EP0133469A1 - Matériaux d'enregistrement électrophotographiques à photosensibilité - Google Patents

Matériaux d'enregistrement électrophotographiques à photosensibilité Download PDF

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Publication number
EP0133469A1
EP0133469A1 EP84107504A EP84107504A EP0133469A1 EP 0133469 A1 EP0133469 A1 EP 0133469A1 EP 84107504 A EP84107504 A EP 84107504A EP 84107504 A EP84107504 A EP 84107504A EP 0133469 A1 EP0133469 A1 EP 0133469A1
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EP
European Patent Office
Prior art keywords
recording materials
materials according
electrophotographic recording
charge
electrophotographic
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
EP84107504A
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German (de)
English (en)
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EP0133469B1 (fr
Inventor
Gerhard Dr. Hoffmann
Peter Dr. Neumann
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BASF SE
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BASF SE
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Publication of EP0133469B1 publication Critical patent/EP0133469B1/fr
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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
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0503—Inert supplements
    • G03G5/051—Organic non-macromolecular compounds
    • G03G5/0514—Organic non-macromolecular compounds not comprising cyclic groups
    • 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
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0503—Inert supplements
    • G03G5/051—Organic non-macromolecular compounds
    • G03G5/0517—Organic non-macromolecular compounds comprising one or more cyclic groups consisting of carbon-atoms only
    • 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
    • G03G5/0662—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic containing metal elements

Definitions

  • the invention relates to electrophotographic recording materials with electrically conductive carriers, charge carrier-producing compounds or sensitizers, charge carrier transporting compounds and special additives.
  • Electrophotographic processes, materials required therefor and various variants for the construction of recording materials are known.
  • Advantages for use in the reproduction sector are materials made of polymeric binders that can be adapted to the special requirements of the respective area of use, low-molecular organic compounds that are soluble in the binders even in higher concentrations and are capable of transporting charge carriers of the electrical current.
  • compounds, in particular dyes or pigments, which generate charge carriers of the electric current by absorption of the actinic light which is radiated imagewise and which can transfer these to the charge-transporting compounds with the aid of the electrical field impressed from the outside by the electrostatic surface charge can be introduced as a separate layer within a composite structure (cf.
  • the multi-layer electrophotographic recording material described in DE-OS 22 20 408 consists of an electrically conductive carrier material, a first, dye-containing, about 0.005 to 2 ⁇ m thick layer of organic electricity generating charge carriers by exposure to actinic light with at least one charge transporting connection.
  • High photosensitivity is particularly desirable in order to reduce the required process times.
  • the necessary exposure time plays an important role.
  • the existing systems are frequently criticized.
  • the object of the present invention was to develop electrophotographic recording materials, in particular for the production of electrophotographic printing forms, such as offset printing forms, which have improved photosensitivity, at the same time a low dark conductivity and good resolution.
  • the compounds used according to the invention are known or can be prepared by known methods, e.g. according to the in Gmelin Handbook of Inorganic Chemistry, Syst. No. 39 rare earths, vol. D 3, 8th edition 1981, pp. 65 ff.
  • the addition of the metal-1,2-diketone complexes according to the invention greatly improves the photosensitivity and at the same time also significantly increases the maximum potential acceptance of the electrophotographic recording materials without changing the dark properties, so that an improved differentiation in relation to the photosensitivity is also achieved occurs between exposed and unexposed areas of the loaded surface.
  • metal halides - such as zinc chloride, magnesium bromide, aluminum chloride - and ketones - such as acetophenone, benzophenone, benzil - can improve the photosensitivity of certain organic photo semiconductor layers even in small amounts (for example, U S 3,037,861, US 3,553,009, US 3,620,723). It has also been confirmed that additions of metal halides and ketones do not produce the effects according to the invention. The effect of the metal 1,3-diketone complexes achieved according to the invention cannot be derived from the known additives for the person skilled in the art.
  • the metal-1,3-diketone complexes which improve the photosensitivity and are used according to the invention can advantageously be used both in single-layer and in multi-layer recording systems applied to electroconductive supports.
  • Suitable single-layer systems preferably have a layer of (a) 45 to 75 parts by weight of a binder, (b) 30 to 60, in particular 35 to 50 parts by weight of a charge-transporting compound, (c) optionally 5 to 25 parts by weight of another on a conductive carrier material , essentially inactive binder, (d) 0.05 up to 0.8 parts by weight of a compound which generates charge carriers upon actinic exposure, in particular a suitable dye and (e) 0.5 to 30, in particular 3 to 15% by weight, based on the proportion of binder, of one or more of the metal-1 according to the invention, 3-diketone complexes.
  • the layers are advantageously applied from an approximately 5% by weight solution in a suitable organic solvent to the cleaned conductive support material in such a way that after the solvent has been flashed off, a dry layer thickness of approximately 0.8 to 40 ⁇ m (depending on the intended use) electrophotographic printing forms, in particular 0.8 to 6 ⁇ m) results.
  • Suitable multilayer systems advantageously have on an electroconductive carrier material (a) a layer with compounds generating charge carriers and (b) a further layer with (b1) at least one charge carrier transporting compound, (b2) at least one organic binder and (b3) optionally further, in particular additives which improve the mechanical properties of the layer, layer (b) containing 0.5 to 30 and preferably 3 to 15% by weight, based on the proportion of binder, of one or more of the metal-1,3-diketone complexes according to the invention .
  • the layer (b) advantageously contains 30 to 60 parts by weight of (bl), 45 to 75 parts by weight of (b2) and, if appropriate, 5 to 25 parts by weight of the additives (b3).
  • the first layer is advantageously applied to the carrier material in a thickness of 0.005 to 5, in particular 0.1 to 0.9 ⁇ m, from solution in a suitable solvent.
  • the second layer is advantageously applied in a thickness that results in a layer thickness of 5 to 25, in particular 7 to 15 ⁇ m, after drying the composite structure.
  • all conductive carrier materials can be used as electrically conductive carriers, insofar as they are suitable for the area of application.
  • Carriers for printing forms advantageously have a thickness of 0.08 to about 0.3 mm.
  • suitable organic binders for the layers depends on the intended use of the recording materials.
  • their film-forming and electrical properties, their adhesive strength on the carrier material and their solubility properties play a special role.
  • Particularly suitable for recording materials for the production of electrophotographic printing plates, and especially for those for offset printing are those which are soluble in basic, aqueous or alcoholic solvents.
  • binders in particular those with high acid numbers, which are readily soluble in basic aqueous-alcoholic solvent systems and have an average molecular weight (weight average) of 800 to 150,000 and in particular 1,200 and 80,000.
  • Suitable are e.g. Copolymers of methacrylic acid and methacrylic acid esters, especially copolymers of styrene and maleic anhydride and of styrene, methacrylic acid and methacrylic acid esters, provided that they have the above solubility condition.
  • binders with free carboxyl groups are known to undesirably increase the dark conductivity of the electrophotographic layers and thereby lead to poor stressing results, such binders can easily be adapted to the charge transport compounds used. It has been shown that copolymers of styrene, maleic anhydride and acrylic or methacrylic acid, which have a copolymerized maleic anhydride content of 5 to 50% by weight and a copolymerized acrylic or methacrylic acid content of 5 to 35 and in particular 10 to 30% by weight .-X have satisfactory electrophotographic layers with sufficient dark conductivity. They have an excellent solubility in washing-out agents from 75% by weight of water, 23% by weight of isobutanol and 2% by weight of sodium carbonate, but are insoluble in offset-typical wiping water.
  • Suitable charge carrier-producing compounds or sensitizers are, for example, for systems applied in one layer, as are also used for the production of electrophotographic printing forms, dyes from the triarylmethane series, xanthene dyes and cyanine dyes. Very good results were obtained with rhodamine B (CI 45170), rhodamine 6 G (CI 45160), malachite green (CI 42000), methyl violet (CI 42535) and crystal violet (CI 42555). In systems applied in multiple layers, the dye or pigment lies in a separate charge carrier Layer before. Azo dyes, phthalocyanines, isoindoline dyes and perylene tetracarboxylic acid derivatives are particularly effective here. Good results are achieved with perylene-3,4: 9,10-tetracarboxylic acid diimide derivatives, as described in DE-OS 31 10 954 and 31 10 960.
  • Suitable compounds carrying electrical charge carriers are known to the person skilled in the art. Mention may be made of oxazole derivatives (08P 11 20 875), oxdiazole derivatives (DBP 10 58 836), triazole derivatives (DBP 10 60 260), azomethines (US 3 041 165), pyrazoline derivatives (DBP 10 60 714) and imidazole derivatives (DBP 11 06 599). Benztriazole derivatives (German patent application P 32 15 968.4) and hydrazone derivatives (German patent application P 32 01 202.0) are preferred. These are usually low molecular weight compounds which are well compatible with the organic binders in the required amount. However, polymeric charge transport compounds can also be used, e.g. Poly (N-vinyl carbazole).
  • the electrophotographic recording material according to the invention can contain conventional additives, e.g. Leveling agent and plasticizer in the photoconductive layer or adhesion promoter between carrier and layer.
  • the electrophotographic recording materials according to the invention are distinguished by a combination of very good properties, in particular a high photoconductivity with a very low dark conductivity, so that the layers are very suitable for copying technology.
  • the high sensitivity to light allows a significant reduction in the exposure time when processing in the repro camera compared to commercially available materials.
  • a good resolution results from a very sharp image reproduction. Thanks to a high charge contrast, even fine halftone dots in the light tonal ranges can be reproduced well.
  • the exposure of the layers leads to very low residual stresses and the images obtained during the concreting are characterized by good basic freedom in the non-image areas.
  • electrophotographic offset printing forms takes place, as usual, by electrostatically charging the electrophotographic recording material by means of a high-voltage corona, followed by imagewise exposure, the development of the present electrostatic, latent charge image by means of a dry or liquid toner, the fixing of the toner by a subsequent melting process and the removal of the unstressed, photo-semiconducting layer by means of a suitable washout solvent.
  • the printing form thus obtained can be prepared in a known manner for offset printing, for example by hydrophilizing and gumming the water-bearing surface.
  • the layers are charged evenly to a surface potential of - 600 volts with a DC corona of - 8.5 kV at a distance of 1 cm and then exposed to the white light of a high pressure xenon lamp with an illuminance of 10 ⁇ w.cm -2 in the layer plane.
  • the photo-induced potential drop during the exposure is tracked over time until the surface potential has fallen below 5% of the originally present value. Then the time is determined which elapses before the surface potential drops by half, corrected by the amount of the dark drop.
  • the half-value photosensitivity as the product of half-life and illuminance in the plate plane is given in ⁇ J.cm -2 .
  • Example 2 The procedure is as in Example 1, but instead of the tris (dipivalomethanato) europium, the same amount of pure dipivalomethane ( C 11 H 20 0 2 ) is used.
  • the half-value photosensitivity is 29.5 ⁇ J.cm -2 .
  • Example 2 The procedure is as in Example 1, but the tris (dipivalomethanato) europium is replaced by tris [1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctanedionato- (4,6 )] - holmium Ho (F00) 3 (C 30 H 30 F 21 HoO 6 ), example 2) or tris (dipivalomethanato) praseodymium Pr (DPM) 3 (C 33 H, 7 PrO 6 ) example 3) .
  • the half-value photosensitivities are 21.6 ⁇ J.cm -2 and 16.5 ⁇ J.cm -2 .
  • this printing plate After a charge, this printing plate is exposed in a camera for 12 seconds using a high-voltage corona. It is then developed with a powder toner that is burned-in at 160 ° C and resistant to abrasion.
  • the unconcrete layer is washed off with a mixture of 0.5% soda, 25% isopropanol and 74.5% water, which exposes the aluminum surface.
  • the solutions are spread over the layer with a cotton ball. The differentiation into hydrophilic and oleophilic areas desired in offset printing is obtained, the carrier surface providing the hydrophilic areas.
  • the printing plate is rinsed with water and the hydrophilicity of the support surface is further increased by wiping with dilute phosphoric acid solution. After inking with bold ink, it is used to print in a known manner in offset printing machines.
  • a layer of 60 parts of a chlorinated perylene-3,4: 9,10-tetrecarboxylic acid diimide bis-benzimidazole with a chlorine content of about 38% and 50 parts of a commercially available copolymer is placed on a polyethylene terephthalate film with a vapor-deposited, conductive aluminum layer in a thickness of about 300 ⁇ from vinyl chloride, acrylic acid and a maleic acid diester in a thickness of about 0.55 ⁇ m applied as a charge-generating layer.
  • a charge transport layer consisting of 45 parts of a commercially available polycarbonate binder with a melting range of 220 to 230 ° C, 10 parts of a polyester with an acid number of about 40 and a molecular weight of about 4,500, 40 is made from a solution in ethyl acetate onto this layer which generates charge carriers Parts of p-diethylaminobenzaldehyde diphenylhydrazone and 4 parts of tris (dipivalomethanato) praseodymium are applied in such a way that after drying off the solvent and drying for 30 minutes at 80 ° C., a dry layer thickness of 12 ⁇ m results.
  • a half-value photosensitivity of 2.35 ⁇ J.cm -2 is determined on this layer.
  • the same layer without tris (dipivalomethano-to) praseodymium has a half-value photosensitivity of about 4.8 ⁇ J.cm -2 .
  • Example 7 If the layer of Example 7 is used as a copy film in a commercially available copier with dry toner, copies of good quality and in large numbers can be produced with it.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photoreceptors In Electrophotography (AREA)
EP84107504A 1983-07-05 1984-06-28 Matériaux d'enregistrement électrophotographiques à photosensibilité Expired EP0133469B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3324089 1983-07-05
DE3324089A DE3324089A1 (de) 1983-07-05 1983-07-05 Elektrophotographische aufzeichnungsmaterialien mit verbesserter photoempfindlichkeit

Publications (2)

Publication Number Publication Date
EP0133469A1 true EP0133469A1 (fr) 1985-02-27
EP0133469B1 EP0133469B1 (fr) 1987-09-09

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ID=6203115

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84107504A Expired EP0133469B1 (fr) 1983-07-05 1984-06-28 Matériaux d'enregistrement électrophotographiques à photosensibilité

Country Status (4)

Country Link
US (1) US4556621A (fr)
EP (1) EP0133469B1 (fr)
JP (1) JPS6064356A (fr)
DE (2) DE3324089A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6148859A (ja) * 1984-08-17 1986-03-10 Konishiroku Photo Ind Co Ltd 正帯電用感光体
US4895783A (en) * 1989-01-03 1990-01-23 Xerox Corporation Overcoated electrophotographic photoreceptor contains metal acetyl acetonate in polymer layer
JPH0588396A (ja) * 1991-09-27 1993-04-09 Fuji Electric Co Ltd 電子写真感光体
US5232808A (en) * 1991-12-20 1993-08-03 Eastman Kodak Company Electrostatographic toner and developer containing a fluorinated β-diketone metal complex charge-control agent
JP2000056488A (ja) * 1998-08-06 2000-02-25 Fuji Electric Co Ltd 電子写真用感光体
US7167615B1 (en) 1999-11-05 2007-01-23 Board Of Regents, The University Of Texas System Resonant waveguide-grating filters and sensors and methods for making and using same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3553009A (en) * 1965-04-28 1971-01-05 Battelle Memorial Institute Process of preparing an electro-photographic material
DE2726116B2 (de) * 1977-06-10 1980-03-27 Hoechst Ag, 6000 Frankfurt Elektrophotographische Druckform
EP0043084A1 (fr) * 1980-06-30 1982-01-06 Hoechst Aktiengesellschaft Couche flexible photosensible, qui peut être laminée
DE3215968A1 (de) * 1982-04-29 1983-11-03 Basf Ag, 6700 Ludwigshafen Elektrographische aufzeichnungsmaterialien mit speziellen ladungstraeger transportierenden verbindungen

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU35193A1 (fr) * 1956-06-04
DE1068115B (fr) * 1957-09-07 1959-10-29
BE581861A (fr) * 1958-08-20
DE1117391B (de) * 1959-03-18 1961-11-16 Kalle Ag Elektrophotographisches Verfahren zur Herstellung von Druckformen
DE1522497C3 (de) * 1966-05-13 1974-09-19 Kalle Ag, 6202 Wiesbaden-Biebrich Verfahren zum Herstellen von Druckformen
US3620723A (en) * 1967-05-29 1971-11-16 Ricoh Kk Electrophotographic copying material containing assistant sensitizers and its manufacturing method
DE2220408C3 (de) * 1972-04-26 1978-10-26 Hoechst Ag, 6000 Frankfurt Elektrophotographisches Aufzeichnungsmaterial und Verfahren zu seiner Herstellung
DE2237680C3 (de) * 1972-07-31 1981-09-10 Hoechst Ag, 6000 Frankfurt Elektrophotographisches Aufzeichnungsmaterial
US4315981A (en) * 1972-07-31 1982-02-16 Hoechst Aktiengesellschaft Organic double layer electrophotographic recording material
US3997342A (en) * 1975-10-08 1976-12-14 Eastman Kodak Company Photoconductive element exhibiting persistent conductivity
DE2625116C2 (de) * 1976-06-04 1984-01-26 Gödecke AG, 1000 Berlin Verfahren zur Herstellung von 4-Hydroxy-aporphin-Derivaten

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3553009A (en) * 1965-04-28 1971-01-05 Battelle Memorial Institute Process of preparing an electro-photographic material
DE2726116B2 (de) * 1977-06-10 1980-03-27 Hoechst Ag, 6000 Frankfurt Elektrophotographische Druckform
EP0043084A1 (fr) * 1980-06-30 1982-01-06 Hoechst Aktiengesellschaft Couche flexible photosensible, qui peut être laminée
DE3215968A1 (de) * 1982-04-29 1983-11-03 Basf Ag, 6700 Ludwigshafen Elektrographische aufzeichnungsmaterialien mit speziellen ladungstraeger transportierenden verbindungen

Also Published As

Publication number Publication date
EP0133469B1 (fr) 1987-09-09
DE3324089A1 (de) 1985-01-17
JPH0416108B2 (fr) 1992-03-23
US4556621A (en) 1985-12-03
JPS6064356A (ja) 1985-04-12
DE3466091D1 (en) 1987-10-15

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