Asymmetric patterned reflective coating

Abstract

The coated article includes a substrate having a first side and a second side, and a patterned coating on at least a portion of the second side of the substrate. The patterned coating includes a first dielectric layer on at least a portion of the second side of the substrate, an absorption layer that is on a first portion of the first dielectric layer, includes a first reflected aesthetic, and does not exist on a second portion of the first dielectric layer and includes a second reflected aesthetic, and a second dielectric layer on at least a portion of the absorption layer. The contrast between the first reflected aesthetic and the second reflected aesthetic forms a pattern. The contrast between the first reflected aesthetic and the second reflected aesthetic is greater when the coated article is viewed from a first direction as compared to when the coated article is viewed from a second direction.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit of priority to U.S. Patent Application No. 18 / 329,661, filed Jun. 6, 2023, and claims the benefit of U.S. Provisional Patent Application No. 63 / 349,652, filed Jun. 7, 2022, and incorporates these disclosures by reference in their entirety as part of this specification.

[0002] The present invention generally relates to reflective coatings and articles coated with reflective coatings.

Background Art

[0003] Technical Problem Reflective coatings are known in the field of building transparent materials. Various methods are known for applying a pattern onto a transparent material or onto a coating that is visible when viewing the transparent material. However, due to the light transmissivity of the transparent material, the pattern is visible when viewed from both directions. This is not advantageous for many transparent material applications. This is because the pattern is only desired to be visible from one direction since it opens up the view through the transparent material from a second direction.

Summary of the Invention

[0004] In one aspect of the present invention, a coated article includes a substrate having a first side and a second side opposite the first side, and a patterned coating on at least a portion of the second side of the substrate. The patterned coating includes a first dielectric layer on at least a portion of the second side of the substrate, an absorption layer that is on a first portion of the first dielectric layer, includes a first reflected aesthetic, and does not exist on a second portion of the first dielectric layer and includes a second reflected aesthetic, and a second dielectric layer on at least a portion of the absorption layer. A contrast between the first reflected aesthetic and the second reflected aesthetic forms a pattern, and the contrast between the first reflected aesthetic and the second reflected aesthetic is greater when the coated article is viewed from a first direction compared to when the coated article is viewed from a second direction.

[0005] Various non-limiting examples and aspects of the present invention are described herein and are set forth in the following numbered paragraphs:

[0006] Paragraph 1: A coated article comprising a substrate having a first side and a second side opposite the first side, and a patterned coating on at least a portion of the second side of the substrate. The patterned coating includes a first dielectric layer on at least a portion of the second side of the substrate, an absorption layer that is on a first portion of the first dielectric layer, includes a first reflected aesthetic, and does not exist on a second portion of the first dielectric layer and includes a second reflected aesthetic, and a second dielectric layer on at least a portion of the absorption layer. A contrast between the first reflected aesthetic and the second reflected aesthetic forms a pattern, and the contrast between the first reflected aesthetic and the second reflected aesthetic is greater when the coated article is viewed from a first direction compared to when the coated article is viewed from a second direction, the coated article.

[0007] Item 2: The coated article according to Item 1, wherein the contrast between the first reflected aesthetic and the second reflected aesthetic is greater when the coated article is viewed from the second side than when viewed from the first side.

[0008] Item 3: The coated article according to Item 1 or Item 2, wherein the ratio of the thickness of the second dielectric layer to the thickness of the first dielectric layer is in the range of 2:1 to 20:1.

[0009] Item 4: The coated article according to Item 3, wherein the ratio of the thickness of the second dielectric layer to the thickness of the first dielectric layer is in the range of 3:1 to 5:1.

[0010] Item 5: The coated article according to any one of Items 1 to 4, wherein the thickness of the second dielectric layer is in the range of 25 nm to 100 nm.

[0011] Item 6: The coated article according to any one of Items 1 to 5, wherein the thickness of the first dielectric layer is in the range of 2 nm to 20 nm.

[0012] Item 7: The coated article according to any one of Items 1 to 6, wherein the absorption layer contains nickel, chromium, iron, stainless steel, niobium, silver below the critical state, or a combination thereof.

[0013] Item 8: The coated article according to any one of Items 1 to 7, further comprising a functional coating on at least a part of the substrate, and on and / or under the patterned coating.

[0014] Item 9: The coated article according to Item 8, wherein the functional coating is a solar control coating.

[0015] Item 10: The coated article according to any one of Items 1 to 9, wherein the thickness of the absorption layer is in the range of greater than 0 nm to 5 nm.

[0016] Item 11: The coated article according to any one of Items 1 to 10, wherein the absorption layer includes a tilted thickness.

[0017] Item 12: The coated article according to any one of Items 1 to 11, wherein the substrate includes glass.

[0018] Item 13: The coated article according to any one of Items 1 to 12, wherein the substrate includes a plastic material.

[0019] Item 14: The coated article according to any one of Items 1 to 13, wherein the coated article is a laminate.

[0020] Item 15: The coated article according to any one of Items 1 to 14, wherein the combined thickness of the first dielectric layer and the second dielectric layer is in the range of 40 nm to 60 nm.

[0021] Item 16: The coated article according to Item 8, wherein the functional coating includes a continuous silver infrared reflection layer.

[0022] Item 17: The coated article according to Item 8, wherein the functional coating includes an indium tin oxide layer and / or a fluorine-doped tin oxide layer.

[0023] Item 18: The coated article according to Item 8, wherein the functional coating includes a halogenated layer.

[0024] Item 19: The coated article according to any one of Items 1 to 18, wherein the coated article is architectural glass.

[0025] Item 20: The contrast between the first reflected appearance and the second reflected appearance is visible to a bird by reflection when viewed from the second side of the coated article, according to any one of Items 1 to 19.

[0026] Item 21: The coated article according to any one of Items 1 to 20, wherein the first dielectric layer has a thickness such that a pattern is not visually recognizable by reflection when viewed from the first side of the coated article, and the second dielectric layer has a thickness such that a pattern is visually recognizable by reflection when viewed from the second side of the coated article.

[0027] Item 22: The ΔE in reflection between the first reflected aesthetic and the second reflected aesthetic when viewed from the first side CMC is less than 4, for the coated article according to any one of Items 1 to 21.

[0028] Item 23: The ΔE in reflection between the first reflected aesthetic and the second reflected aesthetic when viewed from the second side CMC is greater than 8, for the coated article according to any one of Items 1 to 22.

[0029] The present invention is described with reference to the following drawings, and like reference numerals identify like parts throughout.

Brief Description of the Drawings

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Figure 1

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Figure 3A

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Figure 3B

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Figure 3C

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Figure 4A

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Figure 4C

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Figure 6

[0040]

Figure 7

Mode for Carrying Out the Invention

[0041] As used herein, spatial or directional terms such as "left", "right", "inner", "outer", "upper", "lower", etc. are related to the present invention as shown in the drawings. However, it should be understood that the present invention can assume various alternative orientations, and thus such terms should not be considered limiting. Further, as used herein, all numbers used in the specification and claims, representing dimensions, physical properties, processing parameters, amounts of components, reaction conditions, etc., should be understood to be modified in all cases by the term "about". Accordingly, unless indicated otherwise, the numerical values set forth in the following specification and claims are subject to change depending on the desired characteristics sought by the present invention. At the very least, and without limiting the application of the doctrine of equivalents to the claims, each numerical value should be construed in light of at least the number of significant digits reported and by applying ordinary rounding techniques. In addition, all ranges disclosed herein should be understood to include the beginning and ending values of the range, and any sub-ranges subsumed within that range. For example, a range described as "1 to 10" includes any sub-range (including the minimum and maximum values) between the minimum value of 1 and the maximum value of 10, i.e., any sub-range that begins with a minimum value of 1 or more and ends with a maximum value of 10 or less, such as 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc. Further, as used herein, the terms "formed on", "deposited on", or "provided on" mean formed, deposited, or provided on the surface, but not necessarily in contact with the surface. For example, a coating layer "formed on" a substrate does not exclude 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. The terms "visible region", "visible light", or "visible light spectrum" refer to electromagnetic radiation having wavelengths in the range of 380 nm to 800 nm. The terms "infrared region", "infrared ray", or "infrared spectrum" refer to electromagnetic radiation having wavelengths in the range of greater than 800 nm to 100,000 nm.The terms "ultraviolet region", "ultraviolet light" or "ultraviolet (UV) spectrum" mean electromagnetic energy having wavelengths in the range from 300 nm to less than 380 nm. In addition, all documents, including but not limited to issued patents and patent applications, referred to herein shall be considered to "incorporate these disclosures" as part of this specification. As used herein, the term "film" refers to the coated area of a desired or selected coating composition. A "layer" can include one or more "films", and a "coating" or "coating laminate" can include one or more "layers". The term "asymmetric reflectance" means that the visible light reflectance of a coating from one side is different from the visible light reflectance of the coating from the opposite side. The term "critical thickness" means a thickness greater than that at which the coating material forms a continuous, unbroken layer and less than that at which the coating material forms discontinuous layers or islands of coating other than continuous layers. The term "sub-critical thickness" means a thickness less than the critical thickness at which the coating material forms its separated, non-connected regions. The term "isolated" means that the coating material is not a continuous layer, but rather the material is deposited to form isolated regions or islands.

[0042] For illustrative purposes hereinafter, the present invention is described with reference to being used with a building transmissive material, such as, but not limited to, an insulating glass unit (IGU). As used herein, the term "building transmissive material" refers to any transmissive material disposed in a building, such as, but not limited to, windows and skylights. However, the present invention is not limited to being used with such building transmissive materials, but can be practiced with transmissive materials in any desired field, such as laminated or non-laminated residential windows, and / or commercially available windows, insulating glass units, and / or transmissive materials for land, air, space, water, and underwater vehicles, glass and equivalents, mirrors (e.g., magic mirrors, multifunctional mirrors, and / or their equivalents), displays, dynamic glass, coatings including multifunctional patterning (e.g., antennas and / or their equivalents), windows patterned for sensor compatibility (e.g., infrared), consumer goods, and / or their equivalents, and the like. It should be understood, therefore, that the specifically disclosed exemplary embodiments are presented only to illustrate the general concepts of the present invention, and the present invention is not limited to these specific exemplary embodiments. Additionally, a typical "transmissive material" can have a sufficient visible light transmittance in the practice of the present invention to enable viewing of substances through the transmissive material, but the "transmissive material" need not be transmissive to visible light and can be translucent or opaque.

[0043] A non-limiting transmissive material 10 incorporating the features of the present invention is shown in FIG. 1. The transmissive material 10 can have any desired visible light, infrared, or ultraviolet transmission and / or reflection. For example, the transmissive material 10 can have any desired amount of visible light transmission, such as greater than 0% to a maximum of 100%. In one non-limiting embodiment, the transmissive material 10 can have different visible light, infrared, or ultraviolet transmission and / or reflection depending on the direction from which the transmissive material 10 is viewed.

[0044] The transmissive material 10 of FIG. 1 is in the form of a conventional multi-pane glass unit and includes a first ply 12 having a first major surface 14 (first face) and an opposing second major surface 16 (second face). In the non-limiting embodiment shown, the first major surface 14 faces the exterior of the building, i.e., the outer major surface, and the second major surface 16 faces the interior of the building. The transmissive material 10 also includes a second ply 18 having an outer (first) major surface 20 (third face) and an inner (second) major surface 22 (fourth face) and spaced apart from the first ply 12. This numbering of the ply surfaces follows the conventional practice in the window glazing art. The first ply and the second ply 12, 18 can be adhesively bonded together in any suitable manner such as being adhesively bonded to a conventional spacer frame 24. A space or chamber 26 is formed between the two plies 12, 18. The chamber 26 can be filled with a selected atmosphere such as air or a non-reactive gas such as argon or krypton gas. The coating 100 (or any of the other coatings described below) is formed on at least a portion of one of the plies 12, 18, such as but not limited to, on at least a portion of the second face 16 or on at least a portion of the third face 20. However, the coating can also be on the first face or the fourth face, if desired. Examples of multi-pane glass units can be found, for example, in U.S. Pat. Nos. 4,193,236, 4,464,874, 5,088,258, and 5,106,663.

[0045] In a broad implementation of the present invention, the ply 12, 18 of the transmissive material 10 can be of the same or different materials. The ply 12, 18 can include any desired material having any desired properties. For example, one or more of the ply 12, 18 can be transparent or translucent to visible light. "Transparent" means having visible light transmission greater than 0% up to a maximum of 100%. Alternatively, one or more of the ply 12, 18 can be translucent. "Translucent" means passing electromagnetic energy (e.g., visible light) but diffusing this energy so that the object on the side facing the observer is not clearly visible. Examples of suitable materials include plastic substrates (acrylic polymers such as polyacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate and their equivalents, polyalkyl methacrylates, polyurethane, polycarbonate, polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate and their equivalents, polyalkyl terephthalates, polysiloxane-containing polymers, or copolymers of any monomers for preparing these, or any mixtures thereof), ceramic substrates, glass substrates, or mixtures or combinations of any of the above, but are not limited thereto. For example, one or more of the ply 12, 18 can include conventional soda-lime silicate glass, borosilicate glass, or lead glass. The glass can be clear glass. "Clear glass" means glass that is not colored or glass that has not been colored. Alternatively, the glass can be colored glass or glass colored by other means. The glass can be annealed or heat-treated glass. As used herein, the term "heat-treated" means tempered or at least partially tempered. The glass can be of any type, such as conventional float glass, and can have any composition having any desired value of any optical property, such as visible transmission, ultraviolet transmission, infrared transmission, and / or total solar energy transmission."Float glass" means glass formed by the conventional float process in which molten glass is deposited on a molten metal bath and controllably cooled to form a float glass ribbon. Examples of float glass are disclosed in U.S. Patent Nos. 4,466,562 and 4,671,155.

[0046] The first ply and the second plies 12, 18 can each include, for example, clear float glass, or can be tinted or colored glass, or one of the plies 12, 18 can be clear glass and the other ply 12, 18 can be colored glass. Without limitation to the present invention, examples of suitable glasses for the first ply 12 and / or the second ply 18 are described in U.S. Patent Nos. 4,746,347, 4,792,536, 5,030,593, 5,030,594, 5,240,886, 5,385,872, and 5,393,593. The first ply and the second plies 12, 18 can have any desired dimensions, such as length, width, shape, or thickness. In one exemplary automotive transparent material, the first ply and the second ply can each have a thickness of from 1 mm to 10 mm, such as from 1 mm to 8 mm thick, 2 mm to 8 mm, 3 mm to 7 mm, 5 mm to 7 mm, 6 mm thick, etc.

[0047] Referring to FIG. 2, according to one limiting embodiment, the coating 100 includes a patterned coating 120 on at least a portion of the major surface of the substrate 112 (e.g., the second surface 116 of the first ply 12).

[0048] Referring to FIG. 3A, according to a non-limiting embodiment, the patterned coating 120 includes a first dielectric layer 122a on at least a portion of a major surface of the substrate 112 (e.g., the second surface 116 of the first ply 12). The first dielectric layer 122a may be a single layer or may include two or more films of an anti-reflection material and / or a dielectric material such as, but not limited to, metal oxides, alloy oxides, halides, nitrides, oxynitrides, or mixtures thereof. The first dielectric layer 122a may be transparent to visible light. Examples of suitable metal oxides or metal nitrides for the first dielectric layer 122a or any film therein include oxides, nitrides, and / or oxynitrides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum, silicon, and mixtures thereof. The metal oxide may have small amounts of other materials such as manganese in bismuth oxide, tin in indium oxide, etc. In addition, oxides containing zinc and tin (e.g., zinc stannate as defined below), oxides of indium tin alloys, oxides or nitrides of alloys or metal mixtures such as silicon nitride, silicon-aluminum nitride, or aluminum nitride may be used. Further, doped metal oxides such as antimony oxide or indium tin oxide, or nickel or boron-doped silicon oxide may be used. The first dielectric layer 122a may be a substantially single-phase film such as a metal alloy oxide film (e.g., zinc stannate), a mixture of phases composed of oxides of zinc and tin, or may be composed of multiple films. For example, the first dielectric layer 122a may include silicon oxide, silicon nitride, silicon-aluminum nitride, zinc / tin alloy oxide, zinc oxide, tin oxide, and / or titanium dioxide.

[0049] In a non-limiting embodiment, the first dielectric layer 122a may include a zinc / tin alloy oxide. "Zinc / tin alloy oxide" means both a true alloy and a mixture of oxides. The zinc / tin alloy oxide can be obtained from magnetron sputtering vacuum deposition from cathodes of zinc and tin. A non-limiting cathode can include zinc and tin in a ratio such as 10 wt% to 90 wt% zinc and 90 wt% to 10 wt% tin, or 5 wt% to 95 wt% zinc and 95 wt% to 5 wt% tin. However, other ratios of zinc to tin can also be used. A suitable alloy oxide that may be present in the first dielectric layer 122a is zinc stannate. "Zinc stannate" refers to Zn X Sn 1-X O 2-X (the composition of formula 1), where "x" varies in the range greater than 0 to less than 1. For example, "x" can be greater than 0 and can be any fraction or decimal between greater than 0 and less than 1. For example, when x = 2 / 3, formula 1 is Zn 2 / 3 Sn 1 / 3 O 4 / 3 which is more commonly described as "Zn2SnO4". The zinc stannate-containing film has, in a major amount in the film, one or more of the forms of formula 1.

[0050] In another non-limiting embodiment, the first dielectric layer 122a may include zinc oxide. Zinc oxide can be deposited from a zinc cathode containing other materials to improve the sputtering characteristics of the cathode. For example, the zinc cathode may 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 that case, the resulting zinc oxide film may include a small ratio of tin oxide, e.g., up to 10 wt% of tin oxide, e.g., up to 5 wt% of tin oxide. A coating layer deposited from a zinc cathode having up to 10 wt% of tin (added to enhance the conductivity of the cathode) is referred to herein as a "zinc oxide film" even though a small amount of tin may be present. A small amount of tin (e.g., 5 wt% or less, 10 wt% or less, etc.) in the cathode is thought to mainly form tin oxide in the zinc oxide layer.

[0051] In another non-limiting embodiment, the first dielectric layer 122a may include tin oxide.

[0052] In another non-limiting embodiment, the first dielectric layer 122a may include silicon nitride.

[0053] In one non-limiting embodiment, the first dielectric layer 122a may include a multilayer film structure. For example, the first dielectric layer 122a may include a first film such as an alloy oxide film. The first film may include a zinc / tin alloy oxide such as zinc stannate, silicon nitride, silicon-aluminum nitride, or tin oxide. The first dielectric layer 122a may include a second film on the first film, which may be a metal oxide film. For example, the second film may include zinc oxide.

[0054] In a non-limiting embodiment, the first dielectric layer 122a may include a multilayer film structure. For example, the first dielectric layer 122a may include a first film on a substrate. The first film may be a metal oxide, an alloy oxide film, a metal nitride, or an alloy nitride. The first film may include a zinc / tin alloy oxide such as zinc stannate, silicon nitride, silicon-aluminum nitride, or tin oxide. The first dielectric layer 122a may include a second film on the first film in a form that is in direct contact with the first film, and this may be a metal oxide film or an alloy oxide. For example, the second film may be zinc oxide or zinc stannate. On the second film, a third film that is in direct contact with the second film may include zinc oxide.

[0055] The thickness of the first dielectric layer 122a may be at least 1 nm, or at least 2 nm, or at least 5 nm. The thickness of the first dielectric layer 122a may be at most 20 nm, or at most 15 nm. The thickness of the first dielectric layer 122a may be in the range of 1 nm to 20 nm, or 2 nm to 20 nm, or 5 nm to 15 nm.

[0056] The patterned coating 120 includes an absorption layer 124 on at least a portion of the first dielectric layer 122a. The absorption layer, which may also be referred to as a reflective layer, may be made of any known absorption material. For example, the absorption layer 124 may include nickel, chromium, iron, stainless steel, niobium, silver, mixtures thereof, and / or combinations thereof. In one non-limiting embodiment, the absorption layer 124 may include silver below the critical state. As used herein, "silver below the critical state" refers to silver having a thickness below the critical state. The thickness of the absorption layer 124 may be greater than 0 nm, or at least 0.5 nm, or at least 1 nm. The thickness of the absorption layer 124 may be up to 50 nm, or up to 20 nm, or up to 15 nm, or up to 10 nm, or up to 5 nm. For example, the thickness of the absorption layer 124 may range from greater than 0 nm to 20 nm, or greater than 0 nm to 15 nm, or greater than 0 nm to 10 nm, or greater than 0 nm to 5 nm, or from 0.5 nm to 20 nm, or from 0.5 nm to 15 nm, or from 1 nm to 10 nm, or from 1 nm to 5 nm. The absorption layer 124 may have a tapered thickness. As used herein, "tapered thickness" refers to a layer thickness that increases or decreases throughout the layer, creating peaks and valleys of the material.

[0057] The absorption layer 124 may be present on the first portion 126 of the first dielectric layer 122a, where the first portion 126 does not cover the entire portion of the first dielectric layer 122a. The absorption layer 124 on the first portion 126 of the first dielectric layer 122a may have a first reflected aesthetic. The absorption layer 124 may not be present on the second portion 125 of the first dielectric layer 122a. By the absence of the absorption layer 124 on the second portion 125 of the first dielectric layer 122a, a second reflected aesthetic may be produced. The first reflected aesthetic may be different from the second reflected aesthetic. As used herein, the reflected aesthetic refers to the visible light reflection color (a*, b*, L*) as measured by the conventional CIE (1931) and CIELAB systems understood by those skilled in the art. When the first reflected aesthetic and the second reflected aesthetic are different, the contrast between the first reflected aesthetic and the second reflected aesthetic produces a reflected pattern. As used herein, the contrast between the first reflected aesthetic and the second reflected aesthetic is the difference in the reflection color between the first reflected aesthetic and the second reflected aesthetic, such as for producing a reflected pattern, which is the ΔE CMC in the reflection between the first reflected aesthetic and the second reflected aesthetic as described herein, which may be quantified by measurement of

[0058] The absorption layer 124 is formed on the first portion 126 of the first dielectric layer 122a and is not present on the second portion 125 of the first dielectric layer 122a, and a pattern may be generated using any method known in the art, such as masking, laser, and / or stripes.

[0059] The patterned coating 120 includes a second dielectric layer 128a over at least a portion of the absorption layer 124 and a first dielectric layer 122a (in a second portion 125 where the absorption layer 124 is absent). The second dielectric layer 128a may be a single layer or may include two or more layers of an anti-reflection material and / or a dielectric material such as, but not limited to, metal oxides, alloy oxides, metal nitrides, halides, alloy metal nitrides, oxynitrides, alloy metal oxynitrides, or mixtures thereof. The second dielectric layer 128a may be transparent to visible light. Examples of suitable metal oxides, metal nitrides, or metal oxynitrides for the second dielectric layer 128a or any film therein include oxides, nitrides, and / or oxynitrides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, aluminum, silicon, and mixtures thereof. The metal oxide may have small amounts of other materials such as manganese in bismuth oxide, tin in indium oxide, etc. Additionally, oxides containing zinc and tin (e.g., zinc stannate as defined below), oxides of indium tin alloys, alloys or metal mixtures such as silicon nitride, silicon-aluminum nitride, or aluminum nitride may be used. Further, doped metal oxides such as antimony oxide or indium tin oxide, or nickel or boron-doped silicon oxide may be used. The first dielectric layer 122a may be a substantially single-phase film such as a metal alloy oxide film (e.g., zinc stannate), a mixture of phases composed of oxides of zinc and tin, or may be composed of multiple films. For example, the second dielectric layer 128a may include silicon oxide, silicon nitride, zinc / tin alloy oxide, zinc oxide, and / or titanium dioxide.

[0060] In a non-limiting embodiment, the second dielectric layer 128a may include a multilayer film structure. For example, the second dielectric layer 128a may include a first film such as a metal oxide film. The first film may include zinc oxide. The second dielectric layer 128a may include a second film on the first film, which may be an alloy oxide film. For example, the second film may include a zinc / tin alloy oxide such as zinc stannate. The second dielectric layer 128a may include a third film on the second film. The third film may include Si3N4, SiAlN, SiON, SiAlON, zinc oxide, or some combination thereof.

[0061] The thickness of the second dielectric layer 128a may be at least 25 nm, or at least 30 nm, or at least 40 nm, or at least 50 nm. The thickness of the second dielectric layer 128a may be at most 100 nm, or at most 90 nm, or at most 80 nm, or at most 70 nm, or at most 60 nm. The thickness of the second dielectric layer 128a may be in the range of 25 nm to 100 nm, or 30 nm to 90 nm, or 40 nm to 80 nm, or 50 nm to 70 nm, or 50 nm to 60 nm.

[0062] Referring to FIG. 4A, in another non-limiting embodiment, the patterned coating 120 includes a first dielectric layer 122b on at least a portion of a major surface of the substrate 112 (e.g., the second surface 116 of the first ply 12). The first dielectric layer 122b may include a single film or a multi-film structure. For example, the first dielectric layer 122b may include a first film such as an alloy oxide film, a metal oxide film, an alloy nitride film, or a metal nitride film. The first film may include a zinc / tin alloy oxide such as zinc stannate, zinc oxide, silicon nitride, silicon-aluminum nitride, or tin oxide. The first dielectric layer 122b may include a second film on the first film, which may be a metal oxide film. For example, the second film may be zinc oxide or zinc stannate. Optionally, there may be a third film that may include zinc oxide. If the third film is present, the second film may be zinc stannate.

[0063] The first dielectric layer 122b may include any of the materials that may be used for the first dielectric layer 122a.

[0064] The thickness of the first dielectric layer 122b may be at least 25 nm, or at least 30 nm, or at least 40 nm, or at least 50 nm. The thickness of the first dielectric layer 122b may be at most 100 nm, or at most 90 nm, or at most 80 nm, or at most 70 nm, or at most 60 nm. The thickness of the first dielectric layer 122b may be in the range of 25 nm to 100 nm, or 30 nm to 90 nm, or 40 nm to 80 nm, or 50 nm to 70 nm, or 50 nm to 60 nm.

[0065] The patterned coating 120 may include an absorption layer 124 on at least a portion of the first dielectric layer 122b. The absorption layer 124 may be made of any known absorption material. For example, the absorption layer 124 may include nickel, chromium, iron, stainless steel, niobium, silver, mixtures thereof, and / or combinations thereof. In a limiting embodiment, the absorption layer 124 may include silver below the critical state. As used herein, "silver below the critical state" refers to silver having a thickness below the critical state. The thickness of the absorption layer 124 may be greater than 0 nm, or at least 0.5 nm, or at least 1 nm. The thickness of the absorption layer 124 may be at most 50 nm, or at most 20 nm, or at most 15 nm, or at most 10 nm, or at most 5 nm. For example, the thickness of the absorption layer 124 may range from greater than 0 nm to 20 nm, or greater than 0 nm to 15 nm, or greater than 0 nm to 10 nm, or greater than 0 nm to 5 nm, or from 0.5 nm to 20 nm, or from 0.5 nm to 15 nm, or from 1 nm to 10 nm, or from 1 nm to 5 nm. The absorption layer may have a tapered thickness. As used herein, "tapered thickness" refers to a layer thickness that increases or decreases throughout the layer, creating peaks and valleys of the material.

[0066] The absorption layer 124 may be present on a first portion 126 of the first dielectric layer 122b, where the first portion 126 does not cover the entire portion of the first dielectric layer 122b. The absorption layer 124 on the first portion 126 of the first dielectric layer 122b may have a first reflected aesthetic. The absorption layer 124 may not be present on a second portion 125 of the first dielectric layer 122b. By not having the absorption layer 124 on the second portion 125 of the first dielectric layer 122b, a second reflected aesthetic may be produced. The first reflected aesthetic may be different from the second reflected aesthetic.

[0067] The patterned coating 120 may include a second dielectric layer 128b and a first dielectric layer 122b where the absorption layer 124 is absent, on at least a portion of the absorption layer 124. The second dielectric layer 128b may include any of the same materials as the second dielectric layer 128a.

[0068] The second dielectric layer may include a single film or a multi-film structure. For example, the second dielectric layer 128b may include a first film such as an alloy oxide film or a metal oxide. The first film may include a zinc / tin alloy oxide such as zinc stannate, or zinc oxide. The second dielectric layer 128b may include a second film on the first film, which may be a metal oxide film, an alloy of metal oxides, a metal nitride film, an alloy of metal nitrides, a metal oxynitride film, or an alloy of metal oxynitrides. For example, the second film may include zinc oxide, zinc stannate, silicon nitride, or silicon oxynitride. The second dielectric layer 128b may include a third film on the second film, which may be an alloy oxide film. For example, the third film may include zinc stannate, zinc oxide, silicon nitride, or silicon oxynitride.

[0069] The thickness of the second dielectric layer 128b may be at least 1 nm, or at least 2 nm, or at least 5 nm. The thickness of the second dielectric layer 128b may be at most 20 nm, or at most 15 nm. The thickness of the second dielectric layer 128b may be in the range of 1 nm to 20 nm, or 2 nm to 20 nm, or 5 nm to 15 nm.

[0070] The thicknesses of the first dielectric layers 122a and 122b and the second dielectric layers 128a and 128b may be different. For example, in one non-limiting embodiment shown in FIG. 3A, the second dielectric layer 128a may be thicker than the first dielectric layer 122a. The ratio of the thickness of the second dielectric layer 128a to the thickness of the first dielectric layer 122a may be at least 1.5:1, or at least 2:1, or at least 3:1, or at least 4:1. The ratio of the thickness of the second dielectric layer 128a to the thickness of the first dielectric layer 122a may be at most 40:1, or at most 20:1, or at most 15:1, or at most 10:1, or at most 8:1, or at most 5:1, or at most 4:1. The ratio of the thickness of the second dielectric layer 128a to the thickness of the first dielectric layer 122a may be in the range of 1.5:1 to 40:1, or 2:1 to 20:1, or 3:1 to 15:1, or 3:1 to 10:1, or 3:1 to 8:1, or 3:1 to 5:1.

[0071] In another non-limiting embodiment shown in FIG. 4A, the first dielectric layer 122b may be thicker than the second dielectric layer 128b. The ratio of the thickness of the first dielectric layer 122b to the thickness of the second dielectric layer 128b may be at least 1.5:1, or at least 2:1, or at least 3:1, or at least 4:1. The ratio of the thickness of the first dielectric layer 122b to the thickness of the second dielectric layer 128b may be at most 40:1, or at most 20:1, or at most 15:1, or at most 10:1, or at most 8:1, or at most 5:1, or at most 4:1. The ratio of the thickness of the first dielectric layer 122b to the thickness of the second dielectric layer 128b may be in the range of 1.5:1 to 40:1, or 2:1 to 20:1, or 3:1 to 15:1, or 3:1 to 10:1, or 3:1 to 8:1, or 3:1 to 5:1.

[0072] When one of the first dielectric layers 122a, 122b and the second dielectric layers 128a, 128b is thicker than the other, the first reflected appearance and / or the second reflected appearance may vary depending on the direction of viewing the coated article 100 (i.e., the first side 114 with respect to the second side 116 of the substrate) due to the optical interference of the reflected appearance caused by the thickness of the dielectric layer, resulting in an asymmetric reflectance. As used herein, the term "asymmetric reflectance" means that the contrast between the first reflected appearance and the second reflected appearance of the coating from one side is different from the contrast of the coating from the opposite side. As used herein, "optical interference" refers to the interaction of light with the dielectric layer, the conductive layer and the optical absorption layer, and the distortion of light when passing through the dielectric layer, the conductive layer and the optical absorption layer. Thus, the contrast between the first reflected appearance and the second reflected appearance may be greater when viewing the coated article 100 from the first direction compared to when viewing the coated article 100 from the second direction. The first direction corresponds to the direction of viewing the coated article 100 through the side of the coated article 100 that includes the thicker dielectric layer between the first dielectric layers 122a, 122b and the second dielectric layers 128a, 128b. The second direction corresponds to the direction of viewing the coated article 100 through the side of the coated article 100 that includes the thinner dielectric layer between the first dielectric layers 122a, 122b and the second dielectric layers 128a, 128b.

[0073] As a result of the optical interference of the dielectric layer, it has been found that a thicker dielectric layer causes a greater contrast between the first reflected appearance of the first portion 126 and the second reflected appearance of the second portion 125. Due to the optical interference of a thicker dielectric layer (either the first dielectric layers 122a, 122b or the second dielectric layers 128a, 128b), the contrast between the first reflected appearance and the second reflected appearance may be high enough such that the pattern generated by this contrast is visible (to humans in the visible light spectrum) when the coated article 100 is viewed from the first direction. In contrast, the optical interference of a thinner dielectric layer (either the first dielectric layers 122a, 122b or the second dielectric layers 128a, 128b) behaves differently than that caused by a thicker dielectric layer, and as a result, the contrast between the first reflected appearance and the second reflected appearance is low enough such that the pattern generated by this contrast is not visible (to humans in the visible light spectrum) when the coated article 100 is viewed from the second direction.

[0074] As used herein, a pattern that is "visible" or "invisible" refers to the visibility of the pattern to the human eye in the visible light spectrum, unless otherwise specified. For example, alternative visibility as specified herein may include visibility to birds in the ultraviolet spectrum.

[0075] In a non-limiting embodiment, the pattern generated from this contrast is visible in the UV spectrum, and as a result, this pattern is visible to birds. For example, the pattern generated from this contrast may be visible from the first direction and may not be visible to birds from the second direction in the ultraviolet spectrum. Alternatively, the pattern generated from this contrast may be visible to birds from both the first and second directions in the ultraviolet spectrum.

[0076] As a result of either the first dielectric layers 122a and 122b or the second dielectric layers 128a and 128b having a greater thickness than the other, ΔE in reflection between the first reflected appearance and the second reflected appearance CMC may be large when the coated article 100 is viewed from the first direction as compared to when the coated article 100 is viewed from the second direction. For example, ΔE in reflection between the first reflected appearance and the second reflected appearance when the coated article 100 is viewed from the first direction CMC may be at least 6, or at least 7, or at least 8. For example, ΔE in reflection between the first reflected appearance and the second reflected appearance when the coated article 100 is viewed from the second direction CMC may be less than 6, or less than 5, or less than 4, or less than 3, or less than 2, or less than 1. ΔE in reflection between the first reflected appearance and the second reflected appearance when the coated article 100 is viewed from the second direction CMC compared to ΔE in reflection between the first reflected appearance and the second reflected appearance when the coated article 100 is viewed from the first direction CMC may be at least 2:1, or at least 3:1, or at least 5:1, or at least 8:1, or at least 10:1.

[0077] As used herein, ΔE CMC (CIELAB) is a measure of color change using an integrating sphere equipped with a 10° device including D65 illumination and specularly reflected light as described in ASTM designation: D 2244 - 05, unless otherwise specified. For example, a ΔE of up to 4 CMC may be sufficient to make a pattern formed from the contrast between the first reflected appearance and the second reflected appearance unrecognizable. As another example, a ΔE of at least 8 CMC may be sufficient to make a pattern formed from the contrast between the first reflected appearance and the second reflected appearance recognizable.

[0078] For example, in one non-limiting embodiment shown in FIG. 3A, the second dielectric layer 128a is thicker than the first dielectric layer 122a. As a result, the contrast between the first reflected appearance and the second reflected appearance is greater when viewing the coated article 100 from the second side 116 as compared to viewing the coated article 100 from the first side 114. Since the second dielectric layer 128a is thicker than the first dielectric layer 122a, the optical interference of the second dielectric layer 128a is high. As a result, the contrast between the first reflected appearance and the second reflected appearance may be high enough such that the pattern generated by this contrast is visible (to a human in the visible light spectrum) when viewing the coated article 100 from the second side 116 as shown in FIG. 3B. Due to the first dielectric layer 122a being thinner compared to the second dielectric layer 128a, the contrast between the first reflected appearance and the second reflected appearance may be low enough such that the pattern generated by this contrast is not visible (to a human in the visible light spectrum) when viewing the coated article 100 from the first side 114 as shown in FIG. 3C.

[0079] In one non-limiting embodiment, the pattern generated from this contrast is visible in the UV spectrum. As a result, this pattern is visible to birds. For example, the pattern generated from this contrast may be visible from the second side 116 of the coated article 100 and may not be visible to birds from the first side 114 of the coated article 100 in the ultraviolet spectrum. Alternatively, the pattern generated from this contrast may be visible to birds from both the first side 114 and the second side 116 of the coated article 100 in the ultraviolet spectrum.

[0080] As a result of the second dielectric layer 128a having a greater thickness than the first dielectric layer 122a, ΔE in reflection between the first reflected appearance and the second reflected appearance CMCWhen viewed from the second side 116, the coated article 100 may be larger compared to when viewed from the first side 114. For example, the ΔE in reflection between the first reflected aesthetics and the second reflected aesthetics when the coated article 100 is viewed from the second side 116 CMC may be at least 6, or at least 7, or at least 8. For example, the ΔE in reflection between the first reflected aesthetics and the second reflected aesthetics when the coated article 100 is viewed from the first side 114 CMC may be less than 6, or less than 5, or less than 4, or less than 3, or less than 2, or less than 1. The ΔE in reflection between the first reflected aesthetics and the second reflected aesthetics when the coated article 100 is viewed from the first side 114 CMC compared to the ΔE in reflection between the first reflected aesthetics and the second reflected aesthetics when the coated article 100 is viewed from the second side 116 CMC The ratio may be at least 2:1, or at least 3:1, or at least 5:1, or at least 8:1, or at least 10:1.

[0081] In another non-limiting embodiment shown in FIG. 4A, the first dielectric layer 122b is thicker than the second dielectric layer 128b, such that the contrast between the first reflected appearance and the second reflected appearance is greater when viewing the coated article 100 from the first side 114 as compared to viewing the coated article 100 from the second side 116. Since the first dielectric layer 122b is thicker than the second dielectric layer 128b, the optical interference of the first dielectric layer 122b is high, such that the contrast between the first reflected appearance and the second reflected appearance may be high enough that the pattern created by this contrast is visible (to a human in the visible light spectrum) when viewing the coated article 100 from the first side 114 as shown in FIG. 4C. Due to the thinner second dielectric layer 128b, the contrast between the first reflected appearance and the second reflected appearance may be low enough that the pattern created by this contrast is not visible (to a human in the visible light spectrum) when viewing the coated article 100 from the second side 116 as shown in FIG. 4B.

[0082] In one non-limiting embodiment, the pattern created from this contrast is visible in the UV spectrum, such that the pattern is visible to birds. For example, the pattern created from this contrast may be visible from the first side 114 of the coated article 100 and may not be visible to birds from the second side 116 of the coated article 100 in the ultraviolet spectrum. Alternatively, the pattern created from this contrast may be visible to birds from both the first side 114 and the second side 116 of the coated article 100 in the ultraviolet spectrum.

[0083] As a result of the first dielectric layer 122b being thicker than the second dielectric layer 128b, ΔE in the reflection between the first reflected appearance and the second reflected appearance CMCmay be greater when viewing the coated article 100 from the first side 114 as compared to viewing the coated article 100 from the second side 116. For example, the ΔE in reflection between the first reflected aesthetics and the second reflected aesthetics when viewing the coated article 100 from the first side 114 CMC may be at least 6, or at least 7, or at least 8. For example, the ΔE in reflection between the first reflected aesthetics and the second reflected aesthetics when viewing the coated article 100 from the second side 116 CMC may be less than 6, or less than 5, or less than 4, or less than 3, or less than 2, or less than 1. The ΔE in reflection between the first reflected aesthetics and the second reflected aesthetics when viewing the coated article 100 from the second side 116 CMC compared to the ΔE in reflection between the first reflected aesthetics and the second reflected aesthetics when viewing the coated article 100 from the first side 114 CMC The ratio may be at least 2:1, or at least 3:1, or at least 5:1, or at least 8:1, or at least 10:1.

[0084] In another non-limiting embodiment, the coating 100 may further include a functional coating 130. Referring to FIG. 5, in one non-limiting embodiment, the functional coating 130 may be on at least a portion of the patterned coating 120. Referring to FIG. 6, in another non-limiting embodiment, the functional coating 130 may be on at least a portion of the major surface of the substrate 112 (e.g., the second surface 116 of the first ply 12) and under the patterned coating 120 (i.e., between the substrate 112 and the patterned coating 120). The functional coating 130 can be deposited by any conventional method, such as conventional chemical vapor deposition (CVD) methods and / or physical vapor deposition (PVD) methods, but is not limited thereto. Examples of CVD processes include spray pyrolysis. Examples of PVD processes include electron beam evaporation and vacuum sputtering (magnetron sputter vapor deposition (MSVD)). Other coating methods, such as sol-gel deposition, may also be used, but are not limited thereto. In one non-limiting embodiment, the coating 120 can be deposited by MSVD. Examples of MSVD coating apparatuses and methods are well understood by those skilled in the art and are described, for example, in U.S. Pat. Nos. 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.

[0085] As used herein, "functional coating" refers to a coating that imparts functional benefits to a surface beyond surface decoration. Non-limiting examples include coatings that impart optical, structural, electrical, hygienic, thermal, and / or physiochemical properties to a surface. Non-limiting examples of functional coatings include solar control coatings, low-e (low emissivity) coatings, hydrophilic coatings, hydrophobic coatings, lipophilic coatings, low friction coatings, antimicrobial coatings, fingerprint resistant coatings, anti-fog coatings, self-cleaning coatings, easy-to-clean coatings, transparent conductive coatings, and at least one of combinations thereof. Non-limiting examples of suitable functional coatings and coated substrates are disclosed in U.S. Patent Application Publication Nos. 2017 / 0341977, 2018 / 0118614, 2019 / 0204480, U.S. Patents Nos. 7,335,421, 8,865,325, 9,932,267, and 10,479,724, and all of these disclosures are incorporated herein by reference as part of this specification.

[0086] Referring to FIG. 7, the coated article 100 may include two or more functional coatings 130, such as a first functional coating 130a on at least a portion of a major surface of the substrate 112 (e.g., the second surface 116 of the first ply 12) and under the patterned coating 120, and a second functional coating 130b on at least a portion of the patterned coating 120. When the coated article 100 includes two or more functional coatings 130a, 130b, the two or more functional coatings 130a, 130b may be the same or different functional coatings from each other, and may be any functional coatings known in the art, such as the functional coatings described herein.

[0087] The functional coating 130 may be a solar control coating. The functional coating 130 may be a low emissivity (low-e) coating. In one non-limiting embodiment, the functional coating 130 may include a continuous metal layer such as silver, gold, copper, platinum, or nickel-chromium alloy. In another non-limiting embodiment, the functional coating 130 may include an indium tin oxide layer and / or a fluorine-doped tin oxide layer. In another non-limiting embodiment, the functional coating may include a halogenated layer.

[0088] The present disclosure also includes a method of making a coated article. The method may include providing a substrate 112 having a first side 114 and a second side 116 opposite the first side 114. The method may optionally include depositing a functional coating 130 on at least a portion of the second side 116 of the substrate 112. The method may further include depositing a patterned coating 120 on at least a portion of the second side 116 of the substrate 112 (or on at least a portion of the functional coating 130).

[0089] Depositing the patterned coating 120 may include depositing first dielectric layers 122a, 122b on at least a portion of the second side 116 of the substrate. Depositing the patterned coating 120 may further include depositing an absorption layer 124 on a first portion 126 of the first dielectric layers 122a, 122b and not depositing the absorption layer 124 on a second portion 125 of the first dielectric layers 122a, 122b. The absorption layer 124 on the first portion 126 of the first dielectric layers 122a, 122b may generate a first reflected aesthetic, and the second portion 125 of the first dielectric layers 122a, 122b where the absorption layer 124 is not deposited may generate a second reflected aesthetic.

[0090] The deposition of the absorption layer 124 may include masking a second portion 125 of the first dielectric layers 122a, 122b with a mask and depositing the absorption layer 124 on at least a portion of the first dielectric layers 122a, 122b so as to prevent the absorption layer 124 from being deposited on the second portion 125 of the first dielectric layers 122a, 122b. The deposition of the absorption layer 124 may include selectively applying (e.g., in a striped pattern) the absorption layer 124 on a first portion 126 of the first dielectric layers 122a, 122b so that the absorption layer 124 is not applied on the second portion 125 of the first dielectric layers 122a, 122b. The deposition of the absorption layer 124 may include depositing the absorption layer 124 on at least a portion of the first dielectric layers 122a, 122b and laser removing the absorption layer 124 from the second portion 125 of the first dielectric layers 122a, 122b.

[0091] The method may include depositing second dielectric layers 128a, 128b on at least a portion of the absorption layer 124 and on the second portion 125 of the first dielectric layers 122a, 122b where the absorption layer 124 was not applied. The method may optionally include depositing a functional coating 130 on at least a portion of the second dielectric layers 128a, 128b.

[0092] The following examples illustrate various embodiments of the present invention. However, it should be understood that the present invention is not limited to these specific embodiments.

Example

[0093] In the following examples, "Rf" refers to the reflectance on the film side, and "Rg" refers to the reflectance on the glass side. The term "attenuated reflectance" refers to a reduction in reflectance to reduce the mirror effect. Three coated articles were manufactured using the materials and thicknesses shown in Table 1. The coated article of Example 1 produced a visible pattern when viewed from the first side of the substrate. The coated article of Example 2 produced a visible pattern when viewed from the second side of the substrate. The coated article of Example 3 produced a visible pattern when viewed from the second side of the substrate and had an attenuated internal reflectance. [Table 1]

Claims

Claim 1 A coated article comprising: a substrate having a first side and a second side opposite the first side; a patterned coating on at least a portion of the second side of the substrate; wherein the patterned coating comprises: a first dielectric layer on at least a portion of the second side of the substrate; an absorption layer on a first portion of the first dielectric layer, the absorption layer including a first reflected aesthetic and not present on a second portion of the first dielectric layer and including a second reflected aesthetic; a second dielectric layer on at least a portion of the absorption layer; wherein a contrast between the first reflected aesthetic and the second reflected aesthetic forms a pattern; and wherein the contrast between the first reflected aesthetic and the second reflected aesthetic is greater when the coated article is viewed from a first direction as compared to when the coated article is viewed from a second direction. Claim 2 The coated article of claim 1, wherein the contrast between the first reflected aesthetic and the second reflected aesthetic is greater when the coated article is viewed from the second side as compared to when the coated article is viewed from the first side. Claim 3 The coated article of claim 2, wherein a ratio of a thickness of the second dielectric layer to a thickness of the first dielectric layer is in a range of 2:1 to 20:

1. Claim 4 The coated article of claim 2, wherein the thickness of the second dielectric layer is in a range of 25 nm to 100 nm. Claim 5 The coated article of claim 2, wherein the thickness of the first dielectric layer is in a range of 2 nm to 20 nm. Claim 6 The coated article of claim 1, wherein the absorption layer comprises nickel, chromium, iron, stainless steel, niobium, silver below a critical state, or a combination thereof. Claim 7 The coated article of claim 1, further comprising a functional coating on at least a portion of the substrate and on and / or under the patterned coating. Claim 8 The coated article of claim 1, wherein the thickness of the absorption layer is in a range greater than 0 nm to 5 nm. Claim 9 The coated article according to claim 1, wherein the substrate comprises a glass or plastic material.

10. The coated article according to claim 1, wherein a combined thickness of the first dielectric layer and the second dielectric layer ranges from 40 nm to 60 nm.

11. The coated article according to claim 1, wherein the coated article is architectural glass or a laminate.

12. The coated article according to claim 2, wherein the contrast between the first reflected appearance and the second reflected appearance is visible by a bird in reflection when viewed from the second side of the coated article.

13. The first dielectric layer includes a thickness such that no pattern is visible in reflection when viewed from the first side of the coated article, The coated article according to claim 2, wherein the second dielectric layer includes a thickness such that a pattern is visible in reflection when viewed from the second side of the coated article.

14. ΔE in the reflection between the first reflected aesthetic and the second reflected aesthetic when viewed from the first side ＣＭＣ The coated article according to claim 2, wherein ＣＭＣ is less than 4.

15. The ΔE in the reflection between the first reflected aesthetic and the second reflected aesthetic when viewed from the second side ＣＭＣ is greater than 8, the coated article according to claim 2.

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