EP0420580A2 - Verfahren zur Herstellung eines elektrophotographischen, organischen Photoleiters - Google Patents

Verfahren zur Herstellung eines elektrophotographischen, organischen Photoleiters Download PDF

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Publication number
EP0420580A2
EP0420580A2 EP90310488A EP90310488A EP0420580A2 EP 0420580 A2 EP0420580 A2 EP 0420580A2 EP 90310488 A EP90310488 A EP 90310488A EP 90310488 A EP90310488 A EP 90310488A EP 0420580 A2 EP0420580 A2 EP 0420580A2
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EP
European Patent Office
Prior art keywords
layer
resin composition
charge transport
coating solution
transport layer
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EP90310488A
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English (en)
French (fr)
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EP0420580A3 (en
Inventor
Yasuyuki Hanatani
Yasufumi Mizuta
Takeshi Arakawa
Nariaki Tanaka
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Kyocera Mita Industrial Co Ltd
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Mita Industrial Co Ltd
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Priority claimed from JP25290089A external-priority patent/JPH03113454A/ja
Priority claimed from JP25290189A external-priority patent/JPH06103395B2/ja
Priority claimed from JP25657389A external-priority patent/JPH03118549A/ja
Application filed by Mita Industrial Co Ltd filed Critical Mita Industrial Co Ltd
Publication of EP0420580A2 publication Critical patent/EP0420580A2/de
Publication of EP0420580A3 publication Critical patent/EP0420580A3/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/043—Photoconductive layers characterised by having two or more layers or characterised by their composite structure
    • G03G5/047—Photoconductive layers characterised by having two or more layers or characterised by their composite structure characterised by the charge-generation layers or charge transport layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0525—Coating methods

Definitions

  • the present invention relates to a method for manufacturing an electrophotographic organic photocon­ductor having an organic photoconductive layer. More particularly, the invention relates to a method for manufacturing a multilayer-structured electrophoto­graphic organic photoconductor, including the steps of forming a charge transport layer on the surface of a conductive base, forming a charge generating layer on the surface of the charge transport layer, and forming a surface protective layer on the surface of the charge generating layer.
  • Multilayer-structured electrophotographic organic photoconductors are usually manufactured in the following manner.
  • a charge transport layer coating solution containing a resin composition and a solvent is applied onto the surface of a conductive base, which is heated and dried to form a charge transport layer.
  • a charge generating layer coating solution con­taining a resin composition and a solvent is applied onto the surface of the charge transport layer, which is heated and dried to form a charge generating layer.
  • a surface protective layer coating solution containing a resin composition and a solvent is applied onto the surface of the charge generating layer, which is heated and dried to form a surface protective layer.
  • the heating process for each of the above layers is performed not only to vaporize the solvent contained in each coating solution but also to provide each layer with intended properties. If the conditions of heat treatment employed in the heating process are inadequate, the properties of the produced photoconduc­tor such as sensitivity and repeatability will deterio­rate. Furthermore, the surface hardness of the surface protective layer will also drop. It is therefore required that each layer be adequately heated.
  • the conditions of heat treat­ment for the surface protective layer have been deter­mined mainly by actually measuring the relationship between the heat treating time and the pencil hardness of the surface protective layer in the following man­ner.
  • Heat treatment accelerates the crosslinking in the resin composition forming the surface protective layer, and it is believed there is a correlation be­tween the crosslinking degree and the hardness of the surface protective layer. Therefore, in the previous method, it has been judged, on the basis of the prede­termined correlation between the heat treating time and the pencil hardness of the surface protective layer, that sufficient heat treatment is done at the point of time when a prescribed pencil hardness is obtained.
  • the solvent used in the charge generating layer coating solution a solvent that hardly dissolves the charge transport layer is used.
  • a substance of high crystallinity such as ethyl carbazole hydrazone or such as having a butadiene structure
  • the phenomenon is noted that fine, elongated cracks are caused in numerous numbers in the charge transport layer when the charge generating layer coat­ ing solution is applied on the surface of the charge transport layer.
  • This phenomenon is considered attributable to the following cause. Since the crystallinity of the charge transport substance is very high, the charge transport layer is formed with internal strain con­tained. When the charge generating layer coating solution is applied on the surface of the charge trans­port layer a small amount of the charge transport substance is dissolved by the solution although the resin in the charge transport layer is not dissolved. As the charge transport substance is dissolved by the solution, the internal strain in the charge transport layer is released, and the resulting energy acts to cause the cracks.
  • the method for manufacturing an electrophoto­graphic organic photoconductor of this invention comprises the steps of: forming on the surface of a conductive base a charge transport layer consisting of a first resin composition; and forming on the surface of the charge transport layer a charge generating layer con­sisting of a second resin composition, wherein the step of forming the charge transport layer includes: the application of a charge transport layer coating solu­tion containing the first resin composition and a solvent onto the surface of the conductive base for the formation of a layer of the coating solution; and the heat treatment of the coating solution layer at a temperature higher than the glass-transition tempera­ture (Tg) of the first resin composition and lower than the melt-starting temperature of the first resin compo­sition.
  • Tg glass-transition tempera­ture
  • the method for manufacturing an electrophotographic organic photocon­ductor comprises the steps of: forming on the surface of a conductive base a charge transport layer consist­ing of a first resin composition; and forming on the surface of the charge transport layer a charge generat­ing layer consisting of a second resin composition, wherein the step of forming the charge generating layer includes: the application of a charge generating layer coating solution containing the second resin composi­tion and a solvent onto the surface of the charge transport layer for the formation of a layer of the coating solution; and the heat treatment of the coating solution layer at a temperature lower than the melt-­starting temperature of the first resin composition.
  • the method for manufacturing an electrophotographic organic photocon­ductor comprises the steps of: forming on the surface of a conductive base a charge transport layer consist­ing of a first resin composition; forming on the sur­face of the charge transport layer a charge generating layer consisting of a second resin composition; and forming on the surface of the charge generating layer a surface protective layer consisting of a third resin composition, wherein the step of forming the surface protective layer includes: the application of a surface protective layer coating solution containing the third resin composition and a solvent onto the surface of the charge generating layer for the formation of a layer of the coating solution; and the heat treatment of the coating solution layer at a temperature lower than the melt-starting temperature of the charge transport layer consisting of the first resin composition.
  • the method for manufacturing an electrophotographic organic photocon­ductor comprises the step of forming a resin layer on the surface of a conductive base, wherein the step includes the application of a coating solution contain­ing a solvent and a binding resin made of a thermoset­ting resin and the drying of a layer of the coating solution under prescribed conditions, the prescribed drying conditions being determined by examining the reduction of a reactive group present in the thermoset­ting resin by means of infrared absorption spectrosco­py.
  • thermosetting resin is a silicone resin having a silicone oligomer as the main component.
  • the method for manufacturing an electrophotographic organic photo­conductor comprises the steps of: forming on the sur­face of a conductive base a charge transport layer consisting of a first resin composition; and forming on the surface of the charge transport layer a charge generating layer consisting of a second resin composi­tion, wherein the step of forming the charge generating layer includes the application and drying of a charge generating layer coating solution containing the second resin composition and a solvent onto the surface of the charge transport layer while holding the base with the charge transport layer formed thereon at a temperature within the range of 33°C to the glass-transition tem­perature (Tg) of the first resin composition.
  • Tg glass-transition tem­perature
  • the present invention is applicable to a method for manufacturing various multilayer-structured electrophotographic organic photoconductors.
  • the present invention is applicable to a method for manufacturing a photoconductor having a conductive base, a charge transport layer formed on the surface of the conductive base, a charge generating layer formed on the surface of the charge transport layer, and a surface protective layer formed on the surface of the charge generating layer.
  • a charge transport layer coating solution containing a first resin composition and a solvent is first applied onto the surface of the conductive base, and then, the coating solution layer is heated and dried at a pre­scribed temperature.
  • the first resin composition contains a binding resin, a charge transport substance, etc.
  • the heat treating temperature for the coating solution layer should be within the range of temperatures higher than the glass-transition temperature (Tg) of the first resin composition and lower than the melt-starting temperature of the first resin composition, preferably within the range of temperatures at least 10°C higher than the glass-transition temperature (Tg) of the first resin composition and at least 10°C lower than the melt-starting temperature of the first resin composi­tion.
  • the heat treating temperature is lower than the glass-transition temperature (Tg) of the first resin composition, internal strain tends to remain in the charge transport layer. This will cause irregular­ities on the surface of the charge transport layer when a charge generating layer coating solution containing a second resin composition and a solvent is applied on the surface of the charge transport layer. Conversely if the heat treating temperature is higher than the melt-starting temperature of the first resin composi­tion, the formed charge transport layer will melt and deform under its own weight, damaging the surface smoothness of the charge transport layer.
  • Tg glass-transition temperature
  • Heat treatment is performed by storing the conductive base with the coating solution layer formed thereon in a drying oven equipped, for example, with a hot water circulator, a steam circulator, an infrared or tungsten heater, etc.
  • the heat treating time is suitably adjusted in accordance with the formulation of the coating solution, the thickness of the coating solution layer, the heating capacity of the heating oven, etc.
  • the glass-transition temperature (Tg) and melt-starting temperature of the first resin composi­tion are obtained by actually measuring them.
  • a prior known resin As the binding resin contained in the first resin composition, a prior known resin is used. Exam­ples include styrene type polymer, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-acrylate copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyester, alkyd resin, polyamide, polyurethane, acrylic modified urethane resin, epoxy resin, polycarbonate, polyarylate, polysulfone, diallylphthalate resin, silicone resin, ketone resin, polyvinyl butyral resin, polyether resin, phenol resin and the like.
  • charge transport substance a substance with high crystallinity is generally used.
  • its general formula may be represented by one of the following formulae (1) to (4).
  • R1 an alkyl group or alkoxy group is denoted by R1 .
  • R2 and R3 are independently hydrogen, a nitro group, an alkyl group, an alkoxy group, a substituted or non-substituted phenyl group, a benzyl group, a group having an indole ring, an N-­alkylcarbazolyl group, a fluorenoyl group, or a triphenylallyl group.
  • R4 and R5 are independently a substituted amino group (its substituent is an alkyl group, an alkoxy group, halogen, or a nitro group), hydrogen, a nitro group, an alkyl group, an alkoxy group, a substituted or non-substituted phenyl group a benzyl group, a group having an indole ring, an N-­alkylcarbazolyl group, a fluorenoyl group, or a triphenylallyl group.
  • R6 or R7 are independently hydrogen, a nitro group, an alkyl group, an alkoxy group, a substituted or non-substituted phenyl group, a benzyl group, a group having an indole ring, an N-­alkylcarbazolyl group, a fluorenoyl group, or a triphenylallyl group.
  • R8 and R9 are independently a substituted amino group (its substituent is an alkyl group, an alkoxy group, halogen or a nitro group), hydrogen, a nitro group, an alkyl group, an alkoxy group, a substituted or non-substituted phenyl group, a benzyl group, a group having an indole ring, an N-­alkylcarbazolyl group, a fluorenoyl group, or a triphenylallyl group.
  • a charge generating layer coating solution containing a second resin composition and a solvent is first applied onto the surface of the charge transport layer, and then, the coating solution layer is heated and dried at a prescribed temperature.
  • the second resin composition contains a charge generating substance, a binding resin, etc.
  • the charge generating layer coating solution be applied onto the surface of the charge transport layer with the conductive base having the charge transport layer formed thereon kept at a temperature within the range of 33°C to the glass-transition temperature (Tg) of the first resin composition.
  • Tg glass-transition temperature
  • the heat treating temperature for the charge generating coating layer applied on the surface of the charge transport layer should be lower than the melt-­starting temperature of the first resin composition, preferably at least 5°C lower than the melt-starting temperature of the first resin composition. If the heat treating temperature is higher than the melt-­starting temperature of the first resin composition, the charge transport layer will melt and deform under its own weight, thus damaging the surface smoothness of the charge generating layer.
  • the same one as used in the first resin composition can be used.
  • a substance capable of dissolving the binding resin is used as the solvent, while a known substance is used as the charge generat­ing substance.
  • a surface protective layer coating solution containing a third resin composition and a solvent is first applied on the surface of the charge generating surface, and then, the coating solution layer is heated and dried at a prescribed temperature.
  • the third resin composition contains a binding resin or the like.
  • the heat treating temperature for the coating solution layer should be lower than the melt-starting temperature of the first resin composition, preferably at least 5°C lower than the melt-starting temperature of the first resin composition. If the heat treating temperature is higher than the melt-starting tempera­ture of the first resin composition, the charge trans­port layer will melt and deform under its own weight, thus damaging the surface smoothness of the surface protective layer.
  • the binding resin contained in the third resin composition the same one as used in the first resin composition can be used.
  • a substance capable of dissolving the binding resin is used as the solvent.
  • the glass-transition temperature and melt-starting temperature of the first resin composition it is possible to know the desirable heat treating temperatures for forming the charge transport layer, the charge generating layer, and the surface protective layer. Furthermore, by keeping the temperature of the charge transport layer at a pre­ scribed temperature when applying the charge generating layer coating solution, a photoconductor having a good surface condition can be produced without causing cracks in the charge transport layer. This allows the use of a charge transport substance having high crys­tallinity, and therefore, provides a wider selection of materials for use as the charge transport substance.
  • thermosetting resin used in the binding resin contained in each of the charge transport layer, charge generating layer, and surface protective layer coating solutions, the conditions of heat treat­ment for each applied solution layer can be determined in the following manner.
  • the reduction of a reactive group present in the thermosetting resin contained in each solution layer is measured by infrared absorption spectroscopy.
  • the conditions of heat treatment under which there occurs no further reduction of the reactive group or the reactive group is reduced to the minimum in the course of heating is determined as the optimum condi­tions of heat treatment for that layer.
  • the measure­ment can be made either by actually producing a photo­conductor and examining each layer formed thereon or by making a test piece having the same construction as that of the photoconductor and examining each layer formed on the test piece.
  • the reduction of the reactive group be measured by comparing the infrared absorption spectrum of the reactive group present in the thermosetting resin with that of a group different from the reactive group (a group detectable by infrared absorption spectroscopy).
  • a group different from the reactive group present in the thermosetting resin a group whose infrared absorption spectrum does not vary by heating, for example, an alkyl group such as a methyl group, is preferably used.
  • thermosetting resin any of the resins conventionally used in the coating solutions can be used. Examples include silicone resin, polyester, alkyd resin, polyamide, polyurethane, acrylic modified urethane resin, epoxy resin, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, phenol resin or the like.
  • substituent group a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an epoxy group or the like.
  • a combi­nation of two or more thermosetting resins may be used. In that case, it is desirable that the above measure­ment be made with respect to the resin that needs the longest heat treating time.
  • the following description deals with one example of a method for determining the optimum condi­tions of heat treatment for the surface protective layer which is formed using a silicone resin as the thermosetting resin with a silicone oligomer as the main component.
  • the silicone resin uses trifunctional alkylsilane as the starting material, it contains a silanol group (-SiOH). Through dehydration and poly­merization by heating, the silanol group turns into -SiOSi-, reducing the infrared absorption of the hy­droxyl group (-OH).
  • the infrared absorption of the alkyl group for example, a methyl group (-CH3)
  • the alkyl group for example, a methyl group (-CH3)
  • the infrared absorption spectrum of the surface protective layer is measured to obtain the ratio of the absorption peak (3400 cm ⁇ 1) of the hydroxyl group (-OH) to the absorption peak (2900 cm ⁇ 1) of the methyl group (-CH3). Change in the ratio is observed with respect to the time, and the time at which the ratio becomes nearly constant is determined as the completion time of the heat treatment.
  • the optimum conditions of heat treatment for each layer can be determined in a short period of time.
  • the above method can be used to in­spect the finished product.
  • a charge transport layer coating solution was prepared by mixing 100 parts by weight of polyarylate (manufactured by Unichika, Trade name: U-100), 100 parts by weight of 4-(N,N-diethylamino) benzaldehide-­N,N-diphenylhydrazone (manufactured by Kurita Kagaku Kenkyusho), and 900 parts by weight of methylene chloride (CH2Cl2).
  • the coating solution layer was dried by heating at each of the temperatures prescribed in Table 1 for 30 minutes, to form a charge transport layer of 20 ⁇ m thickness (Sample Nos. 1 to 8).
  • the glass-transition temperature (Tg) of the charge transport layer was 58°C, and the melt-starting temperature thereof was 115°C.
  • the coating film condition of the charge transport layer was examined, the results of which are shown in Table 1. From the results shown in Table 1, it was confirmed that a good coating film can be ob­tained when the charge transport layer is heat-treated at a temperature higher than the glass-transition temperature (Tg) of the charge transport layer and lower than the melt-starting temperature thereof.
  • Tg glass-transition temperature
  • a charge generating layer coating solution was prepared by mixing 80 parts by weight of 2,7-dibro­moanthanthrone (manufactured by ICI), 20 parts by weight of metalfree phthalocyanine (manufactured by BASF), 50 parts by weight of polyvinyl acetate (manu­factured by Nippon Gosei Kagaku, Trade name: Y5-N), and 2000 parts by weight of diacetone alcohol. Then, after applying the thus prepared coating solution on top of the charge transport layer (Sample No.
  • Example Nos. 9 to 13 which was formed in Example 1 at a heat treating temperature of 100°C, the coating solution layer was dried by heating at each of the temperatures prescribed in Table 2 for 30 minutes, to form a charge generating layer of 0.5 ⁇ m thickness (Sample Nos. 9 to 13).
  • the coating film condition of the charge generating layer was examined, the results of which are shown in Table 2. From the results of Table 2 it was confirmed that a good coating film can be obtained when the charge generating layer is formed at a temperature lower than the melt-starting temperature of the charge transport layer.
  • a liquid mixture was first prepared by mixing 57.4 parts by weight of 0.02N hydrochloric acid and 86 parts by weight of isopropyl alcohol, and then, while stirring the mixture with its temperature kept at 20 to 25°C, 80 parts by weight of methyltrimethoxysilane and 20 parts by weight of glycidoxypropyltrimethoxysilane were gradually dripped into the mixture. The mixture was then left at room temperature for one hour to obtain a silane hydrolyzate solution.
  • a surface protective layer coating solution was prepared by adding to the silane hydrolyzate solution 10 parts by weight of polyvinyl acetate having an average polymerization degree of 2000, 20 parts by weight of acetic acid, 0.5 parts by weight of triethylamine as a curing agent, 50 parts by weight of fine powder of antimony doped tin oxide (manufactured by Sumitomo Cement) as a conductive additive, and 0.3 parts by weight of a silicone type surfactant.
  • Example No. 10 After applying the coating solution on top of the charge generating layer (Sample No. 10) which was formed in Example 2 at a heat treating temperature of 110°C, the coating solution layer was dried by heating at each of the temperatures prescribed in Table 3 for 30 minutes, to form a surface protective layer of 2.5 ⁇ m thickness (Sample Nos. 14 to 18).
  • the coating film condition of the charge generating layer was examined, the results of which are shown in Table 3. From the results shown in Table 3, it was confirmed that a good coating film can be ob­tained when the surface protective layer is formed at a temperature lower than the melt-starting temperature of the charge transport layer.
  • Heat treating temperature of charge generating layer (°C) Coating film condition 9 100 good 10 110 good 11 115 good 12 118 Irregularities are caused on the charge transport layer 13 125 Irregularities are caused on the charge transport layer Table 3 Sample No. Heat treating temperature of the surface protective layer (°C) Coating film condition 14 100 good 15 110 good 16 115 good 17 118 Irregularities are caused on the charge transport layer 18 125 Irregularities are caused on the charge transport layer
  • a charge transport layer coating solution was prepared by mixing 100 parts by weight of polyarylate (manufactured by Unichika, Trade name: U-100), 100 parts by weight of 4-(N,N-diethylamino) benzaldehide-­N,N-diphenylhydrazone, and 900 parts by weight of methylene chloride (CH2Cl2). After applying the thus prepared coating solution on the surface of an aluminum drum of 78 mm outer diameter and 340 mm in length, the coating solution layer was dried by heating at 100°C for 30 minutes, to form a charge transport layer of 20 ⁇ m thickness.
  • polyarylate manufactured by Unichika, Trade name: U-100
  • CH2Cl2 methylene chloride
  • a charge generating layer coating solution was prepared by mixing 80 parts by weight of 2,7-dibro­moanthanthrone (manufactured by ICI), 20 parts by weight of metalfree phthalocyanine (manufactured by BASF), 50 parts by weight of polyvinyl acetate (manu­factured by Nihon Gosei Kagaku, Trade name: Y5-N), and 2000 parts by weight of diacetone alcohol. Then, after applying the thus prepared coating solution on top of the charge transport layer, the coating solution layer was dried by heating under the same conditions as those of the above, to form a charge generating layer of 0.5 ⁇ m thickness.
  • a liquid mixture was prepared by mixing 57.4 parts by weight of 0.02N hydrochloric acid and 86 parts by weight of isopropyl alcohol, and then, while stir­ring the mixture with its temperature kept at 20 to 25°C, 80 parts by weight of methyltrimethoxysilane and 20 parts by weight of glycidoxypropyltrimethoxysilane were gradually dripped into the mixture. The mixture was then left at room temperature for one hour to obtain a silane hydrolyzate solution.
  • a surface protective layer coating solution was prepared by adding to the silane hydrolyzate solu­tion 10 parts by weight of polyvinyl acetate having an average polymerization degree of 2000, 20 parts by weight of acetic acid, 0.5 parts by weight of triethylamine as a curing agent, 50 parts by weight of fine powder of antimony doped tin oxide (manufactured by Sumitomo Cement) as a conductive additive, and 0.3 parts by weight of a silicone type surfactant.
  • the surface protective layer coating solution was applied on top of the charge generating layer, and cured by heating at 120°C for each of the times prescribed in Table 4, to form a surface protective layer of a sili­cone resin having a thickness of 2.5 ⁇ m.
  • a drum type electrophotographic organic photoconductor was manufactured having multiple photoconductive layers.
  • the polyvinyl acetate (average polymerization degree of 2000) used in this example was prepared by a solution polymerization method in which vinyl acetate monomers were diluted with methyl alcohol and azobisisobutyronitrile (AIBN) was used as the polymerization initiator.
  • AIBN azobisisobutyronitrile
  • the adjustment of the aver­age polymerization degree was performed by controlling the amounts of catalyst, solvent, etc.
  • the infrared absorption spectrum of the surface protective layer was measured after particular heat treating times to obtain the absorption peak (3400 cm ⁇ 1) of the hydroxyl group (-OH) and that (2900 cm ⁇ 1) of the methyl group (-CH3). Then, the ratio of the absorption peak (3400 cm ⁇ 1) of the hydrox­yl group (-OH) to that (2900 cm ⁇ 1) of the methyl group (-CH3) was calculated, and the relationship of the ratio with respect to the heat treating time was exam­ined. The results are shown in Table 4 and Figure 1.
  • a surface protective layer consisting of a silicone resin was prepared to form a photoconductor in the same manner as in Example 4 except that polyvinyl butyral (manufactured by Denki Kagaku Kogyo, denka butyral 5000A) was used instead of polyvinyl acetate.
  • a surface protective layer consisting of a silicone resin was prepared to form a photoconductor in the same manner as in Example 4 except that a butylated melamine resin (manufactured by Mitsui Cyanamide, Yuban 128) was used instead of polyvinyl acetate.
  • the relationship between the heat treating time and the pencil hardness of the surface protective layer was examined.
  • the pencil hardness was measured using a pencil hardness tester manufactured by Mita Kogyo.
  • the pencil hardness H was obtained against the heat treat­ing time 5 minutes, 3H against 10 minutes, 4H against 15 minutes, and 5H against 30 minutes.
  • the relation­ship is shown in Figure 4. As shown in Figure 4, since the pencil hardness reached a stable level after 30 minutes of heat treating time, it was determined that 30 minutes was adequate as the heat treating time.
  • Sensitivity of the photoconductor The photoconductor was mounted on an electrostatic copying tester (manufactured by Gentec, Gentec Cynthia Model 30M), and the surface of the photoconductor was posi­tively charged to measure the surface potential V1 s.p. (V). Next, the photoconductor under the above charged condition was exposed by a halogen lamp, the exposure light source of the electrostatic copying tester, under the conditions of an exposure intensity of 0.92 W/cm2 and an exposure time of 60 msec., to obtain the time needed till the surface potential V1 s.p. is reduced to half, and the half-value exposure 1/2 (Lux ⁇ Sec) was calculated. The results are shown in Table 5 and Figure 5.
  • the photoconductor was mounted in a copying machine (manu­factured by Mita Kogyo, Model DC-111). After producing 500 copies on the copying machine, the surface poten­tial of the photoconductor was measured (the surface potential after repeated exposures to be denoted as V2 s.p. (V)). The difference between the surface potential V1 s.p. and the surface potential V2 s.p. was obtained to obtain the surface potential variation ⁇ V. The results are shown in Table 6.
  • a charge transport layer coating solution was prepared by mixing 100 parts by weight of polyarylate (manufactured by Unitika, Trade name: U-100), 100 parts by weight of 1,1-diphenyl-4,4-di-(diethylamino)phenyl 1,3-butadiene (with a melting point of 169°C) as a charge transport substance, and 900 parts by weight of methylene chloride (CH2Cl2).
  • the coating solution layer was dried by heating at 100°C for 30 minutes, to form a charge transport layer of 20 ⁇ m thickness.
  • the glass-transition temperature (Tg) was 74°C.
  • a charge generating layer coating solution was prepared by mixing 100 parts by weight of 2,7-­dibromoanthanthrone (manufactured by ICI), 50 parts by weight of polyvinyl acetate (manufactured by Nihon Gosei Kagaku, Trade name: Y5-N), and 2000 parts by weight of diacetone alcohol.
  • the charge generating layer coating solution was applied onto the surface of the charge transport layer (Sample Nos. 19 to 24). After that, the coating solution layer was dried by heating at 110°C for 30 minutes to form a charge generating layer of 0.5 ⁇ m thickness.
  • a charge transport layer was prepared in the same manner as in Example 7 except that ethyl carbonate diphenylhydorazone (with the melting point of 152°C) was used as a charge transport substance.
  • the glass-­transition temperature (Tg) of the charge transport layer was 66°C.
  • the charge generating layer coating solution obtained in example 1 was applied onto the surface of the charge transport layer (Sample Nos.25 to 30). After that, the coating solution layer was dried by heating at 110°C for 30 minutes to form a charge generating layer of 0.5 ⁇ m thickness.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Developing Agents For Electrophotography (AREA)
EP19900310488 1989-09-27 1990-09-25 A method for manufacturing an electrophotographic organic photoconductor Withdrawn EP0420580A3 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP252900/89 1989-09-27
JP252901/89 1989-09-27
JP25290089A JPH03113454A (ja) 1989-09-27 1989-09-27 電子写真用有機感光体の製造方法
JP25290189A JPH06103395B2 (ja) 1989-09-27 1989-09-27 電子写真用有機感光体の製造方法
JP25657389A JPH03118549A (ja) 1989-09-29 1989-09-29 電子写真用有機感光体の製造方法
JP256573/89 1989-09-29

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EP0420580A2 true EP0420580A2 (de) 1991-04-03
EP0420580A3 EP0420580A3 (en) 1991-04-24

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EP19900310488 Withdrawn EP0420580A3 (en) 1989-09-27 1990-09-25 A method for manufacturing an electrophotographic organic photoconductor

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EP (1) EP0420580A3 (de)
KR (1) KR910006787A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0697633A3 (de) * 1994-08-08 1997-01-02 Hewlett Packard Co Wiederverwendbarer, inverser, zwei-schichtig zusammengesetzter, organischer Photokonduktor, wobei spezifische Polymere eingesetzt werden die geeignet sind für Diffusionsbeschichtungsverfahren mit nicht chlorierten Lösungsmitteln
EP1146396A2 (de) * 2000-04-10 2001-10-17 Kyocera Mita Corporation Verfahren zur Herstellung eines elektrophotoempfindlichen Materials und elektrophotoempfindliches Material
US7767374B2 (en) * 2005-12-15 2010-08-03 Sharp Kabushiki Kaisha Method for producing electrophotographic photoreceptor having sublimable antioxidant in coating liquid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3850631A (en) * 1973-04-24 1974-11-26 Rank Xerox Ltd Photoconductive element with a polyvinylidene fluoride binder
US4610942A (en) * 1984-02-16 1986-09-09 Canon Kabushiki Kaisha Electrophotographic member having corresponding thin end portions of charge generation and charge transport layers
JPS62157038A (ja) * 1985-12-28 1987-07-13 Konishiroku Photo Ind Co Ltd 正帯電用感光体の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3850631A (en) * 1973-04-24 1974-11-26 Rank Xerox Ltd Photoconductive element with a polyvinylidene fluoride binder
US4610942A (en) * 1984-02-16 1986-09-09 Canon Kabushiki Kaisha Electrophotographic member having corresponding thin end portions of charge generation and charge transport layers
JPS62157038A (ja) * 1985-12-28 1987-07-13 Konishiroku Photo Ind Co Ltd 正帯電用感光体の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 11, no. 391 (P-649)(2838) 22 December 1987, & JP-A-62 157038 (KONISHIROKU PHOTO IND. CO.,LTD.) 13 July 1987, *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0697633A3 (de) * 1994-08-08 1997-01-02 Hewlett Packard Co Wiederverwendbarer, inverser, zwei-schichtig zusammengesetzter, organischer Photokonduktor, wobei spezifische Polymere eingesetzt werden die geeignet sind für Diffusionsbeschichtungsverfahren mit nicht chlorierten Lösungsmitteln
EP1146396A2 (de) * 2000-04-10 2001-10-17 Kyocera Mita Corporation Verfahren zur Herstellung eines elektrophotoempfindlichen Materials und elektrophotoempfindliches Material
EP1146396A3 (de) * 2000-04-10 2002-05-08 Kyocera Mita Corporation Verfahren zur Herstellung eines elektrophotoempfindlichen Materials und elektrophotoempfindliches Material
US6444385B2 (en) 2000-04-10 2002-09-03 Kyocera Mita Corporation Electrophotosensitive material and method of producing the same
US7767374B2 (en) * 2005-12-15 2010-08-03 Sharp Kabushiki Kaisha Method for producing electrophotographic photoreceptor having sublimable antioxidant in coating liquid

Also Published As

Publication number Publication date
EP0420580A3 (en) 1991-04-24
KR910006787A (ko) 1991-04-30

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