• 专利附录
  • 专利说明
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    • 专利摘要:
    GLASS WITH THERMAL RADIATION REFLECTION COATING. The present invention relates to a glazing, comprising at least one substrate (1) and at least one thermal radiation reflection coating (2) on at least one surface of the substrate (1), wherein the coating (2) on the substrate (1) includes at least: an adhesion layer (3); above the adhesion layer (3), a functional layer (4), which contains at least one transparent electrically conductive oxide (TCO); above the functional layer (4); a dielectric barrier layer (5) to regulate the diffusion of oxygen; and above the barrier layer (5), an anti-reflective layer (6); and wherein the barrier layer (5) has a thickness of 10 nm to 40 nm.
    公开号:BR112014017440B1
    申请号:R112014017440-7
    申请日:2013-01-16
    公开日:2020-12-29
    发明作者:Martin Melcher；Jan Hagen；Juliette Ruchmann；Julia Vincent
    申请人:Saint-Gobain Glass France；
    IPC主号:
    专利说明:

    [0001] The invention relates to a panel with thermal radiation reflection coating, a method for its production, and its use.
    [0002] The interior of a motor vehicle can get very hot in summer, with high ambient temperatures and intense direct sunlight. When the outside temperature is lower than the temperature inside the vehicle, which occurs particularly in winter, a cold panel acts as a heat sink, which is perceived as unpleasant by the occupants. High heating performance of the air conditioning system must be provided to avoid excessive cooling of the interior through the motor vehicle windows.
    [0003] Thermal radiation reflection coatings (called “low-E coatings”) are known. Such coating reflects a significant part of solar radiation, in particular, in the infrared band, which, in summer, results in reduced heating of the vehicle interior. In addition, the coating reduces the emission of long-wave thermal radiation from a heated panel inside the vehicle when the coating is applied to the surface of a panel facing the inside of the vehicle. In addition, in the case of low external temperatures, such a coating reduces the external heat emission, from the interior to the external surroundings.
    [0004] A thermal radiation reflection coating may contain, for example, functional layers made of niobium, tantalum or zirconium. Such coatings are known, for example, from US 20110146172 A1, EP 1 218 307 B1, and EP 2 247 549 A2. Such coatings result in the fact that the transmittance of the panel in the visible spectral range is clearly reduced. Consequently, coatings cannot be used on panels where legal requirements with respect to transmittance must be satisfied, for example, windshields or front side windows. Coatings that reflect thermal radiation with functional layers made of silver are also known, for example, from EP 877 006 B1, EP 1 047 644 B1, and EP 1 917 222 B1. However, such coatings are susceptible to corrosion and not sufficiently and mechanically resistant. Consequently, coatings cannot be applied to the surface of a panel facing the interior of the vehicle, where the coating is exposed to air and other environmental influences.
    [0005] Often, after applying the coating, panels are subjected to heat treatment and mechanical transformation. The panels for the automotive sector, for example, windshields, side windows, and rear windows, are typically arched and often provided with pre-tensioning or partial pre-tensioning.
    [0006] The purpose of the present invention is to provide an improved panel with thermal radiation reflection coating, as well as a method for its production. The coating must be transparent and resistant to corrosion and must not be damaged during curvature and pre-tensioning of the panel.
    [0007] The purpose of the present invention is achieved according to the invention by a panel with thermal radiation reflection coating according to claim 1. Preferred embodiments emerge from the dependent claims.
    [0008] The panel according to the invention comprises at least one substrate, and at least one thermal radiation reflection coating on at least one surface of the substrate, wherein the coating on the substrate includes at least: - a layer adhesion, - above the adhesion layer, a functional layer, containing at least one electrically conductive transparent oxide (TCO), - above the functional layer, a dielectric barrier layer to regulate the diffusion of oxygen, and - above the layer barrier, an anti-reflective layer, and in which the barrier layer has a thickness of 10 nm to 40 nm.
    [0009] When a first layer is arranged above a second layer, this means, in the context of the invention, that the first layer is disposed further away from the substrate than the second layer. When a first layer is disposed below a second layer, this means, in the context of the invention, that the second layer is disposed further away from the substrate than the first layer.
    [0010] When the first layer is arranged above or below a second layer, this does not necessarily mean, in the context of the invention, that the first and second layers are located in direct contact with each other. One or a plurality of additional layers can be arranged between the first and the second layer, unless this is explicitly discarded.
    [0011] When a layer or other element contains at least one material, this includes, in the context of the invention, the case in which the layer is made of the material.
    [0012] The thermal radiation reflection coating, according to the invention, has, in the visible spectral range, low absorption and low reflection and, consequently, high transmittance. Consequently, the coating can also be used on panels, for which a significant reduction in transmittance is undesirable, for example for windscreens in buildings, or is legally prohibited, for example, for windshields or front side windows in vehicles motorized. This is the main advantage of the invention. The coating according to the invention is also resistant to corrosion. Consequently, the coating can be applied to the surface of the substrate which is intended, in the position of the installed panel, to face the interior, for example, of a motor vehicle or a building. In summer, the coating, according to the invention, particularly and effectively reduces the emission of thermal radiation from the panel to the interior and, in winter, the external emission of heat to the external surroundings.
    [0013] It has been demonstrated that the oxygen content of the functional layer decisively influences the properties of the thermal radiation reflection coating with respect to emissivity, transmittance in the visible spectral range, and flexibility. An excessively low oxygen content results in a high absorption of visible light and thus low transmittance. An excessively low oxygen content still results in a high laminar resistance and thus an excessively high emissivity. An excessively low oxygen content also results in an often undesirable, significant color impression. An excessively high oxygen content of the functional layer results in the fact that the functional layer is damaged during curvature. Such a failure is particularly evident when cracking within the functional layer. An excessively high oxygen content still results, as well as an excessively low oxygen content, in excessively high laminar resistance and thus in excessively high emissivity.
    [0014] The internal lateral emissivity of the panel, according to the invention, is preferably less than or equal to 25%, particularly preferable, less than or equal to 20%. The term “internal side emissivity” refers to a measurement that indicates how much thermal radiation the panel emits into an internal space, for example, a building or motor vehicle, in the installed position compared to an ideal thermal emitter (a black body) . In the context of the invention, "emissivity" means the normal emission level at 10 ° C according to the EN 12898 standard. The laminar resistance of the coating, according to the invention, is preferably 10 ohm / square at 30 ohm /square. The coating absorption according to the invention in the visible spectral range is preferably from approximately 1% to approximately 15%, particularly preferably from approximately 1% to approximately 7%. The coating absorption can be determined by measuring the absorption of a coated panel and subtracting the absorption of the uncoated panel. The panel according to the invention preferably has, during reflection, a color value a * of -15 to +5, and a color value b * of -15 to +5, seen from the side with the coating according to the invention. The data a * and b * refer to the color coordinates according to the colorimetric model (color space L * a * b *).
    [0015] To obtain the preferred values indicated for emissivity, laminar resistance, absorption, and color values during reflection, the substrate can be subjected to a temperature treatment after the application of the thermal radiation reflection coating. The substrate is preferably heated to a temperature of at least 200 ° C, particularly preferable, of at least 300 ° C. Such temperature treatment influences, in particular, the crystallinity of the functional layer and results in improved transmittance of the coating according to the invention. The temperature treatment also reduces the laminar resistance of the coating, which results in reduced emissivity.
    [0016] After application and before a temperature treatment, the functional layer preferably has an oxygen content so that the laminar resistance of the coating, according to the invention, is from 50 ohm / square to 250 ohm / square , particularly preferable, from 80 ohm / square to 150 ohm / square. The specific resistance of the functional layer is, after application of the coating and before the temperature treatment, preferably from 500 * 10-6 ohm * cm to 3500 * 10-6 ohm * cm, particularly preferable, from 1000 * 10-6 ohm * cm to 2000 * 10-6 ohm * cm. The absorption of the coating in the visible spectral range is, after application and before the temperature treatment, preferably from 8% to 25%, particularly preferable, from 13% to 20%. The oxygen content can, for example, be influenced during application of the functional layer by cathodic sublimation through target selection and / or through the oxygen content of the atmosphere. The oxygen content, which is suitable for laminar resistance and for absorption in the indicated ranges, can be determined by the person skilled in the art, for example, by simulations or experiments.
    [0017] It has been shown that the temperature treatment, due to the diffusion of oxygen, results in oxidation of the functional layer. By means of the barrier layer, according to the invention, the extent of oxidation of the functional layer can be influenced. The range, according to the invention, for the thickness of the barrier layer from 10 nm to 40 nm is particularly advantageous with respect to visible light transmittance, laminar resistance and, in particular, the flexibility of the coating. A thinner barrier layer results in an excessively high oxygen content of the functional layer after temperature treatment. A thicker barrier layer results in an excessively low oxygen content of the functional layer after the temperature treatment. The influence of the barrier layer on the oxygen content of the functional layer is another major advantage of the invention.
    [0018] The thickness of the barrier layer is preferably from 10 nm to 30 nm, particularly preferable, from 12 nm to 30 nm, more particularly preferable, from 15 nm to 25 nm and, in particular, from 18 nm to 22 nm. Particularly good results are thus obtained with respect to visible light transmittance, laminar resistance, and flexibility. However, the thickness of the barrier layer can also be, for example, from 10 nm to 18 nm, or from 12 nm to 18 nm.
    [0019] In addition, the barrier layer influences the corrosion resistance of the coating according to the invention. The thinner barrier layer results in excessive susceptibility to corrosion in a humid atmosphere. Corrosion of the coating results, in particular, in a significant increase in the absorption of visible light by the coating.
    [0020] In addition, the barrier layer influences the optical properties of the thermal radiation reflection coating, in particular, the color impression during light reflection. According to the invention, the barrier layer is dielectric. The refractive index of the barrier layer material is preferably greater than or equal to the refractive index of the functional layer material. The refractive index of the barrier layer material is particularly preferable from 1.7 to 2.3.
    [0021] The values indicated for refractive indices are measured at a wavelength of 550 nm.
    [0022] The barrier layer preferably contains at least one oxide and / or nitride. The oxide and / or nitride can be stoichiometric and / or non-stoichiometric. The particularly preferable barrier layer contains at least silicon nitride (Si3N4). This is particularly advantageous with respect to the influence of the barrier layer on the oxidation of the functional layer and the optical properties of the panel. Silicon nitride can have dopants, for example, titanium, zirconium, boron, hafnium and / or aluminum. Silicon nitride is more particularly preferable doped with aluminum (Si3N4: Al), or doped with zirconium (Si3N4: Zr), or doped with boron (Si3N4: B). This is particularly advantageous with respect to the optical properties, flexibility, smoothness, and emissivity of the coating, as well as the speed of application of the barrier layer, for example, by cathodic sublimation.
    [0023] Silicon nitride is preferably deposited using cathodic sublimation supported by a magnetic field, preferably with a target containing at least silicon. The target for the deposition of a barrier layer containing aluminum doped silicon nitride preferably contains from 80% by weight to 95% by weight of silicon, and from 5% by weight to 20% by weight of aluminum, as well as mixtures related to production. The target for the deposition of a barrier layer containing boron doped silicon nitride preferably contains from 99.9990% by weight to 99.9999% by weight of silicon, and from 0.0001% by weight to 0.001% in boron weight, as well as production-related mixtures. The target for the deposition of a barrier layer containing zirconium doped silicon nitride preferably contains from 60% by weight to 90% by weight of silicon, and from 10% by weight to 40% by weight of zirconium, as well as mixtures related to production. The deposition of silicon nitride is preferably done under the addition of nitrogen as the reaction gas during cathodic sublimation.
    [0024] During a temperature treatment after applying the coating, according to the invention, silicon nitride can be partially oxidized. A barrier layer deposited as Si3N4 then contains, after the temperature treatment, SixNyOz with the oxygen content typically from 0% atomic to 35% atomic.
    [0025] However, the barrier layer may alternatively contain, for example, at least WO3, Nb2O5, Bi2O3, TiO2, Zr3N4 and / or AlN.
    [0026] The adhesion layer results in durable, stable adhesion of the layers deposited above the adhesion layer on the substrate. The adhesion layer still prevents accumulation of ions by diffusing out of the substrate in the boundary region of the functional layer, in particular, sodium ions, if the substrate is made of glass. Such ions can result in corrosion and low adhesion of the functional layer. The adhesion layer is, therefore, particularly advantageous with respect to the stability of the functional layer.
    [0027] The adhesion layer material preferably has a refractive index in the range of the substrate's refractive index. The adhesion layer material preferably has a lower refractive index than the functional layer material. The adhesion layer preferably contains at least one oxide. The particularly preferable adhesion layer contains silicon dioxide (SiO2). This is particularly advantageous with respect to the adhesion of the layers on the substrate deposited above the adhesion layer. Silicon dioxide can have dopants, for example, fluorine, carbon, nitrogen, boron, phosphorus and / or aluminum. Silicon dioxide is more particularly preferable doped with aluminum (SiO2: Al), doped with boron (SiO2: B), or doped with zirconium (SiO2: Zr). This is particularly advantageous with respect to the optical properties of the coating, as well as the speed of application of the adhesion layer, for example, by cathodic sublimation.
    [0028] Silicon dioxide is preferably deposited using cathodic sublimation supported by a magnetic field with a target containing at least silicon. The target for the deposition of an adhesion layer containing aluminum doped silicon dioxide preferably contains from 80% by weight to 95% by weight of silicon, and 5% by weight to 20% by weight of aluminum, as well as mixtures related to production. The target for the deposition of an adhesion layer containing boron doped silicon dioxide preferably contains 99.9990% by weight to 99.9999% by weight of silicon, and 0.0001% by weight to 0.001% by weight of boron, as well as production-related mixtures. The target for the deposition of an adhesion layer containing zirconium doped silicon dioxide preferably contains from 60% by weight to 90% by weight of silicon, and from 10% by weight to 40% by weight of zirconium, as well as mixtures related to production. The deposition of silicon dioxides is preferably done under the addition of oxygen as a reaction gas during cathodic sublimation.
    [0029] The doping of the adhesion layer can also improve the smoothness of the layers applied above the adhesion layer. High smoothness of the layers is particularly advantageous in the case of use of the panel, according to the invention, in the motor vehicle sector, provided that, by this means, a feeling of unpleasant rough surface of the panel is avoided. When the panel, according to the invention, is a side window panel, it can be moved with little friction towards the sealing edges.
    However, the adhesion layer may also contain other materials, for example, other oxides, such as TiO2, Al2O3, Ta2O5, Y2O3, ZnO, and / or ZnSnOx or nitrides, such as AIN.
    [0031] The adhesion layer preferably has a thickness of 10 nm to 150 nm, particularly preferable, from 15 nm to 50 nm, for example, approximately 30 nm. This is particularly advantageous with respect to the adhesion of the coating according to the invention and the prevention of ion diffusion from the substrate to the functional layer.
    [0032] An additional adhesion-promoting layer can be arranged below the adhesion layer, preferably with a thickness of 2 nm to 15 nm. For example, the adhesion layer can contain SiO2, and the additional adhesion promoting layer can contain at least one oxide, such as TiO2, Al2O3, Ta2O5, Y2O3, ZnO, and / or ZnSnOx, or nitride, such as AIN. Advantageously, the adhesion of the coating according to the invention can be further improved by the adhesion-promoting layer. In addition, the adhesion-promoting layer allows for improved adjustment of color values and transmittance or reflection.
    [0033] The functional layer has reflective properties for thermal radiation, in particular, infrared radiation, it is still largely transparent in the visible spectral range. According to the invention, the functional layer contains at least one electrically conductive transparent oxide (TCO). The refractive index of the material of the functional layer is preferably 1.7 to 2.5. The functional layer preferably contains at least indium tin oxide (ITO). Thus, particularly good results are obtained with respect to the emissivity and flexibility of the coating according to the invention.
    [0034] Tin indium oxide is preferably deposited using cathodic sublimation supported by a magnetic field with a target made of indium tin oxide. The target preferably contains from 75% by weight to 95% by weight of indium oxide, and from 5% by weight to 25% by weight of tin oxide, as well as mixtures related to production. The deposition of tin indium oxide is preferably carried out under a protective gaseous atmosphere, for example, argon. A small amount of oxygen can also be added to the protective gas, for example, to improve the homogeneity of the functional layer.
    Alternatively, the target may preferably contain at least 75% by weight to 95% by weight of indium, and from 5% by weight to 25% by weight of tin. The deposition of indium tin oxide is then preferably performed under the addition of oxygen as the reaction gas during cathodic sublimation.
    [0036] The emissivity of the panel, according to the invention, can be influenced by the thickness of the functional layer. The thickness of the functional layer is preferably from 40 nm to 200 nm, particularly preferable from 90 nm to 150 nm and, more particularly preferable, from 100 nm to 130 nm, for example, approximately 120 nm. In this range for the thickness of the functional layer, particularly advantageous values for emissivity and a particularly advantageous ability of the functional layer to withstand mechanical transformation, such as curvature or pre-tensioning without damage, are obtained.
    [0037] However, the functional layer can also include other electrically conductive, transparent oxides, for example, fluorine-doped tin oxide (SnO2: F), antimony-doped tin oxide (SnO2: Sb), indium / zinc oxide mixed (IZO), gallium or aluminum doped zinc oxide, niobium doped titanium oxide, cadmium stanate, and / or zinc stanate.
    [0038] The anti-reflective layer reduces reflections in the spectral band visible on the panel, according to the invention. By means of the anti-reflective layer, in particular, high transmittance in the spectral band visible through the panel, according to the invention, and a neutral color impression of the reflected and transmitted light are obtained. The anti-reflective layer also improves the corrosion resistance of the functional layer. The material of the antireflective layer preferably has a refractive index that is less than the refractive index of the functional layer material. The refractive index of the material of the antireflective layer is preferably less than or equal to 1.8.
    [0039] The anti-reflective layer preferably contains at least one oxide. The particularly preferable anti-reflective layer contains silicon dioxide (SiO2). This is particularly advantageous with respect to the optical properties of the panel and the corrosion resistance of the functional layer. Silicon dioxide can have dopants, for example, fluorine, carbon, nitrogen, boron, phosphorus and / or aluminum. Silicon nitride is more particularly preferable doped with aluminum (SiO2: Al), doped with boron (SiO2: B), or doped with zirconium (SiO2: Zr).
    [0040] However, the antireflection layer may also contain other materials, for example, other oxides, such as TiO2, Al2O3, Ta2O5, Y2O3, ZnO, and / or ZnSnO, or nitrides, such as AlN.
    [0041] The anti-reflective layer preferably has a thickness of 20 nm to 150 nm, particularly preferable, from 40 nm to 100 nm. This is particularly advantageous with respect to poor reflection and high transmittance of visible light, as well as the placement of a selected color impression of the panel and resistance to corrosion of the functional layer.
    [0042] In an advantageous embodiment of the invention, a cover layer is disposed above the thermal radiation reflection coating. The covering layer protects the coating according to the invention against damage, in particular, against scratches. The cover layer preferably contains at least one oxide, particularly preferable, at least titanium oxide (TiOx), ZrO2, HfO2, Nb2O5, Ta2O5, Cr2O3, WO3 and / or CeO2. The thickness of the cover layer is preferably from 2 nm to 50 nm, particularly preferable from 5 nm to 20 nm. Thus, particularly good results are achieved with respect to scratch resistance.
    [0043] The substrate preferably contains glass, particularly preferable, flat glass, float glass, quartz glass, borosilicate glass, solder lime glass, or transparent plastics, preferably rigid transparent plastics, in particular polyethylene, polypropylene , polycarbonate, polymethyl methacrylate, polystyrene, polyamide, polyester, polyvinyl chloride, and / or mixtures thereof.
    [0044] The thickness of the substrate can vary widely and thus be ideally adapted to the needs of the individual case. Preferably, panels with standard thicknesses from 1.0 mm to 25 mm and, preferably, from 1.4 mm to 4.9 mm, are used. The size of the substrate can vary widely and is determined by use according to the invention. The substrate has, for example, in the automotive and architectural sectors, common areas of 200 cm2 all the way up to 20 m2.
    [0045] In an advantageous embodiment of the invention, the substrate has a transmittance in the visible spectral range greater than or equal to 70%. However, the substrate may also have a higher transmittance, for example, greater than or equal to 85%. Since the coating, according to the invention, has low absorption, panels with high transmittance in the visible spectral range that are, for example, suitable as windshields, can be realized. The panel, according to the invention, with thermal radiation reflection coating, preferably has a total transmittance greater than 70%. The term “total transmittance” is based on the method for testing the luminous permeability of motor vehicle windows specified by ECE-R 43, Annex 3, § 9.1.
    [0046] In an alternative advantageous embodiment, the substrate is dyed or colored. In that case, the substrate may preferably have transmittance in the visible spectral range of less than 50%, for example, less than 15%. Thus, panels with a transparent coating, according to the invention, and with reduced transmittance in the visible spectral range, can be made. Such dyed or colored panels may be desirable, for example, for aesthetic or thermal reasons.
    [0047] In an advantageous embodiment of the invention, the substrate is slightly or very curved in one or a plurality of spatial directions. Such curved panels occur, in particular, through glazing in the automotive sector. The typical radii of curvature for curved panels are in the range of approximately 10 cm to approximately 40 m. The radius of curvature does not have to be constant across the entire panel; very curved and much less curved regions can be present in a panel. It is a particular advantage of the invention that a flat substrate can be provided with the coating according to the invention, and that the coating is not damaged during a downstream bending process, which is typically carried out at elevated temperatures of, for example, 500 ° C to 700 ° C.
    [0048] The barrier layer of the coating according to the invention on the curved substrate preferably has a thickness of 10 nm to 30 nm, particularly preferable, 12 nm to 30 nm, more particularly preferable, 15 nm at 25 nm and, in particular, from 18 nm to 22 nm, for example, approximately 20 nm. This is particularly advantageous with respect to the emissivity and transmittance of visible light, as well as the ability of the coating to undergo mechanical transformation, such as curvature or pre-tensioning of the unharmed substrate. However, the thickness of the barrier layer can also be, for example, from 10 nm to 18 nm, or from 12 nm to 18 nm, which is advantageous with respect to material savings and visible light transmittance.
    [0049] In principle, the coating can, of course, also be applied to a curved substrate. The three-dimensional shape of the substrate preferably has no shaded zones, so that the substrate can, for example, be coated by cathodic sublimation.
    [0050] In an alternative advantageous embodiment of the invention, the substrate is flat. Flat panels occur, for example, in glazing in the architectural sector or in large-area glazing of buses, trains or tractors. In the context of the invention, the substrate is considered flat when its primary surfaces, through which an observer sees in the installed position, are not substantially curved, but are, instead, substantially flat. Primary surfaces do not necessarily have to be parallel to the plane.
    [0051] The barrier layer of the coating, according to the invention, on a flat substrate, preferably has a thickness of 10 nm to 25 nm, particularly preferable, from 12 nm to 18 nm and, more particularly preferable, of 14 nm to 16 nm, for example, approximately 15 nm. Since the coating does not need to be curved, the thickness of the barrier layer can be selected thinner than in the embodiment with a curved substrate. Thus, a higher oxygen content of the functional layer is obtained after a temperature treatment, which results in reduced absorption and, thus, higher visible light transmittance with simultaneously low emissivity.
    [0052] The coating, according to the invention, is preferably applied to the surface of the substrate which is intended, in its installed position, to face an interior, for example, the interior of a building or a vehicle. This is particularly advantageous with regard to thermal comfort in the interior. The surface that is intended to face the interior of the panel is referred to in the context of the invention as the internal side surface. The coating, according to the invention, can, in the case of high external temperatures and sunlight, particularly and effectively at least partially reflect the thermal radiation emitted by the entire panel towards the interior. In the case of low external temperatures, the coating, according to the invention, can effectively reflect the thermal radiation emitted from the interior and, thus, reduce the effect of the cold panel as a heat sink.
    [0053] The coating, according to the invention, can be applied to the substrate surface over its entire area. However, the substrate surface may also have regions free of coating. The substrate surface can, for example, have a circumferential coating free edge region, and / or a coating free region that serves as a data transmission window or a communication window. In the coating-free region, the panel is permeable to electromagnetic radiation and, in particular, to infrared radiation.
    [0054] The substrate can also be provided on both surfaces, in each case, with a thermal radiation reflection coating according to the invention.
    [0055] In an advantageous embodiment of the invention, the substrate is connected, via at least one thermoplastic intermediate layer, to a cover panel to form a composite panel (laminated panel). The cover panel is preferably designed to face the external environment in the installed position of the composite panel, while the substrate faces the interior. Alternatively, the cover panel can also be designed to face the interior in the installed position of the composite panel. The coating according to the invention is preferably arranged on the surface of the substrate facing away from the cover panel.
    [0056] The cover panel preferably contains glass, particularly preferable, flat glass, float glass, quartz glass, borosilicate glass, solder lime glass, or transparent plastics, preferably rigid transparent plastics, in particular polyethylene , polypropylene, polycarbonate, polymethyl methacrylate, polystyrene, polyamide, polyester, polyvinyl chloride, and / or mixtures thereof. The cover panel preferably has a thickness of 1.0 mm to 25 mm and, preferably, 1.4 mm to 4.9 mm.
    [0057] The thermoplastic intermediate layer preferably contains thermoplastic plastics, for example, polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), polyurethane (PU), polyethylene terephthalate (PET), or its multiple layers, preferably with thicknesses from 0.3 mm to 0.9 mm.
    [0058] The composite panel has, in a preferred embodiment, total transmittance greater than 70%, and internal side emissivity less than or equal to 25%.
    [0059] In an alternative advantageous embodiment, the composite panel has significantly reduced visible light transmittance of, for example, less than 50%, less than 15%, less than 10%, or less than 6% . This can be achieved by using a dyed or colored cover panel or a dyed or colored substrate. Alternatively, a dyed or colored thermoplastic intermediate layer can be used, or a dyed or colored film can be embedded in the thermoplastic intermediate layer.
    [0060] In a preferred embodiment, the substrate is connected, via at least one thermoplastic intermediate layer, to a cover panel to form a composite panel. The substrate is intended to face an interior in the installed position, while the cover panel faces the external environment. The thermal radiation reflection coating, according to the invention, is applied to the surface of the substrate facing away from the cover panel, that is, on the internal side surface of the substrate. The thickness of the barrier layer is from 10 nm to 40 nm, preferably from 10 nm to 30 nm. The composite panel has a visible light transmittance of less than 15%, preferably less than 10%, which is obtained by means of a dyed cover panel, a dyed substrate, and / or a dyed thermoplastic intermediate layer. The cover panel and the substrate can be curved. Such a composite panel with low transmittance and coating, according to the invention, is particularly advantageous with regard to thermal comfort, and an advantageously low value is obtained for the transmitted solar energy (TTS value [total solar energy transmission]). The thermal radiation reflection coating reduces the emission of solar energy absorbed by the dyed panels inside. In the range indicated for the thickness of the barrier layer, the coating, according to the invention, has advantageous flexibility and corrosion resistance. In addition, it has surprisingly been demonstrated that aesthetic color values can be obtained through the barrier layer with a maximum thickness of 40 nm.
    [0061] In a particularly advantageous embodiment, the coating, according to the invention, is applied on the surface of the substrate facing the interior, with the substrate constituting the panel of a composite panel facing the interior. A sun protection coating is also applied on the substrate surface facing the cover panel, on the surface of the covering panel facing the substrate, or on a carrier film in the thermoplastic intermediate layer. The sunscreen coating is advantageously protected there against corrosion and mechanical damage. The sunscreen coating preferably comprises at least one silver-based metallic layer or an alloy containing silver with a thickness of 5 nm to 25 nm. Particularly good results are obtained with two or three functional layers, which are separated by dielectric layers with thicknesses from 10 nm to 100 nm. The sunscreen coating reflects fractions of sunlight incident outside the visible spectral range, in particular, in the infrared spectral range. Through the sun protection coating, the heating of the interior by direct sunlight is reduced. In addition, the sunscreen coating reduces the heating of the elements in the composite panel arranged behind the sunscreen coating and thus the thermal radiation emitted by the composite panel. By combining the sunscreen coating with the coating, according to the invention, for reflecting thermal radiation, the thermal comfort inside is advantageously improved.
    [0062] The substrate can, for example, also be connected to another panel, via spacers, to form an insulating glass unit. The substrate can also be connected to more than another panel, via intermediate thermoplastic layers and / or spacers.
    [0063] The invention also includes a method for producing a panel, according to the invention, with thermal radiation reflection coating, in which on a substrate, at least (a) an adhesion layer, (b) a functional layer containing at least one electrically conductive, transparent oxide (TCO), (c) a dielectric barrier layer, and (d) an anti-reflective layer are applied in sequence, and (e) the substrate is heated to a temperature of at least 200 ° C.
    [0064] In an advantageous embodiment of the invention, a cover layer is applied after the application of the anti-reflective layer.
    [0065] The individual layers are deposited by methods known per se, preferably by cathodic sublimation supported by magnetic field. This is particularly advantageous with respect to the simple, fast, economical and uniform coating of the substrate. Cathodic sublimation is done in a protective gas atmosphere, for example, argon, or in a reactive gas atmosphere, for example, by adding oxygen or nitrogen.
    [0066] However, the individual layers can also be applied by other methods known to the person skilled in the art, for example, by vapor deposition or chemical vapor deposition (CVD), by plasma accentuated chemical vapor deposition (PECVD), or by wet chemical methods.
    [0067] In step (e) of the process, after applying the thermal radiation reflection coating, the panel is subjected to a temperature treatment. The coated substrate according to the invention is heated to a temperature of at least 200 ° C, particularly preferable, at least 300 ° C. The crystallinity of the functional layer is, in particular, improved by the temperature treatment. Thus, the visible light transmittance and reflection properties related to thermal radiation are significantly improved.
    [0068] In a preferred embodiment of the method, according to the invention, the temperature treatment in step (e) of the process takes place within a curvature process. The coated substrate according to the invention is curved, in the heated state, in one or a plurality of spatial directions. The temperature at which the substrate is heated is preferably from 500 ° C to 700 ° C. It is a particular advantage of the coating, according to the invention to reflect thermal radiation, that it can be subjected to such a curvature process without being damaged.
    [0069] Naturally, other temperature treatment steps can occur before or after the curvature process. Alternatively, a temperature treatment can be carried out using laser radiation.
    [0070] In an advantageous embodiment, after the temperature treatment of the process step (e) and, optionally, after bending, the substrate can be pre-tensioned or partially pre-tensioned. For this, the substrate is adequately cooled in a manner known to you. A prestressed substrate typically has compressive surface stresses of at least 69 MPa. A partially pre-strained substrate typically has compressive surface stresses from 24 MPa to 52 MPa. A pre-tensioned substrate is suitable as a single-pane protective glass, for example, as a side window or rear window of a motor vehicle.
    [0071] In an advantageous embodiment of the invention, after the temperature treatment and, optionally, after the bending process and / or the pre-tensioning process, the substrate is connected, via at least one thermoplastic intermediate layer, to a cover panel to form a composite panel. The substrate is preferably arranged in the compound, so that the surface provided with the coating, according to the invention, faces away from the thermoplastic intermediate layer and the cover panel.
    [0072] The invention further includes the use of the panel, according to the invention, with thermal radiation reflection coating as a panel or as a component of a panel, in particular, as a component of an insulating glazing unit or a composite panel, in buildings, in particular, in access or window areas, as a component embedded in furniture and devices, in particular, electronic devices with a cooling or heating function, for example, as an oven or refrigerator door , or means of transport to operate on land, in the air, or on water, in particular on trains, ships, and motor vehicles, for example, as a windshield, side window, rear window, and / or ceiling panel.
    [0073] The invention is explained in detail below with reference to the exemplary drawings and embodiments. The drawings are schematic representations and not in real scale. The drawings in no way restrict the invention. They represent: Fig. 1 - a cross section through an embodiment of the panel, according to the invention, with thermal radiation reflection coating, Fig. 2 - a cross section through another embodiment of the panel, in accordance with the invention. according to the invention, with thermal radiation reflection coating, Fig. 3 - a cross section through a composite panel comprising a panel, according to the invention, Fig. 4 - a diagram of the number of cracks in the thermal reflection coating thermal radiation, the absorption, and the emissivity of the panels, according to the invention, after a curvature process, as well as the change in the absorption of panels according to the invention in a boiler test as a function of the layer thickness of barrier, Fig. 5 - a diagram of the transmittance in the spectral band visible through a panel, according to the invention, as a function of the thickness of the antireflection layer, and Fig. 6 - a detailed flowchart of an embodiment of the method according to the invention.
    [0074] Fig. 1 represents a cross section through an embodiment of the panel, according to the invention, with substrate 1 and the thermal radiation reflection coating 2. Substrate 1 contains soda lime glass and has a thickness of 2.9 mm. The coating 2 comprises an adhesion layer 3, a functional layer 4, a barrier layer 5, and an anti-reflective layer 6. The layers are arranged in the indicated order with increasing distance from the substrate 1. The precise sequence of layers with materials and exemplary layer thicknesses are shown in Table 1.
    [0075] The individual layers of coating 2 were deposited using cathodic sublimation supported by magnetic field. The target for deposition of the adhesion layer 3 and the anti-reflective layer 6 contained 92% by weight of silicon and 8% by weight of aluminum. The deposition occurred under the addition of oxygen as a reaction gas during cathodic sublimation. The target for deposition of functional layer 4 contained 90% by weight of indium oxide and 10% by weight of tin oxide. The deposition took place under an argon protective gas atmosphere with an oxygen fraction less than 1%. The target for deposition of barrier layer 5 contained 92 wt% silicon and 8 wt% aluminum. The deposition occurred with the addition of nitrogen as the reaction gas during cathodic sublimation. Table 1

    [0076] Fig. 2 represents a cross section through another embodiment of the panel, according to the invention, with the substrate 1 and the thermal radiation reflection coating 2. The coating 1 is configured as in Fig. 1 with the adhesion layer 3, the functional layer 4, the barrier layer 5, and the anti-reflective layer 6. A cover layer 7 is arranged above the coating 2. The cover layer contains Ta2O5 and has a thickness of 10 nm. By means of the covering layer, the coating 2 is advantageously protected against mechanical damage, in particular, against scratches.
    [0077] Fig. 3 represents a cross section through a panel, according to the invention, with thermal radiation reflection coating 2 as part of a composite panel. Substrate 1 is connected to a cover panel 8, via a thermoplastic intermediate layer 9. The composite panel is intended as a windshield for a motor vehicle. The composite panel is curved, as it is customary for panels in the automotive sector. The surface of the substrate 1, which faces away from the cover panel 8 and the thermoplastic intermediate layer 9, is provided with the coating according to invention 2. In the installed position of the composite panel, the cover panel 8 faces the external environment , and substrate 1 faces the internal vehicle. The cover panel contains soda lime glass and is 2.1 mm thick. The thermoplastic intermediate layer 9 contains polyvinyl butyral (PVB) and has a thickness of 0.76 mm.
    [0078] The coating, according to invention 2, has low absorption of visible light. Consequently, the coating 2 does not substantially reduce the transmittance in the spectral range visible through the composite panel. The composite panel has a transmittance in the visible spectral range greater than 70% and meets legal requirements for windshields. The coating according to invention 2 is, in addition, stable against corrosion of atmospheric oxygen and other environmental influences, and can, therefore, be arranged on the surface of the composite panel facing the internal vehicle, so that it results particularly and effectively in an improvement of thermal comfort in the internal vehicle. The coating 2 reflects part of the sunlight on the composite panel, in particular, in the infrared band. The thermal radiation emitted by the warm composite panel in the internal direction of the vehicle is also, at least partially, suppressed by the low emissivity of the coating 2. Thus, the interior is less strongly heated in the summer. In winter, the thermal radiation emitted from the interior is reflected. Consequently, the cold composite panel acts less strongly as an unpleasant heat sink. In addition, the required heat output from the air conditioning system can be reduced, which results in significant energy savings.
    [0079] The coating 2 is preferably applied on the flat substrate 1 before the curvature of the substrate 1. Coating a flat substrate is technically significantly simpler than coating a curved substrate. Substrate 1 is then typically heated to a temperature of 500 ° C to 700 ° C, for example, 640 ° C. On the other hand, the temperature treatment is necessary to bend the substrate 1. On the other hand, the visible light transmittance and the emissivity of the coating 2 are regularly improved by the temperature treatment. The barrier layer according to the invention 5 influences the extent of oxidation of the functional layer 4 during the temperature treatment. The oxygen content of the functional layer 4 is sufficiently low after the temperature treatment that the coating 2 can be subjected to a curvature process. An excessively high oxygen content would result in failure of the functional layer 4 during curvature. On the other hand, the oxygen content of functional layer 4 is high enough after the temperature treatment for high transmittance of visible light and low emissivity. This is a major advantage of the present invention.
    [0080] In an alternative embodiment, the composite panel may also have low visible light transmittance of, for example, less than 10%. Such composite panels can, for example, be used as a rear window or a roof panel. By coating, according to invention 2, which has a barrier layer 5 with a thickness of 10 nm to 40 nm, advantageous color values are also obtained in addition to flexibility and corrosion resistance.
    [0081] Fig. 4 represents observations from the three test panels. The test panels were deposited using cathodic sublimation with the targets and conditions mentioned in Fig. 1. The test panels with the substrate 1 and the thermal radiation reflection coating 2 differed in the thickness of the barrier layer 5. The sequence layers, materials, and layer thicknesses of the test panels are summarized in Table 2. Table 2

    [0082] The substrate 1 was initially flat and was provided with the coating 2, according to the invention. Substrate 1 with coating 2 was then subjected for 10 minutes to a temperature treatment at 640 ° C, curved at the time, and provided with a radius of curvature of approximately 30 cm. Barrier layer 5 was deposited as aluminum doped Si3N4 and is reported as such in the Table. Due to partial oxidation during temperature treatment, the barrier layer may, however, also contain SixNyOz.
    [0083] In part (a) of the diagram, the number of cracks per cm2 in the coating 2, after the curvature process, is plotted in relation to the thickness of the barrier layer 5. It can be discerned that the number of cracks increases a lot if the barrier layer 5 is very thin. The reason for this seems to be the excessively high oxidation of the functional layer 4 during the temperature treatment. The excessively high oxidation of the functional layer 4 cannot be effectively reduced by an excessively thin barrier layer 5.
    [0084] In part (b) of the diagram, the absorption of visible light during passage through the panel is plotted in relation to the thickness of the barrier layer 5. The absorption increases with the thickness of the barrier layer 5. The absorption by the coating 2 it is a function of the oxygen content of the functional layer 4. The oxygen content of the functional layer 4 is a function of the thickness of the barrier layer 5. An excessively thick barrier layer results in an excessively low oxygen content of the functional layer 4. An excessively low oxygen content of the functional layer 4 results in excessively high absorption and thus impairs vision through the panel. In addition, the color values of the panel change undesirably with the increasing thickness of the barrier layer 5.
    [0085] In part (c) of the diagram, the emissivity of the test panels is plotted in relation to the thickness of the barrier layer 5. The emissivity is a function of the thickness of the barrier layer 5.
    [0086] In part (d) of the diagram, a boiler test result (PCT) is presented. In the boiler test, the panel is hermetically sealed in a metallic container partially filled with water and heated for 48 hours at a temperature of 120 ° C. In this process, the panel is exposed to high pressure and hot steam and can be tested for corrosion resistance. In the diagram, the relative change in absorption of the panel after the boiler test, compared to the absorption before the boiler test, is presented as a function of the thickness of the barrier layer 5. A large change in absorption indicates corrosion of the coating 2 during the boiler test. It is discernible that the corrosion resistance of the coating 2 increases with the increasing thickness of the barrier layer 5.
    [0087] The particular advantage of the strip, according to the invention, for the thickness of the barrier layer 5, is evident from the diagram. The thickness of the barrier layer 5, from 10 nm to 40 nm, is selected according to the invention, so that the coating 2 can, on the one hand, undergo a curvature process (that is, not have, after curvature, cracks, or just having a small number of cracks) and, on the other hand, having sufficiently low absorption (less than approximately 15%), sufficiently low emissivity (less than approximately 25%), and advantageous resistance to corrosion.
    [0088] Particularly good results with respect to flexibility, absorption of visible light, and emissivity, are obtained when the thickness of the barrier layer 5 is from 12 nm to 30 nm and, in particular, from 15 nm to 25 nm. By means of a barrier layer 5 with a thickness of 15 nm to 25 nm, absorption less than approximately 7% and emissivity less than approximately 20% are obtained.
    [0089] It can be seen from the diagram that the thickness of the barrier layer 5 can be selected less when the substrate is not being curved. In this case, no consideration of the cracks in the coating 2, which would develop with a curvature process, would need to be taken. Thus, less absorption of visible light and, at the same time, advantageously, less emissivity, can be obtained. When coating 2 is applied to a flat substrate 1, absorption less than 5% and emissivity less than approximately 20% can be obtained with a barrier layer 5 which has a thickness in the range of 12 nm to 18 nm.
    [0090] Table 3 summarizes some properties of the test panels. Square is the laminar resistance of the coating 2. A is the absorption of visible light from the panel. The absorption of coating 2 is calculated by subtracting the absorption of the uncoated substrate 1 by approximately 1.5%. εn is the normal emissivity of the panels. TL indicates the transmittance of the panels for visible light. RL indicates the reflectivity of the panels to visible light. Data a * and b * are based on the color coordinates of the reflection, according to the calorimetric model (color space L * a * b *), observed on the side of the panel provided with the coating 2. Table 3

    [0091] Laminar resistance and absorption before temperature treatment is a function of the oxygen content of functional layer 4. The target and oxygen content of the atmosphere during application of functional layer 4 are appropriately selected for this. Through the temperature treatment, the laminar resistance was significantly reduced, which resulted in advantageously low emissivity. The panels had high transmittance and advantageous color values and can therefore be used, for example, as windshields.
    [0092] Fig. 5 represents the result of a transmittance simulation in the visible spectral range as a function of the thickness of the antireflection layer 6. Substrate 1, adhesion layer 3, functional layer 4, and barrier layer 5 , were configured in the simulation as in Table 2, Example 2. The thickness of the anti-reflective layer 6, made of SiO2, was varied during the simulation. An anti-reflective layer 6 with a thickness in the range of 40 nm to 100 nm results, due to the significantly reduced reflection on the coating 2, in a particularly advantageous transmittance through the panel, greater than or equal to approximately 87%.
    [0093] Fig. 6 represents a flow chart of an exemplary embodiment of the method according to the invention, for producing a panel with thermal radiation reflection coating 2. An adhesion layer 3, a functional layer 4, a barrier layer 5, and an anti-reflective layer 6, are applied in sequence on a surface of a substrate 1 using cathodic sublimation supported by magnetic field. The applied layers 3, 4, 5, 6 form the thermal radiation reflection coating 2. Substrate 1 is subsequently subjected to a temperature treatment at least 200 ° C.
    [0094] Temperature treatment can also occur within a curvature process in which substrate 1 is, for example, heated to a temperature of 640 ° C and curved.
    [0095] Substrate 1 can subsequently be connected, for example, via a thermoplastic intermediate layer 9, to an identically curved cover panel 8, to form a composite panel. The substrate 1 is arranged in the compound, so that the surface of the substrate 1, on which the coating 2 is applied, faces away from the intermediate thermoplastic layer 9.
    [0096] Substrate 1 can also be pre-tensioned after the temperature treatment and, optionally, after curvature. Reference Character List: (1) substrate (2) thermal radiation reflection coating (3) adhesion layer (4) functional layer (5) barrier layer (6) anti-reflective layer (7) covering layer (8) cover panel (9) thermoplastic intermediate layer
    权利要求:
    Claims (16)
    [0001]
    1. Panel for motor vehicles, comprising at least one curved substrate (1) and at least one thermal radiation reflection coating (2) on at least one substrate surface (1), the coating (2) on the substrate (1) includes at least: - an adhesion layer (3), - above the adhesion layer (3), a functional layer (4), containing at least one electrically conductive transparent oxide (TCO), - above the layer functional (4), a dielectric barrier layer (5), to regulate the diffusion of oxygen, and - above the barrier layer (5), an anti-reflective layer (6), and in which the barrier layer (5) has a thickness of 10 nm to 40 nm, characterized by the fact that the coating (2) is applied on the inner lateral surface of the substrate (1), and in which the anti-reflective layer (6) contains at least one oxide with a lower refractive index than or equal to 1.8 and has a thickness of 20 nm to 150 nm.
    [0002]
    2. Panel according to claim 1, characterized by the fact that the barrier layer (5), has a thickness of 10 nm to 30 nm.
    [0003]
    Panel according to either of claims 1 or 2, characterized by the fact that the substrate (1) is connected, via at least one thermoplastic intermediate layer (9), to a cover panel (8), to form a composite panel, and where the coating (2) is arranged on the substrate surface (1) facing away from the cover panel (8).
    [0004]
    4. Panel, according to claim 3, characterized by the fact that the composite panel has a visible light transmittance of less than 10%.
    [0005]
    Panel according to either of Claims 3 and 4, characterized by the fact that a sunscreen coating is laid on the surface of the substrate (1) facing the covering panel (8) or on the surface of the covering panel (8) facing the substrate (1) or in the intermediate thermoplastic layer (9).
    [0006]
    6. Panel according to any one of claims 1 to 5, characterized in that the functional layer (4) contains at least fluorine-doped tin oxide, antimony-doped tin oxide, and / or tin oxide and and, it has a thickness of 40 nm to 200 nm.
    [0007]
    7. Panel according to any one of claims 1 to 6, characterized in that the barrier layer (5) contains silicon nitride.
    [0008]
    Panel according to any one of claims 1 to 7, characterized in that the adhesion layer (3) contains silicon dioxide and has a thickness of 10 nm to 150 nm.
    [0009]
    9. Panel according to any one of claims 1 to 8, characterized in that the anti-reflective layer (6) contains silicon dioxide and has a thickness from 40 nm to 100 nm.
    [0010]
    10. Panel according to any one of claims 1 to 9, characterized in that a cover layer (7), containing at least TiOx, ZrO2, HfO2, Nb2O5, Ta2O5, Cr2O3, WO3, and / or CeO2 , is arranged above the coating (2), and which has a thickness of 2 nm to 50 nm.
    [0011]
    11. Panel according to any one of claims 1 to 10, characterized by the fact that it has an internal lateral emissivity less than or equal to 25%.
    [0012]
    12. Panel according to any one of claims 1 to 11, characterized by the fact that the substrate (1) has a transmittance in the visible spectral range greater than or equal to 70% or less than 50%.
    [0013]
    13. Method for producing a motor vehicle panel with a thermal radiation reflection coating (2) as defined in any one of claims 1 to 12, wherein, on a substrate (1), by cathodic sublimation, at least (a ) an adhesion layer (3), (b) a functional layer (4), containing at least one electrically conductive transparent oxide (TCO), (c) a dielectric barrier layer (5), and (d) a layer anti-reflective (6) are applied in sequence, and (e) the substrate (1) is curved in the process step (e) at a temperature of 500 ° C to 700 ° C, characterized by the fact that the layers (3, 4 , 5, 6) are applied to the inner lateral surface of the substrate (1), and where the anti-reflective layer (6) contains at least one oxide with a refractive index less than or equal to 1.8 and has a thickness of 20 nm to 150 nm.
    [0014]
    14. Method according to claim 13, characterized by the fact that the substrate (1) is pre-tensioned or partially pre-tensioned after the process step (e).
    [0015]
    15. Method according to either of claims 13 or 14, characterized in that the specific resistance of the functional layer (4) before the process step (e) is 500 * 10-6 ohm * cm at 3500 * 10-6 ohm * cm and where the absorption of the coating (2) before the process step (e) is 10% to 25%.
    [0016]
    16. Use of the panel with thermal radiation reflection coating as defined in any of claims 1 to 12, characterized by the fact that it is like a windshield, rear window, side window, and / or roof panel
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-06-30| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-11-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12158005.4|2012-03-05|
    EP12158005|2012-03-05|
    PCT/EP2013/050698|WO2013131667A1|2012-03-05|2013-01-16|Sheet with coating which reflects thermal radiation|
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