TW200908778A - Electroluminescent element containing particles with nanostructures - Google Patents

Abstract

The present invention relates to an electroluminescent element containing particles with nanostructures, to a process for the production of an electroluminescent element according to the invention, and to the use of an electroluminescent element according to the invention as a decorative element and/or luminous element in interior spaces or for external use, preferably on external facades of buildings, in or on pieces of equipment, in or on land vehicles, aircraft or water-craft, or in the advertising sector.

Description

200908778 IX. Description of the Invention: [Technical Field 3 of the Invention] The present invention relates to an electroluminescent device comprising particles having a nanostructure, relating to a method for manufacturing an electroluminescent device according to the present invention, and Regarding the use of an electroluminescent device according to the invention as a decorative element and/or a brightening element in the interior space or for external use, preferably on the exterior facade of the building, in or on the body of the device, on land , in or on an aircraft or watercraft, or in the field of advertising. [Previously, the old electrolysis excitation light (hereinafter also referred to as "EL") means that the bright pigment (also known as the bright substance or the luminoph〇res) is excited by the direct light of the alternating electric field. Electrical excitation technology has recently become increasingly important. It permits the production of non-glare, shadowless, homogeneous shiny surfaces of almost any size. The power consumption and installation depth (H-level and town) are extremely small. In addition to the backlighting of liquid crystal displays, typical applications include backlights with transparent films of text and/or images. To this end, it has been known from the prior art that transparent electroluminescent light configurations, such as electroluminescent light-emitting panels based on glass or transparent plastic materials, can be used, for example, as information carriers, neon advertising, or for packaging purposes. 20 EL components are often produced by screen printing. Therefore, for example, by printing on a silk screen, but also by money, a substrate may be coated with a transparent electrode, and a hair layer (EL layer) is applied thereto. A dielectric layer can be disposed between the first, transparent electrode and the EL layer. Thereafter, it may be, for example, a dielectric layer containing barium titanate having a very high dielectric constant, and then a second electrode which is not necessarily transparent. It can be 200908778, for example, containing a surface with good electrical conductivity such as silver. EP-A2-1 434 470 describes a rear-running electro-optical element, the substrate of which is applied to the substrate in the following order: an ITO layer, a first layer, an electroluminescent layer, and a second layer. Electric 罨 5 10 layers and a back electrode. Chemical t deposition shape This "light-emitting configuration" has a fully formed, ie closed, inorganic electroluminescent layer. In the thin neodymium electroluminescent device, a layer having a separation of carbon nanotubes (CNTs) was used as a field reinforcing layer. δ has also proven to be largely successful with inorganic brightening pigments and alternating voltage excitations based on so-called thick layer techniques. Compared to the thin layer germanium elements cited in EP-A2-1 434 470, the thick layer Eut parts are less complex and therefore less expensive to manufacture. The shiny pigment used in the EL element is embedded in a transparent, organic or ceramic binding agent. The starting material is mostly zinc sulfide, which produces a different, relatively narrow band or broadband emission spectrum according to the heterogeneous or common doping and preparation process. The reason for using zinc sulfide in the EL layer is on the one hand to obtain a relatively high emission brightness of the zinc sulfide EL pigment. The focus of the spectrum determines the emitted light color. The emission color of an EL element can be adapted to a large number of possible colour impressions that may be measured. It comprises doping and co-doping brightening pigments, mixing two or more EL pigments, adding one or more organic and/or inorganic inorganic 2 color conversion and/or coloring pigments to organic and/or inorganic colors. The EL pigment is converted and/or color filtered to coat the EL pigment, the dye is mixed into the polymer matrix to disperse the shell pigment, and the one color conversion and/or color filter layer or film is incorporated into the construction of the El element. The excitation alternating voltage field is summarized with a frequency of hundreds of hertz, and the operating voltage of 200908778 is often in the range of approximately 50 to 150 volts. Higher brightness is generally achieved by increasing the voltage, which is conventionally located in the range of from about 50 to about 200 candelas per square meter. Depending on the doping or co-doping, the frequency increase summary causes a color shift towards a lower wavelength. However, the two parameters must be coordinated to achieve a desired luminous impression. ° From the prior art, EL elements based on thick layer technology (hereinafter also referred to as thick film electroluminescent elements or thick) Film EL elements) are conventionally used with zinc sulfide EL pigments and by screen printing or other printing and/or application according to prior art techniques.

A technique such as knife application, spraying, atomization, and/or dispersion coating or application of an electrode appearing in an EL-illuminating configuration to an EL layer or a corresponding dielectric layer by a PVD process is produced. The EL layer has irregularities due to the different sizes and corresponding pigment size distributions of the v5 particles of 2 to 3 (^111) and the relatively thick EL layer in the range of 20 to 5 〇μηι. For example, due to 15 different sizes of EL pigments, agglomerated EL pigments and/or two or more el pigment stacks. Due to this relatively uneven EL layer, it is customary to Electrical layer (insulating layer). However, if the brightening layer has a layer thickness that prevents the bridge between the two electrodes, it can be omitted. The insulating layer is generally produced by a 糸' 罔 printing process, and the towel is used for forming. The screen printed f* is applied to the surface to be coated via a wire/knife. This procedure results in the inclusion of air bubbles (the moon's micro-gas 'package)' which is subsequently placed in the electroluminescent light formed by screen printing. The edge layer of the component may cause a significant decrease in the dielectric constant. The insulating properties of the corresponding layer are significantly reduced by lL θ5 ^ and 匕. When using a screen printing layer, the time is

* Poverty: I ° Because it is not always possible to avoid small air bubbles or gas bubbles, special 200908778 does not print the b-field, and it is known that the main frequency from 5GHz to qing Hz and higher is from 100 to The required alternating voltage of 200 volts represents a high demand in terms of puncture strength. For this reason, the thick film of this component, known from the prior art, has the advantage that having a dielectric layer is not optimal. The 'right-side redundancy layer of the special 5 mouthpiece does not have a layer thickness that prevents short-circuiting between the two electrodes, and the layer thickness of the insulating layer is greatly limited by the thin layer. Further, there is a disadvantage that the EL element known from the prior art can only be poorly three-dimensionally deformed because the electrode material is easily torn. This can lead to significant damage to surface conductance in some cases. 1 The other drawbacks of the prior art of the rainbow component that cannot be ignored are: - generally require a high excitation voltage to achieve - a specific emission brightness, and the initial brightness value of the EL element lasts from hundreds of hours to about 2500 hours is reduced by half, The so-called half life period is progressing too fast. These anal components are not stable enough for well-known environmental conditions, especially high atmospheric humidity and high-quality lighting requirements of up to 8 (steady emission brightness in TC high-ring temperature and stable hair color) for more than 2 hrs. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a thick film EL element based on zinc sulfide which preferably does not exhibit the above disadvantages. 2〇4 Temple, the thick fox component will be three-dimensionally deformable In addition, the tear film does not occur in the electrode. In addition, the thick film electroluminescent device preferably contains an insulating layer having a high dielectric constant, so that the insulating layer as a whole is relatively thick. Moreover, the component is preferably "moderately excited. To achieve a specific emission brightness. This is achieved by a zinc sulfide-based thick film electroluminescent device comprising - a transparent electrode (1), at least an el layer of at least one dielectric layer, and at least A first and second back electrode. The thick film electroluminescent device based on zinc sulfide according to the present invention is characterized in that it comprises particles having a nanostructure. 5 纟发_范_ 'Please understand "with nano Constructed Sub ,, with language

Refers to a nanoscale material structure selected from the group consisting of: single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (mwcnTs), nanorods, nanohorns 'nano dishes' A nano-cone (i.e., a structure having a sheath in the form of a cone), a metal nanowire, and a combination of the above particles. Corresponding particles having a carbon-based base structure can be composed of, for example, a broken nanotube (single-walled and multi-walled), carbon nanofiber (fish ridge... small plate _, spiral _ type) And similar. Carbon nanotubes are also known internationally as carbon nanotubes (single-walled and multi-walled) carbon nanofibers as carbon nanofibers (fish ridges, small plates, and spirals). For metal nanowires, see wo 2007/022226 A2. A substantially transparent silver nanowire having good electrical conductivity as described in WO 15 2007/022226 A2 is particularly suitable for the present invention. According to the invention, it is therefore possible to use particles having a nanostructure for use in a thick film electroluminescent device according to the invention, surprisingly by means of a particle having a nanostructure in a particular layer of the EL element. Use to achieve the above objectives. In a first aspect of the invention, the particles having a nanostructure are used in a dielectric layer of a thick germanium electroluminescent device according to the present invention. These insulating layers are typically produced by a screen printing process in which a paste for forming a screen print is applied to a surface to be coated via a screen with a knife. In the dielectric layer, the particle system of 9 200908778 should be used, and the particle structure of the wood structure has not reached the low limit of particle permeation. The addition of (4) is caused by direct electrical contact. Conductivity_ is the effect of conductivity:: When the dielectric layer maintains a high dielectric constant and there are significant insulating particles, the (four) age electrical layer does not add a nanostructure interface. thicker. If used in the EL element according to the present invention, the layer of 'f" may cause particles having a nanostructure to appear only in one or all of the dielectric layers, such as both of the dielectric layers. In the first aspect of the present month, the particle system used in accordance with the present invention is contained in at least one of the electrode layers, i.e., the front electrode or the back electrode or both electrode pads. As a result, the resulting π element exhibits significantly improved deformability. Due to the significant size ratio of the particles having a nanostructure, the low percolation limit is also increased in the electrode layer, with the result that the conductivity of the individual electrodes is retained when the EL layer is deformed. Overall, the electrical surface conductivity of the electrode was improved. In the second aspect of the invention, the nanostructure-structured particle system used in accordance with the present invention is contained in the EL layer. As a result, a local electric field increase is achieved in the rainbow layer and the excitation field intensity at the E L pigment of the E L layer is thus locally increased. As a result, the excitation voltage may decrease while the emission brightness remains the same. In a fourth aspect of the invention, the nanostructured particles are used in at least one separate layer, which is disposed between the dielectric layer and the EL layer, and between the two dielectric layers (3⁄4 uses two dielectric layers). Electrical layer) and / or between the transparent front electrode and the EL layer. The separated layer provided in this embodiment containing particles having a nanostructure is also referred to within the scope of the invention as a "floating electrode layer, within the scope of this fourth 10 200908778 5 of the invention" It is also possible to have a plurality of net moving electrode layers containing particles having a nanostructure appear at different positions in the EL element. The floating electrode is a conductive layer or a layer having a high dielectric constant (ε), which is not ohmically connected. To a potential, due to the use of the corresponding floating electrode layer, a more uniform £L emission is achieved, that is, the overall efficiency-efficiency here refers to the efficiency of the EL system [1 secret system increases. The result 'can reduce the voltage while maintaining The brightness of the emission or the monthly transmission is maintained while maintaining the same supply voltage. 10 15 Extremely reaching a so-called "floating electrode", that is, the power without the potential limitation, the two electrodes are connected to the alternating voltage in the opposite band (four) = unfinished ^ Ground overlap. Therefore, by galvanie separatiGn connected to the two electrodes of alternating voltage - "": can be accommodated in a plane or in different planes and can be made two : The upper part of the material is buckled with the third or other f-extreme: the luminescent layer or the plurality of electro-excitation layers are inserted into the electrode to form a brightening effect. The neutrons contained in the different layers of the EL element can be simultaneously present in: the particles having the structure of m can be combined, in particular, the particles of the nanostructure (1) and the electrode layer and a dielectric layer; (2) - an electrode layer and an el layer; (3) - an electrode layer and a floating electrode layer; (4) a dielectric layer and an EL layer; (5) - a dielectric layer and a floating electrode layer (6) - EL layer and - floating electrode layer; 11 200908778 (7) - electrode layer, a dielectric layer and - (8) - electrode layer, a dielectric layer and (9) - dielectric layer In the EL layer and the moving electrode layer; (10) in the 1-pole layer; in the % active electrode layer; and in the "layer", the layer and a floating electrode layer in accordance with the present invention. The EL element comprises a plurality of such layers, and the means are included in two or more of these layers in accordance with the present invention. H constructs can also be included within the scope of the invention, with nanocloths or randomly oriented or directed to the EL element: the riser can be homogenically dispersed 10 15 thick:: spherical particles can be constructed with nanostructures: The particles are used in combination to form a U-shaped member, such as a material, or a spherical particle, or a particle having a second "range of dimensions" = ITO (indium tin) particles and/or agglomerates or aggregates. . The spherical particles have a diameter ranging from (4), preferably from 2 to 30, especially from 3 to 15. The spherical particles independently of the diameter preferably have a length ranging from read to 100 μηη, preferably from 0.5 to 50 μηη, especially from 〇1 to 1 〇. The spherical particles k are preferably cerium (yttria tin oxide) particles, or are generally classified as electrically conductive metals or metal oxides or ferroelectric (titanium ore) particles. In another embodiment of the invention, so-called single-walled carbon nanotubes 2 〇 (S WCNTs) or multi-walled carbon nanotubes (MWCNTs) are used as the particles having a nanostructure. For example, SWCNTs have the advantage of being more transparent than MWCNTs or other particles with nanostructures. However, a disadvantage of SWCNTs is that these particles are relatively expensive. Particularly when the corresponding particles having a nanostructure are used in the transparent electrode on the front side or in the floating electrode 12200908778 adjacent to the transparent electrode on the front side, it is preferable to use SWCNTs, in particular, they are used alone, that is, differently. When MWCNTs are used, since SWCNTs have higher transparency than MWCNTs or other particles having a nanostructure, the EL emission of the produced EL element is not lowered. 5 Within the scope of the present invention, "single-walled carbon nanotubes, (SWCNTs) terms encompass different variations of single-walled carbon nanotubes, which may also include nanofibers. Single-walled carbon nanotubes Substantially substantially in the form of a cylindrical carbon structure having a diameter of a few nanometers. The preparation of these single walled carbon nanotubes is known to those skilled in the art and can be performed using a corresponding process of the prior art, including, for example, catalystization. Vapor deposition (CCVD). These processes often produce different proportions of the diameter, length, chirality, and electronic properties of SWCNTs. They occur in the bundle and are often mixed with a portion of the amorphous carbon. The proportions are divided into the known separation processes for SWCNTs to the electron transfer effect on metal SWCNTs treated by azo salt 15, dielectrophoresis, and one for semi-conductive carbon nanotubes Specific chemical affinity and carbon nanotube coated with single-stranded DNA. The selectivity of these methods can be further improved by intensive centrifugation of pretreated dispersions and using ion exchange chromatography. range Preferably, a pure-phase partial single-wall carbon 20 nm tube is preferably used, that is, it is selected from a group consisting of diameter, length, chirality and electronic properties, and the difference is not more than 5%, which is particularly good. a proportioned portion of single-walled carbon nanotubes of not more than 4%, especially not more than 30%, especially not more than 2%, and most not more than 丨〇%. SWCNTs used according to the invention are generally known and 13 200908778 SWCNTs preferably have an outer diameter 'from 1 nm to 5 〇 nm, preferably from 3 11111 to 25 nm, particularly preferably from 5 nm to 15 nm, and from 1 to 1 〇〇 μηι, preferably. From (μιη to 50 μηι, especially from i μηι to 1〇 的 length. SWCNTs can preferably be used as a primary batch or a pure substance contained in a thermoplastic material, which is homogeneously mixed with 5 layers. The tethering agent. Single-walled carbon nanotubes (SWCNTs) are particularly preferred for the purposes of the present invention because of their thinness and high conductivity, and the results can be achieved in smaller amounts to achieve the desired effect. Other particles with nanostructures are more transparent. If using SWCNTs or MWCNTs or SWCNTs In combination with MWCNTs 10, the size ratio of the relevant particles, that is, the length to diameter of the relevant nanotubes, is generally greater than 1:100, preferably greater than 1:2 〇〇, and particularly preferably greater than ι:ι〇〇〇. The advantage of a large length of nanostructured particles is that micro-tearing can be avoided. Due to the use of particles having a nanostructure according to the invention, in particular in a 15 dielectric layer, it is preferred to have a nanostructure. The particles have a high dielectric constant and/or a suitable electrical conductivity. The dielectric constant of particles having a nanostructure should be summarized as at least 30, preferably at least 5, particularly preferably at least 1 〇〇, most preferably at least 200 or The trend is infinite. Further, it is preferable to use a coarse structure having a nanostructure having a machine or an inorganic insulating layer in the insulating or dielectric layer and/or the EL layer, with the result that the insulation in the individual dielectric layers is increased. If the particles having a nanostructure comprise an inorganic insulating layer, the generalization can be formed from a metal oxide and/or metal nitride layer. If the nanostructured particles in the EL element according to the present invention are contained in the EL layer and/or the dielectric layer, the number of layers in the layer is generally such that it does not reach the osmotic filtration and the low limit. That is, the electrical conductivity due to direct electrical contact between the individual added particles does not result in ohmic conductivity. Therefore, the stepwise step is preferably such that the particles having a nanostructure in the EL layer or in the dielectric layer are present in a filling percentage of less than 2 5%, preferably less than 1% by weight, particularly preferably less than 5% by weight. In the relevant layers, each case is based on the layer weight. If a particle having a nanostructure is present in the transparent front side and/or the back side of the electrode layer, its content in the relevant layer is generally from Ο" to 1 〇 by weight. 4. It is preferably from 0.2 to 5% by weight, particularly preferably from 〇 3 to 2% by weight, in each case. Based on 10 weights. 61 The particles of the right nanostructure appear in the floating electrode layer, and the content thereof is generally 攸〇_1 to 1% by weight, preferably from 〇2 to 5% by weight, particularly preferably from 〇3 to 3% by weight. Each case is based on the layer weight. An EL pigment is contained in the el layer of the EL element according to the present invention. It is coated with particles having a nanostructure in the sense of non-cohesive mixing. Please understand that hybridization (hybridisati〇n) refers to the surface on which the corresponding nanoparticles are attached to the EL pigment. It is additionally within the scope of the present invention that the ~1 很 stone is very unacceptable EL element ^ 3 layer contains nano-tubular particles having a nanostructure and is configured between the front transparent electrode and the electroluminescent layer As a floating electrode, the EL pigment falls on the paddle layer due to the production process and locally increases the electric field strength in the electro floating layer and thereby increases the EL emission or lowers the supply voltage. In this case, it is preferred that the Tween of SWCNTs utilizes it as a particle having a nanostructure. This April 1 & stepwise step can be such that if the element 15 200908778 according to the invention comprises a layer of particles containing a nanostructure and configured as a -floating electrode between the electroluminescent layer and the :insulation layer, The EL pigment falls on the oceanic layer due to the production process and locally increases the electric field strength in the floating layer and thereby increases the emission or lowers the supply voltage. 5' The description describes the general construction of an appropriate EL element which can contain particles having a nanostructure in the above manner. A suitable EL element is comprised of at least one substrate and at least one configuration. It may preferably be applied by screen printing techniques or, for example, by knife application, sneezing, atomizing and/or dispersion coating. The overlay is produced in layers. Thus, the substrate can be coated with a transparent electrode and then applied with a bright layer (electroluminescent layer). The last insulating layer (dielectric layer) and the other electrode can then be deposited on the shiny layer. The starting point for the electroluminescent light arrangement according to the invention is therefore the conductive electrode layer applied to the substrate. 15 [The element may be such that the substrate side provided with the EL· arrangement is illuminated, or the parent I5 is damaged by the transparent substrate being subjected to an electroluminescent light applied to the back.” Furthermore, if the substrate is at least partially transparent, illumination can also be achieved on both sides. In a first embodiment of the invention, the electroluminescent element is formed from the following layers 20 (known construction): a) at least partially transparent substrate, component A, b) at least one electroluminescent arrangement, component B, It is applied to the substrate and contains the following components: at least a portion of the transparent electrode, assembly BA, as the front electrode, 16 200908778 bb) an optional insulating layer, component BB, be) - containing at least an electrical field that can be excited - a layer of brightening pigment (electroluminescence), called an electroluminescent layer or pigment layer, an assembly BC, 5 bd) an optional insulating layer, a component bd, be) a back electrode, a component BE, which can be at least Partially transparent, bf) - strip conductor or a plurality of strip conductors, components ,ρι, for electrical contact assembly BA and component BE, may be applied to the electrodes BA and BE Between front, rear or 10, one or more strip conductors are preferably applied in a single working step. The one or more strip conductors may preferably be applied in the form of a silver busbar prepared from a silver paste. Optionally, a graphite layer can be applied prior to application of the silver bus. c) A protective layer, component CA, or a membrane, component CB. 15 The insulating layers BB and BD may be non-transparent, opaque or transparent. If two insulating layers are present, at least one layer is at least partially transparent. One or more at least partially transparent layers in graphic form may additionally be disposed on substrate A externally and/or between substrate a and the electroluminescent arrangement. In addition to the above layers (components A, B and C), the electroluminescent light 20 element (conventional construction) according to the present invention may comprise one or more reflective layers. The reflective layer can be specially configured on: - external to component A, - between component A and component BA, - if component BB does not exist, between component BA and component BB or BC, 17 200908778 - between component BD and component BE, - between component BE and component BF, - component BF and component CA or CB, - component CA or CB external. 5 If the reflective layer is present, it is preferably arranged between the component BC and the component BD or BE. The reflective layer preferably comprises glass beads, in particular hollow glass beads. The diameter of the glass sphere can vary within wide limits. For example, it may have a size of from 5 μm to 3 mm, preferably from 10 to 2 μm, and particularly from 20 to 100 μη. The hollow glass pellets are preferably embedded in a binding agent. In an alternative embodiment of the invention, the electroluminescent element is comprised of the following layers (inverted layer construction): a) - at least partially transparent substrate, component a, b) at least one electroluminescent arrangement, component b Applied to the substrate and comprising 15 having the following components ba) - a back electrode, an assembly which is at least partially transparent, bb) an optional insulating layer, component bb, be) - containing an electric field that can be excited a layer of at least one bright pigment (light-emitting group) is referred to as an electroluminescent layer or pigment layer, and components BC, bd are optionally an insulating layer, component BD, at least partially transparent, component BA, As a front electrode, bf) - a strip conductor or a plurality of strip conductors, the component Bp, for electrically contacting the component BA and the component BE, may apply one or more strip conductors to the front of the electrodes BA and BE Between, rear or 18 200908778, one or more strip conductors are preferably applied in a single work. a working inflammation

A graphite layer is selectively applied before the flow. Prepared C) an at least partially transparent protective layer, component CA, and / or - film, component CB. In addition, one or more at least partially transparent layers in the form of a graphic may be disposed on the transparent protective layer C and/or between the transparent protective layer C and the EL configuration. For a specific t, a layer in the form of a graphic can take over the function of the protective layer. In a particular embodiment of the inverted inverted layer construction, the superconstructing portions B, C can be applied to the front side of the substrate, component a, and applied to the back side, and also applied to both sides of the substrate (two Side construction). The layers 3-8 to 61? on both sides may be the same, but they may also be different in - or more than one layer, so that the electroluminescent element is equally radiated on both sides or the electroluminescent element has one on each side. Not 15 colors and/or a different brightness and/or a different graphic form. In addition to the above layers (components A, B and C), the electroluminescent element according to the invention having an inverted layer configuration may have one or more reflective layers. The reflective layer can be specially configured to: - external to component A, 20 - 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 ' 19 200908778 - between component BA and component BF, - between component BF and component CA or CB, - component CA or CB. If the reflective layer is present, it is preferably arranged between the component BC and the component BB or BE (if the component BB does not exist). It will be apparent to those skilled in the art that the specific embodiments and features described for the conventional constructions are correspondingly applicable to the inverted layer configuration and the two-sided configuration, unless otherwise indicated. In particular, when the component BC has a layer thickness that prevents the two electrodes, the components ba and BE from being generated, the one or more insulating layers BB and/or may be omitted in both the conventional structure and the inverted structure. Bd. The features of the individual components of the EL component are described below: The gate electrode according to the present invention has a first, at least partially transparent front electrode 8 8 and a second electrode, a back electrode BE. Within the scope of this application, please understand that “at least partially transparent, the term refers to a material having a transmission greater than 60%, preferably greater than 7〇%, particularly preferably greater than 8〇%, especially greater than 90%. One of the electrodes. The back electrode BE does not have to be transparent. 2〇 Suitable electrically conductive materials for the electrodes are basically known to those skilled in the art. In principle, alternating voltage-excited thick films may have a number in the manufacture of this element. Types of electrodes. On the other hand, it is an indium tin oxide (ITO) electrode that is applied to a plastic film by sputtering or vapor deposition. It is very thin (hundreds of inches) and is very turbid and Relatively low surface resistivity (approximate (6) 20 200908778 to 600 Ω). It is also possible to use a paste containing ITO or yttrium (yttria tin oxide) or an intrinsically conductive transparent polymer paste, which can be printed by screen The flat electrode is produced therefrom. It can be applied in substantially any desired configuration, even if applied to the textured surface 5. It can also have relatively good laminability. Non-ITO screen printing layers can also be used ( The term "non-Ting" includes All screen printing layers based on indium tin oxide (IT0), ie intrinsically conductive polymer layers usually having nanoscale electrically conductive pigments. For example, it is possible to use a DuPont brand name Ή62Ε or 7164 enamel screen printing paste, intrinsic conductive poly conjugate system, such as the Orgacon® system from Agfa, available from h_C. Starck GmbH's Clevios® poly(3,4-dioxyethylene thiophene) system, A system for the introduction of organometallics from Ormecon (PEDT-conducting polymer polyoxyethylene thiophene) from the conductive coating or printing ink system of Panip〇l 0Y, and selectively with high flexibility The polyaniline modified by the tethering agent is, for example, based on 15 PU (polyurethane), PMMA (polymethyl methacrylate), PVA (polyvinyl alcohol). It is preferably used from H c Starck GmbH.

The Clevios® poly(3,4-dioxyethylene thiophene) system acts as the material for at least a portion of the transparent electrode of the electroluminescent element. Examples of electrically conductive polymeric membranes are polyaniline, polythiophene, polyacetylene, polypyrrole with or without metal oxide filling (Handbook of Polymers, 1985). According to the present invention, a row of paste formulations for making a portion of the transparent electrode BA is preferably used in an amount of from 10 to 90% by weight, preferably from 2 to 8% by weight, particularly preferably from 30 to 65% by weight (each In the case of Clevios P ^ Clevios PH ^ Clevios P AG &C; Clevios P HCV4 ^ 21 200908778 (^¥1〇8?118, (^¥1〇8?11 500, (based on the total weight of the printed paste) : 16¥1〇8?^1510 or any desired mixture thereof. Dimethyl hydrazine (DMSO), N,N-dimethyl decylamine, N,N-dimercaptoacetamide can be used. As a solvent, ethylene glycol, glycerin, sorbitol, methanol, ethanol, isopropanol, n-propanol, acetone, methyl ethyl methacrylate, dimethylaminoethanol, 5 water or a mixture of two or more of the above solvents. The amount of solvent in the printing paste can vary over a wide range. For example, from 55 to 60% by weight of a solvent may be present in a formulation according to the invention in a paste, in a different formulation according to the invention A solvent mixture of approximately two or more solvents from Μ to 45% by weight is used. SilqUest a 187, Neo Rez 10 R986, Dyn〇l 6〇4 and/or Mixtures of more than one of these may further occur with interface additives and adhesion promoters, in amounts ranging from 〇1 to 5〇wt/〇, preferably from 0.3 to 2.5% by weight, based on the total printed weight. The formulation may contain, for example, Bayderm Finish 85 UD, Bayhydn) 1 PR3., Bayhydrol PR135, or any desired mixture thereof, preferably 15 in an amount of from about 0.5% by weight, preferably from 3 to 5% by weight. The polyurethane foam used in accordance with the present invention for forming a binding agent for the conductive layer after drying of the layer is preferably an aqueous polyurethane fabric. 20 It is particularly preferred for use in the manufacture of a partially transparent coating according to the present invention. The formulation of the paste contains: Columns of the electrode BAR 22 200908778 r \ Substance content / wt% Content / wt% Content / wt% Clevios P HS (HC Starck) 33 1 - - 48 40 Silquest A187 (OSi Specialties) 0.4 0.5 1.2 N-methyl 0 to each ketone 23.7 14.4 10.3 Diethylene glycol 26.3 20.7 30.0 Proglyde/DMM 12.6 12.4 14.5 Bayderm Finish 85 UD (Lanxess) 4.0 4.0 4.0 Substance content / wt% Content / wt% Clevi Os P HS (H.C. Starck) 33 40 Silquest A187 (OSi Specialties) 0.4 1.2 N-Methyl '• pirone 23.7 10.3 Diethylene glycol 26.3 30.0 Proglyde/DMM 12.6 14.5 Bayhydrol P340/1 4.0 I 4.0

The above-mentioned formulation which is detached from the partial transparent electrode BA, the following commercially available printing paste described in the examples can also be used as a ready-made product according to the present invention. Orgacon EL-P1000 from Agfa, The EL-P3000, EL P5000 or EL-P6000 series 'is preferably the ELp3〇〇〇 and the Rainbow (9) series (especially for deformable applications). Tin oxide (NESA) paste can also be used as the corresponding electrode material. The electrically conductive material described above may additionally be applied to a carrier material. Suitable carrier materials are, for example, transparent surfaces and enthalpy. Corresponding carrier materials are detailed below 23 200908778. Within the scope of the invention, one or two carrier substrates can be used. The electrode material can be applied to the corresponding carrier material (substrate), for example by screen printing, knife application, spray, atomization and/or dispersion coating, the substrate then being, for example, from 80 to 12 (TC) The low temperature is dried. 5 In a preferred alternative embodiment, the application of the electrically conductive coating is carried out by vacuum or thermal decomposition. In an alternative embodiment, the electrically conductive coating is particularly preferably a metal or metal oxide. Produced by vacuum or thermal decomposition and preferably having a surface resistivity of from 5 η Ω to 3 〇〇〇 Ω/square, particularly preferably from 0 丨 to 忉 (9) Ω/square, optimally from 10 5 Ω to 30 Ώ/square. A thin, substantially transparent layer having a resistivity, and in a further preferred embodiment, having at least greater than 60% (> 60 to 100%) and especially greater than 76% (> 76 to 100%) of sunlight transmitted. It is also possible to use electrically conductive glass as the electrode. The high surface hardness and its electrical surface resistance can be made up of a layer of thermal decomposition which is adjusted over a wide range from a few milliohms of 15 to 3000 Ω/square. Types of electrically conductive and highly transparent glass, especially floating glass. Isothermal is a decoated glass that is easily deformable and has good scratch resistance; in particular, scratching does not cause electrical disconnection of the electrically conductive surface layer, 20 but only slightly increases in most cases. Surface resistivity. Furthermore, in the case of subsequent application of the material, the conductive surface layer produced by thermal decomposition is thus strongly diffused into the surface due to heat treatment and anchored in the surface to achieve a very high adhesive bond to one of the glass substrates. It is equally advantageous for the present invention. Moreover, these coatings have good homogeneity, i.e., 24 200908778. The surface resistance value is spread to a low degree above the large surface. This property also represents an advantage for the present invention. On polymeric substrates such as PET or PMMA or PC, electrically conductive and highly transparent thin layers can be produced substantially more efficiently and inexpensively on a preferred 5 glass substrate for use in accordance with the present invention. In the layer case, on the polymer film with similar transparency, the electrical surface resistivity is on the average 10 times factor, which is equivalent to 3 〇 on the PET film. The 100 Ω/square is from 3 to 1 〇 ohm/square in the case of the glass layer. The back electrode of the component BE is - such as at least part of the transparent electrode case - a 10 flat electrode, but not necessarily transparent or at least partially Transparent. It is applied to the insulating layer - if present. If an insulating layer does not appear, the back electrode is applied to a layer containing at least one bright material that can be excited by the electrical field. In an alternative embodiment, the back electrode is applied to Substrate A. The back electrode is generally composed of an inorganic or organic electrically conductive 15 material such as a metal such as silver, and is preferably used without damage when the three-dimensionally deformed film element is fabricated by the isostatic pressing high pressure deformation process according to the present invention. The appropriate electrode is also in particular a polymeric electrically conductive coating. The coatings mentioned above together with at least part of the transparent electrode can be used. In addition, polymeric electrically conductive coatings not known to those skilled in the art, which are not at least partially transparent, may be used. 2. For this reason, a suitable material for the back electrode is preferably selected from the group consisting of metals such as silver, carbon, ITO screen printing layer, AT 〇 screen printing layer, non-twisted wire Screen printing layer, which is an intrinsic conductive polymer system containing conventional nanoscale electrically conductive pigments, with a enamel screen printing paste from DuPont's product name 7162E or 7164, intrinsically conductive polymer System, 25 200908778 as obtained from Agfa's Orgacon® system from HC Starck GmbH

Clevios® poly(3,4-dioxyethylenethiophene) system, known as organometallic from Ormecon (PEDT-conducting polymer polyoxyethylene porphin), conductive coating from Panipol OY Layer and printing ink system, and polyaniline modified with high flexibility modifier, such as pu (polyurethane), PMMA (polymethyl methacrylate), PVA (polyethylene) Based on alcohols, in order to improve electrical conductivity, a metal such as silver or carbon may be added to the above materials and/or the material may be supplemented with a layer of the materials. The formulation of the back electrode paste can correspond to a portion of the transparent electrode. 10 However, without this formulation, the following formulations can also be used with the back electrode in accordance with the present invention. The preparation for printing a paste of one of the back electrodes is preferably used from 3 to 9 wt%, preferably from 40 to 80 wt%, particularly preferably from 50 to 70 wt% (print paste in each case) The total weight based on the conductive polymer clevios 15 P, Clevios PH, Clevios PAG, Clevios P HCV4, Clevios P HS 'Clevios PH, Clevios PH 500 'Clevios PH 510 or any desired mixture thereof. Dimercaptosulfoxide (DMSO), N,N-dimercaptocarbamide, N,N-dimethylacetamide, ethylene glycol, glycerol, sorbitol, methanol, ethanol, isopropanol, A mixture of n-propanol, acetone, acetophenone, dimercaptoaminoethanol, 20 water or two or three or more of the above solvents is used as a solvent. The amount of solvent used can vary over a wide range. For example, from 55 to 60% by weight of solvent may be present in a formulation according to the invention in a paste, while a solvent mixture of approximately 40% by weight of three solvents is used in a different formulation according to the invention. Silquest A187, Neo Rez R986, Dynol 604 and/or 26 200908778 A mixture of two or more of these may further be present as an interface additive and an adhesion promoter, preferably in an amount of from 7 to 12% by weight. It can appear, for example, from 0.5h.5 wt% of 85, BayMr〇ipR3,

Bayhydr〇1PR135 or any desired mixture thereof acts as a tethering agent. 5 - In another embodiment of the invention, the back electrode may be filled with graphite. This side can be achieved by adding 5 ink to the above-mentioned compound (4). Apart from the above-mentioned formulation for the back electrode, the following commercially available print pastes mentioned by way of example can also be used as ready-to-use formulations according to the invention: 〇rgacon EL_pi〇〇〇, EL p3 from Agfa 〇〇〇, 虹 p5_ l〇 or EL-P6 〇〇〇 series, preferably EL-P3000 and EL-P6000 series (especially for deformable applications). In this case, graphite may also be added. In particular, for the electrode ', the 〇rgac〇n EL-P4000 series of printing pastes' can be used, especially OrgaconEL-P4010 and EL-4020. The two can be mixed with each other in any desired ratio. 〇rgac〇n EL-P4010 and EL-4020 have 15 containing graphite. It is also possible to use commercially available graphite pastes as back electrodes, such as graphite paste from Acheson, in particular Eiectr〇dag 965 SS or Electrodag 6017 SS. A formulation according to the invention which is particularly useful for the manufacture of a printing paste 20 of the back electrode BE comprises: 27 200908778 Substance content/% by weight Content/% by weight Content/% by weight Clevios P HS 58.0 50.7 64.0 Silquest A187 2.0 1.0 1.6 NMP (eg BASF) 17.0 12.1 14.8 DEG 10.0 23.5 5.9 DPG/DMM 10.0 8.6 10.2 Bayderm Finish 85 UD (Lanxess) 3.0 4.1 3.5 Substance content/% by weight Content/% by weight Clevios P HS 58.0 50.7 Silquest A187 2.0 1.0 NMP (eg BASF) 17.0 12.1 DEG 10.0 23.5 DPG/DMM 10.0 8.6 Bayhydrol P340/1 3.0 4.1 Strip conductors, electrode connections 5 In the case of large surface brightening elements with a bright capacitor construction, surface conduction plays an important role in uniform brightness. The so-called bus bar is often used as a strip conductor in the case of large surface light-emitting elements in which relatively large current flows, in particular in the case of semi-conductive LEP (light-emitting polymers), PLED and/or OLED systems, component BF . In this case, a strip conductor having good electrical conductivity is produced in a cross manner. In this way, for example, a large surface is divided into four small surfaces. The voltage drop in the middle region of a shiny surface is thus significantly reduced, and the brightness uniformity or brightness is reduced 28 200908778 The mid-lightness of the field decreases. In the case of an EL field of zinc sulfide particles used in an embodiment of the invention, the applied alternating voltage is generally from more than 100 volts to more than 200 volts, and only when using a good dielectric or good insulation A small 5 current flows. In the ZnS thick film AC EL element according to the present invention, the problem of current load is therefore significantly smaller than in the case of a semi-conducting LEP or OLED system, so that it is not absolutely necessary to use a bus bar, but a large surface emitting element can be provided. Instead of bus bars. According to the invention, it is preferred that the silver 10 bus bar is printed only at the edge of the electrode layer BA or BE in the case of a region smaller than DIN A3; in the case of a region larger than DIN A3, preferably according to The present invention allows the silver busbar to form at least one additional strip conductor. The electrical connection can be made, for example, by using an electrically conductive and incinerated paste containing tin, zinc, silver, palladium, aluminum, and other suitable conductive metals or combinations and mixtures or alloys thereof. Electrically conductive contact strips are generally applied to electrical conduction by screen printing, brush application, ink jet, knife, roller, by spraying, by dispenser application, or by similar application methods known to those skilled in the art. And at least partially transparent thin coating, and which is then summarized as being heat treated in an oven so that the electrical conduction of the splicing, clamping or plugging of the solder 2 can be used to successfully contact laterally along a substrate edge. Strip applied. If only small electric power is introduced onto the electrically conductive coating, it is suitable to use a spring contact or a %I filled rubber element or a so-called zebra rubber strip. Use a conductive adhesive paste based on a polymer adhesive filled with silver, iron, steel or gold as a conductive adhesive paste. It is also possible to apply a self-adhesive electrically conductive strip of a plated copper pig having an electrically conductive adhesive oriented in the Z direction by pressing. The adhesive layer is applied uniformly and uniformly at a surface pressure of several Newtons per square centimeter, and depending on the design, 0.013 ohms/cm 2 (for example, from D&M International's conductive copper foil tape at A-8451 Heimschuh Ve 1691) or 0.005 ohms (for example, type 1183 from the Electrical Products Division of Texas, USA; according to MIL-STD-200 Method 307, maintaining 5 pounds per square inch (psi) measured on a 1 square foot surface area / 3.4 Newtons per square centimeter) or 〇〇〇 1 ohm 10 ohms (such as type 1345 from 3M) or 0.003 ohms (such as type 3203 from Holland Shielding Systems). However, the contacting can be effected by familiarizing with all processes known to those skilled in the art, such as folding, plugging, clamping, rivets, screws, and the like. Dielectric Tray 15 The EL element according to the present invention preferably has at least one dielectric layer, a component BD disposed between the back electrode, the component BE, and the rainbow layer, the component BC. Corresponding dielectric layers are known to those skilled in the art. The corresponding layer often contains a high dielectric powder such as barium titanate, which is preferably dispersed in a fluorine-containing plastic or a cyanide-based resin. An example of a particularly suitable particle is preferably barium titanate particles in the range of from 丨.0 to 2. 〇 μπι. With a high degree of filling, it can result in a relative dielectric constant of up to 100. The dielectric layer has a thickness generally ranging from 1 to 50 μηη, preferably from 2 to 4 μηηι, particularly preferably from 5 to 25, especially from 8 to 15 μηι. In one embodiment, the EL element according to the present invention may additionally comprise a further dielectric layer of - 30 200908778, one of which is disposed over the other and which together improves the insulating effect or which is interrupted by the floating electrode layer. The use of a second dielectric layer depends on the quality of the first dielectric layer and its freedom from the pinhole. As the filler, for example, BaTi03, SrTi03, KNb03, PbTi03, which are known from the literature, as known to the skilled artisan, are used.

LaTa03 ' LiNb03, GeTe, Mg2Ti04, Bi2(Ti03)3, NiTi03, CaTi03 ' ZnTi03 ' Zn2Ti04, BaSn03, Bi(Sn03)3, CaSn03, PbSn03 'MgSn03, SrSn03, ZnSn03, BaZr03, CaZr03, PbZr03 'MgZr03, SrZr03, ZnSr03, and lead-acid salt-titanate 10 are mixed crystals or a mixture of two or more of these fillers. The preferred filler according to the present invention is Ba^πo3 or pbZr03 or a mixture thereof in the paste for producing the insulating layer, preferably from 5 to 80% by weight, preferably from 1% to 75% by weight, particularly preferably from 40. Up to 70% by weight of the filling (based on the total weight of the paste in each case). 15 A one-part or preferably two-component polyurethane system may be used as a binding agent for this layer, preferably from Bayer MaterialScience (Bayer)

MaterialScience AG), especially for Desmodur and Desmophen or Lufranate, Lupranol, Pluracol or Lupraphen series from BASF AG, from Degussa AG (Evonik), preferably 20 Vestanat, especially Vestanat T And B; or from Dow Chemical Company's preferred Vorastar. It is also possible to use high-flexibility tethering agents, such as those based on PMMA, PVA, in particular Mowiol and Poval from Kuraray Specialties Europe GmbH or Polyvio from Wacker ag or PVB, 31 200908778 Especially from European Kuraray Specialties

Mowital (B 20 η, B 3〇T, B 3〇H, b 30 HH, B45H, B60T, B60H, B60HH, B75H) from Europe GmbH), or Pioloform from Wacker AG, especially pi 〇1〇f〇rm BR18, BM18 5 or BT18. For example, the following materials can be used as a solvent, ethyl acetate, butyl acetate, 1-pyridylpropyl 2-acetate, anthraquinone, dimethyl stupid, 3〇1Na〇1〇〇, 〇—〇1 15 A or a mixture of two or more & some solvents. When pvB is used as a binding agent, it is also possible to use methanol, ethanol, propanol, isopropanol, diacetone 10 alcohol benzyl alcohol, 1-methoxy-2-propanol, butanediol, methoxybutanol. , DTM1, methoxypropyl acetate, methyl acetate, acetic acid, butyl acetate, butoxy, n-butyl glycolate, acetone, methyl ethyl ketone, methyl isobutyl ketone, hexanone ketone , 1-toluene, calcined, cyclohexane, heptane and two or more of the above-mentioned solutions, the amount of which is from 1 to the total amount (based on the total weight of the material), preferably from 2 to 20% by weight, Very good from 3% by weight. Additives such as flow agents and rheological additives may also be added to improve properties. An example of a flow agent is XL480 in a butoxide group from a mixing ratio of 40:60 to 6:4. It can be used from 〇1 to 1% by weight, preferably from (4) to $20, 1/. It is particularly preferred as a further additive from 0.1 to 2% by weight, based on the total f weight in each case. For example, BYK41〇, BYK4l, Βγκ 431, or any desired mixture thereof may be present as a rheological additive sword, a sedimentation behavior of the J material and the filler in the paste. The formulation of the printing paste of the IS-made insulating layer is a component preferred according to the present invention, and/or the BD system contains ··································· % by weight BaTi03 50 50 50 55 Desmophen 1800 (BMS) 25 25 25 22.5 Desmodur L67 MPA/X (BMS) 14 14 14 11.4 Ethyl propyl acetate 8.7 0 4 0 methoxypropyl acetate acetal 0 8.7 4.7 8.6 Additol XL480 (50 weight 0/〇 in butoxy) 2.3 2.3 2.3 2.5 Substance content / wt% content / wt% content / wt% content / wt% BaTi03 55 56.6 59.9 59.9 Desmophen 1800 (BMS) 22.5 20.3 19.9 19.9 Desmodur L67 MPA/X (BMS) 11.4 12.5 11.2 11.2 ethoxypropyl acetate 8.6 7.6 5.7 0 methoxypropyl acetate 0 0 0 5.7 Additol XL480 in butoxy group 50% 2.5 3.0 3.3 3.3 Substance content / wt% Substance content /% by weight BaTi03 55 BaTi03 60.2 Desmophen 1800 (BMS) 22.5 Desmophen 670 (BMS) 14.3 Desmodur L67 MPA/X (BMS) 12 Desmodur N75MPA (BMS) 12.3 Ethoxypropyl acetate 8 ethoxypropyl acetate 10.3 Additol XL480 (50% by weight in butoxy group) 2.5 Additol XL480 (50% by weight in butoxy group) 2.9 EL layer 5 The EL element according to the invention comprises at least one EL layer, component BC. At least 33 200908778 an EL layer may be disposed on the entire inner surface of the first, partially transparent electrode or on one or more partial regions of the first, at least partially transparent electrode. If the EL layer is disposed on a plurality of partial regions, the partial regions are generally summed from each other by a distance of from 5 to 1 mm, preferably from 1 to 5 mm. The 5 EL layer is generally composed of a tethering agent matrix in which EL pigment is homogeneously dispersed. The binder matrix is generally selected to achieve good adhesion to the electrode layer (or dielectric layer to which it is selectively applied). In a preferred embodiment, a system based on PVB or PU is used. In addition to the El pigment, further additives may optionally be present in the matrix of the tethering agent, such as color-switching organic and/or inorganic systems, color additives for daylighting effects, and/or reflective and/or light absorbing effect pigments. Such as aluminum chips or glass chips or mica plate. The EL pigment used in the EL layer generally has a thickness from 丨 to 5 〇 μηι, preferably from 5 to 25 μηη. At least one EL layer, BC is preferably an alternating current thick film powder electroluminescent light 15 (AC-P-EL) bright structure. The thick film AC-EL system has been known since the Dasi zone (~ (4) i 947 and is mostly applied to the IT〇_PEm by screen printing. Because of the vulcanization of the electrophoretic group, especially at relatively high temperatures Deterioration of the display in the water vapor environment. Nowadays, the micro-sealed EL pigment is generally used for the long-life thick film AC EL lamp construction. However, the non-microencapsulation can also be used in the component according to the invention. Pigments, as further described below. Within the scope of the present invention, it is understood that the EL elements are operated by alternating voltages of reference 100 volts and 400 Hz and are emitted in this manner from several cd/m to several hundred cd/m2 The so-called cold light thick film element. These inorganic 34 200908778 thick film alternate "EUt towel, generalizing the station (10) net printing paste. ^ These EL screen printing paste is based on inorganic substances. Appropriate For example, highly pure Zns, (10) Ζη/υ compounds of Groups II and IV of the elemental periodic system, ZnS is particularly preferred. The above substances can be doped or activated by 5 and are also selectively activated together. For example, copper and/or copper is used. Doping vigorously, such as gas, bromine峨 铭 铭 进行 共同 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 , bromine, broken and/or aluminum are co-activated. 1 The EL emission color of the stomach is yellow, light, green, green blue, blue green and white, which can be converted by a mixture of suitable EL pigments or by color conversion. To obtain an emission color of white or red, the color conversion can be carried out in the form of a conversion layer and/or a polymer binder of a corresponding dye and pigment blended with a screen printing ink or a polymer matrix incorporating a pigment of £1. In another embodiment of the invention, the screen printing substrate used to make the EL layer is provided with a transparent, color filter or color conversion dye and/or pigment. In this way, a white emission color or a day can be produced. Luminous effect. In another embodiment, a pigment having an emission from a blue wavelength range of 420 to 480 nm and provided with a color-converting microencapsulation is used in the EL layer. This method can be used to emit white color. In one embodiment, The pigment used in the EL layer is An emitted AC-P-EL pigment in the blue wavelength range of 420 to 480 nm. In addition, the AC-P-EL screen printing substrate preferably contains cerium (II) activated alkaline earth orthophosphate such as (Ba, Sr,Ca)2Si〇4:Eu2+ or YAG Phosphorus such as 35 200908778 Y3Al5012:Ce3+ or Tb3Al50丨2:Ce3+ or Sr2GaS4:Eu2+ or SrS:Eu2+ or (Y,Lu,Gd,Tb)3(Al,Sc,Ga) 5012: Ce3+ or (Zn, Ca, Sr) (S, Se): Eu2+-based wavelength-converting inorganic fine particles. A white emission can also be achieved by this method. 5 According to the prior art, the above EL pigment can be microencapsulated. A good half life period can be achieved by inorganic microencapsulation techniques. An example that may be mentioned here is Luxprint®, an EL screen printing system for EL from DuPont, Pont de Nemours and Companies. Organic microencapsulation techniques and film coating laminations based on different thermoplastic films are also suitable in principle, but have been found to be expensive and do not substantially extend life. Suitable zinc sulfide microencapsulated EL phosphors (pigments) are manufactured by Osram Sylvania, Inc. Towanda under the trade name Glacier GLOTM, High Brite and Long Life, and Rogers C The Durel Division of 〇i*P〇rati〇n) encloses EL Phosphorus with the product name 1 15 PHS001® 咼 Efficiency Green, 1 PHS002® High Efficiency Blue Green Encapsulated EL Layer, 1 PHS003® Long Life The blue is encapsulated in the el structure, and the 1 PHS004® long-lived orange is encapsulated in the EL phosphorus supply. The mean particle diameter of the suitable microencapsulated pigment in the E L layer is generally from 15 to 60 μm, preferably from 20 to 35 μm. It is also possible to use an unencapsulated fine particle EL pigment in the EL layer of the EL element according to the present invention, which preferably has a long life. Suitable micro-encapsulated fine-grained zinc sulfide EL pigments are disclosed, for example, in KUS 6,248,26i and WO 01/34723. It preferably has a cubic crystal structure. The pigment which is not microencapsulated preferably has a mean particle diameter from β30, particularly preferably from 3 to 25 μm, and most preferably from 5 36 200908778 to 20 μm. EL pigments that are not microencapsulated can be used in particular in smaller pigment dimensions of less than 1 μm. The transparency of the glass element can thus increase. To this end, the unencapsulated pigment can be added to the screen printing ink suitable for use in accordance with the present application, which preferably takes into account the specific hygroscopic nature of the pigment and preferably the pigment. General use - for the so-called ιτ◦ layer (oxidized steel tin) or the intrinsically conductive polymerizable transparent layer has a good adhesion and also has a good insulating effect of the tethering agent to strengthen the dielectric and thus the puncture strength at high electric field strength Improved, and in addition to exhibit a good water 10 vapor in the fully cured state, additionally relies on the EL pigment and is used to enhance the life. In one embodiment of the invention, a pigment that is not microencapsulated is used in the AC-P-EL luminescent layer. The half-life of the appropriate pigment in the EL layer, that is, the initial brightness of the ELtl article according to the present invention has been halved. The time is summarized in (9) or ribs and 15 400 Hz from the end to no more than the hour, but usually Not more than from face to 3500 hours. The brightness value (EL emission) is generally from 1 to 2 〇〇 cd/m 2 , preferably from 3 to 1 〇〇 cd/m, particularly preferably from 5 to 4 〇 cd/m 2 ; in the case of a large shiny surface, brightness The value is preferably in the range of from 1 to 50 cd/m2. - However, it is also possible to use a pigment having a longer or shorter half life period and a higher or lower brightness value in the EL layer of the EL element according to the present invention. In another embodiment of the invention, the pigments present in the EL layer have a small mean particle diameter 'or a low degree of filling in the EL layer, or the individual £1^ layer has a small geometric shape, or an individual £1^ layer The spacing between the two is large to make the EL element at least partially transparent or to ensure transparency by a 37 200908778 non-electrically activated light-emitting construction. Appropriate pigment particle diameters, degree of filling, dimensions of the illuminating elements, and spacing of the illuminating elements are mentioned above. The layer contains the above-mentioned selectively doped zns crystals, preferably 5 microencapsulated as described above, preferably in an amount of from 40 to 90% by weight, preferably from 5 to 8% by weight, particularly preferably from 55 to 70% by weight, based on the weight of the paste in each case. One component and preferably two components of polyaminophthalate can be used as the binding agent. According to the invention, it is preferred to use highly flexible materials from Bayer MaterialScience AG, such as Desm〇phen and 10 Desmodur series of paint materials, preferably Desmophen and Desmodur, or Lupranate from BASF AG. Paint materials for the Lupranol, piurac〇i or Lupraphen series. For example, the following may be used as a solvent, ethoxypropyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, acetone 'methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, dioxane Any 15 or more of a mixture of two or more of these solvents, preferably in an amount of from 1 to 50% by weight, more preferably from 2 to 30% by weight, particularly preferably from 15 parts by weight of naphtha. 5 to 15% by weight 'based on the total weight of the paste in each case. It is also possible to use other high-flexibility tethering agents, such as those based on PMMA, PVA, especially from Kuraray Europe GmbH (now 20 known as Kuraray Specialties, Mowiol and Poval or It is Polyvio or PVB from Wacker AG, especially Mowital (B 20 H, B 30 T, B 30 Η, B 30 HH, B 45 H, B 60 T, from European Currie). B 60 Η, B 60 HH, B 75 Η), or Pioloform from Wacker AG, especially Pioloform BR18, 38 200908778 BM18 or BT1. When using a polymer binder such as PVB, it is possible Adding solvents such as methanol, ethanol, propanol, isopropanol, diacetone alcohol, benzoyl alcohol, 1-decyloxy-2-propanol, butanediol, decyloxy-butanol, Dowanol, acetic acid Oxypropyl propyl ester, decyl acetate, ethyl acetate, butyl pentoxide, butoxy, n-butyl glycolate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, hexane a mixture of cyclohexane, heptane and two or more of the above solvents in an amount of from 1 to 30% by weight ( The total weight of the paste is based on, preferably from 2 to 20% by weight, particularly preferably from 3 to 10% by weight. There may also be 10 additives for improving the prevalence and flow from 0.1 to 2% by weight. An example is Additol XL 480 in a butaneoxy group from 40:60 to 60:40. It may occur from 0.01 to 1% by weight, preferably from 0.05 to reduce the settling behavior of the pigment and filler in the paste. 5 wt%, particularly preferably from 0.1 to 2 wt% of rheological additive as further additive, in each case based on the total weight of the paste, such as BYK410, BYK411, BYK 430, 15 BYK 431 or any desired Mixture. The formulation of the printing paste used to make the EL phosphor layer as a component of the preferred embodiment according to the invention BC contains: material content / weight % content / weight % content / weight % content / weight % pigment (Osram Sylvania 55.3 69.7 64.75 65.1 Desmophen D670 (BMS) 18.5 11.9 12.7 13.1 Desmodur N75 MPA (BMS) 16.0 9.0 12.4 11.3 Ethoxypropyl acetate 9.8 9.1 9.9 10.2 Additol XL480 (50% by weight in butoxy group) 0.4 0.3 0.25 0.3 39 200908778

Substance content / wt% wt% ^quantity % 69.7 ~--- 11.9 ----- 9.0 —-- 4.9 — 4.2 Pigment (Osram Sylvania) 61.2 65^ Desmophen D670 (BMS) 15.2 ----- 12.7 Desmodur N75 MPA (BMS) 13.1 -~---- 11.4 methoxypropyl acetate 10.2 __- 5.5 ethoxypropyl acetate 0 5 Additol XL480 (50% by weight in butoxy group) 0.3 0.3 —-_ 0.3 -- ----------- -----J substance content / weight%

0.4 pigment (Osram Sylvania)

Desmophen 1800 (BMS)

Desmodur L67 MPA/X (BMS) Acetate Acetate

Additol XL480 (5 重量% by weight in butoxy group) In addition to components A and B, the El component according to the present invention is a one-layer, component CA, to avoid damage to the electroluminescent element or possible shape. image. Suitable materials for the protective layer are known to those skilled in the art. A suitable protective layer CA is, for example, a protective varnish having high temperature stability, such as a protective lacquer containing polycarbonate and a binding agent. An example of this protective paint is from

WeiBenburg's Pr6li's N〇dphan®HTR. Alternatively, the protective layer may also be formulated on the basis of a flexible polymer such as polyurethane, PMMA, PVA, PVB or the like. Polyamine 40 200908778 carbamate from Bayer MaterialScience AG can be used for this purpose. This formulation may also be provided with a filler. This use is suitable for use with all fillers known to those skilled in the art, for example based on inorganic metal oxides such as Ti 〇 2, zn 〇, zinc lanthanum, etc., having a printing paste of from 10 to 80 parts by weight, preferably from 20 to 70% by weight, particularly preferably from 4 to (4). The formulation may also contain a flow agent and a rheological additive. For example, the following solvents can be used, ethoxypropyl acetate, ethyl acetate, butyl acetate, methoxy = propyl acetate 'acetone, ethyl ketone 'methyl isobutyl ketone, 5 hexanone, scorpion, two ; Benzene, solvent naphtha 100 or a mixture of two or more of these solvents. The formulation of the protective paint C A which is particularly preferred according to the present invention contains, for example:

Substance content / wt% Desmophen 1800 (BMS) 22.9 Additol XL480 (50% by weight in the butyl group) 1.1 Desmodur L67 MPA/X (BMS) 12.9 Ethoxypropyl acetate 10.6 Ti02 52.5 41 200908778 Substrate EL element according to the invention Substrates such as glass, plastic film or the like may be provided on one or both sides on the respective electrodes. In the EL element according to the present invention, it is preferred that at least one of the substrates in contact with the transparent electrode exhibits a pattern of transparent translucent and opaque cover on the inner side. Please understand that, for example, in the sense of red_green_blue translucent for signalling purposes, an opaque covering form is a large surface electroluminescent region that is opaquely covered by a high resolution graphic form and/or in a transparent form. . Further, it is preferable that the substrate contacting the transparent electrode BA becomes a film which can be deformed by cold working at a temperature lower than the glass transition temperature Tg. This provides the possibility of deforming the generated EL element three-dimensionally. It is additionally preferable to make the substrate contacting the back electrode BE a film which is similarly deformable by cold working below Tg. This provides the possibility of deforming the resulting eL element three-dimensionally. 15 £ [The component can be deformed in three dimensions, which may have a radius of curvature of less than 2 mm, preferably less than 1 mm. The deformation angle can be greater than 60. Preferably, it is greater than 75. , especially better than 90. , especially greater than 1〇5. . It is additionally preferred that the EL element can be deformed three-dimensionally and in particular deformed by cold working below Tg and thus obtain a precisely shaped three-dimensional shape. A thermoplastic material can be molded into at least one side of the two-dimensionally deformed member in an injection molding tool. The kneaded EL is opened. The above-mentioned paste (screen printing paste) is usually applied to a transparent plastic film or glass 42 200908778, which in turn has a substantially transparent electrically conductive coating and thus constitutes a visible side. electrode. If any of the dielectrics present and the backside electrodes are subsequently fabricated by printing and/or lamination techniques. However, it is also possible to have a reverse manufacturing process in which the rear side electrode is first fabricated or the back side electrode is used in the form of a metallized film and a dielectric is applied to the electrode. Then, an EL layer is applied and a transparent and electrically conductive upper electrode is applied thereafter. The resulting system can be subsequently selectively laminated to a transparent cover film and thus protected from water vapor and from mechanical damage. In one embodiment of the invention, a strip conductor (silver busbar) can be applied to substrate A as a first layer. However, it is preferably applied to electrode 8 eight or eight in accordance with the present invention, in either operation. They are applied to the individual electrodes or applied together to the electrodes in a single working step. The EL layer is usually applied by screen printing by a printing technique or a dispenser application or a nozzle ink application or by a knife process or a roll coating process or a curtain dumping process 15 or a process, preferably by a wire mesh. The print is applied. The EL layer is preferably added to the surface of the electrode or to the layer that is selectively applied to the back electrode. The present invention further provides for the use of the -EL element according to the invention as a material and/or a brightening element in the L-space or for external use, preferably on the exterior front side of the building, in the body of the device. Or on land, on land, in aircraft or sharpeners in or on the automotive industry or in the advertising field. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in detail below with reference to the drawings. The drawings show preferred embodiments and are not intended to be limiting. 43 200908778 Figures 1 through 7 show, in graphical form, possible different configurations of E L elements in accordance with the present invention, in each case cut. In the following figures, the individual numbers have the following meanings: No. List 5 1 Zinc sulphide thick film AC electroluminescent element (EL element) 2 Substrate/carrier material (top layer or laminate) 3 Transparent electrode (front side) 4 EL Thick film layer 5 EL pigment 10 6 polymer matrix 7 first dielectric layer 8 second dielectric layer 9 back electrode 10 substrate / carrier material (back side electrode) 15 11 nanostructured particles 12 floating electrode 13 further Floating electrode 14 transparent SWCNTs in the front side electrode 15 nano-structured particles in the first insulating layer 20 16 nano-structured particles in the second insulating layer, nano-structured particles 18 in the back electrode layer Particles with nanostructures in the region of the EL pigment 19 Transparent silicon particles between the front side electrode and the EL layer in the immediate vicinity of the SWCNTS 20 EL pigment 44 200908778 21 EL inverter connection: the formula is 100 to 200 volts, 1 〇〇 to 2 〇〇〇 Hz 22 EL emission L Embodiment 3 Figure 1 (prior art): 5 Figure 1 shows a substrate (2) having one of the transparent front side electrodes (3) applied thereto An illustration of an exemplary cross-section of one of the EL elements (1). An EL layer (4) containing a corresponding EL pigment (5) in a polymer matrix (6) is disposed on the side away from the transparent electrode of the substrate. On the side remote from the transparent electrode (3), there is additionally a dielectric layer (7) which is in contact with the EL layer (4). The dielectric layer is followed by a back 10 electrode (9) and another optional substrate (10). Fig. 2 (according to the invention): Fig. 2 shows an illustration of an exemplary cross section of an EL element (1) having a material (2) which has been applied with one of the transparent electrodes (3). On the side of the transparent electrode remote from the substrate is provided an EL layer (4) containing a corresponding 15 EL pigment (5) in a polymer matrix (6). On the side remote from the transparent electrode (3), there is additionally a dielectric layer (7) and (8) which are in contact with the EL layer (4). The dielectric layer is followed by a back electrode (9) and another optional substrate (1). The particles ”” having a nanostructure are contained in the EL layer (4). Fig. 3 (according to the invention): Z〇 Fig. 3 shows that one of the transparent electrodes (3) has been applied according to the invention. An illustration of an exemplary cross-section of the ELit member (1) of the material (2). The side of the transparent electrode remote from the substrate is provided with a corresponding EL pigment (5) in a certain substance (6). The layer 1(4)0 additionally has a layer of 45 200908778 (12) containing a nano-tubular particle having a nanostructure on the side remote from the transparent electrode. The two dielectric layers (7) and (8) are located. After this layer (12), the dielectric layer is followed by a back electrode (9) and another optional substrate (10). Figure 4 (according to the invention): Figure 4 shows that a transparent has been applied according to the invention Illustrative diagram of an exemplary cross-section of an electrode (3) having an EL element (1) of a substrate (2). A single-walled carbon nanotube (14) is contained in the transparent electrode. On the side of the transparent electrode is provided an EL layer (4) containing a corresponding EL pigment (5) in a polymer matrix (6). Particles (11) having a nanostructure are also present in the anal layer. On the side remote from the transparent electrode (3), there is additionally a layer (12) comprising nano-tubular particles having a 10 nm configuration, in contact with the EL layer (4). The two dielectric layers (7) and 8) After the layer (12), the dielectric layers (7) and (8) are separated from each other by a layer (13) in the form of a floating electrode containing one of the particles having a nanostructure. 15,16) is included in both the dielectric layers (7) and (8). The dielectric layer is followed by the back electrode containing the nanostructured particles (17), and has a substrate (10). Figure 5 (according to the invention): Figure 5 shows an illustration of an exemplary cross-section of an EL element (1) with a substrate (2) applied with a transparent electrode according to the invention. The side of the transparent electrode is provided with an EL_ containing a corresponding pigment (5) in a polyester (6). The dielectric layer (7) and (8) are additionally provided on the side away from the transparent electric port. It contacts the layer (4). The dielectric layer is followed by the back electrode (9) and the other selected substrate (10). This layer (4) contains particles with nanostructures in the EL simple zone. Figure 6 Ming): 46 200908778 Figure 6 shows an illustrative cross-section of an exemplary EL element (1) with a substrate (2) applied with a transparent electrode (3) according to the invention. The side of the transparent electrode is first provided with a layer 5 (19) containing particles having a nanostructure (here: SWCNTs) in a polymer matrix (6) and then an EL layer containing a corresponding EL pigment (5). (4) additionally has two dielectric layers (7) and (8) on the side away from the transparent electrode (3), which is connected

Touch the EL layer (4). The dielectric layer is followed by a back electrode (9) and another optional substrate 〇〇). The EL layer (4) contains nano-tubular particles in the region of the EL pigment. The component exhibits an EL emission (22). Fig. 7 (according to the invention): Fig. 7 is a diagram showing an exemplary cross section of an EL element (1) having a substrate (2) to which a transparent electrode (3) has been applied according to the invention. On the side away from the transparent electrode of the substrate, an EL layer (4) containing a corresponding EL pigment (5) in a polymer matrix (6) is first provided. On the side remote from the transparent electric 15 pole (3), there is additionally a floating electrode layer (20) containing particles having a nanostructure, and two dielectric layers (7) and (8), which are in contact with £1. ^ Layer (4). The dielectric layer is followed by a back electrode (9) and another optional substrate (1). The component exhibits £]^ emission (22). An EL inverter connection (21) is provided. BRIEF DESCRIPTION OF THE DRAWINGS 2 20 Figures 1 through 7 show, in graphical form, possible different configurations of EL elements in accordance with the present invention, in each case cut. [Description of main component symbols] 1...Vulcanized thick film AC electroluminescent element (EL element) 2 ·_·Substrate/carrier material (top layer or covering) 47 200908778 3···Transparent electrode (front side) 4. .EL thick film layer 5.. .EL pigment 6.. polymer matrix 7... first dielectric layer 8.. second dielectric layer 9.. back electrode 10.. substrate / Carrier material (back side electrode) 11. Particles with nanostructures 12.. Floating electrode 13. Further floating electrode 14: S WCNTs in transparent front side electrode 15.. First insulating layer Particles having a nanostructure in the middle 16. Particles having a nanostructure in the second insulating layer... Particles having a nanostructure in the back electrode layer 18: Nano in the region of the EL pigment Constructed particles 19.. Transparent SW-layer between the front side electrode and the EL layer 20.. EL pigments in the immediate vicinity of the nano-structured particles 21..EL inverter connection 22..EL emission 48

Claims (1)

200908778 X. Patent Application Range: 1. A thick film electroluminescent device based on vulcanization, comprising a first transparent electrode, at least one electroluminescent layer and a second back electrode, characterized in that the thick film The electroluminescent element comprises particles having a nanostructure. 5. The thick film electroluminescent device of claim 1 wherein the thick film electroluminescent device comprises at least one dielectric layer. 3. The thick film electroluminescent device of claim 1 or 2, wherein the thick film electroluminescent device additionally comprises another dielectric layer. The thick film electroluminescent element 10 of any one of claims 1 to 3 is characterized in that the thick film electroluminescent device additionally comprises a first carrier substrate. 5. The thick film electroluminescent device of any one of claims 1 to 4 wherein the thick film electroluminescent device additionally comprises a second carrier substrate. The thick film electroluminescent device according to any one of claims 1 to 5, characterized in that the nanostructured particles are selected from the group consisting of: single-walled carbon naphthalene Rice tubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), nano-rods, nano-horns, nano-disc, nano-cone, metal nereline and combinations of the above particles. The thick film electroluminescent device according to any one of claims 1 to 6, wherein the nanostructured particles are uniformly dispersed or randomly oriented or guided. 8. The thick film electroluminescent device according to any one of claims 1 to 7, wherein the spherical particles are at the same speed as the thick film electroluminescent light. In the component. 9 μ ^ j, ° month patent range 8th thick film electroluminescent device, characterized in that spherical particles such as ° Hai have a diameter from 1 to 50 nm and / or from 〇〇 1 to 1 〇〇 5 μ Π 1, compared Good from 0.5 to 5 〇μπι, especially good from 〇_1 to 1〇μιη length dimension. The thick film electroluminescent device according to any one of claims 1 to 9, characterized in that SWCNTs or MWCNTs or two types of groups S are used as the particles having the nanostructures, in each case There is at least a 1:100 size ratio. ^ 1. A thick film electroluminescent device according to any one of the preceding claims, wherein the nanostructured particles have a particle size of at least 3 Å, preferably at least 50, particularly preferably at least 1 Å, and most preferably at least 2 Å. 〇 - high dielectric constant, and / or appropriate electrical conductivity. 12. The thick film electroluminescent device of any one of the claims of the invention, wherein the nanostructured particles are present in at least one of the layers of the electrodes, the EL layer Or in the dielectric layer. ^Application: The coffee belongs to the 12-shot-item = the excitation light element. It is characterized in that the particles having the nanostructure appear in the layer. 14. For example, the thick film mine and private grade 20-sequence film electro-excitation element of the 13th item of the Shenqing patent scope is characterized in that the particles having the nano structure are not blasted to the lower limit of the percolation. The fill percentage appears in the EL layer. The pre-existing membrane electroluminescent device of claim 13 or claim 14, wherein the nanostructured pellets are less than 2% by weight, 1% by weight, and particularly preferably less than 0.5% by weight.里/〇的—The percentage of filling appears in the 50 layer of 2009 200978. The thick film electroluminescent device of any one of claims 1 to 15 characterized in that the nanostructured particles are present in the dielectric layer 〇17. The thick film electroluminescent device of the present invention is characterized in that the nanoparticles having the nanostructures are present in the dielectric layer in a percentage of filling which does not reach the lower limit of percolation. 18. The thick film electroluminescent device of claim 16 or 17, wherein the nanostructured particles are less than 2% by weight, preferably less than 1% by weight, particularly preferably less than 0.5% by weight. A fill percentage is present in the dielectric layer. The thick film electroluminescent element of the present invention is characterized in that the nanostructured particles are present in at least one of the electrode layers. 15 20 20. If the scope of the patent application is 19, then, etc.: The particles of the nanostructure are considered as 1::::: The percentage of filling appears in the electrode layer. The application for the full-time (4) item is electrically excited by the / / characteristics of the nano structure, in the _ center of gravity (10). Out; 1 = 44% '(four) in the polar layer. The number of heavy 〇/〇 appears in the electricity • such as the scope of the patent range from 〖 to 21, characterized by the thick film electro-excitation thick film electro-excitation light; the electrical layer contains - containing the The thick-film electroluminescent device of the thick-film electroluminescent device of claim 22, wherein the thick-film electroluminescent device is in a first dielectric layer And a second dielectric layer comprising a nano-structured particle comprising a floating electrode layer containing particles having a nanostructure. 5. The phase electroluminescent device according to any one of the preceding claims, wherein the thick film electroluminescent device comprises in the electroluminescent layer in the sense of non-cohesive mixing. An electroluminescent pigment coated with such nanostructured particles. 25. A method for producing a thick 10-film electroluminescent device as claimed in any one of claims 1 to 24, which is applied by screen printing of the individual layers, dispenser application or ink jetting Print. 26. The method for fabricating a thick film electroluminescent device of claim 25, wherein at least the substrate associated with the transparent electrode exhibits a transparent transparent translucent and opaque cover on the inner side. Shape 15 style. 27. The method for manufacturing a thick film electroluminescent device according to claim 25 or 26, wherein at least the substrate associated with the transparent electrode is cold worked by a glass transition temperature Tg. Deformed. 28. The method for fabricating a thick film 2 〇 electroluminescent element according to any one of claims 25 to 27, wherein at least the substrate associated with the back electrode is lower than The cold working of Tg is deformed. 29. The method for manufacturing a thick film electroluminescent device according to any one of claims 25 to 28, characterized in that the EL element is deformable three-dimensionally, preferably by a cold working process lower than Tg Deformation. The method for manufacturing a thick film electroluminescent device according to any one of claims 25 to 29, wherein a thermoplastic material is molded in a three-dimensional deformation in an injection molding tool. On at least one side of the component. 5 31. A decorative element and/or a brightening element obtained in the interior space as claimed in any one of claims 1 to 24 or as at least one of claims 25 to 30 For external use, preferably on the exterior front of the building, in or on the body of the equipment, in or on land vehicles, aircraft or watercraft, in equipment for buildings, in the automotive industry or in the field of advertising The use of thick film electroluminescent elements. 53