EP0046960A2 - Matériau d'enregistrement électrophotographique - Google Patents

Matériau d'enregistrement électrophotographique Download PDF

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Publication number
EP0046960A2
EP0046960A2 EP81106555A EP81106555A EP0046960A2 EP 0046960 A2 EP0046960 A2 EP 0046960A2 EP 81106555 A EP81106555 A EP 81106555A EP 81106555 A EP81106555 A EP 81106555A EP 0046960 A2 EP0046960 A2 EP 0046960A2
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EP
European Patent Office
Prior art keywords
layer
recording material
charge
cover layer
compound
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.)
Granted
Application number
EP81106555A
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German (de)
English (en)
Other versions
EP0046960B1 (fr
EP0046960A3 (en
Inventor
Wolfgang Dr. Wiedemann
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.)
Hoechst AG
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Hoechst AG
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Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0046960A2 publication Critical patent/EP0046960A2/fr
Publication of EP0046960A3 publication Critical patent/EP0046960A3/de
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Publication of EP0046960B1 publication Critical patent/EP0046960B1/fr
Expired legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14704—Cover layers comprising inorganic material

Definitions

  • the invention relates to an electrophotographic recording material composed of an electrically conductive substrate, optionally an insulating intermediate layer, a photoconductive layer composed of at least one charge-generating compound and a charge-transporting compound and a protective transparent cover layer.
  • Recording materials with a photoconductive layer of at least one layer with a charge-generating compound and charge-transporting compound are known.
  • highly sensitive, organic photoconductor layers (DE-AS 23 14 051) are used on conductive carrier films or tapes due to their high elasticity.
  • very highly sensitive photoconductor systems according to, for example, DE-OS 27 34 288 can be used as endless belts because of their great flexibility, which can be guided over deflecting rollers with a relatively small diameter.
  • an electrophotographic recording material mentioned in claims 1 and 2 which is characterized in that the cover layer consists of a metal oxide or halide applied in a vacuum.
  • Suitable metal oxides are preferably those which can be applied in a vacuum in the range from 10 to 10 bar without damaging the organic materials. These include oxides such as silicon monoxide, cerium dioxide, titanium monoxide, aluminum oxide, magnesium oxide, tantalum oxide or mixed oxides such as barium titanate. Calcium fluoride, cerium trifluoride, lanthanum trifluoride, magnesium fluoride or sodium aluminum fluoride can be used as halides.
  • electrophotographic recording materials can be made available which, with almost the same photosensitivity, significantly improve the abrasion resistance and the service life.
  • the multilayer arrangements can be used more profitably not only on flexible conductive substrates, but also on drums.
  • the photoconductive layer can be in the form of a single layer, as indicated in position 6 in FIG. 1. It can also be in the form of a double-layer arrangement which consists of a layer 2 containing charge carrier-producing compounds, as shown in FIGS. 2 and 3, and a layer containing charge-transporting compounds under the respective position 3, which is generally preferred.
  • the conductive layer support is indicated with 1 in each case.
  • An insulating intermediate layer is indicated at position 4, position 5 shows a layer of charge-generating compound in dispersion.
  • Position 7 indicates the protective cover layer according to the invention.
  • aluminum foil optionally transparent, aluminum-vapor-coated or laminated polyester foil
  • any other layer support made sufficiently conductive can be used.
  • the insulating intermediate layer can be produced by a thermally, anodically or chemically produced aluminum oxide intermediate layer. It can also consist of organic materials. For example, different natural or synthetic resin binders are used that adhere well to a metal or aluminum surface and dissolve little when the other layers are subsequently applied, such as polyamide resins, polyvinylphosphonic acid, polyurethanes, polyester resins or specifically alkali-soluble binders, such as Example styrene-maleic anhydride copolymers.
  • the thickness of such organic intermediate layers can be up to 5 ⁇ m, and that of the aluminum oxide layer is mostly in the range from 0.01 to 1 ⁇ m.
  • Dyes according to DE-OS 22 46 255, 23 53 639 and 23 56 370 can also be used, for example.
  • thin layers of inorganic substances which generate charge carriers and are produced by vapor deposition of selenium, doped selenium, cadmium sulfide etc. are also suitable.
  • the application of a homogeneous, densely packed layer 2 is preferably obtained by vacuum deposition.
  • An advantageous layer thickness range of layer 2 is between 0.005 and 3 ⁇ m, since the adhesive strength and homogeneity of the vapor-deposited compound are particularly favorable here.
  • homogeneous, well covering dye layers with thicknesses of the order of 0.1-3 pm can also be obtained by grinding the dye with a binder, especially with highly viscous cellulose nitrates and / or crosslinking binder systems
  • Example polyisocyanate-crosslinkable acrylic resins, lacquers based on polyisocyanates and hydroxyl-containing P oly-esters or ethers are prepared, and by then applying this dye dispersions 5 on the support, as seen in FIG. 4
  • Organic materials which have an extensive ⁇ electron system are particularly suitable as the charge transport material in layers 3 and 6. These include, in particular, monomeric aromatic or heterocyclic compounds, such as those which have at least one dialkylamino group or two alkoxy groups.
  • Oxdiazole derivatives which are mentioned in German patent 10 58 836, have proven particularly useful. These include in particular 2,5-bis- (p-diethylaminophenyl) -oxdiazole-1,3,4.
  • Suitable monomeric electron donor compounds are, for example, triphenylamine derivatives, more highly condensed aromatic compounds such as pyrene, benzo-condensed heterocycles, and also pyrazoline or imidazole derivatives (DE-PSen 10 60 714, 11 06 599), including triazole, thiadiazole and especially oxazole derivatives, for example 2 -Phenyl-4- (2-chlorophenyl) -5- (4-diethylamino) oxazole, as disclosed in German patents 10 60 260, 12 99 296, 11 20 875.
  • the charge transport layer 3 has practically no photosensitivity in the visible range (420-750 nm). It preferably consists of a mixture of an elec Tronendonator für with a resin binder, if negatively charged.
  • Layer 3 is preferably transparent. However, it is also possible that it does not need to be transparent, for example in the case of a transparent, conductive layer support. It has a high electrical resistance ( ⁇ 10 12 ⁇ ) and prevents the discharge of electrostatic charge in the dark. When exposed, it transports the charges generated in the organic dye layer.
  • the added binder influences both the mechanical behavior such as abrasion, flexibility, film formation etc. and to a certain extent the electrophotographic behavior such as photosensitivity, residual charge and cyclic behavior.
  • Film-forming compounds such as polyester resins, polyvinyl chloride / polyvinyl acetate copolymers, styrene / maleic anhydride copolymers, polycarbonates, silicone resins, polyurethanes, epoxy resins, acrylates, polyvinyl acetals, polystyrenes, cellulose derivatives such as cellulose acetobutyrates etc. are used as binders.
  • Post-crosslinking binder systems such as DD lacquers (for example Desmophen / Desmodur ( R ), Bayer AG), polyisocyanate-crosslinkable acrylate resins, melamine resins, resins made from unsaturated polyesters etc. are also successfully used.
  • the mixing ratio of the charge transporting compound to the binder can vary. However, the requirement for maximum photosensitivity, i.e. as large a proportion of charge-transporting compound as possible and after crystallization to be avoided and increase in flexibility, i.e. as large a proportion of binders as possible, relatively certain limits.
  • a mixing ratio of about 1: 1 parts by weight has generally been found to be preferred, but ratios between 4: 1 to 1: 2 are also suitable.
  • the thicknesses of layers 3 and 6 are preferably between about 3 and 20 pm.
  • Leveling agents such as silicone oils, wetting agents, in particular non-ionic substances, plasticizers of different compositions, such as, for example, based on chlorinated hydrocarbons or based on phthalic acid esters are added to the layer as customary additives. If necessary, sensitizers and / or acceptors can also be added to the charge transport layer, but only to the extent that the optical transparency of the charge transport layer is not significantly impaired.
  • the protective cover layer produced on the organic photoconductor system has a uniform thickness of 0.5-10 ⁇ m, preferably 0.5-5 ⁇ m. This range of thicknesses is suitable because, on the one hand, this does not significantly influence the charge flow during the exposure and discharge process, and on the other hand, a significantly improved abrasion behavior is achieved.
  • the selection of the inorganic vapor deposition materials depends primarily on their evaporation temperature and rate, their resistance to evaporation and the properties of the vapor-deposited protective layers, such as homogeneous film formation, flexibility, surface conductivity (also depending on the air humidity) and the spectral Translucency.
  • Materials such as silicon monoxide or magnesium fluoride can improve the anti-reflective behavior of the photoconductor layer, which is reflected in better utilization of the incident light. They are therefore preferred.
  • these materials can be evaporated in vacuum from electrically heated tungsten, molybdenum or tantalum boats at a substrate temperature of 50 ° C. Electron beam evaporators may also be necessary for certain materials.
  • cover layers according to the invention have the advantage that they prevent surface effects which arise during handling of the photoconductor, for example crystallization effects by hand contact.
  • cover layers according to the invention are preferably used on photoconductor drums as layer supports.
  • the evaporation takes place from tungsten boats, which are heated in a direct current passage.
  • the material to be vapor-coated on one side for comparison purposes is clamped onto a rotating drum and varied from 5 to 15 minutes by means of various vapor deposition times in order to produce different SiO layer thicknesses.
  • the residual charge (U R ) after 0.1 sec., Determined from the above bright discharge curves, is a further measure of the discharge of a photoconductor layer.
  • a recording material vaporized on one side with SiO at 2 g / m 2 according to Example 1 is exposed to the copying process in a copying machine (25 copies / min.)
  • a copying machine 25 copies / min.
  • a magnetic brush device with a two-component toner mixture is used for development.
  • To clean residual toner the material is guided past a rotating brush. It can be seen that surface filming, resulting from the toner / photoconductor surface interaction, limits the useful life of the unprotected surface. After 2,000 copies, clear surface filming is already visible, but not at all on the protected surface.
  • the aperture space (max. Opening) is used for the production of perfect copies of the unprotected material by surface filming, while the material according to the invention can be copied further in the initial aperture position.
  • magnesium fluoride is vapor-deposited as a protective layer instead of silicon monoxide.
  • the photosensitivity has not yet been reduced:
  • the sequence of aluminum-vaporized 125 pm thick polyester film, a layer of charge carrier compound (N, N'-bis (3-methoxypropyl) perylimide according to DE-PS 24 51 781) and a charge transport layer (thickness 8.6 g / m 2 ) consists of To and highly viscous cellulose nitrate, a top layer of silicon monoxide is evaporated to a thickness of about 3 g / m 2 , as indicated in Example 1.
  • a standard abrasion device (Taber Abraser Type 352) under the following conditions:
  • the abrasion in g / m 2 is the quotient of the gravimetrically determined abrasion and the abrasion area.
  • the abrasion of the unprotected material results in approx. 2.5 g / m 2
  • the material provided with a covering layer has an abrasion of 0.9 g / m 2 .
  • Abrasion is therefore reduced by a factor of 3.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
EP81106555A 1980-08-30 1981-08-24 Matériau d'enregistrement électrophotographique Expired EP0046960B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803032775 DE3032775A1 (de) 1980-08-30 1980-08-30 Elektrophotographisches aufzeichnungsmaterial
DE3032775 1980-08-30

Publications (3)

Publication Number Publication Date
EP0046960A2 true EP0046960A2 (fr) 1982-03-10
EP0046960A3 EP0046960A3 (en) 1982-08-04
EP0046960B1 EP0046960B1 (fr) 1985-10-02

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP81106555A Expired EP0046960B1 (fr) 1980-08-30 1981-08-24 Matériau d'enregistrement électrophotographique

Country Status (4)

Country Link
EP (1) EP0046960B1 (fr)
JP (1) JPS5789765A (fr)
AU (1) AU545993B2 (fr)
DE (2) DE3032775A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4489148A (en) * 1983-04-25 1984-12-18 Xerox Corporation Overcoated photoresponsive device
JPS62100766A (ja) * 1985-10-29 1987-05-11 Toyo Ink Mfg Co Ltd 電子写真感光体

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB918234A (en) * 1955-06-06 1963-02-13 Rank Xerox Ltd Improvements in protected photoconductive element and method of making same
DE2220270A1 (de) * 1971-05-06 1972-11-16 International Standard Electric Corp., New York, N.Y. (V.St.A.) Xerografische Speicherfläche
US3867143A (en) * 1969-01-17 1975-02-18 Canon Kk Electrophotographic photosensitive material
DE2733052A1 (de) * 1976-07-27 1978-02-02 Rank Xerox Ltd Lichtempfindliches element und dessen verwendung in einem elektrophotographischen verfahren

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49122337A (fr) * 1973-03-23 1974-11-22

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB918234A (en) * 1955-06-06 1963-02-13 Rank Xerox Ltd Improvements in protected photoconductive element and method of making same
US3867143A (en) * 1969-01-17 1975-02-18 Canon Kk Electrophotographic photosensitive material
DE2220270A1 (de) * 1971-05-06 1972-11-16 International Standard Electric Corp., New York, N.Y. (V.St.A.) Xerografische Speicherfläche
DE2733052A1 (de) * 1976-07-27 1978-02-02 Rank Xerox Ltd Lichtempfindliches element und dessen verwendung in einem elektrophotographischen verfahren

Also Published As

Publication number Publication date
EP0046960B1 (fr) 1985-10-02
JPS5789765A (en) 1982-06-04
DE3032775A1 (de) 1982-05-06
DE3172533D1 (en) 1985-11-07
AU545993B2 (en) 1985-08-08
AU7426481A (en) 1982-03-11
EP0046960A3 (en) 1982-08-04

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