JPH07152194A - Production of electrophotographic organic photoreceptor and cylindrical supporting body - Google Patents

Abstract

PURPOSE:To obtain an org. photoreceptive body having such a cylindrical supporting body that is light in weight, has good conductivity, excellent chemical resistance and heat resistance, and good dimensional accuracy even for such a shape with thin wall and long length, and does not require special surface stabilization treatment, by forming an org. photoreceptive layer on a specified cylindrical supporting body. CONSTITUTION:The cylindrical supporting body 1 used consists of a material essentially comprising crosslinking PPS (polyphenylene sulfide resin) to which high conductive carbon black having <=10<-1>OMEGA.cm volume resistivity is compounded to control the volume resistivity to <=10<4>OMEGA.cm. An org. photoreceptive layer 3 is formed on this supporting body to obtain the photoreceptor. In this method, a base coating layer 2 is formed on the supporting body, and then a charge producing layer 4 and a charge transfer layer 5 are successively formed to constitute the photoreceptive layer 3. However, the base coating layer 2 is not always necessary but formed as required. Thereby, thermal deformation and swelling of the supporting body 1 due to the coating solvent during org. material layers such a the photoreceptive layer 3 are formed is decreased so that deformation of the supporting body 1 is decreased.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic photoconductor for electrophotography, and more particularly to a conductive cylindrical support thereof. The present invention also relates to a method for manufacturing the conductive cylindrical support.

[0002]

2. Description of the Related Art An organic photoconductor for electrophotography used in an electrophotographic apparatus such as a copying machine or a printer to which electrophotography is applied includes a conductive support and an organic photoconductive material provided thereon. And a photosensitive layer made of an organic material. The conductive support is usually formed into a cylindrical shape because of the advantage in designing the device, and a photosensitive layer is formed on the outer surface of the conductive support by coating.

As a material for the cylindrical support, aluminum or aluminum alloy, which is relatively lightweight and has good machinability, has been frequently used. On the other hand, Tokuhei 2-1
No. 7026 discloses a polyphenylene sulfide resin (hereinafter referred to as PPS resin) as a cylindrical support which is lighter in weight, has excellent chemical resistance and heat resistance, does not undergo deterioration such as oxidation even in the air, and is suitable for organic photoconductors. A support manufactured by an injection molding method using a material mainly composed of

[0004]

However, the support made of aluminum or aluminum alloy has a strict dimensional accuracy (roundness ± 50 μm or less, dimensional accuracy of diameter ± 40 μm or less) required for the support and a suitable surface. In order to obtain roughness (maximum height R _max is 0.5 μm to 1.2 μm), it is necessary to individually perform high-precision machining, and further, an inlay for fitting a flange for rotationally driving the photoconductor. It is also necessary to perform processing individually, and there is a problem that the surface may be oxidized or deteriorated under the influence of moisture and oxygen in the atmosphere, and it is necessary to take measures to prevent deterioration such as forming an anodic oxide film on the surface. However, there is a problem that the number of manufacturing steps is high and the manufacturing cost is high.

Further, the support made of a material containing PPS resin as a main component has the following problems. That is, the volume resistivity of PPS resin is usually 10 ¹⁰ Ω.
Since it is as high as −cm to 10 ¹³ Ω · cm, for example, carbon black is added to the PPS resin to give conductivity. In recent years, the market demands for image quality and printing characteristics have become strict, but the conductivity of the support necessary for obtaining an image with good image quality as practically required or good printing characteristics was investigated. However, it is necessary that the volume resistivity of the support is at least 10 ⁴ Ω · cm or less, and if it is about 10 ⁵ Ω · cm or more, the charge on the support when the photoconductor is exposed and when the charge is removed. It was found that the missing of the ink was bad and the residual potential was large, so that good images and printing could not be obtained. The volume resistivity of carbon black is 1 Ω · cm to 10 Ω · c for furnace carbon which is usually called conductive carbon black.
m, and it is necessary to add more than 20% by weight of carbon black in order to reduce the volume resistivity of the support to 10 ⁴ Ω · cm or less. However, if such a large amount of carbon black is added, the material However, there is a problem that the viscosity becomes high and injection molding becomes difficult. Particularly recently, a support having a small diameter (outer diameter of about 30 mm or less), a thin wall (thickness of about 3 mm or less) and a long length (several hundred mm) has become necessary. It is extremely difficult to injection-mold a support having a different shape. In addition, the mechanical strength of the support is reduced.
Furthermore, the thinner and longer the support becomes, the more difficult it becomes to maintain the dimensional accuracy. In the case of a support made of an ordinary linear-type PPS resin as a main component, a layer of an organic material is formed by coating. In the process, a slight deformation, which is not a problem usually caused by the solvent of the coating liquid and heating, becomes a problem, and it is difficult to obtain the dimensional accuracy required for the support. Also, due to the good chemical resistance of PPS resin,
The adhesion of the organic material layer formed by coating on it is poor,
There is also a problem that the photosensitive layer is easily peeled off when the photoreceptor is used, and the practical life is short.

The present invention has been made in view of the above-mentioned points, and it is first of all lightweight, has suitable conductivity, is excellent in chemical resistance and heat resistance, and has a thin and long shape. However, it is possible to provide an organic photoconductor having a cylindrical support that can maintain good dimensional accuracy and can maintain stable quality without causing deterioration such as oxidation even in the atmosphere. Providing an organic photoreceptor having a cylindrical support having a surface roughness. Thirdly, providing an organic photoreceptor having a cylindrical support having high mechanical strength and being hard to be deformed even in a thin-walled and long shape. Fourthly, it is an object of the present invention to provide an organic photoreceptor having a cylindrical support, which has excellent adhesiveness and on which a layer made of an organic material can be formed by coating with good adhesion. A fifth object is to provide a method for producing such a cylindrical support of the first, second, and third problems, particularly a support having a thin wall, a small diameter, and a long shape with high productivity. To do.

[0007]

According to the present invention, the first object is to provide a cross-linking type PPS resin as a main component, which has a high electrical conductivity of 10 ^-1 Ω · cm or less in volume resistivity. The volume resistivity is 10 ⁴ Ω · c by adding carbon black.
This can be solved by using a cylindrical support made of a material having a thickness of m or less and providing an organic photosensitive layer on the support.

The second problem is that the carbon black contained in the cylindrical support has an average particle size of 20 nm to 50 nm.
It is solved by setting to nm. Further, it is preferable to add a dispersant for carbon black at the same time when carbon black is added, because the carbon black can be uniformly contained in the support material. The dispersant may include calcium carbonate or clay.

The third problem is solved by including glass fibers as a reinforcing material in the cylindrical support. As described above, the support material is a cross-linking type PPS resin to which carbon black, a carbon black dispersant, glass fiber and the like are added.
In order to take advantage of the characteristics of the resin, the amount of the resin is at least 40% by weight or more.

The fourth problem is that the surface of the cylindrical support has a wavelength.
It is irradiated with UV light of 180nm to 255nm
Or corona discharge treatment
Will be solved. The fifth issue is the bridge type
The main component is PPS resin, which has a volume resistivity of 10 ^-1Ω ・
Highly conductive carbon black of less than cm is added to the volume
Resistivity is 10^FourMaterial less than Ω · cm, or even more
The average particle size of carbon black is 20 nm to 50 nm
Or the material with glass fiber added
It is solved by injection molding.

The temperature of the mold for injection molding is 120 ° C.
To 150 ° C, molding material temperature is 280 ° C
It is preferable that the temperature is within a range of from ˜330 ° C. Further, it is preferable that the filling time of the material is within the range of 0.05 seconds to 2.5 seconds. As the molding die, the core die has a surface roughness of 1 μm or less at the maximum height R _max , and has a draft in the range of 0.15 ° to 0.25 ° on one side. As for the cavity type, the inner surface does not have a draft, and electroforming is performed using a nickel alloy to finish the surface roughness to a maximum height R _max of 1 μm or less, and a step portion is formed inside the end surface in contact with the fixed type. It is formed and has a structure in which the molding material is filled in the cavity by the side gate method through the step portion, and the fixed mold has at least 3 in the circumferential direction of the cavity mold on the end face in contact with the cavity mold. A spring knock is provided at each location in equal parts, and the structure is such that the injection-molded molded product always remains on the cavity side due to the action of this spring knock when the mold is opened. It is preferable to use a die having the characteristics.

[0012]

[Function] Table 1 shows the mass change (%) of cross-linked type PPS resin and linear type PPS resin after being immersed in acetone, methylene chloride and dichloroethane for 24 hours using cylindrical molded products. 2 shows the evaluated chemical resistance and the heat resistance evaluated by the dimensional change (%) in the diameter direction and the length direction after heating at 120 ° C. for 48 hours.

[0013]

[Table 1]

As can be seen in Table 1, crosslinked PP
S resin is superior in chemical resistance and heat resistance to linear type PPS resin. By forming the support with a material containing a cross-linking type PPS resin as a main component, thermal deformation of the support and swelling by a coating solution solvent when forming a layer made of an organic material such as a photosensitive layer are less likely to occur. Therefore, the deformation of the support is reduced, and it becomes possible to obtain practically sufficient dimensional accuracy even for a photoconductor using a thin, small-diameter, long support.

Further, the carbon black added to impart conductivity to the material containing such a cross-linking type PPS resin as a main component has a volume resistivity of 10 ^-1 Ω · cm or less and is highly conductive. , Carbon black added to the support material in order to reduce the volume resistivity of the support to 10 ⁴ Ω · cm or less by using, for example, highly conductive furnace carbon or channel black having higher conductivity. The amount can be reduced to 20% by weight or less, and the viscosity of the support material can be injection-molded even if it has a small diameter, a thin wall, and a long shape, for example, a temperature of 300.
It becomes possible to keep the melt flow rate (MFR) at 20 ° C. at 20 g / 10 min to 50 g / 10 min.

Further, it is, of course, desirable that the carbon black is dispersed in the support material as uniformly as possible. For that purpose, it is desirable to add a dispersant, and examples of the dispersant include calcium carbonate and clay. The amount of the dispersant added depends on the amount of carbon black added, but is 10% to 30% by weight of the support material. If it is less than 10% by weight, the effect is small, and if it exceeds 30% by weight, the conductivity of the material is adversely affected, which is not preferable.

Further, the surface roughness of the support is determined by the surface roughness of the inner surface of the cavity of the molding die, but is greatly influenced by the particle size of carbon black added to the material.
The average particle size of carbon black is 20 nm to 50 nm
By setting the following, the surface roughness of the support is 0.5 μ at R _max .
It becomes possible to set it in the range of m to 1.2 μm. Furthermore, the addition of glass fibers to the support material reinforces the decrease in mechanical strength due to the addition of carbon black, and 0.49 required for a support having a wall thickness of about 1 mm.
A strength of × 10 ⁸ N / m ² or more can be obtained. The glass fiber preferably has a diameter of about 20 μm and a length of about 3 mm. The amount of glass fiber added depends on the amount of carbon black added, but is 10% to 30% by weight of the support material.
It is said that If it is less than 10% by weight, the effect is small, and if it exceeds 30% by weight, the conductivity of the material, the surface roughness of the support and the like are adversely affected, which is not preferable.

As described above, the support material is a cross-linking type PPS resin to which carbon black, a carbon black dispersant, glass fibers and the like are added. By making the amount of the resin 40% by weight or more, It can be utilized without impairing the features of cross-linked PPS resin. Further, the PPS resin has a drawback that it has poor adhesiveness. In the field of electronic devices and automobiles that use PPS resin as engineering plastics, a method is known to improve the adhesive property by irradiating ultraviolet rays or performing corona discharge to modify the surface. Yes (31st Annual Meeting of the Adhesion Society of Japan (June 1993): P
Improvement of PS adhesiveness, Journal of Japan Adhesion Society, Vol. 29, N
o. 4 (1993): surface modification by ultraviolet rays). However, when a cross-linking type PPS resin is used as the functional material in the support of the photoreceptor, it has been clarified whether these methods are effective without inhibiting the function as the support. There wasn't. The inventors of the present invention irradiate ultraviolet rays having a wavelength of 180 nm to 255 nm to generate ozone from oxygen in the atmosphere by the ultraviolet energy, and the molecular chains on the outermost surface of the cross-linking type PPS resin are cut off to remove moisture in the atmosphere. Adding action, -O
H groups, -COOH groups, etc. are generated and the surface is activated,
It has been found that the wettability of the surface is greatly improved and the adhesiveness is improved without impairing the necessary function as a support.
Also in the case of corona discharge treatment, ozone is generated by the corona discharge energy, and the same effect as in the case of ultraviolet irradiation can be obtained.

The support for a photoreceptor of the present invention is produced by injection-molding a material containing a cross-linking type PPS resin as a main component, carbon black, and a dispersant of carbon black and glass fibers. . By forming the molding die with an appropriate structure and integrally molding under appropriate molding conditions, it is possible to obtain a support with the required shape and surface roughness with high dimensional accuracy.
It becomes possible to manufacture with high productivity. Individually machined, such as when making supports with aluminum alloys,
There is no need to perform surface roughness processing. The temperature of the mold for injection molding is in the range of 120 ° C to 150 ° C, the molding material temperature is in the range of 280 ° C to 330 ° C, sufficient injection pressure is applied, and the filling time of the material is 0.0.
Within the range of 5 seconds to 2.5 seconds, the resin begins to solidify in the cavity (material filling part) even when a thin support having a thickness of 3 mm or less and a length of several hundred mm is injection-molded. It is possible to completely complete the filling of the material before and obtain a support having a good shape, and further, the crystallization of the resin is sufficiently advanced so that the characteristics of the cross-linking type PPS resin can be utilized.

Next, the operation of the molding die used for manufacturing the support of the present invention will be described with reference to the drawings. 3 to 5 are partial cross-sectional views for explaining an embodiment of the molding die of the present invention. FIG. 3 shows a state of mold clamping in which the end surface of the cavity mold 6 and the end surface of the fixed mold 8 are in close contact with each other. 7 is a core mold, and 9 is a cavity filled with a molding material to form a molded product. FIG. 4 shows a state in which the cavity mold 6 and the fixed mold 8 after molding are separated from each other, and 14 is a molded product. The core die 7 is fitted and fixed in the fixed die 8. FIG. 5 is a partially enlarged sectional view of the spring knock 11 and its surroundings in FIG. 3, in which 12 is a spring and 13 is a knockout pin.

A step portion 10 is formed inside the end surface of the cavity die 6 which is in contact with the fixed die 8. As for the size of the step portion 10, the h of the step portion 10 shown in FIG.
It is preferable that w is 2 mm to 5 mm. In the mold clamped state of FIG. 3, the cavity 9 is filled with the molding material by the side gate method through the step portion 10, so that the molding material first fills the step portion 10 and then the thin-walled cylindrical cavity 9 is formed. Therefore, it becomes possible to fill the tip of the cavity 9 uniformly and promptly without causing defects such as welds in the circumferential direction. In order to fill the molding material at a high speed of 0.05 seconds to 2.5 seconds, a gas vent should be provided at the tip of the cavity 9 and the structure should be such that vacuum gas can be vented if necessary. preferable. The inner surface of the cavity mold 6 is electroformed with a nickel alloy in order to improve transferability and releasability, and the surface roughness is finished so that the maximum height R _max is 1 μm or less. There is. By using the cavity mold 6 having such a surface state and filling the cavity 9 with a sufficient injection pressure and solidifying the material, the surface of the support obtained by injection molding has a maximum height R _max of 1 μm or less. It can be rough.

By the way, the photosensitive member is required to have a uniform outer diameter. Therefore, it is not allowed to give a draft to the outer diameter of the molded product. It is extremely difficult to release such a molded product, especially a thin molded product, from the cavity mold 6 without damaging the surface. Therefore, the surface of the core die 7 is finished to be a smooth surface having a surface roughness of 1 μm or less at the maximum height R _max , and has a draft in the range of 0.15 ° to 0.25 ° on one side. Structure and
Further, a spring knock 11 composed of a knockout pin 13 and a spring 12 is provided at each position on the end surface of the fixed mold 8 which contacts the cavity mold 6 and divides the circumferential direction of the cavity mold 6 into at least three equal parts. By adopting such a structure, the spring 12 which is compressed as shown in FIG. 5 at the time of mold clamping is opened and extended at the time of mold opening so that the tip of the knockout pin 13 is fixed to the fixed mold 8 as shown in FIG. Stick out from the end face. The protruding length of the tip of the knockout pin 13 is a length corresponding to m shown in FIG. Therefore, in the process of separating and opening the cavity mold 6 from the fixed mold 8 after molding, the tip of the knockout pin 13 pushes the end surfaces of the cavity mold 6 and the molded product 14 until they are separated by a distance corresponding to the length m. Therefore, the cavity mold 6 and the molded product 14 move integrally, and after the mold is opened, the molded product 14 is removed from the core mold 7 and fixed on the cavity mold 6 side as shown in FIG. . Since the core die 7 has a draft and the surface is finished smoothly, the core die 7 is formed by the molded product 1 when the die is opened.
Get out of 4 smoothly. The molded product 14 contracts in the diametrical direction by the removal of the core mold 7, and the molded product 14 can be taken out from the cavity mold 6 by, for example, knocking out without damaging the surface. When the draft of the core die 7 is less than 0.15 ° on one side, the core die is hard to come off,
On the other hand, if the draft angle exceeds 0.25 ° on one side and becomes large, if the thickness of the support, which is a molded product, is less than about 3 mm, the thinner one becomes too thin to perform molding. It was found. For example, when the draft is 0.25 ° on one side, in a support having an outer diameter of 30 mm, a length of 300 mm, and a wall thickness of 1.5 mm to 3 mm, setting the thicker wall thickness to 1.5 mm to 3 mm results in a thinner one. Thickness is 0.3
mm-0.6 mm, which makes molding extremely difficult. Therefore, the draft is 0.15 ° to 0.25 ° on one side.
Must be within the range.

FIG. 6 is a perspective view showing the molded product taken out from the mold. A ring-shaped convex portion 15 is formed at one end of the cylindrical support 1 so as to correspond to the step portion 10 of the cavity mold 6. Has been done. 16 is a side gate.

[0024]

FIG. 1 is a schematic sectional view of an embodiment of a support for a photosensitive member according to the present invention. FIG. 1 (a) is a vertical sectional view of the support 1.
FIG. 1B is a sectional view taken along line XX of FIG. Also,
FIG. 2 is a schematic cross-sectional view showing the layer structure of an embodiment of the photoconductor, in which a charge generation layer 4 and a charge transport layer 5 are sequentially provided on a support 1 as shown in FIG. Layered photosensitive layer 3
Is provided. The undercoat layer 2 is provided as necessary and is not always necessary.

Example 1 Using the materials 1-1 to 1-4 having the formulations shown in Table 2 and using the molds shown in FIGS. 3 to 5, as shown in Table 3, the support No. 1-support body No. No. 3 is the same molding condition, and the support No. 3 using the material 1-4 whose material resin is a linear type PPS resin. 4 changes the mold temperature, outer diameter 30m
m, length 260.5 mm, inner diameter is 28.5 m on the thin side
m, and the supports 1-1 to 1-4 having a draft (about 0.23 ° on one side) such that the thickness is 26.5 mm on the thick side.

[0026]

[Table 2]

[0027]

[Table 3]

On each of these supports, a photosensitive layer described below was formed under the same conditions to prepare a photosensitive body. That is, alcohol-soluble polyamide resin (manufactured by Toray Industries, Inc .;
Amilan CM8000) 5 parts by weight dissolved in 95 parts by weight of methanol is applied by a dip coating method at a temperature of 120 ° C.
And dried for 15 minutes to form an undercoat layer having a thickness of about 0.5 μm. On this undercoat layer, X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc .; FASTGEN B)
LUE 8120) 10 parts by weight and vinyl chloride resin (manufactured by Nippon Zeon Co., Ltd .; MR-110) 10 parts by weight dichloromethane 686 parts by weight and 1,2-dichloroethane 29.
A coating solution prepared by mixing and dispersing 4 parts by weight with a mixer for 1 hour and further dispersing with an ultrasonic disperser for 30 minutes was applied by a dip coating method and dried at a temperature of 80 ° C. for 30 minutes to give a film thickness of about 0. 5
A charge generation layer of μm was formed. On this charge generation layer, 100 parts by weight of a hydrazone compound represented by the following structural formula (I) (manufactured by Fuji Electric Co., Ltd.), 100 parts by weight of a polycarbonate resin (manufactured by Mitsubishi Gas Chemical Co., Inc .; Iupilon PCZ),
A coating solution consisting of 800 parts by weight of dichloromethane is applied by a dip coating method and dried at a temperature of 90 ° C. for 1 hour to give a film thickness of about 20 μm.
A charge transporting layer was formed to prepare a photoconductor.

[0029]

[Chemical 1]

For each of the photoconductors thus prepared, MFR at the temperature of the support material at 300 ° C., volume resistivity, injection moldability, mechanical strength, chemical resistance (mass when immersed in methylene chloride for 2 hours) Change rate), surface roughness of support (maximum height R _MAX ), dimensional accuracy of outer diameter, dimensional change rate after heat treatment at 120 ° C. for 48 hours, and left for 5 seconds after charging the photoreceptor in the dark. Table 4 shows the potential holding ratio V _k5 , the residual potential V _r after irradiation with monochromatic light having a wavelength of 780 nm at 10 μJ / cm ^2, and the printing characteristics evaluated by mounting on a commercially available semiconductor laser printer.

[0031]

[Table 4]

As shown in Table 4, the linear type P
Support 1 using material 1-4 containing PS resin as a main component 1-
4 is a material whose main component is a cross-linking type PPS resin 1-
Supports 1-1, 1-2 1 using 1, 1-2 1-3
Compared to -3, the chemical resistance is inferior and the dimensional change rate is large. In addition, the photoreceptor 1-3 using the support 1-3 having a high volume resistivity of 10 ⁶ Ω · cm has poor printing characteristics. Cross-linked type P
The effect of the support made of a material containing PS resin as a main component and having a volume resistivity of 10 ⁴ Ω · cm or less is clear.

Example 2 As the support 1-1 of Example 1, an ultraviolet irradiation device (model SUV200NS) manufactured by Sun Engineering Co., Ltd. was used, and the distance between the low-pressure mercury lamp and the support was set to 20 mm,
Wavelength 184.9nm and 2 from 200W low pressure mercury lamp
The surface of the support is irradiated with 53.7 nm ultraviolet light. A substrate having an irradiation time of 10 seconds is referred to as a support 2-1 and a substrate having an irradiation time of 20 seconds is referred to as a support 2-2.

Similarly, using the support 1-1, while rotating, a corona discharge (discharge voltage of about 10 kv,
The gap between the discharge electrode and the support is 2 mm to 3 mm, and the discharge time is 30 seconds) to form a support 2-3. For comparison,
Similarly, the support 1-1 which is not subjected to ultraviolet irradiation and corona discharge is referred to as a support 2-4.

With respect to these supports, the contact angle of the surface with pure water was examined, and a goggle test (JIS K5
400 8.5.1,) to evaluate the adhesiveness. Next, using each of these supports, photoconductors 2-1, 2-2, 2-3, 2-4 were prepared in the same manner as in Example 1, and were mounted on a commercially available semiconductor laser printer to expose the photoconductors. The continuous printing life was examined until the problem started when the layers began to peel.

The results obtained are shown in Table 5.

[0037]

[Table 5]

As shown in Table 5, the support 2 irradiated with ultraviolet rays was used.
The photoconductors 2-1 and 2-2 using 1 and 2-2 and the photoconductor 2-3 using the support 2-3 subjected to corona discharge are the support 2-4 which is not subjected to these treatments. It is obvious that the photosensitive member 2-4 using No. 1 is superior in the cross stitch test and the continuous printing life. It is presumed that the irradiation time of 20 seconds is particularly excellent when the ultraviolet rays of the low-pressure mercury lamp of 200 W are irradiated, and the irradiation time of 15 seconds to 25 seconds is preferable.

Example 3 Using the materials 1-3 shown in Table 2 and the molds shown in FIGS. 3 to 5, injection molding was carried out by changing the mold temperature among the molding conditions as shown in Table 6. , Supports 3-1, 3-2 and 3-3 were produced. The nozzle temperature was slightly changed when changing the mold temperature. Further, in the support 3-3, the filling time of the material was shortened by increasing the mold temperature. Of the thus molded products, the support 3-3 had many burrs and was unusable as a support because of poor molding. Subsequently, using the supports 3-1 and 3-2, photoconductors 3-1 and 3-2 were produced in the same manner as in Example 1, and the V _k5 , V _r, and the printing characteristics were examined, respectively. The results are shown in Table 7.

[0040]

[Table 6]

[0041]

[Table 7]

As can be seen from Tables 6 and 7, even if the same material is used, a good support cannot be obtained unless the injection molding conditions are appropriate, and the mold temperature is 150 ° C. and printing is defective at 100 ° C. Therefore, at 170 ° C., the burr becomes defective. It is estimated that the mold temperature is preferably higher than 100 ° C. and lower than 170 ° C., and preferably within a range of about 120 ° C. to about 160 ° C.

[0043]

Since the present invention is constructed as described above, the following effects can be obtained. The main component is cross-linked PPS resin, which has a volume resistivity of 10 ^-1 Ω.
By using a cylindrical support made of a material having a volume resistivity of 10 ⁴ Ω · cm or less by blending a highly conductive carbon black having a viscosity of 10 cm or less, a body having a light weight and suitable conductivity can be obtained. Cylindrical support that has excellent chemical resistance and heat resistance, can maintain good dimensional accuracy even in thin and long shapes, and does not need to undergo special surface stabilization treatment without causing deterioration such as oxidation even in the air. An organic photoreceptor having is obtained.

By setting the average particle size of the carbon black to be mixed with the support material to 20 μm to 50 μm, the surface roughness R _max is 0.5 μm to 1.2 μm.
An organic photoreceptor having a uniform cylindrical support can be obtained in a suitable range of. When carbon black is added, carbon black can be added uniformly by adding together a dispersant for carbon black, which makes the support uniform and contributes to making the surface roughness uniform, which is preferable. is there.

Furthermore, by adding glass fibers to the support material, it is possible to obtain an organic photoreceptor having a cylindrical support having high mechanical strength and being hard to be deformed even in a thin and long shape. Glass fiber has a diameter of about 20 μm and a length of 3 mm
Those having a shape of about a certain degree are preferable because they do not adversely affect the surface roughness of the support. Thus, even if various kinds of materials are added in this way, if at least 40% by weight or more of the support material is a cross-linking type PPS resin, its characteristics can be exhibited without impairing it.

The surface of the support has a wavelength of 180 nm to 2 nm.
It has excellent adhesiveness by irradiation with 55 nm ultraviolet rays or by corona discharge on the surface, and it has a cylindrical support on which a layer made of an organic material can be formed with good adhesion, thus improving the service life. The obtained organic photoreceptor can be obtained. In addition, the cylindrical support as described above contains a cross-linking type PPS resin as a main component and has a volume resistivity of 10 ^−1.
A material having a volume resistivity of 10 ⁴ Ω · cm or less by blending a highly conductive carbon black of Ω · cm or less, or an average particle diameter of carbon black of 20 μm to 50
It can be manufactured with high productivity by injection molding a material having a thickness of μm or a material further added with glass fiber.

In injection molding, the mold temperature is 120 ° C.
To 150 ° C, molding material temperature is 280 ° C
If the temperature is within the range of 330 ° C. to 330 ° C., the above-mentioned molding material can be molded well, and further, the crystallization of the resin is sufficiently advanced to obtain a support utilizing the characteristics of the cross-linking type PPS resin. Further, when the material filling time is set within the range of 0.05 seconds to 2.5 seconds, it is preferable that a thin and long cylindrical support can be well formed. As for the molding die, the core die fitted in the fixed die has a surface roughness of 1 μm or less at the maximum height R _max and has a range of 0.15 ° to 0.25 ° on one side. The cavity mold has an internal draft and the inner surface of the cavity mold does not have a draft, and the surface roughness is finished by electroforming with a nickel alloy to a maximum height R _max of 1 μm or less. The stepped part is formed inside the contacting end face, and the structure is filled with the molding material by the side gate method through the stepped part.The fixed mold has a cavity mold on the end face in contact with the cavity mold in the circumferential direction. A structure where at least three equal parts are provided with spring knocks at each position, and the injection-molded product always remains on the cavity side due to the action of this spring knock when the mold is opened after molding. A molding die that is characterized as being used. By using the mold having such a configuration, the filling time of the molding material can be easily shortened to 0.05 seconds to 2.5 seconds, and the circumference of the cavity can be increased to the tip of the cavity before the material begins to solidify. The direction can be filled with sufficient material evenly,
A thin and long-shaped support can be molded well. Also,
A support having a surface roughness of 1 μm or less at the maximum height R _max is obtained corresponding to the roughness of the inner surface of the cavity mold. In addition, since the surface of the core mold is smooth and has a draft when opening the mold after injection molding, the core mold can be smoothly removed from the molded product, and then the molded product is removed from the cavity mold, for example, by knocking out. Then, the support, which is a molded product, can be taken out without damaging the surface.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of an embodiment of a support of the present invention, FIG. 1 (a) is a vertical cross-sectional view, and FIG. 1 (b) is a cross-sectional view taken along line XX of FIG. 1 (a).

FIG. 2 is a schematic cross-sectional view of an embodiment of the photoconductor of the present invention.

FIG. 3 is a partial cross-sectional view illustrating a mold clamping state according to an embodiment of the present invention.

FIG. 4 is a partial cross-sectional view of a mold opening state for explaining an embodiment of a mold according to the present invention.

5 is a partial enlarged cross-sectional view of the spring knock portion and its surroundings in FIG.

FIG. 6 is a perspective view showing a molded product taken out from the mold.

[Explanation of symbols]

 1 Support 2 Subbing Layer 3 Photosensitive Layer 4 Charge Generation Layer 5 Charge Transport Layer 6 Cavity Type 7 Core Type 8 Fixed Type 9 Cavity 10 Stepped Part 11 Spring Knock 12 Spring 13 Knockout Pin 14 Molded Product 15 Ring-shaped Convex Part 16 side gate

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[Procedure amendment]

[Submission date] December 16, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 9

[Correction method] Change

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[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

[0026]

[Table 2]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

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Example 2 As the support 1-1 of Example 1, an ultraviolet irradiation device (model SUV200NS) manufactured by Sen Engineering Co., Ltd. was used, and the distance between the low-pressure mercury lamp and the support was set to 20 mm,
Wavelength 184.9nm and 2 from 200W low pressure mercury lamp
The surface of the support is irradiated with 53.7 nm ultraviolet light. A substrate having an irradiation time of 10 seconds is referred to as a support 2-1 and a substrate having an irradiation time of 20 seconds is referred to as a support 2-2.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

By setting the average particle size of the carbon black to be mixed with the support material to 20 nm to 50 nm, the surface roughness R _max is 0.5 μm to 1.2 μm.
An organic photoreceptor having a uniform cylindrical support can be obtained in a suitable range of. When carbon black is added, carbon black can be added uniformly by adding together a carbon black dispersant, which makes the support homogeneous and also contributes to uniform surface roughness. Is.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

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The surface of the support has a wavelength of 180 nm to 2 nm.
It has excellent adhesiveness by irradiation with 55 nm ultraviolet rays or by corona discharge on the surface, and it has a cylindrical support on which a layer made of an organic material can be formed with good adhesion, thus improving the service life. The obtained organic photoreceptor can be obtained. In addition, the cylindrical support as described above contains a cross-linking type PPS resin as a main component and has a volume resistivity of 10 ^−1.
A material having a volume resistivity of 10 ⁴ Ω · cm or less by blending a highly conductive carbon black of Ω · cm or less, or an average particle diameter of carbon black of 20 nm to 50
It is possible to manufacture with good productivity by injection molding a material having a thickness of nm or a material to which glass fiber is further added.

Claims (13)

[Claims] 1. A cross-linked polyphenylene sulfide resin as a main component, which is mixed with a highly conductive carbon black having a volume resistivity of 10 ^-1 Ω · cm or less to make the volume resistivity of 10 ⁴ Ω · cm or less. An organic photoreceptor for electrophotography, comprising an organic photosensitive layer on a cylindrical support made of a material. 2. The photosensitive member according to claim 1, wherein the carbon black contained in the cylindrical support has an average particle diameter of 20 nm.
To 50 nm, an organic photoconductor for electrophotography. 3. The photosensitive member according to claim 1, wherein
An organophotoreceptor for electrophotography, wherein the cylindrical support contains a dispersant of carbon black. 4. The organic photoconductor for electrophotography according to claim 3, wherein the dispersant is calcium carbonate or clay. 5. The organic photoreceptor for electrophotography according to claim 1, wherein the cylindrical support contains glass fiber as a reinforcing material. 6. The photosensitive member according to claim 1, wherein the amount of the crosslinked polyphenylene sulfide resin of the cylindrical support is at least 40% by weight.
The above is an organic photoconductor for electrophotography, which is characterized by the above. 7. The photoreceptor according to claim 1, wherein the surface of the cylindrical support has a wavelength of 180 n.
An organic photoconductor for electrophotography, which is irradiated with ultraviolet rays of m to 255 nm. 8. An electrophotographic organic photoconductor according to claim 1, wherein the surface of the cylindrical support is subjected to corona discharge treatment. 9. The electrophotographic organic photoconductor according to claim 1, wherein the cylindrical support has a wall thickness of 3 mm or less. 10. A cross-linked polyphenylene sulfide resin as a main component, which has a volume resistivity of 10 ⁻¹ Ω · cm.
A method for producing a cylindrical support, characterized in that a material having a volume resistivity of 10 ⁴ Ω · cm or less by blending the following highly conductive carbon black is injection-molded with a mold for the cylindrical support. . 11. The method for manufacturing a cylindrical support according to claim 10, wherein the temperature of a mold for injection molding is 120 ° C.
To 150 ° C., a method for manufacturing a cylindrical support. 12. The method for producing a cylindrical support according to claim 10 or 11, characterized in that the time for filling the material during injection molding is within the range of 0.05 seconds to 2.5 seconds. A method for manufacturing a cylindrical support. 13. The method for manufacturing a cylindrical support according to claim 10, wherein the core die of the die has a surface roughness of 1 μm or less at a maximum height R _max. In addition, one side has a draft in the range of 0.15 ° to 0.25 °, the cavity mold inner surface of the die does not have a draft, and electroforming is performed using a nickel alloy to provide a surface roughness. Is finished to have a maximum height R _max of 1 μm or less, a step portion is formed inside the end face in contact with the fixed mold, and the material is filled by the side gate method through the step portion. , The fixed mold of the mold has at least three equally divided parts in the circumferential direction of the cavity mold on the end surface in contact with the cavity mold, and spring knocks are provided at each position, and the molded product is injection molded when the mold is opened. But this spring knock A method of manufacturing a cylindrical support, characterized in that a mold is used, which is characterized in that it is always left on the cavity mold side by the action of the mold.