Antireflective coatings and articles and methods of forming antireflective coatings and articles

Abstract

Embodiments of antireflective coatings having a neutral color and articles including antireflective coatings having a neutral color are described. In one or more embodiments, a substrate includes a first major surface and an antireflective coating disposed on the first major surface of the substrate and having a reflective surface opposite the first major surface. In one or more embodiments, a point on the reflective surface has a single surface reflectance of less than 5 in angular color change ΔΕ θ under a D65 light source, where ΔΕ θ = √{(a* θ1 – a* θ2 ) 2 +(b* θ1 θ2 2 θ1 θ1 a* and b* values of the point measured from a first angle θ1 and a second angle θ2, where θ1 and θ2 are any two different viewing angles in a range of about 10° to about 60° spaced at least 5 degrees apart relative to a normal vector of the reflective surface.​​​​

Description

[0001] Cross-reference to related applications

[0002] This application is a divisional application of the invention patent application with application number 201980023273.9.

[0003] This application claims the benefit of priority to U.S. Provisional Application No. 62 / 637,666, filed March 2, 2018, in accordance with the Patent Act, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0004] This disclosure relates to antireflective coatings, articles including antireflective coatings, and methods of forming antireflective coatings. More specifically, this disclosure relates to articles having antireflective coatings, and more particularly to articles having antireflective coatings with reduced color shift over a wide range of viewing angles. Background Technology

[0005] Covering articles are frequently used to protect critical components within electronic products to provide user interfaces for input and / or display, and / or to perform other functions. These products include mobile devices (e.g., smartphones, MP3 players, and tablets). Covering articles also include building articles, transportation articles (e.g., articles for automotive applications, trains, aircraft, ships, etc.), and electrical articles. Some applications require that the colors displayed or perceived in reflection and / or transmission do not change significantly with changing viewing angles. If the reflected or transmitted colors do not change significantly with viewing angles, users of the product will perceive changes in the display's color or brightness, which may reduce the perceived quality of the display. In other applications, color changes may negatively impact aesthetic or other functional requirements.

[0006] The optical performance of covered articles can be improved by using various anti-reflective coatings. However, even with anti-reflective coatings, the reflected or transmitted color can still change significantly with different viewing angles, especially over wide viewing angles. In some applications, the reduced optical performance at wide viewing angles can be mitigated because the user of the product can slightly control the viewing angle to minimize perceptible color changes. For example, when using a mobile device (e.g., a telephone or tablet), the user can easily orient the device's display to reduce the viewing angle or reduce variations in the viewing angle. However, in other applications, the user may not have the same level of control over the viewing angle because, for example, the user's viewpoint is fixed relative to the article, the article's orientation is fixed relative to the user, or both. This could be the case in automotive or other vehicle applications, where the user's viewpoint is relatively fixed, and a given article (e.g., a dashboard, control panel, or display) can be viewed over a wide range of angles from the user's perspective and / or can be relatively fixed in orientation relative to the user.

[0007] Therefore, there is a need for new anti-reflective coatings, overlay products with anti-reflective coatings, and methods for manufacturing them, which provide improved color uniformity over a wide range of viewing angles. Summary of the Invention

[0008] Embodiments of an antireflective article are described. In one or more embodiments, the article includes an antireflective coating having a near-neutral color over a wide range of viewing angles. In one or more embodiments, the article is a substrate on which the antireflective coating is disposed.

[0009] In one or more embodiments, the substrate includes a first main surface and a second main surface, wherein the second main surface is opposite to the first main surface and separates the thickness of the substrate from the first main surface. An anti-reflective coating is disposed on the first main surface of the substrate, and at a point on the anti-reflective coating opposite to the first main surface (at the reflective surface as described herein), the article exhibits an angular color change ΔE. θ Under a D65 light source, it exhibits a single surface reflectivity, defined as:

[0010] ΔE θ = √{(a* θ1 – a* θ2 ) 2 + (b* θ1 – b* θ2 ) 2}

[0011] Where a* θ1 With b* θ1 These are the a* and b* values ​​of the point measured from the first angle θ1, where a*θ2 With b* θ2 θ1 and θ2 are the a* and b* values ​​of a point measured from a second angle θ2, where θ1 and θ2 are any two different viewing angles spaced at least 5 degrees apart in the range of approximately 10° to approximately 60° relative to the normal vector of the reflecting surface. In one or more embodiments, ΔE θ Less than 5.

[0012] In one or more embodiments, the reflective surface of the substrate exhibits a unilateral reflective color at viewing angles ranging from about 10° to about 60°, or at all viewing angles ranging from about 10° to about 60°, wherein the a* value is from about -2 to about 1, and the b* value is from about -4 to about 1. In some embodiments, at a viewing angle of about 10°, the reflective surface exhibits a unilateral reflective color, wherein the a* value is from about -2 to about 0, and the b* value is from about -4 to about -1, and / or at a viewing angle of about 60°, the reflective surface exhibits a unilateral reflective color, wherein the a* value is from about -1 to about 1, and the b* value is from about -2 to about 1.

[0013] According to one or more embodiments, the antireflective coating comprises alternating stacks of high-refractive-index and low-refractive-index materials. The low-refractive-index material may be silicon dioxide (SiO2), while the high-refractive-index material may be niobium oxide (Nb2O5) or titanium oxide (TiO2). x In some embodiments, the stack is a four-layer stack, and may be a four-layer stack including a first niobium oxide (Nb2O5) layer disposed on a buffer layer, a first silicon dioxide (SiO2) layer disposed on the first niobium oxide layer, a second niobium oxide (Nb2O5) layer disposed on the first silicon dioxide layer, and a second silicon dioxide (SiO2) layer disposed on the second niobium oxide layer.

[0014] In one or more embodiments, the vehicle includes the aforementioned substrate, wherein the substrate is an interior surface of the vehicle (e.g., a dashboard cover, an indicator panel cover, a control panel cover, a center console cover, a steering wheel cover, a side door component cover, an entertainment unit cover, or a graphics or video display cover).

[0015] According to one or more embodiments, an anti-reflective coating is provided. The anti-reflective coating comprises alternating stacks of high-refractive-index and low-refractive-index materials and includes a reflective surface configured to face an observer. At a point on the reflective surface, the anti-reflective coating exhibits an angular color change ΔE. θ Under a D65 light source, it exhibits a single surface reflectivity, defined as:

[0016] ΔE θ = √{(a* θ1 – a* θ2 ) 2 + (b* θ1– b* θ2 ) 2}

[0017] Where a* θ1 With b* θ1 These are the a* and b* values ​​of the point measured from the first angle θ1, where a* θ2 With b* θ2 The values ​​of a* and b* at a point measured from the second angle θ2, where θ1 and θ2 are any two distinct viewing angles spaced at least 5 degrees apart in the range of approximately 10° to approximately 60° relative to the normal vector of the reflecting surface, and where ΔE θ Less than 5.

[0018] One or more embodiments include a method for producing an antireflective coating. The method includes the steps of: providing a substrate having a first main surface, and depositing an antireflective coating on the first main surface. The antireflective coating comprises a stack of alternating layers of silicon dioxide (SiO2) and niobium oxide (Nb2O5) disposed on the first main surface. At a point on the first main surface having the antireflective coating, the antireflective coating exhibits an angular color change ΔE. θ Under a D65 light source, it exhibits a single surface reflectivity, defined as:

[0019] ΔE θ = √{(a* θ1 – a* θ2 ) 2 + (b* θ1 – b* θ2 ) 2}

[0020] Where a* θ1 With b* θ1 These are the a* and b* values ​​of the point measured from the first angle θ1, where a* θ2 With b* θ2 The values ​​of a* and b* at a point measured from the second angle θ2, where θ1 and θ2 are any two different viewing angles spaced at least 5 degrees apart in the range of approximately 10° to approximately 60° relative to the normal vector of the first principal surface, and where ΔE θ Less than 5.

[0021] It should be understood that the above general description and the following detailed description are merely exemplary and intended to provide an overview or framework for understanding the nature and characteristics of the claims. The accompanying drawings are included to provide further understanding and are incorporated in and form part of this specification. The drawings illustrate one or more embodiments and, together with the description, illustrate the principles and operation of various embodiments. Attached Figure Description

[0022] Figure 1 It is a side view of an article having an anti-reflective coating according to one or more embodiments;

[0023] Figure 2 It is according to one or more embodiments having Figure 1 A side view of the article showing a detailed view of the multi-layered anti-reflective coating;

[0024] Figure 3 It is according to one or more embodiments having including Figure 2 Side view of an article with an anti-reflective coating and an additional optical coating;

[0025] Figure 4 It is a side view of an article having an optical coating including an anti-reflective coating and a buffer layer according to one or more embodiments;

[0026] Figure 5 It is a side view of an article having an optical coating on a substrate having an anti-glare surface, according to one or more embodiments;

[0027] Figure 6 It is a graph showing simulated angular color changes of an antireflective coating according to one or more embodiments, compared to an alternative antireflective coating.

[0028] Figure 7 This is a diagram showing simulated angular color changes of an antireflective coating according to some embodiments of the present disclosure;

[0029] Figure 8 According to one or more embodiments Figure 7 A graph showing the one-sided reflectivity of the antireflective coating;

[0030] Figure 9A and Figure 9B It is a graph of a* and b* values ​​versus reflectance measured at various angles of the example according to one or more embodiments;

[0031] Figure 10A Figure 10B is a graph of a* and b* values ​​versus reflectance measured at various angles of the example according to one or more embodiments;

[0032] Figure 11 This is a graph of measured color values ​​of unilateral reflectance for examples of some embodiments of this disclosure;

[0033] Figures 12A to 12HH It is a graph of the a* and b* values ​​of a sample measured at various angles according to one or more embodiments, versus reflectance.

[0034] Figure 13 It is a graph of the brightness reflectance of the antireflective coating according to one or more embodiments;

[0035] Figure 14 It is a graph showing the color performance of the antireflective coating according to one or more embodiments;

[0036] Figure 15 It is a graph of the specular reflectivity of the antireflective coating according to one or more embodiments;

[0037] Figure 16 It is a contrast ratio diagram of a display with an anti-reflective coating according to one or more embodiments; and

[0038] Figure 17 It is a diagram showing the angular color change of the antireflective coating according to one or more embodiments. Detailed Implementation

[0039] Various embodiments and examples will now be shown in detail with reference to the accompanying drawings.

[0040] The embodiments discussed herein relate to an anti-reflective (AR) coating that exhibits substantially no color change at various viewing angles, including large viewing angles. Therefore, an improved and stable reflective color surface coating that provides a uniform neutral color can be obtained (particularly for large viewing angles and / or large surface areas or curved surfaces). This AR coating can be used with large cover glass that may have ink decorations or other decorative or design components. By providing a uniform neutral color at large viewing angles and / or large or curved surface areas, users can enjoy such decorations or designs without distracting or unpleasant color variations on the surface or at different viewing angles.

[0041] The aforementioned issues are particularly relevant to automobiles or vehicle interiors, where interior surfaces are exposed to harsh and dynamic lighting conditions. Furthermore, vehicles are increasingly equipped with displays and other surfaces covered by glass. For example, current or future vehicles may have glass covering all or part of the dashboard, command panel, center console, steering wheel, side doors, roof, seatbacks, and other interior surfaces. Displays can be present on any or all of these surfaces. However, the position and / or viewing angle of the vehicle occupant relative to the interior surfaces are relatively fixed. This lack of control over viewing position and / or angle, coupled with harsh and constantly changing lighting conditions, presents unique challenges within the vehicle interior. For instance, in addition to the expectations of vehicle manufacturers and users for uniform and aesthetically pleasing interior surfaces and displays, practicality is also important. Poor optical performance or color variations over a range of viewing angles or large surface areas can negatively impact the user's ability to fully utilize information that may be displayed on these interior surfaces. Therefore, as provided by the embodiments disclosed herein, the ability to provide uniform neutral color over large viewing angles and / or large surface areas can allow for an improved user experience in a vehicle.

[0042] While vehicle interiors represent a particularly useful application for the AR coatings described herein, the embodiments disclosed herein are not limited to these scenarios and can be used in any scenario where an anti-reflective coating can be applied. Therefore, the following discussion focuses on AR coatings on articles of manufacture and can include any number of objects, substrates, or surfaces (including glass surfaces and glass used in vehicle interiors).

[0043] Reference Figure 1 Article 100 according to one or more embodiments may include a substrate 110 and an antireflective coating 120 disposed on the substrate. The substrate 110 includes opposing primary surfaces 112, 114 and opposing secondary surfaces 116, 118, wherein the lengths of the secondary surfaces 116, 118 define the thickness t of the substrate 110. Figure 1 In the illustration, the anti-reflective coating 120 is shown to be disposed on the first main surface 112; however, in addition to being disposed on the first main surface 112 or not disposed on the first main surface 112, the anti-reflective coating 120 may be disposed on one or both of the second main surface 114 and / or the opposite subsurface. The anti-reflective coating 120 forms an anti-reflective surface 122.

[0044] The antireflective coating 120 comprises at least one layer of at least one material. The term "layer" may include a single layer or may include one or more sublayers. Such sublayers may be in direct contact with each other. Sublayers may be formed of the same material or two or more different materials. In one or more alternative embodiments, these sublayers may have an intermediate layer of different materials disposed therebetween. In one or more embodiments, a layer may include one or more connected and uninterrupted layers, and / or one or more discontinuous and discontinuous layers (i.e., layers formed of different materials adjacent to each other). Layers or sublayers may be formed by any method known in the art, including discrete deposition or continuous deposition processes. In one or more embodiments, layers may be formed using only continuous deposition processes, or alternatively, layers may be formed using only discrete deposition processes.

[0045] The thickness of the antireflective coating 120 may be about 200 nm or greater, while still providing an article of manufacture exhibiting the optical properties described herein. In some instances, the thickness of the optical coating 120 may range from about 200 nm to about 300 nm, about 240 nm to about 300 nm, about 240 nm to about 280 nm, about 240 nm to about 260 nm, about 250 nm to about 260 nm, or about 250 nm to about 255 nm, and all ranges and subranges therein.

[0046] As used herein, the term "set on" includes coating, depositing, and / or forming a material on a surface using any method known in the art. The set material may constitute a layer as defined herein. The phrase "set on" includes forming a material onto a surface such that the material is in direct contact with the surface, and also includes forming a material on a surface with one or more intermediate materials situated between the set material and the surface. One or more intermediate materials may constitute a layer as defined herein.

[0047] like Figure 2 As shown, the anti-reflective coating 120 may include multiple layers (120A, 120B). In one or more embodiments, the two or more layers may be characterized by having different refractive indices than each other. For example, in some embodiments, the multiple layers may include a first layer 120A with a relatively high refractive index and a second layer 120B with a relatively low refractive index. The difference in refractive index between the first layer and the second layer may be about 0.01 or greater, 0.05 or greater, 0.1 or greater, or even 0.2 or greater. Figure 2 In the embodiment shown, the anti-reflective coating comprises two sections, each section having two layers (120A, 120B).

[0048] Generally, antireflective coatings can comprise a variety of numbers of layers (e.g., 4 layers, 6 layers, etc.). One or more embodiments disclosed herein can achieve the advantages of improved color neutrality and limited or no angular color variation, wherein the antireflective coating has only four layers. Figure 2 One embodiment is an example in which the antireflective coating 120 comprises four layers: a first high refractive index layer 120A1, a first low refractive index layer 120B1, a second high refractive index layer 120A2, and a second low refractive index layer 120B2. By using only four layers to achieve improved optical performance, embodiments of this disclosure can provide simple and / or thin and cost-effective antireflective coatings with excellent performance.

[0049] As used herein, the term "RI" refers to the nominal refractive index, while the terms "low RI" and "high RI" refer to the relative magnitudes of the nominal RI values ​​(e.g., low RI < high RI). In one or more embodiments, when used with the first layer 120B, the term "low RI" includes a range of about 1.3 to about 1.7 or 1.75, or about 1.4 to about 1.55 or 1.5. In one or more embodiments, when used with the second layer 120A, the term "high RI" includes a range of about 1.7 to about 2.5 (e.g., about 1.85 or greater). In some cases, the ranges of low RI and high RI may overlap; however, in most cases, the layers of the antireflective coating 120 have a general relationship with respect to RI: low RI < high RI.

[0050] Exemplary materials suitable for the antireflective coating 120 include silicon dioxide (SiO2) and niobium oxide (Nb2O5). Other suitable materials include Al2O3, GeO2, SiO, and AlO. x N y AlN, SiN x SiO x N y Si u Al v O x N y Ta2O5, TiO xAlternatively, TiO2, ZrO2, TiN, MgO, MgF2, BaF2, CaF2, SnO2, HfO2, Y2O3, MoO3, DyF3, YbF3, YF3, CeF3, polymers, fluoropolymers, plasma-polymerized polymers, siloxane polymers, silsesquioxanes, polyimides, fluorinated polyimides, polyetherimides, polyethersulfone, polyphenylsulfone, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, acrylic polymers, polyurethane polymers, polymethyl methacrylate, other materials suitable for scratch-resistant layers as referenced below, and other materials known in the art. Some examples of suitable materials for the first layer 120A include Nb2O5, Si u Al v O x N y Ta2O5, AlN, Si3N4, AlO x N y SiO x N y HfO2, TiO2, ZrO2, Y2O3, Al2O3, MoO3, and diamond-like carbon can minimize the oxygen content of the first 120A layer, especially in SiN. x or AlN x In the material. AlO x N y The material can be considered as oxygen-doped AlN x And can have AlN x A crystalline structure (e.g., wurtzite) is acceptable, but an AlON crystalline structure is not required. Some examples of suitable materials for the second layer 120B include SiO2, Al2O3, GeO2, SiO, and AlO. x N y SiO x N y Si u Al v O x N y Materials containing nitrogen, such as MgO, MgAl2O4, MgF2, BaF2, CaF2, DyF3, YbF3, YF3, and CeF3, can be used to minimize the nitrogen content of the second layer 120B (e.g., in materials such as Al2O3 and MgAl2O4). In cases where a material with a moderate refractive index is desired, some embodiments may use AlN and / or SiO2. x N y .

[0051] exist Figure 3In the illustrated embodiment, the optical coating 130 disposed on the substrate 110 may include a functional layer 131 on top of the antireflective coating 120. The functional layer 131 may include a low-friction coating, an oleophobic coating, or an easy-to-clean coating. The functional layer 131 may include a material with a refractive index lower than that of the second layer 120B. In some embodiments, the functional layer 131 may include a high-RI layer that also exhibits high hardness. In some embodiments, the functional layer 131 may include an additional coating (e.g., the additional coating may include a low-friction coating, an oleophobic coating, or an easy-to-clean coating) disposed on top of the topmost air-side low-RI layer. Furthermore, when adding to the topmost air-side layer containing the low-RI layer, adding a low-RI layer with a very low thickness (e.g., about 10 nm or less, about 5 nm or less, or about 2 nm or less) has minimal impact on optical performance. The low-RI layer with a very low thickness may include SiO2, an oleophobic or low-friction layer, or a combination of SiO2 and an oleophobic material. Exemplary low-friction layers may include diamond-like carbon, which (or one or more layers of optical coating) may exhibit a coefficient of friction of less than 0.4, less than 0.3, less than 0.2, or even less than 0.1.

[0052] like Figure 4 As shown, the antireflective coating 120 may include a buffer layer 140 disposed on the substrate 110, such that the buffer layer 140 is disposed between the substrate 110 and two or more layers (120A, 120B). The thickness of the buffer layer 140 may be from about 0 nm to about 50 nm, from about 20 nm to about 30 nm, or greater than or equal to about 25 nm. An exemplary suitable material for the buffer layer 140 includes silicon dioxide (SiO2). However, other suitable materials exist for the buffer layer. For example, the refractive index of the exemplary material may have a refractive index close to that of the substrate, or within about 5% of the refractive index of the substrate.

[0053] like Figure 5 As shown, according to one or more embodiments, the first main surface 112 of the substrate 110 may be an anti-glare surface 142. The anti-glare surface 142 of one or more embodiments may be formed by a film or coating disposed on the first main surface of the substrate 110. The film may have a granular or textured surface to provide anti-glare functionality. In one or more embodiments, the first main surface 112 of the substrate 110 may be processed using an anti-glare processing technique to provide the anti-glare surface 142. For example, the anti-glare processing may include chemical or physical surface processing for forming irregularities, and / or etching the first main surface 112 to create etched regions 144. The etched regions may be created using, for example, hydrofluoric acid etching. According to some embodiments, the anti-glare surface 142 may include specific surface features as described below, and may be combined with the anti-reflective coating 120 to provide improved optical performance. Although Figure 5The illustration shows a first main surface 112 with an anti-glare surface 142, but the embodiment is not limited to the arrangement shown. The anti-glare surface may be disposed on a second main surface 114 instead of the first main surface 112, or it may be disposed on both the first and second main surfaces 112 and 114.

[0054] The anti-reflective coating disclosed herein can be used with any type of anti-glare surface, or not. According to one or more preferred embodiments, the anti-glare processing used is a two-step etching of the substrate surface, and the processed surface is characterized by a "flat bottom" topography, rather than some anti-glare surfaces with hemispherical textures. This combination of anti-glare surface and anti-reflective coating can produce a greater degree of superimposed image reduction compared to bare glass or an anti-glare coating without an anti-glare surface. For example, the superimposed image reduction factor of such an anti-glare surface alone can be about 4, while the superimposed image reduction factor of an anti-reflective surface alone can be about 2.5. Using the combination of anti-glare and anti-reflection, the superimposed image reduction factor can be from about 3 to about 3.5. The contrast ratio of the combined AG and AR can be about 5.1, while AR alone is 5.4, AG alone is about 2, and bare glass is about 3. The tactile sensation of the combined AG and AR can be about 7, while AG alone is 6, AR alone is 3, and bare glass is 1.

[0055] In some embodiments, when measurements are taken only at the antireflective surface 122 of the article (e.g., after the uncoated surface has been removed, e.g., Figure 1When the antireflective coating 120 reflects light (e.g., by using a refractive index-matching oil on the rear surface coupled with the absorber, or other known methods) within the optical wavelength range, the average light reflectance exhibited by the antireflective coating 120 is about 9% or less, about 8% or less, about 7% or less, about 6% or less, about 5% or less, about 4% or less, about 3% or less, or about 2% or less. The average reflectance (which may be a photometric average) can range from about 0.4% to about 9%, about 0.4% to about 8%, about 0.4% to about 7%, about 0.4% to about 6%, about 0.4% to about 5%, or about 0.4% to about 2%, and all ranges therein. In some embodiments, the average reflectance (which may be a photometric average) can range from about 0.2% to about 9%, about 0.2% to about 8%, about 0.2% to about 7%, about 0.2% to about 6%, about 0.2% to about 5%, or about 0.2% to about 2%, and all ranges therein. In some cases, the antireflective coating 120 may exhibit such an average light reflectance in other wavelength ranges (e.g., about 450 nm to about 650 nm, about 420 nm to about 680 nm, about 420 nm to about 700 nm, about 420 nm to about 740 nm, about 420 nm to about 850 nm, or about 420 nm to about 950 nm). In some embodiments, the antireflective surface 122 exhibits an average light transmittance of about 90% or higher, 92% or higher, 94% or higher, 96% or higher, or 98% or higher in the optical wavelength range. Unless otherwise stated, the average reflectance is measured at an incident illumination angle of about 0 degrees to about 10 degrees or about 8 degrees (however, such measurements may be provided at incident illumination angles of 45 degrees or 60 degrees).

[0056] Optical interference between reflected waves from the interface of optical coating 130 / air and reflected waves from the interface of optical coating 130 / substrate 110 may cause spectral reflection and / or transmission oscillations, resulting in an appearance color in article 100. The term "transmittance" as used herein is defined as the percentage of incident optical power transmitted through a given wavelength range through a material (e.g., article, substrate, or optical film or portion thereof). The term "reflectance" is similarly defined as the percentage of incident optical power reflected from a material (e.g., article, substrate, or optical film or portion thereof) within a given wavelength range. Transmittance and reflectance can be measured using specific linewidths. In one or more embodiments, the spectral resolution of the characteristics of transmittance and reflectance is less than 5 nm or 0.02 eV. The reflected color may be more pronounced. The angular color of the reflected image shifts with the viewing angle due to the shift in the spectral reflection oscillations at the incident illumination angle. The angular color of the transmitted image also shifts with the viewing angle due to the same shift in the spectral transmission oscillations at the incident illumination angle. The color and angular color shift observed at the incident angle are often distracting or offensive to device users, especially under illumination with sharp spectral characteristics (e.g., fluorescent lighting and some LED lighting), or particularly under uncontrolled ambient lighting conditions and / or wide viewing angles that may occur inside a vehicle. Transmitted angular color shift can also affect reflected color shift, and vice versa. Factors contributing to transmitted and / or reflected angular color shift may also include angular color shift due to a white spot caused by viewing angle or angular color deviation, which may be attributed to material absorption (slightly independent of angle) defined by a particular light source or testing system.

[0057] Oscillations can be described in terms of amplitude. As used herein, the term "amplitude" can include the change from peak to trough of reflectance or transmittance. The phrase "average amplitude" includes the change from peak to trough of reflectance or transmittance, averaged over some oscillation periods or sub-wavelength ranges within an optical wavelength range. As used herein, "optical wavelength range" includes the wavelength range from approximately 400 nm to approximately 800 nm (more specifically, from approximately 450 nm to approximately 650 nm).

[0058] Embodiments of this disclosure include an anti-reflective coating to provide improved optical performance in the presence of colorless or neutral colors, and / or minimal color shift when viewed at varying and / or large viewing angles under a light source. Exemplary light sources include any of CIE F2, CIE F10, CIE F11, CIE F12, and CIE D65. In one or more embodiments, the article exhibits an angular color shift (or angular color change) of about 5 or less, about 4 or less, about 3 or less, or about 2 or less of reflection between a reference viewing angle and any other viewing angle within the range provided herein. As used herein, the phrase “color shift” or “color change” (angle or reference point) refers to a change in a* and b* in the colorimetric system of CIE L*, a*, b* representing reflection. It should be understood that, unless otherwise stated, the L* coordinates of the article described herein are the same at any angle or reference point and do not affect the color shift. For example, the angular color shift ΔE θ The following equation (1) can be used to determine:

[0059] (1) ΔE θ (a*, b*) = √{(a*) θ1 – a* θ2 ) 2 + (b* θ1 – b* θ2 ) 2},

[0060] Where a* θ1 and b* θ1 The coordinates a* and b* of a point on the article represent the coordinates of a first viewing angle θ1 or a reference viewing angle (which may include perpendicular incidence or any viewing angle within the scope described herein), where a* θ2 and b* θ2The a* and b* coordinates represent the same point on the article at the second viewing angle θ2, where the first viewing angle θ1 differs from the second viewing angle θ2. In some cases, when viewed from various viewing angles from the reference viewing angle under a light source, the article exhibits an angular color shift of approximately 10 or less (e.g., 5 or less, 4 or less, 3 or less, or 2 or less). In some cases, the angular color shift of the reflection is approximately 4.1 or less, approximately 4.0 or less, approximately 3.9 or less, approximately 3.8 or less, approximately 3.7 or less, approximately 3.6 or less, approximately 3.5 or less, approximately 3.4 or less, approximately 3.3 or less, approximately 3.2 or less, approximately 3.1 or less, approximately 3.0 or less, approximately 2.9 or less, approximately 2.8 or less, approximately 2.7 or less, approximately 2.6 or less, approximately 2.5 or less, approximately 2.4 or less, approximately 2... 0.3 or less, about 2.2 or less, about 2.1 or less, about 2.0 or less, about 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, or 0.1 or less. In some embodiments, the angular color offset may be about 0. The light source may include standard light sources determined by the CIE, and includes A-series light sources (representing tungsten filament lighting), B-series light sources (daylight simulation light sources), C-series light sources (daylight simulation light sources), D-series light sources (representing natural daylight), and F-series light sources (representing various types of fluorescent lighting). In specific instances, when viewed at an incident illumination angle deviating from the reference illumination angle under a CIE F2, F10, F11, F12, or D65 light source, or more specifically under a CIE D65 light source, the angular color shift of the reflected light from the article is about 4 or less, about 3 or less, about 2 or less, or about 1 or less. More specifically, the angular color shift is measured under a CIE D65 1964 light source. More specifically, in some instances of the embodiments, the angular color shift of the reflected light according to equation (1) is about 4 or less when viewed at an angle ranging from about 10° to about 60°, about 3 or less when viewed at an angle ranging from about 10° to about 60°, or about 2 or less when viewed at an angle ranging from about 10° to about 60°, wherein the reference viewing angle may be in the range of about 10° to about 60° and is different from the viewing angle causing the color shift. For example, for a reference viewing angle of approximately 10°, the angle color shift can fall within the aforementioned range of viewing angles from approximately 10° to approximately 60°. Similarly, for reference viewing angles of approximately 15°, approximately 30°, approximately 45°, or approximately 60°, the angle color shift can fall within the aforementioned range of viewing angles from approximately 10° to approximately 60°.The examples below refer to viewing angles of 10°, 15°, 30°, 45°, and 60°, but viewing angles are not limited to these specific examples and can include any angle from about 10° to about 60°.

[0061] Although the reference viewing angles mentioned above are 10°, 15°, 30°, 45°, and 60°, these are merely examples, and embodiments of this disclosure may include any reference viewing angle within the range of about 0° to about 60° or about 10° to about 60°. For example, when the difference between the first or reference viewing angle and the second viewing angle is at least about 1 degree, 2 degrees, or about 5 degrees, the reference viewing angle may include perpendicular incidence (i.e., about 0 degrees to about 10 degrees), or deviations from perpendicular incidence of 5 degrees, 10 degrees, 15 degrees, 20 degrees, 25 degrees, 30 degrees, 35 degrees, 40 degrees, 50 degrees, 55 degrees, or 60 degrees. The range of incident viewing angles deviating from the reference illumination angle relative to the reference illumination angle can be from about 5 degrees to about 80 degrees, from about 5 degrees to about 70 degrees, from about 5 degrees to about 65 degrees, from about 5 degrees to about 60 degrees, from about 5 degrees to about 55 degrees, from about 5 degrees to about 50 degrees, from about 5 degrees to about 45 degrees, from about 5 degrees to about 40 degrees, from about 5 degrees to about 35 degrees, from about 5 degrees to about 30 degrees, from about 5 degrees to about 25 degrees, from about 5 degrees to about 20 degrees, from about 5 degrees to about 15 degrees, and all ranges and subranges therebetween.

[0062] In one or more embodiments, the color reflected by the article in the CIE L*, a*, b* colorimetric system is such that the distance or reference point color offset at a given angle between the reflection coordinates of the article and a reference point under a light source (which may include standard light sources determined by CIE, including light source A (representing tungsten filament illumination), light source B (daylight simulation light source), light source C (daylight simulation light source), D series light sources (representing natural daylight), and F series light sources (representing various types of fluorescent illumination)) is less than about 5 or less than about 2. In specific instances, when viewed at an incident illumination angle deviating from the reference illumination angle under a CIE F2, F10, F11, F12, or D65 light source, or more specifically under a CIEF2 light source, the color offset of the article reflected is about 2 or less. In other words, as defined herein, the article may present a reflected color (or reflected color coordinates) measured at antireflective surface 122 with a reference point color offset of less than about 2. Unless otherwise stated, the reflected color or reflected color coordinates are measured only on the antireflective surface 122 of the article. However, dual-surface measurement (including reflections on both sides of the article) or single-surface measurement (measuring only the reflections on the antireflective surface 122 of the article) can be used on the antireflective surface 122 of the article and on the opposite side of the article (i.e., Figure 1 The reflected color or reflected color coordinates described herein are measured on the main surface 114 of the article. Among these, single-surface reflectance measurement is often a more challenging metric for achieving low color or low color shift values ​​for anti-reflective coatings, and is relevant to applications where the back surface of an article is bonded to a light-absorbing medium (e.g., black ink) or an LCD or OLED device.

[0063] In one or more embodiments, the reference point may be the origin (0,0) (or color coordinates a*=0, b*=0), coordinates (a*=-2, b*=-2) in the CIE L*, a*, b* colorimetric system, or the reflective color coordinates of the substrate. It should be understood that, unless otherwise stated, the L* coordinates of the article described herein are the same as the reference point and do not affect the color offset. In cases where the reference point of the article is color-off relative to the substrate, the reflective color coordinates of the article are compared with the reflective color coordinates of the substrate.

[0064] In one or more specific embodiments, the reference point color offset of the reflected color may be less than 1 or even less than 0.5. In one or more specific embodiments, the reference point color offset of the reflected color may be 1.8, 1.6, 1.4, 1.2, 0.8, 0.6, 0.4, 0.2, 0, and all ranges and subranges thereof. When the reference point is at color coordinates a*=0, b*=0, the reference point color offset is calculated by equation (2).

[0065] (2) Reference point color offset = √((a* 制品 ) 2 + (b* 制品 ) 2 )

[0066] When the reference point has color coordinates a*=-2 and b*=-2, the color offset of the reference point is calculated by equation (3).

[0067] (3) Reference point color offset = √((a* 制品 +2) 2 + (b* 制品 +2) 2 )

[0068] When the reference point is the color coordinate of the substrate, the color offset of the reference point is calculated by equation (4).

[0069] (4) Reference point color offset = √((a* 制品 – a* 基板 ) 2 + (b* 制品 – b* 基板 ) 2 )

[0070] In some embodiments, the article may present a reflective color (or reflective color coordinates) such that when the reference point is any one of the substrate's color coordinates, color coordinates a*=0, b*=0, and coordinates a*=-2, b*=-2, the reference point color offset is less than 2.

[0071] In one or more embodiments, in the CIE L*, a*, b* colorimetric system, the b* value of the reflection exhibited by the article (measured only at the antireflective surface) can range from about -5 to about 1, from about -5 to about 0, from about -4 to about 1, or from about -4 to about 0 at all incident irradiation angles in the range of about 0 to about 60 degrees (or from about 0 degrees to about 40 degrees or from about 0 degrees to about 30 degrees).

[0072] In some embodiments, under light sources D65, A, and F2, at an incident irradiation angle ranging from about 0 degrees to about 60 degrees, the a* value of the reflection exhibited by the article (at the anti-reflective surface only) ranges from about -5 to about 2 (e.g., -4.5 to 1.5, -3 to 0, -2.5 to 0.25). In some embodiments, under light sources D65, A, and F2, at an incident irradiation angle ranging from about 0 degrees to about 60 degrees, the b* value of the reflection exhibited by the article (at the anti-reflective surface only) ranges from about -7 to about 0.

[0073] In some preferred embodiments, at a viewing angle of about 10 degrees, the a* value of the color coordinates of the unilateral reflection of the article can range from about -2 to about 0, and the b* value can range from about -4 to about -1. At a viewing angle of about 60 degrees, the a* value of the reflection of the article in these embodiments can further range from about -2.5 to about 1, and the b* value can further range from about -3.5 to about 1.

[0074] Within an optical wavelength range of approximately 400 nm to approximately 800 nm, the average light transmittance exhibited by the antireflective surface 122 of one or more embodiments of the article or one or more articles may be approximately 95% or higher (e.g., approximately 9.5% or higher, approximately 96% or higher, approximately 96.5% or higher, approximately 97% or higher, approximately 97.5% or higher, approximately 98% or higher, approximately 98.5% or higher, or approximately 99% or higher). In some embodiments, within an optical wavelength range of approximately 400 nm to approximately 800 nm, the average light reflectance exhibited by the antireflective surface 122 of the article or one or more articles may be approximately 2% or lower (e.g., approximately 1.5% or lower, approximately 1% or lower, approximately 0.75% or lower, approximately 0.5% or lower, or approximately 0.25% or lower). These light transmittance and light reflectance values ​​can be observed across the entire optical wavelength range or within a selected range of the optical wavelength range (e.g., within the 100 nm, 150 nm, 200 nm, 250 nm, 280 nm, or 300 nm wavelength range). In some embodiments, these light reflectance and light transmittance values ​​may be total reflectance or total transmittance (considering the reflectance or transmittance on the antireflective surface 122 and the opposing main surface 114), or they may be observed on one side of the article as if measured only on the antireflective surface 122 (without considering the opposing surface). Unless otherwise stated, the average reflectance or transmittance is measured at an incident illumination angle of about 0 degrees to about 10 degrees (however, such measurements may be provided at incident illumination angles of 45 degrees or 60 degrees).

[0075] In some embodiments, within an optical wavelength range, the average visible light reflectance of the articles of one or more embodiments or the antireflective surface 122 of one or more articles may be about 1% or less, about 0.7% or less, about 0.5% or less, or about 0.45% or less. These light reflectance values ​​may be presented at viewing angles ranging from about 0° to about 20°, from about 0° to about 40°, or from about 0° to about 60°. As used herein, light reflectance is used to simulate the response of the human eye by weighting reflectance with the wavelength spectrum according to the sensitivity of the human eye. According to known conventions such as the CIE color space conventions, light reflectance may also be defined as the illuminance of reflected light or the Y value of the trichromatic stimulus. The average light reflectance in equation (5) is defined as the spectral reflectance related to the spectral response of the eye multiplied by the light source spectrum and the CIE color matching function:

[0076] (5)

[0077] In some embodiments, the average unilateral light reflectance of an article, measured only at perpendicular or near-perpendicular incidence (e.g., 0 to 10 degrees) on the antireflective surface, is less than about 10%. In some embodiments, the average unilateral light reflectance is about 9% or less, about 8% or less, about 7% or less, about 6% or less, about 5% or less, about 4% or less, about 3%, or about 2% or less. In a particular embodiment, the maximum reflected color shift of one or more articles of the antireflective surface 122 (i.e., when the antireflective surface is measured only by unilateral measurement) while exhibiting the above-described average light reflectance value, is less than about 5.0, less than about 4.0, less than about 3.0, less than about 2.0, less than about 1.5, less than about 1.3, less than about 1.2, less than about 1.1, less than about 1.0, less than about 0.9, or less than about 0.8 over the entire viewing angle range of about 10 to about 60 degrees using a D65 light source. These maximum reflectance color shift values ​​represent the highest color point value measured at any angle deviating from approximately 10 degrees to approximately 60 degrees from perpendicular incidence, minus the lowest color point value measured at any angle within the same range. These values ​​can represent the maximum change in the a* value (a* 最高 -a* 最低 ), the maximum change in b* value (b* 最高 -b* 最低 ), the maximum change in the values ​​of a* and b*, or the maximum change in the magnitude √((a* 最高 -a* 最低 ) 2 +(b* 最高 -b* 最低 ) 2 ).

[0078] substrate

[0079] Substrate 110 may include inorganic materials and may include amorphous substrates, crystalline substrates, or combinations thereof. Substrate 110 may be formed from man-made materials and / or naturally occurring materials (e.g., quartz and polymers). For example, in some cases, substrate 110 may be characterized as organic and may be specifically polymeric. Examples of suitable polymers include, but are not limited to: thermoplastics (including polystyrene (PS) (including styrene copolymers and blends)), polycarbonate (PC) (including copolymers and blends), polyesters (including copolymers and blends, and including polyethylene terephthalate and polyethylene terephthalate copolymers), polyolefins (PO) and cyclic polyolefins (cyclic PO), polyvinyl chloride (PVC), acrylic polymers (including polymethyl methacrylate (PMMA) (including copolymers and blends)), thermoplastic polyurethane (TPU), polyetherimide (PEI), and blends of these polymers. Other exemplary polymers include epoxy resins, styrene resins, phenolic resins, melamine resins, and silicone resins.

[0080] In some specific embodiments, substrate 110 may specifically exclude polymer, plastic, and / or metal substrates. The substrate may be characterized as a substrate comprising an alkali (i.e., the substrate comprises one or more alkalis). In one or more embodiments, the refractive index exhibited by the substrate is in the range of about 1.45 to about 1.55.

[0081] In one or more embodiments, the amorphous substrate may comprise glass, which may be strengthened or unstrengthened. Examples of suitable glasses include soda-lime glass, alkali metal aluminosilicate glass, alkali metal-containing borosilicate glass, and alkali metal aluminoborosilicate glass. In some variations, the glass may be free of lithium oxide. In one or more alternative embodiments, substrate 110 may comprise a crystalline substrate (e.g., a glass-ceramic substrate, which may be strengthened or unstrengthened) or may comprise a single-crystal structure (e.g., sapphire). In one or more specific embodiments, substrate 110 comprises an amorphous substrate (e.g., glass) and a crystalline coating (e.g., a sapphire layer, a polycrystalline alumina layer, and / or a spinel (MgAl2O4) layer).

[0082] The substrate 110 may be substantially flat or sheet-like, or may be a bent or otherwise shaped or engraved substrate. In some preferred embodiments, the substrate 110 is a glass and glass substrate material as described above, including glass-ceramic materials, and has a thickness of less than 2.0 mm, or about 0.1 mm to about 2.0 mm, or about 0.3 mm to about 1.7 mm, or about 0.5 mm to about 1.1 mm, or about 0.7 mm to about 1.0 mm. The glass material of the substrate may be chemically strengthened. In some embodiments, the substrate 110 comprises glass or a glass substrate material bonded to a surface at a temperature below the glass transition temperature of the glass or glass substrate material, referred herein to as “cold-formable,” “cold-forming,” “cold-bending,” or “cold-bending” glass, material, or substrate. The surface of the cold-formed material may be non-planar, and the radius of curvature over all or part of the surface may be at least 900 mm, at least 500 mm, or at least 100 mm. The surface may include multiple radii of curvature in one or more regions of the surface, and the multiple radii of curvature may be parallel, non-parallel, coplanar, or non-coplanar axes of curvature. In this case, the substrate 110 may be cold-formed into one or more of these curved portions to produce a complexly curved substrate.

[0083] Substrate 110 may be substantially optically clear, transparent, and free of light scattering. In such embodiments, the average light transmittance exhibited by the substrate in the optical wavelength range may be about 85% or higher, about 86% or higher, about 87% or higher, about 88% or higher, about 89% or higher, about 90% or higher, about 91% or higher, or about 92% or higher. In one or more alternative embodiments, substrate 110 may be opaque in the optical wavelength range, or the average light transmittance exhibited may be less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, or less than about 0%. In some embodiments, these light reflectance and light transmittance values ​​may be total reflectance or total transmittance (considering the reflectance or transmittance on both main surfaces of the substrate), or may be observed on one side of the substrate (measured only on the antireflective surface 122, disregarding the opposing surfaces). Unless otherwise stated, the average reflectance or transmittance is measured at an incident illumination angle of approximately 0 degrees (however, such measurements may be provided at incident illumination angles of 45 degrees or 60 degrees). The substrate 110 may optionally be colored (e.g., white, black, red, blue, green, yellow, orange, etc.).

[0084] Various different processes can be used to provide the substrate 110. For example, when the substrate 110 includes an amorphous substrate (e.g., glass), various forming methods can include floating glass processes and downward stretching processes (e.g., fusion stretching and slot stretching).

[0085] Once formed, substrate 110 can be strengthened to form a reinforced substrate. As used herein, the term "reinforced substrate" can refer to a chemically strengthened substrate, for example, a substrate strengthened by ion exchange, in which smaller ions on the surface of the substrate are exchanged for larger ions. However, other strengthening methods known in the art (e.g., thermal tempering or utilizing the mismatch in the coefficients of thermal expansion between portions of the substrate to create a region of compressive stress and central tension) can be used to form a reinforced substrate.

[0086] In the case of chemically strengthening a substrate by ion exchange treatment, ions in the surface layer of the substrate are replaced or exchanged by larger ions having the same valence or oxidation state. Ion exchange treatment is typically performed by immersing the substrate in a molten salt bath containing larger ions to exchange with smaller ions in the substrate. Those skilled in the art will understand that parameters used for ion exchange treatment include, but are not limited to, the composition and temperature of the bath, immersion time, the number of times the substrate is immersed in the salt bath (or bath), the use of multiple salt baths, additional steps (e.g., annealing, cleaning, and the like), and are generally determined by the composition of the substrate and the desired compressive stress (CS) depth (or layer depth) of the compressive stress layer of the substrate resulting from the strengthening operation. For example, ion exchange of alkali metal glass substrates can be achieved by immersion in at least one molten bath containing a salt (e.g., but not limited to, nitrates, sulfates, chlorides containing larger alkali metal ions). The temperature of the molten salt bath is typically in the range of about 380°C to about 450°C, and the immersion time is in the range of about 15 minutes to about 40 hours. However, different temperatures and immersion times may also be used.

[0087] The degree of chemical strengthening achieved through ion exchange can be quantified based on parameters such as center tension (CT), surface core strength (CS), and depth of layer (DOL). Surface CS can be measured near the surface or within the strengthened glass at different depths. The maximum CS value can include the CS measured at the surface (CSs) of the strengthened substrate. The estimated CT for the internal region adjacent to the compressive stress layer within the glass substrate can be calculated based on CS, physical thickness t, and DOL. CS and DOL are measured using methods known in the art. These methods include, but are not limited to, the measurement of surface stress (FSM) using commercially available instruments (e.g., the FSM-6000 or similar manufactured by Luceo Co., Ltd. (Tokyo, Japan), and the methods for measuring CS and DOL described in ASTM 1422C-99, entitled “Standard Specification for Chemically Strengthened Flat Glass,” and ASTM 1279.19779, entitled “Standard Test Method for Non-Destructive Photoelastic Measurement of Edge and Surface Stresses in Annealed, Heat-Strengthened, and Fully-Tempered Flat Glass,” the contents of which are incorporated herein by reference in their entirety. Surface stress measurement depends on the accurate measurement of the stress optical coefficient (SOC) related to the birefringence of the glass substrate. Next, SOC is measured using methods known in the field, such as the fiber and four-pointbend methods (described in ASTM standard C770-98 (2008) entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," the contents of which are incorporated herein by reference in their entirety), and the bulk cylinder method. The relationship between CS and CT is given by expression (1):

[0088] CT = (CS • DOL) / (t – 2 DOL) (1),

[0089] Where t is the physical thickness (μm) of the glass article. In the various sections of this disclosure, CT and CS are expressed in megapascals (MPa), physical thickness t is expressed in micrometers (μm) or millimeters (mm), and DOL is expressed in micrometers (μm).

[0090] In one embodiment, the surface CS of the reinforced substrate 110 can be 250 MPa or higher, 300 MPa or higher, for example 400 MPa or higher, 450 MPa or higher, 500 MPa or higher, 550 MPa or higher, 600 MPa or higher, 650 MPa or higher, 700 MPa or higher, 750 MPa or higher, or 800 MPa or higher. The DOL of the reinforced substrate can be 10 μm or larger, 15 μm or larger, 20 μm or larger (e.g., 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, or larger), and / or CT can be 10 MPa or higher, 20 MPa or higher, 30 MPa or higher, 40 MPa or higher (e.g., 42 MPa, 45 MPa, or 50 MPa, or higher), but less than 100 MPa (e.g., 95, 90, 85, 80, 75, 70, 65, 60, 55 MPa, or lower). In one or more specific embodiments, the reinforced substrate has one or more of the following: a surface CS greater than 500 MPa, a DOL greater than 15 μm, and a CT greater than 18 MPa.

[0091] Exemplary glasses that can be used in the substrate may include alkali aluminosilicate glass compositions or alkali aluminoborosilicate glass compositions, but other glass compositions are also contemplated. Such glass compositions can be chemically strengthened by ion exchange treatment. An exemplary glass composition comprises SiO2, B2O3, and Na2O, wherein (SiO2 + B2O3) ≥ 66 mol% and Na2O ≥ 9 mol%. In an embodiment, the glass composition comprises at least 6 wt% alumina. In a further embodiment, the substrate comprises a glass composition having one or more alkaline earth metal oxides, such that the content of the alkaline earth metal oxides is at least 5 wt%. In some embodiments, a suitable glass composition further comprises at least one of K2O, MgO, and CaO. In a particular embodiment, the glass composition used in the substrate may contain 61 to 75 mol% SiO2; 7 to 15 mol% Al2O3; 0 to 12 mol% B2O3; 9 to 21 mol% Na2O; 0 to 4 mol% K2O; 0 to 7 mol% MgO; and 0 to 3 mol% CaO.

[0092] Further exemplary glass compositions suitable for substrates include: 60 to 70 mol% SiO2; 6 to 14 mol% Al2O3; 0 to 15 mol% B2O3; 0 to 15 mol% Li2O; 0 to 20 mol% Na2O; 0 to 10 mol% K2O; 0 to 8 mol% MgO; 0 to 10 mol% CaO; 0 to 5 mol% ZrO2; 0 to 1 mol% SnO2; 0 to 1 mol% CeO2; less than 50 ppm As2O3; and less than 50 ppm Sb2O3; wherein 12 mol% ≤ (Li2O + Na2O + K2O) ≤ 20 mol%, and 0 mol% ≤ (MgO + CaO) ≤ 10 mol%.

[0093] A further exemplary glass composition suitable for a substrate comprises: 63.5 to 66.5 mol% SiO2; 8 to 12 mol% Al2O3; 0 to 3 mol% B2O3; 0 to 5 mol% Li2O; 8 to 18 mol% Na2O; 0 to 5 mol% K2O; 1 to 7 mol% MgO; 0 to 2.5 mol% CaO; 0 to 3 mol% ZrO2; 0.05 to 0.25 mol% SnO2; 0.05 to 0.5 mol% CeO2; less than 50 ppm As2O3; and less than 50 ppm Sb2O3; wherein 14 mol% ≤ (Li2O + Na2O + K2O) ≤ 18 mol%, and 2 mol% ≤ (MgO + CaO) ≤ 7 mol%.

[0094] In certain embodiments, the alkali aluminosilicate glass composition suitable for the substrate comprises alumina, at least one alkali metal, more than 50 mol% SiO2 in some embodiments, at least 58 mol% SiO2 in other embodiments, and at least 60 mol% SiO2 in other embodiments, wherein the ratio of (Al2O3+B2O3) / Σ modifier (i.e., the sum of modifiers) is greater than 1, wherein the ratio of the components is expressed in mol% and the modifier is an alkali metal oxide. In certain embodiments, such a glass composition comprises: 58 to 72 mol% SiO2; 9 to 17 mol% Al2O3; 2 to 12 mol% B2O3; 8 to 16 mol% Na2O; and 0 to 4 mol% K2O, wherein the ratio of (Al2O3+B2O3) / Σ modifier (i.e., the sum of modifiers) is greater than 1.

[0095] In other embodiments, the substrate may include an alkali aluminosilicate glass composition comprising: 64 to 68 mol% SiO2; 12 to 16 mol% Na2O; 8 to 12 mol% Al2O3; 0 to 3 mol% B2O3; 2 to 5 mol% K2O; 4 to 6 mol% MgO; and 0 to 5 mol% CaO, wherein: 66 mol% ≤ SiO2 + B2O3 + CaO ≤ 69 mol%; Na2O + K2O + B2O3 + MgO + CaO + SrO > 10 mol%; 5 mol% ≤ MgO + CaO + SrO ≤ 8 mol%; (Na2O + B2O3) - Al2O3 ≤ 2 mol%; 2 mol% ≤ Na2O - Al2O3 ≤ 6 mol%; and 4 mol% ≤ (Na2O + K2O) - Al2O3 ≤ 10 mol%.

[0096] In an alternative embodiment, the substrate may comprise an alkaline aluminosilicate glass composition comprising: 2 mol% or more of Al2O3 and / or ZrO2, or 4 mol% or more of Al2O3 and / or ZrO2.

[0097] Example

[0098] The various embodiments will be further illustrated through the following examples.

[0099] According to one or more embodiments, an antireflective coating is provided, wherein the color shift of unilateral reflection exhibits superior optical performance compared to alternative or previously existing antireflective coatings. For example, such as Figure 6 As shown, the angular color change of the AR coating (coating C) according to an embodiment of the present disclosure is compared with two other coatings: a conventional AR coating with four layers and a deep blue coating A, and an alternative coating B with four layers and a light blue coating according to an embodiment of the present disclosure. The color change of each coating is measured according to three viewing angles of 0°, 30°, and 60°, which roughly correspond to the viewing angles of a car driver when viewing (1) the instrument cluster (“IC”) behind the steering wheel, (2) the center console (“CC”), and (3) the instrument panel (“PD”) or display on the passenger side. The AR coating of the present disclosure is shown as follows. Figure 6 The data point clusters around the origin of coating C exhibit a more pronounced neutral color, as well as... Figure 6 The data points IC, CC, and PD in the narrow range show lower color variation within the viewing angle range.

[0100] Examples of producing one or more embodiments using a reactive sputtering coating machine. For example, exemplary embodiments of the antireflective coating are described herein and provided in Table 1 below. Examples 1 and 2 of the antireflective coating are examples of the present invention having a buffer layer of silicon dioxide and a first Nb2O5 layer, a first SiO2 layer, a second Nb2O5 layer, and a second SiO2 layer arranged sequentially.

[0101]

[0102] Table 1 Examples 1 and 2 of anti-reflective coatings.

[0103] Examples 1 and 2 in Table 1 show the optical performance analysis of color shifts from 0° to 60°, and the optical performance results are shown in... Figure 7 and Figure 8 middle. Figure 7 The illustration shows the color shift of Examples 1 and 2 within the angular range of 0° to 60°. More specifically, at viewing angles near 0°, the initial a* values ​​of the colors in Examples 1 and 2 are in the range of approximately -2 to approximately 0, or more specifically, approximately -1.5 to approximately -1.0, while the b* values ​​within the same viewing angle range are in the range of approximately -2.5 to approximately -1.5. As the viewing angle increases, the a* and b* values ​​of Examples 1 and 2 shift upwards and to the right (as seen on the page). Figure 8 As shown, Examples 1 and 2 have low reflectivity as measured by R-sensitivity (%) at wide angle of incidence (“AOI”, in degrees). More specifically, the R-value is less than 2.0 from about 0° to about 50°, less than 1.0 from about 0° to about 43°, and about 0.2 to 0.4 at 0°.

[0104] The optical performance of Examples 1 and 2 was measured for confirmation, and the results are provided in Table 2, while the results for Example 1 are illustrated in the figure below. Figure 9A and Figure 9B Example 2 is illustrated in Figure 10A and Figure 10B Specifically, Table 2 shows the CIEL*, a*, and b* reflectance coordinates of Examples 1 and 2 at illumination angles of 10°, 15°, 30°, 45°, and 60° under a CIE 1964 illuminator of D65 with an illumination angle of 10°. The coordinates of a* and b* of Example 1 are illustrated in the figure. Figure 9A The measured reflectance Y is illustrated in the figure. Figure 9B Similarly, the coordinates of a* and b* in Example 2 are shown in the figure. Figure 10A In the figure, the measured reflectance Y is shown in the diagram. Figure 10B middle.

[0105]

[0106] Table 2. Reflection color coordinates for Examples 1 and 2.

[0107] Partly due to the above Figure 7 The upward and rightward offset of the values ​​of a* and b* in this disclosure is designed to have a* and b* values ​​starting within a specified range at low incident angles (e.g., about 0° or about 10°). That is, embodiments of this disclosure are not necessarily designed to have a "most neutral" color at low incident angles (because the color shift caused by increasing incident angle will cause the color to deviate from neutrality, so this is...). Figure 7 The origin of the graph (i.e., a*=0 and b*=0). Therefore, in one or more embodiments, as Figure 7 As shown in the chart, the anti-reflective coating is designed to have color values ​​below and / or to the left of the origin. Even at low incident angles, the color values ​​can be intentionally adjusted... Figure 7 The origin is offset, but the color values ​​within the viewing angle range can still be considered neutral or near-neutral. The terms "neutral" and "near-neutral" used in this article are intended to represent color values ​​that appear neutral to the human eye.

[0108] Further examples and comparative examples of the thickness of the antireflective coating are provided below in Tables 3 and 4. More specifically, 100 antireflective coating samples were prepared according to various aspects of embodiments of this disclosure. At a viewing angle of approximately 10°, the AR coating samples were designed to have an a* value ranging from approximately -2 to approximately 0, and a b* value ranging from approximately -4 to approximately -1. At a viewing angle of 10°, the target ranges of a* and b* are... Figure 11 The rectangle in the lower left quadrant of the chart is shown in Table 3 (as seen on the page). As shown in Table 3, the color of each sample was analyzed using a Konica Minolta CM700d integrating sphere spectrometer at an 8° viewing angle according to the specular inclusion component (SCI) method. Two independent measurements were performed for each sample, and the values ​​of L*, a*, b*, and Y in Table 3 were measured for each of these measurements for 100 samples.

[0109]

[0110]

[0111]

[0112]

[0113]

[0114] Table 3. Measured color data of 100 anti-reflective coating samples.

[0115] Measurements were also performed using an Agilent Cary 5000 UV-Vis-NIR spectrometer from 800 to 380 nm. The spectrometer was used with a Universal Measurement Accessory (UMA) for advanced absolute measurement modes at incident angles of 10°, 15°, 30°, 45°, and 60°. The sample was inserted into a sample holder within the UMA compartment to perform specular reflection measurements. A background scan was performed before each new measurement configuration (i.e., polarization). Measurements were performed by incidenting the instrument beam at varying angles in s and p polarization onto the sample-coated surface. First surface reflection was achieved by coupling the sample to 3390 black glass using an index-matching oil close to the sample. Coupling allows light to enter the sample and be absorbed by the black glass, thereby removing the influence of the second surface. The reflection measurements at each polarization and angle were corrected to the ratio of the calculated (true) first surface reflection of 7980 fused silica to the measured first surface reflection of 7980 fused silica. The standard Fresnel equation (found under the "Correction" tab) is used to measure the reflected intensity of s-polarized and p-polarized light. The s and p values ​​are averaged to obtain unpolarized light. All measurements are performed by incident the incident beam onto the coated surface. The UV-Vis-NIR spectrophotometer is configured with an integrating sphere (required for scattering media) or a standard axial detector. The wavelength range is typically 380 to 780 nm, but includes at least 400 to 700 nm.

[0116] For calculations, color or chromaticity is a weighted sum of the object's spectral transmittance (or reflectance), the spectral function of the human eye as a "standard observer," and the spectral distribution of the light source's power. D65, A, and F2 light sources are used at 2° and 10° observer positions. The color coordinates of the D65, A, and F2 light sources and the 10° observer are calculated based on visible light transmittance data. The wavelength range of 770nm to 380nm (in 2nm increments) is used for color calculations.

[0117] The SCI a* and b* values ​​in Table 3 are plotted on [date / time]. Figure 11 In the meantime, most samples fall within the target range of a* and b* values ​​(that is, within the meantime). Figure 11 (within the first rectangle in the lower left quadrant). Figure 11 It also includes the second rectangle shown in the dashed line, and... Figure 11All four quadrants of the chart overlap. This second rectangle represents the expected range of a* and b* values ​​for the AR coating when viewed at a wide viewing angle (e.g., 60°). This range is defined as a* value of approximately -2 to approximately 1, and a b* value of approximately -1 to approximately 1. The AR coating exhibits color values ​​within the first rectangle at lower viewing angles (i.e., 10°), color values ​​within the second rectangle at higher viewing angles (i.e., 60°), and near-neutral colors at viewing angles in between. The AR coating will have the desired performance for near-neutral colors and minimal color shift over a wide range of viewing angles.

[0118] Of the 100 samples in Table 3, 17 samples were selected to determine the precise layer thickness. These selected samples are sample numbers 04, 10, 12, 20, 21, 22, 25, 33, 65, 66, 67, 69, 71, 72, 74, 90, and 93. Layer thickness was modeled based on measured optical / color data. The modeled thicknesses of the silica buffer layer, first Nb₂O₅ layer, first SiO₂ layer, second Nb₂O₅ layer, and second SiO₂ layer for each sample are shown in Table 4. Table 4 also shows the average thicknesses of the silica buffer layer, first Nb₂O₅ layer, first SiO₂ layer, second Nb₂O₅ layer, and second SiO₂ layer for all 17 samples, with the deviation in thickness for each of these layers expressed as the difference between the maximum thickness and the average thickness.

[0119]

[0120] Table 4 shows the modeling thickness of the layers for the selected antireflective coating samples.

[0121] The thicknesses in Table 4 can be considered as physical properties (i.e., physical dimensions measured in units of distance). However, according to one or more embodiments, the layer thickness of the antireflective coating can be defined by optical thickness rather than physical thickness. The optical thickness t used herein... oIt is defined as physical thickness (nm) multiplied by refractive index, while optical thickness is based on a wavelength of 550 nm unless otherwise stated. Therefore, taking into account low-refractive-index materials having a refractive index of about 1.4 to about 1.5 and high-refractive-index materials having a refractive index of about 1.7 to about 2.5, embodiments of this disclosure include a four-layer antireflective coating, wherein from bottom to top there is a first high-refractive-index layer having an optical thickness range of about 15 nm to about 40 nm; a first low-refractive-index layer having an optical thickness range of about 50 nm to about 70 nm; a second high-refractive-index layer having an optical thickness range of about 75 nm to about 310 nm; and a second low-refractive-index layer having an optical thickness range of about 105 nm to about 135 nm. In a further embodiment of this disclosure, the four-layer antireflective coating may have, from bottom to top, a first high refractive index layer with an optical thickness range of about 20 nm to about 35 nm; a first low refractive index layer with an optical thickness range of about 55 nm to about 65 nm; a second high refractive index layer with an optical thickness range of about 80 nm to about 305 nm; and a second low refractive index layer with an optical thickness range of about 110 nm to about 130 nm.

[0122] As shown in Table 5 below, the first surface reflectance values ​​of the samples in Table 4 at all viewing angles of 10°, 15°, 30°, 45°, and 60° under a D65 light source were further analyzed, including the CIE color values ​​of a*, b*, and L*, the CIE tri-stimulus values ​​of X, Y, and Z, and the CIE chromaticity values ​​of x, y, and z. The a* and b* values ​​of sample numbers 4, 10, 12, 20, 21, 22, 25, 33, 65, 66, 67, 69, 71, 72, 74, 90, and 93 are illustrated in the figure. Figure 12A , Figure 12C , Figure 12E , Figure 12G , Figure 12I , Figure 12K , Figure 12M , Figure 12O , Figure 12Q , Figure 12S , Figure 12U , Figure 12W , Figure 12Y , Figure 12AA , Figure 12CC , Figure 12EE ,and Figure 12GG The Y value is shown in the figure. Figure 12B , Figure 12D , Figure 12F , Figure 12H , Figure 12J , Figure 12L , Figure 12N , Figure 12P , Figure 12R , Figure 12T , Figure 12V , Figure 12X , Figure 12Z , Figure 12BB , Figure 12DD , Figure 12FF ,and Figure 12HH .

[0123]

[0124]

[0125]

[0126]

[0127]

[0128] Table 5 shows the reflection color coordinates of the selected samples.

[0129] Certain ranges of a* and b* values ​​may be considered exemplary according to some specific embodiments. Therefore, since the a* and b* values ​​remain within specific ranges at one or more specific viewing angles or within a range of viewing instances, some embodiments of this disclosure can be interpreted as exemplary for certain applications. For example, in one or more embodiments, at a viewing angle of 10°, the a* value may range from about -2 to about 0, while the b* value may range from about -4 to about -1. In one or more embodiments, at a viewing angle of 60°, the a* value may range from about -1 to about 1, while the b* value may range from about -2 to about 1. In one or more embodiments, at a specific viewing angle in the range of about 10° to about 60°, or at all viewing angles in the range of about 10° to about 60°, the a* value may range from about -2 to about 1, while the b* value may range from about -4 to about 1. These exemplary ranges are determined for applications discussed herein (e.g., anti-reflective coatings for vehicle interiors). However, for various viewing angles, the expected ranges of a* and b* may vary based on the intended use, as some users or designers may prefer certain color shifts, or certain viewing angles in some applications may be less likely. In any case, the a* and b* values ​​in Table 5 can be used to determine whether the antireflective coating of the samples meets the expectations for a given use. For example, at 10°, samples 33, 65, 66, 67, 69, 71, 72, and 74 have a* values ​​greater than 0, falling outside the aforementioned preferred range. At 60°, samples 65, 67, and 69 have a* values ​​less than -1, also falling outside the aforementioned preferred range. At a viewing angle of 45°, samples 65, 67, and 90 also have maximum a* values ​​of 1.29, 1.10, and 1.62, respectively, falling outside the aforementioned preferred range. Conversely, sample numbers 4, 10, 12, 20, 21, 22, 25, 69, and 93 are within or closer to the expected range of a* and b*.

[0130] Using the a* and b* values ​​in Table 5, ΔE is calculated using equation (1) for the angular color change between each of the measured angles. θ For example, calculating ΔE θ Where the reference viewing angle or first angle θ1 is each of 10°, 15°, 30°, 45°, and 60°, and the second viewing angle θ2 is each of the other viewing angles not equal to the current θ1. The results are shown in Table 6. The rightmost column of Table 6 shows the maximum ΔE of the reference viewing angle θ1. θ Value (represented as ΔE) θ (θ1)).

[0131]

[0132]

[0133] Table 6 ΔE for the selected sample θ value.

[0134] Examples of anti-glare surfaces

[0135] According to one or more embodiments, the anti-reflective coating is used in conjunction with an anti-glare (AG) surface. The anti-glare surface treatment can affect the performance of the anti-reflective coating. Therefore, selecting an appropriate anti-glare surface can be important for optimal performance, especially in challenging usage environments such as vehicle interiors. In such environments, the anti-glare surface on the glass needs to have minimal glare and provide adequate anti-glare effect and feel, while meeting the required contrast ratio (CR) under sunlight. In this example, according to embodiments of this disclosure, samples were prepared using a chemically etched ultra-low glare (ULS) AG surface on a glass substrate made of Corning® Gorilla® glass with an anti-reflective coating, combined with an easy-clean (ETC) coating, to provide a stable color appearance with a wide viewing angle. Environmental contrast performance was evaluated at the system level to assess the impact of the AG / AR coating on sunlight viewability.

[0136] An anti-glare surface was fabricated on a Corning® Gorilla® glass substrate using a chemical etching method, enabling ultra-low flicker performance suitable for high-resolution displays up to 300 PPI. The optical properties of the anti-glare glass (including SCE / SCI, transmitted haze, gloss, image sharpness (DOI), and flicker) were then analyzed. More information about these properties and how to perform these measurements can be found in (1) C. Li and T. Ishikawa, Effective Surface Treatment on the Cover Glass for Auto-Interior Applications, SID Symposium Digest of Technical Papers Volume 1, Issue 36.4, pp. 467 (2016); (2) J. Gollier, G.A. Piech, S.D. Hart, J.A. West, H. Hovagimian, E.M. Kosik Williams, A. Stillwell, and J. Ferwerda, Display Sparkle Measurement and Human Response, SIDS Symposium Digest of Technical Papers Volume 44, Issue 1 (2013); and (3) J. Ferwerda, A. Stillwell, H. Hovagimian, and E.M. Kosik Williams, Perception of sparkle in anti-glare display screen, Journal of the SID, Vol. 22, Issue 2 (2014), which are incorporated herein by reference.

[0137] To achieve optimal readability, tactile feel on the glass surface, and aesthetic appearance for high-performance touch displays in applications such as automotive interiors, a balance of five metrics—SCE / SCI, transmitted haze, gloss, image sharpness (DOI), and flare—is crucial for maximizing the benefits of anti-glare. Flare is the micro-scattering interaction between the anti-glare surface and LCD pixels, creating bright spots that degrade image quality, especially at high resolutions. A method using a reference pixel power deviation (PPDr) is used to study flare effects on displays of different resolutions. For example, ultra-low flare anti-glare glass with less than 1% PPDr will have an invisible flare effect on displays with less than 300 pixels per inch (PPI). However, a maximum of 4% PPDr is acceptable, depending on end-user preference and the content displayed. In a vehicle or automotive interior environment, approximately 120 to approximately 300 PPI is acceptable, while displays exceeding 300 PPI have reduced values.

[0138] Figure 13 and Figure 14 The illustrations respectively show the calculated changes of a* and b* coordinates as a function of viewing angle for two examples (“AR2.0” and “AR3.0”) according to embodiments of the present disclosure. Figure 13 and Figure 14 As shown, the reflectivity remains below 1% from 0° to 40°, exhibiting a stable reflected color. At the system level, the ambient contrast ratio (CR) is a crucial factor for readability. Performing bidirectional reflectance distribution function (BRDF) and reflectance (SCI, SCE, and specular reflection) measurements provides a comprehensive understanding of the properties of the glass surface with the anti-reflective coating. The scattering and reflection coefficients extracted from the measurements are incorporated into the model, and the ambient contrast ratio is calculated assuming no screen influence on display properties (e.g., brightness (800 nits), reflectance (2%), and scattering coefficient (0.0018)). Modeling shows that the anti-reflective coating according to this disclosure will meet similar readability performance as other anti-reflective coatings, and this has been confirmed using actual samples.

[0139] like Figure 15 The illustration shows the specular reflection of two anti-reflective coatings (“AR1.0” and “AR2.0”) according to one or more embodiments, and an anti-reflective coating (“AR3.0”) according to one or more preferred embodiments, as a function of the incident angle, and compares this with calculated data for bare glass. The contrast ratio was measured under conditions where sunlight does not directly illuminate the display unit, but superimposed reflections reduce the readability of the content. This corresponds to the vehicle's center console (CC) reflecting the passenger's face, or, in a clear sky, the vehicle's instrument cluster (IC) reflecting the driver's face. Figure 16The illustration shows the contrast ratio of different viewing angles (AOV) or incident angles (AOI) of the light rays forming the image. Figure 16 The contrast ratio (CRD) of diffuse light compared to AR2.0 (22 vs. 23.5) was not significantly reduced, but AR3.0 demonstrated a significant advantage by exhibiting markedly better color uniformity than AR2.0. It should be noted that CRD is a measurement relevant to vehicle performance, where ambient light is diffuse. Figure 17 The diagram illustrates the color change (ΔE) from an angle of 8° to 60°. θ ), where θ1 equals 8°, and θ2 equals 15°, 30°, 45°, and 60°. ΔE θ ΔE represents the distance between color coordinates at different angles. θ A smaller value means the coating has a more uniform color when viewed from different angles. Therefore, reducing ΔE... θ The aim is to achieve a uniform appearance for the covering glass of different displays or surfaces in the vehicle (e.g., the instrument cluster (IC) at 0° to 10° to the driver, the center console (CC) at 30° to 45° to the driver, and the passenger-side display (PD) visible from the driver's seat at 60°). Therefore, the significant gain in color uniformity is achieved through ΔE. θ Quantification was performed on the slight decrease in CRD (almost a 4-fold improvement in color uniformity, while CRD was reduced by only 7%).

[0140] Additional examples of producing one or more embodiments using a reactive sputtering coating machine. For example, exemplary embodiments of the antireflective coating are described herein and provided in Table 7 below. Examples 3 to 10 of the antireflective coating are examples of the present invention having a buffer layer of silicon dioxide (adjacent to the substrate) and a first Nb2O5 layer, a first SiO2 layer, a second Nb2O5 layer, and a second SiO2 layer arranged sequentially.

[0141]

[0142] Table 7 Examples 3 to 10.

[0143] The optical properties of the color shift at the first surface reflection angle from 0° to 60° were analyzed using a D65 CIE 1964 light source, as shown in Examples 3 to 6 of Table 7. θ1 = 10°, while θ2 was 15°, 30°, 45°, and 60°. The measured results are shown in Table 8.

[0144]

[0145] A second aspect of this disclosure relates to a method for forming the article described herein. In one embodiment, the method includes the steps of: providing a substrate having a main surface in a coating chamber; creating a vacuum in the coating chamber; forming an optical coating as described herein on the main surface; optionally forming an additional coating on the optical coating comprising at least one of an easy-to-clean coating and a scratch-resistant coating; and removing the substrate from the coating chamber. In one or more embodiments, the optical coating and the additional coating are formed in the same coating chamber or in separate coating chambers without breaking the vacuum.

[0146] In one or more embodiments, the method may include the steps of: loading a substrate onto a carrier, and then using the carrier under loading-locked conditions to move the substrate in and out of different coating chambers to maintain a vacuum while moving the substrate.

[0147] Various deposition methods can be used to form the antireflective coating 120 and / or additional coating 140, including vacuum deposition techniques (e.g., chemical vapor deposition (e.g., plasma-enhanced chemical vapor deposition, low-pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, and plasma-enhanced atmospheric pressure chemical vapor deposition), physical vapor deposition (e.g., reactive or non-reactive sputtering or laser ablation), thermal or electron beam evaporation, and / or atomic layer deposition)). Liquid-based methods (e.g., spraying, dip coating, spin coating, or slot coating (e.g., using sol-gel materials)) can also be used. In the case of vacuum deposition, the antireflective coating 120 and / or additional coating 131 can be formed in a single deposition run using a continuous process. In some cases, vacuum deposition can be performed using a linear PECVD source.

[0148] In some embodiments, the method may include the step of controlling the thickness of the antireflective coating 120 and / or the additional coating 131 such that the target thickness variation of each layer along at least about 80% of the area of ​​the antireflective surface 122 or at any point along the substrate region does not exceed about 4%. In some embodiments, the thickness of the antireflective coating 120 and / or the additional coating 131 varies by no more than about 4% along at least about 95% of the area of ​​the antireflective surface 122.

[0149] Aspect (1) of this disclosure relates to an article comprising: a substrate having a first main surface and a second main surface, the second main surface being opposite to the first main surface and spaced apart from a first side by a thickness of the substrate; and an antireflective coating disposed on the first main surface and having a reflective surface opposite to the first main surface, wherein at a point on the reflective surface having the antireflective coating, the article comprises having an angular color change ΔE. θ The reflectivity of a single surface under a D65 light source is defined as: ΔE θ = √{(a*θ1 – a* θ2 ) 2 + (b* θ1 – b* θ2 ) 2}, where a* θ1 With b* θ1 These are the a* and b* values ​​of the point measured from the first angle θ1, where a* θ2 With b* θ2 The values ​​of a* and b* at a point measured from the second angle θ2, where θ1 and θ2 are any two distinct viewing angles spaced at least 5 degrees apart in the range of approximately 10° to approximately 60° relative to the normal vector of the reflecting surface, and where ΔE θ Less than 5.

[0150] Aspect (2) of this disclosure relates to an article of aspect (1), wherein the reflective surface comprises a unilateral reflective color at a viewing angle ranging from about 10° to about 60°, or at all viewing angles ranging from about 10° to about 60°, wherein the a* value is from about -2 to about 1, and the b* value is from about -4 to about 1.

[0151] Aspect (3) of this disclosure relates to an article of aspect (1) or aspect (2), wherein, at a viewing angle of about 10°, the reflective surface comprises a unilateral reflective color, wherein the a* value is about -2 to about 0 and the b* value is about -4 to about -1.

[0152] Aspect (4) of this disclosure relates to an article of any one of aspects (1) to (3), wherein, at a viewing angle of about 60°, the reflective surface comprises a unilateral reflective color, wherein the a* value is about -1 to about 1, and the b* value is about -2 to about 1.

[0153] Aspect (5) of this disclosure relates to an article of any of aspects (2) to (4), wherein the reflective surface comprises a unilateral reflective color at all viewing angles from about 10° to about 60°, wherein the a* value is from about -2 to about 1 and the b* value is from about -4 to about 1.

[0154] Aspect (6) of this disclosure relates to an article of any one of aspects (1) to (5), wherein θ1 and θ2 are any two different viewing angles within the range of about 10° to about 50°, about 10° to about 40°, about 10° to about 30°, about 10° to about 20°, about 20° to about 60°, about 30° to about 60°, about 40° to about 60°, or about 50° to about 60°.

[0155] Aspect (7) of this disclosure relates to an article of any one of aspects (1) to (5), wherein θ1 and θ2 are any two different viewing angles within the range of about 20° to about 30°, about 30° to about 40°, or about 40° to about 50°.

[0156] Aspect (8) of this disclosure relates to an article of any of aspects (1) to (7), wherein the antireflective coating comprises alternating stacks of high and low refractive index materials.

[0157] Aspect (9) of this disclosure relates to articles of aspect (8), wherein the low refractive index material contains a refractive index in the range of about 1.3 to about 1.7, and the high refractive index material contains a refractive index in the range of about 1.7 to about 2.5.

[0158] Aspect (10) of this disclosure relates to articles of aspect (9), wherein the low-refractive-index material comprises silicon dioxide (SiO2), and the high-refractive-index material comprises niobium oxide (Nb2O5) or titanium oxide (TiO2). n ).

[0159] Aspect (11) of this disclosure relates to an article of any one of aspects (8) to (10), wherein the stack comprises four layers.

[0160] Aspect (12) of this disclosure relates to an article of any one of aspects (8) to (11), wherein the antireflective coating further comprises a buffer layer, wherein the stack is disposed on the buffer layer.

[0161] Aspect (13) of this disclosure relates to an article of aspect (12), wherein the buffer layer comprises silicon dioxide.

[0162] Aspect (14) of this disclosure relates to an article of aspect (12) or aspect (13), wherein the buffer layer comprises a thickness ranging from about 20 nm to about 30 nm.

[0163] Aspect (15) of this disclosure relates to an article of any one of aspects (1) to (14), wherein the antireflective coating comprises a stack comprising a first niobium oxide (Nb2O5) layer disposed on a substrate, a first silicon dioxide (SiO2) layer disposed on the first niobium oxide layer, a second niobium oxide (Nb2O5) layer disposed on the first silicon dioxide layer, and a second silicon dioxide (SiO2) layer disposed on the second niobium oxide layer.

[0164] Aspect (16) of this disclosure relates to an article of aspect (15), wherein the thickness of the first niobium oxide layer is less than that of the second niobium oxide layer.

[0165] Aspect (17) of this disclosure relates to articles of aspect (15) or aspect (16), wherein the thickness of the first silicon dioxide layer is less than that of the second silicon dioxide layer.

[0166] Aspect (18) of this disclosure relates to an article of any one of aspects (15) to (17), wherein the first niobium oxide layer has a thickness of about 11 nm to about 13 nm.

[0167] Aspect (19) of this disclosure relates to an article of aspect (18), wherein the first niobium oxide layer has a thickness of about 11 nm to about 12 nm.

[0168] Aspect (20) of this disclosure relates to an article of any one of aspects (15) to (19), wherein the first silicon dioxide layer has a thickness of about 40 nm to about 45 nm.

[0169] Aspect (21) of this disclosure relates to an article of aspect (20), wherein the first silicon dioxide layer has a thickness of about 41 nm to about 44 nm.

[0170] Aspect (22) of this disclosure relates to an article of any one of aspects (15) to (21), wherein the second niobium oxide layer has a thickness of about 115 nm to about 125 nm.

[0171] Aspect (23) of this disclosure relates to an article of aspect (22), wherein the second niobium oxide layer has a thickness of about 116 nm to about 121 nm.

[0172] Aspect (24) of this disclosure relates to an article of aspect (23), wherein the second niobium oxide layer has a thickness of about 118 nm to about 120 nm.

[0173] Aspect (25) of this disclosure relates to an article of any one of aspects (15) to (24), wherein the second silicon dioxide layer has a thickness of about 80 nm to about 88 nm.

[0174] Aspect (26) of this disclosure relates to an article of aspect (25), wherein the second silicon dioxide layer has a thickness of about 83 nm to about 86 nm.

[0175] Aspect (27) of this disclosure relates to an article of aspect (15), wherein the first niobium oxide layer has a thickness of 12.4 nm, the first silicon dioxide layer has a thickness of 40.4 nm, the second niobium oxide layer has a thickness of 116 nm, and the second silicon dioxide layer has a thickness of 83.8 nm.

[0176] Aspect (28) of this disclosure relates to an article of aspect (15), wherein the first niobium oxide layer has a thickness of 11.9 nm, the first silicon dioxide layer has a thickness of 40.4 nm, the second niobium oxide layer has a thickness of 116.8 nm, and the second silicon dioxide layer has a thickness of 80.8 nm.

[0177] Aspect (29) of this disclosure relates to an article of aspect (27) or aspect (28), further comprising a buffer layer having a thickness ranging from about 20 nm to about 30 nm.

[0178] Aspect (30) of this disclosure relates to an article of any one of aspects (15) to (29), wherein the stack further comprises additional layers of alternating niobium oxide and silicon dioxide disposed on a second silicon dioxide layer.

[0179] Aspect (31) of this disclosure relates to articles of any of aspects (1) to (30), wherein the variation in thickness of any layer in the antireflective coating is + / - 2% or less of the thickness.

[0180] Aspect (32) of this disclosure relates to an article of aspect (31), wherein the thickness of each layer in the antireflective coating varies by + / -2% of the thickness.

[0181] Aspect (33) of this disclosure relates to an article of any one of aspects (1) to (32), wherein the article of article further comprises a functional layer disposed on the top layer of the stack.

[0182] The aspect (34) of this disclosure relates to the article of aspect (33), wherein the functional layer is at least one of an easy-clean layer and an anti-fingerprint layer.

[0183] Aspect (35) of this disclosure relates to articles of any one of aspects (1) to (34), wherein the width of the article is greater than or equal to 600 mm.

[0184] Aspect (36) of this disclosure relates to an article of any one of aspects (1) to (35), further comprising a decorative layer on at least one of a first main surface and a second main surface of a substrate.

[0185] Aspect (37) of this disclosure relates to articles of aspect (36), wherein the decorative layer comprises a coating, the coating comprising ink or pigment.

[0186] Aspect (38) of this disclosure relates to an article of any one of aspects (1) to (37), wherein a first main surface or a second main surface of a substrate comprises an anti-glare surface.

[0187] Aspect (39) of this disclosure relates to an article of aspect (38), wherein the anti-glare surface is an etched area in the first main surface or the second main surface of a substrate or a film disposed on the first main surface.

[0188] Aspect (40) of this disclosure relates to an article of aspect (38) or aspect (39), wherein an anti-glare surface is disposed on a first main surface of a substrate and an anti-reflective coating is disposed on the anti-glare surface.

[0189] Aspect (41) of this disclosure relates to an article of any one of aspects (38) to (40), wherein the anti-glare surface comprises a microtextured surface, the microtextured surface comprising a flat bottom valley structure.

[0190] Aspect (42) of this disclosure relates to an article of aspect (41), wherein the flat bottom valley structure includes a bottom surface and has protrusions on at least two sides of the bottom surface.

[0191] Aspect (43) of this disclosure relates to an article of aspect (42), wherein the bottom surface comprises a region of substantially flat average diameter ranging from about 1 μm, or from about 0.5 μm to about 1 μm.

[0192] The aspects (44) of this disclosure relate to the articles of aspect (42) or aspect (43).

[0193] The article of claim 42 or 43, wherein the average distance between the peaks of the protrusions is less than 10 μm.

[0194] Aspect (45) of this disclosure relates to an article of any one of aspects (38) to (44), wherein the environmental contrast ratio of the substrate having an anti-glare surface and an anti-reflective coating is greater than or equal to 5.

[0195] Aspect (46) of this disclosure relates to an article of aspect (45), wherein the environmental contrast ratio of the substrate having an anti-glare surface and an anti-reflective coating is 5.1.

[0196] Aspect (47) of this disclosure relates to an article of any one of aspects (38) to (46), wherein the degree of superimposed image reduction of the substrate having an anti-glare surface and an anti-reflective coating is greater than or equal to 30%.

[0197] Aspect (48) of this disclosure relates to an article of aspect (47), wherein the degree of reduction of superimposed image of the glass sheet having an anti-glare surface and an anti-reflective coating is 31.

[0198] Aspect (49) of this disclosure relates to an article of any one of aspects (38) to (48), wherein the color uniformity (ΔE / deg) of the substrate having an anti-glare surface and an anti-reflective coating is greater than or equal to 2.

[0199] The aspect (50) of this disclosure relates to the article of aspect (49), wherein the color uniformity (ΔE / deg) of the reflective surface having an anti-glare surface and an anti-reflective coating is 2.6.

[0200] Aspect (51) of this disclosure relates to an article of any one of aspects (1) to (50), wherein the first primary surface and the reflective surface of the substrate are complexly curved.

[0201] Aspect (52) of this disclosure relates to an article of any one of aspects (1) to (51), further comprising: a base having a non-planar support surface, a substrate disposed on the base, and a second main surface of the substrate facing the non-planar support surface.

[0202] Aspect (53) of this disclosure relates to an article of aspect (52), wherein the substrate is cold-formed on a non-planar support surface.

[0203] Aspect (54) of this disclosure relates to articles of aspect (52) or aspect (53), wherein the radius of curvature of the curved surface of the non-planar support surface is greater than or equal to 50 mm, greater than or equal to 100 mm, or greater than or equal to 500 mm.

[0204] Aspect (55) of this disclosure relates to articles of any one of aspects (1) to (54), wherein ΔE θ It is less than 4, or less than 3, or less than 2.

[0205] Aspect (56) of this disclosure relates to an article of any one of aspects (1) to (55), wherein for any two different values ​​of θ1 and θ2 in the range of about 10° to about 30°, ΔE θ It is less than or equal to about 1.7, less than or equal to about 1.5, less than or equal to about 1.4, or less than or equal to about 1.2.

[0206] Aspect (57) of this disclosure relates to an article of any of aspects (1) to (56), wherein for any two different values ​​of θ1 and θ2 in the range of about 15° to about 45°, ΔE θ It is less than or equal to about 2.9, less than or equal to about 2.6, less than or equal to about 2.5, less than or equal to about 2.4, less than or equal to about 2.3, less than or equal to about 2.1, less than or equal to about 2.0, less than or equal to about 1.9, or less than or equal to about 1.8.

[0207] Aspect (58) of this disclosure relates to articles of any of aspects (1) to (57), wherein for any two different values ​​of θ1 and θ2 in the range of about 45° to about 60°, ΔE θ It is less than or equal to about 1.0, less than or equal to about 0.8, less than or equal to about 0.7, less than or equal to about 0.6, less than or equal to about 0.5, or less than or equal to about 0.2.

[0208] Aspect (59) of this disclosure relates to a vehicle comprising articles of any one of aspects (1) to (58).

[0209] Aspect (60) relates to aspect (59) of the vehicle, wherein the article is the interior surface of the vehicle.

[0210] Aspect (61) refers to a vehicle relating to aspect (59) or aspect (60), wherein the article of manufacture is composed of at least a portion of an instrument panel, instrument panel, control panel, center console, steering wheel, side door components, entertainment unit, or graphic or video display.

[0211] Aspect (62) relates to any of the vehicles in aspects (59) to (61), wherein any two points on the reflective surface of the substrate containing the anti-reflective coating have the same angular color change ΔEθ.

[0212] Aspect (63) relates to an antireflective coating comprising alternating stacks of high-refractive-index and low-refractive-index materials, the antireflective coating including a reflective surface configured to face an observer, wherein at a point on the reflective surface, the antireflective coating comprises materials having an angular color variation ΔE θ The reflectivity of a single surface under a D65 light source is defined as: ΔE θ = √{(a* θ1 –a* θ2 ) 2 + (b* θ1 – b* θ2 ) 2}, where a* θ1 With b* θ1 These are the a* and b* values ​​of the point measured from the first angle θ1, where a* θ2 With b* θ2 The values ​​of a* and b* are measured from the second angle θ2, where θ1 and θ2 are any two different viewing angles spaced at least 5 degrees apart in the range of approximately 10° to approximately 60° relative to the normal vector of the top side, and where ΔE θ Less than 5.

[0213] Aspect (64) relates to the antireflective coating of aspect (63), wherein the reflective surface comprises a unilateral reflective color at viewing angles ranging from about 10° to about 60°, or at all viewing angles ranging from about 10° to about 60°, wherein the a* value is from about -2 to about 1, and the b* value is from about -4 to about 1.

[0214] Aspect (65) relates to the antireflective coating of aspect (64), wherein at a viewing angle of about 10°, the reflective surface comprises a unilateral reflective color, wherein the a* value is about -2 to about 0 and the b* value is about -4 to about -1.

[0215] Aspect (66) relates to an antireflective coating of any of aspects (63) to (65), wherein at a viewing angle of about 60°, the reflective surface comprises a unilateral reflective color, wherein the a* value is about -1 to about 1 and the b* value is about -2 to about 1.

[0216] Aspect (67) relates to an antireflective coating of any of aspects (63) to (66), wherein the reflective surface comprises a unilateral reflective color at all viewing angles from about 10° to about 60°, wherein the a* value is from about -2 to about 1 and the b* value is from about -4 to about 1.

[0217] Aspect (68) relates to an antireflective coating of any of aspects (63) to (67), wherein θ1 and θ2 are any two different viewing angles within the range of about 10° to about 50°, about 10° to about 40°, about 10° to about 30°, about 10° to about 20°, about 20° to about 60°, about 30° to about 60°, about 40° to about 60°, or about 50° to about 60°.

[0218] Aspect (69) relates to an antireflective coating of any of aspects (63) to (67), wherein θ1 and θ2 are any two different viewing angles within the range of about 20° to about 30°, about 30° to about 40°, or about 40° to about 50°.

[0219] Aspect (70) relates to an antireflective coating of any of aspects (63) to (69), wherein the low refractive index material contains a refractive index in the range of about 1.3 to about 1.7, and the high refractive index material contains a refractive index in the range of about 1.7 to about 2.5.

[0220] Aspect (71) relates to the antireflective coating of aspect (70), wherein stacked layers comprise alternating layers of silicon dioxide (SiO2) and niobium oxide (Nb2O5).

[0221] Aspect (72) relates to an anti-reflective coating of any of aspects (63) to (71), wherein the stack comprises four layers.

[0222] Aspect (73) relates to an antireflective coating of any of aspects (63) to (72), the antireflective coating further comprising a buffer layer, the stack being disposed on the buffer layer.

[0223] Aspect (74) relates to the antireflective coating of aspect (73), wherein the buffer layer comprises silicon dioxide.

[0224] Aspect (75) relates to the antireflective coating of aspect (73) or aspect (74), wherein the buffer layer comprises a thickness ranging from about 20 nm to about 30 nm.

[0225] Aspect (76) relates to an antireflective coating of any one of aspects (63) to (75), wherein the antireflective coating comprises a silicon dioxide buffer layer and a stack comprising a first niobium oxide (Nb2O5) layer disposed on the buffer layer, a first silicon dioxide (SiO2) layer disposed on the first niobium oxide layer, a second niobium oxide (Nb2O5) layer disposed on the first silicon dioxide layer, and a second silicon dioxide (SiO2) layer disposed on the second niobium oxide layer.

[0226] Aspect (77) relates to the antireflective coating of aspect (76), wherein the thickness of the first niobium oxide layer is less than that of the second niobium oxide layer.

[0227] Aspect (78) relates to an antireflective coating of aspect (76) or aspect (77), wherein the thickness of the first silicon dioxide layer is less than that of the second silicon dioxide layer.

[0228] Aspect (79) relates to an antireflective coating of any of aspects (76) to (78), wherein the first niobium oxide layer has a thickness of about 11 nm to about 13 nm.

[0229] Aspect (80) relates to the antireflective coating of aspect (79), wherein the first niobium oxide layer has a thickness of about 11 nm to about 12 nm.

[0230] Aspect (81) relates to an antireflective coating of any of aspects (76) to (80), wherein the first silicon dioxide layer has a thickness of about 40 nm to about 45 nm.

[0231] Aspect (82) relates to the antireflective coating of aspect (81), wherein the first silicon dioxide layer has a thickness of about 41 nm to about 44 nm.

[0232] Aspect (83) relates to an antireflective coating of any of aspects (76) to (82), wherein the second niobium oxide layer has a thickness of about 115 nm to about 125 nm.

[0233] Aspect (84) relates to the antireflective coating of aspect (83), wherein the second niobium oxide layer has a thickness of about 116 nm to about 121 nm.

[0234] Aspect (85) relates to the antireflective coating of aspect (84), wherein the second niobium oxide layer has a thickness of about 118 nm to about 120 nm.

[0235] Aspect (86) relates to an antireflective coating of any of aspects (76) to (85), wherein the second silicon dioxide layer has a thickness of about 80 nm to about 88 nm.

[0236] Aspect (87) relates to the antireflective coating of aspect (86), wherein the second silicon dioxide layer has a thickness of about 83 nm to about 86 nm.

[0237] Aspect (88) relates to the antireflective coating of aspect (76), wherein the first niobium oxide layer has a thickness of 12.4 nm, the first silicon dioxide layer has a thickness of 40.4 nm, the second niobium oxide layer has a thickness of 116 nm, and the second silicon dioxide layer has a thickness of 83.8 nm.

[0238] Aspect (89) relates to the antireflective coating of aspect (76), wherein the first niobium oxide layer has a thickness of 11.9 nm, the first silicon dioxide layer has a thickness of 40.4 nm, the second niobium oxide layer has a thickness of 116.8 nm, and the second silicon dioxide layer has a thickness of 80.8 nm.

[0239] Aspect (90) relates to an antireflective coating of aspect (88) or aspect (89), wherein the silica buffer layer has a thickness ranging from about 20 nm to about 30 nm.

[0240] Aspect (91) relates to an antireflective coating of any of aspects (76) to (90), wherein the stack further comprises additional layers of alternating niobium oxide and silicon dioxide disposed on a second silicon dioxide layer.

[0241] Aspect (92) relates to an antireflective coating of any of aspects (63) to (91), wherein the thickness of any layer of the antireflective coating varies by + / -2% of the thickness.

[0242] Aspect (93) relates to the antireflective coating of aspect (92), wherein the thickness of each layer in the antireflective coating varies by + / - 2% of the thickness.

[0243] Aspect (94) relates to an antireflective coating of any one of aspects (63) to (93), wherein the width of the reflective surface is greater than or equal to 600 mm.

[0244] Aspect (95) relates to an antireflective coating of any one of aspects (63) to (94), wherein ΔE θ It is less than 4, or less than 3, or less than 2.

[0245] Aspect (96) relates to an antireflective coating of any of aspects (63) to (95), wherein for any two different values ​​of θ1 and θ2 in the range of about 10° to about 30°, ΔE θ It is less than or equal to about 1.7, less than or equal to about 1.5, less than or equal to about 1.4, or less than or equal to about 1.2.

[0246] Aspect (97) relates to an antireflective coating of any of aspects (63) to (96), wherein for any two different values ​​of θ1 and θ2 within the range of about 15° to about 45°, ΔE θ It is less than or equal to about 2.9, less than or equal to about 2.6, less than or equal to about 2.5, less than or equal to about 2.4, less than or equal to about 2.3, less than or equal to about 2.1, less than or equal to about 2.0, less than or equal to about 1.9, or less than or equal to about 1.8.

[0247] Aspect (98) relates to an antireflective coating of any of aspects (63) to (97), wherein for any two different values ​​of θ1 and θ2 in the range of about 45° to about 60°, ΔE θ It is less than or equal to about 1.0, less than or equal to about 0.8, less than or equal to about 0.7, less than or equal to about 0.6, less than or equal to about 0.5, or less than or equal to about 0.2.

[0248] Aspect (99) relates to a method for producing an antireflective coating, comprising the steps of: providing a substrate including a first main surface; depositing an antireflective coating on the first main surface, the antireflective coating comprising a stack having a reflective surface opposite to the first main surface and alternating layers of silicon dioxide (SiO2) and niobium oxide (Nb2O5), wherein at a point on the reflective surface, the antireflective coating comprises having an angular color change ΔE θ The reflectivity of a single surface under a D65 light source is defined as: ΔE θ =√{(a* θ1 – a* θ2 ) 2 + (b* θ1 – b* θ2 ) 2}, where a* θ1 With b* θ1 These are the a* and b* values ​​of the point measured from the first angle θ1, where a* θ2 With b* θ2 The values ​​of a* and b* at a point measured from the second angle θ2, where θ1 and θ2 are any two different viewing angles spaced at least 5 degrees apart in the range of approximately 10° to approximately 60° relative to the normal vector of the first principal surface, and where ΔE θ Less than 5.

[0249] Aspect (100) relates to the method of aspect (99), wherein the antireflective coating further comprises a buffer layer disposed between the stack and the first main surface and disposed on the first main surface.

[0250] Aspect (101) relates to the method of aspect (99) or aspect (100), wherein the reflective surface comprises a unilateral reflective color at viewing angles ranging from about 10° to about 60°, or at all viewing angles ranging from about 10° to about 60°, wherein the a* value is from about -2 to about 1, and the b* value is from about -4 to about 1.

[0251] Aspect (102) relates to a method of any of aspects (99) to (101), wherein at a viewing angle of about 10°, the reflective surface comprises a unilateral reflective color, wherein the a* value is about -2 to about 0 and the b* value is about -4 to about -1.

[0252] Aspect (103) relates to a method of any of aspects (99) to (102), wherein at a viewing angle of about 60°, the reflective surface comprises a unilateral reflective color, wherein the a* value is about -1 to about 1 and the b* value is about -2 to about 1.

[0253] Aspect (104) relates to a method of any of aspects (99) to (103), wherein the reflective surface comprises a unilateral reflective color at all viewing angles from about 10° to about 60°, wherein the a* value is from about -2 to about 1 and the b* value is from about -4 to about 1.

[0254] Aspect (105) relates to the method of any of aspects (99) to (104), wherein θ1 and θ2 are any two different viewing angles within the range of about 10° to about 50°, about 10° to about 40°, about 10° to about 30°, about 10° to about 20°, about 20° to about 60°, about 30° to about 60°, about 40° to about 60°, or about 50° to about 60°.

[0255] Aspect (106) relates to the method of any of aspects (99) to (105), wherein θ1 and θ2 are any two different viewing angles within the range of about 20° to about 30°, about 30° to about 40°, or about 40° to about 50°.

[0256] Aspect (107) relates to a method of any of aspects (99) to (106), wherein the alternating layers of silicon dioxide and niobium oxide comprise: a first niobium oxide layer disposed on a buffer layer; a first silicon dioxide layer disposed on the first niobium oxide layer; a second niobium oxide layer disposed on the first silicon dioxide layer; and a second silicon dioxide layer disposed on the second niobium oxide layer.

[0257] Aspect (108) relates to the method of aspect (107), wherein the step of depositing the antireflective coating comprises the following steps: depositing a first niobium oxide layer on a buffer layer; depositing a first silicon dioxide layer on the first niobium oxide layer; depositing a second niobium oxide layer on the first silicon dioxide layer; and depositing a second silicon dioxide layer disposed on the second niobium oxide layer.

[0258] Aspect (109) relates to the method of aspect (107) or aspect (108), wherein the thickness of the first niobium oxide layer is less than that of the second niobium oxide layer.

[0259] Aspect (110) relates to a method of any of aspects (107) to (109), wherein the thickness of the first silicon dioxide layer is less than that of the second silicon dioxide layer.

[0260] Aspect (111) relates to the method of any of aspects (107) to (110), wherein the first niobium oxide layer has a thickness of about 11 nm to about 13 nm.

[0261] Aspect (112) relates to the method of aspect (111), wherein the first niobium oxide layer has a thickness of about 11 nm to about 12 nm.

[0262] Aspect (113) relates to the method of any of aspects (107) to (112), wherein the first silicon dioxide layer has a thickness of about 40 nm to about 45 nm.

[0263] Aspect (114) relates to the method of aspect (113), wherein the thickness of the first silicon dioxide layer is 40.4 nm.

[0264] Aspect (115) relates to the method of any of aspects (107) to (114), wherein the second niobium oxide layer has a thickness of about 115 nm to about 125 nm.

[0265] Aspect (116) relates to the method of aspect (115), wherein the second niobium oxide layer has a thickness of about 116 nm to about 121 nm.

[0266] Aspect (117) relates to the method of aspect (116), wherein the second niobium oxide layer has a thickness of about 118 nm to about 120 nm.

[0267] Aspect (118) relates to the method of any of aspects (107) to (117), wherein the second silicon dioxide layer has a thickness of about 80 nm to about 88 nm.

[0268] Aspect (119) relates to the method of aspect (118), wherein the second silicon dioxide layer has a thickness of about 83 nm to about 86 nm.

[0269] Aspect (120) relates to the method of aspect (107), wherein the first niobium oxide layer has a thickness of 12.4 nm, the first silicon dioxide layer has a thickness of 40.4 nm, the second niobium oxide layer has a thickness of 116 nm, and the second silicon dioxide layer has a thickness of 83.8 nm.

[0270] Aspect (121) relates to the method of aspect (107), wherein the first niobium oxide layer has a thickness of 11.9 nm, the first silicon dioxide layer has a thickness of 40.4 nm, the second niobium oxide layer has a thickness of 116.8 nm, and the second silicon dioxide layer has a thickness of 80.8 nm.

[0271] Aspect (122) relates to the method of any of aspects (100) to (121), wherein the buffer layer has a thickness ranging from about 20 nm to about 30 nm.

[0272] Aspect (123) relates to a method of any of aspects (100) to (122), wherein the buffer layer is silicon dioxide.

[0273] Aspect (124) relates to the method of any of aspects (100) to (123), wherein the variation in thickness of each of the first and second silicon dioxide layers and the first and second niobium oxide layers is within + / - 2% of the thickness.

[0274] Aspect (125) relates to the method of any of aspects (100) to (124), wherein the stack comprises four layers.

[0275] Aspect (126) relates to any of aspects (99) to (125) of the method, wherein the substrate is a glass sheet, the glass sheet comprising a first main surface, a second main surface opposite to the first main surface, and a secondary surface separating the first and second main surfaces.

[0276] Aspect (127) relates to the method of aspect (126) and further includes the step of forming an anti-glare surface on a first main surface of a glass sheet prior to depositing an anti-reflective coating, wherein the anti-reflective surface is deposited on the anti-glare surface.

[0277] Aspect (128) relates to the method of aspect (127), wherein the step of forming the anti-glare surface includes the step of etching at least a portion of the first main surface.

[0278] Aspect (129) relates to the method of aspect (127) or aspect (128), wherein the anti-glare surface comprises a microtextured surface, the microtextured surface comprising a flat bottom valley structure.

[0279] Aspect (130) relates to the method of aspect (129), wherein the bottom surface comprises a region of approximately 1 μm in average diameter that is substantially flat.

[0280] Aspect (131) relates to the method of aspect (129) or aspect (130), wherein the average distance between the peaks of the protrusions is about 2 μm.

[0281] Aspect (132) relates to any of the methods of aspects (127) to (131), wherein the environmental contrast ratio of the substrate having the anti-glare surface and the anti-reflective coating is greater than or equal to 5.

[0282] Aspect (133) relates to the method of aspect (132), wherein the environmental contrast ratio of the substrate having an anti-glare surface and an anti-reflective coating is 5.1.

[0283] Aspect (134) relates to any of the methods in aspects (127) to (133), wherein the degree of reduction of the superimposed image of the substrate having an anti-glare surface and an anti-reflective coating is greater than or equal to 30%.

[0284] Aspect (135) relates to any of the methods in aspects (127) to (134), wherein the degree of reduction of superimposed image of the substrate having an anti-glare surface and an anti-reflective coating is 31.

[0285] Aspect (136) relates to any of the methods in aspects (127) to (135), wherein the color uniformity (ΔE / deg) of the substrate having an anti-glare surface and an anti-reflective coating is greater than or equal to 2.

[0286] Aspect (137) relates to any of the methods in aspects (127) to (136), wherein the color uniformity (ΔE / deg) of the substrate having an anti-glare surface and an anti-reflective coating is 2.6.

[0287] Aspect (138) relates to the method of any of aspects (99) to (137), where ΔE θ It is less than 4, or less than 3, or less than 2.

[0288] Aspect (139) relates to the method of any of aspects (99) to (138), wherein for any two distinct values ​​of θ1 and θ2 within the range of about 10° to about 30°, ΔE θ It is less than or equal to about 1.7, less than or equal to about 1.5, less than or equal to about 1.4, or less than or equal to about 1.2.

[0289] Aspect (140) relates to the method of any of aspects (99) to (139), wherein for any two distinct values ​​of θ1 and θ2 within the range of about 15° to about 45°, ΔE θIt is less than or equal to about 2.9, less than or equal to about 2.6, less than or equal to about 2.5, less than or equal to about 2.4, less than or equal to about 2.3, less than or equal to about 2.1, less than or equal to about 2.0, less than or equal to about 1.9, or less than or equal to about 1.8.

[0290] Aspect (141) relates to the method of any of aspects (99) to (140), wherein for any two distinct values ​​of θ1 and θ2 within the range of approximately 45° to approximately 60°, ΔE θ It is less than or equal to about 1.0, less than or equal to about 0.8, less than or equal to about 0.7, less than or equal to about 0.6, less than or equal to about 0.5, or less than or equal to about 0.2.

Claims

1. A glass article comprising: A substrate, comprising a first main surface and a second main surface, wherein the second main surface is opposite to the first main surface and spaced apart from the first main surface by the thickness of the substrate; and An anti-reflective coating is disposed on the first main surface, the anti-reflective coating comprising a reflective surface opposite to the first main surface. When the reflective surface is illuminated by a D65 light source and viewed at an angle ranging from 10° to 60°, the maximum change in a* value and the maximum change in b* value of the glass product are less than 5.

0. The anti-reflective coating has a thickness in the range of 200 nm to 300 nm.

2. The glass article according to claim 1, wherein when illuminated by a D65 light source at a viewing angle of 60°, the reflective surface comprises a unilateral reflective color, wherein the b* value ranges from -1 to 1.

3. The glass article according to claim 1, wherein when illuminated by a D65 light source, at viewing angles ranging from 10° to 60°, or at all viewing angles ranging from 10° to 60°, the reflective surface comprises a unilateral reflective color, wherein the a* value is from -2 to 1 and the b* value is from -4 to 1.

4. The glass article of claim 1, wherein the antireflective coating comprises alternating stacks of high-refractive-index material and low-refractive-index material, wherein the low-refractive-index material comprises a refractive index in the range of 1.3 to 1.7, and the high-refractive-index material comprises a refractive index in the range of 1.7 to 2.

5.

5. The glass article according to claim 4, wherein the low refractive index material comprises silicon dioxide (SiO2), and the high refractive index material comprises niobium oxide (Nb2O5) or titanium oxide (TiO2). n ), and wherein the stack comprises four layers, wherein the stack is disposed on an optional buffer layer disposed on the first main surface.

6. The glass article according to claim 5, wherein the antireflective coating comprises a stack comprising a first niobium oxide (Nb₂O₅) layer disposed on the substrate, a first silicon dioxide (SiO₂) layer disposed on the first niobium oxide layer, a second niobium oxide (Nb₂O₅) layer disposed on the first silicon dioxide layer, and a second silicon dioxide (SiO₂) layer disposed on the second niobium oxide layer, and comprising any one of the following: Wherein the thickness of the first niobium oxide layer is less than the thickness of the second niobium oxide layer, and The thickness of the first silicon dioxide layer is less than the thickness of the second silicon dioxide layer.

7. The glass article according to claim 6, wherein at least one of the following is true: The thickness of the first niobium oxide layer is 11 nm to 13 nm. The thickness of the first silicon dioxide layer is 40 nm to 45 nm. The thickness of the second niobium oxide layer is 115 nm to 125 nm, and The thickness of the second silicon dioxide layer is 80 nm to 88 nm.

8. The glass article of claim 7, wherein the thickness variation of each layer in the antireflective coating is + / - 2% of the thickness.

9. The glass article according to claim 1, further comprising: A base having a non-planar support surface, a substrate disposed on the base, the second main surface of the substrate facing the non-planar support surface, wherein the substrate is cold-formed on the non-planar support surface, and wherein the glass article is an interior surface of a vehicle.

10. The glass article according to any one of claims 1 to 9, wherein the first main surface or the second main surface of the substrate includes an anti-glare surface, wherein the anti-glare surface is disposed on the first main surface of the substrate, and the anti-reflective coating is disposed on the anti-glare surface.

11. The glass article according to claim 10, wherein: At a point on the reflective surface containing the anti-reflective coating, the glass article exhibits an angular color change ΔE under a D65 light source. θ The reflectivity of a single surface, ΔE θ Defined as: Where a* θ1 With b* θ1 The a* and b* values ​​of the point are measured from the first angle θ1, where a* θ2 With b* θ2 The values ​​of a* and b* at the point are measured from the second angle θ2, where θ1 and θ2 are any two different viewing angles spaced at least 5 degrees apart in the range of 10° to 60° relative to the normal vector of the reflecting surface. ΔE θ Less than 5.

12. The glass article according to claim 11, further comprising any one of the following: The environmental contrast ratio of the substrate having the anti-glare surface and the anti-reflective coating is greater than or equal to 5. The substrate having the anti-glare surface and the anti-reflective coating has a superimposed image reduction of greater than or equal to 30%, and ΔE θ Less than 2.

13. The glass article of claim 11, wherein any two points on the reflective surface of the substrate comprising the antireflective coating have the same angular color change ΔE. θ .

14. The glass article according to any one of claims 1 to 9, wherein the average visible light reflectance of the reflective surface is 1% or less over a viewing angle range of 0° to 20°.

15. A glass article comprising: A substrate, comprising a first main surface and a second main surface, wherein the second main surface is opposite to the first main surface and spaced apart from the first main surface by the thickness of the substrate; and An anti-reflective coating is disposed on the first main surface, the anti-reflective coating comprising a reflective surface opposite to the first main surface. When the reflective surface is illuminated by a D65 light source and viewed at an angle ranging from 10° to 60°, the glass article exhibits √((a* 最高 -a* 最低 ) 2 +(b* 最高 -b* 最低 ) 2 ) less than 5.0, where a* 最高 This represents the maximum a* value observed within the stated viewing angle range, b* 最高 This represents the maximum b* value observed within the stated viewing angle range, a* 最低 This represents the minimum a* value observed within the stated viewing angle range, b* 最低 This represents the minimum b* value observed within the stated viewing angle range, and The anti-reflective coating has a thickness in the range of 200 nm to 300 nm.

16. The glass article of claim 15, wherein when illuminated by a D65 light source at a viewing angle of 60°, the reflective surface comprises a unilateral reflective color, wherein the b* value ranges from -1 to 1.

17. The glass article of claim 15, wherein when illuminated by a D65 light source, at viewing angles ranging from 10° to 60°, or at all viewing angles ranging from 10° to 60°, the reflective surface comprises a unilateral reflective color, wherein the a* value is from -2 to 1 and the b* value is from -4 to 1.

18. The glass article of claim 15, wherein the antireflective coating comprises alternating stacks of high-refractive-index material and low-refractive-index material, wherein the low-refractive-index material comprises a refractive index in the range of 1.3 to 1.7, and the high-refractive-index material comprises a refractive index in the range of 1.7 to 2.

5.

19. The glass article of claim 18, wherein the low refractive index material comprises silicon dioxide (SiO2) and the high refractive index material comprises niobium oxide (Nb2O5) or titanium oxide (TiO2). n ), and wherein the stack comprises four layers, wherein the stack is disposed on an optional buffer layer disposed on the first main surface.

20. The glass article of claim 19, wherein the antireflective coating comprises a stack comprising a first niobium oxide (Nb₂O₅) layer disposed on the substrate, a first silicon dioxide (SiO₂) layer disposed on the first niobium oxide layer, a second niobium oxide (Nb₂O₅) layer disposed on the first silicon dioxide layer, and a second silicon dioxide (SiO₂) layer disposed on the second niobium oxide layer, and comprising any one of the following: Wherein the thickness of the first niobium oxide layer is less than the thickness of the second niobium oxide layer, and The thickness of the first silicon dioxide layer is less than the thickness of the second silicon dioxide layer.

21. The glass article according to claim 20, wherein at least one of the following is true: The thickness of the first niobium oxide layer is 11 nm to 13 nm. The thickness of the first silicon dioxide layer is 40 nm to 45 nm. The thickness of the second niobium oxide layer is 115 nm to 125 nm, and The thickness of the second silicon dioxide layer is 80 nm to 88 nm.

22. The glass article of claim 21, wherein the thickness variation of each layer in the antireflective coating is + / - 2% of the thickness.

23. The glass article according to any one of claims 15 to 22, wherein the first main surface or the second main surface of the substrate includes an anti-glare surface, wherein the anti-glare surface is disposed on the first main surface of the substrate, and the anti-reflective coating is disposed on the anti-glare surface.

24. The glass article according to claim 23, wherein: At a point on the reflective surface containing the anti-reflective coating, the glass article exhibits an angular color change ΔE under a D65 light source. θ The reflectivity of a single surface, ΔE θ Defined as: Where a* θ1 With b* θ1 The a* and b* values ​​of the point are measured from the first angle θ1, where a* θ2 With b* θ2 The values ​​of a* and b* at the point are measured from the second angle θ2, where θ1 and θ2 are any two different viewing angles spaced at least 5 degrees apart in the range of 10° to 60° relative to the normal vector of the reflecting surface. ΔE θ Less than 5.

25. The glass article of claim 24, further comprising any one of the following: The environmental contrast ratio of the substrate having the anti-glare surface and the anti-reflective coating is greater than or equal to 5. The substrate having the anti-glare surface and the anti-reflective coating has a superimposed image reduction of greater than or equal to 30%, and ΔE θ Less than 2.

26. The glass article of claim 24, wherein any two points on the reflective surface of the substrate comprising the antireflective coating have the same angular color change ΔE. θ .

27. The glass article according to any one of claims 15 to 22, wherein the average visible light reflectance of the reflective surface is 1% or less over a viewing angle range of 0° to 20°.

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