EP3171672B1 - Light capable coating system and an object with at least one coatable surface article, provided with the coating system, and use of the coating system for the production of light capable walls, floors or ceilings - Google Patents

Description

The present invention relates to a luminous coating system and to an article having at least one coatable surface, which is provided with the luminous coating system according to the invention. Furthermore, the invention relates to the use of the inventive luminous coating system for the production of luminous walls, floors and ceilings.

Large-area lighting images have become indispensable in everyday life. They are used as advertising space or as warning signs. However, the technical effort in connection with the production, installation and maintenance of such luminous images is often very high. There has therefore been no lack of attempts to arrive at alternative solutions. For example, the WO 2013/091605 A1 a light image of an imaging material, such as a silver halide-based photographic material, and an electroluminescent device, wherein the electroluminescent device comprises a light-emitting layer containing pigments, in particular zinc sulfide, in an aqueous dispersion and an insulating layer containing titanium dioxide in an aqueous binder matrix, which on the imaging material is attached and forms with this a multi-layer dressing. The electroluminescent device can be connected in one embodiment by means of an adhesive film with a transparent support. The lighting image according to the WO 2013/091605 A1 should be easy to produce, have a particularly good durability and brightness and give the impression of a bright photo. From Of particular importance for this is the multi-layered bond between an imaging material and the electroluminescent device, which allows a solid bond with little to no space between the imaging material and the electroluminescent device.

According to the WO 2013/091604 A1 For example, an electroluminescent device may comprise a luminescent layer containing inorganic electroluminescent particles, in particular doped or encapsulated zinc sulfide, and water-dispersible or water-soluble protective colloids, such as gelatin, and optionally a plasticizer. This luminescent layer should have a thickness of less than 40 μm and be arranged on a support and also have an alcohol-soluble, transparent, conductive front electrode layer. The layers mentioned should be able to be produced in a casting process. The ease of manufacture and good durability of the luminous element according to WO 2013/091604 A1 should be ensured by the presence of a protective colloid. In a preferred embodiment, the luminous element on a carrier should have the following layers: an adhesive layer which improves the adhesion of the overlying layers to the carrier, a transparent and electrically conductive layer as the front electrode, a layer which can be excited by an AC electric field Leuchtsubstanz contains as he, an insulating layer with high dielectricity, a layer of high conductivity as a return electrode, conductors as a connection of the front electrode, a barrier layer and contacts and connections for an AC voltage source.

From the DE 102 19 802 A1 is a powder or wet paint in the form of a polyester or acrylate for electrostatic coating of an object is known in which to a transparent paint powder and / or wet paint, a powder of a luminescent and / or reflective substance, such as strontium aluminate, and organic or inorganic Pigments that glow in the dark after charging by UV radiation in the dark have been added. Such a lacquer should be obtainable in that luminescent and / or reflective particles together with at least partially transparent powder coating particles and / or wet paint in an electrostatic high voltage field in which the surface of the object to be coated forms a potential surface moves to the surface of the article and to you are attached firmly.

The EP 2 334 151 A1 describes a method for producing an electroluminescent element comprising a substrate and an electroluminescent device obtained by spraying the layers of the electroluminescent device, comprising the steps of a) spraying the first electrode onto the substrate or onto an insulating layer applied to the substrate , b) spraying the electroluminescent layer and c) spraying the second electrode. For the production of the electroluminescent layer, reference should be made here to a suspension comprising 30 to 90% by weight of ZnS crystals, 10 to 40% by weight of binder, selected from one and two component polyurethanes, 1 to 50% by weight, solvent selected from ethoxypropyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, solvent naphtha or any mixtures of two or more of these solvents, 0.1 to 2 wt .-% leveling agent and 0.01 to 10 wt .-% rheology additives. With the in the EP 2 334 151 A1 described technical teaching electroluminescent devices should be applied to substrates that are not electrically conductive per se formed and beyond also can not be easily provided with an electroluminescent arrangement due to their spatial configuration. For this purpose, sprayable formulations for the electrodes, the electroluminescent layer and the insulating layer of the electroluminescent arrangement can be used.

The US 8,470,388 relates to a method of making a conformal electroluminescent system comprising the steps of: selecting a substrate; Applying a base backplate film layer to the substrate using an aqueous conductive backplate material; Applying a dielectric film layer to the backplane film layer using a water-based dielectric material; Applying a phosphor film layer to the dielectric film layer using a water-based phosphor material, wherein the phosphor film layer is excited by a source of ultraviolet radiation during use, the source of ultraviolet radiation providing visual cues while the phosphor film layer is being applied, wherein the application of the phosphor film layer is in response is adjusted to the visual cues during the phosphor deposition step to obtain a generally uniform distribution of the phosphor material on the dielectric film layer; and applying an electrode film layer on the phosphor film layer using a substantially transparent, water-based, electrically conductive electrode material, wherein the backplane plate film, the dielectric film layer, the phosphor film layer, and the electrode film layer are respectively applied by conformal spray coating, wherein the phosphor film layer is excitable by an electric field, which is formed when applying an electric charge between the backplane and the electrode film layer over the Phos phorfilmschicht so that the phosphor film layer emits electroluminescent light. In this way, electroluminescent filaments with complex topology should be accessible.

It is generally considered a limitation that electroluminescent coatings are applied only on absolutely smooth, non-absorbent substrates. In many cases this is due to special processes such as screen printing and special tools such as paint guns. It is also disadvantageous that it is not possible to obtain surfaces which are as smooth as usual in the craft industry, for example grinding, for smoothing substrates, as would be required for conventional electroluminescent coating systems.

The solutions known from the prior art for large-area lighting images are still always consuming and error-prone. In particular, such luminous images can often only be installed by expertly qualified and specialized personnel. It would be desirable to be able to resort to less complex and easier to handle solutions.

It is an object of the present invention to provide vivid coating systems that are free of the drawbacks of the prior art and, in particular, allow easy mounting on large areas, while at the same time providing high-quality luminous images which permanently reduce their luminous intensity. and / or color. Furthermore, the invention was based on the object to enable large-area luminous coatings, especially in site-appropriate manner, which also meet decorative requirements.

Accordingly, a luminous coating system has been found according to the features of patent claim 1. It comprises, in this order, a) a back electrically conductive layer, b) a dielectric luminescent layer, c) a front-side electrically conductive transparent or translucent layer, and d) an electrically insulating barrier layer. The barrier layer can also serve as a sealing layer. At least one of the layers a), b), c) and d), in particular all of these layers, are obtainable by means of brush, roller, in particular paint roller, trowel, trowel and / or doctor blade application, or are obtained in this way receive.

The luminous coating system according to the invention is accordingly distinguished by the fact that it can be applied to a variety of substrates using typical painting application methods, as are customary in the artisan building trades. For example, the inventive luminous coating system on all surfaces or substrates are applied, which are common in building related trades, such as floors, ceilings, walls or more generally objects or bodies made of concrete, masonry, plastic or wood or the like.

The rear electrically conductive layer a) is preferably not transparent, in particular not translucent. It can be based on a one- or two-component system. The rear electrically conductive layer a) of the coating system according to the invention is formed from a system consisting of or containing at least one binder and at least one electrically conductive substance or filler based on carbon, for example carbon black, graphite, carbon nanotubes and / or graphene. The rear electrically conductive layer a) is preferably also characterized in that it can be applied or processed by means of a brush, paint rollers, spatula, trowel and / or doctor blade. With the compositions specified above, it is possible in this case to apply reverse electrically conductive layers a), which have good running, leveling and crack-slurrying properties. The rear electrically conductive layer a) of the coating system according to the invention may alternatively or additionally also be in the form of a fabric, or may contain the aforementioned substances. In a suitable embodiment, the weight ratio is from the solids content of the binder to the solids content of the electrically conductive substances, e.g. the electrically conductive fillers, in the rear electrically conductive layer a) in the range of 0.5: 1 to 1.5: 1 and preferably in the range of 0.8: 1 to 1.2: 1, based on the total dry mass of the Layer a) forming components.

In principle, it is also possible to resort to compositions for the rear electrically conductive layer a), as described below for the front-side electrically conductive transparent or translucent layer c).

The dielectric luminescent layer b) is based on a two-component system. Preferably, the dielectric luminescent layer b) is not transparent, especially not translucent. The dielectric luminescent layer b) comprises an electrically insulating rear dielectric layer b1), consisting of or containing electrically non-conductive binder and electrically non-conductive fillers having a permittivity of at least 5, and a, in particular electrically insulating, frontward luminescent layer b2), consisting of or containing at least one binder, in particular an alkyd resin, epoxy resin, acrylate resin and / or polyurethane binder, and at least one electroluminescent particulate material, in particular zinc sulfide, wherein, in particular in addition to the at least one layer a), c) and d) or in addition to all layers a), c) and d), at least one of the layers b1) and b2), in particular both layers, by means of brush, roller, in particular paint roller, trowel, trowel and / or doctor job is available or is obtained. The above-described embodiment has proven to be more useful in technical terms and safer in operation compared to the embodiment in which the luminescent layer and the electrical layer are present in one.

The rear, electrically insulating, dielectric layer b1) generally contains an electrically non-conductive binder and / or electrically non-conductive fillers. The rear dielectric layer b1) is formed in a preferred embodiment from a system consisting of or containing at least one non-electrically conductive binder and at least one non-electrically conductive filler. Such suitable non-conductive binders and non-conductive fillers are known to those skilled in the art. Suitable binders for the rear, electrically insulating, dielectric layer b1) are known to those skilled in the organic binder in question. By way of example, reference is also made to silicatic and calcitic fillers. Particularly suitable is at least one filler selected from a first group consisting of talc, mica, precipitated calcium carbonates, ground calcium carbonates, natural silicas, artificial silicas and feldspars. Preference is given to electrically non-conductive fillers with high permittivity. These electrically non-conductive fillers have a permittivity of at least 5. At least one such filler is preferably selected from a second group consisting of alumina, yttria, zirconia, hafnia, tantalum oxide, lanthana, titania, calcium copper titanate, lead zirconium. Titanate and barium titanate. Barium titanate is particularly preferably used for this purpose. Preferably, the layer b1) comprises at least one, in particular at least two, and very particularly preferably at least three of the said fillers from the first and / or second group. It is also preferred if the non-conductive fillers predominantly from the above-mentioned first and / or second groups
in particular at least 55% by weight, preferably at least 75% by weight, very particularly preferably at least 85% by weight, of the fillers (each dry fraction) are selected from the first and / or second group. In one embodiment, it is preferred if at least one filler from the first group and at least one filler from the second group is included.

The composition which forms the rear, electrically insulating, dielectric layer b1) can also be applied or processed by means of a brush, paint roller, spatula, trowel and / or doctor blade.

With particular preference the components of this composition which, after application to the rear electrically conductive layer a) form the rear, electrically insulating, dielectric layer b1), are selected such that the critical pigment volume concentration (KPVK) is always undershot by at least 5%, and more preferably by at least 10%. In this way, it is possible to reduce or minimize the number of less impact-resistant air pores.

With the compositions specified above, it is possible in this case to apply rear, electrically insulating, dielectric layers b1) which are particularly smooth, leveling, thin-layered and crack-slurring and have high permittivity.

With particular preference, alternatively or additionally, the components of the composition which form the rear electrically conductive layer a) are selected such that the critical pigment volume concentration (KPVK) is always exceeded.

Such coating systems of the invention have proved to be particularly useful, which further have a, in particular smooth or smoothed and / or non-capillary active, substrate for the attachment or support of the rear electrically conductive layer. In this way one obtains very reliably a permanently functioning luminous coating system.

The, in particular electrically insulating, frontward luminescent layer b2) is preferably formed from a one- or two-component system. It is preferably transparent or translucent. The frontward luminescent layer b2) is preferably formed from a System consisting of or containing at least one non-electrically conductive binder, optionally at least one non-electrically conductive filler, and at least one electroluminescent particulate material. The electroluminescent particulate material is preferably based on Cu, Au, Mn, Ag, Fe, Pb, P, As, Sb, Sn, V, Tl, Sc, Co, Ni, Tm, Tb, Dy, Gd, Yb, Sm and or Eu doped ZnS, ZnSe, SrS, CaS and / or CdS, in particular ZnS, or on barium aluminum sulfate doped with said elements, gallium nitride, gallium sulfide, gallium selenide and / or strontium aluminate or any mixtures of the aforementioned substances.

The frontward luminescent layer b2) is usually based on at least one binder and at least one filler. The frontward luminescent layer b2) contains at least one electroluminescent pigment as an electroluminescent particulate material. In an advantageous embodiment, use is made of zinc sulfide pigments for this purpose. Preference is given here to opaque pigments and / or fillers. Furthermore, non-conductive binders and non-conductive fillers, for example those described above for the dielectric layer b1), are preferably used. Particularly suitable binders in this case are those with which it is possible to protect the electroluminescent pigments from moisture. By way of example, alkyd resin, epoxy resin, acrylate, and polyurethane binders may be mentioned here. Suitable binders also include the class of UV-curing binders. Among the UV-curing binders, UV-curing acrylate binders are preferred. In addition, of course, such acrylate binder are suitable in which the curing is not carried out by means of UV radiation, but for example thermally. Very particular preference is given to polyurethane binders, with 2K polyurethane systems being particularly suitable among these polyurethane binders.

Also, it is preferably ensured for the frontward luminescent layer b2) that the critical pigment volume concentration (KPVK) is always undershot, preferably by at least 5% and particularly preferably by at least 10%. In this way it is possible to minimize the number of less impact-resistant air pores in this layer. The compositions specified above can be used to apply frontward luminescent layers b2) which are well-running, leveling, thin-layered, electrically insulating, transparent to opaque and electroluminescent. Also the frontward ones Luminous layer b2) forming composition is preferably applied or processed by means of brush, paint roller, spatula, trowel and / or doctor blade.

It has proved particularly expedient to use such electroluminescent particulate materials which have an average particle size in the range from 10 μm to 100 μm and preferably in the range from 20 μm to 40 μm.

The frontward electrically conductive layer c) can be formed in a preferred embodiment from a system containing or consisting of carbon fibers and / or carbon nanotubes (CNTs) and / or silver nanowires (SNWs) or containing or consisting of graphene or containing or consisting of poly (3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT: PSS). Alternatively or additionally, this frontward electrically conductive layer a) may also consist of or contain polyaniline. Furthermore, it is possible for the frontward electrically conductive layer a) to consist of a system comprising or consisting of at least one binder and at least one electrically conductive fiber material or containing or consisting of at least one metal oxide, in particular indium tin oxide, antimony tin oxide, Fluorine-zinc oxide and / or aluminum-zinc oxide, to form.

The composition forming the frontward electrically conductive layer c) is preferably applied or processed by means of a brush, roller, in particular paint roller, spatula, trowel and / or doctor blade. The frontward electrically conductive layer c) can be made very thin. In particular, the frontward electrically conductive layer c) is present as a substantially transparent or translucent layer. The frontward electrically conductive layer c) of the coating system according to the invention can alternatively also be formed in the form of a fabric or contain the substances mentioned above conductive substances.

The barrier layer d) is generally based on a one- or two-component system, which is preferably substantially transparent or translucent. The barrier layer d) generally contains an electrically non-conductive binder and optionally also at least one electrically non-conductive filler. The barrier layer d) is formed in a preferred embodiment of a system consisting of or containing at least a non-electrically conductive binder and at least one non-electrically conductive filler.

Such suitable non-conductive binders and non-conductive fillers are known to those skilled in the art. Suitable binders for the barrier layer d) are, for example, organic binders known to the person skilled in the art. By way of example, reference is also made to silicate and calcitic fillers for suitable non-conductive fillers. For the barrier layer d), transparent or translucent fillers such as quartz or alabaster are preferably used. Alternatively or additionally, fillers such as glass beads, glass bubbles and / or plastic beads such as PMMA beads can be used for the barrier layer. Particularly good results with regard to the transparency or translucency of this layer are obtained when the barrier layer is substantially or completely unfilled, i. without addition of fillers remains. On the one hand, the barrier layer protects the electroluminescent system from environmental stresses and, on the other hand, protects the environment from the electrical voltage in this electroluminescent system. The composition forming the barrier layer d) is preferably applied or processed by means of a brush, paint roller, spatula, trowel and / or doctor blade. Particularly preferred are the components of this composition, which form the barrier layer d) after application to the frontward electrically conductive layer c), selected such that the critical pigment volume concentration (KPVK) is always below, preferably by at least 5% and especially preferably at least 10%. Most preferably, the barrier layer d) contains no fillers. For this case, the KPVK goes against infinity. In this way, it is possible to minimize the number of less impact-resistant air pores. The compositions specified above can readily be applied to the front-side, electrically conductive layer c), which is very smooth, leveling, substantially transparent or translucent and electrically insulating.

Particularly satisfactory results are also obtained for such luminous coating systems according to the invention, which further comprise at least one electrical insulation layer between the substrate and the back electrically conductive layer, between the back electrically conductive layer and the back dielectric layer, between the back dielectric layer and the front luminous layer . between the frontward luminescent layer and the frontward electrically conductive transparent or translucent layer and / or between the frontward electrically conductive transparent or translucent layer and the barrier layer. Such luminous coating systems according to the invention are very particularly preferred, which furthermore have at least one electrical insulation layer between the substrate and the rear electrically conductive layer. The composition forming the electrical insulation layer is preferably applied or processed by means of a brush, paint roller, spatula, trowel and / or doctor blade.

Particularly preferably, the electrical insulation layer is present between the rear electrically conductive layer and the rear dielectric layer. The electrical insulation layer may be based, for example, on 2K polyurethane systems having a first and a second component, aqueous two-component polyurethane systems being preferred. The weight ratio of the first to the second components K is usually in the range from 10: 1 to 2: 1, preferably in the range from 5: 1 to 3: 1. In an expedient embodiment, the weight ratio of the first to the second components K of a suitable 2K aqueous polyurethane system is 4: 1. Suitable aqueous 2-component polyurethane water-based systems are based, for example, on hydroxy-functional polyesters, e.g. hydroxy-functional acrylic resins, as the first component or as a constituent of the first component and aliphatic polyisocyanates as so-called hardness as a second component or as a component of the second component, for example a 2K mixture of isophorone diisocyanate and hexamethylene-1,6-diisocyanate. For example, in a preferred embodiment, the first component may comprise a hydroxy-functional polyacrylate dispersion, e.g. 60% by weight, a defoamer, e.g. 2.5% by weight, a substrate wetting additive, e.g. 0.5% by weight, a leveling additive, e.g. 1.0% by weight, a thickener, e.g. 1.0% by weight, and water, e.g. 35.0% by weight, and the second component is an aliphatic polyisocyanate, e.g. based on hexamethylene-1,6-diisocyanate (HDI) go back. The above-specified first and second components are present in the 2K mixture, preferably in a ratio of 75% by weight (dry content of the first component) to 25% by weight (dry content of the second component).

Particularly good results also arise with such luminous coating systems according to the invention, in which the at least one binder and the at least a backside electrically conductive layer comprising a filler a) has a pigment / volume concentration (PVK) above the critical pigment / volume concentration. The backside dielectric layer b1) has a pigment / volume concentration (PVK) below the critical pigment / volume concentration, preferably at least 5 percent and more preferably at least 10 percent below the critical pigment / volume concentration. It is also preferred, however, if alternatively or preferably additionally the frontward luminescent layer b2), the frontward electrically conductive transparent or translucent layer c) and / or the electrically insulating barrier layer d), preferably the layers b1), b2), c) and d ), has a pigment / volume concentration (PVK) below the critical pigment / volume concentration. In this case, it is particularly preferred that all layers b1), b2), c) and d) have a pigment / volume concentration (PVK) below the critical pigment / volume concentration, preferably at least 5, except layer a) of the luminous coating system according to the invention Percent, and more preferably at least 10 percent below the critical pigment / volume concentration.

In an advantageous embodiment, the at least one binder of the rear electrically conductive layer a), the rear dielectric layer b1), the frontward luminescent layer b2), the frontward electrically conductive transparent or translucent layer c) and / or the electrically insulating barrier layer d) are based Alkyd resins, epoxy resins or polyurethanes, in particular polyurethanes. It is particularly suitable if the rear dielectric layer and / or the frontward luminescent layer on alkyd resins, epoxy resins, acrylate resins, in particular UV-curing acrylate resins, or polyurethanes, in particular polyurethanes, and / or UV-curing binders In principle, it is possible to resort to UV-curing binders for the layers mentioned, preference being given to UV-curing acrylate resins.

In principle, it is also possible that further layers are to be found between the layers a), b), c) and d), in particular a), b1), b2), c), and d), as long as the sequence of the layers a ), b), c) and d), in particular a), b1), b2), c), and d), is not changed. Nevertheless, it is preferred according to the invention if the layer a) directly follows the layer b) and then c), in particular the layer a) directly the layer b1) and the layer b2) directly the layer c), preferably on the Layer c) directly follows the layer d). In this case, direct means that the affected layers are arranged directly adjacent to one another, in particular applied to one another and one after the other.

In many cases, it has proven to be advantageous to ensure that in the luminous coating systems according to the invention, the mean distance between the rear electrically conductive layer and the front-side electrically conductive transparent or translucent layer is substantially constant.

Such coating systems according to the invention are also preferred in which the rear dielectric layer is reflective or in which the rear dielectric layer is designed to scatter the light.

Particularly good long-term use properties are also associated with such coating system according to the invention, in which the dielectric luminescent layer b) or the front luminescent layer b2) is embedded in the coating system protected against oxygen and / or moisture.

The electroluminescent particulate material is preferably, in particular substantially uniformly, embedded in the binder of the dielectric luminescent layer b) or the front luminescent layer b2).

With the coating system according to the invention, readily coated surfaces such as walls, floors and ceilings can readily be coated.

Such objects according to the invention are preferred, which further comprise a device for generating an alternating electrical voltage field in the dielectric luminescent layer b) or in the frontward luminescent layer b2). The AC electric field is in a suitable embodiment at a frequency in the range of 100 to 5000 Hz, preferably in the range of 100 to 800 Hz, in particular wherein the voltage is greater than 100 V, in particular greater than 150 V and more preferably greater than 200 V.

With the luminous coating system according to the invention, luminous walls, floors and ceilings can be produced, preferably with typical application methods.

With the luminous coating system according to the invention, an electroluminescent system is provided which emits light when an alternating voltage is applied. The luminous coating system according to the invention thereby provides a capacitor which is constantly reloaded when alternating voltage is applied. The rear electrically conductive layer a) and the frontward electrically conductive transparent or translucent layer c) are the electrodes of the capacitor. The dielectric luminescent layer b) or the electrically insulating, rear dielectric layer b1) and the electrically insulating front luminescent layer b2) act as an insulating dielectric, which increases both the dielectric strength and the capacitance of the capacitor.

During the charging process, an electric field is formed between the two electrodes of the capacitor, in which the energy that is supplied to the capacitor by the charging is stored. The electroluminescent particulate material present in the luminous layer b) or in the frontward luminous layer b2) derives its energy from the change in this electric field. When the capacitor is fully charged, the energy stored in the capacitor is maximum, but the field strength of the electric field no longer changes, so that the electroluminescent particulate material which has illuminated during the charging process, goes out.

For the purposes of the present invention, translucent means that a corresponding translucent layer is translucent. Transparency, on the other hand, means that the layer is transparent (translucent) and the light is not or only partially dispersed when the layer passes through. The same applies to several layers.

The transmittance in the case of translucency and optionally in the case of transparency is preferably> 0.2, ie more than 20% of the incident visible light is transmitted. The transmittance T is defined as the quotient between the light intensity behind one or possibly several layers and the intensity in front of said layer or layers. Preferably, the so determined transmittance of a transparent layer, in particular the layer c), the layer d) and / or both layers together, in the sense of the present invention> 0.4, in particular> 0.55, preferably> 0.65, in particular > 0.8. The degree of transmittance is determined at a wavelength of 450 nm, 550 nm and / or 650 nm. It is sufficient for the definition or invention if the transparency characteristic is satisfied for at least one of said wavelengths, but preferably at least for the wavelength 650 nm. It is particularly preferred if the transmittance for all three wavelengths has said values.

In the case of transparency, it is preferred if less than 40%, in particular less than 25%, and very particularly preferably less than 10% of the transmitted radiation is scattered.

The average layer thicknesses of the individual layers forming the luminous coating system are often in the range of 10 to 2000 μm. Such layer thicknesses can be easily obtained with a brush, roller, trowel, spatula or squeegee. In order to obtain a luminous system with the aid of the coating system according to the invention, generally voltages greater than 100 V, in particular greater than 150 V and particularly preferably greater than 200 V are applied, preferably the frequency of the AC electric field in the range from 100 to 5000 Hz, in particular Range of 100 to 800 Hz, lies.

It has been found that the rear electrically conductive layer a) should preferably have a minimum thickness of at least 20 μm, in particular at least 30 μm, preferably at least 40 μm. Furthermore, this layer thickness should preferably not exceed 2000 μm, in particular 200 μm, preferably 100 μm. Particular preference is given to layer thicknesses of the layer a) in the range from 20 to 600 .mu.m, in particular from 25 to 250 .mu.m, preferably from 25 to 100 .mu.m, very particularly preferably from 40 to 80 .mu.m. It has been shown that excellent results are achieved, in particular in the range from 50 to 70 μm. If the stated lower limits are considerably undershot, the conductivity can be lowered and adversely affect the functionality of the coating according to the invention.

It has also been found that the layer b1) should preferably have a layer thickness of at least 20 μm, in particular at least 30 μm, preferably at least 40 μm. It is also preferred if the layer thickness of the layer b1) is not more than 500 μm, preferably not more than 300 μm, in particular not more than 200 μm, particularly preferably not more than 160 μm. Particular preference is given to layer thicknesses of the layer b1) in the range from 20 to 300 .mu.m, in particular from 30 to 200 .mu.m, preferably from 40 to 160 .mu.m, very particularly preferably from 60 to 120 .mu.m. It has been shown that to lower Layer thicknesses may not provide optimal insulation effect. Furthermore, it has been found that excessively selected layer thicknesses can, according to experience, have disadvantages with regard to the luminous effect.

It has also been found that the layer b2) preferably has a layer thickness of at least 15 μm, in particular at least 20 μm, preferably at least 30 μm. It is also preferred if the layer thickness is not more than 300 μm, preferably not more than 150 μm, in particular not more than 120 μm, particularly preferably not more than 80 μm. Particular preference is given to layer thicknesses of the layer b1) in the range from 15 to 150 μm, in particular from 20 to 120 μm, preferably from 20 to 80 μm, very particularly preferably from 30 to 70 μm.

Furthermore, it is preferred if the layer thickness of the layer b1) is greater than the layer thickness of the layer b2), in particular at least 25% larger, preferably at least 50% larger, very particularly preferably at least twice as large.

It is also preferred if the layer thickness of layer b), which preferably results from the sum of the layer thicknesses of b1) and b2), is not more than 500 μm, in particular not more than 300 μm, preferably not more than 250 μm, completely more preferably not more than 200 microns, is.

It has also been found that the layer c) preferably has a layer thickness of at least 5 μm, in particular at least 10 μm, preferably at least 20 μm. It is also preferred if the layer thickness is not more than 100 μm, preferably not more than 80 μm, in particular not more than 60 μm, particularly preferably not more than 40 μm. Particular preference is given to layer thicknesses of the layer c) in the range from 5 to 100 μm or 80 μm, in particular 10 to 60 μm, preferably 10 to 40 μm, very particularly preferably 10 to 30 μm. By the said layer thickness of the layer c), the conductivity can be ensured, wherein the transparency and / or translucency is also optimized.

In particular, it is preferred if the layer c) is thinner than each of the layers a), b), and d), preferably also thinner than the layers b1) and / or b2).

The layer d) preferably has a layer thickness which is at least 30 μm, preferably at least 60 μm, particularly preferably at least 100 μm. The layer thickness d) can in principle be chosen to be very large, so that the layer is several centimeters thick. However, the layer is preferably not more than 10 mm, in particular not more than 1 mm, preferably not more than 5000 μm, particularly preferably not more than 2500 μm, thick. Particular preference is given to layer thicknesses of layer d) in the range from 50 to 1 mm, in particular from 60 to 5000 μm, preferably from 60 to 2500 μm, very particularly preferably from 100 to 2000 μm. The said layer thickness of the layer d) usually provides adequate protection.

In a particularly expedient embodiment, in the luminous coating systems according to the invention, the layer a) has an average, in particular absolute, layer thickness in the range 20 to 600 microns, and / or the layer b) over an average, in particular also absolute, layer thickness of a maximum of 500 μM, and / or the layer c) over an average, in particular absolute, layer thickness in the range of 5 to 80 microns, and / or the layer d) over an average, in particular also absolute, layer thickness of at least 60 microns. In addition, such an embodiment has proven to be particularly suitable, in which the layer a) over an average, in particular absolute, layer thickness in the range of 20 to 600 microns and the layer b) over an average, in particular also absolute, layer thickness of not more than 500 μM, and the layer c) have an average, in particular absolute, layer thickness in the range of 5 to 80 microns and the layer d) have an average, in particular also absolute, layer thickness of at least 60 microns.

In a particularly preferred embodiment, it is provided that the layer thicknesses increase in the order c), a), b), d), in particular wherein the layer thickness of b1) is preferably greater than the layer thickness of b2). It has been found that the specified coating systems obtained in this way give particular luminous and resistant coatings.

For the purposes of the present invention, a layer thickness is basically an average layer thickness, unless express reference is made to an absolute layer thickness. The layer thickness shall be determined in accordance with EN ISO 2808: 2007 (method 6A). It should also be noted that the layer thicknesses obtained are production-related can vary locally. This depends in particular on the application method. It is familiar to the person skilled in the art to determine the layer thickness over a cross-section or possibly several cross-sections which are representative.

With the coating system according to the invention, even larger areas, for example, greater than 1 m ² , can be made contiguous and free electroluminescent without further ado, even with demanding geometries such as sphere, rod, column, corner or edge. Consequently, the present invention eliminates the size limitation previously associated with electroluminescent films. These usually allow only an electroluminescent area of about 1 m ² .

The present invention is accompanied by the surprising finding that the luminous coatings according to the invention can also be applied to surfaces which are not absolutely smooth and / or absorbent, even with the tools commonly used in building ancillary industries such as brushes, rollers, in particular paint rollers, spatulas, trowels and / or doctor blade, with even large-scale decorative lighting images are available. Thus, advantageously, the well-known in the craft usual measures for smoothing surfaces can be omitted. This is attributable inter alia to the fact that even with the components which form the individual layers of the luminous coating system according to the invention, a smoothing of substrate surfaces and a compensation of the absorbency of substrates succeed. Accordingly, it is possible to apply the luminous coating system of the present invention even under site conditions on a relatively rough and absorbent substrate such as a gypsum board in such a manner as to obtain a luminous image. The luminous coating system according to the invention can also be applied to mineral substrates such as concrete, screed and masonry or to an old paint or a plasterboard substrate. For mounting the luminous coating systems according to the invention, it is no longer necessary to resort to highly specialized experts and to complex tools which are usually used for applying electroluminescent coating systems, such as screen printing and paint guns. Such methods and tools tools are usually not available on a construction site.

Figur 1

eine schematische Darstellung des erfindungsgemäßen leuchtfähigen Beschichtungssystems.

Further features and advantages of the invention will become apparent from the following description in which an embodiment of the invention with reference to a schematic drawing is exemplified, without thereby limiting the invention. Showing:

FIG. 1

a schematic representation of the inventive luminous coating system.

The luminous coating system 1, as in FIG. 1 is formed by the rear electrically conductive layer 2, the electrically insulating, backward dielectric layer 4, the electrically insulating frontward luminescent layer 6, the frontward electrically conductive transparent or translucent layer 8 and the electrically insulating barrier layer 10. The individual layers of the conductive coating system 1 can be applied by brush, roller, spatula, trowel or doctor in the order shown. Here, first, the rear electrically conductive layer 2 is applied to the substrate 12.

The features of the invention disclosed in the foregoing description, in the claims and in the drawings may be essential both individually and in any combination for the realization of the invention in its various embodiments.

Claims (20)

1. A luminescent coating system, comprising, in this sequence,

   a) a rearward electrically conductive layer,

   b) a dielectric luminescent layer,

   c) a frontward electrically conductive transparent or translucent layer and

   d) an electrically insulating barrier layer, wherein

   at least one of the layers a), b), c) and d), in particular all these layers, can be obtained or are applied by means of brushes, rollers, in particular paint rollers, spatulas, trowels and/or coating knives, wherein the dielectric luminescent layer b) comprises an electrically insulating rearward dielectric layer b1), containing electrically non-conductive binders and electrically non-conductive fillers with a permittivity of at least 5, and
   an in particular electrically insulating frontward luminescent layer b2), consisting of or containing at least one binder, in particular an alkyd resin, epoxy resin, acrylic resin and/or polyurethane binder, and at least one electroluminescent particulate material, in particular zinc sulphide, wherein the rearward dielectric layer b1) comprising the at least one binder and the at least one filler has a pigment volume concentration (PVC) below the critical pigment volume concentration (CPVC), preferably at least 5 per cent and particularly preferably at least 10 per cent below the critical pigment volume concentration, wherein the rearward electrically conductive layer a) is formed from a system consisting of or containing at least one binder and at least one electrically conductive, carbon-based material, wherein the rearward electrically conductive layer a) has a pigment volume concentration (PVC) above the critical pigment volume concentration (CPVC) and
   wherein, in addition to at least one of the layers a), c) and d) or in addition to all layers a), c) and d), at least one of layers b1) and b2), in particular both layers, can be obtained or is/are applied by means of brushes, rollers, in particular paint rollers, spatulas, trowels and/or coating knives.
2. The coating system according to Claim 1, characterised in that the frontward luminescent layer b2) is an electrically insulating luminescent layer.
3. The coating system according to Claim 1 or 2, further comprising an in particular smooth or smoothed and/or non-capillary active substrate for application or as support of the rearward electrically conductive layer.
4. The coating system according to any one of the preceding claims, characterised in that the electrically conductive carbon-based substance is carbon black, graphite, carbon nanotubes and/or graphene.
5. The coating system according to any one of the preceding claims, characterised in that the non-electrically conductive fillers with a permittivity of at least 5 comprise aluminium oxide, yttrium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide, titanium dioxide, calcium copper titanate, lead zirconate titanate and/or barium titanate.
6. The coating system according to any one of the preceding claims, characterised in that the frontward luminescent layer b2) is formed from a system consisting of or containing at least one non-electrically conductive binder, optionally at least one non-electrically conductive filler, as well as at least one electroluminescent particulate material, preferably based on ZnS, ZnSe, SrS, CaS and/or CdS, in particular ZnS doped with Cu, Au, Mn, Ag, Fe, Pb, P, As, Sb, Sn, V, Tl, Sc, Co, Ni, Tm, Tb, Dy, Gd, Yb, Sm and/or Eu, or based on barium aluminium sulphate, gallium nitride, gallium sulphide, gallium selenide and/or strontium aluminate.
7. The coating system according to Claim 6, characterised in that the electroluminescent particulate material has an average particle size in the range of 20 µm to 40 µm.
8. The coating system according to any one of the preceding claims, characterised in that the frontward electrically conductive layer c) is formed from a system containing or consisting of carbon nanotubes (CNTs) and/or metallic nanowires or their meshes, in particular silver nanowires (SNWs) or their meshes, or containing or consisting of graphene or containing or consisting of poly(3,4-ethylenedioxythiophene) polystyrene sulphonate (PEDOT:PSS) or containing or consisting of polyaniline or of a system containing or consisting of at least one binder and at least one electrically conductive fibre material or containing or consisting of at least one metal oxide, in particular indium tin oxide, antimony tin oxide, fluorine tin oxide and/or aluminium zinc oxide.
9. The coating system according to any one of the preceding claims, furthermore comprising at least one electrical insulation layer between the substrate and the rearward electrically conductive layer, between the rearward electrically conductive layer and the rearward dielectric layer, between the rearward dielectric layer and the frontward luminescent layer b2), between the frontward luminescent layer b2) and the frontward electrically conductive transparent or translucent layer and/or between the frontward electrically conductive transparent or translucent layer and the barrier layer, wherein, in particular in addition to the at least one layer a), b), c) or d) or in addition to all layers a), b), c) or d) or in addition to the at least one layer a), b1), b2), c) or d) or in addition to all layers a), b1), b2), c) or d), at least one of the previously named insulation layers, in particular all these insulation layers, can be obtained or is (are) applied by means of brushes, rollers, in particular paint rollers, spatulas, trowels and/or coating knives.
10. The coating system according to any one of the preceding claims, characterised in that the frontward luminescent layer b2), frontward electrically conductive transparent or translucent layer c) and/or electrically insulating barrier layer d), in particular layers b1), b2), c) and d), comprising the at least one binder and the at least one filler, has/have a pigment volume concentration (PVC) below the critical pigment volume concentration (CPVC), preferably at least 5 per cent and particularly preferably at least 10 per cent below the critical pigment volume concentration.
11. The coating system according to any one of the preceding claims, characterised in that the at least one binder of the rearward electrically conductive layer a), the rearward dielectric layer b1), the frontward luminescent layer b2), the frontward electrically conductive transparent or translucent layer c) and/or the electrically insulating barrier layer d) is based on alkyd resins, epoxy resins, acrylates, in particular UV-curing acrylates, or polyurethanes, in particular polyurethanes.
12. The coating system according to any one of the preceding claims, characterised in that the rearward dielectric layer is designed to be reflective or that the rearward dielectric layer is designed to be light-scattering.
13. The coating system according to any one of the preceding claims, characterised in that the dielectric luminescent layer b) or the frontward luminescent layer b2) is present, embedded in the coating system, protected against oxygen and/or moisture.
14. The coating system according to one of Claims 6 to 13, characterised in that the electroluminescent particulate material is present, embedded in particular substantially equally, in the binder of the dielectric luminescent layer b) and/or the frontward luminescent layer b2).
15. The coating system according to any one of the preceding claims, characterised in that the barrier layer d) does not contain any fillers or that the barrier layer d) contains transparent and/or translucent fillers, in particular selected from the group consisting of quartz, alabaster, glass beads, hollow glass spheres, plastic spheres, in particular PMMA beads, and mixtures thereof.
16. The coating system according to one of Claims 9 to 15, characterised in that the electric insulation layer is based on 2K polyurethane systems, in particular containing hydroxyl functional polyester, e.g. acrylic resin, as first component or as constituent of the first component (component A), and aliphatic polyisocyanates as second component or as constituent of the second component (component B), preferably in a weight ratio in the range of from 10:1 to 2:1, particularly preferably in the range of from 5:1 to 3:1.
17. The coating system according to any one of the preceding claims, characterised in that the average thickness, in particular also the absolute thickness, of layer c) is thinner than the average thickness, in particular also the absolute thickness, of each of the layers a), b) and d), in particular thinner than each of the layers a), b1), b2) and d) and/or wherein the average, preferably also the absolute, layer thicknesses increase in the sequence c), a), b), d), in particular c), a), b2), b1) and d).
18. An item having at least one coatable surface, in particular wall, floor or ceiling, equipped with at least one coating system according to one of Claims 1 to 17.
19. The item according to Claim 18, further comprising
    a device for generating an electric alternating voltage field in the dielectric luminescent layer b) or in the frontward luminescent layer b2), wherein the electric alternative voltage field preferably has a frequency in the range from 100 to 5000 Hz, particularly preferably in the range from 100 to 800 Hz, and wherein the voltage in particular is greater than 100 V, preferably greater than 150 V and particularly preferably greater than 200 V.
20. A use of the coating system according to one of Claims 1 to 17 for producing lucent walls, floors or ceilings.

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