JP2000029233A - Electrophotographic photoreceptor and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor in which image defects due to dust depositing on a conductive supporting body before a film is formed can be prevented without sacrificing the electric characteristics. SOLUTION: This electrophotographic photoreceptor is produced by successively laminating a base coating layer 102 consisting of a non-single crystal carbon film and a photoconductive layer 103 consisting of a non-single crystal material making at least silicon atoms as a base material on a conductive supporting body 101. The conductive supporting body 101 consists of aluminum and has >=0.05 μm to <=5 μm ten-point average roughness (Rz) according to JIS B0601. Before the base coating layer 102 is formed, the supporting body 101 is cleaned with water and a surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to electrophotography which is sensitive to electromagnetic waves such as light (here, light in a broad sense meaning ultraviolet light, visible light, infrared light, X-rays, .gamma.-rays, etc.). The present invention relates to a photoconductor and a method for manufacturing the same.

[0002]

2. Description of the Related Art Materials for forming a photoconductive layer in a solid-state imaging device, an electrophotographic photosensitive member in the field of image formation, and a document reading device have a high sensitivity and an SN ratio [photocurrent (I
p) / (Id)], having an absorption spectrum characteristic matching the spectral characteristic of the electromagnetic wave to be irradiated, having a fast light response, having a desired dark resistance value, and being harmless to the human body during use. In addition, the solid-state imaging device is required to have characteristics such that afterimages can be easily processed within a predetermined time. Particularly in the case of an electrophotographic photosensitive member used in an office as an office machine, non-polluting during use is an important point. A material that has attracted attention from this viewpoint is amorphous silicon (hereinafter, referred to as “a-Si”) in which dangling bonds are modified with a monovalent element such as hydrogen or a halogen atom. For example, JP-A-54-86341 describes application to an electrophotographic photosensitive member.

Conventionally, as a method of manufacturing an electrophotographic photosensitive member for forming an a-Si deposited film on a conductive support, a sputtering method, a method of decomposing a raw material gas by heat (thermal CV
D), a method of decomposing source gas by light (photo CVD)
Numerous methods are known, including a method of decomposing a source gas by plasma (plasma CVD method). Above all, the plasma CVD method, that is, a method of decomposing a raw material gas by direct current or high frequency, microwave glow discharge and the like to form a deposited film on a conductive support, is currently in practical use, for example, in the production of an electrophotographic photosensitive member. Very advanced.

As a layer structure of the deposited film of the electrophotographic photosensitive member, an attempt has been made to use a material other than a-Si in addition to a conventionally deposited film obtained by using a-Si as a base material and appropriately adding a modifying element. ing. For example, JP-A-62-14
JP 8968 discloses a photoconductor in which an intermediate layer mainly composed of a carbon film is laminated on a conductive substrate, and a photoconductive layer is laminated thereon. In Japanese Patent Application Laid-Open No. Sho 62-195677, the surface is made of at least Mo, W, Ta or Ti.
An electrophotographic photoreceptor having a layer containing carbon as a main component on a substrate made of the same has been disclosed. Further, Japanese Patent Application Laid-Open No. 64-408
No. 37 discloses a technique using an organic polymer film containing carbon and hydrogen as main components in a photosensitive member forming member.

[0005]

According to the prior art described above, it has become possible to obtain an electrophotographic photosensitive member having some practical characteristics and uniformity. Further, if the inside of the vacuum reaction vessel is strictly cleaned, it is possible to obtain an electrophotographic photosensitive member having few defects to some extent.

However, in the above-described method of forming a deposited film, a product requiring a relatively large deposited film with a large area, such as an electrophotographic photosensitive member, satisfies the requirements of uniform film quality and various optical and electrical characteristics. However, there still remains a problem that it is difficult to obtain a deposited film with few image defects at a high yield during image formation by an electrophotographic process.

In particular, the a-Si film has a thickness of several μm on the surface of the support.
When dust of the order is attached, it has a property that abnormal growth, that is, a so-called “spherical projection” grows with the dust as a nucleus during film formation. The spherical projection has a shape that is the inverse of the cone starting from the dust on the support,
At the interface between the normal growth portion and the spherical protrusion portion, there are many localized levels, so that the resistance is reduced, and the charged charges pass through the interface to the support. For this reason, a portion having a spherical projection appears as a white point in a solid black image on the image (in the case of reversal development, it appears as a black point in a solid white image). The standard of this so-called “white spot” is becoming stricter year by year, and depending on the size, even if several pieces are present on A3 paper, they may be treated as defective. For this reason, the support used before the film formation is precisely washed, and all the steps of installing the support in the film formation apparatus are performed in a clean room or under vacuum.

However, in order to satisfy the increasingly strict standards in recent years and to perform production while maintaining a good product ratio, the cleanliness of the clean room must be increased more than before. For moving parts, dust generation had to be reduced, which required a great deal of investment and labor costs. Furthermore, large-scale equipment investment such as a vacuum transfer machine is required to perform most of the steps under vacuum, and technically advanced equipment is required, which is a heavy burden.

Furthermore, even with these large human and capital investments, it is difficult to stably operate at a high yield due to slight changes in conditions, aging of the equipment, and human error. Accompanied by

Furthermore, in recent years, improvements have been made in the optical exposure system, developing device, transfer device, and the like in the electrophotographic apparatus to improve the image characteristics of the electrophotographic apparatus. Has been required to be improved. In particular, as a result of the improvement in image resolving power, it has been required to reduce even small-sized white spots, which have not been considered a problem in the past.

An object of the present invention is to solve the above-mentioned problems of the prior art without sacrificing the electrical characteristics, to produce an inexpensive and stable electrophotographic photoreceptor which can be manufactured stably at a high yield. It is to provide a manufacturing method thereof.

[0012]

The electrophotographic photoreceptor of the present invention comprises a conductive support made of aluminum according to JIS B0.
601 has a ten-point average roughness (Rz) of 0.05 μm or more and 5 μm or less, and a subbing layer made of a non-single-crystal carbon film on the conductive support; An electrophotographic photoreceptor characterized by sequentially laminating a photoconductive layer made of a single crystal material.

The method for producing an electrophotographic photoreceptor of the present invention is a method for producing the above-described electrophotographic photoreceptor of the present invention, wherein the JIS of a conductive support made of aluminum is used.
The ten-point average roughness (Rz) in B0601 is 0.05
a step of processing the conductive support after the processing, a step of sequentially laminating an undercoat layer and a photoconductive layer on the conductive support after the cleaning. A method for producing an electrophotographic photoreceptor, characterized in that:

In particular, in the electrophotographic photoreceptor of the present invention, the amount of hydrogen contained in the undercoat layer is 1 to all elements.
It is preferable that it is 0 atomic% or more and 60 atomic% or less.

Particularly, in the electrophotographic photoreceptor of the present invention, the undercoat layer preferably has a thickness of 0.1 μm or more and 10 μm or less.

In the method of manufacturing an electrophotographic photoreceptor of the present invention, it is particularly preferred that the conductive support is washed mainly with water and a surfactant.

Hereinafter, the characteristic structure, operation and effect of the present invention will be described together with the circumstances leading to the present invention.

The electrophotographic photoreceptor of the present invention changes the idea of preventing dust from adhering to the support before film formation as a conventional method of preventing image defects. This is based on the idea that spherical projections do not grow and therefore no image defects occur.

The gist of the invention is that a deposition film having very good wettability is first formed on a support to which dust is adhered, thereby covering the dust and forming a smooth surface, and thereafter, forming a smooth surface. By growing an a-Si film on a proper surface, it is intended to prevent the growth of spherical projections with dust as nuclei.

As a result of examining various materials as a deposited film having good wettability, it is found that the deposited film is compatible with a film forming method generally used for a-Si called a plasma CVD method and requires special equipment investment. A non-single crystalline carbon (hereinafter referred to as “a-C”) film was selected as a candidate material. The aC film was deposited under various conditions, and the wettability with the support was examined. As a result, it was found that aluminum was the most suitable material for the support. It was also found that other materials that can be used as a support, such as stainless steel, iron, copper, chromium, and nickel, have poor wettability, and the aC film itself grows abnormally with dust as nuclei.

However, although it has been found that the aluminum support has the best wettability, it is still not enough to completely cover the dust even at this level, and it is impossible to prevent abnormal growth depending on the size of the dust. There was a case.

Therefore, the present inventors further studied the relationship between the surface shape and the wettability. Then, it was found that when the surface roughness (Rz) was 0.05 μm or more, the wettability with the support became the best and the effect of covering the dust became remarkable.
However, the larger the surface roughness is, the better it is.
On the other hand, it was found that the wettability worsened after the point exceeding m. Although the theoretical consideration of the relationship between the surface roughness and the wettability of the aC film is not yet clear, if it is analogized very macroscopically, if the support surface is not rough at all, the flat support surface It seems that the boundary between the particles and the dust becomes remarkable, so that even if the aC film has wettability, the interface cannot be smoothly filled. Conversely, when the roughness exceeds 5 μm, the water repellency of the support itself increases as seen in lotus leaves,
It is thought that the wettability might be worsened. Also,
When the roughness exceeds 5 μm, another problem that the deposited film is easily peeled off occurs.

Further, it has been clarified in the study that the effect of covering the dust according to the present invention depends on the method of cleaning the support. It is difficult to obtain the effects of the present invention with a support that has been washed with conventional organic washing, for example, with triethane, and the effect of the present invention can be sufficiently obtained with a support that has been washed with pure water and a surfactant. Turned out to be. In order to pursue this reason, several types of supports in a state in which the oils and fats during cutting were not consciously degreased, but slightly oils and fats were prepared, and the correlation with the effect of the present invention was examined. No tendency was obtained. For this reason, it is clear that residual fats and oils are not involved. why,
It is not clear whether the effect of the present invention becomes remarkable in the case of cleaning with pure water and a surfactant, but it is possible that the oxidation state of the outermost surface of the aluminum conductive support may be involved. It seems that there is not.

In any case, the use of the electrophotographic photoreceptor of the present invention makes it possible to greatly reduce investment in clean rooms, vacuum transfer machines, and personnel training, which previously required a large investment. Efficiency can be improved. Furthermore, it is effective in stabilizing the non-defective product ratio, and stable production is always possible. This is thought to be due to a small change in yield due to human influence and a small decrease in the yield rate due to human error.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic cross-sectional view of an example of the electrophotographic photoreceptor of the present invention. Reference numeral 101 denotes an aluminum conductive material finished to a ten-point average roughness (Rz) of 0.05 μm or more and 5 μm or less in JIS B0601. Sexual support. 1
02 is an undercoat layer made of aC according to the present invention. Reference numeral 103 denotes a photoconductive layer made of a-Si, which is made of a single layer whose functions are not separated. The electrophotographic photoreceptor of the present invention is at least effective with this configuration.

The ten-point average roughness (Rz) is from the highest to the fifth measured in the direction of the longitudinal magnification from a straight line parallel to the average line and not crossing the cross-sectional curve at a portion extracted by the reference length from the cross-sectional curve. Is expressed in micrometer (μm) between the average of the altitudes at the top of the mountain and the average of the altitudes at the bottom from the deepest to the fifth. That is, Rz = {(R1 + R3 + R5 + R7 + R9)-(R2 + R4 + R6 + R8 + R10)} / 5. Here, R1, R3, R5, R7, R9
Are the altitudes of the highest to fifth peaks of the extracted portion corresponding to the reference length, and R2, R4, R6, R8, R
10 is 5 from the deepest of the extracted part corresponding to the reference length.
It is the altitude of the valley bottom to the th. Standard length is 0.8μmR
When it is less than z, 0.25 mm is used, and when it exceeds 0.8 μmRz, 0.8 mm is used.

When the surface to be measured is a curved surface, the ten-point average roughness may be obtained along a curve that should appear at the cut.

FIG. 2 is a schematic diagram showing a specific example in which a surface protective layer 204 is further provided for the purpose of protecting the surface in addition to the photoconductive layer 203, improving environmental resistance, and improving electrical characteristics. It is sectional drawing. In the case of the electrophotographic photosensitive member of the present invention, the effect of the present invention can be sufficiently obtained even if the surface protective layer 204 is provided.

FIG. 3 is a schematic cross-sectional view showing a specific example in which a surface protection layer 304 and a lower blocking layer 305 for blocking carrier injection from the conductive support 201 are provided in addition to the photoconductive layer 303. It is. The lower blocking layer 305 is configured to be stacked on the undercoat layer 302.

FIG. 4 shows the structure of the photoconductive layer 403 as a charge transport layer 405 composed of an amorphous material containing at least silicon atoms and carbon atoms, and a charge transport layer composed of an amorphous material containing at least silicon atoms. FIG. 9 is a schematic cross-sectional view showing a specific example when a generation layer 406 is used. When the electrophotographic photosensitive member is irradiated with light, carriers mainly generated in the charge generation layer 406 reach the conductive support 401 through the charge transport layer 405. Even if the electrophotographic photoreceptor of the present invention is of a so-called function-separated type as the structure of the photoconductive layer, the effects of the present invention can be sufficiently obtained.

FIG. 5 is a schematic sectional view showing a specific example in which a surface protective layer 504 is further provided in addition to the configuration of FIG.

The conductive supports 101 to 501 are made of aluminum, and the surface is finished by cutting with a lathe. By appropriately selecting a cutting tool and cutting conditions, the surface roughness (Rz) can be finished to 0.05 μm or more and 5 μm or less. This surface roughness is a value measured according to JIS B0601.

A conductive support made of aluminum,
When the surface roughness is the above value, the growth of spherical projections due to dust attached to the support can be prevented by laminating the undercoat layer made of aC.

The conductive supports 101 to 501 may have a cylindrical shape or a plate-like endless belt shape. The thickness may be appropriately determined so that a desired electrophotographic photosensitive member can be formed. When flexibility is required, it can be made as thin as possible within a range where the function as a support can be sufficiently exhibited. However, the support is usually 10 μm in view of production, handling, mechanical strength and the like.
m or more.

Aluminum conductive support 1 after cutting
In the case of 01 to 501, degreasing and washing are appropriately performed, but in order to sufficiently exert the effects of the present invention, washing with pure water and a surfactant is desirable. At this time, even if a corrosion inhibitor for preventing the corrosion of aluminum is appropriately added, the effect of the present invention is not affected at all.

The undercoat layers 102 to 502 are made of a non-single crystalline carbon film. The undercoat layer can be produced by glow discharge decomposition using a gaseous hydrocarbon as a raw material gas at a normal temperature and a normal pressure with a high frequency. The purpose of the undercoat layer is to obscure the dust adhering on the conductive support made of aluminum so that its history does not reach the photoconductive layer made of a-Si. Therefore, the undercoat layer does not need to be particularly photoconductive. However, since the photocarriers generated in the photoconductive layer need to be smoothly transported to the conductive support, charge transport capability is usually required. In order to have a charge transport ability, a hydrogen atom may be appropriately contained in the aC film. This hydrogen atom content is desirably from 10 atomic% to 60 atomic% based on all atoms.

Further, in order to improve the charge transporting ability, the undercoat layers 102 to 502 may contain atoms for controlling conductivity. Examples of the atom that controls conductivity include a so-called impurity in the semiconductor field, and an atom belonging to Group 3b of the Periodic Table that gives p-type conduction characteristics (hereinafter abbreviated as “Group 3b atom”) or n. An atom belonging to Group 5b of the Periodic Table that gives a type conduction characteristic (hereinafter abbreviated as “Group 5b atom”) can be used. The content of the atom for controlling the conductivity is appropriately determined as desired so that excellent charge transporting ability can be exhibited.
１1 × 10 ⁴ atomic ppm, more preferably 50-5 × 1
0 ³ atomic ppm, optimally 1 × 10 ² to 1 × 10 ³ atomic p
pm.

The thickness of the undercoat layers 102 to 502 is 0.1
It is preferably from 10 μm to 10 μm. When the film thickness is 0.1 μm or more, dust can be sufficiently covered and hidden, and image defects due to dust can be favorably prevented. When the thickness is 10 μm or less, the residual potential is hardly increased, the film formation time is short, and the operation rate of the deposited film forming apparatus and the manufacturing cost are preferable. Generally, depending on the environment in which the conductive support is handled, it is effective to deposit thicker dust when the particle size of the dust is large.
When the particle size is small, the effect is sufficiently exhibited even if it is thin. The particle size and amount of environmental dust can be measured by a commercially available particle counter.

The high-frequency power is preferably as high as possible because the decomposition of hydrocarbon proceeds sufficiently. Specifically, the power is preferably 10 W or more per 1 sccm of the hydrocarbon raw material gas. As a result, the undercoat layer is deteriorated, and therefore, it is preferable to suppress the electric power to a longitude at which abnormal discharge does not occur.

With respect to the pressure in the discharge space, when a film is formed using a raw material gas such as hydrocarbon which is hardly decomposed, a polymer is likely to be generated if collision occurs between decomposed species in the gas phase. High vacuum is desirable. Usually, it is 1 Torr or less, more preferably 0.6 Torr or less, and still more preferably 0.4 Torr or less.

The undercoat layers 102 to 502 are for preventing spherical projections caused by dust adhering to the conductive support before the formation of the undercoat layer and eliminating image defects. However, spherical protrusions due to dust generated from peeling of a film deposited on the structure of the deposition film forming apparatus during film formation cannot be prevented by this undercoat layer. Therefore, it is necessary to carefully control the production conditions of the electrophotographic photosensitive member so that the film adhered to a furnace wall or the like should not be peeled off during the film formation as in the related art.

The lower blocking layer 305 has a function of preventing charge from being injected from the conductive support side to the photoconductive layer side when the electrophotographic photosensitive member is subjected to a charging treatment of a fixed polarity on its free surface. However, such a function is not exhibited when subjected to a charging treatment of the opposite polarity, that is, it has a so-called polarity dependency. In order to provide such a function, the lower blocking layer may contain a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer. As the atoms that control the conductivity,
Group b atoms or Group 5b atoms can be used. The content of the atoms controlling the conductivity contained in the lower blocking layer is appropriately determined as desired so that the object of the present invention can be effectively achieved, but is preferably from 10 to 1
X 10 ⁴ atomic ppm, more preferably 50 to 5 x 10 ³ atomic ppm, and most preferably 1 x 10 ² to 1 x 10 ³ atomic ppm.

Further, the lower blocking layer 305 has a carbon source
Containing at least one of a nitrogen atom, a nitrogen atom and an oxygen atom
Provided in direct contact with the lower blocking layer
To further improve the adhesion with other layers
it can. Carbon atoms and carbon atoms contained in the entire region of the lower blocking layer
Content of nitrogen and / or nitrogen and / or oxygen
In the case of, and the sum of two or more types
And preferably 1 × 10 ^-3~ 50 atomic%, more preferably
Is 5 × 10^-3~ 30 atomic%, optimally 1 × 10^-2-10
Atomic%.

Further, the hydrogen atoms and / or halogen atoms contained in the lower blocking layer 305 compensate for dangling bonds existing in the layer, and are effective in improving the film quality. The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the lower blocking layer is preferably 1 to 50 at%, more preferably 5 to 40 at%, and most preferably 10 to 30 at%.
It is.

The thickness of the lower blocking layer 305 is preferably 0.1 to 5 μm, and most preferably 1 to 4 μm, from the viewpoints of obtaining desired electrophotographic characteristics and economical effects.

The photoconductive layers 103 to 503 usually need to contain hydrogen atoms and / or halogen atoms in the film. This is for compensating the dangling bonds of silicon atoms and improving the layer quality, particularly, the photoconductivity and the charge retention characteristics. Therefore, the content of the hydrogen atom or the halogen atom or the sum of the hydrogen atom and the halogen atom is 10 to 30 atom%, more preferably 15 to 25 atom%, based on the sum of the silicon atom and the hydrogen atom and / or the halogen atom. is there. In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer, for example, the temperature of the support, the inside of a reaction vessel of a raw material used to contain hydrogen atoms and / or halogen atoms, What is necessary is just to control the amount to be introduced into the furnace, the discharge power, and the like.

It is preferable that the photoconductive layers 103 to 503 contain atoms for controlling conductivity as necessary. As the atoms for controlling the conductivity, the same atoms as those for the lower blocking layer 305 can be used. The content of atoms for controlling conductivity is preferably 1 × 10 ^-2 to 1 × 10 ⁴ atomic ppm, more preferably 5 × 10 ^{-2 to} 5 × 10 ³ atomic p.
pm, optimally 1 × 10 ^-1 to 1 × 10 ³ atomic ppm.

Further, it is also effective that the photoconductive layers 103 to 503 contain carbon atoms and / or oxygen atoms and / or nitrogen atoms. The content of the carbon atom and / or the oxygen atom and / or the nitrogen atom is determined by the content of the silicon atom,
Preferably, the sum of oxygen atoms and nitrogen atoms is 1 × 1
0 ^-5 to 10 at%, more preferably 1 x 10 ^-4 to 8 at%, and most preferably 1 x 10 ^{-3 to} 5 at%. The carbon atoms, oxygen atoms, and nitrogen atoms do not necessarily need to be contained in the entire layer, and may be distributed only partially or in the film thickness direction.

The layer thickness of the photoconductive layers 103 to 503 is determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, and is preferably 10 to 5 times.
0 μm, more preferably 20-45 μm, optimally 25
４０40 μm.

On the photoconductive layers 103 to 503, a
It is preferable to form the Si-based surface protective layers 204, 304, and 504. The surface protective layers 204, 304, 5
Reference numeral 04 has a free surface and is provided in order to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electric pressure resistance, use environment characteristics, and durability. The photoconductive layers 103 to 503 constituting the light receiving layer and the surface protective layer 20
Each of the amorphous materials forming 4, 304, 504
Since it has a common component called silicon atom,
Ensuring sufficient chemical stability at the lamination interface is sufficient.

The surface protective layers 204, 304, and 504 have a
Any material can be used as long as it is a -Si material. For example, a-Si (a) containing a hydrogen atom (H) and / or a halogen atom (X) and further containing a carbon atom
-SiC: a-S containing H, X), a hydrogen atom (H) and / or a halogen atom (X), and further containing an oxygen atom
a-Si (a-SiN: H, X) containing i (a-SiO: H, X), a hydrogen atom (H) and / or a halogen atom (X), and further containing a nitrogen atom; H) and / or a-Si containing a halogen atom (X) and further containing at least one of a carbon atom, an oxygen atom and a nitrogen atom
Materials such as (a-SiCON: H, X) are preferably used.

The content of an element selected from carbon, nitrogen and oxygen is preferably in the range of 30% to 90% with respect to the sum of silicon atoms and carbon atoms, nitrogen atoms and oxygen atoms.

The surface protective layers 204, 304, and 504 usually need to contain hydrogen atoms and / or halogen atoms, but the hydrogen content is usually smaller than the total amount of the constituent atoms. 30 to 70 atomic%, preferably 35 to
65 at%, optimally 40 to 60 at%. Also,
The fluorine content is usually 0.01 to 15 atomic%, preferably 0.1 to 10 atomic%, and most preferably 0.6 to 4 atomic%.

Further, the surface protective layers 204, 304, 50
4 may contain an atom for controlling conductivity as necessary.

The thickness of the surface protective layers 204, 304 and 504 is usually from 0.01 to 3 μm, preferably from 0.1 to 2 μm.
m, optimally between 0.5 and 1 μm. Layer thickness 0.01 μm
Above, the surface protective layer is less likely to be lost due to friction or the like during use of the electrophotographic photoreceptor, and if it is 3 μm or less, deterioration of electrophotographic characteristics such as increase in residual potential can be prevented.

The atom for controlling the conductivity used in the present invention, for example, the Group 3b atom includes, specifically, B
(Boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium), and the like, and B, Al, and Ga are particularly preferable. As the group 5b atom, specifically, P (phosphorus), As (arsenic), Sb
(Antimony), Bi (bismuth) and the like.
As is preferred.

Group 3b atom or group 5b atom
For the introduction of a 3b group atom at the time of layer formation.
Source material for introduction of Group 5b atoms
And introduce it into the reaction vessel together with other gases.
I just need. Raw material for introducing group 3b atoms or group 5b
Room temperature can be a raw material for introducing group atoms.
Gaseous at normal pressure or at least easy under layer forming conditions
It is desirable to employ one that can be gasified. Like that
As a raw material for introducing a Group 3b atom, specifically,
For boron atom introduction, B_TwoH₆, B_FourH_Ten, B_FiveH₉,
B_FiveH₁₁, B₆H_{1 0}, B₆H₁₂, B₆H₁₄Borohydride, etc.
BF_Three, BCl_Three, BBr_ThreeSuch as boron halide
It is. In addition, AlCl_Three, GaCl_Three, Ga (C
H_Three)_Three, InCl _Three, TlCl_ThreeAnd so on.
You. Effectively used as a raw material for introducing group 5b atoms
What is used for introducing phosphorus atoms is PH_Three, P_TwoH_FourEtc.
Phosphorus hydride, PH_Four, PF_Three, PF_Five, PCl_Three, PCl_Five,
PBr_Three, PBr_Five, Pl_ThreeAnd the like.
You. In addition, AsH_Three, AsF_Three, AsCl_Three, AsB
r_Three, AsF _Five, SbH_Three, SbF_Three, SbF_Five, SbC
l_Three, SbCl_Five, BiH_Three, BiCl_Three, BiBr_ThreeEtc.
Listed as effective starting materials for introducing group 5b atoms
Can be For atom introduction to control these conductivity
Raw material as needed_TwoAnd / or by He
It may be used after dilution.

As a substance which can be a gas for supplying Si, silicon hydrides (silanes) in a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ or the like can be effectively used. In particular, in terms of ease of handling at the time of forming a layer and good Si supply efficiency, SiH
₄ , Si ₂ H ₆ is preferred.

Then, in order to structurally introduce hydrogen atoms into each of the layers to be formed so as to make it easier to control the introduction ratio of hydrogen atoms, and to obtain film characteristics which achieve the object of the present invention, A desired amount of a gas of a silicon compound containing H ₂ and / or He or a hydrogen atom can be mixed with these gases to form a layer. In addition, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

H ₂ and / or H used as a diluent gas
The optimum flow rate of e is selected as appropriate according to the layer design. However, H ₂ and / or He is used for the Si supply gas.
In general, the control is performed in the range of 3 to 20 times, preferably 4 to 15 times, and most preferably 5 to 10 times.

The source gas for supplying halogen atoms is preferably a gaseous or gasifiable halogen compound such as a halogen gas, a halide, an interhalogen compound containing halogen, or a silane derivative substituted with halogen. Can be Furthermore, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound. Specific examples of the halogen compound that can be suitably used include fluorine gas (F ₂ ) and Br.
F, ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ , IF
_{7 and the} like. Specific examples of the silicon compound containing a halogen atom, ie, a silane derivative substituted with a halogen atom, include, for example, S
Silicon fluoride such as iF ₄ or Si ₂ F ₆ can be mentioned as a preferable example.

As a substance that can serve as a carbon supply gas,
Hydrocarbons in the gaseous state, such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ , and C ₄ H ₁₀ , or gasifiable hydrocarbons are effectively used. In particular, CH ₄ and C ₂ H ₆ are preferable from the viewpoints of ease of handling at the time of forming a layer, good Si supply efficiency, and the like.

Substances that can serve as nitrogen or oxygen supply gas include NH ₃ , NO, N ₂ O, NO ₂ , O ₂ , CO, C
Compounds in a gaseous state or gasifiable such as O ₂ and N ₂ are mentioned as being effectively used.

The atoms contained in each layer may be uniformly distributed throughout the layer, or may be uniformly distributed in the layer thickness direction, but may be distributed unevenly. There may be a part containing. However, in any case, it is necessary to uniformly contain the particles in the in-plane direction parallel to the surface of the support from the viewpoint of making the properties uniform in the in-plane direction.

Similarly, an optimum range of the gas pressure in the reaction vessel is appropriately selected according to the layer design.
10 ^{-4 to} 10 Torr, preferably 5 × 10 ^{-4 to} 5 To
rr, optimally 1 × 10 ^{−4 to} 1 Torr.

Similarly, the optimum range of the discharge power is appropriately selected in accordance with the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 2 to 7 times, preferably 2.5 to 6 times. Optimally, it is set in the range of 3 to 5 times.

The temperature of the support is appropriately selected in an optimum range according to the layer design.
More preferably, the temperature is 200 to 350 ° C.

In the present invention, the preferable ranges of the mixing ratio of the raw material gas, the gas pressure, the temperature of the support, and the discharge power for forming each layer include the above-mentioned ranges. However, it is desirable to determine an optimum value based on mutual and organic relevance in order to form a deposited film having desired characteristics.

The production of the electrophotographic photoreceptor of the present invention is usually carried out by
This is performed 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 CVD method), a sputtering method, a vacuum deposition method, an ion plating method, It can be formed by various thin film deposition methods such as a photo CVD method and a thermal CVD method. 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 produced electrophotographic photoreceptor. 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 electrophotographic photosensitive member having the same are relatively easy to control.

In particular, each layer such as an undercoat layer and a photoconductive layer is preferably formed by a plasma CVD method in which discharge is excited at a discharge frequency of 50 MHz to 450 MHz.

Hereinafter, an apparatus and a method for forming a deposited film by a high-frequency plasma CVD method will be described in detail. FIG. 6 shows high frequency plasma CVD (hereinafter referred to as “RF-PCV”).
FIG. 1 is a schematic configuration diagram illustrating an example of an apparatus for manufacturing an electrophotographic photosensitive member according to a D method).

The structure of the apparatus for manufacturing a deposited film by the RF-PCVD method shown in FIG. 6 is as follows. This device is broadly composed of a deposition device (5100), a source gas supply device (5200), and an exhaust device (5117) for reducing the pressure inside the reaction vessel (5111). In the reaction vessel (5111) in the deposition apparatus (5100), a conductive support (5112) and a heater for heating the support (511) are provided.
3) A source gas introduction pipe (5114) is installed, and a high frequency matching box (5115) is further connected.

The source gas supply device (5200) is made of Si
_{H 4, H 2, CH 4} , NO, cylinder source gas such as B ₂ H _6, GeH ₄ and (5221 to 5226) Valve (5231～
5236, 5241 to 5246, 5251 to 5256)
And mass flow controllers (5211-521)
6), and the cylinder for each source gas is a valve (52).
60) is connected to the gas introduction pipe (5114) in the reaction vessel (5111).

The method of forming a deposited film using this apparatus can be performed, for example, as follows.

First, a conductive support (5112) made of aluminum whose surface has been finished to a surface roughness (Rz) of 0.05 μm or more and 5 μm or less by cutting with a lathe is placed in a reaction vessel (5111). Conductive support (511
2) In the case of an electrophotographic photosensitive member, a cylindrical shape is desirable. The conductive support (5112) is appropriately degreased and washed in advance, but in order to sufficiently exert the effects of the present invention, it is necessary to thoroughly rinse with pure water after washing with pure water and a surfactant. preferable. After the installation, the inside of the reaction vessel (5111) is exhausted by an exhaust device (5117, for example, a vacuum pump). Subsequently, the heater (5113) for heating the support was turned on.
N, and set the temperature of the conductive support (5112) to 50 ° C. to 50 ° C.
Control to a predetermined temperature of 0 ° C.

A source gas for forming a deposited film is supplied to a reaction vessel (51).
11), the gas cylinder valve (523)
1-5236), a leak valve of the reaction vessel (5123)
Is closed, and check that the inlet valve (5
251-5256), outflow valves (5241-524)
6) After confirming that the auxiliary valve (5260) is open, the main valve (5118) is first opened to exhaust the reaction vessel (5111) and the inside of the gas pipe (5116).

Next, the reading of the vacuum gauge (5124) is about 5 ×
At 10 ^-6 Torr, the auxiliary valve (526
0), close the outflow valves (5251-5256). Thereafter, each gas is introduced from the gas cylinders (5221 to 5226) by opening the valves (5231 to 5236), and each gas pressure is adjusted (for example, 2 kg / cm ² ) by the pressure regulators (5261 to 5266). Next, the inflow valve (524)
1-5246) is gradually opened, and each gas is introduced into the mass flow controllers (5211-5216).

After the preparation for film formation is completed as described above, an undercoat layer made of aC is first formed on the conductive support (5112).

When the conductive support (5122) reaches a predetermined temperature, the necessary ones of the outflow valves (5251-5256) and the auxiliary valve (5260) are gradually opened, and the gas cylinders (5221-5226) are opened. A predetermined gas is supplied to the reaction vessel (51) through a gas introduction pipe (5114).
11). Next, each raw material gas is adjusted by a mass flow controller (5211 to 5216) so as to have a predetermined flow rate. At that time, the reaction vessel (511)
1) Main valve (51) while watching vacuum gauge (5124) so that the pressure in 1) becomes a predetermined pressure of 1 Torr or less.
18) Adjust the opening. When the internal pressure becomes stable, R
F power supply (not shown) is set to a desired power, and the reaction vessel (51) is passed through a high-frequency matching box (5115).
RF power is introduced into 11) to generate RF glow discharge. The source gas introduced into the reaction vessel is decomposed by the discharge energy, and a deposited film mainly containing predetermined carbon is formed on the conductive support (5112). After the formation of the desired film thickness, the supply of the RF power is stopped, the outflow valve is closed, the flow of gas into the reaction vessel is stopped, and the formation of the undercoat layer is completed.

By repeating the same operation a plurality of times, an electrophotographic photosensitive member having a multilayer structure such as a lower blocking layer, a photoconductive layer, and a surface protective layer is formed.

When forming each layer, it goes without saying that all outflow valves other than necessary gas are closed, and each gas is supplied to the reaction vessel (511).
1) Close the outflow valves (5251 to 5256), open the auxiliary valve (5260), and open the main valve to avoid remaining in the piping from the outflow valves (5251 to 5256) to the reaction vessel (5111). Valve (51
The operation of fully opening 18) and once evacuating the system to a high vacuum is performed as necessary. In order to make the film formation uniform, the conductive support (511) is used during the film formation.
2) is rotated at a predetermined speed by a driving device (not shown).

It goes without saying that the above-mentioned gas species and valve operation are changed according to the conditions for forming each layer.

Next, high-frequency plasma CVD using a frequency in the VHF band (hereinafter abbreviated as "VHF-PCVD")
A method for manufacturing an electrophotographic photoreceptor by the method will be described.

RF-PC in the manufacturing apparatus shown in FIG.
The deposition apparatus (5100) using the VD method is replaced with a deposition apparatus (6100) shown in FIG.
0), it is possible to obtain an electrophotographic photoreceptor manufacturing apparatus by the VHF-PCVD method.

This apparatus is roughly classified into a reaction vessel (6111) having a vacuum-tight structure and capable of reducing pressure, a supply device (5200) for raw material gas, and an exhaust device (not shown) for reducing the pressure inside the reaction vessel. ). A conductive support (6112), a heater for heating the support (6113), a raw material gas introduction pipe (not shown), and an electrode (6115) are installed in the reaction vessel (6111). 6116) are connected.
The inside of the reaction vessel (6111) is connected to a diffusion pump (not shown) through an exhaust pipe (6121).

The source gas supply device (5200) is made of SiH
_{4, GeH 4, H 2,} CH 4, B 2 H 6, a cylinder of the source gas PH _3, etc. (5221-5226) and the valve (5231～
5236, 5241 to 5246, 5251 to 5256)
And mass flow controllers (5211-521)
6), and the cylinder for each source gas is a valve (52).
60) is connected to a gas introduction pipe (not shown) in the reaction vessel (6111). In addition, the conductive support (6)
A space (6130) surrounded by 112) forms a discharge space.

The formation of a deposited film in this apparatus by the VHF-PCVD method can be performed as follows.

First, the conductive support (6112) is set in the reaction vessel (6111), the support (6112) is rotated by the driving device (6120), and the reaction is performed by the exhaust device (not shown) (for example, a diffusion pump). The inside of the vessel (6111) is evacuated through the exhaust pipe (6121), and the reaction vessel (611) is exhausted.
1) Adjust the pressure within 1 × 10 ⁻⁷ Torr or less. Subsequently, the temperature of the conductive support (6112) is heated to and maintained at a predetermined temperature of 50 ° C to 500 ° C by the support heating heater (6113).

A source gas for forming a deposited film is supplied to a reaction vessel (61).
11), the gas cylinder valve (523)
1 to 5236), confirm that the leak valve (not shown) of the reaction vessel is closed, and check the inflow valve (52
41-5246), the outflow valve (5251-525)
6) After confirming that the auxiliary valve (5260) is open, first open the main valve (not shown) to exhaust the inside of the reaction vessel (6111) and the gas pipe. Next, when the reading of a vacuum gauge (not shown) reaches about 5 × 10 ⁻⁶ Torr, the auxiliary valve (5260) and the outflow valve (5251)
~ 5256) is closed.

Thereafter, gas cylinders (5221 to 522)
From 6), each gas is introduced by opening the valves (5231-5236), and each gas pressure is adjusted to ² kg / cm ² by the pressure regulators (5261-5266). Next, the inflow valves (5241 to 5246) are gradually opened, and each gas is introduced into the mass flow controllers (5211 to 5216).

After the preparation for film formation is completed as described above, an undercoat layer is formed on the conductive support (6112) as follows.

When the conductive support (6112) reaches a predetermined temperature, necessary ones of the outflow valves (5221 to 5256) and the auxiliary valve (5260) are gradually opened, and a predetermined amount is opened from the gas cylinder (5221 to 5226). Of the reaction vessel (611) via a gas introduction pipe (not shown).
It is introduced into the discharge space (6130) in 1). Next, each raw material gas is adjusted by a mass flow controller (5211 to 5216) so as to have a predetermined flow rate. At that time, the pressure in the discharge space (3130) was 500 mTorr.
The opening of the main valve (not shown) is adjusted while watching the vacuum gauge (not shown) so that the pressure becomes the following predetermined pressure.

The undercoat layer made of aC is formed at a stable pressure, for example, at a VHF frequency of 100 MHz.
A power source (not shown) is set to a desired power, and V is applied to the discharge space (6130) through the matching box (6116).
HF power is introduced to cause glow discharge. Thus, in the discharge space (6130) surrounded by the support (6112), the introduced source gas is excited by the discharge energy to be dissociated, and the support gas (6112) is dissociated.
A predetermined deposited film is formed thereon. At this time, simultaneously with the introduction of the VHF power, the output of the heater for heating the support (6113) is adjusted to change the temperature of the conductive support at a predetermined value. In order to achieve uniform formation of the layer, the layer is rotated at a desired rotation speed by a support rotation motor (6120).

After the desired film thickness is formed, the supply of VHF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the undercoat layer is completed.

By repeating the same operation a plurality of times, an electrophotographic photosensitive member having a desired multilayer structure is formed.

When forming each layer, it goes without saying that all outflow valves other than necessary gas are closed, and each gas is supplied to the reaction vessel (611).
1) Close the outflow valves (5251 to 5256), open the auxiliary valve (5260), and open the main valve in order to avoid remaining in the piping from the outflow valves (5251 to 5256) to the reaction vessel (6111). An operation of fully opening a valve (not shown) and once evacuating the system to a high vacuum is performed as necessary.

It goes without saying that the above-mentioned gas species and valve operation are changed according to the production conditions of each layer.

The heating method of the conductive supports (5112, 6112) may be any heating element having a vacuum specification, and more specifically, electric resistance of a winding heater of a sheath heater, a plate heater, a ceramic heater, or the like. Heating elements, heat-emitting lamp heating elements such as halogen lamps and infrared lamps, and heating elements using a liquid or a gas as a heating medium and a heat exchange unit may be used. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum, and copper, ceramics, heat-resistant polymer resins, and the like can be used. In addition, in addition to the reaction container (5111, 6111), a heating-only container is provided, and the conductive support (5112, 6112)
Is heated, and then the conductive support (5112, 6112) is transported in a vacuum into the reaction vessel (5111, 6111).

In particular, the pressure in the discharge space in the VHF-PCVD method is preferably 1 mTorr or more and 500 mTo
rr or less, more preferably 1 mTorr or more and 300 mT
orm, most preferably 1 mTorr to 100 m
Set to Torr or less.

In the VHF-PCVD method, the size and shape of the electrode (6115) provided in the discharge space may be any as long as they do not disturb the discharge.
A cylindrical shape having a diameter of 1 mm or more and 10 cm or less is preferable. At this time, the length of the electrode (6115) also depends on the conductive support (611).
The length can be arbitrarily set as long as the electric field is uniformly applied to 2).

As the material of the electrode (6115), any material can be used as long as its surface becomes conductive. For example, stainless steel, Al, Cr, Mo, Au, In, N
Metals such as b, Te, V, Ti, Pt, Pb, and Fe, alloys thereof, and glass or ceramics whose surfaces are subjected to conductive treatment are usually used.

The electrophotographic photosensitive member of the present invention can be used not only for an electrophotographic copying machine but also for a laser beam printer,
It can be widely used in electrophotographic applications such as CRT printers, LED printers, liquid crystal printers, and laser plate making machines.

[0104]

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

<Embodiment 1> A blocking type electrophotographic photosensitive member was manufactured under the conditions shown in Table 1 by using the deposition film forming apparatus by the RF-PCVD method shown in FIG. In this example, the amount of image defects generated in the deposited film was evaluated by changing the surface roughness (Rz) of the aluminum support to 0.2 μm. Washing of the support after cutting was performed using pure water and a surfactant, and then thoroughly rinsed with pure water and dried.

The amount of dust in the environment in which the support is handled is usually from several to several hundred in a liter of air with a dust amount of 0.3 μm or more, as measured by a particle counter. There were tens of thousands of liters in the liter set to a very dirty state.

[0107]

[Table 1] Spherical protrusions of the electrophotographic photosensitive member obtained in this way, white spots when a black original is copied, film peeling after leaving the produced electrophotographic photosensitive member for one month in a normal temperature and normal humidity environment An evaluation was performed. The specific evaluation method is as follows. The results are shown in Table 3.

[Spherical projections] 15 μm in diameter by microscope
The number of the above spherical projections in the visual field of 10 cm ² was counted.

[White Spot] A black original is placed on a platen, and an image sample obtained when copying on A3 paper is observed.
The number of white spots having a diameter of 0.3 mm or more was counted.

The spherical projections and white spots in the black image were evaluated by relative values when the number of spherical projections and white spots of the electrophotographic photosensitive member of Comparative Example 1 was 100%. ◎: less than 30% ○: 30% or more and less than 60% △: 60% or more and less than 90% ×: 100% or more

[Peeling] The produced electrophotographic photosensitive member was
After leaving in a room temperature and room temperature environment for one month, the presence or absence of peeling of the film was visually inspected. The evaluation criteria are as follows. ○: Not allowed. Δ: No peeling immediately after film formation, but slight peeling occurred one month later. X: Partial peeling has already occurred immediately after film formation.

<Comparative Example 1> Using a deposition film forming apparatus based on the RF-PCVD method shown in FIG. Manufactured. In this comparative example, the undercoat layer according to the present invention was not provided, and the surface roughness (Rz) was 0.2 μm.
The lower blocking layer was provided directly on the aluminum support which was changed to the above, and the amount of image defects generated in the deposited film was compared. Washing,
The dust amount was the same as in Example 1.

[0113]

[Table 2] The thus obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3 together with the results of Example 1.

[0114]

[Table 3] As is evident from Table 3, the electrophotographic photoreceptor provided with the undercoat layer of the present invention showed very good results.

<Embodiment 2> A blocking type electrophotographic photosensitive member was manufactured under the conditions shown in Table 1 by using the deposition film forming apparatus shown in FIG. . In this example, the surface roughness (Rz) of the aluminum support was changed from 0.01 μm to 5.5 μm, and the amount of image defects generated in the deposited film was compared. The cleaning and dust amounts were the same as in Example 1. The thus obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 4.

Comparative Example 2 The same operation as in Example 2 was carried out except that the undercoat layer according to the present invention was not provided and the lower blocking layer was provided directly on the aluminum support. The evaluation results are shown in Table 4.

[0117]

[Table 4] As is clear from Table 4, when the surface roughness (Rz) of the aluminum support is 0.05 μm to 5 μm and the undercoat layer of the present invention is provided, the electrophotographic photoreceptor is very good. The result was obtained.

<Embodiment 3> A blocking type electrophotographic photosensitive member was manufactured under the conditions shown in Table 1 by using the deposited film forming apparatus by the RF-PCVD method shown in FIG. . In this embodiment, the surface roughness (Rz) of the aluminum support is set to 0.08 μm, and the surface shape after cutting is changed to three types as shown in FIG. Compared. Example 1
Same as. The thus obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5.

[0119]

[Table 5] As is clear from Table 5, the effect of the present invention can be obtained regardless of the surface shape of the aluminum support.

<Embodiment 4> A blocking type electrophotographic photosensitive member was manufactured under the conditions shown in Table 1 according to the procedure of the above-mentioned deposited film forming method using the deposited film forming apparatus by the RF-PCVD method shown in FIG. did. In this example, the method of cleaning the aluminum support with pure water and a surfactant was compared with the method of cleaning with an organic solvent (trichlene cleaning). The surface roughness (Rz) of the support was 0.3 μm. The dust amount was the same as in Example 1. The thus obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 6.

[0121]

[Table 6] Regarding the method of cleaning the aluminum support, there was no difference in the image defects on the image in any case, but the number of spherical projections on the surface of the electrophotographic photoreceptor was determined by cleaning with pure water and a surfactant. However, it was found that washing with pure water and a surfactant was more suitable for the electrophotographic photoreceptor of the present invention.

<Embodiment 5> Using a deposition film forming apparatus by RF-PCVD shown in FIG. 6, according to the procedure of the above-mentioned deposition film forming method, a blocking type electrophotographic photosensitive member was manufactured under the conditions shown in Table 1. did. In this embodiment, as the material of the support,
Film formation was performed using aluminum, iron, stainless steel, and chromium. The surface roughness (Rz) of the support was 1.0 μm. The cleaning and dust amounts were the same as in Example 1. The thus obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 7.

[0123]

[Table 7] From the results in Table 7, it was found that aluminum was most suitable as the material of the support.

<Embodiment 6> Using the deposition film forming apparatus by the RF-PCVD method shown in FIG. 6, according to the procedure of the above-mentioned deposition film forming method, the manufacturing conditions A to E of the undercoat layer shown in Table 8
Was combined with the photoconductive layer shown in Table 9 to produce a blocking type electrophotographic photosensitive member. The surface roughness (Rz) of the aluminum support was 0.3 μm. The cleaning and dust amounts were the same as in Example 1. The thus obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1. Further, the amount of hydrogen in the film was measured by infrared absorption spectroscopy of a sample in which an undercoat layer was separately formed on a Si wafer. The evaluation results are shown in Table 10.

[0125]

[Table 8]

[0126]

[Table 9]

[0127]

[Table 10] From the results in Table 10, it was found that although there is no difference on the image, it is more suitable for the number of spherical projections that the hydrogen content in the film of the undercoat layer be about 10 atomic% to 60 atomic%.

<Embodiment 7> Using a deposition film forming apparatus based on the RF-PCVD method shown in FIG. 6, according to the procedure of the above-described deposition film forming method, the blocking type is basically based on the manufacturing conditions of the electrophotographic photosensitive member shown in Table 1. Was prepared. In this example, the thickness of the undercoat layer was changed based on the manufacturing conditions shown in Table 1. Surface roughness of the aluminum support (R
z) was 3.0 μm. Example 1
Same as. The thus obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1. Further, the residual potential was evaluated as follows. The evaluation results are shown in Table 11.

[Residual Potential] The electrophotographic photosensitive member is charged to a constant dark portion surface potential (for example, 400 V). And immediately, a relatively strong light with a constant light amount (for example, 2 Lux · sec)
Is irradiated. A xenon lamp was used as a light source, and light excluding light in a wavelength region of 600 nm or more was irradiated using a filter. At this time, the surface potential of the light portion of the electrophotographic photosensitive member was measured with a surface potentiometer, and this was defined as the residual potential. As a criterion for evaluation of the residual potential, a relative comparison was made with the residual potential in Comparative Example 1 being 1 in which no undercoat layer was provided, and the following three ranks were evaluated. Good: Very low residual potential at less than 0.8, good. Δ: 0.8 to less than 1.5, equivalent to the conventional level. ×: Practically a problem may occur at 1.5 or more.

[0130]

[Table 11] From the results in Table 11, the thickness of the undercoat layer was 0.1 μm to 1 μm.
It has been found that 0 μm, more preferably 1 μm to 10 μm, is suitable.

<Embodiment 8> A function-separated type electrophotographic photosensitive member was prepared under the conditions shown in Table 12 by using the deposition film forming apparatus by the RF-PCVD method shown in FIG. Manufactured. In this example, the surface roughness (Rz) of the aluminum support was 5 μm. The cleaning and dust amounts were the same as in Example 1. The thus obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1. Further, the residual potential was evaluated as follows. The evaluation results are shown in Table 13.

[0132]

[Table 12]

[0133]

[Table 13] As is clear from Table 13, it was found that the effect of the present invention can be obtained without any problem even if the layer configuration of the photosensitive layer is a function-separated type.

<Embodiment 9> VHF-PCVD shown in FIG.
A blocking type electrophotographic photoreceptor was manufactured under the conditions shown in Table 14 below using a deposited film forming apparatus according to the above-described method and according to the procedure of the aforementioned deposited film forming method. The frequency of the VHF power supply is 105
MHz. In this example, the surface roughness (Rz) of the aluminum support was 0.5 μm. The cleaning and dust amounts were the same as in Example 1. The thus obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1. Further, the residual potential was evaluated as follows. The evaluation results are shown in Table 15.

[0135]

[Table 14]

[0136]

[Table 15] As is clear from Table 15, the film formation method was VHF-PC
It has been found that the effect of the present invention can be obtained without any problem even by the VD method.

[0137]

As described above, according to the present invention, it is possible to prevent an image missing flame caused by dust adhering to a conductive support before film formation without sacrificing electric characteristics. As a result, it is possible to produce a high-yield electrophotographic photoreceptor which can be produced at a high yield while minimizing investment in a clean room and other facilities, can be produced stably at a low cost and with a high yield, and is easy to use with high image quality.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of the electrophotographic photosensitive member of the present invention.

FIG. 2 is a schematic sectional view showing an example of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a schematic sectional view showing an example of the electrophotographic photoreceptor of the present invention.

FIG. 4 is a schematic sectional view showing an example of the electrophotographic photoreceptor of the present invention.

FIG. 5 is a schematic sectional view showing an example of the electrophotographic photosensitive member of the present invention.

FIG. 6 is a schematic configuration diagram showing a manufacturing apparatus using an RF glow discharge method as an example of an apparatus for manufacturing the electrophotographic photosensitive member of the present invention.

FIG. 7 is a schematic configuration diagram showing a mass-production type manufacturing apparatus using a VHF glow discharge method as an example of an apparatus for manufacturing the electrophotographic photosensitive member of the present invention.

FIG. 8 is a schematic cross-sectional view showing three types of shapes of a support surface in Example 3.

[Explanation of symbols]

101, 201, 301, 401, 501 Conductive support 102, 202, 302, 402, 502 Underlayer 103, 203, 303, 403, 503 Photoconductive layer 204, 304, 504 Surface protective layer 305 Lower blocking layer 405 , 505 Charge transport layer 406, 506 Charge generation layer 5100, 6100 Deposition device 5111, 6111 Reaction vessel 5112, 6112 Conductive support 5113, 6113 Support heating heater 5114 Source gas introduction pipe 5115, 6115 Matching box 5116 Source gas pipe 5117 Reaction vessel leak valve 5118 Main exhaust valve 5119 Vacuum gauge 5200 Source gas supply device 5211 to 5216 Mass flow controller 5221 to 5226 Source gas cylinder 5231 to 5236 Source gas cylinder valve 241-5246 gas inlet valve 5251 to 5,256 gas outflow valves 5261 to 5266 pressure regulators 6115 electrodes 6120 support rotating motor 6121 exhaust pipe 6130 discharge space

Claims (10)

[Claims] 1. A conductive support made of aluminum, J
The ten-point average roughness (Rz) in IS B0601 is 0.
On the conductive support, a subbing layer made of a non-single-crystal carbon film and a photoconductive layer made of a non-single-crystal material containing at least silicon atoms as a base material are sequentially laminated on the conductive support. An electrophotographic photoreceptor, comprising: 2. The electrophotographic photoreceptor according to claim 1, wherein the amount of hydrogen contained in the undercoat layer is from 10 at% to 60 at% based on all elements. 3. The undercoat layer has no photoconductivity.
Or the electrophotographic photosensitive member according to 2. 4. An undercoat layer having a thickness of 0.1 μm or more and 10 μm or less.
The electrophotographic photoreceptor according to any one of claims 1 to 3, which has a diameter of not more than μm. 5. The electrophotographic photosensitive member according to claim 1, further comprising a lower blocking layer between the conductive support and the photoconductive layer. 6. The electrophotographic photosensitive member according to claim 1, further comprising a surface protective layer on the photoconductive layer. 7. The electrophotographic photoreceptor according to claim 1, wherein the photoconductive layer comprises a charge transport layer and a charge generation layer. 8. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the conductive support is made of aluminum according to JIS B060.
The ten-point average roughness (Rz) in No. 1 is 0.05 μm or more and 5
μm or less, a step of washing the conductive support after the processing, and a step of sequentially laminating an undercoat layer and a photoconductive layer on the washed conductive support. A method for producing an electrophotographic photoreceptor. 9. The electrophotographic photosensitive member according to claim 8, wherein the cleaning of the conductive support is carried out mainly by using water and a surfactant. 10. The electrophotographic photoreceptor according to claim 8, wherein the undercoat layer and / or the photoconductive layer are formed by a plasma CVD method in which a discharge is excited at a discharge frequency of 50 MHz to 450 MHz.