WO2014032642A1

WO2014032642A1 - Organic-electronic layer system

Info

Publication number: WO2014032642A1
Application number: PCT/DE2013/000486
Authority: WO
Inventors: Rudolf Schmidt; Arno Schmuck
Original assignee: Inoviscoat Gmbh
Priority date: 2012-08-27
Filing date: 2013-08-27
Publication date: 2014-03-06
Also published as: DE112013004200A5; DE102012016759A1

Abstract

The invention relates to an organic-electronic layer system comprising at least one carrier and at least one layer containing carbon particles, characterized in that said carbon particles are dispersible in an aqueous medium and are electrically conductive.

Description

Organoelectronic layer system

[01] The invention relates to an organo-electronic layer system comprising at least one support and at least one layer containing carbon particles, a method for producing such a layer system and the use of such a layer system, e.g. as a heat-emitting system, wherein the layer system e.g. i) a luminous element with a luminescent layer which has electroluminescent particles and a back electrode, ii) a luminous image and iii) a heating element.

Such organoelectronic layer systems are known, for example, from WO 2010/133681 A1, WO 2009/030701 A1, EP 906714 A1 and WO 2002/080627 A2, where the carbon particles are incorporated either only as coloring pigments without appreciable conductivity or as additives with low conductivity so they have to be combined with conductive polymers.

[03] In addition, no such organoelectronic layer systems are known whose components are all water-dispersible or soluble in an aqueous medium. This would allow aqueous-based production without the use of organic solvents and thus significantly less expensive production, since explosion protection precautions and solvent extraction and recovery can be dispensed with and would significantly improve the life cycle assessment of such systems by eliminating organic solvents. [04] Furthermore, the conductivity of known organo-electronic layer systems for some applications, e.g. for the production of heating elements, unsatisfactory and they also have insufficient thermal stability.

[05] In the known organoelectronic layer systems, such as e.g. Light-emitting elements can make substances containing heavy metals difficult to dispose of and thus have a negative impact on sustainability. The future of product development can only be based on the principle of closed circuits (see Michael Braungart "http://de.wikipedia.org/wiki/Michael_Braungart" and the concept developed by him "Cradle To Cradle" and "http: // www .brandeins.de / magazin / again - what - done / garbage - is - food.html ").

Bestätigungskopiel [06] It is therefore an object of the invention to provide an environmentally friendly organoelectronic layer system which is sustainable, can be produced inexpensively, has a good eco-balance, has a high conductivity based on carbon particles and is distinguished by good heat stability. [07] This object is achieved with a generic organoelectronic layer system in which at least one layer contains carbon particles which are dispersible in an aqueous medium and have an electrical conductivity.

[08] A layer which is conductive in this way according to the invention is also referred to below as the electrode layer. [09] An organoelectronic layer system according to the invention may in the simplest case be a support and an electrode layer applied directly thereto. After electrical contacting of the electrode layer by known methods, a resistance element is obtained, e.g. for heat dissipation and thus can be used as a heating element. [10] The electrical contacting of the light-emitting element preferably takes place via conductive materials, in particular sheets, which are e.g. with a conductive adhesive tape such as e.g. 3M ™ Electrically Conductive Adhesive Transfer Tape (ECATT) 9723 to the bus bar and / or back electrode.

[11] Instead of only one, 2, 3, 4, 5, 6 or more than 6 separate electrode layers can be applied and the conductivity of the electrode layer (s) can be increased by other, even semitransparent conductive layers.

[12] Preference is given to using a cover layer as barrier layer which protects the organoelectronic layer system from atmospheric oxygen and moisture and optionally from chemicals and mechanical damage. The barrier should be electrically insulating to protect the user from electrical injury. The barrier layer can be omitted at the connection parts for the electrode layer or for other conductive layers. As a barrier layer, for example Actega Terraflex barrier lacquer in addition to a polyethylene or a Polyvinylidenfluoriddispersion (PVDF) is suitable. Alternatively, other commercially available barrier layers made of glass or foil come into question.

In a further embodiment of the invention, the organoelektroni see layer system is a luminous element, which usually consists of support, adhesive layer, front electrode layer, luminescent pigment layer, dielectric and back electrode layer and suitable contacts and if necessary one or more protective layers and its back electrode layer as Electrode layer is formed according to the invention. [15] In WO 2013/091604 A I light-emitting elements are described, which are particularly suitable for being implemented with an electrode layer of the invention as a return electrode. Therefore, with regard to the layers and constituents suitable for light-emitting elements of the invention and the production thereof, the text of WO 2013/091604 A1 is incorporated by reference into the present description, in particular paragraphs [07] to [44] and [48] to [65]. as well as the examples.

[16] An organoelectronic layer system according to the invention may also be a luminous image, which is usually formed from a multilayer composite of an imaging material and a luminous material. As a luminous material for a luminous element of the invention can be used. Instead of a solid multi-layer dressing, a luminous image can also be obtained by passing through or illuminating a separate imaging material by a luminous element of the invention.

[17] In WO 2013/091605 AI luminous images are described, which are particularly suitable to be executed as a multi-layered association with a luminous element of the invention. Therefore, with respect to the layers and components suitable for luminescent images of the invention and their preparation, the text of WO 2013/091605 A1 is incorporated by reference into the present description, in particular paragraphs [12] to [36], the first 3 lines of [37 ] and [38] to [68], wherein the electroluminescent device or the OLED layer dressing described therein is to be equipped with an electrode layer of the invention as a return electrode. It has been found that in an organoelektroni see layer system can be completely dispensed with silver compounds as an electrode layer. The use of carbon particles with electrical conductivity makes it possible to produce almost heavy-metal-free organoelectronic layer systems that are easy to dispose of and thus very sustainable.

[19] It is advantageous if, in addition, the layers required for the production of the organoelectronic layer system are free of organic solvents.

If one or more layers of the organoelectronic layer system and in particular of the luminous element have at least one water-dispersible or water-soluble protective colloid, such organoelectronic layer systems are particularly easy to produce, as i.a. the digestion stability of the casting solution (s) concerned is increased and show improved bending stability. It also greatly simplifies processability and subsequent disposal.

[21] In one embodiment of the invention, at least the electrode layer has a water-dispersible or water-soluble protective colloid. In spite of the known dielectric or insulating effect of such protective colloids in dried layers, this leads to electrode layers with an increased conductivity.

[22] Protective colloid-containing layers of the organoelectronic layer system preferably contain, based on the dry weight, at least 10% by weight, in particular 10% by weight to 40% by weight, of protective colloid. This is particularly advantageous if it is a luminescent pigment layer.

[23] Different materials can be used as protective colloids. Protective colloids or antiflocculants are usually polymer systems intended to prevent agglomeration, coagulation or flocculation of an emulsified, suspended or dispersed substance in suspensions or dispersions. An essential property of protective colloids is that they bind large quantities of water during solvation. As a result, high viscosities are achieved in aqueous solutions as a function of the concentration. Unlike emulsifiers, protective colloids usually do not lower the interfacial tension between a stored polymer particle and the surrounding water. Protective colloids do not form micelles and are used to stabilize dispersions.

As protective colloids both natural products such as gelatin, starch, chitosan, casein and dextrin are used, but also derivatives of natural products, such as cellulose derivatives, eg. Hydroxypropylmethylcellulose (HPMC) or carboxymethylcellulose (CMC) or modified or partially degraded gelatin. It is also possible to use polymers such as polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acids and polyacrylamides as protective colloids, as well as wax emulsions, e.g. a nonionic ethylene-vinyl acetate copolymer wax. Particularly preferred as a protective colloid is gelatin, which in addition to its carrying capacity has a good insulator effect.

[25] In particular, when protective colloids of natural products are used, the use of biocides is recommended to improve the durability of casting solutions. Preference is given to using biocides from the group of benzisothiazolones, for example Proxel (1,2-benzisothiazol-3 (2H) -one). The biocides are preferably applied in amounts of from 0.003 g / m ² to 0.03 g / m ² , in particular from 0.005 g / m ² to 0.01 g / m ² .

[26] In order to achieve a particularly high dispersion stability, it is proposed that the protective colloid has gelatin. As a protective colloid also pure gelatin can be used. As an example, 10 to 30 percent by weight of gelatin may be present in at least one layer, and in the case of a luminous element at least in the luminous layer. [27] The drying of such layers can lead to severe shrinkage, which can destroy the entire layer structure. It is therefore proposed that at least one of the layers comprises a plasticizer.

[28] The plasticizer should be present in the layers and in a luminous element, in particular in the luminescent layer, in an amount which prevents unwanted brittleness, brittleness and deformation of the organoelectronic layer system during drying. The individual components should therefore be coordinated so that the organo-electronic layer system and in particular the luminous element does not break at a bending radius of 0.5 cm. [29] In a preferred embodiment, the layers and, in the case of a luminous element, in particular the luminous layer, based on their dry weight, have at least 10% by weight of protective colloid.

[30] In addition, it is advantageous if the layers and, in the case of a luminous element, in particular the luminescent layer, based on their dry weight, contain not more than 0.1 per cent by weight of water.

It is particularly advantageous if the organoelectronic layer system or the luminous element based on the dry weight of a maximum of 0.05 weight percent, preferably at most 0.005 weight percent organic solvent with the exception of ethanol, isopropanol or butanols, especially with the exception of ethanol and in a particularly advantageous embodiment contains at most 0.05 weight percent, preferably at most 0.005 weight percent organic solvent.

[32] The organo-electronic layer system of the invention comprises a support which may be provided with a subbing layer. This support should preferably be flexible and in particular allow a bend radius desired for the luminous element depending on the intended application. In addition, it is advantageous to select him from the viewpoint of known support materials that he is well suited for the process for applying the layer package.

[33] As support materials can serve clear, transparent and flexible films, which are prepared for example based on the following polymers or mixtures thereof: polyethylene, polyester, cellulose acetate, in particular cellulose triacetate, PET (polyethylene terephthalate), polycarbonate, PLA (Poly Lactic acid), polyamide 6, polyamide 12, PEN (polyethylene naphthalate), PTFE (Teflon ^® = polytetrafluoroethylene), POM (polyoxymethylene), and ETFE (ethylene tetrafluoroethylene). [34] Conductive carrier materials are also suitable for the invention, which can serve, for example, for contacting or for supporting the conductivity of the electrode layer applied thereon. The conductivity can be generated by known methods, for example by subbing, plasma treatment or metal vapor deposition, or by incorporation of conductive substances in the carrier. In addition, the carrier may also consist of intrinsically conductive material, for example of a foil of metal or a metal alloy. [35] The wearer may also be a textile. In particular, when using textiles as a carrier, it is advantageous if the carrier has at least one layer (primer layer) in order to adapt the absorbency and / or the surface finish for the following coating steps. For example, the coating of surfaces with unevenness could lead to errors in the coating. The primer layer (s) may include, for example, a thermoplastic polyurethane to flatten the surface of the backing. Such layers are preferably dilutable with water.

[36] Suitable adhesion layers are the water-based substrateings and surface treatments of the support known for casting processes. Preferably, the adhesive layer contains gelatin, in particular in an amount of 1, 5 g / m ² to 3.2 g / m ² and particularly preferably from 1, 8 g / m ² to 2.8 g / m ² .

[37] In addition, further substances may be added to the adhesive layer, e.g. improve the castability and stability, e.g. Biocides and plasticizers as described above, wetting agents and other Begusshilfsmittel.

[38] The electrode layer can be applied to the substrate directly or separately by one or more additional layers. In one embodiment of the invention, which is particularly suitable as a heating element, the electrode layer is preferably directly or separated by only one or less than 4 layers, in particular less than 3 layers coated on the subsu ^m ierten unsubstrierten or carrier. This results in a good heat transfer to the carrier and the material can be heated to higher temperatures before it comes to damage in the coating.

[39] A preferred embodiment with advantages in terms of producibility and mechanical properties provides that the layer thicknesses of the organoelectronic coating system are between 2 μm and 100 μm, in particular between 5 μm and 50 μm, and particularly preferably between 5 μm and 40 μm. The layer thickness of the electrode layer is preferably between 5 μπι and 20 μπι and in the case of a luminous element, the luminescent layer preferably has a thickness of less than 40 μπι on. [40] The organoelectronic layer system can have, in particular as a light-emitting element, a water-soluble or alcohol-soluble, transparent, conductive front electrode. This front electrode layer should preferably have a thickness of less than 20 μm.

[41] Suitable methods for applying layers, in particular luminescent layers, to a support are e.g. the doctor blade coating, dip coating, spray coating or roller coating, also with counter-rotating roller or in a preferred embodiment, a single or multiple coating by casting methods such as the cascade or curtain casting.

[42] A particularly advantageous method for producing such an organoelectronic see layer system includes the step that at least a portion of the layers, in particular the electrode layer and / or in the case of a luminous element, the luminescent layer, are produced in a casting process. Preferably, all the castable layers of the layer system and, in the case of a luminous element, at least the entire luminous layer and the back electrode layer are each applied successively as a single layer in a single casting process or in the form of multiple layers simultaneously on a support in a multiple casting process. However, individual or all layers can also be applied with a doctor blade to a support or another layer.

[43] In a particularly preferred embodiment of the invention, all castable layers are applied to a carrier simultaneously by a multiple-cast process.

[44] In one preferred embodiment of the invention, the additives described below may be present in one or more layers, preferably at least in the electrode layer, wherein solutions or dispersions of such additives in an aqueous medium are preferably used during the preparation. As dispersions in the context of the invention, e.g. Emulsions or suspensions, regardless of the size of the dispersed particles understood.

The use of gelatin as a protective colloid in the electrode layer can, depending on the layer composition during drying lead to an undesirable bending behavior (curl). Although this can be counteracted by adding a plasticizer, such as glycerol, but this often leads to a reduction in the conductivity of the layer. [46] It has surprisingly been found that gelatin and thus also the plasticizer in the electrode layer can be partly or completely dispensed with if, instead, a suitable binder and an aqueous nonionic emulsion of a copolymer wax are used, and in particular a rheology as emulsion -modifying non-ionic emulsion of a modified ethylene-vinyl acetate (EVA) copolymer wax, as available, for example, from BYK under the trade name Aquatix 8421. As a result, materials with good mechanical properties are possible, which have a factor of 10 to 1000 higher conductivity than without such an additive.

[47] Suitable binders which also give good mechanical properties are e.g. the following substances mentioned by their trade name and manufacturer or supplier: Acronal LN 579 S (BASF), PEG 400 (Sigma-Aldrich), Dispercoll U53 (BASF), Luphen D 207 E (BASF), Mowilith LDM 61 19 (Clariant) Mowilith LDM 7412 (Clariant), Mowilith Nano LDM 9420 (Clariant), Mowilith LDM 7717 (Clariant), Luvitec VA64W (BASF), Luvitec Kl 7 (BASF), Luvitec K30 (BASF) and Tubicoat MEA (CHT R. Breitlich GmbH ), which are preferably used as aqueous preparations, wherein care must be taken that flocculation does not occur with the respective carbon particles used.

[48] In an advantageous embodiment, the suitable binders which, in addition to the effect of replacing gelatin and improving the mechanical properties together with nonionic emulsions such as Aquatix 8421, lead to particularly high conductivity, are aqueous preparations of acrylate copolymers, in particular those self-crosslinking and eg from BASF under the trade name Acronal® A310S. By the addition of such binders, the adhesion of the layers is also improved, whereby the detachment is counteracted by the carrier.

[49] Self-crosslinking preferably begins at room temperature and proceeds at high temperature, e.g. during drying or during lamination faster, whereby the composite layer during manufacture faster stable and e.g. can be rolled up.

[50] The aqueous preparations of binders suitable for the invention preferably have a low pH. This should preferably not exceed 7, in particular not more than 5 and more preferably not more than 4, in order to reliably avoid agglomerates and flocculations of the carbon particles present in the same casting solution. [51] As carbon particles, all designs and compositions can be used which lead to a sufficient for the particular application of the organoelectronic layer system electrical conductivity. This includes, in particular, compositions which have graphite particles, but also other carbon particles with sp 2-hybridized carbon, such as carbon nanotubes or also graphenes.

[52] The carbon particles are preferably in an amount of from 1 g / m ² to 50 g / m ² , more preferably from 5 g / m ² to 30 g / m ^2, and particularly preferably from 7 g / m ² to 25 g / m ^{2 included} in the back electrode layer.

[53] Carbon particles suitable for the invention are also often referred to as carbon black or "carbon black" pigments, such as those manufactured by Orion Engineered Carbons GmbH, formerly the carbon black division of Degussa and Evonik Industries, respectively.

[54] Aqueous dispersions of carbon particles suitable for the invention are stable in the long term if the dispersions have a pH of not more than 5, preferably not more than 4, and in particular about 3.5. [55] The entire casting solution, which is produced for the application of the electrode layer, should also have a low pH. This should preferably not be greater than pH = 5.5, in particular not greater than pH = 4, to safely avoid agglomerates and flocculation of carbon particles - and thus uneven layers.

[56] Carbon particles suitable for the invention can be selected such that the electrode layer has an electrical conductivity suitable for the particular intended use of the organoelectronic layer system.

[57] In a preferred embodiment, the electrical conductivity of the electrode layer - measured as a resistance - of 50 Ω / cm to 5000 Ω / cm, in particular from 150 Ω / cm to 1500 Ω / cm, said conductivity substantially by the coal Particles is caused.

[58] Wetting agents which are particularly suitable for improving the wetting (spread) and which are also excellently compatible with the other constituents of the organoelectronic layer system and in particular the electrode layer are conventional nonionic wetting agents, in particular organically modified polysiloxanes, as described, for example, by Afcona Addi - SDN BHD under the trade name AFCONA - 3585 are available. With such wetting agents, it is also possible to dispense with a subbing of the carrier or an adhesive layer thereon and thus to improve the production costs and the heat stability of the organoelectronic layer system. [59] Another suitable wetting agent is eg Aerosol OT75 (Cytec).

Furthermore, for a very good casting result of at least one casting composition, preferably at least that for the electrode layer, a thickener may be added, for which xanthan is particularly suitable because of the layer compatibility or preparations obtainable from BASF under the trade name Collacral®. [61] In compositions which are intended to be laced as an application method, the addition of such a thickener generally does not lead to any improvement in the desired homogeneous casting pattern.

[62] In an advantageous embodiment of the invention, only so many volatile organic solvents are used in the production of the organoelectronic layer system that the preparation can be carried out without explosion-proof devices.

[63] This is achieved by using, as far as possible, water-based (aqueous) compositions for the formulations used for the preparation of the individual layers of the organoelectronic layer system. Preferably, water-based compositions are used for all layers of the organoelectronic layer system. By water-based composition is meant a composition containing dissolved or dispersed substances and their volatile ingredients, which are largely removed by drying after the preparation of the organoelectronic layer system, at least 50 wt .-%, preferably at least 80 wt .-% and more preferably at least 95% by weight of water. [64] In order for the particular aqueous dispersion to have sufficient dispersion stability for the particular preparation process, it is proposed that the dispersion after addition of the water-dispersible or water-soluble protective colloid have a viscosity of at least 40 mPa s and less than 400 mPa s less than 200 mPas and more preferably less than 120 mPas to avoid sedimentation. For the electrode layer, it is particularly preferred if the viscosity of the pourable solution used for it is in the range of 40 mPa s to 120 mPa s. The viscosity of the dispersion is preferably measured using a rotational viscometer (eg Brookfield viscometer DVU) at a temperature of 40.degree. [65] The invention thus also encompasses organoelectronic layer systems which are produced using water-based preparations.

[66] Furthermore, the luminous element may be e.g. still having the following layers or layer additives: i) one or more antistatic layers, e.g. described in Research Disclosure 38957, September 1996, p. 591 et seq., DC-C. The content of the entire font is hereby incorporated by reference in the application, ii) one or more Begusshilfsmittel such. described in Research Disclosure 38957, September 1996, p. 591 et seq., IX-A. The content of the entire font is hereby incorporated by reference into the application and iii) one or more "non-curling" layers which can improve the flatness of the element. [67] In one embodiment of the invention, one, several or all layers are included or more curing agents (crosslinkers, crosslinkers) are added and thus the layers are cured after casting and drying in order to achieve good water resistance, using a crosslinker or crosslinker which is suitable for the respective matrix. the substances indicated in Research Disclosure 38957, September 1996, page 591 et seq., II-B, in particular glyoxal, divinylsulfone hardener or, for rapid curing, an instantaneous curing agent such as, for example, Hl (see below) For matrices with hydroxyl groups, such as Polyvinyl alcohols, cellulose derivatives or polyethylene glycols come as crosslinkers such as trifunctional isocyanates, such as Desmodur N 3300 used. [68] For the production of the organoelectronic layer system, preference is given to using a casting apparatus which can be adapted to the width required in each case.

[69] The organoelectronic layer system is preferably prepared so that it can be cut with tools such as scissors or cutting rollers without impairing the function. [70] In a further embodiment of the invention, at least one layer, preferably more than one layer and particularly preferably all layers are applied using water-based inks by a printing process, in particular an ink-jet printing process.

[71] The individual layer constituents are in particular dissolved or dispersed to prepare the organoelectronic layer system according to the invention and are preferably converted into a preparation which can be used for aqueous casting solutions. In an advantageous embodiment of the invention, demineralized sterilized water is used. Preferably, for at least one layer, such water-based preparations are used. The concentrations of the solutions depend on the chosen application method and vary depending on the selected wet application. The casting solutions are applied using a state of the art application process.

The organoelektroni see coating systems are suitable as heating or lighting elements, the latter can be used as lighting fixtures in a variety of applications, eg as tent or tarpaulin and also as interior trim of a vehicle use.

Examples

Example 1 - Preparation of the casting solution for an electrode layer according to the invention

[73] An example recipe for preparing a solution for casting an organoelectronic layer system consists of the following substances: 100 g / m ^{2 of} deionized and sterilized water, 46.3 mg / m ^{2 of} an organically modified polysiloxane as aqueous preparation (trade name AFCONA - 3585) having an active ingredient content of 5% by weight (wt .-%), 1, 68 g / m ^{2 of} a wax emulsion as an aqueous preparation (trade name Aquatix 8421) with an active ingredient content of 20 wt .-%, 16.2 g / m ^{2 of} an acrylate copolymer as an aqueous preparation (trade name Acronal® A310S) having an active substance content of 55% by weight and 16.8 g / m ² of electrically conductive, graphite-containing carbon particles as aqueous preparation with an active substance content of 27% by weight.

For the preparation of a casting solution, the water is initially introduced with stirring at 20 ° C and then the other ingredients in the order listed above at intervals of 10 minutes (min) were added. After a further digestion of 15 min, an ultrasonic degassing of 5 min follows. The dispersion is then applied by doctor blade, roller, curtain or cascade casting onto a unsubbed or preferably subbed substrate. The drying time is about 30 minutes at 40 ° C, after which results in a layer thickness of about 35 μιη.

Example 2 - Preparation of the casting solution for a luminous layer according to the invention [75] An example recipe for producing a solution for casting a luminous pigment layer for a luminous element according to the invention consists of the following substances: 4.16 g / m ^{2 of} photographic gelatin, 19.02 g / m ² deionized and sterilized water and 1 1, 83 g / m ² luminescent pigment GTP GG44.

[76] The photographic gelatine is stirred into distilled water at 20 ° C and then the mixture must swell for 1 hour (h). At 45 ° C, the gelatin-water mixture is then slowly digested until the gelatin is completely melted.

[77] The luminescent pigment is added to the aqueous gelatin solution 20 min prior to the addition of water and the dispersion is digested for 15 min. This is followed by an ultrasonic degassing of 5 min. The dispersion is then applied with a wet application of 25 μm by means of doctor blade, roller, Curtain or cascade casting applied to the subbed support. The drying time is approx. 30 min at 40 ° C.

Example 3 - Preparation of an Organoelectronic Layer System According to the Invention

[78] A water-based organoelectronic layer system of the invention is prepared by applying the layer described below (layer package 1) to a polyester substrate (manufacturer: Agfa Gevaert N.V., thickness: 125 μm, trade name Astera 125, subbed on one side). The building blocks used in the layer (see the table below) are commercially available.

[79] The orders of the coating components listed below are given in g / m ² . The values in the curly brackets indicate a reasonable amount range and the values in the square brackets denote quantity ranges for a particularly preferred embodiment with high conductivity and good durability. Thus, in layer 1, 0.005 g / m ² to 0.15 g / m ^{2 of} AFCONA-3585 are used, and particularly preferably 0.01 g / m ² to 0.10 g / m ² .

[80] The amounts stated in each case are not limited to the exemplary embodiment but are generally valid for corresponding layers of the invention or the additives contained therein. For example, applies. the amount of AFCONA-3585 preferably contained therein for layer 1 also in the context of the invention as a preferred amount range for AFCONA-3585 in any layer independently of the other ingredients and independently of the particular structure of the organoelectronic layer system. tems. In addition, the information applies not only to the specific preferred additive (active substance) in the layer, but also to other suitable representatives of the respective drug class. The quantities given eg for AFCONA - 3585 in layer 1 thus also apply to other suitable wetting agents. This applies mutatis mutandis to all active ingredients listed in the table above and the particular class of drug indicated in brackets. The value given in front of the parentheses represents the amount of active ingredient used in the specific embodiment.

[81] The composition and arrangement of the layer and the total amounts of individual substances in the layer and in the entire luminous element are of particular importance for the optimal mode of operation of the invention.

[82] Layer package 1

Layer 1 (electrode layer ^" )

AFCONA - 3585 0.046 {0.005 [0.01 -0, 10] 0, 15}

Aquatix 8421 1, 68 {0,5 [l, 0-4,0] 8,0}

Acronal® A310S 16.2 {0.8 [4.0-25.0] 30.0}

Carbon black 16.8 {5.0 [7.0-25.0] 40.0}

[83] Compared to organoelectronic layer systems prepared according to the state of the art, the layer system described above provides high conductivity with low curl tendency and has high thermal stability when used as a heating element. Due to the high flexibility of the layer, it allows small bending radii of approx. 3 mm (both tensile and compressive) without the conductivity suffers. In the production no organic solvents are used, the use of heavy metals is not necessary and the production costs are low. Expenses for explosion protection do not accrue and production waste need not be disposed of as hazardous waste.

Example 4 - Production of the layer structure for a luminous element according to the invention

[84] A water-based luminous element of the invention is prepared by applying to a polyester substrate (manufacturer: Agfa Gevaert NV, thickness: 125 μm, trade name Astera 125, subbed on one side) successively the layers described below (layer package 2) are applied. The building blocks used (see the table below) are commercially available.

[85] The orders of the coating components listed below are given in g / m ² . The values in the curly brackets indicate a reasonable amount range and the values in the square brackets indicate quantity ranges for a particularly preferred embodiment with high luminance with good durability. So be in the Adhesive layer 1, 5 g / m ² to 3.2 g / m ² gelatin used and more preferably 1.8 g / m ² to 2.8 g / m ² .

[86] The amounts stated in each case are not limited to the exemplary embodiment, but generally apply to corresponding layers of the invention or to the additives contained therein. For example, in the context of the invention, the indication of the amount of gelatin preferably contained therein for the adhesive layer also as preferred amount range for gelatin in any adhesive layer independently of the other ingredients and independently of the respective structure of the luminous element. In addition, the information applies not only to the specific preferred additive (active substance) in the layer, but also to other suitable representatives of the respective drug class. The quantities, e.g. for gelatin in the adhesive layer thus also apply to other suitable protective colloids. This applies mutatis mutandis to all active ingredients listed in the table above and the particular class of drug indicated in brackets. The value in front of the parentheses represents the amount of active ingredient used in the specific embodiment. [87] The composition and arrangement of the individual layers (in the example five superimposed layers) and the total amounts of individual substances in the layers and in the entire luminous element are optimal Functioning of the invention of particular importance.

[88] Layer Package 2 Layer 1 (Adhesive Layer) Gelatin 2.38 {l, 5 [l, 8-2.8] 3.2}

1, 2-Benzisothiazol-3 (2H) -one 0.007 {0.003 [0.005-0.008] 0.015}

Polyethylacrylate 0.24 {0.15 [0.18-0.28] 0.32}

Sodium 2- [methyl oleoylamino] ethane-l-sulfonate 0.095 {0.072 [0.095-0, L] 0, 13}

Nonylphenol polyethylene glycol ether 0.060 {0.05 [0.05-0.2] 0.3}

Layer 2 (front electrode)

Clevios SV4 20.5 {18.0 [19.0-28.0] 36.0}

Nonylphenol polyethylene glycol ether 0.14 {0.10 [0.12-0, 18] 0.20} Layer 3 (light-emitting pigment layer ^')

Gelatine 1,80 {l, 0 [l, 2-3,2] 3,4}

Luminous pigment GG44 18,0 {10,0 [16,0-24,0] 28,0}

Carboxymethylcellulose 0.18 {0.10 [0.12-0.32] 0.34}

Polyethylacrylate 0.480 {0.27 [0.32-0.85] 0.90}

Sodium 2- [methyloleoylamino] ethane 0.192 {0, ll [0.13-0.33] 0.35}

Dynasylan F8815 0.240 {0.01 [0.02-0.25] 0.26}

Layer 4 (dielectric)

Tubicoat MEA 27.4 {20.0 [25.0-35.0] 75.0}

Titanium dioxide 9.14 {0.50 [0.60-10.0] 30.0}

Gelatine 0.640 {0.60 [0.60-0.80] l, 5}

Layer 5 (back electrode)

Proxel U5 0.040 {0.01 [0.02-0.08] 0.16}

Gelatin 8,58 {4,0 [5,0-9,0] 9,2}

Carbon black 7.42 {7.0 [7.2-10.0] 14.0}

Nonylphenol polyethylene glycol ether 0.044 {0.04 [0.042-0.08] 0.10}

Aquatix 8421 22.2 {15.0 [17.0-23.0] 25.0}

[89] Compared to luminous elements manufactured according to the state of the art, the luminous element described above provides a high luminance with a long service life. It allows small bending radii of approx. 3 mm (both tension and pressure) due to the high flexibility of the layers. No organic solvents are used in the production, the use of heavy metals is not necessary and the production costs are low. Expenses for explosion protection do not accrue and production waste need not be disposed of as hazardous waste. Example 5 - Production of an Alternative Layer Structure for a Light-emitting Element According to the Invention

[90] The light-emitting element is prepared as described in Example 4, with the difference that layer 5 is replaced by layer 1 from Example 3. In addition to the advantages described for Example 4, this luminous element has a lower curl inclination and a higher luminous intensity.

Claims

claims:

1. An organoelectronic layer system comprising at least one support and at least one carbon particle-containing layer, characterized in that these carbon particles are dispersible in an aqueous medium and have an electrical conductivity, which layer is also referred to as an electrode layer.

2. An organoelectronic layer system according to claim 1, characterized in that the electrode layer has a conductivity - measured as a resistance - of 50 Ω per cm to 5000 Ω per cm, in particular from 150 Ω / cm to 1500 Ω / cm, wherein the conductivity in the Essentially caused by the carbon particles.

3. Organoelectronic layer system according to one of claims 1 or 2, characterized in that in at least one layer, in particular in the electrode layer, all constituents are dispersible or soluble in an aqueous medium.

4. An organoelectronic layer system according to any one of claims 1 to 3, characterized in that it comprises in at least one layer, in particular in the electrode layer, an aqueous dispersible or in an aqueous medium-soluble wetting agent, in particular an organically modified polysiloxane.

5. An organoelectronic layer system according to any one of claims 1 to 4, characterized in that it comprises in at least one layer, in particular in the electrode layer, a non-ionic aqueous emulsion of a copolymer wax, in particular an unmodified or modified ethylene-vinyl acetate copolymer wax.

6. An organoelectronic layer system according to any one of claims 1 to 5, characterized in that it comprises in at least one layer, in particular in the electrode layer, an aqueous dispersible acrylate copolymer that is crosslinkable, wherein the crosslinking can be carried out preferably already at room temperature.

7. An organoelectronic layer system according to any one of claims 1 to 6, characterized in that at least the electrode layer can be produced by applying aqueous dispersions or solutions.

8. A process for producing an organoelectronic layer system according to one of claims 1 to 7, characterized in that at least the constituents of the electrode layer are applied by an application method, in particular a casting process, as aqueous dispersions or solutions and the layer system then dried and, if necessary. is networked.

9. A process for producing an organoelectronic layer system according to claim 8, characterized in that cascade casting or curtain casting are used as the casting process.

10. Use of an organoelectronic layer system according to one of claims 1 to 7 or of a heat emission system produced according to one of claims 8 or 9.

1 1. An organoelectronic layer system according to one of claims 1 to 7 or a system produced according to one of claims 8 or 9, characterized in that it is a luminous element having the necessary layers and the electrode layer is provided as a return electrode.

12. Illuminated image, characterized in that it comprises an image material which is transilluminated by an organoelectronic layer system according to claim 1 1.

13. An organoelectronic layer system according to any one of claims 1 to 7 or 1 1 or a system prepared according to any one of claims 8 or 9, characterized in that at least one layer comprises a water-dispersible or water-soluble protective colloid.

14. An organoelectronic layer system according to claim 13, characterized in that the water-dispersible or water-soluble protective colloid-containing dispersion has a viscosity of less than 400 mPa · s, in particular less than 200 mPa · s.

15. An organoelectronic layer system according to any one of claims 13 or 14, characterized in that the protective colloid comprises gelatin.

16. An organoelectronic layer system according to any one of claims 1 to 7 or 1 1 or 13 to 15 or of a system according to any one of claims 8 or 9, characterized characterized in that based on the dry weight contains a maximum of 0.05 wt .-% organic solvent with the exception of ethanol.

An organoelectronic layer system according to one of claims 1 to 7 or 1 1 or 13 to 16 or a system produced according to one of claims 8 or 9, characterized in that it does not break at a bending radius of 0.5 cm.