JPH0713346A - Manufacture of electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To provide a method for manufacturing an electrophotographic photosensitive body which is free from the coating fault and provides the high image quality free from the image fault, continuously and efficiently. CONSTITUTION:In the manufacturing method for the electronicphotograpic photosensitive body having a photosensitive layer on an electric conductive supporting body, the electrophotographic photosensitive body is manufacured by cooling a supporting body 6 through the contact of a cooled device 1 with the supporting body 6, and in other method, the electrophotogrphic photosensitive body is manufactured by heating drying the supporting body through the contact of a heated device with the supporting body. Accordingly, the electrophotographic photosensitive body which is free from the coating fault and provides the high inage quality free from the image fault can be manufactured continuously and efficiently.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an electrophotographic photosensitive member, and more particularly to a method for continuously manufacturing an electrophotographic photosensitive member having no image defect.

[0002]

2. Description of the Related Art An electrophotographic photosensitive member is manufactured by forming a photosensitive layer on a support and, if necessary, a conductive layer and an intermediate layer. As a method of forming each of these layers, there is a method of directly depositing a substance on the surface of a support by a method such as vacuum deposition, sputtering, and CVD as in the examples of a selenium photoconductor and an amorphous silicon photoconductor.
A method of preparing a coating solution in which a binder resin or the like is dispersed or dissolved in a solvent and adhering it to the surface of a support by a coating means is excellent in mass productivity and production cost. In recent years, electrophotographic photoreceptors, particularly OPC (organic photoreceptor) Widely used in the manufacture of.

As a drying method used in the drying step after applying the coating liquid, there are methods such as natural drying and air drying which do not heat, but industrially, a method of heating and drying with hot air or infrared rays is generally used. It is used for. After the heating and drying is completed, it is cooled and the process proceeds to the next step. As a cooling method, there are natural cooling such as leaving it to stand and ventilation cooling.

[0004]

However, the conventional cooling method has the following problems. 1) In natural cooling, it takes a long time to cool the support, so that dust or the like adheres to the coated and dried surface, causing a coating defect in the next coating step. 2) Since air is blown during blast cooling, dust rises a lot, and dust adheres to the coating / drying surface, causing coating defects in the next coating process. 3) In any of the conventional cooling methods, when the thickness of the support is large and the heat capacity is large, the cooling rate of the support is slow and the time required for the cooling process is long, so that there is a problem that the production efficiency cannot be improved.

Further, when the electrophotographic photosensitive member is required to have high sensitivity and high image quality, it is often the case that the photosensitive member has a multi-layered structure in which the functions are separated. A layer which is applied to the substrate for the purpose of controlling charge injection property, preventing diffuse reflection of light and complementing defects of the support. Intermediate layer: a layer which is located between the photosensitive layer and the support or between the photosensitive layer and the conductive layer and which functions as a barrier layer for injecting charges. Charge generation layer: A layer that generates charges upon exposure. Charge transport layer: A layer in which charges generated in the charge generation layer are transported.

In the case of such a multilayer structure, a low coating defect rate is required for each layer. Therefore, in the conventional cooling method, in order to secure a good non-defective rate, dust attached during cooling is a problem at present. Furthermore, when each layer is continuously applied, it is necessary to cool the production line as quickly as possible in order to operate the production line efficiently, which is a problem.

Further, the conventional heating and drying method has the following problems. 1) In hot air drying, dust blows up much because it blows air, and since it takes time to raise the temperature of the support, it takes time to dry to the touch (when the surface is wet and dust adheres The time in the dry state) becomes longer, and dust or the like adheres to the dried surface of the coating during continuous coating, which causes coating defects. 2) It is difficult to control the surface temperature of the material to be dried by a method of heating with infrared rays or the like, and it is necessary to rotate the support by some means in order to make the temperature distribution uniform. However, when a rotating device is provided in the drying furnace, it causes dust generation, and dust and the like adhere to the coating / drying surface during continuous coating, which causes coating defects. 3) In the conventional drying method, when the thickness of the support is large and the heat capacity is large, the temperature rising rate of the support is slow and the drying process takes a long time. There is a problem that the thickness becomes thin and the sensitivity of the electrophotographic photosensitive drum becomes non-uniform in the upper and lower parts. Furthermore, when the electrophotographic photosensitive member has a multi-layer structure, a low coating defect rate is required for each layer.

Further, in the conventional drying method, in the case of an electrophotographic photosensitive member aiming at high image quality, the characteristics such as sensitivity and dark decay are easily influenced by the drying temperature, and it is necessary to minimize the temperature distribution in the drying oven. However, if the amount of air in the hot air drying oven is reduced or the rotating means of the support is eliminated, image defects due to uneven drying temperature will occur. Therefore, the current situation is that it always poses a problem in ensuring a good yield rate.

It is an object of the present invention to provide a method for solving the above-mentioned problems and stably producing a high quality electrophotographic photosensitive member free from coating defects and image defects for a long period of time.

[0010]

That is, the first aspect of the present invention is to provide a method for producing an electrophotographic photosensitive member having a photosensitive layer on a conductive support by bringing a cooled device into contact with the support. A method for manufacturing an electrophotographic photosensitive member, which comprises cooling the body.

The second aspect of the present invention is a method for producing an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein a heated device is brought into contact with the support to heat and dry the support. And a method for producing an electrophotographic photosensitive member.

First, the first aspect of the present invention will be described.

As the cooling means used in the present invention, a cooled device is brought into contact with the surface of the support which is not used for image formation, and the support is cooled. An example of the material of the device to be brought into contact is a heat conductive material. Examples of good materials include metals such as iron, aluminum and copper or alloys thereof, heat resistant resins such as phenol resin and silicon resin, and inorganic materials such as carbon, asbestos, glass and ceramics. Moreover, these composite materials can also be used. Further, the surface of the heat-conducting material may be covered with an elastic material such as silicon rubber, fluororubber, asbestos or glass wool for the purpose of improving the contact property with the support.

As an example of the cooling method of the device brought into contact with the support, there is a method of incorporating a cooling part of a heat pump inside the device. When it is necessary to sufficiently control the temperature stability of the cooling device, a cooling medium may be circulated inside and cooled by a heat exchanger. It is preferable to control the surface temperature of the apparatus that is brought into contact with the support so that the surface temperature of the support becomes a target temperature and that the surface temperature of the support does not fluctuate even in continuous production. Similarly for the temperature distribution, it is preferable to control the surface temperature of the support so that it falls within the target temperature range at any part, and therefore the surface temperature of the device to be contacted may be divided into several parts and controlled. Good.

The shape of the device to be brought into contact is selected depending on the shape of the support. For example, when an image is formed on the outer surface in a cylindrical shape, an object to be cooled is inserted inside the cylinder in order to improve adhesion. After that, it is possible to add a mechanism for expanding and expanding the outer shape of the device.

The method for producing an electrophotographic photosensitive member according to the present invention, in which a cooled device is brought into contact with the support of the photosensitive member to cool the support, may be used in combination with another cooling method (for example, blow cooling, natural cooling). It is possible.

Next, the second invention will be described.

The heating means used in the present invention heats the support by bringing a heated device into contact with the surface of the support which is not used for image formation. An example of the material of the contacting device is a heat conductive material. Examples of good materials include metals such as iron, aluminum and copper or alloys thereof, heat resistant resins such as phenol resin and silicon resin, and inorganic materials such as carbon, asbestos, glass and ceramics. Moreover, these composite materials can also be used. Further, the surface of the heat-conducting material may be covered with an elastic material such as silicon rubber, fluororubber, asbestos or glass wool for the purpose of improving the contact property with the support.

Examples of the heating method of the device brought into contact with the support include a method of energizing the device itself and a method of incorporating an electric heater or the like inside. However, when the solvent of the coating liquid is flammable, it is necessary to pay sufficient attention to electric sparks, overheating, etc., and it is also possible to circulate a heat medium, steam, etc. inside and heat by a heat exchanger.

With respect to the surface temperature of the device which is brought into contact with the support, the surface temperature of the support is set to a target temperature,
Further, it is preferable to control so that the surface temperature of the support does not change even in continuous production. Similarly for the temperature distribution, it is preferable to control the surface temperature of the support so that it falls within the target temperature range at any part, and therefore the surface temperature of the device to be contacted may be divided into several parts and controlled. Good.

The shape of the device to be contacted is selected depending on the shape of the support. For example, when an image is formed on the outer surface in a cylindrical shape, an object to be heated is inserted inside the cylinder in order to improve adhesion. After that, it is possible to add a mechanism for expanding and expanding the outer shape of the device.

The method for producing an electrophotographic photosensitive member according to the present invention, in which a heated device is brought into contact with a support to heat and dry the support, is different from other drying methods (for example, a method of heating and drying with hot air or infrared rays). It is also possible to use together.

Next, items common to the first and second aspects of the present invention will be described.

As the material of the support used in the present invention, one having a good thermal conductivity is suitable, and the following examples can be given. Metals such as aluminum, copper, nickel and silver or alloys thereof; conductive metal oxides such as antimony oxide, indium oxide and tin oxide, carbon fiber, carbon black, and graphite powder mixed with resin. .

The coating liquid used in the present invention is as follows.

The coating liquid used for coating the conductive layer is, for example, metal powder of aluminum, copper, nickel, silver or the like; conductive metal oxide such as antimony oxide, indium oxide or tin oxide; polypyrrole, polyaniline, polymer electrolyte. Polymer conductive material such as; carbon fiber, carbon black, graphite powder; or conductive material such as conductive powder whose surface is coated with these conductive materials, and acrylic resin, polyester resin, polyamide resin, polyvinyl acetate resin Thermoplastic resin such as polycarbonate resin and polyvinyl butyral resin; thermosetting resin such as polyurethane resin, phenol resin and epoxy resin; binder resin such as photocuring resin; alcohols such as methanol, ethanol, butanol and isopropyl alcohol; methyl ethyl ketone Ketones such as amine, acetone, methyl isobutyl ketone, and cyclohexanone; ethers such as diethyl ether and tetrahydrofuran; esters such as ethyl acetate and propyl acetate; hydrocarbons such as normal hexane and toluene; and other suitable solvents Examples thereof include those obtained by adding additives as required.

The coating liquid for the intermediate layer is, for example, gelatin, ethylene / acrylic acid copolymer, nitrocellulose resin, polyamide resin, polyvinyl alcohol resin,
Polyvinyl alcohol resin and other resins such as methanol, ethanol, butanol, isopropyl alcohol, and other alcohols; methyl ethyl ketone, acetone, methyl isobutyl ketone, and other ketones; others dissolved in a suitable solvent, with addition of additives as necessary There are some.

The photosensitive layer may have a single layer structure or a laminated structure in which the charge generating layer and the charge transporting layer are functionally separated.

Examples of the coating liquid for the charge generating layer of the laminated structure photoreceptor include azo pigments such as sudan red and chlordian blue; phthalocyanine pigments such as copper phthalocyanine and titanyl phthalocyanine; quinone pigments such as anthanthrone; berylylene pigment; indigo. Charge generating substances such as pigments and thermoplastic resins such as acrylic resin, polyester resin, polyamide resin, polyvinyl acetate resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl benzal resin; thermosetting of polyurethane resin, phenol resin, epoxy resin, etc. Binder resin such as resin, alcohol such as methanol, ethanol, butanol, isopropyl alcohol; keto such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone Ethers such as diethyl ether and tetrahydrofuran; Esters such as ethyl acetate and propyl acetate; Hydrocarbons such as normal hexane and toluene; those dispersed in other suitable solvents; and additives if necessary There are things like

Examples of the coating liquid for the charge transport layer include charge transport substances such as hydrazone compounds, stibene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, and triarylmethane compounds, and acrylic resins, polyester resins, Thermoplastic resin such as polyarylate resin, polyvinyl chloride resin, polycarbonate resin, polyvinyl butyral resin, polymethacrylate resin; binder resin such as polyurethane resin, phenol resin, thermosetting resin such as epoxy resin, methanol, ethanol, butanol , Alcohols such as isopropyl alcohol; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; ethers such as diethyl ether and tetrahydrofuran; acetic acid Esters such as chill and propyl acetate; hydrocarbons such as normal hexane, petroleum ether and toluene; halogenated hydrocarbons such as monochlorobenzene and dichloromethane, and those dispersed in other suitable solvents, and additives as necessary The thing which added. Further, an example of a coating liquid in which a conductive polymer is dissolved in a solvent is also given. Further, a substance that reduces wear such as Teflon powder may be dispersed.

Furthermore, the coating method used in the manufacturing method of the present invention can be applied not only to the conductive layer, intermediate layer, charge generation layer and charge transport layer of the electrophotographic photoreceptor but also to other layers such as an overcoat layer. .

As the solvent used in the present invention, a solvent having good solubility with respect to the binder resin in the coating liquid, dispersibility with respect to the pigment and coating property is selected.

In the preparation of the coating solution for the electrophotographic photoreceptor used in the present invention, simple stirring and mixing may be performed, but if necessary, a dispersing means such as a ball mill, a roll mill or a sand mill is used.

Examples of the coating method used in the present invention include a dip coating method, a spray coating method, a roll coater coating method and a gravure coater coating method.

The method for producing an electrophotographic photosensitive member of the present invention can be applied to the production of a photosensitive drum generally used in electrophotographic apparatuses such as a copying machine, a laser printer, an LED printer and a liquid crystal shutter printer.

[0036]

EXAMPLES The present invention will be described in more detail with reference to specific examples. Example 1 An example of a cooling device used in the present invention is shown in FIG. Cooling water 11 is supplied to the contact cooling device 1 from a cooling water tank 2 by a pump 3. The cooling water tank 2 is controlled by the cooler 4 so that the water temperature becomes constant. The contact cooling device 1 is made of silicone rubber, and has a structure in which the internal pressure can be adjusted by the pressure regulating valve 5, so that the whole can be expanded or contracted. After the application of the support (aluminum cylinder) 6 is completed, the application liquid adhering to the inner surface of the cylinder is peeled off and removed. After drying, the support body 6 is carried onto the contact cooling device 1 by a carrying means including a cylinder chucking jig 7, a vertically extending / contracting arm 8, a carrying unit 9 and a carrying rail 10 and inserted into the contact cooling device. The pressure in the contact cooling device is adjusted by the pressure regulating valve to expand the contact cooling device. After the heating and cooling are completed, the pressure in the contact cooling device is adjusted again to shrink the contact cooling device, and then it is transferred to the next step by the transfer means.

Next, an electrophotographic photosensitive member is manufactured. 10%
1 part of 2000 parts of conductive titanium oxide coated with tin oxide containing antimony oxide, 2500 parts of phenol resin, 2000 parts of methyl cellosolve, 500 parts of methanol.
It was dispersed for 2 hours by a sand mill using m glass beads to prepare a conductive layer coating solution.

Aluminum cylinder (φ120 mm × 3
The coating material for conductive layer was applied by dipping onto 60 mm, thickness 5 mm) and dried by a drying device at 160 ° C. for 20 minutes. After the completion of drying, it was cooled for 10 minutes by the cooling device shown in FIG. The temperature of the cooling water is 15 ° C, the surface temperature of the cooling device is 18
C., and the surface temperature of the support after completion of cooling was 23.degree. The thickness of the conductive layer was 20 μm.

Next, re-precipitation-purified N-methoxymethylated nylon 6, 1000 parts, 250 parts of 6,12,66,610 copolymer nylon were dissolved in 5000 parts of methanol and 5000 parts of butanol, and the solution was opened to an opening diameter of 0. It was filtered with a 0.5 μm filter to remove residual non-dissolved matter, dust and the like to prepare a coating solution for the intermediate layer. This intermediate layer coating solution was dip-coated on an aluminum cylinder coated with a conductive layer and dried at 95 ° C. for 7 minutes by a drying device. After the completion of drying, it was cooled for 7 minutes by the cooling device shown in FIG. Cooling water temperature is 1
The surface temperature of the cooling device was 5 ° C, and the surface temperature of the support was 23 ° C after the completion of cooling. The thickness of the intermediate layer was 0.50 μm. The above steps are repeated to continuously apply the conductive layer and the intermediate layer-coated aluminum cylinder to 1000
I made a book. As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products having coating defects, the number of defective coated aluminum cylinders was 31.

Example 2 400 parts of the following structural formula disazo pigment,

[0041]

[Chemical 1]

200 parts of polyvinyl butyral resin (butyralization ratio 68%, average molecular weight 24000) and 5000 parts of cyclohexanone were dispersed for 14 hours in a sand mill using φ1 mm glass beads, and tetrahydrofuran 5
000 parts were added, and this solution was further centrifuged (7000
After removing the bead residue, dust and the like at (rpm, 30 minutes), the coating liquid for the charge generation layer was prepared by further filtering with a filter having an opening diameter of 5.0 μm to remove residual non-dissolved substances and dust. Non-defective aluminum cylinder coated with the intermediate layer in Example 1 (φ120 mm × 360 mm, wall thickness 5 m
m) was coated with the above charge generation layer coating solution by dip coating, and dried at 85 ° C. for 7 minutes by a drying device. After the completion of drying, it was cooled for 7 minutes by the cooling device shown in FIG. Cooling water temperature is 1
The surface temperature of the cooling device was 5 ° C, and the surface temperature of the support was 23 ° C after the completion of cooling. The film thickness of the charge generation layer was 0.15 μm. The above steps were repeated to continuously produce 1000 charge generation layer-coated aluminum cylinders. As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products due to coating defects,
There were 20 defective coated aluminum cylinders.

Example 3 1000 parts of a styryl compound having the following structural formula,

[0044]

[Chemical 2]

1000 parts of a polycarbonate resin is dissolved in 5000 parts of monochlorobenzene and 3000 parts of dichloromethane, and the solution is filtered through a filter having an opening diameter of 5.0 μm to remove residual insoluble matter, dust and the like, and a charge transport layer coating solution. Was adjusted.

The above charge transport layer coating liquid was further applied by dip coating onto a non-defective aluminum cylinder (φ120 mm × 360 mm, wall thickness 5 mm) coated with the charge generation layer in Example 2, and dried at 130 ° C. for 40 minutes by a drying device. did.

After the completion of drying, it was cooled for 10 minutes by the cooling device shown in FIG. The temperature of the cooling water was 15 ° C, the surface temperature of the cooling device was 18 ° C, and the surface temperature of the support was 23 ° C after the completion of cooling.

The film thickness of the charge transport layer was 25 μm. The above process was repeated to continuously produce 1000 charge transport layer-coated aluminum cylinders. The 1000 coated aluminum cylinders were visually inspected, and as a result of separating defective products due to coating defects, the number of defective coated aluminum cylinders was 26.

Example 4 An example of the contact cooling device used in Example 4 is shown in FIG. The contact cooling device 1 is made of silicon rubber and is controlled by an internal cooling pipe 4 so that the surface temperature becomes constant. The outer diameter of the contact cooling device is the same as the inner diameter of the support (aluminum cylinder) 6, and the material is silicon rubber, which is elastic and therefore adheres well to the support. After the application of the support is completed, the coating liquid adhering to the inner surface of the cylinder is peeled off and removed, and after drying, the contact cooling device 1 is provided by a transfer means including a cylinder chucking jig 7, a vertical expansion / contraction arm 8, a transfer unit 9 and a transfer rail 10. It is carried on and inserted into the contact cooling device. After the cooling is completed, it is carried to the next step by the carrying means.

A coating liquid for charge transport layer exactly the same as in Example 3 was prepared. The above coating material was applied by dip coating onto an aluminum cylinder on which a charge generation layer had been applied, exactly as in Example 3, and dried at 130 ° C. for 40 minutes using a drying device.

After the completion of drying, it was cooled for 10 minutes by the cooling device shown in FIG. The temperature of the cooling water was 12 ° C, the surface temperature of the cooling device was 18 ° C, and the surface temperature of the support was 23 ° C after the completion of cooling.

The film thickness of the charge transport layer was 25 μm. The above process was repeated to continuously produce 1000 charge transport layer-coated aluminum cylinders. The 1000 coated aluminum cylinders were visually inspected and defective products due to coating defects were separated. As a result, the number of defective coated aluminum cylinders was 30.

Comparative Example 1 A cooling device used in this comparative example is shown in FIG. The support 6 after drying includes a cylinder chucking jig 7, an up-and-down telescopic arm 8,
The transport unit 9 and the transport rail 10 transport the transport unit 9 to the front of the blower cooling device (blower 12), and after cooling, the transport unit transports it to the next step.

The same conductive layer coating solution and intermediate layer coating solution as in Example 1 were prepared. The paint for the conductive layer was applied by dip coating on an aluminum cylinder exactly the same as in Example 1, and dried at 160 ° C. for 20 minutes by a dryer. After the completion of the drying, the support was cooled by the blower cooling device shown in FIG. 3 until the surface temperature of the support became 23 ° C. It took 15 minutes to cool. The film thickness of the conductive layer was 20 μm.

The paint for the intermediate layer was dip-coated on the aluminum cylinder coated with the conductive layer, and dried at 95 ° C. for 7 minutes by a dryer. After the completion of drying, the substrate was cooled by the air blow cooling device shown in FIG. 3 until the surface temperature of the substrate reached 23 ° C. It took 10 minutes to cool. The thickness of the intermediate layer is 0.5
was μm.

The above steps were repeated to continuously produce 1000 conductive layer and intermediate layer coated aluminum cylinders.
The 1000 coated aluminum cylinders were visually inspected, and as a result of separating defective products due to coating defects, the number of defective coated aluminum cylinders was 93.

As a result of observing a defective aluminum cylinder coated with a conductive layer, hardened dust of the coating liquid for a conductive layer was found inside the intermediate layer. Defective products frequently occurred after the latter half of continuous coating, and it can be said that the dust produced by the continuous coating in the drying step, which hardens the conductive layer coating liquid, adheres to the coating surface during cooling.

Comparative Example 2 The same charge generation layer coating solution as in Example 2 was prepared. The above charge generation layer coating material was further applied by dip coating onto the non-defective aluminum cylinder coated with the intermediate layer prepared in Comparative Example 1 and dried at 85 ° C. for 7 minutes by a drying device.

After the completion of the drying, the air was cooled by the air blow cooling device shown in FIG. 3 until the surface temperature of the support became 23 ° C. 1
It took 0 minutes. The film thickness of the charge generation layer was 0.15 μm. The above steps were repeated to continuously produce 1000 charge generation layer-coated aluminum cylinders. This 100
As a result of visually inspecting 0 coated aluminum cylinders and separating defective products due to coating defects, the number of defective coated aluminum cylinders was 43. As a result of observing the defective charge generation layer-coated aluminum cylinder, dust was found inside the charge generation layer.

Comparative Example 3 A coating liquid for charge transport layer exactly the same as in Example 3 was prepared. The above charge transport layer coating material was further applied by dip coating onto the good quality charge generation layer coated aluminum cylinder prepared in Comparative Example 2 and dried at 130 ° C. for 40 minutes by a drying device.

After the completion of the drying, the air was cooled by the air blow cooling device shown in FIG. 3 until the surface temperature of the support became 23 ° C. 1
It took 2 minutes. The film thickness of the charge transport layer was 25 μm. The above process was repeated to continuously produce 1000 charge transport layer-coated aluminum cylinders. This 1000
As a result of visually inspecting the coated aluminum cylinders of this book and separating defective products in which dust was seen inside the charge transport layer, 50 defective coated aluminum cylinders were found.

Comparative Example 4 A coating liquid for charge transport layer exactly the same as in Example 3 was prepared. The above charge transport layer coating material was further applied by dip coating onto the good quality charge generation layer coated aluminum cylinder prepared in Comparative Example 2 and dried at 130 ° C. for 40 minutes by a drying device.

After the completion of drying, the substrate was cooled by natural cooling until the surface temperature of the support reached 23 ° C. It took 22 minutes to cool. The thickness of the charge transport layer was 25 μm.
The above process was repeated to continuously produce 1000 charge transport layer-coated aluminum cylinders. As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products in which dust was found inside the charge transport layer, 40 defective coated aluminum cylinders were found.

[Evaluation of Actual Machine] The electrophotographic photoreceptors prepared in Examples 3 and 4 and Comparative Examples 3 and 4 were charged, exposed, and developed.
The transfer and cleaning process was mounted on a copier, which repeats every 0.8 seconds. As a result, in Examples 3 and 4, uniform high-quality images without image defects were obtained. In Comparative Examples 3 and 4, image defects due to dust in the photosensitive layer were found.

The results of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 1.
Summarized in. Comparing Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, and Examples 3 and 4 with Comparative Examples 3 and 4, the defective rate is low in the case of contact cooling, but defective in the case of blast cooling and natural cooling. The rate is high. Also, from the result of image evaluation, contact cooling produces a good image with few image defects.

[0066]

Example 5 FIG. 4 shows an example of a drying apparatus used in the present invention. Circulating oil 31 heated by a pump 23 is supplied from an oil heating tank 22 to the contact heating device 21. The oil heating tank 22 is controlled by an electric heater 24 so that the oil temperature is constant. The contact heating device 21 is made of silicone rubber and has a structure in which the internal pressure can be adjusted by the pressure regulating valve 25, and the whole can be expanded or contracted. After the application of the support (aluminum cylinder) 26 is completed, the application liquid adhering to the inner surface of the cylinder is peeled off and removed. The supporting body 26 is carried onto the contact heating device 21 by a carrying means including a cylinder chucking jig 27, an up-and-down telescopic arm 28, a carrying unit 29, and a carrying rail 30, and is inserted into the contact heating device. The pressure inside the contact heating device is adjusted by the pressure regulating valve to expand the contact heating device. After the heating and drying is completed, the pressure in the contact heating device is adjusted again to contract the pressure, and then it is conveyed to the next step by the conveying means. The entire apparatus was installed in a class 1000 clean room.

Next, an electrophotographic photosensitive member is manufactured. 10%
1 part of 2000 parts of conductive titanium oxide coated with tin oxide containing antimony oxide, 2500 parts of phenol resin, 2000 parts of methyl cellosolve, 500 parts of methanol.
It was dispersed for 2 hours by a sand mill using m glass beads to prepare a conductive layer coating solution.

Aluminum cylinder (φ120 mm × 3
(60 mm, thickness 5 mm), the above coating composition was applied by dipping, and the coating liquid adhering to the inner surface of the cylinder was peeled off and removed, and then dried at 160 ° C. for 15 minutes by the drying device shown in FIG. The thickness of the conductive layer was 20 μm.

The above steps were repeated to continuously produce 1000 conductive layer-coated aluminum cylinders.

As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products having dust adhering to the surface of the conductive layer, 32 defective coated aluminum cylinders were found.
It was a book.

Example 6 N-methoxymethylated nylon 6,1000 reprecipitated and purified
Parts, 250 parts of 6,12,66,610 copolymer nylon were dissolved in 5000 parts of methanol and 5000 parts of butanol to prepare a coating solution for the intermediate layer. Further, this solution was filtered through a filter having an opening diameter of 0.5 μm to remove residual non-dissolved material, dust and the like. Non-defective aluminum cylinder coated with a conductive layer in Example 5 (φ120 mm × 360 mm, wall thickness 5 mm)
The above coating material was further applied by dipping on the coating liquid, and the coating liquid adhering to the inner surface of the cylinder was peeled off and removed, and then dried at 95 ° C. for 7 minutes by the drying device shown in FIG. The thickness of the intermediate layer is 0.5
It was 0 μm. The above process was repeated to continuously produce 1000 intermediate layer coated aluminum cylinders. As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products in which dust adhered to the surface of the intermediate layer, there were 3 defective aluminum cylinders.

Example 7 400 parts of the following structural formula disazo pigment,

[0074]

[Chemical 3]

200 parts of polyvinyl butyral resin (butyralization rate 68%, average molecular weight 24000) and 5000 parts of cyclohexanone were dispersed in a sand mill using φ1 mm glass beads for 24 hours, and further 5000 parts of tetrahydrofuran were added to obtain a coating liquid for charge generation layer. It was adjusted. Further, the liquid was subjected to centrifugal separation (7,000 rpm, 30 minutes) to remove beads, dust and the like.

A non-defective aluminum cylinder coated with the intermediate layer in Example 6 (φ120 mm × 360 mm, wall thickness 5 m)
m) was coated with the above coating by dipping, the coating liquid adhering to the inner surface of the cylinder was peeled off and removed, and then dried at 85 ° C. for 7 minutes by the drying device shown in FIG. The thickness of the charge generation layer is 0.
It was 15 μm. The above steps were repeated to continuously produce 1000 charge generation layer-coated aluminum cylinders. As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products in which dust adhered to the surface of the charge generation layer, the number of defective coated aluminum cylinders was 2.

Example 8 1000 parts of a styryl compound having the following structural formula,

[0078]

[Chemical 4]

1000 parts of a polycarbonate resin was dissolved in 5000 parts of monochlorobenzene and 3000 parts of dichloromethane to prepare a charge transport layer coating solution. Further, this liquid was filtered with a filter having an opening diameter of 1.0 μm to remove residual non-dissolved matter, dust and the like.

The above coating material was further applied by dip coating on a good quality aluminum cylinder (φ120 mm × 360 mm, wall thickness 5 mm) coated with the charge generation layer in Example 7, and the coating liquid adhering to the inner surface of the cylinder was peeled off and removed. It dried at 130 degreeC for 40 minutes by the drying device shown in FIG. The film thickness of the charge transport layer was 25 μm. The above steps are repeated to continuously charge the aluminum cylinder coated with the charge transport layer to 1000 times.
I made a book. As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products with dust adhering to the surface, there were 16 defective coated aluminum cylinders.

Example 9 An example of the contact heating and drying apparatus used in Example 9 is shown in FIG.
The contact heating device 21 is made of silicon rubber and is controlled by an internal electric heater 24 so that the surface temperature becomes constant. The outer diameter of the contact heating device has the same size as the inner diameter of the support (aluminum cylinder) 26. Further, since the material is silicon rubber and it has elasticity, it is in good contact with the support. After the coating is completed, the support peels off the coating liquid adhering to the inner surface of the cylinder, and the support is a cylinder chucking jig 27, an up-and-down telescopic arm 28, and a transport unit 29.
Then, it is carried on a contact heating device composed of a carrier means composed of a carrier rail 30 and inserted into the contact heating device. After the heating and drying is completed, it is carried to the next step by the carrying means.

A coating liquid for charge transport layer exactly the same as in Example 8 was prepared. The above paint was applied by dip coating onto an aluminum cylinder on which a charge generation layer had been coated, exactly as in Example 8, and the coating liquid adhering to the inner surface of the cylinder was peeled off and removed. 1 at 130 ° C. by the contact dryer shown in FIG.
It was dried for 5 minutes. The film thickness of the charge transport layer was 25 μm.
The above process was repeated to continuously produce 1000 charge transport layer-coated aluminum cylinders. As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products in which dust adhered to the surface of the charge transport layer, there were 15 defective coated aluminum cylinders.

Comparative Example 5 A coating solution for the conductive layer was prepared in exactly the same manner as in Example 5.
The above coating material was applied by dip coating on an aluminum cylinder exactly the same as in Example 5, and the coating liquid adhering to the inner surface of the cylinder was peeled off and removed.
It dried at 20 degreeC for 20 minutes. The thickness of the conductive layer was 20 μm. The above process was repeated to continuously produce 1000 conductive layer-coated aluminum cylinders. As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products in which dust adhered to the conductive layer surface, there were 84 defective coated aluminum cylinders.

As a result of observing the surface of the defective aluminum cylinder coated with the conductive layer, hardened dust of the coating liquid for the conductive layer adhered. Defective products frequently occurred after the latter half of continuous coating, and it can be said that dust that hardens the conductive layer coating liquid generated in the drying step due to continuous coating accumulates and adheres to the undried coating surface. Although there was a difference in the drying time between Example 5 and Comparative Example 5, the heating rate was higher in the contact heating, so that the dry curing state was the same.

Comparative Example 6 A coating solution for the intermediate layer was prepared in exactly the same manner as in Example 6.
The above coating for the intermediate layer was applied by dip coating on an aluminum cylinder on which a conductive layer had been coated in exactly the same manner as in Example 6, and the coating liquid adhering to the inner surface of the cylinder was peeled off and removed, and then dried at 95 ° C. for 9 minutes with a hot air dryer. did. The thickness of the intermediate layer was 0.5 μm. The above process was repeated to continuously produce 1000 intermediate layer coated aluminum cylinders.
As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products with dust adhering to the surface of the intermediate layer, there were 35 defective coated aluminum cylinders.

As a result of observing the surface of the defective intermediate layer-coated aluminum cylinder, the dry dust of the intermediate coating solution was found to have adhered. Although there was a difference in the drying time between Example 6 and Comparative Example 6, the heating state was higher in the contact heating, so that the drying state was the same.

Comparative Example 7 The same charge generation layer coating solution as in Example 7 was prepared. The above charge generation layer coating material was further applied by dip coating onto an aluminum cylinder to which the intermediate layer had been applied exactly as in Example 6, and the coating liquid adhering to the inner surface of the cylinder was peeled off and removed, and then the hot air drier was used for 9 minutes at 85 ° C. Dried. The film thickness of the charge generation layer was 0.15 μm. The above process is repeated to continuously charge the aluminum cylinder coated with the charge generation layer 10 times.
I made 00 books. As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products in which dust adhered to the surface of the charge generation layer, the number of defective coated aluminum cylinders was 26. As a result of observing the surface of the defective charge generation layer-coated aluminum cylinder, dry dust of the charge generation coating liquid was attached. In addition, Example 7 and Comparative Example 7
Although there was a difference in the drying time, contact heating was the same in the dry state because the temperature rising rate was faster.

Comparative Example 8 A coating liquid for charge transport layer exactly the same as in Example 8 was prepared. The above charge transporting layer coating material was applied by dip coating on an aluminum cylinder on which a charge generating layer had been coated in exactly the same manner as in Example 8, and the coating liquid adhering to the inner surface of the cylinder was peeled off and removed. Min dried.
The film thickness of the charge transport layer was 25 μm. The above process was repeated to continuously produce 1000 charge transport layer-coated aluminum cylinders. As a result of visually inspecting these 1000 coated aluminum cylinders and separating defective products in which dust adhered to the surface of the charge transport layer, 50 defective coated aluminum cylinders were found. As a result of observing the surface of the defective charge transport layer-coated aluminum cylinder, dry dust of the charge transport coating solution was attached. In addition, although there is a difference in the drying time between Example 8 and Comparative Example 8, the heating rate was higher in the contact heating, so that the drying state was the same.

Comparative Example 9 A coating liquid for charge transport layer exactly the same as in Example 8 was prepared. The above coating material was applied by dip coating on an aluminum cylinder on which a charge generation layer had been coated, exactly as in Example 8, and the coating liquid adhering to the inner surface of the cylinder was peeled off and removed, and then dried at 160 ° C. for 15 minutes by an infrared dryer. The aluminum cylinder was rotated at 5 rpm in the dryer so that the surface temperature became uniform.

The thickness of the charge transport layer was 25 μm. The above process was repeated to continuously produce 1000 charge transport layer-coated aluminum cylinders. As a result of visual inspection of these 1000 coated aluminum cylinders and separating defective products in which dust adhered to the surface of the charge transport layer, the number of defective coated aluminum cylinders was 98. As a result of observing the surface of the aluminum cylinder in which the coating was poor, hardened dust of the coating liquid for the charge transport layer adhered.

[Evaluation of Actual Machine] The electrophotographic photosensitive members prepared in Examples 8 and 9 and Comparative Examples 8 and 9 were charged, exposed, and developed.
The transfer and cleaning process was mounted on a copier, which repeats every 0.8 seconds. As a result, in Examples 8 and 9, uniform high-quality images without image defects were obtained. The result of measuring the thickness of the charge transport layer is 2 for both the upper and lower parts of the image area.
It was 5 μm. In Comparative Examples 8 and 9, there was a difference in density between the upper part and the lower part of the halftone image, and the result of measuring the film thickness of the charge transport layer was 25 μm in the lower part of the image area, but the upper part was 22 μm in Comparative Example 8, and the comparative example. In No. 9, it was 20 μm.

The results of Examples 5-9 and Comparative Examples 5-9 are shown in Table 2.
Summarized in. Comparing Example 5 with Comparative Example 5, Example 6 with Comparative Example 6, Example 7 with Comparative Example 7, and Examples 8 and 9 with Comparative Examples 8 and 9, the contact heating drying has a low defect rate, In the case of hot air drying and infrared heating drying, the defect rate is high. Also, from the result of image evaluation, contact heating drying gave a good image with little difference in density between the upper part and the lower part of the halftone image.

[0093]

[0094]

As is clear from the above, by cooling the support by bringing the cooled device into contact with the support, it is possible to obtain a high quality image with less dust deposition and less image defects during cooling. The photographic photoreceptor can be produced in good yield. Also, the cooling time is shortened and the production efficiency is improved.

By heating and drying the support by bringing the heated device into contact with the support, adhesion of dust during drying is small, the thickness of the coating film is uniform, and there are no coating defects or image defects and a high level. It is possible to manufacture an electrophotographic photosensitive member that can obtain an image quality with a good yield. Further, the drying time is shortened and the production efficiency is improved.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an example of a contact cooling device used in a manufacturing method of the present invention.

FIG. 2 is a schematic configuration diagram of an example of a contact cooling device used in the manufacturing method of the present invention.

FIG. 3 is a schematic configuration diagram of a conventional blast cooling device.

FIG. 4 is a schematic configuration diagram of an example of a contact heating device used in the manufacturing method of the present invention.

FIG. 5 is a schematic configuration diagram of an example of a contact heating device used in the manufacturing method of the present invention.

[Explanation of reference symbols] 1 contact cooling device 2 cooling water tank 3 pump 4 cooler (cooling pipe) 5 pressure regulating valve 6 support (aluminum cylinder) 7 cylinder chucking jig 8 up-and-down telescopic arm 9 transfer unit 10 transfer rail 11 cooling Water 12 Blower 21 Contact heating device 22 Oil heating tank 23 Pump 24 Electric heater 25 Pressure regulating valve 26 Support (aluminum cylinder) 27 Cylinder chucking jig 28 Vertical expansion / contraction arm 29 Transfer unit 30 Transfer rail 31 Circulating oil

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Junichi Kishi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (4)

[Claims] 1. A method for manufacturing an electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the support is cooled by bringing a cooled device into contact with the support. Manufacturing method. 2. The contact between the support and the device is achieved by pressurizing and delivering a liquid into the device made of a resilient material to expand the device.
A method for producing the electrophotographic photosensitive member described. 3. A method for producing an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein a heated device is brought into contact with the support to heat and dry the support. Body manufacturing method. 4. The contact between the support and the device is performed by pressurizing and feeding a liquid into the device made of a resilient material to expand the device.
A method for producing the electrophotographic photosensitive member described.