• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    article coated with low emissivity (low-e) coating having low visible transmission. this invention relates to a coated article which includes a low emissivity (low-e) coating. in certain exemplary embodiments, the low-e coating is provided over a substrate (eg, glass substrate) and includes at least first and second infrared (ir) reflective layers (eg, silver-based layers) which are separately spaced through contact layers (eg nicr-based layers) and a dielectric layer, or which include a material such as silicon nitride. in certain exemplary embodiments, the coated article has a low visible transmission (e.g., no greater than 60%, more preferably no greater than about 55%, and most preferably no greater than about 50% ).
    公开号:BR112016002513B1
    申请号:R112016002513-0
    申请日:2013-08-16
    公开日:2021-06-22
    发明作者:Bernd Disteldorf；Anton Dietrich；Krishna SWAMYNAIDU
    申请人:Guardian Glass, LLC；Guardian Europe S.A.R.L.；
    IPC主号:
    专利说明:

    [0001] This invention relates to a coated article that includes a low-emissivity (low-E) coating. In certain exemplary embodiments, the low-E coating is provided over a substrate (eg, glass substrate) and includes at least first and second infrared (IR) reflective layers (eg, silver-based layers) which are spaced apart from each other by contact layers (eg NiCr-based layers) and a dielectric layer or including a material such as silicon nitride. In certain exemplary embodiments, the coated article (monolithic abd/or IG window unit form) has a low visible transmission (e.g., not greater than 60%, more preferably not greater than about 55%, and more preferably not greater than about 50%). In certain exemplary embodiments, the coated article may be heat treated (e.g., thermally tempered and/or heat bent), and is intended to be substantially thermally stable after heat treatment (HT) in that it that its ΔE* value (reflective glass side) due to the HT is not greater than 5.0, and more preferably not greater than 4.5. Articles coated in accordance with certain exemplary embodiments of this invention may be used in the context of insulating glass (IG) window units, vehicle windows, other types of windows, or in any other suitable application. BACKGROUND OF THE INVENTION
    [0002] Coated articles are known in the art for use in window applications such as insulating glass (IG) window units, vehicle windows and/or the like. It is known that in certain cases, heat treatment (eg, heat-quenching, heat-bending, and/or heat-strengthening) of such coated articles is desirable for the purposes of tempering, bending, or the like. Heat treatment (HT) of coated articles typically requires the use of temperature(s) of at least 580 degrees C, more preferably at least about 600 degrees C and even more preferably at least 620 degrees C. Such high temperatures ( for example, for 5 to 10 minutes or more) often causes coatings to break and/or deteriorate or change in an unpredictable way. Thus, it is desired that coatings be able to withstand such heat treatments (e.g., heat temper), if desired, in a predictable manner which does not significantly damage the coating.
    [0003] In certain situations, coated article designers strive for a combination of desirable visible transmission, desirable color, low emissivity (or emittance), and low laminar strength (Rs). The low emissivity (low-E) and low laminar strength characteristics allow such coated articles to block a significant amount of IR radiation, so as to reduce, for example, unwanted heating of vehicles or building interiors.
    [0004] US Patent No. 7,521,096, incorporated herein by reference, discloses a low-E coating that utilizes zinc oxide (ZnO) contact layers below the silver-based IR reflective layers, and above the layer Silver-based IR reflector (Ag) at the bottom utilizes a NiCrOx contact layer followed by a central tin oxide (SnO2) dielectric layer. Although the ZnO contact layers below the silver-based IR reflective layers provide good structural properties for silver development, ZnO has been observed to degrade the chemical, environmental and mechanical durability of the coating in certain cases. Furthermore, the thick SnO2 dielectric layer was observed to exhibit micro-crystallization and post-HT stress which causes roughness between the SnO2, ZnO and Ag interfaces, which can lead to degradation of durability and affect transmitted color.
    [0005] U.S. Patent No. 5,557,462 discloses a low-E coating with a large amount of SiN/NiCr/Ag/NiCr/SiN/NiCr/Ag/NiCr/SiN layers. However, the coated article of the '462 patent was designed for a high visible transmission of at least 63%. The '462 patent at column 3, lines 12 to 15 teaches that visible transmission below 70% (monolithic coated article) and below 63% (GI window units) are undesirable. Thus, the '462 patent teaches directly away from coated articles with visible transmission less than 63%. Furthermore, as explained in large part in US Patent No. 8,173,263, the coated articles of the '462 patent are not heat treatable because after heat treatment the laminar strength (Rs) rises such as from 3 to 5 to well over 10, turbidity tends to settle down, and the reflective value of the glass side ΔE* is undesirable because it is above 5.0.
    [0006] Consequently, it would be desirable to provide a coated article which is characterized by one or more of: (i) low visible transmission, (ii) good durability, and (iii) thermal stability over the HT so as to make a real a glass side reflective value ΔE* not greater than about 5.0, more preferably not greater than about 4.5.
    [0007] The term ΔE* (and ΔE) is well understood in the art and is reported along with various techniques for its determination, in ASTM 2244-93, as well as being reported in Hunter et. al., The Measurement of Appearance, 2nd Ed. Cptr. 9, page 162 et seq. [John Wiley & Sons, 1987]. As used in the technique, ΔE* (and ΔE) is a way of adequately expressing the change (or lack thereof) of reflectance and/or transmittance (and thus also the appearance of color) in an article after or due to heat treatment. . ΔE can be calculated by the "ab" technique, or by the Hunter technique (designated by employing an "H" subscript symbol). ΔE corresponds to the Hunter Lab scale L, a, b (or Lh, ah, bh). Likewise, ΔE* corresponds to CIE LAB Scale L*, a*, b*. Both are considered useful, and equivalent for purposes of this invention. For example, as reported in Hunter et. al. referenced above, the coordinate/rectangular scale technique (CIE LAB 1976) known as the L*, a*, b* scale can be used, where: L* is (CIE 1976) luminosity units; a* is (CIE 1976) red-green units; b* is (CIE 1976) yellow-blue units; and the distance ΔE* between L*oa*ob*o and L*1 a*1 b*1 is: ΔE* = [(ΔL*)2 + (Δa*)2 + (Δb*)2]1/2, where: ΔL* = L*1 - L*o; Δa* = a*1 - a*o; Δb*= b*1 - b*o where the subscript "o" represents the coating (coated article) before heat treatment and the index "1" represents the coating (coated article) after heat treatment; and the numbers employed (eg, a*, b*, L*) are those calculated by the coordinate technique (CIE LAB 1976) L*, a*, b* mentioned above. When, for example, the reflective values of the glass side ΔE* are measured, then the reflective values of the glass side a*, b* and L* are used. Similarly, ΔE can be calculated using the above equation for ΔE*, that is, ΔE* = [(ΔL*)2 + (Δa*)2 + (Δb*)2]1/2, by substituting a*, b*, L* with Hunter Lab values ah, bh, Lh. Also within the scope of this invention and the quantification of ΔE* are the equivalent numbers if converted in these calculations by any other technique that employs the same concept of ΔE* as defined above. BRIEF SUMMARY OF THE EXAMPLE MODES OF THE INVENTION
    [0008] This invention relates to a coated article that includes a low emissivity (low-E) coating. In certain exemplary embodiments, the low-E coating is provided over a substrate (eg, glass substrate) and includes at least first and second infrared (IR) reflective layers (eg, infrared-based layers. silver) which are spaced apart through contact layers (eg NiCr-based layers) and a dielectric layer of a material such as or including silicon nitride. In certain exemplary embodiments, the coated article has a low visible transmission (e.g., no more than 60%, more preferably no more than about 55%, more preferably no more than about 50%. In certain embodiments. for example, the coated article may be heat treated (e.g., thermally tempered and/or heat-curved), and is designed to be substantially thermally stable after heat treatment (HT) where its ΔE* value (reflective of the glass side) due to the HT is not greater than 5.0, more preferably not greater than 4.5. Such a low ΔE* value indicates that the coated article has approximately the same transmission and color characteristics as seen by eye bare, both before and after heat treatment (e.g. heat tempering). Articles coated in accordance with certain exemplary embodiments of this invention may be used in the context of insulating glass (IG) window units, windows vehicles, other types of windows, or any other suitable application.
    [0009] Furthermore, in certain exemplary embodiments of this invention, the coating includes a layer (e.g., coating) of or including zirconium oxide and/or zirconium oxynitride. In certain exemplary embodiments, this layer of or including zirconium oxide and/or zirconium oxynitride is substantially thinner than each of the silver-comprising IR reflective layers in the coating.
    [0010] It is desired to provide a coated article that is characterized by one, two, or all three of: (i) low visible transmission, (ii) good durability, and (iii) thermal stability after HT in order to design a glass side reflective ΔE* value not greater than 5.0, more preferably not greater than 4.5.
    [0011] In certain exemplary embodiments of this invention, a coated article is provided that includes a coating supported by a glass substrate, the coating comprising: first and second infrared (IR) reflective layers comprising silver, the first IR reflective layer being located closer to the glass substrate than is the second IR-reflecting layer; a first contact layer comprising NiCr located on and in direct contact with the first IR reflective layer comprising silver; a dielectric layer comprising silicon nitride located on and directly in contact with the first contact layer comprising NiCr; a second contact layer comprising NiCr located on and directly in contact with the layer comprising silicon nitride; the second IR reflective layer comprising silver located on and directly in contact with the second contact layer comprising NiCr; a third contact layer comprising NiCr located over and directly in contact with the second IR-reflective layer; another dielectric layer comprising silicon nitride located on and directly in contact with the third contact layer comprising NiCr; a layer comprising zirconium oxide located on and directly in contact with another dielectric layer comprising silicon nitride; wherein the silver-comprising second IR-reflective layer is thicker than the silver-comprising first IR-reflective layer; wherein each of the first and second IR reflective layers comprising silver is at least twice as thick as the layer comprising zirconium oxide; and wherein the coated article has a visible transmission, measured monolithically, of not more than 60%. BRIEF DESCRIPTION OF THE DRAWINGS
    [0012] FIGURE 1 is a cross-sectional view of a coated article according to an exemplary embodiment of this invention.
    [0013] FIGURE 2 is a cross-sectional view showing the coated article of Fig. 1 provided in a GI window unit according to an exemplary embodiment of this invention. DETAILED DESCRIPTION OF THE EXAMPLE MODES OF THE INVENTION
    [0014] The coated articles contained herein can be used in applications such as IG window units, laminated window units (eg for use in vehicle or construction applications), vehicle windows, monolithic architectural windows, residential windows , and/or any other suitable application that includes single substrates or multiple glass substrates.
    [0015] In certain exemplary embodiments of this invention, the coating includes a double silver stack. Referring to Fig. 1, for example, in certain exemplary embodiments of this invention, there is provided a coated article which includes a coating supported by a glass substrate, the coating comprising: first 9 and second 19 infrared reflective layers ( IR) comprising or consisting essentially of silver, the first IR-reflective layer 9 being located closer to the glass substrate 1 than is the second IR-reflective layer 19; a first contact layer comprising NiCr 7 located under and directly in contact with the first IR reflective layer comprising silver 9, a second contact layer 11 located over and directly in contact with the first IR reflective layer comprising silver 9; a dielectric layer comprising silicon nitride 14 located on and directly in contact with the first contact layer comprising NiCr 11; a third contact layer comprising NiCr 17 located on and directly in contact with the layer comprising silicon nitride 14; the second IR-reflective layer comprising silver 19 located on and directly in contact with the second layer comprising NiCr 17; a fourth contact layer comprising NiCr 21 located over and directly in contact with the second IR-reflective layer 19, and wherein the second IR-reflective layer comprising silver 19 is at least thicker than the first IR-reflective layer comprising silver 9. In certain preferred embodiments, it has been observed that surprisingly beneficial results can be achieved when the second IR-reflective layer comprising silver 19 is thicker than the first IR-reflective layer comprising silver 9, more preferably when the second IR reflective layer 19 is at least 10 Angstroms (Â) thicker (more preferably at least 20 Angstroms thicker) than the first IR reflective layer comprising silver 9. The coating includes three dielectric layers 3, 14 and 24 of silicon nitride or including silicon nitride as shown in Fig. 1. Furthermore, the coating includes a layer (eg coating) 27 or of zirconium oxide or including zirconium oxide and/or zirconium oxynitride. In certain exemplary embodiments, this layer of zirconium oxide and/or zirconium oxynitride or including 27 is thinner than one or both of the 9 IR reflective layers, 19 comprising silver in the coating. In certain exemplary embodiments of this invention, each of the IR reflective layers comprising silver 9 and 19 is at least twice as thick, and more preferably at least three times as thick as layer 27 or including zirconium oxide. and/or zirconium oxynitride. In certain exemplary embodiments of this invention, the coating includes only two reflective layers of IR 9, 19 of or including silver or the like.
    [0016] In order to increase durability along with optical and thermal properties and avoid significant structural changes before and after HT, articles coated in accordance with certain exemplary embodiments of this invention have a central dielectric layer 14 of or which includes silicon nitride and lower contact layers 7, 17 are based on NiCr (as opposed to ZnO). It has also been found that using metallic or substantially metallic (perhaps partially nitride) NiCr in layers 7, 11, 17 and/or 21 improves chemical, mechanical and environmental durability (compared to the use of lower ZnO contact layers below the upper contact layers of silver NiCr and/or highly oxidized above silver). It was also observed that the ejection deposit silicon nitride inclusive layer 14 in an amorphous state, so that it is amorphous in both the coated and HT states, contributes to the overall stability of the coating. For example, 5% HCl at 65 degrees C for one hour will remove the coating of U.S. Patent No. 7,521,096, while the coating shown in Fig. 1 and the examples here will survive this HCl test. And in a high temperature and high humidity environment, there is less damage to the coating of Fig. 1 and the examples contained herein after ten days of exposure than the coating of the '096 patent after two days of exposure. And with respect to highly corrosive chemicals such as those used for "brick washing", the corrosion resistance is such that edge blanking does not need to be performed in certain embodiments of example IG and laminate. Similarly, for the mechanical abrasion tests, thermal cycling and salt fog tests, the coatings in the attached examples were observed to be better than those in the '096 patent. Furthermore, it has been observed that the fabrication of the upper Ag-based IR-reflective layer 19 thicker than the lower Ag-based IR-reflective layer 9 improves certain optical characteristics of the coating. The coating can be used as coated, or heat treated, due to the relatively low ΔE* values discussed here. For example, when the coating 30 is located on surface #2 of a GI window unit (as shown in Fig. 2), the low reflective ΔE* values of the glass side due to heat treatment indicate that the article Coated has approximately the same transmission and color characteristics as seen with the naked eye, both before and after heat treatment (eg heat temper), and thus can be used as coated or heat treated without significantly affecting its optical characteristics.
    [0017] In certain exemplary embodiments of this invention such as Fig. 1, heat-treated or non-heat-treated coated articles having multiple IR-reflective layers (e.g., two separately spaced silver-based layers) are capable of design a laminar strength (Rs) less than or equal to 5.0 (more preferably less than or equal to 4.0, even more preferably less than or equal to 3.0). The terms "thermal treatment" and "heat treatment" as used herein mean heating the article to a temperature sufficient to achieve heat tempering, heat bending and/or heat strengthening of the inclusive glass article. This definition includes, for example, heating a coated article in an oven or oven to a temperature of at least about 580 degrees C, more preferably at least about 600 degrees C, for a period sufficient to allow for tempering, bending. and/or thermal reinforcement. In certain cases, the HT can be for at least about 4 or 5 minutes. The coated article may or may not be heat treated in different embodiments of this invention.
    [0018] Figure 1 is a side cross-sectional view of a coated article according to a non-limiting exemplary embodiment of this invention. The coated article includes substrate 1 (e.g., clear, green, bronze, or blue-green glass substrate of about 1.0 to 10.0 mm thick, more preferably from about 1.0 mm to 3.5 mm. mm thick), and the low-E coating (or layer system) 30 provided over substrate 1 directly or indirectly. The coating (or layer system) 30 includes, for example: lower dielectric silicon nitride layer 3 which can be Si3N4, or of the Si-rich type silicon nitride for haze reduction, or any other silicon nitride with suitable stoichiometry in different embodiments of this invention, lower contact layer 7 (which makes contact with the bottom IR reflective layer 9), first conductive infrared (IR) reflective layer preferably metallic or substantially metallic 9, upper reflective layer 11 ( which makes contact with layer 9), dielectric and/or inclusive silicon nitride based layer 14, lower contact layer 17 (which makes contact with IR reflective layer 19), second conductive and preferably metallic or substantially metallic 19, upper contact layer 21 (which makes contact with layer 19), dielectric silicon nitride layer 24 which may be Si3N4, Si-rich type for reduction of turbidity, or any other silicon nitride with stoichiometry suitable in different embodiments of this invention, and the coating layer 27 of material or including a material such as zirconium oxide (e.g. ZrO2) and/or zirconium oxynitride. The "contact" layers 7, 11, 17, and 21 each come into contact with an IR-reflecting layer (for example, the Ag-based layer). The aforementioned layers 3 to 27 make up the low-E (ie low emissivity) coating 30 which is provided on the glass or plastic substrate 1. The layers 3 to 27 can be deposited by ejection onto the substrate 1 in certain exemplary embodiments of this invention, with each layer being deposited by vacuum ejection using one or more targets as needed (ejector targets can be ceramic or metallic). Metallic or substantially metallic layers (eg layers 7, 9, 11, 17, 19 and 21) can be ejected into an atmosphere containing argon gas, while layers subjected to nitride (eg layers 3, 7, 11, 14, 17, 21 and 24) can be ejected into an atmosphere containing a mixture of nitrogen and argon gas. Contact layers 7, 11, 17 and 21 may or may not be nitride in different exemplary embodiments of this invention.
    [0019] In monolithic cases, the coated article only includes a glass substrate 1 as illustrated in Fig. 1. However, the monolithic coated articles contained herein can be used in devices such as laminated vehicle windshields, window units with IG, and others more. As for IG window units, an IG window unit can include two separately spaced glass substrates. An example GI window unit is illustrated and described, for example, in U.S. Patent Document No. 2004/0005467, the disclosure of which is incorporated herein by reference. Fig. 2 shows an example IG window unit including the coated glass substrate 1 shown in Fig. 1 coupled to another glass substrate 2 via spacers, seals 40 or the like, with an opening 50 being defined therebetween. This gap 50 between the substrates in the IG window unit arrangements can in certain cases be filled with a gas such as argon (Ar). An exemplary IG unit may comprise a pair of separately spaced transparent glass substrates each about 3 to 4 mm thick, one of which is coated with a coating 30 contained herein in certain exemplary cases, where the opening 50 between substrates can be around 5 to 30 mm, more preferably around 10 to 20 mm, and most preferably around 16 mm. In certain exemplary cases, the low-E coating 30 may be provided on the surface of each substrate facing the aperture (the coating is shown on the inner main surface of the substrate 1 in Fig. 2 which faces the aperture 50, but instead it may be on the inner main surface of the substrate 2 which faces the opening 50). Substrate 1 or substrate 2 can be the outermost substrate of the GI window unit outside the building (for example, in Fig. 2 substrate 1 is the substrate closest to the outside of the building, and the cladding 30 is provided on surface #2 of the IG window unit).
    [0020] In certain exemplary embodiments of this invention, one, two, three or all four contact layers 7, 11, 17, 21 may be or include NiCr (any suitable Ni:Cr ratio), and may or not be subjected to nitride (NiCrNx). In certain exemplary embodiments, one, two, three or all four of these NiCr 7, 11, 17, 21 inclusive layers are substantially or completely unoxidized. In certain exemplary embodiments, layers 7, 11, 17 and 21 may all be metallic NiCr or substantially metallic NiCr (although trace amounts of other elements may be present). In certain exemplary embodiments, one, two, three or all four NiCr-based layers 7, 11, 17, 21 may comprise from 0 to 10% oxygen, more preferably from 0 to 5% oxygen, and more preferably from 0 to 2% oxygen (% atomic). In certain exemplary embodiments, one, two, three or all four of these layers 7, 11, 17, 21 may contain from 0 to 20% nitrogen, more preferably from 1 to 15% nitrogen, and most preferably from about 1 to 12% nitrogen (% atomic). The NiCr 7, 11, 17 and/or 21 based layers may or may not be embedded with other materials such as stainless steel, Mo, or the like. It has been observed that the use of NiCr-based contact layers 7 and/or 17 under the silver-based IR-reflective layers 9, 19, increases the durability of the coated article (compared to if layers 7 and 17 were in place of ZnO).
    [0021] Dielectric layers 3, 14 and 24 may be of or include silicon nitride in certain embodiments of this invention. Silicon nitride layers 3, 14 and 24 can, among other things, improve the heat treatability of the coated articles and protect the other layers during optional HT, for example, such as heat-tempering or the like. One or more of the silicon nitride of layers 3, 14, 24 may be of the stoichiometric type (i.e. Si3N4), or alternatively of the Si-rich type of silicon nitride in different embodiments of this invention. The presence of free Si in an inclusive layer of silicon nitride rich in Si 3 and/or 14 can, for example, allow certain atoms such as sodium (Na) that migrate out of glass 1 during HT to be more efficiently interrupted by the inclusive Si-rich silicon nitride layers before they can reach the silver and damage it. Thus, it is believed that Si-rich SIxNy can reduce the amount of damage done to silver layers during HT in certain exemplary embodiments of this invention, thus allowing laminar strength (Rs) to decrease or remain approximately the same in a satisfactorily. In addition, it is believed that Si-rich SIxNy in layers 3, 14 and/or 24 can reduce the amount of damage (eg oxidation) done to silver and/or NiCr during HT in certain optional example modalities of this invention. In certain exemplary embodiments, when Si-rich silicon nitride is used, the Si-rich silicon nitride layer (3, 14 and/or 24) as deposited can be characterized by SIxNy layers, where x/y can be from 0.76 to 1.5, more preferably from 0.8 to 1.4, even more preferably from 0.82 and 1.2. Any and/or all silicon nitride layers discussed herein may be embedded with other materials such as stainless steel or aluminum in certain exemplary embodiments of this invention. For example, any and/or all of the silicon nitride layers 3, 14, 24 discussed herein may optionally include from about 0 to 15% aluminum, more preferably from about 1 to 10% aluminum, in certain embodiments. example of this invention. Silicon nitride from layers 3, 14, 24 can be deposited by ejecting a Si or SiAl target into an atmosphere containing argon and nitrogen gas in certain embodiments of this invention. Small amounts of oxygen can also be provided in certain cases in silicon nitride layers.
    [0022] Infrared (IR) reflecting layers 9 and 19 are preferably substantially or entirely metallic and/or conductive, and may comprise or consist essentially of silver (Ag), gold, or any other suitable IR reflecting material. The 9 and 19 IR reflective layers help to allow the coating to have low-E and/or good solar control characteristics.
    [0023] Other layers below or above the illustrated coating can also be provided. Thus, although the layer system or coating is "on" or "supported by" substrate 1 (directly or indirectly), other layers can be provided in between. Thus, for example, the coating of Fig. 1 can be considered "on" and "supported by" substrate 1, even if other layers are provided between layer 3 and substrate 1. Furthermore, certain illustrated coating layers they can be removed in certain embodiments, while others can be added between the various layers, or the various layers can be split with other layers added between the dividing sections in other embodiments of this invention without departing from the overall spirit of certain embodiments of this invention.
    [0024] Although various thicknesses and materials can be used in the layers in different embodiments of this invention, the example thicknesses and materials for the respective layers in the glass substrate 1 in the embodiment of Fig. 1 are as follows, from the substrate of glass visibly (recited physical thickness): Example Materials/Thicknesses; Modality of Fig. 1

    [0025] The second IR reflective layer comprising silver 19 is at least as thick as the first IR reflective layer comprising silver 9. In certain preferred embodiments, it has surprisingly been found that beneficial results can be obtained when the second reflective layer comprises silver. IR comprising silver 19 is thicker than the first IR reflective layer comprising silver 9, more preferably when the second IR reflective layer 19 is at least 10 angstroms (Â) thicker (more preferably at least 20 angstroms thicker ) than the first IR reflective layer comprising silver 9.
    [0026] In certain exemplary embodiments, the layer of zirconium oxide and/or zirconium oxynitride or including zirconium oxide and/or zirconium oxynitride 27 is thinner than each of the IR 9 reflective layers 9, 19 comprising silver in coating 30. In certain exemplary embodiments of this invention, each of the IR reflective layers comprising silver 9 and 19 is at least twice as thick, and more preferably at least three times as thick as layer 27 or including silver oxide. zirconium and/or zirconium oxynitride.
    [0027] In certain exemplary embodiments, the central silicon nitride-based layer 14 is thicker than each of the other silicon nitride-based layers 3 and 24, preferably by at least 100 angstroms, more preferably by at least 300 angstroms, and most preferable at 400 angstroms. Furthermore, in certain exemplary embodiments, each of the silicon nitride-based layers 3, 14 and 24 is at least twice as thick as the zirconium oxide inclusive layer 27, more preferably at least three times as thick. thick, and most preferable at least four or five times thicker.
    [0028] The 30 coating offers good durability and allows for lower internal and external reflection compared to a low-E coating, based solely on silver. However, delta-E* values are typically in the range of 4 to 5. The coating, and coated articles including the coating, can be designed to appear blue light in transmission and reflection, but may become a little more neutrals after the optional HT.
    [0029] In certain exemplary embodiments of this invention, the coated articles contained herein may have the following optical and solar characteristics shown in Table 2, when measured monolithically (before and/or after the optional HT). The laminar resistances (Rs) here take into account all IR breast cells (eg silver layers 9, 19). Note that "before heat treatment" means as quenched, but prior to high temperature heat treatment such as heat quenching as described herein. Optical/Solar Characteristics (Monolithic - Before Heat Treatment)
    Optical/Solar Characteristics (Monolithic - After Heat Treatment)

    [0030] It can be seen from the above that heat treatment (eg thermal temper) slightly increases the visible transmission of the coated article.
    [0031] In certain exemplary laminate embodiments of this invention, coated articles contained herein that have optionally been heat treated to a degree sufficient for tempering, and that have been coupled to another glass substrate to form an IG unit, may have the optical/solar characteristics cited above in a frame as shown in Fig. 2 (eg where the two glass slides are each 6mm thick of clear glass with a 16mm gap between them filled with argon/air 90 /10). Such IG window units can have a visible transmission of about 20 to 55% in certain exemplary embodiments of this invention.
    [0032] The following examples are provided for the purpose of example only, and are not intended to be limiting unless specifically claimed. EXAMPLES 1 to 3
    The following Examples 1 to 3 were prepared by ejection coatings on 6 mm thick clear/transparent glass substrates so as to have approximately the layer stacks described in Fig. 1 with the respective thicknesses shown in the "example" column in the table above in relation to the layer thicknesses.
    Shown below are the optical characteristics of Examples 1 to 3 measured for a monolithic coated article as shown in Fig. 1. All measured values in the table immediately below are pre-HT. Note that "f" refers to film reflection, i.e. reflection from the film side of the coated article, while "g" refers to reflection from the glass side. Monolithic (Pre-HT)

    [0035] It can be seen from the above examples that the coated articles measured monolithically had low desirable visible transmission, and had reasonably desirable reflective color from the glass side. In particular, monolithic aa*g (a* color reflective of the glass side) was in a desirable range of about -5 to -1, and b*g (b* color reflective of the glass side) was in a desirable range of about - 5 to -10. Furthermore, the glass side reflection (RgY) was good in that it was below 10%, more preferably not greater than 9%. These are desirable features, especially when the coated article is to be placed in an IG window unit as shown in Fig. 2.
    [0036] The optical characteristics of Examples 1 to 3 measured for a monolithic coated article after heat-tempering are shown below. Monolithic (Pre-HT)

    [0037] It can be seen from the above examples that the coated articles measured monolithically had desirable low visible transmission, and had reasonably desirable reflective glass side color. In particular, monolithic aa*g (a* color reflective of the glass side) was in a desirable range in Examples 2-3 of about 0 to -2, and b*g (b* color reflective of the glass side) was in a desirable range in Example 2-3 of about -8 to -12. Furthermore, the glass side reflection (RgY) was good as it was below 10%. These are desirable features, especially when the coated article is to be placed in an IG window unit as shown in Fig. 2.
    [0038] Optical characteristics of the IG window units including the coated articles of Examples 1 to 3 are presented below, i.e. when the coated articles are located in the IG window units as shown in Fig. 2 (on the surface #2 of the IG unit, so that the reflective values on the glass side are indicative of appearance). These values are for a non-HT coated article used in the IG unit (i.e., not heat-hardened). IG unit (without HT)

    [0039] Although the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but rather is intended to cover the various modifications and equivalent provisions included within the spirit and scope of the appended claims. ç
    权利要求:
    Claims (22)
    [0001]
    1. Coated article including a coating (30) supported by a glass substrate (1), characterized in that the coating (30) comprises: first and second infrared (IR) reflective layers comprising silver (9, 19) , the first IR-reflective layer (9) being located closer to the glass substrate (1) than is the second IR-reflective layer (19); a first contact layer comprising NiCr (11) located over and in direct contact with the first IR reflective layer comprising silver (9); a dielectric layer comprising silicon nitride (14) located on and directly in contact with the first contact layer comprising NiCr (11); a second contact layer comprising NiCr (17) located on and directly in contact with the layer comprising silicon nitride (14); the second IR reflective layer comprising silver (19) located on and directly in contact with the second contact layer comprising NiCr (17); a third contact layer comprising NiCr (21) located over and directly in contact with the second IR-reflective layer (19); another dielectric layer comprising silicon nitride (24) located on and directly in contact with the third contact layer comprising NiCr (21); a layer comprising zirconium oxide (27) located on and directly in contact with another dielectric layer comprising silicon nitride (24); wherein the second IR-reflective layer comprising silver (19) is thicker than the first IR-reflective layer comprising silver (9); wherein each of the first and second IR reflective layers comprising silver (9, 19) is at least twice as thick as the layer comprising zirconium oxide (27); and wherein the coated article has a visible transmission, measured monolithically, of not more than 60%.
    [0002]
    2. Coated article according to claim 1, characterized in that each of the first and second IR reflective layers comprising silver (9, 19) is at least three times thicker than the layer comprising zirconium oxide ( 27).
    [0003]
    3. Coated article according to claim 1, characterized in that each of the first and second IR reflective layers comprising silver (9, 19) is at least four times thicker than the layer comprising zirconium oxide ( 27).
    [0004]
    4. Coated article according to any one of claims 1 to 3, characterized in that the layer comprising zirconium oxide (27) further comprises nitrogen.
    [0005]
    5. Coated article according to any one of claims 1 to 4, characterized in that the second IR-reflective layer comprising silver (19) is at least 10 angstroms (A) thicker than the first IR-reflective layer which comprises silver (9).
    [0006]
    6. Coated article according to any one of claims 1 to 5, characterized in that the second IR-reflective layer comprising silver (19) is at least 20 angstroms (A) thicker than the first IR-reflective layer which comprises silver (9).
    [0007]
    7. Coated article according to any one of claims 1 to 6, characterized in that the second IR-reflective layer comprising silver (19) is at least 30 angstroms (A) thicker than the first IR-reflective layer which comprises silver (9).
    [0008]
    8. Coated article according to any one of claims 1 to 7, characterized in that the dielectric layer comprising silicon nitride (14) which is located on and directly in contact with the first contact layer comprising NiCr (11 ) is amorphous.
    [0009]
    9. Coated article according to any one of claims 1 to 8, characterized in that the first contact layer comprising NiCr (11) is substantially metallic or metallic and does not contain more than about 5% (atomic %) of oxygen.
    [0010]
    10. Coated article according to any one of claims 1 to 9, characterized in that the second contact layer comprising NiCr (17) is substantially metallic or metallic and does not contain more than about 5% (atomic %) of oxygen.
    [0011]
    11. Coated article according to any one of claims 1 to 10, characterized in that the third contact layer comprising NiCr (21) is substantially metallic or metallic and does not contain more than about 5% (atomic %) of oxygen.
    [0012]
    12. Coated article according to any one of claims 1 to 11, characterized in that said first, second and/or third contact layer (11, 17, 21) still contains nitrogen.
    [0013]
    13. Coated article according to any one of claims 1 to 12, characterized in that said coated article has a visible transmission of about 20 to 60% measured monolithically.
    [0014]
    14. Coated article according to any one of claims 1 to 13, characterized in that said coated article is not thermally hardened and has a visible transmission of about 20 to 55% measured monolithically.
    [0015]
    15. Coated article according to any one of claims 1 to 13, characterized in that the coated article is thermally hardened.
    [0016]
    16. Coated article according to claim 15, characterized in that the coated article is heat treated and has a reflective value ΔE* on the glass side not greater than 5.0, due to heat treatment.
    [0017]
    17. Coated article according to claim 16, characterized in that the coated article is heat treated and has a reflective value ΔE* on the glass side not greater than 4.5, due to heat treatment.
    [0018]
    18. Coated article according to any one of claims 1 to 17, characterized in that the first IR-reflective layer comprising silver (9) is 110 to 145 A thick, and the second IR-reflective layer comprising silver ( 19) is 150 to 215 A thick.
    [0019]
    19. Coated article according to any one of claims 1 to 18, characterized in that the layer comprising zirconium oxide (27) is 25 to 50 A thick.
    [0020]
    20. Coated article according to any one of claims 1 to 19, characterized in that the coating (30) has a laminar resistance (Rs) less than or equal to 4.0 ohms/square.
    [0021]
    21. GI window unit, characterized in that it includes the coated article as defined in any one of claims 1 to 20, and another glass substrate (2) that is coupled to said coated article.
    [0022]
    22. Coated article including a coating (30) supported by a glass substrate (1), the coating characterized in that it comprises: first and second infrared (IR) reflecting layers comprising silver (9, 19), the first IR-reflective layer (9) being located closer to the glass substrate (1) than is the second IR-reflective layer (19); a first contact layer (11) located over and in direct contact with the first IR reflective layer comprising silver (9); a dielectric layer comprising silicon nitride (14) located on and directly in contact with the first contact layer (11); a second contact layer (17) located over and directly in contact with the layer comprising silicon nitride (14); the second IR reflective layer comprising silver (19) located over and directly in contact with the second contact layer (17); a third contact layer (21) located over and directly in contact with the second IR-reflective layer (19); another dielectric layer comprising silicon nitride (24) located on and directly in contact with the third contact layer (21); a layer comprising zirconium oxide (27) located on and directly in contact with another dielectric layer comprising silicon nitride (24); wherein the second IR-reflective layer comprising silver (19) is thicker than the first IR-reflective layer comprising silver (9); wherein each of the first and second IR reflective layers comprising silver (9, 19) is at least twice as thick as the layer comprising zirconium oxide (27); and wherein the coated article has a visible transmission, measured monolithically, of not more than 60%.
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    同族专利:
    公开号 | 公开日
    US10294150B2|2019-05-21|
    CN110104961B|2022-03-01|
    ES2873178T8|2022-01-03|
    US10378271B2|2019-08-13|
    CN105814002B|2019-05-21|
    JP6389258B2|2018-09-12|
    WO2015023292A8|2016-03-03|
    TR201908549T4|2019-07-22|
    KR20160043991A|2016-04-22|
    CN110104961A|2019-08-09|
    CN106164717B|2020-11-06|
    PL3033641T3|2019-10-31|
    EP3033641B1|2019-04-03|
    US20190256411A1|2019-08-22|
    EP3033641A4|2017-03-08|
    ES2873178T3|2021-11-03|
    US10570058B2|2020-02-25|
    US20160185660A1|2016-06-30|
    BR112016002513A2|2017-08-01|
    US9873634B2|2018-01-23|
    BR112016002708A2|2017-08-22|
    EP3033641A1|2016-06-22|
    CN106164717A|2016-11-23|
    ES2730473T3|2019-11-11|
    US20190338582A1|2019-11-07|
    BR112016002708A8|2020-01-28|
    JP2016534969A|2016-11-10|
    KR102151000B1|2020-09-03|
    JP2016532626A|2016-10-20|
    WO2015023303A1|2015-02-19|
    RU2016109089A|2017-09-20|
    RU2016109090A3|2018-03-01|
    EP3033312B1|2021-05-19|
    WO2015023292A9|2016-04-14|
    CN105814002A|2016-07-27|
    US20160177618A1|2016-06-23|
    MX2016002011A|2016-05-18|
    JP6328763B2|2018-05-23|
    KR20160043993A|2016-04-22|
    PL3033312T3|2021-11-02|
    EP3033312A1|2016-06-22|
    WO2015023292A1|2015-02-19|
    EP3553040A1|2019-10-16|
    RU2016109090A|2017-09-21|
    US20180105460A1|2018-04-19|
    RU2674417C2|2018-12-07|
    EP3033312A4|2017-03-08|
    RU2655064C2|2018-05-23|
    MX2016002012A|2016-05-18|
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    法律状态:
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-02-27| B25A| Requested transfer of rights approved|Owner name: CENTRE LUXEMBOURGEOIS DE RECHERCHES POUR LE VERRE ET LA CERAMIQUE (C.R.V.C.) SARL (LU) ; GUARDIAN GLASS, LLC (US) |
    2020-03-17| B25A| Requested transfer of rights approved|Owner name: GUARDIAN GLASS, LLC (US) ; GUARDIAN EUROPE S.A.R.L. (LU) |
    2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/08/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/US2013/055357|WO2015023292A1|2013-08-16|2013-08-16|Coated article with low-e coating having low visible transmission|
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