EP0534004B1 - Matériau d'enregistrement photosensible - Google Patents

Matériau d'enregistrement photosensible Download PDF

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Publication number
EP0534004B1
EP0534004B1 EP91202470A EP91202470A EP0534004B1 EP 0534004 B1 EP0534004 B1 EP 0534004B1 EP 91202470 A EP91202470 A EP 91202470A EP 91202470 A EP91202470 A EP 91202470A EP 0534004 B1 EP0534004 B1 EP 0534004B1
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Prior art keywords
layer
recording material
charge
compound
ctm
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German (de)
English (en)
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EP0534004A1 (fr
Inventor
Marcel Jacob C/O Agfa-Gevaert N.V. Monbaliu
Luc Jerome C/O Agfa-Gevaert N.V. Vanmaele
David Richard C/O Agfa-Gevaert N.V. Terrell
Stefaan Karel C/O Agfa-Gevaert N.V. De Meutter
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to DE69115482T priority patent/DE69115482T2/de
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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
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0618—Acyclic or carbocyclic compounds containing oxygen and nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/062—Acyclic or carbocyclic compounds containing non-metal elements other than hydrogen, halogen, oxygen or nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered

Definitions

  • the present invention relates to photosensitive recording materials suitable for use in electrophotography.
  • photoconductive compounds are used to form a latent electrostatic charge image on the surface of a recording material containing such compounds.
  • the latent electrostatic charge image is made visible with a finely divided colouring material, called toner, is transferred to a suitable substrate and is fixed by heat, pressure and/or solvent to said substrate.
  • the formation of said latent image can proceed by the use in said recording material of so-called charge generating material (CGM) and charge transporting material (CTM) and by a process comprising the following steps :
  • the photosensitive recording material may incorporate the charge generating material and charge transporting material in separate contacting layers or in a single layer.
  • the photoconductive layer or layers must have a certain minimum overall thickness, usually at least 10 micron.
  • High sensitivity photoconductive recording materials have therefore, in general , the layer whose sole function is charge transport as an outermost layer and a fairly thin charge generation material layer or layer of combined charge generation-charge transport material between the charge transporting layer and a conductive base serving as contacting electrode.
  • the sign of the electrostatic chargeability of the photosensitive recording material will depend upon whether the CTM or CTM's in the charge transporting layer preferentially transport electrons or positive holes. In the case of hole-transport the photosensitive recording material will be negatively chargeable and in the case of electron transport the photosensitive recording material will be positively chargeable.
  • Patent literature in the field frequently deals with hole-transporting CTM's, but little literature is available concerning electron-transporting CTM's.
  • the scarcity of efficient electron-transporting CTM's is underlined by the predominance of negatively chargeable organic photoconductors (OPC's) in the commercially available photoconductive recording systems.
  • OPC's negatively chargeable organic photoconductors
  • n-CTM's A search has revealed that only a small number of efficient and practically useful electron transporting materials, called n-CTM's, are available because of the following problems :
  • TNF 2,4,7-trinitrofluorenone
  • CGM's radiation-activated charge-generation materials
  • n-CTM electron-transporting compounds
  • n-CTM's electron-transporting compounds called n-CTM's for use in photosensitive recording materials having :
  • a photosensitive recording material which comprises an electrically conductive support having thereon a layer containing a charge transporting compound (n-CTM-compound) capable of accepting and transporting electrons which have been obtained by radiation-activated charge-generation from a charge generating compound (CGM-compound) present in said material, characterized in that said n-CTM-compound corresponds to the following general formula (A) : wherein : each of R1 and R2 (same or different) represents an alkyl group including a substituted alkyl group, a cycloalkyl group including a substituted cycloalkyl group, an aryl group including a substituted aryl group, COOR4, COR4, CSR4, POR4R5, SO2R6, or together form a member selected from the group consisting of : R3 represents each of R4, R5 and R7 independently represents an alkyl, aryl or aralkyl group; R6 represents an alkyl, aryl
  • an electrophotographic recording material of the present invention comprises an electrically conductive support having thereon a photosensitive charge generating layer in contiguous relationship with a charge transporting layer, characterized in that said charge transporting layer contains one or more n-CTM compounds corresponding to a general formula (A) as defined above.
  • the content of the n-CTM compound used according to the present invention in a negative charge transport layer is preferably in the range of 20 to 70 % by weight with respect to the total weight of said layer.
  • the thickness of the charge transporting layer is preferably in the range of 5 to 50 »m, and more preferably in the range of 5 to 30 »m.
  • an electrophotographic recording material of the present invention comprises an electrically conductive support having thereon a positively chargeable photoconductive recording layer which contains in an electrically insulating organic polymeric binder at least one p-type pigment substance and at least one n-type photoconductive charge transport substance, wherein (i) at least one of the n-type charge transport substances is a compound corresponding to general formula (A) as defined above, (ii) said layer has a thickness in the range of 4 to 40 »m and comprises 5 to 40 % by weight of said p-type pigment substance and 0.0001 to 15 % by weight of at least one of said n-type charge transport substance(s) that is (are) molecularly distributed in said electrically insulating organic polymeric binder material that has a volume resistivity of at least 1014 Ohm-m, and wherein (iii) said recording layer in electrostatically charged state requires for 10 % and 90 % discharge respectively exposures to conductivity increasing electromagnetic radiation that differ by a factor 4.5 or less.
  • the p-type pigment may be inorganic or organic and may have any colour including white. It is a finely divided substance dispersible in the organic polymeric binder of said photoconductive recording layers.
  • the support of said photoconductive recording layer is pre-coated with an adhesive and/or a blocking layer (rectifier layer) reducing or preventing charge injection from the conductive support into the photoconductive recording layer, and optionally the photoconductive recording layer is overcoated with an outermost protective layer, more details about said layers being given furtheron.
  • a blocking layer rectifier layer
  • said photoconductive recording layer has a thickness in the range of 5 to 35 »m and contains 6 to 30 % by weight of said p-type pigment material(s) and 0.001 to 12 % by weight of said n-type transport substance(s).
  • n-type material is understood a material having n-type conductance, which means that the photocurrent (I n ) generated in said material when in contact with an illuminated transparent electrode having negative electric polarity is larger than the photocurrent (I p ) generated when in contact with a positive illuminated electrode (I n /I p > 1).
  • p-type material is understood a material having p-type conductance, which means that the photocurrent (I n ) generated in said material when in contact with an illuminated transparent electrode having positive electric polarity is larger than the photocurrent (I p ) generated when in contact with a negative illuminated electrode (I p /I n > 1).
  • At least one of the n-CTM compounds according to the above defined general formula (A) is applied in combination with a resin binder to form a charge transporting layer adhering directly to a charge generating layer on an electrically conductive support.
  • a resin binder to form a charge transporting layer adhering directly to a charge generating layer on an electrically conductive support.
  • the charge transporting layer obtains sufficient mechanical strength and obtains or retains sufficient capacity to hold an electrostatic charge for copying purposes.
  • the specific resistivity of the charge transporting layer is not lower than 109 ohm.cm.
  • the resin binders are selected with the aim of obtaining optimal mechanical strength, adherence to the charge generating layer and favourable electrical properties.
  • Suitable electronically inactive binder resins for use in the charge transporting layer are e.g. cellulose esters, acrylate and methacrylate resins, e.g. cyanoacrylate resin, polyvinyl chloride, copolymers of vinyl chloride, e.g. copolyvinyl/acetate and copolyvinyl/maleic anhydride, polyester resins, e.g. copolyesters of isophthalic acid and terephthalic acid with glycol, aromatic polycarbonate resins and polyester carbonate resins.
  • cellulose esters e.g. cellulose esters, acrylate and methacrylate resins, e.g. cyanoacrylate resin, polyvinyl chloride, copolymers of vinyl chloride, e.g. copolyvinyl/acetate and copolyvinyl/maleic anhydride, polyester resins, e.g. copolyesters of isophthalic acid and terephthalic acid with glycol, aromatic
  • a polyester resin particularly suited for use in combination with aromatic polycarbonate binders is DYNAPOL L 206 (registered trade mark of Dynamit Nobel for a copolyester of terephthalic acid and isophthalic acid with ethylene glycol and neopentyl glycol, the molar ratio of tere- to isophthalic acid being 3/2).
  • Said polyester resin improves the adherence to aluminium that may form a conductive coating on the support of the recording material.
  • Suitable aromatic polycarbonates can be prepared by methods such as those described by D. Freitag, U. Grigo, P. R. Müller and W. Nouvertné in the Encyclopedia of Polymer Science and Engineering, 2nd ed., Vol. II, pages 648-718, (1988) published by Wiley and Sons Inc., and have one or more repeating units within the scope of following general formula (I) : wherein : X represents S, SO2, R19, R20, R21, R22, R25 and R26 each represents (same or different) hydrogen, halogen, an alkyl group or an aryl group, and R23 and R24 each represent (same or different) hydrogen, an alkyl group, an aryl group or together represent the necessary atoms to close a cycloaliphatic ring, e.g. cyclohexane ring.
  • Aromatic polycarbonates having a molecular weight in the range of 10,000 to 200,000 are preferred. Suitable polycarbonates having such a high molecular weight are sold under the registered trade mark MAKROLON of Wegriken Bayer AG, W-Germany.
  • binder resins are silicone resins, polystyrene and copolymers of styrene and maleic anhydride and copolymers of butadiene and styrene.
  • An example of an electronically active resin binder is poly-N-vinylcarbazole or copolymers of N-vinylcarbazole having a N-vinylcarbazole content of at least 40 % by weight.
  • the ratio wherein the charge-transporting compound and the resin binder are mixed can vary. However, relatively specific limits are imposed, e.g. to avoid crystallization.
  • spectral sensitizing agents can have an advantageous effect on the charge transport.
  • these dyes are used in an amount not substantially reducing the transparency in the visible light region (420 - 750 nm) of the charge transporting layer so that the charge generating layer still can receive a substantial amount of the exposure light when exposed through the charge transporting layer.
  • the charge transporting layer may contain compounds substituted with electron-donor groups forming an intermolecular charge transfer complex, i.e. donor-acceptor complex wherein the hydrazone compound represents an electron donating compound.
  • useful compounds having electron-donating groups are hydrazones such as 4-N,N-diethylamino-benzaldehyde-1,1-diphenylhydrazone (DEH), amines such as tris(p-tolylamine) (TTA) and N,N′-diphenyl-N,N′-bis(3-methyl-phenyl)-[1,1-biphenyl]-4,4′-diamine (TPD) etc.
  • TTA tris(p-tolylamine)
  • TTD N,N′-diphenyl-N,N′-bis(3-methyl-phenyl)-[1,1-biphenyl]-4,4′-diamine
  • UV-stabilizers Compounds acting as stabilising agents against deterioration by ultra-violet radiation, so-called UV-stabilizers, may also be incorporated in said charge transport layer.
  • UV-stabilizers are benztriazoles.
  • silicone oils For controlling the viscosity of the coating compositions and controlling their optical clarity silicone oils may be added to the charge transport layer.
  • the charge transport layer used in the recording material according to the present invention possesses the property of offering a high charge transport capacity coupled with a low dark discharge. While with the common single layer photoconductive systems an increase in photosensitivity is coupled with an increase in the dark current and fatigue such is not the case in the double layer arrangement wherein the functions of charge generation and charge transport are separated and a photosensitive charge generating layer is arranged in contiguous relationship to a charge transporting layer.
  • any of the organic pigment dyes belonging to one of the following classes and able to transfer electrons to electron transporting materials may be used :
  • Inorganic substances suited for photogenerating negative charges in a recording material according to the present invention are e.g. amorphous selenium and selenium alloys e.g. selenium-tellurium, selenium-tellurim-arsenic and selenium-arsenic and inorganic photoconductive crystalline compounds such as cadmium sulphoselenide, cadmiumselenide, cadmium sulphide and mixtures thereof as disclosed in US-P 4,140,529.
  • Said photoconductive substances functioning as charge generating compounds may be applied to a support with or without a binding agent.
  • they are coated by vacuum-deposition without binder as described e.g. in US-P 3,972,717 and 3,973,959.
  • the photoconductive substances When dissolvable in an organic solvent the photoconductive substances may likewise be coated using a wet coating technique known in the art whereupon the solvent is evaporated to form a solid layer.
  • the binding agent(s) should be soluble in the coating solution and the charge generating compound dissolved or dispersed therein.
  • the binding agent(s) may be the same as the one(s) used in the charge transport layer which normally provides best adhering contact.
  • a plasticizing agent e.g. halogenated paraffin, polybiphenyl chloride, dimethylnaphthalene or dibutyl phthalate.
  • the thickness of the charge generating layer is preferably not more than 10 »m, more preferably not more than 5 »m.
  • an adhesive layer or barrier layer may be present between the charge generating layer and the support or the charge transport layer and the support.
  • Useful for that purpose are e.g. a polyamide layer, nitrocellulose layer, hydrolysed silane layer, or aluminium oxide layer acting as blocking layer preventing positive or negative charge injection from the support side.
  • the thickness of said barrier layer is preferably not more than 1 micron.
  • the conductive support may be made of any suitable conductive material.
  • Typical conductors include aluminum, steel, brass and paper and resin materials incorporating or coated with conductivity enhancing substances, e.g. vacuum-deposited metal, dispersed carbon black, graphite and conductive monomeric salts or a conductive polymer, e.g. a polymer containing quaternized nitrogen atoms as in Calgon Conductive polymer 261 (trade mark of Calgon Corporation, Inc., Pittsburgh, Pa., U.S.A.) described in US-P 3,832,171.
  • the support may be in the form of a foil, web or be part of a drum.
  • An electrophotographic recording process comprises the steps of :
  • the photo-exposure of the charge generating layer proceeds preferably through the charge transporting layer but may be direct if the charge generating layer is uppermost or may proceed likewise through the conductive support if the latter is transparent enough to the exposure light.
  • the development of the latent electrostatic image commonly occurs preferably with finely divided electrostatically attractable material, called toner particles that are attracted by coulomb force to the electrostatic charge pattern.
  • the toner development is a dry or liquid toner development known to those skilled in the art.
  • toner particles deposit on those areas of the charge carrying surface which are in positive-positive relation to the original image.
  • toner particles migrate and deposit on the recording surface areas which are in negative-positive image value relation to the original.
  • the areas discharged by photo-exposure obtain by induction through a properly biased developing electrode a charge of opposite charge sign with respect to the charge sign of the toner particles so that the toner becomes deposited in the photo-exposed areas that were discharged in the imagewise exposure (ref. : R.M. Schaffert "Electrophotography” - The Focal Press - London, New York, enlarged and revised edition 1975, p. 50-51 and T.P. Maclean "Electronic Imaging” Academic Press - London, 1979, p. 231).
  • electrostatic charging e.g. by corona
  • the imagewise photo-exposure proceed simultaneously.
  • Residual charge after toner development may be dissipated before starting a next copying cycle by overall exposure and/or alternating current corona treatment.
  • Recording materials according to the present invention depending on the spectral sensitivity of the charge generating layer may be used in combination with all kinds of photon-radiation, e.g. light of the visible spectrum, infra-red light, near ultra-violet light and likewise X-rays when electron-positive hole pairs can be formed by said radiation in the charge generating layer.
  • photon-radiation e.g. light of the visible spectrum, infra-red light, near ultra-violet light and likewise X-rays when electron-positive hole pairs can be formed by said radiation in the charge generating layer.
  • they can be used in combination with incandescent lamps, fluorescent lamps, laser light sources or light emitting diodes by proper choice of the spectral sensitivity of the charge generating substance or mixtures thereof.
  • the toner image obtained may be fixed onto the recording material or may be transferred to a receptor material to form thereon after fixing the final visible image.
  • a recording material according to the present invention showing a particularly low fatigue effect can be used in recording apparatus operating with rapidly following copying cycles including the sequential steps of overall charging, imagewise exposing, toner development and toner transfer to a receptor element.
  • the evaluations of electrophotographic properties determined on the recording materials of the following examples relate to the performance of the recording materials in an electrophotographic process with a reusable photoreceptor.
  • the measurements of the performance characteristics were carried out by using a sensitometric measurement in which the discharge was obtained for 8 different exposures including zero exposure.
  • the photoconductive recording sheet material was mounted with its conductive backing on an aluminium drum which was earthed and rotated at a circumferential speed of 5 cm/s.
  • the recording material was sequentially charged with a corona at a voltage of -4.3 kV or +4.3 kV operating with a corona current of about 1 »A per cm of corona wire.
  • the recording material was exposed (simulating image-wise exposure) with a light dose of monochromatic light obtained from a monochromator positioned at the circumference of the drum at an angle of 45° with respect to the corona source.
  • the photo-exposure lasted 400 ms.
  • the exposed recording material passed an electrometer probe positioned at an angle of 180° with respect to the corona source.
  • a halogen lamp producing 54.000 mJ/m2 positioned at an angle of 270° with respect to the corona source a new copying cycle started.
  • Each measurement relates to 40 copying cycles in which the photoconductor is exposed to the full light source intensity for the first 5 cycles, then sequentially to the light source the light output of which is moderated by grey filters of optical densities 0.5, 1.0, 1.5, 2.0, 2.5, 3.0 and 3.5 each for 5 cycles and finally to zero light intensity for the last 5 cycles.
  • the electro-optical results quoted in the EXAMPLES 1 to 6 hereinafter refer to charging level at zero light intensity (CL) and to discharge at a light intensity corresponding to the light source intensity moderated by a grey filter with an optical density of 1.0 to a residual potential RP except in the case of 780 nm exposure in which the grey filter has an optical density of 1.5.
  • the % discharge is : (CL-RP) CL x 100
  • the charging level CL is only dependent upon the thickness of the charge transport layer and its specific resistivity.
  • CL expressed in volts should be preferably ⁇ 30 d, where d is the thickness in »m of the charge transport layer.
  • the half-wave reduction potential measurements were carried out using a polarograph with rotating (500 rpm) disc platinum electrode and standard saturated calomel electrode at room temperature (20°C) using a product concentration of 10 ⁇ 4 mole and an electrolyte (tetrabutylammonium perchlorate) concentration of 0.1 mole in spectroscopic grade acetonitrile. Ferrocene was used as a reference substance having a half-wave oxidation potential of +0.430 V.
  • a photoconductor sheet was produced by first doctor blade coating a 100 »m thick polyester film pre-coated with a vacuum-deposited conductive layer of aluminium with a 1 % solution of ⁇ -aminopropyltriethoxy silane in aqueous methanol. After solvent evaporation and curing at 100 °C for 30 minutes, the thus obtained adhesion/blocking layer was doctor blade coated with a dispersion of charge generating pigment to thickness of 0.6 micron.
  • Said dispersion was prepared by mixing 5 g of the ⁇ -form of purified metal-free phthalocyanine, 5 g of aromatic polycarbonate MAKROLON CD 2000 (registered trade mark) and 132.86 g of dichloromethane for 16 hours in a ball mill. Subsequently 23.81 g of dichloromethane was added to the dispersion to produce the composition and viscosity for coating.
  • n-CTM-concentrations in the charge transport layers of Examples 1 to 12 are given in Table 3.
  • the charging level (CL) expressed in volt [V], received exposure dose (It), and the residual potential (RP) and % discharge of each recording material are also given in Table 3.
  • the photoconductive recording materials of Examples 14 to 25 were produced as for Examples 1 to 13 except that the adhesion/blocking layer was produced by coating the aluminium-coated polyester film with a 3 % solution of ⁇ -aminopropyltriethoxysilane in aqueous methanol instead of a 1 % solution, the ⁇ -form of metal-free triazatetrabenzoporphine (already described in unpublished EP-A 89121024.7) was applied at a concentration of 40 % in the charge generating layer instead of the ⁇ -form of metal-free phthalocyanine at a concentration of 50 % by weight.

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Claims (10)

  1. Un matériau d'enregistrement photosensible comportant un support électroconducteur portant dessus une couche renfermant un composé de transfert de charge (composé n-CTM) capable d'accepter et transporter les électrons obtenus à partir d'un composé générateur de charge (composé CGM) contenu dans ce matériau suite à une génération de charge activée par rayonnement, caractérisé en ce que ce composé n-CTM est conforme à la formule générale (A) suivante :
    Figure imgb0033
     dans laquelle :
    R¹ et R² identiques ou différents représentent chacun un groupement alkyle, y compris un groupement alkyle substitué, un groupement cycloalkyle, y compris un groupement cycloalkyle substitué, un groupement aryle, y compris un groupement aryle substitué, COOR⁴, COR⁴, CSR⁴, POR⁴R⁵, SO₂R⁶, où constituent ensemble un élément choisi parmi :
    Figure imgb0034
     R³ représente :
    Figure imgb0035
     R⁴, R⁵, et R⁷ indépendamment l'un de l'autre représentent chacun un groupement alkyle, aryle ou aralkyle;
    R⁶ représente un groupement alkyle, aryle, aralkyle, un atome de F ou de Cl;
    R⁸ représente un groupement alkyle, aryle, aralkyle, alcoxy, COR⁴, COOR⁴, CN, NO₂, un atome de F ou de Cl, ou un groupement SO₂R⁶;
    R⁹ représente l'hydrogène, NHCOR⁴, NHCO(CH₃)=CH₂, NHCOOR⁴, alkyle, alcoxy, ou R⁹ et R¹⁰ représentent ensemble les atomes nécessaires pour compléter un noyau contigu carbocyclique ou hétérocyclique;
    R¹¹ représente un atome d'hydrogène, un groupement alkyle, aryle, aralkyle, alcoxy, COR⁴, COOR⁴, CN, NO₂, un atome de F ou de Cl, un groupement SO₂R⁶ ou NR¹³R¹⁴;
    R¹² représente un atome d'hydrogène, un groupement alkyle, aryle, alcoxy, CN, NO₂, un atome de F ou de Cl, un groupement COR⁴, COOR⁴ ou SO₂R⁶;
    R¹³ et R¹⁴ indépendamment l'un de l'autre représentent chacun un groupement alkyle, un groupement aryle, COOR⁴ ou COR⁴; et
    n représente 0, 1 ou 2.
  2. Matériau d'enregistrement photosensible suivant la revendication 1, caractérisé en ce que ce composé CGM est contenu dans une couche photosensible, génératrice de charge et ce composé n-CTM est contenu dans une couche de transfert de charge étant en contact direct avec cette couche génératrice de charge.
  3. Matériau d'enregistrement photosensible suivant la revendication 1, caractérisé en ce que ce support conducteur est en contact avec une couche d'enregistrement photoconductrice capable d'être chargée positivement contenant dans un liant organique polymère électriquement isolant au moins une substance de pigment photoconducteur de type p et au moins une substance de transfert de charge de type n, caractérisé en ce que (i) cette substance de transfert de charge de type n est un composé n-CTM conforme à la formule générale (A), (ii) cette couche d'enregistrement présente une épaisseur comprise entre 4 et 40 »m et comprend 5 à 40 % en poids de cette substance de pigment de type p ainsi que 0,0001 à 15 % en poids d'au moins une de ces substances de transfert de charge de type n qui est (sont) répartie(s) sous forme de molécules dans ce matériau liant organique polymère électriquement isolant présentant une résistance en volume d'au moins 10¹⁴ Ω/m, et (iii) cette couche d'enregistrement en état électrostatiquement chargé requiert pour une décharge respectivement de 10 % et 90 % des expositions aux rayons électromagnétiques augmentant la conductivité qui diffèrent d'un facteur 4,5 ou moins.
  4. Matériau d'enregistrement photosensible suivant la revendication 3, caractérisé en ce que cette couche d'enregistrement photoconductrice présente une épaisseur comprise entre 5 et 35 »m, et contient 6 à 30 % en poids d'au moins une de ces substances à pigment de type p et 0,001 à 12 % en poids d'au moins une de ces substances de transfert de type n.
  5. Matériau d'enregistrement photosensible suivant la revendication 3 ou 4, caractérisé en ce que cette substance de pigment de type p est un pigment organique de l'une des catégories suivantes :
    a) naphto- et phtalocyanines, telles que les naphto- et phtalocyanines exemptes de métal, les naphto- et phtalocyanines à base de métal, d'oxyde métallique, d'halogène-métal et de siloxysilicium-métal;
    b) pigments de quinoxaline;
    c) pigments de dioxazine de la formule générale :
    Figure imgb0036
     dans laquelle :
    X représente Cl, CONHC₆H₅, NHOCCH₃, NHC₆H₅, CONH₂;
    Y représente p-chlorophényle, NHC₆H₅, NHOCCH₃, NH₂, OC₆H₅, H;
    Z représente H, alcoxy, p. ex. OC₂H₅ ou O-iso.C₃H₇, Cl, NO₂ ou COC₆H₅;
    ou Z et Y constituent ensemble un noyau hétérocyclique substitué ou non;
    d) pigments polyazoïques de type p, y compris les pigments bisazoïques, trisazoïques et tétrakisazoïques.
  6. Matériau d'enregistrement photosensible suivant la revendication 2, caractérisé en ce qu'au moins un de ces composés n-CTM est appliqué en combinaison avec une résine agglomérante afin de former une couche de transfert de charge adhérant directement à cette couche génératrice de charge, où l'une de ces deux couches est de son côté supportée par ce support électroconducteur.
  7. Matériau d'enregistrement photosensible suivant la revendication 6, caractérisé en ce que la résine agglomérante fait en sorte que la résistivité de la couche de transfert de charge ne soit pas inférieure à 10⁹ Ω.cm.
  8. Matériau d'enregistrement photosensible suivant la revendication 6 oder 7, caractérisé en ce que la résine agglomérante est un ester cellulosique, une résine à l'acrylate ou au méthacrylate, le chlorure de polyvinyle, le poly(acétate-co-vinyle), le poly(anhydride maléique-co-vinyle), une résine de polyesters, une résine aromatique de polycarbonates, une résine de polycarbonates d'ester, une résine de silicone, le polystyrène, un copolymère styrène-anhydride maléique ou un copolymère N-vinylcarbazole à teneur en N-vinylcarbazole d'au moins 40 % en poids.
  9. Matériau d'enregistrement photosensible suivant l'une quelconque des revendications précédentes, caractérisé en ce que la teneur en composé n-CTM dans la couche qui le renferme est de 20 à 70 % en poids par rapport au poids total de cette couche.
  10. Matériau d'enregistrement photosensible suivant la revendication 1 ou 2, caractérisé en ce que l'épaisseur de la couche renfermant le(s) composé(s) n-CTM est comprise entre 5 et 50 »m.
EP91202470A 1991-09-24 1991-09-24 Matériau d'enregistrement photosensible Expired - Lifetime EP0534004B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP91202470A EP0534004B1 (fr) 1991-09-24 1991-09-24 Matériau d'enregistrement photosensible
DE69115482T DE69115482T2 (de) 1991-09-24 1991-09-24 Lichtempfindliches Aufzeichnungsmaterial

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP91202470A EP0534004B1 (fr) 1991-09-24 1991-09-24 Matériau d'enregistrement photosensible

Publications (2)

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EP0534004A1 EP0534004A1 (fr) 1993-03-31
EP0534004B1 true EP0534004B1 (fr) 1995-12-13

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DE (1) DE69115482T2 (fr)

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CA2016687A1 (fr) * 1989-05-31 1990-11-30 Agfa-Gevaert Naamloze Vennootschap Colorants et elements donneurs de colorants utilisables dans le chromo-transfert thermique par sublimation
EP0402980A1 (fr) * 1989-06-16 1990-12-19 Agfa-Gevaert N.V. Matériau d'enregistrement électrophotographique

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EP0534004A1 (fr) 1993-03-31
DE69115482T2 (de) 1996-07-18
DE69115482D1 (de) 1996-01-25

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