EP0919877B1 - Verfahren zur Herstellung eines elektrophotographischen lichtempfindlichen Elements - Google Patents

Verfahren zur Herstellung eines elektrophotographischen lichtempfindlichen Elements Download PDF

Info

Publication number
EP0919877B1
EP0919877B1 EP98309737A EP98309737A EP0919877B1 EP 0919877 B1 EP0919877 B1 EP 0919877B1 EP 98309737 A EP98309737 A EP 98309737A EP 98309737 A EP98309737 A EP 98309737A EP 0919877 B1 EP0919877 B1 EP 0919877B1
Authority
EP
European Patent Office
Prior art keywords
photosensitive member
layer
salt
chemical conversion
electrophotographic photosensitive
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
EP98309737A
Other languages
English (en)
French (fr)
Other versions
EP0919877A1 (de
Inventor
Tomohiro Kimura
Yoichi Kawamorita
Shintetsu Go
Hideaki Nagasaka
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.)
Canon Inc
Original Assignee
Canon Inc
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
Application filed by Canon Inc filed Critical Canon Inc
Publication of EP0919877A1 publication Critical patent/EP0919877A1/de
Application granted granted Critical
Publication of EP0919877B1 publication Critical patent/EP0919877B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • G03G5/104—Bases for charge-receiving or other layers comprising inorganic material other than metals, e.g. salts, oxides, carbon
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
    • 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
    • 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

Definitions

  • Electrophotographic photosensitive members are constituted basically of a photosensitive layer on which a latent image is formed by electrostatic charging and exposure to light and a substrate on which the photosensitive layer is provided.
  • electrophotographic photosensitive members are required to have sensitivities, electric properties and optical characteristics in accordance with electrophotographic processes applied.
  • Faulty images are exemplified typically by image lines, black spots in white background areas, white spots in black background areas, background fog in white background areas, and also interference fringes caused by factors such as surface shape of substrates and uneven layer thickness of photosensitive members in the case of apparatus such as digital copying machines and laser beam printers in which exposure is effected using a light source having a single wavelength. Accordingly, in the manufacture of photosensitive members, some countermeasures must be taken in advance so that these faulty images do not occur.
  • Substrates having not been treated at all after molding usually do not necessarily have any surface state as it is which is most suited for photosensitive members. Hence, problems caused by the surface state may occur in many instances.
  • substrates having a certain degree of performance can be obtained.
  • the treating solutions contain chromium, it is very difficult to dispose of waste liquor, and also this is not preferable in view of environmental safety.
  • the crystal state of the surface can not be said to be suited for substrates of electrophotographic photosensitive members. It can be effective to a certain degree with regard to electrophotographic performance, but, with regard to images, no satisfactory image quality has been achieved because the surface structure and shape are unsuited. Thus, under existing circumstances, those satisfying all performances have not been available.
  • the film formed on the substrate surface prevents any non-uniformity from being caused in electrophotographic performances and images by electric charges injected locally from the substrate to the photosensitive layer.
  • This method is a good method in order to attain such an aim.
  • it in order to form the layer uniformly without causing any uneven layer thickness on the substrate surface, it must be formed in a certain larger thickness, and a thickness of about 5 or 6 ⁇ m or more under usual conditions for its formation.
  • the layer must be formed in a much larger thickness than the thickness actually required as a charge injection blocking layer, resulting in an increase in cost.
  • an electrophotographic photosensitive member having good electrophotographic properties, that causes no faulty images in any environment of from low temperature/low humidity to high temperature/high humidity, and which also may less cause potential variations.
  • it is intended to provide a process by which such an electrophotographic photosensitive member can be produced with ease, at a low cast and stably.
  • the present invention provides a process of producing an electrophotographic photosensitive member, comprising the steps of:
  • An electrophotographic photosensitive member produced by the process of the present invention has an aluminium substrate and a photosensitive layer provided thereon, and the substrate contains aluminium, oxygen and titanium, or aluminium, oxygen and zirconium, at its surface portion underlying the photosensitive layer.
  • the above electrophotographic photosensitive member can be obtained by subjecting the aluminum substrate to chemical conversion with an aqueous acid solution containing a salt of titanium or a salt of zirconium, and thereafter forming the photosensitive layer.
  • the chemical conversion referred to in the present invention is treatment where a substrate is brought into contact with a specific solution to form on the substrate a coating having specific composition, without applying any electrical external force as in anodizing.
  • Metals of the metal salts used in the present invention are titanium and zirconium.
  • the aluminium substrate having a chemical conversion coating of the present invention in which any one of titanium and zirconium is present together with aluminium and oxygen has very good properties as a substrate for electrophotographic photosensitive members.
  • the salt of titanium and the salt of zirconium may preferably be fluorine compounds.
  • the salt of titanium may include titanium hydrofluoric acid, a sodium salt, potassium salt or ammonium salt thereof, and titanium sulfate.
  • the salt of zirconium may include zirconium potassium fluoride and zirconium sulfate.
  • the aqueous acid solution may preferably contain the metal salt in a concentration of from 0.01 to 2 g/liter as weight of metal.
  • the aqueous acid solution may also preferably contain fluorine ions in a concentration ranging from 0 to 10 g/liter. Within this range, etching reaction may appropriately take place on the substrate surface and a uniform coating can be formed with ease.
  • the aqueous acid solution of the present invention may preferably have a pH adjusted within the range of from 1.0 to 5.5 using ammonia or sodium hydroxide. If it has a pH below 1.0, the etching reaction may take place violently to make it difficult to obtain a good coating. If it has a pH above 5.5, the coating may be formed at so low a rate that only a thin coating can be obtained, making it difficult to obtain a remarkable effect of the present invention.
  • the aqueous acid solution may preferably be heated to 30 to 90°C when used.
  • either method of dipping and spraying may be used. Dipping is preferred in view of production efficiency.
  • the substrate having been subjected to the chemical conversion is used after it is washed and dried.
  • composition of the substrate surface portion in the present invention is measured by the Auger electron ray spectroscopy, and is defined to be the one within the range of from the uppermost surface to a depth of 5 nm (50 ⁇ ).
  • the titanium or zirconium may be contained in an amount ranging from 4 to 100 atom%.
  • the chemical conversion coating containing titanium or zirconium, formed on the substrate surface may preferably have a total layer thickness of 1 pm or smaller, and more preferably 5 nm (50 ⁇ ) or larger. If the coating is in a layer thickness larger than 1 ⁇ m, electric charges can escape with difficulty in excess to tend to cause an increase in residual potential or cause ghost. If it is in a layer thickness smaller than 5 nm (50 ⁇ ) (5 ⁇ 10 -3 ⁇ m), remarkable effects of the present invention may be obtained with difficulty.
  • the aqueous acid solution may preferably further contain a phosphoric acid, a phosphate, a tannin or a tannic acid.
  • the phosphoric acid and phosphate may include phosphoric acid or a sodium, potassium or ammonium salt thereof, and pyrophosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid or a sodium salt or potassium salt thereof.
  • organic phosphoric acid compounds may be used as exemplified by phytic acid, nitrodiethanolethylene phosphonic acid, 2-hydroxyethylmethacryl-1-acid phosphonic acid, 2-ethylhexyl acid phosphonic acid and ethane-1-hydroxy-1,1-diphosphonic acid.
  • the phosphoric acid or phosphate in the aqueous acid solution may preferably be in a concentration ranging from 0.05 to 50 g/liter in terms of phosphate ions. Within this range, an especially uniform and good chemical conversion coating can be formed and also the treating solution can have an especially good stability.
  • the tannin or tannic acid may include quebracho tannin, depside tannin, Chinese tannic acid, Vietnamese tannic acid, hamamelitannic acid, chebulinic acid, sumac tannin, Chinese gallotannin and ellagitannin.
  • the tannin or tannic acid in the aqueous acid solution may preferably be in a concentration ranging from 0.1 to 10 g/liter.
  • the aqueous acid solution may preferably contain hydrofluoric acid, borofluoric acid, hydrosilicofluoric acid or a salt of any of these. These compounds have the function to etch the substrate surface when the substrate is subjected to chemical conversion, and hence a very uniform chemical conversion coating can be formed.
  • the chemical conversion coating of the present invention it is preferable for the chemical conversion coating of the present invention to contain phosphorus and fluorine.
  • aluminium substrate so long as it comprises aluminium, which may include pure aluminium and aluminium alloys such as Al-Mn, Al-Mg, Al-Cu, Al-Si, Al-Mg-Si and Al-Cu-Si types.
  • aluminium of 6000 types such as JIS A6063 and aluminium of 3000 types such as JIS A3003 may be used.
  • shape It may preferably be in the form of a drum.
  • the photosensitive layer of the electrophotographic photosensitive member used in the present invention will be described below.
  • Constitution of the photosensitive layer in the present invention is grouped roughly into a single-layer type in which a charge-generating material and a charge-transporting material are contained in the same layer and a multi-layer type having a charge generation layer containing a charge-generating material and a charge transport layer containing a charge-transporting material.
  • An electrophotographic photosensitive member having the multi-layer type photosensitive layer will be described below.
  • the photosensitive layer may be constituted in the manner that the charge generation layer and the charge transport layer are layered on the substrate in this order or conversely the charge transport layer and the charge generation layer are layered in this order.
  • the charge transport layer is formed by coating a coating solution prepared by dissolving a charge-transporting material such as a polycyclic aromatic compound having a biphenylene, anthracene, pyrene or phenanthrene structure, a nitrogen-containing cyclic compound such as indole, carbazole, oxadiazole or pyrazoline, a hydrazone compound or a styryl compound in a resin having film forming properties, followed by drying.
  • a charge-transporting material such as a polycyclic aromatic compound having a biphenylene, anthracene, pyrene or phenanthrene structure
  • a nitrogen-containing cyclic compound such as indole, carbazole, oxadiazole or pyrazoline
  • a hydrazone compound or a styryl compound in a resin having film forming properties
  • the resin having film forming properties may include polyesters, polycarbonates, polystyrenes, polymethacrylates and polyarylates.
  • the charge transport layer may preferably have a layer thickness of from 5 to 40 ⁇ m, and preferably from 10 to 30 ⁇ m.
  • the charge generation layer is formed by coating a dispersion prepared by dispersing a charge-generating material such as an azo pigment such as Sudan Red or Dyan Blue, a quinone pigment such as pyrene, quinone or anthanthrone, a quinocyanine pigment, a perylene pigment, an indigo pigment such as indigo or thioindigo or a phthalocyanine pigment in a resin such as polyvinyl butyral, polystyrene, or polyvinyl acetate or acrylate, followed by drying, or formed by vacuum deposition of the above pigment.
  • a charge-generating material such as an azo pigment such as Sudan Red or Dyan Blue
  • a quinone pigment such as pyrene, quinone or anthanthrone
  • a quinocyanine pigment a perylene pigment
  • an indigo pigment such as indigo or thioindigo or a phthalocyanine pigment
  • a resin such as polyvinyl butyral,
  • the charge generation layer may preferably have a layer thickness of 5 ⁇ m or smaller, and more preferably from 0.1 to 3 ⁇ m.
  • the single-layer type photosensitive layer is formed by coating a coating fluid prepared by dispersing and dissolving the charge-generating material and the charge-transporting material in the resin, followed by drying.
  • Such a photosensitive layer may preferably have a layer thickness of from 5 to 40 ⁇ m, and more preferably from 10 to 30 ⁇ m.
  • a subbing layer having the function as a barrier and the function of adhesion may be provided between the support and the photosensitive layer.
  • the subbing layer is formed by coating a solution prepared by dissolving casein, polyvinyl alcohol, nitro cellulose, ethylene-acrylic acid copolymer, alcohol-soluble polyamide, polyurethane or gelatin, followed by drying.
  • the subbing layer may preferably have a layer thickness of from 0.1 to 3 ⁇ m.
  • a protective layer may be provided on the photosensitive layer.
  • the protective layer may be constituted of a material including polyester, polyacrylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamide-imide, polysulfone, polyacrylic ether, polyacetal, phenol, acrylic, silicone, epoxy, urea, allyl, alkyd, butyral, phenoxy, phosphazene, acryl-modified epoxy, acryl-modified urethane and acryl-modified polyester resins.
  • the protective layer may preferably have a layer thickness of from 0.2 to 10 ⁇ m.
  • a lubricant such as polytetrafluoroethylene, polyvinylidene fluoride, fluorine type graft polymer, silicone type graft polymer, fluorine type block polymer, silicone type block polymer or silicone oil may be incorporated in order to improve cleaning performance and wear resistance.
  • Additives such as an antioxidant may further be added for the purpose of improving weatherability.
  • conductive powder such as conductive tin oxide or conductive titanium oxide may be dispersed for the purpose of resistance control.
  • Fig. 1 schematically illustrates the construction of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member.
  • reference numeral 1 denotes a drum type electrophotographic photosensitive member which is rotatingly driven around an axis 2 in the direction of an arrow at a given peripheral speed.
  • the photosensitive member 1 is uniformly electrostatically charged on its periphery to a positive or negative, given potential through a primary charging means 3.
  • the photosensitive member thus charged is then exposed to light 4 emitted from an exposure means (not shown) for slit exposure or laser beam scanning exposure. In this way, electrostatic latent images are formed successively on the periphery of the photosensitive member 1.
  • the electrostatic latent images thus formed are subsequently developed by toner by the operation of a developing means 5.
  • the toner-developed images formed by development are then transferred successively by the operation of a transfer means 6, to the surface of a transfer medium 7 fed from a paper feed section (not shown) to the part between the photosensitive member 1 and the transfer means 6 in the manner synchronized with the rotation of the photosensitive member 1.
  • the transfer medium 7 which has received the images is separated from the surface of the photosensitive member, is led through an image fixing means 8, where the images are fixed, and is then printed out of the apparatus as a copied material (a copy).
  • the surface of the photosensitive member 1 from which images have been transferred is brought to removal of the toner remaining after the transfer, through a cleaning means 9.
  • the photosensitive member is cleaned on its surface, further subjected to charge elimination by pre-exposure light 10 emitted from a pre-exposure means (not shown), and then repeatedly used for the formation of images.
  • the primary charging means 3 is a contact charging means making use of a charging roller, the pre-exposure is not necessarily required.
  • the apparatus may be constituted of a combination of plural components integrally joined as a process cartridge from among the constituents such as the above electrophotographic photosensitive member 1, primary charging means 3, developing means 5 and cleaning means 9 so that the process cartridge is detachably mountable to the body of the electrophotographic apparatus such as a copying machine or a laser beam printer.
  • the primary charging means 3, the developing means 5 and the cleaning means 9 may be integrally supported in a cartridge together with the photosensitive member 1 to form a process cartridge 11 that is detachably mountable to the body of the apparatus through a guide means such as a rail 12 provided in the body of the apparatus.
  • the exposure light 4 is light reflected from, or transmitted through, an original, or light irradiated by the scanning of a laser beam, the driving of an LED array or the driving of a liquid crystal shutter array according to signals obtained by reading an original through a sensor and converting the information into signals.
  • the electrophotographic photosensitive member may be not only applied in electrophotographic copying machines, but also widely applied in the fields where electrophotography is applied, e.g., laser beam printers, CRT printers, LED printers, liquid-crystal printers and laser beam engravers.
  • aqueous acid solution (trade name: PALCOAT 3753, available from Nihon Parkerizing Co., Ltd.; pH: 3.8) containing phytic acid as an organic phosphoric acid and titanium hydrofluoric acid and titanium ammonium fluoride as salts of metals was kept at a temperature of 40°C, and the abovealuminium cylinder was immersed in this aqueous acid solution to make chemical conversion for 1 minute, which was then washed with pure water, followed by air-drying.
  • the chemical conversion coating thus formed was in a layer thickness of 20 nm (200 ⁇ ).
  • This dispersion was dip-coated on the aluminium cylinder having been subjected to chemical conversion, followed by drying with heating at 95°C for 10 minutes to form a charge generation layer with a layer thickness of 0.2 ⁇ m.
  • a solution prepared by dissolving 50 parts by weight of a triarylamine compound represented by the following formula and 50 parts by weight of bisphenol-Z polycarbonate resin in 400 parts by weight of monochlorobenzene was dip-coated on the charge generation layer, followed by drying with heating at 110°C for 1 hour to form a charge transport layer with a layer thickness of 20 ⁇ m.
  • the surface portion of the substrate having been subjected to chemical conversion, washing and drying was examined by elementary analysis using a scanning Auger electron ray spectroscope while making argon ion etching from the uppermost surface in the depth direction of the substrate.
  • aluminum, titanium and oxygen were detected as main constituent elements.
  • Their graphic representation is given in Fig. 2.
  • the relationship between depth and sputter time is 11 nm/min (110 ⁇ /min) in terms of SiO 2 . This value is appropriately changeable.
  • compositional ratio of elements at the uppermost surface of the substrate and a depth of 5 nm (50 ⁇ ) from the uppermost surface is shown in Table 1 as elementary percentage regarding the amount of aluminium element as 100.
  • the chemical conversion coating on the substrate surface comprises an oxidized aluminium coating in which titanium has been incorporated.
  • nitrogen, fluorine, phosphorus and so forth are detected as other elements contained. These elements are considered to be those originally contained in the phosphoric acid and fluorine compound in the aqueous acid solution used when the chemical conversion is made, and incorporated in the chemical conversion coating.
  • the electrophotographic photosensitive member obtained was left for 48 hours in environment of normal temperature/normal humidity (23°C, 60%RH), high temperature/high humidity (32.5°C, 85%RH) or low temperature/low humidity (15°C, 10%RH), and thereafter set in a commercially available laser beam printer of a reverse development system to reproduce solid white images in each environment.
  • normal temperature/normal humidity 23°C, 60%RH
  • high temperature/high humidity 32.5°C, 85%RH
  • low temperature/low humidity 15°C, 10%RH
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that a solution (trade name: PALCOAT 3756, available from Nihon Parkerizing Co., Ltd.; pH: 3.2) containing tannic acid, an ammonium salt and zirconium fluoride and zirconium sulfate as salts of metals was used as the aqueous acid solution for chemical conversion.
  • a solution (trade name: PALCOAT 3756, available from Nihon Parkerizing Co., Ltd.; pH: 3.2) containing tannic acid, an ammonium salt and zirconium fluoride and zirconium sulfate as salts of metals was used as the aqueous acid solution for chemical conversion.
  • the chemical conversion coating was in a layer thickness of 15 nm (50 ⁇ ).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that a solution (trade name: PALCOAT 3753T, available from Nihon Parkerizing Co., Ltd.; pH: 3.2) containing phytic acid and containing zirconium hydrofluoric acid and zirconium ammonium fluoride as salts of metals was used as the aqueous acid solution for chemical conversion. Evaluation was made similarly. The results are shown in Tables 1 and 2. The chemical conversion coating was in a layer thickness of 18 nm (180 ⁇ ).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that a solution (trade name: ALUSURF 301N-1, available from Nihon Paint Co., Ltd.; pH: 4.0) containing phosphoric acid and containing zirconium fluoride and a sodium salt of zirconium hydrofluoric acid as salts of metals was used as the aqueous acid solution for chemical conversion. Evaluation was made similarly. The results are shown in Tables 1 and 2. The chemical conversion coating was in a layer thickness of 30 nm (300 ⁇ ).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the chemical conversion was not carried out. Evaluation was made similarly. The results are shown in Table 2.
  • Ammonia water with a concentration of 0.3% was prepared, and this was heated to 95°C.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that this aluminium cylinder was used instead. Evaluation was made similarly. The results are shown in Table 2.
  • Chemical conversion was carried out by immersing an aluminium cylinder for 1 minute in, in place of the aqueous acid solution of the present invention, a chromium phosphate type solution for chemical conversion (trade name: ALUCHROME 3701, available from Nihon Parkerizing Co., Ltd.) kept at 30°C, containing neither titanium nor zirconium, to form a chromate type chemical conversion coating on the surface of the cylinder.
  • a chromium phosphate type solution for chemical conversion (trade name: ALUCHROME 3701, available from Nihon Parkerizing Co., Ltd.) kept at 30°C, containing neither titanium nor zirconium, to form a chromate type chemical conversion coating on the surface of the cylinder.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that this aluminium cylinder was used instead. Evaluation was made similarly. The results are shown in Table 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Photoreceptors In Electrophotography (AREA)

Claims (6)

  1. Verfahren zur Herstellung eines elektrophotografischen lichtempfindlichen Elements mit den Schritten:
    ein Aluminiumsubstrat wird ohne irgendeine äußere elektrische Kraft anzulegen einer chemischen Umwandlung mit einer wässrigen Säurelösung unterzogen, die ein Titansalz oder ein Zirkoniumsalz enthält, und
    eine lichtempfindliche Schicht wird auf diesem gebildet.
  2. Verfahren nach Anspruch 1, wobei das Titansalz und das Zirkoniumsalz Fluorverbindungen sind.
  3. Verfahren nach Anspruch 1 oder Anspruch 2, wobei die wässrige Säurelösung einen pH von 1,0 bis 5,5 aufweist.
  4. Verfahren nach Anspruch 1, 2 oder 3, wobei die wässrige Säurelösung eine Temperatur von 30°C bis 90°C hat.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei die wässrige Säurelösung des Weiteren wenigstens eine Verbindung ausgewählt aus der Gruppe bestehend aus einer Phosphorsäure, einem Phosphat, einem Tannin und einer Gallotanninsäure enthält.
  6. Verfahren nach einem der Ansprüche 1 bis 5, wobei die wässrige Säurelösung des Weiteren wenigstens eine Verbindung ausgewählt aus der Gruppe bestehend aus Fluorwasserstoffsäure, Fluorborsäure, Fluorsilansäure und irgendeinem Salz von diesen enthält.
EP98309737A 1997-12-01 1998-11-27 Verfahren zur Herstellung eines elektrophotographischen lichtempfindlichen Elements Expired - Lifetime EP0919877B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP330386/97 1997-12-01
JP33038697 1997-12-01
JP33038697 1997-12-01

Publications (2)

Publication Number Publication Date
EP0919877A1 EP0919877A1 (de) 1999-06-02
EP0919877B1 true EP0919877B1 (de) 2004-02-18

Family

ID=18232029

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98309737A Expired - Lifetime EP0919877B1 (de) 1997-12-01 1998-11-27 Verfahren zur Herstellung eines elektrophotographischen lichtempfindlichen Elements

Country Status (4)

Country Link
EP (1) EP0919877B1 (de)
KR (1) KR100312951B1 (de)
CN (1) CN1222833C (de)
DE (1) DE69821728T2 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6432603B1 (en) * 1998-11-27 2002-08-13 Canon Kabushiki Kaisha Process for producing electrophotographic photosensitive member
US6248490B1 (en) 1998-12-01 2001-06-19 Canon Kabushiki Kaisha Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
KR100864316B1 (ko) * 2007-07-03 2008-10-20 (주)켐스 전자 사진 감광체 드럼용 알루미늄 파이프의 표면 화학처리방법
CN104357822A (zh) * 2014-10-24 2015-02-18 无锡伊佩克科技有限公司 一种环保型钢铁表面处理液及其使用方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5413979B2 (de) * 1975-01-23 1979-06-04
US4518669A (en) * 1982-11-06 1985-05-21 Canon Kabushiki Kaisha Electrophotographic photosensitive member
JPH0715589B2 (ja) * 1988-09-26 1995-02-22 富士ゼロックス株式会社 電子写真感光体、その基体の処理方法および電子写真感光体の製造方法
JPH03140965A (ja) * 1989-10-27 1991-06-14 Olympus Optical Co Ltd 電子写真感光体
DE4412138A1 (de) * 1994-04-08 1995-10-12 Henkel Kgaa Chromfreies Verfahren zur No-Rinse Behandlung von Aluminium und seinen Legierungen sowie hierfür geeignete wäßrige Badlösungen

Also Published As

Publication number Publication date
CN1241730A (zh) 2000-01-19
DE69821728D1 (de) 2004-03-25
KR19990062682A (ko) 1999-07-26
CN1222833C (zh) 2005-10-12
KR100312951B1 (ko) 2001-12-12
DE69821728T2 (de) 2005-01-20
EP0919877A1 (de) 1999-06-02

Similar Documents

Publication Publication Date Title
EP1006414B1 (de) Elektrophotographisches lichtempfindliches Element, Prozesskartusche und elektrophotographischer Apparat
JPH0448387B2 (de)
US4617245A (en) Light receiving member having tapered reflective surfaces between substrate and light receiving layer
EP0823668B1 (de) Elektrophotographisches photoempfindliches Element, Prozesskassette und elektrophotographisches Gerät unter Verwendung desselben
EP0919877B1 (de) Verfahren zur Herstellung eines elektrophotographischen lichtempfindlichen Elements
JP4143238B2 (ja) 電子写真感光体の製造方法
US6953647B2 (en) Electrophotographic photosensitive member, process for producing electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
US6080491A (en) Substrate for electrophotographic photoconductor and electrophotographic photoconductor using the same
JP3755859B2 (ja) 電子写真感光体、電子写真感光体の製造方法、プロセスカートリッジ及び電子写真装置
JP2000227672A (ja) 電子写真感光体、プロセスカートリッジ及び電子写真装置
JP2003345042A (ja) 電子写真感光体、及び該電子写真感光体を有するプロセスカートリッジ及び電子写真装置
JP2004101701A (ja) 電子写真感光体、該感光体の製造方法
JP3894023B2 (ja) 画像形成方法及び画像形成装置
JP2004101630A (ja) 電子写真感光体、該感光体の製造方法
JP2000162807A (ja) 電子写真感光体、該感光体の製造方法、プロセスカートリッジ及び電子写真装置
JP2004037641A (ja) プロセスカートリッジ、電子写真装置及びそれらに用いられる電子写真感光体
JP2024067567A (ja) 電子写真感光体用支持体、電子写真感光体、プロセスカートリッジ、画像形成装置、及び画像形成方法
JP2004029428A (ja) 電子写真感光体、プロセスカートリッジ及び電子写真装置
JP2003186224A (ja) 電子写真感光体、プロセスカートリッジ及び電子写真装置
JP2000162808A (ja) 電子写真感光体、該感光体の製造方法、プロセスカートリッジ及び電子写真装置
JPH06282089A (ja) 感光体
JP2003186211A (ja) 電子写真感光体用基体の製造方法、電子写真感光体及び画像形成装置
JP2004133198A (ja) 電子写真感光体、及び電子写真感光体の製造方法、プロセスカートリッジ及び電子写真装置
JP2003173037A (ja) 電子写真感光体用支持体、電子写真感光体及び画像形成装置
JPH0530261B2 (de)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 19991015

AKX Designation fees paid

Free format text: DE FR GB IT

17Q First examination report despatched

Effective date: 20020802

RTI1 Title (correction)

Free format text: PROCESS FOR PRODUCING ELECTROPHOTOGRAPHIC PHOTOSENSITIVE MEMBER

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RTI1 Title (correction)

Free format text: PROCESS FOR PRODUCING ELECTROPHOTOGRAPHIC PHOTOSENSITIVE MEMBER

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RIN1 Information on inventor provided before grant (corrected)

Inventor name: NAGASAKA, HIDEAKI

Inventor name: GO, SHINTETSU

Inventor name: KAWAMORITA, YOICHI

Inventor name: KIMURA, TOMOHIRO

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69821728

Country of ref document: DE

Date of ref document: 20040325

Kind code of ref document: P

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20041119

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20121130

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20121128

Year of fee payment: 15

Ref country code: IT

Payment date: 20121107

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20121214

Year of fee payment: 15

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20131127

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140731

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69821728

Country of ref document: DE

Effective date: 20140603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140603

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131127

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131202