by, for example, a plasma CVD method, a reaction on the surface is caused on the substrate surface. It is particularly strongly affected by the amount of remaining water molecules. As a result, the composition and structure of the interface of the deposited film changes depending on the amount of water adsorbed at the position of the substrate, and as a result, the charge injection property from the substrate portion changes during the electrophotographic process, thereby reducing the image density. A surface potential difference that can be changed appears.

In the method of the present invention, the substrate surface is washed with CO ₂ water before forming a deposited film by the plasma CVD method, and
By pulling up and drying with warm water of O ₂ , the surface of the substrate can be effectively made uniform, and the above-mentioned unevenness in image density can be eliminated.

Further, carbonate ions have the effect of increasing the surface activity by uniformly and slightly dissolving the entire aluminum surface and forming an interface through which good charge exchange can be performed when forming a deposited film. For this reason, improvement of electrification,
It has become possible to improve the electrophotographic characteristics, such as reducing the residual potential and the light sensitivity.

The present invention is a novel surface treatment method for improving image defects and the like generated during the production of an electrophotographic photosensitive member and further improving the electrophotographic characteristics. It has different effects.

Further, in the method of the present invention, after the cutting step, C
By providing a pre-cleaning step before the cleaning step with O ₂ water, the effect of the cleaning step can be completely improved by removing fats and oils and halogen-based residuals that reduce the effect of the cleaning step. In particular, by performing ultrasonic cleaning with water or water to which a surfactant is added in the pre-cleaning step, the effect of the method of the present invention can be significantly improved.

One example of a procedure for actually forming an electrophotographic photosensitive member by the method of manufacturing an electrophotographic photosensitive member of the present invention using a cylinder made of an aluminum alloy as a substrate will be described with reference to FIG. The case where the deposited film forming apparatus shown in FIG. 2B is used will be described below.

Lathe with air damper for precision cutting (PNEU
MO PECLUSION INC.) Is set with a diamond bite (trade name: Miracle bite, manufactured by Tokyo Diamond) so as to obtain a rake angle of 5 ° with respect to the cylinder center angle. Next, the base was chucked to the rotating flange of the lathe, and the peripheral nozzle was sprayed with white kerosene from the attached nozzle and the suction speed of the cutting powder from the attached vacuum nozzle.
Under the conditions of 00 m / min and a feed rate of 0.01 mm / R, mirror cutting is performed so that the outer shape becomes 108 mm.

After the substrate has been cut, the surface of the substrate is processed by a substrate pretreatment device. The substrate pretreatment apparatus shown in FIG. 1 includes a processing unit 102 and a substrate transport mechanism 103. The processing unit 102 includes a substrate loading table 111, a pre-substrate cleaning bath 121, a cleaning bath 131 using CO ₂ water, a drying bath 141,
It consists of a substrate carrier 151. Pre-cleaning tank 121, C
O ₂ water cleaning tank 131, CO ₂ hot water dry layer 14
Both have a temperature controller (not shown) for keeping the temperature of the liquid constant. The transport mechanism 103 includes the transport rail 1
65 and the transfer arm 161.
Is a moving mechanism 162 that moves on the rail 165,
01 for holding the chuck 01 and the air cylinder 1 for raising and lowering the chucking mechanism 163
It consists of 64.

After cutting, the substrate 1 placed on the loading table 111
01 is transported to the cleaning tank 121 by the transport mechanism 103. Ultrasonic treatment is performed in the aqueous surfactant solution 122 in the pre-cleaning tank 121 to clean the cutting oil and chips adhering to the surface.

Next, the substrate 101 is transported to the CO ₂ water cleaning tank 131 by the transport mechanism 103, and further cleaned with CO ₂ water maintained at a temperature of 25 ° C. As for CO ₂ water, the conductivity is measured at any time by an industrial conductivity meter (trade name: α900R / C, manufactured by HORIBA, Ltd.).
It is controlled so as to be maintained at S / cm. The substrate 101, which has been washed with CO ₂ water, is transported by
It is moved to a drying tank 141 using hot O ₂ water, pulled up using CO ₂ hot water maintained at a temperature of 60 ° C., and subjected to drying using an elevating device (not shown). The conductivity of CO ₂ hot water is measured at any time by an industrial conductivity meter (trade name α900R / C, manufactured by HORIBA, Ltd.), and the conductivity is maintained at approximately 20 μS / cm by dissolving carbon dioxide as necessary. Control so that The substrate 101 after the drying step is carried to the carrier 151 by the carrier mechanism 103.

Next, on the substrate which has been subjected to the cutting and pretreatment, amorphous silicon is deposited on the substrate by the apparatus for forming a photoconductive member deposited film by the plasma CVD method shown in FIGS. 2 (a) and 2 (b). A main deposited film is formed.

In FIGS. 2A and 2B, 2
Reference numeral 01 denotes a reaction vessel having a vacuum tight structure. Also 2
Reference numeral 02 denotes a microwave introduction dielectric window formed of a material (for example, quartz glass, alumina ceramics or the like) capable of efficiently transmitting microwave power into the reaction vessel 201 and maintaining vacuum tightness. Reference numeral 203 denotes a waveguide for transmitting microwave power, which includes a rectangular portion extending from the microwave power source to the vicinity of the reaction vessel and a cylindrical portion inserted into the reaction vessel. The waveguide 203 is connected to a microwave power supply (not shown) together with a stub tuner (not shown) and an isolator (not shown). The dielectric window 202 is hermetically sealed to the inner wall of the cylindrical portion of the waveguide 203 to maintain the atmosphere in the reaction vessel. 20
Reference numeral 4 denotes an exhaust pipe having one end open to the reaction vessel 201 and the other end communicating with an exhaust device (not shown). Reference numeral 206 denotes a discharge space surrounded by the base 205. The power supply 211 is a DC power supply (bias power supply) for applying a DC voltage to the bias electrode 212, and is electrically connected to the electrode 212.

The production of an electrophotographic photosensitive member using such a deposited film forming apparatus is performed as follows.

First, the reaction vessel 201 is evacuated through the exhaust pipe 204 by a vacuum pump (not shown), and the pressure in the reaction vessel is adjusted to 1 × 10 ⁻⁷ Torr or less. Then
The temperature of the base 205 is heated and maintained at a predetermined temperature by the heater 207. Therefore, a source gas such as a silane gas as a source gas for amorphous silicon, a diborane gas as a doping gas, and a helium gas as a diluting gas is introduced into the reaction vessel 201 through a gas introducing unit (not shown). Microwave power supply (not shown) at the same time
Generates a microwave having a frequency of 2.45 GHz,
It is introduced into the reaction vessel 201 through the waveguide 203 through the dielectric window 202. Further, a DC voltage is applied to the bias electrode 212 to the base 205 by a DC power supply 211 electrically connected to the bias electrode 212 in the discharge space 206. Thus, in the discharge space 206 surrounded by the base 205, the source gas is excited by microwave energy to be dissociated, and further the bias gas 212
The deposited film is formed on the surface of the substrate 205 while constantly receiving ion bombardment on the substrate 205 by the electric field between the substrate 205 and the substrate 205. At this time, the rotating shaft 20 on which the base 205 is installed
By rotating the substrate 9 by the motor 210 and rotating the substrate 205 around the central axis in the direction of the base line of the substrate, a deposited film layer is formed uniformly over the entire periphery of the substrate 205.

In the method of the present invention, particularly when pre-cleaning is performed, it is desirable to perform water-based cleaning containing a surfactant or the like. There is no particular limitation on the quality of the water before dissolving the surfactant in the case of the aqueous cleaning, but pure water of a semiconductor grade, particularly ultrapure water of an ultra LSI grade is desirable. Specifically, the resistivity at a water temperature of 25 ° C. is 1
MΩ · cm, preferably 3 MΩ · cm, optimally 5 MΩ
-Water with cm as the lower limit. The upper limit may be a value equal to or less than the theoretical resistance value (18.25 MΩ · cm), but from the viewpoint of cost and productivity, it is 17 MΩ · cm, preferably 15 MΩ · cm, and most preferably 13 MΩ · cm. .

The amount of fine particles is not more than 10,000 μm, preferably not more than 1,000, and most preferably not more than 100 per 1 ml of particles having a particle size of 0.2 μm or more. The amount of microorganisms is such that the total viable count is 100 or less, preferably 1
0 or less, optimally 1 or less. Organic matter (TO
C) is 10 mg or less, preferably 1 mg per liter.
Hereinafter, the optimal amount is 0.2 mg or less.

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

If the temperature of the water in the cleaning step is too high, an oxide film is generated on the substrate to cause peeling of the deposited film, and if the temperature is too low, the cleaning effect is reduced. For this reason, the temperature of water is 5 ° C. or more and 90 ° C. or less, preferably 10 ° C. or less.
C. to 55.degree. C., optimally 15 to 40.degree. The temperature of the hot water in the hot water drying step is 30 ° C. or higher and 9
The temperature is 0 ° C or lower, preferably 35 ° C or higher and 80 ° C or lower, and most preferably 40 ° C or higher and 70 ° C or lower.

The surfactant used in the pre-cleaning step of the method of the present invention may be an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant or a mixture thereof. Any of them is possible. Among them, anionic surfactants such as carboxylate, sulfonate, sulfate monoester salt and phosphate ester salt and nonionic surfactant such as fatty acid ester are particularly effective. As the builder, phosphates, carbonates, silicates, borates and the like are effective. As a chelating agent, gluconate, EDTA, NTA, phosphate and the like are effective.

In the method of the present invention, the use of ultrasonic waves in the pre-cleaning step is effective in improving the effect. The frequency of the ultrasonic wave is preferably 100 Hz or more and 10 MHz.
The frequency is more preferably 1 kHz or more and 5 MHz or less, and most preferably 10 kHz or more and 100 kHz or less. The output of the ultrasonic wave is preferably 0.1 W / liter or more and 1 kW /
1 liter or less, more preferably 1 W / liter or more and 1
00W / liter or less.

In the present invention, the quality of the water used in the washing step with water in which carbon dioxide is dissolved is very important. Water is preferred. Specifically, the resistivity at a water temperature of 25 ° C. is 1 MΩ · cm,
Preferably, the water has a lower limit of 3 MΩ · cm, and optimally 5 MΩ · cm. The upper limit of the resistance value is the theoretical resistance value (1
8.25 MΩ · cm) or less, but 17 MΩ · cm, preferably 15 MΩ, in terms of cost and productivity.
Cm, optimally 13 MΩcm.

The amount of the fine particles is 0.2 μm or more, 10000 or less, preferably 1000 or less, and optimally 100 or less in 1 ml. The amount of microorganisms is such that the total viable count is 100 or less, preferably 1
0 or less, optimally 1 or less. Organic matter (TO
C) is 10 mg or less, preferably 1 mg per liter.
Hereinafter, the optimal amount is 0.2 mg or less.

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 achieve water quality of

The amount of carbon dioxide dissolved in water can be any amount up to the saturation solubility. However, if the amount is too large, foaming occurs when the water temperature fluctuates, and adheres to the surface of the base to cause spots on the spot. May cause outbreaks. Further, when the amount of dissolved carbon dioxide is large, the pH may be lowered to damage the substrate, and when the amount of dissolved carbon dioxide is too small, the effect becomes insufficient. Therefore, it is necessary to optimize the dissolved amount of carbon dioxide according to the situation while considering the quality and the like required for the substrate.
The preferred amount of dissolved carbon dioxide in the method of the present invention is 60% or less, more preferably 40% or less of the saturated solubility.

In the method of the present invention, it is practical to control the dissolved amount of carbon dioxide by the conductivity or pH of water. When controlled by conductivity, the preferred range is 2 μS / c.
m or more and 40 μS / cm or less, more preferably 4 μS / cm
cm or more and 30 μS / cm or less, optimally 6 μS / cm or more and 25 μS / cm or less. When the pH is controlled, the preferred range is 3.8 or more and 6.0 or less, and more preferably 4.0 or more and 5.0 or less. By performing such management, the effect of the method of the present invention becomes remarkable. The conductivity is measured by a conductivity meter or the like, and a value converted to 25 ° C. by temperature correction is used.

[0074] The temperature of the water causes the peeling of the deposited film oxide film is generated in too high on the substrate, the effect is sufficiently obtained in the method of the present invention the cleaning effect is too low on the contrary smaller I can't. For this reason, the temperature of the water is 5 ° C. or more and 90 ° C.
° C or lower, preferably 10 ° C or higher and 55 ° C or lower, optimally 1 ° C or lower.
5 ° C. or higher and 40 ° C. or lower.

As a method for dissolving carbon dioxide in water,
Either a method using bubbling or a method using a diaphragm may be used. In the method of the present invention, it is important to use water in which carbon dioxide is dissolved, and when a carbonate such as sodium carbonate is used to obtain a carbonate ion, a cation such as sodium ion acts as an interfering factor. Would.

When the substrate surface is washed with the CO ₂ water thus obtained, there are a method of washing by dipping, a method of spraying by applying water pressure, and the like.

When washing by dipping, CO ₂
Basically, the substrate is immersed in a water tank into which water has been introduced. When the application of ultrasonic waves, the flow of water, the bubbling by air introduction, or the like is used in combination, the effect of the method of the present invention becomes more remarkable.

If the pressure of the water to be sprayed is too weak, the effect is small, and if it is too strong, a pear-skinned pattern is generated on the obtained image of the electrophotographic photosensitive member, particularly on a halftone image. Therefore, the water pressure is 2 kg · f
/ Cm ² or more and 300 kg · f / cm ² or less, preferably 1
0 kg · f / cm ² or more and 200 kg · f / cm ² or less, optimally 20 kg · f / cm ² or more and 150 kg · f / cm ²
The following is assumed. However, the unit kg · f /
cm ² means kilograms of gravity per square centimeter, and 1 kg · f / cm ² is equal to 98066.5 Pa.

The method of spraying water is to spray water pressurized by a pump from a nozzle, or to mix water pumped by a pump with high-pressure air before the nozzle,
There is a method of blowing by the pressure of air.

The flow rate of the water is from 1 liter / min to 200 liter / m per substrate from the viewpoints of effect and economy.
in, preferably 2 l / min to 100 l / min, optimally 5 l / min to 50 l / min.

If the temperature of water is too high, an oxide film is formed on the substrate to cause peeling off of the deposited film, and the effect of the method of the present invention cannot be sufficiently obtained. Is difficult to keep stable. Conversely, if it is too low, the effect of the method of the present invention is still not sufficient. For this reason, the temperature of water is 15 ° C or more and 80 ° C or less, preferably 20 ° C or more and 75 ° C or less, and most preferably 25 ° C or more and 60 ° C or less.
It is as follows.

If the time of the cleaning treatment with CO ₂ water is too long, an oxide film is formed on the substrate, and if the time is too short, the effect is small, so that the time is 10 seconds to 30 minutes, preferably 20 seconds to 20 minutes. Hereinafter, it is optimally 30 seconds or more and 10 minutes or less.

In the method of the present invention, it is important that the substrate surface is cut immediately before the formation of the deposited film in order to minimize the formation of an oxide film on the substrate surface, which adversely affects the formation of the deposited film. .

If the time from the cutting to the cleaning treatment with CO ₂ water is too long, an oxide film is generated again on the substrate surface, and if the time is too short, the process is not stable. The time is from 2 minutes to 8 hours, optimally from 3 minutes to 4 hours.

In the method of the present invention, when hot water drying with CO ₂ hot water is performed, the quality of the water used is very important. Before the carbon dioxide dissolution, pure water of semiconductor grade, particularly ultra LSI grade, is used. Ultrapure water is desirable. Specifically, as a resistivity at a water temperature of 25 ° C., 1 MΩ · c
m, preferably 3 MΩ · cm, most preferably 5 MΩ · cm. The upper limit of the resistance value is the theoretical resistance value (1
8.25 MΩ · cm) or less, but from the viewpoint of cost and productivity, 17 MΩ · cm, preferably 15 MΩ · cm.
MΩ · cm, optimally 13 MΩ · cm.

The amount of fine particles is 0.2 μm or more, 10000 or less, preferably 1000 or less, and optimally 100 or less in 1 ml. The amount of microorganisms is such that the total viable count is 100 or less, preferably 1
0 or less, optimally 1 or less. Organic matter (TO
C) is 10 mg or less, preferably 1 mg per liter.
Hereinafter, the optimal amount is 0.2 mg or less.

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 achieve water quality of

The amount of carbon dioxide dissolved in the water can be any amount up to the saturation solubility. However, if it is too large, it foams when the water temperature fluctuates and adheres to the surface of the substrate to cause spot-like stains. May cause. Furthermore, when the amount of dissolved carbon dioxide is large, the pH may be lowered and the substrate may be damaged. On the other hand, if the amount of dissolved carbon dioxide is too small, the effect of the method of the present invention cannot be obtained. Therefore, it is necessary to optimize the dissolved amount of carbon dioxide according to the situation while taking into account the quality required for the substrate and the like. However, the preferred amount of dissolved carbon dioxide in the method of the present invention is 60% or less of the saturated solubility. , More preferably 40% or less.

In the method of the present invention, it is practical to control the dissolved amount of carbon dioxide by the conductivity or pH of water. When controlled by conductivity, a preferable range is 5 μS / c.
m or more and 40 μS / cm or less, more preferably 6 μS / cm
cm to 35 μS / cm, optimally 8 μS / cm to 30 μS / cm. When the pH is controlled, the preferred range is 3.8 or more and 6.0 or less, and more preferably 4.0 or more and 5.0 or less. By performing such management, the effect of the method of the present invention becomes remarkable. The conductivity is measured by a conductivity meter or the like, and a value converted to 25 ° C. by temperature correction is used.

As a method for dissolving carbon dioxide in water,
Either a method using bubbling or a method using a diaphragm may be used. In the method of the present invention, it is important to use water in which carbon dioxide is dissolved, and when a carbonate such as sodium carbonate is used to obtain carbonate ions, cations such as sodium ions act as inhibitors. Would.

If the temperature of the hot water is too high, an oxide film is generated on the substrate, which may cause peeling of the deposited film. Conversely, if the temperature of the hot water is too low, the drying becomes insufficient and the effect of the method of the present invention is sufficient. I can't get it. For this reason, the temperature of water is 30 ° C. or more and 9
The temperature is 0 ° C or lower, preferably 35 ° C or higher and 80 ° C or lower, and most preferably 40 ° C or higher and 70 ° C or lower.

The pulling speed at the time of pulling and drying is very important, and the preferable range is 100 mm / min or more, and optimally 300 mm / min or more and 1000 mm / m.
in.

The time from the cleaning treatment with CO ₂ water to the introduction into the deposition film forming apparatus is too long, the effect is small, and if it is too short, the process is not stable. The time is from minutes to 4 hours, optimally from 3 minutes to 2 hours.

In the method of the present invention, magnesium can be contained in order to improve the workability of the substrate. The preferred magnesium content is 0.1 wt% to 10 wt%, more preferably 0.2 wt% to 5 wt%.
wt% or less.

Further, in the method of the present invention, H, Li, N
a, K, Be, Ca, Ti, Cr, Mn, Fe, Co,
Ni, Cu, Ag, Zn, Cd, Hg, B, In, C,
Si, Ge, Sn, N, P, As, O, S, Se, F,
Any substance such as Cl, Br and I can be appropriately contained in aluminum.

In the method of the present invention, the shape of the substrate may be arbitrary, but a cylindrical shape is particularly preferable. The size of the substrate is not particularly limited, but is practically 20 mm in diameter.
The length is preferably 500 mm or more and 10 mm or less and 1000 mm or more in length.

The photoreceptor used in the method of the present invention may be any of an amorphous silicon photoreceptor, a selenium photoreceptor, a cadmium sulfide photoreceptor, and an organic photoreceptor. The effect is remarkable when a non-single crystal photoreceptor is used.

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

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

The band gap width of the deposited film was changed.
Nitrogen as a gas for improving characteristics such as
(N_Two), Ammonia (NH_ThreeGas containing nitrogen atoms such as
S; oxygen (O _Two), Nitric oxide (NO), nitrogen dioxide
(NO_Two), Nitrous oxide (N_TwoO), carbon monoxide (C
O), carbon dioxide (CO_TwoGas containing oxygen atoms, such as
Methane (CH_Four), Ethane (C_TwoH₆), Ethylene (C_TwoH
_Four), Acetylene (C_TwoH_Two), Propane (C_ThreeH₈)
Hydrocarbon; germanium tetrafluoride (GeF_Four), Nitrogen fluoride
(NF_Three) Or a mixture of these compounds
Used.

In the method of the present invention, diborane (B ₂ H ₆ ), boron fluoride (BF)
₃ ) A dopant gas such as phosphine (PH ₃ ) may be simultaneously introduced into the discharge space.

In the electrophotographic photoreceptor manufactured by the method of the present invention, the total thickness of the deposited film deposited on the substrate is not particularly limited, but is preferably 5 μm to 100 μm, more preferably 10 μm to 70 μm, and In particular, when the thickness was 15 μm or more and 50 μm or less, a particularly good image as an electrophotographic photosensitive member could be obtained.

In the method of the present invention, the effect of the pressure in the discharge space during the deposition of the deposited film was observed in any region. In particular, when the pressure in the discharge space was 0.5 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 the uniformity of the deposited film.

In the method of the present invention, the substrate temperature at the time of depositing a deposited film is effective in the range of 100 ° C. to 500 ° C., but is particularly preferably 150 ° C. to 450 ° C., preferably 20 ° C.
0 ° C to 400 ° C, optimally 250 ° C to 350 ° C
A remarkable effect was confirmed by the following.

The heating means for the substrate in the method of the present invention may be a heating element of a vacuum specification, and more specifically, a winding heater of a sheath-like heater, a plate-like heater, or the like.
Electric resistance heating elements such as ceramic heaters; heat radiation lamp heating elements such as halogen lamps and infrared lamps; heating elements formed by heat exchange means using a liquid or gas as a heating medium; Examples of the surface material of the heating means include metals such as stainless steel, nickel, aluminum, and copper; ceramics; and heat-resistant polymer resins. In addition, a method 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 can be used. The above means can be used alone or in combination.

In the method of the present invention, the energy for generating the plasma may be any of DC, RF, microwave, etc. In particular, when the microwave is used for the energy for generating the plasma, it may be caused by surface defects of the substrate. Abnormal growth appears remarkably, and microwaves are absorbed by the adsorbed moisture, and the interface changes become more remarkable, so that the effect of the method of the present invention becomes more remarkable.

In the method of the present invention, when microwaves are used to generate plasma, any microwave power may be used as long as discharge can be generated.
It is set to W or more and 10 kW or less, preferably 500 W or more and 4 kW or less.

In the method of the present invention, it is effective to apply a voltage (bias voltage) to the discharge space during the formation of the deposited film, and it is preferable that an electric field is applied at least in a direction in which cations collide with the substrate. If no bias is applied, the effect of the present invention is significantly reduced,
DC component voltage is 1V or more and 500V or less, preferably 5V or less.
It is desirable to apply a bias voltage of V or more and 100 V or less during formation of the deposited film in order to obtain the effects of the present invention.

In the method of 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 (AlN), boron nitride, or the like. (BN), silicon nitride (Si
N), silicon carbide (SiC), silicon oxide (SiO ₂ ), beryllium oxide (BeO), Teflon (trade name, manufactured by DuPont), polystyrene, and other materials with low microwave loss are generally used.

In the method for forming a deposited film in which a discharge space is surrounded by a plurality of substrates, the distance between the substrates is 1 mm or more and 50 mm or more.
mm or less. The number of substrates may be any as long as a discharge space can be formed, but is preferably 3 or more, more preferably 4 or more.

The method of the present invention can be applied to the production of any electrophotographic photoreceptor. In particular, a substrate is provided so as to surround a discharge space, and a microwave is supplied from at least one end of the substrate by a waveguide. There is a great effect when a deposited film is formed by the configuration introduced.

FIG. 6 schematically shows an example of a general transfer type electrophotographic apparatus using the electrophotographic photosensitive member manufactured by the method of the present invention.

In this figure, reference numeral 601 denotes an electrophotographic photosensitive member as an image carrier, which is driven to rotate around an axis 601a in the direction of an arrow at a predetermined peripheral speed. The electrophotographic photosensitive member is uniformly charged at a predetermined positive or negative potential on its peripheral surface by a charging means 602 during the rotation process, and then exposed by a light exposure unit (not shown) by an exposure unit.
(Slit exposure, laser beam scanning exposure, etc.). As a result, an electrostatic latent image corresponding to the exposure image is sequentially formed on the peripheral surface of the photoconductor.

Next, the electrostatic latent image is developed with toner by developing means 604, and the developed toner image is transferred between the photosensitive member 601 and the transfer means 605 from a paper feeding unit (not shown) by the transfer means. It is sequentially transferred onto the surface of the transfer material P that has been synchronized.

The transfer material P having undergone the image transfer is separated from the photoreceptor surface and introduced into the image fixing means 608, where the image is fixed, and then printed out as a copy.

The surface of the photoreceptor 601 after the image transfer is cleaned by removing the transfer residual toner by the cleaning unit 606, and after being subjected to the charge removal treatment by the pre-exposure unit 607, the surface is repeatedly used.

As the uniform charging means 602 for the photosensitive member 601, a corona charging device is generally widely used. Also, a corona charging device is generally widely used for the transfer device 605. As an electrophotographic apparatus, of the above-described components such as the photoconductor, the developing unit, and the cleaning unit, a plurality of components are integrally combined as an apparatus unit, and the unit is detachably attached to the apparatus body. Is also good. In this case, the charging unit and / or the developing unit may be provided in the device unit.

When the electrophotographic apparatus is used as a copying machine or a printer, the light image exposure L may be reflected light or transmitted light from the original, or a laser beam based on a signal obtained by reading the original and forming a signal. It may be obtained by scanning, driving an LED array, driving a liquid crystal shutter array, or the like.

When used as a facsimile printer, the light image exposure L is an exposure for printing received data. FIG. 7 is a block diagram showing an example of this case.

The controller 711 controls the image reading unit 710 and the printer 719. The entire controller 711 is controlled by the CPU 717. Image reading unit 71
The read data from 0 is transmitted to the partner station through the transmission circuit 713. The data received from the partner station is
12 and sent to the printer 719. The image memory 716 stores predetermined image data. The printer controller 718 controls the printer 719.
714 is a telephone.

The image information received from the line 715 (image information from a remote terminal connected via the line) is
After being demodulated by the receiving circuit 712, the decoding process is performed by the CPU 717 and sequentially stored in the image memory 716.
The image of the page is recorded. The CPU 717 reads out one page of image information from the memory 716 and sends out the decoded one page of image information to the printer controller 718. The printer controller 718 includes a CPU 71
When the printer receives the image information of one page from the printer 7, it controls the printer to record the image information of the page.

The CPU 717 is connected to the printer 719.
During the recording by, the image information of the next page is received.

As described above, image reception and recording are performed.

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. It can be widely used in the field.

Next, the production of the electrophotographic photoreceptor of the present invention and the evaluation of the produced photoreceptor will be described in detail with reference to experimental examples, but the present invention is not limited thereto.

(Experimental Example 1) The amount of carbon dioxide dissolved in water in the washing step was changed to examine the correlation with the occurrence of image defects.

A cylindrical substrate made of aluminum having a silicon atom content of 100 ppm and having a diameter of 108 mm, a length of 358 mm and a thickness of 5 mm was treated on the surface of the substrate in the same manner as in the above-described procedure of the method for producing an electrophotographic photosensitive member of the present invention. Cutting was performed.

Fifteen minutes after the end of the cutting step, cleaning with a detergent (nonionic surfactant), cleaning with CO ₂ water, and pull-up and drying with hot CO ₂ water were performed using the surface treatment apparatus shown in FIG. 1 under the conditions shown in Table 1. Done. The hot water in the pull-up drying step has a conductivity of 20 μS / c by dissolving carbon dioxide in pure water having a resistivity of 10 MΩ · cm.
m. At that time, CO _{2 in} the cleaning process
As water, the conductivity is adjusted from 1 μS / cm to 50 by dissolving carbon dioxide in pure water having a resistivity of 10 MΩ · cm.
Water at μS / cm was used.

[0129]

[Table 1] Thereafter, an amorphous silicon deposited film was formed on the substrate under the conditions shown in Table 2 by using the deposited film forming apparatus shown in FIGS. 2A and 2B. A photoreceptor was produced. In FIG. 4, 401,
Reference numerals 402, 403 and 404 denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer, respectively.

[0130]

[Table 2] The electrophotographic characteristics of the electrophotographic photoreceptor thus manufactured were evaluated as follows. The process speed of the produced electrophotographic photosensitive member was previously set to 200 to 80 for experiments.
A Canon copier NP6060, modified so that it can be arbitrarily changed within the range of 0 mm / sec.
A voltage of about 7 kV was applied to perform corona charging, an image was formed on transfer paper by a normal copying process, and the image quality was evaluated according to the following procedure and criteria. In this way, ten electrophotographic photoreceptors manufactured under the same manufacturing conditions were evaluated for each. Table 3 shows the evaluation results.

[0131]

[Table 3] The image defect evaluation process speed was changed, and an image sample having the largest number of image defects among image samples obtained when the entire halftone original and the character original were placed on the original plate and copied was selected and evaluated. As an evaluation method, an image sample was observed with a magnifying glass, and evaluation was performed according to the following criteria according to the state of white spots within the same area.

◎ ・ ・ ・ Good ○ ・ ・ ・ Some small white spots △ ・ ・ ・ Some white spots but no problem in character recognition × ・ ・ ・ Some white spots Some parts are difficult to read.

The process speed for evaluating black spots was changed, and an image was output such that the average density of the image obtained by placing the entire halftone original on the platen was 0.4 ± 0.1. Among the image samples obtained in this manner, the most noticeable one was selected and evaluated. As a method of evaluation, these images were
Observe at 0cm away, check for black spots,
The evaluation was performed according to the following criteria.

◎: No black spots are observed on any copy. ・ ・ ・: Some black spots are recognized, but slight and no problem. Δ: On any copy. Black spots are also observed,
Slight, no problem for practical use. X: Large black spots are observed on all copies.

Evaluation of Electrophotographic Characteristics The surface potential of the photosensitive member obtained at the developing position when the same charging voltage was applied at a normal process speed was evaluated as a relative value as charging ability. However, the charging ability of the electrophotographic photosensitive member obtained in Comparative Experimental Example 1 described later was set to 100%.

Evaluation of Electrophotographic Characteristics After applying the same charging voltage at a normal process speed,
The light amount obtained when the light was irradiated and the potential was lowered to a constant potential was evaluated as a sensitivity as a relative value. However, the charging ability of the electrophotographic photosensitive member obtained in Comparative Experimental Example 1 was set to 100%.

Evaluation of environmental properties・ ・ ・: No substance relating to destruction of ozone layer is used in the pretreatment step ×: A substance relating to destruction of the ozone layer is used in the pretreatment step.

(Experimental Example 2) The amount of carbon dioxide dissolved in the warm water in the drying step was changed to examine the correlation with the occurrence of image defects.

The surface of the same substrate was cut in the same procedure as in Experimental Example 1. As in Experimental Example 1, cleaning with a detergent (nonionic surfactant), cleaning with CO ₂ water, and cleaning with C ₂ were performed using the surface treatment apparatus shown in FIG.
Pull-up drying with O ₂ warm water was performed. The water in the washing step was performed by dissolving carbon dioxide in pure water having a resistivity of 10 MΩ · cm so that the conductivity was fixed at 10 μS / cm. At this time, as the CO ₂ hot water for the drying process,
Water having conductivity of 1 μS / cm to 50 μS / cm by dissolving carbon dioxide in 10 MΩ · cm pure water was used.

[0140]

[Table 4] The electrophotographic photosensitive member thus manufactured was evaluated in the same manner as in Experimental Example 1. The results are shown in Table 5.

[0141]

[Table 5] Comparative Example 1 An aluminum substrate having a silicon atom content of 100 ppm was cut in the same procedure as in Example 1.

The substrate after the cutting was processed on the surface of the substrate under the conditions shown in Table 6 by a conventional substrate surface cleaning apparatus shown in FIG.

[0143]

[Table 6] The substrate cleaning apparatus shown in FIG. 8 includes a processing tank 802 and a substrate transport mechanism 803. The processing tank 802 includes a substrate loading table 811, a substrate cleaning tank 821, and a substrate discharge table 851. The cleaning tank 821 has a temperature controller (not shown) for keeping the temperature of the liquid constant. Transport mechanism 803
Comprises a transfer rail 865 and a transfer arm 861. The transfer arm 861 has a moving mechanism 862 that moves on the rail 865, and a chucking mechanism 86 that holds the base 801.
3 and an air cylinder 864 for moving the chucking mechanism 863 up and down.

After cutting, the substrate 80 placed on the loading table 811
1 was transported to the cleaning tank 821 by the transport mechanism 803.
Washing for removing cutting oil and chips adhering to the surface was performed with trichloroethane (trade name: Eterna VG, manufactured by Asahi Kasei Kogyo Co., Ltd.) 822 in the washing tank 821.

After the cleaning, the substrate 801 was transported to the discharge table 851 by the transport mechanism 803.

Thereafter, FIG. 2A and FIG.
An amorphous silicon deposited film was formed on the substrate under the conditions shown in Table 2 using the deposited film forming apparatus shown in (b) to produce a blocking type electrophotographic photoreceptor having the layer configuration shown in FIG.

The electrophotographic photosensitive member thus manufactured was evaluated in the same manner as in Experimental Example 1. The results are shown in Tables 3 and 5.

(Comparative Experimental Example 2) As in Experimental Example 1, an aluminum substrate having a silicon atom content of 100 ppm was cut in the same procedure, and 15 minutes after the end of the cutting step, the detergent (non-ionic) was used under the conditions shown in Table 7. (Surfactant), cleaning with pure water, and lifting and drying. 1 was used as the surface treatment apparatus, except that pure water in which carbon dioxide was not dissolved was used in the cleaning tank 131 and the drying tank 141.

[0149]

[Table 7] Further, thereafter, an amorphous silicon deposited film was formed on the substrate under the conditions shown in Table 2 using the deposited film forming apparatus shown in FIGS. 2A and 2B, and the blocking type shown in FIG. An electrophotographic photosensitive member was manufactured.

The electrophotographic photosensitive member thus produced was evaluated in the same manner as in Experimental Example 1. The results are shown in Tables 3 and 5.

As is clear from the results shown in Tables 3 and 5, the electrophotographic photosensitive member manufactured by the method of the present invention has a CO ₂ water conductivity of 6 μS / cm to 1 μm in the washing step.
In the range of 5 μS / cm, and the conductivity of CO ₂ hot water in the drying step is in the range of 10 μS / cm to 25 μS / cm,
Very good results were obtained for image defects.

(Experimental Example 3) After cutting an aluminum substrate in which the content of silicon atoms was changed in the same procedure as in Experimental Example 1,
Fifteen minutes after the completion of the cutting step, washing with CO ₂ water and lifting and drying were performed under the conditions shown in Table 8 using the surface treatment apparatus shown in FIG.

[0153]

[Table 8] However, at this time, the water in the cleaning step has a resistivity of 10 MΩ.
Using water having a conductivity of 10 μS / cm and a pH of about 5.0 by dissolving carbon dioxide in cm of pure water,
As the CO ₂ warm water used in the pull-up drying step, warm water having a conductivity of 20 μS / cm and a pH of about 4.2 by dissolving carbon dioxide in pure water having a resistivity of 10 MΩ · cm was used. 2A and FIG.
An amorphous silicon deposited film was formed on the substrate under the conditions shown in Table 2 using the deposited film forming apparatus shown in (b) to produce a blocking type electrophotographic photoreceptor having the layer configuration shown in FIG.

The electrophotographic photosensitive member thus manufactured was evaluated in the same manner as in Experimental Example 1. The results are shown in Table 9.

[0155]

[Table 9] As is evident from Table 9, the electrophotographic photoreceptor produced by the method of the present invention gives very good results on image defects when silicon atoms are contained in the base aluminum in a range of 1 ppm to 1% by weight. Was.

(Experimental Example 4) The same substrate as in Experimental Example 1 was cut in the same procedure, and 15 minutes after the end of the cutting step, the surface treatment apparatus shown in FIG. Done.

Thereafter, FIG. 2A and FIG.
An amorphous silicon deposited film was formed on the substrate under the conditions shown in Table 2 using the deposited film forming apparatus shown in FIG.
Inhibition type electrophotographic photoreceptor having the layer constitution shown in was prepared.

In this experimental example, an electrophotographic photosensitive member was manufactured by changing the water quality (resistivity) of pure water used in the washing step and the drying step using CO ₂ water in the same manner in the washing step and the drying step. The electrophotographic photosensitive member thus obtained was placed in the above-mentioned modified copy machine NP6060 manufactured by Canon Inc., and evaluated in the same procedure as in Experimental Example 1. Ten electrophotographic photosensitive members manufactured under the same manufacturing conditions were evaluated. The results are shown in Table 10.

[0159]

[Table 10] The same evaluation was performed on the electrophotographic photosensitive members produced in Comparative Experimental Examples 1 and 2, and the results are also shown in Table 10. However, the cost evaluation in Table 10 was performed based on the following criteria.

Evaluation of Cost When a required amount of a required cleaning liquid is obtained. A: very inexpensive. O: inexpensive. Δ: somewhat expensive. X: expensive.

[0161] As apparent from Table 10, when the resistivity of pure water used in the drying step by washing and CO ₂ heated by CO ₂ water over 1 M.OMEGA · cm before dissolving carbon dioxide, in the method of the present invention The produced electrophotographic photoreceptor gave very good results on image quality.

[0162]

Next, the present invention will be described based on Examples and Comparative Examples.
This will be specifically described.

Example 1 108 mm in diameter and 358 in length made of aluminum containing 100 ppm of silicon atoms
The surface of a cylindrical substrate having a thickness of 5 mm and a thickness of 5 mm was cut in the same manner as in the above-described procedure of the method for producing an electrophotographic photosensitive member of the present invention.

Fifteen minutes after the end of the cutting step, the surface of the substrate was treated by the surface treatment apparatus shown in FIG. 1 under the conditions shown in Table 11. However, a mixture of a nonionic surfactant and an anionic surfactant was used as the detergent.

[0165]

[Table 11] Thereafter, an amorphous silicon deposited film was formed on the substrate under the conditions shown in Table 2 by using the deposited film forming apparatus shown in FIGS. 2A and 2B. A photoreceptor was produced.

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

After the appearance of the produced electrophotographic photosensitive member was evaluated by visual observation of film peeling, a copier NP60 manufactured by Canon Inc. was evaluated.
60 was placed in a copying machine modified for experiment, and an image was prepared on a transfer paper by a normal copying process, and the image quality was evaluated. However, at that time, a voltage of 6 kV was applied to the charger to perform corona charging. The evaluation results are shown in Table 12.

[0168]

[Table 12] In Table 12, the evaluations of "image defect", "black spots", "electrophotographic properties" and "environmental properties" were performed according to the same criteria as in Table 3 described above. The procedure was performed according to the following procedures and criteria.

Evaluation of Image Unevenness A3 grid paper (manufactured by KOKUYO Co., Ltd.) was placed on a platen of a copying machine, and the aperture of the copying machine was changed. The image was changed so as to obtain an image in a range up to the start of fogging, and ten copies with different densities were output.

These images were observed at a distance of 40 cm from the eyes to check for a difference in density, and evaluated according to the following criteria.

◎: No image unevenness is recognized on any copy. ・ ・ ・: There is a copy in which image unevenness is recognized and a copy in which no image unevenness is recognized, but both are slight and have no problem at all. Image unevenness is observed on any copy, but image unevenness is slight on at least one copy and does not hinder practical use. X: 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 platen and copied on a white background was observed, and the fogging of the white background was evaluated.

◎: Good ○: Slight fog in part Δ: Fog is present on the entire surface, but there is no hindrance to character recognition ×: Part where characters are difficult to read due to fog There is.

(Comparative Example 1) An aluminum substrate similar to that of Example 1 except that it did not contain silicon atoms was cut in the same procedure as in Example 1, and a conventional apparatus for cleaning the surface of the substrate shown in FIG. The surface of the substrate was cleaned under the conditions shown in Table 6 according to the method.

Thereafter, an amorphous silicon deposited film was formed on the substrate under the conditions shown in Table 13 using the deposited film forming apparatus shown in FIG. An electrophotographic photosensitive member was manufactured.

[0176]

[Table 13] The electrophotographic photoreceptor thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 12 together with Example 1.

(Comparative Example 2) An aluminum substrate similar to that of Example 1 was cut by the same procedure as that of Example 1 except that silicon atoms were not contained. The surface was cleaned. The substrate cleaning apparatus shown in FIG. 9 includes a rotating shaft 90 for fixing and rotating the substrate 901.
2. It comprises an injector 903 and a nozzle 904 for ejecting the cleaning liquid to the substrate.

In this comparative example, the surface of the substrate was cleaned under the conditions shown in Table 14 according to the conventional method using this cleaning apparatus.

[0179]

[Table 14] Then, using the deposited film forming apparatus shown in FIG.
An amorphous silicon deposited film was formed on the substrate under the conditions of No. 3, and a blocking type electrophotographic photosensitive member having the layer configuration shown in FIG.

The electrophotographic photoreceptor thus obtained was evaluated in the same manner as in Example 1, and the results are shown in Table 12 together with Example 1 and Comparative Example 1.

From the results shown in Table 12, the electrophotographic photoreceptor manufactured by the method of the present invention is much better in any of the items shown in the table than the electrophotographic photoreceptor manufactured by the conventional method. Gave the result.

Example 2 An electrophotographic photoreceptor was manufactured by the method of the present invention while changing the layer structure from that of Example 1. That is, after cutting the same substrate as in Example 1 by the same procedure,
Fifteen minutes after the end of the cutting step, the surface of the substrate was treated under the conditions shown in Table 11 using the surface treatment apparatus shown in FIG.

Thereafter, FIG. 2A and FIG.
Using the deposited film forming apparatus shown in FIG.
Forming an amorphous silicon deposited film on the substrate,
A blocking type electrophotographic photosensitive member having the layer configuration shown in FIG. 5 was produced.

[0184]

[Table 15] In FIG. 5, reference numeral 501 denotes an aluminum substrate, 505 denotes an infrared absorbing layer, 502 denotes a charge injection blocking layer, 503 denotes a photoconductive layer, and 504 denotes a surface layer.

The thus obtained electrophotographic photosensitive member was evaluated in the same procedure as in Example 1. As a result, this photoreceptor gave very good results in any of the items, as in the case of Example 1.

Example 3 The same substrate as in Example 1 was cut in the same procedure, and 15 minutes after the end of the cutting step, the surface of the substrate was treated with the surface treatment apparatus shown in FIG. Done.

Thereafter, an amorphous silicon deposited film was formed on the substrate under the conditions shown in Table 13 using the deposited film forming apparatus shown in FIG. 3 to produce a blocking type electrophotographic photosensitive member having the layer structure shown in FIG. .

The electrophotographic photosensitive member thus obtained was evaluated according to the same procedure and criteria as in Example 1. As a result, this photoreceptor gave very good results in any of the items as in Example 1.

Example 4 The same substrate as in Example 1 was cut by the same procedure, and 15 minutes after the end of the cutting process, using the surface treatment apparatus shown in FIG. Was performed.

Thereafter, a deposited film made of an organic optical semiconductor was formed on the substrate to produce an electrophotographic photosensitive member.

The electrophotographic photoreceptor thus obtained gave good results with high image quality as compared with the electrophotographic photoreceptor manufactured by the conventional method, similarly to the case of the amorphous silicon photoreceptor.

Example 5 The same substrate as in Example 1 was cut by the same procedure, and 15 minutes after the end of the cutting step, the surface of the substrate was treated using the surface treatment apparatus shown in FIG. Was performed.

Thereafter, a deposited film made of selenium was formed on the substrate to produce an electrophotographic photosensitive member.

The electrophotographic photoreceptor thus obtained gave higher image quality than the electrophotographic photoreceptor manufactured by the conventional method, similarly to the case of the amorphous silicon photoreceptor.

[0195]

As described above, according to the method of the present invention,
Before the step of forming a functional film, after performing a step of washing the surface of the substrate with water in which carbon dioxide is dissolved and a step of drying with warm water in which carbon dioxide is dissolved, a functional film, particularly, plasma is formed on the aluminum substrate. Since an electrophotographic photosensitive member is manufactured by forming a non-single-crystal deposited film containing hydrogen atoms and / or fluorine atoms and silicon atoms by a CVD method, an electrophotographic photosensitive member that provides a uniform high-quality image can be manufactured at low cost. In addition, it can be provided stably.

[Brief description of the drawings]

FIG. 1 is a schematic vertical sectional view of a pre-processing apparatus used in a method of manufacturing an electrophotographic photoreceptor of the present invention.

FIG. 2 is a schematic cross-sectional view of an apparatus for forming a deposited film on a cylindrical substrate by a microwave plasma CVD method.
Is a longitudinal sectional view, and (b) is a transverse sectional view.

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

FIG. 4 is a schematic cross-sectional view illustrating a layer configuration of an example of an electrophotographic photosensitive member.

FIG. 5 is a schematic sectional view showing a layer configuration of another example of the electrophotographic photosensitive member.

FIG. 6 is a schematic configuration diagram of a general transfer type electrophotographic apparatus.

FIG. 7 is a block diagram showing a configuration of a facsimile using the electrophotographic apparatus of FIG. 6 as a printer.

FIG. 8 is a schematic vertical sectional view of one example of a cleaning apparatus for cleaning a substrate by a conventional method.

FIG. 9 is a schematic longitudinal sectional view of another example of a cleaning apparatus for cleaning a substrate by a conventional method.

[Explanation of symbols]

By 101,801,901 base 102,802 processor 103,803 base transport mechanism 111,811 base-on stand 121 base before washing tank 122 before the cleaning liquid 131 CO ₂ cleaning tank 132 CO ₂ water 141 drying vessel 142 CO ₂ heated by water Pull-up drying tank 151, 851 Substrate transfer table 161, 861 Transfer arm 162, 862 Moving mechanism 163, 863 Chucking mechanism 164, 864 Air cylinder 165, 865 Rail 201 Reaction vessel 202 Microwave introduction window 203 Waveguide 204 Exhaust pipe 207 Heater 209 Rotating shaft 210 Motor 211 DC power supply 212 Bias electrode 301 Reaction vessel 302 Base plate 303 Wall 304 Top plate 305 Cathode electrode 306 Base 307 Source gas inflow valve 308 Leak Lube 309 Exhaust valve 310 Vacuum gauge 311 Mass flow controller 312 Heater 313 High frequency power supply 314 Motor 401, 501 Base 402, 502 Charge injection blocking layer 403, 503 Photoconductive layer 404, 504 Surface layer 505 Infrared absorption layer 601 Electrophotographic photosensitive member 601a Axis 602 Charging unit 604 Developing unit 605 Transfer unit 606 Cleaning unit 607 Pre-exposure unit 608 Image fixing unit 710 Image reading unit 711 Controller 712 Receiving circuit 713 Transmission circuit 714 Telephone 715 Line 716 Image memory 717 CPU 718 Printer controller 719 Printer 821 Substrate cleaning tank 822, 905 Cleaning liquid 902 Rotating axis 903 Injector 904 Nozzle

Continuation of front page (56) References JP-A-2-111955 (JP, A) JP-A-64-79754 (JP, A) JP-A-5-281758 (JP, A) JP-A-61-23739 (JP, A) JP-A-2-306251 (JP, A) JP-A-2-310369 (JP, A) JP-A-5-11481 (JP, A) JP-A-4-320268 (JP, A) 4-335355 (JP, A) JP-A-4-335356 (JP, A) JP-A-5-303212 (JP, A) JP-A-5-88392 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 5/00

Claims (9)

(57) [Claims] In a method for manufacturing an electrophotographic photoreceptor including a step of forming a functional film on an aluminum substrate, carbon dioxide is applied to the surface of the substrate before the step of forming the functional film.
The substrate is washed with water in which carbon dioxide is dissolved by introducing the same and warm water in which carbon dioxide is dissolved by introducing carbon dioxide.
By immersing and lifting the substrate from the warm water
A method for producing an electrophotographic photoreceptor, wherein the lifting and drying is performed. 2. The conductivity of water in which carbon dioxide is dissolved is 2 μm.
S / cm or more and 40 μS / cm or less and conductivity of hot water in which carbon dioxide is dissolved is 5 μS / cm or more and 40 μS / c.
2. The method of claim 1, wherein m is less than or equal to m. 3. The pH of water in which carbon dioxide is dissolved is 3.8.
Not less than 6.0 and p of warm water in which carbon dioxide is dissolved
The method according to claim 1, wherein H is 4.0 or more and 6.0 or less. 4. The water in which carbon dioxide is dissolved and the warm water in which carbon dioxide is dissolved are obtained by dissolving carbon dioxide in pure water having a resistivity of 1 MΩ · cm or more.
The method according to any one of claims 1 to 4. 5. The temperature of water in which carbon dioxide is dissolved is 5 ° C. or more and 90 ° C. or less, and the temperature of hot water in which carbon dioxide is dissolved is 30 ° C. or more and 90 ° C. or less. The method described in. 6. The temperature of water in which carbon dioxide is dissolved is 20 ° C.
The method according to claim 5, wherein the temperature is not less than 40 ° C and the temperature of the hot water in which carbon dioxide is dissolved is not less than 40 ° C and not more than 70 ° C. 7. The step of forming a functional film on an aluminum substrate includes forming a non-single-crystal deposited film containing hydrogen atoms and / or fluorine atoms and silicon atoms on the aluminum substrate by a plasma CVD method. The method according to any one of claims 1 to 6, comprising: 8. The method according to claim 1, wherein the aluminum substrate contains at least a trace amount of silicon atoms.
The method described in the section. 9. The amount of silicon atoms contained in the aluminum substrate is 1 ppm or more and 1% or less on a weight basis.
The described method.