EP0046959A2 - Electrophotographic recording material - Google Patents
Electrophotographic recording material Download PDFInfo
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- EP0046959A2 EP0046959A2 EP81106554A EP81106554A EP0046959A2 EP 0046959 A2 EP0046959 A2 EP 0046959A2 EP 81106554 A EP81106554 A EP 81106554A EP 81106554 A EP81106554 A EP 81106554A EP 0046959 A2 EP0046959 A2 EP 0046959A2
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- resin
- recording material
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- polyisocyanate
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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
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
- G03G5/14713—Macromolecular material
- G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G5/14769—Other polycondensates comprising nitrogen atoms with or without oxygen atoms in the main chain
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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
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
- G03G5/14713—Macromolecular material
- G03G5/14717—Macromolecular material obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G5/14734—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
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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
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
- G03G5/14713—Macromolecular material
- G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G5/14752—Polyesters
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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
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
- G03G5/14713—Macromolecular material
- G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G5/14756—Polycarbonates
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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
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
- G03G5/14713—Macromolecular material
- G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G5/1476—Other polycondensates comprising oxygen atoms in the main chain; Phenol resins
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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
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
- G03G5/14713—Macromolecular material
- G03G5/14791—Macromolecular compounds characterised by their structure, e.g. block polymers, reticulated polymers, or by their chemical properties, e.g. by molecular weight or acidity
Definitions
- the invention relates to an electrophotographic recording material composed of an electrically conductive layer support, optionally an insulating intermediate layer, a photoconductive layer composed of at least one compound generating a charge carrier and at least one charge transporting compound and a protective transparent cover layer.
- Photoconductive layer comprising at least one layer with a charge-generating and charge-transporting compound
- highly sensitive, organic photoconductor layers (DE-AS 23 14 051) are used on conductive carrier films or tapes due to their high elasticity.
- very highly sensitive photoconductor systems according to DE-OS 27 34 288, for example can be used as endless belts because of their great flexibility, which can be guided over deflecting rollers with a relatively small diameter.
- an electrophotographic recording material mentioned in claims 1 and 2 which is characterized in that the top layer consists of a surface-abrasion-resistant organic binder made of polyurethane resin, polycarbonate resin, phenoxy resin, polyacrylate or polymethacrylate resin, polyisocyanate and hydroxyl group-containing Polyester or ether, consists of polyisocyanate and hydroxyl-containing acrylic or epoxy resin, or of polyisocyanate prepolymer or polyisocyanates with temporarily blocked isocyanate groups.
- the binders are non-cross-linking, post-cross-linking or self-cross-linking.
- electrophotographic recording materials can be made available which, with almost the same photosensitivity, significantly improve the abrasion resistance and the service life.
- the abrasion-resistant top layer can be applied by coating, dipping or (electrostatic) spraying with subsequent drying and optionally hardening.
- the multilayer arrangements can be used more profitably not only on flexible conductive substrates, but also on drums.
- the photoconductive layer can be in the form of a single layer, as indicated in position 6 in FIG. 1. It can also be in the form of a double-layer arrangement consisting of one.
- the conductive layer support is indicated with 1 in each case.
- An insulating intermediate layer is indicated under position 4, position 5 shows a layer of charge-generating compound in dispersion.
- Position 7 indicates the protective cover layer according to the invention.
- Aluminum foil, optionally transparent, with aluminum can be used as the conductive layer support steamed or laminated polyester film is used, however, any other layer that has been made sufficiently conductive can be used.
- the insulating intermediate layer can be produced by a thermally, anodically or chemically produced aluminum oxide intermediate layer. It can also consist of organic materials. For example, different natural or synthetic resin binders are used that adhere well to a metal or aluminum surface and dissolve little when the other layers are subsequently applied, such as polyamide resins, polyvinylphosphonic acid, polyurethanes, polyester resins or specifically alkali-soluble binders, such as Example styrene-maleic anhydride copolymers.
- the thickness of such organic intermediate layers can be up to 5 pm, and that of the aluminum oxide layer is mostly in the range from 0.01 to 1 pm.
- Dyes according to DE-OS 22 46 255, 23 53 639 and 23 56 370 can also be used, for example.
- thin charge carriers are also generating.
- Layers of inorganic substances such as those produced by vapor deposition of selenium, doped selenium, cadmium sulfide, etc., are suitable.
- the application of a homogeneous, densely packed layer 2 is preferably obtained by vacuum deposition.
- An advantageous layer thickness range of layer 2 is between 0.005 and 3 pm, since the adhesive strength and homogeneity of the vapor-deposited compound are particularly favorable here.
- homogeneous, well covering Dye layers with thicknesses of the order of 0.1-3 pm also by grinding the dye with a binder, in particular with highly viscous cellulose nitrates and / or crosslinking binder systems, for example polyisocyanate-crosslinkable acrylic resins, paints based on polyisocyanates and hydroxyl-containing polyester or ether and by subsequently applying these dye dispersions 5 to the layer support, as can be seen from FIG. 4.
- a binder in particular with highly viscous cellulose nitrates and / or crosslinking binder systems, for example polyisocyanate-crosslinkable acrylic resins, paints based on polyisocyanates and hydroxyl-containing polyester or ether and by subsequently applying these dye dispersions 5 to the layer support, as can be seen from FIG. 4.
- Organic materials which have an extensive X-electron system are particularly suitable as the charge transport material in layers 3 and 6. These include, in particular, monomeric aromatic or heterocyclic compounds, such as those which have at least one dialkylamino group or two alkoxy groups.
- Oxdiazole derivatives which are mentioned in German patent 10 58 836, have proven particularly useful. These include in particular 2,5-bis (p-diethylaminophenyl) oxdiazole-1,3,4.
- Suitable monomeric electron donor compounds are, for example, triphenylamine derivatives, more highly condensed aromatic compounds such as pyrene, benzo-condensed heterocycles, and also pyrazoline or imidazole derivatives (DE-PSen 10 60 714, 11 06 599), including triazole, thiadiazole and especially oxazole derivatives, for example 2 -Phenyl-4- (2-chlorophenyl) -5- (4-diethylamino) oxazole, as disclosed in German patents 10 60 260, 12 99 296, 11 20 875.
- the charge transport layer 3 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.
- Layer 3 is preferably transparent. However, it is also possible that it does not need to be transparent, for example in the case of a transparent, conductive layer support. It has a high electrical resistance (2: 10 12 ⁇ ) and prevents the discharge of electrostatic charge in the dark. 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.
- Post-crosslinking binder systems such as DD varnishes (for example Desmophen / Desmodur ( R ), Bayer AG ), polyisocyanate-crosslinkable acrylate resins, melamine resins, unsaturated polyester resins etc. have been successfully used.
- 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 approximately 1: 1 parts by weight has generally been found to be preferred, but ratios between 4: 1 to 1: 2 are also suitable.
- the thicknesses of layers 3 and 6 are preferably between about 3 and 20 pm.
- Leveling agents such as silicone oils, wetting agents, in particular non-ionic substances, plasticizers of different compositions, such as, for example, based on chlorinated hydrocarbons or based on phthalic acid esters are added to the layer as customary additives. If necessary, sensitizers and / or acceptors can also be added to the charge transport layer, however only to the extent that the optical transparency of the charge transport layer is not significantly impaired.
- micronized organic or inorganic powders of up to about 30% by weight, preferably 10% by weight, have also proven to be advantageous. To a certain extent, this improves the abrasion resistance and significantly improves the rougher, matt surface, in particular the adhesion promoter for the subsequent top layer.
- Preferred organic powders can be: micronized polypropylene waxes, polyethylene waxes, polyamide waxes or polytetrafluoroethylene and polyvinylidene fluoride powders.
- Inorganic powders based on silicon dioxide, such as aerosils, can be used.
- Both non-crosslinking and postcrosslinking and self-crosslinking binders are suitable as surface abrasion-resistant organic binders for the top layer.
- Polyurethane resin polycarbonate resin, phenoxy resin, polyacrylate or polymethacrylate are mentioned as non-crosslinking, organic binders. They can be used alone or in a mixture. Aromatic or aliphatic, non-reactive, linear polyurethanes or a binder composed of dihydroxydiphenylalkane and phosgene are preferably used. Polysulfones, polyphenylene oxides and polyvinyl acetates are also suitable.
- postcrosslinking binders two-component systems made of aliphatic and / or aromatic polyisocyanate resin, hydroxyl-containing, saturated or unsaturated polyester or ether or polyisocyanate-crosslinking hydroxyl-containing acrylic or epoxy resins, one-component systems made of moisture-curing polyisocyanate prepolymer or polyurethane resin , or temporarily blocked polyisocyanates with crosslinkable isocyanate groups when heated.
- thermosetting binders are pure acrylic resins, preferably aqueous dispersions, or externally crosslinking thermosetting acrylic resins, optionally with the addition of melamine resins.
- Epoxy resin systems with hardeners and unsaturated thermosetting polyester resins with and without accelerators can also be used successfully.
- the cover layer consists of a self-crosslinking polyisocyanate and the photoconductive layer contains a compound with hydroxyl groups.
- the organic binders mentioned for the protective cover layer 7 are outstandingly suitable because of their homogeneous film formation and flexibility, their abrasion behavior and the application possibilities. The influence on the photosensitivity of the recording material is negligible.
- the protective cover layer is optically transparent in a thin arrangement.
- the coherent layer which is preferably produced on an organic photoconductor system in a double layer arrangement has a uniform thickness of approximately 0.5-10 ⁇ m, preferably 0.5-5.0 ⁇ m.
- the film surface turns out to be smooth, which is necessary for optimal cleaning.
- the adhesion between the cover layer and the photoconductor system is also high enough to withstand mechanical influences, for example from the cleaning brush.
- the abrasion is significantly improved compared to the photoconductor system to be coated. It is essential that the cover layer behaves triboelectrically like the photoconductor layer. At 40 - 50 ° C as the storage temperature, the cover layer does not stick and no component sweats out of the photoconductor layer.
- the cover layer also serves to prevent crystallization effects. can arise from contact with the photoconductor surface.
- the electrical conductivity of the cover layer is low enough not to influence the charging capacity of the photoconductor.
- the materials mentioned allow the cover layer to be electrically permeable, so that charges can flow off from the surface when exposed to light, possibly to a low residual voltage.
- the electrostatic charge image is completely retained after exposure until image development, which is necessary, since otherwise the resolution of the copy decreases.
- the specific electrical resistance is not changed by moisture in the environment.
- the film surface is free of hydrophilic compo so that the surface resistance is not changed by the climate.
- the preferred application systems are coatings on a coating machine, preferably by means of flow application on, for example, photoconductor tapes, and spray technologies, optionally also electrostatically for applying the top layer on drums.
- a coating machine preferably by means of flow application on, for example, photoconductor tapes, and spray technologies, optionally also electrostatically for applying the top layer on drums.
- a special embodiment of the recording material according to the invention consists in dispersing additives of micronized organic or inorganic powders in the photoconductive layer; this significantly improves adhesion and abrasion properties.
- photoconductive layers are coated with, for example, hydroxyl-containing binders, in particular with cellulose esters such as cellulose nitrates, with a polyfunctional aromatic / aliphatic polyisocyanate or polyisocyanate prepolymer, thereby producing an adhesion-promoting transition zone of curing between the photoconductive layer / cover layer.
- hydroxyl-containing binders in particular with cellulose esters such as cellulose nitrates
- a polyfunctional aromatic / aliphatic polyisocyanate or polyisocyanate prepolymer thereby producing an adhesion-promoting transition zone of curing between the photoconductive layer / cover layer.
- a double layer of photoconductor which, in the given order, consists of aluminum-vapor-coated 75 ⁇ m thick polyester film as an electrically conductive substrate, a vapor-deposited layer of N, N I- dimethylperylimide (CI 71 129) and a charge transport layer of 2.5 bis (4- diethylaminophenyl) -oxdiazole-l, 3,4 (To) and highly viscous cellulose nitrate in a weight ratio of 65:35 is built up, a solution of the abrasion-resistant binders given in the table is applied by flow application with immediate subsequent drying, which takes 5 minutes. The layer thicknesses of the individual protective cover layers with the different binders are in the range of 2 ⁇ 0.5 ⁇ m. Both the photosensitivity and the abrasion behavior of the material with and without a top layer are tested under the same conditions. The results are summarized in the table.
- the measurement of the photosensitivity is carried out as follows: To determine the light discharge curves, the test sample moves on a rotating plate through a charging device to an exposure station, where it is continuously exposed to a xenon lamp. A heat absorption glass and a neutral filter with 15% transparency are connected upstream of the xenon lamp. The light intensity in the measuring plane is in the range of 40 - 60 ⁇ W / cm 2 ; it is measured with an optometer immediately after determining the light decay curve. The charge level (U) and the photo-induced Light decay curves are recorded by an electrometer using a transparent probe. The photoconductor layer is characterized by the charge level (U) and the time (T 1/2 ) after which half the charge (U o / 2) is reached. The product of T l / 2 and the measured light intensity I ( ⁇ W / cm 2 ) is the half-value energy E 1/2 ( ⁇ J / cm 2 ).
- 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 abrasion of both materials is measured on a standard abrasion device (Taber Abraser Type 352) under the following conditions:
- the abrasion in g / m 2 is the quotient of the gravimetrically determined abrasion in mg and the abrasion area.
- the thickness of this protective cover layer is about 0.5 ⁇ m after drying; with constant photosensitivity, the applied, glossy layer improves abrasion and increases the fatigue strength.
- a photoconductive system produced in accordance with Example 2 is tested in a dry toner copier with regard to its surface properties and its photosensitivity.
- a magnetic brush device with a two-component toner mixture is used for development; the layer is guided past a rotating brush to clean the residual toner from the photoconductor surface. It shows that under the same copying conditions the copy quality is the same with and without the top layer.
- There are 5,000 copies in the continuous copy test already strong surface films on the photoconductor layer without a protective cover layer are visible and the surface is matte, on the other hand only slight surface films are visible on one with a cover layer and the surface is still shiny.
- micronized polyethylene wax (PE) or micronized polytetrafluoroethylene (PTFE) can also be dispersed into a charge transport layer composed of 65 parts of To and 35 parts of cellulose nitrate.
- PE polyethylene wax
- PTFE micronized polytetrafluoroethylene
- Photosensitivity and abrasion are determined according to the information in Example 1.
- An aqueous dispersion of self-crosslinking, thermosetting pure acrylic resin is applied to the photoconductor layers described in Example 4 without and with micronized powder additive and is dried for about 10 minutes at 110 ° C. in a forced-air drying cabinet.
- micronized powder additives especially in combination with cover layers, result in a significant reduction in abrasion.
- the abrasion is determined with:
- a solution of polycarbonate I in tetrahydrofuran is layered onto a photoconductor layer, as described in Example 1, by means of machine coating / flow application in a thickness of approximately 2 pm. After drying, an abrasion of 0.04 g / m 2 is measured.
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Abstract
Elektrophotographisches Aufzeichnungsmaterial aus elektrisch leitendem Schichtträger, isolierender Zwischenschicht und mindestens einer photoleitfähigen Schicht enthaltend mindestens eine Ladungsträger erzeugende Verbindung und mindestens eine Ladungen transportierende Verbindung sowie einer schützenden transparenten Deckschicht, aus einem Oberflächen-abriebfesten Bindemittel aus Polyurethan-, Polycarbonat-, Phenoxy-, Polyacrylat- oder Polymethacrylat-Harz, aus Polyisocyanat und Hydroxylgruppen-haltigem Polyester oder -ether, aus Polyisocyanat und Hydroxylgruppen-haltigem Acryl- oder Epoxidharz, oder aus Polyisocyanat-Präpolymer oder Polyisocyanaten mit temporär blockierten Isocyanat-Gruppen.Electrophotographic recording material composed of an electrically conductive substrate, an insulating intermediate layer and at least one photoconductive layer containing at least one charge-generating compound and at least one charge-transporting compound and a protective transparent cover layer, made of a surface-abrasion-resistant binder made of polyurethane, polycarbonate, phenoxy, polyacrylate or polymethacrylate resin, from polyisocyanate and hydroxyl-containing polyester or ether, from polyisocyanate and hydroxyl-containing acrylic or epoxy resin, or from polyisocyanate prepolymer or polyisocyanates with temporarily blocked isocyanate groups.
Description
Die Erfindung betrifft ein elektrophotographisches Aufzeichnungsmaterial aus einem elektrisch leitenden Schichtträger, gegebenenfalls einer isolierenden Zwischenschicht, einer photoleitfähigen Schicht aus mindestens einer Ladungsträger erzeugenden Verbindung und mindestens einer Ladungen transportierenden Verbindung und einer schützenden transparenten Deckschicht.The invention relates to an electrophotographic recording material composed of an electrically conductive layer support, optionally an insulating intermediate layer, a photoconductive layer composed of at least one compound generating a charge carrier and at least one charge transporting compound and a protective transparent cover layer.
Bei dem aus der US-PS 2,297,691 bekannten und heute viel verwendeten elektrophotographischen Verfahren zur Herstellung von Kopien ist nach der Übertragung des auf der Photoleiterschicht auf trockenem Wege entwickelten Tonerbildes auf den Kopieträger stets eine gründliche Reinigung der Photoleiterschicht erforderlich. Das Reinigen geschieht in der Regel durch Abbürsten oder Abwischen der Schicht mit dafür geeigneten Bürsten bzw. Geweben. Bei Kopiermaschinen, die mit Flüssigentwicklern arbeiten, wird die Wirkung der mechanischen Reinigung häufig durch Mitverwendung einer Reinigungsflüssigkeit verstärkt. Neben diesen Reinigungsoperationen ist die photoleitfähige Schicht auch noch anderen sie schädigenden Einflüssen ausgesetzt. Zum Beispiel unterliegt sie der Einwirkung des Trockenentwicklers sowie der Entwicklerstation (Gegenspannung und bei der Flüssigentwicklung darüber hinaus der Einwirkung der Entwicklerflüssigkeit. Sie ist auch der in der Aufladestation erzeugten ionisierten Luft ausgesetzt. Es ist bekannt, daß die erforderlichen Reinigungsvorgänge und die anderen erwähnten Einflüsse zu einer Beeinträchtigung oder sogar mechanischen Beschädigung der Photoleiterschicht führen und damit eine Verminderung ihrer Gebrauchsdauer zur Folge haben.In the known and US Patent No. 2,297,691 much used today electrophotographic process for producing copies after the transfer of the developed on the photoconductor layer dry way toner image on the K opieträger always necessary to thoroughly clean the photoconductor layer. The cleaning is usually done by brushing or wiping the layer with suitable brushes or fabrics. In copying machines that work with liquid developers, the effect of mechanical cleaning is often enhanced by the use of a cleaning liquid. In addition to these cleaning operations, the photoconductive layer is also exposed to other influences that damage it. For example, it is subject to the action of the dry developer as well as the developer station (counter voltage and, in the case of liquid development, the action of the developer liquid. It is also exposed to the ionized air generated in the charging station. It is known that the requ Such cleaning processes and the other influences mentioned lead to impairment or even mechanical damage to the photoconductor layer and thus to a reduction in its service life.
Aufzeichnungsmaterialien mit einer photoleitfähigen Schicht aus mindestens einer Schicht mit Ladungsträger erzeugender und Ladungen transportierender Verbindung sind bekannt. So werden zum Beispiel hochempfindliche, organische Photoleiterschichten (DE-AS 23 14 051) aufgrund ihrer hohen Elastizität auf leitfähigen Trägerfolien bzw. -bändern verwendet.Recording materials with a photoconductive layer comprising at least one layer with a charge-generating and charge-transporting compound are known. For example, highly sensitive, organic photoconductor layers (DE-AS 23 14 051) are used on conductive carrier films or tapes due to their high elasticity.
Insbesondere lassen sich sehr hochempfindliche Photoleitersysteme gemäß zum Beispiel DE-OS 27 34 288 wegen ihrer großen Flexibilität als Endlosbänder einsetzen, ·die über Umlenkwalzen mit relativ kleinem Durchmesser geführt werden können.In particular, very highly sensitive photoconductor systems according to DE-OS 27 34 288, for example, can be used as endless belts because of their great flexibility, which can be guided over deflecting rollers with a relatively small diameter.
Es ist auch bekannt (US-PS 2,901,348, US-PS 4,148,637, DE-OS 24 52 623), Photoleiterschichten mit einer zusätzlichen Deckschicht aus anorganischen oder organischen Materialien zu schützen. Nachteilig daran ist, daß sie entweder auf den weniger flexiblen aus Selen bestehenden oder Selen enthaltenden Schichten oder auf generell weniger empfindlichen organischen Photoleitersystemen angewandt werden. Außerdem müssen diese Deckschichten zur besseren Haltbarkeit mit Silankupplern, wie Chlorsilan, versetzt werden oder enthalten zusätzlich eine photoleitfähige organische Verbindung.It is also known (US Pat. No. 2,901,348, US Pat. No. 4,148,637, DE-OS 24 52 623) to protect photoconductor layers with an additional cover layer made of inorganic or organic materials. The disadvantage of this is that they are used either on the less flexible layers consisting of or containing selenium or on generally less sensitive organic photoconductor systems. In addition, these cover layers must be mixed with silane couplers, such as chlorosilane, for better durability or additionally contain a photoconductive organic compound.
Aufgabe der Erfindung ist es daher, die aus organischen Materialien bestehenden, zum Beispiel in Photoleiterdoppelschichtanordnung hochlichtempfindlichen Photoleitersysteme mit einer sie vor mechanischen oder gegebenenfalls sonstigen nachteiligen Einflüssen schützenden Deckschicht aus gegen sichtbares Licht transparenten Materialien zu versehen, die die Funktion der Photoleiterschicht nicht wesentlich beeinträchtigen und allgemein die Gebrauchsdauer solcher Systeme erhöhen.It is therefore an object of the invention to provide the photoconductor systems which are made of organic materials and are highly light-sensitive, for example in a photoconductor double-layer arrangement, with a cover layer made of transparent materials which protect them from mechanical or possibly other adverse influences and which do not substantially impair the function of the photoconductor layer and generally increase the service life of such systems.
Die gestellte Aufgabe wird durch ein in den Ansprüchen 1 und 2 genanntes elektrophotographisches Aufzeichnungsmaterial gelöst, welches dadurch gekennzeichnet ist, daß die Deckschicht aus einem Oberflächen-abriebfesten organischen Bindemittel aus Polyurethanharz, Polycarbonatharz, Phenoxyharz, Polyacrylat- oder Polymethacrylatharz, aus Polyisocyanat und Hydroxylgruppen-haltigem Polyester oder -ether, aus Polyisocyanat und Hydroxylgruppen-haltigem Acryl- oder Epoxidharz, oder aus Polyisocyanat-Präpolymer oder Polyisocyanaten mit temporär blockierten Isocyanat-Gruppen besteht. Die Bindemittel sind nichtvernetzend, nach- oder selbstvernetzend.The object is achieved by an electrophotographic recording material mentioned in
Hierdurch wird erreicht, daß elektrophotographische Aufzeichnungsmaterialien zur Verfügung gestellt werden können, die bei nahezu gleichbleibender Photoempfindlichkeit die Abriebfestigkeit und die Gebrauchsdauer deutlich verbessern.The result of this is that electrophotographic recording materials can be made available which, with almost the same photosensitivity, significantly improve the abrasion resistance and the service life.
Die abriebfeste Deckschicht kann durch Beschichten, Tauchen oder auch (elektrostatisches) Sprühen mit nachfolgender Trocknung und gegebenfalls Härtung aufgebracht werden.The abrasion-resistant top layer can be applied by coating, dipping or (electrostatic) spraying with subsequent drying and optionally hardening.
Durch die Erhöhung der Abriebfestigkeit und damit der Gebrauchsdauer wird weiterhin erreicht, daß die Mehrfachschichtanordnungen nicht nur auf flexiblen leitenden Schichtträgern, sondern auch auf Trommeln rentabler eingesetzt werden können.By increasing the abrasion resistance and thus the service life, it is also achieved that the multilayer arrangements can be used more profitably not only on flexible conductive substrates, but also on drums.
Schematisch wird das erfindungsgemäße elektrophotographische Aufzeichnungsmaterial durch die beigefügten Figuren 1 bis 4 wiedergegeben. So kann die photoleitfähige Schicht als Einfachschicht vorliegen wie dies unter Position 6 in Figur 1 angedeutet ist. Sie kann auch als Doppelschichtanordnung vorliegen, die aus einer . Ladungsträger erzeugende Verbindungen enthaltenden Schicht 2, wie dies in Figuren 2 und 3 zum Ausdruck kommt, und aus einer Ladungen transportierende Verbindungen enthaltenden Schicht unter der jeweiligen Position 3 besteht, was im allgemeinen bevorzugt ist. Der leitende Schichtträger ist jeweils mit 1 angegeben. Unter Position 4 ist eine isolierende Zwischenschicht angedeutet, Position 5 zeigt eine Schicht aus Ladungen erzeugender Verbindung in Dispersion. Mit Position 7 ist die erfindungsgemäße schützende Deckschicht angezeigt.The electrophotographic recording material according to the invention is shown schematically by the attached FIGS. 1 to 4. For example, the photoconductive layer can be in the form of a single layer, as indicated in
Als leitende Schichtträger kommen zum Beispiel Aluminium-Folie, gegebenenfalls transparente, mit Aluminium bedampfte oder kaschierte Polyester-Folie zum Einsatz, jedoch kann jeder andere genügend leitfähig gemachte Schichtträger verwendet werden.Aluminum foil, optionally transparent, with aluminum can be used as the conductive layer support steamed or laminated polyester film is used, however, any other layer that has been made sufficiently conductive can be used.
Die isolierende Zwischenschicht kann durch eine thermisch, anodisch oder chemisch erzeugte Aluminiumoxid-Zwischenschicht hergestellt werden. Sie kann auch aus organischen Materialien bestehen. So werden unterschiedliche Natur- bzw. Kunstharzbindemittel verwendet, die gut auf einer Metall- bzw. Aluminium-Oberfläche haften und beim nachfolgenden Anbringen der weiteren Schichten wenig angelöst werden, wie zum Beispiel Polyamidharze, Polyvinylphosphonsäure, Polyurethane, Polyesterharze oder spezifisch alkalilösliche Bindemittel, wie zum Beispiel Styrol-Maleinsäureanhydrid-Copolymerisate. Die Dicke solcher organischen Zwischenschichten kann bis zu 5 pm betragen, die der Aluminiumoxidschicht liegt größtenteils im Bereich von 0,01 - 1 pm.The insulating intermediate layer can be produced by a thermally, anodically or chemically produced aluminum oxide intermediate layer. It can also consist of organic materials. For example, different natural or synthetic resin binders are used that adhere well to a metal or aluminum surface and dissolve little when the other layers are subsequently applied, such as polyamide resins, polyvinylphosphonic acid, polyurethanes, polyester resins or specifically alkali-soluble binders, such as Example styrene-maleic anhydride copolymers. The thickness of such organic intermediate layers can be up to 5 pm, and that of the aluminum oxide layer is mostly in the range from 0.01 to 1 pm.
Die Schicht 2 bzw. 5 besitzt die Funktion einer Ladungsträgererzeugungsschicht. Die dabei eingesetzten Ladungsträger erzeugenden Verbindungen bestimmen in besonderem Maße die spektrale Lichtempfindlichkeit des photoleitfähigen Systems. Als Ladungsträger erzeugende Substanzen können Farbstoffe unterschiedlichster Klassen eingesetzt werden. Beispielsweise seien genannt:
- Perylen-3,4,9,10-tetracarbonsäureanhydrid bzw. Perylen-3,4,9,10-tetracarbonsäureimidderivate nach DE-OS 22 37 539; oder gemäß DE-PS 22 32 513 N,N'-Bis-(3-methoxypropyl)-3,4,9,10-perylentetracarbonsäureimid; polynukleare Chinone nach DE-OS 22 37 678; cis- bzw. trans-Perinone nach DE-OS 22 39 923; Thioindigo-Farbstoffe nach DE-OS 22 37 680; Chinacridone nach DE-OS 22 37 679; Kondensationsprodukte aus Benzo-4,10-thioxanthen-3,11-dicarbonsäureanhydrid und Aminen nach DE-OS 23 55 075; Phthalocyanin-Derivate nach DE-OS 22 39 924 und Farbstoffe, die durch Kondensation nach der Vorschrift Bull. Chem. Soc. Japan 25, 411 - 413 / 1952 aus Perylen-3, 4, 9, 10-tetracarbonsäureanhydrid und o-Phenylendiamin oder 1,8-Diaminophthalin hergestellt werden, gemäß DE-OS 23 14 051.
- Perylene-3,4,9,10-tetracarboxylic anhydride or perylene-3,4,9,10-tetracarboximide derivatives according to DE-OS 22 37 539; or according to DE-PS 22 32 513 N, N'-bis (3-methoxy propyl) -3,4,9,10-perylenetetracarboximide; polynuclear quinones according to DE-OS 22 37 678; cis or trans perinones according to DE-OS 22 39 923; Thioindigo dyes according to DE-OS 22 37 680; Quinacridones according to DE-OS 22 37 679; Condensation products of benzo-4,10-thioxanthene-3,1-dicarboxylic acid anhydride and 1-amines according to DE-OS 23 55 075; Phthalocyanine derivatives according to DE-OS 22 39 924 and dyes, which by condensation according to the Bull. Chem. Soc. Japan 25, 411 - 413/1952 can be prepared from perylene-3, 4, 9, 10-tetracarboxylic anhydride and o-phenylenediamine or 1,8-diaminophthalene, according to D EO S 23 14 051.
Ferner können beispielsweise Farbstoffe nach den DE-OS 22 46 255, 23 53 639 und 23 56 370 eingesetzt werden.Dyes according to DE-OS 22 46 255, 23 53 639 and 23 56 370 can also be used, for example.
Wie erwähnt, sind auch dünne Ladungsträger erzeugende . Schichten aus anorganischen Stoffen, wie sie durch Aufdampfen von Selen, dotiertem Selen, Cadmiumsulfid usw. hergestellt werden, geeignet.As mentioned, thin charge carriers are also generating. Layers of inorganic substances, such as those produced by vapor deposition of selenium, doped selenium, cadmium sulfide, etc., are suitable.
Das Aufbringen einer homogenen, dicht gepackten Schicht 2 wird bevorzugt durch Aufdampfen im Vakuum erhalten. Ein vorteilhafter Schichtdickenbereich der Schicht 2 liegt zwischen 0,005 und 3 pm, da hier Haftfestigkeit und Homogenität der aufgedampften Verbindung besonders günstig sind.The application of a homogeneous, densely packed
In Kombination mit der Zwischenschicht oder als Ersatz der Zwischenschicht können homogene, gut abdeckende Farbstoffschichten mit Dicken von größenordnungsmäßig O,1 - 3 pm auch durch Vermahlen des Farbstoffs mit einem Bindemittel, insbesondere mit hochviskosen Cellulosenitraten und/oder vernetzenden Bindemittelsystemen, zum Beispiel Polyisocyanat-vernetzbaren Acrylharzen, Lacken auf Basis von Polyisocyanaten und Hydroxylgruppen-haltigem Polyester oder -ether und durch anschließendes Aufbringen dieser Farbstoffdispersionen 5 auf den Schichtträger hergestellt werden, wie dies aus Figur 4 hervorgeht.In combination with the intermediate layer or as a replacement of the intermediate layer, homogeneous, well covering Dye layers with thicknesses of the order of 0.1-3 pm also by grinding the dye with a binder, in particular with highly viscous cellulose nitrates and / or crosslinking binder systems, for example polyisocyanate-crosslinkable acrylic resins, paints based on polyisocyanates and hydroxyl-containing polyester or ether and by subsequently applying these
Als dem Ladungstransport dienendes Material in Schicht 3 bzw. 6 sind vor allem organische Verbindungen geeignet, die ein ausgedehntes X-Elektronensystem besitzen. Hierzu gehören insbesondere monomere aromatische bzw. heterocyclische Verbindungen, wie solche, die mindestens eine Dialkylaminogruppe oder zwei Alkoxygruppen aufweisen. Bewährt haben sich besonders Oxdiazol-Derivate, die in der deutschen Patentschrift 10 58 836 genannt sind. Hierzu gehören insbesondere das 2,5-Bis-(p-diethylaminophenyl)-oxdiazol-l,3,4. Weitere geeignete monomere Elektronendonatorverbindungen sind zum Beispiel Triphenylaminderivate, höher kondensierte aromatische Verbindungen wie Pyren, benzokondensierte Heterocyclen, außerdem Pyrazolin- oder Imidazolderivate (DE-PSen 10 60 714, 11 06 599), hierher gehören auch Triazol-, Thiadiazolsowie besonders Oxazolderivate, zum Beispiel 2-Phenyl-4-(2-chlorphenyl)-5-(4-diethylamino)-oxazol, wie sie in den deutschen Patentschriften 10 60 260, 12 99 296, 11 20 875 offenbart sind.Organic materials which have an extensive X-electron system are particularly suitable as the charge transport material in
Die Ladungstransportschicht 3 weist im sichtbaren Bereich (420 - 750 nm) praktisch keine Photoempfindlichkeit auf. Sie besteht vorzugsweise aus einem Gemisch einer Elektronendonatorverbindung mit einem Harzbindemittel, wenn negativ aufgeladen werden soll.The
Die Schicht 3 ist vorzugsweise transparent. Es ist jedoch auch möglich, daß sie, etwa bei transparentem, leitfähigem Schichtträger, nicht transparent zu sein braucht. Sie besitzt einen hohen elektrischen Widerstand (2: 1012Ω) und verhindert im Dunkeln das Abfließen der elektrostatischen Ladung. Bei Belichtung transportiert sie die in der organischen Farbstoffschicht erzeugten Ladungen.
Neben den bisher beschriebenen Ladungsträger erzeugenden und den transportierenden Verbindungen beeinflußt das zugesetzte Bindemittel sowohl das mechanische Verhalten wie Abrieb, Flexibilität, Filmbildung etc. als auch in gewissem Umfang das elektrophotographische Verhalten wie Photoempfindlichkeit, Restladung und zyklisches Verhalten.In addition to the charge generating and transporting compounds described so far, 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.
Als Bindemittel werden filmbildende Verbindungen wie Polyesterharze, Polyvinylchlorid/Polyvinylacetat-Mischpolymerisate, Styrol-Maleinsäureanhydrid-Copolymerisate, Polycarbonate, Silikonharze, Polyurethane, Epoxidharze, Acrylate, Polyvinylacetale, Polystyrole, CelluloseDerivate wie Celluloseacetobutyrate etc. eingesetzt. Außerdem werden nachvernetzende Bindemittelsysteme wie DD-Lacke (zum Beispiel Desmophen/Desmodur(R), Bayer AG), polyisocyanatvernetzbare Acrylatharze, Melaminharze, ungesättigte Polyester-Harze etc. erfolgreich angewandt.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. Post-crosslinking binder systems such as DD varnishes (for example Desmophen / Desmodur ( R ), Bayer AG ), polyisocyanate-crosslinkable acrylate resins, melamine resins, unsaturated polyester resins etc. have been successfully used.
Wegen der kombinierten Vorteile (hohe Photoempfindlichkeit, Blitzempfindlichkeit, hohe Flexibilität) ist der Einsatz von Cellulosenitraten, insbesondere der hochviskosen Typen bevorzugt.Because of the combined advantages (high photosensitivity, flash sensitivity, high flexibility), the use of cellulose nitrates, in particular the highly viscous types, is preferred.
Das Mischungsverhältnis der ladungstransportierenden Verbindung zu dem Bindemittel kann variieren. Jedoch sind durch die Forderung nach maximaler Photoempfindlichkeit, d.h. möglichst großem Anteil an ladungstransportierender Verbindung und nach zu vermeidender Auskristallisation sowie Erhöhung der Flexibilität, d.h. möglichst großem Anteil an Bindemitteln, relativ bestimmte Grenzen gesetzt. Es hat sich allgemein ein Mischungsverhältnis von etwa l : 1 Gewichtsteilen als bevorzugt erwiesen, jedoch sind auch Verhältnisse zwischen 4 : 1 bis 1 : 2 geeignet.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 approximately 1: 1 parts by weight has generally been found to be preferred, but ratios between 4: 1 to 1: 2 are also suitable.
Die Dicken der Schichten 3 bzw. 6 liegen vorzugsweise zwischen etwa 3 und 20 pm.The thicknesses of
Als übliche Zusätze werden der Schicht Verlaufmittel wie Silikonöle, Netzmittel, insbesondere nicht-ionogene Substanzen, Weichmacher unterschiedlicher Zusammensetzung wie zum Beispiel auf Basis chlorierter Kohlenwassetstoffe oder auf Basis von Phthalsäureester zugegeben. Gegebenenfalls können der Ladungstransportschicht als Zusatz auch Sensibilisatoren und/oder Akzeptoren zugefügt werden, jedoch nur in dem Maße, daß die optische Transparenz der Ladungstransportschicht nicht wesentlich beeinträchtigt wird.Leveling agents such as silicone oils, wetting agents, in particular non-ionic substances, plasticizers of different compositions, such as, for example, based on chlorinated hydrocarbons or based on phthalic acid esters are added to the layer as customary additives. If necessary, sensitizers and / or acceptors can also be added to the charge transport layer, however only to the extent that the optical transparency of the charge transport layer is not significantly impaired.
In Verbindung mit der erfindungsgemäßen Deckschicht haben sich auch Zusätze mikronisierter organischer oder anorganischer Pulver bis zu ca. 30 Gew.-%, bevorzugt 10 Gew.-%, als vorteilhaft erwiesen. Dadurch wird in gewissem Umfang die Abriebfestigkeit verbessert und durch die rauhere, matte Oberfläche, besonders die Haftvermittlung für die nachfolgende Deckschicht deutlich verbessert. Bevorzugte organische Pulver können sein: mikronisierte Polypropylenwachse, Polyethylenwachse, Polyamidwachse oder Polytetrafluorethylen- sowie Polyvinylidenfluorid-Pulver. Als anorganische Pulver sind solche auf Basis Siliziumdioxid, wie Aerosile einsetzbar.In conjunction with the top layer according to the invention, additions of micronized organic or inorganic powders of up to about 30% by weight, preferably 10% by weight, have also proven to be advantageous. To a certain extent, this improves the abrasion resistance and significantly improves the rougher, matt surface, in particular the adhesion promoter for the subsequent top layer. Preferred organic powders can be: micronized polypropylene waxes, polyethylene waxes, polyamide waxes or polytetrafluoroethylene and polyvinylidene fluoride powders. Inorganic powders based on silicon dioxide, such as aerosils, can be used.
Als Oberflächen-abriebfeste organische Bindemittel für die Deckschicht kommen sowohl nichtvernetzende als auch nachvernetzende und selbstvernetzende Bindemittel in Betracht.Both non-crosslinking and postcrosslinking and self-crosslinking binders are suitable as surface abrasion-resistant organic binders for the top layer.
Als nichtvernetzende, organische Bindemittel werden Polyurethanharz, Polycarbonatharz, Phenoxyharz, Polyacrylat oder Polymethacrylat genannt. Sie können allein oder in Mischung eingesetzt werden. Vorzugsweise werden aromatische oder aliphatische, nicht reaktive, lineare Polyurethane oder ein Bindemittel aus Dihydroxydiphenylalkan und Phosgen verwendet. Es sind auch Polysulfone, Polyphenylenoxide und Polyvinylacetate geeignet.Polyurethane resin, polycarbonate resin, phenoxy resin, polyacrylate or polymethacrylate are mentioned as non-crosslinking, organic binders. They can be used alone or in a mixture. Aromatic or aliphatic, non-reactive, linear polyurethanes or a binder composed of dihydroxydiphenylalkane and phosgene are preferably used. Polysulfones, polyphenylene oxides and polyvinyl acetates are also suitable.
Als nachvernetzende Bindemittel sind geeignet: Zweikomponentensysteme aus mit aliphatischem und/oder aromatischem Polyisocyanatharz vernetzendem, Hydroxylgruppen-haltigem, gesättigtem oder ungesättigtem Polyester oder -ether oder polyisocyanatvernetzende Hydroxylgruppen-haltige Acrylaoder Epoxid-Harze, Einkomponentensysteme aus feuchtigkeitshärtendem Polyisocyanat-Präpolymer oder lufttrocknendem Polyurethanharz (Polyurethanalkydharz), oder temporär blockierte Polyisocyanate mit beim Erhitzen vernetzungsfähigen Isocyanat-Gruppen.The following are suitable as postcrosslinking binders: two-component systems made of aliphatic and / or aromatic polyisocyanate resin, hydroxyl-containing, saturated or unsaturated polyester or ether or polyisocyanate-crosslinking hydroxyl-containing acrylic or epoxy resins, one-component systems made of moisture-curing polyisocyanate prepolymer or polyurethane resin , or temporarily blocked polyisocyanates with crosslinkable isocyanate groups when heated.
Als selbstvernetzende, gegebenenfalls wärmehärtbare Bindemittel sind Reinacrylharze, vorzugsweise wäßrige Dispersionen, oder fremd vernetzende wärmehärtbare Acrylharze, gegebenenfalls unter Zusatz von Melaminharzen, geeignet. Epoxidharzsysteme mit Härtern, sowie ungesättigte wärmehärtende Polyesterharze mit und ohne Beschleuniger können auch erfolgreich eingesetzt werden.Suitable as self-crosslinking, optionally thermosetting binders are pure acrylic resins, preferably aqueous dispersions, or externally crosslinking thermosetting acrylic resins, optionally with the addition of melamine resins. Epoxy resin systems with hardeners and unsaturated thermosetting polyester resins with and without accelerators can also be used successfully.
Es hat sich auch als vorteilhaft erwiesen, wenn die Deckschicht aus einem selbstvernetzenden Polyisocyanat besteht und die photoleitfähige Schicht eine,Verbindung mit Hydroxylgruppen enthält.It has also proven to be advantageous if the cover layer consists of a self-crosslinking polyisocyanate and the photoconductive layer contains a compound with hydroxyl groups.
Die genannten organischen Bindemittel für die schützende Deckschicht 7 sind wegen ihrer homogenen Filmbildung und Flexibilität, ihrem Abriebverhalten und den Antragsmöglichkeiten hervorragend geeignet. Die Beeinflussung der Photoempfindlichkeit des Aufzeichnungsmaterials ist vernachlässigbar gering.The organic binders mentioned for the
Die schützende Deckschicht ist in dünner Anordnung optisch transparent. Die bevorzugt auf einem organischen Photoleitersystem in Doppelschichtanordnung erzeugte zusammenhängende Schicht hat eine gleichmäßige Dicke von etwa 0,5 - 10 pm, vorzugsweise von 0,5 - 5,0 um. Die Filmoberfläche erweist sich als glatt, was für eine optimale Reinigung notwendig ist. Auch die Adhäsion zwischen Deckschicht und Photoleitersystem ist groß genug, um mechanischer Einwirkung, zum Beispiel durch die Reinigungsbürste, standzuhalten. Der Abrieb ist im Vergleich zu dem zu beschichtenden Photoleitersystem deutlich verbessert. Wesentlich ist, daß sich die Deckschicht triboelektrisch wie die Photoleiterschicht verhält. Bei 40 - 50°C als Lagertemperatur verklebt sich die Deckschicht nicht, und es schwitzt auch keine Komponente aus der Photoleiterschicht aus. Die Deckschicht dient auch zur Verhinderung von Auskristallisationseffekten, die . durch Berührung mit der Photoleiteroberfläche entstehen können. Die elektrische Leitfähigkeit der Deckschicht ist gering genug , um die Aufladfähigkeit des Photoleiters nicht zu beeinflussen. Andererseits gewähren die genannten Materialien der Deckschicht elektrische Durchlässigkeit, so daß beim Belichten Ladungen von der Oberfläche - bis gegebenenfalls auf eine geringe Restspannung - abfließen können. Das elektrostatische Ladungsbild bleibt nach Belichtung bis zur Bildentwicklung vollkommen erhalten, was notwendig ist, da sonst die Auflösung der Kopie abnimmt. Der spezifische elektrische Widerstand wird durch Feuchtigkeit der Umgebung nicht verändert. Schließlich ist die Filmoberfläche frei von hydrophilen Komponenten, damit der Flächenwiderstand nicht durch das Klima verändert wird.The protective cover layer is optically transparent in a thin arrangement. The coherent layer which is preferably produced on an organic photoconductor system in a double layer arrangement has a uniform thickness of approximately 0.5-10 μm, preferably 0.5-5.0 μm. The film surface turns out to be smooth, which is necessary for optimal cleaning. The adhesion between the cover layer and the photoconductor system is also high enough to withstand mechanical influences, for example from the cleaning brush. The abrasion is significantly improved compared to the photoconductor system to be coated. It is essential that the cover layer behaves triboelectrically like the photoconductor layer. At 40 - 50 ° C as the storage temperature, the cover layer does not stick and no component sweats out of the photoconductor layer. The cover layer also serves to prevent crystallization effects. can arise from contact with the photoconductor surface. The electrical conductivity of the cover layer is low enough not to influence the charging capacity of the photoconductor. On the other hand, the materials mentioned allow the cover layer to be electrically permeable, so that charges can flow off from the surface when exposed to light, possibly to a low residual voltage. The electrostatic charge image is completely retained after exposure until image development, which is necessary, since otherwise the resolution of the copy decreases. The specific electrical resistance is not changed by moisture in the environment. Finally, the film surface is free of hydrophilic compo so that the surface resistance is not changed by the climate.
Die bevorzugten Antragssysteme sind Beschichtungen an einer Streichmaschine, vorzugsweise mittels Fließerantrag auf zum Beispiel Photoleiterbänder, sowie Sprühtechnologien, gegebenenfalls auch elektrostatisch für den Antrag der Deckschicht auf Trommeln. Bei Beschichtungen von Trommeln durch Tauchen ist einschränkend zu berücksichtigen, daß das Photoleitersystem anlösungsstabil gegen die nachfolgende Tauchbeschichtung mit Deckschichtmaterialien ist.The preferred application systems are coatings on a coating machine, preferably by means of flow application on, for example, photoconductor tapes, and spray technologies, optionally also electrostatically for applying the top layer on drums. When coating drums by dipping, it must be taken into account that the photoconductor system is solution-stable against the subsequent dip coating with top layer materials.
Eine besondere Ausführungsform des erfindungsgemäßen Aufzeichnungsmaterials besteht darin, daß man in die photoleitfähige Schicht Zusätze von mikronisierten organischen oder anorganischen Pulvern dispergiert; dadurch werden die Haftvermittlung und die Abriebeigenschaften deutlich verbessert.A special embodiment of the recording material according to the invention consists in dispersing additives of micronized organic or inorganic powders in the photoconductive layer; this significantly improves adhesion and abrasion properties.
In weiterer Ausführungsform werden photoleitfähige Schichten mit zum Beispiel hydroxylhaltigen Bindemitteln, insbesondere mit Celluloseestern wie Cellulosenitraten, mit einem polyfunktionellen aromat./aliphatischen Polyisocyanat oder Polyisocyanat-Präpolymeren, beschichtet und dadurch eine haftvermittelnde Übergangszone der Durchhärtung zwischen photoleitfähiger Schicht/Deckschicht erzeugt.In a further embodiment, photoconductive layers are coated with, for example, hydroxyl-containing binders, in particular with cellulose esters such as cellulose nitrates, with a polyfunctional aromatic / aliphatic polyisocyanate or polyisocyanate prepolymer, thereby producing an adhesion-promoting transition zone of curing between the photoconductive layer / cover layer.
Die Erfindung wird anhand der Beispiele näher erläutert, ohne sie hierauf zu beschränken.The invention is explained in more detail with the aid of the examples, without being restricted thereto.
Auf eine Photoleiterdoppelschicht, die in der angegebenen Reihenfolge aus Aluminium-bedampfter 75 pm dicker Polyesterfolie als elektrisch leitendem Schichtträger, einer aufgedampften Schicht aus N,NI-Dimethylperylimid (C. I. 71 129) sowie einer Ladungstransportschicht aus 2,5-Bis-(4-diethylaminophenyl)-oxdiazol-l,3,4 (To) und hochviskosem Cellulosenitrat im Gewichtsverhältnis 65 : 35 aufgebaut ist, wird eine Lösung aus den in der Tabelle angegebenen abriebfesten Bindemitteln durch Fließerantrag mit unmittelbar nachfolgender Trocknung, die 5 Minuten dauert, angetragen. Die Schichtdicken der einzelnen schützenden Deckschichten mit den unterschiedlichen Bindemitteln liegen im Bereich von 2 ± 0,5 µm. Unter gleichen Bedingungen werden sowohl die Photoempfindlichkeit wie auch das Abriebverhalten des Materials mit und ohne Deckschicht getestet. Die Ergebnisse sind in der Tabelle zusammengefaßt.On a double layer of photoconductor, which, in the given order, consists of aluminum-vapor-coated 75 μm thick polyester film as an electrically conductive substrate, a vapor-deposited layer of N, N I- dimethylperylimide (CI 71 129) and a charge transport layer of 2.5 bis (4- diethylaminophenyl) -oxdiazole-l, 3,4 (To) and highly viscous cellulose nitrate in a weight ratio of 65:35 is built up, a solution of the abrasion-resistant binders given in the table is applied by flow application with immediate subsequent drying, which takes 5 minutes. The layer thicknesses of the individual protective cover layers with the different binders are in the range of 2 ± 0.5 µm. Both the photosensitivity and the abrasion behavior of the material with and without a top layer are tested under the same conditions. The results are summarized in the table.
Die Messung der Photoempfindlichkeit wird wie folgt durchgeführt: Zur Ermittlung der Hellentladungskurven bewegt sich die Meßprobe auf einem sich drehenden Teller durch eine Aufladevorrichtung hindurch zu einer Belichtungsstation, wo sie mit einer Xenonlampe kontinuierlich belichtet wird. Ein Wärmeabsorptionsglas und ein Neutralfilter mit 15 % Transparenz sind der Xenonlampe vorgeschaltet. Die Lichtintensität in der Meßebene liegt im Bereich von 40 - 60 µW/cm2; sie wird unmittelbar nach Ermittlung der Hellabfallkurve mit einem Optometer gemessen. Die Aufladungshöhe (U ) und die photoinduzierte Hellabfallkurve werden über ein Elektrometer durch eine transparente Sonde oszillographisch aufgezeichnet. Die Photoleiterschicht wird durch die Aufladungshöhe (U ) und diejenige Zeit (T1/2) charakterisiert, nach der die Hälfte der Aufladung (Uo/2) erreicht ist. Das Produkt aus Tl/2 und der gemessenen Lichtintensität I (µW/cm2) ist die Halbwertsenergie E1/2 (µJ/cm2).The measurement of the photosensitivity is carried out as follows: To determine the light discharge curves, the test sample moves on a rotating plate through a charging device to an exposure station, where it is continuously exposed to a xenon lamp. A heat absorption glass and a neutral filter with 15% transparency are connected upstream of the xenon lamp. The light intensity in the measuring plane is in the range of 40 - 60 µW / cm 2 ; it is measured with an optometer immediately after determining the light decay curve. The charge level (U) and the photo-induced Light decay curves are recorded by an electrometer using a transparent probe. The photoconductor layer is characterized by the charge level (U) and the time (T 1/2 ) after which half the charge (U o / 2) is reached. The product of T l / 2 and the measured light intensity I (µW / cm 2 ) is the half-value energy E 1/2 (µJ / cm 2 ).
Die Restladung (UR) nach 0,1 sec, ermittelt aus obigen Hellentladekurven, ist ein weiteres Maß für die Entladung einer Photoleiterschicht.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.
Zur Prüfung des Abriebverhaltens werden an einem Norm-Abriebgerät (Taber Abraser Typ 352) der Abrieb beider Materialien unter folgenden Bedingungen gemessen:
Der Abrieb in g/m2 ist der Quotient aus dem gravimetrisch ermittelten Abrieb in mg und der Abriebfläche.
Ein photoleitfähiges System, wie in Beispiel 1 beschrieben, jedoch mit 50 Gew.-Teilen To, 25 Gew.-Teilen Polyesterharz und 25 Gew.-Teilen Polyvinylchlorid/Polyvinylacetat-Copolymer in ca. 10 g/m2 Dicke, wird mit einer wäßrigen Polyacrylat-Dispersion (4 % in H20; Acrylsäureester/Styrol-Mischpolymerisat) in einem Maschinenstrich durch Fließerantrag aufgetragen. Die Dicke dieser schützenden Deckschicht beträgt nach Trocknung ca. 0,5 um; bei gleichbleibender Photoempfindlichkeit wird durch die aufgebrachte, glänzende Schicht der Abrieb verbessert und die Dauerstandsfestigkeit erhöht.A photoconductive system as described in Example 1, but with 50 parts by weight of To, 25 parts by weight of polyester resin and 25 parts by weight of polyvinyl chloride / polyvinyl acetate copolymer in a thickness of approx. 10 g / m 2 , is used with a aqueous polyacrylate dispersion (4% in H 2 0; acrylic acid ester / styrene copolymer) applied in one machine stroke by flow application. The thickness of this protective cover layer is about 0.5 µm after drying; with constant photosensitivity, the applied, glossy layer improves abrasion and increases the fatigue strength.
Die Werte der folgenden Tabelle werden analog Beispiel 1 ermittelt:
Ein gemäß Beispiel 2 hergestelltes photoleitfähiges System wird in einem Trockentonerkopiergerät hinsichtlich seiner Oberflächeneigenschaften und seiner Photoempfindlichkeit getestet. Zur Entwicklung dient eine Magnetbürsteneinrichtung mit einem Zweikomponententonergemisch, zur Reinigung der Photoleiteroberfläche von restlichem Toner wird die Schicht an einer rotierenden Bürste vorbeigeführt. Dabei zeigt sich, daß unter gleichen Kopierbedingungen die Kopienqualität mit und ohne Deckschicht gleich ist. Im Dauerkopierversuch sind nach 5.000 Kopien bereits starke Oberflächenverfilmungen auf der Photoleiterschicht ohne schützende Deckschicht sichtbar und die Oberfläche ist matter, dagegen sind nur geringfügige Oberflächenverfilmungen auf einer solchen mit Deckschicht erkennbar und die Oberfläche ist noch glänzend.A photoconductive system produced in accordance with Example 2 is tested in a dry toner copier with regard to its surface properties and its photosensitivity. A magnetic brush device with a two-component toner mixture is used for development; the layer is guided past a rotating brush to clean the residual toner from the photoconductor surface. It shows that under the same copying conditions the copy quality is the same with and without the top layer. There are 5,000 copies in the continuous copy test already strong surface films on the photoconductor layer without a protective cover layer are visible and the surface is matte, on the other hand only slight surface films are visible on one with a cover layer and the surface is still shiny.
Zur Verbesserung des Abriebverhaltens können auch zu einer Ladungstransportschicht aus 65 Teilen To und 35 Teilen Cellulosenitrat 5 Gew.-%, bezogen auf Festanteil, mikronisiertes Polyethylen-Wachs (PE) oder mikronisiertes Polytetrafluorethylen (PTFE) eindispergiert werden. Bei der nachfolgenden Beschichtung auf einem Aluminium-Polyesterschichtträger, der mit N,N'-Dimethylperylimid bedampft ist, werden matte, homogene Photoleiterschichten erhalten.In order to improve the abrasion behavior, 5% by weight, based on solids content, of micronized polyethylene wax (PE) or micronized polytetrafluoroethylene (PTFE) can also be dispersed into a charge transport layer composed of 65 parts of To and 35 parts of cellulose nitrate. In the subsequent coating on an aluminum-polyester layer support, which is vapor-coated with N, N'-dimethylperylimide, matt, homogeneous photoconductor layers are obtained.
Photoempfindlichkeit und Abrieb werden gemäß den Angaben in Beispiel 1 bestimmt.
Auf die in Beispiel 4 beschriebenen Photoleiterschichten ohne und mit mikronisiertem Pulverzusatz wird in etwa 2 µm Dicke eine wäßrige Dispersion aus selbstvernetzendem, wärmehärtbaren Reinacrylharz aufgetragen und ca. 10 Minuten bei 110°C im Umlufttrockenschrank getrocknet.An aqueous dispersion of self-crosslinking, thermosetting pure acrylic resin is applied to the photoconductor layers described in Example 4 without and with micronized powder additive and is dried for about 10 minutes at 110 ° C. in a forced-air drying cabinet.
Die homogenen Anordnungen werden einem Abriebtest gemäß Beispiel 1 unterzogen und ergeben:
Hiermit zeigt sich, daß mikronisierte Pulverzusätze, insbesondere in Kombination mit Deckschichten eine deutliche Abriebverminderung ergeben.This shows that micronized powder additives, especially in combination with cover layers, result in a significant reduction in abrasion.
Verschiedene Polycarbonate als Bindemittel (Makrolon(R) 2405, Bayer AG (I) und Lexan(R) 141, General Electric (II)) und ein Polysulfon (Polysulfon(R) 1700 der Union Carbide) zeigten auf Aluminium-Folie, 100 pm dick, geschleudert und ca. 5 Minuten bei 110°C getrocknet, eine sehr gute Abriebfestigkeit.Various polycarbonates as binders (Makrolon (R) 2405, Bayer AG (I) and Lexan (R) 141, General Electric (II)) and a polysulfone (Polysulfon (R) 1700 from Union Carbide) showed on aluminum foil, 100 pm thick, spun and dried for approx. 5 minutes at 110 ° C, very good abrasion resistance.
Gemäß Beispiel 1 wird der Abrieb festgestellt mit:
Auf eine Photoleiterschicht, wie in Beispiel 1 beschrieben, wird eine Lösung aus Polycarbonat I in Tetrahydrofuran mittels Maschinenstrich/Fließerantrag in ca. 2 pm Dicke geschichtet. Nach Trocknung wird ein Abrieb von 0,04 g/m2 gemessen.A solution of polycarbonate I in tetrahydrofuran is layered onto a photoconductor layer, as described in Example 1, by means of machine coating / flow application in a thickness of approximately 2 pm. After drying, an abrasion of 0.04 g / m 2 is measured.
Claims (11)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19803032774 DE3032774A1 (en) | 1980-08-30 | 1980-08-30 | ELECTROPHOTOGRAPHIC RECORDING MATERIAL |
DE3032774 | 1980-08-30 |
Publications (4)
Publication Number | Publication Date |
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EP0046959A2 true EP0046959A2 (en) | 1982-03-10 |
EP0046959A3 EP0046959A3 (en) | 1982-07-28 |
EP0046959B1 EP0046959B1 (en) | 1985-10-02 |
EP0046959B2 EP0046959B2 (en) | 1990-12-19 |
Family
ID=6110782
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81106554A Expired - Lifetime EP0046959B2 (en) | 1980-08-30 | 1981-08-24 | Electrophotographic recording material |
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Country | Link |
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US (1) | US4390609A (en) |
EP (1) | EP0046959B2 (en) |
JP (1) | JPS5789764A (en) |
AU (1) | AU540031B2 (en) |
DE (2) | DE3032774A1 (en) |
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EP0394142A2 (en) * | 1989-04-20 | 1990-10-24 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member |
EP0433949A2 (en) * | 1989-12-22 | 1991-06-26 | Eastman Kodak Company | Thermally assisted transfer of electrostatographic toner particles to a thermoplastic bearing receiver |
EP0433950A2 (en) * | 1989-12-22 | 1991-06-26 | Eastman Kodak Company | Thermally assisted method of transferring small electrostatographic toner particles to a thermoplastic bearing receiver |
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JPS58117554A (en) * | 1982-01-04 | 1983-07-13 | Kanto Denka Kogyo Kk | Carrier for electrophotography |
US4482599A (en) * | 1982-07-06 | 1984-11-13 | Exxon Research & Engineering Co. | Support layer for electric discharge transfer materials |
US4495263A (en) * | 1983-06-30 | 1985-01-22 | Eastman Kodak Company | Electrophotographic elements containing polyamide interlayers |
US4599286A (en) * | 1984-12-24 | 1986-07-08 | Xerox Corporation | Photoconductive imaging member with stabilizer in charge transfer layer |
US4563408A (en) * | 1984-12-24 | 1986-01-07 | Xerox Corporation | Photoconductive imaging member with hydroxyaromatic antioxidant |
US5250990A (en) * | 1985-09-30 | 1993-10-05 | Canon Kabushiki Kaisha | Image-bearing member for electrophotography and blade cleaning method |
US4863822A (en) * | 1987-03-09 | 1989-09-05 | Ricoh Company Ltd. | Electrophotographic photoconductor comprising charge generating and transport layers containing adjuvants |
JPS6479752A (en) * | 1987-09-21 | 1989-03-24 | Seiko Epson Corp | Organic electrophotographic sensitive body |
DE3832453A1 (en) * | 1987-09-25 | 1989-04-06 | Minolta Camera Kk | PHOTO-SENSITIVE ELEMENT |
JP2719141B2 (en) * | 1988-01-20 | 1998-02-25 | 株式会社リコー | Electrophotographic photoreceptor |
US5888654A (en) * | 1988-02-08 | 1999-03-30 | Courtaulds Performance Films | High performance epoxy based laminating adhesive |
JP2595635B2 (en) * | 1988-03-24 | 1997-04-02 | 富士電機株式会社 | Electrophotographic photoreceptor |
US5102757A (en) * | 1988-09-13 | 1992-04-07 | Fuji Xerox Co., Ltd. | Electrophotographic photosensitive member and image forming process |
US5006435A (en) * | 1988-10-05 | 1991-04-09 | Fuji Xerox Co., Ltd. | Electrophotographic photosensitive member with additive in charge generating layer |
US4983481A (en) * | 1989-01-03 | 1991-01-08 | Xerox Corporation | Electrostatographic imaging system |
US5055366A (en) * | 1989-12-27 | 1991-10-08 | Xerox Corporation | Polymeric protective overcoatings contain hole transport material for electrophotographic imaging members |
US5096795A (en) * | 1990-04-30 | 1992-03-17 | Xerox Corporation | Multilayered photoreceptor containing particulate materials |
US5096796A (en) * | 1990-05-31 | 1992-03-17 | Xerox Corporation | Blocking and overcoating layers for electroreceptors |
US5089364A (en) * | 1990-10-26 | 1992-02-18 | Xerox Corporation | Electrophotographic imaging members containing a polyurethane adhesive layer |
US5187496A (en) * | 1990-10-29 | 1993-02-16 | Xerox Corporation | Flexible electrographic imaging member |
JP2790380B2 (en) * | 1990-12-07 | 1998-08-27 | キヤノン株式会社 | Electrophotographic photosensitive member, electrophotographic apparatus and facsimile using the same |
US5149609A (en) * | 1990-12-14 | 1992-09-22 | Xerox Corporation | Polymers for photoreceptor overcoating for use as protective layer against liquid xerographic ink interaction |
US5166021A (en) * | 1991-04-29 | 1992-11-24 | Xerox Corporation | Photoconductive imaging members with polycarbonate fluorosiloxane polymer overcoatings |
US5686214A (en) * | 1991-06-03 | 1997-11-11 | Xerox Corporation | Electrostatographic imaging members |
JPH0588382A (en) * | 1991-09-30 | 1993-04-09 | Idemitsu Petrochem Co Ltd | Electrophotographic sensitive body |
US5626998A (en) * | 1995-06-07 | 1997-05-06 | Xerox Corporation | Protective overcoating for imaging members |
US5728499A (en) * | 1997-06-13 | 1998-03-17 | Sinonar Corp. | Protective layer composition of electrophotographic photoreceptor |
US6197463B1 (en) | 1998-05-15 | 2001-03-06 | Mitsubishi Chemical Corporation | Electrophotographic photosensitive bodies |
US6326429B1 (en) * | 1999-08-04 | 2001-12-04 | Pcc Structurals, Inc. | Polymeric organic carbonate materials useful as fillers for investment casting waxes |
US7147978B2 (en) * | 2001-10-26 | 2006-12-12 | Samsung Electronics Co., Ltd. | Electrophotographic photoreceptors with novel overcoats |
KR100503076B1 (en) * | 2002-11-28 | 2005-07-21 | 삼성전자주식회사 | Overcoat layer composition and organic photoconductor using the same |
US20070092817A1 (en) * | 2005-10-25 | 2007-04-26 | Xerox Corporation | Imaging member |
US8883384B2 (en) * | 2005-12-13 | 2014-11-11 | Xerox Corporation | Binderless overcoat layer |
US7759032B2 (en) * | 2005-12-13 | 2010-07-20 | Xerox Corporation | Photoreceptor with overcoat layer |
US7572561B2 (en) * | 2006-02-22 | 2009-08-11 | Xerox Corporation | Imaging member |
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- 1981-08-18 AU AU74265/81A patent/AU540031B2/en not_active Ceased
- 1981-08-24 EP EP81106554A patent/EP0046959B2/en not_active Expired - Lifetime
- 1981-08-24 DE DE8181106554T patent/DE3172532D1/en not_active Expired
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0394142A2 (en) * | 1989-04-20 | 1990-10-24 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member |
EP0394142A3 (en) * | 1989-04-20 | 1991-03-27 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member |
EP0433949A2 (en) * | 1989-12-22 | 1991-06-26 | Eastman Kodak Company | Thermally assisted transfer of electrostatographic toner particles to a thermoplastic bearing receiver |
EP0433950A2 (en) * | 1989-12-22 | 1991-06-26 | Eastman Kodak Company | Thermally assisted method of transferring small electrostatographic toner particles to a thermoplastic bearing receiver |
EP0433949A3 (en) * | 1989-12-22 | 1992-04-15 | Eastman Kodak Company | Thermally assisted transfer of electrostatographic toner particles to a thermoplastic bearing receiver |
EP0433950A3 (en) * | 1989-12-22 | 1992-04-15 | Eastman Kodak Company | Thermally assisted method of transferring small electrostatographic toner particles to a thermoplastic bearing receiver |
Also Published As
Publication number | Publication date |
---|---|
EP0046959A3 (en) | 1982-07-28 |
AU540031B2 (en) | 1984-10-25 |
US4390609A (en) | 1983-06-28 |
JPH0363064B2 (en) | 1991-09-27 |
EP0046959B1 (en) | 1985-10-02 |
AU7426581A (en) | 1982-03-11 |
JPS5789764A (en) | 1982-06-04 |
DE3172532D1 (en) | 1985-11-07 |
DE3032774A1 (en) | 1982-05-06 |
EP0046959B2 (en) | 1990-12-19 |
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