JP2706993B2 - Equipment for manufacturing substrates for photoconductive members - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field to which the Invention Belongs] The present invention relates to a method for making a metal body suitable for use as a constituent member of an electric or electronic device, particularly a base for a photoconductive member such as an electrophotographic photosensitive member. The present invention relates to a surface treatment device for a metal body.

[Description of Prior Art]

As a substrate of a photoconductive member such as an electrophotographic photoreceptor,
Where cylindrical or endless belt-shaped metal bodies are used, these metal bodies are required to have a surface shape suitable for the application, and therefore the surface of those metal bodies is subjected to various cutting processes or Polishing is performed.

As the metal body, an aluminum alloy is generally used as an optimal one, and its surface is subjected to the above-described processing to obtain a desired surface, and a light receiving layer according to the intended use is formed on the surface.

However according to the conventional cutting method to grinding processing method, Si-Al-Fe-based in the alloy structure, Fe-Al-based intermetallic compounds such as _{TiB 2, Al, Mg, Ti} , Si, oxides such as Fe there or worse interposed, other possible holes by H ₂ will be present, sometimes surface defects such grain boundary level difference occurring between crystal orientations different neighboring Al tissues occurring.

In addition, when an aluminum alloy is applied to a substrate, a surface with an extremely high cleanliness is used, but the surface of such an aluminum alloy is active even under an ultra-high vacuum of 10 ^-9 mmHg because its surface is active. Then, an oxide film having a thickness of about 30 ° is formed.

Where there is such a problem, a substrate obtained by surface processing by a conventional cutting method or polishing method eventually causes various problems and defects in the function of a photoconductive member manufactured using the same. Become.

That is, for example, when it is an electrophotographic photoreceptor, the photoreceptive layer formed on the substrate becomes poor in uniformity or homogeneity, or has electrical, optical, and / or photoconductive properties. Often becomes non-uniform, causing defects in the image, and eventually becomes unsuitable for practical use. This point is remarkable when the light receiving layer is formed of silicon or a non-single-crystal material mainly containing silicon.

The problem caused by such a conventional processing method is eliminated, and a metal body is surface-processed to produce a component for an electric or electronic device, in particular, a substrate used for an electrophotographic photosensitive member or the like. There is a device described in the issue.

The electrophotographic photosensitive member using the substrate manufactured by this apparatus was satisfactory for the time being. However, there are problems such as the occurrence of image defects due to the fine powder of the base material generated by the collision being embedded in the base, the time required for cleaning after processing the substrate, and the longer processing time of the substrate. Have.

[Object of the invention]

The main objects of the present invention are various physical problems caused by the above-mentioned conventional processing method, a problem that an oxide film is formed on the substrate surface, and fine powder of the substrate material generated by collision is embedded in the substrate. The surface of the metal body is eliminated by eliminating the problem of being a component of an electric or electronic device,
In particular, it is an object of the present invention to provide an apparatus for manufacturing an optimal substrate for an electrophotographic photosensitive member or the like.

Another object of the present invention is to use a substrate obtained by the above-described method and form a desired light-receiving layer on the processed surface, so that the electrical, optical and photoconductive properties are substantially always stable. It has excellent light fatigue resistance, has no deterioration phenomenon even when used repeatedly, has excellent durability and moisture resistance, and has no or almost no residual potential observed. If necessary, hydrogen atoms (H)
It is another object of the present invention to provide an apparatus for manufacturing a substrate suitable for manufacturing a light receiving member having a light receiving layer made of amorphous silicon a-Si (H, X) containing a halogen atom (X).

[Structure and effect of the invention]

The inventors of the present invention have made an object to provide a substrate for an electric or electronic device, particularly an electrophotographic photoreceptor, having an optimum surface shape and free from the problems caused by the above-mentioned conventional surface processing method. As a result of intensive studies, as a result of using rigid rigid spheres and colliding them with a predetermined speed from the side to the surface of a predetermined metal body, for example, when the metal body is an aluminum alloy, any metal The surface of the metal body can be formed into a preferable surface shape without any intervening compounds, metal oxides, etc., and no vacancies, and no occurrence of surface defects such as grain boundary steps. When performed in the presence of a liquid containing a long-chain hydrocarbon, the formation of an oxide film does not occur even under normal pressure conditions, and the fine powder of the base material generated by the collision quickly cleans the liquid. Of the substrate surface The photoreceptive layer mainly composed of a-Si (H, X) is formed by the glow discharge method on the processed surface of the substrate obtained without being removed from the substrate and being embedded on the substrate. The light-receiving layer is uniform and homogeneous, and the light-receiving member is such that light that has passed through the light-receiving layer during use is a layer interface,
Reflected on the surface of the substrate, where they interfere,
It has been found that the image to be formed is efficiently prevented from being striped and that the output image is of extremely excellent quality, and the present invention has been completed based on the knowledge. .

That is, the present invention is a cylindrical rotating container integrally formed with a multi-perforated plate and having a plurality of rigid spheres housed therein,
Substrate holding means rotating coaxially with the container in the container;
In the lower part of the rotating container, a coating liquid retaining means for protecting the surface of the conductive member cylindrical substrate, and circulating the surface coating liquid in the retaining means, at a position substantially horizontal to the axis of the rotating container,
The present invention relates to an apparatus for manufacturing a substrate for a photoconductive member, comprising a jet supply means for jetting the circulating coating liquid.

In addition, the kinetic energy of the hard spheres given by the energy of the surface coating liquid supplied by pressurized ejection is 0.05 m to 2.0 m obtained when the hard spheres fall naturally, preferably 0.1 m to 0.5 m. Corresponding to the
The present invention relates to the above-described apparatus for manufacturing a substrate for a photoconductive member, wherein the coating liquid is ejected at a pressure that gives the energy.

Substrates used for surface treatment with the apparatus of the present invention may be conductive or electrically insulating.

As the conductive substrate, for example, NiCr, stainless steel, Al, C
Metals such as r, Mo, Au, Nb, Ta, V, Ti, Pt, and Pb, and alloys thereof.

Examples of the electrically insulating substrate include films or sheets of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide, glass, ceramics, and paper. It is preferable that at least one surface of these electrically insulating substrates is subjected to a conductive treatment, and a light-receiving layer is provided on the conductive-treated surface.

For example, in the case of glass, NiCr, Al, Cr, Mo,
Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ + Sn
O ₂ ) or the like to provide conductivity by providing a thin film or a metal resin film such as a polyester film such as NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb. , Ta, V,
A thin film of a metal such as Tl or Pt is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, or the like, or the surface is laminated with the metal to impart conductivity to the surface. The shape of the substrate can be any shape such as a cylindrical shape and a plate shape, but the shape can be appropriately determined depending on the application and the desired. For example, if the light receiving member is to be used as an electrophotographic image forming member, it is desirable to have a cylindrical shape for continuous high-speed copying. The thickness of the base is appropriately determined so that a desired light receiving member can be formed. However, when flexibility is required for the light receiving member, the thickness is within a range in which the function as the base is sufficiently exhibited. It can be as thin as possible. However, from the viewpoints of production and handling of the substrate, mechanical strength, etc., usually 10
μ or more.

In the apparatus of the present invention, the surface of the base is treated,
That is, a hard true sphere used for forming a desired uneven shape on the surface or a hard sphere having an uneven surface shape (usually, φ = 0.
For example, various hard spheres made of metal such as stainless steel, aluminum, steel, nickel, and brass, ceramics, or plastics may be used as the material (4 to 2.0 mm). Among these, hard balls made of stainless steel or steel are preferable from the comprehensive viewpoint including durability, cost and the like. And even if the hardness of such a sphere is higher than the hardness of the base,
Alternatively, the hardness may be lower, but when the sphere is used repeatedly, the hardness is preferably higher than the hardness of the base.

Further, in the apparatus of the present invention, the surface coating liquid used for forming the desired irregular shape on the surface of the substrate by using the above-mentioned hard spheres is, in any case, uniformly applied to the surface of the substrate. Like, and as thin as possible,
The coating film formed thereon solidifies as quickly as possible, and the solidified film is washed away by the washing operation without leaving any unevenness, and at the same time the substrate surface is absolutely clean without leaving any drying unevenness (sagging). It is required to be dried to a state. From the above, the surface coating liquid is (a) a low-viscosity liquid, (b) having a charge eliminating action, (c) having a coating action, (d) a coating film to be formed (coat). (E) that the processed surface is dried to an absolutely clean state without leaving any drying unevenness after the coating film (coat) is washed away. It is necessary to satisfy the conditions (a) to (e).

Therefore, a solution obtained by dissolving a long-chain hydrocarbon in an appropriate organic solvent is generally used as the surface coating liquid.

As the long-chain hydrocarbon, a typical example is polybutene. Preferred polybutenes are those represented by the following general formula. That is, Here, n in the formula represents an integer of 3 to 40. Among the polybutenes represented by the above general formula, those in which n is 3 to 20 are particularly preferred.

In addition, the polybutene itself includes the above (a).
There are some which satisfy the conditions of (e) to (e), and in that case, the surface coating liquid can be substantially composed of the polybutene.

The organic solvent is the long-chain hydrocarbon (polybutene)
May be dissolved to give a surface coating solution satisfying the above conditions (a) to (e). Examples thereof include ether, heptane, toluene, trichloroethylene, and trichloroethane. And the like. However, among these organic solvents, trichloroethane is the most preferable for the following reasons.

That is, trichloroethane dissolves the polybutene extremely efficiently, and the resulting liquid has a moderate viscosity, is extremely malleable, and forms a uniform and extremely thin film covering the surface of the substrate. The thin film does not interfere with the formation of the spherical trace depression on the substrate surface by the impinging hard spheres, and causes the solidification of the thin film immediately after the formation of the spherical trace depression, which is further used for the cleaning operation of the solidified film. The solidified film is quickly eluted from the processed surface of the substrate and washed away, and the exposed processed surface of the substrate is dried to an absolutely clean state without leaving any cleaning unevenness.

The surface coating solution obtained by dissolving the polybutene in trichloroethane is important in the liquid composition ratio of both substances, and the polybutene is used in a ratio of 1: 4 to 4: 1 with respect to trichloroethane.
It is usually within the range, but the ratio is most preferably 1: 1.

By the way, the substrate processed by the device of the present invention is
To explain the case where a rigid true sphere is used, the surface shape is as shown in FIG. That is, FIG.
In the example shown in FIG. 2, a plurality of spheres 23, 23,... Having substantially the same diameter are made to fly with substantially the same kinetic energy by jetting a surface coating liquid toward different portions of the surface 22 of the substrate 21. A plurality of spherical trace depressions 24, 24, 24,... Having substantially the same curvature (R) and substantially the same width are uniformly formed so as to overlap each other to form a regular irregular shape. Things. In this case, in order to form the dents 24, 24, which overlap each other, it is necessary to jump and collide the spheres 23, 23,. Needless to say.

The example shown in FIG. 4 (B) shows two types of plural spheres 23, 23... And 23 ′, 2 having different diameters toward the surface 22 of the base 21.
3 ′ ... are sputtered with substantially the same kinetic energy or different kinetic energies by the ejection of the surface coating liquid, and two types of spherical trace depressions 24, 24 ... and 24 ′ having different curvatures and widths are formed on the surface of the substrate. , 24 'are uniformly generated so as to overlap each other to form irregularly shaped irregularities.

Further, in the example shown in FIG. 4C (front view (upper) and cross-sectional view (lower) of the surface of the base), a plurality of spheres 24, 24, having substantially the same diameter, are directed toward the surface 22 of the base 21. By spraying the surface coating liquid, the spheres are jumped with almost the same kinetic energy alone or in a state where a plurality of spheres are overlapped, and a plurality of depressions 24, 24 having substantially the same diameter and substantially the same width are formed on the surface of the base. The present invention relates to a support which is uniformly formed so as to overlap each other to form irregular shapes irregularly.

The base having the surface of the spherical trace concave shape shown in FIGS. 4 (A) to 4 (C) is manufactured by the apparatus of the present invention, but in FIGS. 4 (A) to 4 (C). For simplicity, the description of the surface coating liquid is omitted.

FIG. 6 is a schematic sectional view of an image forming member which is an example of the photoconductive member. In the figure, 61 is a substrate, 62 is a charge injection blocking layer, 63 is a photoconductive layer, and 64 is a surface protective layer.

The charge injection blocking layer is made of, for example, a-Si containing a hydrogen atom and / or a halogen atom, and is used as a substance that controls conductivity, and is commonly used as an impurity of a semiconductor. Contains atoms of elements belonging to Group V. The thickness of the charge injection blocking layer is preferably 0.
01-10 μm, more preferably 0.05-8 μm, optimally 0.07
It is preferable that the thickness be 5 μm.

Instead of the charge injection blocking layer, for example, Al ₂ O ₃ , SiO ₂ , Si
_A barrier layer made of an electrically insulating material such as ₃ N ₄ or polycarbonate may be provided, or the charge injection blocking layer and the barrier layer may be used in combination.

The photoconductive layer is made of, for example, a-Si containing a hydrogen atom and a halogen atom, and optionally contains a material that controls conductivity different from that used for the charge injection blocking layer. The thickness of the photoconductive layer is preferably 1 to 100 μm, more preferably 1 to 80 μm, and most preferably 2 to 50 μm.

The surface protective layer is made of, for example, SiCx, SiNx or the like, and the layer thickness is preferably 0.01 to 10 μm, more preferably 0.02 to 5 μm.
m, and most preferably 0.04 to 5 μm.

FIG. 5 shows an apparatus for producing a photoconductive member by the glow discharge decomposition method. The deposition tank 41 is composed of a base plate 42, a tank wall 43, and a top plate 44.
A support according to the invention, for example made of an aluminum alloy, on which a cathode electrode 45 is provided and on which an a-Si deposited film is formed
Reference numeral 46 is provided at the center of the cathode electrode 45, and also serves as an anode electrode.

In order to form an a-Si deposited film on a support using this manufacturing apparatus, first, the source gas inflow valve 47 and the leak valve 48 are closed, the exhaust valve 49 is opened, and the inside of the deposition tank 41 is exhausted. . When the reading of the vacuum gauge 40 becomes 5 × 10 ⁻⁶ Torr, the source gas inflow valve 47 is opened, and the mixture ratio is adjusted to a predetermined mixture in the mass flow controller 51, for example, SiH ₄ gas, Si ₂ H ₆ gas. The opening degree of the exhaust valve 49 is adjusted with reference to the reading of the vacuum gauge 40 so that the pressure in the deposition tank 41 becomes a desired value with the raw material mixed gas using SiF ₄ gas or the like. After confirming that the surface temperature of the drum-shaped support 46 is set to a predetermined temperature by the heater 52, the high-frequency power supply 53
Is set to a desired electric power to generate glow discharge in the deposition tank 41.

During the layer formation, the drum-shaped support 46 is rotated at a constant speed by the motor 54 in order to achieve uniform layer formation. In this way, a-
A Si deposition film can be formed.

An apparatus for manufacturing a substrate for a photoconductive member according to the present invention will be described below with reference to examples shown in the drawings, but the apparatus is not limited thereto.

FIG. 1 is a schematic cross-sectional view showing a typical example of an apparatus for manufacturing a substrate for a photoconductive member according to the present invention.

In FIG. 1, reference numeral 1 denotes a peripheral wall of the apparatus. The peripheral wall forms a circular shape portion 11 to form a space A corresponding to the shape, and a bottom center portion of the circular shape portion projects into a lower semicircle shape 12 to serve as a means for retaining the coating liquid. A semicircular space B is formed. The apparatus peripheral wall 1 is integrally formed with a pressure-resistant, heat-resistant and chemical-resistant metal plate made of, for example, stainless steel so as to completely seal the inside.

The device surrounding wall 1 forms a housing having a horizontally long appearance, and the housing is hermetically fixed by both side walls (not shown) having a shape formed by spaces A and B. Reference numeral 2 denotes an apparatus support table, and the protrusion 12 is fitted around the support table to support and fix the entire apparatus.

Numeral 3 is a cylindrical rotary container which is installed in the center of the space A with a space having an appropriate width, and is formed integrally with a multi-perforated plate such as a punching metal, and has a housing side wall (not shown). ) Is rotatably supported at both ends,
One end thereof is connected to a driving means (not shown) so as to rotate as a whole. Are rigid spheres or rigid spheres having an irregular surface shape, and are accommodated in the rotating container 3, and when the container is rotated, the effect of the perforated irregularities on the inner wall surface of the container is obtained. As shown in the drawing, the container is lifted to a position near the horizontal point of the rotating container by the centrifugal force as shown in FIG. Numeral 5 is a cylindrical substrate (for example, an aluminum cylinder for producing a support), and a driving means (not shown) is provided in the rotating container 3 by a housing side wall coaxially with the container.
And is installed so as to be pivotally supported on a rotating shaft 6 connected to the rotating shaft 6.

The surface coating liquid 7 extends to the center of the space A on the side of the cylindrical rotary container 3 and is fixed from the side of the peripheral wall 1 by an appropriate fixing means, and has liquid ejection holes 71, 71,. It is a spout tube.

Reference numeral 8 denotes an opening of a supply pipe 81 for the surface coating liquid 9 communicating from the side wall of the housing 1 to the semicircular space B. The feed pipe 81
It communicates with the ejection pipe 7 via a pump means. Reference numeral 82 denotes a reservoir tank for the surface coating liquid, and a discharge pipe 84 provided with a valve means 84 'is provided at the bottom of the tank to remove unnecessary substances such as metal fine powder settled at the lower portion due to the reservoir. So that the surface coating solution is always kept in a clear state. Then, the discharged surface coating liquid is supplied from the supply tank 83. The surface coating liquid needs to be replaced after a certain number of cycles, in which case the valve means 82 'is closed and the valve means 8 is closed.
4 'is opened, the surface coating liquid in the system is extracted from the discharge pipe 84, and new surface coating liquid is supplied from the supply tank 83 into the system.

FIG. 2 is a schematic sectional view showing another example of the apparatus for manufacturing a substrate for a photoconductive member according to the present invention, in which liquid stopping bars 32, 32,. Are fixedly installed on the inner peripheral surface of the wall in parallel with the longitudinal direction, and rigid ball locking rod-shaped bars 31, 31,... Are fixedly installed.

The operation of the apparatus of the embodiment shown in FIG. 2 is the same as that of the apparatus shown in FIG.
Flow smoothly into the rotating container 3, and the lifting of the rigid spheres 4, 4,.

The apparatus of the embodiment shown in FIG. 3 is a modification of the apparatus of the embodiment shown in FIG. 2, in which locking bar-shaped bars 31, 31,.
The blade bars 31 ', 31',... These blade bars 31 ', 3
The provision of 1 ′,... Allows the rigid spheres 4, 4,... To be lifted more smoothly, and at the same time allows the rigid spheres 4, 4,. It will be a place to be.

In order to explain the operation of the apparatus for manufacturing a substrate for a photoconductive member of the present invention shown in FIG. 1, a cylindrical substrate 5 is set in a rotating container 3 in which a required number of rigid spheres 4, 4,. , Supply tank
A surface coating liquid [for example, polybutene + trichloroethane (1: 1) liquid] is supplied from 83 and the surface coating liquid 9 is jetted from the ejection hole 71 of the ejection pipe 7 to the surface of the rotary container 3. The sprayed surface coating liquid flows down through the holes in the multi-perforated wall of the rotary container 3 into the rotary container, reaches the surface of the cylindrical substrate installed in the system, and forms a liquid film 9 'on the surface. To form The remaining surface coating liquid further flows down and wets the surface of the rigid spheres 4, 4,... Accommodated in the lower part of the rotary container, and the liquid further flows through the hole of the multi-perforated wall of the rotary container 3 to form the space B. Flows into. The surface coating liquid accumulated in the space B enters the accumulation tank 82 via the feed pipe 81 by the pump action, stays there, and is circulated to the jet pipe 7. When a certain amount of the surface coating liquid is supplied into the system, the valve means 83 'is closed to stop the supply from the supply tank. At this point, the rotation of the rotating container 3 and the cylindrical base 5 is started.

The rotating container 3 and the cylindrical substrate 5 rotate in the forward direction or the reverse direction, but preferably in the opposite directions.

The rotation speed of the rotating container 3 is preferably such that the hard spheres are arranged in one or two layers at the injection position. If the rotation speed is too low, the centrifugal force acting on the sphere is so small that the rigid spheres are not lined up neatly, and the height at which they can be lifted along the inner wall surface becomes low. On the other hand, when the rotation speed is high, the hard spheres are aligned neatly by the centrifugal force and the inner wall surface can be lifted to a high position. However, in order to fly the hard spheres with the coating liquid, it is necessary to increase the injection pressure in opposition to the centrifugal force, and the perforation rate of the rotary container is substantially reduced, thereby reducing the processing efficiency.

On the other hand, the cylindrical substrate 5 is adjusted to the speed at which the hard spheres 4, 4,.

By operating as described above, the formation of the trace depression on the surface of the cylindrical substrate is performed in a state where the surface of the cylindrical substrate is completely covered with the thin liquid film of the surface coating liquid.

The above operation can be performed under the conditions of normal pressure and normal temperature, but if it is desired to increase the collision of the hard sphere against the surface of the cylindrical base, the condition where the ejection pressure of the liquid is increased or the vacuum condition is used. It is preferable to carry out.

After a certain time, the rotation of the rotating container 3 and the cylindrical base 5 is stopped,
When the supply of the surface coating liquid is stopped, a cylindrical substrate having a thin solidified film covering the entire surface and having a spherical trace concave shape is obtained. Even if this cylindrical substrate is taken out of the system and stored as it is until it is used, its surface is completely shielded from the outside air by a solidified film. However, there is no chance that a problem such as formation of an oxide film on the surface occurs.

According to the above-described apparatus of the present invention, after the treated cylindrical substrate is unloaded, a new cylindrical substrate is loaded into the system, and the above-described operation can be continuously repeated with respect to the substrate. The substrate can be manufactured continuously.

The apparatus according to the present invention is designed so that any size cylindrical body can be used regardless of its size. As an example, for a cylindrical rotating container 3, 30
The size is 0mm (diameter) x 450mm (length), and the liquid ejection holes 71
Distance between the horizontal position of the cylindrical rotating container 3 and 50 mm
100 mm.

The surface coating liquid jet pipe 7 has a diameter of about 15 mm,
The nozzle-type liquid ejection holes 71, 71,... Have an angle of about 5 mm to 50 mm so that the angle of the ejected liquid therefrom is not too large and the ejected liquids do not interfere with each other. The rotating shaft 6 can be replaced according to the size (diameter and length) of the surface-processed cylindrical substrate.

As described above, the cylindrical rotary container 3 is integrally formed with a multi-perforated plate such as a punched metal, but the size of the hole is smaller than that of the rigid sphere used in order to prevent the rigid sphere from jumping out of the container. Small (for a hard sphere of 0.4-2.0mm,
The hole is preferably about 0.3 to 1.9 mm). The higher the piercing rate (the ratio of the area of the hole to the total area of the container) with respect to the container 3 is, the higher the work efficiency is, but the strength of the container (about 1.5 kg of 0.6 mm SUS ball is required) is required. Depending on the material of the container, the maximum perforation rate is about 71% to 78%,
Usually, about 50% is preferable from the viewpoint of workability.

The liquid stopping bars 32, 32,... And the hard ball locking bar bars 31, 31,.
Are provided at regular intervals of 100 mm to 150 mm.

In the above description, the case where the number of cylindrical substrates is one has been described. However, in the apparatus of the present invention, it is needless to say that the surface of a plurality of cylindrical substrates can be processed by one operation. It is possible.

In any case, the substrate obtained by processing the surface by the above-described operation is subjected to a solvent washing treatment to elute the solidified film, dry the surface in an absolutely clean state, and then form a film (photoreceptor). When the film is carried into a layer forming (not shown) apparatus, the solvent washing treatment can be performed according to the apparatus of the present invention.

In this case, after finishing the surface processing, the surface coating liquid is removed from the system to make the inside of the system clean, and then the cleaning liquid is supplied from a cleaning liquid (for example, trichloroethane) tank (not shown) to the supply pipe 81.
To the jet pipe 7 through the jet port 71, and jets laterally from the jet hole 71.
At that time, the rotating container 3 is stopped, and the cylindrical base 5 is rotated. The cleaning liquid accumulated in the space B is circulated or the valve 82 'is closed, the valve 84' is opened, and the cleaning liquid is discharged out of the system through the discharge pipe 84.

The substrate obtained by surface processing with the apparatus of the present invention described above has a desired spherical trace depression formed without leaving a flat portion on the surface, and the entire surface is covered with a solidified film and is shielded from the outside air. If the washing liquid is washed using a solvent such as trichloroethane, elution of the solidified film proceeds extremely efficiently, and the surface can be dried very efficiently without leaving any drying unevenness. It is optimal as a substrate for a photoconductive member.

The operation and effect of the present invention described above can be clearly understood from the following experimental results.

Experiment 1 In the apparatus shown in FIG. 1, the size: 300 mm (diameter) ×
Using a cylindrical rotating container with a diameter of 450 mm (length), a hole diameter of 0.5 mm and a piercing rate of 50%, and a device containing 2.5 kg of SUS hard spheres of 0.6 mm diameter in the container, 80 mm (diameter) A base cylinder made of aluminum alloy having a size of 360 mm (length) and a thickness of 5 mm is set on the rotating shaft 6. Polybutene: trichloroethane =
The (1: 1) surface coating solution was treated for 25 minutes at an ejection pressure of 0.6 kg / cm ² from the ejection port 71 and at a container rotation speed of 30 rpm.

The surface-finished substrate cylinder is taken out of the apparatus and washed with trichloroethane [warm bath (ultrasonic wave), cold bath,
Steam bath], and a photoconductive member having the structure shown in FIG. 6 is manufactured using the photoconductive member manufacturing apparatus shown in FIG. 5 according to the glow discharge decomposition method described in detail above under the following conditions. did.

In this case, the apparatus shown in FIG. 1 with a variable liquid jet outlet mounting device was used. Then, the opening angle of the liquid jet port is 0 °, 45 °, with respect to the horizontal (0 °).
Other conditions were the same as above, with −45 ° and 60 °. A plurality of surface-processed drums of the obtained drum were washed as described above, and formed into a film as described above to produce a plurality of electrophotographic photosensitive drum samples.

Evaluation A plurality of electrophotographic photoreceptor drum samples obtained in this manner were measured using a known image exposure apparatus at a wavelength of 780 nm and a spot diameter of 8
An image is exposed by irradiating a laser of 0 μm, an image is obtained by performing development and transfer, and an image defect is obtained for the obtained image.
The occurrence of image unevenness and interference fringes was observed. The observation results are summarized in Table 2.

As is evident from the results shown in Table 1, the substrate cylinder surface-treated by the apparatus of the present invention having the liquid ejection port mounted substantially horizontally is extremely suitable as a substrate for a light receiving member such as an electrophotographic photosensitive member. And provided a light-receiving member having excellent characteristics.

It has also been found that the spread angle of the liquid at the injection port is preferably set to 10 to 30 degrees. And when it is 10 degrees or less, it is necessary to reduce the cut cross section of the ejected liquid,
The hydraulic pressure kgf / cm ² actually applied to the rotating container surface increases,
If the surface of the container is significantly damaged, and if it is set to 30 degrees or more, the spreading area on the surface of the container becomes large, and the injection pressure is increased.
It was also found that it was necessary to set the value higher than the predetermined value.

Experiment 2 Using the apparatus shown in FIG.
1 kgf / cm ^2, to 0.4 kgf / cm ² and 1.0 kgf / cm ^2, except that the opening angle of the liquid ejecting port to 0 ° relative to the horizontal (0 °) was treated in the same manner as in Experiment 1. The obtained product was washed in the same manner as in Experiment 1, and an electrophotographic photosensitive drum was produced. Thus, a plurality of electrophotographic photosensitive drum samples were prepared.

Evaluation Each of the plurality of electrophotographic photosensitive drum samples obtained in Experiment 2 was exposed to an image with a laser having a wavelength of 780 nm and a spot diameter of 80 μm using a known image exposure apparatus, and developed and transferred to perform image transfer. And the occurrence of image defects, image unevenness, and interference fringes was observed for the obtained image. Table 3 shows the observation results.

Experiment 3 and Experiment 4 (Experiment 3) Using an apparatus shown in FIG. 2 using a rotating container provided with a liquid stopper bar 32 and a locking rod-like bar, the opening angle of the liquid ejection port was adjusted. The treatment was carried out for 22 minutes in the same manner as in Experiment 1 except that the angle was 0 ° with respect to the horizontal (0 °). After washing the obtained surface-treated drum in the same manner as in Experiment 1, a photosensitive drum for electrophotography was produced.

(Experiment 4) Using the apparatus shown in FIG. 3 using a rotating container provided with a liquid stopper bar 32 'and a grade bar, the opening angle of the liquid ejection port was set to be horizontal (0 °). , And the treatment was carried out in the same manner as in Experiment 1 except that the treatment time was set to 20 minutes. After washing the obtained surface-treated drum in the same manner as in Experiment 1, a photosensitive drum for electrophotography was produced.

Evaluation The electrophotographic photosensitive drums obtained in Experiments 3 and 4 were subjected to wavelength 780 nm and spot diameter 80 μm using a known image exposure apparatus.
An image was exposed by irradiating the laser, and an image was obtained by performing development and transfer, and the occurrence of image defects, image unevenness, and interference fringes in the obtained image was observed. The observation results are summarized in Table 4.

As is clear from the results shown in Table 4, the second aspect of the present invention
It has been found that the substrate cylinder surface-treated by the apparatus shown in FIGS. 3 and 3 gives a light receiving member having extremely good characteristics in a short time.

[Summary of Effects of the Invention] As described above, instead of supplying the coating liquid as a shower at an extremely low pressure, the coating liquid is ejected from a side surface at a predetermined pressure. Thus, the fine powder of the base material generated by the above-mentioned process is not embedded in the base, and the unevenness formed by the collision can be narrowly distributed to a certain size.

(2) Kinetic energy is applied to the rigid sphere attached to the inner wall of the rotating container to collide with the surface of the base cylinder, so that the condition setting range is widened and the condition setting is easy.

(3) In order to obtain a desirable state of a spherical trace depression based on the energy of natural fall, the rotating container should be φ500 mm to φ1
It is necessary to have a large diameter of 000mm, but (2)
Since the kinetic energy is applied as described above, the required minimum rotating container diameter is sufficient.

(4) Since the coating liquid supply system is pressurized, the container and the like can be quickly cleaned with a cleaning liquid such as triethane when the equipment is changed.

[Brief description of the drawings]

FIG. 1 (A) is a schematic cross-sectional view showing an example of the apparatus for manufacturing a substrate for a photoconductive member of the present invention. FIG. 1B is an enlarged sectional view of the rotating container. FIG. 2 (A) is a schematic partial sectional view showing another embodiment of the apparatus for manufacturing a photoconductive member base according to the present invention. FIG. 2 (B) is an enlarged sectional view of the rotating container of the apparatus of FIG. 2 (A). FIGS. 3 (A) and 3 (B) are a schematic view and an enlarged sectional view of a part of a rotating container wall of the apparatus of FIG. 2 (A) for showing another example of the present invention. FIGS. 4 (A), (B) and (C) are schematic views for explaining the uneven shape of the substrate surface formed by the apparatus of the present invention. FIG. 5 is a view showing an apparatus for manufacturing a photoconductive member by a glow discharge decomposition method. FIG. 6 is a schematic cross-sectional view of an image forming member according to Examples and Comparative Examples. 1, 2 and 3, 1 ... peripheral wall of the device (housing), 2 ... support base, 3 ... rotating container, 4 ... rigid sphere, 5 ... cylindrical body, 6 ... rotating shaft, 7 ... Ejection pipe, 8 ... Supply pipe opening, 9 ... Surface coating liquid, 11 ... Circular part, 12 ... Semi-circular projection, 31 ... Lock bar-shaped bar, 31 '... Blade・ Bar, 32: Liquid stop bar, 71: Liquid ejection, 81: Feeding pipe, 82: Reservoir tank, 83: Supply tank, 84: Discharge pipe, 82 ', 83', 84 ' ... Valve means. In FIG. 4, 21... Base, 22... Surface, 23, 23 ′ sphere, 24, 24 ′, recess. In FIG. 5, 41: deposition tank, 42: base plate, 43: tank wall, 44: top plate, 45: cathode electrode, 46: support (anode electrode), 47: source gas inflow Valve, 48 Leak valve, 49 Exhaust valve, 50 Vacuum gauge, 51 Mass flow controller, 52 Heater, 53 High frequency power supply, 54 Motor. In FIG. 6, reference numeral 61 denotes a base, 62 denotes a charge injection blocking layer, 63 denotes a photoconductive layer, and 64 denotes a surface protective layer.

 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Keiichi Murai 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-B-63-20912 (JP, B2)

Claims (3)

(57) [Claims] 1. A cylindrical rotary container integrally formed of a multi-perforated plate and having a plurality of rigid spheres housed therein, a substrate holding means rotating in the container coaxially with the container, A coating liquid accumulating means for protecting the surface of the conductive member cylindrical substrate at a lower portion of the rotating container, and a surface coating liquid in the accumulating means is circulated. An apparatus for manufacturing a substrate for a photoconductive member, comprising: a jet supply means for jetting a coating liquid. 2. The method according to claim 1, wherein the kinetic energy of the hard spheres given by the energy of the coating liquid supplied under pressure is 0.05 to 2.0 m, preferably 0.1 to 0.5 m, obtained when the hard spheres fall naturally. 2. The device according to claim 1, wherein the coating liquid is ejected at a pressure which corresponds to the energy of the position and which gives said energy. 3. The position where the circulating coating liquid is ejected is located in a range of 45 degrees upward and 45 degrees downward from a position horizontal to the axis of the rotating container. The device according to (1).