EP0194624A2 - Matériau d'enregistrement électrophotographique - Google Patents

Matériau d'enregistrement électrophotographique Download PDF

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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
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German (de)
English (en)
Other versions
EP0194624B1 (fr
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/fr
Publication of EP0194624A3 publication Critical patent/EP0194624A3/de
Application granted granted Critical
Publication of EP0194624B1 publication Critical patent/EP0194624B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03G5/0664—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.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
EP86103130A 1985-03-14 1986-03-08 Matériau d'enregistrement électrophotographique Expired - Lifetime EP0194624B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853509147 DE3509147A1 (de) 1985-03-14 1985-03-14 Elektrophotographisches aufzeichnungsmaterial
DE3509147 1985-03-14

Publications (3)

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

Family

ID=6265192

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86103130A Expired - Lifetime EP0194624B1 (fr) 1985-03-14 1986-03-08 Matériau d'enregistrement électrophotographique

Country Status (4)

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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0364890A2 (fr) * 1988-10-19 1990-04-25 BASF Aktiengesellschaft Elément d'enregistement électrophotographique panchromatique
EP0430597A2 (fr) * 1989-11-28 1991-06-05 New Oji Paper Co., Ltd. Element électrophotographique sensible au laser
EP0488511A1 (fr) * 1990-11-26 1992-06-03 New Oji Paper Co., Ltd. Matériau pour une plaque d'impression, lithographique, électrophotographique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1800967A1 (de) * 1967-10-05 1969-08-21 Ricoh Kk Kopiermaterial fuer Dreifarben-Elektrophotographie
DE2137325A1 (de) * 1970-07-24 1972-01-27 Canon K.K., Tokio Organisches, lichtempfindliches Material für die Elektrophotographie
US4063948A (en) * 1975-06-14 1977-12-20 Hoechst Aktiengesellschaft Material for electrophotographic reproduction
EP0004944A2 (fr) * 1978-04-21 1979-10-31 Hoechst Aktiengesellschaft Matériau pour enregistrement électrophotographique

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL99369C (fr) * 1956-06-04
NL100993C (fr) * 1956-06-27
US3180729A (en) * 1956-12-22 1965-04-27 Azoplate Corp Material for electrophotographic reproduction
NL242505A (fr) * 1958-08-20
DE1447907A1 (de) * 1964-01-11 1968-12-05 Kalle Ag Elektrophotographischer Mehrfarbendruck
ZA6807938B (fr) * 1967-12-04
JPS4946264B1 (fr) * 1969-01-17 1974-12-09
DE2214055A1 (de) * 1972-03-23 1973-09-27 Agfa Gevaert Ag Sensibilisierte elektrophotographische schichten
US4066453A (en) * 1973-05-02 1978-01-03 Hoechst Aktiengesellschaft Process for the preparation of printing forms
DE2353639C2 (de) * 1973-10-26 1983-08-04 Hoechst Ag, 6230 Frankfurt Elektrophotographisches Aufzeichnungsmaterial
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 (de) * 1967-10-05 1969-08-21 Ricoh Kk Kopiermaterial fuer Dreifarben-Elektrophotographie
DE2137325A1 (de) * 1970-07-24 1972-01-27 Canon K.K., Tokio Organisches, lichtempfindliches Material für die Elektrophotographie
US4063948A (en) * 1975-06-14 1977-12-20 Hoechst Aktiengesellschaft Material for electrophotographic reproduction
EP0004944A2 (fr) * 1978-04-21 1979-10-31 Hoechst Aktiengesellschaft Matériau pour enregistrement électrophotographique

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0364890A2 (fr) * 1988-10-19 1990-04-25 BASF Aktiengesellschaft Elément d'enregistement électrophotographique panchromatique
EP0364890A3 (fr) * 1988-10-19 1991-10-30 BASF Aktiengesellschaft Elément d'enregistement électrophotographique panchromatique
EP0430597A2 (fr) * 1989-11-28 1991-06-05 New Oji Paper Co., Ltd. Element électrophotographique sensible au laser
EP0430597A3 (en) * 1989-11-28 1991-08-21 Oji Paper Co. Ltd. Laser-sensitive electrophotographic material
EP0488511A1 (fr) * 1990-11-26 1992-06-03 New Oji Paper Co., Ltd. Matériau pour une plaque d'impression, lithographique, électrophotographique
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
US4657836A (en) 1987-04-14
DE3509147A1 (de) 1986-09-18
EP0194624B1 (fr) 1993-06-09
JPS61217051A (ja) 1986-09-26
DE3688531D1 (de) 1993-07-15
EP0194624A3 (en) 1988-08-03

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