CN118973975A

CN118973975A - Article coated with a multilayer coating stack

Info

Publication number: CN118973975A
Application number: CN202380031667.5A
Authority: CN
Inventors: F·法理德; A·V·瓦格内; P·A·麦德维克; A·甘卓; P·费舍尔
Original assignee: Vitro SAB de CV
Current assignee: Vitro SAB de CV
Priority date: 2022-03-31
Filing date: 2023-03-30
Publication date: 2024-11-15

Abstract

An article coated by a multilayer coating stack, comprising: an article; and a multilayer coating stack comprising: a first layer disposed over the article, the first layer comprising a metal oxide or a metal nitride; a functional layer disposed over the first layer, the functional layer comprising indium doped tin oxide; and a second layer disposed over the functional layer, the second layer comprising silicon oxide.

Description

Article coated with a multilayer coating stack

Cross Reference to Related Applications

The present application claims priority from U.S. provisional patent application No. 63/325,870 filed on 3 months 31 of 2022 and U.S. provisional patent application No. 63/405,147 filed on 9 months 9 of 2022, the disclosures of which are incorporated herein by reference in their entireties.

Technical Field

The present disclosure relates to articles coated with a multilayer coating stack, in some non-limiting embodiments, comprising a transparent member having the multilayer coating stack on a surface.

Background

Transparent members are included in vehicles and building structures to allow interior users to look outward (and vice versa) and to allow light to enter the interior of the vehicle or building structure. As sunlight is incident on the transparent member, the radiative heat transfer between the transparent member and the interior of the vehicle or building structure may change the temperature therein, which may be undesirable. Low emissivity coatings applied over the transparency have been developed to reduce radiative heat transfer between the transparency and the interior. These low emissivity coatings are subject to environmental conditions and can change significantly in color and performance if the coating deteriorates. Thus, there is a need to protect low emissivity coatings.

Disclosure of Invention

According to some non-limiting aspects of the present disclosure, an article coated by a multilayer coating stack comprises: an article; and a multilayer coating stack comprising: a first layer disposed over the article, the first layer comprising a metal oxide or a metal nitride; a functional layer disposed over the first layer, the functional layer comprising indium doped tin oxide; and a second layer disposed over the functional layer, the second layer comprising silicon oxide.

In some non-limiting aspects, the silicon oxide of the second layer may be silicon aluminum oxide. The first layer may include: a bottom layer disposed over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and a capping layer disposed over the underlayer, the capping layer comprising silicon oxide. The coated article may consist essentially of or consist of: a first layer disposed over the article, the first layer comprising: a bottom layer disposed over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and a capping layer disposed over the underlayer, the capping layer comprising silicon oxide; a functional layer disposed over the first layer; and a second layer disposed over the functional layer, the second layer comprising silicon oxide. The coated article may have the following structure: a first layer disposed directly over the article, the first layer comprising: a bottom layer disposed directly over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and a capping layer disposed directly over the underlayer, the capping layer comprising silicon oxide; a functional layer disposed directly over the first layer; and a second layer disposed directly over the functional layer, the second layer comprising silicon oxide.

In some non-limiting aspects, the coated article can further include a protective layer disposed over the second layer. The protective layer may include a metal oxynitride layer disposed over the second layer and a metal oxide layer disposed over the metal oxynitride layer, which may be titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, silicon aluminum oxide, or a combination thereof. The coated article may consist essentially of or consist of: a first layer disposed over the article, the first layer comprising: a bottom layer disposed over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and a capping layer disposed over the underlayer, the capping layer comprising silicon oxide; a functional layer disposed over the first layer; and a second layer disposed over the functional layer, the second layer comprising silicon oxide; and a protective layer disposed over the second layer, the protective layer comprising: a metal oxynitride layer disposed over the second layer; and a metal oxide layer disposed over the metal oxynitride layer, the metal oxide layer comprising at least one of titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, silicon aluminum oxide, or a combination thereof. The coated article may have the following structure: a first layer disposed directly over the article, the first layer comprising: a bottom layer disposed directly over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and a capping layer disposed directly over the underlayer, the capping layer comprising silicon oxide; a functional layer disposed directly over the first layer; and a second layer disposed directly over the functional layer, the second layer comprising silicon oxide; and a protective layer disposed directly over the second layer, the protective layer comprising: a metal oxynitride layer disposed directly over the second layer; and a metal oxide layer disposed directly over the metal oxynitride layer, the metal oxide layer comprising at least one of titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, silicon aluminum oxide, or a combination thereof.

In some non-limiting aspects, the coated article can comprise glass or plastic. The functional layer may have a thickness of less than 160 nm. The second layer may be substantially free of aluminum oxide and silicon aluminum oxynitride. In one embodiment, the second layer and/or the protective layer may have a thickness of less than 70 nm. In another embodiment, the second layer, the protective layer, and/or combinations thereof may have a thickness of 70-100nm, such as 75-97nm, or 80-95nm. The second layer may be the outermost layer. The protective layer may be the outermost layer. The functional layer may be substantially free of silver. The coated article may be mounted in the body of a vehicle or in an insulating glass unit.

According to some non-limiting aspects of the present disclosure, a transparency includes a coated article, wherein a multilayer coating stack is disposed on a surface of the transparency. The coated article comprises: an article; and a multilayer coating stack comprising: a first layer disposed over the article, the first layer comprising a metal oxide or a metal nitride; a functional layer disposed over the first layer, the functional layer comprising indium doped tin oxide; and a second layer disposed over the functional layer, the second layer comprising silicon oxide.

In some non-limiting aspects, the transparency can include a vehicle window, wherein the multilayer coating stack is disposed on an interior surface of the vehicle window. The transparent member may comprise an insulating glass unit for a building structure. The insulating glass unit may include: a first transparent member having a first surface and a second surface; and a second transparent member having a third surface and a fourth surface, wherein a gap is defined between the second surface and the third surface, wherein the first surface is exposed to an outdoor side of the building structure and the fourth surface is exposed to an indoor side of the building structure, wherein the multilayer coating stack is disposed on the fourth surface.

Drawings

The present disclosure will be described with reference to the following drawings, wherein like reference numerals identify like elements throughout.

Fig. 1A illustrates a side view (not to scale) of an article coated by a multilayer coating stack according to some aspects of the present disclosure.

Fig. 1B illustrates a side view (not to scale) of an article coated by a multilayer coating stack according to some aspects of the present disclosure.

Fig. 1C illustrates a side view (not to scale) of an article coated by a multilayer coating stack according to some aspects of the present disclosure.

Fig. 1D illustrates a side view (not to scale) of an article coated by a multilayer coating stack according to some aspects of the present disclosure.

Fig. 2 shows a cross-sectional view (not to scale) of a multilayer coating stack applied over a transparency mounted in a vehicle body.

Fig. 3 shows a cross-sectional view (not to scale) of a multilayer coating stack applied over a transparent member in an insulating glass unit installed in a building structure.

Detailed Description

As used herein, spatial or directional terms, such as "left", "right", "inner", "outer", "above", "below", and the like, are related to the present disclosure as shown in the accompanying drawings. However, it is to be understood that the present disclosure may assume various alternative orientations and, accordingly, such terms are not to be considered as limiting. Furthermore, as used herein, all numbers expressing dimensions, physical characteristics, processing parameters, amounts of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as being modified in any case by the term "about". Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims can vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Furthermore, it is to be understood that all ranges disclosed herein are inclusive of the range start value and the range end value, as well as any and all subranges subsumed therein. For example, a stated range of "1 to 10" should be considered to include any and all subranges between (including) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 1 to 3.3, 4.7 to 7.5, 5.5 to 10, and so forth. "a" and "an" refer to one or more.

Further, as used herein, the terms "formed over," "deposited over," "disposed over," or "provided over" means formed, deposited, disposed, or provided on, but not necessarily in contact with, a surface. For example, a coating layer "disposed over" a substrate does not preclude the presence of one or more other coating layers or films of the same or different composition located between the formed coating layer and the substrate.

As used herein, the term "film" refers to the coated area of a desired or selected coating composition. A "layer" may include one or more "films" and a "coating" or "coating stack" may contain one or more "layers".

In addition, all documents cited herein, such as but not limited to issued patents and patent applications, are to be considered "incorporated by reference" in their entirety.

The present disclosure relates to an article coated by a multilayer coating stack comprising: an article; and a multilayer coating stack comprising: a first layer disposed over the article, the first layer comprising a metal oxide or a metal nitride; a functional layer disposed over the first layer, the functional layer comprising indium doped tin oxide (ITO); and a second layer disposed over the functional layer, the second layer comprising silicon oxide.

Referring to fig. 1A and 1B, a non-limiting embodiment of a coated article 100, 110 according to the present disclosure is shown. The coated article 100, 110 comprises an article 102 over which a multi-layer coating stack is applied. The multilayer coating stack is applied over the surface of the article 102. The multilayer coating stack includes a first layer 104 disposed over the article 102, the first layer including a metal oxide or metal nitride. The multilayer coating stack includes a functional layer 106 disposed over the first layer 104, the functional layer including indium-doped tin oxide. The multilayer coating stack includes a second layer 108 disposed over the functional layer 106, the second layer including silicon oxide.

Non-limiting examples of suitable materials for the article 102 include glass or plastic. The article 102 may comprise a ceramic material.

Non-limiting examples of suitable plastic materials include acrylic polymers, such as polyacrylates; polyalkylmethacrylates such as polymethyl methacrylate, polyethyl methacrylate, polypropylene methacrylate, and the like; polyurethane; a polycarbonate; polyalkylene terephthalates such as polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate and the like; a polysiloxane-containing polymer; or copolymers of any of the monomers used to prepare these, or any mixtures thereof.

Non-limiting examples of suitable glass materials include conventional soda lime silicate glass, borosilicate glass, or lead glass. The glass may be a colorless glass. "colorless glass" refers to glass that is free of coloration or color. Alternatively, the glass may be tinted glass or otherwise colored glass. The glass may be annealed or heat-treated glass. As used herein, the term "heat treatment" refers to tempering or at least partially tempering. The glass may be of any type, such as conventional float glass, and may have any composition possessing any optical properties, such as any value of visible light transmission, ultraviolet light transmission, infrared light transmission, and/or total solar energy transmission. "float glass" refers to glass formed by a conventional float process in which molten glass is deposited onto a molten metal bath and cooled in a controlled manner to form a float glass ribbon. Examples of float glass processes are disclosed in U.S. Pat. nos. 4,466,562 and 4,671,155.

The article 102 may comprise, for example, clear float glass, or may be tinted or colored glass. The article 102 may have any desired size, such as length, width, shape, or thickness. In one non-limiting embodiment, where the article is an automotive transparency, the article 102 may be 1-10mm thick, such as 1-8mm thick, such as 2-8mm, such as 3-7mm, such as 5-7mm, such as 4-6mm thick. In one non-limiting embodiment, where the article is a building transparency, the article 102 may be 1-30mm thick, such as 2.5-25mm thick, such as 2.5-10mm.

With continued reference to fig. 1A and 1B, the multilayer coating stack may be disposed over a surface of the article 102, and the multilayer coating stack may include a first layer 104 disposed over the article 102, the first layer including a metal oxide or a metal nitride. The first layer 104 may be a single film (fig. 1A) or a multi-film (fig. 1B) layer.

Referring to fig. 1B, the first layer 104 may be a multi-film layer comprising a bottom layer 112 disposed over the article 102 and a cover layer 114 disposed over the bottom layer 112. The bottom layer 112 may comprise at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, silicon aluminum nitride, or mixtures thereof.

Zinc oxide or tin oxide may include "zinc/tin alloy oxides" which refer to both true alloys and mixtures of oxides. Zinc oxide can be deposited from zinc cathodes including other materials to improve the sputtering characteristics of the cathode. Thus, zinc/tin alloy oxides can be obtained from the cathodes of zinc and tin by magnetron sputtering vacuum deposition. For example, the zinc cathode can include a small amount (e.g., up to 20 wt%, up to 15 wt%, up to 10 wt%, or up to 5 wt%) of tin to improve sputtering. In this case, the resulting zinc oxide film will comprise a small percentage of tin oxide, for example up to 10% by weight tin oxide, for example up to 5% by weight tin oxide. A coating layer deposited from a zinc cathode having up to 10 wt% tin (added to enhance the conductivity of the cathode) is referred to herein as a "zinc oxide film", even though small amounts of tin may be present. A non-limiting cathode may include zinc and tin in a ratio of 5 wt% to 95 wt% zinc and 95 wt% to 5 wt% tin, such as 10 wt% to 90 wt% zinc and 90 wt% to 10 wt% tin. However, other zinc to tin ratios may be used.

"Zinc stannate" refers to the composition of Zn _XSn_1-XO_2-X (formula 1), where "x" varies from greater than 0 to less than 1. For example, "x" may be greater than 0 and may be any fraction or decimal between greater than 0 and less than 1. For example, when x=2/3, formula 1 is Zn _2/3Sn_1/3O_4/3, which is generally described as "Zn ₂SnO₄". The zinc stannate-containing film has a major amount of one or more forms of formula 1 in the layer.

The capping layer 114 may comprise silicon oxide, which is defined as a compound comprising both silicon and oxygen. The silicon oxide may include, for example, silicon oxide, silicon aluminum oxide, silicon oxynitride, silicon aluminum oxynitride, or any mixture thereof. The silicon oxide may include a silicon metal oxide, such as silicon aluminum oxide.

The first layer 104 may have a thickness of less than 70nm, for example less than 50nm. The first layer 104 may have a thickness of 20-70nm, such as 30-50nm.

In non-limiting embodiments where the first layer includes a bottom layer 112 and a cover layer 114, the bottom layer 112 may have a thickness of less than 30nm, such as less than 20nm, and the cover layer 114 may have a thickness of less than 50nm, such as less than 40nm. The underlayer 112 may have a thickness of 10nm to 30nm, for example 10nm to 20nm. The cap layer 114 may have a thickness of 20nm to 50nm, for example 20nm to 40nm. Alternatively, the first layer may be composed of a bottom layer 112 and a cover layer 114.

With continued reference to fig. 1A and 1B, the multilayer coating stack may include a functional layer 106 disposed over the first layer 104. The functional layer 106 may comprise indium doped tin oxide. Alternatively, the functional layer may be composed of indium-doped tin oxide. The functional layer 106 may be in direct contact with the first layer 104.

The functional layer 106 may have a thickness of less than 160nm, such as less than 150nm, less than 120nm, or less than 110nm. For embodiments in which the coated article 100, 110 is a transparency installed in a vehicle, the functional layer may have a thickness of 55-110nm, such as 60-100nm, or 70-90nm. For embodiments in which the coated article 100, 110 is a transparent member in an insulating glass unit installed in a building structure, the functional layer may have a thickness of 100-160nm, such as 110-150nm, or 120-140nm.

The functional layer 106 may be substantially free of silver-containing compounds. By "substantially free" of silver is meant that the functional layer 106 contains less than 1 wt% silver, or that no silver is intentionally added to the functional layer 106. The functional layer 106 may be free of silver-containing compounds and contain 0wt% silver-containing compounds.

With continued reference to fig. 1A and 1B, the multilayer coating stack may include a second layer 108 disposed over the functional layer 106. The second layer 108 may comprise silicon oxide. The silicon oxide may include silicon oxide, silicon aluminum oxide, silicon oxynitride, silicon aluminum oxynitride. The silicon oxide may include a silicon metal oxide, such as silicon aluminum oxide.

The second layer 108 may have a thickness of less than 70nm, such as less than 60nm, such as less than 55nm, or less than 40nm. The thickness of the second layer 108 may be 10-70nm, such as 20-60nm or 30-55nm. The second layer 108 may provide protection for the functional layer 106.

Alternatively, the thickness of the second layer 108 may be 70-100nm, 72-95nm, or 80-95nm. Such a thicker second layer (compared to the above-mentioned range of less than 70 nm) may exhibit improved anti-reflective properties. The second layer 108 may have a thickness of at most 100nm or at most 95nm.

The second layer 108 may be substantially free of aluminum oxide or silicon aluminum oxynitride. By "substantially free" of alumina is meant that the second layer 108 contains less than 5wt% alumina, or no alumina is intentionally added to the layer. By "substantially free" of aluminum oxynitride, it is meant that the second layer 108 contains less than 5 wt.% aluminum oxynitride or no aluminum oxynitride is intentionally added to the layer. The second layer 108 may be free of alumina and/or aluminum oxynitride, containing 0 wt.% alumina and/or aluminum oxynitride.

As shown in fig. 1A and 1B, the second layer 108 may be the outermost layer on the coated article 100, 110, such that no coating layer is disposed thereon.

Referring to fig. 1B, the coated article 110 may consist essentially of or consist of: a first layer 104 disposed over the article 102, the first layer 104 comprising: a bottom layer 112 disposed over the article 102, the bottom layer 112 comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and a capping layer 114 disposed over the underlayer 112, the capping layer 114 comprising silicon oxide; a functional layer 106 disposed over the first layer 104; and a second layer 108 disposed over the functional layer 106, the second layer 108 comprising silicon oxide.

Referring to fig. 1B, the coated article 110 may have a layered structure in which the first layer 104 is disposed directly over the article 102, the first layer 104 comprising: a bottom layer 112 disposed directly over the article 102, the bottom layer 112 comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and a capping layer 114 disposed directly over the underlayer 112, the capping layer 114 comprising silicon oxide; a functional layer 106 disposed directly over the first layer 104; and a second layer 108 disposed directly over the functional layer 106, the second layer 108 comprising silicon oxide. As used herein, a first layer described as being disposed "directly" over a second layer means that the first layer is over and in direct contact with at least a portion of the second layer, without any intervening layers between the first layer and the second layer at the point of direct contact.

Referring to fig. 1C and 1D, the coated article 120, 130 may further comprise a protective layer 122 disposed over the second layer 108. It will be appreciated that the components of the coated articles 120, 130 in fig. 1C and 1D with the same element numbers have the same features as those described with respect to the coated articles 100, 110 in fig. 1A and 1B.

The protective layer 122 may be a single film (FIG. 1C) or multiple film (FIG. 1D) layer.

Referring to fig. 1D, the protective layer 122 may be a multi-film layer including a metal oxynitride layer 132 disposed over the second layer 108 and a metal oxide layer 134 disposed over the metal oxynitride layer 132.

The metal oxynitride layer 132 contains metal oxynitride, which is defined as a compound containing metal, oxygen, and nitrogen. Non-limiting examples of metal oxynitrides include silicon oxynitride and silicon aluminum oxynitride, or any mixture thereof. The metal oxynitride layer 132 may comprise silicon aluminum oxynitride.

The thickness of the metal oxynitride layer 132 may be less than 50nm, for example less than 40nm. The thickness of the metal oxynitride layer 132 may be 10-50nm, for example 20-40nm.

The metal oxide layer 134 may include a metal oxide, which is defined as a compound including a metal and oxygen. Non-limiting examples of metal oxides include at least one of titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, silicon aluminum oxide, or combinations thereof. The metal oxide may include titanium dioxide.

The thickness of the metal oxide layer 134 may be less than 20nm, for example less than 10nm. The thickness of the metal oxide layer 134 may be 1-20nm, such as 2-15nm or 5-10nm.

The thickness of the protective layer 122 (including both the metal oxynitride layer 132 and the metal oxide layer 134) may be less than 70nm, such as less than 50nm. The thickness of the second layer 108 may be 10-70nm, such as 15-60nm, or 20-50nm. Alternatively, the thickness of the second layer 108 may be 70-100nm, such as 72-97nm or 80-95nm.

The sum of the thicknesses of the second layer 108 and the optional protective layer 122 (the layer over the functional layer 106) may be 70-100nm, e.g., 72-97nm, or 80-95nm, which may exhibit improved anti-reflective properties. The sum of the thicknesses of the second layer 108 and the optional protective layer 122 (the layer above the functional layer 106) may be at most 100nm or at most 95nm.

As shown in fig. 1C and 1D, the protective layer 122 may be the outermost layer on the coated article 120, 130, and thus no coating layer is disposed thereon.

Referring to fig. 1D, the coated article 130 may consist essentially of or consist of: a first layer 104 disposed over the article 102, the first layer 104 comprising: a bottom layer 112 disposed over the article 102, the bottom layer 112 comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, silicon aluminum nitride, or a combination thereof; and a capping layer 114 disposed over the underlayer 112, the capping layer 114 comprising silicon oxide; a functional layer 106 disposed over the first layer 104; a second layer 108 disposed over the functional layer 106, the second layer 108 comprising silicon oxide; and a protective layer 122 disposed over the second layer 108, the protective layer 122 comprising: a metal oxynitride layer 132 disposed over the second layer 108; and a metal oxide layer 134 disposed over the metal oxynitride layer 132, the metal oxide layer 134 comprising at least one of titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, silicon aluminum oxide, or a combination thereof.

Referring to fig. 1D, the coated article 130 may have a layered structure in which the first layer 104 is disposed directly over the article 102, the first layer 104 comprising: a bottom layer 112 disposed directly over the article 102, the bottom layer 112 comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, silicon aluminum nitride, or a combination thereof; and a capping layer 114 disposed directly over the underlayer 112, the capping layer 114 comprising silicon oxide; a functional layer 106 disposed directly over the first layer 104; a second layer 108 disposed directly over the functional layer 106, the second layer 108 comprising silicon oxide; and a protective layer 122 disposed directly over the second layer 108, the protective layer 122 comprising: a metal oxynitride layer 132 disposed directly over the second layer 108; and a metal oxide layer 134 disposed directly over the metal oxynitride layer 132, the metal oxide layer 134 comprising at least one of titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, silicon aluminum oxide, or a combination thereof.

Tables 1-4 below provide non-limiting examples of coated articles useful according to the present disclosure, including the thickness and preferred thickness of the various layers. The order in which the layers are arranged above the base is reported from top to bottom of the table.

The following are non-limiting embodiments of the coated article.

TABLE 1

The following are non-limiting embodiments of the coated article.

TABLE 2

The following are non-limiting embodiments of the coated article.

TABLE 3 Table 3

The following are non-limiting embodiments of the coated article.

TABLE 4 Table 4

Any of the layers described herein may be deposited over the substrate or another layer by any suitable method, such as, but not limited to, chemical Vapor Deposition (CVD) and/or Physical Vapor Deposition (PVD) methods. Examples of CVD processes include spray pyrolysis. Examples of PVD processes include electron beam evaporation and vacuum sputtering (e.g., magnetron Sputter Vapor Deposition (MSVD)). Other coating methods may also be used, such as, but not limited to, sol gel deposition. In one non-limiting embodiment, the coating layer is deposited by MSVD. Examples of MSVD coating apparatus and methods will be well understood by those of ordinary skill in the art and are described, for example, in the following U.S. patents: 4,379,040;4,861,669;4,898,789;4,898,790;4,900,633;4,920,006;4,938,857;5,328,768; and 5,492,750.

Referring to fig. 2 and 3, coated articles 200, 300 are shown according to some non-limiting embodiments. The components with the same last two digits of the element number may have the same or similar characteristics. For example, the components 102, 202, 302 each refer to an article with the last two digits "02" and may have the same or similar characteristics as each other.

Referring to fig. 2, a coated article 200 is shown that includes a multilayer coating stack applied over a transparency mounted in a vehicle body. In fig. 2, the coated article 200 includes an article 202 (also referred to herein as a transparency or ply) having a multilayer coating stack 236 thereon. The article 202 may be a transparency in a vehicle. The type of vehicle is not particularly limited and may include, for example, an automobile or an airplane. The transparency 202 may be a window of a vehicle, such as a front or rear windshield of a vehicle, a driver or passenger door or window, a sunroof or roof window, or the like.

The multi-layer coating stack 236 can comprise, consist essentially of, or consist of any of the coating stacks described in this disclosure.

The transparency 202 coated by the multilayer coating stack 236 may be installed in a vehicle body 238. Non-limiting examples of the vehicle body 238 include: in the case of a sunroof, in the case of a car window, in the case of a car door or frame, or in the case of an aircraft fuselage. The transparency 202 may be secured to a mechanical device (mechanism) by which the transparency, such as a window or sunroof, may be opened and closed, as is widely known in the vehicle arts.

With continued reference to fig. 2, the transparency 202 may have a single ply, however, a multi-ply transparency is also within the scope of the disclosure. The transparency 202 can include a first major surface 240 (surface No. 1) and an opposite second major surface 242 (surface No. 2). In the non-limiting embodiment shown, the first major surface 240 faces the exterior of the vehicle, and is therefore an exterior major surface, and the second major surface 242 faces the interior of the vehicle. A multi-layer coating stack 236 may be formed over at least a portion of the transparency 202. In some preferred embodiments, the multilayer coating stack 236 can be disposed over the second major surface 242 (e.g., the interior surface) of the transparency 202. The multilayer coating stack 236 may be disposed above the innermost surface of the transparency 202.

Referring to fig. 3, a coated article 300 is shown that includes a multilayer coating stack applied over a transparent member mounted in an insulating glass unit in a building structure. In fig. 3, the coated article 300 includes an article 302a, 302b (also referred to herein as a transparency or ply) having a multi-layer coating stack 336 over at least one surface of the article 302a, 302 b. The transparent members 302a, 302b may be transparent members in an Insulated Glass Unit (IGU) installed for the building structure. The type of building structure is not particularly limited and may include, for example, a building. Insulating glass units may include, for example, windows or skylights. However, it should be understood that the coated article 300 described herein is not limited to use with such architectural transparencies, but may be implemented with transparencies in any desired field, such as, but not limited to, laminated or non-laminated residential and/or commercial windows, insulating glass units, and/or transparencies for land, air, space, water, and underwater vehicles.

The multi-layer coating stack 336 can comprise, consist essentially of, or consist of any of the coating stacks described in this disclosure.

The transparencies 302a, 302b coated by the multilayer coating stack 336 may be installed in a building structure 344. Non-limiting examples of building structure 344 include openings for windows or skylights in commercial or residential buildings. The transparencies 302a, 302b may be secured to a mechanical device by which the transparencies, such as windows or skylights, may be opened and closed, as is widely known in the construction of transparencies.

With continued reference to fig. 3, the transparent members 302a, 302b may have two plies, such as the first ply 302a and the second ply 302b shown. However, other plies may be included in the transparency, such as three-ply or four-ply transparencies. Alternatively, the transparency may have a single ply.

In broad practice, plies 302a, 302b may be of the same or different materials. Plies 302a, 302b may each comprise, for example, clear float glass, or may be tinted or colored glass, or one ply 302a, 302b may be clear glass while the other ply 302a, 302b is colored glass. Although not limiting, examples of glasses suitable for use in first ply 302a and/or second ply 302b are described in the following U.S. patents: 4,746,347;4,792,536;5,030,593;5,030,594;5,240,886;5,385,872; and 5,393,593.

The example transparent members 302a, 302b of fig. 3 are in the form of insulating glass units and include a first ply 302a having a first major surface 340 (surface No. 1) and an opposite second major surface 342 (surface No. 2). In the non-limiting embodiment shown, the first major surface 340 faces the exterior of the building, i.e., is the exterior major surface exposed to the outdoor side of the building structure, and the second major surface 342 faces the interior of the building. Second ply 302b has an inner (third) major surface 348 (surface No. 3) and an outer (fourth) major surface 350 (surface No. 4) and is spaced apart from first ply 302a. The fourth major surface 350 is the surface exposed to the indoor side of the building structure. This numbering of ply surfaces is consistent with conventional practice in door and window arrangement technology (fenestration art). First ply 302a and second ply 302b may be joined in any suitable manner, such as by adhesive bonding to a conventional spacer frame. A gap 346 may be formed between the two plies 302a, 302 b. A gap 346 may be defined between the second major surface 342 and the third major surface 348. The gap 346 may be filled with a selected atmosphere, such as air, or a non-reactive gas, such as argon or krypton. A multi-layer coating stack 336 may be formed over at least a portion of one of plies 302a, 302 b. In some preferred embodiments, the multilayer coating stack 336 is disposed above the fourth major surface 350 (e.g., the interior surface). The multilayer coating stack 336 may be disposed over the innermost surface of the transparent members 302a, 302 b. Examples of insulating glass units can be found, for example, in the following U.S. patents: 4,193,236;4,464,874;5,088,258; and 5,106,663.

The multilayer coating stack described in this disclosure and applied over an article (e.g., a transparency) can act as a solar control coating. The term "solar control coating" as used herein refers to a coating comprising one or more layers or films that affect the solar properties of a coated article, such as, but not limited to, the amount of solar radiation (e.g., visible light, infrared radiation, or ultraviolet radiation) reflected from, absorbed by, or transmitted through the coated article; sunshade coefficient; emissivity, etc. The solar control coating may block, absorb, or filter selected portions of the solar spectrum, such as, but not limited to, the IR, UV, and/or visible spectrum or portions thereof.

The following numbered clauses illustrate various aspects of the present disclosure:

Clause 1: an article coated by a multilayer coating stack, comprising: an article; and a multilayer coating stack comprising: a first layer disposed over the article, the first layer comprising a metal oxide or metal nitride; a functional layer disposed over the first layer, the functional layer comprising indium-doped tin oxide; and a second layer disposed over the functional layer, the second layer comprising silicon oxide.

Clause 2: the coated article of clause 1, wherein the silicon oxide of the second layer comprises silicon aluminum oxide.

Clause 3: the coated article of clause 1 or 2, wherein the first layer comprises: a bottom layer disposed over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, silicon aluminum nitride; and a capping layer disposed over the underlayer, the capping layer comprising silicon oxide.

Clause 4: the coated article of any of clauses 1-3, consisting essentially of or consisting of: a first layer disposed over the article, the first layer comprising: a bottom layer disposed over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and a capping layer disposed over the underlayer, the capping layer comprising silicon oxide; a functional layer disposed over the first layer; and a second layer disposed over the functional layer, the second layer comprising silicon oxide.

Clause 5: the coated article of any of clauses 1-4, wherein: a first layer disposed directly over the article, the first layer comprising: a bottom layer disposed directly over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and a capping layer disposed directly over the underlayer, the capping layer comprising silicon oxide; a functional layer disposed directly over the first layer; and a second layer disposed directly over the functional layer, the second layer comprising silicon oxide.

Clause 6: the coated article of any of clauses 1-5, further comprising a protective layer disposed over the second layer.

Clause 7: the coated article of clause 6, wherein the protective layer comprises a metal oxynitride layer disposed over the second layer and a metal oxide layer disposed over the metal oxynitride layer, the metal oxide layer comprising at least one of titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, or silicon aluminum oxide.

Clause 8: the coated article of clause 6 or 7, consisting essentially of or consisting of: a first layer disposed over the article, the first layer comprising: a bottom layer disposed over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and a capping layer disposed over the underlayer, the capping layer comprising silicon oxide; a functional layer disposed over the first layer; and a second layer disposed over the functional layer, the second layer comprising silicon oxide; and a protective layer disposed over the second layer, the protective layer comprising: a metal oxynitride layer disposed over the second layer; and a metal oxide layer disposed over the metal oxynitride layer, the metal oxide layer comprising at least one of titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, or silicon aluminum oxide.

Clause 9: the coated article of any of clauses 6-8, wherein: a first layer disposed directly over the article, the first layer comprising: a bottom layer disposed directly over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and a capping layer disposed directly over the underlayer, the capping layer comprising silicon oxide; a functional layer disposed directly over the first layer; a second layer disposed directly over the functional layer, the second layer comprising silicon oxide; and a protective layer disposed directly over the second layer, the protective layer comprising: a metal oxynitride layer disposed directly over the second layer; and a metal oxide layer disposed directly over the metal oxynitride layer, the metal oxide layer comprising at least one of titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, or silicon aluminum oxide.

Clause 10: the coated article of any of clauses 1-9, wherein the article comprises glass or plastic.

Clause 11: the coated article of any of clauses 1-10, wherein the functional layer has a thickness of less than 160 nm.

Clause 12: the coated article of any of clauses 1-11, wherein the second layer is substantially free of aluminum oxide and silicon aluminum oxynitride.

Clause 13: the coated article of any of clauses 1-12, wherein the second layer and/or the protective layer has a thickness of less than 70 nm.

Clause 14: the coated article of any of clauses 1-13, wherein the second layer is the outermost layer.

Clause 15: the coated article of any of clauses 6-13, wherein the protective layer is the outermost layer.

Clause 16: the coated article of any of clauses 1-15, wherein the functional layer is substantially free of a silver-containing compound.

Clause 17: the coated article of any of clauses 1-16, mounted in a vehicle body or in an insulating glass unit.

Clause 18: the coated article of any of clauses 6-17, wherein the second layer, protective layer, and/or combination thereof has a thickness of 70-100nm, preferably 72-97nm, or most preferably 80-95nm.

Clause 19: a transparency comprising the coated article of any of clauses 1-18, wherein the multilayer coating stack is disposed on a surface of the transparency.

Clause 20: the transparency of clause 19, wherein the transparency comprises a vehicle window.

Clause 21: the transparency of clause 20, wherein the multilayer coating stack is disposed on an interior surface of the vehicle window.

Clause 22: the transparency of clause 19, wherein the transparency comprises an insulating glass unit for a building structure.

Clause 23: the transparency according to clause 22, wherein the insulating glass unit comprises: a first transparent member having a first surface and a second surface; and a second transparent member having a third surface and a fourth surface, wherein a gap is defined between the second surface and the third surface, wherein the first surface is exposed to an outdoor side of the building structure and the fourth surface is exposed to an indoor side of the building structure, wherein the multilayer coating stack is disposed on the fourth surface.

Examples

Examples 1-5 are examples of coated articles according to the invention. While the embodiments describe a coating stack on a single piece of glass, it should be understood that the coating may be applied to laminated glass, automotive glass, insulating glass units, and the like.

The coated substrates of examples 1-5 were prepared according to table 5, wherein the sheet resistance properties of each coated substrate were reported:

TABLE 5

Sheet resistance was measured using Suragus EddyCus TF lab 2020. The measured sheet resistance of the coated substrates is known to correlate with the emissivity properties of the coated substrates, so the sheet resistance measurements of the coated substrates in examples 1-5 indicate that they also exhibit low emissivity properties. For example 5 with a thicker second layer, the sample exhibited improved anti-reflective properties relative to the uncoated glass.

Those skilled in the art will readily appreciate that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Accordingly, the particular embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof.

Claims

1. An article coated by a multilayer coating stack, comprising:

An article; and

A stack of layers of the coating layer, the multilayer coating stack comprises:

a first layer disposed over the article, the first layer comprising a metal oxide or metal nitride;

A functional layer disposed over the first layer, the functional layer comprising indium-doped tin oxide; and

A second layer disposed over the functional layer, the second layer comprising silicon oxide.

2. The coated article of claim 1, wherein the silicon oxide of the second layer comprises silicon aluminum oxide.

3. The coated article of claim 1, wherein the first layer comprises:

a bottom layer disposed over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and

A capping layer disposed over the underlayer, the capping layer comprising silicon oxide.

4. The coated article of claim 1 consisting essentially of or consisting of:

a first layer disposed over the article, the first layer comprising:

A capping layer disposed over the underlayer, the capping layer comprising silicon oxide;

a functional layer disposed over the first layer; and

5. The coated article of claim 1, wherein:

A first layer disposed directly over the article, the first layer comprising:

A bottom layer disposed directly over the article, the bottom layer comprising at least one of zinc oxide, tin oxide, zinc stannate, silicon nitride, or silicon aluminum nitride; and

A capping layer disposed directly over the underlayer, the capping layer comprising silicon oxide;

a functional layer disposed directly over the first layer; and

A second layer disposed directly over the functional layer, the second layer comprising silicon oxide.

6. The coated article of claim 1, further comprising a protective layer disposed over the second layer, wherein the protective layer is preferably the outermost layer.

7. The coated article of claim 6, wherein the protective layer comprises a metal oxynitride layer disposed over the second layer and a metal oxide layer disposed over the metal oxynitride layer, the metal oxide layer comprising at least one of titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, or silicon aluminum oxide.

8. The coated article of claim 6 consisting essentially of or consisting of:

a first layer disposed over the article, the first layer comprising:

a functional layer disposed over the first layer;

A second layer disposed over the functional layer, the second layer comprising silicon oxide; and

A protective layer disposed over the second layer, the protective layer comprising:

a metal oxynitride layer disposed over the second layer; and

A metal oxide layer disposed over the metal oxynitride layer, the metal oxide layer comprising at least one of titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, silicon aluminum oxide.

9. The coated article of claim 6, wherein:

A first layer disposed directly over the article, the first layer comprising:

a functional layer disposed directly over the first layer;

a second layer disposed directly over the functional layer, the second layer comprising silicon oxide; and

A protective layer disposed directly over the second layer, the protective layer comprising:

a metal oxynitride layer disposed directly over the second layer; and

A metal oxide layer disposed directly over the metal oxynitride layer, the metal oxide layer comprising at least one of titanium oxide, zinc oxide, zirconium oxide, titanium aluminum oxide, or silicon aluminum oxide.

10. The coated article of claim 1, wherein the article comprises glass or plastic.

11. The coated article of claim 1, wherein the functional layer has a thickness of less than 160 nm.

12. The coated article of claim 1, wherein the second layer is substantially free of aluminum oxide and silicon aluminum oxynitride; and/or

The functional layer is substantially free of silver-containing compounds.

13. The coated article of claim 6, wherein the second layer and/or protective layer has a thickness of less than 70 nm; and/or

Wherein the second layer, the protective layer and/or combinations thereof have a thickness of 70-100 nm.

14. The coated article of claim 1, wherein the second layer is the outermost layer; and/or

The coated article is mounted in a vehicle body or in an insulating glass unit.

15. A transparency comprising the coated article of claim 1, wherein the multilayer coating stack is disposed on a surface of the transparency.