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    • 专利摘要:
    TRANSPARENT GLASS PLATE WITH ELECTRICALLY CONDUCTIVE COATING. The present invention relates to a transparent glass plate, which comprises at least one transparent substrate (1) and at least one electrically conductive coating (2) on at least one surface of the transparent substrate (1), where - the electrically coating conductive (2) has at least two functional layers (3) arranged on top of each other and each functional layer (3) comprises at least. a layer of a highly refractive optical material (4) with a refractive index greater than or equal to 2.1,. on top of the layer of a highly refractive optical material (4), a smoothing layer (5), which contains at least one non - crystalline oxide,. on top of the smoothing layer (5), a first compatible layer (6),. on top of the first compatible layer (6), an electrically conductive layer (7), e.g. on top of the electrically conductive layer (7), a second compatible layer (8), - the total layer thickness of all electrically and conductive layers (7) is from 40 nm to 75 nm, and - the electrically conductive coating (2 ) has a surface resistance of less than 1 ohm / square, and where the layer of a highly refractive optical material (4) contains at least one mixed silicon / metal nitride.
    公开号:BR112014012695B1
    申请号:R112014012695-0
    申请日:2012-10-04
    公开日:2021-01-19
    发明作者:Christoph Schmitz；Klaus Fischer；Sebastian Janzyk；Marcus Neander；Ulrich Billert；David Luxembourg
    申请人:Saint-Gobain Glass France；
    IPC主号:
    专利说明:

    [0001] The invention relates to a transparent panel with an electrically conductive coating, a method for its production, and its use.
    [0002] The field of view of a motor vehicle window, in particular a windshield, must be kept free of ice and condensation. In the case of motor vehicles with an internal combustion engine, a stream of air heated by the heat of the engine, for example, can be directed towards the window.
    [0003] Alternatively, the window may have an electric heating function. From DE 103 52 464 A1, for example, a composite glazing panel is known in which electrically heated wires are placed between two panels. The specific heat capacity P, for example, of approximately 600 W / m2, can be adjusted by the ohmic resistance of the wires. Because of the design and safety aspects, the number of wires, as well as the diameters of the wires, must be kept as small as possible. The wires must not be visible or must be difficult to perceive in daylight and at night with the headlight illuminated.
    [0004] Electrically conductive, transparent coatings are also known, in particular based on silver. Such electrically conductive coatings can be used as coatings with reflective properties for the infrared range or even as heatable coatings. WO 03/024155 A2 discloses, for example, an electrically conductive coating with two layers of silver. Such coatings usually have sheet resistances in the range of 3 ohm / square to 5 ohm / square.
    [0005] The specific heat capacity P of an electrically heated coating with a squared sheet resistance, an operating voltage U, and a distance h between two distribution bars can be calculated with the formula P = U2 / (Square * h2 ). The distance h between two distribution bars is, in typical passenger car windshields, approximately 0.8 m, which corresponds to approx. at the height of the panel. In order to obtain a desired specific heat capacity P of 600 W / m2 with a sheet resistance of 4 ohm / square, an operating voltage U of approximately 40 V is required. Since the motor vehicle integrated voltage is usually 14 V, a power source or voltage converter is required to generate an operating voltage of 40 V. A voltage increases from 14 V to 40 V is always associated with losses power line and additional costs for additional components.
    [0006] US 2007/0082219 A1 and US 2007/0020465 A1 disclose electrically conductive, transparent coatings with at least three layers of silver. In US 2007/0082219 A1, sheet resistances close to 1 ohm / square are reported for coatings based on the three layers of silver. An operating voltage U = 14 V, a square sheet resistance = 1 ohm / square and a distance h = 0.8 m produce a specific heat capacity P of approximately 300 W / m2.
    [0007] In order to provide an adequate specific heat capacity P, for example, of approximately 500 W / m2, in particular for heating relatively large panels, a further reduction in the sheet resistance of the electrically heated coating is essential. This can be achieved with an electrically heated coating, typically with three layers of silver by increasing the thickness of the individual silver layers. However, an excessive layer thickness of the silver layers results in inadequate optical properties of the panel, in particular with respect to transmittance and color appearance, such that legal regulations, as specified, for example, in ECE R 43 (“Uniform Provisions Concerning the Approval of Safety Glazing and Composite Glass Materials ”), cannot be fulfilled.
    [0008] Suitably low foil strength can also be achieved through the use of four layers of silver in the conductive coating, with the optical properties of the panel meeting legal requirements as a result of lower layer thicknesses of the individual silver layers. . However, applying coatings with four or more layers of silver is technically complicated and expensive.
    [0009] The purpose of the present invention is to provide a transparent panel with an improved electrically conductive coating. The electrically conductive coating must, in particular, have a lower squared sheet resistance compared to the prior art and thus have an improved specific heat capacity P as well as improved reflective properties for the infrared range. The panel must have high transmittance and high color neutrality and be economically productive.
    [0010] The object of the present invention is achieved according to the invention by a transparent panel with an electrically conductive coating according to claim 1. Preferred embodiments arise from the subclaims.
    [0011] The transparent panel according to the invention comprises at least one transparent substrate and at least one electrically conductive coating on at least one surface of the transparent substrate, wherein - the electrically conductive coating has at least two functional layers arranged one on top on the other and each functional layer comprises at least - a layer of a highly refractive optical material with a refractive index greater than or equal to 2.1. - on top of the layer of a highly refractive optical material, a smoothing layer, which contains at least one non-crystalline oxide, - on top of the smoothing layer, a first adaptation layer, - above the first adaptation layer, a layer electrically conductive, and - on top of the electrically conductive layer, a second adaptation layer, - the total layer thickness of all electrically conductive layers is 40 nm to 75 nm, and - the electrically conductive coating has a foil resistance. less than 1 ohm / square.
    [0012] If a first layer is disposed above a second layer, this means, in the context of the invention, that the first layer is disposed further away from the transparent substrate than the second layer. If 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 transparent substrate than the first layer. The upper functional layer is that functional layer that is at the greatest distance from the transparent substrate. The lowest layer is that functional layer that is at the minimum distance from the transparent substrate.
    [0013] In the context of the invention, a layer can be made of a material. However, a layer can also comprise two or more individual layers of different materials. A functional layer according to the invention comprises, for example, at least one layer of highly refractive optical material, a smoothing layer, a first and a second adaptation layer, and an electrically conductive layer.
    [0014] If a 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 in direct contact with each other. One or more other layers can be arranged between the first and second layers, as long as this is not explicitly discarded.
    [0015] According to the invention, the electrically conductive coating is applied at least on a transparent substrate surface. However, both surfaces of the transparent substrate can also be provided with an electrically conductive coating according to the invention.
    [0016] The electrically conductive coating can extend over the entire surface of the transparent substrate. Alternatively, however, the electrically conductive coating can extend over only a part of the surface of the transparent substrate. The electrically conductive coating preferably extends over at least 50%, particularly preferably at least 70%, and most particularly preferably over at least 90% of the surface of the transparent substrate.
    [0017] The electrically conductive coating can be applied directly to the surface of the transparent substrate. The electrically conductive coating can alternatively be applied to a carrier film that is adhesively bonded to the transparent substrate.
    [0018] The particular advantage of the invention results in particular from the layers of a highly refractive optical material within each functional layer. In the context of the invention, "highly refractive optical material" refers to a material whose refractive index is greater than or equal to 2.1. According to the prior art, the sequence of the layers is known in which the electrically conductive layers are arranged in each case between two dielectric layers. These dielectric layers usually include silicon nitride. It has been surprisingly demonstrated that the layers of a highly refractive optical material according to the invention result in a reduction of the sheet resistance of the electrically conductive coating simultaneously with good optical characteristics of the transparent panel, in particular higher transmittance and neutral color effect. Advantageously low values for the sheet resistance and, thus, high specific heat capacities can be obtained by means of the layers of a highly refractive optical material together with the smoothing layers according to the invention. In particular, values can be obtained for the sheet resistance for which, according to the prior art, high layer thicknesses of the electrically conductive layers were essential, thereby greatly reducing the transmittance through the panels so that the requirements for transmittance of a motor vehicle window panel according to ECE R 43 are not reached.
    [0019] The reported values for the refractive indices are measured at a wavelength of 550 nm.
    [0020] The transparent panel according to the invention with an electrically conductive coating preferably has a total transmittance greater than 70%. The term “total transmittance” is based on the process for testing the light permeability of motor vehicle windows specified by ECE-R 43, Annex 3, § 9.1.
    [0021] The electrically conductive coating has, according to the invention, a foil resistance of less than 1 ohm / square. The sheet resistance of the electrically conductive coating is preferably 0.4 ohm / square to 0.9 ohm / square, particularly preferably 0.5 ohm / square to 0.8 ohm / square, for example, approximately 0, 7 ohm / square. In this range for sheet strength, advantageously high specific heat capacities P are obtained. In addition, the electrically conductive coating has, in this range for sheet strength, reflective properties particularly good for the infrared range.
    [0022] To increase the total transmittance and / or to reduce the sheet resistance, the transparent panel with an electrically conductive coating can be subjected to a heat treatment, for example, at a temperature of 500 ° C to 700 ° C.
    [0023] It has been demonstrated that the electrically conductive coating according to the invention can be subjected to such heat treatment without the coating being damaged. The transparent panel according to the invention can also be curved, convexly or concave, without damaging the coating. These are the biggest advantages of the electrically conductive coating according to the invention.
    [0024] In a preferred embodiment of the invention, the electrically conductive coating has three functional layers. Technically complicated and expensive production of an electrically conductive coating with four or more electrically conductive layers can thus be avoided.
    [0025] The layer of a highly refractive optical material preferably has a refractive index n of 2.1 to 2.5, particularly preferably of 2.1 to 2.3.
    [0026] The layer of a highly refractive optical material preferably contains at least one mixed silicon / metal nitride, particularly preferably mixed silicon / zirconium nitride. This is particularly advantageous with respect to the foil strength of the electrically conductive coating. Mixed silicon / zirconium nitride preferably has dopants. The layer of a highly refractive optical material, for example, may contain a mixed aluminum-doped silicon / zirconium nitride (SiZrNx: Al).
    [0027] Mixed silicon / zirconium nitride is preferably deposited by sputtering supported by magnetic field with a target containing from 40% by weight to 70% by weight of silicon, from 30% by weight to 60% by weight zirconium, and from 0% by weight to 10% by weight of aluminum as well as mixtures related to production. The target particularly preferably contains 45% by weight to 60% by weight of silicon, 35% by weight to 55% by weight of zirconium, and 3% by weight to 8% by weight of aluminum as well as related mixtures. with production. The deposition of mixed silicon / zirconium nitride preferably occurs under the addition of nitrogen as the reaction gas during sputtering.
    [0028] However, the layer of a highly refractive optical material can also contain, for example, at least mixed silicon / aluminum nitride, mixed silicon / hafnium nitride, or mixed silicon / titanium nitride. Alternatively, the layer of a highly refractive optical material may contain, for example, MnO, WO3, Nb2O5, Bi2O3, TiO2, Zr3N4, and / or AlN.
    [0029] The layer thickness of each layer of a highly refractive optical material, which is disposed between two electrically conductive layers, is preferably from 35 nm to 70 nm, particularly preferably from 45 nm to 60 nm. In this range for the layer thickness, particularly advantageous foil strengths of the electrically conductive coating and particularly good optical characteristics of the transparent panel are obtained. In the context of the invention, a layer of a highly refractive optical material is arranged between two electrically conductive layers, if at least one electrically conductive layer is arranged on top of the layer of a highly refractive optical material and if at least one electrically conductive layer is arranged below the layer of a highly refractive optical material. According to the invention, the layer of a highly refractive optical material is not in direct contact with the adjacent electrically conductive layers.
    [0030] The layer thickness of the lowest layer of a highly refractive optical material is preferably from 20 nm to 40 nm. Particularly good results are thus obtained.
    [0031] In an advantageous embodiment of the invention, a cover layer is arranged on top of the top functional layer. The covering layer protects the layers under it against corrosion. The cover layer is preferably dielectric. The cover layer, for example, may contain silicon nitride and / or tin oxide.
    [0032] The cover layer preferably contains at least one highly refractive optical material with a refractive index greater than or equal to 2.1. The cover layer particularly preferably contains at least one mixed silicon / metal nitride, in particular mixed silicon / zirconium nitride, such as mixed silicon / aluminum doped zirconium nitride. This is particularly advantageous with respect to the optical properties of the transparent panel according to the invention. However, the cover layer may also contain other mixed silicon / metal nitrides, for example, mixed silicon / aluminum nitride, mixed silicon / hafnium nitride, or mixed silicon / titanium nitride. Alternatively, the cover layer can also contain, for example, MnO, WO3, Nb2O5, Bi2O3, TiO2, Zr3N4, and / or AlN.
    [0033] The layer thickness of the cover layer is preferably from 20 nm to 40 nm. Particularly good results are thus obtained.
    [0034] According to the invention, each functional layer of the electrically conductive coating includes at least one smoothing layer. The smoothing layer is arranged below the first adaptation layer, preferably between the layer of a highly refractive optical material and the first adaptation layer. The smoothing layer is preferably in direct contact with the first adaptation layer. The smoothing layer performs an optimization, in particular smoothing the surface for an electrically conductive layer subsequently applied on top. An electrically conductive layer deposited on a smoother surface has a higher degree of transmittance with a simultaneously lower foil resistance.
    [0035] According to the invention, the smoothing layer preferably contains at least one non-crystalline oxide. The oxide may be amorphous or partially amorphous (and thus partially crystalline), but it is not completely crystalline. The non-crystalline smoothing layer has low roughness and thus forms an advantageously smooth surface for the layers to be applied on the smoothing layer. The non-crystalline smoothing layer further effects an improved surface structure of the layer deposited directly on top of the smoothing layer, which is preferably the first adaptation layer. The smoothing layer, for example, can contain at least one oxide of one or more of the elements tin, silicon, titanium, zirconium, hafnium, zinc, gallium, and indium.
    [0036] The smoothing layer preferably contains a mixed non-crystalline oxide. The smoothing layer most particularly preferably contains a mixed tin / zinc oxide. Mixed oxide may have dopants. The smoothing layer, for example, may contain a mixed tin / zinc oxide doped with antimony (SnZnOx: Sb). The mixed oxide preferably has a substoichiometric oxygen content. A method for producing mixed tin / zinc oxide layers by reactive sputtering is known, for example, from DE 198 48 751 C1. The mixed tin / zinc oxide is preferably deposited with a target containing from 25% by weight to 80% by weight of zinc, from 20% by weight to 75% by weight of tin, and from 0% by weight to 10% by weight of antimony as well as mixtures related to production. The target particularly preferably contains 45 wt% to 75 wt% zinc, 25 wt% to 55 wt% tin, and 1 wt% to 5 wt% antimony as well as related mixtures with the production of other metals. The deposition of mixed tin / zinc oxides occurs with the addition of oxygen as the reaction gas during sputtering.
    [0037] The layer thickness of a smoothing layer is preferably from 3 nm to 20 nm, particularly preferably from 4 nm to 12 nm. The smoothing layer preferably has a refractive index of less than 2.2.
    [0038] The electrically conductive layer preferably contains at least one metal, for example, gold or copper, or an alloy, particularly preferably silver or an alloy containing silver. However, the electrically conductive layer may also contain other electrically conductive materials known to the person skilled in the art.
    [0039] In an advantageous embodiment of the invention, the electrically conductive layer contains at least 90% by weight of silver, preferably at least 99.9% by weight of silver. The electrically conductive layer is preferably applied using conventional metal layer deposition methods, for example, by vacuum methods such as sputtering supported by magnetic field.
    [0040] The electrically conductive layer preferably has a layer thickness of 8 nm to 25 nm, particularly preferably 10 nm to 20 nm. This is particularly advantageous with respect to the transparency and sheet strength of the electrically conductive layer.
    [0041] The total layer thickness of all electrically conductive layers is, according to the invention, from 40 nm to 75 nm. In this range for the total thickness of all electrically conductive layers, with distances h between distribution bars typical for motor vehicle windows, in particular windshields, and an operating voltage U from 12 V to 15 V, a capacity suitably high specific heat P and, at the same time, suitably high transmittance are advantageously obtained. In addition, in this range for the total thickness of all electrically conductive layers, the electrically conductive coating has particularly good reflective properties for the infrared range. Excessively low total thicknesses of the layers of all electrically conductive layers produce an excessively high squared sheet resistance and thus an excessively low specific heat capacity P as well as reduced reflective properties for the infrared range. Excessively high total thicknesses of the layers of all electrically conductive layers considerably reduce the transmittance through the panel, such that the requirements for the transmittance of motor vehicle windows according to ECE R 43 are not met. It has been shown that particularly good results are obtained with a total layer thickness of all electrically conductive layers from 50 nm to 60 nm, in particular from 51 nm to 58 nm. This is particularly advantageous with respect to the sheet resistance of the electrically conductive coating and the transmittance of the transparent panel.
    [0042] The first adaptation layer and / or the second adaptation layer preferably contains ZnOi-δ zinc oxide with 0 <δ <0.01, for example, aluminum doped zinc oxide (ZnO: Al). Zinc oxide is preferably deposited sub-stoichiometrically in relation to oxygen to prevent an excess oxygen reaction with the silver-containing layer. The zinc oxide layer is preferably deposited by sputtering supported by a magnetic field. The target preferably contains from 85% by weight to 100% by weight of zinc oxide and 0% by weight to 15% by weight of aluminum as well as mixtures related to production. The target particularly preferably contains from 90% by weight to 95% by weight of zinc oxide and from 5% by weight to 10% by weight of aluminum as well as production-related mixtures. Alternatively, the target preferably contains 95% by weight to 99% by weight of zinc and 1% by weight to 5% by weight of aluminum, with the deposition of the layers occurring under the addition of oxygen as the reaction gas. The thickness of the layers of the first adaptation layer and the second adaptation layer are preferably from 3 nm to 20 nm, particularly preferably from 4 nm to 12 nm.
    [0043] In an advantageous embodiment of the transparent panel according to the invention, at least one functional layer includes at least one blocking layer. The blocking layer is in direct contact with the electrically conductive layer and is disposed immediately above or immediately below the electrically conductive layer. Thus, no other layer is disposed between the electrically conductive layer and the blocking layer. The functional layer can also include two blocking layers, preferably with a blocking layer disposed immediately above and a blocking layer disposed immediately below the electrically conductive layer. Most preferably, each functional layer includes at least one blocking layer. The blocking layer preferably contains niobium, titanium, nickel, chromium, and / or alloys thereof, particularly nickel-chromium alloys. The layer thickness of the blocking layer is preferably from 0.1 nm to 2 nm. Thus, good results are obtained. A blocking layer immediately below the electrically conductive layer serves, in particular, to stabilize the electrically conductive layer during heat treatment and to improve the optical quality of the electrically conductive coating. A blocking layer immediately above the electrically conductive layer prevents contact of the electrically sensitive conductive layer with the oxidizing reactive atmosphere during the deposition of the next layer by reactive sputtering, for example, the second adaptation layer, which preferably contains zinc oxide.
    [0044] Blocking layers, for example, based on titanium or nickel-chromium alloys, are known to you according to the prior art. Typically, blocking layers with a thickness of approximately 0.5 nm or even a few nanometers are used. It has been surprisingly demonstrated that the configuration according to the invention of the electrically conductive coating results in a reduced susceptibility of the coating to defects, which are, for example, caused by corrosion or surface defects of the transparent substrate. Consequently, blocking layers with significantly reduced layer thickness can be used in the electrically conductive coating according to the invention. The particular advantage of particularly thin blocking layers is the increased transmittance and color neutrality of the transparent panel according to the invention with an electrically conductive coating as well as lower production costs. Particularly good results are obtained with a layer thickness of the blocking layers from 0.1 nm to 0.5 nm, preferably from 0.1 nm to 0.3 nm, in particular from 0.2 nm to 0.3 nm.
    [0045] The transparent substrate preferably contains glass, particularly preferably flat glass, float glass, quartz glass, borosilicate glass, calcium soda glass, or clear plastics, preferably rigid clear plastics, in particular polyethylene, polypropylene, polycarbonate, methacrylate of polymethyl, polystyrene, polyamide, polyester, polyvinyl chloride, and / or mixtures thereof. Examples of suitable types of glass are known from DE 697 31 268 T2, page 8, paragraph [0053].
    [0046] The thickness of the transparent substrate can vary widely and thus be ideally adapted to the requirements of the individual case. Preferably, panels with standard thicknesses from 1.0 mm to 25 mm and preferably from 1.4 mm to 2.6 mm are used. The size of the transparent substrate can vary widely and is determined by use according to the invention. The transparent substrate has, for example, in the automotive sector and in the architecture sector, usual areas of 200 cm2 up to 4 m2.
    [0047] The transparent substrate can have any three-dimensional shape. Preferably, the three-dimensional shape has no shadow zones such that, for example, it can be coated by sputtering. The transparent substrate is preferably planar or light or enormously curved in one or a plurality of spatial directions. The transparent substrate can be colorless or dyed.
    [0048] In an advantageous embodiment of the invention, the transparent substrate is connected by means of at least one thermoplastic interlayer to a second panel to form a composite panel. The electrically conductive coating according to the invention is preferably applied to the surface of the transparent substrate facing the thermoplastic interlayer. Thus, the electrically conductive coating is advantageously protected against damage and corrosion.
    [0049] The composite panel preferably has a total transmittance greater than 70%.
    [0050] The thermoplastic interlayer preferably contains thermoplastic plastics, for example, polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), polyurethane (PU), polyethylene terephthalate (PET), or multiple layers thereof, preferably with thicknesses from 0.3 mm to 0.9 mm.
    [0051] The second panel preferably contains glass, particularly preferably flat glass, float glass, quartz glass, borosilicate glass, calcium soda glass, or clear plastics, preferably rigid clear plastics, in particular polyethylene, polypropylene, polycarbonate, methacrylate of polymethyl, polystyrene, polyamide, polyester, polyvinyl chloride, and / or mixtures thereof. The second panel preferably has a thickness of 1.0 mm to 25 mm and particularly preferably 1.4 mm to 2.6 mm.
    [0052] The electrically conductive coating preferably extends over the entire surface of the transparent substrate, minus a region free of coating similar to the circumferential matrix with a width of 2 mm to 20 mm, preferably from 5 mm to 10 mm. The coating-free region is preferably hermetically sealed by the thermoplastic intercalated layer or an acrylate adhesive as a vapor diffusion barrier. The electrically conductive corrosion-sensitive coating is protected against moisture and atmospheric oxygen by the vapor diffusion barrier. If the composite panel is provided as a motor vehicle window, for example, as a windshield, and if the electrically conductive coating is used as an electrically heated coating, the circumferential coating-free region also provides electrical insulation between the coating which carries the voltage and body of the motor vehicle.
    [0053] The transparent substrate can be free of coating in at least one other region that serves, for example, as a data transmission window or a communication window. In the other region without coating, the transparent panel is permeable to electromagnetic radiation and, in particular, to infrared radiation.
    [0054] The electrically conductive coating can be applied directly to the surface of the transparent substrate. Alternatively, the electrically conductive coating can be applied to a carrier film that is embedded between two interleaved layers. The carrier film preferably contains a thermoplastic polymer, in particular polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), polyurethane (PU), polyethylene terephthalate (PET), or combinations thereof.
    [0055] The transparent substrate, for example, can also be connected to a second panel by means of spacers to form an insulating pane. The transparent substrate can also be connected to more than one other panel via the interleaved thermoplastic layers and / or spacers. If the transparent substrate is connected to one or a plurality of other panels, one or a plurality of these other panels can also have an electrically conductive coating.
    [0056] In a preferred embodiment, the electrically conductive coating according to the invention is an electrically heated coating. In this case, the electrically conductive coating is suitably electrically contacted.
    [0057] In another preferred embodiment, the electrically conductive coating according to the invention is a coating with reflective properties for the infrared range. For this, the electrically conductive coating does not need to be electrically contacted. In the context of the invention, "coating with reflective properties for the infrared range" is understood to mean, in particular, a coating that has a reflectance of at least 20% in the wavelength range from 1000 nm to 1600 nm. Preferably, the electrically conductive coating according to the invention has a reflectance greater than or equal to 50% in the wavelength range from 1000 nm to 1600 nm.
    [0058] In an advantageous embodiment of the invention, the electrically conductive coating is connected via collection conductors to a voltage source and a voltage applied to the electrically conductive coating preferably has a value of 12 V to 15 V. The conductors collection devices, called distribution bars, are used to transfer electrical energy. Examples of suitable distribution bars are known from DE 103 33 618 B3 and EP 0 025 755 B1.
    [0059] The distribution bars are advantageously produced by printing a conductive paste. If the transparent substrate is curved after the application of the electrically conductive coating, the conductive paste is preferably baked before the curvature and / or at the moment of the curvature of the transparent substrate. The conductive paste preferably contains silver particles and glass chips. The layer thickness of the cooked conductive paste is preferably from 5 μm to 20 μm.
    [0060] In an alternative embodiment, strips of thin and narrow metal sheets or metallic wires are used as distribution bars, which preferably contain copper and / or aluminum; in particular, strips of copper foil with a thickness of preferably 10 μm to 200 μm, for example, approximately 50 μm, are used. The width of the copper foil strips is preferably from 1 mm to 10 mm. The electrical contact between the electrically conductive coating and the distribution bar, for example, can be produced by welding or bonding with an electrically conductive adhesive. If the transparent substrate is part of a composite glass, the foil strips or metallic wires can be placed on the electrically conductive coating during the assembly of the composite layers. In the subsequent autoclave process, an electrical contact between the distribution bars and the coating is obtained through the action of heat and pressure.
    [0061] In the automotive sector, sheet conductors are commonly used as power lines to contact distribution bars inside composite panels. Examples of sheet conductors are described in DE 42 35 063 A1, DE 20 2004 019 286 U1, and DE 93 13 394 U1.
    [0062] Flexible sheet conductors, sometimes also called "flat conductors" or "flat strip conductors", are preferably manufactured from a tinned copper strip with a thickness of 0.03 mm to 0.1 mm and a width from 2 mm to 16 mm. Copper has been shown to be successful for such conductive tracks, since it has good electrical conductivity as well as good processability in sheets. At the same time, material costs are low. Other electrically conductive materials that can be processed into sheets can also be used. Examples for this are aluminum, gold, silver, or tin and alloys thereof.
    [0063] For electrical insulation and stabilization, the tinned copper strip is applied over a carrier material made of plastic or laminated with it on both sides. The insulating material contains, as a rule, a film based on polyamide of 0.025 mm to 0.05 mm thick. Other plastics or materials with the required insulation properties can also be used. A plurality of electrically conductive layers isolated from each other can be located on a conductive sheet strip.
    [0064] The sheet conductors that are suitable for contacting electrically conductive layers in composite panels have a total thickness of only 0.3 mm. Such thin sheet conductors can easily be embedded in the thermoplastic layer interspersed between the individual panels.
    [0065] Alternatively, thin metallic wires can also be used as power lines. Metal wires contain, in particular, copper, tungsten, gold, silver, or aluminum or alloys of at least two of these metals. The alloys may also contain molybdenum, rhenium, osmium, iridium, palladium, or platinum.
    [0066] The invention further includes a method for producing a transparent panel according to the invention with an electrically conductive coating, in which at least two functional layers are applied one after the other on a transparent substrate and applying each functional layer one after the another at least (a) a layer of a highly refractive optical material with a refractive index greater than or equal to 2.1 (b) a smoothing layer, containing at least one non-crystalline oxide, (c) a first layer of adaptation, (d) an electrically conductive layer, and (e) a second adaptation layer are applied.
    [0067] In an advantageous embodiment, a blocking layer is applied before or after the application of at least one electrically conductive layer.
    [0068] In an advantageous embodiment of the invention, a cover layer is applied after the application of the top functional layer.
    [0069] The individual layers are deposited by methods known to you, for example, by sputtering supported by magnetic field. Sputtering occurs in an atmosphere of protective gas, for example, of argon, or in an atmosphere of reactive gas, for example, through the addition of oxygen or nitrogen.
    [0070] The layer thicknesses of the individual layers with the desired properties with respect to transmittance, sheet strength, and color values emerge for the person skilled in the art in a simple way through simulations in the range of layer thicknesses indicated above.
    [0071] In an advantageous embodiment of the invention, the transparent substrate and a second panel are heated to a temperature of 500 ° C to 700 ° C and the transparent substrate and the second panel are congruently connected to a thermoplastic interlayer. The heating of the panel can occur within a process of curvature. The electrically conductive coating, in particular, must be suitable to withstand the bending process and / or the lamination process without damage. The properties, in particular, the sheet strength of the electrically conductive coating described above are regularly improved by heating.
    [0072] The electrically conductive coating can be connected to at least two distribution bars before heating the substrate.
    [0073] The invention further includes the use of the transparent panel according to the invention as a panel or as a component of a panel, in particular as a component of an insulating glazing or a composite panel, in buildings or in means of transport for travel by land, air, or water, in particular motor vehicles, for example, as a windshield, rear window, side window, and / or roof panel or as a component of a windshield, window rear, side window, and / or roof panel, in particular to heat a window and / or to reduce the heat of an internal space. The panel according to the invention is used, in particular, as a panel with reflective properties for the infrared range and / or as an electrically heated panel.
    [0074] In the following, the invention is explained in detail with reference to the exemplary drawings and embodiments. The drawings are a schematic representation and are not scaled. The drawings in no way restrict the invention.
    [0075] They represent:
    [0076] Fig. 1 is a cross section through an embodiment of the transparent panel according to the invention with an electrically conductive coating,
    [0077] Fig. 2 is a plan view of a transparent panel according to the invention as part of a composite panel,
    [0078] Fig. 3 is a cross section A-A 'through the composite panel of Fig. 2, and
    [0079] Fig. 4 is a detailed flow diagram of an embodiment of the method according to the invention.
    [0080] Fig. 1 represents a cross section through an embodiment of the transparent panel according to the invention with an electrically conductive coating with the transparent substrate 1 and the electrically conductive coating 2. The substrate 1 contains float glass and has a thickness of 2.1 mm. The electrically conductive coating 2 comprises three functional layers 3 (3.1, 3.2, and 3.3), which are arranged congruently on top of each other. Each functional layer 3 comprises - a layer of highly refractive optical material 4 (4.1, 4.2 and 4.3), - a smoothing layer 5 (5.1, 5.2, and 5.3), - a first adaptation layer 6 (6.1, 6.2, and 6.3) - an electrically conductive layer 7 (7.1, 7.2, and 7.3), - a blocking layer 11 (11.1, 11.2, and 11.3), and - a second adaptation layer 8 (8.1, 8.2, and 8.3).
    [0081] The layers are arranged in the order indicated with increasing distance from the transparent substrate 1. A cover layer 9 is arranged on top of the top functional layer 3.3. The exact layer sequence with suitable materials and exemplary layer thicknesses are shown in Table 1.
    [0082] The individual layers of the electrically conductive coating 2 were deposited by cathode ray spraying. The target for the deposition of the adaptation layers 6, 8 contained 92% by weight of zinc oxide (ZnO) and 8% by weight of aluminum. The target for the deposition of the smoothing layers 5 contained 68% by weight of tin, 30% by weight of zinc, and 2% by weight of antimony. The deposition occurred under the addition of oxygen as a reaction gas during sputtering. The target for the deposition of the layers of a highly refractive optical material 4 as well as the cover layer 9 contained 52.9% by weight of silicon, 43.8% by weight of zirconium, and 3.3% by weight of aluminum. The deposition occurred under the addition of nitrogen as a reaction gas during sputtering.
    [0083] Advantageously, by means of the embodiment according to the invention of the electrically conductive coating 2 with the layers of a highly refractive optical material 4 and the smoothing layers 5, a reduced foil strength compared to the prior art and, thus, improved reflection properties for the infrared range and an improved specific heat capacity were obtained. The optical properties of the transparent panel according to the invention with an electrically conductive coating satisfy the legal requirements for glazing in the automotive industry.
    [0084] Fig. 2 and Fig. 3 each represent a detail of a transparent panel according to the invention with an electrically conductive coating as part of a composite panel. The composite panel is provided as a windshield for a passenger car. The transparent substrate 1 is connected by means of a thermoplastic intermediate layer 17 to a second panel 12. Fig. 2 represents a plan view of the surface of the transparent substrate 1 facing away from the thermoplastic intermediate layer. The transparent substrate 1 is the panel facing the interior of the passenger car. The transparent substrate 1 and the second panel 12 contain float glass and are 2.1 mm thick each. The thermoplastic intermediate layer 17 contains polyvinyl butyral (PVB) and has a thickness of 0.76 mm.
    [0085] An electrically conductive coating 2 is applied to the surface of the transparent substrate 1 facing the thermoplastic intermediate layer 17. The electrically conductive coating 2 is an electrically heated coating and, for this, it is electrically contacted. The electrically conductive coating 2 extends over the entire surface of the transparent substrate 1 minus a region free of coating similar to the circumferential matrix with a width b of 8 mm. The coating-free region serves for electrical insulation between the coating that carries the electrically conductive voltage 2 and the vehicle body. The coating-free region is hermetically sealed by gluing the intermediate layer 17 in order to protect the electrically conductive coating 2 against damage and corrosion.
    [0086] A distribution bar 13 is arranged for the electrical contact of the electrically conductive coating 2 in each case on the upper and lower outer edge of the transparent substrate 1. The distribution bars 13 were printed on the electrically conductive coating 2 using a paste. conductive and cooked silver. The layer thickness of the cooked silver paste is 15 μm. The distribution bars 13 are electrically conductively connected to the regions of the electrically conductive coating 2 which are located under them.
    [0087] The feed lines 16 are made of tinned copper sheets with a width of 10 mm and a thickness of 0.3 mm. Each supply line 16 is, in each case, welded to one of the distribution bars 13. The electrically conductive coating 2 is connected via the distribution bars 13 and the supply lines 16 to a voltage source 14. The supply source voltage 14 is the 14 V integrated voltage of a motor vehicle.
    [0088] A layer of opaque color with a width of 20 mm is applied equal to the matrix as a masking impression 15 on the second panel 12, at the edge of the surface facing the thermoplastic intermediate layer 17. The masking impression 15 hides the filament of adhesive with which the composite panel is attached within the vehicle body. The masking print 15 serves, at the same time, as protection of the adhesive against UV radiation and as well as protection against premature aging of the adhesive. In addition, the distribution bars 13 and the supply lines 16 are hidden by the masking print 15.
    [0089] Fig. 3 represents a section along A-A 'through the composite panel of Fig. 2 in the region of the lower edge. The transparent substrate 1 with the electrically conductive coating 2, the second panel 12, the thermoplastic intermediate layer 17, a distribution bar 13, and a feed line 16 as well as the masking impression 15 are observed.
    [0090] Fig. 4 represents a flow diagram of an exemplary embodiment of the method according to the invention for producing a transparent panel with an electrically conductive coating 2.
    [0091] Examples
    [0092] A transparent panel according to the invention with an electrically conductive coating has been produced. The layer sequence and layer thicknesses for Examples 1 and 2 according to the invention are shown in Table 1. After coating the transparent substrate 1, the sheet resistance of the electrically conductive coating 2 was determined. The transparent substrate 1 provided with the electrically conductive coating 2 was then curved at a temperature of approximately 650 ° C. The curvature process lasted approximately 10 min. Then, the transparent substrate 1 was laminated with a second panel 12 similarly curved with a thickness of 2.1 mm through an intermediate thermoplastic layer 17 at a temperature of approximately 140 ° C and a pressure of approximately 12 bar. The intercalated thermoplastic layer contained polyvinyl butyral (PVB) and had a thickness of 0.76 mm. The electrically conductive coating 2 was arranged facing the intermediate thermoplastic layer 17.
    [0093] The measured values for squared sheet resistance before and after heat treatment are summarized in Table 3. Table 1

    [0094] Comparative Examples
    [0095] The Comparative Examples were performed in exactly the same way as in the Examples. The difference was in the electrically conductive coating 2. Unlike the Examples, none of the layers of a highly refractive optical material according to the invention was arranged between each two electrically conductive layers of silver, but instead dielectric layers containing silicon nitride were. Such layers containing silicon nitride are known according to the prior art for the separation of electrically conductive layers. In Comparative Example 1, the electrically conductive coating also included, unlike the Example according to the invention, only a smoothing layer containing antimony-doped tin-zinc oxide, which was disposed under the lowest silver layer. In Comparative Example 2, the electrically conductive coating included, as in the Example according to the invention, a total of three smoothing layers containing antimony-doped tin-zinc oxide, with each smoothing layer arranged in each case under a electrically conductive silver layer. The layer thicknesses of the electrically conductive layers, which contained silver, were selected in the Comparative Examples exactly as in Example 1 according to the invention. The exact sequence of layers with layer thicknesses and materials of the Comparative Examples are shown in Table 2.
    [0096] The measured values for squared sheet strength before and after heat treatment are summarized in Table 3. Table 2

    Table 3

    [0097] Due to the same thickness of the electrically conductive layers, the comparison between Example 1 according to the invention and the Comparative Examples illustrates the effect of the configuration according to the invention of the electrically conductive coating 2 with the layers of a highly optical material refractive 4 on the sheet resistance. The electrically conductive coating 2 in Example 1 according to the invention surprisingly had, before heat treatment, a squared sheet resistance reduced by 16% compared to Comparative Example 1. The heat treatment resulted in a further reduction in sheet resistance Squared. After heat treatment and lamination, the squared sheet resistance of the electrically conductive coating 2 in the Example according to the invention was decreased by 19% compared to Comparative Example 1.
    [0098] The decrease in squared sheet resistance of the electrically conductive coating 2 in Example 1 according to the invention compared to Comparative Example 1 cannot be attributed exclusively to the presence of the additional smoothing layers 5.2 and 5.3, as is clear from from Comparative Example 2. The additional straightening layers in Comparative Example 2, in fact, result in a reduction in the square strength of the Compared Sheet compared to Comparative Example 1 by 13% before heat treatment and by 15% after heat treatment. The especially low sheet strength of Example 1 with the layers according to the invention of a highly refractive optical material 4.2 and 4.3, however, is not obtained in Comparative Example 2. In Example 1 according to the invention, the sheet resistance Squared is reduced compared to Comparative Example 2 by 5% before heat treatment and by 6% after heat treatment.
    [0099] Example 2 according to the invention had the same layer sequence as Example 1. However, layer thicknesses were selected differently than in Example 1. In particular, the electrically conductive coating 2 in Example 2 had thicker electrically conductive layers 7. In this way, it was possible to further reduce the sheet resistance of the electrically conductive coating 2.
    [00100] Table 4 summarizes the optical properties of the composite glass manufactured from the transparent panel according to the invention with an electrically conductive coating of Example 2, the second panel 12, and the thermoplastic intermediate layer 17. TL (A) refers to the total transmittance of light type A, Ra * (D65 / 8 °), and Rb * (D65 / 8 °) the chromaticity coordinate in the color space L * a * b * with light reflection type D65 and an angle of incidence of 8 °, Ta * (D65 / 8 °) and Tb * (D65 / 8 °) the chromaticity coordinates in the color space L * a * b * with light transmittance of type D65 and an incidence angle of 8 °. The total transmittance through the transparent panel according to the invention was greater than 70% after the heat treatment. The color values in the L * a * b * color space were favorable. The transparent panel according to the invention meets the legal requirements regarding transmittance and neutral coloring and can be used as motor vehicle glazing. Table 4


    [00101] In other experiments, it was demonstrated that for the electrically conductive coating 2 according to the invention, the sheet resistances at a minimum of approximately 0.4 ohm / square can be obtained with a transmittance through the transparent panel greater than 70%.
    [00102] The squared sheet resistance of the electrically conductive coating 2 is significantly reduced by means of the layers according to the invention of a highly refractive optical material 4 and the smoothing layer 5 according to the invention. The transparent panel according to the invention has high transmittance and high color neutrality. The lower squared sheet resistance results in an improvement of the specific heat capacity P when the electrically conductive coating 2 is used as an electrically heated coating with, at the same time, good optical properties of the transparent panel. This result was unexpected and surprising for the person skilled in the art.
    [00103] List of Reference Characters: (1) transparent substrate (2) electrically conductive coating (3) functional layer (3.1), (3.2), (3.3) first, second, third functional layers (4) layer of a material highly refractive optical (4. (1) (4.2), (4.3) first, second, third layers of a highly refractive optical material (5) smoothing layer (5. (1) (5.2), (5.3) first, second , third smoothing layers (6) first adaptation layer (6. (1) 6.2), (6.3) first, second, third of the first adaptation layer (7) electrically conductive layer (7. (1) (7.2), (7.3) first, second, third electrically conductive layers (8) second adaptation layer (8.1), (8.2), (8.3) first, second, third of the second layer of (11) blocking layer (11. (1) ( 11.2), (11.3) first, second, third blocking layers (12) second panel (13) distribution bar (14) voltage source (15) masking print (16) power line (17 ) thermoplastic intermediate layer the width of the region masked by (15) b width of the region without coating A-A 'section line
    权利要求:
    Claims (15)
    [0001]
    1. Transparent panel comprising at least one transparent substrate (1) and at least one electrically conductive coating (2) on at least one surface of the transparent substrate (1), wherein - the electrically conductive coating (2) has at least two layers functional (3) arranged on top of each other and each functional layer (3), characterized by the fact that it comprises at least one layer of a highly refractive optical material (4) with a refractive index greater than or equal to 2, 1, the one above the layer of a highly refractive optical material (4), a smoothing layer (5), which contains at least one non-crystalline oxide, the one above the smoothing layer (5), a first adaptation layer (6), the one above the first adaptation layer (6), an electrically conductive layer (7), and the one above the electrically conductive layer (7), a second adaptation layer (8), - the total thickness of the layer of all electrically conductive layers (7) is 40 nm at 75 nm, and - the electrically conductive coating (2) has a sheet resistance of less than 1 ohm / square, and where the layer of a highly refractive optical material (4) contains at least one mixed silicon / metal nitride .
    [0002]
    2. Transparent panel according to claim 1, characterized by the fact that the electrically conductive coating (2) is an electrically heated coating.
    [0003]
    3. Transparent panel according to claim 1, characterized by the fact that the electrically conductive coating (2) is a coating with reflective properties for the infrared range.
    [0004]
    Transparent panel according to any one of claims 1 to 3, characterized in that the electrically conductive coating (2) has three functional layers (3) arranged on top of each other.
    [0005]
    Transparent panel according to any one of claims 1 to 4, characterized in that the electrically conductive coating (2) has a sheet resistance of 0.4 ohm / square to 0.9 ohm / square.
    [0006]
    6. Transparent panel according to any one of claims 1 to 5, characterized in that the total layer thickness of all electrically conductive layers (7) is from 50 nm to 60 nm.
    [0007]
    7. Transparent panel according to any one of claims 1 to 6, characterized in that the layer of a highly refractive optical material (4) contains at least one mixed silicon / zirconium nitride, such as mixed silicon nitride / zirconium doped with aluminum.
    [0008]
    8. Transparent panel according to any one of claims 1 to 7, characterized by the fact that each layer of highly refractive optical material (4) disposed between two electrically conductive layers (7) has a thickness of 35 nm to 70 nm , preferably from 45 nm to 60 nm.
    [0009]
    Transparent panel according to any one of claims 1 to 8, characterized in that the smoothing layer (5) contains at least one mixed non-crystalline oxide, preferably a mixed tin / zinc oxide, such as mixed oxide tin / zinc doped with antimony and preferably has a thickness of 3 nm to 20 nm, particularly preferably 4 nm to 12 nm.
    [0010]
    Transparent panel according to any one of claims 1 to 9, characterized in that the electrically conductive layer (7) contains at least silver or an alloy containing silver and preferably has a layer thickness of 8 nm to 25 nm, particularly preferably from 10 nm to 20 nm.
    [0011]
    11. Transparent panel according to any one of claims 1 to 10, characterized in that the first adaptation layer (6) and / or the second adaptation layer (8) contains ZnO1-δ zinc oxide with 0 < δ <0.01, such as zinc oxide doped with aluminum and preferably has a thickness of 3 nm to 20 nm, particularly preferably 4 nm to 12 nm.
    [0012]
    Transparent panel according to any one of claims 1 to 11, characterized in that at least one functional layer (3), preferably each functional layer (3) includes at least one blocking layer (11), which is arranged immediately above and / or immediately below the electrically conductive layer (7) and which preferably contains at least niobium, titanium, nickel, chromium, or alloys thereof, particularly preferably nickel-chromium alloys, and wherein the blocking layer ( 11) has a thickness of 0.1 nm to 2 nm, preferably from 0.1 nm to 0.3 nm.
    [0013]
    13. Transparent panel according to any one of claims 1 to 12, characterized in that a covering layer (9) is arranged above the upper functional layer (3) and in which the covering layer (9) preferably contains at least a highly refractive optical material with a refractive index greater than or equal to 2.1, particularly preferably a mixed silicon / metal nitride, in particular mixed silicon / zirconium nitride, such as mixed silicon / zirconium nitride doped with aluminum.
    [0014]
    Transparent panel according to any one of claims 1 to 13, characterized in that the transparent substrate (1) is connected to a second panel (12) by means of at least one intermediate thermoplastic layer (17) to form a composite panel and wherein the total transmittance of the composite panel is preferably greater than 70%.
    [0015]
    15. Method for producing a transparent panel with an electrically conductive coating (2) as defined in any one of claims 1 to 14, the method characterized by the fact that at least two functional layers (3) are applied one after the other on a transparent substrate (1) and to apply each functional layer (3) one after the other at least (a) a layer of a highly refractive optical material (4) with a refractive index greater than or equal to 2.1, (b ) a smoothing layer (5), containing at least one non-crystalline oxide, (c) a first adaptation layer (6), (d) an electrically conductive layer (7), and (e) a second adaptation layer (8) are applied.
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    同族专利:
    公开号 | 公开日
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    JP2015509866A|2015-04-02|
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    法律状态:
    2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-29| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-12-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-19| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12150547|2012-01-10|
    EP12150547.3|2012-01-10|
    PCT/EP2012/069566|WO2013104438A1|2012-01-10|2012-10-04|Transparent panel with electrically conductive coating|
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