JP2987922B2 - Photoreceptor whose surface is roughened to cross lines - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreceptor having a surface protective layer, and more particularly, to a photoreceptor having a surface roughened by countless intersecting linear scratches. And a photoreceptor having a surface protective layer formed thereon.

2. Description of the Related Art In recent years, as a photosensitive layer used in an electrophotographic photosensitive member,
Various materials composed of an inorganic photoconductive material such as selenium or an organic photoconductive material have been proposed. In general, a photosensitive layer having a low hardness is exposed to abrasion of a transfer sheet, a cleaning member, a developer, etc. in repeated use. The body is shaved and easily scratched.

Therefore, in order to solve such a problem, a technique of providing a surface protective layer on the surface of a photosensitive layer having insufficient hardness has been proposed.

As one type of such a surface protective layer, a vacuum thin film such as a plasma-polymerized film of an appropriate organic compound or a vapor-deposited film of a metal compound has been proposed (for example, JP-A-60-32055).

Problems to be Solved by the Invention A photoreceptor having such a surface protective layer is more durable than a photoreceptor having no surface protective layer, and has a sufficient film strength for long-term use under normal temperature and normal humidity. However, the moisture resistance after long-term use cannot be said to be sufficient, and repeated use in a high-humidity environment may cause blurring, flow, etc. of the copied image.

The present invention has been made in view of such circumstances,
Conventionally, instead of forming the surface protection layer directly on the untreated photosensitive layer, the surface of the photosensitive layer was roughened by countless intersecting linear scratches, and then the surface protection was made of a vacuum thin film. The problem is solved by forming a layer on the photosensitive layer.

Means for Solving the Problems That is, the present invention relates to a photoconductor having a photoconductive photosensitive layer on a conductive support and a surface protective layer formed of a vacuum thin film on the photoconductive photosensitive layer. A vacuum thin film is formed on the photoconductive photosensitive layer roughened by the intersecting linear scratches, and the average value of the crossing angles of the linear scratches is 30 to 150 degrees, which is perpendicular to the photoconductor surface moving direction. The average value of the angles at which the reference line in the direction to intersect each linear scratch is 15 to 75 degrees, and the average value of the length between the adjacent intersections of the reference line and each linear scratch is
The present invention relates to a photoreceptor, wherein the photosensitive member has a width of 200 μm or less and an average value of the width of each linear scratch is 30 μm or less.

In the photoconductor of the present invention, a photoconductive photosensitive layer is formed on a conductive support. Such a photosensitive layer is not particularly limited as long as the photosensitive layer generally requires a surface protective layer. Specifically, a selenium-based photosensitive layer, for example, one having a single-layer structure of a selenium-arsenic alloy, one having a laminated structure in which selenium and a selenium-tellurium alloy are provided in this order, and various photoconductive substances dispersed in an appropriate resin And a resin layer provided on a photosensitive layer having a high hardness such as an a-Si photosensitive layer.

The present invention forms countless linear scratches on the surface of the photosensitive layer. In the present invention, the linear flaw is formed so as to have a certain flaw shape and surface roughness (depth of flaw) described below.

In FIG. 1, a part of the surface of the photosensitive layer is extracted, and the shape of the scratch on the surface is schematically shown.

Figure 1 shows a regular wound shape,
As shown in FIG. 2, this shape may be irregular or irregular.

The shape of the flaw is determined by the intersection angle (θ (degree)) and the inclination angle (α,
β (degree)), pitch (l (μm)), width of the wound (w (μ
m)).

In the present invention, the intersection angle is 30 to 150 degrees, preferably 60 to 120 degrees, and the inclination angle, (α, β), is 15 to 75 degrees, preferably 30 to 60 degrees. If it is smaller than these values, problems such as toner filming, fusing, blade abrasion, and generation of image noise of polishing streaks occur. On the other hand, if the values are larger than these values, problems such as residual toner after wiping and generation of image noise of polishing stripes occur.

The pitch (l) is 200 μm or less, preferably 120 μm or less. The lower limit is not particularly limited, but may be about 1 μm. The width (w) of the scratch is 30 μm or less, preferably 20 μm
It is as follows. The lower limit may be about 1 μm.
If the pitch or the width of the scratch is too large, there is no effect on improving the moisture resistance, and the resolution of the image is reduced.

In the present invention, the shape of the wound (θ, α, β, l, w)
Is indicated by the value obtained as follows.

First, a part of the surface of the photoreceptor after roughening the surface of the photosensitive layer or forming a vacuum thin film is photographed with an optical microscope (magnification ×
75, × 300 each one). Next, on the photograph, a 0.25 mm length portion perpendicular to the direction in which the photoreceptor surface moves in actual use is extracted, and the length direction is set as a reference line.

The intersection angle (θ) (degree) of the wound is measured for each wound line that intersects with the reference line by measuring the angle between adjacent upper right and upper left scratches (the angle located in a direction parallel to the reference line). The arithmetic parallel value is obtained and is set to θ.

The angle of inclination (α, β) (degree) of the wound is measured by measuring the angle at which the reference line intersects with each of the wound lines and calculating the arithmetic average of the angles.
β (α: the angle between the upper right scratch and the reference line, β: the angle between the upper left scratch and the reference line).

The pitch (l) (μm) of the flaw is obtained by measuring the length between intersecting points of intersection between the reference line and each flaw line, calculating the arithmetic average value, and setting this to l.

The width (w) (μm) of the flaw is obtained by measuring the thickness of each flaw line that intersects with the reference line, obtaining the arithmetic average value, and defining this as w.

Each of the above numerical values is set so that the arithmetic average value in a portion randomly extracted from three or more places from the surface of the photoconductor falls within the above range.

Maximum height (Rt) for surface roughness (depth of scratch)
(Μm) and center line average roughness (Ra) (μm).

The maximum height (Rt) (μm) is 0.05 to 0.4 μm, preferably 0.06 to 0.3 μm.

The center line average roughness is 0.008 to 0.025 μm, preferably 0.00
9 to 0.02 μm.

If the maximum height (Rt) or the center line average roughness (Ra) is smaller than the above range, there is no effect on the improvement of moisture resistance. Problems such as filming, fusion, and generation of image noise of polishing streaks occur.

In the present invention, the maximum height (Rt) and the center line average roughness (Ra) refer to those measured according to the method described in JIS B0601-1982.

As shown in Fig. 5, the maximum height (R _t ) is defined as the interval between the two straight lines when the extracted portion is sandwiched between two straight lines parallel to the parallel line of the portion extracted by the reference flow from the roughness curve. The value measured in the direction of the vertical magnification of the curve and expressed in micrometers (μm).

The “roughness curve” is 0.02 from the cross-sectional curve of the reference length (the contour that appears at the cut edge when the workpiece is cut).
5 shows a curve obtained by cutting off a surface waviness component longer than a wavelength of 5 mm.

The “reference length” is a length of a portion obtained by extracting a fixed length of the cross-sectional curve. In the present invention, 2.5 mm is used as the reference length.

The center line average roughness (Ra) is obtained by extracting a portion having a measurement length 1 from the roughness curve in the direction of the center line, setting the center line of the extracted portion as the X axis and the direction of the longitudinal magnification as the Y axis. When a curve is represented by y = f (x), a value obtained by the following equation is represented by a micrometer (μm).

The “center line” refers to a straight line in which, when a straight line parallel to the average line of the roughness curve is drawn, the area surrounded by the straight line and the roughness curve is equal on both sides of the straight line.

The method of roughening the surface by applying innumerable intersecting linear scratches to the surface of the photosensitive layer is not particularly limited,
For example, natural fibers (animal hair such as wool, deer, rabbit hair, cotton,
Hemp, etc.), chemical fibers (rayon, acetate, nylon,
Polypropylene, acrylic, polyester, Teflon, etc.), glass fiber or stainless steel fiber, etc., solidified with resin, or three-dimensionally entangled by the action of moisture, heat, pressure, etc. Mechanical polishing means (buff abrasion, brush polishing, etc.) for pressing and rubbing a cloth or brush with the same.

When the mechanical polishing means is used as described above, an abrasive (particles made of a resin or an inorganic substance), water, a surfactant, a cutting oil, or the like may be interposed between the rubbing member and the photosensitive layer. It is not necessary. When an abrasive is used, a felt, a cloth, or a brush in which abrasive particles are produced or bonded may be used.

The surface roughness is determined by the type, size, thickness or density of the fiber, or, if abrasive particles are used, the type of abrasive particles, particle shape, particle size, particle size distribution, amount, and the pressing force of the polishing machine. , Can be controlled by the rubbing force.

In particular, the organic tourism layer is formed by dipping,
When the surface is extremely smooth, it is effective to roughen the surface by performing buff polishing, brush polishing, etc. while discharging a liquid in which abrasive particles are dispersed in a solvent such as pure.

For example, a wool felt disk-shaped buff (diameter 20c
When the photosensitive drum having a resin-dispersed organic photosensitive layer having a diameter of 80 mm and a length of 330 mm in (m) is roughened by buffing, polishing agent: WA # 6000 (trade name; Fujimi Abrasive Industry) Abrasive material : 2.5g / Discharge: 1 / min Drum rotation speed: 100-500rpm Buff rotation speed: 50-1000rpm Buff feed: 0.3-5cm / sec Buff center deviation: 4.5-6cm Buff load: Under polishing conditions of 0.5-7kg And a surface viscosity suitable for the present invention. Of course, the above conditions are exemplary,
The conditions for achieving the surface roughness of the present invention are not limited at all.

Further, in the present invention, it is necessary to control the angles (θ, α, β) of the linear scratches on the surface of the photosensitive layer.

When buffing is performed to form a linear scratch on the surface and roughen the surface, the angle of the scratch can be substantially controlled by the following equation.

In the formula, Bv: the velocity component in the tangential direction at the outer edge of the buff Bx: the component in the longitudinal direction of the photoreceptor of the buff moving speed by scanning Dy: the velocity component in the tangential direction on the outer peripheral surface of the drum R: buff diameter L: buff center deviation Therefore, the angle of the flaw can be freely controlled by adjusting the number of rotations of the buff, the number of rotations of the photosensitive drum, the moving speed of the buff, and the amount of buff center deviation.

In the case of brush polishing, as shown in FIG. 6, two brush rollers are arranged in a non-parallel manner, the photoreceptor is rotated, and the brush roller is pressed and rotated while reciprocating in the direction of arrow a.

Also, as shown in FIG. 7, the brush roller is arranged in parallel with the longitudinal direction of the photoconductor, the photoconductor is rotated, and the brush roller is pressed and rotated while reciprocating the brush roller in the direction of arrow b. Is also good.

The angles (θ, α, β) of the surface flaw can be controlled by appropriately setting the arrangement, the number of rotations, the moving speed, and the like of the brush roller and the photoconductor.

A vacuum thin film is formed on the surface of the photosensitive layer having the above-mentioned surface flaw to form a surface protective layer. In this way, a photoreceptor in which the photosensitive layer (2) and the surface protective layer (3) are sequentially formed on the conductive support (1) is obtained (FIG. 8). As such a surface protective layer (3), an amorphous hydrocarbon film formed by a plasma polymerization method, or Al ₂ O ₃ , Bi ₂ O ₃ , Ce ₂ O ₃ , Cr ₂ O ₃ , In
₂ O ₃ , MgO, SiO, SiO ₂ , SnO ₂ , Ta ₂ O ₃ , TiO, TiO ₂ , Zr
Metal oxides such as O ₂ and Y ₂ O ₃ , metal nitrides such as Si ₃ N ₄ and Ta ₂ N, and metal sulfides such as MgF ₂ , LiF, NdF ₂ , LaF ₂ , C ₃ F ₂ and CeF ₃ Metal compound films such as metal carbides such as SiC, TiC, and metal sulfides such as ZnS, CdS, and PbS are formed using a so-called vacuum thin film forming technique such as a vapor deposition sputtering method or an ion plating method. Can be

When a surface protective layer is provided by a plasma polymerization method, a sputtering method, an ion plating method, or the like, the photosensitive layer under the protective layer is protected from being deteriorated by bombardment of electrons or ions in plasma, heat or the like. Once on
A photoreceptor having a configuration in which a resin layer is provided has been proposed (for example, Japanese Patent Application Laid-Open No. Hei 01-133303) (FIG. 9), but in the case of a photoreceptor having such a configuration, whatever the type of the photosensitive layer is, By applying the present invention, durability and moisture resistance after printing are improved.

Due to the film stress inherently contained in the vacuum thin film on the surface of the photosensitive layer subjected to the surface roughening treatment according to the present invention, as shown in FIGS. , Into the film thickness direction. As a result, the photosensitive layer surface
Numerous spots are isolated like islands by the cracks. Therefore, it is considered that the surface flow, which is a cause of image blur and flow, is prevented by the presence of the crack portion, and problems such as deterioration of moisture resistance after long-term use, blur of the copied image, and flow can be solved. I have.

As another effect of the present invention, it is possible to prevent an increase in residual potential after repeated copying and generation of streak-like image noise due to a decrease in sensitivity. This effect is remarkable when the surface protective layer is provided on the organic photosensitive layer and the resin layer. It is considered that this is because the charge accumulated at the interface between the surface protective layer and the photosensitive layer leaks from the crack and neutralizes the charge of the opposite polarity on the surface of the photosensitive member.

The thickness of the surface protective layer is 0.01 to 5 µm, preferably 0.04 to 1 µm, assuming that the surface protective layer is formed on a mirror-like surface without fine irregularities. With such a thickness, the form of the unevenness on the surface of the photosensitive layer appears on the surface protective layer in almost the same shape. If the thickness is more than 5 μm, cracks, which are considered to be based on internal stress, are not formed in the formed vacuum thin film, and the above-mentioned problem still remains. If the film thickness is less than 0.01 μm, the film strength is reduced, causing problems such as scratches, film shaving, etc., resulting in an insufficient surface protection layer.

 Hereinafter, the present invention will be described using examples.

The photoreceptor was prepared by combining the following photosensitive layer, roughening of the photosensitive layer, and surface protective layer as shown in Table 1.

Further, Table 2 shows the case where a resin layer was further formed on the surface of the photosensitive layer, and the photosensitive member was manufactured by combining the resin layer with a roughened surface.

The surface shape (θ, α, β, l, and w) and surface roughness (Rt and Ra) of the obtained photoreceptor and various characteristics of the photoreceptor (moisture resistance, image noise due to photoreceptor scar, image due to residual toner wipe) Noise, presence or absence of black streaks, toner fusion, blade wear, adhesion, film loss, and reduced sensitivity).
And Table 2.

Hereinafter, a method for preparing a photosensitive layer, a method for surface roughening, a method for preparing a vacuum thin film, and an evaluation method will be specifically described.

Preparation of Organic Photosensitive Layer (a) (Functional Separation Type for Negative Charging) Bisazo pigment chlorodian blue (CDB) 1 part by weight,
A mixture of 1 part by weight of a polyester resin (manufactured by Toyobo Co., Ltd .: V200) and 100 parts by weight of cyclohexanone was dispersed with a sand grinder for 13 hours. This dispersion was applied by dipping on a cylindrical aluminum substrate having a diameter of 80 mm and a length of 330 mm, and dried to form a charge generation layer having a thickness of 0.3 μm.

Next, 1 part by weight of 4-diethylaminobenzaldehyde-diphenylhydrazone (DEH) and 1 part by weight of polycarbonate (K-1300 manufactured by Teijin Chemicals Ltd.) were dissolved in 6 parts by weight of tetrahydrofuran (THF), and the solution was charged. The charge transporting layer having a thickness of 15 μm after drying was applied on the layer and dried to obtain an organic photosensitive layer (a).

Preparation of organic photosensitive layer (b) (binder type for positive charging) 25 parts by weight of special α-type pigment phthalocyanine (manufactured by Toyo Ink Co., Ltd.), acrylic melamine thermosetting resin (manufactured by Dainippon Ink Co., Ltd .: A-405 and super A mixture of 50 parts by weight of a mixture of becamine J820), 25 parts by weight of 4-diethylaminobenzaldehyde-diphenylhydrazone and 500 parts by weight of an organic solvent (a mixture of 7 parts by weight of xylene and 3 parts by weight of butanol) was ground and dispersed in a ball mill for 10 hours. . This dispersion has the diameter
It was applied on a cylindrical aluminum substrate of 80 mm × 330 mm by dipping and dried and baked (at 150 ° C. for 1 hour) to obtain an organic photosensitive layer (b) having a thickness of 15 μm.

Production of selenium-based photosensitive layer (c) Se-containing selenium-arsenic alloy single-layer structure having a thickness of about 50 μm is known by vacuum evaporation by resistance heating, which is a conventional method, using an evaporation apparatus shown in FIG. As photosensitive layer (C)
I got

Preparation of Amorphous Silicone Photosensitive Layer (d) Step (I): In the glow discharge decomposition apparatus shown in FIG. 12, first, the inside of the reaction chamber (733) is evacuated to a high vacuum of about 10 ^-4 Torr,
First to third and fifth control valves (707), (708), (70
9) and (711) are opened, B diluted to 200 ppm with H ₂ gas from the first tank (701), 100% SiH ₄ gas from the second tank (702), and H ₂ from the third tank (703). ₂ H ₄ gas and further C ₂ H ₄ gas from the fifth tank (705) are flowed into the flow controllers (713), (714), (715) and (717) under a pressure gauge of 1 kg / cm ^2. Was. And adjust the scale of each flow controller,
300sccm flow rate of H _2, SiH ₄ gas flow rate 90sccm, B ₂ H ₄ (200
as ppm / H ₂₎ 100sccm, by setting C ₂ H ₄ so that the 120 sccm, flowing into the reaction chamber (733) within. After each flow rate was stabilized, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr. On the other hand, as the substrate (752), the diameter is 80mm
× Preheated to 250 ° C using a cylindrical aluminum with a length of 330 mm, a high-frequency power supply (739) is turned on while the gas flows are stable and the internal pressure is stable, and 200 W is applied to the electrode plate (736).
(Frequency 13.56 MHz) was applied to generate glow discharge. The glow discharge is continued for 3.5 minutes, and the conductive substrate (752) has a thickness of about 0.35 μm containing hydrogen and boron.
Was formed.

Step (2): After forming the first layer, the flow rate of the C ₂ H ₄ mass flow controller (717) was reduced to 0 within 30 seconds by turning off the control valve (711) without stopping the application of power from the high frequency power supply. . Other conditions were the same as in the step (1) to form a second layer having a thickness of 0.05 μm.

Step (3): After forming the second layer, the application of power from the high-frequency power supply (739) was stopped, the flow rate of the mass flow controller was set to 0, and the inside of the reaction chamber (733) was sufficiently degassed. Thereafter, 400 sccm of H ₂ gas from the first tank (701), 200 sccm of 100% SiH ₄ from the second tank (702), and the third tank (703)
20 sccm of B ₂ H ₆ gas diluted to 200 ppm with H ₂ and ₂ sccm of O ₂ gas from the sixth tank (706) flow into the reaction chamber, adjust the internal pressure to 1.0 Torr, and turn on the high frequency power supply Then, a power of 300 W was applied. Continue discharging for about 4 hours.
A third layer having a thickness of 28 μm was formed, and an amorphous silicon-based photosensitive layer (d) was formed on a cylindrical aluminum substrate.

Preparation of cadmium sulfide / resin dispersion photosensitive layer (e) CdS · nCdCO ₃ (0 <n4) Photoconductive powder is dispersed together with thermosetting acrylic resin, applied to a cylindrical aluminum substrate to about 30 μm, and thermoset. Thus, a cadmium sulfide / resin dispersion photosensitive layer (e) was prepared.

Preparation of Photosensitive Layer Having Resin Layer on Photosensitive Layer (Formation of Resin Layer (A)) 1 part by weight of polycarbonate (K-1300 manufactured by Teijin Chemicals Ltd.) is dissolved in 10 parts by weight of THF, and this solution is applied on the photosensitive layer. Coating was performed so that the film thickness after drying was 0.06 μm, and drying was performed to form a resin layer.

(Formation of Resin Layer (B)) An acrylic melamine thermosetting resin is dissolved in an organic solvent (a mixture of 7 parts by weight of xylene and 3 parts by weight of butanol),
The solution is dried and baked on the photosensitive layer to a thickness of 0.06 μm.
Was applied and fired to form a resin layer.

Roughening of photosensitive layer Examples 1-4, 7-11, 13-16, 19-21 The surface of the photosensitive layer obtained above was treated under the conditions shown in Table 3 with a buffing machine shown in FIG. It was roughened.

The photoreceptor was fixed by chucking (301), and a wool felt disk-shaped buff (diameter 20 cm) (303) was set at a predetermined buffing position. As shown in FIG. 11, the buff shift is the distance between the center line in the longitudinal direction of the photoconductor (304) and the center point of the disk-shaped buff (303).

Next, while rotating the photoconductor (304) in the direction of arrow d (work rotation) and rotating the disc-shaped buff in the direction of arrow c,
A load (buff load) was applied to the disc-shaped buff (303) from the direction of arrow a, the disc-shaped buff (303) was pressed against the photoconductor (304), and reciprocated (buffed) in the direction of arrow b. Pure water or pure water in which an abrasive was dispersed was discharged at a rate of 1 / mm from the liquid discharge nozzle (302) toward the contact surface between the photoconductor and the disk-shaped buff in accordance with the movement of the buff.

Examples 5, 6, 17, 18, 22 As shown in FIG. 6, non-parallel cylindrical brushes having a diameter of 5 cm (angle 60 °: Examples 5 and 17, and angle 80 °: Example 2)
2, angle 100 °: placed in Examples 6 and 18),
While rotating at 120 rpm, the brush roller was pressed against the photosensitive member at 450 rpm, and at this time, the brush was moved at a speed of 1 cm / sec in a direction parallel to the axis of the photosensitive member to roughen the surface of the photosensitive member.

The buffing process or the brush polishing process was performed for about 2 minutes to complete the photoreceptor surface roughening process.

After the surface was roughened, the photoreceptor was subjected to ultrasonic cleaning in pure water, and further washed with pure water at 60 ° C., and then taken up in a dry air atmosphere at a speed of about 1 cm / sec and dried.

The degree of surface roughening of the photoreceptor was represented by a maximum height (Rt) and a center line average roughness (Ra). In addition, the surface roughness profile measuring machine of Surfcom 550A (brand name) (made by Tokyo Seimitsu Co., Ltd.) was used for the measurement.

Finally, a surface protective layer was formed on the photoreceptor whose surface was roughened as described above, using the method described below.

Plasma amorphous hydrocarbon film (1) (referred to as PAC (1))
In the glow discharge decomposition apparatus shown in FIG. 12, first, the inside of the reaction tank (733) was evacuated to a high vacuum of about 10 ⁻⁴ Torr, and then the first, second and third control valves (707, 708) were used. , 709) and release hydrogen gas from the first tank (701) and the second tank (70).
2) Flow butadiene gas and methane tetrafluoride gas from the third tank (703) into the first, second, and third flow controllers (713, 714, 715) at an output pressure of 1.5 kg / cm, respectively. Was. Then, the scale of each flow controller is adjusted, the flow rate of the hydrogen gas is set to 300 sccm, the flow rate of the butadiene gas is set to 15 sccm, and the flow rate of the methane tetrafluoride gas is set to 90 sccm. Then, it was allowed to flow into the reaction chamber (733) from the main pipe (732). After each flow rate was stabilized, the pressure regulating valve (745) was adjusted so that the pressure in the reaction chamber (733) became 0.5 Torr. On the other hand, as the substrate (752),
The drum on which the above-mentioned organic photosensitive layer was formed was used.

Next, the substrate (752) was fixed to the ground electrode (735) in the reaction chamber (733). The substrate (752) was heated from room temperature to 50 ° C. over about 15 minutes before gas introduction. When the gas flow rate and pressure are stable, turn on the low-frequency power supply (741) previously connected by the connection selection switch (744), and apply 150 W power to the power input electrode (736) at a frequency of 80 KHz. And perform the plasma polymerization reaction for about 2 minutes.
An amorphous hydrocarbon film having a thickness of 0.1 μm was formed thereon.

After the film formation was completed, the application of power was stopped, the control valves other than hydrogen gas were closed, and only hydrogen gas flowed into the reaction chamber (733) at a flow rate of 100 sccm, the pressure was maintained at 1 Torr, and the temperature was lowered to about 30 ° C. . Thereafter, the control valve (707) for hydrogen gas was closed, the inside of the reaction chamber (733) was sufficiently evacuated, the vacuum in the reaction chamber (733) was broken, and the photoconductor of the present invention was taken out.

Plasma amorphous hydrocarbon film (2) (referred to as PAC (2))
First, in the glow discharge decomposition apparatus shown in FIG. 12, the inside of the reaction tank (733) is evacuated to a high vacuum of about 10 ^-4 Torr, and then the first and second control valves (707, 708) are opened. And the first tank (70
1) Hydrogen gas and butadiene gas from the second tank (702) were flowed into the first and second flow controllers (713, 714) at an output pressure of 1.5 kg / cm, respectively. Then, the scale of each flow controller is adjusted so that the flow rate of hydrogen gas is set to 300 sccm and the flow rate of butadiene gas is set to 15 sccm, and the reaction chamber is fed from the main pipe (732) through the intermediate mixer (731). (733). Reaction chamber (733) after each flow rate is stabilized
The pressure regulating valve (745) was adjusted so that the internal pressure became 1.0 Torr. On the other hand, as the substrate (752), the drum on which the above-mentioned organic photosensitive layer was formed was used.

Next, the substrate (752) was fixed to the ground electrode (735) in the reaction chamber (733). The substrate (752) was heated from room temperature to 50 ° C. over about 15 minutes before gas introduction. When the gas flow rate and pressure are stable, turn on the low-frequency power supply (741) previously connected by the connection selection switch (744), and apply 150 W power to the power input electrode (736) at a frequency of 80 KHz. And perform the plasma polymerization reaction for about 3.5 minutes.
An amorphous hydrocarbon film having a thickness of 0.1 μm was formed thereon.

After the film formation was completed, the application of power was stopped, the control valves other than hydrogen gas were closed, and only hydrogen gas flowed into the reactant (733) at a flow rate of 100 sccm, the pressure was maintained at 1 Torr, and the temperature was lowered to about 30 ° C. . Thereafter, the control valve (707) for hydrogen gas was closed, the inside of the reaction chamber (733) was sufficiently evacuated, the vacuum in the reaction chamber (733) was broken, and the photoconductor of the present invention was taken out.

By making the high-frequency (13.56 MHz) sputtering of the aluminum oxide film (referred to Al ₂ O _3), to form a surface protective layer on the organic photosensitive layer. The above-mentioned organic photosensitive layer was fixed to a ground electrode in a vacuum chamber of a high-frequency sputtering deposition apparatus (not shown). The opposite high-frequency application electrode is approximately
The target was covered with a 5 mm aluminum oxide Al ₂ O ₃ plate.

After the inside of the vacuum chamber was evacuated to a high vacuum of about 10 ⁻⁷ Torr using an exhaust pump, argon gas for sputtering was introduced into the vacuum chamber and the pressure was set at 5 × 10 ⁻² Torr. Next, 200W to the electrode
Was applied at a frequency of 13.56 MHz to perform sputtering for about 10 minutes, thereby forming a 0.1 μm-thick surface protection layer made of Al ₂ O ₃ on the substrate. After the film formation was completed, the application of power was stopped, the inside of the vacuum layer was evacuated, the vacuum in the vacuum layer was broken, and the photoreceptor having the surface protective layer according to the present invention was taken out.

Preparation of Silicon Oxide Film (referred to as SiO Film) A surface protective layer was formed using a vapor deposition apparatus shown in FIG.
As the substrate (503), the drum on which the above-described organic photosensitive layer was formed was used. The substrate (503) is used as a substrate support member (502).
The attached boat (504) was loaded with silicon monoxide SiO powder.

Next, the inside of the vacuum layer (501) is evacuated to a high vacuum of about 10 ^-7 Torr using an exhaust pump (511), and then power is applied to the electrode (506) to raise the temperature of the boat (504) to 1080 ° C. did. When the temperature of the boat (504) stabilizes, the motor (51
2) Activate and rotate the substrate (503) at about 10 revolutions / minute, and open the shutter (508), which was previously closed, by operating the rotation introduction terminal (501) for about 3 minutes. The substrate is deposited under a vacuum of about 10 ^-5 Torr (50
3) A surface protection layer of about 0.15 μm SiO was formed thereon.

After the surface protective layer is formed, the power supply to the electrode (506) is stopped, and the inside of the vacuum layer (501) is sufficiently evacuated.
The vacuum in 1) was broken to take out the photoreceptor having the surface protective layer according to the present invention.

Characteristics of the photoreceptors obtained in Examples and Comparative Examples were evaluated for the following items.

Incidentally, for the negatively charged photoconductors (a) and (e),
For the copying machine (EP5400; manufactured by Minolta Camera Co., Ltd.), for the positively charged photoconductors (b), (c), and (d), the copying machine (EP5400;
550Z (Minolta Camera Co., Ltd.).

Moisture resistance After performing 100,000 live shots in an indoor atmosphere,
Actual shooting was performed under an environment of a relative humidity of 85%, and the presence or absence of image deletion was visually observed, and ranking was performed as follows.

：: No image deletion was observed and good. ×: In some character images, image deletion was observed and characters could not be identified.

Image Noise (Scars) 10 photos of the effects of photoreceptor surface scars on images
After performing 00 times, the exposure amount was adjusted to obtain a halftone image having an image density of 0.50. The streak-like image noise in the image was visually observed, and the correspondence between the noise and the scar on the surface of the photoreceptor was examined, and the images were ranked as follows.

Good: No noise corresponding to scratches was observed. Good: Noise corresponding to slight scratches was recognized, but no problem in practical use. X: Inappropriate in practical use. Image noise (left unwiped). After 10,000 times, a blank document was copied to obtain a blank image. The noise due to the unwiped residue in the image was visually observed and ranked as follows.

：: no wiping left on image, good ×: wiping left unrecognized and unsuitable for practical use Filming fusion Filming fusion of toner was carried out in a room atmosphere with 10
After performing the test many times, the photoreceptor was taken out of the actual machine, and the presence or absence of filming fusion on the photoreceptor surface was visually observed, and ranked as follows.

：: No filming fusion on the photoreceptor surface, good image ×: Filming fusion on the photoreceptor observed Blade wear Blade wear was performed 10,000 times in a room atmosphere, and then the actual machine was used. Take out the cleaning blade, observe the wear amount of the photoconductor contact part of the blade with an optical microscope,
The ranking was performed as follows.

：: The wear amount from the tip is within 100 μm and the wear is uniform. ×: The wear is uneven and the wear from the tip exceeds 100 μm. The surface of the photoreceptor is observed with a 300x optical microscope (viewing area 0.08 mm ² ), and the image is analyzed with an image analyzer Luzex 5000 (trade name) manufactured by Nireco, and the area ratio of the surface protective layer to the defect is calculated. did. Observation was performed at any 20 points on the drum, and the largest value was adopted.

 The membrane defect ratio was ranked as follows.

Adhesion evaluation A cross-cut test according to JIS-K5400 standard was performed to evaluate the adhesion of the surface protective layer to the organic photoreceptor, and ranked as follows.

Evaluation of sensitivity reduction Mount the prototype photoconductor on the actual machine, adjust the exposure amount,
A halftone image with an image density of 0.50 was obtained.

Thereafter, after making 10,000 copies of A4 paper, a halftone image was obtained with the same exposure, the image density was obtained, and the difference from the initial image density of 0.50 was obtained.

For example, if the image density after copying 10,000 sheets is 0.55, the difference 0.05 is regarded as the sensitivity reduction.

The surface potential setting of the actual machine was 600 [V], and the phenomenon bias setting was 150 [V].

In the list of examples, the quality of sensitivity reduction was shown based on the following evaluation criteria.

The image density was set using a Konica Densitometer Sakura Densitometer PDA65 (trade name).

The photoreceptors of Examples 1 to 22 had good moisture resistance after printing and showed no practical problems. Examples 1, 15
As for the image, no image deletion was observed even after 600,000 actual photographs were taken, either in an indoor atmosphere or in a high humidity atmosphere.

As in the case of the photoreceptors shown in Comparative Examples 1 and 5, when the vacuum thin film was directly provided without performing the surface roughening treatment, no problem was recognized in terms of image noise, but after 10,000 copies of the actual image, Image flow was observed in actual shooting in a high humidity environment (35 ° C, 85%).

When the angle of the flaw is too large (scratching too much) as in the case of the photoconductors shown in Comparative Examples 2 and 6, no high-humidity image flow was observed after 100,000 copies were actually taken. The resulting image noise was unsuitable for practical use.

As in the case of the photoreceptors shown in Comparative Examples 3 and 7, when the surface roughness is large and the pitch of the scratches is too large, a problem occurs with respect to the adhesion of the vacuum thin film layer. It was recognized and was unsuitable for practical use.

When the angle of the scratch is too small (the scratch is too lazy) as in the photoreceptors shown in Comparative Examples 4 and 8, after 100,000 copies are actually taken,
No high-humidity image deletion was observed, but in actual photography, image noise corresponding to polishing was generated, and after 100,000 copies of actual photography, toner filming and fusing occurred, and blade abrasion was remarkably impractical. Met.

Further, in the present invention, the photoreceptor having an organic photosensitive layer and the photoreceptor having a resin layer on the photosensitive layer were evaluated for the presence or absence of a decrease in sensitivity.
When the thickness was 30 μm or less, no reduction in sensitivity was observed, or the level had no practical problem.

Effects of the Invention A photosensitive member having a structure in which a vacuum thin film is formed on the surface of a photosensitive layer that has been subjected to fine surface roughening treatment according to the present invention has excellent moisture resistance even after repeated copying. Further, in the case of a photosensitive member having an organic photosensitive layer and a photosensitive member having a resin layer on the photosensitive layer and having a pitch l of 30 μm or less, a decrease in light sensitivity was prevented.

[Brief description of the drawings]

1 and 2 schematically show linear scratches on the surface of the photosensitive layer. FIG. 3 is a view schematically showing a partial cross-sectional curve of the photosensitive layer surface. FIG. 4 is a diagram for explaining the maximum height. 5 and 6 are views for explaining a brush polishing method. 7 and 8 are schematic cross-sectional views of the photoconductor. FIG. 9 is a diagram schematically showing a buff polishing method. FIG. 10 is a diagram for explaining buffing. FIG. 11 is a diagram showing a schematic configuration example of a glow discharge decomposition device. FIG. 12 is a diagram showing a schematic configuration example of a vapor deposition apparatus.

Continuation of the front page (72) Inventor Issei Osawa 2-3-1-13 Azuchicho, Chuo-ku, Osaka-shi, Osaka Osaka International Building Minolta Camera Co., Ltd. (72) Inventor Seiji Kojima 2 Azuchi-cho, Chuo-ku, Osaka-shi, Osaka No. 3-13 Osaka International Building Minolta Camera Co., Ltd. (72) Inventor Kenji Masaki 2-3-13 Azuchicho, Chuo-ku, Osaka City, Osaka Prefecture Osaka International Building Minolta Camera Co., Ltd. (56) References 3-152546 (JP, A) JP-A-57-74744 (JP, A) JP-A-64-4754 (JP, A) JP-A-2-139566 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03G 5/147

Claims (3)

(57) [Claims] 1. A photoreceptor having a photoconductive photosensitive layer on a conductive support and a surface protective layer formed of a vacuum thin film on the photoconductive photosensitive layer, the surface of which is roughened by countless intersecting linear scratches. A vacuum thin film is formed on the surfaced photoconductive photosensitive layer, and the average value of the intersection angle of the linear scratch is 30 to
150 degrees, the average value of the angle of intersection of the reference line in the direction perpendicular to the photoconductor surface movement direction and each linear flaw is 15 to 75 degrees, the average value of the length between the adjacent intersections of the reference line and each linear flaw is 200 μm
The photoreceptor is characterized in that the average value of the width of each linear flaw is 30 μm or less. 2. A photoreceptor having a photoconductive photosensitive layer on a conductive support, a resin layer on the photosensitive layer, and a surface protective layer formed of a vacuum thin film on the resin layer, the surfaces of which are innumerably crossing each other. A vacuum thin film is formed on the resin layer roughened by the linear scratch, and the average value of the intersection angle of the linear scratch is
30 to 150 degrees, the average value of the angle of intersection of the reference line in the direction perpendicular to the photoconductor surface movement direction and each linear scratch is 15 to 75 degrees, the average of the length between adjacent intersections of the reference line and each linear scratch Value is 200
A photoreceptor wherein the average value of the width of each linear scratch is 30 μm or less. 3. The photoconductor according to claim 1, wherein said photoconductive photosensitive layer is an organic photosensitive layer.