Heat-treatable coated article having an anti-reflective coating on a substrate - Patent Application 20070122997

Abstract

A coated article comprising a first antireflective (AR) coating supported by a glass substrate, the first coating may comprise, in a direction away from the glass substrate, a first high refractive index dielectric layer, a first low refractive index dielectric layer, a second high refractive index dielectric layer, a second low refractive index dielectric layer, a third high refractive index dielectric layer, a first medium refractive index dielectric layer, a third low refractive index dielectric layer, and an overcoat layer, the first coating does not comprise a silver and / or gold based IR reflective layer, and the first coating is such that, from the perspective of an observer of the coated article, upon heat treatment of at least about 580° C., the coated article has a film side reflectance ΔE of 3.0 or less. * The coated article may be configured to have a ΔE * The values ​​can be measured either with a substantially symmetrical / similar AR coating on the other side of the same glass substrate, or with no AR coating on the other side of the glass substrate.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Patent Application No. 17 / 674,082, filed February 17, 2022, the contents of which are incorporated herein in their entirety.

[0002] The present disclosure relates to coated articles that include a coating on a substrate (e.g., a glass substrate). Such coated articles can have improved antireflective properties upon thermal treatment. [Background technology]

[0003] The subject matter of this disclosure relates to coated articles that include an antireflective (AR) coating on a substrate (e.g., a glass substrate). The coating can be designed to reduce color change from an observer's perspective across the coated article upon heat treatment (e.g., heat tempering) and / or improve one or more of other optical properties, such as providing a substantially neutral coloration, reducing color shading and / or thermal stability, reducing haze, providing lower visible reflectance, and / or reducing the effects of aging (e.g., more stable reflectance over time in the as coated (AC) and / or heat treated (HT) state). One or more such coatings can be provided on a given substrate, such as a single such AR coating on one side of a glass substrate, or a pair of such AR coatings on both sides of a glass substrate. Such coated articles can be used in connection with window monoliths, storefront window glass, museum showcase glass, picture and photograph frame glass, retail display case window glass, table top glass, insulating glass (IG) window units, laminated glass, and / or other suitable applications.

[0004] Coated articles having AR coatings are known in the art. Such coated articles are often subjected to a heat treatment, such as heat tempering. Unfortunately, such coated articles have a substantially different appearance in terms of color before and after the heat treatment, respectively (high reflectance ΔE * In other words, heat treatment causes a significant change in the reflective coloration of the coated article, which is undesirable because the coated article will have a significantly different appearance from the observer when it is heat treated than when it is not heat treated.

[0005] Low reflectance ΔE * It has proven particularly difficult to design a given AR coating to have a low reflection color shift upon heat treatment, such as heat tempering.

[0006] No. 11,112,538 (hereby incorporated by reference in its entirety) discloses an anti-reflective (AR) coating on a glass substrate that may include the following layers from the glass substrate outward: [Table 1]

[0007] Unfortunately, the above AR coatings from Table 11 of U.S. Pat. No. 11,112,538 suffer from at least: (i) undesirably large haze values ​​upon heat treatment; and (ii) substantially different appearances in terms of color (high reflectance ΔE ) before and after heat treatment, respectively, when the AR coating is provided on only one side of the glass substrate. * value), (iii) the desired ΔE *It has been found that such applications may be disadvantageous in terms of realizing one or more of: (i) requiring asymmetric / different AR coatings on both sides of the same glass substrate to achieve these values; and / or (ii) undesirably large reflectance changes upon aging.

[0008] It would therefore be desirable to provide a coated article that improves one or more of the above properties (i), (ii), and / or (iii). Summary of the Invention

[0009] The subject matter of the present disclosure is a coated article comprising a first antireflective (AR) coating supported by a glass substrate, the first coating comprising, in a direction away from the glass substrate, a first high refractive index dielectric layer, a first low refractive index dielectric layer, a second high refractive index dielectric layer, a second low refractive index dielectric layer, a third high refractive index dielectric layer, a first medium refractive index dielectric layer, a third low refractive index dielectric layer, and an overcoat layer, the first coating being free of a silver and / or gold based IR reflective layer, and the first coating being such that, from the perspective of an observer of the coated article, upon heat treatment of at least about 580° C., the coated article has a film side reflectance ΔE of 3.0 or less. * The present invention provides a coated article configured to have a coating value.

[0010] In certain embodiments, the third high refractive index layer is located between the second low refractive index layer and the first medium refractive index layer. In certain embodiments, the first coating is such that the coated article has a film side reflection ΔE of 2.5 or less. * In certain embodiments, the first coating is configured to provide a coated article with a film side reflectance ΔE value of 2.0 or less. * The input is configured to have a value.

[0011] In certain embodiments, the first coating provides a glass-side reflectance of the coated article of 2.5 or less. *In certain embodiments, the first coating is configured to provide a coated article with a glass-side reflectance ΔE value of 2.0 or less. * The input is configured to have a value.

[0012] In certain embodiments, the first coating on the glass substrate has a visible reflectance of 5% or less.In certain embodiments, the first coating on the glass substrate has a visible reflectance of 1% or less.

[0013] In certain embodiments, the coated article has a visible transmission of at least 70%.In certain embodiments, the coated article has a visible transmission of at least 90%.

[0014] In certain embodiments, the AR coating is provided on only one side of the glass substrate, such that there is no AR coating provided on the side of the glass substrate opposite the AR coating.

[0015] In certain embodiments, all layers of the first coating are transparent dielectric layers.

[0016] In certain embodiments, the coated article is heat treated to have a haze value of 0.50 or less.

[0017] In certain embodiments, the coated article is heat tempered.

[0018] In certain embodiments, the first coating is adapted to provide a coated article with a film side reflectance a of -4 to 0, before and / or after any optional heat treatment. * value, and film side reflection b of -10 to -5 * In certain embodiments, the coated article has a film side reflectance a of -3 to -1 before and / or after any optional heat treatment. * value, and film side reflection b of -9 to -6 * The input is configured to have a value.

[0019] In certain embodiments, the first high index layer, the second high index layer, and the third high index layer each have a refractive index (n) of at least 2.15, and the first low index layer, the second low index layer, and the third low index layer each have a refractive index (n) of 1.7 or less.

[0020] In a particular embodiment, the dielectric second low refractive index layer comprises an oxide of silicon.

[0021] In certain embodiments, the dielectric third high refractive index layer comprises an oxide of niobium.

[0022] In certain embodiments, the first low index layer, the second low index layer, and the third low index layer each comprise an oxide of silicon.

[0023] In certain embodiments, the first high refractive index layer comprises an oxide of titanium.

[0024] In certain embodiments, the second high refractive index layer and the third high refractive index layer each comprise an oxide of niobium.

[0025] In certain embodiments, the medium refractive index layer comprises an oxide of silicon and an oxide of niobium.

[0026] In a particular embodiment, the overcoat layer comprises an oxide of Zr and Si.

[0027] In certain embodiments, the first low refractive index layer of the first coating is at least twice as thick as the second low refractive index layer of the first coating.

[0028] In certain embodiments, the third low refractive index layer of the first coating is at least twice as thick as the second low refractive index layer of the first coating.

[0029] In certain embodiments, the second high index layer and the third high index layer are substantially the same thickness, plus or minus 15%.

[0030] In certain embodiments, the upper second coating is on the side of the glass substrate opposite the first coating, and the second coating comprises, in a direction away from the glass substrate, a dielectric first high index layer, a dielectric first low index layer, a dielectric second high index layer, a dielectric second low index layer comprising an oxide of silicon, a dielectric third high index layer comprising an oxide of niobium, a dielectric first medium index layer, where the third high index layer comprising an oxide of niobium is located between the second low index layer comprising an oxide of silicon and the first medium index layer and is in direct contact with the second low index layer and the first medium index layer, a dielectric third low index layer, and an overcoat layer.

[0031] The disclosed subject matter also provides a coated article comprising a first antireflective (AR) coating supported by a glass substrate, the first coating comprising, in a direction away from the glass substrate, a dielectric first high refractive index layer, a dielectric first low refractive index layer, a dielectric second high refractive index layer, a dielectric second low refractive index layer comprising an oxide of silicon, a dielectric third high refractive index layer comprising an oxide of niobium, a dielectric first medium refractive index layer, the third high refractive index layer being located between the second low refractive index layer and the first medium refractive index layer and in direct contact with the second low refractive index layer and the first medium refractive index layer; a dielectric third low refractive index layer; and an overcoat layer, the first coating being free of an IR reflective layer based on silver and / or gold, the first coating being such that, from the perspective of an observer of the coated article, the coated article has a film side reflectance ΔE of 3.0 or less upon heat treatment of at least about 580° C. * A coated article is provided, the coated article being configured to have a value.

[0032] The subject matter of the present disclosure also relates to a coated article comprising first and second anti-reflective (AR) coatings supported by a glass substrate, the first AR coating and the second AR coating being provided on opposite sides of the glass substrate, each comprising, in a direction away from the glass substrate, a first high refractive index dielectric layer, a first low refractive index dielectric layer, a second high refractive index dielectric layer, a second low refractive index dielectric layer comprising an oxide of silicon, a third high refractive index dielectric layer comprising an oxide of niobium, a first medium refractive index dielectric layer, and a third high refractive index dielectric layer comprising an oxide of niobium. the refractive index layer comprises a dielectric first medium refractive index layer, a dielectric third low refractive index layer, and an overcoat layer, the dielectric third low refractive index layer being located between the second low refractive index layer and the first medium refractive index layer, the dielectric third low refractive index layer being in direct contact with the second low refractive index layer and the first medium refractive index layer, the first coating and the second coating being free of an IR reflective layer based on silver and / or gold, and the first AR coating and the second AR coating being such that, from the perspective of an observer of the coated article, the coated article has a film side reflectance ΔE of 3.0 or less upon heat treatment of at least about 580°C. * A coated article is provided, the coated article being configured to have a value.

[0033] The disclosed subject matter also includes a method of making a transparent coated glass product having a coated article comprising a first coating on a glass substrate, the first coating comprising, from the glass substrate outwardly, a dielectric first high refractive index layer, a dielectric first low refractive index layer, a dielectric second high refractive index layer, a dielectric second low refractive index layer comprising an oxide of silicon, a dielectric third high refractive index layer comprising an oxide of niobium, a dielectric first medium refractive index layer, where the third high refractive index layer comprising an oxide of niobium is located between the second low refractive index layer comprising an oxide of silicon and the first medium refractive index layer and in direct contact with the second low refractive index layer and the first medium refractive index layer, a dielectric third low refractive index layer, and an overcoat layer, the first coating does not include an IR reflective layer based on silver and / or gold, and heat treating the coated article at a temperature of at least 580° C., such that the heat treatment causes the coated article to have, from the perspective of an observer of the coated article, a film side reflection ΔE of 3.0 or less due to the heat treatment. * Provide a way to realize values.

[0034] The foregoing has outlined rather broadly the features and technical advantages of the present application in order that the detailed description that follows may be better understood.

[0035] Additional features and advantages of the application will be described hereinafter which form the subject of the claims of this application. Those skilled in the art will appreciate that the conception and specific embodiments disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the application. Those skilled in the art will also appreciate that such equivalent constructions do not depart from the spirit and scope of the application as set forth in the appended claims. The novel features which are believed to be characteristic of the application, both as to its organization and method of operation, together with further objects and advantages, will be better understood from the following description. [Brief description of the drawings]

[0036] [Figure 1]1 is a cross-sectional view of a coated article (heat treated or non-heat treated) having a monolithic structure according to an exemplary embodiment of the presently disclosed subject matter. [Diagram 2] 2 is a cross-sectional view of a coated article (heat treated or unheat treated) having a monolithic structure according to another exemplary embodiment of the subject matter of this disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0037] Reference will now be made in detail to the embodiments, one or more examples of which are illustrated in the drawings. Each example is provided for the purpose of explaining the embodiments, and is not intended to limit the disclosure. Indeed, it will be apparent to those skilled in the art that various modifications and variations of the embodiments can be made without departing from the scope or spirit of the disclosure. For example, features illustrated or described as part of one embodiment can be used with another embodiment to yield still a further embodiment. It is therefore intended that aspects of the disclosure include such modifications and variations.

[0038] For clarity, and not by way of limitation, this detailed description is divided into the following subsections. 6.1. Definitions and 6.2. Coatings.

[0039] 6.1.Definition It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the subject matter of the present disclosure.

[0040] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a "compound" includes a mixture of compounds.

[0041] The term "about" or "approximately" means within an acceptable error range of a particular value as measured by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system.

[0042] As used herein, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements does not include only those elements, but may also include other elements that are not expressly listed or inherent to such process, method, article, or apparatus.

[0043] In the detailed description of the present specification, references to "an embodiment," "an embodiment," "an exemplary embodiment," "in various embodiments," and the like indicate that the described embodiment may include a particular feature, structure, or characteristic, but not all embodiments necessarily include the particular feature, structure, or characteristic. Furthermore, such phrases do not necessarily refer to the same aspect. Furthermore, when a particular feature, structure, or characteristic is described with respect to an embodiment, it is presented as being within the knowledge of a person skilled in the art to affect such feature, structure, or characteristic with respect to other embodiments, whether or not explicitly described. After reading the description, it will be clear to a person skilled in the art how to implement the present disclosure in alternative embodiments.

[0044] It should be noted that, as used herein, the terms "oxide" and "nitride" include various stoichiometric ratios. For example, the term "silicon oxide" includes stoichiometric SiO2 as well as non-stoichiometric silicon oxide. As another example, the term "titanium oxide" includes stoichiometric TiO2 as well as non-stoichiometric titanium oxide.

[0045] Various embodiments of the subject matter of the present disclosure will now be described in more detail below.

[0046] Coating Exemplary embodiments of the presently disclosed subject matter relate to a coated article that includes a glass substrate 1, on which a coating 10 is provided. An anti-reflective (AR) coating 10, or a pair of AR coatings 10, 20, can be provided on the glass substrate 1. Other coatings, such as low-E coatings, can also be provided. In certain exemplary embodiments, the coating 10 (and / or 20) exhibits a low reflectance ΔE upon heat treatment (HT) (e.g., thermal tempering). * Coating 10 (and / or 20) can be designed to reduce color change across the coated article at HT, at least from the perspective of an observer at normal viewing angles, so as to achieve a low reflectance ΔE value of 3.0 or less (more preferably 2.5 or less, even more preferably 2.0 or less, and most preferably about 1.5 or less) at HT. *The AR coatings may be configured to achieve one or more of improved thermal stability to achieve AR values, reduced haze values ​​at HT, substantially achromatic coloration to the observer, reduced color shading, low visible reflectance, and / or reduced aging effects (e.g., low reflectance change upon aging, and / or more stable visible reflectance over time in the as-coated (AC) and / or heat treated (HT) states). One or more such coatings may be provided on a given substrate, such as a single such AR coating 10 on one side of a glass substrate 1 as shown in FIG. 1, or a pair of such AR coatings 10, 20 on both sides of a glass substrate 1 as shown in FIG. 2. Such coated articles (see, for example, FIGS. 1 and 2) may be used in conjunction with single pane window glass, storefront window glass, museum showcase glass, picture and picture framing glass, retail display case window glass, table top glass, insulating glass (IG) for window units, laminated glass, and / or other suitable applications. The coatings may be provided directly or indirectly on the glass substrate. In certain exemplary embodiments, the coating may be an anti-reflective (AR) coating. From an observer's perspective, the visible color change due to HT (e.g., heat tempering) may be reduced or minimized, such that non-heat treated and heat treated versions of the coated article appear similar to the observer.

[0047] In certain exemplary embodiments, a low refractive index layer (e.g., silicon oxide based such as SiO2 based) 5 and an adjacent high refractive index layer (e.g., NbO x Modifying the above identified coatings from Table 11 of U.S. Pat. No. 11,112,538 by adding a niobium oxide-based (e.g., niobium oxide-based) 6 to the center of the layer stack has been shown to provide improved haze values, improved thermal stability upon heat treatment (HT) (i.e., lower reflectance ΔE *It has been surprisingly and unexpectedly found that the coating 20 of the present invention provides one or more of the following: a substantially achromatic coloration to the observer, reduced mottle, low visible reflectance, and / or reduced aging effects (e.g., low reflectance change upon aging, and / or more stable visible reflectance over time in the as-coated (AC) and / or heat-treated (HT) state). The same is true for the corresponding layers 5' and 6' of the coating 20. In certain exemplary embodiments, the layer stack of the coatings (10 and / or 20) can include two co-sputtered layers 7, 7', 9, 9' to improve durability. NbO x 6, 6′ having a central low refractive index layer (e.g., SiO x ) 5, 5' show improved thermal stability and therefore lower reflectance ΔE * It has been found that TiO reduces haze and reduces color shift during HT, providing excellent optical properties. x An undercoat 2, 2' may be provided for additional thermal stability. SiO x 3, 5, and 8 provide dense microstructures resulting in lower aging effects.

[0048] Coatings 10 and 20 can be provided directly or indirectly on glass substrate 1. Coatings 10 and 20 are designed to reduce color change of the fully coated article from the observer's perspective upon heat treatment (e.g., thermal tempering). In certain exemplary embodiments, coatings 10 and 20 can be anti-reflective (AR) coatings. In contrast to U.S. Pat. No. 11,112,538, which requires application of two different coatings on both sides / opposite sides of the glass substrate, certain exemplary embodiments in this case provide a desirably low ΔE by either (a) using an AR coating (e.g., 10) on only one side of glass substrate 1 as shown in FIG. 1, and / or (b) using essentially the same layer stack design on both sides of the glass as shown in FIG. 2 to achieve low color shift due to HT (e.g., thermal tempering). *The present invention provides a coated article that can achieve a value of 0.1 to 0.5. From the observer's perspective, the visible color change due to HT can be reduced or minimized, so that the non-heat-treated and heat-treated versions of the coated article appear similar to the observer. In certain exemplary embodiments, the first coating 10 and the second coating 20 are designed such that the coated article achieves a substantially achromatic coloration from the observer's perspective both before and after HT. The first coating 10 and the second coating 20 can have the same or different layer stacks in different embodiments of the subject matter of the present disclosure.

[0049] Most typical antireflective (AR) coatings themselves have achromatic reflective coloration, such as blue, purple, or pink coloration, and therefore cannot achieve achromatic reflective coloration by themselves. Moreover, the non-neutral coloration of typical antireflective (AR) coatings deteriorates after heat treatment (HT), such as heat tempering. Thus, exemplary embodiments of the subject matter of the present disclosure relate to antireflective coated articles that can achieve achromatic visible reflective coloration both before and after heat treatment, such as heat tempering, which is advantageous for reasons discussed herein.

[0050] In certain exemplary embodiments of the presently disclosed subject matter, the coated article can optionally be "heat treated" (HT) and is preferably designed to be heat treatable. As used herein, the terms "heat treated", "heat treated" and "heat treating" refer to heating the article to a temperature sufficient to achieve heat tempering, heat bending and / or heat strengthening of the glass containing the article. This definition includes, for example, heating the coated article in an oven or furnace at a temperature of at least about 580°C, more preferably at least about 600°C, for a time sufficient to allow strengthening, bending and / or heat strengthening. In certain examples, HT can be for at least about 4 minutes or 5 minutes. The coated article may or may not be heat treated in different embodiments of the presently disclosed subject matter.

[0051] Value ΔE * is known in the art and is important in determining whether there is consistency or substantial consistency during heat treatment (HT) in the context of the subject matter of this disclosure. * , b * For illustrative purposes, Δa * The term refers to the color value a resulting from heat treatment. * Here is a simple example of how ΔΕ changes. * The term is well understood in the art and is reported in ASTM 2244-93, along with various techniques for determining it, as well as in Hunter et.al., The Measurement of Appearance, 2nd Ed. Cptr. 9, page 162 et seq. [John Wiley & Sons, 1987]. As used in the art, ΔE * (and ΔE) are measures of the change (or lack thereof) in reflectance and / or transmittance (and thus color appearance) in an article after or due to HT. ΔE can be calculated by the "ab" method or by the Hunter method (denoted by the use of the "H" subscript). ΔE* is the CIE LAB scale L * , a * , b * For example, as reported in Hunter et al., referenced above, * , a * , b * A Cartesian coordinate / scale technique known as the scale (CIE LAB 1976) can be used, in which case L * is the (CIE 1976) unit of lightness, a * is the (CIE 1976) red-green unit, b * is the (CIE 1976) yellow-blue unit, L * o a * 0b * o and L * ia * ib * Distance ΔE between i and * teeth: ΔE * = [(ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2 ] 1 / 2 (1) where: ΔL * =L * 1-L * o (2) Δa * =a * 1-a * o (3) Δb * =b * 1-b * o (4) where the subscript "o" represents the coating (coated article) before heat treatment, the subscript "1" represents the coating (coated article) after heat treatment, and the numbers used (e.g.,* , b * , L * ) is the aforementioned (CIE LAB 1976) L * , a * , b * It is calculated by the coordinate technique. Similarly, ΔE is a * , b * , L * Hunter Lab's value a h , b h , L h This can be calculated using equation (1) by replacing

[0052] FIG. 1 is a cross-sectional view of a coated article according to an exemplary embodiment of the subject matter of the present disclosure. The glass substrate 1 (e.g., water clear, green, bronze, gray, blue, or cyan glass) can be about 1.0-12.0 mm thick, more preferably about 4-8 mm thick, with an example glass substrate thickness being about 6 mm thick. All layers shown in FIG. 1 (and FIG. 2) are transparent dielectric layers, and all of the layers can be deposited by sputter deposition or any other suitable technique. The AR coating provides a broad anti-reflection range in the spectrum, and can be based, for example, on the 1 / 4-1 / 2-1 / 4 AR principle, where, from the glass substrate outward, the coatings can each include a medium refractive index 1 / 4 wave layer, a high refractive index 1 / 2 wave layer, a low refractive index 1 / 4 wave layer, and then air. Additionally, in certain exemplary cases, a thin hydrophobic layer can be provided on the AR coating, and / or in certain exemplary embodiments, a thin layer can be added between the high and low refractive index layers to improve interfacial adhesion. In the embodiment of Figure 1, a single AR coating 10 is provided. In the embodiment of Figure 1, a low-E coating (not shown) can be provided on the side of the glass substrate 1 opposite the coating 10 and can be used in window monoliths or insulated glass window unit applications. Examples of low-E coatings are described, for example, in U.S. Patent Nos. 11,236,014, 11,168,023, and 10,882,997, the disclosures of which are incorporated herein by reference in their entireties. Instead of a low-E coating on the side of the glass substrate 1 opposite the AR coating 10, another substantially identical AR coating can be symmetrically provided, as shown by AR coating 20 in Figure 2.

[0053] In the embodiment of FIG. 2, an anti-reflective (AR) coating 10 is provided on one side of the glass substrate 1, and another AR coating 20 is provided on the other side of the glass substrate 1. In certain exemplary embodiments, the coatings 10 and 20 can be the same or similar. In the embodiment of FIG. 2, the material of each layer of the coatings 10 and 20 can be of the same material, but the thickness of the layers can differ between the two coatings. In certain exemplary embodiments, the coatings 10 and 20 do not include any infrared (IR) reflective layer based on silver or gold. The AR coating 10 includes sputter-deposited layers 2, 3, 4, 5, 6, 7, 8, and 9, while the AR coating 20 includes corresponding sputter-deposited layers 2', 3', 4', 5', 6', 7', 8', and 9'. The corresponding layers in the coatings 10 / 20 can be of similar material and / or similar thickness.

[0054] 1-2, layers 2, 2', 4, 4', 6 and 6' are high refractive index layers having a refractive index (n) of at least about 2.15, more preferably at least about 2.20, and most preferably at least about 2.25. High refractive index layers 2, 2', 4, 4', 6 and 6' are each made of titanium oxide (e.g., TiO x (wherein x is 1.5 to 2.0, more preferably 1.8 to 2.0, and examples include TiO2) or niobium oxide (e.g., NbO x(wherein x is 1.4 to 2.1, more preferably 1.5 to 2.0, examples include Nb2O5 and NbC2). Note that all refractive index (n) values ​​discussed herein are at a wavelength of 550 nm. Layers 3, 3', 5, 5', 8, and 8' are low refractive index layers having a refractive index (n) less than about 1.8, more preferably less than about 1.7, and most preferably less than about 1.6. Low refractive index layers 3, 3', 5, 5', 8, and 8' can each be or include a low refractive index transparent dielectric material such as silicon oxide (e.g., SiO2) or any other suitable low refractive index material. In certain exemplary embodiments of the subject matter of the present disclosure, the silicon oxide (e.g., SiO2) of any of layers 3, 3', 5, and / or 5' can be doped with other materials such as aluminum (Al) and / or nitrogen (N). For example, and without limitation, any of layers 3, 3', 5, 5', 8, and / or 8' can be or include silicon oxide (e.g., SiO2) and can include about 0-8% (more preferably 1-5%) Al and / or about 0-10% (more preferably about 1-5%) N. Similarly, in certain exemplary embodiments, the titanium oxide and / or niobium oxide of high index layers 2, 2', 4, 4', 6, and 6' can be doped with other materials. The combination of layers 2 and 3 (or layers 2' and 3') can be, for example, a medium index layer (e.g., NbSiO2) having a refractive index (n) of 1.70 to 2.10, more preferably 1.75 to 2.0, and even more preferably 1.75 to 1.95. x) can be substituted. The medium index layers 7, 7', 9, and 9' each have a refractive index (n) between 1.70 and 2.10, more preferably between 1.75 and 2.0, and even more preferably between 1.75 and 1.95. In certain exemplary embodiments, the medium index layers 7 and 7' can be of another medium index material, such as a combination of niobium oxide and silicon oxide (also known as niobium silicon oxide), or a combination of titanium oxide and silicon oxide (also known as titanium silicon oxide), or any other suitable medium index material. In certain exemplary embodiments, the medium index layers 9 and 9' can be of a medium index material, such as a combination of zirconium oxide and silicon oxide (also known as zirconium silicon oxide), or any other suitable medium index material. The zirconium in layers 9, 9' helps to improve the durability of the respective coatings 10 and 20. It is noted that the stacking sequence from either of the embodiments of FIG. 1 or FIG. 2 can be repeated, so that, for example, another sequence of layers 2-8 can be provided on top of the layers illustrated in each coating of FIG. 1-FIG. 2. In certain exemplary embodiments, each layer can include other materials, such as dopants, and of course it will be understood that in certain alternative embodiments of the presently disclosed subject matter, other layers can also be provided, or certain layers can be omitted and different materials can be used.

[0055] In general, other layers may also be provided elsewhere in the coating. Thus, although coatings 10 and 20 or layers thereof are "on" or "supported (directly or indirectly) by" substrate 1, other layers may be provided between them. Thus, for example, even when other layers may be provided between coatings 10 and 20 or layers thereof, the layers or coatings are considered to be "on" substrate 1 (i.e., as used herein, the terms "on" and "supported by" are not limited to "direct contact"). However, in exemplary embodiments, there may be direct contact as shown in Figures 1 and 2.

[0056] A low refractive index layer (e.g., silicon oxide-based such as SiO2-based) 5 (and / or 5') and an adjacent high refractive index layer (e.g., NbO x Modifying the above identified coatings from Table 11 of U.S. Pat. No. 11,112,538 by adding a niobium oxide-based (e.g., niobium oxide-based, such as niobium oxide-based) 6 (and / or 6') to the center of the layer stack has been shown to provide improved haze values, improved thermal stability upon heat treatment (HT) (i.e., lower reflectance ΔE * It has been surprisingly and unexpectedly found that the coating 20 of the present invention provides one or more of the following: a substantially achromatic coloration to the observer, reduced mottle, low visible reflectance, and / or reduced aging effects (e.g., low reflectance change upon aging, and / or a more stable visible reflectance over time in the as-coated (AC) and / or heat-treated (HT) state). The same is true for the corresponding layers 5' and 6' of the coating 20. Co-sputtered layers 7, 7', 9, 9' can be provided to improve durability. NbO x 6, 6′ having a central low refractive index layer (e.g., SiO x ) 5, 5' show improved thermal stability and therefore lower reflectance ΔE * It has been found that TiO reduces haze and reduces color shift during HT, providing excellent thermal stability and excellent thermal conductivity. x An undercoat 2, 2' may be provided for additional thermal stability. SiO x One or more of the inclusion layers 3, 5, 8 may be provided for a dense microstructure, resulting in lower aging effects.

[0057] In certain exemplary embodiments, the first low index layer 3 can be at least twice as thick (more preferably at least three times as thick) as the second low index layer 5, and / or the third low index layer 8 can be at least twice as thick (more preferably at least three times as thick, or at least four times as thick) as the second low index layer 5. In certain exemplary embodiments, the second high index layer 4 and the third high index layer 6 can be substantially the same thickness, i.e., the same thickness plus / minus about 15%.

[0058] Returning to the embodiment of Figures 1-2, various thicknesses may be used without conflicting with one or more of the needs discussed herein. According to certain exemplary embodiments, exemplary thicknesses (in Angstroms) and materials of each layer 2-9 of coating 10 on glass substrate 1 in certain exemplary embodiments to obtain desired visible light transmission, low visible light reflectance, fairly achromatic reflection coloration, low haze, and thermal stability during optional HT are as follows (layers are listed in order of departure from glass substrate 1): Table 1 below provides exemplary materials and thicknesses of AR coating 10 and / or 20 before and / or after optional HT. Of course, similar materials / thicknesses can be provided for layers 2'-9' of coating 20: [Table 2]

[0059] In certain exemplary embodiments of the subject matter of the present disclosure, prior to any optional heat treatment (HT), such as heat tempering, heat bending, and / or heat strengthening, a coated article according to the embodiment of FIG. 1 and / or FIG. 2 may have the color / optical properties shown in Table 2, Illuminant C, 2 degree observer. Table 3 also provides exemplary data after HT. Note that TY and T vis represents the visible light transmittance through the coated article of FIG. 1 in Table 2, RY represents the visible reflectance of the coated article from the viewpoint of the intended observer, and a below RY represents the visible light transmittance through the coated article of FIG. * value and b * The values ​​represent the respective CIE visible reflectance coloration of the fully coated article from the perspective of the intended observer, and are intended to indicate the achromatic reflectance coloration of the fully coated article. The "g" subscript indicates from the glass side of the coated article (e.g., the embodiment of FIG. 1), and the "f" subscript indicates from the film / coating side of the coated article. f A under Y * , b * The value is related to the reflection color value of the "film" side, R gA under Y * , b * The values ​​refer to the reflective color values ​​on the glass side. ΔE in Table 3 indicates the thermal stability. * Values ​​are at normal viewing angle, or approximately 8 degree viewing angle. [Table 3] [Table 4]

[0060] From Table 2 (before HT) and Table 3 (after HT) above, it can be seen that the fully coated article has high visible transmittance, low visible reflectance due to the AR coatings 10 and / or 20, good thermal stability, low haze, and a neutral appearance from the intended observer's point of view.

[0061] Having generally discussed embodiments of the present disclosure, the disclosure may be further understood by the following non-limiting examples. EXAMPLES

[0062] Example 1 according to an exemplary embodiment of the subject matter of the present disclosure is compared below with Comparative Example (CE) 1. As shown in FIG. 2 of the present application, each has the same coating on both sides of the glass substrate 1 to represent symmetrical coatings. Specifically, each has an AR coating, and the coating of Example 1 shown below is provided symmetrically on both sides of the glass substrate 1 of Example 1 as shown in FIG. 2 of the present application, and the coating of CE1 on both sides of the glass substrate is based on the coating from Table 11 of U.S. Patent U.S. Patent No. 11,112,538. [Table 5] [Table 6]

[0063] The coatings on the glass substrates of Example 1 and Comparative Example 1 (CE1) had the following optical properties as measured monolithically using a Perkin Elmer instrument, both before and after heat tempering (HT). These measurements were made on the same coating on both sides of the glass substrate, as shown, for example, in FIG. 2 for Example 1. Note that all coatings had visible transmissions well above 70% before and after HT (e.g., heat tempering, heat strengthening, and / or heat bending) at temperatures of at least 580° C. The data for Example 1 are in the two right-most columns, and the data for CE1 are in the second and third columns from the left of the table. “AC” represents the as-coated condition, which is before HT, such as heat tempering, and “HT” represents the heat treated / heat treated condition, such as heat tempering. For example, if coating 20 is removed from FIG. 2 / Example 1, ΔE * Note that the values ​​are approximately half of those shown below when both coatings 10 and 20 are present. [Table 7]

[0064] From the above table, it can be seen that Example 1, which adds layers 5 and 6 to the coating as shown in Figures 1 and 2, has improved haze and thermal stability (ΔE * It can be seen that the results are unexpectedly and surprisingly improved for ΔE 1.5. For example, upon HT, Example 1 has a desirably low ΔE * Comparative Example 1 had an undesirably high ΔE value of 6.9. *values. This demonstrates that the addition of layers 5 and 6 to the coating surprisingly and unexpectedly significantly improved the thermal stability of the coated article. The thermal stability of the glass side was improved as well. As another example, after HT, Example 1 had a desirably low haze value of 0.4, while Comparative Example 1 had an undesirably high haze value of 0.9. This demonstrates that the addition of layers 5 and 6 to the coating surprisingly and unexpectedly reduced the haze value of the coated article. Example 1 had a slightly better (lower) film side reflectance (R f It can also be seen that aging had a significant effect on the film side reflection (R f Y) did not adversely affect Example 1 as much as CE1.

[0065] These and other modifications and variations to the subject matter of the present disclosure may be made by those skilled in the art without departing from the spirit and scope of the subject matter of the present disclosure, as more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged in whole or in part. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the subject matter of the present disclosure, as further set forth in such appended claims.

Claims

1. 1. A coated article comprising a first anti-reflective (AR) coating supported by a glass substrate, the first coating having a surface oriented in a direction away from the glass substrate that: a dielectric first high refractive index layer; a dielectric first low refractive index layer; a dielectric second high refractive index layer; a dielectric second low refractive index layer; a third high refractive index dielectric layer; a dielectric first medium refractive index layer; a dielectric third low refractive index layer, and an overcoat layer; the first coating does not include an IR-reflective layer based on silver and / or gold; and wherein, from the viewpoint of an observer of the coated article, the first coating provides a film-side reflectance ΔE of 3.0 or less when the coated article is heat-treated at a temperature of at least about 580°C. * A coated article configured to have a value.

2. 10. The coated article of claim 1, wherein the third high refractive index layer is located between the second low refractive index layer and the first medium refractive index layer and is in direct contact with the second low refractive index layer and the first medium refractive index layer.

3. The first coating provides a coated article with a film-side reflectance ΔE of 2.5 or less. * The coated article of claim 1 configured to have a value.

4. The first coating provides a coated article with a film-side reflectance ΔE of 2.0 or less. * The coated article of claim 1 configured to have a value.

5. The first coating provides a glass-side reflectance ΔE of 2.5 or less for the coated article. * The coated article of claim 1 configured to have a value.

6. The first coating provides a glass-side reflection ΔE of 2.0 or less for the coated article. * The coated article of claim 1 configured to have a value.

7. The coated article of claim 1 , wherein the first coating on the glass substrate has a visible reflectance of 5% or less.

8. The coated article of claim 1 , wherein the first coating on the glass substrate has a visible reflectance of 1% or less.

9. The coated article of claim 1 , wherein the coated article has a visible light transmittance of at least 70%.

10. The coated article of claim 1 , wherein the coated article has a visible light transmittance of at least 90%.

11. 10. The coated article of claim 1, wherein the AR coating is provided on only one side of the glass substrate, such that no AR coating is provided on the side of the glass substrate opposite the AR coating.

12. The coated article of claim 1 , wherein all layers of the first coating are transparent dielectric layers.

13. The coated article of claim 1 , wherein the coated article is heat treated and has a haze value of 0.50 or less.

14. The coated article of claim 1 , wherein the coated article is heat tempered.

15. The first coating is such that the coated article has a film side reflectance a of -4 to 0 before and / or after any optional heat treatment. * value, and film side reflection b of -10 to -5 * The coated article of claim 1 configured to have a value.

16. The first coating is such that the coated article has a film side reflectance a of -3 to -1 before and / or after any optional heat treatment. * value, and film side reflection b of -9 to -6 * The coated article of claim 1 configured to have a value.

17. 2. The coated article of claim 1, wherein the first high refractive index layer, the second high refractive index layer, and the third high refractive index layer each have a refractive index (n) of at least 2.15, and the first low refractive index layer, the second low refractive index layer, and the third low refractive index layer each have a refractive index (n) of 1.7 or less.

18. The coated article of claim 1 , wherein the dielectric second low refractive index layer comprises an oxide of silicon.

19. The coated article of claim 1 , wherein the dielectric third high refractive index layer comprises an oxide of niobium.

20. The coated article of claim 1 , wherein the first low refractive index layer, the second low refractive index layer, and the third low refractive index layer each comprise an oxide of silicon.

21. The coated article of claim 1 , wherein the first high refractive index layer comprises an oxide of titanium.

22. The coated article of claim 1 , wherein the second high refractive index layer and the third high refractive index layer each comprise an oxide of niobium.

23. The coated article of claim 1 , wherein the medium refractive index layer comprises an oxide of silicon and an oxide of niobium.

24. The coated article of claim 1 , wherein the overcoat layer comprises oxides of Zr and Si.

25. 10. The coated article of claim 1, wherein the first low refractive index layer of the first coating is at least twice as thick as the second low refractive index layer of the first coating.

26. 10. The coated article of claim 1, wherein the third low refractive index layer of the first coating is at least twice as thick as the second low refractive index layer of the first coating.

27. 10. The coated article of claim 1, wherein the second high refractive index layer and the third high refractive index layer are substantially the same thickness, plus or minus 15%.

28. a second coating on a side of the glass substrate opposite the first coating, the second coating having a surface oriented in a direction away from the glass substrate: a dielectric first high refractive index layer; a dielectric first low refractive index layer; a dielectric second high refractive index layer; a dielectric second low refractive index layer comprising an oxide of silicon; a third high refractive index dielectric layer comprising niobium oxide; a dielectric first medium refractive index layer, wherein the third high refractive index layer containing the oxide of niobium is located between the second low refractive index layer containing the oxide of silicon and the first medium refractive index layer and is in direct contact with the second low refractive index layer and the first medium refractive index layer; a dielectric third low refractive index layer, and The coated article of claim 1 comprising an overcoat layer.

29. 1. A coated article comprising a first anti-reflective (AR) coating supported by a glass substrate, the first coating having a surface oriented in a direction away from the glass substrate that: a dielectric first high refractive index layer; a dielectric first low refractive index layer; a dielectric second high refractive index layer; a dielectric second low refractive index layer comprising an oxide of silicon; a dielectric third high refractive index layer of niobium oxide; a dielectric first medium refractive index layer, wherein the third high refractive index layer is disposed between the second low refractive index layer and the first medium refractive index layer and is in direct contact with the second low refractive index layer and the first medium refractive index layer; a dielectric third low refractive index layer, and an overcoat layer; the first coating does not include an IR-reflective layer based on silver and / or gold; and wherein, from the viewpoint of an observer of the coated article, the first coating provides a film-side reflectance ΔE of 3.0 or less when the coated article is heat-treated at a temperature of at least about 580°C. * A coated article configured to have a value.

30. 1. A coated article comprising first and second anti-reflective (AR) coatings supported by a glass substrate, the first AR coating and the second AR coating being provided on opposite sides of the glass substrate, each having a thickness in a direction away from the glass substrate of: a dielectric first high refractive index layer; a dielectric first low refractive index layer; a dielectric second high refractive index layer; a dielectric second low refractive index layer comprising an oxide of silicon; a third high refractive index dielectric layer comprising niobium oxide; a dielectric first medium refractive index layer, wherein the third high refractive index layer containing the oxide of niobium is located between the second low refractive index layer containing the oxide of silicon and the first medium refractive index layer and is in direct contact with the second low refractive index layer and the first medium refractive index layer; a dielectric third low refractive index layer, and an overcoat layer; the first coating and the second coating do not include an IR-reflective layer based on silver and / or gold; and wherein, from the viewpoint of an observer of the coated article, the first AR coating and the second AR coating are such that the coated article has a film-side reflectance ΔE of 3.0 or less upon heat treatment of at least about 580°C. * A coated article configured to have a value.

31. 1. A method for making a transparent coated glass article, comprising: a coated article comprising a first coating on a glass substrate, the first coating comprising, from the glass substrate outwardly, a dielectric first high refractive index layer, a dielectric first low refractive index layer, a dielectric second high refractive index layer, a dielectric second low refractive index layer comprising an oxide of silicon, a dielectric third high refractive index layer comprising an oxide of niobium, a dielectric first medium refractive index layer, the third high refractive index layer comprising an oxide of niobium being located between the second low refractive index layer comprising an oxide of silicon and the first medium refractive index layer and in direct contact with the second low refractive index layer and the first medium refractive index layer, a dielectric third low refractive index layer, and an overcoat layer, the first coating not comprising an IR reflective layer based on silver and / or gold; heat treating the coated article at a temperature of at least 580°C, wherein said heat treating causes said coated article to have a film-side reflection ΔE of 3.0 or less from the perspective of an observer of said coated article due to said heat treating. * and heat treating to achieve the value.

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