JPH06324506A - Manufacture of electrophotographic photoreceptive member - Google Patents

Abstract

PURPOSE:To manufacture an electrophotographic photoreceptive member capable of obtaining a uniform, high-quality image having no image density irregularity. CONSTITUTION:The process for forming a non-monocrystal deposit film containing silicon atom, hydrogen atom and/or fluorine atom on a conducting substrate by the plasma CVD method is included to manufacture an electrophotographic photoreceptive member. The contact angle of the substrate surface with water is suppressed to 90 deg. or below in the process for washing the substrate surface after cutting with the washing water before the process for forming the deposit film and after the process for cutting the surface of the substrate.

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 light-receiving member having a functional film formed on a conductive substrate.

The present invention is particularly applicable to plasma C on conductive substrates.
The present invention relates to a method for producing a light-receiving member for electrophotography, in which a non-single-crystal deposited film containing silicon atoms, fluorine atoms and hydrogen atoms is formed as a functional film by the VD method.

[0003]

2. Description of the Related Art Conventionally, as a device member used in a light receiving member for electrophotography, a non-single crystal deposited film, for example, an amorphous deposited film such as amorphous silicon compensated with hydrogen and / or halogen (eg, fluorine, chlorine, etc.). Is proposed,
Some of them are put to practical use.

Conventionally, as a method of forming such a deposited film, a sputtering method, a method of decomposing a raw material gas by heat (thermal CVD method), a method of decomposing a raw material gas by light (optical CV)
D method), a method of decomposing the raw material gas by plasma (plasma CVD method), and many other methods are known. Among them, the plasma CVD method, that is, the method of decomposing the raw material gas by direct current, high frequency or microwave glow discharge to basically form a thin film deposition film is most suitable for the method of forming an amorphous silicon deposition film for electrophotography. Therefore, the practical application is very advanced now. Such an example is described in, for example, JP-A-54-86341.

[0005] These amorphous silicon light receiving members are non-polluting and have the characteristics of high image quality and high durability, and the amorphous silicon light receiving members currently put into practical use sufficiently show the characteristics. There is something.
However, in order for the amorphous silicon light-receiving member to become more and more popular in the future, cost reduction, further improvement in electrical characteristics, and further high durability are desired.

Further, in recent years, global-scale environmental pollution has become a problem, and there is an urgent need to improve not only the substances that cause environmental pollution but also the use in the manufacturing stage. Although the amorphous silicon photoreceptive member itself is non-polluting, it is necessary to reexamine from the viewpoint of cleaning the cylinder to packaging after the manufacturing at the stage of manufacturing it.

As a substrate for depositing the amorphous silicon light receiving member, a metal is used so as to withstand electrophotographic processes such as charging, exposure, development, transfer and cleaning, and to keep high position accuracy in order not to deteriorate image quality. Is often used. In this case, aluminum alloys, which are particularly excellent in workability and dimensional stability, are widely adopted. Generally, when processing these substrates, lathe processing is performed using an oil-based substance such as cutting oil. Therefore, the residue of the oil-based substance is always attached to the processed substrate, and further, cutting powder during processing, dust in the air, and the like are also attached. If these residues are adhered due to insufficient cleaning, it is not possible to form a defect-free and uniform deposited film, or sufficient electrical characteristics cannot be obtained, causing image defects especially when used for a long time. The problem is known.

Therefore, when manufacturing the electrophotographic light-receiving member, it is necessary to carefully wash the substrate with great care.

Under these circumstances, for example, Japanese Patent Laid-Open No. 61-171
Japanese Unexamined Patent Publication No. 798 describes a technique relating to a method for processing a substrate of an electrophotographic photosensitive member. This publication discloses a technique for obtaining an electrophotographic photoreceptor of good quality such as amorphous silicon by cutting a substrate with a cutting oil having a specific component. Also, in the publication, after cutting,
The substrate is triethane (trichloroethane: C ₂ H ₃ C
l ₃ ) is described.

In Japanese Patent Laid-Open No. 61-273551, S
When e and the like are vapor-deposited on an aluminum substrate to produce an electrophotographic photosensitive member, as a pretreatment of the substrate, it is possible to use a technique such as alkali cleaning, trichlene cleaning, ultraviolet irradiation cleaning with a mercury lamp, and the like. It is described that as the pretreatment of (1), liquid degreasing cleaning for removing oil and fat adhering to the surface of the cylindrical aluminum substrate, vapor degreasing cleaning and pure water cleaning are performed. The photoreceptor prepared by using the substrate washed by such a method has some characteristics and is widely used at present without any particular problems.
The use of organic solvents such as trichloroethane has a negative effect not only on the human body but also on the local environment, and therefore its use must be avoided.

In order to solve this problem, in recent years, several methods of cleaning the substrate with water have been proposed in place of the aforementioned cleaning.

Japanese Unexamined Patent Publication (Kokai) No. 1-130159 discloses a technique for cleaning an electrophotographic photosensitive member support with a water jet. The publication mentions Se and an organic photoconductor as well as amorphous silicon as an example of the photoconductor, but does not mention any problems peculiar to the plasma CVD method at all.

When an aluminum alloy cylinder is used as the substrate, the manufacture of the electrophotographic light-receiving member by these conventional techniques is specifically carried out as follows.

Lathe with air damper for precision cutting (PNE
UMO PRECLSION INC. A diamond bite (trade name: Miracle bite, made by Tokyo Diamond) is set in the product) so as to obtain a rake angle of 5 ° with respect to the center angle of the cylinder. Next, while vacuum chucking the substrate to the rotary flange of this lathe, spraying white kerosene from the attached nozzle and suctioning chips from the vacuum nozzle also attached, the peripheral speed was 1000 m / min and the feed speed was 0.
Mirror cutting is performed so that the outer shape becomes 108 mm under the condition of 01 mm / R.

After the cutting, the substrate surface is treated by the method shown in FIG. The cleaning conditions are: cleaning medium: pure water at 50 ° C. (high-purity water with a specific resistance of 10 MΩ · cm), pressure of the cleaning medium at the nozzle: 100 kg / c
m ² , substrate rotation speed: 100 rpm. In FIG. 5, a base 501 that rotates in the direction of the arrow a is indicated by an arrow b.
The cleaning medium 503 is sprayed in the tangential direction of the outer peripheral surface of the substrate 501 from the nozzle 502a of the injector 502 that moves in the direction to be cleaned.

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

In FIG. 3, the reaction vessel 301 is composed of a base plate 302, a wall 303 and a top plate 304. A cathode electrode 305 is provided in the reaction container 301. The substrate 306 on which the amorphous silicon deposited film is formed is installed in the center of the cathode electrode 305 and also serves as the anode electrode.

In order to form an amorphous silicon deposited film on the substrate 306 using this deposited film forming apparatus, first, the source gas inflow valve 307 and the leak valve 308.
Is closed, the exhaust valve 309 is opened, and the inside of the reaction container 301 is exhausted. The reading of the vacuum gauge 310 is about 5 × 10 ^-6 Tor
When the temperature reaches r, the raw material gas inflow valve 307 is opened to supply the raw material gas such as SiH ₄ gas adjusted to a predetermined mixing ratio in the mass flow controller 311 to the reaction vessel 30.
1. Then, after confirming that the surface temperature of the substrate 306 is set to a predetermined temperature by the heater 312, the high frequency power source 313 is set to a desired power to cause glow discharge in the reaction vessel 301.

During formation of the deposited film, the substrate 306 is moved to the motor 31 in order to make the deposited film uniform.
Rotate at a constant speed by 4. In this way the substrate 3
An amorphous silicon deposition film can be formed on 06.

[0020]

However, in these conventional methods for producing a photoreceptive member for electrophotography, the requirements for optical and electrical characteristics with uniform film quality are satisfied, especially in the region where the deposition rate of the deposited film is high. In addition, there remains a problem to be solved that it is difficult to constantly and stably obtain a deposited film of high image quality at the time of image formation by an electrophotographic process with a high yield (high yield).

That is, it is very difficult to visually confirm the state of oil remaining on the surface of the substrate after cleaning the substrate and other factors that cause stains, and therefore the above-mentioned problems occur.

In the past, the main purpose of copying was to print only originals (so-called line copy).
These spots and stains did not cause any problems. However, recently, as the image quality of a copying machine has increased, many originals including halftones such as photographs have been copied, which has become a problem. In particular, in color copiers that have become widespread in recent years, such unevenness and spots cause unevenness in color and become more visually apparent, which has become a serious problem.

Since these irregularities and spots are minute, they cannot be detected even if an electrode is attached to the portion and the conductivity is measured. However, as a photoreceptor member for electrophotography, charging, exposure, and
When developing, especially when a halftone and uniform image is formed, even a slight difference in potential on the surface of the electrophotographic light-receiving member is visually noticeable as uneven image density.

Further, in recent years, a plasma CVD method using microwave glow discharge decomposition, that is, a microwave plasma CVD method has been industrially attracting attention as a deposited 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 microwave plasma CVD technology that takes advantage of these advantages is US Pat.
No. 504,518. The technique described in the patent is to obtain a good quality deposited film at a high deposition rate by a microwave plasma CVD method under a low pressure of 0.1 Torr or less.

Furthermore, a technique for improving the utilization efficiency of the raw material gas by the microwave plasma CVD method is disclosed in Japanese Patent Laid-Open No. Sho 60.
No. 186849. The technique disclosed in the publication is generally arranged so that a substrate is arranged so as to surround a means for introducing microwave energy so as to form an internal chamber (that is, a discharge space), thereby significantly improving the utilization efficiency of raw material gas. It is the one.

Further, Japanese Patent Application Laid-Open No. 61-283116 discloses an improved microwave technique for manufacturing a semiconductor member. That is, in this publication, an electrode (bias electrode) is provided in the discharge space for plasma potential control, and a desired voltage (bias voltage) is applied to the bias electrode to control the ion bombardment of the deposited film while depositing the film. The technique of improving the characteristics of the deposited film by performing the above is disclosed. However, in the electrophotographic light-receiving member produced by such a microwave plasma CVD method, the above-mentioned problems become more prominent.

On the other hand, such a problem is that even if a substrate which has been washed in the conventional process is used, a method other than the plasma CVD method (manufacturing a light-receiving member for Se electrophotography by vacuum deposition,
It does not occur at all in the electrophotographic light-receiving member manufactured by the blade coating method or the dipping method or the like).

Similarly, even in the device manufactured by the plasma CVD method, the above-mentioned problem does not occur in a device such as a solar cell in which the subtle difference in the characteristics depending on the position on the substrate does not affect the performance.

The object of the present invention is to overcome various problems in the conventional method for manufacturing a photoreceptive member for electrophotography as described above,
An object of the present invention is to provide an easy-to-use method for producing a light-receiving member for electrophotography, which can be stably formed at a high yield at a low cost.

Further, an object of the present invention is to quantify the uneven density of the image and the invisible cleaning unevenness on the surface after cleaning the substrate, which is considered to be one of the causes of the unevenness, and the stain.
A method of manufacturing a photoreceptive member for electrophotography, which overcomes the conventional problems, solves the problem of uneven density of images and the generation of stains peculiar to the plasma CVD method, and can obtain a uniform high-quality image. To provide.

[0032]

The method for producing a light-receiving member for electrophotography of the present invention comprises a step of cutting the surface of a conductive substrate with a predetermined accuracy, a step of washing the surface of the substrate after cutting with water, and A method for manufacturing a photoreceptive member for electrophotography, comprising the step of forming a non-single crystal deposited film containing one or both of hydrogen atoms and fluorine atoms and silicon atoms on a conductive substrate by a plasma CVD method. The contact angle between the surface of the conductive substrate after cleaning and water is 90 ° or less.

In order to solve the above-mentioned problems, the inventors of the present invention have conducted a study by paying attention to the physical property values of the surface of the substrate after cleaning. As a result, hydrogen atoms and A step of cutting a surface of a conductive substrate with a predetermined accuracy in a method for producing a non-single-crystal deposited film containing one or both of fluorine atoms and a silicon atom and manufacturing a photoreceptor member for electrophotography. After the subsequent step of washing the substrate surface with water, there is no part that repels water on the substrate surface, that is, even if it is sufficiently degreased, the contact angle with water is very large. I have found

However, even when the step of cleaning the surface of the substrate with water is performed and a substrate having a large contact angle with water on the surface is used, a method other than the plasma CVD method (Se by vacuum deposition) is used.
In the electrophotographic light-receiving member produced by the production of the electrophotographic light-receiving member, the OPC electrophotographic light-receiving member by the blade coating method, the dipping method, or the like, almost no unevenness or stain on the image was observed.

Further, the surface of the conductive substrate is cut with a predetermined accuracy, and the substrate surface after cutting is subjected to chlorine-based solvent or organic solvent such as 1-1-1 trichloroethane (hereinafter abbreviated as triethane). When cleaning is performed using the above, the contact angle of the surface of the substrate can be varied from a relatively small one to a relatively large one depending on the washing condition. Even if a non-single-crystal deposited film containing one or both of fluorine atoms and silicon atoms is formed to manufacture an electrophotographic light-receiving member, any contact including those having a contact angle of a specific value or more No unevenness or stains on the image were observed even in the electrophotographic light-receiving member prepared using the corner substrate.

For this reason, conventionally, if even degreasing is sufficiently carried out (if there is no part that repels water), the occurrence of unevenness or stains on the image and the contact angle of water on the substrate surface before the formation of the deposited film It was thought that there was no correlation between them.

However, the inventors of the present invention did not notice unevenness or stains on an image for the first time when plasma CVD was performed using a substrate whose contact angle between the surface of the substrate and water, which had not been regarded as a problem in the past, was washed with water. As a result of diligent investigations, it was thought that this might occur as a problem, and when water was washed, all of the above problems were solved by keeping the contact angle between the substrate surface after washing and water below a specified value. The present invention has been completed based on the knowledge that it can be obtained.

The mechanism of the relationship between the contact angle on the surface of the substrate after cleaning and the unevenness or smear on the image has not been clarified in many points, but the present inventor currently thinks as follows. That is, when, for example, an amorphous silicon deposited film is formed on a substrate by the plasma CVD method, the reaction includes the decomposition process of the source gas in the vapor phase, the transport process of active species from the discharge space to the substrate surface, and the surface on the substrate surface. The reaction process can be divided into three parts. Above all, 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. Especially when washing with water without worrying about the contact angle, microscopically the part with a large contact angle on the substrate surface and the small contact angle, and the part with a large water adsorption coexist in a mosaic pattern, When a deposited film is formed by plasma CVD, the growth of the deposited film becomes non-uniform and uneven film quality occurs. When plasma CVD is performed using a substrate that has been washed with water in this way, the moisture adsorbed on the surface of the substrate has a significantly greater effect than in other cases.

An example of a procedure for actually forming an electrophotographic light-receiving member by the method for producing an electrophotographic light-receiving member of the present invention using an aluminum alloy cylinder as a base is shown in FIG.
The pretreatment apparatus shown in FIG. 2 and the deposited film forming apparatus shown in FIGS. 2A and 2B will be described below.

Lathe with air damper for precision cutting (PNE
UMO PRECLSION INC. A diamond bite (trade name: Miracle bite, made by Tokyo Diamond) is set in the product) so as to obtain a rake angle of 5 ° with respect to the center angle of the cylinder. Next, while vacuum chucking the substrate to the rotary flange of this lathe, spraying white kerosene from the attached nozzle, and suctioning chips from the vacuum nozzle also attached, the peripheral speed was 1000 m / min and the feed rate was 0.01 mm. Under the condition of / R, mirror cutting is performed so that the outer shape becomes 108 mm.

After the cutting, the substrate surface is treated by the substrate pretreatment device. The substrate pretreatment apparatus shown in FIG. 1 includes a processing section 102 and a substrate transfer mechanism 103. The processing unit 102 includes a substrate loading table 111 and a substrate cleaning tank 1.
21, pure water contact tank 131, drying tank 141, substrate unloading table 1
It consists of 51. Cleaning tank 121, pure water contact tank 131
Both are equipped with a temperature control device (not shown) for keeping the temperature of the liquid constant. The transport mechanism 103 includes a transport rail 16
5 and the transfer arm 161, and the transfer arm 161 is
Moving mechanism 162 for moving on rail 165, base 101
And a chucking mechanism 163 for holding the chucking mechanism and an air cylinder 164 for moving the chucking mechanism 163 up and down.

After cutting, the substrate 1 placed on the input table 111
01 is transported to the cleaning tank 121 by the transport mechanism 103. The cutting oil and chips adhering to the surface are cleaned by ultrasonic waves of a frequency of 60 kHz and an output of 400 W oscillated by an ultrasonic oscillator composed of a ferrite oscillator 123 in a surfactant aqueous solution 122 in a cleaning tank 121. .

Next, the substrate 101 is carried to the pure water contact tank 131 by the carrying mechanism 103, immersed in pure water having a resistivity of 5 MΩ-cm and kept at a temperature of 25 ° C., and then 30 kg · f / from the nozzle 132. High-pressure water is jetted at a pressure of cm ² , and at the same time, the substrate 101 is rotated via the motor 184 and the rotary gear 183. After the process is completed, when the substrate 101 is pulled up, 0.5 kg · f / cm ^{2 of} pure water vapor is discharged from the nozzle 181.
With a pressure of 1000 mm to form a steam atmosphere 182
It is pulled up at a speed of / min. Then, the carrier 10
3 is moved to the drying tank 141, and high-temperature high-pressure air is blown from the nozzle 142 to be dried.

The substrate 101 having undergone the drying process is carried to the carry-out table 151 by the carrying mechanism 103. Amorphous silicon is mainly used by the apparatus for forming a photoconductive member deposited film by the plasma CVD method shown in FIGS. 2A and 2B on the substrate on which the cutting process and the pretreatment are completed. Form a deposited film.

2 (a) and 2 (b),
Reference numeral 201 denotes a reaction vessel having a vacuum airtight structure. Reference numeral 202 denotes microwave power for the reaction vessel 201.
It is a microwave introduction dielectric window formed of a material (for example, quartz glass, alumina ceramics, etc.) that can efficiently penetrate into the inside and maintain vacuum tightness. Reference numeral 203 denotes a waveguide for transmitting microwave power, which includes a rectangular portion from the microwave power source to the vicinity of the reaction container and a cylindrical portion inserted in the reaction container. The waveguide 203 is connected to a microwave power source (not shown) together with a stub tuner (not shown) and an isolator (not shown). The dielectric window 202 is hermetically sealed at the end of the cylindrical waveguide 203 to maintain the atmosphere in the reaction vessel. Reference numeral 204 is an exhaust pipe having one end opened to the reaction vessel 201 and the other end communicating with an exhaust device (not shown). Two
Reference numeral 06 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.

Production of the electrophotographic light-receiving member using such a deposited film forming apparatus is carried out as follows. First, the inside of the reaction container 201 is evacuated by a vacuum pump (not shown) through the exhaust pipe 204, and the pressure inside the reaction container 201 is reduced to 1
It is adjusted to × 10 ^-7 Torr or less. Then heater 20
7, the temperature of the base 205 is heated and maintained at a predetermined temperature. Therefore, the raw material gas is passed through a gas introduction means (not shown),
A raw material gas such as silane gas as a raw material gas for amorphous silicon, diborane gas as a doping gas, and helium gas as a diluent gas is introduced into the reaction vessel 201. At the same time, a microwave power source (not shown) generates a microwave having a frequency of 2.45 GHz, and the reaction container 2 passes through the waveguide 203 and the dielectric window 202.
Microwave is introduced into 01. Further, the DC power supply 2 electrically connected to the bias electrode 212 in the discharge space 206.
11, a DC voltage is applied to the bias electrode 212 with respect to the substrate 205. Thus, in the discharge space 206 surrounded by the substrate 205, the source gas is excited by the energy of microwaves and dissociated, and the bias electrode 21
A 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 2 and the substrate 205. At this time, the rotary shaft 2 on which the base 205 is installed
09 is rotated by a motor 210 and the substrate 205 is rotated around the central axis in the substrate generatrix direction, whereby a deposited film layer is formed uniformly over the entire circumference of the substrate 205.

In the present invention, the value of the contact angle of the substrate surface is 0 ° or more and 90 ° or less, preferably 5 ° or more and 88 ° or less,
Optimally, 10 ° or more and 85 ° or less are suitable for the present invention.

As a method of measuring the contact angle, as shown in FIG. 8, a method of measuring the contact angle θ between the substrate 801 and the water droplet 802 by making a water droplet 802 on the substrate 801 to a certain size by using a syringe. It was

As a method for reducing the contact angle, it is possible to use a high-pressure jet, a combination of air bubbling and vapor jet, or a method in which pure water and vapor are swung at high speed during cleaning. The invention is effective.

The pressure when using a high pressure flow is 0.1
kgf / cm²Above, 50kgf / cm²Below, good
0.5kg ・ f / cm is better²40kgf /
cm ²Below, optimally 1kgf / cm²Above, 30k
gf / cm²The following are suitable for the present invention.

The pressure for bubbling air is 0.
1kgf / cm²Above 10kg ・ f / cm²Less than,
Preferably 0.2 kgf / cm²Above, 8kgf /
cm ²Below, optimally 0.3 kgf / cm²Above 5
kgf / cm²The following are suitable for the present invention.

The pressure when using steam injection is 0.1 k
g · f / cm ² or more, 20kg · f / cm ² or less, preferably 0.3kg · f / cm ² or more, 10 kg · f / c
m ² or less, optimally 0.5 kg · f / cm ² or more, 5 k
A value of g · f / cm ² or less is suitable for the present invention.

When rocking at high speed, the rocking speed is 2
00 mm / min or more and 3000 mm / min or less, preferably 300 mm / min or more and 2500 mm / mi
n or less, optimally 400 mm / min or more, 2000 m
m / min or less is suitable for the present invention.

Pressure unit in the present invention kg · f / cm ²
Means gravity kilogram per square centimeter, 1
kg · f / cm ² is equal to 98066.5 Pa.

In the present invention, the purpose is to reduce the contact angle, and any method is effective.

The washing liquid used in the washing step is preferably water or a mixture of water and a surfactant.

In the present invention, the quality of water used for washing before the addition of the surfactant may be any,
Particularly, semiconductor grade pure water is desirable. Specifically, as the resistivity at a water temperature of 25 ° C., the lower limit value is 1 MΩ-cm or more, preferably 3 MΩ-cm or more, and most preferably 5 MΩ-c.
m or more is suitable for the present invention. The upper limit can be any value up to the theoretical resistance value (18.25 MΩ-cm), but from the viewpoint of cost and productivity, it is 18.2 MΩ-cm or less, preferably 18.0 MΩ-cm or less, and most preferably. 1
7.8 MΩ-cm or less is suitable for the present invention. As the amount of fine particles, 0.2 μm or more is 10 in 1 ml.
000 or less, preferably 1000 or less, optimally 1
00 or less is suitable for the present invention. As the microbial amount, 100 or less, preferably 10 or less, and most preferably 1 or less per 1 ml of total viable bacteria are suitable for the present invention. Organic matter amount (TOC) is 10m in 1 liter
g or less, preferably 1 mg or less, optimally 0.2 mg or less is suitable for the present invention.

As a method of obtaining the above-mentioned water of 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 improve the quality of the water used.

If the temperature of the water is too high, an oxide film will be formed on the substrate, which may cause the deposited film to peel off. On the other hand, if it is too low, the cleaning effect is small and the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of water is 5 ℃
As described above, 90 ° C. or less, preferably 10 ° C. or more and 75 ° C. or less, most preferably 15 ° C. or more and 55 ° C. or less are suitable for the present invention.

The surfactant used in the washing step may be any of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof. It is possible. It is also effective in the present invention to add an additive such as sodium tripolyphosphate.

The use of ultrasonic waves in the cleaning step is particularly important in order to bring out the effects of the present invention. As the ultrasonic oscillator, a magnetostrictive oscillator such as ferrite is used. As a method of inputting ultrasonic waves to the cleaning tank, such a vibrator is placed in the liquid of the cleaning tank, is adhered to the bottom or wall of the cleaning tank, or a horn is installed from a vibrator installed nearby. There is a method of transmitting ultrasonic waves to the cleaning tank.
Further, it is effective to use a plurality of vibrators in one cleaning tank at the same time in order to adjust the output and make the cleaning effect uniform. The frequency of ultrasonic waves has been used frequently in the comparatively low frequency region because of strong cavitation action and large cleaning effect, but in the present invention, it is easy to cause physical damage to the substrate surface. Not preferable.
Further, the relatively high frequency region is not practical in the present invention because the cleaning effect is low. Specifically, preferably 5
kHz or more and 10 MHz or less, more preferably 10 kHz
z or more and 5 MHz or less, optimally 20 kHz or more, 1M
Below Hz is effective. The ultrasonic output is preferably 0.1 W / liter or more and 500 W / liter or less, more preferably 1 W / liter or more and 100 W / liter or less. The water quality used in the pure water contact process has a lower limit of 1 kΩ as the resistivity when the water temperature is 25 ° C.
-Cm or more, preferably 1 MΩ-cm or more, optimally 3
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 (18.25MΩ-cm), but from the viewpoint of cost and productivity, it is 18.2M.
Ω-cm or less, preferably 18.0 MΩ-cm or less, most preferably 17.8 MΩ-cm or less is suitable for the present invention. As the amount of fine particles, 0.2 μm or more is 10000 or less, preferably 1000 or less in 1 ml.
Optimally, 100 or less are suitable for the present invention. As the microbial amount, 100 or less, preferably 10 or less, and most preferably 1 or less per 1 ml of total viable bacteria are suitable for the present invention. The amount of organic matter (TOC) is 10 mg or less, preferably 1 mg or less, and optimally 0.
2 mg or less is suitable for the present invention.

As a method for obtaining the above-mentioned water of 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 improve the quality of the water used.

As a method of rotating the substrate that has been carried in, the method of directly rotating the substrate is best, but other methods may be used. The rotation speed of the substrate is 5 rpm or more,
3000 rpm or less, preferably 10 rpm or more, 25
00 rpm or less, optimally 30 rpm or more, 2000r
pm or less is suitable for the present invention.

From the economical viewpoint, the flow rate of water is 1 liter / min or more per substrate and 200 liter / min.
Or less, preferably 2 liters / min or more, 100 liters / min or less, optimally 5 liters / min or more,
50 liters / min or less is suitable for the present invention.

If the temperature for contacting with water is too high, an oxide film will be formed on the substrate, which may cause peeling of the deposited film, and the effect of the present invention cannot be sufficiently obtained. Further, if it is too low, the effect cannot be obtained sufficiently. Therefore, the temperature of water is 5 ° C or higher and 90 ° C or lower, preferably 10 ° C or higher and 55 ° C or lower, and most preferably 15 ° C or higher and 4 ° C.
A temperature of 0 ° C or lower is suitable for the present invention.

If the treatment time of the pure water contact treatment is too long, an oxide film is formed on the substrate, and if it is too short, the effect of the present invention is small, so that the treatment time is 10 seconds or longer and 30 minutes or shorter, preferably 20 seconds or longer. 20 minutes or less, optimally 30 seconds or more, 10
Minutes or less are suitable for the present invention.

It is important to cut the surface of the substrate immediately before the formation of the deposited film in order to remove the influence of the oxide film or the like on the surface of the substrate during the formation of the deposited film.

If the time from cutting to the contact with pure water is too long, an oxide film will be formed again on the surface of the substrate, and if it is too short, the process will not be stable, so that the time is 1 minute or more and 16 hours or less, preferably 2 minutes. As described above, 8 hours or less, optimally 3 minutes or more and 4 hours or less are suitable for the present invention.

If the time from the contact with pure water to the deposition film forming apparatus is too long, the effect of the present invention will be small, and if it is too short, the process will not be stable, and therefore, 1 minute or more, 8 minutes or more.
A time of not more than 2 minutes, preferably not less than 2 minutes and not more than 4 hours, optimally not less than 3 minutes and not more than 2 hours is suitable for the present invention.

The present invention is possible if the surface of the substrate material for forming the deposited film is a metal.
Stainless steel, Al, Cr, Mo, Au, In, Nb, T
Although e, V, Ti, Pt, Pd, Fe and the like are effective, particularly in the case of aluminum, a remarkable effect is recognized. When aluminum is used as the base material, it is preferable to contain 1% by weight to 10% by weight of magnesium (Mg) in order to improve machinability. Further, it is effective that the aluminum purity before containing magnesium is 95% by weight or more, optimally 99% by weight or more. The surface roughness of the substrate, that is, the cutting accuracy is preferably 10 s or less, and optimally 5
s or less is suitable for the present invention. The substrate may have any shape, but a cylindrical one is particularly suitable for the present invention. The size of the substrate is not particularly limited, but the diameter is practically 20
mm or more, 500 mm or less, length 10 mm or more, 100
It is preferably 0 mm or less.

As the source gas for the deposited film used in the present invention, silane (SiH ₄ ), disilane (Si ₂ H ₆ ),
Silicon tetrafluoride (SiF ₄ ), disilicon hexafluoride (Si ₂ F ₆ )
Amorphous silicon forming raw material gas or a mixed gas thereof can be used.

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

Further, the band gap width of the deposited film is changed.
Nitrogen (N₂),ammonia
(NH₃) And other elements containing a nitrogen atom, oxygen (O₂),one
Nitric oxide (NO), nitrogen dioxide (NO₂), Nitrous oxide
(N₂O), carbon monoxide (CO), carbon dioxide (C
O₂) Element containing oxygen atom such as methane (CH_Four), Eta
(C₂H₆), Ethylene (C₂H_Four),acetylene
(C₂H₂), Propane (C ₃H₈) Etc. hydrocarbons, four
Germanium fluoride (GeF_Four), Nitrogen fluoride (NF₃)etc
Fluorine compounds or mixed gas thereof can be used.

Further, in the present invention, diborane (B ₂ H ₆ ) and boron fluoride (B) are used for the purpose of doping.
A dopant gas such as F ₃ ) or phosphine (PH ₃ ) may be introduced into the discharge space at the same time.

In the electrophotographic light-receiving member, the total thickness of the deposited film deposited on the substrate may be 5 μm.
Or more, 100 μm or less, more preferably 10 μm or more,
When the thickness is 70 μm or less, most preferably 15 μm or more and 50 μm or less, a particularly good image can be obtained as a light receiving member for electrophotography.

The effect of the pressure of the discharge space during the deposition of the deposited film is recognized in any region, but especially 0.5 mTorr
Above, 100 mTorr or less, preferably 1 mTorr
Above 50 mTorr, particularly good results in terms of stability of discharge and uniformity of deposited film can be obtained with good reproducibility.

In the present invention, the substrate temperature during deposition of the deposited film is effectively in the range of 100 ° C. to 500 ° C., but particularly 150 ° C. to 450 ° C., preferably 20 ° C.
0 ° C or higher, 400 ° C or lower, optimally 250 ° C or higher, 35
A remarkable effect is confirmed at 0 ° C or lower.

In the present invention, the heating means for the substrate may be a heating element of vacuum specification, and more specifically, an electric resistance heating element such as a wound heater of a sheath heater, a plate heater, a ceramics heater, a halogen. Examples include a heat-radiating lamp heating element such as a lamp and an infrared lamp, and a heating element using a heat exchange means using liquid, gas or the like as a heating medium.
As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used. In addition to the above, a method of providing a heating-dedicated container separately from the reaction container and heating and then transporting the substrate into the reaction container in a vacuum can also be used. The above means can be used alone or in combination.

The energy for generating plasma is D
Although any of C, RF, microwaves, etc. is possible, particularly when microwaves are used as the energy for plasma generation, the microwaves are absorbed by the adsorbed moisture, and the change in the interface becomes more remarkable, The effect of the present invention becomes more remarkable.

When microwaves are used for plasma generation, microwave power may be in any range as long as discharge can be generated, but 100 W or more, 1
A value of 0 kW or less, preferably 500 W or more and 4 kW or less is suitable.

In the present invention, it is effective to apply a voltage (bias voltage) to the discharge space during formation of the deposited film,
It is preferable that the electric field be applied at least in the direction in which the cations collide with the substrate. When no bias is applied, the effect of the present invention is significantly reduced. Therefore, the voltage of the DC component is 1 V or more and 500 V or less, preferably 5 V or more and 10
It is desirable to apply a bias voltage of 0 V or less during the formation of the deposited film in order to obtain the effects of the present invention.

In the present invention, when microwaves are introduced into the reaction vessel using a dielectric window, the material of the dielectric window is alumina (Al ₂ O ₃ ), aluminum nitride (Al
N), boron nitride (BN), silicon nitride (SiN), silicon carbide (SiC), silicon oxide (SiO ₂ ), beryllium oxide (BeO), Teflon, polystyrene and other materials with low microwave loss are usually used. It

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

The present invention can be applied to any method for manufacturing a light receiving member for electrophotography, but in particular, a base is provided so as to surround a discharge space, and a micro waveguide is provided at least from one end side of the base by a waveguide. A great effect is obtained when a deposited film is formed by the structure in which waves are introduced.

FIG. 6 shows a schematic structural example of a general transfer type electrophotographic apparatus using the electrophotographic light-receiving member manufactured by the method of the present invention.

In the figure, reference numeral 601 denotes an electrophotographic light receiving member as an image bearing member, which is rotationally driven around an axis 601a in the arrow direction at a predetermined peripheral speed. This electrophotographic light-receiving member receives uniform charge of a predetermined positive or negative potential on its peripheral surface by the charging means 602 during its rotation process, and then is subjected to a light image exposure L (slit) by an image exposing means (not shown) by an exposing section. Exposure, laser beam scanning exposure, etc.). As a result, electrostatic latent images corresponding to the exposed image are sequentially formed on the peripheral surface of the light receiving member.

This electrostatic latent image is then toner-developed by the developing means 604, and the toner developed image is transferred by the transfer means 605.
A light receiving member 601 and a transfer unit 605 from a paper feeding unit (not shown).
In the meantime, the light is transferred to the surface of the transfer material P which is synchronized with the rotation of the light receiving member 601.

The transfer material P which has received the image transfer is separated from the surface of the light receiving member and introduced into the image fixing means 608, where it is subjected to the image fixing and then printed out as a copy. .

After the image transfer, the surface of the light receiving member 601 is cleaned by removing the transfer residual toner by the cleaning unit 606, and is further subjected to charge removal processing by the pre-exposure unit 607, and then repeatedly used for image formation. To be done. As the uniform charging means 602 of the light receiving member 601, a corona charging device is generally widely used. In addition, the transfer device 60
The corona charging device is also widely used for the No. 5 device. The electrophotographic apparatus is configured by integrally combining a plurality of constituent elements such as the above-described light receiving member, developing unit, and cleaning unit as an apparatus unit, and this unit is detachable from the apparatus main body. You may In this case, charging means and / or
You may comprise with a developing means.

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

When used as a facsimile printer, the optical 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 section 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 the receiving circuit 71.
2 is sent to the printer 719. Image memory 7
Predetermined image data is stored in 16. The printer controller 718 controls the printer 719. 7
14 is a telephone.

The image information received from the line 715 (image information from the remote terminal connected through the line) is
After demodulation by the reception circuit 712, decoding processing is performed by the CPU 717, and when sequentially stored in the image memory 716, image recording of the page is performed. The CPU 717 is the memory 7
The image information for one page is read from 16 and the decoded image information for one page is sent to the printer controller 718. Upon receiving the image information of one page from the CPU 717, the printer controller 718 controls the printer to record the image information of the page.

The CPU 717 is the printer 719.
The image information of the next page is being received during recording by.

Images are received and recorded as described above.

The light-receiving member for electrophotography manufactured by the method of the present invention can be used not only in electrophotographic copying machines, but also in electrophotography such as laser beam printers, CRT printers, LED printers, liquid crystal printers and laser plate making machines. It can also be widely used in application fields.

[0097]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

(Examples 1-8, Comparative Examples 1-2) Purity 9
A surface of a cylindrical substrate made of 9.5% aluminum having a diameter of 108 mm, a length of 358 mm and a wall thickness of 5 mm was cut by the same procedure as the procedure of the method for manufacturing the electrophotographic light-receiving member according to the present invention. After 15 minutes from the end of the cutting process, the surface treatment apparatus shown in FIG. 1 was used to pretreat the surface of the substrate while changing the water pressure, vapor pressure, pulling rate, and rotation speed under the conditions shown in Table 1. However, polyethylene glycol nonyl phenyl ether was used as the surfactant, and this was made into a 1 wt% aqueous solution. In this example,
The amount of cleaning liquid was 100 liters.

[0099]

[Table 1] A substrate washed in this way was prepared, water droplets were dropped on the surface of the substrate, and the contact angle was measured at any point on the surface.

After that, an amorphous silicon deposited film is formed on the substrate under the conditions of Table 2 by using the deposited film forming apparatus shown in FIGS. 2A and 2B, and the layer shown in FIG. A blocking type electrophotographic light receiving member having a constitution was produced. In FIG. 4, 401, 402, 403 and 404 respectively indicate an aluminum substrate, a charge injection blocking layer, a photoconductive layer and a surface layer.

[0101]

[Table 2] The electrophotographic characteristics of the prepared electrophotographic light-receiving member were evaluated as follows.

The prepared electrophotographic light-receiving member was put in a copying machine manufactured by Canon Inc. and a copying machine in which NP6650 was modified for an experiment, and a voltage of 6 kV was applied to the charger to carry out corona charging. An image was prepared on a transfer paper, and the image quality was evaluated by the following procedure. Thus, the electrophotographic light-receiving member produced under the same production conditions was evaluated. The evaluation results are shown in Table 3.

Evaluation of image unevenness A3 graph paper (manufactured by KOKUYO Co., Ltd.) is placed on the platen of the copying machine, and the exposure amount of the original is changed by changing the diaphragm of the copying machine. It was changed so that an image in a range up to the start of fogging was obtained, and 20 copies having different densities were output.

These images were observed at a distance of 30 cm from the eyes to check whether a difference in density was recognized, and evaluation was carried out according to the following criteria. ⊚: No image unevenness is observed on any of the copies. ○: There are some copies where image unevenness is recognized and others where it is not recognized. However, all of them are slight and there is no problem at all. Δ: Image unevenness is observed on any copy. However, most of the image unevenness is slight in degree, and there is no practical problem. X: Large image unevenness is observed on all copies.

Evaluation of white spots An original halftone original was placed on the original table of a copying machine, and an image was output so that the average density of the image obtained when copying was 0.3 ± 0.1.

These images were observed at a distance of 30 cm from the eyes to check if white spots were observed, and evaluated according to the following criteria. ⊚: No white spots are observed on any of the copies. 〇… Some had slight white spots. But,
There is no problem at all. Δ: White spots are observed on any copy. However, most of the white spots are slight in degree, and there is no practical problem. X: Large white spots are observed on all copies.

[0107]

[Table 3] As described above, good results were obtained when the contact angle was 90 ° or less.

(Examples 9 to 16 and Comparative Examples 3 and 4) Using the substrates prepared under the same conditions as in Example 1, as shown in FIG.
Further, using the deposited film forming apparatus shown in FIG. 2B, an amorphous silicon deposited film is formed on the substrate under the conditions shown in Table 4, and the blocking type of the layer structure shown in FIG. A light-receiving member for electrophotography was prepared.

Table 5 shows the results of evaluation of the electrophotographic light-receiving member thus produced by the same method as in Example 1.

[0110]

[Table 4]

[0111]

[Table 5] As described above, even when the composition of the electrophotographic light-receiving member was changed, good results were obtained when the contact angle was 90 ° or less.

(Examples 17 to 20) Of the substrates prepared under the same conditions as in Example 1 by using the substrates having different types of substrates, a substrate having a good contact angle was used. ) And the deposited film forming apparatus shown in FIG.
Under the same conditions as above, a blocking type electrophotographic light-receiving member having the layer structure shown in FIG. 4 was prepared. Table 6 shows the results of evaluation of the electrophotographic light-receiving member thus produced by the same method as in Example 1.

[0113]

[Table 6] (Examples 21 to 25) Of the substrates prepared under the same conditions as in Example 1 by using the substrates having different Al purities, substrates having a good contact angle are used, and as shown in FIG. , Fig. 2
Using the deposited film forming apparatus shown in (b), a blocking type electrophotographic light receiving member having the layer structure shown in FIG. 4 was prepared under the same conditions as in Example 1. Table 7 shows the results of evaluating the electrophotographic light-receiving member thus produced by the same method as in Example 1.

However, the purity of Al indicates the purity before containing Mg.

[0115]

[Table 7] As described above, good results were obtained when the purity of Al was 95.0% or more.

(Examples 26 to 30) Using the substrates prepared under the same conditions as in Examples 21 to 25, using the deposited film forming apparatus shown in FIGS. 2 (a) and 2 (b). Example 9
Under the same conditions as in Nos. 16 to 16, a blocking type electrophotographic light-receiving member having the layer structure shown in FIG. 4 was prepared. Table 8 shows the results of evaluating the electrophotographic light-receiving member thus produced by the same method as in Example 1.

[0117]

[Table 8] Even if the composition of the electrophotographic light-receiving member was changed as described above, good results were obtained at 95.0% or more.

(Examples 31 to 35) Of the substrates prepared under the same conditions as in Example 1 by using the substrates whose surface roughness was changed, the substrate having a good contact angle was used.
Using the deposition film forming apparatus shown in (a) and FIG. 2 (b), a blocking type electrophotographic light receiving member having the layer structure shown in FIG. 4 was prepared under the same conditions as in Example 1.

Table 9 shows the results of evaluation of the electrophotographic light-receiving member thus produced by the same method as in Example 1.

[0120]

[Table 9] (Examples 36 to 40) Using a substrate prepared under the same conditions as in Examples 31 to 35, FIG. 2 (a) and FIG. 2 (b).
Using the deposition film forming apparatus shown in FIG. 4, under the same conditions as in Examples 9 to 16, a blocking type electrophotographic light receiving member having a layer structure shown in FIG. 4 was prepared. Table 10 shows the results of evaluation of the electrophotographic light-receiving member thus produced by the same method as in Example 1.

[0121]

[Table 10] As described above, even when the composition of the electrophotographic light-receiving member was changed, good results were obtained when the surface roughness was 10 s or less.

[0122]

As described above, according to the present invention, in a method for producing a photoreceptive member for electrophotography, which comprises a step of forming a functional film on a conductive substrate, particularly hydrogen on the conductive substrate is used. In a method of manufacturing a photoreceptor member for electrophotography, which comprises a step of forming a non-single-crystal deposited film containing one or both of atoms and fluorine atoms and silicon atoms by a plasma CVD method, a substrate surface after washing and water By making the contact angle with 90 ° or less, it becomes possible to solve the conventional problems, provide a uniform high-quality image, and inexpensively and stably manufacture the electrophotographic light-receiving member. .

Further, according to the present invention, it has been found that the following unexpected effects can be obtained.

The temperature dependence of the dark potential and the bright potential of the electrophotographic light-receiving member was improved. At the same time, color reproducibility was improved, and a higher quality electrophotographic light-receiving member could be provided.

[Brief description of drawings]

FIG. 1 is a schematic vertical cross-sectional view of a pretreatment apparatus used for carrying out the method for manufacturing a photoreceptor member for electrophotography of the present invention.

FIG. 2A is a schematic vertical cross-sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by a microwave plasma CVD method. (B) is a cross-sectional view of the deposited film forming apparatus of (a).

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

FIG. 4 is a cross-sectional view showing a layer structure of a light receiving member for electrophotography.

FIG. 5 is a schematic view of a conventional pretreatment device.

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

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

FIG. 8 is a schematic diagram of a method for measuring a contact angle.

[Explanation of symbols]

 101, 801 Substrate 102 Processing Tank 103 Substrate Transfer Mechanism 111 Substrate Loading Table 121 Substrate Cleaning Tank 122 Cleaning Solution 123 Ferrite Oscillator 131 Pure Water Contact Tank 132, 142, 172 Nozzle 141 Drying Tank 151 Substrate Unloading Table 161 Transfer Arm 162 Moving Mechanism 163 Chucking mechanism 164 Air cylinder 165 Rail 181 Steam nozzle 182 Steam atmosphere 183 Rotating gear 184 Rotating motor 201 Reaction vessel 202 Microwave introduction window 203 Waveguide 204 Exhaust pipe 205 Base 206 Discharge space 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 Raw material gas inflow valve 308 Leak valve 309 Exhaust valve 310 Vacuum gauge 311 Mass flow controller 312 Heater 313 High frequency power supply 314 Motor 401 Base body 402 Charge injection blocking layer 403 Photoconductive layer 404 Surface layer 501 Base body 502 Injector 502-a nozzle 503 Cleaning medium 802 Water droplet

Claims (1)

[Claims] 1. A step of cutting the surface of a conductive substrate with a predetermined accuracy, a step of washing the surface of the substrate after cutting with water, and one or both of hydrogen atoms and fluorine atoms on the conductive substrate. A method of manufacturing a photoreceptive member for electrophotography, comprising a step of forming a non-single-crystal deposited film containing silicon atoms by a plasma CVD method, wherein the contact angle between the surface of the conductive substrate after cleaning and water is A method for producing a light-receiving member for electrophotography, which is 90 ° or less.