EP0194624A2 - Electrophotographic recording material - Google Patents

Electrophotographic recording material Download PDF

Info

Publication number
EP0194624A2
EP0194624A2 EP86103130A EP86103130A EP0194624A2 EP 0194624 A2 EP0194624 A2 EP 0194624A2 EP 86103130 A EP86103130 A EP 86103130A EP 86103130 A EP86103130 A EP 86103130A EP 0194624 A2 EP0194624 A2 EP 0194624A2
Authority
EP
European Patent Office
Prior art keywords
recording material
material according
photoconductor
sensitizing dyes
bis
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
EP86103130A
Other languages
German (de)
French (fr)
Other versions
EP0194624B1 (en
EP0194624A3 (en
Inventor
Werner Dr. Dipl.-Chem. Franke
Richard Brahm
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
Original Assignee
Hoechst AG
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 Hoechst AG filed Critical Hoechst AG
Publication of EP0194624A2 publication Critical patent/EP0194624A2/en
Publication of EP0194624A3 publication Critical patent/EP0194624A3/en
Application granted granted Critical
Publication of EP0194624B1 publication Critical patent/EP0194624B1/en
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
    • G03G5/02—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
    • G03G5/09—Sensitisors or activators, e.g. dyestuffs

Definitions

  • the present invention relates to an electrophotographic recording material consisting of an electrically conductive support and at least one photoconductive layer containing photoconductors, sensitizing dyes, binders and conventional additives.
  • photoconductors for electrophotographic reproduction which are sensitive to radiation down to the short-wave visible part of the spectrum and whose radiation sensitivity in the visible part of the spectrum can be expanded by adding one or more sensitizing dyes which transmit longer-wave energy to transmit the energy Light are enabled on the photoconductor.
  • panchromatic sensitizations have advantages in that the light sources used in reproduction technology with a high proportion of red are better used. In practice, this means shorter exposure times and thus time and energy savings. It is also possible because of the improved sensitivity to reduce the proportion of photoconductor in the photoconductive layer.
  • sensitizer Since a sensitizer usually does not cover the entire visible area of the spectrum, it is necessary to mix several sensitizers. It is. but very difficult to obtain sensitizations that meet the diverse needs of reproductive technology.
  • the object of the present invention was to sensitize electrophotographic recording material with organic or inorganic photoconductor in such a way that sensitization from the area the intrinsic sensitivity of the photoconductor is obtained up to about 700 nm, the individual sensitizations overlapping as possible so that the resulting sensitization corresponds to the emission of a light source emitting in the entire visible region, such as an Hg-Ga burner.
  • the sensitization should be such that sensitization maxima are present which are in the area of the emission of conventional lasers, such as argon ion lasers, krypton lasers or LED diodes. It was also an object of the invention to use a mixture of dyes which are derived from the same heterocycle for reasons of compatibility.
  • the solution to the problem is based on an electrophotographic recording material composed of an electrically conductive substrate and at least one photoconductive layer composed of photoconductor, sensitizing dyes, binders and conventional additives. It is characterized in that at least three sensitizing dyes are present, at least two of which are of the 3,3'-dimethylindolenine type, which sensitize in different wavelength ranges.
  • bis- (3,3'-dimethylindolenyl) tri- and pentamethine cyanines are present as sensitizing dyes of the 3,3'-dimethylindolenine type, as represented by the attached formulas Nos. 1 and 2.
  • cyanine dyes from the group Astrazonorange R (CI 48040) - represented as Formula 3 -, Astrazonorange G (CI 48035), Astrazon Yellow 3G (CI 48055), Astrazon Yellow 5G (CI 48065) and Basic Yellow 52115 (CI 48060) according to the invention are additionally used used.
  • sensitizing dyes have different effects for different types of photoconductors. Therefore, when using inorganic photoconductor such as zinc oxide, bis-benzoxazole trimethine cyanine is used as the sensitizing dye in the photoconductive layer (formula 4). Compounds - this type are proposed in the German patent application, file number P 34 05 487.1, as a sensitizing dye.
  • the selection and mixing ratio of the dyes according to the invention ensure that various organic or inorganic photoconductors can be sensitized well in a range from about 400 to 700 nm.
  • the spectral sensitizing dye according to formula No. 1 used according to the invention is characterized by intensive sensitization in red with a sensitization maximum at 670 nm and a shoulder at 640 nm. For example, it is more intense and sensitizes longer-wave than the commonly used brilliant green, as shown in the attached FIG. 2 going on.
  • sensitizing dye according to formula No. 2 used in admixture with sensitizing dye No. 1 sensitizes in the green with a sensitizing maximum at 560 nm and a shoulder at approx. 500 nm.
  • Figure 3 shows the spectral sensitization by dye according to formula 2.
  • the sensitizing dye according to formula No. 3 sensitizes in blue with a maximum around 500 nm, as can be seen from the attached FIG. 1.
  • the sensitization characteristics can generally be found in the spectrograms attached in FIGS. 1 to 3.
  • 1 shows the sensitization characteristic in the range from 400 to about 700 nm by mixing three different dyes for organic photoconductors (mixture of the dyes according to formula 1 + 2 + 3) or ZnO photoconductors (mixture of the dyes according to formula 1 + 2 + 4) at.
  • the sensitizing dyes 1, 2 and 4 according to the invention are prepared by the procedures customary in the chemistry of cyanine dyes and known to the person skilled in the art. (W. Koenig, B. 57, 685 (1924), DE-PS 410.487, A. Claisen, B. 36, 3667 (1903)).
  • the concentration of the sensitizing dyes according to the invention depends on the photoconductor used in the individual case, the desired effect and on the sensitizing dyes used themselves. Usually 0.05 to 1.0 percent by weight of individual dyes, based on the weight of the photoconductor, are added.
  • the effect of the sensitizing dye according to formula No. 1 can be increased by changing the mixing ratio from, for example, 1: 1: 1 to 0.5: 1: 1 for the sensitizing dyes 1, 2 and 4.
  • the photoconductive layer can be in either a single or multiple layer arrangement, with charge carrier generation and charge transport taking place jointly or separately.
  • Both organic and inorganic compounds can be used as photoconductors.
  • Monomers such as polymeric aromatic carbocyclic or heterocyclic compounds may be mentioned as organic photoconductors.
  • Oxdiazole derivatives such as 2,5-bis (4'-diethylaminophenyl) -1,3,4-oxdiazole, described in DE-PS 10 58 836 (corresponding to US Pat. No. 3,189,447), or oxazole derivatives, such as 2-vinyl, are preferably used.
  • suitable polymeric compounds are vinylaromatic polymers, such as polyvinylanthracene, polyacenaphthylene or copolymers.
  • Poly-N-vinylcarbazole or copolymers of N - vinylcarbazole with an N-vinylcarbazole content of at least about 40 percent by weight have proven particularly useful.
  • polyester resins such as mixed polyesters of iso- and terephthalic acid with glycol, or silicone resins, such as three-dimensionally crosslinked phenylmethylsiloxanes, or so-called reaction resins, as are known under the name DD lacquers, are suitable.
  • Polycarbonate resins can also be used well.
  • Binders which are soluble in aqueous or alcoholic solvent systems, optionally with the addition of acid or alkali, are particularly suitable for the preferred use of the recording material according to the invention for the production of printing forms.
  • Ge Suitable binders are high-molecular substances which carry alkali-solubilizing groups, such as acid anhydride, carboxyl, phenol, sulfonic acid, sulfonamide or sulfonimide groups. Copolymers with anhydride groups can be used with particularly good success, since the absence of free acid groups means that the dark conductivity of the photoconductive materials. Layer is thin despite good alkali solubility.
  • Zinc oxide is preferably mentioned as the inorganic photoconductor.
  • the grain size of the photoconductive zinc oxide used is approximately 0.1 to 15 ⁇ m.
  • Suitable binders with a specific resistance of 10 7 to 10 14 a.cm in this case are polymeric or resinous binders or mixtures thereof. Suitable for this are polyurethane, polyester, polycarbonates, polystyrenes, chlorinated rubber, acrylic resins, alkyd resins, silica resins or vinyl acetate copolymers, such as vinyl chloride acetate resin.
  • the photoconductive layer with zinc oxide as the photoconductor can contain between 50 and about 95 percent by weight of the photoconductive particles.
  • a preferred weight ratio of the binder to the particles is between 1: 4 and 1:10.
  • the layer supports of the recording material can be flat or cylindrical and can be made in a known manner from a metal plate, a metal foil, from metallized paper or papers or fo lines that are coated with an electrically conductive plastic.
  • toner images can be produced on the recording material according to the invention, but it is also possible to transfer either the charge image or the toner image to an image receiving material.
  • a printing form or a printed circuit can also be obtained after imaging, development and stripping of the photoconductor layer at the non-image locations and, if appropriate, etching away the metal layer at the non-image locations.
  • the electrophotographic recording material can contain leveling agents and plasticizers and / or adhesion promoters as conventional additives in the photoconductive layer and / or between the support and the photoconductive layer.
  • a printing plate for offset printing was produced from this recording material in the following manner.
  • the photoconductive layer was charged to -430 V in the dark with the aid of a corona, then exposed in a repro camera at aperture 14 for eight seconds using an Hg-Ga burner (5000 W M023-Sylvania).
  • the resulting latent charge image was developed with a commercially available dry toner using a magnetic roller and the toner image was fixed by heat.
  • a 100 ⁇ m thick aluminum foil was provided with a photoconductive layer.
  • the photoconductive layer was prepared as follows: 100 parts by weight of photoconductive zinc oxide were mixed together with 40 parts by weight of a 50% solution of a modified multipolymer of the vinyl acetate in toluene. The mixture was ball-milled for about 3 hours and then applied to the paper support by means of a wire knife to a dry layer weight of about 30 g / m 2 . The solution had been added in a ratio of 1: 1: 1 each 0.5% individual dye, based on the weight of the photoconductor, of sensitizing dye according to formulas 1, 2 and 4.
  • the layer was charged with a corona (voltage 5 kV negative, distance 25 mm) and with an argon ion laser in the power range 0.2 to 0.5 mW (nominal power 50 mW, output power 15 mW) at a feed rate of 400 lines / cm illustrated in a conventional machine which is used for the production of printing forms and further processed in the manner customary for ZnO printing plates.
  • a corona voltage 5 kV negative, distance 25 mm
  • an argon ion laser in the power range 0.2 to 0.5 mW (nominal power 50 mW, output power 15 mW) at a feed rate of 400 lines / cm illustrated in a conventional machine which is used for the production of printing forms and further processed in the manner customary for ZnO printing plates.

Abstract

Die Erfindung betrifft elektrophotographisches Aufzeichnungsmaterial, bestehend aus einem elektrisch leitenden Schichtträger und mindestens einer photoleitfähigen Schicht, enthaltend Photoleiter, Sensibilisierungsfarbstoffe, Bindemittel und übliche Zusätze, dadurch gekennzeichnet, daß mindestens drei Sensibilisierungs-farbstoffe vorhanden sind, von denen mindestens zwei vom 3,3'-Dimethylindolenin-Typ sind, wie Bis-(3,3'-di-methylindolenyl)-tri-und-pentamethincyanine, die in unterschiedlichen Wellenlängenbereichen sensibilisieren. Man erzielt hierdurch die Sensibilisierung verschiedener organischer wie anorganischer Photoleiter in einem Bereich von etwa 400 bis 700 nm.The invention relates to electrophotographic recording material, consisting of an electrically conductive support and at least one photoconductive layer containing photoconductor, sensitizing dyes, binders and conventional additives, characterized in that at least three sensitizing dyes are present, at least two of which are from 3,3'- Dimethylindolenine types, such as bis- (3,3'-dimethylindolenyl) tri-and-pentamethine cyanines, which sensitize in different wavelength ranges. This achieves the sensitization of various organic and inorganic photoconductors in a range from approximately 400 to 700 nm.

Description

Die vorliegende Erfindung betrifft ein elektrophotographisches Aufzeichnungsmaterial, bestehend aus einem elektrisch leitenden Schichtträger und mindestens einer photoleitfähigen Schicht, enthaltend Photoleiter, Sensibilisierungsfarbstoffe, Bindemittel und übliche Zusätze.The present invention relates to an electrophotographic recording material consisting of an electrically conductive support and at least one photoconductive layer containing photoconductors, sensitizing dyes, binders and conventional additives.

Es ist bekannt, für die elektrophotographische Reproduktion Photoleiter zu verwenden, die bis in den kurzwelligen sichtbaren Teil des Spektrums strahlungsempfindlich sind und deren Strahlungsempfindlichkeit im sichtbaren Teil des Spektrums dadurch erweitert werden kann, daß man einen oder mehrere Sensibilisierungsfarbstoffe zusetzt, die zur Übertragung der Energie längerwelligen Lichtes auf den Photoleiter befähigt sind. Hierzu gehören Farbstoffe der verschiedensten Verbindungsklassen.It is known to use photoconductors for electrophotographic reproduction which are sensitive to radiation down to the short-wave visible part of the spectrum and whose radiation sensitivity in the visible part of the spectrum can be expanded by adding one or more sensitizing dyes which transmit longer-wave energy to transmit the energy Light are enabled on the photoconductor. This includes dyes from a wide variety of compound classes.

Es ist bekannt (DE-AS 25 26 720, entsprechend US-PS 4,063,948), für die elektrophotographische Reproduktion ein elektrophotographisches Aufzeichnungsmaterial zu verwenden, das in der photoleitfähigen Schicht einen im blauen Spektralbereich sensibilisierenden Cyaninfarbstoff enthält. Eine derartige Sensibilisierung ermöglicht es jedoch nicht, auch Strahlung im zum Beispiel grünen und roten Gebiet des Spektrums zu registrieren.It is known (DE-AS 25 26 720, corresponding to US Pat. No. 4,063,948) to use an electrophotographic recording material for electrophotographic reproduction which contains a cyanine dye sensitizing in the blue spectral range in the photoconductive layer. However, such sensitization does not make it possible to register radiation in the green and red areas of the spectrum, for example.

Es ist auch bekannt (DE-OS 14 47 907, entsprechend US-PS 3,458,310), Photoleiterschichten bis ins sichtbare Rot zu sensibilisieren. Man verwendet hierzu zum Beispiel Mischungen aus Acridingelb, Acridinorange, Rhodaminfarbstoff und Brillantgrün, die in einer oder auch getrennt in verschiedenen Schichten zugesetzt werden (DE-OS 23 53 639, entsprechend US-PS 3,992,205), wobei sich die Wirkung der Einzelfarbstoffe addiert oder auch eine davon abweichende Sensibilisierung auftritt (DE-OS 28 17 428, entsprechend US-PS 4,252,880).It is also known (DE-OS 14 47 907, corresponding to US PS 3,458,310) to sensitize photoconductor layers to visible red. Mixtures of acridine yellow, acridine orange, rhodamine dye and brilliant green are used for this purpose, which are added in one or else separately in different layers (DE-OS 23 53 639, corresponding to US Pat. No. 3,992,205), the effect of the individual dyes adding up or else a different sensitization occurs (DE-OS 28 17 428, corresponding to US Pat. No. 4,252,880).

Derartige panchromatische Sensibilisierungen bringen insofern Vorteile, als die in der Reproduktionstechnik verwendeten Lichtquellen mit einem hohen Rotanteil besser ausgenutzt werden. Dies bedeutet für die Praxis kürzere Belichtungszeiten und damit Zeit- und Energieersparnis. Auch ist es wegen der verbesserten Empfindlichkeit möglich, den Photoleiteranteil in der photoleitfähigen Schicht herabzusetzen.Such panchromatic sensitizations have advantages in that the light sources used in reproduction technology with a high proportion of red are better used. In practice, this means shorter exposure times and thus time and energy savings. It is also possible because of the improved sensitivity to reduce the proportion of photoconductor in the photoconductive layer.

Da in der Regel ein Sensibilisatör allein das gesamte sichtbare Gebiet des Spektrums nicht überdeckt, ist es erforderlich, mehrere Sensibilisatoren zu mischen. Es ist. aber sehr schwierig, damit Sensibilisierungen zu erhalten, die den vielgestaltigen Wünschen der Reproduktionstechnik gerecht werden.Since a sensitizer usually does not cover the entire visible area of the spectrum, it is necessary to mix several sensitizers. It is. but very difficult to obtain sensitizations that meet the diverse needs of reproductive technology.

Der vorliegenden Erfindung lag die Aufgabe zugrunde, elektrophotographisches Aufzeichnungsmaterial mit organischem oder auch anorganischem Photoleiter derart zu sensibilisieren, daß eine Sensibilisierung vom Gebiet der Eigenempfindlichkeit des Photoleiters bis über etwa 700 nm erhalten wird, wobei sich die Einzelsensibilisierungen möglichst überlappen, damit die resultierende Sensibilisierung der Emission einer im ganzen sichtbaren Gebiet emittierenden Lichtquelle, wie zum Beispiel einem Hg-Ga-Brenner, entspricht. Andererseits sollte die Sensibilisierung aber derart sein, daß Sensibilisierungsmaxima vorhanden sind, die im Gebiet der Emission von üblichen Lasern, wie Argonionenlaser, Kryptonlaser oder LED-Dioden, liegen. Es war auch Ziel der Erfindung, eine Mischung von Farbstoffen zu verwenden, die sich aus Gründen der Verträglichkeit vom gleichen Heterocyclus ableiten.The object of the present invention was to sensitize electrophotographic recording material with organic or inorganic photoconductor in such a way that sensitization from the area the intrinsic sensitivity of the photoconductor is obtained up to about 700 nm, the individual sensitizations overlapping as possible so that the resulting sensitization corresponds to the emission of a light source emitting in the entire visible region, such as an Hg-Ga burner. On the other hand, the sensitization should be such that sensitization maxima are present which are in the area of the emission of conventional lasers, such as argon ion lasers, krypton lasers or LED diodes. It was also an object of the invention to use a mixture of dyes which are derived from the same heterocycle for reasons of compatibility.

Die Lösung der Aufgabe geht aus von einem elektrophotographischen Aufzeichnungsmaterial aus einem elektrisch leitenden Schichtträger und mindestens einer photoleitfähigen Schicht aus Photoleiter, Sensibilisierungsfarbstoffen, Bindemittel und üblichen Zusätzen. Sie ist dadurch gekennzeichnet, daß mindestens drei Sensibilisierungsfarbstoffe vorhanden sind, von denen mindestens zwei vom 3,3'-Dimethylindolenin-Typ sind, die in unterschiedlichen Wellenlängenbereichen sensibilisieren.The solution to the problem is based on an electrophotographic recording material composed of an electrically conductive substrate and at least one photoconductive layer composed of photoconductor, sensitizing dyes, binders and conventional additives. It is characterized in that at least three sensitizing dyes are present, at least two of which are of the 3,3'-dimethylindolenine type, which sensitize in different wavelength ranges.

In bevorzugter Ausführung sind erfindungsgemäß als Sensibilisierungsfarbstoffe vom 3,3'-Dimethyl-indolenin-Typ Bis-(3,3'-dimethylindolenyl)-tri- und -pentamethincyanine, wie durch die beigefügten Formeln Nr. 1 und 2 dargestellt, vorhanden.In a preferred embodiment, according to the invention, bis- (3,3'-dimethylindolenyl) tri- and pentamethine cyanines are present as sensitizing dyes of the 3,3'-dimethylindolenine type, as represented by the attached formulas Nos. 1 and 2.

Als Sensibilisierungsfarbstoffe werden zusätzlich Cyaninfarbstoffe aus der Gruppe Astrazonorange R (C.I. 48040) - als Formel 3 dargestellt -, Astrazonorange G (C.I. 48035), Astrazongelb 3G (C.I. 48055), Astrazongelb 5G (C.I. 48065) und Basic Yellow 52115 (C.I. 48060) erfindungsgemäß eingesetzt.As sensitizing dyes, cyanine dyes from the group Astrazonorange R (CI 48040) - represented as Formula 3 -, Astrazonorange G (CI 48035), Astrazon Yellow 3G (CI 48055), Astrazon Yellow 5G (CI 48065) and Basic Yellow 52115 (CI 48060) according to the invention are additionally used used.

Es hat sich gezeigt, daß die Sensibilisierungsfarbstoffe für verschiedene Photoleitertypen unterschiedlich wirksam sind. Deshalb werden bei Verwendung von anorganischem Photoleiter, wie Zinkoxid, als Sensibilisierungsfarbstoff Bis-benzoxazol-trimethincyanine in der photoleitfähigen Schicht verwendet (Formel 4). Verbindungen-dieser Art sind in der deutschen Patentanmeldung, Aktenzeichen P 34 05 487.1, als Sensibilisierungsfarbstoff vorgeschlagen.It has been shown that the sensitizing dyes have different effects for different types of photoconductors. Therefore, when using inorganic photoconductor such as zinc oxide, bis-benzoxazole trimethine cyanine is used as the sensitizing dye in the photoconductive layer (formula 4). Compounds - this type are proposed in the German patent application, file number P 34 05 487.1, as a sensitizing dye.

Durch Auswahl und Mischungsverhältnis der erfindungsgemäßen Farbstoffe wird erreicht, daß verschiedene organische oder anorganische Photoleiter in einem Bereich von etwa 400 bis 700 nm gut sensibilisiert werden können.The selection and mixing ratio of the dyes according to the invention ensure that various organic or inorganic photoconductors can be sensitized well in a range from about 400 to 700 nm.

Der erfindungsgemäß verwendete spektrale Sensibilisierungsfarbstoff nach Formel Nr. 1 zeichnet sich durch eine intensive Sensibilisierung im Rot mit einem Sensibilisierungsmaximum bei 670 nm und einer Schulter bei 640 nm aus. Er ist zum Beispiel intensiver und sensibilisiert längerwellig als das üblicherweise verwendete Brillantgrün, wie dies aus der beigefügten Figur 2 hervorgeht.The spectral sensitizing dye according to formula No. 1 used according to the invention is characterized by intensive sensitization in red with a sensitization maximum at 670 nm and a shoulder at 640 nm. For example, it is more intense and sensitizes longer-wave than the commonly used brilliant green, as shown in the attached FIG. 2 going on.

Der in Abmischung mit Sensibilisierungsfarbstoff Nr. 1 verwendete Sensibilisierungsfarbstoff nach Formel Nr. 2 sensibilisiert im Grün mit einem Sensibilisierungsmaximum bei 560 nm und einer Schulter bei ca. 500 nm.The sensitizing dye according to formula No. 2 used in admixture with sensitizing dye No. 1 sensitizes in the green with a sensitizing maximum at 560 nm and a shoulder at approx. 500 nm.

Figur 3 gibt die spektrale Sensibilisierung durch Farbstoff nach Formel 2 wieder. Der Sensibilisierungsfarbstoff nach Formel Nr. 3 sensibilisiert im Blau mit einem Maximum um 500 nm, wie dies aus der beigefügten Figur 1 hervorgeht.Figure 3 shows the spectral sensitization by dye according to formula 2. The sensitizing dye according to formula No. 3 sensitizes in blue with a maximum around 500 nm, as can be seen from the attached FIG. 1.

Die Sensibilisierungscharäkteristiken sind generell den in Figuren 1 bis 3 beigefügten Spektrogrammen zu entnehmen. Hierbei gibt Figur 1 die Sensibilisierungscharakteristik im Bereich von 400 bis etwa 700 nm durch Mischung dreier verschiedener Farbstoffe für organische Photoleiter (Mischung der Farbstoffe nach Formel 1 + 2 + 3) oder ZnO-Photoleiter (Mischung der Farbstoffe nach Formel 1 + 2 + 4) an.The sensitization characteristics can generally be found in the spectrograms attached in FIGS. 1 to 3. 1 shows the sensitization characteristic in the range from 400 to about 700 nm by mixing three different dyes for organic photoconductors (mixture of the dyes according to formula 1 + 2 + 3) or ZnO photoconductors (mixture of the dyes according to formula 1 + 2 + 4) at.

Die Herstellung der erfindungsgemäßen Sensibilisierungs- farbstoffe 1,2 und 4 erfolgt nach den in der Chemie der Cyaninfarbstoffe üblichen und dem Fachmann bekannten Verfahrensweisen. (W. König, B. 57, 685 (1924), DE-PS 410.487, A. Claisen, B. 36, 3667 (1903)).The sensitizing dyes 1, 2 and 4 according to the invention are prepared by the procedures customary in the chemistry of cyanine dyes and known to the person skilled in the art. (W. Koenig, B. 57, 685 (1924), DE-PS 410.487, A. Claisen, B. 36, 3667 (1903)).

Die Konzentration der erfindungsgemäßen Sensibilisierungsfarbstoffe hängt von dem im Einzelfall verwendeten Photoleiter, dem erwünschten Effekt und von den verwendeten Sensibilisierungsfarbstoffen selbst ab. Üblicherweise werden 0,05 bis 1,0 Gewichtsprozent Einzelfarbstoffe, bezogen auf das Gewicht des Photoleiters, zugesetzt. Man kann durch Veränderung des Mischungsverhältnisses von zum Beispiel 1:1:1 auf 0,5:1:1 für die Sensibilisierungsfarbstoffe 1, 2 und 4 die Wirkung des Sensibilisierungsfarbstoffes nach Formel Nr. 1 verstärken.The concentration of the sensitizing dyes according to the invention depends on the photoconductor used in the individual case, the desired effect and on the sensitizing dyes used themselves. Usually 0.05 to 1.0 percent by weight of individual dyes, based on the weight of the photoconductor, are added. The effect of the sensitizing dye according to formula No. 1 can be increased by changing the mixing ratio from, for example, 1: 1: 1 to 0.5: 1: 1 for the sensitizing dyes 1, 2 and 4.

Die photoleitfähige Schicht kann sowohl in Einfach- als auch in Mehrfachschiehtanordnung vorliegen, wobei Ladungsträgererzeugung und Ladungstransport gemeinsam oder getrennt erfolgen.The photoconductive layer can be in either a single or multiple layer arrangement, with charge carrier generation and charge transport taking place jointly or separately.

Als Photoleiter kommen sowohl organische als auch anorganische Verbindungen in Frage. Als organische Photoleiter seien monomere wie polymere aromatische carbocyclische oder heterocyclische Verbindungen genannt.Both organic and inorganic compounds can be used as photoconductors. Monomers such as polymeric aromatic carbocyclic or heterocyclic compounds may be mentioned as organic photoconductors.

Vorzugsweise werden Oxdiazolderivate, wie 2,5-Bis-(4'-diethylaminophenyl)-1,3,4-oxdiazol, beschrieben in DE-PS 10 58 836 (entsprechend US-PS 3,189,447), oder Oxazolderivate, wie 2-Vinyl-4-(2'-chlorphenyl)-5-(4'-diethylaminophenyl)-oxazol oder 2-Phenyl-4-(2'-chlorphenyl)-5-(4'-diethylaminophenyl)-oxazol, beschrieben in DE-PS 10 60 260 (entsprechend US-PS 3,112,197) bzw. 11 20 875 (entsprechend US-PS 3,257,203), eingesetzt. Es sind auch Pyrazolinderivate gut einsetzbar, wie sie aus der deutschen Auslegeschrift 10 60 714, entsprechend US-PS 3,180,729, bekannt sind, oder Hydrazonverbindungen, beispielsweise bekannt aus DE-OS 29 19 791, entsprechend US-PS 4,278,747.Oxdiazole derivatives, such as 2,5-bis (4'-diethylaminophenyl) -1,3,4-oxdiazole, described in DE-PS 10 58 836 (corresponding to US Pat. No. 3,189,447), or oxazole derivatives, such as 2-vinyl, are preferably used. 4- (2'-chlorophenyl) -5- (4'-diethylaminophenyl) oxazole or 2-phenyl-4- (2'-chlorophenyl) -5- (4'-diethylaminophenyl) oxazole, described in DE-PS 10 60 260 (corresponding to US Pat. No. 3,112,197) or 11 20 875 (corresponding to US Pat. No. 3,257,203). Pyrazoline derivatives such as are known from German Patent Application 10 60 714, corresponding to US Pat. No. 3,180,729, or hydrazone compounds, known, for example, from DE-OS 29 19 791, corresponding to US Pat. No. 4,278,747, can also be used.

Als polymere Verbindungen sind beispielsweise vinylaromatische Polymere, wie Polyvinylanthracen, Polyacenaphthylen oder Mischpolymerisate geeignet. Ganz besonders bewährt haben sich Poly-N-vinylcarbazol oder Mischpolymerisate des N-Vinylcarbazols mit einem N-Vinylcarbazol-Gehalt von mindestens etwa 40 Gewichtsprozent.Examples of suitable polymeric compounds are vinylaromatic polymers, such as polyvinylanthracene, polyacenaphthylene or copolymers. Poly-N-vinylcarbazole or copolymers of N - vinylcarbazole with an N-vinylcarbazole content of at least about 40 percent by weight have proven particularly useful.

Als Bindemittel sind hinsichtlich der Flexibilität der Filmbildungseigenschaften und der Haftfestigkeit bekannte Natur- bzw. Kunstharze geeignet. Bei ihrer Auswahl spielen außer den filmbildenden und elektrischen Eigenschaften sowie wegen der Haftfestigkeit auf dem Schichtträger auch Löslichkeitseigenschaften eine Rolle. So sind beispielsweise Polyesterharze, wie Mischpolyester aus Iso- und Terephthalsäure mit Glykol, oder Silikonharze, wie dreidimensional vernetzte Phenylmethyl-siloxane, oder sogenannte Reaktionsharze, wie sie unter der Bezeichnung DD-Lacke bekannt sind, geeignet. Auch Polycarbonatharze sind gut einsetzbar. Zur bevorzugten Verwendung des erfindungsgemäßen Aufzeichnungsmaterials zur Herstellung von Druckformen sind solche Bindemittel besonders geeignet, die in wäßrigen oder alkoholischen Lösungsmittelsystemen, gegebenenfalls unter Säure- oder Alkalizusatz, löslich sind. Geeignete Bindemittel sind hiernach hochmolekulare Substanzen, die alkalilöslich machende Gruppen tragen, wie Säureanhydrid-, Carboxyl-, Phenol-, Sulfosäure-, Sulfonamid- oder Sulfonimidgruppen. Mischpolymerisate mit Anhydridgruppen können, mit besonders gutem Erfolg verwendet werden, da durch das Fehlen freier Säuregruppen die Dunkelleitfähigkeit der photoleitfähigen . Schicht gering ist trotz guter Alkalilöslichkeit.Known natural or synthetic resins are suitable as binders with regard to the flexibility of the film-forming properties and the adhesive strength. In addition to the film-forming and electrical properties and the adhesive strength on the substrate, solubility properties also play a role in their selection. For example, polyester resins, such as mixed polyesters of iso- and terephthalic acid with glycol, or silicone resins, such as three-dimensionally crosslinked phenylmethylsiloxanes, or so-called reaction resins, as are known under the name DD lacquers, are suitable. Polycarbonate resins can also be used well. Binders which are soluble in aqueous or alcoholic solvent systems, optionally with the addition of acid or alkali, are particularly suitable for the preferred use of the recording material according to the invention for the production of printing forms. Ge Suitable binders are high-molecular substances which carry alkali-solubilizing groups, such as acid anhydride, carboxyl, phenol, sulfonic acid, sulfonamide or sulfonimide groups. Copolymers with anhydride groups can be used with particularly good success, since the absence of free acid groups means that the dark conductivity of the photoconductive materials. Layer is thin despite good alkali solubility.

Als anorganischer Photoleiter wird Zinkoxid vorzugsweise genannt. Die Korngröße des eingesetzten photoleitfähigen Zinkoxids beträgt etwa 0.1 bis 15 µm. Geeignete Bindemittel mit einem spezifischen Widerstand von 107 bis 1014 a.cm sind in diesem Fall polymere oder harzartige Bindemittel oder auch Mischungen hieraus. Geeignet sind hierfür Polyurethan, Polyester, Polycarbonate, Polystyrole, chlorierter Gummi, Acrylharze, Alkydharze, Silicanharze oder Vinylacetat-Mischpolymerisate, wie Vinylchloridacetatharz.Zinc oxide is preferably mentioned as the inorganic photoconductor. The grain size of the photoconductive zinc oxide used is approximately 0.1 to 15 μm. Suitable binders with a specific resistance of 10 7 to 10 14 a.cm in this case are polymeric or resinous binders or mixtures thereof. Suitable for this are polyurethane, polyester, polycarbonates, polystyrenes, chlorinated rubber, acrylic resins, alkyd resins, silica resins or vinyl acetate copolymers, such as vinyl chloride acetate resin.

Die photoleitfähige Schicht mit Zinkoxid als Photoleiter kann zwischen 50 und etwa 95 Gewichtsprozent der photoleitfähigen Teilchen enthalten. Ein bevorzugtes Gewichtsverhältnis des Bindemittels zu den Teilchen liegt zwichen 1:4 und 1:10.The photoconductive layer with zinc oxide as the photoconductor can contain between 50 and about 95 percent by weight of the photoconductive particles. A preferred weight ratio of the binder to the particles is between 1: 4 and 1:10.

Die Schichtträger des Aufzeichnungsmaterials können flächig oder zylindrisch ausgebildet sein und in bekannter Weise aus einer Metallplatte, einer Metallfolie, aus metallisiertem Papier oder Papieren oder Folien, die mit einem elektrisch leitenden Kunststoff beschichtet sind, bestehen.The layer supports of the recording material can be flat or cylindrical and can be made in a known manner from a metal plate, a metal foil, from metallized paper or papers or fo lines that are coated with an electrically conductive plastic.

Auf dem erfindungsgemäßen Aufzeichnungsmaterial können in bekannter Weise auf diesem selbst Tonerbilder erzeugt werden, es ist aber auch möglich, entweder das Ladungsbild oder Tonerbild auf ein Bildempfangsmaterial zu übertragen.In the known manner, toner images can be produced on the recording material according to the invention, but it is also possible to transfer either the charge image or the toner image to an image receiving material.

In bekannter Weise kann man auch nach Bebilderung, Entwicklung und Entschichtung der Photoleiterschicht an den Nichtbildstellen und gegebenenfalls Wegätzen der Metallschicht an den Nichtbildstellen eine Druckform oder eine gedruckte Schaltung erhalten.In a known manner, a printing form or a printed circuit can also be obtained after imaging, development and stripping of the photoconductor layer at the non-image locations and, if appropriate, etching away the metal layer at the non-image locations.

Das elektrophotographische Aufzeichnungsmaterial kann als übliche Zusätze in der photoleitfähigen Schicht Verlaufmittel und Weichmacher und/oder zwischen Schichtträger und photoleitfähiger Schicht Haftvermittler enthalten.The electrophotographic recording material can contain leveling agents and plasticizers and / or adhesion promoters as conventional additives in the photoconductive layer and / or between the support and the photoconductive layer.

Nachstehende Beispiele sollen die Erfindung näher erläutern, jedoch nicht hierauf begrenzen:The following examples are intended to explain the invention in more detail, but not to limit it thereto:

Beispiel 1example 1

Zu einer Lösung aus 8 g 2-Vinyl-4-(2'-chlorphenyl-5-(4'-diethylaminophenyl)-oxazol und 18 g eines Mischpolymerisates aus Styrol und Maleinsäurenahydrid, in einer Mischung aus 90 g Methylglykol, 140 g Tetrahydrofuran und 40 g Butylacetat 85 Xig, wurden je 0,04 g der Sensibilisierungsfarbstoffe Nr. 1, 2 und 3 zugesetzt. Die Lösung wurde auf eine oberflächlich elektrochemisch aufgerauhte und anodisierte Aluminiumfolie aufgebracht, die auf ihrer Oberfläche, wie in DE-OS 16 21 478 (entsprechend US-PS 4,153,461) beschrieben, mit Polyvinylphosphonsäure vorbehandelt wurde. Nach dem Verdunsten des Lösungsmittels erhielt man eine im Bereich von etwa 420 bis 730 nm lichtempfindliche Schicht. Das Sensibilisierungsspektrogramm kann der beigefügten Figur 1 entnommen werden.To a solution of 8 g of 2-vinyl-4- (2'-chlorophenyl-5- (4'-diethylaminophenyl) oxazole and 18 g of a copolymer of styrene and maleic acid hydride, in a mixture of 90 g of methyl glycol, 140 g of tetrahydro furan and 40 g butylacetate 85 Xig, 0.04 g each of sensitizing dyes Nos. 1, 2 and 3 were added. The solution was applied to an electrochemically roughened and anodized aluminum foil, the surface of which was pretreated with polyvinylphosphonic acid as described in DE-OS 16 21 478 (corresponding to US Pat. No. 4,153,461). After the solvent had evaporated, a photosensitive layer in the range from about 420 to 730 nm was obtained. The sensitization spectrogram can be found in the attached FIG. 1.

Aus diesem Aufzeichnungsmaterial wurde auf folgende Weise eine Druckform für Offsetdruck hergestellt. Es wurde die photoleitfähige Schicht im Dunkeln mit Hilfe einer Corona auf -430 V aufgeladen, dann in einer Reprokamera bei Blende 14 acht Sekunden mit einem Hg-Ga-Brenner (5000 W M023-Sylvania) belichtet. Das entstandene latente Ladungsbild wurde mit einem handelsüblichen Trockentoner mit Hilfe einer Magnetwalze entwickelt und das Tonerbild durch Wärme fixiert. Nach Entfernen der photoleitfähigen Schicht an den nicht mit Toner bedeckten Stellen mit einer Lösung, die man dadurch erhält, daß man 50 g Na2Si03 x 9 H20 in 250 g Glycerin (86 %ig) löste und mit 390 g Ethylenglykol und 310 g Methanol verdünnte, wurde eine Flachdruckform erhalten, mit der in hoher Auflage gedruckt werden konnte.A printing plate for offset printing was produced from this recording material in the following manner. The photoconductive layer was charged to -430 V in the dark with the aid of a corona, then exposed in a repro camera at aperture 14 for eight seconds using an Hg-Ga burner (5000 W M023-Sylvania). The resulting latent charge image was developed with a commercially available dry toner using a magnetic roller and the toner image was fixed by heat. After removing the photoconductive layer at the points not covered with toner with a solution which is obtained by dissolving 50 g Na 2 Si0 3 x 9 H 2 0 in 250 g glycerol (86%) and with 390 g ethylene glycol and Diluted 310 g of methanol, a planographic printing plate was obtained with which it was possible to print in large numbers.

Beispiel 2Example 2

Eine Lösung von 10 g 2-Phenyl-4-(2'-chlorphenyl)-5-(4'-diethyl-aminophenyl)-oxazol, 15 g eines Mischpolymerisates aus Styrol und Maleinsäureanhydrid mit einem Erweichungspunkt von 210 *C, 116 g Tetrahydrofuran, 33 g Butylacetat, 76 g Methylglykol und 1,5 g der Sensibilisierungsfarbstoffe der Formeln 1, 2 und 3, im Verhältnis 1:1:0,5, wurde auf eine aluminiumbedampfte, 100 im dicke Polyesterfolie aufgebracht. Nach dem Verdunsten des Lösungsmittels resultierte eine etwa 5 um dicke photoleitfähige Schicht mit einer spektralen Empfindlichkeit von ca. 400 nm bis etwa 730 nm.A solution of 10 g of 2 - phenyl-4- (2'-chlorophenyl) -5- (4'-diethyl-aminophenyl) -oxazole, 15 g of a copolymer of styrene and maleic anhydride having a softening point of 210 * C, 116 g of tetrahydrofuran , 33 g of butyl acetate, 76 g of methyl glycol and 1.5 g of the sensitizing dyes of the formulas 1, 2 and 3, in a ratio of 1: 1: 0.5, were applied to an aluminum-vaporized 100 in thick polyester film. After the solvent had evaporated, an approximately 5 μm thick photoconductive layer with a spectral sensitivity of approximately 400 nm to approximately 730 nm resulted.

Nach dem Belichten der Vorlage mit MH-Strahlern, dem Entwickeln mit einem elektrophotographischen Entwickler und Entfernen der Photoleiterschicht an den Nichtbildstellen nach dem in der DE-PS 23 22 047 (entsprechend US-PS 4,066,453) beschriebenen Verfahren wurde die freigelegte aufgedampfte Aluminiumschicht durch Behandeln mit 2 n Natronlauge entfernt. Man erhielt auf diese Weise eine gedruckte Schaltung.After exposure of the original with MH radiators, development with an electrophotographic developer and removal of the photoconductor layer at the non-image locations by the method described in DE-PS 23 22 047 (corresponding to US Pat. No. 4,066,453), the exposed, evaporated aluminum layer was treated with 2 n sodium hydroxide solution removed. A printed circuit was obtained in this way.

Ähnliche Ergebnisse resultierten, wenn statt des angegebenen Oxazols 2,5-Bis-(4'-diethylaminophenyl)-1,3,4- oxdiazol als Photoleiter verwendet wurde.Similar results were obtained when 2,5-bis- (4'-diethylaminophenyl) -1,3,4-oxdiazole was used as the photoconductor instead of the specified oxazole.

Beispiel 3Example 3

Eine 100 µm starke Aluminiumfolie wurde mit einer photoleitfähigen Schicht'versehen. Die photoleitfähige Schicht wurde wie folgt hergestellt: 100 Gewichtsteile photoleitfähiges Zinkoxid wurden zusammen mit 40 Gewichtsteilen einer 50 %igen Lösung eines modifizierten Multipolymeren des Vinylacetats in Toluol vermischt. Die Mischung wurde etwa 3 Stunden in der Kugelmühle gemahlen und dann mittels einer Drahtrakel zu einem Trokkenschichtgewicht von etwa 30 g/m2 auf den Papierschichtträger aufgetragen. Der Lösung waren im Verhältnis von 1:1:1 je 0,5 % Einzelfarbstoff, bezogen auf das Gewicht des Photoleiters, an Sensibilisierungsfarbstoff nach den Formeln 1, 2 und 4 zugefügt worden.A 100 μm thick aluminum foil was provided with a photoconductive layer. The photoconductive layer was prepared as follows: 100 parts by weight of photoconductive zinc oxide were mixed together with 40 parts by weight of a 50% solution of a modified multipolymer of the vinyl acetate in toluene. The mixture was ball-milled for about 3 hours and then applied to the paper support by means of a wire knife to a dry layer weight of about 30 g / m 2 . The solution had been added in a ratio of 1: 1: 1 each 0.5% individual dye, based on the weight of the photoconductor, of sensitizing dye according to formulas 1, 2 and 4.

Die Schicht wurde mittels einer Corona (Spannung 5 kV negativ, Abstand 25 mm) aufgeladen und mit einem Argonionen-Laser im Leistungsbereich 0,2 bis 0,5 mW (Nennleistung 50 mW, Ausgangsleistung 15 mW) bei einem Vorschub von 400 Linien/cm in einem üblichen Automaten, der zur Herstellung von Druckformen dient, bebildert und in der bei ZnO-Druckplatten üblichen Weise weiterbehandelt.The layer was charged with a corona (voltage 5 kV negative, distance 25 mm) and with an argon ion laser in the power range 0.2 to 0.5 mW (nominal power 50 mW, output power 15 mW) at a feed rate of 400 lines / cm illustrated in a conventional machine which is used for the production of printing forms and further processed in the manner customary for ZnO printing plates.

Claims (12)

1. Elektrophotographisches Aufzeichnungsmaterial, bestehend aus einem elektrisch leitenden Schichtträger und mindestens einer photoleitfähigen Schicht, enthaltend Photoleiter, Sensibilisierungsfarbstoffe, Bindemittel und übliche Zusätze, dadurch gekennzeichnet, daß mindestens drei Sensibilisierungsfarbstoffe vorhanden sind, von denen mindestens zwei vom 3,3'-Dimethyl- indolenin-Typ sind, die in unterschiedlichen Wellenlängenbereichen sensibilisieren.1. Electrophotographic recording material, consisting of an electrically conductive support and at least one photoconductive layer containing photoconductor, sensitizing dyes, binders and conventional additives, characterized in that at least three sensitizing dyes are present, at least two of which are 3,3'-dimethylindolenine -Type are that sensitize in different wavelength ranges. 2. Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß die Sensibilisierungsfarbstoffe vom 3,3'-Dimethyl-indolenin-Typ Bis-(3,3'-dimethylindolenyl)-tri- und -pentamethincyanine darstellen.2. Recording material according to claim 1, characterized in that the sensitizing dyes of the 3,3'-dimethyl-indolenine type are bis (3,3'-dimethylindolenyl) tri- and pentamethine cyanines. 3. Aufzeichnungsmaterial nach Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß als Sensibilisierungsfarbstoff zusätzlich ein Cyaninfarbstoff aus der Gruppe Astrazonorange R (C.I. 48040), Astrazonorange G (C.I. 48035), Astrazongelb 3G (C.I. 48055), Astrazongelb 5G (C.I. 48065) und Basic Yellow 52115 (C.I. 48060) vorhanden ist.3. Recording material according to claims 1 or 2, characterized in that a cyanine dye from the group Astrazonorange R (CI 48040), Astrazonorange G (CI 48035), Astrazon Yellow 3G (CI 48055), Astrazon Yellow 5G (CI 48065) and Basic as the sensitizing dye Yellow 52115 (CI 48060) is present. 4. Aufzeichnungsmaterial nach Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß als Sensibilisierungsfarbstoff zusätzlich ein Bis-benzoxazol-trimethincyanin vorhanden ist.4. Recording material according to claims 1 or 2, characterized in that a bis-benzoxazole trimethine cyanine is additionally present as the sensitizing dye. 5. Aufzeichnungsmaterial nach Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß der Photoleiter eine organische Verbindung darstellt aus der Gruppe der Oxazol-, Oxdiazol-, Hydrazon- oder Pyrazolin-Derivate.5. Recording material according to claims 1 to 4, characterized in that the photoconductor is an organic compound from the group of oxazole, oxdiazole, hydrazone or pyrazoline derivatives. 6. Aufzeichnungsmäterial nach Anspruch 5, dadurch gekennzeichnet, daß der Phötoleiter 2,5-Bis-(4'-diethylaminophenyl)-oxdiazol-1,3,4 ist.6. Recording material according to claim 5, characterized in that the photoconductor is 2,5-bis (4'-diethylaminophenyl) oxdiazole-1,3,4. 7. Aufzeichnungsmaterial nach Anspruch 5, dadurch gekennzeichnet, daß der Photoleiter 2-Vinyl-4-(2'- chlorphenyl)-5-(4'-diethylaminophenyl)-oxazol ist.7. Recording material according to claim 5, characterized in that the photoconductor is 2-vinyl-4- (2'-chlorophenyl) -5- (4'-diethylaminophenyl) oxazole. 8. Aufzeichnungsmaterial nach Anspruch 5, dadurch gekennzeichnet, daß der Photoleiter 2-Phenyl-4-(2'- chlorphenyl)-5-(4'-diethylaminophenyl)-oxazol ist.8. Recording material according to claim 5, characterized in that the photoconductor is 2-phenyl-4- (2'-chlorophenyl) -5- (4'-diethylaminophenyl) oxazole. 9. Aufzeichnungsmaterial nach Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß der Photoleiter eine anorganische Verbindung darstellt.9. Recording material according to claims 1 to 4, characterized in that the photoconductor is an inorganic compound. 10. Aufzeichnungsmaterial nach Anspruch 9, dadurch gekennzeichnet, daß der Photoleiter Zinkoxid ist.10. Recording material according to claim 9, characterized in that the photoconductor is zinc oxide. 11. Aufzeichnungsmaterial nach Anspruch 1 zur Herstellung von Druckformen mit einer Metallunterlage oder metallisierter Folie als Schichtträger.11. Recording material according to claim 1 for the production of printing forms with a metal base or metallized film as a layer support. 12. Aufzeichnungsmaterial nach Ansprüchen 1 und 11, dadurch gekennzeichnet, daß die photoleitfähige Schicht als Bindemittel ein Styrol-Maleinsäureanhydrid-Mischpolymerisat oder ein Phenolharz enthält.12. Recording material according to claims 1 and 11, characterized in that the photoconductive layer contains as a binder a styrene-maleic anhydride copolymer or a phenolic resin.
EP86103130A 1985-03-14 1986-03-08 Electrophotographic recording material Expired - Lifetime EP0194624B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3509147 1985-03-14
DE19853509147 DE3509147A1 (en) 1985-03-14 1985-03-14 ELECTROPHOTOGRAPHIC RECORDING MATERIAL

Publications (3)

Publication Number Publication Date
EP0194624A2 true EP0194624A2 (en) 1986-09-17
EP0194624A3 EP0194624A3 (en) 1988-08-03
EP0194624B1 EP0194624B1 (en) 1993-06-09

Family

ID=6265192

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86103130A Expired - Lifetime EP0194624B1 (en) 1985-03-14 1986-03-08 Electrophotographic recording material

Country Status (4)

Country Link
US (1) US4657836A (en)
EP (1) EP0194624B1 (en)
JP (1) JPS61217051A (en)
DE (2) DE3509147A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0364890A2 (en) * 1988-10-19 1990-04-25 BASF Aktiengesellschaft Panchromatic electrophotographical recording element
EP0430597A2 (en) * 1989-11-28 1991-06-05 New Oji Paper Co., Ltd. Laser-sensitive electrophotographic element
EP0488511A1 (en) * 1990-11-26 1992-06-03 New Oji Paper Co., Ltd. Electrophotographic lithograph printing plate material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1800967A1 (en) * 1967-10-05 1969-08-21 Ricoh Kk Electrophotographic copying material with coating of
DE2137325A1 (en) * 1970-07-24 1972-01-27 Canon K.K., Tokio Organic photosensitive material for electrophotography
US4063948A (en) * 1975-06-14 1977-12-20 Hoechst Aktiengesellschaft Material for electrophotographic reproduction
EP0004944A2 (en) * 1978-04-21 1979-10-31 Hoechst Aktiengesellschaft Material for electrophotographic recording

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU35193A1 (en) * 1956-06-04
NL100993C (en) * 1956-06-27
US3180729A (en) * 1956-12-22 1965-04-27 Azoplate Corp Material for electrophotographic reproduction
BE581861A (en) * 1958-08-20
DE1447907A1 (en) * 1964-01-11 1968-12-05 Kalle Ag Multicolor electrophotographic printing
ZA6807938B (en) * 1967-12-04
JPS4946264B1 (en) * 1969-01-17 1974-12-09
DE2214055A1 (en) * 1972-03-23 1973-09-27 Agfa Gevaert Ag SENSITIZED ELECTROPHOTOGRAPHIC LAYERS
US4066453A (en) * 1973-05-02 1978-01-03 Hoechst Aktiengesellschaft Process for the preparation of printing forms
DE2353639C2 (en) * 1973-10-26 1983-08-04 Hoechst Ag, 6230 Frankfurt Electrophotographic recording material
JPS54150128A (en) * 1978-05-17 1979-11-26 Mitsubishi Chem Ind Electrophotographic photosensitive member
ZA839316B (en) * 1982-12-16 1984-08-29 Vickers Plc Photoconductive compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1800967A1 (en) * 1967-10-05 1969-08-21 Ricoh Kk Electrophotographic copying material with coating of
DE2137325A1 (en) * 1970-07-24 1972-01-27 Canon K.K., Tokio Organic photosensitive material for electrophotography
US4063948A (en) * 1975-06-14 1977-12-20 Hoechst Aktiengesellschaft Material for electrophotographic reproduction
EP0004944A2 (en) * 1978-04-21 1979-10-31 Hoechst Aktiengesellschaft Material for electrophotographic recording

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0364890A2 (en) * 1988-10-19 1990-04-25 BASF Aktiengesellschaft Panchromatic electrophotographical recording element
EP0364890A3 (en) * 1988-10-19 1991-10-30 BASF Aktiengesellschaft Panchromatic electrophotographical recording element
EP0430597A2 (en) * 1989-11-28 1991-06-05 New Oji Paper Co., Ltd. Laser-sensitive electrophotographic element
EP0430597A3 (en) * 1989-11-28 1991-08-21 Oji Paper Co. Ltd. Laser-sensitive electrophotographic material
EP0488511A1 (en) * 1990-11-26 1992-06-03 New Oji Paper Co., Ltd. Electrophotographic lithograph printing plate material
US5213930A (en) * 1990-11-26 1993-05-25 Oji Paper Co., Ltd. Electrophotographic lithograph printing plate material having a mixture of sensitizing dyes

Also Published As

Publication number Publication date
DE3688531D1 (en) 1993-07-15
DE3509147A1 (en) 1986-09-18
EP0194624B1 (en) 1993-06-09
JPS61217051A (en) 1986-09-26
US4657836A (en) 1987-04-14
EP0194624A3 (en) 1988-08-03

Similar Documents

Publication Publication Date Title
DE3124396C2 (en)
DE3626497C2 (en) Electrophotographic recording material
DE2939483C2 (en) Electrophotographic recording material
DE1908345A1 (en) Electrophotographic recording material
DE3138252C2 (en)
DE1060714B (en) Material for electrophotographic reproduction
DE3208455A1 (en) ELECTROPHOTOGRAPHIC LIGHT SENSITIVE PRINT MATERIALS
DE3148961C2 (en)
EP0004944B1 (en) Material for electrophotographic recording
DE2631629A1 (en) ELECTROPHOTOGRAPHIC RECORDING MATERIAL
EP0089603B1 (en) Electrophotographic recording material
DE1912589A1 (en) Electrophotographic recording material
EP0194624B1 (en) Electrophotographic recording material
DE3513747A1 (en) ELECTROPHOTOGRAPHIC RECORDING MATERIAL
EP0031481A1 (en) Material for electrographical reproduction
US3585026A (en) Treatment of background areas of developed electrophotographic elements with carboxy substituted triarylamine photoconductors with an alkaline medium to reduce opacity
DE3222100C2 (en)
EP0152047B1 (en) Electrophotographic material
DE1797137C3 (en)
DE3941542C2 (en) Electrophotographic printing plate
DE1099846B (en) Material for electrophotographic reproduction
DE2016395A1 (en) Electrophotographic recording material
DE4029565A1 (en) ELECTROPHOTOGRAPHIC PHOTO-RECEPTOR AND ELECTROPHOTOGRAPHIC PRESSURE PLATE PROVIDERS CONTAINING A PHTHALOCYANINE PIGMENT AND A THIOBARBITARY SAE DERIVATIVE
DE3832903A1 (en) ELECTROPHOTOGRAPHIC PRINT PLATE
DE2028367A1 (en) Flectrophotographic recording material with a comparatively low gamma value

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: A2

Designated state(s): DE FR GB NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB NL

17P Request for examination filed

Effective date: 19881222

17Q First examination report despatched

Effective date: 19910306

RBV Designated contracting states (corrected)

Designated state(s): DE GB

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE GB

REF Corresponds to:

Ref document number: 3688531

Country of ref document: DE

Date of ref document: 19930715

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19930823

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

Ref country code: GB

Payment date: 19940221

Year of fee payment: 9

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

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

Ref country code: DE

Payment date: 19940518

Year of fee payment: 9

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19950308

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

Effective date: 19950308

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

Ref country code: DE

Effective date: 19951201