US3860421A - N-alkyl morpholine treatment of a selenium-containing photoconductive layer - Google Patents

N-alkyl morpholine treatment of a selenium-containing photoconductive layer Download PDF

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US3860421A
US3860421A US408248A US40824873A US3860421A US 3860421 A US3860421 A US 3860421A US 408248 A US408248 A US 408248A US 40824873 A US40824873 A US 40824873A US 3860421 A US3860421 A US 3860421A
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imaging layer
selenium
compound
imaging
photoconductive
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US408248A
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Bela Telek
Thomas Skaper
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Xerox Corp
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Xerox Corp
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Priority to DE19742447455 priority patent/DE2447455A1/en
Priority to JP49117022A priority patent/JPS5068337A/ja
Priority to FR7435221A priority patent/FR2248539B1/fr
Priority to NL7413776A priority patent/NL7413776A/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14Inert intermediate or cover layers for charge-receiving layers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/005Materials for treating the recording members, e.g. for cleaning, reactivating, polishing
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147Cover layers
    • G03G5/14708Cover layers comprising organic material

Definitions

  • the photoconductive imaging layer comprises amorphous selenium or selenium alloys.
  • the photoconductive imaging layer is treated with a liquid containing at least one N-substituted morpholine compound of the formula wherein R is a saturated aliphatic hydrocarbon radical having in the range of. fromabout 8 to about 30 carbon atoms.
  • This invention relates to a method, an imaging member prepared according to said method and the use of said imaging member in an imaging process. More specifically, this invention involves methods for preconditioning and reconditioning the imaging layer of an electrophotographic imaging member, the overcoated electrophotographic imaging member resulting from such treatment and an imaging process employing said overcoated electrophotographic imaging member.
  • the developed image can then be read or permanently affixed to the photoconductor in the event that the imaging layer is not to be reused. This latter practice is usually followed with respect to the binder-type photoconductive films where the photoconductive layer is also an integral part of the finished copy.
  • the latent image can be developed on the imaging surface of a reusable photoconductor or transferred to another surface, such as a sheet of paper, andthereafter developed.
  • the latent image is developed on the imaging surface of a reusable photoconductor, it is subsequently transferred to another substrate and then permanently affixed thereto.
  • Any one of a variety of well known techniques can be used to permanently affix the Y toner image to the transfer sheet, including overcoating with transparent films and solvent or thermal fusion of the toner particles to the supportive substrate.
  • the relative efficiency which these cleaning means remove toner residues is often dependent upon a number of variables; including the presence of an additive in the developer composition, the presence of an overcoa'ting on the photoreceptor surface, the relative electrostatic attraction of the toner to the photoreceptor surface and the physical force exerted by the cleaning means against the photoreceptor surface. Since the imaging surface of selenium photoreceptors are sensitive to abrasion the pressure contact between the above cleaning means and this surface must be kept to a minimum in order to prevent damage to the imaging surface. This frictional contact of the cleaning means against the photoreceptor surface can also result in erosion of the cleaning member, U.S. Pat. No. 3,682,689. The blade cleaning type device previously referred to is especially vulnerable to this type of wear. If the photoreceptor surface is somewhat irregular, especially if it has minute projections, the pressure contact of the leading edge of a blade cleaning means against this'surface can result in the rapid deterioration of the cleaning blade.
  • the principal object of this invention to provide a method for minimizing the adverse effect of the above and similar residues on photoconductive insulating layers comprising amorphous selenium or selenium alloys.
  • the object of this invention to provide a method for preconditioning new electrophotographic imaging members whereinthe photoresponsive layer comprises amorphous selenium or selenium alloys.
  • Still yet a further object of this invention is to provide an overcoated imaging member wherein said overcoating improves abrasion and moisture resistance in addition to enhancing solid density development.
  • Still yet a further object of this invention is to provide an electrophotographic imaging method employing the above overcoated imaging member.
  • an imaging member having a photoconductive imaging layer comprising amorphous selenium or selenium alloy is treated with a conditioning effect amount of at least one N-substituted morpholine compound of the formula wherein, R is a saturated aliphatic hydrocarbon radical having in the range of from about 8 to 30 carbon atoms.
  • a dilute solution of one or more of the above compounds is applied to the amorphous selenium or selenium alloy imaging layer of the photoreceptor and then excess solution removing after a predetermined period of time.
  • the preferred compound used in the methods of this invention is N-lauryl-morpholine.
  • a conductive substrate having coated on at least one surface thereof a photoconductive film comprising amorphous selenium, a selenium alloy, or mixtures thereof.
  • Any of the conductive substrates traditionally used in the preparation of electrophotographic imaging members are suitable for use in preparation of the overcoated electrophotographic imaging members of this invention.
  • Such substrates can be flexible or inflexible; organic or inorganic; and transparent ,or opaque.
  • Representative of substrates which have proven suitable for use in such devices include aluminum, nickel, chromium, polyethylene terephthalate overcoated with a thin metal film, or metalized plastic films.
  • an interfacial barrier layer is deposited on such substrate in order to provide a blocking contact against premature injection of carriers from the conductive substrate into the photoconductive insulating layer.
  • This interfacial barrier layer can be an insulating material such as a dielectric film of an inorganic oxide. It is generally preferred that such interfacial barrier layers be capable of rectification.
  • the residence time of the conditioning solution on the imaging layer required to impart the desired beneficial results is quite extensive, generally in excess of about 20 minutes.
  • concentration of conditioning compound in the appropriate solvent is from about 5 to about 10 grams per milliliters solvent
  • residence time of the solution on the imaging layer need only be about 5 minutes in order to impart the desired beneficial finish.
  • concentration of conditioning compound is substantially in excess of 10 grams per 100 milliliters solvent
  • the increased viscosity of the conditioning solution creates problems in uniformity of application and penetration of the conditioning compounds into the microporous surface of the imaging layer.
  • Solvents which are suitable for use as vehicles for dispensing the conditioning compounds on the imaging layer must be compatible with the imaging layer (not interfere with or bring about changes in the electronic and/or physical properties) and must also be compatible with the environment in which such conditioning takes place.
  • Representative of solvents which are suitable for preparation of the conditioning solution include methanol, ethanol, n-propanol, isopropanol, and n-butanol.
  • the conditioning solution can be applied to the imaging layer of the imaging member by any one of a number of standard coating techniques including aerosol application or a wipeon application.
  • the conditioning solution must provide for the uniform coverage of the surface of the imaging layer with sufficient conditioning compound to effectively remove the organic buffing compound residues (if any), enhance abrasion resistance, enhance moisture resistance and- /or enhance charge acceptance. In order to enhance on or more of these properties, it is not necessarily required that such treatments enhance all such proper ties.
  • the conditioning compound has a relatively small aliphatic hydrogen substituent (8 carbon atoms)
  • the relative abrasion resistance of the imaging layer is not enhanced to the extent it would be where such substituent has in excess of about 20 carbon atoms.
  • charge acceptance is substantially improved where the imaging layer is conditioned with compounds having such relatively short chain hydrocarbon substituents.
  • the solution is allowed to saturate the surface of said imaging layer for a period of anywhere from about 3 to 10 minutes (preferably about 5 minutes).
  • nonabsorbed and nonadsorbed conditioning materials are removed from said surface by wiping said surface with a soft, damp fabric or sponge.
  • the wiper used in removing excess conditioning agent is ordinarilly wetted with the same solvent vehicle used in application of the conditioning compounds to the imaging layer.
  • the imaging surface is dried with a soft absorbent fabric or other suitable means. It is generally preferred that the solvents used in dispensing and removal of the conditioning compounds from the surface of the photoreceptor be highly volatile and thus capable of evaporation from said surface without any residual trace thereof remaining on said surface.
  • Conditioning of the drum in the manner described above does not alter the appearance of the imaging layer since the conditioning compounds are present in such small quantities and thus are not readily detectable except by sophisticated analytical techniques.
  • the quantity of conditioning compound capable of extraction from said layer is equal to about 0.6 to about 1.5 milligrams; or approximately 0.2 to about 0.5 micrograms per square centimeter.
  • the presence of the conditioning compound on the imaging layer can be detected by infrared spectroscopy after 4,000 copies.
  • an electrophotographic imaging member conditioned according to the method of this invention is placed in an electrostatographic copier, and copy tested to 10,000 copies (2 copies per cycle of photoreceptor).
  • the cleaning apparatus of this copier comprises a polyurethane blade which translates laterally across the surface of the photoreceptor.
  • the developer composition used in this copier contains a nonsmearing additive intended to enhance removal of residual toner from the surface of the photoreceptor.
  • Comparison of efficiency of cleaning both prior to and subsequent to conditioning of the imaging layer of the photoreceptor reveals a reduction of about 70 percent in the frictional forces between the blade and the imaging layer.
  • Comparison of charge acceptance of the conditioned and unconditioned portion of the photoreceptor reveals about a 10 percent increase in charge acceptance in the conditioned areas.
  • This treatment of selenium and selenium alloys photoreceptors provides the surface of said photoreceptor with a finish which substantially extends their useful lives in addition to reducing servicing requirements of both the photoreceptor and the cleaning means used in removal of toner residues from the imaging layer of said photoreceptor.
  • An electrophotographic imaging member having an imaging layer comprising an alloy of arsenic and selenium (65 percent by weight selenium to 35 percent by weight arsenic) is sectioned off and alternate sections conditioned with a solution comprising 5 percent N- laurylmorpholine in isopropyl alcohol.
  • the conditioning solution is applied with a cotton cloth and allowed to reside on the photoreceptor for an interval of approximately 5 minutes prior to removal of excess conditioning compound with. isopropyl alcohol.
  • the photoreceptor is wiped dry with a soft cotton cloth in those areas where the conditioner was applied.
  • the photoreceptor is sensitized by charging with a positive corotron which is maintained at 8,000 volts.
  • Measurement of the surface potential on the photoreceptor indicates that those areas which have been conditioned with the N-laurylmorpholine can support a surface potential of about 800 volts whereas those regions on the photorecptor not so conditioned can only support a surface potential of about 700 volts.
  • the photoreceptor is then placed in a standard Xerox 4,000 copier and several copies prepared therefrom. Examination of these copies clearly indicates that those areas of the photoreceptor which have been conditioned with the N-lauryl morpholine do produce copies of improved density even after 4,000 copying cycles.
  • the photoreceptor is then removed and examined. It appears that the conditioned sections of the photoreceptor are substantially freer of toner residues than those sections not treated with the conditioning solution; thus, indicating more efficient blade cleaning action.
  • Example II The procedures of Example I are repeated except for the substitution of a conditioning solution containing about 1 gram N-lauryl morpholine per 100 milliliters
  • EXAMPLE Ill The procedures of Example [I are repeated except that the conditioning solution is allowed to remain on the imaging layer of the electrophotographic imaging member for a period of about 25 minutes prior to removal of nonabsorbed compounds with isopropyl alcohol.
  • the charge acceptance and solid density development are improved over that attained in Example II but still are not comparable to that of Example I.
  • Example IV The procedures of Example I are repeated except for the substitution of a conditioning solution containing grams N-lauryl morpholine per 100 grams isopropyl alcohol. Due to the increased viscosity of this conditioning solution over that of Example I, the application of a uniform film on the imaging layer is somewhat more difficult. Following removal of excess conditioning compounds, the imaging layer is evaluated in the same manner as in Example I. Both charge acceptance and solid density development are inferior to that of Example I. It is believed that due to the increase in viscosity, the conditioning compound does not wet the imaging layer as efficiently as does the conditioning solution of Example I. Thus, the effectiveness of the conditioning compound is substantially reduced, resulting in less efficient and complete absorption and adsorption on the imaging layer.
  • Example I The procedure of Example I is repeated except for the substitution of N-palmityl-morpholine for N-laurylmorpholine.
  • EXAMPLE XIV In order to determine quantitatively the extent to which N-lauryl-morpholine reduces the frictional force between the cleaning blade and the photoreceptor surface in Example I, the photoreceptor is removed from the copier and installed in a testing fixture. A portion of the polyurethane blade is removed from the copier and installed in a holder in the testing fixture. The combined weight of the blade and holder is approximately grams. The blade is rested on the surface of the photoreceptor (blade area in contact with photoreceptor 20 millimeters X 2.2 millimeters). As the blade is drawn across the surface of the photoreceptor, the force required to advance the blade increases as the blade tra verses from the conditioned to the unconditioned portions of the photoreceptor.
  • Such change in force is measured on a simple spring scale (Ohaus, Dial Type scale) which is attached to the blade holder. From such measurements. the coefficient of friction (u) for the conditioned areas of the drum is calculated to be in the range of from about 0.025 to 0.030; and the coefficient of friction for the unconditioned areas of the drum cal: culated to be in the range of from about 0.08 to 0.10.
  • said method comprising depositing on said imaging layer a charge acceptance effective amount of at least one compound of the formula wherein R is a saturated aliphatic hydrocarbon radical having from about 8 to about 30 carbon atoms.
  • the photoconductive imaging layer comprises a selenium/arsenic alloy.
  • the photoconductive imaging layer comprises a selenium/tellurium alloy.
  • said method comprising depositing on said imaginglayer a moisture resistant effective amount of at least one compound of the formula alloy.
  • R is a saturated aliphatic hydrocarbon radical having from about 8 to about 30 carbon atoms.
  • the photoconductive imaging layer comprises a selenium/arsenic alloy.
  • the photoconductive imaging layer comprises a selenium/tellurium alloy.
  • said method comprising depositing on said imaging layer an abrasion resistance effective amount of at least one compound of the formula l L 1L wherein R is a saturated aliphatic hydrocarbon radical having from about 8 to about 30 carbon atoms. 14. The method of claim 13 wherein said compound is N-lauryl-morpholine.
  • the photoconductive imaging layer comprises a selenium/arsenic alloy.
  • the photoconductive imaging layer comprises a selenium/tellurium 17.
  • the photoconductive imaging layer comprises a selenium/tellurium 17.
  • about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
  • a method for extending the useful life of an electrophotographic imaging member having a photoconductive imaging layer comprising selenium or selenium alloys 'said method comprising depositing on said imaging layer a life extending amount of at least one compound of the formula wherein R is a saturated aliphatic hydrocarbon radical having from about 8 to about 30 carbon atoms.
  • the photoconductive imaging layer comprises a selenium/arsenic alloy.
  • the photoconductive imaging layer comprises a selenium/tellurium alloy.
  • An electrophotographic imaging member comprising a conductive substrate having operatively disposed in relation thereto a photoconductive imaging layer comprising amorphous selenium or selenium alloy, the surface of said imaging layer having deposited thereon a conditioning effective amount of at least one compound of the formula wherein R is a saturated aliphatic hydrocarbon radical having from about 8 to about 30 carbon atoms.
  • th photoconductive imaging layer comprises a seleniumlarsenic alloy.
  • An electrophotographic imaging process comprising:
  • an electrophotography imaging member comprising a conductive substrate having operatively disposed in relation thereto a photoconductive imaging layer comprising amorphous selenium or selenium alloy, the surface of said imaging layer having deposited thereon a conditioning effective amount of at least one compound of the formula wherein R is a saturated aliphatic hydrocarbon radicaldhaving from about 8 to about 30 carbon atoms; an b. forming a latent image on said photoreceptor.
  • R is a saturated aliphatic hydrocarbon radicaldhaving from about 8 to about 30 carbon atoms
  • the photoconductive imaging layer comprises a selenium/arsenic alloy.

Abstract

WHEREIN R is a saturated aliphatic hydrocarbon radical having in the range of from about 8 to about 30 carbon atoms. The application of such materials to the imaging layer of the imaging member provides said layer with a finish which is capable of protecting said layer from abrasion and the adverse effects of humidity while at the same time enhancing charge acceptance thus improving solid density development.

Methods for conditioning electrophotographic imaging members wherein the photoconductive imaging layer comprises amorphous selenium or selenium alloys. According to this method, the photoconductive imaging layer is treated with a liquid containing at least one N-substituted morpholine compound of the formula

Description

United States'Patent 1191 Telek et al.
[ Jan. 14, 1975 N-ALKYL MORPHOLINE TREATMENT OF A SELENIUM-CONTAINING PHOTOCONDUCTIVE LAYER [75] Inventors: Bela Telek; Thomas Skaper, both of Penfield, NY.
[73] Assignee: Xerox Corporation, Stamford,
Conn.
[22] Filed: Oct. 19, 1973 [21] Appl. No.: 408,248
52 us. c1 96/1.5, 117/201, 117/215 Primary Examiner -David Klein Assistant Examiner-John R. Miller Attorney, Agent, or Firm-James J. Ralabate; James P. OSullivan; John H. Faro [S7] ABSTRACT Methods for conditioning electrop'hotographic imaging members wherein the photoconductive imaging layer comprises amorphous selenium or selenium alloys. According to this method, the photoconductive imaging layer is treated with a liquid containing at least one N-substituted morpholine compound of the formula wherein R is a saturated aliphatic hydrocarbon radical having in the range of. fromabout 8 to about 30 carbon atoms.
The application of such materials to'the imaging layer of the imaging member provides said layer'with a tinish which is capable of protecting said layer from abrasion and the adverse effects of humidity while at the same time enhancing charge acceptance thus improving solid density development.
34 Claims, N0 Drawings N-ALKYL MORPHOLINE TREATMENT OF A SELENIUM-CONTAINING PHOTOCONDUCTIVE LAYER BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a method, an imaging member prepared according to said method and the use of said imaging member in an imaging process. More specifically, this invention involves methods for preconditioning and reconditioning the imaging layer of an electrophotographic imaging member, the overcoated electrophotographic imaging member resulting from such treatment and an imaging process employing said overcoated electrophotographic imaging member.
2. Description of the Prior Art The formation and development of images on an imaging layer of photoconductive materials by electrostatic means is well known. The best known of the commercial processes, more commonly known as xerography, involves forming a latent electrostatic image on the imaging layer of imaging member by first uniformly electrostatically charging the surface of the imaging layer in the dark and then exposing this electrostatically charged surface to a light and shadow image. The light struck areas of the imaging layer are thus rendered conductive and the electrostatic charge selectively dissipated in these irradiated areas. After the photoconductor is exposed, the latent electrostatic image on this image bearing surface is rendered visible by development with finely divided colored electroscopic powder material, known in the art as toner. This toner will be principally attracted to those areas on the image bearing surface which retain the electrostatic charge and thus form a visible powder image.
The developed image can then be read or permanently affixed to the photoconductor in the event that the imaging layer is not to be reused. This latter practice is usually followed with respect to the binder-type photoconductive films where the photoconductive layer is also an integral part of the finished copy.
In so-called plain paper copying systems, the latent image can be developed on the imaging surface of a reusable photoconductor or transferred to another surface, such as a sheet of paper, andthereafter developed. When the latent image is developed on the imaging surface of a reusable photoconductor, it is subsequently transferred to another substrate and then permanently affixed thereto. Any one of a variety of well known techniques can be used to permanently affix the Y toner image to the transfer sheet, including overcoating with transparent films and solvent or thermal fusion of the toner particles to the supportive substrate.
Prior to recycling of the photoreceptor, untransferred toner particles adhering to the surface of the imaging layer of the photoreceptor must be removed in order to prevent deterioration in quality in subsequent copies. Various devices have been employed in the past for removal of these toner residues from the surface of the photoreceptor. Typical of such cleaning means include rotating brushes of the type disclosed in U.S. Pat. No. 2,832,977; cleaning webs of the type disclosed in U.S. Pat. No. 3,186,833; and blade cleaning devices of the type disclosed in U.S. Pat. No. 3,634,077. The relative efficiency which these cleaning means remove toner residues is often dependent upon a number of variables; including the presence of an additive in the developer composition, the presence of an overcoa'ting on the photoreceptor surface, the relative electrostatic attraction of the toner to the photoreceptor surface and the physical force exerted by the cleaning means against the photoreceptor surface. Since the imaging surface of selenium photoreceptors are sensitive to abrasion the pressure contact between the above cleaning means and this surface must be kept to a minimum in order to prevent damage to the imaging surface. This frictional contact of the cleaning means against the photoreceptor surface can also result in erosion of the cleaning member, U.S. Pat. No. 3,682,689. The blade cleaning type device previously referred to is especially vulnerable to this type of wear. If the photoreceptor surface is somewhat irregular, especially if it has minute projections, the pressure contact of the leading edge of a blade cleaning means against this'surface can result in the rapid deterioration of the cleaning blade.
In order to minimize the possibility of this occuring, ex-
treme care is exercised in the manufacture of photoreceptors. Such care must be exercised at all stages of preparation of this multilayer component since any defects in any of the underlying layers can be translated into a surface imperfection in the outer layer of photo-' conductive materials.
During servicing of heavily toner laden photoreceptors, it has been common practice to buff the photoreceptor surface with a pumicing agent in order to remove accumulated toner residues and thus restore the photoreceptor surface to its virgin state. Such pumicing agents are also used in the reconditioning of such photoreceptor surfaces in order to remove minor scratches which have developed over extended periods of use. These same buffing compounds are now being employed in the dressing of new photoreceptors in order to insure that any imperfections (especially minor projections) are removed prior to the installation of the photoreceptor into a copier employing a blade cleaning device. Unfortunately, a number of the commercial buffing compounds used in preconditioning and reconditioning selenium photoreceptors also contain residues which adhere to the imaging surface of the photoreceptor thereby imparing its electrophotographic properties. One type of residue which has proven to be particularly troublesome is glycerol monostearate. The extent to which this substance can disrupt the electrophotographic properties of the photoreceptor varies with the particular composition of the imaging layer of said photoreceptor. For example, where the photoconductive insulating layer comprises an arsenic-selenium alloy the effects of this substance on the photoreceptor are more pronounced.
It is, therefore, the principal object of this invention to provide a method for minimizing the adverse effect of the above and similar residues on photoconductive insulating layers comprising amorphous selenium or selenium alloys.
More specifically, it is the object of this invention to provide a method for preconditioning new electrophotographic imaging members whereinthe photoresponsive layer comprises amorphous selenium or selenium alloys.
It is yet another object of this invention to provide a method for reconditioning used electrophotographic imaging members wherein the photoresponsive layer comprises amorphous selenium alloys.
It is yet a further object of this invention to provide the imaging surface of said imaging member with an overcoating during preconditioning which improves both abrasion and moisture resistance in addition to enhancing solid density development.
It is yet a further object of this invention to provide the imaging surface of said imaging member with an overcoating during reconditioning which improves both abrasion and moisture resistance in addition to enhancing solid density development.
Still yet a further object of this invention is to provide an overcoated imaging member wherein said overcoating improves abrasion and moisture resistance in addition to enhancing solid density development.
Still yet a further object of this invention is to provide an electrophotographic imaging method employing the above overcoated imaging member.
SUMMARY OF THE INVENTION The above and related objects are achieved by providing a method for conditioning the amorphous selenium or selenium alloy photoconductive layer of an electrophotographic imaging member. According to this method, an imaging member having a photoconductive imaging layer comprising amorphous selenium or selenium alloy is treated with a conditioning effect amount of at least one N-substituted morpholine compound of the formula wherein, R is a saturated aliphatic hydrocarbon radical having in the range of from about 8 to 30 carbon atoms. I
In the preferred embodiments of this invention, a dilute solution of one or more of the above compounds is applied to the amorphous selenium or selenium alloy imaging layer of the photoreceptor and then excess solution removing after a predetermined period of time. The preferred compound used in the methods of this invention is N-lauryl-morpholine.
DESCRIPTION OF THE INVENTION INCLUDING PREFERRED EMBODIMENTS The electrophotographicimaging member which can be treated in accord with the methods of this invention comprises a conductive substrate having coated on at least one surface thereof a photoconductive film comprising amorphous selenium, a selenium alloy, or mixtures thereof. Any of the conductive substrates traditionally used in the preparation of electrophotographic imaging members are suitable for use in preparation of the overcoated electrophotographic imaging members of this invention. Such substrates can be flexible or inflexible; organic or inorganic; and transparent ,or opaque. Representative of substrates which have proven suitable for use in such devices include aluminum, nickel, chromium, polyethylene terephthalate overcoated with a thin metal film, or metalized plastic films. Ordinarily, prior to the deposition of the photoconductive insulating layer on such substrate, an interfacial barrier layer is deposited on such substrate in order to provide a blocking contact against premature injection of carriers from the conductive substrate into the photoconductive insulating layer. This interfacial barrier layer can be an insulating material such as a dielectric film of an inorganic oxide. It is generally preferred that such interfacial barrier layers be capable of rectification. Once the conductive substrate has been prepared and an interfacial barrier layer formed thereon (where desired), the substrate is placed in a vacuum evaporation chamber and a photoconductive insulating layer of selenium, selenium alloy or mixtures thereof deposited on the appropriate surface of the substrate. Deposition of such photoconductive materials is allowed to proceed until the deposit forms a substantially uniform film having a thickness in the range of from about 0.1 to about 100 microns.
During the evaporation of such photoconductive materials, minute dust particles in the vacuum evaporation chamber can also codeposit along with the selenium'on the conductive substrate, thus, forming blemishes in the photoconductive coating. In order to minimize the effect of such asperities, the photoconductive surface is gently buffed with a pumicing agent until such imper- .fections are substantially removed. As indicated previsufficient quantities to affect one or more of the above improvements. A typical solution of such conditioning agent should contain'sufficient conditioning compound to impart the desired beneficial results and yet facilitate processing of the photoreceptor. For example, in the event that about 1 gram conditioning compound is dissolved in about 100 milliliters of appropriate solvent, the residence time of the conditioning solution on the imaging layer required to impart the desired beneficial results is quite extensive, generally in excess of about 20 minutes. Where the concentration of conditioning compound in the appropriate solvent is from about 5 to about 10 grams per milliliters solvent, the residence time of the solution on the imaging layer need only be about 5 minutes in order to impart the desired beneficial finish. Where the concentration of conditioning compound is substantially in excess of 10 grams per 100 milliliters solvent, the increased viscosity of the conditioning solution creates problems in uniformity of application and penetration of the conditioning compounds into the microporous surface of the imaging layer. Solvents which are suitable for use as vehicles for dispensing the conditioning compounds on the imaging layer must be compatible with the imaging layer (not interfere with or bring about changes in the electronic and/or physical properties) and must also be compatible with the environment in which such conditioning takes place. Representative of solvents which are suitable for preparation of the conditioning solution include methanol, ethanol, n-propanol, isopropanol, and n-butanol.
Subsequent to preparation of the conditioning solution, it can be applied to the imaging layer of the imaging member by any one of a number of standard coating techniques including aerosol application or a wipeon application. Whatever the mode of application of the conditioning solution to the imaginglayer that is ul timately selected, it must provide for the uniform coverage of the surface of the imaging layer with sufficient conditioning compound to effectively remove the organic buffing compound residues (if any), enhance abrasion resistance, enhance moisture resistance and- /or enhance charge acceptance. In order to enhance on or more of these properties, it is not necessarily required that such treatments enhance all such proper ties. For example, where the conditioning compound has a relatively small aliphatic hydrogen substituent (8 carbon atoms), the relative abrasion resistance of the imaging layer is not enhanced to the extent it would be where such substituent has in excess of about 20 carbon atoms. However, charge acceptance is substantially improved where the imaging layer is conditioned with compounds having such relatively short chain hydrocarbon substituents.
Subsequent to application of a conditioning solution over substantially the entire imaging layer of an electrophotographic imaging member, the solution is allowed to saturate the surface of said imaging layer for a period of anywhere from about 3 to 10 minutes (preferably about 5 minutes). Subsequent to saturation of the photoreceptor, nonabsorbed and nonadsorbed conditioning materials are removed from said surface by wiping said surface with a soft, damp fabric or sponge. The wiper used in removing excess conditioning agent is ordinarilly wetted with the same solvent vehicle used in application of the conditioning compounds to the imaging layer. After removal of excess conditioning compounds, the imaging surface is dried with a soft absorbent fabric or other suitable means. It is generally preferred that the solvents used in dispensing and removal of the conditioning compounds from the surface of the photoreceptor be highly volatile and thus capable of evaporation from said surface without any residual trace thereof remaining on said surface.
Conditioning of the drum in the manner described above does not alter the appearance of the imaging layer since the conditioning compounds are present in such small quantities and thus are not readily detectable except by sophisticated analytical techniques. For example, where an electrophotographic imaging member having an imaging layer of a surface area equal to about 3,000 square centimeters is conditioned in the manner described above, the quantity of conditioning compound capable of extraction from said layer is equal to about 0.6 to about 1.5 milligrams; or approximately 0.2 to about 0.5 micrograms per square centimeter. The presence of the conditioning compound on the imaging layer can be detected by infrared spectroscopy after 4,000 copies. In a typical evaluation of the efficacy of the conditioning procedure, an electrophotographic imaging member conditioned according to the method of this invention is placed in an electrostatographic copier, and copy tested to 10,000 copies (2 copies per cycle of photoreceptor). The cleaning apparatus of this copier comprises a polyurethane blade which translates laterally across the surface of the photoreceptor. The developer composition used in this copier contains a nonsmearing additive intended to enhance removal of residual toner from the surface of the photoreceptor. Comparison of efficiency of cleaning both prior to and subsequent to conditioning of the imaging layer of the photoreceptor reveals a reduction of about 70 percent in the frictional forces between the blade and the imaging layer. Comparison of charge acceptance of the conditioned and unconditioned portion of the photoreceptor reveals about a 10 percent increase in charge acceptance in the conditioned areas.
This treatment of selenium and selenium alloys photoreceptors provides the surface of said photoreceptor with a finish which substantially extends their useful lives in addition to reducing servicing requirements of both the photoreceptor and the cleaning means used in removal of toner residues from the imaging layer of said photoreceptor.
The examples which follow further define, describe and illustrate the methods of this invention. Apparatus and techniques used in these examples are standard or as hereinbefore described. Parts and percentages appearing in such examples are by weight unless stipulated otherwise.
EXAMPLE I An electrophotographic imaging member having an imaging layer comprising an alloy of arsenic and selenium (65 percent by weight selenium to 35 percent by weight arsenic) is sectioned off and alternate sections conditioned with a solution comprising 5 percent N- laurylmorpholine in isopropyl alcohol. The conditioning solution is applied with a cotton cloth and allowed to reside on the photoreceptor for an interval of approximately 5 minutes prior to removal of excess conditioning compound with. isopropyl alcohol. Subsequent to the removal of excess conditioning compounds, the photoreceptor is wiped dry with a soft cotton cloth in those areas where the conditioner was applied. Following conditioning, the photoreceptor is sensitized by charging with a positive corotron which is maintained at 8,000 volts. Measurement of the surface potential on the photoreceptor indicates that those areas which have been conditioned with the N-laurylmorpholine can support a surface potential of about 800 volts whereas those regions on the photorecptor not so conditioned can only support a surface potential of about 700 volts. The photoreceptor is then placed in a standard Xerox 4,000 copier and several copies prepared therefrom. Examination of these copies clearly indicates that those areas of the photoreceptor which have been conditioned with the N-lauryl morpholine do produce copies of improved density even after 4,000 copying cycles. The photoreceptor is then removed and examined. It appears that the conditioned sections of the photoreceptor are substantially freer of toner residues than those sections not treated with the conditioning solution; thus, indicating more efficient blade cleaning action.
EXAMPLE II The procedures of Example I are repeated except for the substitution of a conditioning solution containing about 1 gram N-lauryl morpholine per 100 milliliters EXAMPLE Ill The procedures of Example [I are repeated except that the conditioning solution is allowed to remain on the imaging layer of the electrophotographic imaging member for a period of about 25 minutes prior to removal of nonabsorbed compounds with isopropyl alcohol. The charge acceptance and solid density development are improved over that attained in Example II but still are not comparable to that of Example I.
EXAMPLE IV The procedures of Example I are repeated except for the substitution of a conditioning solution containing grams N-lauryl morpholine per 100 grams isopropyl alcohol. Due to the increased viscosity of this conditioning solution over that of Example I, the application of a uniform film on the imaging layer is somewhat more difficult. Following removal of excess conditioning compounds, the imaging layer is evaluated in the same manner as in Example I. Both charge acceptance and solid density development are inferior to that of Example I. It is believed that due to the increase in viscosity, the conditioning compound does not wet the imaging layer as efficiently as does the conditioning solution of Example I. Thus, the effectiveness of the conditioning compound is substantially reduced, resulting in less efficient and complete absorption and adsorption on the imaging layer.
EXAMPLE v The procedure of Example I is repeated except for the substitution of N-capryly-morpholine for N-laurlymorpholine.
EXAMPLE VI The procedure of Example I is repeated except for the substitution of N-capryl-morpholine for N-lauryl morpholine.
EXAMPLE VII The procedure of Example [is repeated except for the substitution of N-myristyl-morpholine for N-laurylmorpholine.
' EXAMPLE vm The procedure of Example I is repeated except for the substitution of N-palmityl-morpholine for N-laurylmorpholine.
EXAMPLE IX The procedure of Example I is repeated except for the substitution of N-stearyl-morpholine for N-laurylmorpholine.
EXAMPLE X The procedure of Example I is repeated except for the substitution of N-arachidyl-morpholine for N-lauryl-morpholine.
EXAMPLE XI The procedure of Example I is repeated except for the substitution of N-behenyl-morpholine for N-laurylmorpholine.
EXAMPLE XII The procedure of Example I is repeated except for the substitution of N-lignoceryl-morpholine for N-lauryl-morpholine.
EXAMPLE XIII The procedure of Example I is repeated except for the substitution of N-cerotyl-morpholine forN-laurylmorpholine.
EXAMPLE XIV In order to determine quantitatively the extent to which N-lauryl-morpholine reduces the frictional force between the cleaning blade and the photoreceptor surface in Example I, the photoreceptor is removed from the copier and installed in a testing fixture. A portion of the polyurethane blade is removed from the copier and installed in a holder in the testing fixture. The combined weight of the blade and holder is approximately grams. The blade is rested on the surface of the photoreceptor (blade area in contact with photoreceptor 20 millimeters X 2.2 millimeters). As the blade is drawn across the surface of the photoreceptor, the force required to advance the blade increases as the blade tra verses from the conditioned to the unconditioned portions of the photoreceptor. Such change in force is measured on a simple spring scale (Ohaus, Dial Type scale) which is attached to the blade holder. From such measurements. the coefficient of friction (u) for the conditioned areas of the drum is calculated to be in the range of from about 0.025 to 0.030; and the coefficient of friction for the unconditioned areas of the drum cal: culated to be in the range of from about 0.08 to 0.10.
What is claimed is:
l. A method of enhancing the charge acceptance of an electrophotographic imaging member having a photoconductive imaging layer comprising amorphous selenium or selenium alloy,
said method comprising depositing on said imaging layer a charge acceptance effective amount of at least one compound of the formula wherein R is a saturated aliphatic hydrocarbon radical having from about 8 to about 30 carbon atoms.
2. The method of claim 1 wherein said compound is N-lauryl-morpholine.
3. The method of claim 1, wherein the photoconductive imaging layer comprises a selenium/arsenic alloy.
4. The method of claim 1, wherein the photoconductive imaging layer comprises a selenium/tellurium alloy.
5. The method of claim 1, wherein about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
6. The method of claim I wherein a compound of the above formula is first dissolved in a lower alkyl alcohol and thev resulting solution applied to the surface of the imaging layer.
7. A method for enhancing the moisture resistance of an electrophotographic imaging member having a photoconductive imaging layer comprising amorphous selenium or selenium alloy,
said method comprising depositing on said imaginglayer a moisture resistant effective amount of at least one compound of the formula alloy.
wherein R is a saturated aliphatic hydrocarbon radical having from about 8 to about 30 carbon atoms.
8. The method of claim 7 wherein said compound is N-lauryl-morpholine.
9. The method of claim 7, wherein the photoconductive imaging layer comprises a selenium/arsenic alloy.
10. The method of claim 7, wherein the photoconductive imaging layer comprises a selenium/tellurium alloy.
11. The method of claim 7, wherein about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
12. The method of claim 7, wherein the compound of the above formula is first dissolved in a lower alkyl alcohol and the resulting solution applied to the surface of the imaging layer.
13. A method for enhancing the abrasion resistance of an e'lectrophotographic imaging member having a photoconductive imaging layer comprising amorphous selenium or selenium alloy,
said method comprising depositing on said imaging layer an abrasion resistance effective amount of at least one compound of the formula l L 1L wherein R is a saturated aliphatic hydrocarbon radical having from about 8 to about 30 carbon atoms. 14. The method of claim 13 wherein said compound is N-lauryl-morpholine.
15. The method of claim 13 wherein the photoconductive imaging layer comprisesa selenium/arsenic alloy.
16. The method of claim 13, wherein the photoconductive imaging layer comprises a selenium/tellurium 17. The method of claim 13, wherein about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
18. The method of claim 13, wherein the compound of the above formula is first dissolved in a lower alkyl alcohol and the resulting solution applied to the surface of the imaging layer.
19. A method for extending the useful life of an electrophotographic imaging member having a photoconductive imaging layer comprising selenium or selenium alloys 'said method comprising depositing on said imaging layer a life extending amount of at least one compound of the formula wherein R is a saturated aliphatic hydrocarbon radical having from about 8 to about 30 carbon atoms.
20. The method of claim 19, wherein said compound is N-lauryl-morpholine.
21. The method of claim 19, wherein the photoconductive imaging layer comprises a selenium/arsenic alloy.
22. The method of claim 19, wherein the photoconductive imaging layer comprises a selenium/tellurium alloy.
23. The method of claim 19, wherein about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
'24. The method of claim 19, wherein a compound of the above formula is first dissolved in a lower alkyl alcohol and the resulting solution applied to the surface of the imaging layer.
25. An electrophotographic imaging member comprising a conductive substrate having operatively disposed in relation thereto a photoconductive imaging layer comprising amorphous selenium or selenium alloy, the surface of said imaging layer having deposited thereon a conditioning effective amount of at least one compound of the formula wherein R is a saturated aliphatic hydrocarbon radical having from about 8 to about 30 carbon atoms.
26. The imaging member of claim 25, wherein said compound is N-lauryl-morpholine.
27. The imaging member of claim 25, wherein th photoconductive imaging layer comprises a seleniumlarsenic alloy.
28. The imaging member of claim 25, wherein the photoconductive imaging layer comprises a selenium/- tellurium alloy.
29. The imaging member of claim 25, wherein about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
30. An electrophotographic imaging process comprising:
a". providing an electrophotographie imaging member comprising a conductive substrate having operatively disposed in relation thereto a photoconductive imaging layer comprising amorphous selenium or selenium alloy, the surface of said imaging layer having deposited thereon a conditioning effective amount of at least one compound of the formula wherein R is a saturated aliphatic hydrocarbon radicaldhaving from about 8 to about 30 carbon atoms; an b. forming a latent image on said photoreceptor. 31. The process of claim 30, wherein said compound is N-lauryl-morpholine.
32. The process of claim 30, wherein the photoconductive imaging layer comprises a selenium/arsenic alloy.
about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3 860 421 Patent NO- I I Dated January 14 I975 Inventofls) Bela Telek and Thomas Skaper It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 2, line 68, change "comprises amorphous selenium alloys" to comprises amorphous selenium or selenium alloys-.
Column 3, line 36, change "8 to 30" to 8 to about 30-.
Column 3, line 42, change "removing" to --removed.
Column 5, line 8, change on to one.
Column 5, line 12, change "hydrogen" to -hydrocarbon-.
Column 6, line 40, change "photorecptor" to --photoreceptor-.
Column 6, line 43, change "4,000" to 4000.
Column 7, line 28 and 29 change "N-caprylymorpholine for N-laurly-morpholine" to N- caprylyl-morpholine for N-laurylmorpholine.
Claim 1, line 1, change "of" first we:surfs;jut-s Eigned and sealed this 17th day of June 1975,
ficmx'trra:1.1+:v inner E ements;
and Tradermwks

Claims (34)

1. A method of enhancing the charge acceptance of an electrophotographic imaging member having a photoconductive imaging layer comprising amorphous selenium or selenium alloy, said method comprising depositing on said imaging layer a charge acceptance effective amount of at least one compound of the formula
2. The method of claim 1 wherein said compound is N-lauryl-morpholine.
3. The method of claim 1, wherein the photoconductive imaging layer comprises a selenium/arsenic alloy.
4. The method of claim 1, wherein the photoconductive imaging layer comprises a selenium/tellurium alloy.
5. The method of claim 1, wherein about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
6. The method of claim 1 wherein a compound of the above formula is first dissolved in a lower alkyl alcohol and the resulting solution applied to the surface of the imaging layer.
7. A method for enhancing the moisture resistance of an electrophotographic imaging member having a photoconductive imaging layer comprising amorphous selenium or selenium alloy, said method comprising depositing on said imaging layer a moisture resistant effective amount of at least one compound of the formula
8. The method of claim 7 wherein said compound is N-lauryl-morpholine.
9. The method of claim 7, wherein the photoconductive imaging layer comprises a selenium/arsenic alloy.
10. The method of claim 7, wherein the photoconductive imaging layer comprises a selenium/tellurium alloy.
11. The method of claim 7, wherein about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
12. The method of claim 7, wherein the compound of the above formula is first dissolved in a lower alkyl alcohol and the resulting solution applied to the surface of the imaging layer.
13. A method for enhancing the abrasion resistance of an electrophotographic imaging member having a photoconductive imaging layer comprising amorphous selenium or selenium alloy, said method comprising depositing on said imaging layer an abrasion resistance effective amount of at least one compound of the formula
14. The method of claim 13 wherein said compound is N-lauryl-morpholine.
15. The method of claim 13 wherein the photoconductive imaging layer comprises a selenium/arsenic alloy.
16. The method of claim 13, wherein the photoconductive imaging layer comprises a selenium/tellurium alloy.
17. The method of claim 13, wherein about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
18. The method of claim 13, wherein the compound of the above formula is first dissolved in a lower alkyl alcohol and the resulting solution applied to the surface of the imaging layer.
19. A method for extending the useful life of an electrophotographic imaging member having a photoconductive imaging layer comprising selenium or selenium alloys said method comprising depositing on said imaging layer a life extending amount of at least one compound of the formula
20. The method of claim 19, wherein said compound is N-lauryl-morpholine.
21. The method of claim 19, wherein the photoconductive imaging layer comprises a selenium/arsenic alloy.
22. The method of claim 19, wherein the photoconductive imaging layer comprises a selenium/tellurium alloy.
23. The method of claim 19, wherein about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
24. The method of claim 19, wherein a compound of the above formula is first dissolved in a lower alkyl alcohol and the resulting solution applied to the surface of the imaging layer.
25. AN ELETROPHOTOGRAPHIC IMAGING MEMBER COMPRISING A CONDUCTIVE SUBSTRATE HAVING OPERATIVELY DISPOSED IN RELATION THERTO A PHOTOCONDUCTIVE IMAGING LAYER COMPRISING AMORPHOUS SELENIUM OR SELENIUM ALLOY, THE SURFACE OF SAID IMAGING LAYER HAVING DEPOSITED THEREON A CONDITIONING EFFECTIVE AMOUNT OF AT LEAST ONE COMPOUND OF THE FORMULA
26. The imaging member of claim 25, wherein said compound is N-lauryl-morpholine.
27. The imaging member of claim 25, wherein the photoconductive imaging layer comprises a selenium/arsenic alloy.
28. The imaging member of claim 25, wherein the photoconductive imaging layer comprises a selenium/tellurium alloy.
29. The imaging member of claim 25, wherein about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
30. An electrophotographic imaging process comprising: a. providing an electrophotographic imaging member comprising a conductive substrate having operatively disposed in relation thereto a photoconductive imaging layer comprising amorphous selenium or selenium alloy, the surface of said imaging layer having deposited thereon a conditioning effective amount of at least one compound of the formula
31. The process of claim 30, wherein said compound is N-lauryl-morpholine.
32. The process of claim 30, wherein the photoconductive imaging layer comprises a selenium/arsenic alloy.
33. The process of claim 30, wherein the photoconductive imaging layer comprises a selenium/tellurium alloy.
34. The process of claim 30, wherein about 0.2 to about 0.5 micrograms of the above compound is deposited per square centimeter of the surface of the imaging layer.
US408248A 1973-10-19 1973-10-19 N-alkyl morpholine treatment of a selenium-containing photoconductive layer Expired - Lifetime US3860421A (en)

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DE19742447455 DE2447455A1 (en) 1973-10-19 1974-10-04 METHOD FOR CONDITIONING SELENIUM PHOTORECEPTORS
JP49117022A JPS5068337A (en) 1973-10-19 1974-10-11
FR7435221A FR2248539B1 (en) 1973-10-19 1974-10-18
NL7413776A NL7413776A (en) 1973-10-19 1974-10-21 METHOD FOR CONDITIONING SELEENPLA-

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US4078924A (en) * 1976-09-13 1978-03-14 Xerox Corporation Imaging surface smoothing with roughened nickel foil
US5394156A (en) * 1993-11-26 1995-02-28 Motorola, Inc. Digital range turn-around for tracking, telemetry and control transponder

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JPS60221766A (en) * 1984-04-18 1985-11-06 Stanley Electric Co Ltd Electrophotographic sensitive body

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US3355289A (en) * 1962-05-02 1967-11-28 Xerox Corp Cyclical xerographic process utilizing a selenium-tellurium xerographic plate
US3501294A (en) * 1966-11-14 1970-03-17 Xerox Corp Method of treating the surface of a xerographic plate with a metal salt of a fatty acid to improve image transfer
US3713820A (en) * 1971-09-07 1973-01-30 Ibm Electrophotographic charge transport layer
US3748128A (en) * 1972-05-24 1973-07-24 Eastman Kodak Co Process in which heterocyclic n alkoxides and acyloxides exhibit an imagewise change in triboelectric charging properties

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US3355289A (en) * 1962-05-02 1967-11-28 Xerox Corp Cyclical xerographic process utilizing a selenium-tellurium xerographic plate
US3501294A (en) * 1966-11-14 1970-03-17 Xerox Corp Method of treating the surface of a xerographic plate with a metal salt of a fatty acid to improve image transfer
US3713820A (en) * 1971-09-07 1973-01-30 Ibm Electrophotographic charge transport layer
US3748128A (en) * 1972-05-24 1973-07-24 Eastman Kodak Co Process in which heterocyclic n alkoxides and acyloxides exhibit an imagewise change in triboelectric charging properties

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4078924A (en) * 1976-09-13 1978-03-14 Xerox Corporation Imaging surface smoothing with roughened nickel foil
US5394156A (en) * 1993-11-26 1995-02-28 Motorola, Inc. Digital range turn-around for tracking, telemetry and control transponder

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FR2248539B1 (en) 1977-07-08
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JPS5068337A (en) 1975-06-07
DE2447455A1 (en) 1975-04-24

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