EP0231835B1 - Matériau d'enregistrement électrophotographique - Google Patents

Matériau d'enregistrement électrophotographique Download PDF

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Publication number
EP0231835B1
EP0231835B1 EP87100968A EP87100968A EP0231835B1 EP 0231835 B1 EP0231835 B1 EP 0231835B1 EP 87100968 A EP87100968 A EP 87100968A EP 87100968 A EP87100968 A EP 87100968A EP 0231835 B1 EP0231835 B1 EP 0231835B1
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EP
European Patent Office
Prior art keywords
recording material
charge
pyrazoline
layer
pigment
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
EP87100968A
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German (de)
English (en)
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EP0231835A2 (fr
EP0231835A3 (en
Inventor
Wolfgang Dr. Wiedemann
Michael Drexler
Hans-Jürgen Fürderer
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Hoechst AG
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Hoechst AG
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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
    • G03G5/02—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
    • G03G5/0664—Dyes
    • G03G5/0666—Dyes containing a methine or polymethine group
    • G03G5/0668—Dyes containing a methine or polymethine group containing only one methine or polymethine group
    • G03G5/067—Dyes containing a methine or polymethine group containing only one methine or polymethine group containing hetero rings
    • 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
    • G03G5/0631—Heterocyclic compounds containing one hetero ring being five-membered containing two hetero atoms

Definitions

  • the present invention relates to an electrophotographic recording material composed of an electrically conductive layer support, optionally an adhesion-promoting insulating intermediate layer and at least one binder-containing photoconductive layer which contains a charge-generating compound and a pyrazoline derivative as charge-transporting compound.
  • the invention particularly relates to a recording material in which the photoconductive layer consists of a charge generation and charge transport layer.
  • the recording material according to the invention is also suitable for a lithographic printing form or printed circuit which can be produced by electrophotographic means if it consists of a correspondingly suitable electrically conductive layer support and a photoconductive layer with binders which can be stripped of alkali.
  • the object of the present invention was therefore to create a highly light-sensitive, electrophotographic recording material from preparatively very easily accessible photoconductor compounds of the pyrazolines, which adheres very well with high flexibility and has a very low sensitivity to pre-exposure.
  • R1 and R2, 3 are hydrogen and R4, respectively.
  • R5 Are halogen, chlorine and bromine being preferred, such as 1,3-diphenyl-5- (2-chlorophenyl) pyrazoline or 1,3-diphenyl-5- (2,4-dichlorophenyl) pyrazoline.
  • the charge-transporting compounds of the general formula I can furthermore be halogen-substituted in the phenyl substituent in the 1-position.
  • the pyrazoline derivatives according to the invention are exceptionally strongly fluorescent ( ⁇ FL ⁇ 500 nm) and can therefore also be used as fluorescent dyes, “laser dyes” and as optical brighteners, for example of PVC plastics.
  • the charge transport compounds according to the invention have very good film formation with various binders and an extraordinarily low tendency to crystallize, even at a relatively high concentration.
  • the films remain flexible and adhere very well, even in a double-layer arrangement.
  • a number of pigments can be used as charge generation layers; condensation products of perylene-3.4.9.10.-tetracarboxylic acid dianhydride with alkylamines, arylamines, aralkylamines and o-aryldiamines, as indicated in the attached formula table II, are particularly advantageous for this purpose.
  • the residual discharge level By adding certain electron acceptor compounds such as 9-bromanthracene, the residual discharge level and Improve consistency even more, especially in cyclical behavior.
  • the ability to activate the charge-transporting compounds with halogenated anthracene or acridine derivatives in the 9 or 10 position is particularly advantageous.
  • Position 1 indicates the electrically conductive layer support
  • position 2 indicates the layer generating the charge carrier
  • position 3 indicates the layer carrying the charges
  • Position 4 shows an adhesion-promoting, insulating intermediate layer
  • position 5 shows layers which indicate a charge-generating layer as a pigment layer in dispersion, for example with a binder
  • Position 6 shows a photoconductive monolayer of dispersed pigment, photoconductor and binder.
  • Aluminum foil optionally transparent, aluminum-coated, sputtered or aluminum-clad polyester foil, is preferably used as the electrically conductive layer support, but any other sufficiently conductive support material can also be used.
  • the arrangement of the photoconductive system can also be on a drum, on flexible endless belts, for example made of nickel or steel etc., or on plates (for example made of aluminum).
  • All materials known for this purpose such as aluminum, zinc, magnesium, copper plates or multi-metal plates, can be used as layer supports for the electrophotographic production of printing forms or printed circuits.
  • Surface-coated aluminum foils have proven particularly useful.
  • the surface finish consists of a mechanical or electrochemical roughening and, if necessary, a subsequent anodization and treatment with polyvinylphosphonic acid.
  • an adhesion-promoting insulating intermediate layer optionally also a thermally, anodically or chemically produced aluminum oxide intermediate layer (FIG. 3, position 4), has the aim of reducing the charge carrier injection from the metal into the photoconductor layer in the dark. On the other hand, it should not hinder the flow of charge during the exposure process.
  • the intermediate layer acts as a barrier layer, it also serves to improve the adhesion between the layer support surface and the pigment layer and the photoconductor layer and should be able to be stripped off water or alcohol-alkaline for the production of printing forms.
  • Different natural or synthetic resin binders can be used for the intermediate layer, however, preference is given to using materials which are good on one Metal, especially aluminum surface, adhere and are slightly dissolved when subsequent layers are applied.
  • These include polyamide resins, polyvinyl alcohols, polyvinylphosphonic acid, polyurethanes, polyester resins, furthermore polycarbonates, phenoxy resins, cellulose nitrates, vinyl chloride-vinyl acetate copolymers, also copolymers of styrene and butadiene, (meth) acrylic acid esters and maleic anhydride.
  • Binders such as polycarbonates, polyester resins and especially vinyl chloride-vinyl acetate copolymers, which are also present in the charge transport layer, have proven particularly useful.
  • the thickness of organic intermediate layers can be up to 5 ⁇ m, that of an aluminum oxide intermediate layer is generally in the range from 0.01 to 1 ⁇ m. Organic intermediate layers in this thickness range are also preferably applied.
  • Layer 2 or 5 (FIGS. 2 to 4) has the function of a layer generating charge carriers; the pigment used determines the spectral photosensitivity of the photoconductive system through its absorption behavior.
  • the following pigments can advantageously be used: Perylene-3.4.9.10.-tetracarboxylic acid dianhydride as well as ⁇ diimide derivatives (for example Formula Table II, AC), bis-benzimidazole pigments such as cis and trans-perinones (for example formulas E, F), furthermore perylene-3.4.9.10.-tetracarboxylic acid benzimidazole derivatives (for example formula D), quinacridone and dioxazine derivatives, polynuclear quinones, for example 4.10-dibromoanthanthrone ( Formula G, CI 59.300), flavanthrone etc., indigo and thioindigo pigments, benzothioxanthene derivatives according to DE-OS 23 28 727 (for example formula H), phthalocyanines (metal-containing CI 74.160 and metal-free CI 74.250), for example ⁇ -Cu phthalocyanine etc., mono-, bis- and
  • the application of a homogeneous, densely packed pigment layer is preferably obtained by evaporating the pigment onto the support in vacuo.
  • the dye can be evaporated without decomposition under conditions of 1.33 ⁇ 10 ⁇ 6 to 10 ⁇ 8 bar and 240 to 290 ° C heating temperature.
  • the temperature of the substrate is below 50 ° C. This gives layers with tightly packed dye molecules. This is advantageous over all other possibilities of producing very thin, homogeneous layers in that an optimal charge generation rate can be obtained in the pigment layer.
  • the extremely finely dispersed distribution of the pigment enables a large concentration of excited dye molecules that inject charges into the transport layer.
  • the charge transport through the pigment layer is not or only slightly hampered by binders.
  • An advantageous layer thickness range of the vapor-deposited pigment is between 0.005 and 3 ⁇ m. A thickness range between 0.05 and 1.5 ⁇ m is particularly preferred since the adhesive strength and homogeneity of the vapor-deposited pigment are particularly favorable here.
  • a uniform pigment layer thickness can also be achieved by other coating techniques. This subheading includes mechanical rubbing of the finely powdered material into the electrically conductive substrate, electrolytic or electrochemical processes or electrostatic spray technology.
  • Well covering pigment layers with thicknesses of the order of 0.05 to 3 ⁇ m can also be obtained by grinding the pigment with binders, in particular with cellulose nitrates, epoxy resins, PVC / PVAC copolymers, styrene-maleic anhydride copolymers, polymethacrylates, polyvinyl acetates, polyurethanes, polyvinyl butyrals, polyvinyl carbonates Polyesters etc. as well as their mixtures and subsequent coating of these dispersions according to position 5 in FIG. 4 are produced.
  • Thermal post-crosslinking binder systems such as reactive resins (DD lacquers) can also be used.
  • the pigment / binder ratio can vary within wide limits, but preference is given to pigment primers with a pigment content of over 50% and a correspondingly high optical density.
  • the charge-transporting layer 3 with the charge transport compounds according to the invention is preferably transparent and, without the pigment layer, has practically no photosensitivity in the visible range (450 to 750 nm). It consists of a mixture of an electron donor compound (organic photoconductor) with a binder. Layer 3 has a high electrical resistance of greater than 10 12 ⁇ . It prevents the flow of the preferably negative electrostatic charge in the dark; when exposed, it transports the charges generated in the pigment layer.
  • the mixing ratio of the charge transporting compound to the binder can vary. However, the requirement for maximum photosensitivity, that is to say the largest possible proportion of charge-transporting compound, and to avoid crystallization to be avoided and increase in flexibility, that is to say the largest possible proportion of binders, set relatively certain limits.
  • a mixing ratio of about 1: 1 parts by weight has generally proven to be preferred, but ratios between 4: 1 and 1: 4 are also suitable.
  • the surprisingly low tendency towards crystallization of a number of the charge transport compounds according to the invention also permits organic photoconductor / binder ratios of 4: 1, in particular with polycarbonate, without crystallization taking place and the film-forming properties deteriorating.
  • acceptors bring about a reduction in the residual discharge in the photoconductive system and also an improved constancy of the cyclic parameters, without the other good electrophotographic properties such as photosensitivity, charge acceptance, dark decay, pre-exposure sensitivity etc. being impaired. They are preferably contained in the charge transport layer in an amount of up to 10 percent by weight, based on the total coating.
  • Advantageous charge transport layers are composed of approximately 50-70 percent by weight charge transport compound, 20-40 percent by weight polycarbonate, approximately 10 percent by weight vinyl chloride-vinyl acetate copolymer and up to 6 percent by weight electron acceptor compound. With these settings, optimal copy quality is achieved even at higher temperatures and humidity. In addition, the pre-exposure sensitivity is surprisingly low.
  • the added binder influences both the mechanical behavior, such as abrasion, flexibility, film formation, adhesion, etc., and to a certain extent the electrophotographic behavior, such as photosensitivity, residual charge and cyclical behavior under normal conditions, as well as under higher conditions Temperature (20 to 50 ° C) and humidity (greater than 80% relative humidity).
  • Polyester resins polyvinyl acetates, polycarbonates, silicone resins, polyurethanes, epoxy resins, phenoxy resins, poly (meth) acrylates and copolymers (for Example with styrene), polystyrenes and styrene copolymers (for example with butadiene), cellulose derivatives, such as cellulose acetobutyrates etc., are used.
  • the photoconductive layer preferably contains polyester resins, vinyl chloride-vinyl acetate copolymers, polycarbonates or mixtures thereof as binders.
  • the photoconductive layer contains an alkali-strippable binder.
  • Styrene-maleic anhydride copolymers sulfonyl urethanes, phenolic resins or copolymers of vinyl acetate with an unsaturated carboxylic acid are preferably used as alkali-releasable resins.
  • thermally post-crosslinking binder systems such as reactive resins, which are composed of an equivalent mixture of hydroxyl-containing polyesters or polyethers and polyfunctional isocyanates, polyisocyanate-crosslinkable acrylate resins, melamine resins, unsaturated polyester resins, etc., have been used successfully.
  • polyvinyl chloride copolymers of vinyl chloride and vinyl acetate, polyvinylidene chlorides, polyacrylonitriles and cellulose nitrates can be used, in particular also blended with the above binders; a proportion of up to about 10 percent by weight, based on the solids content of the charge transport layer, has proven to be advantageous.
  • the layer thickness is also important for the optimal photosensitivity of the charge transport layer: layer thicknesses between approximately 2 and 25 ⁇ m are generally used. A thickness range of 5 to 18 ⁇ m has proven to be advantageous. However, if the mechanical requirements and the electrophotographic parameters allow for charging, exposure and development processes, the specified limits can be extended upwards or downwards on a case-by-case basis.
  • Leveling agents such as silicone oils, wetting agents, in particular nonionic substances, plasticizers of different compositions, such as, for example, those based on chlorinated hydrocarbons or those based on phthalic acid esters are considered to be customary additives.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)

Claims (13)

  1. Matériau d'enregistrement électrophotographique comprenant un substrat conducteur de l'électricité, éventuellement une couche intermédiaire isolante facilitant l'adhérence et au moins une couche photoconductrice renfermant un liant, qui contient un composé formant porteur de charges et un dérivé de pyrazoline comme composé transporteur de charges, caractérisé en ce que le composé transporteur de charges correspond à la formule générale I suivante:
    Figure imgb0018
     dans laquelle n vaut 0 ou 1, et R₁, R₂, R₃, R₄, R₅ représentent un atome d'hydrogène ou d'halogène, au moins un de ces substituants étant un halogène.
  2. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que le composé transporteur de charges correspond à la formule 1, et R₁, R₂, R₃, R₄, R₅ représentent un atome d'hydrogène, de chlore ou de brome.
  3. Matériau d'enregistrement selon la revendication 2, caractérisé en ce que le composé transporteur de charges est
    la 1-phényl-3-(2-chlorostyryl)-5-(2-chlorophényl)pyrazoline ou
    la 1-phényl-3-(2,4-dichlorostyryl)-5-(2,4-dichlorophényl)pyrazoline.
  4. Matériau d'enregistrement selon la revendication 1 ou 2, caractérisé en ce que le composé transporteur de charges est
    la 1,3-diphényl-5-(2-chlorophényl)pyrazoline ou
    la 1,3-diphényl-5-(2,4-dichlorophényl)pyrazoline.
  5. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que la couche photoconductrice comprend une couche génératrice de charges et une couche transporteuse de charges.
  6. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que la couche photoconductrice renferme, comme liant, une résine polyester, un copolymère chlorure de vinyle/acétate de vinyle, un polycarbonate ou un mélange de ces substances.
  7. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que la couche photoconductrice renferme un liant éliminable par une base alcaline.
  8. Matériau d'enregistrement selon la revendication 7, caractérisé en ce que la couche photoconductrice renferme, comme liant, un copolymère styrène/anhydride maléique, un sulfonyluréthane, une résine phénolique ou un copolymère d'acétate de vinyle avec un acide carboxylique insaturé.
  9. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que la couche photoconductrice renferme un pigment formant porteur de charges.
  10. Matériau d'enregistrement selon la revendication 9, caractérisé en ce que les pigments présents sont des produits de condensation du dianhydride d'acide pérylène-3,4,9,10-tétracarboxylique avec des alkylamines, des arylamines, des aralkylamines ou des o-aryldiamines.
  11. Matériau d'enregistrement selon la revendication 9, caractérisé en ce que le pigment présent est de la phtalocyanine contenant ou non un métal.
  12. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que la couche photoconductrice renferme des composés accepteurs d'électrons.
  13. Matériau d'enregistrement selon la revendication 12, caractérisé en ce que des dérivés d'anthracène ou d'acridine substitués en position 9 ou 10 par un atome d'halogène sont présents en tant qu'accepteurs d'électrons.
EP87100968A 1986-02-01 1987-01-23 Matériau d'enregistrement électrophotographique Expired - Lifetime EP0231835B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863603139 DE3603139A1 (de) 1986-02-01 1986-02-01 Elektrophotographisches aufzeichnungsmaterial
DE3603139 1986-02-01

Publications (3)

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EP0231835A2 EP0231835A2 (fr) 1987-08-12
EP0231835A3 EP0231835A3 (en) 1988-05-04
EP0231835B1 true EP0231835B1 (fr) 1992-11-11

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EP87100968A Expired - Lifetime EP0231835B1 (fr) 1986-02-01 1987-01-23 Matériau d'enregistrement électrophotographique

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US (1) US4762760A (fr)
EP (1) EP0231835B1 (fr)
JP (1) JPS62191856A (fr)
DE (2) DE3603139A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01307759A (ja) * 1988-06-06 1989-12-12 Fuji Electric Co Ltd 電子写真用感光体
US5238763A (en) * 1991-12-31 1993-08-24 Xerox Corporation Electrophotographic imaging member with polyester adhesive layer and polycarbonate adhesive layer combination

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3180729A (en) * 1956-12-22 1965-04-27 Azoplate Corp Material for electrophotographic reproduction
DE2220408C3 (de) * 1972-04-26 1978-10-26 Hoechst Ag, 6000 Frankfurt Elektrophotographisches Aufzeichnungsmaterial und Verfahren zu seiner Herstellung
US3837851A (en) * 1973-01-15 1974-09-24 Ibm Photoconductor overcoated with triarylpyrazoline charge transport layer
US4030923A (en) * 1975-12-11 1977-06-21 International Business Machines Corporation Mixture of binder materials for use in connection with a charge transport layer in a photoconductor
JPS6028342B2 (ja) * 1978-06-21 1985-07-04 コニカ株式会社 電子写真感光体
JPS5521080A (en) * 1978-08-03 1980-02-14 Ricoh Co Ltd Electrophotographic photoreceptor
JPS5546725A (en) * 1979-08-23 1980-04-02 Olympus Optical Co Ltd Aperture priority type ee camera
US4307167A (en) * 1980-03-03 1981-12-22 International Business Machines Corporation Layered electrophotographic plate having tetramethyl benzidene based disazo dye
DE3246036C2 (de) * 1982-12-09 1984-11-29 Hoechst Ag, 6230 Frankfurt Elektrophotographisches Aufzeichnungsmaterial
JPS6097360A (ja) * 1983-11-01 1985-05-31 Canon Inc 電子写真感光体
US4490452A (en) * 1983-12-09 1984-12-25 International Business Machines Corporation Xerographic photoconductors with cross-linked epoxy binder
JPS60177355A (ja) * 1984-02-24 1985-09-11 Canon Inc 電子写真感光体

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Publication number Publication date
US4762760A (en) 1988-08-09
DE3782506D1 (de) 1992-12-17
EP0231835A2 (fr) 1987-08-12
DE3603139A1 (de) 1987-08-13
EP0231835A3 (en) 1988-05-04
JPS62191856A (ja) 1987-08-22

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