EP0040402A2 - Matériau d'enregistrement électrophotographique - Google Patents

Matériau d'enregistrement électrophotographique Download PDF

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Publication number
EP0040402A2
EP0040402A2 EP81103696A EP81103696A EP0040402A2 EP 0040402 A2 EP0040402 A2 EP 0040402A2 EP 81103696 A EP81103696 A EP 81103696A EP 81103696 A EP81103696 A EP 81103696A EP 0040402 A2 EP0040402 A2 EP 0040402A2
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EP
European Patent Office
Prior art keywords
layer
dye
charge
photosensitivity
weight
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
EP81103696A
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German (de)
English (en)
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EP0040402A3 (en
EP0040402B1 (fr
Inventor
Wolfgang Dr. Wiedemann
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Hoechst AG
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Hoechst AG
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Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0040402A2 publication Critical patent/EP0040402A2/fr
Publication of EP0040402A3 publication Critical patent/EP0040402A3/de
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Publication of EP0040402B1 publication Critical patent/EP0040402B1/fr
Expired legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
    • G03G5/0646—Heterocyclic compounds containing two or more hetero rings in the same ring system
    • G03G5/0657—Heterocyclic compounds containing two or more hetero rings in the same ring system containing seven relevant rings

Definitions

  • the invention relates to an electrophotographic recording material composed of an electrically conductive layer support, optionally an insulating intermediate layer and a photoconductive layer composed of at least one layer containing an N, N-substituted 3,4,9,10-perylenetetracarboxylic acid bisimide as the charge carrier-producing dye.
  • the invention relates in particular to such a recording material, the photoconductive layer of which consists of a charge-generating and a charge-transporting double layer.
  • Photoconductive layers of this arrangement are known, for example, from DE-OS 21 08 992 (US Pat. No. 3,904,407). There, a photoconductive layer is described which consists of a perylene tetracarboxylic acid bisimide dye layer and a charge-transporting layer arranged above it, mainly composed of polymeric photoconductors.
  • a disadvantage of this arrangement is that such a system has insufficient adhesion to the layer support and very long drying times (2 to 24 hours) are necessary in the production, which does not guarantee technical suitability or production.
  • photoconductor double layers are known; the disadvantages described above by using highly conductive monomeric orga rectify the photoconductor, and which can be processed with a number of binders to form well-adhering and highly light-sensitive photoconductor layers.
  • these photoconductor layers also have certain defects: For example, the vapor-deposited dye layers can only be covered with difficulty in the subsequent coating with a charge-transporting layer.
  • the solution to this problem is an electrophoto graphic recording material of the type mentioned above and it is characterized in that the dark crystal modification of N, N'-bis (3-methoxypropyl) -3,4,9,10-perylenetetracarboximide is present as the charge-generating dye.
  • condensation product which can be prepared from perylene-3,4,9,10-tetracarboxylic anhydride and 3-methoxypropylamine, a dye is made available which surprisingly eliminates the deficiencies and disadvantages described, so that this dark dye as a charge-generating compound is extremely advantageous for photoconductive Purposes.
  • the condensation product itself is known from DE-PS 24 51'781 as a black dye for polyethylene, polyvinyl chloride, paints, inks and aqueous dye preparations.
  • the dye according to the invention has the advantage in continuous evaporation in a vacuum vapor deposition system that, in comparison with other perylene tetracarboxylic acid derivatives, such as N, N'-dimethylperylene tetracarboxylic acid imide, at a significantly lower temperature under otherwise comparable conditions such as vacuum, geometry, Evaporation rate and layer thickness can be applied.
  • the dye according to the invention is initially deposited in a strong red shade on the layer support.
  • X-ray diffraction Investigations show that the dye in the vapor deposition layer is initially present in this metastable "red" crystal modification, as represented by the X-ray diffraction diagram according to FIG. 8b.
  • the crystal form changes gradually or, in the case of a subsequent coating, immediately into the "dark" crystal modification, as represented by the X-ray diffraction diagram according to FIG. 8a.
  • the originally "red” dye vapor deposition layer can be very easily dispersed by converting its crystal structure or a dye vapor deposition layer that has already been converted into the dark crystal form.
  • the spectral photosensitivity with the dye according to the invention is expanded by approximately 80 nm towards the longer wavelength range, as can be seen from FIG. 7, curve K 1.
  • Position 1 indicates the electrically conductive layer support
  • position 2 indicates the charge layer that generates the charge carrier
  • position 3 indicates the layer that transports the charge
  • Position 4 indicates the insulating intermediate layer
  • position 5 shows layers which represent a charge carrier-producing dye layer in dispersion.
  • position 6 a photoconductive single layer of photoconductor, dye and binder, etc. is recorded.
  • Aluminum foil optionally transparent, aluminum-coated or aluminum-clad polyester foil, is preferably used as the electrically conductive layer support, but any other support material made sufficiently conductive can also be used.
  • the arrangement The photoconductor layer can also be applied on a drum, on flexible endless belts, for example made of nickel or steel, etc., or on plates.
  • the aim of introducing an insulating intermediate layer is to reduce the charge carrier injection from the metal into the photoconductor layer in the dark. On the other hand, it should not hinder the flow of charge during the exposure process.
  • the intermediate layer acts as a barrier layer.
  • the intermediate layer may also serve to improve the adhesion between the substrate surface and the dye layer or photoconductor layer.
  • Different natural or synthetic resin binders can be used for the intermediate layer, but preference is given to using materials which adhere well to a metal, in particular aluminum surface and which are poorly dissolved when subsequent layers are applied.
  • These include polyamide resins, polyvinylphosphonic acid, polyurethanes, polyester resins or specific alkali-soluble binders, such as styrene-maleic anhydride copolymers.
  • the thickness of organic intermediate layers may contain up to 5 / .mu.m, which is an aluminum oxide interlayer is generally in the range of 0.01 - 1 micron.
  • the dye layer 2 or 5 made of or with N, N'-bis (3-methoxypropyl) perylenetetracarboximide has the function of a layer which generates charge carriers; the dye used determines the spectral photosensitivity of the multilayer photoconductive system through its absorption behavior, which is shown in FIG. 6, curve 1.
  • the application of a homogeneous, densely packed dye layer is preferably obtained by evaporating the dye onto the support in vacuo.
  • the dye can be evaporated without decomposition under the conditions of 1.33 x 10 -6 -10 -8 bar and a heating temperature of 180-240 ° C.
  • the temperature of the substrate is below 50 ° C.
  • An advantageous layer thickness range of the vapor-deposited dye is between 0.005 and 3 / um.
  • a thickness range between 0.05 and 1.5 / ⁇ m is particularly preferred, since the adhesive strength and homogeneity of the vapor-deposited dye are particularly favorable here.
  • the dye molecules form a "red", metastable modification in the continuous vapor deposition in a vapor deposition system with high evaporation rates, which gradually changes at room temperature or when heated to a dark crystal modification. During the subsequent coating immediately F ARB change occurs from red to blue green.
  • the dye is repeatedly evaporated onto a rotating drum arrangement, corresponding to a lower evaporation rate, the more stable, blue-olive-green dye layer is formed immediately.
  • the perylene tetracarboxylic acid derivative according to the invention can be prepared by condensing perylene-3,4,9,10-tetracarboxylic anhydride and 3-methoxypropylamine in water for 7 hours in an autoclave at 130-140 ° C.
  • the dye is obtained in very dark, brownish black crystals in higher yield and is easily accessible and usable after cleaning by dispersing in a weakly alkaline medium and washing without alkali.
  • the dark crystal form according to the invention is used for all further electrophotographic examinations.
  • a uniform dye thickness can also be achieved by other coating techniques. This subheading includes mechanical rubbing of the finely powdered dye material into the electrically conductive substrate, electrolytic or electrochemical processes or gun spray technology.
  • pigment layers having thicknesses of the order of 0.1 to 3 / um by grinding the dye with a binder, especially with highly viscous Ceiluvantitraten and / or crosslinking binder systems, for example, polyisocyanate crosslinkable acrylic resins, reactive resins such as epoxides, or postcrosslinking systems which are composed of equivalent mixtures of hydroxyl-containing polyesters or polyethers and polyfunctional isocyanates, and are prepared by subsequent coating of these dye dispersions according to position 5 in FIGS. 4 and 5.
  • the ratio of dye / binder can vary within wide limits, but preference is given to pigmented primers with a pigment content of over 50% and correspondingly high optical density.
  • the inverse arrangement of the charge carrier-generating layer 5 in FIG. 5 on the charge-transporting layer 3, when using a p-transport connection, provides photoconductor double layers which have a high photosensitivity when charged positively.
  • Organic materials which have an extensive ⁇ -electron system are particularly suitable as the charge transport material. These include both monomeric and polymeric aromatic or heterocyclic compounds.
  • the monomers used are in particular those which have at least one dialkylamino group or two alkoxy groups.
  • Heterocyclic compounds such as oxdiazole derivatives, which are mentioned in German Patent 10 58 836 (US Pat. No. 3,189,447), have proven particularly useful. These include in particular 2,5-bis- (p-diethylaminopheny, l) -oxdiazol-1,3,4.
  • Suitable monomeric electron donor compounds are, for example Triphenylamine derivatives, more highly condensed aromatic compounds such as pyrene, benzo-fused heterocycles, and also pyrazoline or imidazole derivatives (DE-PS 10 60 714, 11 06 599 corresponding to US-PS 3,180,729, GB-PS 938,434).
  • This subheading also includes triazole, thiadiazole and especially oxazole derivatives, for example 2-phenyl-4- (2'-chlorophenyl) -5 (4'-diethylamino) oxazole, as described in German patents 10 60 260, 12 99 296, 11 20,875 (U.S. Patent 3,112,197, UK Patent 1,016,520, U.S. Patent 3,257,203).
  • Formaldehyde condensation products with various aromatics such as, for example, condensates of formaldehyde and 3-bromopyrene, have proven to be suitable as polymers (DE-OS 21 37 288 corresponding to US Pat. No. 3,842,038).
  • polyvinyl carbazole provides useful photosensitivity as a transport polymer, for example in a double layer arrangement.
  • the charge-transporting layer has practically no photosensitivity in the visible range (420 - 750 nm). It preferably consists of a mixture of an electron donor compound with a resin binder if negative charging is to be carried out. It is preferably transparent, but this does not appear to be necessary in the case of a transparent, conductive layer support.
  • Layer 3 has a high electrical resistance of greater than 10 12 ⁇ and prevents it from falling off in the dark flow of electrostatic charge. When exposed, it transports the charges generated in the organic dye layer.
  • the added binder influences both the mechanical behavior such as abrasion, flexibility, film formation etc. and to a certain extent the electrophotographic behavior such as photosensitivity, residual charge and cyclic behavior.
  • Film-forming compounds such as polyester resins, polyvinyl chloride / polyvinyl acetate copolymers, styrene / maleic anhydride copolymers, polycarbonates, silicone resins, polyurethanes, epoxy resins, acrylates, polyvinyl acetals, polystyrenes, cellulose derivatives such as cellulose acetobutyrates etc. are used as binders.
  • thermally post-crosslinking binder systems such as R are eeducationharze, composed of an equivalent mixture of hydroxyl-containing polyesters or polyethers and polyfunctional isocyanates, etc. successfully applied polyisocyanatvernetzbare acrylate resins, melamine resins, unsaturated polyester resins.
  • the mixing ratio of the charge transporting compound to the binder can vary. However, the requirement for maximum photosensitivity, i.e. as large a proportion of charge-transporting compound as possible and after crystallization to be avoided and increase in flexibility, i.e. as large a proportion of binders as possible, relatively certain limits.
  • a mixing ratio of about 1: 1 parts by weight has generally been found to be preferred, but ratios between 4: 1 to 1: 2 are also suitable.
  • polymeric charge transport compounds such as bromopyrene resin, polyvinyl carbazole, binder proportions of around or below 30% are suitable.
  • the respective requirements of a copying machine on the electrophotographic and mechanical properties of the recording material can be met within a wide range by adjusting the layers differently, for example the viscosity of the binder and the proportion of the charge transport compound.
  • layer thicknesses between approximately 3 and 20 ⁇ m are generally used. Particularly advantageous has a thickness range of 4 - / proved to 12th.
  • Leveling agents such as silicone oils, wetting agents, in particular nonionic substances, plasticizers of different compositions, such as, for example, those based on chlorinated hydrocarbons or those based on phthalic acid esters are considered to be customary additives. If necessary, conventional sensitizers and / or acceptors can also be added to the charge-transporting layer, but only to the extent that their optical transparency is not significantly impaired.
  • the dye N, N'-bis (3-methoxypropyl) perylene-3,4,9,10-tetracarboxylic acid diimide hereinafter referred to as perylimide, is placed on an aluminum-vapor-coated polyester film in a vacuum vapor deposition system at 1.33 x 10 - 7 - 10 -8 bar evaporated within 2 minutes at 180 - 220 ° C; for comparison, N, N'-dimethyl-perylene-3,4,9,10-tetracarboxylic acid diimide can only be evaporated at temperatures around 280 ° C. under the same conditions.
  • the homogeneously evaporated dye layers have layer weights in the range of 100-300 mg / m 2 . The layer support is completely covered.
  • the residual charge (U R ) after 0.1 sec., Determined from the above bright discharge curves, is a further measure of the discharge of a photoconductor layer.
  • the spectral photosensitivity is reduced Pre-connection of filters determined according to the method given above: in the case of negative charging (800 - 850 V), the half-life (T 1/2 ) in msec. determined for the respective wavelength range.
  • the spectral photosensitivity is obtained by plotting the reciprocal values of the product of half-life, T l / 2 in seconds, and light intensity I in / uW / cm 2 against the wavelength ⁇ in nm.
  • the reciprocal of T 1/2 x I (1 / E l / 2 ) means the light energy related to the unit area, which must be irradiated in order to discharge the layer to half of the initial voltage U.
  • perylimide In a vacuum evaporation system at 1.33 x 10 -7 bar and temperatures below 300 ° C (measured on the dye surface) perylimide is continuously evaporated onto an aluminum-vaporized polyester film at a speed of the order of 30 m / min.
  • the strong red colored layer has a layer weight of approx. 200 mg / m 2.
  • the dye vapor deposition layer is then continuously coated with a solution of 65 parts by weight of oxdiazole and 35 parts by weight of cellulose nitrate of standard type 4 E (DIN 53 179) in THF and dried, thereby beating the color immediately changed from red to dark green.
  • the layer weight is about 8 g / m 2 .
  • perylimide 6 g are dispersed in a solution of 35 parts by weight of oxdiazole, 19 parts by weight of cellulose nitrate as in Example 4 and 270 parts by weight of THF and intensively ground in a ball mill at 3,000 revolutions / min for 2 hours.
  • the finely disperse dye dispersion solution is then applied to a 100 / um aluminum foil in 8 - stratified 9 g / m 2 thickness (after drying).
  • a mixture of 84 parts by weight of perylimide dye and 14 parts by weight of a polyisocyanate crosslinkable acrylic resin, about 10% strength, in butyl acetate is ground intensively in a ball mill for 2 hours. Before the coating, 2 parts by weight of polyfunctional aliphatic isocyanate are stirred into the finely dispersed coating batch, diluted to about 5% and layered on aluminum foil (100 ⁇ m ) in a thickness of 360 mg / m 2 .
  • the insoluble for the subsequent coating of the transport layer pigment precoat is as in Example 4 with a solution of 65 parts by weight oxadiazole and 35 parts by weight of cellulose nitrate in 7 - / dip-coated 8 m in thickness.
  • the good photosensitivity different by coating 50 weight parts oxadiazole with 50 parts by weight of binder in about 8 / is achieved by thickness (THF solvent) on a perylimide vapor-deposited layer (200 mg / m 2 in thickness) is indicated by the following table.
  • the values in the table show that the mechanical properties (flexibility, abrasion resistance, etc.) of a photoconductor layer are largely determined by the type and amount of the binder.
  • highly adhesive and highly sensitive photoconductor layers are achieved with a large number of binders, the selection of which can therefore be made easily after the mechanical stress when used as an electrophotographic recording material.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
EP81103696A 1980-05-21 1981-05-14 Matériau d'enregistrement électrophotographique Expired EP0040402B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3019326 1980-05-21
DE3019326A DE3019326C2 (de) 1980-05-21 1980-05-21 Elektrophotographisches Aufzeichnungsmaterial

Publications (3)

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EP0040402A2 true EP0040402A2 (fr) 1981-11-25
EP0040402A3 EP0040402A3 (en) 1981-12-02
EP0040402B1 EP0040402B1 (fr) 1984-12-19

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EP81103696A Expired EP0040402B1 (fr) 1980-05-21 1981-05-14 Matériau d'enregistrement électrophotographique

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EP (1) EP0040402B1 (fr)
JP (1) JPS5723943A (fr)
AU (1) AU541409B2 (fr)
DE (2) DE3019326C2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061088A1 (fr) * 1981-03-20 1982-09-29 BASF Aktiengesellschaft Matériau d'enregistrement électrophotographique
EP0088607A2 (fr) * 1982-03-05 1983-09-14 Mita Industrial Co. Ltd. Matériau organique photosensible pour l'électrophotographie
EP0100581A2 (fr) * 1982-08-03 1984-02-15 Mita Industrial Co. Ltd. Matériau photosensible pour l'électrophotographie
US5876887A (en) * 1997-02-26 1999-03-02 Xerox Corporation Charge generation layers comprising pigment mixtures

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3246036C2 (de) * 1982-12-09 1984-11-29 Hoechst Ag, 6230 Frankfurt Elektrophotographisches Aufzeichnungsmaterial
DE3417951A1 (de) * 1984-05-15 1985-11-21 Hoechst Ag, 6230 Frankfurt Elektrophotographisches aufzeichnungsmaterial
US4578334A (en) * 1984-11-23 1986-03-25 Eastman Kodak Company Multi-active photoconductive insulating elements and method for their manufacture
US4618560A (en) * 1984-11-23 1986-10-21 Eastman Kodak Company Multi-active photoconductive insulating elements exhibiting very high electrophotographic speed and panchromatic sensitivity and method for their manufacture
US4717636A (en) * 1985-04-23 1988-01-05 Canon Kabushiki Kaisha Electrophotographic photosensitive member containing polyvinylarylal
US5686213A (en) * 1996-07-31 1997-11-11 Xerox Corporation Tunable imaging members and process for making

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3904407A (en) * 1970-12-01 1975-09-09 Xerox Corp Xerographic plate containing photoinjecting perylene pigments
DE2451781B1 (de) * 1974-10-31 1976-01-08 Basf Ag Perylen-3,4,9,10-tetracarbonsaeurebisimidfarbstoff
FR2361749A1 (fr) * 1976-08-13 1978-03-10 Basf Ag Utilisation de derives du perylene dans les systemes conducteurs et des semi-conducteurs
FR2379841A1 (fr) * 1977-02-07 1978-09-01 Ciba Geigy Ag Procede electrophotographique de production d'images

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE763388A (fr) * 1971-02-24 1971-08-24 Xerox Corp Nouvelle plaque xerographique contenant des pigments de perylene photo-injecteurs,
DE2237539C3 (de) * 1972-07-31 1981-05-21 Hoechst Ag, 6000 Frankfurt Elektrophotographisches Aufzeichnungsmaterial

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3904407A (en) * 1970-12-01 1975-09-09 Xerox Corp Xerographic plate containing photoinjecting perylene pigments
DE2451781B1 (de) * 1974-10-31 1976-01-08 Basf Ag Perylen-3,4,9,10-tetracarbonsaeurebisimidfarbstoff
FR2361749A1 (fr) * 1976-08-13 1978-03-10 Basf Ag Utilisation de derives du perylene dans les systemes conducteurs et des semi-conducteurs
FR2379841A1 (fr) * 1977-02-07 1978-09-01 Ciba Geigy Ag Procede electrophotographique de production d'images

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061088A1 (fr) * 1981-03-20 1982-09-29 BASF Aktiengesellschaft Matériau d'enregistrement électrophotographique
EP0088607A2 (fr) * 1982-03-05 1983-09-14 Mita Industrial Co. Ltd. Matériau organique photosensible pour l'électrophotographie
EP0088607A3 (en) * 1982-03-05 1984-04-11 Mita Industrial Co. Ltd. Organic photosensitive material for electrophotography
EP0100581A2 (fr) * 1982-08-03 1984-02-15 Mita Industrial Co. Ltd. Matériau photosensible pour l'électrophotographie
EP0100581A3 (en) * 1982-08-03 1984-04-25 Mita Industrial Co. Ltd. Photosensitive material for electrophotography
US5876887A (en) * 1997-02-26 1999-03-02 Xerox Corporation Charge generation layers comprising pigment mixtures

Also Published As

Publication number Publication date
DE3019326C2 (de) 1983-03-03
JPH0115865B2 (fr) 1989-03-20
AU7063181A (en) 1981-11-26
EP0040402A3 (en) 1981-12-02
DE3019326A1 (de) 1981-12-03
EP0040402B1 (fr) 1984-12-19
DE3167804D1 (en) 1985-01-31
AU541409B2 (en) 1985-01-10
JPS5723943A (en) 1982-02-08

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