JP2001337474A - Method for manufacturing light-accepting member, light- accepting member and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-accepting member which can maintain good cleaning property for a long time without splashing of a toner or melt sticking of a toner by improving the solid lubricating property of the surface of the light- accepting member to be used for an electrophotographic device and by preventing distortion or vibration of a cleaning blade. SOLUTION: The light-accepting member has a surface layer consisting of a non-single crystal carbon film containing at least hydrogen atoms and/or halogen atoms on a conductive base body. The surface layer has a diamond structure and a graphite structure in such a manner that the amount of the graphite structure increases toward the outermost surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light receiving member used in an electrophotographic apparatus for performing scrape cleaning by a cleaning blade, and more particularly to a light receiving member which is excellent in cleaning properties and provides high quality images even when used for a long time. Light receiving member.

[0002]

2. Description of the Related Art Various materials such as inorganic materials such as selenium, cadmium sulfide, zinc oxide, amorphous silicon (hereinafter referred to as a-Si), and organic materials can be used as materials for a light receiving member used in an electrophotographic photosensitive member. Proposed. Among these, non-single-crystal deposited films containing silicon atoms typified by a-Si as main components, for example, hydrogen and / or
Amorphous films such as a-Si containing halogen (eg, fluorine, chlorine, etc.) (eg, compensating for hydrogen or dangling bonds) have been proposed as high performance, highly durable, pollution-free photoreceptors, some of which have been proposed. Has been put to practical use. JP-A-54-86341, USP 4,265,99
No. 1 discloses an electrophotographic photosensitive member in which a photoconductive layer is mainly formed of a-Si.

An a-Si photosensitive member represented by a-Si has a high surface hardness and a long wavelength light (600
(nm to 700 nm), and has excellent features such as little deterioration due to repeated use. For example, it is widely used as an electrophotographic photosensitive member such as a high-speed copying machine or an LBP (laser beam printer). ing.

As a method of forming a silicon-based non-single-crystal deposited film, there are a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), a method of decomposing a source gas by light (photo CVD method), and a method of decomposing a source gas by plasma. Many methods are known, such as a method of decomposing gas (plasma CVD method). Above all, a raw material gas is decomposed by a plasma CVD method, that is, a direct current or a high frequency (RF, VHF) or a glow discharge generated by using a microwave, and a glass, quartz, heat-resistant synthetic resin film, stainless steel, aluminum, etc. The method of forming a deposited film on a desired substrate is not limited to the method of forming an amorphous silicon deposited film for electrophotography and the like, and the method of forming a deposited film for other uses is currently in very practical use. Various devices have been proposed for this purpose.

[0005] JP-A-1-120707 describes an aC: H film containing graphite microcrystals. However, this publication discloses a technique for controlling the electrical conductivity of the aC: H film, and does not disclose any knowledge about solid lubricity and cleaning properties of the surface layer.

[0006]

Since the surface hardness of the a-Si light receiving member is extremely high as compared with other photoconductors, a blade type cleaning system having a high cleaning ability as a cleaning means is widely used. .

[0007] However, in such a blade-type cleaning system, the cleaning performance is greatly affected by the slipperiness of the surface of the light receiving member that comes into contact. In particular, during initial operation after the light receiving member is installed in the electrophotographic apparatus, there is no developer serving as a lubricant between the surface of the light receiving member and the cleaning blade. The member may be damaged.
Even when the blade is not turned, the cleaner blade may be deteriorated or damaged due to the chatter phenomenon in which the cleaner blade vibrates finely.

When the copying process is repeatedly performed in such a state, fine particles of the developer and the external additives (such as strontium titanate and silica) contained in the developer are scattered in the corona charger, and the corona charger is scattered. It may adhere to a wire electrode (hereinafter, referred to as a charger wire) and cause uneven discharge. When discharge unevenness occurs due to contamination of the charger wire, in normal development (a method of developing a non-exposed portion on the surface of the light receiving member), a streak-like white spot on an image, a scale-like black haze spreading over the entire image, Black spots (0.1 to 0.3 mmφ) that occur locally without periodicity and the like occur, and the quality of the output image is reduced. Also, when the charger wire dirt occurs, abnormal discharge is induced between the dirt portion and the light receiving member,
An image defect is generated by destroying the surface of the light receiving member. Furthermore, when the frictional resistance is high, frictional heat is generated between the light receiving member and the cleaning blade, and the frictional heat may cause a fusion phenomenon in which the developer is firmly attached to the surface of the light receiving member. Although this fusion phenomenon is minute at a stage that does not affect the image in the initial stage, the fine fusion becomes a nucleus by repeated use and gradually grows to become a black streak-like image defect.

The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide an electronic apparatus for performing scrape cleaning by a blade by repeating charging, exposure, development, transfer, separation, and cleaning steps sequentially. In the photographic apparatus, the frictional resistance between the light receiving member and the cleaning blade at the time of the initial operation is reduced, and the cleaning blade is prevented from being turned up and the cleaning blade from being deteriorated, thereby preventing the toner from being scattered. An object of the present invention is to provide a light receiving member that does not cause cleaning failure, fusion of a developer, and the like.

[0010]

Means for Solving the Problems The present inventors have focused on the slipperiness and cleaning properties of a surface layer composed of a non-single-crystal carbon film containing at least hydrogen atoms and / or halogen atoms, and have studied. As a result, the outermost surface of the light receiving member has a graphite structure to improve the solid lubricity in the initial state of the surface, and no curling or chatter of the cleaning blade occurs under any cleaning conditions, resulting in poor cleaning and toner scattering. It has been found that toner fusion can be prevented.

According to the present invention, a plasma is generated between a cathode electrode to which high-frequency power is applied and an opposing conductive substrate in a reaction vessel capable of reducing pressure, and at least hydrogen atoms and / or
Or, in a light receiving member forming a surface layer made of a non-single-crystal carbon film containing a halogen atom, this surface layer has a diamond structure and a graphite structure, and the graphite structure increases toward the outermost surface side And a method for manufacturing the same, and an electrophotographic apparatus using the same.

That is, the present invention is as follows. 1. In a reaction vessel capable of reducing pressure, a plasma is generated between a cathode electrode to which high-frequency power is applied and an opposing conductive substrate, and a surface made of a non-single-crystal carbon film containing at least hydrogen atoms and / or halogen atoms In the method for producing a light-receiving member for forming a layer, the temperature at the time of laminating the surface layer, the flow rate ratio of the applied power / the gas for forming the layer is reduced, or the pressure in the reaction vessel is reduced. A method for producing a light receiving member, characterized in that at least one of the surface layers has a diamond structure and a graphite structure, and the graphite structure increases toward the outermost surface. 2. 2. The method for manufacturing a light receiving member according to the above 1, wherein the temperature at the time of laminating the surface layer is raised in a range of 10 ° C. to 300 ° C. 3. 3. The method for manufacturing a light receiving member according to the above 1 or 2, wherein the applied power / flow rate ratio (W / (ml / min)) is reduced in a range of 1 to 30. 4. The method for producing a light receiving member according to any one of the above items 1 to 3, wherein the internal pressure of the reaction vessel is reduced in a range of 0.1 Pa to 60 Pa. 5. In the surface layer, the thickness of the region where the graphite structure increases toward the outermost surface is 0.1 nm to 10 nm.
The method for producing a light receiving member according to any one of the above items 1 to 4, wherein the thickness is 0 nm. 6. The method for manufacturing a light receiving member according to any one of the above 1 to 5, wherein the halogen atom contained in the surface layer is a fluorine atom. 7. The surface layer is formed by depositing by decomposing at least a hydrocarbon-based gas and / or a fluorine-based gas by a plasma CVD method using a high frequency of 50 to 450 MHz. A method for manufacturing the light receiving member according to one of the above. 8. The method for producing a light receiving member according to any one of the above items 1 to 7, wherein the light receiving member comprises at least the surface layer and the photoconductive layer, and an intermediate layer is provided between both layers. 9. 9. The method for manufacturing a light receiving member according to the above item 8, wherein the intermediate layer is made of any of non-single-crystal SiC, non-single-crystal SiN, and non-single-crystal SiO. 10. A light receiving member manufactured by the manufacturing method according to claim 1. 11. The thickness of the region where the graphite structure of the surface layer is distributed more than the diamond structure is 0.1 nm to 100 nm.
11. The light receiving member according to the above item 10, wherein 12. The method according to the above item 10 or 11, wherein the surface layer is deposited and formed by decomposing at least a hydrocarbon-based gas and / or a fluorine-based gas by a plasma CVD method using a high frequency of 50 to 450 MHz. Light receiving member. 13. 13. The light receiving member according to any one of the above items 10 to 12, wherein the light receiving member comprises at least a surface layer and a photoconductive layer, and an intermediate layer is provided between both layers. 14． The intermediate layer is made of non-single-crystal SiC, non-single-crystal SiN,
14. The light receiving member according to any one of the above items 10 to 13, wherein the light receiving member is made of any one of non-single-crystal SiO. 15. An electrophotographic apparatus in which charging, exposure, development, transfer, and cleaning are sequentially repeated, wherein the light receiving member according to any one of the above items 10 to 14 is used. 16. The electrophotographic apparatus according to the above item 15, wherein the cleaning method is a scrape cleaning using an elastic rubber blade, and a layer rich in a graphite structure on the outermost surface is rubbed and polished in an early stage of operation of the apparatus.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies to overcome the problems such as blade turning and blade chattering described above. As a result, a non-single-crystal hydrogenated carbon film (hereinafter referred to as a -C: H) or a non-single-crystal fluorinated carbon film (hereinafter a-C: F) was used to obtain a surface layer having high hardness and excellent solid lubricity.

Further, as a result of an examination focusing on the structure of the surface layer, the structure of the surface layer is composed of a diamond structure and a graphite structure, and the more diamond structures are distributed, the higher the hardness tends to be. It has been found that the more the number of particles distributed, the lower the hardness and the higher the solid lubricity.

In order to improve the mechanical strength of the light receiving member by utilizing the characteristics of this structure, the surface layer is distributed with a large number of diamond structures on the substrate side, and the outermost surface is further improved in order to improve the solid lubricity of the surface. A study was made to distribute a large amount of graphite structure on the side.

When a light receiving member having a surface layer in which a large amount of a graphite structure is distributed on the outermost surface is mounted on an electrophotographic apparatus configured to perform scrape cleaning by a cleaner blade, the blade is turned up or chattered in a warming-up process in an initial state. It was found that no damage occurred. Further, since the hardness of the film is extremely low in the region where the graphite structure is distributed in a large amount, all of the film is scraped off by the blade in the warming-up step, and it is finally found that only the film in which the diamond structure is largely distributed remains.

At this time, the developer is sufficiently adhered to the cleaner blade, and the lubricating property of the cleaner blade itself is enhanced. A photographic device becomes feasible.

The thickness of the region where the graphite structure is distributed more than the diamond structure is 0.1 nm to
100 nm is desirable. When the film thickness is less than 0.1 nm, the solid lubricity is impaired. When the film thickness exceeds 100 nm, the electric resistance of the surface becomes low, and the electric charge leaks in the plane direction, whereby the electrostatic latent image pattern may be broken.

Hereinafter, the present invention will be specifically described with reference to the drawings.

FIG. 1 is a schematic view illustrating a light receiving member according to the present invention. FIG. 1A shows a photoreceptor member in which a photoconductive layer is referred to as a single-layer type having no functional separation. On a substrate 101, a charge injection blocking layer 102, an aS containing at least hydrogen
This is a light receiving member in which a photoconductive layer 103 made of i and a surface layer formed of a non-single-crystal hydrogenated carbon film or a non-single-crystal fluorinated carbon film are sequentially laminated. The surface layer includes a diamond structure layer 104 and a graphite structure layer 105.

FIG. 1B shows a light-receiving member which is called a function-separated type since the photoconductive layer is separated into two functions, a charge generation layer and a charge transport layer. A charge injection blocking layer 102 is provided on a substrate 101 as necessary, and a charge transport layer 106 and a charge generation layer 107 are separated from each other in function.
Photoconductive layer 103 made of a-Si containing at least hydrogen
Are deposited, and a surface layer composed of a non-single-crystal hydrogenated carbon film or a non-single-crystal fluorinated carbon film is sequentially laminated thereon. This surface layer is a diamond structure layer 10
4 and the graphite structure layer 105.

The positional relationship between the charge transport layer 106 and the charge generation layer 107 may be reversed, and when the function separation is performed by changing the composition, the composition may be changed continuously.

In the light receiving member shown in FIGS. 1A and 1B, each layer may have a continuous composition change and may not have a clear interface. Further, the charge injection blocking layer 102 may be omitted as necessary.

FIG. 2 is a schematic view for explaining another light receiving member according to the present invention. An intermediate layer is provided between the photoconductive layer 203 and the surface layer 204 made of non-single-crystal carbon for the purpose of improving adhesion. 208 are provided.

FIG. 2A shows a photoreceptor member in which the photoconductive layer is referred to as a single-layer type having no functional separation. On a substrate 201, a charge injection blocking layer 202, a-Si containing at least hydrogen
A photoconductive layer 203 and an intermediate layer 208 consisting of
This is a light receiving member in which a surface layer composed of a non-single-crystal hydrogenated carbon film or a non-single-crystal fluorinated carbon film is sequentially laminated thereon. This surface layer is composed of a diamond structure layer 204 and a graphite structure layer 205.

FIG. 2B shows a photoreceptor called a function-separated type in which the photoconductive layer is separated into two functions, a charge generation layer and a charge transport layer. A charge injection blocking layer 202 is provided on the base 201 as necessary, and a charge transport layer 206 and a charge generation layer 207 are separated from each other in function, and a photoconductive layer 203 made of a-Si containing at least hydrogen, and This is a light receiving member in which an intermediate layer 208 is deposited, and a surface layer composed of a non-single-crystal hydrogenated carbon film or a non-single-crystal fluorinated carbon film is sequentially stacked thereon. This surface layer is composed of a diamond structure layer 204 and a graphite structure layer 205.

The positional relationship between the charge transport layer 206 and the charge generation layer 207 may be reversed, and when the function separation is performed by changing the composition, the composition may be changed continuously.

As the material of the intermediate layer 208, the photoconductive layer 20
An a-SiC layer having an intermediate composition between the third layer and the surface layer 204 may be used, but a-SiO, a-SiN, or the like may be used. The composition of the intermediate layer 208 may be changed continuously.

The light receiving member of the present invention is manufactured by a vacuum deposition film forming method. Specifically, for example, a glow discharge method (an AC discharge CVD method such as a low frequency CVD method, a high frequency CVD method, or a microwave CVD method, or a DC discharge CV method).
D method, etc.), a sputtering method, a vacuum evaporation method, an ion plating method, a photo CVD method, a thermal CVD method, and other various thin film deposition methods. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the light-receiving member to be produced. The glow discharge method, particularly the high-frequency glow discharge method using a power supply frequency in the RF band or the VHF band, is preferable because the conditions for manufacturing the light receiving member are relatively easy to control.

Plasma C for forming a non-single-crystal carbon film
A wide range of frequencies can be used as the discharge frequency used in the VD method. Industrially, a high frequency of 1 to 450 MHz, particularly 13.56 MHz, which is called an RF or VHF frequency band, can be suitably used. In addition, especially 50 to
When a high frequency in a frequency band called 450 MHz VHF is used, both transparency and hardness can be further increased.
It is more preferable when used as a surface layer.

Gases used for obtaining the effects of the present invention include CH ₄ , C ₂ H ₂ , C ₂ H ₄ , C ₂ H ₆ , C ₃ H ₈ , C ₄
Hydrocarbons H _10, etc., or fluorocarbon such as substituted some hydrogen with fluorine, can also be used in any gas as long as it can produce an active carbon radicals in plasma. A mixture of these gases or a mixture diluted with another gas such as a rare gas can also be used. In particular, since a high quality film may not be obtained by itself with a gas having a high degree of unsaturation alone, it is necessary to dilute with a hydrogen gas or an inert gas.

Hereinafter, an apparatus and a method for forming a deposited film by a high-frequency plasma CVD method will be described in detail.

FIG. 3 shows a deposition apparatus by a plasma CVD method using a 13.56 MHz high frequency power supply for manufacturing a light receiving member having a surface layer of aC: H according to the present invention. FIG. 4 is a diagram schematically showing an example of the above.

This apparatus is roughly composed of a deposition apparatus and an exhaust apparatus (not shown) for reducing the pressure inside the reaction vessel. A cylindrical conductive substrate 302 is mounted on a conductive support 303 connected to the ground in the reaction vessel 301. A heating heater (not shown) is built in the conductive receiving base 303 so that the cylindrical conductive base 302 can be heated to an arbitrary temperature. The conductive pedestal 303 is connected to a rotating motor 312 by a rotating shaft 304. During the film formation, the cylindrical conductive substrate 302 rotates so that the film is deposited in the entire circumferential direction.
A source gas introduction pipe 306 is attached to the reaction vessel 301 so that a source gas can be supplied from a source gas supply device (not shown). The reaction vessel 301 has a cathode electrode 305 made of a conductive material, and a high-frequency power supply 309 is connected to the cathode electrode via a matching box 308. A vacuum gauge 310 is attached to the reaction vessel 301 so that the internal pressure of the discharge space can be measured. The reaction vessel 301 is connected to an exhaust device (not shown) via an exhaust port 311 so that vacuum evacuation is possible.

An example of a method for forming a light receiving member using the apparatus shown in FIG. 3 will be described below.

First, a cylindrical conductive substrate 302 whose surface is mirror-finished using a lathe, for example, is placed on a conductive pedestal 303.
And a heater (not shown) for heating the substrate in the reaction vessel 301.

Next, the source gas introduction valve 307 is closed, and the reaction vessel 301 is once evacuated through an exhaust port 311 by an exhaust device (not shown).
07 is opened, and an inert gas for heating, for example, argon is introduced into the reaction vessel 301 from the gas supply pipe 306 as an example,
The vacuum gauge 31 is adjusted so that the inside of the reaction vessel 301 has a desired pressure.
While monitoring 0, the exhaust speed of the exhaust device (not shown) and the flow rate of the heating gas are adjusted. Thereafter, the cylindrical conductive substrate 302 is heated by a substrate heating heater (not shown) by operating a temperature controller (not shown), and the temperature of the cylindrical conductive substrate 302 is controlled to a predetermined temperature of 20 ° C. to 500 ° C. I do. When the cylindrical conductive substrate 302 has been heated to a desired temperature, the source gas introduction valve 307 is closed to stop the gas from flowing into the reaction vessel 301.

Next, a predetermined raw material gas, for example, a material gas such as silane gas, disilane gas, methane gas, or ethane gas, a diborane gas,
After mixing a doping gas such as a phosphine gas by a mixing panel (not shown), the mixture is gradually introduced into the reaction vessel 301 through a source gas introduction valve 307. next,
Each raw material gas is adjusted to a predetermined flow rate by a mass flow controller (not shown). At that time, the evacuation speed is adjusted while watching the vacuum gauge 310 so that the inside of the reaction vessel 301 has a predetermined pressure of 133 Pa or less. Next, adjustment is made while watching the vacuum gauge 310 so as to stably maintain the predetermined pressure.

After the preparation for film formation is completed by the above procedure, a photoconductive layer is formed on the cylindrical conductive substrate 302. After confirming that the internal pressure has stabilized, the high-frequency power supply 309 is set to a desired power and the high-frequency power is supplied to the matching box 3.
08 to the cathode electrode 305 to generate a high-frequency glow discharge. At this time, the matching box 308
Is adjusted so that the reflected wave is minimized. The value obtained by subtracting the reflected power from the high-frequency incident power is adjusted to a desired value. Each source gas introduced into the reaction vessel 301 is decomposed by the discharge energy, and a predetermined deposited film is formed on the cylindrical conductive substrate 302. After the desired film thickness is formed, the supply of the high-frequency power is stopped, and the reaction vessel 3
After the flow of each raw material gas into the gas chamber 01 is stopped and the deposition chamber is once pulled up to a high vacuum, the layer formation is completed. By repeating the above operations, a lower blocking layer and a photoconductive layer are formed.

Next, a surface layer made of aC: H is formed. Once the inside of the reaction vessel 301 is pulled up to a high vacuum,
A predetermined source gas, for example, CH
₄ , reaction after mixing hydrocarbon gas such as C ₂ H ₆ , C ₃ H ₈ , C ₄ H ₁₀ and diluting gas such as hydrogen gas, helium gas, argon gas etc. by mixing panel (not shown) It is introduced into the container 301. Next, each raw material gas is adjusted to a predetermined flow rate by a mass flow controller (not shown). At this time, the vacuum gauge 31 is adjusted so that the inside of the reaction vessel 301 has a predetermined pressure of 133 Pa or less.
Adjust the pumping speed while watching 0. After confirming that the internal pressure has stabilized, the high-frequency power source 309 is set to a desired power, and the power is supplied to the cathode electrode 305 to generate a high-frequency glow discharge. At this time, the matching box 308 is adjusted so that the reflected wave is minimized, and the value obtained by subtracting the reflected power from the high-frequency incident power is adjusted to a desired value.

This discharge energy causes the reaction vessel 30
Each raw material gas introduced into 1 is decomposed, and a predetermined aC: H deposition film is formed on the photoconductive layer. After the desired film thickness is formed, the supply of the high-frequency power is stopped, and the reaction vessel 3
Then, the flow of each source gas to 01 is stopped and the deposition chamber is once pulled up to a high vacuum, and then the formation of the surface layer is completed.

During the film formation, the cylindrical conductive substrate 302 is rotated at a predetermined speed by the rotating motor 312 so that the film is deposited on the entire circumference of the cylindrical substrate.

However, when the surface layer is an aC: F deposited film, the deposition gas is CF ₄ , C ₂ F ₆ , CHF ₃ , CH
Fluorine gas such as ₂ F ₂ , CH ₃ F, etc. and H ₂ , CH ₄ , C
_{2 H 6, C 3 H 8} , C 4 H 10 , etc. of the gas is used. If necessary, these source gases for supplying fluorine may be changed to He, A
It may be diluted with a gas such as r or Ne before use.

In order to configure the surface layer of the light receiving member of the present invention to have a diamond structure and a graphite structure, and to increase the graphite structure toward the outermost surface side: Raise the temperature within a certain range.

(2) The ratio of the applied power to the formation of the surface layer / the flow rate of the layer forming gas (ml / min) is reduced within a certain range.

(3) The pressure in the reaction vessel at the time of forming the surface layer is reduced within a certain range. It can be realized by adopting at least one of the operations described above. The range of the temperature rise is 10 ° C to 300 ° C, preferably 50 ° C to 200 ° C.
° C, and the effect of increasing the graphite structure is greater as the temperature is increased. For (W / ml / min), an operation of increasing the gas flow rate while keeping the applied power constant, an operation of decreasing the applied power while keeping the gas flow rate constant, or changing both to meet the conditions Although there is an operation, any method may be used, and the range of reduction is 1 to 30, preferably 5 to 20, and the greater the degree of reduction, the greater the effect of increasing the graphite structure. The range of the reduction of the reaction pressure is 0.1 Pa to 60 Pa, preferably 1 Pa to 50 P.
a, the greater the degree of reduction, the greater the effect of increasing the graphite structure.

FIG. 4 is a diagram schematically showing an example of a frictional resistance tester.

The blade 402 is set on the dynamic strain measuring device 403, supported by the arm 406,
A load of 100 g is applied by the weight 405 placed on the. The width of the blade 402 in contact with the light receiving member 401 was 5 cm with respect to the generatrix direction of the light receiving member 401.

While the blade 402 is in contact with the surface of the light receiving member 401 at an angle of 35 degrees, the light receiving member 401 is rotated in the direction of arrow X at a speed of 400 mm / sec. At this time, the surface of the light receiving member 401 and the blade 402
Is measured by the dynamic strain measuring device 403.

The blade 402 used for the above measurement is made of urethane rubber, has a thickness of 3 mm, and has a dynamic strain measuring device 40.
3 to 5 m
m.

FIG. 5 is a schematic view showing an example of an electrophotographic apparatus for explaining an image forming process of the electrophotographic apparatus. The light receiving member 501 can be controlled in temperature by a sheet heater 523 provided inside. Then, it rotates in the arrow X direction as required. Around the light receiving member 501, a main charger 502, an electrostatic latent image forming portion 503, a developing device 504, a transfer material supply system 505, and a transfer charger 506 are provided.
(A), separation charger 506 (b), cleaner 525,
A transport system 508, a static elimination light source 509, and the like are provided as needed.

Hereinafter, an example of the image forming process will be described more specifically. The light receiving member 501 is uniformly charged by the main charger 502 to which a high voltage of 6 to 8 kv is applied.
The light emitted from the lamp 510 is reflected on the original 512 placed on the original platen glass 511 at the portion of the electrostatic latent image, passes through the mirrors 513, 514, 515, and forms an image by the lens 518 of the lens unit 517. Mirror 516
, Is projected as light carrying information, and an electrostatic latent image is formed on the light receiving member 501. A developer having a negative polarity is supplied to the latent image from the developing device 504 to form a developer image. Note that this exposure may be performed by scanning and exposing light carrying information using an LED array, a laser beam, a liquid crystal shutter, or the like without using reflection from the original 512.

On the other hand, a transfer material P such as paper is supplied to a transfer material supply system 5.
05, the leading end supply timing is adjusted by the registration roller 522, and the supply is performed toward the light receiving member 501. In the gap between the transfer charger 506 (a) to which the high voltage of 7 to 8 kv is applied and the light receiving member 501, a positive electric field having a polarity opposite to that of the developer is applied to the transfer material P from the back surface. Is transferred to the transfer material P. Then, 12-14 kVp-p, 3
It is separated from the light receiving member 501 by a separation charger 506 (b) to which a high AC voltage of 00 to 600 Hz is applied. Subsequently, the transfer material P reaches the fixing device 524 through the transfer conveyance system 508, where the developer image is fixed, and is carried out of the device.

The developer remaining on the light receiving member 501 is collected by a cleaning roller 507 of a cleaner 525 and a cleaning blade 521 made of an elastic material such as silicone rubber or urethane rubber. Will be erased by

Reference numeral 520 denotes a blank exposure LED, which is a light receiving member as necessary so that unnecessary developer does not adhere to a non-image area such as a portion of the light receiving member 501 exceeding the width of the transfer material P and a margin. It is provided for exposing 501.

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

[0057]

EXAMPLE 1 A lower surface layer 104 and an upper surface layer 10 previously described with reference to FIG. 1 under the conditions shown in Table 2 on a partially masked Si wafer substrate as a sample for evaluating the surface layer.
The layers corresponding to No. 5 were respectively deposited to prepare aC: H surface layer samples A ′, B ′, and C ′.

Next, the structure and film thickness of the aC: H surface layer sample were measured. Further, the plasma C shown in FIG.
Using a VD apparatus, a blocking layer and a photoconductive layer were laminated on a cylindrical conductive substrate under the conditions shown in Table 1 and then a-
C: Light receiving members A, B, and C on which an H surface layer was deposited were manufactured.

[0059]

[Table 1]

[0060]

[Table 2]

The prepared surface layer samples A ′ to C ′ and the light receiving members A to C were measured and evaluated as follows.

(Layer Structure and Film Thickness) The surface layer sample deposited on the Si wafer substrate was confirmed by an infrared absorption method that the lower surface layer 104 was a diamond structure film and the upper surface layer 105 was a graphite structure film. . However, a film having an SP ² binding amount larger than the SP ³ binding amount was defined as a graphite structure film.

Further, the film thickness of the lower surface layer 104 and the upper surface layer 105 was measured by measuring the level difference between the portion having no deposited film and the portion where the surface layer was deposited by masking the surface layer sample.

(Measurement of frictional resistance) Each of the light receiving members was measured by a frictional resistance measuring device shown in FIG.
The frictional resistance generated between the rotating blade 01 and the blade 402 when the rotating member 01 is rotated at 400 mm / sec in the arrow X direction from the stationary state is read by the strain meter 403.

The evaluation of the frictional resistance is a relative comparison with the frictional resistance value in Comparative Example 2 described later being 100. Therefore, the smaller the numerical value, the smaller the frictional resistance and the better the light receiving member.

(Method of Evaluating Cleaning Failure) Hereinafter, a method of evaluating a cleaning failure will be described with reference to FIG.

The light receiving members A to C were mounted on a modified copy machine NP-6085 made by Canon having the configuration shown in FIG. Next, the moving speed of the light receiving member 501 is set to 400 mm / sec.
The non-paper passing durability equivalent to 10,000 A4 plates was performed without performing the developing process. Then, with the developing unit 504 set further, the original 512 having a reflection density of 0.3
Under the environmental conditions of 5 ° C. and a relative humidity of 10%, the moving speed of the light receiving member 501 was 400 mm / sec, and 100,000 sheets of A4 size continuous paper were passed.

Next, the charging current amount of the main charger 502 is adjusted so that the dark portion potential at the position of the developing device 504 becomes 400 V, and the document 512 having a reflection density of 0.3 is placed on the document table 511.
, And the lighting voltage of the halogen lamp 510 was adjusted such that the bright portion potential became 200 V, thereby creating an A3-size halftone image. This image is used to evaluate a cleaning defect that occurs in the form of a stripe.

The evaluation of the cleaning failure is a relative comparison in which the number of streaky images generated in Comparative Example 1 is 100.
Therefore, the smaller the numerical value, the less the cleaning failure and the better the cleaning.

(Fusing evaluation method)
4 so that the dark area potential at 400 becomes 400 V.
02, the solid white document 512 was placed on the document table 511, and the lighting voltage of the halogen lamp 510 was adjusted so that the bright portion potential became 50 V, thereby creating an A3-size solid white image. The image is used to observe black spots generated by the fusion of the developer, and the surface of the light receiving member is observed using a microscope.

The evaluation of the fusion is a relative comparison where the number of fusion occurrences in Comparative Example 2 is 100. Therefore, the smaller the numerical value, the smaller the number of occurrences of fusion, indicating that the image is good.

(Evaluation Method of Charger Wire Stain) After the end of the durability, the charging current amount of the main charger 502 is adjusted so that the dark portion potential at the position of the developing device 504 becomes 400 V, and the solid white document 412 is placed on the document table 511. After adjusting the lighting voltage of the halogen lamp 510 so that the bright portion potential becomes 50 V, the original 512 having a reflection density of 0.3 is placed. The potential unevenness at this time was measured, and the degree of contamination of the charger wire was quantified based on the obtained potential difference.

The evaluation of the charger wire contamination is a relative comparison with the potential difference in Comparative Example 2 described later being 100. Therefore, the smaller the numerical value is, the less occurrence of the charger wire contamination is, and the better the image forming process is.

Comparative Example 1 Except that the graphite structure film of the surface layer was not formed,
A surface layer sample D ′ and a light receiving member D were manufactured in the same manner as in Example 1. Friction resistance and poor cleaning, fusion,
Evaluation of the charger wire contamination was performed.

Comparative Example 2 A light-receiving member was manufactured in the same manner as in Example 1 except that the manufacturing conditions for the surface layer were changed to those in Table 3 to obtain an a-SiC: H surface layer.

[0076]

[Table 3]

In the same manner as in Example 1, the light receiving member was evaluated for defective cleaning, fusion, and contamination of the charger wire.

The evaluation results of Example 1, Comparative Example 1, and Comparative Example 2 are shown in Tables 4 and 5, and the durability results are shown in Table 6.

[0079]

[Table 4]

[0080]

[Table 5]

[0081]

[Table 6]

As a result of the above evaluations, the light-receiving member provided with the aC: H surface layer having a graphite structure film as the outermost surface of the present invention has excellent surface properties and maintains high image quality even after long-term use. It turns out that it is possible.

Example 2 A-C was prepared in the same manner as in Example 1 except that the surface layer was deposited under the conditions shown in Table 7 as a sample for evaluating the surface layer.
An H surface layer sample E ′ was prepared.

[0084]

[Table 7]

Next, the film thickness of the aC: H surface layer sample E ′ was measured in the same manner as in Example 1 (Table 8).

[0086]

[Table 8]

Further, after the blocking layer and the photoconductive layer were laminated on the cylindrical conductive substrate under the conditions shown in Table 9 by using the high frequency power of 105 MHz in the plasma CVD apparatus shown in FIG. A light receiving member E was manufactured by depositing a C: H surface layer, and evaluated for frictional resistance, poor cleaning, fusion, and charger wire contamination in the same manner as in Example 1. Table 10 shows the evaluation results.

[0088]

[Table 9]

[0089]

[Table 10]

As a result of the above evaluation, it was found that the effect of the present invention can be obtained even when an aC: H surface layer whose outermost surface is made of a graphite structure by VHF power is prepared.

Example 3 A surface layer sample F ′ was prepared in the same manner as in Example 1 except that an aC: F surface layer was deposited under the conditions shown in Table 11 as a sample for evaluating the surface layer. Table 12 shows the layer constitution and the film thickness.

[0092]

[Table 11]

[0093]

[Table 12]

Further, after the blocking layer and the photoconductive layer were laminated on the cylindrical conductive substrate by the plasma CVD apparatus shown in FIG. 3 under the conditions shown in Table 9, an aC: F surface layer was deposited under the conditions shown in Table 11. Thus, a light receiving member F was manufactured. Friction resistance, poor cleaning, fusion,
Evaluation of the charger wire contamination was performed. Table 13 shows the evaluation results of Example 3.

[0095]

[Table 13]

As a result of the above evaluations, it was found that the effect of the present invention can be obtained even when an aC: F surface layer having a graphite structure on the outermost surface was prepared.

Example 4 A blocking layer and a photoconductive layer were laminated on a cylindrical conductive substrate under the conditions shown in Table 1 using the plasma CVD apparatus shown in FIG. The light receiving member G provided with the a-SiC intermediate layer, the light receiving member H provided with the a-SiN intermediate layer, and the a-SiO intermediate layer were formed by laminating the layers and further depositing a surface layer under the conditions shown in Table 4. The provided light receiving member I was manufactured.

[0098]

[Table 14]

[0099]

[Table 15]

[0100]

[Table 16]

The light receiving members G to I were evaluated for poor cleaning, fusion, and charger wire contamination in the same manner as in Example 1. The results are shown in Table 17.

[0102]

[Table 17]

As a result of the above evaluation, the effect of the present invention can be obtained even when any intermediate layer composed of a-SiC, a-SiN, or a-SiO is provided between the photoconductive layer and the surface layer. Turned out to be.

[0104]

According to the present invention, as described above, according to the present invention, a photoreceptor member for forming a surface layer composed of a non-single-crystal carbon film containing at least hydrogen atoms and / or halogen atoms on a conductive substrate is manufactured. In this method, the surface layer has a diamond structure and a graphite structure, and by increasing the graphite structure toward the outermost surface side, the solid lubricity of the surface of the light receiving member is significantly improved, and the frictional resistance at the time of initial startup is improved. Can be reduced. As a result, the damage to the blade is reduced, the blade is less chattered due to friction, the cleaning property is excellent, the toner is not scattered, and the wire contamination and the fusion can be prevented.

The present invention may be appropriately performed within the scope of the gist.
It goes without saying that a modified combination can be made, and the present invention is not limited to the above embodiments.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a light receiving member according to the present invention.

FIG. 2 is a schematic sectional view showing another example of the light receiving member according to the present invention.

FIG. 3 is a schematic configuration diagram illustrating an example of a deposition apparatus applicable to the present invention and used for manufacturing a light receiving member by a PCVD method.

FIG. 4 is a schematic cross-sectional view illustrating an example of a frictional resistance measuring device for measuring the frictional resistance of the light receiving member surface.

FIG. 5 is a schematic sectional view illustrating an example of an electrophotographic apparatus.

[Explanation of symbols]

 101, 201 conductive substrate 102, 202 charge injection blocking layer 103, 203 photoconductive layer 104, 204 surface layer (diamond structure) 105, 205 surface layer (graphite structure) 106, 206 charge generation layer 107, 207 charge transport layer 208 Intermediate layer 301 Reaction vessel 302 Conductive substrate 303 Cradle 304 Rotating shaft 305 Cathode electrode 306 Gas introduction tube 307 Gas introduction valve 308 High frequency matching box 309 High frequency power supply 310 Vacuum system 311 Exhaust port 312 Motor 401 Light receiving member 402 Blade 403 Strain gauge 404 Receiving tray 405 Weight 406 Arm 501 Light receiving member 502 Main charger 503 Electrostatic latent image forming part 504 Developer 505 Transfer paper supply system 506 (a) Transfer charger 506 (b) Separation charger 507 Cleaner Roller 508 Conveying system 509 Static elimination light source 510 Halogen lamp 511 Document table 512 Document 513-516 Mirror 517 Lens unit 518 Lens 519 Paper feed guide 520 Blank exposure LED 521 Cleaning blade 522 Registration roller 523 Surface heater 524 Fixer 525 Cleaner

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C23C 16/26 C23C 16/26 G03G 5/082 G03G 5/082 (72) Inventor Ryuji Okamura Ota-ku, Tokyo Shimomaruko 3-chome 30-2 Canon Inc. F-term (reference) 2H068 CA03 DA05 DA06 DA07 DA12 DA15 DA16 DA19 EA24 EA32 EA33 EA35 EA36 FC15 4K030 AA04 AA06 AA09 BA24 BA27 BA28 BA37 BA40 BA44 BB03 BB05 JA04 JA03 JA10 JA16 JA18 LA17

Claims (16)

[Claims] 1. A plasma is generated between a cathode electrode to which high-frequency power is applied and a conductive substrate facing the cathode electrode in a reaction vessel capable of reducing pressure and contains at least hydrogen atoms and / or halogen atoms. In the method for manufacturing a light receiving member for forming a surface layer made of a non-single-crystal carbon film, the temperature at the time of laminating the surface layer is increased, the applied power / flow rate ratio of the layer forming gas is reduced, or The light receiving member is characterized in that the surface layer has a diamond structure and a graphite structure and the graphite structure increases toward the outermost surface side by at least one of the conditions for lowering the internal pressure. Production method. 2. The temperature at the time of laminating said surface layer is 10 ° C. to 30 ° C.
The method according to claim 1, wherein the temperature is raised within a range of 0 ° C. 3. The applied power / flow rate ratio (W / ml / mi)
The method according to claim 1, wherein n) is reduced in a range of 1 to 30. 4. 4. The internal pressure of the reaction vessel is set to 0.1 Pa to 60 Pa.
The method for producing a light receiving member according to claim 1, wherein the light receiving member is reduced in a range of Pa. 5. In the surface layer, the thickness of the region where the graphite structure increases toward the outermost surface is 0.1%.
5. The method for manufacturing a light receiving member according to claim 1, wherein the thickness is in the range of 100 nm to 100 nm. 6. The method according to claim 1, wherein a halogen atom contained in the surface layer is a fluorine atom. 7. The deposition method according to claim 1, wherein the surface layer is formed by decomposing at least a hydrocarbon-based gas and / or a fluorine-based gas by a plasma CVD method using a high frequency of 50 to 450 MHz. The method for producing a light receiving member according to any one of claims 1 to 6. 8. The light-receiving member according to claim 1, wherein the light-receiving member comprises at least the surface layer and the photoconductive layer, and an intermediate layer is provided between the two layers. Production method. 9. The method according to claim 8, wherein the intermediate layer is made of one of non-single-crystal SiC, non-single-crystal SiN, and non-single-crystal SiO. 10. A light-receiving member manufactured by the manufacturing method according to claim 1. 11. The film thickness of a region where the graphite structure of the surface layer is distributed more than the diamond structure has a thickness of 0.1 n.
The light receiving member according to claim 10, wherein the thickness is from m to 100 nm. 12. The method according to claim 1, wherein the surface layer is formed by decomposing at least a hydrocarbon-based gas and / or a fluorine-based gas by a plasma CVD method using a high frequency of 50 to 450 MHz. 10 or 11
3. The light receiving member according to claim 1. 13. The light receiving member according to claim 10, wherein the light receiving member comprises at least a surface layer and a photoconductive layer, and an intermediate layer is provided between both layers. 14. The method according to claim 10, wherein the intermediate layer is made of one of non-single-crystal SiC, non-single-crystal SiN, and non-single-crystal SiO. Light receiving member. 15. An electrophotographic apparatus in which charging, exposure, development, transfer, and cleaning are sequentially repeated, wherein the light receiving member according to claim 10 is used. 16. The electrophotography according to claim 15, wherein the cleaning method is a scrape cleaning using an elastic rubber blade, and a layer rich in a graphite structure on the outermost surface is rubbed and polished in an early stage of operation of the apparatus. apparatus.