Classifications

• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
  • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
  • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes

Definitions

• the invention relates to a planar electroluminescent (EL) luminous system based on at least one inorganic thick-film AC electro-electrcence (EL) element, a process for its production and its use.
• the electroluminescent (EL) system according to the invention is characterized in particular by this in that an electroluminescence (EL) emission takes place only in the areas in which there is an overlap of the electrodes used in each case in the element.
• the at least two EL elements can be operated with temporally variable brightness values and overlapping luminous regions, so that, for example, a flowing water can be represented.
• EP 1 026 923 B1 discloses an electroluminescent lamp for emitting light in a plurality of colors starting from a front surface side of a transparent substrate.
• the intended construction of the lamp is based on a first light-transmissive electrode layer on the rear side of the substrate, on which a first phosphor layer and an interposed light-permeable electrode layer and a second phosphor layer and a backward ge Elöktrodentik are applied.
• some dyes are disclosed which provide appropriate coloration depending on the arrangement in the various layers wherein the dye, which is closer to the back electrode of the at least two elements, has a color with a longer wavelength than the more distant dye ,
• this publication discloses a multicolor and multilayer EL lamp system with complete light-transmissive electrode layers, which, however, does not produce any surface discontinuous, i. flat interrupted, shows the emission of electroluminescence.
• an electroluminescent (EL) luminous system based on at least one inorganic thick-film AC electroluminescent element (EL element) which is at least single-layered,
• the at least one EL element used in the at least one-layer electroluminescent (EL) luminous system according to the invention has at least two electrically conductive planar electrodes, these electrode surfaces being arranged relative to one another so that there is no complete covering of the electrode surfaces. This ensures that the EL emission takes place only in the areas in which an overlap of the two corresponding electrode surface elements is given.
• the electrodes used in the respective EL elements can be designed graphically in the context of the present invention.
• an incomplete coverage of the electrodes is understood to mean that in general from 1 to 99%, preferably from 5 to 90%, particularly preferably from 1 to 85%, are present. particular 1 5 to 80%, especially 20 to 70%, cover the respective at least two corresponding electrodes.
• any combination of two electrode surface elements which include at least one electroluminescent layer and optionally an insulating layer (dielectric layer), can be used as an electroluminescent capacitor for generating luminous effects (electroluminescence (EL) arrangement).
• EL electroluminescence
• floating electrode ie a non-floating electrode
• two electrodes are connected to alternating voltage in such a way that they are charged oppositely, wherein the electrodes preferably do not completely overlap one another
• Layers are arranged and are brought into interaction with a third or further electrode or electrodes above, below or below them.
• a electro-luminescent layer or several electro-luminescent layers are arranged between the electrodes in order to produce luminous effects.
• the various electrodes can be controlled in a variety of combinations of galvanic coupling or separation.
• a "floating electrode 11 is driven by a galvanic separation of the two connected to AC voltage electrodes.
• the electroluminescent lighting system according to the invention may comprise one or more EL elements. If the electroluminescent luminous system according to the invention comprises an EL element, it is referred to as single-layered, ie in the context of the present invention an electroluminescent element in the electroluminescent luminous system is defined as a layer. If several electroluminescent elements are provided in the electroluminescent lighting system according to the invention, then the Eiektrolumineszenz lighting system accordingly referred to as multi-layered.
• the remainder of the structure of the electroluminescent system according to the invention corresponds to the structure of conventional systems known from the prior art.
• an EL layer is generally arranged, with the EL emissions occurring only in the covering electrode areas, as already explained.
• the emission color can be one or more colors, depending on the structure of the pigment layer.
• the electroluminescent system can be changed and designed by the graphic design of at least one of the two at least required electrodes per electroluminescent element.
• an electroluminescence emission corresponding to the graphic design of the planar electrodes is thus achieved by the EL system according to the invention.
• different dynamic lighting effects can be achieved by applying varying alternating voltages with respect to voltage level and optionally the frequency. These luminous effects are particularly pronounced when the electroluminescent system according to the invention has at least two electroluminescent elements, which are controlled independently of one another.
• Another object of the present invention is a process for producing such multilayer EL system according to the invention by means of screen printing.
• the EL luminous system is subjected to a three-dimensional deformation, for example by being placed in an injection molding tool to form a 3D EL luminous system.
• a three-dimensional deformation for example by being placed in an injection molding tool to form a 3D EL luminous system.
• injection molding tool for example, with molded thermoplastic molding, subjected.
• Another object of the present invention is the use of the EL system according to the invention as a lamp, as a promotional object, as an artistic structure and the like.
• the electroluminescent systems provided according to the invention are thus generally based on a thick-film inorganic AC element, which can be produced, for example, with conventional fluid bed and Zyiindersieb- druck ⁇ nl ⁇ gen.
• a thick-film inorganic AC element which can be produced, for example, with conventional fluid bed and Zyiindersieb- druck ⁇ nl ⁇ gen.
• FIG. 1 shows a schematic section of an exemplary inventive EL system (1) based on at least one inorganic thick-film AC electroluminescent (EL) element
• Figure 2 a schematic plan view of an inventive EL
• FIG. 3 shows a schematic plan view of the contoured front electrode 42 of an EL lighting system according to the invention
• FIG. 4 shows a schematic top view of the contoured back-molding (43) of an EL lighting system according to the invention.
• FIG. 1 shows a schematic section of an exemplary inventive EL luminous system (1) based on at least two inorganic thick-film AC electroluminescent (EL) elements (2, 3).
• the EL luminous system according to the invention can generally have a Any number of inorganic thick film AC electroluminescent (EL) elements include and are not limited to the presence of two electroluminescent elements as exemplified in FIG.
• EL elements are used in the electroluminescent luminous system since the layer structure is complex and the luminous effect becomes less favorable as the number of layers and electroluminescent elements increases the individual electrode layers and EL layers do not provide 1% light transmission.
• the basic principle according to the invention can be extended to any large number of EL elements.
• an insulating layer can be arranged, which in FIG. 1 is identified by the reference number (44) between the two electroluminescent elements (2). and (3).
• the lower electrode and / or the lower insulation layer can not be translucent opaque be formed (electroluminescent emission visible to the upper observer (26)) or it may be the top electrode and / or the upper insulating layer not opaque opaque formed (electroluminescence emission visible to the lower observer (27)).
• an EL emission region 1 (31, 31 ') of the upper EL element 1 (2) and an EL emission region 2 (32, 32') of the lower EL element are shown 2 (3). Furthermore, the representation is selected such that the two EL emission regions (31, 31 ', 32, 32') have an overlapping region (33, 33 '). However, this choice of the individual emission regions is chosen arbitrarily in this figure and can be changed as desired in the context of the present invention.
• the emissivity fields are determined by the choice of the EL pigments (EL phosphors, electroluminescent phosphors) (1 6, 1 7) in the EL layers (1 2, 1 3).
• the electroluminescence used in one of the electroluminescent layers Pigments generally have a thickness of 1 to 50 ⁇ m, preferably 5 to 25 ⁇ m.
• Thick-film AC-EL elements often comprise zinc sulfide electro-luminophores which, however, are subject to very high degradation especially at higher temperatures and in a water vapor environment. Therefore, for long-lived thick film AC electroluminescent elements, microencapsulated EL pigments are generally used. However, it is also possible to use non-microencapsulated pigments in the EL elements of the present invention, as further explained below.
• electro-luminescent layers of all electroluminescent elements which are used in the electroluminescent system according to the invention wherein the individual electroluminescent layers may be the same or different.
• the electroluminescent element used according to the invention comprises at least one electroluminescent layer as layer BC.
• the layer BC can also be formed from several layers with electroluminescence effect.
• the at least one electroluminescent layer BC is generally arranged between the cover electrode (component BA) or, if appropriate, a dielectric layer (component BB) and the dielectric layer (component BD).
• the electroluminescent layer can be arranged immediately after the dielectric layers BB and BD or optionally one or more further layers can be arranged between the respective dielectric layers BB and BD and the electroluminescent layer BC.
• the Elektroluminesze ⁇ z layer BC disposed immediately in connection to the dielectric layers BB and BD.
• the at least one ES electroluminescent layer can be arranged on the entire inner surface of the cover electrode (component BA) or insulation layer (component BD) or can be arranged on one or more partial surfaces of the cover electrode.
• the electroluminescent layer is not closed but arranged on a plurality of partial surfaces, for example the cover electrode, the partial surfaces generally have a spacing of 0.5 to 500 mm, preferably of 0.5 to 50.0 mm , more preferably 1 to 5 mm from each other.
• the electro-luminescent layer consists of two or more juxtaposed electroluminescent layer elements with different EL pigments, so that different colors can be produced by the EL element.
• the electroluminescent layer is generally composed of a binder matrix with homogeneously dispersed EL pigments therein.
• the binder matrix is generally selected such that a good adhesion bond is provided on the top electrode layer (component BA) or the dielectric layer (component BB) and the dielectric layer (component BD).
• PVB or PU-based systems are used.
• further additives may optionally be present in the binder matrix, such as color-converting organic and / or inorganic systems, color additives for a day and night light effect and / or reflective and / or light-absorbing effect pigments, such as aluminum flakes, glass flakes or mica platelets.
• the proportion of the electroluminescent pigments in the total mass of the electroluminescent layer is from 20 to 75% by weight, preferably from 50 to 70% by weight.
• the electro-luminescent pigments used in the electro-luminescent layer generally have a thickness of from 1 to 50 ⁇ m, preferably from 5 to 25 ⁇ m.
• Thick-film AC-EL elements have been known since Destriau 1 947 and are usually applied by screen printing to ITO-PET films. Since zinc sulfide E-prisms have a very high degradation during operation, especially at higher temperatures and in a water vapor environment, today, for long-lived thick-fumed AC-EL lamp assemblies, generally microencapsulated EL pigments are used. However, it is also possible to use non-microencapsulated pigments in the electro-luminescent element used according to the invention, as will be explained further below.
• Suitable electroluminescent screen printing pastes are generally based on inorganic substances. Suitable substances are, for example, high-purity ZnS, CdS, Zn x Cd 1 . X S x S gleiche ⁇ the groups IiB and IV of the Periodic Table of the Elements, with ZnS is particularly preferably used.
• the aforementioned substances may be doped or activated and optionally further co-activated. For doping, for example copper and / or manganese are used. Coactivation takes place, for example, with chlorine, bromine, iodine and aluminum. The content of alkali and rare earth metals is generally very low in the abovementioned substances, if they are present at all. Very particular preference is given to using ZnS, which is preferably doped or activated with copper and / or manganese and is preferably co-activated with chlorine, bromine, iodine and / or aluminum.
• Common electroluminescent emission colors are yellow, green, green-blue, blue-green and white, where the emission color can be generated white or red by mixtures of suitable EL pigments or by color conversion.
• the color conversion can generally take place in the form of a converting layer and / or the addition of corresponding dyes and pigments in the polymeric binder of the screen printing inks or the polymeric matrix in which the electroluminescent pigments are incorporated.
• the screen printingmix used for producing the electroluminescent layer is generally provided with translucent, color-filtering or color-converting dyes and / or pigments. In this way, an emission color white or a day-night light effect can be generated.
• pigments are used in the electroluminescent layer which have an emission in the blue wavelength range of 420 to 480 nm and are optionally provided with a color-converting microencapsulation. In this way, the color white can also be emitted,
• the AC-P-EL screen printing matrix preferably has wavelength-converting inorganic fine particles based on europium (II) activated alkaline earth-ortho-silicate silicate phosphors, such as (Ba, Sr, Ca) 2 SiO 4 IEu 2 + , or as well YAG YAG phosphors such as Y 3 Al 5 O 12 ICe 3+, or Tb 3 Al 5 O 12: Ce 3+, or Sr 2 Ga 4: Eu 2+, or SrSiEu 2 +, or ⁇ Y, Lu, Gd , Tb) 3 (Al, Sc, Ga) 5 O 12 ) Ce 3 + or (Zn, Ca, Sr) (S, Se): Eu 2+ . Also in this way, a white emission can also be achieved.
• europium (II) activated alkaline earth-ortho-silicate silicate phosphors such as (Ba, Sr, Ca) 2 SiO 4 IEu 2 + , or as
• the above-mentioned EL pigments can be microencapsulated. Due to the inorganic microencapsulation technology, good half-lives can be achieved.
• One example is called here from E. L du Pont de Nemours and Companies the electroluminescent screen printing system Luxprint ® for EL.
• Organic microencapsulation technologies and film-wrap laminates based on the various thermoplastic films are also suitable in principle.
• Suitable zinc sulfide microencapsulated EL pigments are sold by Osram Sylvania, Inc. Towanda under the trade name GIA cierGLO ® Standard, High Brite ® and Long Life ® and by the company Durei
• the average particle diameters of the microvectored pigments used in the electroluminescent layer are generally 15 to 60 ⁇ m, preferably 20 to 35 ⁇ m.
• non-microencapsulated fine-grained electroluminescent pigments can also be used in the electroluminescent layer of the electroluminescent element used in accordance with the invention.
• Suitable non-microsized fine-grain zinc sulfide electroluminescent phosphors are e.g. in US 6,248,261 and WO 01/34723, the disclosure of which is incorporated by reference into the present invention. These preferably have a cubic crystal structure.
• the non-microencapsulated pigments preferably have average particle diameters of from 1 to 30 .mu.m, particularly preferably from 2 to 15 .mu.m, very particularly preferably from 5 to 10 .mu.m.
• non-microencapsulated electroluminescent pigments can be used with smaller pigment dimensions down to less than 10 ⁇ m,
• the starting materials for the electroluminescent layer used in accordance with the present application can therefore also be admixed with uncapped pigments, preferably taking into account the specific hygroscopic properties of the pigments, preferably the ZnS pigments.
• binders are generally used which, on the one hand, have good adhesion to so-called 1TO layers (indium-tin oxide) or intrinsically conductive polymeric transparent layers, and furthermore have a good insulating effect, reinforce the dielectric and thus improve the Dielectric strength at high electrical FeId- strengths cause, and additionally have a good water vapor barrier in the cured state and additionally protect the phosphorus pigments and life-longing effect.
• the half-lives of the suitable pigments in the electroluminescent layer ie the time in which the initial brightness of the electroluminescent element used according to the invention has dropped to half. are generally at 1 00 or 80 volts and 400 hertz 400 to 7000 hours.
• the brightness values are generally 1 to 200 Cd / m 2 , more preferably 1 to 100 Cd / m 2 , in particular in the range of 5 to 70 Cd / m 2 .
• pigments with longer or shorter half-lives and higher or lower brightness values can also be used in the electroluminescent layer of the electroluminescent element used in the electroluminescent device according to the invention.
• the pigments present in the electroluminescent layer have such a small average particle diameter, or such a low degree of filling in the electroluminescent layer, or the individual electro-luminescent layers are embodied geometrically so small, or the distance of the individual electroluminescent layers is chosen to be so large that the electroluminescent element is designed as non-electrically activated luminous structure as at least partially transparent or a see-through is ensured, Suitable Pigmentteiiche ⁇ trimmesser, Gregrade, dimensions of the luminous elements and distances of Leuchtelerrtente are vorste- hend called.
• the electroluminescent layer has pigments of different colors.
• the electroluminescent layer preferably has two, more preferably three, in particular four, especially five, more particularly six, pigments of different colors.
• the pigment layer can be configured multicolored.
• the differently colored pigments can be arranged in the electroluminescent layer such that different colored surfaces, contours and / or structures are formed in this layer.
• the electroluminescent layer in the electroluminescent element is based on an EL pigment emitting the color green and in the electroluminescent layer on homogeneously dispersed color conversion pigments.
• color conversion pigments "EL Color Converting Pigments FA-OOO Series" 1 from Sinloihi Co., Ltd. Japan come into question, and it is also possible to add a color-converting substance, such as rhodamine, so that a white emission is achieved.
• a locally and wavelength-different light field is possible by selecting at least two electroluminescent layers arranged side by side with different EL pigments. Such a locally and wavelength different light field can be achieved.
• the electroluminescent layer itself is contoured and / or structured. It is possible that the electroluminescent layer is not filled with pigment in the entire layer plane.
• the regions of the electroluminescent layer not filled with pigment can be filled with transparent, opaque, and / or opaque insulation material to form a closed layer.
• the filled with transparent, opaque and / or opaque insulation material areas may in turn be contoured and / or structured.
• the electroluminescent luminous system according to the invention comprises more than two electroluminescent elements, it is preferred according to the invention for the pigment-filled regions of the electroluminescent layer not to overlap or only partially overlap,
• the electroluminescent lighting system according to the invention comprises more than two electroluminescent elements, it is also preferred according to the invention for regions of two or more electroluminescent elements filled in particular with different material to be present cover or at least overlap. For example, areas filled with pigment of a particular color may overlap in one layer with regions in another layer which are filled with differently colored pigment and / or with transparent, opaque and / or opaque insulation material.
• the electroluminescent layer in the electroluminescent element is based on a green-emitting EL pigment and in the electroluminescent layer homogeneously dispersed color conversion pigments.
• color conversion pigments "EL Color Converting Pigment FA-000 Series" from the company Sinloihi Co., Ltd. Japan in question.
• a color-converting substance such as rhodamine
• color-converting admixtures can be added to the polymeric binder matrix. As a result, such Welien artnverschiebept can be achieved by a few 10 to about 1 00 nm in terms of a Stokes shift.
• color-filtering, translucent or transient graphical layers (6, 7, 14, 15) can be used for the design of the emission colors.
• These graphic print layers (6, 7, 14, 15) can also have masking opaque properties or reflective or semi-damaging properties.
• day-night effects can be generated with these print layers (6, 7, 14, 15).
• luminescent organic substances and inorganic pigments can be used in these printing layers.
• the electroluminescent system according to the invention is operated by an electroluminescent voltage supply with an alternating voltage in the range from 200 Hz to more than 1 000 Hz.
• the electroluminescent luminous system has a flexible design.
• the electroluminescent layer is therefore preferably produced by screen printing, as this results in a good Fiexibiitician and foldability of the resulting electroluminescent layer.
• a polymeric elastic binder matrix preferably polyurethane-based, and more preferably in a two-component embodiment, is used in this binder polymer, the zinc-sulfidic EL pigments are then dispersed.
• the inventively provided electroluminescent system based on zinc sulfide thick-film AC alternating current electroluminescence is thus an electroluminescent system, which is particularly suitable for the required flexibility or deformability.
• isolation layers dielectric layers
• the individual insulation layers may be the same or different.
• the insulating layer (4) or the insulating layer (5) can be used as the printing substrate film.
• an insulating layer can also be laminated or laminated on as intermediate film; As a result, the production process can be simplified and / or the three-dimensional deformability of the resulting electroluminescent lighting system according to the invention can be improved.
• the insulating layers (4, 5) in the form of transparent films will be described as a printing substrate.
• the electroluminescent lighting system according to the invention comprises more than two electroluminescent elements, it may also comprise more than just the two insulating layers (4, 5).
• the description of the insulation layer disclosed below also applies in this case to all other insulation layers.
• the insulating film (4, 5) is in single or multiple use in sheet form or in roll form with a thickness of generally 5 .mu.m up to 2 mm, preferably with a thickness of 20 .mu.m to 500 .mu.m, especially preferably used with a thickness of 70 microns to 250 microns, most preferably with a thickness of 75 microns to 1 75 microns.
• the insulating film (4, 5) is preferably transparent and may have high-gloss, matt, semi-matt and / or textured surfaces.
• the surface of the insulating layer (4, 5) to the observer (26, 27) can moreover be embodied in a mirrored manner or be provided with a so-called "hardcoat” coating Moreover, in principle, it can additionally be used in a graphically printed manner usually polycarbonate (PC), PET, PET-G, PMMA, PVC, or PVF (Tedlar ®) or any desired blends of the aforementioned polymers used
• the film (4) should moreover have sufficient temperature resistance without excessive shrinkage, since during the drying of the individual layers an increased temperature substantially affects the drying time.
• pre-tempered films (4) can be used in which the shrinkage problem with respect to the exact positioning of the individual printed layers is substantially reduced.
• the film (4) can be provided on the underside with a graphic design in the sense of masking, translucent or translucent layers.
• Corresponding dielectric layers can also be obtained starting from dielectrically acting powders, such as, for example, barium titanate, which are preferably dispersed in fluorine-containing plastics or in cyan-based resins.
• dielectrically acting powders such as, for example, barium titanate, which are preferably dispersed in fluorine-containing plastics or in cyan-based resins.
• particularly suitable particles are barium titanate particles in the range of preferably 1, 0 to 2.0 microns, these can give a relative high dielectric constant of up to 1 00 at a high degree of filling.
• the dielectric layer in the case of dielectrically acting powders has a thickness of generally 1 to 50 ⁇ m, preferably 2 to 40 ⁇ m, more preferably 5 to 25 ⁇ m, especially 8 to 20 ⁇ m.
• this layer is preferably designed to be flexible and foldable. This is achieved, for example, by a polyurethane-based and more particularly by a two-component PU screen printing ink, it being possible to add barium titanate (BaTiO 3 ) pigments of the abovementioned type to increase the relative dielectric constant. In this way, a relative dielectric constant of 30 to 200 can be achieved.
• this layer can also be used for the reflection of the electroluminescence emission. If, in addition to electroluminescent emission at the top, electroluminescence down emission is still required, then BaTiO 3 competing should not occur.
• the dielectric layer can also be carried out twice or more times, since especially in screen printing the installation of small air bubbles (micro-bubbles) can not be avoided and in a double screen printing this problem can be solved.
• the electrode (8) is preferably arranged by screen printing and can be contoured graphically.
• the other electrodes used in the context of the present invention are generally applied by means of screen printing and can also be contoured graphically. In the following, the materials used for the electrodes are described in more detail:
• Suitable electrically conductive materials for the electrodes are known per se to those skilled in the art.
• several types of electrodes are suitable for the production of thick-film EL elements with AC excitation.
• they are indium-tin sputtered or vapor-deposited on plastic films in a vacuum Oxide electrodes (indium tin oxides, ITO), they are very thin (some 1 00 ⁇ ) and offer the advantage of high transparency with a relatively low sheet resistance (approx. 60 to 600 ⁇ ).
• Non-ITO screen printing layers encompasses all screen printing layers which are not based on indium-tin-oxide (ITO)
• ITO indium-tin-oxide
• ie intrinsically conductive polymer layers with usually nanoscale electrically conductive pigments for example the ATO screen-printing pastes with the designations 7162E or 7164 from DuPont
• the intrinsically conductive polymer systems such as Orgacon ® system from Agfa, the Baytron ® poly (3,4-ethylenedioxythiophene) system H. C.
• tin oxide (NESA) pastes are also usable as the corresponding electrode material.
• the electrically conductive coating is a thin and largely transparent layer which is formed by means of a vacuum or a pyrolytically produced metallic or metal-oxide thin layer and which is preferably a thin layer.
• the sheet resistance in small EL lighting arrangements (1) can be relatively large and should be chosen correspondingly lower for large EL lighting arrangements (1).
• a high surface resistance can often be compensated by an optimal arrangement of the respective busbars (1 8) to (21) of the electrode.
• Electrodes of intrinsically conductive polymers should generally be smaller than 5k ⁇ / square, preferably 100 to 2000 ⁇ / square, more preferably 200 to 1500 ⁇ / square, especially 200 to 1000 ⁇ / square, especially 300 to 600 ⁇ / square.
• the electrode materials can be applied, for example, by screen printing, knife coating, spraying, brushing onto corresponding carrier materials (substrates), by vacuum or pyrolytically onto corresponding carrier materials (substrates), preferably subsequently drying at low temperatures of, for example, 80 to 110 ° C.
• the back electrode (component BE) is - as with the at least partially transparent cover electrode (component BA) - a planar electrode, which, however, need not be transparent or at least partially transparent.
• This is generally made of electrically conductive materials built up inorganic or organic base, for example, metals such as silver.
• Suitable electrodes are further in particular polymeric electrically conductive coatings.
• the coatings already mentioned above with regard to the at least partially transparent cover electrode can be used.
• it is possible to use those polymeric, electrically conductive coatings which are known to the person skilled in the art and which are not at least partially transparent.
• Suitable materials of the back electrode are thus preferably selected from the group consisting of metals such as silver, carbon, ITO screen printing layers, ATO screen printing layers, non-ITO screen printing layers, ie intrinsically conductive polymeric systems with usually nanoscale electrically conductive pigments, for example ATO screen printing pastes with the designation 7162E or 71 64 by DuPont, intrinsically conductive polymer systems such as Orgacon ® system from Agfa, the Clevios ® poly (3,4-ethylenedioxythiophene) ⁇ system of HC Starck GmbH, which (as an organic metal PEDT conductive polymer polyethyle- ne-dioxythiophene) system of Ormecon, conductive coating and printing ink systems from Panipof Oy and optionally with highly flexible binders, for example based on PU (polyurethanes), PMMA (polymethyl methacrylate), PVA (polyvinyl alcohol) or Modified Polyaniiin, wherein the above materials
• the cover electrode (component BA) comprises nanostructured particles.
• the back-electrode comprises particles with nanostructures.
• both the top electrode and the back electrode comprise particles with nanostructures.
• particles with nanostructures is understood to mean nanoscale material structures, which are selected from the group consisting of single-walled carbon nano-tubes (SWCNTs) 1 Mu-ti-wall carbon nano-tubes (MWCNTs), nanohorns, nanodisks, nanocones (ie cone-shaped structures)
• SWCNTs single-walled carbon nano-tubes
• MWCNTs Mu-ti-wall carbon nano-tubes
• nanohorns nanohorns
• nanodisks nanocones (ie cone-shaped structures)
• Corresponding particles with carbon-based nanostructures may, for example, consist of carbon nanotubes (single-shell and multi-shelled), carbon nanofibers (herringbone, leaflet or helical) and the like.
• Carbon nanotubes are also known internationally as carbon nanotubes, (single-walled and multi-walled), and carbon nanofibers as carbon nanofibers (of the heartbeat, platelet, or screw type).
• fractionally pure singly walled carbon nanotubes are preferably used, i. Fractions of single-walled carbon nanotubes which differ in a parameter selected from the group consisting of diameter, length, chirality and electronic properties, at most by 50%, more preferably at most 40%, especially at most 30 %, especially not more than 20%, especially not more than 1 0%.
• the partially transparent electrically conductive flachige top electrode and / or the rear electrode on the basis of an intrinsically conductive polymer, for example, Clevios ® P from HC Starck.
• the electrical conductivity and the deformability-increasing admixtures such as nanoscale particles based on SWCNTs, or silver nanowires, or nano-cones or nanotubes, be added, whereby the transparency is not significantly affected.
• busbar systems are arranged especially in the contact region of the two planar electrodes, and thus the electrical contacts can be designed with a low contact resistance by means of crimping, piercing, clamping or electrically conductive bonding.
• busbars of all electroluminescent elements which are used in the electroluminescent system according to the invention, the individual busbars being the same or different.
• the busbars (1 8) to (21) used for the electrical supply to the electrodes are also preferably produced with the respective electrical connections (22) to (25) by screen printing.
• the corresponding busbars can be formed by highly conductive printable pastes. These pastes may be, for example, opaque silver pastes, copper pastes or carbon pastes.
• the corresponding pastes may also comprise particles with nanostructures in the sense of the present invention.
• Corresponding printing pastes are essentially not subject to any aspect of sheet resistance. restriction. Usually, however, they have a sheet resistance in the range of below 10 milliohms / square to several 100 milliohms / square.
• busbars for a uniform EL emission is suitable.
• the electrical connections (22) to (25) are chosen so that optimal Kunststoff ⁇ réelle is possible depending on the type of application.
• the EL lighting system (1) according to the invention in the form of a film usually bordering positions are favorable for the connections and conventional crimp connections or terminal connections or connections with an electrically conductive adhesive can then be used, in the case of using the EL device according to the invention.
• Lighting system (1) in the form of an injection-molded Einlegitzguss envisages the EL terminals (22) to (25) may be provided in almost any position, the EL emission regions (31, 32, 33) are preferably not selected as a position for the connections.
• the EL layers 1 and 2 (1 2 and 1 3) with the largely homogeneously dispersed EL pigments (16 and 17) in a suitable polymeric binder matrix are likewise preferably applied by means of screen printing, which applies to further electroluminescent layers, if appropriate present in the context of the present invention, also.
• the present invention also includes EL lighting systems in which a somewhat thinner EL layer (1 2) is printed and additionally one or more, preferably two dielectric layers, which are preferably transparent in the present case, are used. In both cases, the most transparent or translucent EL layer (12) should be chosen. This can be achieved as already stated or by having some fine-grained Re EL Pigment ⁇ (16) can be used. Typically, microencapsulated EL pigments (16) with a d 50 in the range from 25 to 30 ⁇ m are used.
• EL pigments (1 6) with a d 50 from 5 microns to 1 7 microns a good translucency with sufficient EL emission (28, 28 ')
• the degree of filling of EL pigments for example below 70 wt .-% be reduced.
• the use of corresponding electroluminescent pigments with the previously defined d 50 values or fill levels may also be advisable for the remaining electroluminescent layers, so that a corresponding transparency, if desired, is achieved.
• the EL layer (12) can also be made in a point-like manner.
• the individual EL pigment points can have a geometrically exact form, such as a circle, an ellipse, a triangle, a quadrangle, a polygon or a star, or an artistically designed form.
• the individual EL pigment points can furthermore be arranged geometrically exactly or arbitrarily in the sense of, for example, a frequency-modulated arrangement.
• the intermediate region between the EL pigment dots should be filled with an insulating layer, the insulating layer preferably having a lower relative dielectric constant compared with that of the EL pigment layer (1 2).
• This embodiment of the pigment layer may also be used for the others Pigment layers of the electroluminescent lighting arrangement according to the invention be advised.
• color-converting dyes or pigments can be incorporated into the polymeric binder matrix of the EL layers provided in the electroluminescent light-emitting system according to the invention in order to achieve a color conversion of a few 10 nm to about 100 nm.
• Typical are hereby pink organic dye pigments from Sinloihi ® be mentioned, which bring about a largely white EL emission in conjunction with a greenish-emitting EL pigment (1 6) (28).
• EL pigment (16) mixtures of two or more EL pigments with different emission wavelengths.
• the electrode 2 (9) is produced in analogy to the electrode 1 (8), wherein according to the invention only the overlapping electrode regions (8, 9) form an EL element (31), with regard to the exact configuration of the electrode 2 (9),
• the composition of the electrode material reference is made to the above statements and to the following description of electroluminescent elements.
• the insulating layer (44) is preferably made in the form of a transparent screen printing layer, but may also be formed in the form of a film analogous to the film (4). Before and / or after the production of the insulating layer (44), graphic prints (1 4, 1 5) can be arranged analogously to the graphic design (6).
• the electroluminescent element 2 (3) is produced in the case of a bilaterally lit EL system (1) in analogy to the EL system 1 (2).
• the electrode 3 (1 0) with the busbar (20) and the EL terminal 3 (24) is arranged according to the desired electrode contour by screen printing on the insulating layer (44) or the graphic design (1 5). Subsequently, the EL layer 2 (1 3) in analogy to the EL layer 1 (1 2) applied by screen printing. With regard to the exact configuration of the EL layer 2 (1 3), reference is made to the above comments on the EL layer 1 (1 2).
• the electrode 4 (1 1) with the busbar (25) and the EL connection 4 (25) is preferably contoured and more preferably applied by means of screen printing.
• the graphic design 4 (7) can be optionally arranged.
• the conclusion forms the insulating layer (5), which can be formed by screen printing. Alternatively or additionally, one or more transparent films can be arranged by laminating.
• the electrode 4 (1 1) does not necessarily have to be transparent and can be made opaque and preferably reflective, for example, and the graphic design 4 (7) can omitted and the insulation (5) can be made opaque.
• FIG. 2 shows a schematic plan view of an EL system (2, 3, 34) with the EL light fields (36, 37) on the film (35). Furthermore, the busbar (38) of the front electrode with the front electrode contact (40) and the busbar (39) of the rear electrode with the back electrode contact (41) are shown schematically. The two EL light fields (36, 37) are formed by overlapping regions of the front electrode (FIG.
• busbars (38, 39) and the BusbarANDe (40, 41) made invisible by the appropriate graphical design or often the busbars ( 38, 39) and contacts (40, 41) are arranged at a lateral edge or at the lateral edges and are thus preferably not visible.
• FIG. 3 shows a schematic plan view of the contoured front electrode (42) with the front electrode busbar (38) and the front electrode contact (40) on the substrate (35).
• FIG. 4 shows a schematic plan view of the contoured rear electrode 43 with the back electrode bus bar 39 and the back electrode contact 41 on the substrate 35.
• the individual electroluminescent elements may be the same or different:
• the electroluminescent element consists of the following layers (conventional structure):
• At least one electroluminescent device, component B, applied to the substrate comprising the following components:
• component BA an at least partially transparent electrode
• component BA as a front electrode (cover electrode)
• component BB optionally an isoiation layer
• component BB bc) a layer containing at least one luminescent pigment (electropoluminophore) which can be excited by an electric field
• the printed conductor or printed conductors can be applied in the form of a silver bus, preferably made of a silver paste. It may be possible to apply a graphite layer before applying the silver bus.
• the insulating layers BB and BD may be opaque, opaque or transparent, wherein at least one of the layers must be at least partially transparent when two insulating layers are present.
• one or more at least partially transparent graphically designed layers can also be arranged.
• the electroluminescent element according to the invention can have one or more reflection layer (s).
• the reflection layer (s) may or may in particular be arranged:
• component A between component A and component BA, between component BA and component BB or BC, if component BB is missing, between component BD and component BE, between component BE and component BF, between component BF and component CA, respectively CB, outside on component CA or CB.
• the reflection layer layer if present, is arranged between component BC and component BD or BE, if component BD is missing.
• the reflection layer preferably comprises glass beads, in particular
• the diameter of the glass beads can in wide
• Borders are changed. Thus, they can have a size d 50 of generally 5 ⁇ m to 3 mm, preferably 10 to 200 ⁇ m, especially preferred. zugt 20 to 1 00 microns, have.
• the hollow glass beads are preferably embedded in a binder.
• the electro-luminescence element consists of the following layers (inverse layer structure):
• component B at least one electroluminescent arrangement, component B, applied to the substrate, comprising the following components
• component BE which may be at least partially transparent, bb) optionally an insulating layer, component BB, bc) a layer containing at least one excitable by an electric field luminescent pigment (electroluminophore), Eugenktrollu- mineszenz layer or pigment layer called , Component BC, bd) optionally an insulating layer, component BD, ba) an at least partially transparent electrode, component BA, as a front electrode (cover electrode), bf) a conductor track or a plurality of conductor tracks, component BF, for electrical contacting of both component BA and component BE, wherein the conductor track or the conductor tracks before, after or between the electrodes BA and BE can be applied or, wherein preferably the conductor track or the conductor tracks are applied in one step.
• the printed conductor or printed conductors can be applied in the form of a silver bus, preferably made of a silver paste. It may be possible to apply a graphite layer before applying the silver bus,
• an at least partially transparent protective layer component CA and / or a film, component CB.
• one or more at least partially transparent graphically designed layers can be arranged on the transparent protective layer C and / or between the transparent protective layer C and the electro-etching system.
• the graphically designed layers can assume the function of the protective layer.
• the abovementioned structures B, C can be mounted both on the front side of the substrate, component A, and on the back side, as well as on both sides of the substrate (two-sided construction).
• the layers BA to BF on both sides may be identical, but they may differ in one or more layers, so that, for example, the electro-luminescent element radiates equally on both sides or the electroluminescent element on each side a different color and / or has a different brightness and / or a different graphic design.
• the electroluminescent element according to the invention with inverse layer structure can have one or more reflection layer (s).
• the reflection layer (s) may or may in particular be arranged:
• component A and component BE between component A and component BE, between component BE and component BB, between component BB and component BC, between component BC and component BD, between component BD and component BA, between component BA and component BF, - between Component BF and component CA or CB, on component CA or CB.
• the reflective layer layer if present, is preferably arranged between component BC and component BB or BE if component BB is missing. It will be apparent to those skilled in the art that the specific embodiments and features of the conventional structure, unless otherwise specified, apply mutatis mutandis to inverse layer construction and two-sided construction.
• the one or more insulation layer (s) BB and / or BD both in the conventional construction and in the inverse construction, can be dispensed with in particular if the component BC has a layer thickness which prevents a short circuit between the two electrode components BA and BE ,
• the expression "at least partially transparent” means an electrode which is made of a material which has a transmission of generally more than 60%, preferably more than 70%, particularly preferably more than 80%. , especially more than 90%.
• the remindeiektrode BE does not necessarily have to be transparent
• Suitable electrically conductive materials for the electrodes are known per se to the person skilled in the art.
• several types of electrodes are suitable for the production of thick-film EL elements with alternating voltage excitation.
• these are sputtered or evaporated indium tin oxide electrodes (indium tin oxide, ITO) on plastic films. They are very thin [some 100 ⁇ ] and offer the advantage of high transparency with a relatively low surface resistance (about 60 to 600 ⁇ ).
• a printing paste for producing the partially transparent electrode BA from 10 to 90% by weight, preferably from 20 to 80% by weight, particularly preferably from 30 to 65% by weight, based in each case on the total weight of the printing paste, Clevi, are preferred according to the invention.
• solvents dimethylsulfoxide (DMSO), N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol, glycerol, sorbitol, methanol, ethanol, isopropanol, N-propanol, acetone, methyl ethyl ketone, dimethylaminoethanol, water or mixtures of two or three or more of the solvents mentioned are used.
• the amount of solvent can vary widely in the printing paste. Thus, in a formulation of a paste according to the invention, 55 to 60% by weight of solvent may be contained, while in another inventive formulation about 35 to 45% by weight of a solvent mixture of two or more solvents may be used.
• an interfacial additive and Adhesion activator Silquest Al 87, Neo Rez R98 ⁇ , Dynol 604 and / or mixtures of two or more of these substances may be included.
• the amount thereof is 0, 1 to 5.0 wt .-%, preferably 0.3 to 2.5 wt .-%, based on the total weight of the printing paste.
• Suitable binders in the formulation are Bayderm Finish 85 UD, Bayhydrol PR340 / 1, Bayhydrol PRI 35 or any mixtures thereof, preferably in amounts of from about 0.5 to 10% by weight, preferably 3 to 5% by weight. to be included.
• the polyurethane dispersions used according to the invention, which after drying the layer form the binder for the conductive layer, are preferably aqueous polyurethane dispersions.
• Particularly preferred formulations of printing pastes according to the invention for producing the partially transparent electrode BA include:
• Electrode materials can be applied to appropriate support materials (substrates), for example Mitteis screen printing, knife coating, spraying, spraying and / or painting, which are then preferably dried at low temperatures of, for example, 80 to 1 to 20 0 C.
• appropriate support materials for example, Mitteis screen printing, knife coating, spraying, spraying and / or painting, which are then preferably dried at low temperatures of, for example, 80 to 1 to 20 0 C.
• the application of the electrically conductive coating takes place by means of vacuum or pyrolytically.
• the electrically conductive coating of a thin or substantially transparent layer produced by means of vacuum or pyrolytically produced metallic or metal oxide which preferably has a sheet resistance of 5 m ⁇ / square to 3000 ⁇ / square, particularly preferably a sheet resistance of 0, 1 to 1 .000 ⁇ / square, very particularly preferably 5 to 30 ⁇ / square, and in another preferred embodiment has a daily permeability of at least greater than 60% (> 60 to 1 00%) and in particular greater than 76% (> 76 to 1 00%).
• electrically conductive glass can also be used as the electrode.
• a particularly preferred type of electrically conductive and highly transparent glass, especially float glass, represent pyrolytically produced layers having a high surface hardness and their e »lectrical surface resistance can be adjusted in a very wide range of generally from a few milliohms to 3,000 ⁇ / square.
• Such pyrolytically coated glasses can be well deformed and have a good scratch resistance, in particular scratches do not lead to an electrical interruption of the electrically conductive surface layer, but only to a mostly slight increase in sheet resistance.
• pyrolytically produced conductive surface layers are so strongly diffused into the surface by the temperature treatment and anchored in the surface that an extremely high adhesion to the glass substrate is given in a subsequent application of material, which is also very advantageous for the present invention.
• coatings have a good homogeneity, ie a low scattering of the surface resistance value over large surface areas. get up. This feature also provides an advantage to the present invention.
• Electrically conductive and highly transparent thin layers can be produced on a glass substrate, which is preferably used according to the invention, much more efficiently and cost-effectively than on polymeric substrates such as PET or PMMA or PC.
• the surface resistivity of glass coatings is 10 times more favorable than on a polymer film with comparable transparency, ie, for example, 3 to 10 D / square for glass layers compared to 30 to 100 ⁇ / square on PET films.
• the back electrode component BE is - as in the case of the at least partially transparent electrode - a planar electrode, which, however, does not have to be transparent or at least partially transparent. This is generally applied to the insulation layer, if any. If no insulation layer is present, the back electrode is applied to the layer containing at least one luminescent substance that can be excited by an electrical field. In an alternative embodiment, the back electrode is applied to the substrate A.
• the return electrode is generally constructed from electrically conductive materials on an inorganic or organic base, for example, from metals such as silver, with preferred are such materials used ⁇ the which are not damaged during the application of isostatic high-pressure forming process for the preparation of the inventive three-dimensionally formed film element.
• Suitable electrodes are furthermore, in particular, polymeric, electrically conductive coatings.
• the coatings already mentioned above with regard to the at least partially transparent electrode can be used.
• such known to the expert pofymeren electrically conductive coatings are used, which are not at least partially transparent.
• the formulation of the Druckp ⁇ ste for the return electrode may correspond to the partially transparent electrode.
• a printing paste for the preparation of the back electrode 30 to 90% by weight, preferably 40 to 80% by weight, particularly preferably 50 to 70% by weight, based in each case on the total weight of the printing paste, of the conductive polymers Clevios P, Cievios PH, Clevios P AG, CIevios P HCV4, Clevios P HS, Cievios PH, Clevios PH 500, Clevios PH 510 or any mixtures thereof.
• Ais solvents may include dimethylsulfoxide (DMSO), N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol, glycerol, sorbitoi, methanol, ethanol, isopropanol, N-propanol, Acfon, MethylethyJketon, dimethylaminoethanol, water or mixtures of two or three or more of these solvents are used.
• the amount of solvent used can vary widely. Thus, in a formulation according to the invention, one paste may contain from 55 to 60% by weight of solvent, while in another formulation according to the invention about 40% by weight of a solvent mixture of three solvents may be used.
• Neo Rez R986, Dynol 604 or mixtures of two or more of these substances may preferably be contained in an amount of 0, 7 to 1, 2 wt .-%.
• binder for example, 0.5 to 1, 5 wt .-% UD-85, Bayhydrol PR340 / 1, Bayhydrol PR l 35 or belibige mixtures thereof may be included.
• the back electrode can be filled with graphite. This can be achieved by adding graphite to the formulations described above.
• the printing pastes of the Orgacon EL-P4000 series can be used especially for the back electrode. Both can be mixed together in any ratio.
• Orgacon EL-P401 0 and EL-4020 already contain graphite.
• graphite pastes can also be used as the back electrode, for example graphite pastes from Acheson, in particular Electrodag 965 SS or Electrodag 601 7 SS.
• a particularly preferred formulation according to the invention of a printing paste for producing the back electrode BE comprises:
• the surface conductance plays an important role for uniform luminance.
• component BF so-called bus bars are used, in particular for halved LEP (light-emitting polymers), PLED and / or OLED systems, in which relatively large currents flow.
• bus bars are used, in particular for halved LEP (light-emitting polymers), PLED and / or OLED systems, in which relatively large currents flow.
• very good electrically conductive tracks are produced in the manner of a cross. In this way, for example, a large area is divided into four small areas.
• the voltage drop in the central region of a luminous surface is substantially reduced and reduces the uniformity of the luminance or the drop in brightness in the middle of a luminous field.
• a zinksulfidischen particulate EL-FeId used in one embodiment of the invention generally greater than 1 00 volts are applied to over 200 volts AC, and it flows when using a good dielectric or good insulation very low currents. Therefore, in the present invention ZnS thick-film AC-EL element the problem of the current load is much lower than with semiconducting LEP or OLED systems so that the A ⁇ set of bus bars is not absolutely necessary, but large luminous elements without the use of bus -bars can be provided.
• the silver bus it is sufficient for the silver bus to be printed on areas below DIN A3 only at the edge of the electrode layer BA or BE; in areas above A3, it is preferred according to Inventive ⁇ that the silver coach forms at least one additional conductor track,
• the electrical connections may be made, for example, using electrically conductive and stovable pastes with tin, zinc, silver, palladium, aluminum, and other suitable conductive metals or combinations and mixtures or alloys thereof.
• the electrically conductive contact strips are generally applied to the electrically conductive and at least partially transparent thin coatings by means of screen printing, brush application, ink jet, doctor blade, roller, spraying or dispensing application or comparable application methods known to the person skilled in the art, and then generally in an oven thermally treated, so that usually attached laterally along a substrate edge strips can be contacted by soldering, terminals or plug electrically conductive.
• conductive adhesive pastes based on silver, palladium, copper or gold filled polymer adhesive are preferably used. It is also possible to apply self-adhesive electrically conductive strips, for example, of tinned copper foil with an adhesive which is electrically conductive in the z-direction, by means of pressing.
• the adhesive layer is generally pressed uniformly with a surface area of several N / cm 2 , and values of 0.01 3 ⁇ / cm 2 (for example, Conductive Copper Foil Tape VE 1691 from D & M International, depending on the design, A-8451 home shoe) or 0.005 ⁇ (for example Type 1 1 83 from 3M Electrical Products Division, Austin, Texas, USA, according to MIL-STD-200 Method 307 maintained at 5 psi / 3.4 N / cm 2 measured over 1 sq in surface area) or 0.001 ⁇ (for example Type 1 345 from 3M) or 0.003 ⁇ (for example Type 3202 from Holland Shielding Systems BV).
• 0.01 3 ⁇ / cm 2 for example, Conductive Copper Foil Tape VE 1691 from D & M International, depending on the design, A-8451 home shoe
• 0.005 ⁇ for example Type 1 1 83 from 3M Electrical Products Division, Austin, Texas, USA, according to MIL-STD-200 Method 307 maintained at
• the contacting can be carried out by all methods familiar to the person skilled in the art, for example crimping, inserting, clamping, riveting, screwing. dielectric layer
• the EL element according to the invention preferably has at least one dielectric layer, component BD, which is provided between the back electrode component BE and the EL layer component BC.
• a further dielectric layer BB may also be present between the cover electrode component BA and the EL layer component BC.
• Corresponding dielectric layers are known to the person skilled in the art. Corresponding layers often have high dielectric powders, such as barium titanate, which are preferably dispersed in fluorine-containing plastics or on cyan-based resins. Examples of particularly suitable particles are barium titanate particles in the range of preferably 1, 0 to 2.0 microns. These can give a relative dielectric constant of up to 100 at a high filling level.
• high dielectric powders such as barium titanate, which are preferably dispersed in fluorine-containing plastics or on cyan-based resins.
• barium titanate particles in the range of preferably 1, 0 to 2.0 microns. These can give a relative dielectric constant of up to 100 at a high filling level.
• the dielectric layer has a thickness of generally 1 to 50 ⁇ m, preferably 2 to 40 ⁇ m, particularly preferably 5 to 25 ⁇ m, especially 8 to 20 ⁇ m.
• the EL element according to the invention can additionally also have a further dielectric layer, which are arranged above one another and together improve the insulation effect or which is interrupted by a floating electrode layer.
• the use of a second die cast layer may depend on the quality and pinhole freedom of the first dielectric layer.
• fillers inorganic insulating materials are used, which are known to those skilled in the literature, for example: BaTiO 3 , SrTiO 3 , KNbO 3 , PbTiO 3 , LaTaO 3 , LiNbO 3 , GeTe, Mg 2 TiO 4 , Bi 2 (TiO 3 J 3 , NiTiO 3 , CaTiO 3 , ZnTiO 3 , Zn 2 TiO 4 , BaSnO 3 , Bi (SnO 3 J 3 , CaSnO 3 , PbSnO 3 , MgSnO 3 , SrSnO 3 , ZnSnO 3 , BaZrO 3 , CaZrO 3 , PbZrO 3 , MgZrO 3 , SrZrO 3 , ZnZrO 3 and lead zikonate titanate mixed crystals or mixtures of two or more of these fillers.
• Preferred fillers according to the invention are BaTiO 3 or PbZrO 3 or mixtures thereof, preferably in quantities of from 5 to 80% by weight, preferably from 10 to 75% by weight, particularly preferably from 40 to 70% by weight, in each case on the total weight of the paste, in the paste for the production of the insulating layer.
• Binders for this layer may be one-component or preferably two-component polyurethane systems, preferably Bayer MaterialScience AG, in turn Desmodur and Desmophen or the coating raw materials of the Lupranate, Lupranol, Pluracol or Lupraphen series from BASF AG; Degussa AG (Evonik), preferably Vestanat, again particularly preferred Vestanat T and B; or the Dow Chemical Company, again preferably Vorastar; be used.
• Bayer MaterialScience AG Desmodur and Desmophen or the coating raw materials of the Lupranate, Lupranol, Pluracol or Lupraphen series from BASF AG; Degussa AG (Evonik), preferably Vestanat, again particularly preferred Vestanat T and B; or the Dow Chemical Company, again preferably Vorastar; be used.
• highly flexible binders for example those based on PMMA, PVA, in particular Mowiol and Poval from Kuraray Specialties Europe GmbH or Poiyvioi from Wacker AG, or PVB, in particular Mowital from Kuraray Specialties Europe GmbH (B 20 H, B 30 T, B 30 H, B 30 HH, B 45 H, B 60 T, B 60 H, B 60 HH, B 75 H), or Pioloform, in particular Pioloform BRI 8, BM 18 or BTI 8, from Wacker AG.
• PMMA polymethyl methacrylate
• PVA in particular Mowiol and Poval from Kuraray Specialties Europe GmbH or Poiyvioi from Wacker AG
• PVB in particular Mowital from Kuraray Specialties Europe GmbH (B 20 H, B 30 T, B 30 H, B 30 HH, B 45 H, B 60 T, B 60 H, B 60 HH, B 75 H)
• Pioloform in particular Pioloform BRI 8, BM 18 or BTI 8, from Wacker AG.
• solvents examples include ethyl acetate, butyl acetate, 1-methoxypropyl acetate-2, toluene, xylene, Solvesso 100, Shellsoi A or mixtures of two or more of these solvents.
• Examples of flow agents are Additol XL480 in butoxyl in a mixing ratio of 40:60 to 60:40. 0.01 to 10% by weight, preferably 0.05 to 5% by weight, may be used as further additives. especially preferably 0.1 to 2% by weight, in each case based on the total paste mass.
• As rheology additives which reduce the settling behavior of pigments and fillers in the paste BYK 41 0, BYK 41 1, BYK 430, BYK 431 or any mixtures thereof may be present, for example.
• a printing paste for the preparation of the insulating layer as component BB and / or BD contain:
• the EL element according to the invention comprises at least one EL layer, component BC.
• the at least one EL layer may be arranged on the entire inner surface of the first partially transparent electrode or on one or more surfaces of the first at least partially transparent electrode.
• the partial surfaces generally have a spacing of 0.5 to 1 0.0 mm, preferably 1 to 5 mm from each other.
• the EL layer is generally composed of a binder matrix having homogeneously dispersed EL pigments therein.
• the binder matrix is generally selected such that a good adhesion bond is provided on the electrode layer (or the dielectric layer, if applied thereon).
• PVB or PU based systems are used.
• further additives may optionally be present in the binder matrix, such as color-converting organic and / or inorganic systems, color additives for a day and night light effect and / or reflective and / or light-absorbing effect pigments such as aluminum flakes or glass fiakes or mica platelets.
• the EL pigments used in the EL layer generally have a thickness of 1 to 50 ⁇ m, preferably 5 to 25 ⁇ m,
• the at least one EL layer BC is an AC thick-film Pu Iver electroluminescent (AC-P-EL) light-emitting structure.
• AC-P-EL AC thick-film Pu Iver electroluminescent
• EL elements are understood to be thick-film EL systems which are operated by means of alternating voltage at normatively 1 00 volt and 400 hertz and thus a so-called kaites Emit light of a few cd / m 2 up to a few 100 cd / m 2 (thick-film AC-EL elements).
• EL screen pastes are generally used,
• Such EL Siebdgingpaste ⁇ are generally based on inorganic substances. Suitable substances are, for example, high-purity ZnS, CdS, Zn x Cd 1 . X S compounds of groups II and IV of the Periodic Table of the Elements, with particular preference ZnS is used.
• the abovementioned substances can be doped or activated and, if appropriate, further co-activated. For doping, for example, copper and / or manganese are used. Coactivation takes place, for example, with chlorine, bromine, iodine and aluminum. The content of alkali and side earth metals is generally very low in the above-mentioned substances, if any.
• ZnS is very particularly preferably used, which is preferably doped or activated with copper and / or manganese and is preferably co-activated with chlorine, bromine, iodine iodine and / or aluminum.
• Typical EL emission colors are yellow, orange, green, green-blue, blue-green and white, whereby the emission color can be obtained white or red by mixtures of suitable EL pigments or by color conversion.
• Color conversion can generally take the form of a converting layer and / or the addition of appropriate dyes and pigments in the polymeric binder of the screen printing inks or the polymeric matrix in which the EL pigments are incorporated, carried out.
• the screen printing mats used for producing the EL layer are provided with translucent, color-filtering or color-converting dyes and / or pigments. In this way, an emission color white or a day-night ⁇ light effect can be generated.
• pigments are used in the EL layer which have an emission in the blue wavelength range from 420 to 480 nm and are provided with a color-converting microencapsulation. In this way, the color white can be emitted.
• pigments used in the EL layer are AC-P-EL pigments which have an emission in the blue wavelength range from 420 to 480 nm.
• the AC-P-EL screen printing matrix preferably comprises wavelength-controlling inorganic fine particles based on europium (II) activated alkaline earth ortho-silicate luminescent pigments such as (Ba, Sr, Ca) 2 SiO 4 ) Eu 2 + or YAG luminescent pigments such as Y 3 Al 5 O 12 ICe 3+ or Tb 3 Al 5 O 12 : Ce 3+ or Sr 2 GaS 4 ) Eu 2+ or SrSiEu 2+ or (Y, Lu, Gd, Tb) 3 (ALSc, Ga) 5 O 12 ) Ce 3+ or (Zn, Ca, Sr) (S, Se): Eu 2 + . Also in this way a white emission can be achieved.
• europium (II) activated alkaline earth ortho-silicate luminescent pigments such as (Ba, Sr, Ca) 2 SiO 4 ) Eu 2 + or YAG luminescent pigments such as Y 3 Al 5 O 12 ICe 3+ or T
• the above-mentioned EL pigments can be microencapsulated. Due to the inorganic microencapsulation technology, good half-lives can be achieved.
• One example is the EL screen printing system Luxprint ® for EL from E. I here.
• Organic micro-encapsulation technologies and film clad laminates based on the various thermoplastic films are basically also suitable, but have proven to be expensive and not significantly extended in life.
• Suitable zinc sulfide microencapsulated EL luminescent pigments are available from Osram Sylvania, Inc. Towanda GlacierGLOe under the trade name Standard, High Brite and Long Life and the Durel Division of Rogers Corporation, under the trade names 1 PHSOO I ® High-Efficiency Green Encapsulated EL Phosphor, 1 PHS002 ® High Efficiency Blue-Green Encapsulated EL Phosphor, 1 PHS003 ® Long-Life Blue Encapsulated EL phosphor, 1 PHS004 ® Long-Life Orange Encapsulated EL phosphor offered.
• the average particle diameters of the microencapsulated pigments suitable in the EL layer are generally from 15 to 60 ⁇ m, preferably from 20 to 35 ⁇ m.
• Non-microencapsulated fine-grained EL pigments preferably having a long service life, can also be used in the EL layer of the EL element according to the invention.
• Suitable non-microscope fine-grained zinc sulfide EL pigments are described, for example, in US Pat. No. 6,248,261 and US Pat in WO 01/34723. These preferably have a cubic crystal structure.
• the non-microencapsulated pigments preferably have average particle diameters of from 1 to 30 .mu.m, particularly preferably from 3 to 25 .mu.m, very particularly preferably from 5 to 20 .mu.m.
• Specially non-microencapsulated EL pigments can be used with smaller pigment dimensions down to less than 10 microns. As a result, the transparency of the glass element can be increased.
• non-encapsulated pigments can be added to the screen printing inks suitable according to the present application, preferably taking into account the special hygroscopic properties of the pigments, preferably the ZnS pigments.
• binders are generally used which on the one hand have good adhesion to so-called ITO layers (indium-tin oxide) or intrinsically conductive polymeric transparent layers, and furthermore have good insulating properties, reinforce the dielectric and thus improve the dielectric strength at high electric field strengths cause and additionally in the cured state have a good water vapor barrier and additionally protect the EL pigments and extend life span.
• pigments are used in the AC-P-EL luminescent layer, which are not mikververkapseit.
• the half-lives of the suitable pigments in the EL layer ie the time in which the initial brightness of the EL element according to the invention has dropped to half, are generally 100 and 80 volts and 400 hertz 400 to a maximum of 5000 hours, but usually not more than 1000 to 3500 hours.
• the brightness values (EL emission) are generally 1 to 200 cd / m 2 , preferably 3 to 100 cd / m 2 , particularly preferably 5 to 40 cd / m 2 ; For large illuminated areas, the brightness values are preferably in the range from 1 to 50 cd / m 2 . However, it is also possible to use pigments with longer or shorter half-lives and higher or lower brightness values in the EL layer of the EL element according to the invention.
• the pigments present in the EL layer have such a small average particle diameter, or such a low degree of filling in the EL layer, or the individual EL layers are embodied geometrically so small, or the distance of the individual EL layers is chosen so large, so that the EL element is designed with not electrically activated lighting structure as at least partially transparent or a review is guaranteed.
• Suitable pigment particle diameters, fill levels, dimensions of the luminous elements and distances of the luminous elements are mentioned above.
• the layer contains the abovementioned optionally doped ZnS crystals, preferably microencapsulated as described above, preferably in an amount of from 40 to 90% by weight, preferably from 50 to 80% by weight, particularly preferably from 55 to 70% by weight. , in each case based on the weight of the paste.
• binders one- and preferably two-component polyurethanes can be used.
• high ⁇ flexible materials of Bayer MaterialScience AG for example, the lacquer raw materials of Desmophen and Desmodur series, preferably Desmophen and Desmodur, or the lacquer raw materials of Lupranate-, Lupranol-, Pluracol or Lupraphen ranges from BASF AG.
• binders for example those based on PMMA, PVA, in particular Mowiol and Povai from Kuraray Specialties GmbH or Polyviol from Wacker AG, or PVB, in particular Mowital from Kuraray Specialties GmbH (B 20 H, B 30 T, B 30 H, B 30 HH, B 45 H, B 60 T, B 60 H, B 60 HH, B 75 H), or Pioloform, in particular Pioloform BRl 8, BMl 8 or BTl 8, from Wacker AG.
• PMMA polymethyl methacrylate
• PVA in particular Mowiol and Povai from Kuraray Specialties GmbH or Polyviol from Wacker AG
• PVB in particular Mowital from Kuraray Specialties GmbH
• Pioloform in particular Pioloform BRl 8, BMl 8 or BTl 8, from Wacker AG.
• solvents such as methanol, ethanol can also be used , Propanol, isopropanol, diacetone alcohol, benzyl alcohol, 1 - methoxypropanol-2, butylglycol, methoxybutanol, dowanol, methoxypropyl acetate, methyl acetate, ethyl acetate, butyl acetate, butoxy, glycolic acid n-butyl ester.
• additives for improving the flow behavior and the course can be contained.
• flow control agents are Additol XL480 in butoxy-1 in a mixing ratio of 40:60 to 60:40.
• Further additives may be 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 2% by weight, in each case based on the total paste mass, of rheology additives which reduce the settling behavior of pigments and fillers in the paste, for example BYK 410, BYK 41 1, BYK 430, BYK 431 or any mixtures thereof.
• Particularly preferred formulations of printing pastes according to the invention for producing the EL luminous pigment layer as component BC include:
• the EL element according to the invention contains a protective layer, component CA, in order to avoid destruction of the electroluminescent element or the optionally present graphical representations.
• Suitable materials of the protective layer are known to the person skilled in the art.
• Suitable protective layers CA are, for example, high-temperature-resistant protective lacquers, such as conformal lacquers containing polycarbonates and binders.
• An example of such Schutziack is Noriphan ® HTR from Pröll, Weissenburg.
• the protective layer can also be formulated on the basis of flexible polymers such as polyurethanes, PMMA, PVA, PVB. Polyurethanes from Bayer MaterialScience AG can be used for this purpose.
• This formulation can also be provided with fillers. Suitable for this purpose are all fillers known to the person skilled in the art, for example based on anoretic acid. ganic metal oxides such as TiO 2 , ZnO, lithopone, etc with a degree of filling of. 1 0 to 80 wt .-% of the printing paste, preferably from 20 to 70%, particularly preferably from 40 to 60%.
• the formulations may contain leveling agents as well as rheology additives.
• solvents for example, ethoxypropyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xyiol, solvent naphtha 100 or mixtures of two or more of these solvents can be used.
• particularly preferred formulations of the protective lacquer CA include, for example:
• the EL element according to the invention may have substrates on one or both sides of the respective electrodes, such as, for example, glasses, plastic films or the like, in addition to the textile carrier material.
• At least the substrate, which is in contact with the transparent electrode is designed on the inside graphically translucent and opaque covering.
• An opaque covering design is understood to be a large-area electroluminescent region which is opacified by a high-resolution graphic design and / or is translucent, for example, in the sense of red-green-blue translucent for signage purposes.
• the substrate which is in contact with the transparent electrode BA is a film which is cold stretchable below the glass transition temperature Tg. This gives rise to the possibility of deforming the resulting EL element three-dimensionally.
• the substrate which is in contact with the back electrode BE, is a film which is also cold-stretchable below Tg. This results in the possibility of deforming the resulting EL element three-dimensionally.
• the EL element is thus three-dimensional deformable, wherein the radii of curvature may be less than 2 mm, preferably less than 1 mm.
• the deformation angle can be greater than 60 °, preferably greater than 75 °, particularly preferably greater than 90, in particular greater than 1 05 °.
• the EL element is three-dimensionally deformable and in particular is cold bendable deformable below Tg and thus obtains a precisely shaped three-dimensional shape.
• the three-dimensionally deformed element can be formed in an injection molding tool on at least one side with a thermoplastic material.
• the above pastes are applied to transparent plastic foils or glasses, which in turn have a substantially transparent electrically conductive coating and thereby represent the electrode for the visible side.
• the dielectric, if present, and the backside electrode are produced by printing technology and / or lamination technology.
• the backside electrode is first produced or the backside electrode in the form of a metallized foil is used and the dielectric is applied to this electrode. Subsequently, the EL layer and then the transparent and electrically conductive upper electrode are applied. The system obtained can then optionally be laminated with a transparent cover film and thus protected against water vapor or also against mechanical damage.
• the conductor tracks can be applied as a first layer to the substrate A. According to the invention, however, they are preferably applied to the electrodes BA or BE, either individually in two operations on the electrodes, or in one working step, the electrodes together.
• the EL layer is usually applied by printing by means of screen printing or dispenser application or inkjet application or else by a doctor blade process or a roller coating process or a curtain casting process or a transfer process, preferably by screen printing.
• the EL layer is applied to the surface of the electrode or to the optionally applied to the Juckelekfrode insulation layer.
• the present invention relates to an at least single-layered planar EL lighting system (1) based on at least one thick-film inorganic AC-EL element (2 and / or 3, abbreviated as 2/3 by way of example below). with at least two electrically conductive planar electrodes, wherein at least one of the at least two flat electrodes is made substantially transparent, and at least one of the two electrodes has a graphically designed contour and the two electrode surfaces do not completely cover each other, so that one EL Emission takes place only in the areas of the EL lighting system in which an overlap of the two corresponding electrodes is given.
• an EL layer is arranged between the two corresponding electrodes, wherein the EL emission in the overlapping electrode regions may have a different emission color.
• the present invention relates to a single-layer planar EL luminous system (1) based on at least one inorganic thick-film AC-EL element (2) with at least two electrically conductive planar electrodes, wherein at least one of the at least two planar electrodes is made substantially transparent, at least one of the two electrodes has a graphically shaped contour and the two electrode surfaces do not completely cover each other, so that an EL emission takes place only in the areas of the EL luminous system, in which an overlap of the two corresponding electrodes is given, wherein the EL luminous system is formed in a single layer.
• single-layered design is understood to mean that only one EL element, comprising two electrodes and one EL layer and optionally one insulation layer, is provided in the EL luminous system (1).
• the present invention relates to an at least single-layer planar EL luminous system (1) based on at least one inorganic thick-film AC EL element (2/3) with at least two electrically conductive planar electrodes, wherein at least one of the at least two planar electrodes is made substantially transparent, at least one of the two
• Electrodes having a graphically shaped contour and the two electrode surfaces are not completely covered, so that an EL emission takes place only in the areas of the EL lighting system, in which an overlap of the two corresponding electrodes is the given, the EL lighting system is multi-layered , in particular two-layered.
• two-layered design is understood to mean that two EL elements, comprising in each case two electrodes and one EL layer and optionally one insulation layer, are provided in the EL lighting system (1).
• the present invention relates to an at least single-layered planar EL lighting system (1)
• the resulting electroluminescent luminous system according to the invention is thus multi-layered (in the sense of more than two layers).
• the present invention relates to an at least single-layered planar EL lighting system (1) based on at least one thick-film inorganic AC-EL element (2/3) with at least two electrically conductive planar electrodes, wherein at least one of the at least two planar electrodes is made substantially transparent, at least one of the two
• Electrodes having a graphically shaped contour and the two electrode surfaces do not completely overlap, so that an EL emission takes place only in the areas of the EL lighting arrangement, in which an overlap of the two corresponding E- electrodes is given, wherein the at least one EL Layer (1 2 /
• the EL lighting system according to the invention in the sense of the present invention thus be designed as a multilayer, the homogeneous distribution can be realized in one, in several or in all EL elements.
• the binder matrix can be used in one, in several or in all EL elements.
• the present invention relates to an at least single-layer planar EL luminous system (1) based on at least one inorganic thick film AC-EL element (2/3) with at least two electrically conductive planar electrodes, at least one of the at least two planar electrodes is made substantially transparent, at least one of the two electrodes has a graphically shaped contour and the two electrode surfaces do not completely cover each other so that an EL emission takes place only in those areas of the EL lighting system in which a Covering the two corresponding electrodes is given, wherein the at least one EL element (2/3) is designed to be substantially transparent or translucent translucent.
• the EL lighting system according to the invention in the sense of the present invention should be multi-layered, the corresponding largely transparent or translucent translucent embodiment can be in one, in several or in all EL Be realized elements.
• the term "transparent” basically means a material which, in the applied state, has a transmission of generally more than 60%, preferably more than 70%, particularly preferably more than
• the EL emission (28, 29, 30) can be emitted upward and / or the EL emission (28 1 , 29 ', 30') downwards.
• the present invention relates to an at least single-layer planar EL lighting system (1)
• these graphic layers have masking, opaque, translucent, translucent, color-filtering, color-converting, semitransparent and / or specular surface regions.
• These areas may be at one or more of the graphical elements
• the present invention relates to an at least single-layered planar EL luminous system (1) based on at least one thick-film inorganic AC EL element (2 /
• At least two electrically conductive planar electrodes wherein at least one of the at least two planar electrodes is made substantially transparent, at least one of the two electrodes has a graphically designed contour and the two electrode surfaces do not completely cover each other, so that an EL Emission takes place only in the areas of the EL lighting arrangement in which an overlap of the two corresponding E- ied electrodes is given, wherein in the case of an at least two-layer EL lighting system, the different EL layers (1 2, 1 3) EL pigments (1 6/1 7) with different emission wavelengths.
• the present invention relates to an at least single-layered planar EL luminous system (1) based on at least one thick-film inorganic AC EL element (2/3) with at least two electrically conductive flat electrodes, where at least one of the at least two planar electrodes is made substantially transparent, at least one of the two electrodes has a graphically shaped contour and the two electrode surfaces do not completely cover each other so that an EL emission takes place only in the regions of the EL luminous system wherein an overlap of the two corresponding electrodes is given, wherein at least one of the EL layers has a polymeric binder matrix and / or color-mixing admixtures in the sense of a Sfokes shift by a few 10 to about 1 00 nm.
• the polymeric binder matrix may also be present in several of the EL layers, for example in two or in all EL layers.
• the color-converting admixtures can also be present in a plurality of the EL layers, for example in two or in all EL layers,
• the present invention relates to an at least single-layered planar EL luminous system (1) based on at least one thick-film inorganic AC EL element (2 /
• Spaces between the individual dots are preferably filled with a transparent binder matrix having a lower relative dielectric constant compared to the relative dielectric constant of the respective EL films.
• This configuration can be realized both in one of the EL layers present in the EL device according to the invention and in a plurality of EL layers, for example in two or all EL layers.
• the present invention relates to an at least single-layered planar EL luminous system (1) based on at least one inorganic thick film AC EL element (2/3) with at least two electrically conductive planar electrodes, wherein at least one at least one of the two electrodes has a graphically shaped contour and the two electrode surfaces do not completely cover each other so that an EL emission takes place only in those areas of the EL luminous system in which an overlap the two corresponding electrodes is given, wherein the entire EL lighting system (1) is deformable without stress whitening.
• the present invention in a twelfth embodiment, relates to an at least single-layer planar EL lighting system (1)
• EP 0 371 425 A is incorporated by reference into the present invention.
• the present invention relates to a least single-layered planar EL lighting system (1) based on at least one thick-film inorganic AC-EL element (2/3) with at least two electrically conductive planar electrodes, at least one at least one of the two electrodes has a graphically shaped contour and the two electrode surfaces do not completely cover each other so that an EL emission takes place only in the regions of the EL luminous system in which an overlap of the two corresponding electrodes is given, the entire EL lighting arrangement (1) being deformable below Tg by means of an isostatic high-pressure deformation method, for example according to the method described in EP 0 371 425 A and corresponding to the 3D-EL.
• IMD process in mold decoration, back-molding of EL film n according to the method which is described in EP 0 978 220 A
• deformable and hinterspritzbar deformable and hinter moussebar
• the present invention relates to an at least single-layered planar EL lighting system (1) based on at least one thick-film inorganic AC-EL element (2/3) with at least two electrically conductive planar electrodes, wherein at least one at least one of the two electrodes has a graphically shaped contour, and the at least two planar electrodes are made substantially transparent Both electrode surfaces do not completely cover each other, so that an EL emission takes place only in the regions of the EL luminous system in which an overlap of the two corresponding electrodes is given, wherein at least one EL element with the respective EL connections is connected to an AC voltage and the EL-E element in dependence on the height of the voltage and the frequency causes an EL emission and caused by the temporal change of the voltages or the frequencies dynamic light effects.
• the present invention relates to a method for producing an at least single-layer planar EL lighting system (1) based on at least one inorganic thick-film AC EL element (2/3) with at least two electrically conductive flat electrodes, at least one at least one of the two electrodes has a graphically shaped contour and the two electrode surfaces do not completely cover each other, so that an EL emission takes place only in the regions of the EL lighting system, in which an overlap of the two corresponding electrodes is given by means of screen printing and lamination.
• an EL layer is arranged between each two corresponding electrodes and the EL emission can have a different emission color in the overlapping electrode regions.
• a screen printing method for producing the layers (8, 18, 22, 1 2, 9, 23, 10, 24, 13, 11, 21) is preferably used, and these layers (8, 18 , 22, 1 2, 9, 23, 10, 24, 13, 11, 21) are preferably optionally printed on the film (4) or the film (5),
• Another object of the present invention is the application of the EL-Leuchtsytems invention as a lamp, as an advertising object and / or as an artistic entity.
• electrode 1 upper sheet-like electrically conductive and substantially transparent thin layer, preferably designed by screen printing graphically
• electrode 2 planar electrically conductive and largely transparent thin layer, preferably designed graphically by screen printing
• Electrode 3 sheet-like electrically conductive and largely transparent thin layer, preferably designed graphically by screen printing
• Electrode 4 sheet-like electrically conductive and either substantially transparent or opaque thin layer, preferably designed graphically by screen printing 1 2 EL layer 1 1 3 EL layer 2

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• 2008
  • 2008-10-24 WO PCT/EP2008/064428 patent/WO2009053458A1/de active Application Filing
  • 2008-10-24 EP EP08842339A patent/EP2215892A1/de not_active Withdrawn
  • 2008-10-24 KR KR1020107008934A patent/KR20100086466A/ko not_active Application Discontinuation
  • 2008-10-24 US US12/739,444 patent/US20100308713A1/en not_active Abandoned
  • 2008-10-24 JP JP2010530469A patent/JP2011501372A/ja not_active Withdrawn
  • 2008-10-24 TW TW097140948A patent/TW200926889A/zh unknown

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