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    ARTICLES INCLUDING ANTI-CONDENSATION COATINGS AND / OR LOW ELECTROSPOSITION AND / OR METHODS OF MANUFACTURING THE SAME. Certain exemplary embodiments of the present invention relate to articles including anti-condensation and / or low electrodeposition coatings that are exposed to an external environment and / or methods of manufacturing them. In certain exemplary embodiments, anti-condensation and / or low electrodeposition coatings can be resistant in an external environment. The coating may also have sufficiently low sheet resistance and hemispheric emissivity so that the glass surface is more likely to retain heat from the inside area, thereby reducing (and sometimes completely eliminating) the presence of condensation on it. The articles of certain exemplary modalities can be, for example, skylights, vehicle windows or windshields, IG units, VIG units, refrigerator / freezer doors and / or similar.
    公开号:BR112013014077B1
    申请号:R112013014077-1
    申请日:2011-11-29
    公开日:2020-11-10
    发明作者:Jean-Marc Lemmer；Nestor P. Murphy；David D. Mclean；Richard Blacker
    申请人:Guardian Glass, LLC；
    IPC主号:
    专利说明:

    [001] This application is a Continuation-in-Part (CIP) (Continuation-in-Part) of Patent Applications Nos. of U.S. Series 12 / 923,082 filed on August 31, 2010 and 12 / 662,894, the latter is a CIP of 12 / 659,196 filed on February 26, 2010, the content of which is incorporated herein by reference. CAMPODAINVENTION
    [002] Certain exemplary embodiments of the present invention refer to articles including anti-condensation and / or low-E coating and / or methods of manufacturing them. More particularly, certain exemplary embodiments of the present invention refer to articles including anti-condensation and / or low electrodeposition coating that are exposed to an external environment and / or methods of manufacturing them. In certain exemplary embodiments, anti-condensation and / or low electrodeposition coatings can resist in an external environment and may also have a low hemispheric emissivity so that the glass surface is more likely to retain heat from the internal area, thereby reducing (and sometimes completely eliminating) the presence of condensation on it. Items of certain exemplary embodiments can be, for example, skylights, vehicle windows or windshields, IG units, VIG units, refrigerator / freezer doors / or similar. BACKGROUND AND SUMMARY OF EXEMPLARY MODALITIES OF THE INVENTION
    [003] It is known that moisture condenses on skylights, refrigerator / freezer doors, vehicle windows and / or other glass products. Condensation formation in skylights decreases the aesthetic appeal of the blade. Similarly, condensation on refrigerator / freezer doors in supermarkets or the like sometimes makes it difficult for customers to quickly and easily locate the products they are looking for. And condensation formation in automobiles is often a problem in the morning, as drivers often have to scrape snow or ice and / or turn on the car's defroster and / or windshield wiper to drive more safely. Moisture and fog on the windshield sometimes present a similar problem, although they can also present potentially more significant safety risks as the driver crosses mountainous areas, since a sudden drop in temperature, etc.
    [004] Several anti-condensation products have been developed over the years to address these and / or other issues in a variety of applications. See, for example, U.S. Patent Nos. 6,818,309; 6,606,833; 6,144,017; 6,052,965; 4,910,088, the contents of each are incorporated by reference. As mentioned above, certain approaches use active heating elements to reduce the formation of condensation, for example, as in vehicle defrosters, actively heated refrigerator / freezer doors, etc. These active solutions unfortunately take time to function in the vehicle context and then address the problem once it has occurred. In the case of refrigerator / freezer doors, such active solutions can be expensive and / or energy inefficient.
    [005] Some attempts have been made to incorporate a thin film anti-condensation coating on a window. These attempts generally involved pyrolytically depositing a 4000-6000 angstrom-thick fluorine-doped tin oxide (FTO) coating on the outer surface (for example, surface 1) of a window such as, for example , a skylight. Although pyrolytic deposition techniques are known to have "hard coatings", the FTO unfortunately scratches very easily, changes color over time and suffers from other disadvantages.
    [006] In this way, it will be understood that there is a need in the art of articles including improved anti-condensation coatings and / or low-film thin electrodeposition and / or methods of manufacturing them.
    [007] One aspect of certain exemplary modalities refers to anti-condensation and / or low electrodeposition coatings that are suitable for exposure to an external environment and / or methods of manufacturing them. The external environment in certain exemplary cases may be the exterior and / or the interior of a vehicle or home (as opposed to, for example, a more protected area between adjacent substrates).
    [008] Another aspect of certain exemplary modalities refers to anti-condensation and / or low electrodeposition coatings that have a low foil resistance and a hemispherical emissivity so that the glass surface is more likely to retain heat from the inside area, thereby reducing (and sometimes completely eliminating) the presence of condensation on it.
    [009] Yet another aspect of certain exemplary modalities refers to coated articles having an anti-condensation and / or low electrodeposition coating formed on an external surface and one or more low electrodeposition coatings formed on one or more respective internal surfaces of the article. In certain exemplary embodiments, the anti-condensation coating can be thermally tempered (for example, at a temperature of at least 580 degrees C for at least about 2 minutes, more preferably at least about 5 minutes) or annular (for example, at a temperature lower than that required for tempering).
    [0010] The articles of certain exemplary modalities can be, for example, skylights, vehicle windows or windshields, IG units, VIG units, refrigerator / freezer doors and / or similar.
    [0011] Certain exemplary embodiments of the present invention refer to a skylight comprising: first and second spaced glass substrates, substantially parallel; a plurality of spacers arranged to help maintain the first and second substrates in a spaced relationship, substantially parallel to each other; and an edge seal sealing the first and second substrates; and an anti-condensation coating provided on an external surface of the first substrate exposed to an environment external to the skylight, the anti-condensation coating comprising the layers that continue to distance themselves from the first substrate: a layer comprising a silicon nitride and / or silicon oxinitride , a layer comprising a transparent conductive oxide (TCO), a layer comprising silicon nitride and a layer comprising at least one zirconium oxide, zirconium nitride, aluminum oxide and aluminum nitride, where the anti-condensation coating has a hemispheric emissivity of less than 0.23 and a sheet resistance of less than 30 ohms / square. The TCO can be of or including ITO or similar in certain embodiments of the present invention.
    [0012] Certain exemplary embodiments of the present invention refer to a skylight. First and second spaced glass substrates, substantially parallel, are provided. A plurality of spacers are arranged to help maintain the first and second substrates in substantially parallel, substantially parallel, with each other. An edge seal helps seal the first and second substrates. An anti-condensation coating is provided on an external surface of the first substrate exposed to an environment external to the skylight. The anti-condensation coating comprises the thin film layers that continue to be deposited in the order that keeps moving away from the first substrate: a barrier layer including silicon, a first contact layer including silicon, a layer comprising a transparent conductive oxide (TCO), a second layer contact layer including silicon and a zirconium oxide layer. The anti-condensation coating has a hemispherical emissivity of less than 0.23 and a sheet resistance of less than 30 ohms / square.
    [0013] Certain exemplary embodiments of the present invention refer to a coated article comprising: a coating supported by a substrate, where the coating is an anti-condensation coating comprising the layers that continue to distance themselves from the first substrate: a layer comprising silicon nitride and / or silicon oxynitride, a layer comprising a transparent conductive oxide (TCO), a layer comprising silicon nitride and a layer comprising one or more zirconium oxide, zirconium nitride, aluminum oxide and aluminum nitride, where the anti-condensation coating is arranged on an external surface of the substrate so that the anti-condensation coating is exposed to an external environment, and the anti-condensation coating has a hemispheric emissivity of less than 0.23 and a sheet resistance of less than 30 ohms / square.
    [0014] Certain exemplary embodiments of the present invention refer to a coated article comprising a coating supported by a substrate. The coating is an anti-condensation coating comprising the thin film layers that are deposited in the order that continues to distance themselves from the first substrate: a first barrier layer including silicon, a first contact layer including silicon, a layer comprising a transparent conductive oxide (TCO ), a second contact layer including silicon and a zirconium oxide layer. The anti-condensation coating is disposed on an external surface of the substrate so that the anti-condensation coating is exposed to an external environment. The anti-condensation coating has a hemispherical emissivity of less than 0.23 and a sheet resistance of less than 30 ohms / square.
    [0015] According to certain exemplary modalities, the external environment is the interior of a house or vehicle. According to certain exemplary modalities, the external environment is the environment outside the house or vehicle. According to certain exemplary embodiments, a low electrodeposition coating is provided on the substrate opposite the anti-condensation coating.
    [0016] In certain exemplary embodiments, the coated article can be formed into a skylight, window, insulating glass (IG) window (Insulating Glass), vacuum insulation glass (VIG) window, Vacuum Insulating Glass, door refrigerator / freezer and / or vehicle window or windshield. The anti-condensation coating can be provided on surface one and / or on surface four of an IG or VIG unit, for example.
    [0017] In certain exemplary embodiments, a method of manufacturing an Insulating Glass Unit (IGU) is provided. A first glass substrate is provided. A plurality of layers is disposed, directly or indirectly, on a first main surface of the first glass substrate, the plurality of layers including, in order to distance themselves from the first glass substrate: a first layer comprising silicon oxynitride having an index of refraction of 1.5-2.1, one layer comprising ITO having a retraction index of 1.7-2.1 and a second layer comprising silicon oxinitride having a retraction index of 1.5-2.1.0 first glass substrate is heat treated with the plurality of layers arranged on it. A second glass substrate is provided in a substantially parallel, spaced relation with respect to the first glass substrate so that the main surface of the first glass substrate faces away from the second glass substrate. The first and second glass substrates are sealed together.
    [0018] According to certain exemplary embodiments, the first and second layers comprising silicon oxinitride have retraction rates of 1.7-1.8 and / or the layer comprising ITO has a retraction rate of 1.8-1, 93.
    [0019] According to certain exemplary modalities, said hot treatment involves laser annealing, exposure to NIR-SWIR radiation and / or heating in an oven.
    [0020] In certain exemplary embodiments, a method of manufacturing an insulating glass unit (IGU) is provided. A first glass substrate is provided. A plurality of layers is arranged, directly or indirectly, on a main surface of the first glass substrate, with the plurality of layers including, in order to distance themselves from the first glass substrate: a first layer comprising silicon oxinitride, a layer comprising ITO and a second layer comprising silicon oxinitride. The first glass substrate is heat treated with the plurality of layers arranged on it. A second glass substrate is provided in a spaced, substantially parallel relationship to the first glass substrate so that the first largest surface of the first glass substrate faces away from the second glass substrate. The first substrate with the plurality of layers on the first major surface of the first glass substrate has a hemispheric emissivity less than or equal to about 0.20 and a sheet resistance less than or equal to 20 ohms / square following said hot treatment.
    [0021] In certain exemplary embodiments, an insulating glass unit (IGU) is provided. IGU includes a first glass substrate. A plurality of layers is disposed by the method of "sputtering", directly or indirectly, on a main surface of the glass substrate, the plurality of layers including, in order to distance themselves from the first glass substrate: a first layer comprising oxynitride silicon having a refractive index of 1.5-2.1, a layer comprising ITO having a refractive index of 1.7-2.1 and a second layer comprising silicon oxinitride having a refractive index of 1.5 -2.1. A second glass substrate is provided in a substantially parallel, spaced relationship with the first glass substrate, with the first main surface of the first glass substrate facing away from the second glass substrate when assembled. An edge seal joins the first and second glass substrates. The first glass substrate is heat treated with the plurality of layers arranged on it. The first substrate with the plurality of layers on the first main surface of the first glass substrate has a hemispherical emissivity less than or equal to about 0.20 and a sheet resistance less than or equal to 20 ohms / square following said hot treatment.
    [0022] The characteristics, aspects, advantages and exemplary modalities described here can be combined to obtain additional modalities. BRIEF DESCRIPTION OF THE DRAWINGS
    [0023] These and other characteristics and advantages can be understood better and more completely by reference to the detailed description that follows of exemplary illustrative modalities together with the drawings, of which:
    [0024] Figure 1 is a coated article including an anti-condensation coating according to an exemplary embodiment;
    [0025] Figure 2 is an insulating glass unit including an anti-condensation coating (for example, of any embodiment of the present invention such as the embodiment of Figure 1 and / or Figure 6) disposed on an external surface exposed to the outside atmosphere of according to an exemplary modality.
    [0026] Figure 3 is an insulating glass unit including an anti-condensation coating (for example, of any embodiment of the present invention such as the embodiment of Figure 1 and / or Figure 6) disposed on an internal surface exposed to the internal environment of according to an exemplary modality.
    [0027] Figure 4 is an insulating glass unit including anti-condensation coating (for example, of any embodiment of the present invention such as the embodiment of Figure 1 and / or Figure 6) disposed on the outer and inner surfaces of the glass unit insulation according to an exemplary modality.
    [0028] Figure 5 is a graph illustrating the performance of an exemplary modality, a current condensation product and an unprotected glass substrate as the temperature, humidity and dew point change over a period of 18 hours;
    [0029] Figure 6 is a coated article including an anti-condensation coating according to an exemplary embodiment of the present invention.
    [0030] Figure 7 is a coated article including an anti-condensation coating according to an exemplary embodiment; and
    [0031] Figure 8 is a schematic view of a system incorporating an IV heater according to certain exemplary modalities. DETAILED DESCRIPTION OF EXEMPLARY MODALITIES OF THE INVENTION
    [0032] With reference now more particularly to accompanying drawings where equal reference numbers indicate equal parts in the various views.
    [0033] Certain exemplary embodiments of the present invention refer to thin film anti-condensation coatings that are exposed to the environment. Such coatings have a low hemispheric emissivity in certain exemplary embodiments, which helps the glass surface to retain heat provided from the inside. For example, in exemplary skylight applications and / or another building window, the glass surface retains more heat from inside the building. In exemplary vehicle applications, the windshield retains more heat from inside the vehicle. This helps to reduce (and sometimes even prevent) the initial formation of condensation. As mentioned above, such anti-condensation coatings can be provided on a surface (or multiple surfaces) exposed to the environment in certain exemplary cases. In this way, the anti-condensation coatings of certain exemplary modalities can be robust in order to be able to withstand such conditions.
    [0034] Figure 1 is a coated article including an anti-condensation coating according to an exemplary embodiment. The exemplary embodiment of Figure 1 includes a glass substrate 1 supporting a multilayer thin film anti-condensation coating 3. Anti-condensation coating 3 has a low hemispheric emissivity. In certain exemplary embodiments, the spherical emissivity is less than 0.25, more preferably less than 0.23, more preferably still less than 0.2 and sometimes even less than 1.0-1, 5. This is achieved by providing a layer of transparent conductive oxide (TCO) 5 so that a suitably low sheet strength is achieved. In the example in Figure 1, TCO is indium tin oxide (ITO) (Indium Tin Oxide). A sheet resistance of 10-30 ohms / square will generally be sufficient to obtain the desired hemispheric emissivity values. Certain exemplary embodiments described here provide a sheet resistance of 13-27 ohms / square, with the example provided below providing a sheet resistance of 17 ohms / square. In certain exemplary cases, it is possible to select a TCO 5 so that the resistance drops to as low as about 5 ohms / square, although this low value is not necessary in all embodiments of the present invention. Figure 6 illustrates a coated article including similar layers, except that in Figure 6 layers 11 and 13 of the modality are not present. In the embodiment of Figure 6, layer 9b that includes silicon oxinitride can both be a barrier layer including silicon and a lower contact layer, and be made up of a combination of layers 9b and 11 of the embodiment of Figure 1. In the embodiments of In Figure 1 and Figure 6, the coating layer 7 can be of or include zirconium oxide, aluminum oxide, aluminum nitride and / or aluminum oxinitride in exemplary embodiments of the present invention. Layers 9a, 9b and 11 of or including silicon nitride and / or silicon oxinitride can be doped with aluminum (for example, from about 0.5 to 5% Al) in certain exemplary embodiments, as is known in technique, so that the target can be conductive during sputtering of the layer.
    [0035] With reference to Figures 1 and 6, TCO 5 is protected from the environment by a layer of zirconium oxide 7. A barrier layer including silicon 11 can be provided between TCO 5 and substrate 1 also to help protect TCO 5, for example, sodium migration. In the example in Figure 1, the barrier layer including silicon 11 is silicon nitride and the barrier layer of silicon nitride 11 is provided adjacent to a layer of titanium oxide 13. The barrier layer of silicon nitride 11 and the titanium oxide layer 13 help with the optics of the general article. It will be understood that a low / high / low layer stacking system can also be used to improve the optics of the final product in certain exemplary cases. In certain exemplary embodiments, the silicon nitride barrier layer 11 can be oxidized, for example, so that it is a layer of silicon oxynitride. In other words, layer 11 may be of or include silicon oxynitride, for example, in certain exemplary embodiments. In certain exemplary embodiments, a barrier layer comprising silicon nitride (e.g., SiNN4 or other suitable stoichiometry) can replace the barrier layer including silicon 11 and the titanium oxide layer 13 in the example in Figure 1.
    [0036] Layers 9a and 9b including additional silicon can be intercalated with TCO 5. As shown in the example in Figure 1, layer 9a including upper silicon is a layer of silicon nitride, where layer 9b including lower silicon is a layer of silicon oxynitride. It will be understood that any suitable combination of silicon with oxygen and / or nitrogen can be used in modalities other than the present invention.
    [0037] The following table provides exemplary physical thicknesses and thickness ranges for the modality of Figure 1:

    [0038] The thicknesses for layers 9b, 5, 9a and 7 for the modality of Figure 6 are similar and the table above is also applicable to these layers. However, in the embodiment of Figure 6, layer 9b based on silicon nitride and / or silicon oxinitride can be thicker, for example, from about 10-200 nm thick, more preferably from about 10-100 nm thick. As noted above, other TCOs can be used in place of, or in addition to, ITO. For example, certain exemplary modalities may incorporate an ITO / Ag / ITO merger. Certain exemplary modalities may incorporate zinc oxide, aluminum doped zinc oxide (AZO), p-type aluminum oxide, doped or non-doped Ag, FTO and / or similar. When Ag is incorporated into the layer stacking system as a TCO, the layers comprising Ni and / or Cr can be provided directly adjacent (by contacting) the Ag. In certain exemplary embodiments, each layer in the layer stacking system can be deposited by sputtering. In certain exemplary embodiments, one or more layers can be deposited using a different technique. For example, when FTO is incorporated as TCO 5, it can be pyro- litically deposited (for example, using combustion vapor deposition or CVD (Combustion Vapor Deposition).
    [0039] In certain exemplary embodiments, the diamond-like carbon layer (DLC) can be provided directly on and contacting zirconium oxide. This can help to create a more resistant hydrophilic type coating, in certain exemplary cases. Hydrophilic coatings usually involve a contact angle less than or equal to 10 degrees. Zirconium oxide deposited by sputtering tends to have a contact angle less than about 20 degrees. However, formation of DLC on top of DLC on top of zirconium oxide helps with its wetting capacity and creates a harder layer. When tempered, for example, a stack of zirconium oxide / DLC layers reaches a contact angle less than or equal to about 15 degrees. In this way, a hydrophilic, resistant coating can be obtained. It is noted that this layer can be created by providing a layer of zirconium nitride followed by a layer of DLC which, when tempering, will produce a layer of zirconium oxide followed by a layer of DLC. See, for example, Patent Application Serial No. 12 / 320,664, which describes a heat-treated coated article including DLC and / or zirconium in its coating. The contents of this application as a whole are hereby incorporated by reference.
    [0040] In addition or alternatively, in certain exemplary embodiments, a thin hydrophilic and / or photocatalytic coating can be provided over zirconium oxide. Such a layer may comprise TiO2 anatase, BiO, BiZr, SnO and / or any other suitable material. Such a layer can also assist with wetting capacity and / or provide self-cleaning properties to the article.
    [0041] In certain exemplary embodiments, the protective zirconium oxide layer 7 can be replaced with aluminum oxide and / or aluminum oxinitride. Furthermore, in certain exemplary embodiments, layer 7 may initially be deposited in a multilayer form to include a first layer of or including zirconium nitride directly on the silicon nitride inclusion layer 9a, and a second layer of or including carbon diamond type (DLC). Then, heat treatment (e.g., thermal tempering including at temperature (s) of at least about 580 degrees C) is desired, the coated article is heat treated and the layer including coating DLC burns during hot treatment and the layer including zirconium nitride turns into zirconium oxide in this way resulting in a heat treated coated article having a heat treated layer stack where layer 7 is made up of or includes zirconium oxide (see, for example, Figures 1 and 6).
    [0042] Although not shown in the examples in Figure 1 or Figure 6, a low silver electrodeposition coating can be provided on the glass substrate opposite the anti-condensation coating 3. For example, the low silver electrodeposition coating can be any low electrodeposition coatings described in Order Nos. Serial 12 / 385,234; 12 / 385,802; 12 / 461,792; 12 / 591,611; and 12 / 654,594, the contents of which are incorporated by reference. Of course, other low electroplating coatings commercially available from the applicant of the present invention and / or other low electroplating coatings can also be used in connection with different embodiments of the present invention. When the coated article is tempered, it can be carried through a "face down" tempering furnace. In other words, when the coated article is tempered, the anti-condensation coating can face the rollers.
    [0043] In certain exemplary embodiments, visible transmission may be high when the anti-condensation coating is applied. For example, in certain exemplary embodiments, the visible transmission will preferably be at least about 50%, more preferably at least about 60%, most preferably at least about 65%. In certain exemplary modalities, the visible transmission can be 70%, 80% or even greater.
    [0044] The coated article shown in Figure 1 or Figure 6 can be incorporated into an insulating glass (IG) unit. For example, Figure 2 is an insulating glass unit including an anti-condensation coating arranged on the external surface exposed to the outside atmosphere according to an exemplary embodiment. The IG unit in the example of Figure 2 includes a first substrate and a second glass substrate 1 and 21 spaced substantially parallel. These substrates define a space or gap 22 between them. The first and second substrates 1 and 21 are sealed using an edge seal 23 and a plurality of pillars 25 helps to maintain the distance between the first and second substrates 1 and 21. The first substrate 1 supports the anti-condensation coating 3. As will be understood from the exemplary modality of Figure 2, the anti-condensation coating 3 is exposed to the external environment. This is a departure from common practices, where coatings with low E are generally protected from the external environment. The arrangement in Figure 2 is made possible by the durability of the anti-condensation coating 3.
    [0045] Although not shown in Figure 2, similar to that described above, low E coating (for example, a low E coating based on silver) can be provided on an internal surface of one of the first and second substrates 1 and 21 In other words, although not shown in Figure 2, a low E coating can be produced on surface 2 or surface 3 of the IG unit shown in Figure 2.
    [0046] When the exemplary embodiment of Figure 2 is provided in relation to a skylight application, for example, the external substrate 1 can be tempered and the internal substrate 21 can be laminated, for example, for safety purposes. This can be true of other IG unit products, too, depending on the desired application. In addition, it will be understood that the structure of the IG unit shown in the example of Figure 2 can be used in connection with generally vertical and generally horizontal applications. In other words, the structure of the IG unit shown in the example in Figure 2 can be used on a refrigerator / freezer door that is either generally vertical or generally horizontal.
    [0047] In certain exemplary embodiments, the space or gap 22 between the first and second substrates 1 and 21 can be evacuated and / or filled with an inert gas (such as argon, for example) and the edge seal 23 can provide a hermetic sealing, for example, in the formation of a vacuum insulated glass unit (VIG).
    [0048] Figure 2 shows an IG unit having two glass substrates. However, the exemplary anti-condensation coatings described here can be used in connection with products containing first, second and third substantially parallel glass substrates (also sometimes referred to as "triple glass" products). The anti-condensation coating can be arranged on surface 1 (the outer surface exposed to the environment) and the low electrodeposition coatings can be arranged on one or more internal surfaces (surfaces other than surface 1 and surface 6). For example, the anti-condensation coating can be disposed on surface 1 and low electrodeposition coating can be disposed on surfaces 2 and 5, 3 and 5, etc., in different embodiments of the present invention. Such triple-glass products can be IG units containing three slides or substrates, VIG trip units containing three slides or substrates, etc., in different embodiments of the invention.
    [0049] As indicated above, certain exemplary modalities can be used in relation to vehicle windshields, windows, mirrors and / or similar. The hemispheric emissivity of a vehicle's exterior glass surfaces is typically greater than about 0.84. However, by reducing hemispheric emissivity to the bands identified above (and / or others), the glass surface can retain more heat provided by the vehicle's interior. This, in turn, can result in reduced or eliminated condensation formation on the blade surface when a moving vehicle goes from colder to warmer weather (for example, in mountainous areas), condensation and / or reduced ice formation or disposed of on the slide when parked and left overnight, etc. The anti-condensation coating in vehicle applications can be provided on the side of the glass that is external to the vehicle cabin.
    [0050] The zirconium oxide coating is advantageous for vehicle window applications, since it has a comparatively low coefficient of friction. More particularly, this lower coefficient of friction facilitates up and down movement of windows.
    [0051] Certain exemplary modalities can be used in connection with any suitable vehicle including, for example, automobiles; trucks; trains; boats; ships and other vessels; airplanes; tractors and other work equipment, etc. In vehicle rearview applications, the coating optics can be adjusted in such a way that "double glare" does not occur.
    [0052] The inventors of the present application have also found that the anti-condensation coating of certain exemplary embodiments can be used to help satisfy the so-called "0.30 / 0.30 standard". In short, the 0.30 / 0.30 standard refers to a U value less than or equal to 0.30 and a solar heat gain coefficient (SHGC) (Solar Heat Gain Coefficient) less than or equal to 0.30. Legislation in force in the United States would give a tax credit for investigating windows, skylights, doors, etc., that meet these criteria.
    [0053] Figure 3 is an insulating glass unit including an anti-condensation coating (for example, see the coating of Figure 1 and / or Figure 6) disposed on an internal surface exposed to the internal environment according to an exemplary embodiment. The example modality of Figure 3 is similar to the example modality of Figure 2, except that the exemplary modality of Figure 3 has anti-condensation coating 3 located on surface 4, which is the outer surface of the inner glass substrate 1 that is exposed to the interior of the building instead of the external environment.
    [0054] In certain exemplary embodiments, the inner substrate 1 can be annealed (instead of tempered). The anti-condensation coating can remain the same or substantially the same between the exemplary embodiments of Figure 2 and Figure 3, although the modifications described above in relation to Figures 1, 2 and / or 6 can be made in connection with a modality such as Figure 3. One change that could be made is to increase the thickness of the ITO to obtain the desired U-value performance. In such cases where the ITO is thickened, the thickness of the other layers can also be adjusted so that the desired optical properties are obtained. Additional layers can also be added to obtain the desired optical properties. The other structural elements remain the same between Figures 2 and 3 and similar modifications can be made to them.
    [0055] When the anti-condensation coating 3 is placed on the surface 4 as shown in Figure 3, the U value was determined to be 0.29. When an additional low electrodeposition coating is provided on surface 2 of the IG unit, the U value was found to drop to 0.23. Certain exemplary modalities may also provide an SHGC less than or equal to 0.30, thereby helping to satisfy the 0.30 / 0.30 standard.
    [0056] In products with low U values (eg IG or VIG units with anti-condensation coating on surface 4, VIG units with two or three blades, etc.), condensation can become a problem, for example, a since the glass is not heated because of the low emissivity coatings. A solution to this challenge is presented in Figure 4, which is an insulating glass unit including anti-condensation coatings arranged on the external and internal surfaces of the insulating glass unit according to an exemplary embodiment. In the example of Figure 4, first and second substrates 1a and 1b are provided. First and second anti-condensation coatings 3a and 3b are provided on surfaces 1 and 4, respectively. In certain exemplary embodiments, additional low-electrodeposition coatings can also be provided on one or both of the inner surfaces (surfaces 2 and / or 3). In this way, it is possible to provide a product that exhibits U-value reduction and anti-condensation behaviors.
    [0057] Figure 5 is a graph illustrating the performance of an exemplary modality, a current anti-condensation product and an uncoated glass substrate as the temperature, humidity and dew point change over a period of 18 hours. The images in Figure 5 each have a "criss-cross" pattern printed on them to help demonstrate the presence or absence of condensation. As can be seen from Figure 5, there is virtually no condensation formed on those samples that were produced according to an exemplary modality. In contrast, the comparative example, which includes pyrolytically deposited FTO, shows some condensation being formed in the first observed period, with the level of condensation increasing greatly in the second and third periods observed, and decreasing slightly in the fourth period observed. In fact, the "criss-cross" pattern is significantly blurred in the second period observed and hardly visible during the third. The uncoated glass sample shows significant condensation during all observed periods. The "criss-cross" pattern, in the second and third periods observed, cannot be seen. The examples in Figure 5 then demonstrate that the exemplary modalities described here provide superior performance when compared to the current comparative example and uncoated glass.
    [0058] Figure 7 is a coated article including an anti-condensation coating according to an exemplary embodiment. The stack of the example layer in Figure 7 is similar to the stack of the exemplary layer described earlier in that it includes a layer of TCO 5 interspersed by the first and second layers including silicon 9a and 9b. In the exemplary embodiment of Figure 7, the first and second layers including silicon 9a and 9b comprise silicon oxinitride. The first and second layers comprise silicon oxinitride 9a and 9b interspersed with a TCO 5 layer comprising ITO. Exemplary thicknesses and refractive indices for each layer are provided in the table below:

    [0059] Other variants of this stack of layers are possible in different embodiments of the present invention. Such variants can include, for example, using partially or integrally oxidized and / or nitri layers given to the first and / or second silicon inclusion layers, adding a protective coating layer comprising ZrOx, adding one or more layers of index compatibility (for example, comprising TiOX) between the glass substrate and the second layer including silicon, etc. For example, certain exemplary embodiments may involve modifying the layer stack of the example in Figure 7 in order to replace the top layer comprising SiOxNy with SiN, adding a layer comprising ZrOx (for example, to potentially increase durability), both replacing the top layer comprising SiOxNy with SiN and adding a layer comprising ZrOx, etc. In this way, it will be understood that the possible modifications listed here can be used in any combination or subcombination.
    [0060] Modifications can also be made to satisfy the so-called "R5 window" classification (U value of the integral window <0.225) with a low emissivity (for example, <0.20). To meet such standards, the thickness of the TCO layer can be increased. The projected ITO thickness increases and performance metrics are provided in the table below. It will be understood that layers including silicon can also be adjusted to maintain acceptable optics and / or that dielectric layers such as layers comprising titanium oxide can be added. It is noted that the glass substrates are assumed to be 3 mm transparent glass substrates, that a low electrodeposition coating is provided on surface 2 and that a 1.27 cm (1/2 ") gap filled with approximately 90% Are 10% air is provided in IGU modes.

    [0061] The example embodiment of Figure 7 is advantageously very durable, for example, after heat treatment, although it does not include a coating layer comprising ZrOx or similar. It was then found to be suitable for use as a so-called Surface coating 4. As is known, the fourth surface of an IGU, for example, is the surface furthest from the sun (and then typically facing the interior of a building). In this way, the exemplary layer stack of Figure 7 is particularly well suited for use in an assembly similar to that shown in Figure 3. It will also be understood that the exemplary modality of Figure 7 is suitable for use in relation to other glasses where it is provided on a more internal surface facing the interior of the building (for example, on the surface 6 of a triple IGU, etc.).
    [0062] As mentioned above, the layer stack in the example in Figure 7 is heat treatable in certain exemplary embodiments. Such hot treatment can be carried out using an infrared (IR) heater, box or other oven, a laser annealing process, etc. Additional exemplary details of heat treatment are provided below. The following two tables include performance data for the Figure 7 monolithic layer stack after hot IV treatment and post heat treatment in a loop oven (for example, at 650 degrees C), respectively.
    [0063] Monolithic Ring Performance Data (Post-treatment IV)

    [0064] Performance Data of Monolithic Temperate (650 handle oven)

    [0065] As indicated above, the exemplary embodiment of Figure 7 can be treated with heat using, for example, an infrared (IR) heater, a box or another oven, a laser annealing process, etc. A post-deposition hot treatment step can be advantageous in helping to recrystallize the ITO layer and in helping to achieve desired emissivity and optics (for example, including those described above). In an exemplary process, the glass can be heated to a temperature of approximately 400 ° C to help achieve these goals. In certain exemplary embodiments, the temperature of the glass will not exceed 460 ° C, in order to help reduce the likelihood of permanent (or at least non-temporary) stress changes being introduced into the glass.
    [0066] Certain exemplary embodiments may use a laser diode array in connection with a laser annealing process. It has been found that a laser diode array with the following parameters advantageously helps to reduce the sheet resistance to about 20 ohms / square (from, for example, about 65 ohms / square in the non-deposited state), helps achieve a substantially uniform coating appearance and helps satisfy the performance metrics listed above: • Laser energy - 1 kW • Emission wavelength - 975 nm • Scan rate - 75 mm / s • Spot size - nominally 12.5 mm x 2 mm
    [0067] An oven having multiple zones can also be used for hot treatment of certain exemplary modalities. Zone temperature, line speed, temperature trend (for example, up / down), suction, trim of the element (for example, through the oven), cooling air settings (for example, pressure and flow trend ) and / or other factors can be adjusted to help achieve the desired performance characteristics. In certain exemplary embodiments, a ten-zone oven can be used to perform the heat treatment. A partial subset of the zones can help with the ITO recrystallization process, while other zones can help to slowly cool the substrate before it leaves the oven. In an example where a ten zone oven is used, zones 1-3 were found to be active in the ITO recrystallization process, heating the coating to a temperature close to 400 degrees C, while the rest of the oven slowly helped to cool the glass before leaving for the cooling air sections. It will be understood that it would be desirable in certain exemplary cases to maintain a low outlet temperature in order to help reduce the likelihood of breakage. In fact, glass is very sensitive to thermal break in the temperature range involved in the reseal process, particularly at temperatures above 200 degrees C.
    [0068] Additional parameters that influence thermal break include the temperature differential across the thickness of the glass, as well as the differential across its surface. The first was found to have a great impact on the thermal break compared to the coated substrates. The top and bottom surface temperatures of uncoated glass exiting the oven were almost identical, and most of the clear glass resisted the annealing process after the initial profile was established (line speed, zone temperature, cooling air, none trend). However, the top surface of the coated product was measured to be as much as (250 ° F) greater at the outlet of the oven. This is because heat is lost faster through conductive transfer to the rollers than the radiant transfer from the coated top surface.
    [0069] However, by identifying and understanding these differential and trend heating and cooling, it is possible to reduce this difference and, in turn, help to reduce the likelihood of breakage. Exemplary oven profiles for 3.2 mm and 2.3 mm glass are provided in the tables below, respectively. 3.2 mm Oven Profile

    [0070] The following parameters have been used in connection with this exemplary heating profile: • Line Speed: 60 feet / min • Aspiration: 0 • Edges (Zones 1-3): 5-10 (50%) - center, all other 100% • Primary Cooling: Setpoint = 0 and closed damper • Medium Range Cooling: 1 "H2O, setpoint = 0 and open damper • After Cooler: 1" H2O, setpoint = 0 and open damper 2.3 mm Oven Profile

    [0071] The following parameters have been used in connection with this exemplary heating profile: • Line speed: 70 feet / min • Aspiration: 0 • Edges (Zones 1-3): 5-10 (50%) - center, all other 100% • Primary Cooling: 1 "H2O, top only, setpoint = 0 and open damper • Mid Range Cooling: Setpoint = 0 and closed damper • After Cooler: 1" H2O, setpoint = 0 and open muffler
    [0072] As yet another option, IR radiation adjusted in wavelength can be used for hot treatment in certain exemplary modalities. Exemplary techniques are shown in U.S. Patent Applications Serial No. 12 / 923,082 filed on August 31, 2010, the entire contents of which are hereby incorporated by reference. The TCO layer can preferably and selectively be heat treated using specifically adjusted near-infrared-infrared radiation (NIR-SWIR), for example. Selective heating of the coating can, in certain exemplary embodiments, be achieved using IR emitters with peak results at spectral wavelengths where ITO is absorbing significantly, but where the substrate (eg glass) has reduced or minimal absorption. In certain exemplary embodiments, the coating will preferably be heated, thereby improving its properties while at the same time keeping the base substrate temperatures low.
    [0073] When preferably heating the coating using high intensity wavelength IR radiation techniques, described here, hot treatment of the ITO layer is possible at lower substrate temperatures and / or shorter heating times than would be required by conventional means. Preferential heating is achieved using IR wavelengths that are absorbed much more strongly by the coating than by the substrate. High-intensity IR radiation can be provided, for example, by quartz lamps or laser emitters.
    [0074] In the case of laser emitters, laser diode arrangements can be advantageous, for example, given their lower cost of ownership compared to other common types of lasers (and the availability of wavelength results of around 800- 1050 nm (eg 940 nm) is well compatible with the spectral characteristics of the coating). However, excimer (CO2, YAG, quartz and / or other types of lasers and / or lamps can also be used in different modalities. For example, it is noted that a wavelength of 810 nm is common for some diode lasers ( and in general it can be used in connection with coatings of type low E, for example) and that a wavelength of 1032 nm is common for some YAG lasers. Also, certain exemplary modalities can use other lasers (for example, CO2 or other lasers) to heat the glass very quickly and then indirectly heat the coating. In certain exemplary embodiments, electromagnetic radiation may be focused on a very high aspect ratio rectangular beam spanning the width of the glass. The glass may be being transported on a belt conveyor in a direction perpendicular to the long axis of the rectangle. In certain exemplary embodiments, a "step and repeat" process can be employed, for example, in order to radiate smaller sections in a co controlled so that the entire substrate is finally irradiated. In addition, other sizes and shapes can be used including, for example, substantially square shapes, circular shapes, etc.
    [0075] In general, higher energy densities have been found to be preferred because they allow for shorter heating times and higher temperature gradients of the coating through the crude substrate. With shorter heating times, less heat is transferred from the coating through the glass by conduction and a lower temperature can be maintained.
    [0076] Figure 8 is a schematic view of a system incorporating an IV heater according to certain exemplary modalities. The exemplary system of Figure 8 includes a coating apparatus 102 for deposition by physical vapor in one or more layers of thin film on a substrate, for example, by sputtering. Downstream of the coating apparatus 102 is an IV heater 104. In certain exemplary embodiments, a sputtering apparatus at room temperature can be used to deposit ITO on a substrate. A transport system 106 transports a substrate through the coating device 102, where the layer or layer stack is deposited and to the heater IV 104. The heater IV 104, in turn, is adjusted to focus NIR-SWIR radiation on the substrate with the coating on it. The wavelength of the IR radiation is selected so as to preferably heat the coating or a particular layer in the coating, for example, compared to the substrate and / or any other layers in a multilayer coating.
    [0077] Although certain exemplary embodiments have been described as including an IR heater downstream of the coating apparatus, it will be understood that different exemplary embodiments can locate a coating apparatus within a vacuum chamber of the coating apparatus. Also, in certain exemplary modalities, the IV hot treatment can be carried out at any time once the layer to be treated with heat or activated having been deposited. For example, certain exemplary modalities can perform an IV hot treatment just before the deposition of the ITO layer, while certain exemplary modalities can perform an IV hot treatment once all of the layers in a layer stack have been deposited. In certain exemplary modalities, multiple IV heat treatments can be performed at different times during the deposition process.
    [0078] A shortwave infrared (SWIR) oven (Shortwave Infrared) incorporating quartz lamps can be used in certain exemplary modalities. A peak IR emission wavelength of 1.15 pm can be used to heat the coating. This wavelength was determined by analyzing the spectral characteristics of the coating and the glass substrate, although other wavelengths are certainly possible. In fact, an exemplary warming wavelength range of 0.8-2.5 pm has been determined. Most preferably, the IR emission range is 1-2 pm. The techniques described in U.S. Patent Applications Nos. Series 12 / 923.082, for example, can be used to establish optimal or preferred IR emission ranges for heat treatment of other coatings (for example, other TCO, metallic coatings, etc.) on glass, too.
    [0079] The energy density of the SWIR ovens is 10.56 kW / ft2 (the bulb output is 80 W / in, mounted in 2.54 cm (1 ") centers.) Heating times can vary from 12 -130 sec with 12 sec intervals, for example. Heating elements can be about 10.16 cm (4 ") from the glass surface, although the heating elements can be raised or lowered in exemplary ways different from this one invention.
    [0080] By targeting the IR wavelengths absorbed by the coating, it is possible to generate a large thermal gradient between the coating and the raw substrate. Because the thermal mass of the coating is very small compared to glass, glass essentially acts as an extinguishing mechanism. The increase in crude glass temperature is mainly attributed to direct heat transfer by IR absorption, rather than conduction from the coating.
    [0081] It was found that the final crystallinity of the film is obtained after only 48-60 sec. heating, although shorter or longer times are certainly possible.
    [0082] The initial oxidation level of ITO in the samples used here has been optimized for low leaf resistance following quenching (which results in additional oxidation of ITO). It is likely that an optimal difference exists for ITO with hot treatment using NIR radiation. When the initial oxidation level of ITO is optimized for heating with NIR, it must be possible to significantly reduce the amount of heating required. Theoretically, this time should be reduced to 48-60 sec. required for recrystallization using the same heating process. Additional decreases in heating time can be achieved by optimizing energy density vs. heating time needs.
    [0083] The IV heating techniques described here preferably heat the ITO in the coating so that the glass substrate remains below its transition temperature, which is about 480 degrees C for float glass. Preferably, the glass substrate remains below 450 degrees C and more preferably below 425 degrees C. In certain exemplary embodiments, where a peak emission of 1.15 pm is applied for 108 sec., The sheet strength of the exemplary coating it is about a third of its equivalent without deposition, and the corresponding emissivity and absorption drops to about half of its counterpart values without deposition. In the meantime, the substrate temperature reaches a maximum of only about 400 degrees C, which is below its transition temperature.
    [0084] NIR generally includes IV having a wavelength of 0.75-1.4 pm and SWIR generally includes IV having a wavelength of 1.4-3 pm. Certain exemplary modalities can generally operate within these wavelengths. The temperature of the substrate preferably does not exceed 480 degrees C, more preferably 450 degrees C, more preferably still 425 degrees C and sometimes 400 degrees C, as a result of such NIR-SWIR heating.
    [0085] Although certain exemplary embodiments have been described here with respect to anti-condensation coating, the coatings described here can be used in connection with other applications. For example, the exemplary coatings described here can be used in connection with a refrigerator / freezer and / or other product applications, skylights, etc.
    [0086] In certain exemplary modalities, following hot treatment or activation using the techniques described here, a coated article can be taken to a manufacturer or another location, for example, for further processing such as, for example, cutting, dimensioning, incorporation in an additional item (for example, an insulating glass unit, skylight, vehicle, glass, etc.). Preferably, catastrophic breakage or failure of the hot treated coated article will not result as a result of changes in the glass caused by the heat treatment process.
    [0087] "Peripheral" and "on the edge" seals here do not mean that the seals are located on the periphery or absolute edge of the unit, but on the contrary they mean that the seal is at least partially located on or near (for example, within five centimeters (two inches)) from an edge of at least one substrate of the unit. Likewise, "edge" as used here is not limited to the absolute edge of a glass substrate, but can also include an area on or near (for example, within about two inches) an absolute edge of the (s) substrate (s).
    [0088] As used herein, the term "about", "supported by" and the like should not be interpreted to mean that two elements are directly adjacent to each other unless explicitly stated. In other words, a first layer can be said to be "over" or "supported by" a second layer, even if there are one or more layers between them.
    [0089] It will be understood that certain exemplary embodiments can incorporate one or more coating by low electrodeposition on a surface of one or more glass substrates facing the air gap between them (for example, surfaces 2 and / or 3 in an IGU; surfaces 2, 3, 4 and / or 5 in a triple IGU, etc.). A low surface electrodeposition coating 4 disposed on transparent glass, for example, can help improve the overall window u value, for example, by reflecting the infrared heat back into the building. The glass in certain exemplary embodiments may be transparent float glass from 2.3 mm to 6 mm in certain exemplary embodiments. In such modalities, the hemispheric emissivity can be reduced to 0.3 and the resistance of the sheet to 30 ohms / square. Preferably, emissivity can be reduced to 0.23-0.30 and sheet strength to 30 ohms / square and sometimes emissivity can be reduced to less than or equal to about 0.2 and sheet strength to less than or equal to about 20 ohms / square.
    [0090] Although the invention has been described in relation to what is considered here to be the most practical and preferred modality, it should be understood that the invention should not be limited to the disclosed modality, but on the contrary, it is intended to comprise various modifications and equivalent provisions included in the spirit and scope of the attached claims.
    权利要求:
    Claims (16)
    [0001]
    1. Coated article, characterized by the fact that it comprises: a glass substrate (1) supporting a plurality of layers (3) deposited with sputtering, directly or indirectly, on a first main surface thereof, the plurality of layers (3) including, in order to distance themselves from the glass substrate (1): a first layer (9b) comprising silicon oxinitride having a refractive index of 1.5-2.1, a layer (5) comprising indium tin oxide (ITO) having a refractive index of 1.7-2.1 and a second layer (9a) comprising silicon oxinitride having a refractive index of 1.5-2, 1; and wherein the substrate (1) with the plurality of layers (3) on the first main surface of the first glass substrate (1) has a hemispherical emissivity less than or equal to 0.20 and a lower leaf resistance than or equal to 20 ohms / square following said hot treatment.
    [0002]
    2. Insulating glass unit (IGU), characterized by the fact that it comprises the coated article as defined in claim 1, further comprising: a second glass substrate (21) in spaced relation, parallel to the first glass substrate (1) , the first main surface of the first glass substrate (1) facing away from the second glass substrate (21) when mounted and an edge seal (23) sealing the first and second glass substrates (1.21).
    [0003]
    3. Method of manufacturing an insulating glass unit (IGU) as defined in claim 2, the method characterized by the fact that it comprises: providing a first glass substrate (1); arranging a plurality of layers (3), directly or in-directly, on a first main surface of the first glass substrate (1), the plurality of layers (3) including, in order to distance itself from the first glass substrate (1 ): a first layer (9b) comprising silicon oxinitride having a refractive index of 1.5-2.1, a layer comprising ITO (5) having a refractive index of 1.7-2.1 and a second layer (9a) comprising silicon oxinitride having a refractive index of 1.5-2.1; heat treating the first glass substrate (1) with the plurality of layers (3) arranged on it; providing a second glass substrate (21) in a spaced relation, parallel to the first glass substrate (1) so that the first main surface of the first glass substrate (1) faces away from the second glass substrate (21 ) and seal the first and second glass substrates.
    [0004]
    4. Method according to claim 3, characterized by the fact that the first (9b) and second layers (9a) comprising silicon oxynitride have refractive indices of 1.7-1.8.
    [0005]
    5. Method according to claim 3 or 4, characterized by the fact that the layer comprising ITO (5) has a refractive index of 1.8-1.93.
    [0006]
    6. Method according to claim 5, characterized by the fact that the layer comprising ITO (5) has a retraction index of 1.88.
    [0007]
    Method according to any one of claims 3 to 6, characterized in that the first substrate with the plurality of layers (3) on the first main surface of the first glass substrate (1) has a lower hemispheric emissivity than which is equal to 0.23 following said hot treatment.
    [0008]
    Method according to any one of claims 3 to 7, characterized in that the first substrate with the plurality of layers (3) on the first main surface of the first glass substrate (1) has a lower hemispheric emissivity than that or equal to 0.20 following said hot treatment.
    [0009]
    Method according to any one of claims 3 to 8, characterized in that the first substrate with the plurality of layers (3) on the first main surface of the first glass substrate (1) has a lower sheet resistance than which is equal to 20 ohms / square following said hot treatment.
    [0010]
    Method according to any one of claims 3 to 9, characterized in that said hot treatment includes a laser annealing process.
    [0011]
    11. Method according to claim 10, characterized by the fact that said laser annealing process involves a laser diode array operated at an energy of 1 kW and an emission wavelength of 975 nm.
    [0012]
    12. Method according to any one of claims 3 to 11, characterized in that said heat treatment uses an oven having a plurality of zones.
    [0013]
    13. Method according to claim 12, characterized in that a partial subset of said zones recrystallizes the layer comprising ITO (5).
    [0014]
    Method according to any one of claims 3 to 13, characterized in that the temperature of the first glass substrate (1) remains below 425 degrees C during said heat treatment.
    [0015]
    Method according to any one of claims 3 to 14, characterized in that said hot treatment includes infrared hot treatment.
    [0016]
    16. Method according to claim 15, characterized by the fact that said infrared hot treatment is carried out at a wavelength of 1-2 microns.
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    同族专利:
    公开号 | 公开日
    WO2012078395A3|2012-08-16|
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    TR201820154T4|2019-01-21|
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    MX2013006370A|2013-08-15|
    US20180100348A1|2018-04-12|
    CA2819242C|2015-06-30|
    EP2649020B1|2018-10-17|
    US20190010752A1|2019-01-10|
    BR112013014077A2|2016-09-20|
    RU2017107176A3|2020-05-20|
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    EP2649020A2|2013-10-16|
    US9863182B2|2018-01-09|
    WO2012078395A2|2012-06-14|
    US8524337B2|2013-09-03|
    RU2613236C2|2017-03-15|
    RU2017107176A|2019-01-21|
    US10072456B2|2018-09-11|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-06-04| B06T| Formal requirements before examination|
    2019-12-31| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-05-26| B25A| Requested transfer of rights approved|Owner name: GUARDIAN GLASS, LLC (US) |
    2020-07-07| B09A| Decision: intention to grant|
    2020-11-10| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/11/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/926,714|US8524337B2|2010-02-26|2010-12-06|Heat treated coated article having glass substrate and indium-tin-oxideinclusive coating|
    US12/926,714|2010-12-06|
    PCT/US2011/062283|WO2012078395A2|2010-12-06|2011-11-29|Articles including anticondensation and/or low-e coatings and/or methods of making the same|
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