US3352669A - Photoconductive member and processes of preparing and using same - Google Patents

Photoconductive member and processes of preparing and using same Download PDF

Info

Publication number
US3352669A
US3352669A US341774A US34177464A US3352669A US 3352669 A US3352669 A US 3352669A US 341774 A US341774 A US 341774A US 34177464 A US34177464 A US 34177464A US 3352669 A US3352669 A US 3352669A
Authority
US
United States
Prior art keywords
barrier layer
photoconductive
supporting substrate
selenium
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US341774A
Other languages
English (en)
Inventor
William J Murphy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xerox Corp
Original Assignee
Xerox Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to GB1052970D priority Critical patent/GB1052970A/en
Application filed by Xerox Corp filed Critical Xerox Corp
Priority to US341774A priority patent/US3352669A/en
Priority to NL6500309A priority patent/NL6500309A/xx
Priority to FR3223A priority patent/FR1422625A/fr
Priority to DE1497194A priority patent/DE1497194C3/de
Application granted granted Critical
Publication of US3352669A publication Critical patent/US3352669A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • G03G5/10—Bases for charge-receiving or other layers
    • G03G5/102—Bases for charge-receiving or other layers consisting of or comprising metals
    • 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
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/142—Inert intermediate layers
    • G03G5/144—Inert intermediate layers comprising inorganic material

Definitions

  • This invention relates to electrophotography and more particularly to an improved photoconductive member adapted for use in electrophotography.
  • electrophotography it is known electrostatic images on the surface of a photoconductive insulating layer are produced by uniformly charging the insulating layer and then dissipating this charge on that portion of the layer which is exposed to light.
  • the latent image formed thereon will correspond to the configuration of the light image passing through the master to be reproduced.
  • This image is rendered visible by depositing on the insulating layer a finely divided developing material comprising a colorant called a toner and a toner carrier.
  • the developing material will be attracted to that portion of the layer retaining a charge thereby distributing itself over the layer in a manner corresponding to the electrostatic image.
  • the powder image may then be transformed to paper or other recording surfaces by placing the surface of the paper in contact with the powdered layer and applying an electrostatic charge to the paper.
  • the paper upon being separated from the insulating layer, will bear the powdered image which may subsequently be made permanent by heating or other suitable fixing means.
  • the means supporting the photoconductive insulating material above described usually comprises a metallic or conductive backing member supporting on one surface thereof a barrier layer or interfacial barrier. Over this barrier layer or to form an interfacial barrier, the above mentioned photoconductive electrically insulating material is then deposited.
  • Several suitable processes may be followed to form this photoconductive layer such as, for example, that process disclosed in United States Patent 2,970,906.
  • a purpose of the barrier in a photoconductive plate of the type described in the above patents is to reduce the charge leakage in the absence of activating radiation (dark discharge) but not preventing the charge dissipation in the presence of such radiation.
  • the barrier also must be designed to prevent or reduce variation in performance of the plate upon reuse or/and recycling of the plate. This variation in performance upon recycling is known as charge fatigue.
  • the interface or barrier layer prevents the passage of charge from the conductive backing member to the photoconductive insulating layer and hence prevents discharge of the said photoconductive layer.
  • barrier layers have been used to form barrier layers. Many, however, have inherent disadvantages making them commercially undesirable. Those, for example, which coat the metallic or conducting surface in a non-uniform manner are not suitable since the plate potential will vary as will other properties along the surface. Also, materials reactive with the photoconductive material will, over a period of time, cause a variation in the performance of the photoconductive plate due to changes in the chemical composition thereof. This reactivity has been observed when selenium is used as the photoconductive material. Because of the chemical reaction of the selenium with the barrier layer, non-uniform performance of the electrophotographic process occurred. Another problem encountered is that of adhesion of the photoconductive material to the barrier layers heretofore used. Poor and non-uniform adhesion of the photoconductive layer to the barrier layer leads to plate failure by element separation in use.
  • Another object of this invention is to provide an improved electrophotographic plate comprising a novel barrier layer which will substantially minimize dark discharge and charge fatigue.
  • Another object is to provide a novel method for the production of an electrophotographic plate.
  • Still another object of this invention is to provide a barrier layer which will reduce significantly any chemical reaction with the photoconductive material.
  • Another still further object of this invention is to provide a barrier layer for use in an electrophotographic plate which will maintain at a minimum the variation of properties in the photoconductive material during use.
  • Yet another still further object of this invention is to provide an electrophotographic plate which performs in a substantially consistent manner upon reuse.
  • a further object of this invention is to provide an electrophotographic plate having desirable adhesion of the photoconductor to the barrier layer.
  • a photoconductive member comprising a barrier layer obtained by contacting an aqueous mineral acid solution containing chromic acid anhydride (G0,) or chromic acid (H CrO in a predominating amount, with a conductive supporting substrate.
  • chromic acid anhydride G0,
  • H CrO chromic acid
  • Typical water soluble salts are: potassium dichromate, KzCI'gO sodium dichromate, Na Cr O ammonium dichromate (NH Cr O and mixtures thereof.
  • predominating amount for the purposes of this disclosure, is meant in an amount by Weight of at least about 50% of the solute used in said acidic water solvent, to about 100%.
  • the supporting substrate may be of several desirable conductive materials such as aluminum, copper, nickel, magnesium, tin, zinc, cadmium, silver, ferrous material, their alloys and mixtures thereof.
  • the preferred supporting substrate is a brass material having from about 60% to about copper and the remainder zinc.
  • a chromate conversion activator is normally used.
  • Any suitable activator may be used such as, for example, zinc chloride, halogenated mineral acids, alkali metal chlorides, acid soluble bromides, thiocyanates, thisulfates, iodates, fluorides, arsenates, acetates and mixtures thereof.
  • activators are potassium bromide, potassium iodate, sodium thiocyanate, sodium thiosulfate, hydrochloric acid, hydrobromic acid, ammonium bromide, sodium bro mide, zinc bromide, zinc chloride, sodium sulfite, sodium r, O sulfate, sodium acetate and mixtures thereofrlt has been considered, however, that the activator may promote oxidation-reduction reactions between the metal surface to be treated and the particular chromium compound present in the solution. It has been further considered that the activators cause formation of a chromic compound at the surface of the metal forming thereon a chromate type.
  • any suitable photoconductive layer or material may be used such as amorphous selenium, zinc oxide, zinc-cadmium sulfide, tetragonal lead monoxide, titanium dioxide and mixtures thereof.
  • the barrier layer thickness may be controlled to obtain desirable properties or optimum combinations of desirable properties depending on the material of the supporting substrate, the formulation, concentration and other materials used and functional needs, etc.
  • the CrO or H' CrO can be used in an acid medium such as, for example, H PO HCl HNO H 80 and mixtures thereof.
  • a barrier layer having a thickness of up to about one-half micron is formed by contacting thesurface of the conductive supporting substrate with an aqueous nitric acid. solution containing the CrO or H CrO moiety.
  • aqueous nitric acid. solution containing the CrO or H CrO moiety containing the CrO or H CrO moiety.
  • the proportions of this material will vary depending upon the particular desired result; however, it is preferred that an acid solution containing nitric acid and a composition comprising from about 80% to 95% CrO and from about 5% to Na SO be used. It is considered also that commercial grade materials may be used which, of course, will contain a number of minor impurities, none of which are known to have any appreciable effect upon the desired barrier layer.
  • Example I A chromic acid solution from which the barrier layer is formed is prepared by mixing for each gallon of water about two ounces of a composition containing about 6% Na SO about 90% CrO about 2% Cr (SO and the remainder various substantially insignificant impurities.
  • a brass support or supporting substrate having a composition of about 70% copper and about 30% zinc is used in the form of a brass foil, or a brass plate, or a brass drum. All of these brass supports can be used and will function in substantially the same manner.
  • the brass support is immersed in the aqueous working chromic acid solution above defined. The solution is maintained at. a temperature of about 100 F. while the support is immersed for a period of about twenty seconds.
  • the treated support is rinsed for a period of about sixty seconds with water at a temperature of about 100 F.
  • the rinsing is followed by two cold tap water rinses and then a cold deionized Water rinse, all about fifteen seconds each.
  • the treated support is then dried for about fifteen minutes at a temperature of about 100 F.
  • the treated support is then placed in a high vacuum evaporator where selenium is deposited on the support by known vacuum evaporation methods such as that described in U.S. Patent 2,970,906.
  • Other known methods to deposit the selenium may also be used.
  • the selenium coating is accomplished by conducting vaporized selenium from a body of selenium to a plate in an upwardly directed path for approximately ten minutes while maintaining the treated support at a temperature of from about 100 C. to about 120 C.
  • Other suitable selenium deposition methods such as spraying and hot pressing suitable for use in the present process are disclosed in the above noted patent U.S. 2,970,906.
  • a selenium layer of about 40 microns is thereby formed over the barrier layer to provide the finished xerographic plate.
  • Example II A working solution is prepared by admixing one gallon of water with one ounce of a composition containing about 13% Na SO and about 86% CIO;,, and about 12 ml. of a concentrated nitric acid (40 B.).
  • the brass supporting substrate is immersed in a manner similar to that described in Example I.
  • the support is immersed while maintaining the solution at a temperature of from about F. to about 145 F.
  • the support is maintained in the solution for a period of about ten to sixty seconds and then upon removing is rinsed with water in the same manner as indicated above in Example I.
  • the treated support is then dried for a period of about ten to twenty-five minutes at a temperature of about 85 F. to about 145 F. and coated with selenium by the method disclosed in Example I.
  • the photoconductive plate produced has a barrier layer over the brass support and has coated thereon a selenium layer ranging from about 20 to 80 microns.
  • Example III Various chromic acid solutions are formulated by mixing with one gallon of water from about two to about sixteen ounces of a material containing about 90% CrO about 2% Cr (SO about 6% Na SO and the remainder various substantially insignificant impurities.
  • the process using each of the solutions formulated is as follows:
  • a brass support having a composition of about 70% copper and about 30% zinc and in the form of a foil, plate or drum, is immersed in the solution as above indicated.
  • the brass support is maintained in the solution for a period of about ten to thirty seconds at a temperature of from about 85 F. to about 145 F.
  • the support is then removed from the working solution and rinsed with water at a temperature of from about 85 F. to about 145 F. for a period of about thirty to ninety seconds.
  • the support is then further rinsed by cold tap water and subsequently a cold deionized water rinse, each rinse conducted from about ten to about twenty-five seconds.
  • the treated sup! port is then dried for about ten to about twenty-five minutes at a temperature of about F. to about F.
  • the selenium coating is then deposited thereon in a manner similar to that discussed in the above Examples I and II.
  • Example IV The working solution described in Example I is deposited'in a suitable containing vessel and a continuous brass foil strip is passed therethrough. Prior to entering the vessel containing the chromic acid solution, the foil will pass through a triohloroethylene vapor degreaser. After the foil has passed through'the chromic acid solution, it is fed through a. hot water rinse tank, two-spray cold water rinsing means, a cOld deionized spray rinsing means, and then through a drying oven. The brass strip isthen re-rolled on a take-up spool and is ready for selenium deposition.
  • the specific chromic acid working solution contains about eight ounces of a composition containing about 7% Na SO 91% Q0 and about 2% Cr (SO per gallon of Water.
  • the temperature of this solution is kept at about 100 F. and the foil maintained in the solution for a period of about thirty-five seconds.
  • the hot water rinse is adjusted to a temperature of about 100 F., the oven is maintained at a temperature of about F. and the foil remains in the oven for approximately one and one-half minutes.
  • the foil from the take-up spool is then transported to a high vacuum evaporator where selenium is deposited on the foil by any known method, forexample, one described in United States Patent 2,970,906.
  • the final photoconductive plate prepared has a barrier layer with a selenium photoconductive layer of about 60 microns thickness.
  • a photoconductive member comprising an electrically conductive supporting substrate, a barrier layer in electro-chemical contact with and directly overlying at least a portion of said supporting substrate, and a substantially vitreous photoconductive insulating layer comprising amorphous selenium substantially permanently aflixed to said barrier layer, said barrier layer obtained by contacting said supporting substrate with an aqueous mineral acid solution comprising a member selected from the group consisting of H CrO CrO their Water soluble salts, and mixtures thereof.
  • the process for the production of a photoconductive plate adapted for use in electrophotography which comprises contacting a mineral acid solution of a member selected from the group consisting of CrO H CrO their water soluble salts and mixtures thereof; and about 0.10% to about 15 Na SO based on the total weight of the solute used, with an electrically conductive metallic supporting substrate comprising from about 5% to about 40% zinc and the remainder copper to form thereon a barrier layer, said acid solution contacted with said electrically conductive supporting substrate until a barrier layer having a thickness of from about 0.0005 to about 2.0 microns is formed thereon, and subsequently depositing over at least a portion of said barrier layer a substantially vitreous photoconductive insulating material comprising amorphous selenium.
  • the process for the production of a photoconductive plate adapted for use in electrophotography which comprises contacting a nitric acid solution of about 80% to about 95% CrO and from about 5% to about 15% N21 SO based on the total weight or" the solute used, with an electrically conductive metallic supporting substrate comprising from about 5% to about 40% zinc and the remainder copper to form thereon a barrier layer, said acid solution contacted with said electrically conductive supporting substrate until a barrier layer having a thickness not greater than about 0.5 micron is formed thereon, and subsequently depositing over at least a portion of said barrier layer a substantially vitreous photoconductivet insulating material comprising amorphous selenium.
  • the process for the production of a photoconductive plate adapted for use in electrophotography which comprises contacting a mineral acid solution comprising nitric acid and a solute comprising CrO in an amount of from about to about based on the total weight of the solute and the remainder of said solute a chromate conversion activator, with an electrically conductive metallic supporting substrate comprising from about5% to about 40% zinc and the remainder copper to form thereon a barrier layer, and subsequently depositing over at least a portion of said barrier layer a substantially vitreous photoconductive insulating material comprising amorphous selenium.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Photoreceptors In Electrophotography (AREA)
US341774A 1964-01-31 1964-01-31 Photoconductive member and processes of preparing and using same Expired - Lifetime US3352669A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
GB1052970D GB1052970A (enrdf_load_stackoverflow) 1964-01-31
US341774A US3352669A (en) 1964-01-31 1964-01-31 Photoconductive member and processes of preparing and using same
NL6500309A NL6500309A (enrdf_load_stackoverflow) 1964-01-31 1965-01-12
FR3223A FR1422625A (fr) 1964-01-31 1965-01-25 élément photoconducteur pour l'électro-photographie
DE1497194A DE1497194C3 (de) 1964-01-31 1965-01-27 Verfahren zur Herstellung eines elektrophotographischen Aufzeichnungsmaterials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US341774A US3352669A (en) 1964-01-31 1964-01-31 Photoconductive member and processes of preparing and using same

Publications (1)

Publication Number Publication Date
US3352669A true US3352669A (en) 1967-11-14

Family

ID=23338982

Family Applications (1)

Application Number Title Priority Date Filing Date
US341774A Expired - Lifetime US3352669A (en) 1964-01-31 1964-01-31 Photoconductive member and processes of preparing and using same

Country Status (4)

Country Link
US (1) US3352669A (enrdf_load_stackoverflow)
DE (1) DE1497194C3 (enrdf_load_stackoverflow)
GB (1) GB1052970A (enrdf_load_stackoverflow)
NL (1) NL6500309A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3440045A (en) * 1964-09-01 1969-04-22 Azoplate Corp Electrophotographic process for the manufacture of a highly heat-resistant image
US3620723A (en) * 1967-05-29 1971-11-16 Ricoh Kk Electrophotographic copying material containing assistant sensitizers and its manufacturing method
US3634078A (en) * 1965-10-06 1972-01-11 Kalle Ag Aluminum supports for planographic printing plates
US4123271A (en) * 1974-01-22 1978-10-31 Mita Industrial Company, Limited Alkali metal dichromate as memory resistance improver for zinc oxide photoconductors in electrostatic photography
US4265987A (en) * 1976-01-20 1981-05-05 Coulter Systems Corporation Lithographic printing plate and method for the preparation of same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2035380A (en) * 1933-05-13 1936-03-24 New Jersey Zinc Co Method of coating zinc or cadmium base metals
US2434525A (en) * 1943-08-23 1948-01-13 Rheem Mfg Co Coating on metals
US2760891A (en) * 1951-12-24 1956-08-28 Borg Warner Protective coating and method of applying same to metal parts
US2824031A (en) * 1954-04-20 1958-02-18 Metal & Thermit Corp Dip process for forming transparent surface conversion coatings on zinc, and compositions for dip solutions
US2904414A (en) * 1954-08-04 1959-09-15 Allied Res Products Inc Formulation for producing a protective bright chemically polished surface on zinc and cadmium
US3121032A (en) * 1960-09-27 1964-02-11 M & T Chemicals Inc Process for applying a protective transparent coating to zinc and cadmium and composition therefor
US3231375A (en) * 1962-03-23 1966-01-25 Rca Corp Electrostatic printing

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2035380A (en) * 1933-05-13 1936-03-24 New Jersey Zinc Co Method of coating zinc or cadmium base metals
US2434525A (en) * 1943-08-23 1948-01-13 Rheem Mfg Co Coating on metals
US2760891A (en) * 1951-12-24 1956-08-28 Borg Warner Protective coating and method of applying same to metal parts
US2824031A (en) * 1954-04-20 1958-02-18 Metal & Thermit Corp Dip process for forming transparent surface conversion coatings on zinc, and compositions for dip solutions
US2904414A (en) * 1954-08-04 1959-09-15 Allied Res Products Inc Formulation for producing a protective bright chemically polished surface on zinc and cadmium
US3121032A (en) * 1960-09-27 1964-02-11 M & T Chemicals Inc Process for applying a protective transparent coating to zinc and cadmium and composition therefor
US3231375A (en) * 1962-03-23 1966-01-25 Rca Corp Electrostatic printing

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3440045A (en) * 1964-09-01 1969-04-22 Azoplate Corp Electrophotographic process for the manufacture of a highly heat-resistant image
US3634078A (en) * 1965-10-06 1972-01-11 Kalle Ag Aluminum supports for planographic printing plates
US3620723A (en) * 1967-05-29 1971-11-16 Ricoh Kk Electrophotographic copying material containing assistant sensitizers and its manufacturing method
US4123271A (en) * 1974-01-22 1978-10-31 Mita Industrial Company, Limited Alkali metal dichromate as memory resistance improver for zinc oxide photoconductors in electrostatic photography
US4265987A (en) * 1976-01-20 1981-05-05 Coulter Systems Corporation Lithographic printing plate and method for the preparation of same

Also Published As

Publication number Publication date
DE1497194A1 (de) 1969-05-22
DE1497194C3 (de) 1975-02-13
NL6500309A (enrdf_load_stackoverflow) 1965-08-02
GB1052970A (enrdf_load_stackoverflow)
DE1497194B2 (de) 1974-07-04

Similar Documents

Publication Publication Date Title
US3552848A (en) Xerographic plate
US3294578A (en) Deposition of a metallic coat on metal surfaces
US5182006A (en) Zincate solutions for treatment of aluminum and aluminum alloys
EP1006414B1 (en) Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
US2766119A (en) Aluminum photographic surfaces
US3352669A (en) Photoconductive member and processes of preparing and using same
US3748137A (en) Photosensitive and thermosensitive elements and process for development
US4123267A (en) Photoconductive element having a barrier layer of aluminum hydroxyoxide
US5437887A (en) Method of preparing aluminum memory disks
US2976181A (en) Method of gold plating by chemical reduction
GB1014271A (en) Deposition of nickel-cobalt alloy on aluminium substrates
US4098655A (en) Method for fabricating a photoreceptor
US2034057A (en) Electrodeposited cooking utensil
US3684368A (en) Xerographic apparatus
US3489560A (en) Photoconductive layer comprising a selenium compound and a solid hydrophobic metal salt of a fatty acid
US6953647B2 (en) Electrophotographic photosensitive member, process for producing electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
US1892051A (en) Electroplated chromium aritcle
US4008082A (en) Method for producing an electrophotographic recording material
US3622400A (en) Thermal-coated booms for spacecraft
EP0919877A1 (en) Electrophotographic photosensitive member, process for producing electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
JPS6135550B2 (enrdf_load_stackoverflow)
JPH061387B2 (ja) 電子写真画像形成部材の製造方法
US3791853A (en) Thermal coated booms for spacecraft
JP3257177B2 (ja) 電子写真感光体用導電性基体および感光体
US3615882A (en) Method of making a mirror